TW201736439A - Liquid crystal display element, liquid crystal optical element, and composition for liquid crystal structure-stabilizing film - Google Patents

Abstract

Provided is a liquid crystal structure-stabilizing film by which even ULH alignment is obtained without application of physical stress, in other words, a liquid crystal structure-stabilizing film having good initial ULH alignment. A ULH-mode liquid crystal display element obtained using cholesteric liquid crystal and a liquid crystal structure-stabilizing film in which a polymer for expressing anisotropy by polarized UV irradiation is used.

Description

Liquid crystal display element, liquid crystal optical element, and liquid crystal structure stabilization film composition

The present invention relates to a liquid crystal display device using a liquid crystal alignment mode in which a reaction rate is extremely fast and an optical reaction is linearly applied to a voltage, and a liquid crystal cell, a substrate, and a film for stabilizing the liquid crystal structure, which are necessary for the production of the liquid crystal structure. To form a composition of such a film or the like.

In terms of liquid crystal display elements that are generally popular, for example, TN (Twisted Nematic) mode, IPS (In Plane Switching) mode, VA (Vertical Alignment) mode, etc., but in any of the driving methods, the On/Off of the liquid crystal is spent. The time, that is, the problem of slow reaction rate or the change seen from the viewing angle, that is, the viewpoint of the viewing angle dependence.

On the other hand, although it has not been put to practical use, it is attracting attention as a next-generation liquid crystal drive method, such as a blue phase or ULH (Uniform Lying Helix) which is a liquid crystal driving method which has a very fast reaction speed and no viewing angle dependence. In particular, in ULH, in addition to a very fast reaction speed, it also has a feature that the driving voltage is relatively low and the applied voltage exhibits a linear optical reaction, and is expected to be applied to various display media.

ULH is one of liquid crystal driving methods using cholesteric liquid crystal. By holding a cholesteric liquid crystal on a substrate having a transparent electrode and imparting physical shear stress or electrical stimulation or the like, a spiral can be uniformly formed on the substrate plane. This alignment state is referred to as ULH, but by applying an electric field thereto, the optical axis of the spiral is subjected to In Plane Switching, whereby a linear optical reaction can be obtained.

On the other hand, in the ULH alignment, it is very difficult to obtain a uniform alignment state, and when placed under an electric field, there is a problem in that the alignment state of the ULH is irreversibly changed. In this case, a liquid crystal structure in which a liquid crystal is added to a condensed liquid crystal, and a polymer network structure is formed by UV irradiation after ULH formation, thereby achieving a stabilization of ULH alignment (Patent Document 1), and further A method of forming a ULH by applying a liquid crystal injection while applying a shear stress (Non-Patent Document 1) or forming an alignment layer having a periodic structure by photolithography to make the ULH alignment method (Non-Patent Document 2) )Wait.

[Previous Technical Literature] [Patent Literature]

[Patent Document 1] US 7,038,743 B2

[Non-patent literature]

[Non-Patent Document 1] Liquid Crystals, 24:3, 329-334, 1998

[Non-Patent Document 2] Mol. Cryst. Liq. Cryst. Vol. 544: pp. 37/[1025] - 49/[1037], 2011

Various methods are used in the alignment stabilization of ULH or the improvement of alignment uniformity. However, in the production process of a liquid crystal display, it is extremely difficult to inject liquid crystal and perform alignment treatment while applying shear stress, and further, it is caused by a polymerizable compound. In the stabilization process, it is also necessary to implement the state of equal ULH alignment, and the improvement of the alignment uniformity of the ULH is also a technically significant problem. Therefore, an object of the present invention is to provide a liquid crystal structure stabilized film which can obtain an equal and excellent ULH alignment without applying physical stress, and a ULH liquid crystal display element including the liquid crystal structure stabilized film.

In order to achieve the above-mentioned object, it has been found that in order to obtain an equal and good ULH alignment, there is a film which is in contact with a helical structure composed of cholesteric liquid crystal and which is stabilized (hereinafter, also referred to as The liquid crystal structure stabilized film) is effective in achieving the problem, and it is necessary to make the surface of the liquid crystal structure stabilized film small and small and the interaction with the liquid crystal is small, and the present invention has been completed.

That is, the present invention encompasses the following.

[1] A composition for forming a film for stabilizing a liquid crystal structure (synonymous with the above-mentioned "liquid crystal structure stabilizer"), comprising a polyimine precursor selected from the group consisting of polyimine, polyamine, and polyamine ,Polyacrylic acid a group of esters, polymethacrylates, poly-N-substituted maleimine, polystyrene, polyitaconate, and polyorganosiloxane, and exhibiting anisotropy by polarized ultraviolet radiation 1 kind of polymer.

[2] At least one of the aforementioned polymers has the following formulas (1) to (5) in the main chain:

[wherein, Z ₁ to Z ₄ are each independently and are at least one selected from the group consisting of a hydrogen atom, a methyl group, and a benzene ring, and R ₁ is a hydrogen atom, a methyl group, an ethyl group, a propyl group, or an isopropyl group. An organic group selected from the group consisting of a group, an isobutyl group, and a t-butyl group, and R ₂ is a hydrogen atom, a fluorine atom, or the following formula:

(wherein R ₃ is a hydrogen atom or an alkyl chain having 1 to 18 carbon atoms, m is an integer of 1 to 3, and a black dot is a bonding site.) The organic group represented by a black dot and another organic group Bonding. The composition described in [1] of the polyimine precursor of any of the structures represented by the polyimine.

[3] The at least one polymer described above has the following formulas (6) to (10) in the main chain:

(wherein X ₁ and X ₂ are each independently a carbon atom or a nitrogen atom, and Y ₁ and Y ₂ are each independently a hydrogen atom, a methyl group, a cyano group, a fluorine atom or a chlorine atom, and X ₃ is an oxygen atom. Or a sulfur atom, X ₄ is a single bond, a carbon atom, an oxygen atom, or a sulfur atom, and R ₄ and R ₅ are each independently a hydrogen atom, a methyl group, a methoxy group, a dimethylamino group, a fluorine atom, or Chlorine atom, p is an integer from 1 to 4, q is an integer from 1 to 3, and the dotted line is a bond with another organic group.)

The composition described in [1] of the polyimine precursor of any of the structures represented by the present invention or the polyimine.

[4] The at least one polymer described above has the following formula (6) to (8) or (11):

(wherein X ₁ and X ₂ are each independently a carbon atom or a nitrogen atom, and Y ₁ and Y ₂ are each independently a hydrogen atom, a methyl group, a cyano group, a fluorine atom or a chlorine atom, and X ₃ is an oxygen atom. Or a sulfur atom, X ₄ is a single bond, a carbon atom, an oxygen atom, or a sulfur atom, and R ₄ and R ₅ are each independently a hydrogen atom, a methyl group, a methoxy group, a dimethylamino group, a fluorine atom, or Chlorine atom, Ar is 2,5-extended furyl, thiophene-2,5-diyl, pyrimidine-2,5-diyl, pyridine-2,5-diyl, phenyl, 1,4- or 2 , 6-strandyl, 2,5- or 2,6-benzofuranyl, or 2,5- or 2,6-benzothiophenyl, a hydrogen bonded to the aromatic ring One part of the atom may be substituted by a methyl group, a methoxy group, a dimethylamino group, a fluorine atom, or a chlorine atom, p is an integer of 1 to 4, and a black point is a hydrogen atom or a bond with another organic group. A composition described in [1] which is a polymer which is a part of a side chain.

[5] The aforementioned at least one polymer has the following general formula:

(In the formula, the dotted line is a bond with another organic group.)

The structure (12) or (13) and the structures of the above general formulas (6) to (11) are represented as polyacrylate, polymethacrylate, poly N substituted maleimide, or a part of the side chain. The composition described in [1] of polystyrene, polyitaconate or polyoxyalkylene.

[6] A film for forming a ULH alignment for cholesteric liquid crystal The composition according to any one of [1] to [5].

[7] A film for forming a film of the composition according to any one of claims 1 to 5, and a film for activating the liquid crystal structure in which the obtained film is irradiated with polarized ultraviolet rays to exhibit anisotropy (hereinafter) The manufacturing method of "liquid crystal structure stabilized film").

[8] In the polarized ultraviolet ray irradiation step, the anisotropy is represented by the method described in [7] by decomposition, isomerization or crosslinking.

[9] In the polarized ultraviolet ray irradiation step, the anisotropy is expressed by the method of [7] or [8] in which the polarized ultraviolet ray is irradiated to the film surface from the vertical direction.

[10] The polarized ultraviolet ray irradiation step includes a polarized ultraviolet ray having an irradiation wavelength of 250 nm to 400 nm irradiated with ultraviolet rays, a step of irradiating at least 2 mJ or more of the irradiation energy, and further heating at 80 to 300 ° C for 5 minutes or more after the irradiation [7]. Or the method described in any one of [9].

[11] comprising a polyimide precursor, polyimine, polyamine, polyacrylate, polymethacrylate, poly-N-substituted maleimide, polystyrene, polyitaconate, and At least one polymer selected from the group consisting of a polyorganosiloxane and a film for stabilizing the liquid crystal structure by anisotropic ULH alignment of the cholesteric liquid crystal.

[12] A substrate having a liquid crystal structure stabilization film attached to the film according to [11].

[13] A liquid crystal cell in which a liquid crystal structure liquid crystal cell is contained between the substrates having the liquid crystal structure stabilization film described in [12] in which the liquid crystal structure is stabilized.

[14] The cholesteric liquid crystal is a liquid crystal cell described in [13] of a cholesteric liquid crystal containing a liquid crystal compound represented by the following general formula.

(wherein, X ₁ and X ₂ are each independently a bond group selected by a single bond, an ester bond or an ether bond, L is an integer represented by 6 to 20, and R ₈ is an alkyl group having 4 to 10 carbon atoms. )

[15] A liquid crystal display element comprising a polarizing plate and a liquid crystal cell according to [13] or [14].

According to the present invention, by using a liquid crystal structure stabilized film which exhibits anisotropy by polarized ultraviolet light irradiation, good ULH alignment can be obtained without applying external stress or the like.

The reason why the liquid crystal display element having the above-described excellent characteristics can be obtained by the present invention is not necessarily clear, but it can be presumed as follows. In other words, in order to determine the directionality of the spiral structure composed of cholesteric liquid crystal and to stabilize it, in place of the physical shear stress or electrical stimulation used in the prior art, A treatment for causing a certain anisotropy of the liquid crystal structure stabilization film (hereinafter, also referred to as alignment treatment) is required. As the alignment treatment, a rubbing method generally performed in the field of liquid crystal display elements using nematic liquid crystals tends to cause film cutting or adhesion of dust from cloth during the alignment treatment, and the influence of vibration or hairiness of the drum. The extension of the film tends to become uneven. Since the ULH alignment is in a very fine alignment state, it is considered that if there is unevenness in the lower layer or the like, a good alignment cannot be obtained, but since the light alignment is non-contact type, the cutting from the friction or the adhesion of the dust does not occur, and Controlled by molecular degree, a very uniform alignment state can be formed. Further, the alignment treatment by light generally tends to be smaller than the alignment treatment by friction, and the alignment control force of the liquid crystal (also referred to as the strength of interaction with the liquid crystal) is small. From the above, it is considered that in the constitution of the present invention, a good ULH liquid crystal display element can be obtained.

Fig. 1 is a schematic view showing a unit cell for ULH alignment of a cholesteric liquid crystal obtained by a film formed on a substrate.

Fig. 2 is a view showing an evaluation result of initial alignment and a case where ULH alignment is good.

Fig. 3 is a view showing an evaluation result of initial alignment and a case where ULH alignment is poor.

Hereinafter, each constituent element of the present invention will be described in detail.

1. Liquid crystal structure stabilized film

The liquid crystal display device of the present invention comprises a liquid crystal structure stabilized film which exhibits anisotropy by polarized ultraviolet light irradiation.

In the liquid crystal structure stabilization film, a film obtained by applying a liquid crystal structure stabilizer which dissolves a photosensitive polymer material in an organic solvent to a substrate or the like is irradiated with radiation such as ultraviolet rays to express various directions. A functional film of the opposite sex.

In the liquid crystal structure stabilized film used in the present invention, as a mechanism for exhibiting anisotropy by polarized ultraviolet light irradiation, for example, 1) decomposition of a polymer in a predetermined direction by ultraviolet irradiation, and anisotropic expression, 2 A reaction occurs in a polymer site in a certain direction by polarized ultraviolet light irradiation (isomerization or dimerization), and anisotropic is exhibited, and 3) ultraviolet rays are irradiated at a set angle to generate a reaction in a side chain in a specific direction ( Isomerization or dimerization, etc., produces anisotropic, etc., but is not limited to a good ULH alignment.

2. Liquid crystal structure stabilizer

The composition (liquid crystal structure stabilizer) for forming a liquid crystal structure stabilization film which exhibits anisotropy by irradiation with polarized ultraviolet rays is obtained by irradiating radiation such as ultraviolet rays to obtain liquid crystal alignment property. The polymer is contained in a form in which the organic solvent is dissolved. The liquid crystal structure stabilizer contains 1 to 15% by mass, more preferably 2 to 10% by mass, based on the polymer. It is preferably 2 to 8 mass%.

Examples of such materials are, for example, polyimine precursors, polyimine, polyamine, polyacrylate, polymethacrylate, poly-N-substituted maleimide, polystyrene, Polyacetate, polyoxyalkylene, etc., but are not limited thereto. In the liquid crystal display application, the use environment becomes severe, and from the viewpoint of the reliability of the display element, a heat-resistant resin such as a polyimide or a polyimide is excellent, and a display element is produced by firing at a low temperature. Opinion or unity. From the viewpoint of the ease of synthesis of the polymer, a polyacrylate-based material or a polymethacrylate is preferred.

2.1. Polymer 2.1.1. Polymer (I) Polyimine Precursor, or Polyimine

The polyimine precursors are poly-proline and polyphthalate. The polyglycolic acid is obtained by reacting a diamine component with a tetracarboxylic acid component, and the polyglycolic acid ester can be obtained by condensation polymerization of a diester body of a tetracarboxylic acid and a diamine. The polyimine can be obtained by subjecting the polyimine precursor to a heat dehydration reaction and dehydration condensation using a catalyst such as an acid or a base.

The polyimine precursor has a structure represented by the following formula [A].

(wherein R ¹ is a tetravalent organic group. R ² is a divalent organic group. A ¹ and A ² are each independently a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. A ³ and A ⁴ are each independently A hydrogen atom, an alkyl group having 1 to 5 carbon atoms or an ethylene group. n is a positive integer.)

In the case of a polyimine-based polymer, a tetracarboxylic dianhydride represented by the following formula [B] and a diamine represented by the following formula [C] can be used as a raw material, which can be easily obtained. Polyammonic acid composed of a structural formula of a repeating unit represented by the following formula [D] or a polyiminoid obtained by imidating the polyphosphonium amide.

(wherein R ¹ and R ² are synonymous with the definition of the formula [A].)

(wherein R ¹ and R ² are synonymous with the definition of the formula [A].)

2.1.1.1. Diamine

The diamine component is a diamine having two first- or second-order amine groups in the molecule, and examples of the tetracarboxylic acid component include tetracarboxylic acid, tetracarboxylic dianhydride, and tetracarboxylic acid. Examples of the dihalide or the like and the tetracarboxylic acid diester include dialkyl tetracarboxylate or dialkyl tetracarboxylate dihalide.

The diamine used in the polyimine-based polymer contained in the liquid crystal structure stabilizer of the present invention is not particularly limited, and R ² may be used in a range that does not impair the characteristics of the obtained ULH liquid crystal display device. A diamine of the following construction. Further, the point in the formula is a moiety directly bonded to an amine group.

In the present invention, these diamine structures play a very important role in the improvement of friction resistance, so that it is preferable to actively introduce them, especially Y-82 or Y-94 to Y-108.

2.1.1.2. Tetracarboxylic dianhydride

The tetracarboxylic dianhydride can be represented by the following general formula (TC).

X is a tetravalent organic group, and its structure is not particularly limited.

The type of the tetracarboxylic dianhydride used in the present invention is not particularly limited, and may be used in combination of one type or two types or more depending on the characteristics of the voltage holding property and the accumulated electric charge when the liquid crystal structure stabilized film is formed.

The specific X is, for example, the following, but is not limited to such a configuration.

In the case of preparing a soluble polyimine, the solubility in a solvent is an important physical property. Therefore, from the viewpoint of solubility, an alicyclic tetracarboxylic anhydride represented by X-1 to 26 is preferred, and X-2 is preferable. , X-3, X-4, X-6, X-9, X-10, X-11, X-12, X-13, X-14, X-15, X-16, X-17, X -18, X-19, X-20, X-21, X-22, X-23, X-24, X-25, X-26 are preferred. On the other hand, in terms of orientation, X27~46-like aromatic tetracarboxylic dianhydride is preferred, especially X-27, X-28, X-33, X-34, X-35, X-40. X-41, X-42, X-43, X-44, X-45, X-46 are preferred.

It is especially preferred to have X-1, X-2, X-18~22, X-25, X-26 with appropriate orientation and solubility.

2.1.1.3. Preferred Polyimine Precursor, or Polyimine (1)

A polyimine precursor or a polyimine contained in a composition (liquid crystal structure stabilizer) for forming a liquid crystal structure stabilization film which exhibits anisotropy by polarized ultraviolet light irradiation, which is important in the present invention. Examples of the type include those having the following structures (1) to (5) in the main chain structure.

(wherein Z ₁ to Z ₄ are each independently, and at least one selected from the group consisting of a hydrogen atom, a methyl group, and a benzene ring, and R ₁ is a hydrogen atom, a methyl group, an ethyl group, a propyl group, or an isopropyl group. The organic group selected from the group consisting of a group, an isobutyl group, and a t-butyl group, and R ₂ is a hydrogen atom, a fluorine atom, or an organic group represented by the following formula: The black dots are bonded to another organic group. )

(In the formula, R ₃ is a hydrogen atom or an alkyl chain having 1 to 18 carbon atoms, and m is an integer of 1 to 3. The black point is a bonding site.)

The structure of (1) and (4) indicates the structure of the polyimide precursor, and the structure of (5) can be derived by firing a material having such a structure at a high temperature. Partially ruthenium imidization of a part of the polyimide precursor In the case where the yttrium imide is converted into a solvent-soluble polyimine (also known as soluble polyimine) in the form of a shape or a purpose, in which case the structure of (1) to (5) is mixed. form.

The structure represented by (5) in the present invention is important by applying a paint containing a polyimide precursor or a paint containing soluble polyimine (collectively referred to as a liquid crystal structure stabilizer). The substrate is heated and fired and derivatized as (5). The calcination temperature at this time is often between 200 ° C and 250 ° C. When the temperature is too low, the imidization time is too high, and if the temperature is too high, the decomposition reaction is also carried out. Therefore, it is preferably 210 ° C to 240 ° C.

Further, in the usual synthesis method, the alkyl group having 1 to 8 carbon atoms of A ¹ and A ² represented by the formula [A] and the formula [A] may be introduced into the polymer of the formula [D] obtained above. The alkyl group or the ethylidene group having 1 to 5 carbon atoms of A ³ and A ⁴ shown.

The cyclobutane ring in the polymer [5] used is decomposed by ultraviolet irradiation, and the film containing the polymer [5] is irradiated with polarized ultraviolet rays, and a decomposition portion and a non-decomposition portion are formed on the surface of the film to form The delay is also a uniaxially oriented film.

When the ultraviolet ray is irradiated, the decomposed product is generated, but the decomposed product can be removed by heat treatment or solvent washing, and by performing such treatment, the reorientation of the polymer chain can be further promoted, so that the alignment of the liquid crystal can be achieved. The quality is improved. When the heat treatment is performed, the heating temperature is preferably between 150 ° C and 250 ° C. However, if the temperature is low, the sublimation or evaporation of the decomposed product cannot be sufficiently promoted. If the temperature is too high, the decomposition of the polymer chain may occur. Therefore, it is more preferably 200 ° C ~ 230 ° C. Although the heating time is not particularly limited, if the decomposition product is too short, the decomposition product is not sufficiently removed, so it is preferably 5 to 30 minutes.

Further, in the case of performing film cleaning, it is preferred to use a solvent which dissolves a decomposition product, that is, bismaleimide. The solvent for dissolving the bismaleimide is not particularly limited, but the organic solvent alone may have a possibility that the polymer itself is also eluted, and thus the alignment property is lowered. Therefore, it is preferably water or water. It is preferred to carry out contact treatment with a mixed solvent of an organic solvent.

In terms of a mixed solvent of water and an organic solvent, the quality of the water and the organic solvent is preferably 20/80 to 80/20, more preferably 40/60 to 60/40. The organic solvent may, for example, be 2-propanol, methanol, ethanol, 1-methoxy-2-propanol, ethyl lactate, diacetone alcohol, methyl 3-methoxypropionate, or 3- Ethyl ethoxypropionate. Among them, 2-propanol, methanol, or ethanol is preferred, and 2-propanol is preferred.

After the contact treatment, one or both of washing (washing) or drying with a low boiling point solvent such as water, 2-propanol or acetone may be carried out for the purpose of removing the organic solvent to be used.

In the contact treatment of the liquid crystal structure stabilized film, it is preferred that the film such as the immersion treatment or the spray treatment is sufficiently contacted with the liquid. In the contact treatment, it is preferred that the film be subjected to an immersion treatment of preferably from 10 seconds to 1 hour, more preferably from 1 minute to 30 minutes, with water or an aqueous liquid composed of a mixed solvent of water and an organic solvent. The contact treatment may be normal temperature or heating, but is preferably carried out at 10 to 80 ° C, more preferably at 20 to 50 ° C. In addition, it is possible to apply means such as ultrasonic waves to increase contact.

2.1.1.4. Preferred Polyimine Precursor, or Polyimine (2)

In the general formula [A], the polyimine precursor or the polyimine having the structure represented by the following (6) to (10) in R ₂ may be contained in the liquid crystal structure stabilizer of the present invention.

(wherein X ₁ and X ₂ are each independently a carbon atom or a nitrogen atom, and Y ₁ and Y ₂ are each independently a hydrogen atom, a methyl group, a cyano group, a fluorine atom or a chlorine atom, and X ₃ is an oxygen atom. Or a sulfur atom, X ₄ is a single bond, a carbon atom, an oxygen atom, or a sulfur atom, and R ₄ and R ₅ are each independently a hydrogen atom, a methyl group, a methoxy group, a dimethylamino group, a fluorine atom, or Chlorine atom, p is an integer from 1 to 4, q is an integer from 1 to 3, and the dotted line is a bond with another organic group.)

The structure represented by the general formulae (6) to (10) is isomerized, dimerized, decomposed, or the like by ultraviolet irradiation or the like, and thus the polyimine film having such a structure is irradiated with polarized ultraviolet rays. Delay and uniaxial alignment can be imparted in the portion that does not become a structural change portion. Particularly preferred is a polyimine precursor or polyimine having the following structure.

In the stabilization of a liquid crystal structure using a polyimine precursor or a polyimide having such a structure, the film is formed by yttrium imidation or in a soluble polyimine state by firing at a high temperature. By irradiating the polarized ultraviolet ray, heating it, or irradiating the polarized ultraviolet ray in the state of a poly lysine film, it is baked and imidated, and the realignment of a polymer chain is accelerated, and the delay can be improved. The firing temperature is preferably from 180 ° C to 250 ° C, and more preferably from 200 ° C to 230 ° C from the viewpoint of the imidization reaction or re-alignment.

Wash with pure water or solvent as necessary.

2.1.2. Polymer (II) Polymer with specific side chain (1)

The liquid crystal structure stabilizer of the present invention may contain a polymer which is a polymer having a structure represented by the following formula (6) to (8) or (11) as a part of a side chain.

(wherein X ₁ and X ₂ are each independently a carbon atom or a nitrogen atom, and Y ₁ and Y ₂ are each independently a hydrogen atom, a methyl group, a cyano group, a fluorine atom or a chlorine atom, and X ₃ is an oxygen atom. Or a sulfur atom, X ₄ is a single bond, a carbon atom, an oxygen atom, or a sulfur atom, and R ₄ and R ₅ are each independently a hydrogen atom, a methyl group, a methoxy group, a dimethylamino group, a fluorine atom, or Chlorine atom, Ar is 2,5-extended furyl, thiophene-2,5-diyl, pyrimidine-2,5-diyl, pyridine-2,5-diyl, phenyl, 1,4- or 2 , 6-strandyl, 2,5- or 2,6-benzofuranyl, or 2,5- or 2,6-benzothiophenyl, a hydrogen bonded to the aromatic ring One part of the atom may be substituted by a methyl group, a methoxy group, a dimethylamino group, a fluorine atom, or a chlorine atom. p is an integer of 1 to 4, and a black point is a hydrogen atom or a bond with another organic group.

The general formulae (6) to (8) and (11) are known to initiate an isomerization reaction or a dimerization reaction by the above-mentioned light irradiation, and the polarized ultraviolet rays are irradiated to the polymer having such a side chain. The portion of the non-structural change portion can impart retardation and uniaxial alignment. A more specific configuration is as follows, but is not limited thereto.

The polymer having such a side chain structure is not particularly limited to a polymer main chain structure, but preferably, for example, a polyimide precursor, a polyimine, a polyamine, a polyacrylate, or a polymethacrylate Ester, poly N substituted maleimide, polystyrene, polyitaconate, polyoxyalkylene, and the like.

When such a polymer is used in the liquid crystal structure stabilizer of the present invention, it can be obtained by firing and irradiating ultraviolet rays after film formation. However, when the polymer has liquid crystallinity, Heating near the liquid crystal phase transition temperature can promote realignment and improve liquid crystal alignment. The preferred temperature for the re-alignment treatment cannot be limited depending on the structure of the polymer, but the liquid crystal phase transition temperature is previously investigated by DSC (differential scanning calorimetry) or POM (observation of a polarizing microscope with an additional thermal mechanism), and is used in advance. The nearby temperature domain is preferred.

2.1.3. Polymer (III) polymer with specific side chain (2)

Polyacrylates, polymethacrylates, poly-N-substituted maleimides, polystyrene, polyitanic acid esters, polyfluorene oxides having a configuration represented by the following general formula as a part of the side chain may also be used. The alkane is in the optical alignment.

(In the formula, the dotted line is a bond with another organic group.)

It is known that the structures of the formulae (12) and (13) exhibit liquid crystallinity by their own hydrogen bonding, and the above-mentioned polymers having side chains are mostly liquid crystallinity. In particular, the above formulae (6) to (11) cause isomerization or crosslinking reaction by ultraviolet irradiation, so that the polymer containing the formulae (6) to (11) and (12) (13) has light. Reactive liquid crystalline polymer. The hydrogen-bonding liquid crystal polymer is irradiated with polarized ultraviolet light, and self-organization is caused by heating, and retardation can be obtained. As a result, it can be used as a liquid crystal structure stabilized film. Specific examples of the photoreactive side chain are, for example, the following formulas (8-4) to (8-11), (10-1), and (11-1), and the specificity of the liquid crystal side chain is, for example, the following formula (12-1). ) is even shown in (12-3), (13-1), and (13-2), but is not limited thereto.

Wherein A, B, and D are each independently a single bond, -O-, -CH ₂ -, -COO-, -OCO-, -CONH-, -NH-CO-, -CH=CH-CO-O -, or -O-CO-CH=CH-; Y ₁ is a ring selected from a monovalent benzene ring, a naphthalene ring, a biphenyl ring, a furan ring, a pyrrole ring, and an alicyclic hydrocarbon having 5 to 8 carbon atoms, or The same or different 2~6 rings selected by the substituents are bonded through the bonding group B, and the hydrogen atoms bonded to each other are independent of each other, and can be -COOR ₀ (formula) Wherein R ₀ is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, -NO ₂ , -CN, -CH=C(CN) ₂ , -CH=CH-CN, a halogen group, and a carbon number of 1 to 5. An alkyl group or an alkyloxy group having 1 to 5 carbon atoms; X is a single bond, -COO-, -OCO-, -N=N-, -CH=CH-, -C≡C-, -CH= CH-CO-O-, or -O-CO-CH=CH-, when the number of X is 2, X may be the same or different from each other; i is an integer from 1 to 12, and l is an integer from 0 to 12, m is an integer from 1 to 3, and n is an integer from 0 to 2 (but B is a single bond when n=0).

When such a polymer is used as the photo-alignment film, the polarized ultraviolet ray is irradiated after the film formation, and heating is performed in the vicinity of the liquid crystal phase transformation temperature, whereby the re-alignment can be further promoted, and the liquid crystal alignment property can be improved. The preferred temperature for the re-alignment treatment is not limited by the structure of the polymer, but the liquid crystal phase transition temperature is previously investigated by DSC (differential scanning calorimetry) or POM (observation by a polarizing microscope with an additional thermal mechanism). The liquid crystal temperature domain is better.

2.1.4. Polymer (IV) Other polymers

The liquid crystal structure stabilizer of the present invention can be used only for the polymer component for forming a liquid crystal structure stabilized film which exhibits anisotropy by polarized ultraviolet light irradiation, and does not impair the range of properties, and has other characteristics. A polymer component other than the above may be used in combination.

Examples of preferred materials for the polymer other than the above include polyacrylic acid, soluble polyimine, polyphthalate, and the like.

For example, in the liquid crystal structure stabilizer, 100 parts by mass of the polymer exhibiting anisotropy with respect to the polarized ultraviolet light, preferably 10 to 1000 parts by mass, of the non-photosensitive polyamine and the polyimide. More preferably, it contains 10 to 800 parts by mass.

2.2. Additives

The liquid crystal structure stabilizer of the present invention may contain components other than the above polymer component. In an example, a solvent or a compound which improves film thickness uniformity or surface smoothness when a liquid crystal structure stabilizer is applied, a compound which improves the adhesion between the liquid crystal structure stabilized film and the substrate, and the like.

Specific examples of the solvent (lean solvent) which improves the uniformity of the film thickness or the surface smoothness can be exemplified as follows.

For example, isopropyl alcohol, methoxymethylpentanol, methyl cellosolve, ethyl cellosolve, butyl cellosolve, methyl cellosolve acetate, ethyl cellosolve acetate, butyl Carbitol, ethyl carbitol, ethyl carbitol acetate, ethylene glycol, ethylene glycol monoacetate, ethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether, propylene glycol, Propylene glycol monobutyl ether, propylene glycol monoacetate, propylene glycol monomethyl ether, propylene glycol-tert-butyl ether, dipropylene glycol monomethyl ether, diethylene glycol, diethylene glycol monoacetate, diethylene glycol Alcohol dimethyl ether, dipropylene glycol monoacetate monomethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monoacetate monoethyl ether, dipropylene glycol monopropyl ether, two Propylene glycol monoacetate monopropyl ether, 3-methyl-3-methoxybutyl acetate, tripropylene glycol methyl ether, 3-methyl-3-methoxybutanol, diisopropyl ether , ethyl isobutyl ether, diisobutylene, pentyl acetate, butyl butyl ester, butyl ether, diisobutyl ketone, methyl cyclohexene, propyl ether, dihexyl ether, 1-hexanol , n-hexane, n-pentane, n-octane , diethyl ether, methyl lactate, ethyl lactate, methyl acetate, ethyl acetate, n-butyl acetate, propylene glycol monoethyl ether, methyl pyruvate, ethyl pyruvate Ester, 3-methoxypropionic acid methyl ester, 3-ethoxypropionic acid methyl ethyl ester, 3- Ethyl methoxypropionate, 3-ethoxypropionic acid, 3-methoxypropionic acid, 3-methoxypropionic acid propyl ester, 3-methoxypropionic acid butyl ester, 1-methyl Oxy-2-propanol, 1-ethoxy-2-propanol, 1-butoxy-2-propanol, 1-phenoxy-2-propanol, propylene glycol monoacetate, propylene glycol diethyl Acid ester, propylene glycol-1-monomethyl ether-2-acetate, propylene glycol-1-monoethyl ether-2-acetate, dipropylene glycol, 2-(2-ethoxypropoxy)propanol A solvent having a low surface tension such as methyl lactate, ethyl lactate, n-propyl lactate, n-butyl lactate or isoamyl lactate.

These poor solvents may be used in combination of one type or plural types. When the solvent is used, it is preferably 5 to 80% by mass, more preferably 20 to 60% by mass, based on the total amount of the solvent contained in the liquid crystal structure stabilizer.

Examples of the compound which improves the uniformity of the film thickness or the surface smoothness include a fluorine-based surfactant, an anthrone-based surfactant, and a nonionic surfactant.

More specifically, for example, EFTOP EF301, EF303, EF352 (manufactured by Tochem Products Co., Ltd.), MEGAFAC F171, F173, R-30 (manufactured by Dainippon Ink Co., Ltd.), Fluorad FC430, FC431 (manufactured by Sumitomo 3M Co., Ltd.), Asahiguard AG710, Surflon S-382, SC101, SC102, SC103, SC104, SC105, SC106 (made by Asahi Glass Co., Ltd.). The use ratio of the surfactant is preferably 0.01 to 2 parts by mass, more preferably 0.01 to 1 part by mass, per 100 parts by mass of the resin component contained in the liquid crystal structure stabilizer.

Specific examples of the compound which enhances the adhesion between the liquid crystal structure stabilized film and the substrate include a functional decane as shown below. a compound or an epoxy group-containing compound or the like.

For example, 3-aminopropyltrimethoxydecane, 3-aminopropyltriethoxydecane, 2-aminopropyltrimethoxydecane, 2-aminopropyltriethoxydecane, N-( 2-Aminoethyl)-3-aminopropyltrimethoxydecane, N-(2-aminoethyl)-3-aminopropylmethyldimethoxydecane, 3-ureidopropyl Trimethoxydecane, 3-ureidopropyltriethoxydecane, N-ethoxycarbonyl-3-aminopropyltrimethoxydecane, N-ethoxycarbonyl-3-aminopropyltriethyl Oxydecane, N-triethoxydecylpropyltriamine, N-trimethoxydecylpropyltriamine, 10-trimethoxydecyl-1,4,7-tri Azadecane, 10-triethoxydecyl-1,4,7-triazadecane, 9-trimethoxydecyl-3,6-diazaindolyl acetate, 9-three Ethoxy decyl-3,6-diazaindolyl acetate, N-benzyl-3-aminopropyltrimethoxydecane, N-benzyl-3-aminopropyltriethoxy Decane, N-phenyl-3-aminopropyltrimethoxydecane, N-phenyl-3-aminopropyltriethoxydecane, N-bis(ethylene oxide)-3-aminopropyltrimethyl Oxydecane, N-bis(ethylene oxide)-3-aminopropyl Triethoxy decane, ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, new Butyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerol diglycidyl ether, 2,2-dibromoneopentyl glycol diglycidyl ether, 1,3 ,5,6-tetraglycidyl-2,4-hexanediol, N,N,N',N'-tetraglycidyl-m-xylylenediamine, 1,3-bis(N,N- Diglycidylaminomethyl)cyclohexane, N,N,N',N'-tetraglycidyl-4, 4'-diaminodiphenylmethane, and the like.

Further, in addition to the adhesion between the substrate and the film, further For the purpose of preventing deterioration of electrical characteristics due to backlighting, the following phenolic resin additives, blocked isocyanates, hydroxyethylguanamine crosslinking agents, and the like can be introduced. Specific additives are as follows, but are not limited to this configuration.

The liquid crystal structure stabilizer of the liquid crystal display device of the present invention preferably contains a crosslinkable additive which can improve the friction resistance.

Examples of the crosslinkable additive include a phenol resin additive, an amine based plastic additive, an epoxy additive, an acrylic additive, a decane coupling agent, a blocked isocyanate additive, an oxazoline compound, and a β-hydroxy group. The alkylmidamide-based crosslinking agent or the like is not limited thereto.

Specific examples of the phenol resin-based additive are as follows, but are not limited thereto.

Amino based plastic additive

The crosslinkable compound having at least one substituent selected from the group consisting of a hydroxyl group or an alkoxy group may, for example, be an amine-based resin having a hydroxyl group or an alkoxy group, for example, a melamine resin, a urea resin, or a guanamine resin. , glycoluril-formaldehyde resin, amber-nonylamine-formaldehyde resin, ethyl urea-formaldehyde resin, and the like.

As the crosslinkable compound, for example, a melamine derivative, a benzoguanamine derivative or a glycoluril in which a hydrogen atom of an amine group is substituted with a methylol group or an alkoxymethyl group or both can be used. The melamine derivative and the benzoguanamine derivative may also be present as a dimer or a trimer. It is preferred that each of the triazine rings has an average of three or more and six or less hydroxymethyl groups or alkoxymethyl groups.

Examples of such a melamine derivative or a benzoguanamine derivative include, for example, MX-750 in which 3.7 methoxymethyl groups are substituted on average per one triazine ring of a commercially available product, and average per one triazine ring. Replace 5.8 methoxy groups Methoxy MW-30 (above, manufactured by SANWA CHEMICAL CO., LTD.) or Cymel 300, 301, 303, 350, 370, 771, 325, 327, 703, 712, etc. methoxymethylated melamine, Cymel 235, Methoxymethylated butoxymethylated melamine of 236, 238, 212, 253, 254, etc., butoxymethylated melamine of Cymel 506, 508, etc., methoxymethylation of carboxyl group like Cymel1141 Butoxymethylated melamine, Cymel 1123-like methoxymethylated ethoxymethylated benzoguanamine, Cymel 1123-10-like methoxymethylated butoxymethylated benzoguanamine, Cymel 1128 Butoxy-methylated benzoguanamine, Cymel 1125-80 carboxyl-containing methoxymethylated ethoxymethylated benzoguanamine (above, manufactured by Mitsui-Cyanamid). Further, examples of the glycoluril include, for example, Cymel 1170-like butoxymethylated glycoluril, Cymel 1172-like methylolated glycoluril, and POWDER LINK 1174-like methoxymethylolated glycoluril.

Epoxy additive

Aspects of a crosslinkable compound having an epoxy group or an isocyanate group, such as bisphenol acetone glycidyl ether, phenol novolac epoxy resin, cresol novolac epoxy resin, triglycidyl isocyanurate, tetrahydration Glycerylamino diphenyl, tetraglycidyl-m-xylylenediamine, tetraglycidyl-1,3-bis(aminoethyl)cyclohexane, tetraphenyl glycidyl etherethane, Triphenyl glycidyl etherethane, bisphenol hexafluoroacetamethylene diglycidyl ether, 1,3-bis(1-(2,3-epoxypropoxy)-1-trifluoromethyl- 2,2,2-trifluoromethyl)benzene, 4,4-bis(2,3-epoxypropoxy)octafluorobiphenyl, triglycidyl-p-aminophenol, tetraglycidyl M-xylenediamine, 2-(4-(2,3- Epoxypropoxy)phenyl)-2-(4-(1,1-bis(4-(2,3-epoxypropoxy)phenyl)ethyl)phenyl)propane, 1, 3-bis(4-(1-(4-(2,3-epoxypropoxy)phenyl)-1-(4-(1-(4-(2,3-epoxypropoxy)oxy) Phenyl)-1-methylethyl)phenyl)ethyl)phenoxy)-2-propanol, etc. The compound containing two or more epoxy groups, specifically, for example, the following compounds.

Oxetane

The crosslinkable compound having an oxetane group is a crosslinkable compound having at least two oxetanyl groups represented by the following formula [4].

Specifically, it is a crosslinkable compound represented by the following formula [4a] - formula [4k].

Blocked isocyanate additive

The compound containing two or more blocked isocyanate groups may, for example, be a compound having a blocked isocyanate group represented by the following formula (5).

Z is independently an alkyl group having 1 to 3 carbon atoms, a hydroxyl group or an organic group represented by the following formula (6), and at least one of Z is an organic compound represented by the following formula (6) base.

Specifically, the compound is as follows.

A compound containing two or more blocked isocyanate groups other than the above formula (7), for example, the following compounds.

Oxazoline compound

Examples of the oxazoline compound include 2,2'-bis(2-oxazoline), 1,2,4-cis-(2-oxazolinyl-2)-benzene, 4-furan-2- Methyl-2-phenyl-4H-oxazol-5-one, 1,4-bis(4,5-dihydro-2-oxazolyl)benzene, 1,3-bis(4,5-di Hydrogen-2-oxazolyl)benzene, 2,3-bis(4-isopropenyl-2-oxazolin-2-yl)butane, 2,2'-bis-4-benzyl-2-oxo Oxazoline, 2,6-bis(isopropyl-2-oxazolin-2-yl)pyridine, 2,2'-isopropylidene bis(4-tert-butyl-2-oxazoline), 2,2'-isopropylidene bis(4-phenyl-2-oxazoline), 2,2'-extended methyl bis(4-tert-butyl-2-oxazoline), and 2, 2'-Extended methyl bis(4-phenyl-2-oxazoline). In addition to these, a polymer or oligomer having an oxazolyl group like Epocros (trade name, manufactured by Nippon Shokubai Co., Ltd.) can be mentioned.

Primid crosslinker

The Primid crosslinking agent is a compound having a hydroxyalkylguanamine group. When the component (B) has a hydroxyalkylguanamine group, the other structure is not particularly limited. From the viewpoint of availability, etc., a compound represented by the following formula (2) is preferable.

X ₂ is an aliphatic hydrocarbon group having 1 to 20 carbon atoms or an n-valent organic group containing an aromatic hydrocarbon group. n is an integer from 2 to 6.

R ₂ and R ₃ each independently represent a hydrogen atom, an alkyl group having 1 to 4 carbon atoms which may have a substituent, an alkenyl group having 2 to 4 carbon atoms which may have a substituent, or a carbon number which may have a substituent 2~ 4-alkynyl group. Further, at least one of R ₂ and R ₃ is a hydrocarbon group substituted with a hydroxyl group.

Among them, the atom directly bonded to the carbonyl group in X ₂ of the formula (2) is a carbon atom which does not form an aromatic ring, and is preferably from the viewpoint of liquid crystal alignment. Further, X _{2 of the} formula (2) is preferably an aliphatic hydrocarbon group and more preferably 1 to 10 carbon atoms from the viewpoint of liquid crystal alignment and solubility.

In the formula (2), n is preferably from 2 to 4 from the viewpoint of solubility.

In the formula (2), at least one of R ₂ and R ₃ is a structure represented by the following formula (3), and is preferably from the viewpoint of reactivity, and is more preferably a structure represented by the following formula (4). .

In the formula (3), R ₄ to R ₇ are each independently a hydrogen atom, a hydrocarbon group or a hydrocarbon group substituted with a hydroxyl group.

Preferred examples of the component (B) include the following compounds.

One type of the crosslinkable additive may be added, but a plurality of types may be added without impairing the characteristics of the present invention.

The amount of addition is preferably from 0.1% by weight to 30% by weight, more preferably from 0.5% by weight to 10% by weight.

Crosslinkable compound having a polymerizable unsaturated bond

Examples of the crosslinkable compound having a polymerizable unsaturated bond include trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, dipentaerythritol penta(meth)acrylate, and tri (( a crosslinkable compound having three polymerizable unsaturated groups in a molecule such as methyl) acrylonitrile ethoxy ethoxy trimethylolpropane or glycerol polyglycidyl ether poly(meth) acrylate, and further Diol (meth) acrylate, diethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, propylene glycol di (a) Acrylate, polypropylene glycol di(meth)acrylate, butanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, ethylene oxide bisphenol A type II Acrylate, propylene oxide bisphenol type di(meth) acrylate, 1,6-hexanediol di(meth) acrylate, glycerol di(meth) acrylate, pentaerythritol di(meth) acrylate Ester, ethylene glycol diglycidyl ether di(meth) acrylate, diethylene glycol diglycidyl ether di(meth) acrylate, benzene a crosslinkable compound having two polymerizable unsaturated groups in a molecule such as diglycidyl dicarboxylate di(meth)acrylate or hydroxypivalic acid neopentyl glycol di(meth)acrylate, And 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 2-phenoxy-2-hydroxypropyl (A Acrylate, 2-(methyl)propenyloxy-2-hydroxypropyl phthalate, 3-chloro-2-hydroxypropyl (meth) acrylate, glycerol mono(methyl) A crosslinkable compound having one polymerizable unsaturated group in the molecule such as acrylate, 2-(meth)acryloyloxyethyl phosphate or N-methylol (meth) acrylamide.

Further, a compound represented by the following formula [5] can also be used.

(In the formula [5], A ₁ is a group selected from a cyclohexyl ring, a bicyclohexyl ring, a benzene ring, a biphenyl ring, a biphenyl ring, a naphthalene ring, an anthracene ring, an anthracene ring, or a phenanthrene ring, and A ₂ is The group selected by the following formula [5a] or the formula [5b], n is an integer of 1 to 4).

The above compound is an example of a crosslinkable compound, but is not limited thereto. In addition, the crosslinkable compound contained in the liquid crystal alignment agent of the present invention may be one type or a combination of two or more types.

Thiacyclopropane compound

Examples of the thietane compound include phenyl glycidyl ether, butyl glycidyl ether, 3,3,3-trifluoromethyl propylene oxide, styrene oxide, and hexafluoropropylene oxide. Cyclohexene oxide, N-glycidyl phthalimide, (nonafluoro-N-butyl) epoxide, perfluoroethyl glycidyl ether, epichlorohydrin, epibromohydrin, N, N-diglycidylaniline, and 3-[2-(perfluorohexyl)ethoxy]-1,2-epoxypropane, ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl Ether, propylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, polypropylene glycol diglycidyl Ether, neopentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerol diglycidyl ether, 2,2-dibromoneopentyl glycol diglycidyl ether, And 3-(N,N-diglycidyl)aminopropyltrimethoxydecane, 1,3,5,6-tetraglycidyl-2,4-hexanediol, N,N,N', N'-tetraglycidyl-m-xylenediamine, 1,3-bis(N,N-diglycidylaminomethyl)cyclohexane, N,N,N',N'-tetrahydration The glycidyl group of glyceryl-4,4'-diaminodiphenylmethane and 3-(N-allyl-N-glycidyl)aminopropyltrimethoxydecane, according to, for example The method described in J. Org. Chem., 28, 229 (1963) is substituted with sulfur to convert the glycidyl group to an ethylenethio group.

Aziridine compound

The aziridine compound may, for example, be 2,4,6-paran (1'-aziridine)-1,3,5-triazine or ω-aziridinepropionic acid-2,2-dihydroxyl. Methyl-butanol triesters, 2,4,6-gin(2-methyl-1-aziridine)-1,3,5-triazine, 2,4,6-paran (2-ethyl -1-aziridine)-1,3,5-triazine, 4,4'-bis(extended ethyliminocarbonylamino)diphenylmethane, bis(2-ethyl-1-nitrogen Procyridyl) phenyl-1,3-dicarboxylic acid decylamine, ginseng (2-ethyl-1-aziridine)benzene-1,3,5-tricarboxylic acid decylamine, bis(2-ethyl -1- aziridine) decanoic acid decylamine, 1,6-bis(extended ethyliminocarbonylamino)hexane, 2,4-diethylethyltoluene, 1,1'- Carbonyl-bis-extended ethyl imine, polymethyl-bis-extended ethyl urea (C2~C4), and N,N'-bis(4,6-diethylethylamino-1,3 , 5-triazin-2-yl)-hexamethylamine. In addition to these, for example, an oligomer or polymer having an aziridine group can also be mentioned.

Cyclic carbonate

In the case of using a compound which improves the adhesion to the substrate, the amount thereof is preferably 0.1 to 30 parts by mass, more preferably 1 to 20, per 100 parts by mass of the polymer component contained in the liquid crystal structure stabilizer. Parts by mass. When the amount of use is less than 0.1 part by mass, the adhesion improving effect cannot be expected, and if it is more than 30 parts by mass, the liquid crystal alignment property may be deteriorated.

In the liquid crystal structure stabilizer of the present invention, in addition to the above, the electrical properties of the dielectric constant or the electrical conductivity of the liquid crystal structure stabilized film are not affected, and the dielectric properties of the liquid crystal structure stabilized film can be changed. A crosslinkable compound for the purpose of improving the hardness or density of the film when the liquid crystal structure is stabilized.

2.3. Modulation of organic solvent and liquid crystal structure stabilizer

In the liquid crystal structure stabilizer of the present invention, the organic solvent (solvent) used in the liquid crystal structure stabilizer of the present invention is an organic solvent used for dissolving each polymer, and the organic solvent in which the polymer component is dissolved is not particularly limited. Its specific example is as follows.

For example, N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, N-methylcaprolactam, 2-pyrrolidone , N-ethylpyrrolidone, N-vinylpyrrolidone, dimethyl hydrazine, tetramethyl urea, pyridine, dimethyl hydrazine, γ-butyrolactone, 3-methoxy-N, N - dimethylpropanamide, 3-ethoxy-N,N-dimethylpropanamide, 3-butoxy-N,N-dimethylpropanamide, 1,3-dimethyl- Imidazolinone, ethyl amyl ketone, methyl decyl ketone, methyl ethyl ketone, methyl isoamyl ketone, methyl isopropyl ketone, cyclohexanone, ethylene carbonate, propylene carbonate, digan Alcohol dimethyl ether, 4-hydroxy-4-methyl-2-pentanone, and the like. These may be used alone or in combination.

The organic solvent contained in the liquid crystal structure stabilizer is preferably from 90 to 99% by mass, more preferably from 93 to 98% by mass.

3. Formation of liquid crystal structure stabilized film

The liquid crystal structure stabilizer of the present invention is preferably used for a liquid crystal structure stabilization film used for forming a liquid crystal display element by a photo-alignment method.

A method of forming a liquid crystal structure stabilized film using the liquid crystal structure stabilizer of the present invention, and forming a coating film by applying the liquid crystal structure stabilizer of the present invention to a substrate, and irradiating the coating film with radiation .

When the liquid crystal structure stabilizer of the present invention is used for a liquid crystal display element having a TN type or ECB type liquid crystal cell, a pair of substrates provided with a patterned transparent conductive film are used as a pair. A coating film is formed by applying the liquid crystal structure stabilizer of the present invention to the surface of the transparent conductive film.

In either case, as the substrate, for example, glass such as float glass or soda lime glass, polyethylene terephthalate, polybutylene terephthalate, polyether oxime, or polycarbonate may be used. A transparent substrate made of plastic. For the transparent conductive film, for example, an ITO film made of In ₂ O ₃ -SnO ₂ or a NESA (registered trademark) film made of SnO ₂ can be used. As the metal film, a film made of a metal such as chromium can be used. The pattern of the transparent conductive film and the metal film can be formed by the light after forming the transparent conductive film by, for example, no pattern. A method of forming a pattern by an etching method, a sputtering method, or the like, a method of using a mask having a desired pattern, and the like when forming a transparent conductive film.

When the liquid crystal structure stabilizer is applied to the substrate, a functional decane compound, titanate or the like may be applied to the substrate and the electrode in order to improve the adhesion between the substrate, the conductive film or the electrode and the coating film.

The liquid crystal structure stabilizer is applied onto the substrate, preferably by a suitable coating method such as an offset printing method, a spin coating method, a roll coater method, or an inkjet printing method, and then the coated surface is prepared. Heating (prebaking), then The baking film (baking after exposure) is formed to form a coating film. The prebaking conditions are, for example, 0.1 to 5 minutes at 40 to 120 ° C, and the post-exposure baking condition is preferably 120 to 300 ° C, more preferably 150 to 250 ° C, preferably 5 to 200 minutes, more preferably 10 ~100 minutes. The film thickness of the coating film after the post-exposure baking is preferably 0.001 to 1 μm, more preferably 0.005 to 0.5 μm.

By coating the thus formed coating film, linearly polarized light or partially polarized radiation or unpolarized radiation is irradiated to impart alignment ability to the liquid crystal. Here, as the radiation, for example, ultraviolet light and visible light containing light having a wavelength of 150 to 800 nm can be used, but ultraviolet light having a wavelength of 250 to 400 nm is preferable. When the radiation to be used is linearly polarized or partially polarized, the irradiation may be performed from the vertical direction on the substrate surface, or may be performed from the oblique direction in order to impart the pretilt angle, or may be combined. When irradiating unpolarized radiation, the direction of irradiation needs to be oblique.

As the light source to be used, for example, a low pressure mercury lamp, a high pressure mercury lamp, a xenon lamp, a metal halide lamp, an argon resonance lamp, a xenon lamp, an excimer laser or the like can be used. The ultraviolet light in the preferred wavelength range can be obtained by a combination of the above-mentioned light source and, for example, a filter, a diffraction grating, or the like.

Irradiated amount of radiation aspect, preferably 1J / m ² or more less than 10,000J / m ^2, more preferably 10 ~ 3,000J / m ^2. In addition, when the liquid crystal alignment ability is imparted to the coating film formed by the conventional liquid crystal structure stabilizer, a radiation irradiation amount of 10,000 J/m ² or more is required. However, when the liquid crystal structure stabilizer of the present invention is used, the amount of radiation irradiation in the photo-alignment method is 3,000 J/m ² or less, and further, it is possible to impart good liquid crystal alignment ability to 1,000 J/m ² or less. The productivity improvement of the liquid crystal display element and the manufacturing cost are reduced.

4. Method of manufacturing liquid crystal display element

The liquid crystal display element formed using the liquid crystal structure stabilizer of the present invention can be produced, for example, as follows.

4.1. Liquid crystal cell

First, as described above, a pair of substrates on which a liquid crystal structure stabilization film is formed are prepared, and a liquid crystal cell having a liquid crystal structure between the pair of substrates is manufactured. The following two methods are exemplified to produce a liquid crystal cell.

The first method is a conventional method. First, the liquid crystal structure stabilizes the film to face the gap (cell gap), and the two substrates are opposed to each other, and the peripheral portions of the two substrates are bonded together using a sealant, and the surface of the substrate is bonded to the substrate. After the filling liquid crystal is injected into the cell gap of the sealant region, the liquid crystal cell can be manufactured by sealing the injection hole.

The second method is a method called the ODF (One Drop Fill) method. Applying, for example, a UV curable sealant to a designated place on one of the two substrates forming the liquid crystal structure stabilized film, and further dropping the liquid crystal on the liquid crystal structure stabilized film surface, and then liquid crystal The structure stabilized film is bonded to the other substrate in a facing manner, and then the sealing agent is cured by irradiating the entire surface of the substrate with ultraviolet light, whereby a liquid crystal cell can be manufactured.

In the case of using any of the methods, it is preferred to remove the flow alignment during liquid crystal filling by heating the liquid crystal cell to the liquid crystal used to obtain the temperature of the isotropic phase and then slowly cooling to room temperature.

The method of obtaining the cell gap is not particularly limited, and for example, a method in which a spacer bead (aluminum oxide ball) is uniformly spread on a substrate provided with a liquid crystal structure stabilization film or a method of bonding is performed, or a sealant is not dispersed. After dispersion of the spacer beads, by coating. A method of providing a cell gap by lamination, and a substrate or the like provided with a structure in which a specific cell gap is formed by using a photoresist or the like in advance. Since the alignment of the ULH is strongly influenced by foreign matter or the like, it is preferable that the state of the spacer is not included in the pixel. Therefore, it is preferable to disperse the spacer beads in the sealant to secure the cell gap, and to use a substrate provided with a structure in which a specific cell gap is formed by using a photoresist or the like in advance.

As the sealing agent, for example, an epoxy resin containing a curing agent or the like can be used.

4.2. Cholesterol-like liquid crystal

The liquid crystal used in the ULH alignment mode is a cholesteric liquid crystal, but in order to obtain a more stable ULH alignment, it is necessary to use a liquid crystal which can obtain a strong flexural effect. The liquid crystal which can obtain the flexoelectric effect is, for example, a liquid crystal of a double liquid crystal cell type, and a ULH alignment can be obtained by using a cholesteric liquid crystal having such a structure, but is not limited to such a structure.

(wherein, X ₁ and X ₂ are each independently a bond group selected by a single bond, an ester bond or an ether bond, and L is an integer represented by 6 to 20.)

Further, in order to obtain a cholesteric liquid crystal property having a short twist period using a liquid crystal having such a structure, it is preferable to use a chiral reagent to which a strong helical twist power of 1 to 5% by weight is added, and a cholesteric liquid crystal property can be obtained. The structure is not particularly limited, and a particularly preferred chiral agent may, for example, be the following compounds.

(wherein, X ₁ and X ₂ are each independently a bond group selected by a single bond, an ester bond or an ether bond, and R ₈ is an alkyl group of 3 to 10).

4.3. Orientation processing

The cholesteric liquid crystal is injected into the liquid crystal cell in which the liquid crystal structure stabilized film is provided, and heat treatment is performed while applying an electric field, thereby shifting to ULH alignment. For example, when the temperature rises until the liquid crystal used becomes the temperature of the isotropic phase, it is confirmed that the liquid crystal is completely converted into an isotropic phase, and the liquid crystal cell is gradually returned to room temperature while applying a voltage, whereby the ULH alignment can be induced.

Since the conditions vary depending on the cell gap or the type of liquid crystal used, the temperature drop rate or the type or intensity of the applied voltage is not limited, but the temperature drop rate from the temperature of the isotropic phase is preferably per minute. 1~30°C, more preferably 1~10°C, the applied voltage is 1~10V/μm, preferably It is preferable that the rectangular wave of the electric field intensity of about 2 to 8 / μm is AC, the frequency is 1 to 1 KHz, and more preferably 10 to 300 Hz.

4.4. Polarizer

Further, the liquid crystal display element of the present invention can be obtained by attaching a polarizing plate to the outer surface of the liquid crystal cell. Here, a desired liquid crystal display element can be obtained by appropriately adjusting the angle formed by the polarization direction of the linearly polarized radiation irradiated on the two substrates on which the liquid crystal structure stabilized film is formed and the angle between each substrate and the polarizing plate. .

In the case of the polarizing plate used for the outer side of the liquid crystal cell, for example, a polarizing plate in which a polarizing film called "H film" is held by a cellulose acetate protective film or a polarizing plate composed of an H film itself is used. The "H film" is a polarizing film obtained by absorbing iodine while extending the polyvinyl alcohol.

[Examples]

The invention will be further illustrated by the following examples. However, the invention is not limited to the embodiments described herein.

5. Modulation and evaluation of liquid crystal structure stabilizer 5.1. Abbreviations

The abbreviations of the compounds used in the examples and comparative examples are as follows.

<organic solvent>

NMP: N-methyl-2-pyrrolidone

GBL: γ-butyrolactone

BCS: butyl cellosolve

IPA: 2-propanol

<tetracarboxylic dianhydride>

TC-1: 1,3-dimethyl-1,2,3,4-cyclobutane tetracarboxylic dianhydride

<Diamine>

DA-1: p-phenylenediamine

DA-2: 2-(N-tert-butoxycarbonylaminomethyl)-1,4-phenylenediamine

DA-3: 1,2-bis(4-aminophenoxy)ethane

DA-4: N-(tert-butoxycarbonyl)-N-(4-aminobenzyl)-4-phenylethylamine

DA-5: 4-aminophenyl-4-aminocinnamate

<additive>

Additive A: a compound represented by Primid XL552 (manufactured by Ems-Chemie) and the following formula (Additive-1)

Additive B: FHB N-α-(9-fluorenylmethoxycarbonyl)-N-τ-t-butoxycarbonyl-L-histidine

M-1: 4-((6-Methylacryloxy)hexyl)oxybenzoic acid

M-2: 4-((6-Methylacryloxy)hexyl)oxycinnamic acid

M-3: E -4'-((6-(methacryloxy)hexyl)oxy)-[1,1'biphenyl]-4-yl 3-(4-methoxyphenyl )Acrylate

Further, in the following chemical formula, Me is a methyl group and Bu is a n- Butyl and Boc are t-butoxy groups.

5.2. Evaluation method of liquid crystal structure stabilizer

The measurement method of each characteristic is as follows.

[viscosity]

The viscosity of the polyglycolate and the polyaminic acid solution was measured using an E-type viscometer TVE-22H (manufactured by Toki Sangyo Co., Ltd.), a sample volume of 1.1 mL (ml), and a conical rotor TE-1 (1° 34', R24), measured at a temperature of 25 °C.

[molecular weight]

The molecular weight of the polyglycolate and the poly-proline is measured by a GPC (normal temperature colloidal osmosis chromatography) apparatus, and the number average molecular weight is calculated as a polyethylene glycol (polyethylene oxide) conversion value (hereinafter, also referred to as Mn) and weight average molecular weight (hereinafter, also referred to as Mw).

GPC device: manufactured by Shodex (GPC-101)

Pipe column: made by Shodex (KD803, and KD805 in series)

Column temperature: 50 ° C

Dissolution: N,N-dimethylformamide (lithium bromide-hydrate (LiBr.H ₂ O) as an additive is 30 mmol/L (liter), phosphoric acid. Anhydrous crystal (o-phosphoric acid) is 30 mmol/L, Tetrahydrofuran (THF) is 10ml/L)

Flow rate: 1.0ml/min

Standard sample for the calibration curve: TSK standard polyethylene oxide (weight average molecular weight (Mw) of about 900,000, 150,000, 100,000, and 30,000) manufactured by Tosoh Corporation and polyethylene glycol manufactured by Polymer Laboratories Ltd. The molecular weight (Mp) is about 12,000, 4,000, and 1,000). The measurement is avoided by overlapping the peaks, so the mixing is performed separately. Four types of samples of 900,000, 100,000, 12,000, and 1,000, and 2 samples of 3 types of samples of 150,000, 30,000, and 4,000.

[Determination of sulfhydrylation rate]

The oxime imidization ratio of polyimine was measured as follows. Put 20 mg of polyimine powder into the NMR sample tube (NMR sampling tube standard, 5 (manufactured by Kusano Scientific Co., Ltd.), adding dimethylated dimethyl hydrazine (DMSO-d6, 0.05% by mass of TMS (tetramethyl decane) mixed product) (0.53 mL), and applying ultrasonic waves to completely dissolve. This solution was subjected to a NMR measuring machine (JNW-ECA500) (manufactured by JEOL Datum Ltd.) to measure a proton NMR of 500 MHz.

The sulfhydrylation rate is determined by protons derived from protons that have not changed before and after imidization, and the peak value of the proton is used and the proton peak of the NH group derived from proline is present in the vicinity of 9.5 to 10.0 ppm. The cumulative value is obtained by the following equation.

醯 imidization rate (%) = (1-α.x/y) × 100

In the above formula, x is the proton peak cumulative value of the NH group derived from proline, y is the peak cumulative value of the reference proton, and α is the relative case of polyproline (the imidization ratio is 0%). The ratio of the number of reference protons of one of the NH protons of proline.

5.3. Modulation of liquid crystal structure stabilizer Example 1 Synthesis Example 1 Polymerization of Polymer and Adjustment of Liquid Crystal Structure Stabilizer AL-1 system

In a 100 ml four-necked flask equipped with a nitrogen introduction tube and a mechanical stirrer, DA-1 (1.94 g: 18.00 mmol) and DA-2 (0.47 g: 2.00 mmol) were weighed, and NMP 85.1 g was added thereto. After stirring in a nitrogen atmosphere and confirming complete dissolution, the solution was cooled to 10 ° C or lower, and TC-1 (9.18 g: 19.60 mmol) was gradually added thereto, and the mixture was returned to room temperature to carry out a reaction for 24 hours to obtain 12% by mass. Polylysine solution (PAA-1 below). The weight average molecular weight of PAA-1 thus obtained was 38,600.

PAA-1 was weighed in an Erlenmeyer flask equipped with a stirrer, and 80 g was weighed, and NMP 112g, BCS, 48.0g, FHB 1.15g (12% by mass relative to PAA) and Additive-1 0.96g (relative PAA solids) were added. The mixture was stirred at room temperature for 6 hours to obtain a liquid crystal structure stabilizer (hereinafter referred to as AL-1).

Example 2 Synthesis Example 2 Polymerization of Polymer and Modulation of Liquid Crystal Structure Stabilizer AL-2

In a 200-ml four-necked flask equipped with a nitrogen introduction tube and a mechanical stirrer, DA-3 (2.44 g: 10.00 mmol) and DA-4 (3.41 g: 10.00 mmol) were weighed, and 67.23 g of NMP was added thereto. Stirring was carried out under a nitrogen atmosphere to completely dissolve. The solution was cooled to 10 ° C or lower, and TC-1 (8.90 g: 19.00 mmol) was gradually added thereto, and the mixture was returned to room temperature, and the mixture was stirred for 24 hours to cause a reaction. After completion of the reaction, 60.0 g of the polyamic acid solution obtained above was weighed and placed in a 200 ml eggplant type flask equipped with a stir bar, and added separately. NMP 30.0 g, acetic anhydride (6.53 g: 64.00 mmol), and pyridine (0.84 g: 10.67 mmol) were stirred at room temperature for 30 minutes, and then reacted at 55 ° C for 3 hours. After completion of the reaction, the reaction solution was gradually poured into 200 ml of methanol cooled to 10 ° C or lower while stirring, and the solid was precipitated by stirring for a while. The solid was recovered by filtration, and the recovered solid was washed with 300 ml of methanol twice, and dried by vacuuming at 60 ° C to obtain a polyimine powder (hereinafter SPI-1: 9.0 g of imine) Conversion rate: 68%, weight average molecular weight: 32000).

The obtained polyimine powder was weighed in a 100 ml Erlenmeyer flask equipped with a stirrer, 2.00 g, and NMP 18.00 g, and stirred at room temperature for 24 hours, and after confirming complete dissolution, FHB (0.24 g: relative) was added. Polyimine solid content is divided into 12% by mass), Additive-1 (0.20 g: relative to polyamidiene solid content is 10% by mass), NMP (3.33 g), BCS (10.00 g), and is allowed to stand at room temperature for 24 hours. The liquid crystal structure stabilizer (hereinafter referred to as AL-2) of the present invention was obtained by stirring.

Example 3 Synthesis Example 3

In a 200 ml 4-necked flask equipped with a nitrogen introduction tube and a mechanical stirrer, DA-5 (1.14 g: 4.50 mmol) was weighed, NMP (5.60 g) was added, and the mixture was stirred at room temperature under nitrogen to completely dissolve. Thereafter, TC-2 (0.83 g: 4.20 mmol) and NMP (5.6 g) were added, and the mixture was reacted at room temperature for 10 hours to obtain a polyaminic acid solution (hereinafter PAA-3). The weight average molecular weight of PA-3 was 35,500.

By adding NMP (10.0 g) and BCS (5.0 g) to the polyamic acid solution (10 g), the mixture was stirred at room temperature for 5 hours to obtain a liquid crystal structure stabilizer (hereinafter referred to as AL-3).

Example 4 Synthesis Example 4 Polymerization of Polymer and Modulation of Liquid Crystal Structure Stabilizer AL-4

M-1 (2.99 g: 9.00 mmol) and M-2 (1.83 g: 6.00 mmol) were weighed separately in a 100 ml branched eggplant flask equipped with a three-way piston and a stir bar, and dissolved in THF (44.57 g). After several degassing and nitrogen substitution by a diaphragm pump, AIBN (0.12 g: 0.5 mmol) was added, followed by degassing and nitrogen substitution. Thereafter, the reaction was carried out at 50 ° C for 30 hours to obtain a polymer solution of methacrylate. The polymer solution was added dropwise to diethyl ether (500 ml), and the obtained precipitate was filtered. The obtained solid was washed with diethyl ether, and dried under reduced pressure in an oven at 40 ° C to obtain a methacrylate polymer powder. The polymer had a weight average molecular weight of 42,000.

To 2.0 g of the obtained powder, 18.0 g of NMP was added, and the mixture was stirred at room temperature for 3 hours. A methacrylate polymer solution (PM-1 below) having a solid content concentration of 10.0% by weight was obtained. The polymer was completely dissolved when the stirring was completed. NMP (3.33 g) and BCS (10.00 g) were added to the PM-1, and the mixture was stirred at room temperature for 6 hours to obtain a liquid crystal structure stabilizer (hereinafter referred to as AL-4) of the present invention.

Example 5 Synthesis Example 5 Polymerization of Polymer and Modulation of Liquid Crystal Structure Stabilizer AL-5

In a 100 ml branched eggplant flask equipped with a three-way piston and a stirrer, M-3 (10.29 g, 20.0 mmol) was dissolved in NMP (94.1 g), and after several degassing and nitrogen substitution by a diaphragm pump. AIBN (0.164 g, 1.0 mmol) was added, followed by degassing and nitrogen substitution. Thereafter, the reaction was carried out at 50 ° C for 24 hours to obtain a polymer solution of methacrylate. The polymer solution was dropped to methanol (1000 ml), and the obtained precipitate was filtered. The precipitate was washed with methanol, and dried under reduced pressure in an oven at 40 ° C to obtain a methacrylate polymer powder (hereinafter, PM-2). The polymer had a weight average molecular weight of 39,000.

CH ₂ Cl ₂ (99.0 g) was added to the obtained PM-2 (1.0 g), and the mixture was stirred at room temperature for 5 hours to be dissolved to obtain a liquid crystal structure stabilizer (AL-5).

The following table shows the composition of the polymer prepared in the above synthesis example and the composition of the liquid crystal structure stabilizer.

6. Modulation and evaluation of liquid crystal structure stabilized film <Production of cell for ULH evaluation>

A substrate formed by patterning with a pattern of 10 mm × 40 mm in 30 mm × 40 mm ITO (Indium Tin Oxide), and a liquid crystal structure stabilizer which was prepared in Examples 1 to 5 was used, and polymerization was carried out so as to have a film thickness of 100 nm. The film is subjected to alignment treatment through each step. The detailed film formation conditions and alignment treatment conditions are as follows.

Example 6 Light alignment treatment using polymer film of AL-1

AL-1 was spin-coated on an ITO glass substrate by a spin coating method, dried at 80 ° C for 1 minute using a hot plate, and further heated at 230 ° C for 30 minutes using an IR oven to obtain a poly醯 imine film. The obtained polyimide film was irradiated with ultraviolet rays of 254 nm at 600 mJ/cm ² through a polarizing plate, and then heated at 230 ° C for 30 minutes using an IR oven to obtain a substrate having a liquid crystal structure stabilization film.

Example 7 Light alignment treatment using polymer film of AL-2

AL-2 was spin-coated on an ITO glass substrate by a spin coating method, dried at 80 ° C for 1 minute using a hot plate, and further fired at 230 ° C for 15 minutes using an IR oven.醯 imine film. The obtained polyimide film was irradiated with a polarizing plate at a wavelength of 300 mJ/cm ² at 254 nm, and then ultrasonically washed with a mixed solvent of IPA and pure water for 5 minutes, dried with an air gun, and then dried at 230 ° C using an IR oven. The substrate was heated for 15 minutes to obtain a substrate having a liquid crystal structure stabilization film.

Example 8 Light alignment treatment using polymer film of AL-3

AL-3 was spin-coated on an ITO glass substrate by a spin coating method, dried at 80 ° C for 1 minute using a hot plate, and further heated and baked at 200 ° C for 30 minutes using an IR oven to obtain a polyfluorene. Imine film. The obtained polyimide film was heated to 240 ° C on a hot plate, and irradiated with a polarizing plate of ultraviolet light of 313 nm at 20 mJ/cm ^{2 to} obtain a substrate having a liquid crystal structure stabilized film.

Example 9 Light alignment treatment using polymer film of AL-4

AL-3 was spin-coated on an ITO glass substrate by a spin coating method, dried at 80 ° C for 1 minute using a hot plate, and irradiated with a polarizing plate to irradiate ultraviolet rays of 313 nm at 10 mJ/cm ² , and then a hot plate was used. The film was heated at 140 ° C for 15 minutes to obtain a substrate with a liquid crystal structure stabilized film.

Example 10 Light alignment treatment using AL-5 polymer film

AL-4 was spin-coated on an ITO glass substrate by a spin coating method, dried at 80 ° C for 1 minute using a hot plate, and irradiated with a polarizing plate at 300 mJ/cm ² of 313 nm ultraviolet light, and then a hot plate was used. The film was heated at 180 ° C for 15 minutes to obtain a substrate with a liquid crystal structure stabilized film.

Comparative example 1 Friction alignment treatment using AL-1

AL-1 was spin-coated on an ITO glass substrate by a spin coating method, dried at 80 ° C for 1 minute using a hot plate, and further heated at 230 ° C for 30 minutes using an IR oven to obtain a poly醯 imine film. The film surface of the obtained polyimide film was rubbed with rayon cloth (YA-20R manufactured by Yoshikawa Chemical Co., Ltd.) (roller diameter: 120 mm, number of rotations of the drum: 700 rpm, moving speed: 50 mm/sec, press-in length: 0.2 mm) ,get on The alignment treatment was performed to obtain a substrate with a liquid crystal structure stabilization film.

Comparative example 2 Friction alignment treatment using AL-2

The AL-1 of Example 1 was replaced with AL-2, and the substrate attached to the film was obtained in the same manner.

<Preparation of liquid crystal cell and observation of ULH alignment>

Two substrates of the liquid crystal structure stabilization film prepared in each of Examples 5 to 8 were prepared, and a sealant of 6.0 μm or 4.0 μm spacer beads was mixed on the liquid crystal structure stabilization film of one of the substrates ( Xenon Chemical Co., Ltd. XN-1500T) is applied by a dispenser, and then the other substrate is bonded to each other such that the liquid crystal structure stabilizes the film surface and the alignment direction becomes 0°, and the sealant is thermally cured. Make an empty cell.

The empty unit cell obtained as described above was placed on a hot plate heated to 80° C., liquid crystal was used in ULH mode manufactured by Merck, and liquid crystal was injected by capillary injection, and the liquid crystal injection port was sealed to prepare a crystal for ULH evaluation. Cell. Its mode diagram is shown in Figure 1.

<Observation of initial alignment of ULH>

The alignment was evaluated using a polarizing microscope (POM) equipped with a table capable of heating and cooling. The liquid crystal cell obtained as described above was mounted on a heating and cooling stage, and the temperature was raised until the temperature of the liquid crystal became an isotropic phase. After confirming that the liquid crystal phase became completely isotropic, 14 Vp-p (cell gap) was applied by the function signal generator. In the case of 4.0 μm or a rectangular wave AC voltage of 20 Vp-p (in the case of a cell gap of 6.0 μm), the temperature was lowered to 50° C. at a rate of 3° C./min to be converted into ULH. After the ULH state was reached, the application of the voltage was stopped, the temperature was returned to room temperature, the polarizing plate was placed in a crossed Nicols state, the liquid crystal cell was rotated, and the initial alignment was evaluated by confirming the bright state and the dark state. The results are shown in Table 3, Figure 2 and Figure 3.

When Comparative Examples 5 and 6 and Comparative Examples 1 and 2 were compared, the alignment of the light alignment and the ULH of the friction was largely different. From this point, it is understood that the alignment of the ULH is good for the light alignment. Further, in the examples 7 and 8 in which the materials were significantly different, a good ULH alignment was obtained, and it is estimated that the liquid crystal structure stabilized film is not limited to a specific type, and a good ULH alignment can be obtained. In this case, it is considered that the rubbing treatment tends to cause uneven alignment, film cutting, dust adhesion, etc., but does not cause them in the light alignment, so that a good ULH can be obtained. Orientation. In the case of the examples, it was confirmed that the bright state and the dark state were clearly observed as shown in Fig. 2, and the ULH alignment was good. On the other hand, in the case of the comparative example, as shown in Fig. 3, even if the liquid crystal cell was rotated, the bright state and the dark state could not be observed, and the ULH alignment property was poor.

[industrial use]

Therefore, the liquid crystal display element of the present invention produced is excellent in performances such as display characteristics and electrical characteristics.

Claims (15)

A composition for forming a film for stabilizing a liquid crystal structure, characterized by comprising a polyimine precursor, a polyimine, a polyamine, a polyacrylate, a polymethacrylate, a poly N A polymer comprising at least one of a group consisting of maleic imine, polystyrene, polyitaconate, and polyorganosiloxane, and exhibiting anisotropy by irradiation with polarized ultraviolet rays. The composition according to claim 1, wherein the at least one of the polymers has the following formulas (1) to (5) in the main chain: [wherein, Z ₁ to Z ₄ are each independently and are at least one selected from the group consisting of a hydrogen atom, a methyl group, and a benzene ring, and R ₁ is a hydrogen atom, a methyl group, an ethyl group, a propyl group, or an isopropyl group. An organic group selected from the group consisting of a group, an isobutyl group, and a t-butyl group, and R ₂ is a hydrogen atom, a fluorine atom, or the following formula: (wherein R ₃ is an organic group represented by a hydrogen atom or an alkyl chain having 1 to 18 carbon atoms, m is an integer of 1 to 3, and a black dot is a bonding site), and a black dot is a bond with another organic group. A polyimine precursor, or a polyimine, of any of the structures indicated. The composition according to claim 1, wherein the at least one polymer has the following formulas (6) to (10) in the main chain: (wherein X ₁ and X ₂ are each independently a carbon atom or a nitrogen atom, and Y ₁ and Y ₂ are each independently a hydrogen atom, a methyl group, a cyano group, a fluorine atom or a chlorine atom, and X ₃ is an oxygen atom. Or a sulfur atom, X ₄ is a single bond, a carbon atom, an oxygen atom, or a sulfur atom, and R ₄ and R ₅ are each independently a hydrogen atom, a methyl group, a methoxy group, a dimethylamino group, a fluorine atom, or a chlorine atom, p is an integer of 1 to 4, q is an integer of 1 to 3, and a dotted line is a polyimine precursor of any structure represented by a bond with another organic group, or a photosensitive polyimine . The composition according to claim 1, wherein the at least one of the polymers has the following formula (6) to (8) or (11): (wherein X ₁ and X ₂ are each independently a carbon atom or a nitrogen atom, and Y ₁ and Y ₂ are each independently a hydrogen atom, a methyl group, a cyano group, a fluorine atom or a chlorine atom, and X ₃ is an oxygen atom. Or a sulfur atom, X ₄ is a single bond, a carbon atom, an oxygen atom, or a sulfur atom, and R ₄ and R ₅ are each independently a hydrogen atom, a methyl group, a methoxy group, a dimethylamino group, a fluorine atom, or Chlorine atom, Ar is 2,5-extended furyl, thiophene-2,5-diyl, pyrimidine-2,5-diyl, pyridine-2,5-diyl, phenyl, 1,4- or 2 , 6-strandyl, 2,5- or 2,6-benzofuranyl, or 2,5- or 2,6-benzothiophenyl, a hydrogen bonded to the aromatic ring One part of the atom may be substituted by a methyl group, a methoxy group, a dimethylamino group, a fluorine atom, or a chlorine atom, p is an integer of 1 to 4, and a black point is a hydrogen atom or a bond with another organic group. A polymer that is constructed as part of a side chain. The composition according to claim 1, wherein the at least one of the polymers has the following general formula: (wherein, the dotted line is a bond with another organic group), the structure (12), or (13) is a part of the side chain of polyacrylate, polymethacrylate, poly N substituted maleimide , polystyrene, polyitanic acid ester, or polyoxyalkylene. The composition according to any one of claims 1 to 5, which is a composition for forming a film for ULH alignment of a cholesteric liquid crystal. A method for producing a film for structuring a liquid crystal structure, comprising the steps of forming a film of the composition according to any one of claims 1 to 5, and irradiating the obtained film with polarized ultraviolet rays to exhibit anisotropy A step of. The method according to claim 7, wherein in the polarized ultraviolet ray irradiation step, the anisotropy is expressed by decomposition, isomerization or crosslinking. The method according to claim 7 or 8, wherein in the polarized ultraviolet ray irradiation step, the anisotropy is expressed by irradiating the film surface with a polarized ultraviolet ray from a vertical direction. The method according to any one of claims 7 to 9, wherein the polarized ultraviolet ray irradiation step includes a polarized ultraviolet ray having an irradiation wavelength of 250 nm to 350 nm irradiated with ultraviolet rays, and at least an irradiation energy is irradiated at 5 mJ or more, and further irradiated at 100 Å. The step of heating at 300 ° C for 5 minutes or more. A film for stabilizing a liquid crystal structure, which comprises a polyimide precursor, a polyimine, a polyamine, a polyacrylate, a polymethacrylate, a poly N-substituted maleimide, Polymerization of at least one selected from the group consisting of polystyrene, polyitaconate, and polyorganosiloxane And an anisotropy that causes the cholesteric liquid crystal to undergo ULH alignment. A substrate having a liquid crystal structure stabilized film, which is characterized by having the film of claim 11. A liquid crystal cell characterized by containing a cholesteric liquid crystal between substrates having a liquid crystal structure stabilization film described in claim 12 in which the liquid crystal structure stabilization film is disposed opposite to each other. The liquid crystal cell according to claim 13, wherein the cholesteric liquid crystal is a cholesteric liquid crystal containing a liquid crystal compound represented by the following general formula. (wherein, X ₁ and X ₂ are each independently, and are a bond group selected from a single bond, an ester bond or an ether bond, L is an integer represented by 6 to 20, and R ₈ is an alkyl group having 4 to 10 carbon atoms) . A liquid crystal display device comprising a polarizing plate and a liquid crystal cell described in claim 13 or 14.