WO2020175560A1 - Resin composition, resin film, and liquid crystal display element - Google Patents

Abstract

The present invention provides a normal-type liquid crystal display element in which it is possible to suppress separation of the element, generation of air bubbles, and reductions in optical characteristics, even in a severe environment that is exposed to high temperatures and high humidity, or to irradiation with light, for a long period of time.　This normal-type liquid crystal display element has a liquid crystal layer in which a liquid crystal composition, which includes a polymerizable compound and liquid crystals arranged between a pair of substrates that comprise electrodes, is cured by applying active energy rays and/or heat to the liquid crystal composition, the normal-type liquid crystal display element also comprising a resin film on at least one of the substrates, and furthermore assuming a scattering state when voltage is not applied and assuming a transparent state when voltage is applied, wherein the normal-type liquid crystal display element is characterized in that the resin film is obtained using a resin composition that includes a compound having groups indicated in formula [1].　The * symbol represents a site for bonding to other structures.

Description

Specification

Title of invention: Resin composition, resin film and liquid crystal display device

Technical field

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

Background technology

As a liquid crystal display element, a TN (Twisted Nematic) mode has been put into practical use. In this mode, it is necessary to use a polarizing plate to switch the light by utilizing the optical rotation property of the liquid crystal. If a polarizing plate is used, the light utilization efficiency will be low.

[0003]As a liquid crystal display element that does not use a polarizing plate, there is an element that switches between a transparent state (also called a transparent state) and a scattering state of liquid crystal. In general, those using a high molecular dispersion liquid crystal (also referred to as PD LC (Polymer Dispersed Liquid Crystal)) or a polymer network liquid crystal (PN LC (Polymer Network Liquid Crystal)) are known. ing. In these liquid crystal display elements, a liquid crystal composition containing a polymerizable compound that is polymerized by ultraviolet rays is placed between a pair of substrates equipped with electrodes, and the liquid crystal composition is cured by irradiation with ultraviolet rays to It forms a complex with a cured product of a polymerizable compound (for example, a polymer network). Then, in this liquid crystal display element, the scattering state and the transmitting state of the liquid crystal are controlled by applying a voltage.

In a liquid crystal display device using PD LC or PN LC, the liquid crystal is oriented in a random direction when no voltage is applied, resulting in a cloudy (scattering) state, and when voltage is applied, the liquid crystal is aligned in the electric field direction. There is a normal type liquid crystal display element that transmits light and becomes a transmissive state (also called a normal type element). In this case, since the liquid crystal is random when no voltage is applied, there is no need for a liquid crystal alignment film or alignment treatment for orienting the liquid crystal in one direction. Therefore, in this liquid crystal display element, the electrode and the liquid crystal layer (composite of the liquid crystal and the cured product of the polymerizable compound) are in direct contact with each other (Patent References 1 and 2).

Prior art documents

Patent literature

[0004] Patent Document 1: Japanese Patent No. 3 5 5 2 3 2 8

Patent Document 2: Japanese Patent No. 4 6 3 0 9 5 4

Summary of the invention

Problems to be Solved by the Invention

[0005] The polymerizable compound in the liquid crystal composition has a role of forming a polymer network to obtain desired optical characteristics and a role of enhancing the adhesion between the liquid crystal layer and the electrode. However, since an inorganic electrode such as To O (Indium Tin Oxide) is used in this device, the compatibility with the organic polymerizable compound, that is, the adhesiveness tends to be low. If the adhesion is low, the element will peel off or bubbles will be generated due to the harsh environment such as long-term use, especially the environment exposed to high temperature and high humidity or light irradiation, and the optical characteristics of the scattering state and the transparent state. More likely to cause

[0006] Therefore, the present invention provides a normal type liquid crystal capable of suppressing peeling of elements, generation of bubbles, and deterioration of optical characteristics even in a harsh environment exposed to high temperature and high humidity and irradiation of light for a long time. An object is to provide a display element.

Means for solving the problem

[0007] As a result of intensive research conducted by the present inventor to achieve the above object, the present inventor has completed the present invention having the following points.

That is, a liquid crystal composition containing a liquid crystal and a polymerizable compound, which is disposed between a pair of substrates provided with electrodes, has a liquid crystal layer that is hardened by applying at least one of active energy rays and heat, and A transmission-scattering normal type liquid crystal display device comprising a resin film on at least one of the substrates, which is in a scattering state when no voltage is applied, and is in a transparent state when a voltage is applied,

The compound in which the resin film has a group represented by the following formula [1] (also referred to as a specific compound). 〇 2020/175 560 3 卩 (：171? 2020 /007782

A liquid crystal display device characterized by being obtained using a resin composition containing

[0008] [Chemical 1]

[0009] A symbol represents a binding site with another structure.

Effect of the invention

According to the present invention, even in a harsh environment exposed to high temperature and high humidity or light irradiation for a long time, peeling of an element, generation of bubbles, and deterioration of optical characteristics can be suppressed. A liquid crystal display device is obtained.

The mechanism by which the liquid crystal display device having the above-mentioned excellent characteristics is obtained by the present invention is not necessarily clear, but it is presumed as follows.

[001 1] Since the specific compound contained in the resin composition for producing the resin film of the liquid crystal display element has a disulfide bond (3-3) and a thioketone (〇 = 3) group, Adhesion with the metal electrode is enhanced. In addition, since the amino group (1\1) in the characteristic compound exhibits weak basicity, it is thought that the reaction of the polymerizable compound in the liquid crystal composition is promoted and a stronger polymer network can be formed. To be

Thus, the liquid crystal display device using the resin composition containing the specific compound becomes the liquid crystal display device having the above characteristics. Therefore, the liquid crystal display device of the present invention can be used for a liquid crystal display for display, a dimming window for controlling light blocking and light transmission, an optical shutter device, and the like.

MODE FOR CARRYING OUT THE INVENTION

[0012] <Specific compound>

The specific compound is the compound of the above formula [1].

Specific examples of the specific compound include the following formula [13]. 〇 2020/175 560 4 卩 (：171? 2020 /007782

丁¹は、 下記式 ［1 ^_ 8］ 〜式 ［1 _ 1"1］ から選ばれる少なくとも 1種の構 造を示す。 [0013] [Chemical 2]

Ding ¹ shows at least one structure selected from the following formula [ ^1_8 ] to formula [1_1"1].

[0014] [Chemical Formula 3]

[0015] D represents an alkyl group having 1 to 3 carbon atoms.

[0016] Among them, the formula [1 _ 10], the formula [1 _ 0] or the formula [1 _ 0 1] is preferable.

Ding ² represents a single bond or an organic group having 1 to 18 carbon atoms. Of these, a single bond or an organic group having 1 to 6 carbon atoms is preferable.

Ding ³ shows the structure of the above formula [1].

[0017] More specific examples of the specific compound include the following formula [1-13], and it is preferable to use this.

[0018] [Chemical 4]

[0019] From the viewpoint of adhesion between the resin film and the metal electrode, the use ratio of the specific compound is from 0.1 to 30 with respect to 100 parts by mass of all the polymers contained in the resin composition. Parts by mass are preferred. More preferably, it is 0.5 to 20 parts by mass. Most preferred 〇 2020/175 560 5 卩 (：171? 2020 /007782

The amount is 1 to 15 parts by mass. Further, the specific compound may be used alone or in combination of two or more depending on each characteristic.

[0020] <Polymer>

The resin composition containing a specific compound of the present invention preferably comprises a polymer having at least one structure (also referred to as a specific structure.) Selected from the following formulas [2 _ _3] to the formula [2 _丨] ..

It is preferable that the specific structure is contained in the repeating unit that constitutes the polymer. The repeating unit containing a specific structure is preferably contained in an amount of 10 to 70 mol %, more preferably 20 to 60 mol %, based on the entire repeating units constituting the polymer.

Further, the polymers having a specific structure may be used alone or in combination of two or more, depending on each characteristic.

[0021] [Chemical 5]

[0022] X represents a hydrogen atom or a benzene ring.

Among them, the formulas [2-8] to [formula] are preferable. More preferred are formula [2-3] to formula [2-6]. From the viewpoint of the adhesion between the liquid crystal layer and the resin film, the formula [2-3], the formula [2_10], the formula [2_01], or the formula [2_㊀] is particularly preferable.

By using a specific structure, photoreaction with the reactive group of the polymerizable compound in the liquid crystal composition occurs in the process of irradiation with ultraviolet light or heating during the production of the liquid crystal display element, 〇 2020/175 560 6 卩 (：171? 2020 /007782

It is considered that the adhesion between the layer and the resin film becomes strong.

The polymer is not particularly limited, but at least one polymer selected from acrylic polymers, methacrylic polymers, novolac resins, polyhydroxystyrenes, polyimide precursors, polyimides, polyamides, polyesters, celluloses and polysiloxanes. Coalescence is preferred. More preferred are polyimide precursors or polyimides.

When a polyimido precursor or polyimido (collectively referred to as polyimido polymer) is used as a polymer, they are a polyimido precursor or a polyimido precursor obtained by reacting a diamine component with a tetracarboxylic acid component. Polyimide is preferred.

[0023] The polyimide precursor has, for example, a structure of the following formula [8].

[0024] [Chemical 6]

2価の有機基を示す。 ¹及び八 ²は それぞれ、 水素原子又は炭素数

[0025] represents a tetravalent organic group.

Indicates a divalent organic group. Each ¹ and eight ² is a hydrogen atom or a carbon atoms

And a hydrogen atom, an alkyl group having 1 to 5 carbon atoms or an acetyl group. n is a positive integer.

[0026] The diamine component is a diamine having two primary or secondary amino groups in the molecule, and the tetracarboxylic acid component is a tetracarboxylic acid compound, a tetracarboxylic dianhydride, or a tetracarboxylic acid. Examples thereof include a dihalide compound, a tetracarboxylic acid dialkyl ester compound, and a tetracarboxylic acid dialkylester dihalide compound.

[0027] From the reason that the polyimide-based polymer can be obtained relatively easily by using the tetracarboxylic acid dianhydride of the following formula [M] and the diamine of the following formula [0] as the raw materials, A polyamic acid having the structural formula of the repeating unit of the formula \¥0 2020/175 560 7 卩(: 17 2020/007782

Polyimide prepared by imidizing polyamic acid is preferable.

[0028] [Chemical 7]

[0029] ¹ and ² are the same as defined in the formula [8].

[0030] [Chemical 8]

式 ［八］ で定義したものと同じである。 [0031]

It is the same as the one defined in Equation [8].

[0032] Further, according to a usual synthetic method, the polymer of the formula [mouth] obtained above is added to the polymer of the formula [8] having ¹ and ² alkyl groups having 1 to 8 carbon atoms, and ³ and eight ⁴ alkyl group or an acetyl group with carbon number from 1 to 5 can also be introduced.

As a method of introducing the specific structure into the polyimide-based polymer, it is preferable to use a diamine having the specific structure as a part of the raw material. In particular, it is preferable to use a diamine having a structure of the following formula [2] (also referred to as a specific diamine). [0033] [Chemical 9]

^_ ( 0 1^~1 ₃ ) ^_、 ^_ 0 1^~1 ₂〇 ^_、 ^_〇

〇一、 一〇〇 ( 0 1^~1 ₃ ) —、 一 ( 0 1^~1 ₃ ) 〇〇一、 一[0034] X ¹ is a single bond, ^_ 〇 ^_ ..

^_ (0 1 ^to 1 ₃ ) ^_ , ^_ 0 1 ^to 1 ₂ 〇 ^_ , ^_ 〇

○ 1, 100 (0 1 ^~ 1 ₃ )--, 1 (0 1 ^~ 1 ₃ ) 0 ○ 1, 1

^_〇〇〇 ^_又は ^_〇〇〇^_が好 〇 2020/175560 8 卩（：171? 2020 /007782 Indicates at least one kind selected from 001 and 100_. Among them, single bond, ^_ 〇 ^_ , ^_ 〇 1 ^to 1 ₂ 〇 ^_ ,

^_ 〇 〇 ^_ or ^_ 〇 〇 ^_ is preferred 〇 2020/175 560 8 卩 (：171? 2020 /007782

Good More preferred are the ease of the availability of raw materials and synthetic, single bond, one hundred and one, a ^_ Rei_1-1 ₂ 〇 one or ten thousand and one.

X ² represents a single bond, an alkylene group having 1 to 18 carbon atoms, or an organic group having 6 to 24 carbon atoms, which has a cyclic group selected from a benzene ring, a cyclohexane ring and a heterocycle. An arbitrary hydrogen atom of is an alkyl group having 1 to 3 carbon atoms, an alkoxyl group having 1 to 3 carbon atoms, a fluorine-containing alkyl group having 1 to 3 carbon atoms, a fluorine-containing alkoxyl group having 1 to 3 carbon atoms, or a fluorine atom. It may be replaced. Of these, a single bond, an alkylene group having 1 to 12 carbon atoms, a benzene ring or a cyclohexane ring is preferable. From the viewpoint of adhesiveness between the liquid crystal layer and the resin film, more preferred is a single bond or an alkylene group having 1 to 12 carbon atoms.

0 1^~1 ₃ ) —、 一 ( 0 1^~1 ₃ ) 〇〇一、 一 〇〇〇一及び一〇〇〇_から選ばれる少なくとも 1種を示す。 なかでも、 単 結合、 一〇一、 一〇〇〇一又は一〇〇〇一が好ましい。 より好ましいのは、 単結合又は一〇 <3〇一である。 1 (〇 1 ^~ 13 ₃ ) —, 10 1 ^~ 1 ₂ 0 1, 1, 10

0 1 ^to 1 ₃ ) —, 1 (0 1 ^to 1 ₃ ) Indicates at least one selected from 0, 1, 1, 0, 1 and 1, 00_. Among them, single bond, 101, 100111 or 100001 is preferable. More preferred is a single bond or 10 <301.

X ⁴ represents at least one structure selected from the above formula [2-8] to formula [2__]. Among them, the formulas [2-8] to [formula] are preferable. Equations [2-8] to [2-6] are more preferable. From the viewpoint of adhesion between the liquid crystal layer and the resin film, particularly preferred are Formula [2-8], Formula [2-10], Formula [2-¢1], or Formula [2-6]. ..

X n represents an integer of 1 to 4. Of these, 1 or 2 is preferable.

[0035] As the specific diamine, it is preferable to use a diamine of the following formula [23]. [0036] [Chemical 10]

[0037] X represents the structure of the above formula [2]. The details of X ¹ to X ⁴ and the formula in Formula [2], and preferable combinations are as in Formula [2]. \¥02020/175560 9 卩(: 17 2020/007782

B is an integer from 1 to 4. Among them, 1 is preferable.

[0038] More specific diamines include the following formulas [23-1] to [23-1

2] are mentioned, and it is preferable to use these.

[0039] [Chemical 11]

[0040] 1 represents an integer of 2 to 12.

[0041] [Chemical 12]

[0042] Gate 2 represents an integer of 0 to 12. 113 represents an integer of 2 to 12.

[0043] Among them, the formula [23-1], the formula [23-2], the formula [23-5] to the formula [2 ₃ 1 7], the formula [23-1 1] or the formula [23-1 2] Is preferred. More preferred are formula [2 ₃ _5] to formula [2 ₃ — 7], formula [2 ₃ _ 11] or formula [2 ₃ —

1 2] 〇 2020/175 560 10 (:171? 2020/007782

From the viewpoint of the optical characteristics of the liquid crystal display device and the adhesiveness between the liquid crystal layer and the resin film, the use ratio of the specific diamine is preferably 10 to 70 mol% with respect to the entire diamine component. More preferred is 20 to 60 mol %. The specific diamine may be used alone or in combination of two or more, depending on each characteristic.

A diamine other than the specific diamine (also referred to as other diamine) can also be used as the diamine component for producing the polyimide polymer.

[0044] Specifically, International Publication No. 〇 201 5/01 2368 (201 May 1.

29 publication), other diamine compounds described on pages 27 to 30, and diamine compounds of the formulas [0 8 1] to [0 8 14] described on pages 30 to 32 of the publication. Can be mentioned. Further, other diamines may be used alone or in combination of two or more, depending on each characteristic.

Examples of the tetracarboxylic acid component for producing a polyimide-based polymer include tetracarboxylic acid dianhydride represented by the following formula [3], tetracarboxylic acid which is a tetracarboxylic acid derivative thereof, tetracarboxylic acid dihalide, and tetracarboxylic acid. It is preferable to use a carboxylic acid dialkyl ester or a tetracarboxylic acid dialkyl ester dihalide (all collectively referred to as a specific tetracarboxylic acid component).

[0045] [Chemical 13]

[0046] represents at least one structure selected from the following formula [33] to formula [3 I].

[0047] \¥02020/175560 11 11 (: 17 2020/007782

[Chemical 14]

[0048] ~. Each represents a hydrogen atom, a methyl group, a chlorine atom or a benzene ring. ^£ and represent a hydrogen atom or a methyl group, respectively.

[0049] Among them, those in the formula [3] are represented by the formula [33], the formula [30], and the formula [3] in view of easiness of synthesis and easiness of polyreactivity in producing a polymer. 1], the formula [3 ㊀], the formula [31 ¹ ], the formula [3], the formula [31<] or the formula [3 1] are preferable. More preferred are formula [38], formula [36], formula [31 ¹ ], formula [3], formula [31<], or formula [3 I]. From the viewpoint of the optical characteristics of the liquid crystal display element, the formula [38], the formula [36], the formula [31 ¹ ], the formula [3] or the formula [3 I] is particularly preferable.

The ratio of the specific tetracarboxylic acid component used is preferably 1 mol% or more based on all tetracarboxylic acid components. More preferred is 5 mol% or more, and particularly preferred is 10 mol% or more. Most preferably, it is 10 to 90 mol% from the viewpoint of optical characteristics of the liquid crystal display device.

[0050] Other tetracarboxylic acid components other than the specific tetracarboxylic acid component can be used for the polyimide-based polymer. Examples of other tetracarboxylic acid components include the following tetracarboxylic acid compounds, tetracarboxylic acid dianhydrides, dicarboxylic acid dihalide compounds, dicarboxylic acid dialkyl ester compounds and dialkyl ester dihalide compounds.

Specifically, International Publication Gazette 〇 201 5/01 2368 (201 5. 1. \¥02020/175560 12 卩(: 17 2020/007782

29 publication), pages 34 to 35, and other tetracarboxylic acid components.

The specific tetracarboxylic acid component and the other tetracarboxylic acid component may be used alone or in combination of two or more, depending on each characteristic.

The method for synthesizing the polyimide polymer is not particularly limited. Usually, it is obtained by reacting a diamine component and a tetracarboxylic acid component. Specific examples include the method described on pages 35 to 36 of International Publication No. 201 5/01 2368 (Published May 29, 201).

[0051] The reaction between the diamine component and the tetracarboxylic acid component is usually performed in a solvent containing the diamine component and the tetracarboxylic acid component. The solvent used at that time is not particularly limited as long as it can dissolve the formed polyimide precursor.

[0052] Specifically, 1\1-methyl-2-pyrrolidone, 1\1-ethyl-2-pyrrolidone, arbutyrolactone, 1\1, 1\1_ dimethylformamide, 1\1, 1\ Examples include 1_dimethyl acetamide, dimethyl sulfoxide, and 1,3-dimethyl-imidazolidinone. Further, when the solvent solubility of the polyimide precursor is high, methyl ethyl ketone, cyclohexanone, cyclopentanone, 4-hydroxy-4-methyl-2-pentanone or a solvent represented by the following formula [mouth 1] to formula [03] is used. Can be used.

[0053] [Chemical 15]

[01] [02] [03]

炭素数 1〜 3のアルキル基を示す。 〇³は、 炭素数 1〜 4の アルキル基を示す。 [0054]

An alkyl group having 1 to 3 carbon atoms is shown. ○ ³ represents an alkyl group having 1 to 4 carbon atoms.

These may be used alone or in combination. Further, even a solvent that does not dissolve the polyimide precursor may be used as a mixture with the above-mentioned solvent as long as the formed polyimide precursor does not precipitate. In an organic solvent Since the water content of the water inhibits the polymerization reaction and causes hydrolysis of the formed polyimide precursor, it is preferable to use dehydrated and dried organic solvent.

In the polymerization reaction of the polyimide precursor, the total number of moles of the tetracarboxylic acid component when the total number of moles of the diamine component is 1.0 is preferably 0.8 to 1.2. When the total number of moles of the tetracarboxylic acid component is less than 1.0, that is, when the total number of moles of the tetracarboxylic acid component is smaller than the number of moles of the diamine component, the polymer has an amino group-terminated structure, 1 If it is larger than 0.0, that is, if the total number of moles of the tetracarboxylic acid component is larger than the number of moles of the diamine component, the polymer end has a carboxylic acid anhydride or dicarboxylic acid structure. In the present invention, since the effect of the specific compound is higher, the total number of moles of the tetracarboxylic acid component is greater than 1.0, that is, the total number of moles of the tetracarboxylic acid component is greater than the number of moles of the diamine component. Is also preferably large. Specifically, when the total number of moles of the diamine component is 1.0, the total number of moles of the tetracarboxylic acid component is preferably 1.05 to 1.20.

[0055] Polyimide is a polyimide obtained by ring closure of a polyimide precursor, and in this polyimide, the ring closure rate (also referred to as imidation rate) of amide acid groups is not necessarily 100%. It is not necessary and can be adjusted arbitrarily according to the application and purpose. Among them, 30 to 80% is preferable from the viewpoint of the solubility of the polyimide polymer in the solvent. More preferred is 40 to 70%.

[0056] The molecular weight of the polyimido polymer was measured by the GPC (Gel Permeation Chromatography) method in consideration of the strength of the resin film obtained therefrom and the workability and coating property during resin film formation. The Mw (weight average molecular weight) is preferably 5,000 to 1,000,000. More preferably, it is 10,000 to 150,000.

<Resin composition>

The resin composition contains a specific compound, and preferably forms a resin film. \¥0 2020/175 560 14 卩(: 17 2020/007782

Is a solution for preparing a solution containing a specific compound, a polymer and a solvent. In that case, two or more kinds of specific compounds and polymers can be used.

The content of the polymer component in the resin composition of the present invention can be appropriately changed according to the setting of the thickness of the resin film to be formed, but a uniform and defect-free resin film is formed. It is preferably 1% by weight or more from the standpoint of making it possible, and is preferably 10% by weight or less from the viewpoint of storage stability of the solution. Above all, 2 to 8% by weight is preferable, and 3 to 7% by weight is particularly preferable.

All the polymer components in the resin composition may be a polymer having a specific structure, or may be a mixture of polymers having no specific structure. In that case, the ratio of the polymer having no specific structure to be used is preferably 10 to 400 parts by mass relative to 100 parts by mass of the polymer having a specific structure. More preferred is 10 to 300 parts by mass. Particularly preferred is 10 to 200 parts by mass.

The content of the solvent in the resin composition can be appropriately selected from the viewpoint of obtaining the coating method of the resin composition and the desired film thickness. Among them, the content of the solvent in the resin composition is preferably 50 to 99.9 mass% from the viewpoint of forming a uniform resin film by coating. More preferably, it is 60 to 99 mass %. Particularly preferred is 65 to 99% by mass.

[0059] The solvent used in the resin composition is not particularly limited as long as it is a solvent that dissolves the polymer. In particular, when the polymer is a polyimide precursor, polyimide, polyamide or polyester, or when the solubility of acrylic polymer, methacrylic polymer, novolac resin, polyhydroxystyrene, cellulose or polysiloxane in the solvent is low. It is preferable to use the following solvents (also referred to as solvents).

[0060] For example, 1\1 ,1\1—dimethylformamide, 1\1 ,1\1—dimethylacetamide, 1\1 _methyl-2-pyrrolidone, 1\1 _ethyl-2-pyrrolidone , Dimethyl sulfoxide, arbutyrolactone, 1, 3-dimethyl-2-imidazolidino 〇 2020/175 560 15 卩 (：171? 2020 /007782

And methyl ethyl ketone, cyclohexanone, cyclopentanone, 4-hydroxy _ 4-methyl-2-pentanone and the like. Among them, it is preferable to use 1\1_methyl-2-pyrrolidone, 1\1-ethyl-2-pyrrolidone or ^-butyrolactone. Further, these may be used alone or in combination.

[0061] When the polymer is an acrylic polymer, a methacrylic polymer, a novolac resin, polyhydroxystyrene, cellulose or polysiloxane, further, the polymer is a polyimide precursor, polyimide, polyamide or polyester, When the solubility of these polymers in a solvent is high, the following solvent (also referred to as solvent) can be used.

[0062] Specific examples of solvent solvents are described on pages 58 to 60 of International Publication No. 〇 2 0 1 4/1 7 1 4 9 3 (2 0 1 4 1 .0.2 3 publication). Solvents such as Among them, 1-hexanol, cyclohexanol, 1,2-ethanedine

-, 1,2-propanediol, propylene glycol monobutyl ether, ethylene glycol monobutyl ether, dipropylene glycol dimethyl ether, cyclohexanone, cyclopentanone or the above formula [0 1] to formula [mouth 3] It is preferable to use.

In addition, when using these solvents, for the purpose of improving the coating property of the resin composition, 1\1_methyl-2-pyrrolidone, 1\1_ethyl-2-pyrrolidone of the above-mentioned solvents 8 or ^_ Butyrolactone is preferably used in combination. It is more preferable to use arbutyrolactone together.

[0063] Since these solvent mills can enhance the coating property and surface smoothness of the resin film when the resin composition is applied, the polymer can be used as a polymer precursor, a polyimide, a polyamide or a polyester. When the above is used, it is preferable to use it together with the solvent Eight kinds. At that time, the amount of the solvent is preferably 1 to 99% by mass of the whole solvent contained in the resin composition. Among them, 10 to 99 mass% is preferable. More preferable is 20 to 95% by mass.

In order to increase the film strength of the resin film, the resin composition contains an epoxy group and an isocyanate. 〇 2020/175 560 16 卩 (：171? 2020 /007782

It is preferable to introduce a compound (collectively referred to as a specific crosslinkable compound) having at least one selected from a nate group, an oxetane group, a cyclocarbonate group, a hydroxy group, a hydroxyalkyl group and a lower alkoxyalkyl group. .. In that case, it is necessary for the compound to have two or more of these groups. Specific examples of the crosslinkable compound having an epoxy group or an isocyanate group include epoxy groups or isocyanates described on pages 63 to 64 of International Publication WO 201 4/1 7 1 493 (201 4.1 0.23 publication). Examples thereof include crosslinkable compounds having a group.

[0064] Specific examples of the crosslinkable compound having an oxetane group are described in International Publication WO^/O 201.

〜式 ［4 !＜］ の架橋性化合物が挙げられる。 Formula published on pages 58 to 59 of 1/13275 1 (published on January 27, 2011)

~ Crosslinkable compounds of the formula [4 !<] are mentioned.

[0065] Specific examples of the crosslinkable compound having a cyclocarbonate group include compounds represented by the formula [5-1] disclosed on pages 76 to 82 of International Publication No. 0201 2/01 4898 (published on Feb. 2, 2011). ~ Crosslinkable compounds of the formula [5-42] are mentioned.

[0066] Specific examples of the crosslinkable compound having a hydroxyl group, a hydroxyalkyl group and a lower alkoxyalkyl group are described in International Publication No. WO 201 4/1 7 1 493 (2 01 4.1 0 23), pages 65 to 66. Melamine derivative or benzoguanamine derivative described on page 62, and the formula [6-1 on page 62 to 66 of International Publication WO 201 1/1 3275 1 (201 1.1 0.27 publication). ]-The crosslinkable compound of a formula [6_48] is mentioned.

[0067] The ratio of the specific crosslinkable compound used in the resin composition is set to be all polymer components.

0.1 to 100 parts by mass is preferable with respect to 100 parts by mass. More preferred is 0.1 to 50 parts by mass, because the crosslinking reaction proceeds and the desired effect is exhibited. Particularly preferred is 1 to 30 parts by mass.

It is preferable to introduce at least one kind of generator (also referred to as a specific generator) selected from a photoradical generator, a photoacid generator and a photobase generator into the resin composition.

[0068] Specific examples of the specific generator are described in International Publication No. 201 4/1 7 1 493 (201 4 〇 2020/175 560 17 卩(: 171-1? 2020/007782

.1 0.23 publication), pages 54-56. Among them, it is preferable to use a photo-radical generating agent as the specific generating agent from the viewpoint of the adhesiveness between the liquid crystal layer and the resin film.

As the resin composition, a compound that improves the film thickness uniformity and the surface smoothness of the resin film when the resin composition is applied can be used. Furthermore, a compound or the like that improves the adhesion between the resin film and the substrate can also be used.

Examples of the compound that improves the uniformity of the film thickness and the surface smoothness of the resin film include a fluorine-based surfactant, a silicone-based surfactant, and a nonionic surfactant. Specific examples thereof include the surfactants described on page 67 of International Publication Gazette \^/〇 201 4/1 7 1 493 (published 20 1 4.1 0.23). Further, the use ratio is preferably 0.01 to 2 parts by mass with respect to 100 parts by mass of all polymer components. More preferred is 0.01 to 1 part by mass.

[0069] Specific examples of the compound that improves the adhesiveness between the resin film and the substrate are described on pages 67 to 69 of WO 0201 4/1 7 1 493 (published 201 4.10.23). Compounds. Further, the use ratio thereof is preferably 0.1 to 30 parts by mass with respect to 100 parts by mass of all polymer components. More preferably, it is 1 to 20 parts by mass.

[0070] In addition to the compounds other than the above, the resin composition may be added with a dielectric or a conductive substance for the purpose of changing electrical properties such as the dielectric constant and conductivity of the resin film.

<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. Above all, it is preferable to use a liquid crystal having a positive dielectric anisotropy for the liquid crystal display element of the present invention. At that time, from the viewpoints of low voltage driving and dispersion characteristics, those having a large anisotropy of dielectric constant and a large anisotropy of refractive index are preferable. Further, as the liquid crystal, two or more kinds of liquid crystal can be mixed and used according to the physical properties such as the phase transition temperature, the dielectric anisotropy and the refractive index anisotropy. In order to drive a liquid crystal display element as an active element such as a TFT (Thin Fiber Imistor), it is required that the liquid crystal has a high electric resistance and a high voltage holding ratio (also called VHR). Therefore, it is preferable to use a fluorine-based or chlorine-based liquid crystal as the liquid crystal, which has a high electric resistance and whose VHR does not decrease due to active energy rays such as ultraviolet rays.

[0071] Further, the liquid crystal display device can be made into a guest-host type device by dissolving a dichroic dye in the liquid crystal composition. At that time, an element that absorbs (scatters) when no voltage is applied and becomes transparent when a voltage is applied is obtained. Moreover, in this device, the direction of the director of the liquid crystal (orientation direction) changes by 90 degrees depending on the presence or absence of voltage application. Therefore, by utilizing the difference in the light absorption characteristics of the dichroic dye, this device can obtain higher contrast than the conventional guest-host type device that performs switching in random alignment and vertical alignment. In the case of a guest-host type device in which a dichroic dye is dissolved, it becomes colored when the liquid crystal is aligned in the horizontal direction, and becomes opaque only in the disturbed state. Therefore, it is possible to obtain an element that switches from a colored opaque state to a colored transparent state and a colorless transparent state when no voltage is applied, as a voltage is applied.

[0072] The polymerizable compound in the liquid crystal composition is for forming a polymer network (also referred to as a curable resin) through a polymerization reaction due to active energy rays and heat during production of the liquid crystal display element. The polymerization reaction in the present invention is preferably one that proceeds by irradiation with ultraviolet rays.

As for the polymerizable compound, a polymer obtained by polymerizing the polymerizable compound may be introduced into the liquid crystal composition in advance. However, when handling the liquid crystal composition, that is, suppressing the increase in the viscosity of the liquid crystal composition and 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, but it is necessary that a temperature at which a part or the whole of the liquid crystal composition exhibits a liquid crystal phase exists when the polymerizable compound is dissolved in the liquid crystal. .. Even when a part of the liquid crystal composition exhibits a liquid crystal phase, the liquid crystal display element can be visually inspected and the entire inside of the element has almost uniform transparency and scattering. 〇 2020/175 560 19 卩(：171? 2020/007782

It is sufficient if the characteristics are obtained.

[0073] The polymerizable compound may be a compound that is polymerized by ultraviolet rays or heat, and in that case, the polymerization may proceed in any reaction mode to form a curable resin. Specific reaction modes include radical polymerization, cationic polymerization, anionic polymerization and polyaddition reaction.

[0074] Among them, the reaction mode of the polymerizable compound is preferably radical polymerization from the viewpoint of optical characteristics of the liquid crystal display device. At that time, as the polymerizable compound, the following radical-type polymerizable compound or an oligomer thereof can be used. Further, as described above, it is also possible to use a polymer obtained by polymerizing these polymerizable compounds.

[0075] Specific examples of radical-type polymerizable compounds or oligomers thereof are described in International Publication

The radical-type polymerizable compounds described on pages 69 to 71 of 201 5/1 46987 (published 201 5.1 10.1) are mentioned.

From the viewpoint of the adhesiveness between the liquid crystal layer and the resin film, the proportion of the radical-type polymerizable compound or its oligomer used is 70 to 150 parts by mass with respect to 100 parts by mass of the liquid crystal in the liquid crystal composition. preferable. More preferably, it is 80 to 110 parts by mass. Further, the radical-type polymerizable compound may be used alone or in combination of two or more, depending on each characteristic.

For the purpose of promoting radical polymerization of the polymerizable compound, it is preferable to introduce a radical initiator (also referred to as a polymerization initiator) that generates a radical by ultraviolet rays into the liquid crystal composition.

Specific examples thereof include radical initiators described on pages 71 to 72 of International Publication No. WO 205/146987 (published on May 5, 2010).

From the viewpoint of adhesion between the liquid crystal layer and the resin film, the radical initiator is preferably used in an amount of 0.01 to 20 parts by mass relative to 100 parts by mass of the liquid crystal in the liquid crystal composition. More preferred is 0.05 to 10 parts by mass. In addition, the radical initiator may be used alone or in combination of two or more, depending on each characteristic. \¥02020/175 560 20 (: 17 2020/007782

[0076] It is preferable to introduce a compound of the following formula [48] (also referred to as a specific liquid crystal additive compound) into the liquid crystal composition.

[0077] [Chemical 16]

[0078] 3 ¹ represents at least one structure selected from the following formulas [4-8] to the formula [4_ ". Among them, the formula [4-8], the formula [4_!〇], the formula [4_〇], the formula [4_], the formula [4-6], or the formula [4_dry] is preferable. More preferred are formula [4-8], formula [4_!〇], formula [4_〇] or formula [4-6]. Especially preferred is the formula [4-8] or the formula [4_ !0].

[0079] [Chemical 17]

[0080] 3 represents a hydrogen atom or a benzene ring.

（01^~1₃） —、 _01^~1₂〇一、 — 0 〇N H—、 一 1^ 1-10〇一、 一 0〇 （01^~1₃） —、 一 （01^~1₃） 00—、 一 <3〇〇一及び一〇 0〇_から選ばれる少なくとも 1種を示す。 なかでも、 単 結合、 _〇一、 一0^1₂〇一、

_0〇〇一又は一〇 0〇_が好 ましい。 より好ましいのは、 単結合、 一〇一、 一0〇〇一又は一〇〇〇一で ある。 3 ² is a single bond, _ 〇 1,

(01 ^~ 1 ₃ )--, _01 ^~ 1 ₂ 0 1, --0 0 NH--, 1 1^ 1-10 0 1, 1 0 0 (01 ^~ 1 ₃ )--, 1 (01 ^~ 1 ₃ ) 00-- , 1 <3 001 and at least 1 selected from 100 _. Among them, a single bond, _ 0 1, 1 0^1 ₂ 0 1,

_0.001 or 100_ is preferred. More preferred are single bonds, 101, 100001 or 100001.

3 ³ is a single bond or one (Rei_1 ^~ 1 _{2) 3} - shows a (3 is an integer from 1 1 5). 20/175560 21 卩 (: 171? 2020 /007782

Among them, a single bond or one (Rei_1 ^~ 1 _{2) 3} - (3 is an integer from 1 1 0) is favored arbitrary. More preferred are one (Rei_1 ^~ 1 _{2) 3} - (3 is an integer from 1 1 0).

である。 3 ⁴ is a single bond, one hundred and one, one Rei_rei_1 ^~ 1 ₂ -, represents at least one Bareru selected from ten thousand and one and ten thousand and one. Of these, a single bond, _001 or 100001 is preferred. More preferred is

Is.

^3-5, a benzene ring, a divalent organic group having 1 7-5 1 carbon atoms with a divalent cyclic group, or steroid skeleton selected from the cyclohexane ring and heterocyclic, any of the said cyclic group Hydrogen atom is an alkyl group having 1 to 3 carbon atoms, 1 to 3 carbon atoms

It may be substituted with a C 3 alkoxy group, a C 1 to C 3 fluorine-containing alkyl group, a C 1 to C 3 fluorine containing alkoxy group, or a fluorine atom. Of these, a benzene ring or a cyclohexane ring, or a divalent organic group having a carbon number of 17 to 51 and having a steroid skeleton is preferable. More preferred is a divalent organic group having a carbon number of 17 to 51 and having a benzene ring or a skeleton skeleton.

である。 3 ⁶ is a single bond, ^_ 〇 ^{_, _} 0 \ ~ \ 2 ^{_, _ _} 0 0 1 ^- 1 _2, ^_ 0 1 ^- 1 ₂ 〇 ^_, selected from the group consisting of ^_ hundred 〇 first and ten thousand and one Indicates at least one Of these, a single bond, 101, 100111 or 100001 is preferable. More preferred is a single bond,

Is.

3 ^7, a benzene ring, shows a cyclic group selected from the cyclohexane ring and heterocyclic, any of hydrogen atoms on these cyclic groups, an alkyl group of from 1 to 3 carbon atoms, an alkoxy group having a carbon number of 1 to 3 It may be substituted with a fluorine-containing alkyl group having 1 to 3 carbon atoms, a fluorine-containing alkoxy group having 1 to 3 carbon atoms, or a fluorine atom. Of these, a benzene ring or a cyclohexane ring is preferable.

3 ^8, an alkyl group having a carbon number of 1 to 1-8, an alkenyl group of carbon number 2-1 8, carbon number 1 to 1-8 fluorine-containing alkyl group of from 1 to alkoxy groups and number of carbon atoms of 1 to 1 to 8 carbon atoms At least one selected from 18 fluorine-containing alkoxy groups is shown. Of these, an alkyl group or an alkoxy group having 1 to 18 carbon atoms or an alkenyl group having 2 to 18 carbon atoms is preferable. More preferably, the carbon number is 1 to 1. \¥0 2020/175 560 22 卩 (: 17 2020 /007782

2 is an alkyl group or an alkoxy group.

3 represents an integer from 0 to 4. Among them, 0 to 2 is preferable.

Specific liquid additive compound has a portion of rigid structure such as a benzene ring or a cyclohexane ring, and a portion of the polymerization reaction by ultraviolet rays or heat represented by 3 ¹ of the formula [4 _3]. Therefore, when the specific liquid crystal additive compound is included in the liquid crystal composition, the rigid structure portion of the specific liquid crystal additive compound enhances the vertical alignment of the liquid crystal and accelerates the driving of the liquid crystal due to the voltage application, and The drive voltage can be lowered. Further, by 3 ¹ site in the formula [4 3] are reacted with the polymerizable compound, it is possible to keep the polymer network dense state.

More specific specific liquid crystal compound addition following formula [4 ₃ _ 1] to the formula - include compounds of [4 3 1 1], it is preferable to use them.

[0081] [Chemical 18] First. It's a ten" [4¾-1]

[0082] 3 ^& indicates 1001 or 1001, respectively. Each 3 has 1 carbon

~ 12 shows an alkyl group. Each 1 represents an integer of 1 to 10. Each 2 represents an integer of 1 or 2.

[0083] \\0 2020/175 560 23 卩(: 17 2020/007782

[Chemical 19]

を示す。

はそれぞ れ、 炭素数 1〜 1 2のアルキル基又はアルコキシ基を示す。 3はそれぞれ 、 1〜 1 0の整数を示す。 4はそれぞれ、 1又は 2の整数を示す。 [0084] 3. Is a single bond,

Indicates.

Are each an alkyl group or an alkoxy group having 1 to 12 carbon atoms. Each 3 represents an integer of 1 to 10. 4 is an integer of 1 or 2, respectively.

[0085] [Chemical 20]

[0086] 3 ⁶ respectively show a _〇 one or ten thousand and one. Each of 3^ represents a divalent organic group having a steroid skeleton and having 17 to 51 carbon atoms. 3 ⁹ show respectively a carbon number 1-1 2 alkyl or alkenyl group of carbon number 2-1 8. Five Each represents an integer of 1 to 10.

From the viewpoint of adhesion between the liquid crystal layer and the resin film, the specific liquid crystal additive compound is preferably used in a proportion of 0.1 to 30 parts by mass relative to 100 parts by mass of the liquid crystal in the liquid crystal composition. More preferably, it is 0.5 to 20 parts by mass. Particularly preferred is 1 to 10 parts by mass. In addition, the specific liquid crystal additive compound may be used alone or in combination of two or more depending on each characteristic.

The liquid crystal composition may be prepared by mixing the liquid crystal, the polymerizable compound, and the specific liquid crystal additive compound together, or by previously mixing the polymerizable compound and the specific liquid crystal additive compound with the liquid crystal. There is a method of doing.

Among them, in the present invention, a method of mixing a mixture of the polymerizable compound and the specific liquid crystal additive compound in advance with the liquid crystal is preferable.

When the liquid crystal composition is prepared as described above, heating can be performed depending on the solubility of the polymerizable compound and the specific liquid crystal additive compound. The temperature at that time is preferably less than 100 °C.

<Method of manufacturing liquid crystal display device>

The substrate used for the liquid crystal display element is not particularly limited as long as it is a highly transparent substrate, and in addition to a glass substrate, a plastic substrate such as an acrylic substrate, a polycarbonate substrate, a PET (polyethylene terephthalate) substrate, or the like. These films can be used. In particular, when used for a light control window or the like, a plastic substrate or film is preferable. In addition, from the viewpoint of process simplification, the T0 electrode for driving the liquid crystal, the Z0 (Ind i um Z i nc Ox i de) electrode,

It is preferable to use a substrate on which an I G Z 0 (Indium Ga U ium Zi nc Oxide) electrode, an organic conductive film, or the like is formed. Further, in the case of a reflective liquid crystal display element, if only one substrate is used, a substrate such as a silicon wafer or a metal such as aluminum or a substrate on which a dielectric multilayer film is formed can be used.

The liquid crystal display element has a resin film obtained from a resin composition containing a specific compound on at least one of the substrates. In particular, it is preferable that both substrates have a resin film. 〇 2020/175 560 25 卩 (：171? 2020 /007782

[0087] The method of applying the resin composition is not particularly limited, but industrially, screen printing, offset printing, flexo printing !^, ink jet method, dip method, mouth coater method, slit coater method, spinner, spinner Method, spray method, etc., and can be appropriately selected according to the type of substrate and the desired film thickness of the resin film.

[0088] After applying the resin composition onto the substrate, a heating means such as a hot plate, a heat-circulation type oven, or an 8 (infrared) type oven is used depending on the type of the substrate and the solvent used for the resin composition. The solvent can be evaporated at a temperature of 30 to 300°C, preferably 30 to 250°C to form a resin film. In particular, when a plastic substrate is used as the substrate, it is preferable to process at a temperature of 30 to 150 ^°

である。 特 に好ましいのは、 1 0 ~ 2 5 0门〇1である。 If the thickness of the resin film after firing is too thick, it is disadvantageous in terms of power consumption of the liquid crystal display element, and if it is too thin, the reliability of the element may be deteriorated.

Is. Particularly preferred is 10 to 250.

The liquid crystal composition used for the liquid crystal display element is the liquid crystal composition as described above, and a spacer for controlling the electrode gap (also referred to as a gap) of the liquid crystal display element is included therein. It can also be introduced.

[0091] The method of injecting the liquid crystal composition is not particularly limited, and examples thereof include the following methods. That is, when using a glass substrate as the substrate, prepare a pair of substrates having a resin film formed thereon, apply the sealant on four pieces of the substrate on one side except for a part, and then, the surface of the resin film is An empty cell is produced by sticking the substrates on the other side so that they are on the inside. Then, a method of injecting the liquid crystal composition under reduced pressure from a place where the sealant is not applied to obtain a liquid crystal composition injection cell can be mentioned. Furthermore, when using a plastic substrate or film as the substrate, prepare a pair of substrates with a resin film formed on it, and then use the ◯◯ (○ 0" 〇 卩 丨 丨 beating) method or ink jet on one of the substrates. The liquid crystal composition may be dropped by a method such as a method, and then the other substrate may be bonded to obtain a liquid crystal composition injection cell.

The gap of the liquid crystal display element can be controlled by the spacer or the like. That way 〇 2020/175 560 26 卩 (: 171-1? 2020/007782

Examples thereof include a method of introducing a spacer having a target size into the liquid crystal composition and a method of using a substrate having a column spacer of a target size as described above. When a plastic or film substrate is used as the substrate and the substrates are laminated by laminating, the gap can be controlled without introducing a spacer.

The size of the gap of the liquid crystal display element is preferably 1 to 100. The more preferable range is 1 to 5001. Particularly preferred is 2 to 3001. If the gap is too small, the contrast of the liquid crystal display device will decrease, and if it is too large, the drive voltage of the device will increase.

The liquid crystal display device is obtained by curing the liquid crystal composition to form a liquid crystal layer in a state where part or all of the liquid crystal composition exhibits liquid crystallinity. The liquid crystal composition is cured by irradiating the liquid crystal composition injecting cell with ultraviolet rays or heating. In the present invention, as described above, irradiation with ultraviolet rays is preferable.

が好ましい。 なかでも、 3 1 0〜 3 7 0 n が好ましい。 また、 紫外線を照射した後に、 加熱処理を行っても良い。 その際の温度とし ては、 4 0〜 1 2 0 °〇が好ましい。 より好ましいのは、 4 0〜 8 0 °〇である [0095] Examples of the light source of the ultraviolet irradiation device used for irradiation of ultraviolet rays include a metal halide lamp and a high-pressure mercury lamp. The wavelength of ultraviolet rays is 2

Is preferred. Of these, 310 to 370 n is preferable. Further, heat treatment may be performed after irradiation with ultraviolet rays. The temperature at that time is preferably 40 to 120°. More preferred is 40 to 80°

Examples of the apparatus used for heating include heating means used after applying the resin composition onto the substrate. Further, the temperature at that time is appropriately selected depending on the temperature at which the reaction of the polymerizable compound proceeds and the type of the substrate. Specifically, preferably 8 0 ^° 〇_～2 0 0 ° 〇. Example

[0096] The present invention is described in more detail below by referring to Examples, but the invention is not limited thereto.

The abbreviations used below are as follows.

"Specific compound" 〇 2020/175 560 27 2020/0077 82

[0097] [Chemical 21]

[0098] "Compounds used for polyimide-based polymer"

<Specific diamine>

[0099] [Chemical 22]

[0100] <Other diamines>

[0101] [Chemical 23]

[0102] <Specific tetracarboxylic acid component>

[0103] [Chemical 24]

[0104] "Crosslinkable compound"

[0105] \¥02020/175560 28 卩 (: 171? 2020 /007782

[Chemical 25]

[0106] "Solvent"

1\/1?: 1\1-methyl-2-pyrrolidone

Arumi: arptyrolactone

M3: Ethylene glycol monobutyl ether

Mami: Propylene glycol monobutyl ether

〇 1\/1 ： Propylene glycol monomethyl ether

"Compounds used for liquid crystal compositions"

<Specific liquid crystal added compound>

[0107] [Chemical 26]

<Polymerizable compound>

: I Sumi X (Osaka Organic Chemical Industry Co., Ltd.)

2: 2-Hydroxyethyl methacrylate (Tokyo Chemical Industry Co., Ltd.)

[¾3: <8丫八 [¾8 0 1\/1-400 (Nippon Kayaku Co., Ltd.)

[¾4: 跳巳跳 〇 [¾丫1_230 (manufactured by Daicel-Ornex Co.) Lens IV!

<Photo radical initiator>

1 :| [¾〇 080 11 [¾mi 1 84 (Miyahachi 3 companies) 〇 2020/175 560 29 卩(: 171-1? 2020/007782

<Liquid crystal>

1_ 1 :1\/11_ ○ 1 301 8 (Merck)

"Measurement of molecular weight of polyimide-based polymers"

Room temperature gel permeation chromatography (◦ 〇 device (◦ 〇 _ 101) (manufactured by Showa Electric Co., Ltd.) and column (<0-803, <0-805) (manufactured by 306 father company) It was measured in this way.

[0109] Column temperature: 50° 〇

（リッ トル） 、 リン酸 ·無水 結晶 （〇—リン酉愛）

テトラヒドロフラン （丁 1^~1 ） が 1 001 I /!_） Eluent:! 1 \ 1, 1 \ 1_ dimethylformamide as Ami de (additives, lithium bromide over hydrate (_ I Snake "1 ^to 1 ₂ 〇)

(Little), Phosphoric acid, anhydrous crystal (○-phosphorus love)

Tetrahydrofuran (1 ^to 1) is 1 001 I /!_)

Flow rate: 1.001 I/min

Standard sample for making calibration curve: Ding 3 <Standard polyethylene oxide (Molecular weight: about 900,000, 150,000, 100,000 and 30,000) (Tosoh Corporation) and Polyethylene glycol (Molecular weight; Approx. 1 2,000, 4,000 and 1,000) (manufactured by Polymer Laboratory).

"Measurement of imidization ratio of polyimido polymer"

（核磁気共鳴） サンプル管 （ IV! サン プリングチューブスタンダード， ¢ 5 （草野科学社製） ） に入れ、 重水素化 ジメチルスルホキシド （口1\/13〇一 6， 〇. 05質量％丁1\/13 （テトラメ チルシラン） 混合品） （0.53111 I） を添加し、 超音波をかけて完全に溶解 させた。 この溶液を

測定機 （」 \^/_巳〇八500） （日本電子デー タム社製） にて 500 IV! 1^~12のプロトン IV! を測定した。 イミ ド化率は、 イミ ド化前後で変化しない構造に由来するプロトンを基準プロトンとして決 め、 このプロトンのピーク積算値と、 9.5 〇1〜 1 0.0 付近に現 れるアミ ド酸の 1\11^~1基に由来するプロトンピーク積算値とを用い以下の式に よって求めた。 Polyimide powder

(Nuclear magnetic resonance) Put in a sample tube (IV! Sampling tube standard, ¢5 (made by Kusano Science Co., Ltd.)) and add deuterated dimethyl sulfoxide (mouth 1\/13 〇 1,6, 〇.05 mass% 1 1\ /13 (Tetramethylsilane) mixture) (0.53111 I) was added, and ultrasonic waves were applied to completely dissolve it. This solution

500 IV! 1 ^to 12 protons IV! were measured with a measuring machine ("\^/_Mitsuhachi 500) (manufactured by JEOL DATAM). The imidation rate is determined by using the proton derived from the structure that does not change before and after imidization as the reference proton, and the peak integrated value of this proton and the 1\11% of the amide acid appearing around 9.5 0 to 1 0.0. It was calculated by the following formula using the integrated value of the proton peak derived from ^~ 1 group.

X 1 00 20/175560 30 卩（：171? 2020 /007782 [0110] Imidization rate (%) =

X 100 20/175560 30 卩 (: 171? 2020 /007782

(X is the integrated value of the proton peak derived from the 1^(·! group of amide acid,; / is the integrated value of the peak of the reference proton, and << is the amide acid in the case of polyamic acid (imidization rate is 0%) The ratio of the number of reference protons ^to one 1\11 ^to 1 group of protons.)

"Synthesis of Polyimide Polymers"

<Synthesis example 1>

〇 I） 及び巳 2 （1. 249, 4. 33〇1〇1〇 1） を 1\/1? （1 5. 1 9 ） 中で混合し、 25^°〇で 8時間反応させ、 樹脂固形分濃度 25質量％のポリ アミ ド酸溶液 （1） を得た。 このポリアミ ド酸の数平均分子量 （IV! ともい う。 ） は 27, 200、 重量平均分子量 （1\/1 ともいう。 ） は 81 , 800 であった。 〇 1 (2.709, 1 3. 801010 丨), 巳 1 (1.09 ₉ ,1 0.

〇I) and Mimi 2 (1. 249, 4.33 〇 1 〇 1 〇 1) are mixed in 1\/1? (1 5. 1 9) and reacted at 25 ^° 〇 for 8 hours. A polyamic acid solution (1) having a concentration of 25 mass% was obtained. The number average molecular weight (also called IV!) of this polyamidic acid was 27,200, and the weight average molecular weight (also called 1\/1) was 81,800.

<Synthesis example 2>

〇I) and Mi 2 (1.2 1 9, 4. 23 〇 1 〇 1 〇 1) are mixed in 1\/1? (1 5.59) and allowed to react at 25 ^° 〇 for 8 hours. A polyamic acid solution (2) having a solid content concentration of 25 mass% was obtained. The IV! value of this polyamidic acid was 28,900 and 1\/1 was 82,800.

<Synthesis example 3>

〇 I） 及び巳 1 （〇. 7 1 ₉, 6. 57〇1〇1〇 1） を 1\/1? （1 5. 4₉ ） 中で混合し、 25^°〇で 8時間反応させ、 樹脂固形分濃度 25質量％のポリ アミ ド酸溶液 （3） を得た。 このポリアミ ド酸の IV!门は 26, 300、 1\/1 は 78, 300であった。 〇 1 (2.70 _9, 1 3.801010丨), eight 1 (1. 73 6.

〇 I) and Snake 1 (〇. 7 1 _9, 6. 57_Rei_1_rei_1_rei 1) was mixed with 1 \ / 1? (1 5.4 ₉₎ in the reacted for 8 hours at 25 ^° 〇, A polyamic acid solution (3) having a resin solid content concentration of 25% by mass was obtained. The IV! value of this polyamic acid was 26,300 and 1\/1 was 78,300.

<Synthesis example 4>

24, 1 00、 1\/1 は 74, 800であった。 〇I) and Tami 2 (1.789, 6.22 〇1 〇1 〇1) were mixed in 1\/1? (20.59) and reacted at 60 ^° 〇 for 4 hours, then 〇 1 (3.009, 1 5.3 Rei_1_rei_1_rei丨) and 1 \ / 1? a (1 0.3 ₉₎ was added, reacted at 40 ° 〇 6 hours, the resin 〇 2020/175560 31 We obtained a polyamic acid solution (4) with a solid concentration of 25 mass% (:171? 2020/007782).

24, 100 and 1\/1 were 74,800.

<Synthesis example 5>

After dilution of the IV! In pressurized example 6% by weight made of Polyamide acid solution obtained in Synthesis Example 4 (4) (20.0 _9), acetic anhydride imide catalyst (2.30 ₉₎ and pyridine ( 1.80 ₉₎ was added and reacted at 60 ° 〇 4 hours. This reaction solution was put into methanol (500 I) and the obtained precipitate was separated by filtration. Methanol wash|cleaned this deposit, it dried under reduced pressure at 100 ^° C, and the polyimide powder (5) was obtained. The imidization rate of this polyimide was 58%, IV! n was 22,100, and IV! was 62,700.

<Synthesis example 6>

A polyamic acid solution (6) having a resin solid content concentration of 25 mass% was obtained. The IV! n of this polyamic acid was 19,500 and 1\/1\« was 63,200.

<Synthesis example 7>

111〇 1） 、 八2 （〇. 49 ， 2. 4 1 |11111〇 1） 、 巳 1 （〇. 39 ， 3 .

及び巳 2 （〇. 69 ， 2. 4 1 〇1111〇 1） をアー巳 1_ （ 1 0. 4₉） 中で混合し、 60°〇で 4時間反応させた後、 〇 1 （2. 009 , 1 0.

と· ^_巳 1_ （5. 1 8₉） を加え、 40°〇で 6時間反 応させ、 樹脂固形分濃度が 25質量％のポリアミ ド酸溶液 （7） を得た。 こ のポリアミ ド酸の IV! nは 1 6, 900、 1\/1 は59, 400であった。 〇 2 (〇 .649, 2.56 〇 1111 〇 丨), 8 1 (〇 .96, 3.

111 〇 1), 8 2 (〇.49, 2.4 1 | 11111 〇 1), Min 1 (〇. 39, 3.

And Snake 2 (〇. 69, 2.4 1 Rei_1111_rei 1) were mixed in earth Snake 1_ (1 0.4 _9), was reacted with 60 ° 〇 4 hours, 〇 1 (2.009 , Ten.

And ^ ^ _ 1_ (5.18 ₉ ) were added and reacted at 40° for 6 hours to obtain a polyamido acid solution (7) having a resin solid content concentration of 25% by mass. The IV! n of this polyamic acid was 16,900 and 1\/1 was 59,400.

<Synthesis example 8>

〇1〇 1） 、 巳 1 （〇. 469, 4. 25〇1〇1〇 1） 及び巳 2 （ 1. 2 1 ₉ , 〇 2020/175560 32 卩（：171? 2020 /007782 〇 3 (5.009, 22.3 〇 1 〇 10 丨), 8 1 (3.36, 1 2.

0 1 0 1), 1 (0.469, 4.25 0 1 0 1 1) and 2 (1.2 1 ₉ 1, 〇 2020/175 560 32 卩 (：171? 2020 /007782

4. 23 ○ 10 10 丨) was mixed in 1\/1? (3 ○ ₁₉ ) and allowed to react at 40 ° 〇 for 6 hours. Polyamide acid with a resin solids concentration of 25 mass% A solution (8) was obtained. The IV! n of this polyamic acid was 21 1,700 and 1\/1 was 63,900.

<Synthesis example 9>

Made of Polyamide acid solution obtained in Synthesis Example 8 (8) was diluted 1 \ / 1? To pressurized example 6% by weight (20.0 _9), acetic anhydride imide catalyst (2.20 ₉₎ and added pyridine (1.70 ₉₎ was reacted for 3 hours at 60 ° 〇. This reaction solution was put into methanol (500 I) and the obtained precipitate was separated by filtration. Methanol wash|cleaned this deposit, it dried under reduced pressure at 100 ^° C, and the polyimide powder (9) was obtained. The imidization ratio of this polyimide was 51%, and IV! n was 19,300, 58,900.

<Synthesis example 1>

（1 5. 4₉） を加え、 撹拌して溶解させ、 〇 4 （2. 709, 9.

を加え、 1 5 °〇で 1 5時間反応させたUnder nitrogen atmosphere, 8 1 (○. 739, 2. 76 ○ 1 ○ 10 1), 8 2 (0.37 9 ,1.82 ○ 1111 ○ 1), and 2 (1.32, 4.61) Rei_1111_rei 1), pyridine emissions (1 81 ₉₎

(1 5. 4 ₉ ) was added, and the mixture was stirred and dissolved to give 〇 4 (2.709, 9.

And reacted at 15 ° for 15 hours

.. Thereafter, addition of acryloyl torque chloride de (〇. Rei_4 _9), 4 hours of reaction at 1 5 ^° 〇. This reaction solution was put into water (5009), and the obtained precipitate was filtered off. This precipitate was washed with isopropyl alcohol and dried under reduced pressure at 100 ^° C to obtain polyamic acid alkyl ester powder (10). The IV! n of this polyamic acid alkyl ester was 17 and 200, and 1\/1 was 38 and 500.

[0111] Table 1 shows the polyimide-based polymers obtained in the synthesis examples.

[0112] 〇 2020/175 560 33 卩 (：171? 2020 /007782

[table 1]

[0113] *1: Polyamide acid.

*2: Polyamic acid alkyl ester.

"Production of resin composition"

<Example 1>

Synthesis Example made of Polyamide acid solution obtained in the first method (1) (1 0.0 9), T1s (〇. 20 ₉₎ and 1 \ / 1? A (1 6.0 ₉₎ was added, 25 The mixture was stirred at 0° for 4 hours. Thereafter, 603 (1 5.7 ₉₎ was added, and stirred at 25 ^° 〇 6 hours to obtain a resin composition (1). No abnormality such as turbidity or precipitation was observed in this resin composition, and it was a uniform solution.

<Example 2>

Synthesis Example made of Polyamide acid solution obtained in second approach (2) (1 .09), T1s (〇. 20 ₉₎ and 1 \ / 1? A (1 6.0 ₉₎ was added, 25 ° Stirred for 4 hours at ◯. Thereafter, 603 (1 5.7 ₉₎ was added, and stirred at 25 ^° 〇 6 hours, the resin 20/175560 34 卩 (: 171? 2020 /007782

A composition (2) was obtained. No abnormality such as turbidity or precipitation was observed in this resin composition, and it was a uniform solution.

<Example 3>

In made of Polyamide acid solution obtained by the method of Synthesis Example 3 (3) (1 .09), T1s (〇. 20 ₉₎ and 1 \ / 1? A (1 6.0 ₉₎ was added, 25 ° Stirred for 4 hours at ◯. Thereafter, 603 (1 5.7 ₉₎ was added, and stirred at 25 ^° 〇 6 hours to obtain a resin composition (3). No abnormality such as turbidity or precipitation was observed in this resin composition, and it was a uniform solution.

<Example 4>

To the polyamide acid solution (4) (1 0.09) obtained by the method of Synthesis Example 4, add Ding 1 (○. 1 3 ₉ ) and 1\/1? (1 6.0 ₉ ) and add The mixture was stirred at 0° for 4 hours. Thereafter, 603 (7.83 ₉₎ and M. (7.83 ₉₎ was added, and stirred at 25 ° 〇 6 hours to obtain a resin composition (4). No abnormalities such as turbidity or precipitation were observed in this resin composition, and it was a uniform solution.

<Example 5>

(0. 1 8₉) 、 巳〇3 (7. 83₉) 及び 巳 (7. 8 3₉) を加え、 25°〇で 6時間撹拌して、 樹脂組成物 (5) を得た。 この樹 脂組成物には、 濁りや析出などの異常は見られず、 均一な溶液であった。To the polyamide acid solution (4) (1 0.09) obtained by the method of Synthesis Example 4, add Ding 1 (○. 1 3 ₉ ) and 1\/1? (1 6.0 ₉ ) and add The mixture was stirred at 0° for 4 hours. afterwards,

(0.18 ₉ ), Mitsumi 3 (7.89 ₉ ) and Mitsumi (7.83 ₉ ) were added, and the mixture was stirred at 25° O for 6 hours to obtain a resin composition (5). No abnormalities such as turbidity or precipitation were observed in this resin composition, and it was a uniform solution.

<Example 6>

The polyimide powder obtained by the method of Synthesis Example 5 (5) (2.50 _9), 1 \ / 1 (27.4 ₉₎ was added, and stirred to dissolve at 70 ° 〇 24 hours. Thereafter, Ding 1 (0.25 ₉₎ and Snake Rei_3 the (1 1.8 ₉₎ was added, and stirred at 25 ° 〇 6 hours to obtain a resin composition (6). No abnormalities such as turbidity or precipitation were observed in this resin composition, and it was a uniform solution.

<Example 7>

Polyimide powder obtained by the method of Synthesis Example 5 (5) (2.50 ₉₎ 〇 2020/175 560 35 卩 (: 171-1? 2020/007782

Snake 1_ a (7.83 ₉₎ was added, and stirred to dissolve at 70 ° 〇 24 hours. Thereafter, T1s (〇. 1 8 ₉₎ <2 (〇. 08 ₉₎ and Rei_1 \ / 1 viewed (3 1.3 ₉₎ was added, and stirred for 6 hours at 25 ° ◦, resin composition Got (7). No abnormalities such as turbidity or precipitation were observed in this resin composition, and it was a uniform solution.

<Example 8>

In made of Polyamide acid solution obtained by the method of Synthesis Example 6 (6) (1 .09), T1s (〇 1 39.) And - ^ - snake 1_ a (0.33 ₉₎ was added, 25 ° 〇 The mixture was stirred for 4 hours. After that, 〇 1//1 (3 1. 3 ₉ ) was added and stirred at 25° 〇 for 6 hours to obtain a resin composition (8). The resin composition is not observed abnormalities such turbidity or precipitation was uniform ^_ solution.

<Example 9>

In made of Polyamide acid solution obtained by the method of Synthesis Example 6 (6) (1 .09), T1s (〇 20 _9.) And - ^ - snake 1_ a (0.33 ₉₎ was added, 25 ° 〇 The mixture was stirred for 4 hours. Thereafter, <2 (〇. 1 8 ₉₎ and Rei_1 \ / 1 M. (3 1.3 ₉₎ was added, 2 5 ^° ● Among stirred for 6 hours to obtain a resin composition (9). No abnormalities such as turbidity or precipitation were observed in this resin composition, and it was a uniform solution.

<Example 10>

In made of Polyamide acid solution obtained by the method of Synthesis Example 7 (7) (1 .09), Ding 1 (Yes Yes 8 _9.) And - ^ - snake 1_ a (0.33 ₉₎ was added, 25 ° The mixture was stirred at ◯ for 4 hours. Thereafter, <2 (〇. 1 3 ₉₎ and Rei_1 \ / 1 M. (3 1.3 ₉₎ was added, 2 5 ^° ● Among stirred for 6 hours to obtain a resin composition (1 0). No abnormalities such as turbidity or precipitation were observed in this resin composition, and it was a uniform solution.

<Example 11>

In made of Polyamide acid solution obtained by the method of Synthesis Example 8 (8) (1 .09), T1s (〇. 25 ₉₎ and 1 \ / 1? A (1 9.9 ₉₎ was added, 25 ° Stirred for 4 hours at ◯. Then, added M. (1 1.8 ₉₎ was obtained by stirring at 25 ^° 〇 6 hours, the resin sets Narubutsu the (1 1). No abnormality such as turbidity or precipitation was observed in this resin composition, and it was a uniform solution. 20/175560 36 卩 (: 171? 2020 /007782

<Example 1 2>

The polyimide powder obtained by the method of Synthesis Example 9 (9) (2.50 _9), 1 \ / 1 (27.4 ₉₎ was added, and stirred to dissolve at 70 ° 〇 24 hours. afterwards,

(0. 08₉) 、 603 (7. 83₉) 及び 巳 (3. 92₉) を加え、 25 °〇で 6時間撹拌して、 樹脂組成物 (1 2) を得 た。 この樹脂組成物には、 濁りや析出などの異常は見られず、 均一な溶液で あった。 71 (0. 25 ₉ ),

(0.08 _9), 603 (7.83 ₉₎ and M. (3.92 ₉₎ was added, and stirred at 25 ° 〇 6 hours to obtain a resin composition (1 2). No abnormalities such as turbidity or precipitation were observed in this resin composition, and it was a uniform solution.

<Example 13>

Polyamide acid alkyl ester powder obtained in Synthesis Example 1 (10) (2.

1\/1? (3 1. 3 ₉ ) was added to 50 ₉ ) and stirred at 40° 〇 for 24 hours to dissolve. To this solution, Ding 1 (0.1 3 ₉₎ and Snake Rei_3 (7.83 ₉₎ was added, and stirred for 1 5 hours at 25 ° 〇, to obtain a resin composition (1 3). No abnormalities such as turbidity or precipitation were observed in this resin composition, confirming that it was a uniform solution.

<Comparative example 1>

To the polyamide acid solution (1) (1 〇 .〇 9) obtained by the method of Synthesis Example 1, IV! (1 6.09) and ## 3 (1 5. 79) were added, and the mixture was added at 25 ° 〇. After stirring for 6 hours, a resin composition (14) was obtained. No abnormalities such as turbidity and precipitation were observed in this resin composition, and it was a uniform solution.

<Comparative example 2>

The polyimide powder obtained by the method of Synthesis Example 5 (5) (2.50 _9), 1 \ / 1 (27.4 ₉₎ was added, and stirred to dissolve at 70 ° 〇 24 hours. Thereafter, Snake Rei_3 (1 1.8 ₉₎ was added, and stirred at 25 ° 〇 6 hours to obtain a resin composition (1 5). No abnormalities such as turbidity or precipitation were observed in this resin composition, and it was a uniform solution.

<Comparative example 3>

To the polyamic acid solution (6) (1 0.09) obtained by the method of Synthesis Example 6, was added ^^ _Mi! !_ (○.339) and 〇IV!Mi (3 1. 3 ₉ ). 6 hours at 25 ° 〇 2020/175 560 37 卩(: 171? 2020/007782

By stirring, a resin composition (16) was obtained. No abnormalities such as turbidity or precipitation were observed in this resin composition, and it was a uniform solution.

The resin compositions obtained in Examples and Comparative Examples are shown in Tables 2-4.

[0114] [Table 2]

[0115] [Table 3]

[0116] [Table 4]

[0117] *3: The numerical value in parentheses indicates the amount of the specific compound introduced (mass part) relative to 100 parts by mass of the polymer. 20/175560 38 卩 (: 171? 2020 /007782

*4: The value in parentheses indicates the amount of the crosslinkable compound introduced (100 parts by mass) with respect to 100 parts by mass of the polymer.

"Preparation of liquid crystal composition"

<Production of liquid crystal composition ()>

（〇. 3〇 9） 、

（ 〇.

（〇. 30₉） を混合し、 60^°〇で 2時間撹拌して、 重合性化合物の溶液を作製した。 その後、 作製した重合性化合物の溶液、 ！_ 1 （6. 009） 及び 1 （0. 1 09） を混合し、 25^°〇で 6時間撹拌し て、 液晶組成物 （ ） を得た。 (1.209),

(〇.309),

(○.

(〇. 30 ₉₎ were mixed and stirred for 2 hours at 60 ^° 〇, to prepare a solution of a polymerizable compound. After that, the prepared solution of the polymerizable compound,! _ 1 (6.009) and 1 (0.109) were mixed and stirred at 25 ^° for 6 hours to obtain a liquid crystal composition ().

<Production of Liquid Crystal Composition (Mimi)>

（〇. 30₉） 、

（1. 20₉） 、

（ 〇.

（〇. 30₉） を混合し、 60^°〇で 2時間撹拌して、 重合性化合物の溶液を作製した。 その一方で、 31 （0. 20₉） 及び !_ 1 （5. 80₉） を混合し、 25°◦で 2時間撹拌して特定液晶添加化合物を含 む液晶を作製した。 その後、 作製した重合性化合物の溶液、 特定液晶添加化 合物を含む液晶、 及び 1 （〇. 1 09） を混合し、 25^°◦で 6時間撹拌し て、 液晶組成物 （巳） を得た。 (1.20 _9),

(〇. 30 _9),

(1.20 _9),

(○.

(〇. 30 ₉₎ were mixed and stirred for 2 hours at 60 ^° 〇, to prepare a solution of a polymerizable compound. Meanwhile, a mixture of 31 (0.20 ₉₎ and! _ 1 (5.80 _9), stirred for 2 hours to a particular liquid crystal additive compound was prepared including a liquid crystal with 25 ° ◦. Then, the prepared solution of the polymerizable compound, the liquid crystal containing the specific liquid crystal additive compound, and 1 (〇. 09) were mixed and stirred at 25 ^° ◦ for 6 hours to obtain a liquid crystal composition (Mi). It was

<Preparation of liquid crystal composition (<3)>

（〇. 30₉） 、

（1. 20₉） 、

（ 〇.

（〇. 30₉） を混合し、 60^°〇で 2時間撹拌して、 重合性化合物の溶液を作製した。 その一方で、 32 （0. 40₉） 及び !_ 1 （5. 60₉） を混合し、 25°◦で 2時間撹拌して特定液晶添加化合物を含 む液晶を作製した。 その後、 作製した重合性化合物の溶液、 特定液晶添加化 合物を含む液晶、 及び 1 （〇. 1 09） を混合し、 25^°◦で 6時間撹拌し て、 液晶組成物 （＜3） を得た。 (1.20 _9),

(〇. 30 _9),

(1.20 _9),

(○.

(〇. 30 ₉₎ were mixed and stirred for 2 hours at 60 ^° 〇, to prepare a solution of a polymerizable compound. Meanwhile, 32 were mixed (0.40 ₉₎ and! _ 1 (5.60 _9), stirred for 2 hours to a particular liquid crystal additive compound was prepared including a liquid crystal with 25 ° ◦. After that, the prepared solution of the polymerizable compound, the liquid crystal containing the specific liquid crystal additive compound, and 1 (〇. 09) were mixed and stirred at 25 ^° ◦ for 6 hours to give a liquid crystal composition (<3). Obtained.

"Production of liquid crystal display element (glass substrate)"

The resin compositions obtained by the methods of the above Examples and Comparative Examples were pressure-filtered with a membrane filter having a pore size of 1. The resulting solution is diluted with pure water and 〇 2020/175 560 39 卩 (：171? 2020 /007782

1 x 0 x 1 0 0 01 01 丨 〇 washed with ropyl alcohol) Glass substrate with electrodes (length: 1 0 0 111 01, width: 1 0 0 01 111, thickness: 0. 7 0 1 111) ) Spin coating on the I-side of the plate and 100 on the hot plate. Heat treatment was performed for 5 minutes at ◯ and for 30 minutes at 210° 〇 for 30 minutes in a heat-circulation clean oven to obtain a resin-coated glass substrate with a film thickness of 100 n. Two I-sized substrates with this resin film were prepared, and 20 spacers were applied to the resin film surface of one of the substrates. Then, on the resin film surface of the substrate coated with the spacer, the liquid crystal composition () to (○) was dropped by the method of 〇 〇 (〇 0 "〇 卩 Don 1 1 9), and then the other The substrates were laminated so that the resin film surfaces of the substrates face each other to obtain a liquid crystal display element before treatment.

ドラン プを用いて、 3 5 0 n 以下の波長をカッ トし、 照射時間 6 0秒で紫外線照 射を行った。 これにより、 液晶表示素子 （ガラス基板） を得た。 [0118] The liquid crystal display element before this treatment was

Using a damp, wavelengths below 350 n were cut, and UV irradiation was performed for an irradiation time of 60 seconds. As a result, a liquid crystal display element (glass substrate) was obtained.

"Production of liquid crystal display element (plastic substrate)"

、 厚さ ： 〇. 1 01 01） の 丨 丁〇面上にバーコーターにて塗布をし、 熱循環型 オーブンにて 1 2 0 °〇で 2分間加熱処理をして、 膜厚が 1 0 0 n mの樹脂膜 付きの丨 丁〇基板を得た。 この樹脂膜付きの丨 丁〇基板を 2枚用意し、 その —方の基板の樹脂膜面に、 2 0 のスぺーサーを塗布した。 その後、 その 基板のスぺーサーを塗布した樹脂膜面に、 〇ロ （〇 0「〇卩 ド丨 丨叩） 法 にて前記液晶組成物 （ ） 〜 （〇 を滴下し、 次いで、 他方の基板の樹脂膜 面が向き合うように貼り合わせを行い、 処理前の液晶表示素子を得た。 なお 、 〇ロ 法にて、 液晶組成物の滴下及び貼り合わせを行う際には、 丨 丁〇電 極付き 巳丁基板の支持基板としてガラス基板を用いた。 その後、 紫外線を 照射する前に、 その支持基板を外した。 The resin compositions obtained by the methods of Examples and Comparative Examples were pressure-filtered with a membrane filter having a pore size of 1. The obtained solution was washed with pure water. 1 x 0 x 150 0 01 01 I Dixel Ming board with electrodes (vertical: 1 500 1 01, horizontal:

, Thickness: 0. 01 01 01) Apply on the surface with a bar coater, and heat-treat for 2 minutes at 120° in a heat-circulation oven to obtain a film thickness of 10 We obtained a substrate with a 0 nm resin film. We prepared two substrates with this resin film, and applied 20 spacers to the resin film surface of the other substrate. After that, the liquid crystal composition () to (○) was dropped on the resin film surface of the substrate coated with the spacer by the 〇 ((0 0 ”○ 卩 丨 丨 beating) method, and then the other substrate The liquid crystal display element before treatment was obtained by pasting so that the resin film surfaces of the liquid crystal surface of the liquid crystal composition faced each other. A glass substrate was used as a supporting substrate for the attachment plate, and then the supporting substrate was removed before irradiation with ultraviolet rays.

[0119] For the liquid crystal display element before this treatment, the above-mentioned "Production of liquid crystal display element (glass substrate)

By irradiating ultraviolet rays in the same manner as in “,” a liquid crystal display element (plastic substrate) is obtained. 〇 2020/175 560 40 卩 (：171? 2020 /007782

It was

"Evaluation of optical characteristics (scattering characteristics and transparency)"

In this evaluation, the liquid crystal display element (glass substrate and plastic substrate) was applied with no voltage (〇 V) and the voltage was applied (AC drive:

は、 」 丨 3 < 7 1 3 6に準拠し、 ヘーズメータ （1^~1 2 _ 3 , スガ試験機社製） で測定した 。 なお、 本評価では、 電圧無印加状態の 1^~1 3 2 6が高いほど散乱特性に優れ 、 電圧印加状態での 1^~1 3 2 6が低いほど透明性に優れるとした。 (Haze) was measured. that time,

Was measured with a haze meter (1 ^to 12_3, manufactured by Suga Test Instruments Co., Ltd.) in accordance with "3"<7 1 3 6. In this evaluation, it was determined that the higher the value of 1 ^to 1 3 26 in the non-voltage-applied state, the more excellent the scattering characteristics, and the lower the value of 1 ^to 1 3 26 in the voltage-applied state, the higher the transparency.

[0120] In addition, as a stability test of the liquid crystal display element in a high temperature and high humidity environment, measurement after storage in a constant temperature and humidity chamber at a temperature of 80 ^° and humidity of 90% [¾ 1 ^to 1 for 24 hours I also went. Specifically, the smaller the change from 1 ^to 1 326 after storage in a constant temperature and humidity chamber, compared ^to the initial value from 1 ^to 1 326, the better the evaluation.

[0121] Furthermore, as a stability test of the liquid crystal display element against irradiation of light, a tabletop type II V curing device (1 ^to 10 3 3 2 8 1 ^to 1 1 1) (made by SenRite) was used. Observation was also performed after irradiating 5"/○ ² of ultraviolet rays in terms of 3 65 n 〇! Specifically, the smaller the change of 1 ^to 1 3 to 6 after the irradiation of ultraviolet rays with respect ^to the initial value of 1 ^to 1 3 to 6, the better the present evaluation.

[0122] Initially, after storage in a constant temperature and humidity chamber (constant temperature and humidity) and after irradiation with ultraviolet rays (ultraviolet rays)

The measurement results of Example 6 are summarized in Tables 5 to 7.

"Evaluation of adhesion between liquid crystal layer and resin film (resin film and electrode)"

In this evaluation, the liquid crystal display elements (glass substrate and plastic substrate) were stored for 24 hours in a thermo-hygrostat at a temperature of 80 ^° and a humidity of 90% [¾!! It was performed by confirming the presence or absence of air bubbles (as a stability test of the liquid crystal display element under high temperature and high humidity environment). Specifically, the evaluation was conducted with the element not peeled (the state where the liquid crystal layer and the resin film, or the resin film and the electrode are peeled off) and the case where no air bubbles were generated in the element. To be excellent (good indication in the table). At that time, in Examples 14 to 18, in addition to the standard test, as an emphasizing test, a temperature of 80° 〇 and a humidity of 90% [¾! Stored for hours 〇 2020/175 560 41 卩 (：171? 2020 /007782

I also confirmed later. The evaluation method is the same as above.

[0123] In addition, a desktop type II V curing device (1 ^to 10 3 3 2 8 1 ^to 1 1 1 1

) (Manufactured by Senlite Co., Ltd.)

We also checked after irradiation (as a stability test for the liquid crystal display device against light irradiation). Specifically, those in which the element did not peel and those in which no bubbles were generated in the element were considered to be excellent in this evaluation (good display in the table).

[0124] The results of the adhesion (adhesion) between the liquid crystal layer and the resin film (resin film and electrode) after the initial storage in a constant temperature and humidity chamber (constant temperature and humidity) and after irradiation with ultraviolet rays (ultraviolet rays) are shown in Table 8- It is summarized in Table 10.

<Example 14 to Example 28 and Comparative Example 4 to Comparative Example 6>

Any one of the resin compositions (1) to (16) obtained by the method of Examples and Comparative Examples and the liquid crystal compositions (8) to (○) were used to obtain a liquid crystal display element by the above method. Fabrication, evaluation of optical characteristics (scattering characteristics and transparency), and evaluation of adhesion between the liquid crystal layer and the resin film (resin film and electrode) were performed, with Examples 14 to 20 being Examples 26 to Example 28, Comparative Example 4 and Comparative Example 5 were produced and each evaluation of a liquid crystal display device using a glass substrate, Examples 21 to Example 25 and Comparative Example 6 are, A plastic substrate was used.

[0125] Furthermore, in the evaluation of the adhesion between the liquid crystal layer and the resin film (resin film and electrode) in Examples 14 to 18, the standard test and the emphasis test were performed at a temperature of 80°C and a humidity of 20°C. Evaluations were also made when stored for 90 hours in a constant temperature and humidity chamber of 90% [¾ 1 ^to 1 (other conditions are the same as the above conditions).

[01 26] \\0 2020/175 560 42 卩(: 17 2020/007782

[Table 5]

[0127]

\\0 2020/175 560 43 卩(: 17 2020/007782

[Table 6]

[0128] [Table 7]

[0129] 〇 2020/175 560 44

[Table 8]

[0130] [Table 9]

[0131] [Table 10]

[0132] A lot of bubbles were observed in the device 5. 〇 2020/175 560 45 卩 (：171? 2020 /007782

*6: A small amount of air bubbles were found in the element (more than *5).

*7: Bubbles were found in the device (*6 more).

*8: Many air bubbles were found in the element (more than *7).

[0133] As described above, the liquid crystal display element of the example using the resin composition containing the specific compound was compared with the comparative example not using it, after the storage in the constant temperature and humidity chamber, and after 1 ^to The change of 1 3 2 ₆ became smaller. In addition, in the examples, neither peeling of the liquid crystal display element nor generation of bubbles was observed even after storage in a constant temperature and constant humidity tank and after irradiation with ultraviolet rays. These results were the same even when a plastic substrate was used as the substrate of the liquid crystal display element. Specifically, it is a comparison between Example 14 and Comparative Example 4, a comparison between Example 19 and Comparative Example 5, and a comparison between Example 22 and Comparative Example 6.

In addition, when a polyimido polymer is used as the polymer, the polymer terminal has a carboxylic acid or dicarboxylic acid structure, that is, when the diamine component and the tetracarboxylic acid component are polymerized, If the total number of moles of the components is greater than the number of moles of the diamine component, one having a structure with an amino group at the polymer end (the total number of moles of the tetracarboxylic acid component during the above-mentioned polymer reaction is The generation of bubbles in the liquid crystal display element during the stress test was suppressed compared to the smaller one). Specifically, in comparison under the same conditions, Example 14 and Example 15 are compared.

Furthermore, when a specific diamine having a specific structure was used as the polymer, generation of bubbles in the liquid crystal display element in the highlighting test was suppressed. Specifically, it is a comparison between Example 15 and Example 16 in the comparison under the same conditions.

[0134] In addition, when the specific crosslinkable compound was introduced into the resin composition, generation of bubbles in the liquid crystal display element in the highlight test was suppressed. Specifically, it is a comparison between Example 17 and Example 18 under the same conditions.

[0135] When the liquid crystal composition containing the specific liquid crystal additive compound was used, the driving voltage of the liquid crystal display element was lower than that when it was not used. Specifically, in comparison under the same conditions, there are a comparison between Example 19 and Example 20 and a comparison between Example 22 and Example 23. 〇 2020/175 560 46 卩 (：171? 2020 /007782

Industrial availability

[0136] By using a resin film obtained from a resin composition containing a compound having a specific structure, it is possible to prevent the exfoliation of the element even in a harsh environment exposed to high temperature and high humidity or light irradiation for a long time. A liquid crystal display device capable of suppressing the generation of bubbles and the deterioration of optical properties can be obtained.

Further, the liquid crystal display element of the present invention can be suitably used for a normal type element that is in a scattering state when no voltage is applied and is in a transparent state when a voltage is applied. Furthermore, this device can be used in liquid crystal displays for display purposes, and in dimming windows and optical shutter devices that control the blocking and transmission of light. A plastic substrate can be used.

[0138] Note that Japanese patent application filed on Feb. 27, 1992 2 0 1 9— 0 3 4

The entire contents of the specification, claims and abstract of No. 306 are cited herein and incorporated as the disclosure of the specification of the present invention.

Claims

\¥0 2020/175 560 47 卩(: 17 2020/007782 Claims [Claim 1] A liquid crystal composition comprising a liquid crystal and a polymerizable compound arranged between a pair of substrates provided with electrodes, and a liquid crystal layer cured by applying at least one of active energy rays and heat. Further, a normal scattering type liquid crystal display element, which comprises a resin film on at least one of the substrates, and which is in a scattering state when no voltage is applied and is in a transparent state when a voltage is applied, wherein the resin film is A liquid crystal display device obtained by using a resin composition containing a compound having a group of the following formula [1]. [Chemical 1]

The symbol represents a binding site with another structure. [Claim 2] The compound having a group of the formula [1] is represented by the following formula [13] The liquid crystal display element described in 1. [Chemical Formula 2] Ding 1-Ding 2-Ding 3 [1 3] Ding ¹ is the following formula [1 _ 8]

At least one structure selected from is shown. Ding ² represents a single bond or an organic group having 1 to 18 carbon atoms. Ding ³ shows the structure of the above formula [1]. 〇 2020/175 560 48 卩 (：171? 2020 /007782 [Chemical 3]

Hohachi represents an alkyl group having 1 to 3 carbon atoms. [Claim 3] The liquid crystal surface ^ according to claim 1 or 2, wherein the resin composition contains a polymer having at least one structure selected from the following formula [2-3] to formula [2-]. ^ Element. [Chemical 4]

VIII represents a hydrogen atom or a benzene ring. [Claim 4] The polymer is at least one selected from acrylic polymers, methacrylic polymers, novolak resins, polyhydroxystyrenes, polyimide precursors, polyimides, polyamides, polyesters, celluloses and polysiloxanes. Item 3. The liquid crystal display device according to item 3. [Claim 5] The liquid crystal according to claim 4, wherein the polymer is a polyimide precursor obtained by a reaction of a diamine component and a tetracarboxylic acid component, or a polyimide obtained by imidizing the polyimide precursor. Display element. 〇 2020/175 560 49 卩 (：171? 2020 /007782 [Claim 6] The diamine component, the formula [2-8] to the formula [2_丨] of claim 5 comprising a diamine having at least one structure is that selected from liquid Akirahyo _/ ": _? . [Claim 7] The diamine is liquid according to claim 6 having the structure of Formula [2] Akirahyo _{/ ":?} Yu. [Chemical 5] -ー (— X ² one X ³ — X ⁴ [2] X ¹ is a single bond, one hundred and one, One NH - one (Rei_1 ^~ 1 ₃₎ - one Rei_1 ^~ 1 ₂ 〇 - one Rei_rei_1 \ 11 ^~ 1,

〇 one, one hundred (01 ^to 1 to ₃₎ -,

(〇 1 ^to 1 ₃ ) At least one kind selected from 001, 100001 and 100001 is shown. X ² represents a single bond, an alkylene group having 1 to 18 carbon atoms, or a cyclic group selected from a benzene ring, a cyclohexane ring and a heterocycle, and an organic group having 6 to 24 carbon atoms. The above arbitrary hydrogen atom is an alkyl group having 1 to 3 carbon atoms, an alkoxyl group having 1 to 3 carbon atoms, a fluorine-containing alkyl group having 1 to 3 carbon atoms, a fluorine-containing alkoxyl group having 1 to 3 carbon atoms, or fluorine. It may be substituted with an atom. X ³ is a single bond, ,

Indicates at least one kind selected from 001 and 100_. X ⁴ represents at least one selected from the above formula [2_3] to formula [2_丨]. X n represents an integer of 1 to 4. [Claim 8] The diamine is a liquid crystal display device according to claim 7, which is the following formula [2 _3]. [Chemical 6]

〇 2020/175 560 50 卩 (：171? 2020 /007782 X represents the structure of the above formula [2]. The subscript indicates an integer of 1 to 4. [Claim 9] The liquid crystal display element according to any one of claims 5 to 8, wherein the tetracarboxylic acid component contains a tetracarboxylic acid dianhydride represented by the following formula [3]. [Chemical 7]

Represents at least one structure selected from the following formula [33] to formula [3I]. [Chemical 8]

2 eight to _two . Each represents a hydrogen atom, a methyl group, a chlorine atom or a benzene ring. ^£ and are respectively hydrogen atom or methyl group 〇 [Claim 10] In the reaction between the diamine component and the tetracarboxylic acid component, the total number of moles of the tetracarboxylic acid component is 1.05 to 1 when the total number of moles of the diamine component is 1.0. The liquid crystal display device according to any one of claims 5 to 9, wherein the liquid crystal display device is 20. [Claim 11] The liquid crystal display device according to any one of claims 1 to 10, wherein the liquid crystal composition contains a compound represented by the following formula [48]. \¥0 2020/175 560 51 卩(: 17 2020/007782 [Chemical 9]

3 ¹ represents at least one structure selected from the following formulas [4-8] to the formula [4 _ ". 3 ² is a single bond, _ 〇 1, _ _NH —, _ |\! (〇!·!

1 ^~ 1 ₃ ) _,

(Rei_1 ^~ 1 ₃₎ hundred one, indicating at least one Bareru selected from _〇_〇_〇 first and one 〇_〇_〇_. 3 ³ is a single bond or a single (<3 1 ^to 1 ₂ ) ( 3 is an integer of 1 to 15). 3 ⁴ is a single bond, one hundred and one, one hundred 1 ^to 1 ₂ - represents at least one selected from _〇_〇_〇 first and one 〇_〇_〇_. 3 ⁵ shows a benzene ring, a cyclohexane ring, and Ru is selected from heterocyclic divalent cyclic group, or a divalent organic group of 1 7-5 1 carbon atoms having a steroid skeleton, optionally on the cyclic group The hydrogen atom of is substituted with an alkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, a fluorine-containing alkyl group having 1 to 3 carbon atoms, a fluorine-containing alkoxy group having 1 to 3 carbon atoms or a fluorine atom. It may be. 3 ⁶ is a single bond, 101, 1

— , — 0 0 1 ^~ 1 ₂ ^{— —} 0 1 ^~ 1 ₂ ○-

Indicates at least one selected from 3 ^7, benzene ring represents a cyclohexane ring and a cyclic group selected from heterocyclic, any water atom on these cyclic groups, an alkyl group, an alkoxy group of from 1 to 3 carbon atoms from 1 to 3 carbon atoms It may be substituted with a fluorine-containing alkyl group having 1 to 3 carbon atoms, a fluorine-containing alkoxy group having 1 to 3 carbon atoms, or a fluorine atom. 3 ⁸ is an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, a fluorine-containing alkyl group having 1 to 18 carbon atoms, an alkoxy group having 1 to 18 carbon atoms and 1 to 8 carbon atoms At least one selected from 18 fluorine-containing alkoxy groups is shown.

Indicates an integer from 0 to 4. \\02020/175 560 52 20201007782 [Chemical 10]

38 indicates a hydrogen atom or a benzene ring. [Claim 12] The compound of the formula [48] is represented by the following formula [43-1] to formula [43-1 1 ] At least 1 sort(s) selected from these, The liquid crystal display element of Claim 11. [Chemical 11]

3 ³ each shows _〇 one or 10,001. Each 3 represents an alkyl group having 1 to 12 carbon atoms. Each 1 represents an integer from 1 to 10. 2 is an integer of 1 or 2, respectively. \\0 2020/175 560 53 卩(: 17 2020/007782 [Chemical 12]

Indicates a single bond, 1001 or 10 ⁽ 301), respectively.

Each represents an alkyl group or an alkoxy group having 1 to 12 carbon atoms. Each 3 represents an integer of 1 to 10. Each 4 represents an integer of 1 or 2. [Chemical 13]

^3-6 respectively show a _〇 one or ten thousand and one. Each of the three groups represents a divalent organic group having a steroid skeleton and having 17 to 51 carbon atoms. Each 39 represents an alkyl group having 1 to 12 carbon atoms or an alkenyl group having 2 to 18 carbon atoms. Each 5 represents an integer of 1 to 10. [Claim 13] The resin composition further comprises a crosslinkable compound having at least one selected from an epoxy group, an isocyanate group, an oxetane group, a cyclocarbonate group, a hydroxy group, a hydroxyalkyl group and a lower alkoxyalkyl group, Claim 1-Claim 12 〇 2020/175 560 54 卩 (：171? 2020 /007782 Liquid crystal display device. [Claim 14] The liquid crystal display element according to any one of claims 1 to 13, wherein the substrate of the liquid crystal display element is a glass substrate or a plastic substrate. [Claim 15] A resin film for use in the liquid crystal display device according to any one of claims 1 to 14, which is a resin formed from a resin composition containing a compound having a group of the formula [1]. film. [Claim 16] A resin composition for forming a resin film according to claim 15, comprising a compound having a group of the formula [1].