CN116348501A

CN116348501A - Liquid crystal composition, method for manufacturing liquid crystal display element, and liquid crystal display element

Info

Publication number: CN116348501A
Application number: CN202180066645.3A
Authority: CN
Inventors: 三宅一世; 野田尚宏
Original assignee: Nissan Chemical Corp
Current assignee: Nissan Chemical Corp
Priority date: 2020-08-06
Filing date: 2021-08-05
Publication date: 2023-06-27
Also published as: KR20230048356A; TW202219255A; JPWO2022030602A1; WO2022030602A1

Abstract

A method of manufacturing a liquid crystal display element, comprising the steps of: the radical polymerizable compound is polymerized in a state in which a liquid crystal composition containing a liquid crystal and the radical polymerizable compound represented by the following formula (a) is brought into contact with a radical generating film.

(in the formula (A), M represents a radically polymerizable group, R ₁ ～R ₃ Each independently represents a single bond or an alkylene group having 1 to 6 carbon atoms which may be inserted into the bonding group, ar represents an aromatic hydrocarbon group which may have a substituent, X ₁ X is X ₂ Each independently represents a hydrogen atom or an aromatic hydrocarbon group which may have a substituent，R ₁ X ₁ 、R ₂ X ₂ And R is equal to ₁ X ₁ R is R ₂ X ₂ The bonded carbon atoms may together form a ring, but R ₁ X ₁ 、R ₂ X ₂ And R is ₃ The total number of carbon atoms is 1 or more).

Description

Liquid crystal composition, method for manufacturing liquid crystal display element, and liquid crystal display element

Technical Field

The present invention relates to a method for manufacturing a liquid crystal display element, which is capable of manufacturing a weak anchor film by an inexpensive method without involving a complicated process and to which a stabilization technique for a polymer-based liquid crystal layer is applied, a liquid crystal display element for realizing further low-voltage driving, a liquid crystal composition usable for the same, and a radical polymerizable compound.

Background

In recent years, liquid crystal display elements have been widely used in displays of mobile phones, computers, televisions, and the like. Liquid crystal display devices have characteristics such as thin, light weight, and low power consumption, and are expected to be applied to various fields such as VR (Virtual Reality) and ultra-high definition displays in the future. In a display system of a liquid crystal display, various display modes such as TN (Twisted Nematic), IPS (In-Plane Switching), VA (Vertical Alignment: vertical alignment) and the like have been proposed, and a film (liquid crystal alignment film) for guiding liquid crystal to a desired alignment state is used In all the modes.

In particular, in products including touch panels such as tablet PCs, smartphones, and smarttvs, IPS mode in which display is not easily disturbed even when touched is preferable, and in recent years, a technique using FFS (Frindge Field Switching: fringe field switching) liquid crystal display elements and a technique using a non-contact technique using photo-alignment has been increasingly used in terms of improvement of contrast and improvement of viewing angle characteristics.

However, FFS has a problem that the manufacturing cost of the substrate is high as compared with IPS, and a display defect peculiar to FFS mode called Vcom shift occurs. Further, although photoalignment has an advantage that the size of a producible element can be increased and the display characteristics can be greatly improved as compared with the rubbing method, it is possible to cite a technical problem in principle of photoalignment (in the case of a decomposition type, there is a defective display due to a decomposition product, in the case of an isomerization type, there is sintering due to insufficient alignment force, or the like). In order to solve these problems, various studies have been made by manufacturers of liquid crystal display elements and manufacturers of liquid crystal alignment films.

On the other hand, in recent years, an IPS mode using the weak anchor technique has been proposed, and it is reported that: by using this method, the contrast can be improved and the voltage driving can be greatly reduced compared with the conventional IPS mode (see patent document 1).

Specifically, the method comprises the following steps: an IPS mode liquid crystal display device was fabricated by using a liquid crystal alignment film having strong anchoring energy on a substrate on one side, and treating the other substrate side having an electrode for generating a lateral electric field so as to have no alignment regulating force of liquid crystal at all.

In recent years, a weak anchor IPS mode has been proposed in which a weak state is produced using a thick polymer brush or the like (see patent document 2). With this technique, a large increase in contrast ratio and a large decrease in driving voltage are achieved.

On the other hand, there is a technical problem that the response speed, particularly the response speed at the time of voltage OFF (OFF), is significantly reduced. The reason for this is that the driving voltage is low, and therefore, the influence of response to an electric field weaker than that of the normal driving method and the anchoring force of the alignment film are extremely small, and therefore, it takes time to restore the liquid crystal.

As a method for solving this problem, a method of weakly anchoring only to the pixel electrode has been proposed (see patent document 3). Reported are: this makes it possible to achieve both an improvement in brightness and a response speed.

Prior art literature

Patent literature

Patent document 1: patent publication No. 4053530

Patent document 2: japanese patent laid-open No. 2013-231757

Patent document 3: japanese patent laid-open No. 2017-211566

Disclosure of Invention

Technical problem to be solved by the invention

In order to suppress a response speed delay at the time of driving by weakly anchoring only the electrode of the IPS comb teeth electrode, it is necessary to prepare a technique for applying different materials to a very small region in order to weakly anchor only the electrode, and the like, which is considered to be a large technical problem in practical industrialization.

Different from this, a method of improving the response speed by narrowing the cell gap has also been studied. In general, a liquid crystal display element has a tendency to respond faster as the cell gap is narrower. However, on the other hand, there is a problem that transmittance is lowered. In order to solve this problem, a liquid crystal having a large birefringence (Δn) is used. By setting the product (retardation) of the cell gap D and an to 300nm to 400nm (measurement wavelength 550 nm), the decrease in transmittance can be solved. However, when Δn is increased, it is not possible to change only the parameter, and it is considered that the basic physical properties of the liquid crystal are greatly changed because parameters such as Δε (dielectric constant anisotropy) and elastic modulus are also changed. For example, in the case of weak anchoring alignment, it is considered that there is a possibility that liquid crystal is aligned in the vertical direction, and the like. Therefore, it is an important technical problem to obtain stable weak anchoring characteristics even if parameters such as Δn and Δε are changed.

It is believed that: if such technical problems can be solved, the panel manufacturer is a great cost advantage, and it is advantageous in terms of suppressing the consumption of the battery, improving the image quality, and the like.

The present invention has been made to solve the above-described problems, and an object of the present invention is to provide a method for manufacturing a liquid crystal display element, a liquid crystal composition and a radical polymerizable compound which can be used for the liquid crystal display element, by which a weakly anchored transverse electric field liquid crystal display element can be stably manufactured without generating a pretilt angle in a narrow cell gap, a transverse electric field liquid crystal display element which can achieve both a low driving voltage and a fast response speed at the time of turning Off (Off) and in which a decrease in VHR (voltage holding ratio) is small even at a high temperature can be manufactured.

Means for solving the technical problems

The present inventors have conducted intensive studies to solve the above-described problems, and as a result, have found that the above-described problems can be solved, and have completed the present invention having the following gist.

Namely, the present invention includes the following.

[1] A method of manufacturing a liquid crystal display element, comprising the steps of: the radically polymerizable compound is polymerized in a state in which a liquid crystal composition containing a liquid crystal and the radically polymerizable compound represented by the following formula (A) is brought into contact with a radical generating film.

[ chemical 1]

(in the formula (A), M represents a radically polymerizable group; R ₁ ～R ₃ Each independently represents a single bond or an alkylene group having 1 to 6 carbon atoms which may be inserted into the bonding group; ar represents an aromatic hydrocarbon group which may have a substituent; x is X ₁ X is X ₂ Each independently represents a hydrogen atom or an aromatic hydrocarbon group which may have a substituent; r is R ₁ X ₁ 、R ₂ X ₂ And R is equal to ₁ X ₁ R is R ₂ X ₂ The bonded carbon atoms may together form a ring, but R ₁ X ₁ 、R ₂ X ₂ And R is ₃ The total number of carbon atoms is 1 or more. )

[2]According to [1]]The method for manufacturing the liquid crystal display element, wherein R in the formula (A) ₃ Is a straight-chain alkylene group having 1 to 6 carbon atoms, X ₁ And X ₂ Is a hydrogen atom.

[3] The method of producing a liquid crystal display element according to [1] or [2], wherein M in the formula (A) is selected from the following structures.

[ chemical 2]

(wherein, represents a bonding site. R) ^b Represents a linear alkyl group having 2 to 8 carbon atoms, E represents a member selected from the group consisting of single bonds, -O-, -NR ^c -a bonding group in the group consisting of S-, ester bonds and amide bonds. R is R ^c Represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. R is R ^d Represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. )

[4] The method for producing a liquid crystal display element according to any one of [1] to [3], wherein the radical generating film is a uniaxially oriented radical generating film.

[5] The method for producing a liquid crystal display element according to any one of [1] to [4], wherein the step of polymerizing is performed under an electric field-free condition.

[6] The method for producing a liquid crystal display element according to any one of [1] to [5], wherein the radical generating film is a film obtained by immobilizing an organic group which induces radical polymerization.

[7] The method for producing a liquid crystal display element according to any one of [1] to [5], wherein a composition containing a polymer and a compound having a radical-generating organic group is applied and cured to form a film, and the radical-generating organic group is immobilized in the film, whereby the radical-generating film is obtained.

[8] The method for producing a liquid crystal display element according to any one of [1] to [5], wherein the radical generating film comprises: polymers containing organic groups that induce free radical polymerization.

[9] The method for producing a liquid crystal display element according to [8], wherein the polymer containing an organic group that induces radical polymerization is at least one polymer selected from the group consisting of polyimide precursors, polyimides, polyureas, and polyamides obtained by using a diamine component containing a diamine containing an organic group that induces radical polymerization.

[10] The method of producing a liquid crystal display element according to [9], wherein the radical polymerization-inducing organic group is an organic group represented by the following formulas [ X-1] to [ X-18], [ W ], [ Y ] or [ Z ].

[ chemical 3]

(X-1]～[X-18]Wherein, represents a bonding site; s is S ₁ And S is ₂ Each independently represents-O-, -NR-, or-S-; r represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms (of the alkyl groups having 1 to 10 carbon atoms, the-CH of the alkyl group having 2 to 10 carbon atoms) ₂ Part of the groups may be replaced by oxygen atoms. But at S ₂ R or NR in the alkyl radical-CH ₂ In the case where a part of the radicals is replaced by oxygen atoms, said oxygen atoms are not directly bonded to S ₂ Or N. ). R is R ₁ And R is ₂ Each independently represents a hydrogen atom, a halogen atom or an alkyl group having 1 to 4 carbon atoms. )

[ chemical 4]

(W)]、[Y]And [ Z ]]Wherein Ar represents an aromatic hydrocarbon group selected from the group consisting of phenylene, naphthylene, and biphenylene which may have an organic group and/or a halogen atom as a substituent; r is R ⁹ And R is ¹⁰ Each independently represents an alkyl group having 1 to 10 carbon atoms or an alkoxy group having 1 to 10 carbon atoms, when R ⁹ And R is ¹⁰ When alkyl, the terminal groups may be bonded to each other to form a ring structure; q represents any one of the following structures.

[ chemical 5]

(wherein R is ¹¹ represents-CH ₂ -, -NR-, -O-; or-S-, R independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms; * Indicating the bonding site. ). S is S ³ Represents a single bond, -O-, -NR- (R represents a hydrogen atom or an alkyl group having 1 to 14 carbon atoms), or-S-. R is R ¹² Represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms or an alkoxy group having 1 to 10 carbon atoms. )

[11] The method for producing a liquid crystal display element according to [9] or [10], wherein the diamine containing an organic group that induces radical polymerization is a diamine having a structure represented by the following formula (6), the following formula (7) or the following formula (7').

[ chemical 6]

(in the formula (6), R ⁶ Represents a single bond, -CH ₂ -、-O-、-COO-、-OCO-、-NHCO-、-CONH-、-NH-、-CH ₂ O-、-N(CH ₃ )-、-CON(CH ₃ ) -or-N (CH) ₃ )CO-，

R ⁷ Represents a single bond or an alkylene group having 1 to 20 carbon atoms which is unsubstituted or substituted with a fluorine atom, and at least 1-CH of any of the alkylene groups ₂ -or-CF ₂ Each independently substituted with a group selected from the group consisting of-ch=ch-, a 2-membered carbocyclic ring, and a 2-membered heterocyclic ring, and, in turn, any of the groups listed below, namely-O-, -COO-, -OCO-, provided that-NHCO-, -CONH-or-NH-are not adjacent to each other, may be substituted with these groups;

R ⁸ represents a compound selected from the following formula [ X-1 ]]～[X-18]A radical polymerization reactive group represented by the formula (I).

[ chemical 7]

(X-1]～[X-18]Wherein, represents a bonding site; s is S ₁ And S is ₂ Each independently represents-O-, -NR-, or-S-; r represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms (of the alkyl groups having 1 to 10 carbon atoms, the-CH of the alkyl group having 2 to 10 carbon atoms) ₂ Part of the groups may be replaced by oxygen atoms. But at S ₂ R or NR in the alkaneOf radicals-CH ₂ In the case where a part of the radicals is replaced by oxygen atoms, said oxygen atoms are not directly bonded to S ₂ Or N. ). R is R ₁ R is R ₂ Each independently represents a hydrogen atom, a halogen atom or an alkyl group having 1 to 4 carbon atoms. ))

[ chemical 8]

[ chemical 9]

(in the formulae (7) and (7'), T ¹ T and T ² Each independently is a single bond, -O-, -S-, -COO-, -OCO-, -NHCO-, -CONH-, -NH-, -CH ₂ O-、-N(CH ₃ )-、-CON(CH ₃ ) -or-N (CH) ₃ )CO-，

S represents a single bond or an alkylene group having 1 to 20 carbon atoms which is unsubstituted or substituted with a fluorine atom, and 1 or more-CH S of the alkylene group ₂ -or-CF ₂ Each independently substituted with a group selected from the group consisting of-ch=ch-, a 2-membered carbocyclic ring, and a 2-membered heterocyclic ring, and, in turn, any of the groups listed below, namely-O-, -COO-, -OCO-, provided that-NHCO-, -CONH-or-NH-are not adjacent to each other, can be replaced by these groups,

e is a single bond, -O-, -C (CH) ₃ ) ₂ -、-NH-、-CO-、-NHCO-、-COO-、-(CH ₂ ) _m -、-SO ₂ -、-O-(CH ₂ ) _m -O-、-O-C(CH ₃ ) ₂ -、-CO-(CH ₂ ) _m -、-NH-(CH ₂ ) _m -、-SO ₂ -(CH ₂ ) _m -、-CONH-(CH ₂ ) _m -、-CONH-(CH ₂ ) _m NHCO-, or-COO- (CH) ₂ ) _m -OCO-, m is an integer from 1 to 8,

j is an organic group represented by a formula selected from the following formulae [ W ], [ Y ] and [ Z ].

[ chemical 10]

(W)]、[Y][ Z ]]Wherein, is expressed as T ² Is a bonding site of (2); ar represents an aromatic hydrocarbon group selected from the group consisting of phenylene, naphthylene, and biphenylene which may have an organic group and/or a halogen atom as a substituent; r is R ⁹ And R is ¹⁰ Each independently represents an alkyl group having 1 to 10 carbon atoms or an alkoxy group having 1 to 10 carbon atoms; q represents any one of the following structures.

[ chemical 11]

(wherein R is ¹¹ represents-CH ₂ -, -NR-, -O-; or-S-; r independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms; * Indicating the bonding site. ). S is S ³ Represents a single bond, -O-, -NR- (R represents a hydrogen atom or an alkyl group having 1 to 14 carbon atoms), or-S-. R is R ¹² Represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms or an alkoxy group having 1 to 10 carbon atoms. ) In the formula (7'), q are each independently 0 or 1, at least 1 q is 1, and p represents an integer of 1 to 2. )

[12] The method of manufacturing a liquid crystal display element according to any one of [1] to [11], comprising the steps of:

preparing a first substrate having the radical generating film and a second substrate which may have a radical generating film;

Disposing the first substrate and the second substrate so that the radical generating film of the first substrate faces the second substrate;

filling the liquid crystal composition between the first substrate and the second substrate; a kind of electronic device with high-pressure air-conditioning system

The polymerization reaction is carried out.

[13] The method of manufacturing a liquid crystal display element according to [12], wherein the second substrate is a second substrate having no radical generating film.

[14] The method of manufacturing a liquid crystal display element according to [12], wherein the second substrate is a substrate coated with a liquid crystal alignment film having uniaxial alignment.

[15] The method of manufacturing a liquid crystal display element according to [14], wherein the liquid crystal alignment film having uniaxial alignment is a liquid crystal alignment film for horizontal alignment.

[16] The method for manufacturing a liquid crystal display element according to any one of [12] to [15], wherein any one of the first substrate and the second substrate is a substrate having comb-teeth electrodes.

[17] A liquid crystal composition comprising a liquid crystal and a radical polymerizable compound represented by the following formula (A).

[ chemical 12]

[18]According to [17]]The liquid crystal composition, wherein R in the formula (A) ₃ Is a straight-chain alkylene group having 1 to 6 carbon atoms, X ₁ And X ₂ Is a hydrogen atom.

[19] The liquid crystal composition according to [17] or [18], wherein M in the formula (A) is selected from the following structures.

[ chemical 13]

(wherein, represents a bonding site. R) ^b Represents a linear alkyl group having 2 to 8 carbon atoms; e represents a single bond selected from the group consisting of, -O-, -NR ^c -a bonding group in the group consisting of S-, ester bonds and amide bonds. R is R ^c Represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. R is R ^d Represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. )

[20] A liquid crystal display element is characterized by comprising a first substrate, a second substrate arranged opposite to the first substrate, and liquid crystal filled between the first substrate and the second substrate,

the liquid crystal display element is formed by bringing a liquid crystal composition containing the liquid crystal and a radical polymerizable compound represented by the following formula (a) into contact with the radical generating film of the first substrate having the radical generating film, and polymerizing the radical polymerizable compound.

[ chemical 14]

[21] The liquid crystal display element according to [20], wherein any one of the first substrate and the second substrate is a substrate having comb-teeth electrodes.

[22] The liquid crystal display element according to [20] or [21], wherein the liquid crystal display element is a low-voltage-driven transverse electric field liquid crystal display element.

[23] A radical polymerizable compound represented by the following formula (A).

[ 15]

(in the formula (A), M, R) ₁ 、R ₂ 、R ₃ 、X ₁ 、X ₂ Ar is any one of the following combinations (i) to (v). )

(i) M is the following structure (C), R ₁ X ₁ Is 1-amyl, R ₂ Is a single bond, X ₂ Is a hydrogen atom, R ₃ A combination of a single bond and Ar being phenyl.

(ii) M is the following structure (B), R ₁ X ₁ Is 1-propyl, R ₂ Is a single bond, X ₂ Is a hydrogen atom, R ₃ A combination of a single bond and Ar being phenyl.

(iii) M is the following structure (C), R ₁ X ₁ Is ethyl, R ₂ X ₂ Is ethyl, R ₃ A combination of 1, 2-ethylene and Ar is phenyl.

(iv) M is the following structure (C), R ₁ X ₁ Is 1-propyl, R ₂ Is a single bond, X ₂ Is a hydrogen atom, R ₃ A combination of 1, 2-ethylene and Ar is phenyl.

(v) M is the following structure (D), R ₁ Is a single bond, X ₁ Is a hydrogen atom, R ₂ Is a single bond, X ₂ Is a hydrogen atom, R ₃ A combination of 1, 2-ethylene and Ar is phenyl.

[ 16]

(Structure (B), structure (C) and Structure (D) represents a bonding site;)

Effects of the invention

According to the present invention, a method for manufacturing a liquid crystal display element, a liquid crystal composition and a radical polymerizable compound which can be used for the liquid crystal display element, and a method for manufacturing a liquid crystal display element, in which a weak anchoring transverse electric field liquid crystal display element can be stably manufactured without generating a pretilt angle in narrow cell gap formation, a response speed at the time of switching Off (Off) and a low VHR drop even at high temperature can be simultaneously realized can be manufactured.

Drawings

Fig. 1 is a schematic cross-sectional view showing one example of a transverse electric field liquid crystal display element of the present invention.

Fig. 2 is a schematic cross-sectional view showing other examples of the transverse electric field liquid crystal display element of the present invention.

Detailed Description

The present invention uses an additive (radical polymerizable compound of a specific structure) capable of suppressing the occurrence of a pretilt angle accompanying the formation of a weakly anchored film and stably producing a highly reliable weakly anchored transverse electric field liquid crystal display element even in the narrowing of a cell gap. For example, a method for manufacturing a weakly anchored in-plane-switching liquid crystal display element, comprising the steps of: a step of preparing a liquid crystal composition containing a liquid crystal and a radical polymerizable compound having a specific structure between a first substrate having a radical generating film and a second substrate having a liquid crystal alignment film; and imparting sufficient energy to the unit to cause the radically polymerizable compound to undergo polymerization. Preferably, a method for manufacturing a liquid crystal cell comprises the steps of: preparing a first substrate having a radical generating film subjected to an alignment treatment by rubbing or photo-alignment, and a second substrate having a liquid crystal alignment film without the radical generating film; manufacturing units in a manner that the respective substrates are opposite; and filling a liquid crystal composition containing a liquid crystal and a radical polymerizable compound having a specific structure between the first substrate and the second substrate. For example, a method for manufacturing a low-voltage-driven in-plane-switching-mode liquid crystal display device includes a radical generating film subjected to an alignment treatment on one substrate, a liquid crystal alignment film subjected to a uniaxial alignment treatment on the other substrate, and a comb electrode for driving liquid crystal on either substrate.

In the present invention, the "weakly anchored film" means a film having no alignment regulating force of liquid crystal molecules at all in the in-plane direction; or a film in which the alignment regulating force is weaker than the intermolecular force between the liquid crystals even if the liquid crystal molecules are present, and the liquid crystal molecules cannot be uniaxially aligned in any direction only by using the film. In addition, the weakly anchored film is not limited to a solid film, but also includes a liquid film covering a solid surface. In general, in a liquid crystal display element, a liquid crystal alignment film, which is a film that restricts alignment of liquid crystal molecules, is used in pairs to align liquid crystal, but in the case of using the weak anchor film and the liquid crystal alignment film in pairs, liquid crystal can be aligned. The reason for this is that the alignment regulating force of the liquid crystal alignment film is also transmitted in the thickness direction of the liquid crystal layer by the intermolecular force between the liquid crystal molecules, and as a result, the liquid crystal molecules close to the weak anchor film are also aligned. Therefore, when the liquid crystal alignment film for horizontal alignment is used as the liquid crystal alignment film, a horizontal alignment state can be produced in the entire liquid crystal cell. The horizontal alignment means a state in which long axes of liquid crystal molecules are aligned substantially parallel to a liquid crystal alignment film surface, and an oblique alignment of about several degrees is included in the category of horizontal alignment.

The applicant of the present application proposes a method for manufacturing a zero-face anchoring film comprising the steps of: in a state where a liquid crystal composition containing a liquid crystal and a radical polymerizable compound is brought into contact with a radical generating film, sufficient energy is applied to polymerize the radical polymerizable compound (refer to claim 1 of international publication No. 2019/004433). Examples of the radical polymerizable compounds used in the proposals are [0077] to [0086] of International publication No. 2019/004433.

The present inventors have made intensive studies to stably produce a weak anchor transverse electric field liquid crystal display element without generating a pretilt angle in a narrow cell gap, and to produce a transverse electric field liquid crystal display element which can achieve both a low driving voltage and a fast response speed at Off (Off) and which has little VHR drop even at high temperature, by using the proposed technique. As a result, it has been found that by using a radical polymerizable compound having a specific structure as the radical polymerizable compound, a weakly anchored transverse electric field liquid crystal display element can be stably produced without generating a pretilt angle in narrowing the cell gap, and a transverse electric field liquid crystal display element can be produced which can achieve both a low driving voltage and a fast response speed at Off (Off) and which has little VHR drop even at high temperatures.

The radically polymerizable compound having a specific structure is represented by the following formula (a).

[ chemical 17]

The method for manufacturing a liquid crystal display element of the present invention comprises the steps of: the radical polymerizable compound is polymerized in a state in which a liquid crystal composition containing a liquid crystal and the radical polymerizable compound represented by formula (a) is brought into contact with a radical generating film. The inventors speculated that in this step, a change is generated on the surface of the radical generating film by polymerization reaction of a radical polymerizable compound using radicals generated by the radical generating film, thereby obtaining a weakly anchored film. However, it is difficult to confirm whether the change in the surface of the radical generating film in this step is a change in the radical generating film itself or a change caused by the formation of a polymerized layer of the radical polymerizable compound on the radical generating film. Thus, the result of this step has not been determined.

In the present invention, by performing the above steps, a weakly anchored in-plane switching mode liquid crystal display element can be stably manufactured without generating a pretilt angle in narrowing a cell gap, and a in-plane switching mode liquid crystal display element which can achieve both a low driving voltage and a fast response speed at Off (Off) and which has little VHR drop even at high temperature can be manufactured. The present inventors have recognized how the radical polymerizable compound represented by the formula (a) contributes to it as follows.

M of the radically polymerizable compound represented by the formula (A) contributes to radical polymerization of the radically polymerizable compound. This can form a weak anchor film, and can reduce the driving voltage.

Further, the present inventors speculated that Ar (aromatic hydrocarbon group which may have a substituent) of the radical polymerizable compound represented by the formula (a) contributes to suppression of occurrence of pretilt angle, improvement of response speed, and high VHR at high temperature.

In addition, the inventors speculated that in the formula (A), M and Ar are not too close, and that a group having a certain size between M and Ar [ -C (R) ₁ X ₁ )(R ₂ X ₂ )R ₃ -]Has the effect of further accelerating the response speed.

In the present specification, the term "narrow cell gap" means a cell gap of 3.5 μm or less.

[ composition for Forming free radical-generating film ]

The radical generating film forming composition for forming a radical generating film used in the present invention contains a polymer and a radical generating group as components. In this case, the composition may be a composition containing a polymer in which a group capable of generating a radical is bonded, or a composition containing a compound having a group capable of generating a radical and a polymer as a base resin. By applying such a composition and curing it to form a film, a radical generating film in which a radical generating group is fixed in the film can be obtained. The group capable of generating a radical is preferably an organic group which induces radical polymerization.

Examples of the organic group which induces radical polymerization include organic groups represented by the following formulas [ X-1] to [ X-18], [ W ], [ Y ] and [ Z ].

[ chemical 18]

(X-1]～[X-18]Wherein, represents a bonding site; s is S ₁ And S is ₂ Each independently represents-O-, -NR-, or-S-; r represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms (of the alkyl groups having 1 to 10 carbon atoms, the-CH of the alkyl group having 2 to 10 carbon atoms) ₂ Part of the groups may be replaced by oxygen atoms. But at S ₂ R or NR in the alkyl radical-CH ₂ In the case where a part of the radicals is replaced by oxygen atoms, said oxygen atoms are not directly bonded to S ₂ Or N. ). R is R ₁ R is R ₂ Each independently represents a hydrogen atom, a halogen atom or an alkyl group having 1 to 4 carbon atoms. )

[ chemical 19]

[ chemical 20]

(wherein R is ¹¹ represents-CH ₂ -, -NR-, -O-; or-S-; r is independently of each otherThe standing represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms; * Indicating the bonding site. ). S is S ³ Represents a single bond, -O-, -NR- (R represents a hydrogen atom or an alkyl group having 1 to 14 carbon atoms), or-S-. R is R ¹² Represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms or an alkoxy group having 1 to 10 carbon atoms. )

As the polymer, at least 1 polymer selected from the group consisting of polyimide precursors, polyimides, polyureas, polyamides, polyacrylates, polymethacrylates, and polysiloxanes is preferable.

In order to obtain the radical generating film used in the present invention, in the case of using the polymer having an organic group that induces radical polymerization, it is preferable to use, as a monomer component, a monomer having a photoreactive side chain containing at least one selected from the group consisting of a methylpropenyl group, a propenyl group, a vinyl group, an allyl group, a coumarin group, a styryl group, and a cinnamoyl group; or a monomer having a radical-generating site in a side chain which is decomposed by ultraviolet irradiation. On the other hand, since the radical-generating monomer itself spontaneously undergoes polymerization to form an unstable compound, it is considered that the polymer derived from a diamine having a radical generating site is preferable in terms of ease of synthesis, and polyimide precursors such as polyamic acid and polyamic acid ester, polyimide, polyurea, polyamide and the like are more preferable.

The polymer containing an organic group that induces radical polymerization is preferably at least one polymer selected from the group consisting of polyimide precursors, polyimides, polyureas, and polyamides obtained using a diamine component containing a diamine containing an organic group that induces radical polymerization.

Specifically, the diamine containing an organic group that induces radical polymerization is, for example, a diamine having a side chain capable of generating radicals and performing polymerization, and examples thereof include diamines having a structure represented by the following formula (6), but are not limited thereto.

[ chemical 21]

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[ chemical 22]

(X-1]～[X-18]Wherein, represents a bonding site; s is S ₁ And S is ₂ Each independently represents-O-, -NR-, or-S-; r represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms (of the alkyl groups having 1 to 10 carbon atoms, the-CH of the alkyl group having 2 to 10 carbon atoms) ₂ Part of the groups may be replaced by oxygen atoms. But at S ₂ R or NR in the alkyl radical-CH ₂ In the case where a part of the radicals is replaced by oxygen atoms, said oxygen atoms are not directly bonded to S ₂ Or N. ). R is R ₁ R is R ₂ Each independently represents a hydrogen atom, a halogen atom or an alkyl group having 1 to 4 carbon atoms. ))

2 amino groups (-NH) in formula (6) ₂ ) The bonding position of (c) is not limited. Specifically, examples of the bonding group to the side chain include the

positions

2 and 3 and the

positions

2 and 4 on the benzene ring,2,5, 2,6, 3,4, 3, 5. Among them, from the viewpoint of reactivity in the synthesis of polyamic acid, the 2,4 position, the 2,5 position, or the 3,5 position is preferable. If ease in synthesizing diamine is also considered, the 2,4 position or the 3,5 position is more preferable.

As the diamine having a photoreactive group containing at least 1 selected from the group consisting of a methylpropenyl group, a propenyl group, a vinyl group, an allyl group, a coumarin group, a styryl group and a cinnamoyl group, specifically, the following compounds are exemplified, but not limited thereto.

[ chemical 23]

(wherein J ¹ Is a bonding group selected from the group consisting of single bond, -O-, -COO-, -NHCO-, and-NH-, J ² Represents a single bond or an alkylene group having 1 to 20 carbon atoms which is unsubstituted or substituted with a fluorine atom. )

Among diamines containing an organic group that induces radical polymerization, diamines having a site that generates a radical by decomposition by ultraviolet irradiation as a side chain may be exemplified by diamines having a structure represented by the following formula (7) or formula (7'), but are not limited thereto.

[ chemical 24]

[ chemical 25]

/>

S represents a single bond, or is unsubstituted or pro-fluoridatedSub-substituted alkylene having 1 to 20 carbon atoms, and any one or more of-CH's of the alkylene ₂ -or-CF ₂ Each independently substituted with a group selected from the group consisting of-ch=ch-, a 2-membered carbocyclic ring, and a 2-membered heterocyclic ring, and, in turn, any of the groups listed below, namely-O-, -COO-, -OCO-, provided that-NHCO-, -CONH-or-NH-are not adjacent to each other, can be replaced by these groups,

j is an organic group represented by a formula selected from the following formulae [ W ], [ Y ], [ Z ],

[ chemical 26]

[ chemical 27]

(wherein R is ¹¹ represents-CH ₂ -, -NR-, -O-; or-S-; r independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms; * Indicating the bonding site. ). S is S ³ Represents a single bond, -O-, -NR- (R represents a hydrogen atom)A child or an alkyl group having 1 to 14 carbon atoms), or-S-. R is R ¹² Represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms or an alkoxy group having 1 to 10 carbon atoms. ) In the formula (7'), q are each independently 0 or 1, at least 1 q is 1, and p represents an integer of 1 to 2. )

2 amino groups (-NH) in the above formula (7) ₂ ) The bonding position of (c) is not limited. Specifically, examples of the bonding group to the side chain include a position of 2,3, a position of 2,4, a position of 2,5, a position of 2,6, a position of 3,4, and a position of 3,5 on the benzene ring. Among them, from the viewpoint of reactivity in the synthesis of polyamic acid, the 2,4 position, the 2,5 position, or the 3,5 position is preferable.

In particular, in view of ease of synthesis, height of versatility, characteristics, and the like, the structure represented by the following formula is most preferable, but not limited thereto.

[ chemical 28]

(wherein n is an integer of 2 to 8.)

Among the diamines represented by the formulas (7) and (7'), the structure represented by the following formula is most preferable in view of ease of synthesis, high versatility, characteristics, and the like, but is not limited thereto.

[ chemical 29]

(wherein n is an integer of 2 to 8, E is a single bond, -O-, -C (CH) ₃ ) ₂ -、-NH-、-CO-、-NHCO-、-CONH-、-COO-、-OCO-、-(CH ₂ ) _m -、-SO ₂ -、-O-(CH ₂ ) _m -O-、-O-C(CH ₃ ) ₂ -、-C(CH ₃ ) ₂ -O-、-CO-(CH ₂ ) _m -、-(CH ₂ ) _m -CO-、-NH-(CH ₂ ) _m -、-(CH ₂ ) _m -NH-、-SO ₂ -(CH ₂ ) _m -、-(CH ₂ ) _m -SO ₂ -、-CONH-(CH ₂ ) _m -、-(CH ₂ ) _m -NHCO-、-CONH-(CH ₂ ) _m NHCO-, or-COO- (CH) ₂ ) _m -OCO-, m is an integer from 1 to 8. )

The diamine may be used in an amount of 1 or 2 or more kinds depending on the properties such as liquid crystal alignment property, sensitivity in polymerization, voltage holding property, and accumulated charge in the production of radical generating film.

The amount of the diamine containing an organic group that induces radical polymerization is preferably 5 to 50 mol%, more preferably 10 to 40 mol%, and particularly preferably 15 to 30 mol% based on the whole diamine component for polymer synthesis contained in the radical-generating film-forming composition.

In the case of obtaining the polymer used for the radical generating film of the present invention from diamine, it is possible to use diamine other than diamine containing an organic group which induces radical polymerization as a diamine component, as long as the effect of the present invention is not impaired. Specifically, there may be mentioned: p-phenylenediamine, 2,3,5, 6-tetramethyl-p-phenylenediamine, 2, 5-dimethyl-p-phenylenediamine, m-phenylenediamine, 2, 4-dimethyl-m-phenylenediamine, 2, 5-diaminotoluene, 2, 6-diaminotoluene, 2, 5-diaminophenol, 2, 4-diaminophenol, 3, 5-diaminobenzyl alcohol, 2, 4-diaminobenzyl alcohol, 4, 6-diaminoresorcinol, resorcinol 4,4' -diaminobiphenyl, 3' -dimethyl-4, 4' -diaminobiphenyl, 3' -dimethoxy-4, 4' -diaminobiphenyl, 3' -dihydroxy-4, 4' -diaminobiphenyl 3,3' -dicarboxy-4, 4' -diaminobiphenyl, 3' -difluoro-4, 4' -diaminobiphenyl, 3' -bis (trifluoromethyl) -4,4' -diaminobiphenyl 3,4' -diaminobiphenyl, 3' -diaminobiphenyl, 2' -diaminobiphenyl, 2,3' -diaminobiphenyl, 4' -diaminodiphenylmethane, 3' -diaminodiphenylmethane, 3,4' -diaminodiphenylmethane, 2' -diaminodiphenylmethane, 2,3' -diaminodiphenylmethane, and 4,4' -diaminodiphenyl ether, 3' -diaminodiphenyl ether, 3,4' -diaminodiphenyl ether, 2' -diaminodiphenyl ether, 2,3' -diaminodiphenyl ether, 4' -sulfonyldiphenylamine, 3' -sulfonyldiphenylamine, bis (4-aminophenyl) silane, bis (3-aminophenyl) silane, dimethyl-bis (4-aminophenyl) silane, dimethyl-bis (3-aminophenyl) silane, 4' -thiodiphenylamine, 3' -thiodiphenylamine, 4' -diaminodiphenylamine, 3' -diaminodiphenylamine, 3,4' -diaminodiphenylamine, 2' -diaminodiphenylamine, 2,3' -diaminodiphenylamine, N-methyl (4, 4' -diaminodiphenyl) amine, N-methyl (3, 3' -diaminodiphenyl) amine, N-methyl (3, 4' -diaminodiphenyl) amine, N-methyl (2, 2' -diaminodiphenyl) amine, N-methyl (2, 3' -diaminodiphenyl) amine 4,4' -diaminobenzophenone, 3' -diaminobenzophenone, 3,4' -diaminobenzophenone, 2' -diaminobenzophenone, 2,3' -diaminobenzophenone, 1, 4-diaminonaphthalene, 1, 5-diaminonaphthalene, 1, 6-diaminonaphthalene, 1, 7-diaminonaphthalene, 1, 8-diaminonaphthalene, 2, 5-diaminonaphthalene, 2, 6-diaminonaphthalene, 2, 7-diaminonaphthalene, 1, 2-bis (4-aminophenyl) ethane, 1, 2-bis (3-aminophenyl) ethane, 1, 3-bis (4-aminophenyl) propane, 1, 3-bis (3-aminophenyl) propane, 1, 4-bis (4-aminophenyl) butane, 1, 4-bis (3-aminophenyl) butane, bis (3, 5-diethyl-4-aminophenyl) methane, 1, 4-bis (4-aminophenoxy) benzene, 1, 3-bis (4-aminophenoxy) benzene, 1, 4-bis (4-aminophenyl) benzene, 1, 3-bis (4-aminophenyl) benzene, 1, 4-bis (4-aminobenzyl) benzene, 1, 3-bis (4-aminophenoxy) benzene, 4' - [1, 4-phenylenebis (methylene) ] diphenylamine, 4' - [1, 3-phenylenebis (methylene) ] diphenylamine, 3,4' - [1, 4-phenylenebis (methylene) ] diphenylamine, 3,4' - [1, 3-phenylenebis (methylene) ] diphenylamine, 3' - [1, 4-phenylenebis (methylene) diphenylamine, 1, 4-phenylenebis [ (1, 4-phenylenebis (methylene) ] diphenylamine [ (1, 4-phenylene) ] bis [ (1, 4-methylenephenyl) ] diphenylamine ], 1, 4-methyleneketone ], 1, 3-bis [ (1, 4-methylenediphenyl) ] diphenylamine ], 1, 3-4-methylenebis [ (1, 4-methylenephenyl) ] diphenylamine 1, 3-phenylenebis (4-aminobenzoate), 1, 3-phenylenebis (3-aminobenzoate), bis (4-aminophenyl) terephthalate, bis (3-aminophenyl) terephthalate, bis (4-aminophenyl) isophthalate, bis (3-aminophenyl) isophthalate, N- (1, 4-phenylene) bis (4-aminobenzamide), N- (1, 3-phenylene) bis (4-aminobenzamide), N- (1, 4-phenylene) bis (3-aminobenzamide), N, N- (1, 3-phenylene) bis (3-aminobenzamide), N-bis (4-aminophenyl) terephthalamide, N-bis (3-aminophenyl) terephthalamide, N-bis (4-aminophenyl) isophthalamide, N, N-bis (3-aminophenyl) isophthalamide, 9, 10-bis (4-aminophenyl) anthracene, 4' -bis (4-aminophenoxy) diphenylsulfone, 2' -bis [4- (4-aminophenoxy) phenyl ] propane, 2' -bis [4- (4-aminophenoxy) phenyl ] hexafluoropropane, 2,2 '-bis (4-aminophenyl) hexafluoropropane, 2' -bis (3-amino-4-methylphenyl) hexafluoropropane, 2 '-bis (4-aminophenyl) propane, 2' -bis (3-amino-4-methylphenyl) propane, trans-1, 4-bis (4-aminophenyl) cyclohexane, 3, 5-diaminobenzoic acid, 2, 5-diaminobenzoic acid, bis (4-aminophenoxy) methane, 1, 2-bis (4-aminophenoxy) ethane 1, 3-bis (4-aminophenoxy) propane, 1, 3-bis (3-aminophenoxy) propane, 1, 4-bis (4-aminophenoxy) butane, 1, 4-bis (3-aminophenoxy) butane, 1, 5-bis (4-aminophenoxy) pentane, 1, 5-bis (3-aminophenoxy) pentane, 1, 6-bis (4-aminophenoxy) hexane, 1, 6-bis (3-aminophenoxy) hexane, 1, 7-bis (4-aminophenoxy) heptane, 1, 7-bis (3-aminophenoxy) heptane, 1, 8-bis (4-aminophenoxy) octane, aromatic diamines such as 1, 8-bis (3-aminophenoxy) octane, 1, 9-bis (4-aminophenoxy) nonane, 1, 9-bis (3-aminophenoxy) nonane, 1, 10-bis (4-aminophenoxy) decane, 1, 10-bis (3-aminophenoxy) decane, 1, 11-bis (4-aminophenoxy) undecane, 1, 11-bis (3-aminophenoxy) undecane, 1, 12-bis (4-aminophenoxy) dodecane, and 1, 12-bis (3-aminophenoxy) dodecane; alicyclic diamines such as bis (4-aminocyclohexyl) methane and bis (4-amino-3-methylcyclohexyl) methane; aliphatic diamines such as 1, 3-diaminopropane, 1, 4-diaminobutane, 1, 5-diaminopentane, 1, 6-diaminohexane, 1, 7-diaminoheptane, 1, 8-diaminooctane, 1, 9-diaminononane, 1, 10-diaminodecane, 1, 11-diaminoundecane, and 1, 12-diaminododecane; diamines having a urea structure such as 1, 3-bis [2- (p-aminophenyl) ethyl ] urea and 1, 3-bis [2- (p-aminophenyl) ethyl ] -1-t-butoxycarbonyl urea; diamines having a nitrogen-containing unsaturated heterocyclic structure such as N-p-aminophenyl-4-p-aminophenyl (t-butoxycarbonyl) aminomethylpiperidine; diamines having an N-Boc group (Boc means t-butoxycarbonyl) such as N-t-butoxycarbonyl-N- (2- (4-aminophenyl) ethyl) -N- (4-aminobenzyl) amine.

The other diamines may be used in 1 kind or 2 or more kinds in combination depending on the liquid crystal alignment property, sensitivity in polymerization, voltage holding property, accumulated charge and other properties when they are formed into radical generating films.

In the synthesis of the polyamide acid, the tetracarboxylic dianhydride which reacts with the diamine component is not particularly limited. Specifically, there may be mentioned pyromellitic acid, 2,3,6, 7-naphthalene tetracarboxylic acid, 1,2,5, 6-naphthalene tetracarboxylic acid, 1,4,5, 8-naphthalene tetracarboxylic acid, 2,3,6, 7-anthracene tetracarboxylic acid, 1,2,5, 6-anthracene tetracarboxylic acid, 3',4' -biphenyl tetracarboxylic acid, 2, 3',4' -biphenyl tetracarboxylic acid, bis (3, 4-dicarboxyphenyl) ether, 3',4,4' -benzophenone tetracarboxylic acid, bis (3, 4-dicarboxyphenyl) sulfone, bis (3, 4-dicarboxyphenyl) methane, 2-bis (3, 4-dicarboxyphenyl) propane, 1, 3-hexafluoro-2, 2-bis (3, 4-dicarboxyphenyl) propane bis (3, 4-dicarboxyphenyl) dimethylsilane, bis (3, 4-dicarboxyphenyl) diphenylsilane, 2,3,4, 5-pyridinetetracarboxylic acid, 2, 6-bis (3, 4-dicarboxyphenyl) pyridine, 3',4,4' -diphenylsulfone tetracarboxylic acid, 3,4,9, 10-perylene tetracarboxylic acid, 1, 3-diphenyl-1, 2,3, 4-cyclobutanetetracarboxylic acid, oxydiphthalic acid, 1,2,3, 4-cyclobutanetetracarboxylic acid, 1,2,3, 4-cyclopentanetetracarboxylic acid, 1,2,4, 5-cyclohexanedicarboxylic acid, 1,2,3, 4-tetramethyl-1, 2,3, 4-cyclobutanetetracarboxylic acid, 1, 2-dimethyl-1, 2,3, 4-cyclobutanetetracarboxylic acid, 1, 3-dimethyl-1, 2,3, 4-cyclobutanetetracarboxylic acid, 1,2,3, 4-cycloheptanetetracarboxylic acid, 2,3,4, 5-tetrahydrofurantetracarboxylic acid, 3, 4-dicarboxyl-1-cyclohexylsuccinic acid, 2,3, 5-tricarboxyl cyclopentylacetic acid, 3, 4-dicarboxyl-1, 2,3, 4-tetrahydro-1-naphthalenesuccinic acid, 1,2,3, 4-dicarboxyl-1-naphthalenesuccinic acid, bicyclo [3, 0] octane-2, 4,6, 8-tetracarboxylic acid, bicyclo [4,3,0] nonane-2, 4,7, 9-tetracarboxylic acid, bicyclo [4, 0] decane-2, 4,8, 10-tetracarboxylic acid, tricyclo [6.3.0.0<2,6> ] undecane-3,5,9,11-tetracarboxylic acid, 1,2,3, 4-butanetetracarboxylic acid, 4- (2, 5-dioxotetrahydrofuran-3-yl) -1,2,3, 4-tetrahydronaphthalene-1, 2-dicarboxylic acid dianhydrides of tetracarboxylic acids such as bicyclo [2, 2] oct-7-ene-2, 3,5, 6-tetracarboxylic acid, 5- (2, 5-dioxotetrahydrofuranyl) -3-methyl-3-cyclohexane-1, 2-dicarboxylic acid, tetracyclo [6,2,1, 0<2,7> ] dodecane-4, 5,9, 10-tetracarboxylic acid, 3,5, 6-tricarboxydexyl norbornane-2:3, 5:6-dicarboxylic acid, 1,2,4, 5-cyclohexane-tetracarboxylic acid, and the like.

Of course, the tetracarboxylic dianhydride may be used in an amount of 1 or 2 or more in combination depending on the properties such as liquid crystal alignment property, sensitivity during polymerization, voltage holding property, and accumulated charge in the formation of a radical generating film.

In the synthesis of the polyamide acid ester, the structure of the dialkyl tetracarboxylic acid ester to be reacted with the diamine component is not particularly limited, and specific examples thereof are given below.

Specific examples of the aliphatic tetracarboxylic acid diester include: dialkyl 1,2,3, 4-cyclobutane tetracarboxylic acid esters, dialkyl 1, 2-dimethyl-1, 2,3, 4-cyclobutane tetracarboxylic acid esters, dialkyl 1, 3-dimethyl-1, 2,3, 4-cyclobutane tetracarboxylic acid esters, dialkyl 1,2,3, 4-tetramethyl-1, 2,3, 4-cyclobutane tetracarboxylic acid esters, dialkyl 1,2,3, 4-cyclopentane tetracarboxylic acid esters, dialkyl 2,3,4, 5-tetrahydrofuran tetracarboxylic acid esters, dialkyl 1,2,4, 5-cyclohexane tetracarboxylic acid esters, dialkyl 3, 4-dicarboxyl-1-cyclohexylsuccinic acid esters, dialkyl 3, 4-dicarboxyl-1, 2,3, 4-tetrahydro-1-naphthalene succinic acid esters, dialkyl 1,2,3, 4-butane tetracarboxylic acid esters, dialkyl bicyclo [3, 0] octane-2, 4,6, 8-tetracarboxylic acid esters, dialkyl 3,3', 4' -dicyclohexyl tetracarboxylic acid esters, 2, 5-dicarboxyl-1, 4, 5-dicarboxyl-tricarboxylic acid esters, 3, 4-tetra-cyclohexane tetracarboxylic acid esters, 1,3, 4-tetra-butanetetracarboxylic acid esters, 1,3, 4-dicarboxyl-1, 4-butanetetracarboxylic acid esters: 7, 8-dialkyl ester, hexacyclo [6.6.0.1<2,7>.0<3,6>.1<9,14>.0<10,13> ] hexadecane-4,5,11,12-tetracarboxylic acid-4, 5:11, 12-dialkyl esters, dialkyl 4- (2, 5-dioxotetrahydrofuran-3-yl) -1,2,3, 4-tetrahydronaphthalene-1, 2-dicarboxylic acid esters, and the like.

Examples of the dialkyl aromatic tetracarboxylic acid esters include dialkyl pyromellitates, dialkyl 3,3',4' -biphenyltetracarboxylic acid esters, dialkyl 2,2', 3' -biphenyltetracarboxylic acid esters, dialkyl 2, 3', 4-biphenyltetracarboxylic acid esters, dialkyl 3,3',4' -benzophenone tetracarboxylic acid esters, dialkyl 2, 3',4' -benzophenone tetracarboxylic acid esters, dialkyl bis (3, 4-dicarboxyphenyl) ether esters, dialkyl bis (3, 4-dicarboxyphenyl) sulfones,

dialkyl

1,2,5, 6-naphthalene tetracarboxylic acid esters, and

dialkyl

2,3,6, 7-naphthalene tetracarboxylic acid esters.

In the synthesis of the polyurea polymer, the diisocyanate to be reacted with the diamine component is not particularly limited, and may be used in terms of availability and the like. The specific structure of the diisocyanate is shown below.

[ chemical 30]

Wherein R is ₂ And R is ₃ Represents an aliphatic hydrocarbon group having 1 to 10 carbon atoms.

The aliphatic diisocyanates represented by K-1 to K-5 have poor reactivity but have the advantage of improving solvent solubility, and the aromatic diisocyanates represented by K-6 to K-13 have the effect of improving heat resistance while being rich in reactivity, but have the disadvantage of reducing solvent solubility. In terms of versatility and characteristics, K-1, K-7, K-8, K-9, and K-10 are preferable, K-12 is preferable from the viewpoint of electric characteristics, and K-13 is preferable from the viewpoint of liquid crystal alignment. The diisocyanate may be used in combination of 2 or more, and it is preferable to apply various applications depending on the desired properties.

In addition, a part of the diisocyanate may be replaced with the tetracarboxylic dianhydride described above, and the resulting polymer may be used as a copolymer of a polyamic acid and a polyurea, or may be used as a copolymer of a polyimide and a polyurea by chemical imidization.

In the synthesis of the polyamide, the structure of the dicarboxylic acid to be reacted is not particularly limited, but specific examples are given below. Examples of the aliphatic dicarboxylic acid include: dicarboxylic acids such as malonic acid, oxalic acid, dimethylmalonic acid, succinic acid, fumaric acid, glutaric acid, adipic acid, hexadienedioic acid, 2-methyladipic acid, trimethyladipic acid, pimelic acid, 2-dimethylglutaric acid, 3-diethylsuccinic acid, azelaic acid, sebacic acid, and suberic acid.

Examples of the alicyclic dicarboxylic acid include: 1, 1-cyclopropanedicarboxylic acid, 1, 2-cyclopropanedicarboxylic acid, 1-cyclobutanedicarboxylic acid, 1, 2-cyclobutanedicarboxylic acid, 1, 3-cyclobutanedicarboxylic acid, 3, 4-diphenyl-1, 2-cyclobutanedicarboxylic acid, 2, 4-diphenyl-1, 3-cyclobutanedicarboxylic acid, 1-cyclobutene-1, 2-dicarboxylic acid, 1-cyclobutene-3, 4-dicarboxylic acid, 1-cyclopentanedicarboxylic acid, 1, 2-cyclopentanedicarboxylic acid, 1, 3-cyclopentanedicarboxylic acid, 1-cyclohexanedicarboxylic acid, 1, 2-cyclohexanedicarboxylic acid, 1, 3-cyclohexanedicarboxylic acid, 1,4- (2-norbornene) dicarboxylic acid, norbornene-2, 3-dicarboxylic acid, bicyclo [2.2.2] octane-2, 3-dicarboxylic acid, 2, 5-dioxo-1, 4-bicyclo [2.2.2] octane-2, 3-dicarboxylic acid, adamantane dicarboxylic acid, 1, 3-dioctane dicarboxylic acid, adamantane dicarboxylic acid, 3, 6-adamantane dicarboxylic acid, 1, 3-dioctane dicarboxylic acid, 6-adamantane dicarboxylic acid, etc.

Examples of the aromatic dicarboxylic acid include: phthalic acid, isophthalic acid, terephthalic acid, 5-methyl isophthalic acid, 5-tert-butyl isophthalic acid, 5-amino isophthalic acid, 5-hydroxy isophthalic acid, 2, 5-dimethyl terephthalic acid, tetramethyl terephthalic acid, 1, 4-naphthalene dicarboxylic acid, 2, 5-naphthalene dicarboxylic acid, 2, 6-naphthalene dicarboxylic acid, 2, 7-naphthalene dicarboxylic acid, 1, 4-Anthracene dicarboxylic acid, 1, 4-anthraquinone dicarboxylic acid, 2, 5-biphenyldicarboxylic acid, 4' -biphenyldicarboxylic acid, 1, 5-biphenylene dicarboxylic acid, 4' -terphenyl dicarboxylic acid 4,4' -diphenylmethane dicarboxylic acid, 4' -diphenylethane dicarboxylic acid, 4' -diphenylpropane dicarboxylic acid, 4' -diphenylhexafluoropropane dicarboxylic acid 4,4' -diphenyl ether dicarboxylic acid, 4' -dibenzyl dicarboxylic acid, 4' -stilbene dicarboxylic acid, 4' -diphenylacetylene dicarboxylic acid (4, 4' -tolandicarboxylic acid) 4,4' -carbonyl dibenzoic acid, 4' -sulfonyl dibenzoic acid, 4' -dithiodibenzoic acid, p-phenylene diacetic acid, 3' -p-phenylene dipropionic acid 4-carboxycinnamic acid, p-phenylene diacrylate, 3' - [4,4' - (methylenedi-p-phenylene) ] dipropionic acid, 4' - [4,4' - (oxo-di-p-phenylene) ] dibutyric acid, (isopropylidene-di-p-phenylene dioxy) dibutyric acid, dicarboxylic acids such as bis (p-carboxyphenyl) dimethylsilane.

Examples of the dicarboxylic acid containing a heterocycle include: 1,5- (9-oxofluorene) dicarboxylic acid, 3, 4-furandicarboxylic acid, 4, 5-thiazole dicarboxylic acid, 2-phenyl-4, 5-thiazole dicarboxylic acid, 1,2, 5-thiadiazole-3, 4-dicarboxylic acid, 1,2, 5-oxadiazole-3, 4-dicarboxylic acid, 2, 3-pyridinedicarboxylic acid, 2, 4-pyridinedicarboxylic acid, 2, 5-pyridinedicarboxylic acid, 2, 6-pyridinedicarboxylic acid, 3, 4-pyridinedicarboxylic acid, 3, 5-pyridinedicarboxylic acid, and the like.

The above-mentioned dicarboxylic acids may be those having the structure of an acid dihalide or an anhydride. These dicarboxylic acids are particularly preferably dicarboxylic acids which can impart a linear structure to the polyamide, from the viewpoint of maintaining the alignment of the liquid crystal molecules. Among them, it is preferable to use, terephthalic acid, isophthalic acid, 1, 4-cyclohexanedicarboxylic acid, 4' -biphenyldicarboxylic acid, 4' -diphenylmethane dicarboxylic acid, 4' -diphenylethane dicarboxylic acid, 4' -diphenylpropane dicarboxylic acid 4,4' -diphenylhexafluoropropane dicarboxylic acid, 2-bis (phenyl) propane dicarboxylic acid, 4-terphenyl dicarboxylic acid, 2, 6-naphthalene dicarboxylic acid, 2, 5-pyridine dicarboxylic acid, or acid dihalides thereof, and the like. These compounds sometimes exist as isomers and may be mixtures containing them. In addition, 2 or more compounds may be used in combination. The dicarboxylic acids used in the present invention are not limited to the above exemplified compounds.

When the polyamide acid, the polyamide acid ester, the polyurea, and the polyamide are obtained by reacting a diamine (also referred to as "diamine component") as a raw material with a component selected from the group consisting of tetracarboxylic dianhydride (also referred to as "tetracarboxylic dianhydride component"), tetracarboxylic diester, diisocyanate, and dicarboxylic acid as a raw material, a known synthesis method can be used. Generally, the following method is: the diamine component is reacted with one or more components selected from the group consisting of tetracarboxylic dianhydride component, tetracarboxylic diester, diisocyanate and dicarboxylic acid in an organic solvent.

The reaction of the diamine component with the tetracarboxylic dianhydride component is relatively easy to carry out in an organic solvent, and no by-products are produced, which is advantageous in this respect.

The organic solvent used in the above reaction is not particularly limited as long as it is an organic solvent that dissolves the polymer produced. Further, even an organic solvent in which the polymer is not dissolved may be used in combination with the solvent in such a range that the polymer to be produced does not precipitate. Since moisture in the organic solvent may inhibit the polymerization reaction and may cause hydrolysis of the polymer to be produced, it is preferable to use an organic solvent which is dehydrated and dried.

Examples of the organic solvent include: n, N-dimethylformamide, N-dimethylacetamide, N-diethylformamide, N-methylformamide, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, 1, 3-dimethyl-2-imidazolidinone, 3-methoxy-N, N-dimethylpropaneamide, N-methylcaprolactam, dimethyl sulfoxide, tetramethylurea, pyridine, dimethyl sulfone, hexamethylsulfoxide, gamma-butyrolactone, isopropanol, methoxymethylpentanol, dipentene, ethylpentanone, methylnonylketone, methylethylketone, methylisopentone, methylisopropylketone, methyl cellosolve, ethyl cellosolve, methyl cellosolve acetate, butyl cellosolve acetate, ethyl cellosolve acetate, butyl carbitol, ethyl carbitol, ethylene glycol monoacetate, ethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether, propylene glycol monoacetate, propylene glycol, ethylene glycol methyl ethyl acetate, ethylene glycol methyl acetate, propylene glycol methyl acetate, ethylene glycol methyl acetate, ethyl acetate, methyl, ethyl acetate, propylene glycol monomethyl ether, propylene glycol monobutyl ether, propylene glycol-t-butyl ether, dipropylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, diethylene glycol monoacetate, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, dipropylene glycol monoacetate monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monoacetate monoethyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monoacetate monopropyl ether, 3-methyl-3-methoxybutyl acetate, tripropylene glycol methyl ether, 3-methyl-3-methoxybutanol, diisopropyl ether, ethylisobutyl ether, diisobutylene, amyl acetate, butyl butyrate, butyl ether, diisobutyl ketone, methylcyclohexene, propyl ether, dihexyl ether, dioxane, n-hexane, n-pentane, n-octane, diethyl ether, cyclohexanone, ethylene carbonate, propylene carbonate, methyl lactate, ethyl lactate, methyl acetate, ethyl acetate, n-butyl acetate, propylene glycol monoethyl ether acetate, methyl pyruvate, ethyl pyruvate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, 3-ethoxypropionic acid, 3-methoxypropionic acid, propyl 3-methoxypropionate, butyl 3-methoxypropionate, diglyme, 4-hydroxy-4-methyl-2-pentanone, 2-ethyl-1-hexanol, and the like. These organic solvents may be used alone or in combination.

When the diamine component and the tetracarboxylic dianhydride component are reacted in an organic solvent, the following methods are exemplified: a method in which a solution obtained by dispersing or dissolving a diamine component in an organic solvent is stirred, and a tetracarboxylic dianhydride component is added directly or by dispersing or dissolving in an organic solvent; conversely, a method in which a diamine component is added to a solution obtained by dispersing or dissolving a tetracarboxylic dianhydride component in an organic solvent; a method of alternately adding the tetracarboxylic dianhydride component and the diamine component, and the like, and any of these methods may be used. In the case where the diamine component or the tetracarboxylic dianhydride component contains a plurality of compounds, the compounds may be reacted in a state of being mixed in advance, or may be reacted sequentially, or may be further mixed with a low-molecular-weight body obtained by the respective reactions to prepare a high-molecular-weight body. .

The temperature at which the diamine component and the tetracarboxylic dianhydride component are reacted can be arbitrarily selected, and is, for example, in the range of-20 to 100℃and preferably-5 to 80 ℃. The reaction can be carried out at any concentration, and for example, the total amount of the diamine component and the tetracarboxylic dianhydride component is 1 to 50% by mass, preferably 5 to 30% by mass, relative to the reaction solution.

In the polymerization reaction, the ratio of the total mole number of the tetracarboxylic dianhydride component to the total mole number of the diamine component can be arbitrarily selected according to the molecular weight of the polyamic acid to be obtained. As in the case of the usual polycondensation reaction, the molar ratio becomes closer to 1.0, and the molecular weight of the produced polyamic acid becomes larger. The preferable range is 0.8 to 1.2.

The method for synthesizing the polymer used in the present invention is not limited to the above method, and in the case of synthesizing a polyamic acid, a corresponding polyamic acid can be obtained by a known method by reacting a tetracarboxylic acid derivative such as a tetracarboxylic acid or a tetracarboxylic dihalide of a corresponding structure instead of the tetracarboxylic dianhydride, as in the case of a usual method for synthesizing a polyamic acid. In the case of synthesizing polyurea, a diamine may be reacted with a diisocyanate. In the production of the polyamic acid ester or polyamide, a diamine and a component selected from the group consisting of a tetracarboxylic acid diester and a dicarboxylic acid are reacted with a diamine in the presence of a known condensing agent or after being derivatized into an acid halide by a known method.

In addition, polyimide can be obtained by ring-closing (imidizing) the polyamic acid. In the present specification, the imidization ratio refers to the ratio of the imide group to the total amount of imide groups and carboxyl groups derived from tetracarboxylic dianhydride. The imidization ratio of polyimide is not necessarily 100%, and can be arbitrarily adjusted according to the application and purpose. The imidization ratio of the polyimide in the present invention is preferably 30% or more in view of improving the voltage holding ratio, and is preferably 80% or less in view of suppressing the whitening characteristic, that is, the precipitation of the polymer in the varnish.

As a method for imidizing the polyamic acid to form a polyimide, thermal imidization of a solution of the polyamic acid by directly heating the solution, and catalyst imidization of a solution of the polyamic acid by adding a catalyst thereto can be mentioned.

The temperature at which the polyamic acid is thermally imidized in the solution is usually 100 to 400 ℃, preferably 120 to 250 ℃, and is preferably conducted while removing water generated by the imidization reaction from the system.

The catalyst imidization of the polyamic acid can be performed by adding a basic catalyst and an acid anhydride to a solution of the polyamic acid, and stirring the mixture at a temperature of usually-20 to 250 ℃, preferably 0 to 180 ℃. The amount of the basic catalyst is usually 0.5 to 30 mol times, preferably 2 to 20 mol times, that of the amide acid group, and the amount of the acid anhydride is usually 1 to 50 mol times, preferably 3 to 30 mol times, that of the amide acid group. The basic catalyst may be pyridine, triethylamine, trimethylamine, tributylamine, trioctylamine, or the like, and pyridine is preferable because it has an appropriate basicity for the reaction to proceed. The acid anhydride may be acetic anhydride, trimellitic anhydride, pyromellitic anhydride, or the like, and if acetic anhydride is used, purification after completion of the reaction is easy, so that it is preferable. The imidization rate based on catalyst imidization can be controlled by adjusting the catalyst amount and the reaction temperature, the reaction time, and the like.

In the case of recovering the produced polymer from the reaction solution of the polymer, the reaction solution may be put into a poor solvent and precipitated. Examples of the poor solvent for precipitation include methanol, acetone, hexane, butyl cellosolve, heptane, methyl ethyl ketone, methyl isobutyl ketone, ethanol, toluene, benzene, water, and the like. The polymer precipitated by adding the poor solvent may be recovered by filtration and then dried at normal temperature or under reduced pressure, at normal temperature or by heating. In addition, if the operation of redissolving the polymer obtained by precipitation recovery in an organic solvent and reprecipitating recovery is repeated 2 to 10 times, impurities in the polymer can be reduced. Examples of the poor solvent include alcohols, ketones, and hydrocarbons, and if 3 or more of these poor solvents are used, the purification efficiency is further improved, which is preferable.

In addition, in the case where the radical generating film contains a polymer containing an organic group that induces radical polymerization, the radical generating film forming composition used in the present invention may contain other polymers than the polymer containing an organic group that induces radical polymerization. In this case, the content of the other polymer in the total polymer component is preferably 5 to 95% by mass, more preferably 30 to 70% by mass.

In the case of considering the strength of the radical generating film obtained by coating the radical generating film, the operability at the time of forming the coating film, the uniformity of the coating film, and the like, the molecular weight of the polymer of the radical generating film forming composition is preferably 5,000 ～ 1,000,000, more preferably 10,000 ～ 150,000, in terms of the weight average molecular weight measured by GPC (gel permeation chromatography (Gel Permeation Chromatography)) method.

The radical generating film used in the present invention is obtained by coating a composition of a compound having a radical generating group and a polymer and curing the same to form a film, and as the polymer at this time, a polymer selected from the group consisting of a polyimide precursor produced by the above production method, polyimide, polyurea, polyamide, polyacrylate, polymethacrylate, and the like, which is at least 1 polymer obtained by using diamine containing the above radical-inducing polymer-containing organic group as a diamine component for 0 mol% of the total of synthesized diamine components of the polymer contained in the radical generating film forming composition, can be used. Examples of the compound having a radical generating group to be added at this time include the following.

The compound that generates a radical by heat is a compound that generates a radical by heating to a temperature equal to or higher than the decomposition temperature. Examples of such a radical thermal polymerization initiator include: ketone peroxides (methyl ethyl ketone peroxide, cyclohexanone peroxide, etc.), diacyl peroxides (acetyl peroxide, benzoyl peroxide, etc.), hydroperoxides (hydrogen peroxide, t-butyl hydroperoxide, cumene hydroperoxide, etc.), dialkyl peroxides (di-t-butyl peroxide, dicumyl peroxide, dilauroyl peroxide, etc.), ketals (dibutyl cyclohexane peroxide, etc.), alkyl peresters (t-butyl peroxyneodecanoate, t-butyl peroxypivalate, t-amyl peroxy-2-ethylcyclohexanoate, etc.), persulfates (potassium persulfate, sodium persulfate, ammonium persulfate, etc.), azo compounds (azobisisobutyronitrile, 2' -bis (2-hydroxyethyl) azobisisobutyronitrile, etc.). Such radical thermal polymerization initiators may be used alone or in combination of 1 or more than 2 kinds.

The compound that generates a radical by light is not particularly limited as long as it is a compound that starts radical polymerization by light irradiation. Examples of such a radical photopolymerization initiator include: benzophenone, michler's ketone, 4' -bis (diethylamino) benzophenone, xanthone, thioxanthone, isopropylxanthone, 2, 4-diethylthioxanthone, 2-ethylanthraquinone, acetophenone, 2-hydroxy-2-methylbenzophenone, 2-hydroxy-2-methyl-4 '-isopropylacetone, 1-hydroxycyclohexylphenyl ketone, isopropylbenzoin ether, isobutylbenzoin ether, 2-diethoxyacetophenone, 2-dimethoxy-2-phenylacetophenone, camphorquinone, benzanthrone 2-methyl-1- [4- (methylthio) phenyl ] -2-morpholino-1-propanone, 2-benzyl-2-dimethylamino-1- (4-morpholinylphenyl) -butanone-1, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, 4' -di (t-butylperoxycarbonyl) benzophenone, 3,4 '-tri (t-butylperoxycarbonyl) benzophenone, 2,4, 6-trimethylbenzoyl diphenyl phosphine oxide, 2- (4' -methoxystyryl) -4, 6-bis (trichloromethyl) -s-triazine, 2- (3 ',4' -Dimethoxystyryl) -4, 6-bis (trichloromethyl) -s-triazine, 2- (2 ',4' -dimethoxystyryl) -4, 6-bis (trichloromethyl) -s-triazine, 2- (2 '-methoxystyryl) -4, 6-bis (trichloromethyl) -s-triazine, 2- (4' -pentyloxylstyryl) -4, 6-bis (trichloromethyl) -s-triazine, 4- [ p-N, N-bis (ethoxycarbonylmethyl) ] -2, 6-bis (trichloromethyl) -s-triazine, 1, 3-bis (trichloromethyl) -5- (2 '-chlorophenyl) -s-triazine, 1, 3-bis (trichloromethyl) -5- (4' -methoxyphenyl) -s-triazine, 2- (p-dimethylaminostyryl) benzoxazole, 2- (p-dimethylaminostyryl) benzothiazole, 2-mercaptobenzothiazole, 3 '-carbonylbis (7-diethylaminocoumarin), 2- (o-chlorophenyl) -4,4',5,5 '-tetraphenyl-1, 2' -biimidazole, 2 '-bis (2-chlorophenyl) -4,4',5 '-tetrakis (4-ethoxycarbonylphenyl) -1,2' -biimidazole, 2 '-bis (2, 4-dichlorophenyl) -4,4',5,5 '-tetraphenyl-1, 2' -biimidazole, 2 '-bis (2, 4-dibromophenyl) -4,4',5 '-tetraphenyl-1, 2' -biimidazole, 2 '-bis (2, 4, 6-trichlorophenyl) -4,4',5,5 '-tetraphenyl-1, 2' -biimidazole, 3- (2-methyl-2-dimethylaminopropionyl) carbazole, 3, 6-bis (2-methyl-2-morpholinopropionyl) -9-n-dodecylcarbazole, 1-hydroxycyclohexylphenyl ketone, bis (5-2, 4-cyclopentdien-1-yl) -bis (2, 6-difluoro-3- (1H-pyrrol-1-yl) -phenyl) titanium, 3',4' -tetrakis (t-butylperoxycarbonyl) benzophenone, 3',4' -tetrakis (t-hexylperoxycarbonyl) benzophenone, 3 '-bis (methoxycarbonyl) -4,4' -bis (t-butylperoxycarbonyl) benzophenone, 3,4 '-bis (methoxycarbonyl) -4,3' -bis (t-butylperoxycarbonyl) benzophenone, 2- (3-methyl-3H-benzothiazol-2-naphthalen-2-yl) -2-ethanone, 3- (3, 3-ethyl-2-benzoyl) -2-ethanone, or the like. These compounds may be used alone or in combination of 2 or more.

In addition, even in the case where the radical generating film contains a polymer containing an organic group that induces radical polymerization, the compound having a radical generating group may be contained in order to promote radical polymerization when energy is applied.

The radical generating film forming composition may contain an organic solvent which dissolves or disperses the polymer component and contains components other than the radical generator as needed. Such an organic solvent is not particularly limited, and examples thereof include organic solvents exemplified in the synthesis of the polyamic acid described above. Among them, from the viewpoint of solubility, N-methyl-2-pyrrolidone, γ -butyrolactone, N-ethyl-2-pyrrolidone, 1, 3-dimethyl-2-imidazolidinone, 3-methoxy-N, N-dimethylpropane amide and the like are preferable. N-methyl-2-pyrrolidone or N-ethyl-2-pyrrolidone is particularly preferable, and a mixed solvent of two or more kinds may be used.

In addition, it is preferable to use a solvent that improves the uniformity and smoothness of the coating film in combination with an organic solvent having high solubility of the component containing the radical-generating film-forming composition.

Examples of the solvent that improves the uniformity and smoothness of the coating film include: isopropyl alcohol, methoxy methyl amyl alcohol, methyl cellosolve, ethyl cellosolve, butyl cellosolve (ethylene glycol monobutyl ether), methyl cellosolve acetate, butyl cellosolve acetate, ethyl cellosolve acetate butyl carbitol, ethyl carbitol acetate, ethylene glycol monoacetate, ethylene glycol monoisopropyl ether, propylene glycol monoacetate propylene glycol monomethyl ether, propylene glycol monobutyl ether, propylene glycol-t-butyl ether, dipropylene glycol monomethyl ether, diethylene glycol monoacetate, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, dipropylene glycol monoacetate monomethyl ether, dipropylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, dipropylene glycol monoethyl ether, dipropylene glycol monoacetate monoethyl ether, ethylene glycol dipropylene glycol monopropyl ether, dipropylene glycol monoacetate monopropyl ether, 3-methyl-3-methoxybutyl acetate, tripropylene glycol methyl ether, 3-methyl-3-methoxybutanol, diisopropyl ether, ethylisobutyl ether, diisobutylene, amyl acetate, butyl butyrate, butyl ether, diisobutyl ketone, methylcyclohexene, propyl ether, dihexyl ether, n-hexane, n-pentane, n-octane, diethyl ether, methyl lactate, ethyl lactate, n-propyl lactate, n-butyl lactate, isoamyl lactate, methyl acetate, ethyl acetate, n-butyl acetate, propylene glycol monoethyl ether acetate, methyl pyruvate, ethyl pyruvate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, 3-ethoxypropionic acid, 3-methoxypropionic acid, propyl 3-methoxypropionate, butyl 3-methoxypropionate, 1-methoxy-2-propanol, 1-ethoxy-2-propanol, 1-butoxy-2-propanol, 1-phenoxy-2-propanol, propylene glycol diacetate, propylene glycol-1-monomethyl ether-2-acetate, propylene glycol-1-monoethyl ether-2-acetate, dipropylene glycol, 2- (2-ethoxypropoxy) propanol, 2-ethyl-1-hexanol, and the like. These solvents may be mixed in plural. When these solvents are used, the total amount of the solvents contained in the radical-generating film-forming composition is preferably 5 to 80% by mass, more preferably 20 to 60% by mass.

The radical generating film forming composition may contain components other than those described above. As an example thereof, there may be mentioned: a compound that improves film thickness uniformity and surface smoothness when the radical generating film forming composition is applied, a compound that improves adhesion between the radical generating film forming composition and the substrate, a compound that further improves film strength of the radical generating film forming composition, and the like.

Examples of the compound for improving film thickness uniformity and surface smoothness include a fluorine-based surfactant, a silicone-based surfactant, and a nonionic surfactant. More specifically, examples thereof include: EFTOP EF301, EF303, EF352 (manufactured by Mitsubishi materials electronics Co., ltd.), MEGAFAC F171, F173, R-30 (manufactured by DIC Co., ltd.), fluoro FC430, FC431 (manufactured by 3M Co., ltd.), asahigivard AG710, SURFION S-382, SC101, SC102, SC103, SC104, SC105, SC106 (manufactured by AGC Co., ltd.), and the like. When these surfactants are used, the use ratio thereof is preferably 0.01 to 2 parts by mass, more preferably 0.01 to 1 part by mass, relative to 100 parts by mass of the total amount of the polymers contained in the radical-generating film-forming composition.

Specific examples of the compound for improving the adhesion between the radical generating film forming composition and the substrate include a compound containing a functional silane and a compound containing an epoxy group. Examples include: 3-aminopropyl trimethoxysilane, 3-aminopropyl triethoxysilane, 2-aminopropyl trimethoxysilane, 2-aminopropyl triethoxysilane, N- (2-aminoethyl) -3-aminopropyl trimethoxysilane, N- (2-aminoethyl) -3-aminopropyl methyldimethoxysilane, 3-ureidopropyl trimethoxysilane, 3-ureidopropyl triethoxysilane, N-ethoxycarbonyl-3-aminopropyl trimethoxysilane, N-ethoxycarbonyl-3-aminopropyl triethoxysilane, N-triethoxysilylpropyl trivinyltriamine, N-trimethoxysilylpropyl trivinyltriamine, 10-trimethoxysilyl-1, 4, 7-triazadecane, 10-triethoxysilyl-1, 4, 7-triazadecane, 9-trimethoxysilyl-3, 6-diazanonylacetic acid ester, 9-triethoxysilyl-3, 6-diazanonylacetic acid ester, N-benzyl-3-aminopropyl trimethoxysilane, N-benzyl-3-aminopropyl triethoxysilane, N-phenyl3-aminopropyl-triethoxysilane, N-trimethoxysilyl-1, 4, 7-triazadecane, 9-trimethoxysilyl-3, 6-diazanonylpropyl-3, 9-triethoxysilane, N-benzyl-3-aminopropyl trimethoxysilane, N-aminopropyl silane, 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-dibromoneopentyl glycol diglycidyl ether, 1,3,5, 6-tetraglycidyl-2, 4-hexanediol, N, N, N ' -tetraglycidyl-m-xylylenediamine, 1, 3-bis (N, N-diglycidyl aminomethyl) cyclohexane, N ' -tetraglycidyl-4, 4' -diaminodiphenylmethane, 3- (N-allyl-N-glycidyl) aminopropyl trimethoxysilane, 3- (N, N-diglycidyl) aminopropyl trimethoxysilane, and the like.

In order to further improve the film strength of the radical generating film, phenol compounds such as 2,2' -bis (4-hydroxy-3, 5-dihydroxymethylphenyl) propane and tetrakis (methoxymethyl) bisphenol may be added. In the case of using these compounds, the amount is preferably 0.1 to 30 parts by mass, more preferably 1 to 20 parts by mass, relative to 100 parts by mass of the total amount of the polymers contained in the radical-generating film-forming composition.

Further, in addition to the above, a dielectric or conductive substance for changing the dielectric constant, conductivity, or other electrical characteristics of the radical generating film may be added to the radical generating film in a range not to impair the effects of the present invention.

[ free radical generating film ]

The radical generating film of the present invention can be obtained, for example, by using the above radical generating film-forming composition. For example, the radical generating film-forming composition used in the present invention may be applied to a substrate, dried, and sintered to obtain a cured film, or the cured film may be used as a radical generating film as it is. The cured film may be subjected to alignment treatment by rubbing, irradiation of polarized light, light of a specific wavelength, or the like, or treatment with an ion beam, or the like, to prepare an alignment film for PSA, and then UV may be irradiated to a liquid crystal display element filled with liquid crystal.

The substrate to which the radical generating film-forming composition is applied is not particularly limited as long as it is a substrate having high transparency, and a substrate having a transparent electrode for driving liquid crystal formed thereon is preferable.

Specific examples thereof include substrates having transparent electrodes formed on plastic sheets such as glass sheets, polycarbonate, poly (meth) acrylate, polyethersulfone, polyarylate, polyurethane, polysulfone, polyether, polyetherketone, trimethylpentene, polyolefin, polyethylene terephthalate, (meth) acrylonitrile, triacetyl cellulose, diacetyl cellulose, and cellulose acetate butyrate.

In the substrate usable in the IPS mode liquid crystal display device, an electrode pattern such as a standard IPS comb-tooth electrode or PSA fishbone electrode, or a protrusion pattern such as MVA can be used.

In addition, in a high-function element such as a TFT-type element, a component in which an element such as a transistor is formed between an electrode for driving liquid crystal and a substrate can be used.

In the case of targeting a transmissive liquid crystal display element, the substrate described above is generally used, but in the case of targeting a reflective liquid crystal display element, if it is a single-sided substrate only, an opaque substrate such as a silicon wafer may be used. In this case, a material such as aluminum that reflects light may be used for the electrode formed on the substrate.

Examples of the method for applying the radical-generating film-forming composition include spin coating, printing, inkjet, spray, and roll coating, and transfer printing is widely used industrially from the viewpoint of productivity and is also suitably used in the present invention.

The drying step after the application of the radical generating film forming composition is not necessarily required, but it is preferable to include the drying step in the case where the time from the application to the firing is not fixed on each substrate or in the case where the firing is not immediately performed after the application. The drying is not particularly limited as long as the solvent is removed to such an extent that the shape of the coating film is not deformed by transportation of the substrate or the like. For example, the following methods are mentioned: drying for 0.5 to 30 minutes, preferably 1 to 5 minutes, on a hot plate at a temperature of 40 to 150 ℃, preferably 60 to 100 ℃.

The coating film formed by applying the radical generating film forming composition by the above method can be made into a cured film by sintering. In this case, the sintering temperature may be usually carried out at any temperature of 100 to 350 ℃, preferably 140 to 300 ℃, more preferably 150 to 230 ℃, and even more preferably 160 to 220 ℃. For the sintering time, sintering may be generally performed in any time of 5 to 240 minutes. Preferably 10 to 90 minutes, more preferably 20 to 90 minutes. The heating can be performed by a generally known method, for example, a hot plate, a hot air circulation oven, an IR (infrared) oven, a belt furnace, or the like.

The thickness of the cured film may be selected as required, but is preferably 5nm or more, more preferably 10nm or more, and in this case, the reliability of the liquid crystal display element is improved. In addition, the thickness of the cured film is preferably 300nm or less, more preferably 150nm or less, because the power consumption of the liquid crystal display element does not become extremely large.

The first substrate having the radical generating film may be obtained in the above manner, but the radical generating film may be subjected to a uniaxial orientation treatment. Examples of the method for performing the uniaxial orientation treatment include a photo orientation method, a tilt vapor deposition method, friction, and a uniaxial orientation treatment by a magnetic field.

When the alignment treatment is performed by performing the rubbing treatment in one direction, for example, the rubbing roller around which the rubbing cloth is wound is rotated, and the substrate is moved so that the rubbing cloth contacts the film. In the case of using the photo-alignment method, the alignment treatment can be performed by irradiating the entire surface of the film with polarized UV light having a specific wavelength and heating the film as necessary.

In the case of the first substrate of the present invention on which the comb-teeth electrodes are formed, the direction may be selected according to the electric properties of the liquid crystal, but in the case of using the liquid crystal having positive dielectric anisotropy, it is preferable that the rubbing direction be substantially the same as the direction in which the comb-teeth electrodes extend.

As a process for producing the weak anchor and the strong anchor, a method of irradiating radiation in an arbitrary pattern through a photomask or the like is given. The method is a step of irradiating the radical generating film with radiation in advance to eliminate the radical generating site, and thus the weak anchoring state is not formed. Examples of the radiation used in the step include polarized light, light of a specific wavelength, and ion beam. Particularly, light having a wavelength at which absorbance of the corresponding portion reaches the highest is preferably irradiated to the photoradical generation site.

The second substrate of the present invention may or may not have a radical generating film. The second substrate is preferably a conventionally known substrate having a liquid crystal alignment film.

In the present invention, the first substrate may be a substrate having comb-teeth electrodes, and the second substrate may be a counter substrate. In the present invention, the second substrate may be a substrate having comb-teeth electrodes, and the first substrate may be a counter substrate.

< liquid Crystal cell >)

After forming a radical generating film on a substrate by the above method, the liquid crystal cell of the present invention is obtained by disposing the substrate (first substrate) having the radical generating film and a known substrate (second substrate) having a liquid crystal alignment film so that the radical generating film and the liquid crystal alignment film face each other, sandwiching a spacer, fixing the spacer with a sealant, and injecting a liquid crystal composition containing a liquid crystal and a radical polymerizable compound, and sealing the resulting mixture. In this case, the size of the spacer used is usually 1 to 30. Mu.m, preferably 2 to 10. Mu.m.

The method of injecting the liquid crystal composition containing the liquid crystal and the radical polymerizable compound is not particularly limited, and examples thereof include: a vacuum method of depressurizing the inside of the liquid crystal cell to inject a mixture containing a liquid crystal and a polymerizable compound; and a dropping method in which a mixture containing a liquid crystal and a polymerizable compound is dropped and then sealed.

Radical polymerizable Compound and liquid Crystal composition

The radically polymerizable compound of the present invention is represented by the following formula (A).

[ 31]

The alkylene group having 1 to 6 carbon atoms with a bonding group interposed therebetween means a 2-valent group having a bonding group interposed between carbon and carbon in the alkylene group having 1 to 6 carbon atoms, or a 2-valent group having a bonding group interposed between the alkylene group having 1 to 6 carbon atoms and the carbon atom bonded thereto.

As a group of the bonding group(s), examples thereof include a carbon-carbon unsaturated bond, an ether bond (-O-): ester bond (-COO-or-OCO-), amide bond (-CONH-or-NHCO-), etc. Examples of the unsaturated bond include a carbon-carbon double bond, but an alkylene group having 1 to 6 carbon atoms, which has a carbon-carbon double bond inserted therein, preferably has a carbon-carbon double bond in the interior, and is not at the terminal thereof.

Examples of the alkylene group having 1 to 6 carbon atoms into which the bonding group can be inserted include an alkylene group having 1 to 6 carbon atoms, an oxyalkylene group having 1 to 6 carbon atoms, and the like. The oxygen atom in the oxyalkylene group having 1 to 6 carbon atoms is, for example, the same as M, R in the formula (A) ₁ 、R ₂ And R is ₃ The bonded carbon atoms are bonded.

The alkylene group having 1 to 6 carbon atoms may be a linear alkylene group, a branched alkylene group or a cyclic alkylene group.

Examples of the aromatic hydrocarbon group which may have a substituent include a phenyl group and a naphthyl group which may have a substituent.

Examples of the substituent include a halogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a haloalkyl group having 1 to 4 carbon atoms, and a haloalkoxy group having 1 to 4 carbon atoms. The halogenation of the haloalkyl and haloalkoxy groups may be perhalogenation or may be a partial halogenation. Examples of the halogen atom include a fluorine atom and a chlorine atom.

As R ₁ Examples thereof include a single bond and an alkylene group having 1 to 6 carbon atoms. The alkylene group having 1 to 6 carbon atoms is more specifically a linear alkylene group having 1 to 6 carbon atoms.

As R ₂ Examples thereof include a single bond and an alkylene group having 1 to 6 carbon atoms. The alkylene group having 1 to 6 carbon atoms is more specifically a linear alkylene group having 1 to 6 carbon atoms.

As R ₃ Examples thereof include a single bond and an alkylene group having 1 to 6 carbon atoms. The alkylene group having 1 to 6 carbon atoms is more specifically a linear alkylene group having 1 to 6 carbon atoms.

As X ₁ Examples thereof include a hydrogen atom and a phenyl group.

As X ₂ Examples thereof include a hydrogen atom and a phenyl group.

A _r Examples thereof include phenyl groups.

R ₁ X ₁ 、R ₂ X ₂ R is R ₃ The total number of carbon atoms of (2) is not particularly limited as long as it is 1 or more.

In addition, R ₁ 、R ₂ R is R ₃ The total number of carbon atoms of (2) may be 18 or less, 15 or less, or 10 or less, for example.

In addition, at X ₁ X is X ₂ In the case of a hydrogen atom, as long as R ₁ 、R ₂ R is R ₃ The total number of carbon atoms of (2) is not particularly limited, and may be 1 or more.

In the case of X ₁ X is X ₂ In the case where at least one of them is an aromatic hydrocarbon group which may have a substituent, R ₁ 、R ₂ R is R ₃ The total number of carbon atoms of (2) may be 0.

As R ₁ X ₁ 、R ₂ X ₂ Bonded to R ₁ X ₁ And R is ₂ X ₂ Examples of the ring formed by the carbon atoms of (a) include hydrocarbon rings having 3 to 13 carbon atoms into which a bonding group can be inserted. The bonding groups are as described above.

Examples of the radically polymerizable compound represented by the formula (A) include radically polymerizable compounds represented by the following formulas (A-1) to (A-3).

[ chemical 32]

Wherein M represents a polymerizable group capable of radical polymerization,

R ₁ ～R ₃ each independently represents a single bond or an alkylene group having 1 to 6 carbon atoms which may be inserted into the bonding group,

Ar、Ar ₁ ar and Ar ₂ Each independently represents an aromatic hydrocarbon group which may have a substituent,

R ₁₁ r is R ₁₂ Each independently represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms which may be inserted into the bonding group.

In the formula (A-1), R ₁₁ 、R ₁₂ Bonded to R ₁₁ And R is ₁₂ Together may form a ring.

In the formula (A-1), R ₁₁ 、R ₁₂ And R is ₃ The total number of carbon atoms of (2) may be 1 or more. The total number of carbon atoms may be 18 or less, 15 or less, or 10 or less.

In the formula (A-2), R ₁ 、R ₁₂ And R is ₃ The total number of carbon atoms in (a) is not particularly limited, and may be 0. The total number of carbon atoms may be 18 or less, 15 or less, or 10 or less, for example.

In the formula (A-3), R ₁ 、R ₂ And R is ₃ The total number of carbon atoms in (a) is not particularly limited, and may be 0. The total number of carbon atoms may be 18 or less, 15 or less, or 10 or less, for example.

R is as follows ₁₁ Is R ₁ X ₁ Middle X ₁ In the case of a hydrogen atom. R is R ₁₂ Is R ₂ X ₂ Middle X ₂ In the case of a hydrogen atom.

The radically polymerizable group M of the radically polymerizable compound is preferably a polymerizable group selected from the following structures.

[ 33]

Examples of the radical polymerizable compound contained in the formula (A) and the formula (A-1) include the following radical polymerizable compounds.

[ chemical 34]

(i) Add-1 corresponds to formula (A) wherein M is of the following structure (C), R ₁ X ₁ Is 1-amyl, R ₂ Is a single bond, X ₂ Is a hydrogen atom, R ₃ A combination of a single bond and Ar being phenyl.

(ii) Add-3 corresponds to formula (A) wherein M is a structure (B) or R ₁ X ₁ Is 1-propyl, R ₂ Is a single bond, X ₂ Is a hydrogen atom, R ₃ A combination of a single bond and Ar being phenyl.

(iii) Add-6 corresponds to formula (A) wherein M is of the following structure (C), R ₁ X ₁ Is ethyl, R ₂ X ₂ Is ethyl, R ₃ A combination of 1, 2-ethylene and Ar is phenyl.

(iv) Add-8 corresponds to formula (A) wherein M is of the following structure (C), R ₁ X ₁ Is 1-propyl, R ₂ Is a single bond, X ₂ Is a hydrogen atom, R ₃ A combination of 1, 2-ethylene and Ar is phenyl.

(v) Add-12 corresponds to formula (A) wherein M is of the following structure (D), R ₁ Is a single sheetBond, X ₁ Is a hydrogen atom, R ₂ Is a single bond, X ₂ Is a hydrogen atom, R ₃ A combination of 1, 2-ethylene and Ar is phenyl.

[ 35]

(Structure (B), structure (C) and Structure (D) represents a bonding site;)

The liquid crystal composition contains at least a liquid crystal and the radical polymerizable compound.

The content of the radical polymerizable compound in the liquid crystal composition is preferably 0.5 mass% or more, more preferably 1 mass% or more, preferably 10 mass% or less, more preferably 5 mass% or less, based on the total mass of the liquid crystal and the radical polymerizable compound.

In addition, a plurality of other compounds having a monofunctional radical polymerizable group (hereinafter, sometimes referred to as "other radical polymerizable compounds") may be used in combination in the liquid crystal composition, unlike the above-described radical polymerizable compounds.

Other radical polymerizable compounds have an unsaturated bond capable of undergoing radical polymerization in the presence of an organic radical, and examples thereof include: methacrylate monomers such as t-butyl methacrylate, hexyl methacrylate, 2-ethylhexyl methacrylate, nonyl methacrylate, lauryl methacrylate, and n-octyl methacrylate; acrylic ester monomers such as t-butyl acrylate, hexyl acrylate, 2-ethylhexyl acrylate, nonyl acrylate, lauryl acrylate and n-octyl acrylate; vinyl monomers such as styrene, styrene derivatives (e.g., o-, m-, p-methoxystyrene, o-, m-, p-butoxystyrene, o-, m-, p-chloromethylstyrene, etc.), vinyl esters (e.g., vinyl acetate, vinyl propionate, vinyl benzoate, etc.), vinyl ketones (e.g., vinyl methyl ketone, vinyl hexyl ketone, methyl isopropenyl ketone, etc.), N-vinyl compounds (e.g., N-vinyl pyrrolidone, N-vinyl pyrrole, N-vinyl carbazole, N-vinyl indole, etc.), and (meth) acrylic derivatives (e.g., acrylonitrile, methacrylonitrile, acrylamide, isopropylacrylamide, methacrylamide, etc.), vinyl halides (e.g., vinyl chloride, vinylidene chloride, tetrachloroethylene, hexachloroprene, vinyl fluoride, etc.), but are not limited thereto. In addition, these compounds are preferably compatible with liquid crystals.

Further, as the other radical polymerizable compound, a compound represented by the following formula (1) is also preferable.

[ 36]

(in the formula (1), R ^a And R is ^b Each independently represents a linear alkyl group having 2 to 8 carbon atoms, E represents a member selected from the group consisting of single bonds, -O-, -NR ^c -a bonding group in the group consisting of S-, ester bonds and amide bonds. R is R ^c Represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. )

At least one of the radical polymerizable compounds contained in the liquid crystal composition is preferably a compound having one polymerizable unsaturated bond in one molecule, that is, a compound having a monofunctional radical polymerizable group, which has compatibility with the liquid crystal.

The radical polymerizable compound represented by the formula (1) is not particularly limited, but is preferably a compound in which E is an ester bond (—c (=o) -O-or-O-C (=o) -bond), and more preferably a compound represented by the following structure, from the viewpoints of ease of synthesis, compatibility with liquid crystal, and polymerization reactivity.

[ 37]

The liquid crystal composition preferably contains a radical polymerizable compound having a Tg of 100 ℃ or less, which is a polymer obtained by polymerizing a radical polymerizable compound.

These various radically polymerizable monomers may be used alone or in combination of 2 or more. In addition, these monomers preferably have compatibility with liquid crystals.

The Tg of the polymer obtained by polymerizing the radical polymerizable compound is preferably 100℃or lower, more preferably 0℃or lower.

The liquid crystal is generally a substance in a state of exhibiting properties of both solid and liquid, and a typical liquid crystal phase is nematic liquid crystal and smectic liquid crystal, and the liquid crystal usable in the present invention is not particularly limited. For example, 4-pentyl-4' -cyanobiphenyl.

Next, sufficient energy is applied to the liquid crystal cell into which the mixture (liquid crystal composition) containing the liquid crystal and the radical polymerizable compound is introduced to cause the radical polymerizable compound to undergo polymerization reaction. This can be performed, for example, by applying heat or UV irradiation, and the radically polymerizable compound is polymerized in this case, thereby exhibiting desired characteristics. Among them, UV irradiation is preferable in that patterning of orientation is possible and further polymerization is performed in a short time.

In addition, heating may be performed during UV irradiation. The heating temperature during the UV irradiation is preferably in a temperature range where the introduced liquid crystal exhibits liquid crystallinity, and is usually 40 ℃ or higher, preferably at a temperature lower than the temperature at which the liquid crystal becomes isotropic phase.

The wavelength of UV irradiation at the time of UV irradiation is preferably selected so that the reaction quantum yield of the polymerizable compound to be reacted is at the highest, and the UV irradiation amount is usually 0.01 to 30J/cm ² Preferably 10J/cm ² Hereinafter, when the UV irradiation amount is small, it is preferable to increase the period of time in manufacturing by reducing the UV irradiation time while suppressing a decrease in reliability including damage to the members constituting the liquid crystal display.

In addition, the heating in the case of performing polymerization only by heating without UV irradiation is preferably performed in a temperature range of a reaction temperature of the polymerizable compound and less than a decomposition temperature of the liquid crystal. Specifically, the temperature is 100-150 ℃.

When sufficient energy is applied to polymerize the radical polymerizable compound, it is preferable that no electric field is applied to the radical polymerizable compound.

< liquid Crystal display element >)

The liquid crystal cell obtained in the above manner can be used to manufacture a liquid crystal display element.

The liquid crystal display device includes, for example, a first substrate, a second substrate disposed opposite to the first substrate, and liquid crystal filled between the first substrate and the second substrate. The liquid crystal display element is formed by polymerizing a radical polymerizable compound in a state in which a liquid crystal composition containing a liquid crystal and the radical polymerizable compound represented by formula (a) is brought into contact with a radical generating film of a first substrate having the radical generating film.

For example, a reflective liquid crystal display element can be produced by providing a reflective electrode, a transparent electrode, a λ/4 plate, a polarizing film, a color filter layer, and the like as necessary in a liquid crystal cell according to a conventional method. In addition, a backlight, a polarizing plate, a λ/4 plate, a transparent electrode, a polarizing film, a color filter layer, and the like can be provided as needed in a liquid crystal cell according to a conventional method, thereby manufacturing a transmissive liquid crystal display element.

Fig. 1 is a schematic cross-sectional view showing an example of a transverse electric field liquid crystal display element of the present invention, which is an example of an IPS mode liquid crystal display element.

In the transverse electric field liquid crystal display element 1 illustrated in fig. 1, the liquid crystal 3 is sandwiched between the comb-teeth electrode substrate 2 provided with the liquid crystal alignment film 2c and the counter substrate 4 provided with the liquid crystal alignment film 4a. The comb-teeth electrode substrate 2 has: a base material 2a, a plurality of linear electrodes 2b formed on the base material 2a and arranged in a comb-like shape, and a liquid crystal alignment film 2c formed on the base material 2a so as to cover the linear electrodes 2 b. The counter substrate 4 has a base material 4b and a liquid crystal alignment film 4a formed on the base material 4 b. The liquid crystal alignment film 2c is, for example, a weak anchor film obtained by chemically changing a radical generating film. The liquid crystal alignment film on the comb-shaped electrode substrate side is obtained by, for example, polymerizing a radical polymerizable compound in a state where a liquid crystal composition containing a liquid crystal and the radical polymerizable compound is brought into contact with a radical generating film.

In the transverse electric field liquid crystal display element 1, if a voltage is applied to the linear electrodes 2b, an electric field is generated between the linear electrodes 2b as indicated by the electric field lines L.

Fig. 2 is a schematic cross-sectional view showing other examples of the transverse electric field liquid crystal display element of the present invention, which is an example of an FFS mode liquid crystal display element.

In the transverse electric field liquid crystal display element 1 illustrated in fig. 2, the liquid crystal 3 is sandwiched between the comb-teeth electrode substrate 2 provided with the liquid crystal alignment film 2h and the counter substrate 4 provided with the liquid crystal alignment film 4a. The comb-teeth electrode substrate 2 includes a base material 2d, a surface electrode 2e formed on the base material 2d, an insulating film 2f formed on the surface electrode 2e, a plurality of linear electrodes 2g formed on the insulating film 2f and arranged in a comb-teeth shape, and a liquid crystal alignment film 2h formed on the insulating film 2f so as to cover the linear electrodes 2 g. The counter substrate 4 has a base material 4b and a liquid crystal alignment film 4a formed on the base material 4 b. The liquid crystal alignment film 2h is, for example, a weak anchor film obtained by chemically changing a radical generating film. The liquid crystal alignment film on the comb-shaped electrode substrate side is obtained by, for example, polymerizing a radical polymerizable compound in a state where a liquid crystal composition containing a liquid crystal and the radical polymerizable compound is brought into contact with a radical generating film.

In the transverse electric field liquid crystal display element 1, if a voltage is applied to the surface electrode 2e and the linear electrode 2g, an electric field is generated between the surface electrode 2e and the linear electrode 2g as indicated by the electric field lines L.

Examples

The present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples. The abbreviations of the compounds and the measurement methods of the respective properties are as follows.

(diamine)

DA-1 to DA-5: compounds represented by the following formulas (DA-1) to (DA-5)

[ 38]

(tetracarboxylic dianhydride)

TC-1 to TC-3: compounds represented by the following formulas (TC-1) to (TC-3)

[ 39]

(additive)

Add-1 to Add-12: compounds represented by the following formulas (Add-1) to (Add-12)

Add-C1 to Add-C3: compounds represented by the following formulas (Add-C1) to (Add-C3)

AD-1: a compound represented by the following formula (AD-1)

[ 40]

[ chemical 41]

(solvent)

THF: tetrahydrofuran (THF)

CH ₂ Cl ₂ : dichloromethane (dichloromethane)

CHCl ₃ : chloroform (chloroform)

NMP: n-methyl-2-pyrrolidone

BCS: butyl cellosolve

GBL: gamma-butyrolactone

(reagent)

TEA: triethylamine

DMAP: 4-dimethylaminopyridine

(others)

BHT: dibutyl hydroxy toluene

< measurement of viscosity >

The viscosity of the polyamic acid solution was measured using an E-type viscometer TVE-22H (manufactured by DONGMACHINE Co., ltd.) under conditions of a sample size of 1.1mL (milliliter), a conical rotor TE-1 (1 DEG 34', R24), and a temperature of 25 ℃.

< determination of molecular weight >

Molecular weights of the polyimide precursor, polyimide and the like were measured using a normal temperature Gel Permeation Chromatography (GPC) apparatus (GPC-101) (manufactured by Showa Denko Co., ltd.), and columns (GPC KD-803, GPC KD-805) (manufactured by Showa Denko Co., ltd.).

Column temperature: 50 DEG C

Eluent: n, N-dimethylformamide (as an additive, lithium bromide monohydrate (libr.h) ₂ O) 30mmol/L, phosphoric acid/anhydrous crystals (orthophosphoric acid) 30mmol/L, tetrahydrofuran (THF) 10mL/L

Flow rate: 1.0 mL/min

Standard sample for standard curve preparation: TSK-standard polyethylene oxide (molecular weight: about 900,000, 150,000, 100,000 and 30,000) (manufactured by Tosoh Co., ltd.) and polyethylene glycol (molecular weight: about 12,000, 4,000 and 1,000) (manufactured by Polymer Laboratories Co.).

< determination of imidization Rate >)

20mg of polyimide powder was placed in an NMR sample tube (sample tube size: NMR available from Katsuji Co., ltd.)

) In (3), deuterated dimethyl sulfoxide (DMSO-d) ₆ 0.05 mass% Tetramethylsilane (TMS) mixture) 1.0mL, and was completely dissolved by applying ultrasonic waves. For this solution, proton NMR at 500MHz was measured by using a Fourier transform type superconducting nuclear magnetic resonance apparatus (FT-NMR) 'AVANCE III' (manufactured by BRUKER).

The chemical imidization rate is determined by using protons derived from structures that do not change before and after imidization as reference protons, and is determined by using the peak cumulative value of the protons and the peak cumulative value of protons derived from NH groups of amic acid occurring in the vicinity of 9.5 to 10.0 ppm. In the formula, x is a proton peak integrated value of NH group derived from amic acid, y is a peak integrated value of reference proton, and α is a number ratio of reference proton to 1 proton of NH group of amic acid in the case of polyamic acid (imidization ratio is 0%).

Imidization ratio (%) = (1- α·x/y) ×100

Synthesis of an additive for Weak anchoring IPS

The passage of the products described in the following Synthesis examples ¹ H-NMR analysis identified (analysis conditions were as follows).

The device comprises: a Fourier transform superconducting nuclear magnetic resonance apparatus (FT-NMR) 'AVANCE III' (manufactured by BRUKER) was 500MHz.

Solvent: CDCl ₃ (deuterated chloroform) or DMSO-d ₆ (deuterated dimethyl sulfoxide).

Reference substance: tetramethylsilane (TMS) (δ0.0ppm for) ¹ H)。

Synthesis example 1 Synthesis of Add-1 (1-phenylhexyl methacrylate (1-phenylhexyl methacrylate))

[ chemical 42]

1-phenyl-1-hexanol (1-phenyl-1-hexanol) (25.0 g:0.140 mol), TEA (21.3 g:0.210 mol) and CH were weighed into a 500mL four-necked flask equipped with a stirrer ₂ Cl ₂ (300 mL) and allowed to dissolve. After the solution was cooled to 0℃in an ice bath, methacryloyl chloride (methacryloyl chloride) (16.1 g:0.155 mol) was slowly added dropwise while keeping the internal temperature below 5℃and the temperature was returned to room temperature and stirred for 18 hours. After confirming the completion of the reaction by HPLC, ethyl acetate (200 mL) was added to the reaction solution, which was washed 3 times with a 10% aqueous solution of potassium carbonate (100 mL) using a separating funnel, and 3 times with pure water (100 mL). After washing, dehydration was performed with magnesium sulfate, and solvent was distilled off using a rotary evaporator, whereby a crude product was obtained. Purification was performed by silica gel column chromatography (developing solvent: n-hexane/ethyl acetate=8/2 (capacity ratio)), and Add-1 (29.3 g: yield 82%) was obtained by solvent distillation and vacuum drying. By passing through ¹ H-NMR measurement was confirmed to be the target. BHT (0.01 mol% in the polymerization inhibitor) was added.

¹ H-NMR(500MHz)in DMSO-d ₆ ：7.35-7.27(5H)、6.01(1H)、5.75-5.72(1H)、5.69(1H)、1.90-1.85(3H)、1.79-1.85(2H)、1.25-1.18(6H)、0.83-0.82(3H)[ppm]

Synthesis example 2 Synthesis of Add-2 (1-phenylbutyl methacrylate (1-phenylbutyl methacrylate))

[ chemical 43]

1-phenyl-1-butanol (25.0 g:0.166 mol), TEA (25.3 g:0.250 mol) and CH were weighed into a 500mL four-necked flask equipped with a stirrer ₂ Cl ₂ (300 mL) and allowed to dissolve. After the solution was cooled to 0℃in an ice bath, methacryloyl chloride (methacryloyl chloride) (20.8 g: 0.199mol) was slowly added dropwise while keeping the internal temperature below 5℃and the temperature was returned to room temperature and stirred for 18 hours. After confirming the completion of the reaction by HPLC, ethyl acetate (200 mL) was added to the reaction solution, which was washed 3 times with a 10% aqueous solution of potassium carbonate (100 mL) using a separating funnel, and 3 times with pure water (100 mL). After washing, dehydration was performed with magnesium sulfate, and solvent was distilled off using a rotary evaporator, whereby a crude product was obtained. Purification was performed by silica gel column chromatography (developing solvent: n-hexane/ethyl acetate=8/2 (capacity ratio)), and Add-2 (31.2 g: yield 86%, colorless transparent liquid) was obtained by solvent distillation and vacuum drying. By passing through ¹ H-NMR measurement was confirmed to be the target. BHT (0.01 mol% in the polymerization inhibitor) was added.

¹ H-NMR(500MHz)in DMSO-d ₆ ：7.36-7.28(5H)、6.12(1H)、5.77-5.74(1H)、5.69(1H)、1.90-1.87(3H)、1.76-1.73(2H)、1.37-1.29(2H)、0.88-0.84(3H)[ppm]

Synthesis example 3 Synthesis of Add-3 (1-phenylbutyl acrylate (1-phenylbutyl acrylate))

[ 44]

1-phenyl-1-butanol (25.0 g:0.166 mol), TEA (25.3 g:0.250 mol) and THF (300 mL) were weighed and dissolved in a 500mL four-necked flask equipped with a stirrer. After the solution was cooled to 0℃in an ice bath, acryloyl chloride (acryloyl chloride) (16.6 g: 0.183mol) was slowly added dropwise while keeping the internal temperature below 5℃and the mixture was allowed to return to room temperature and stirred for 18 hours. After confirming the completion of the reaction by HPLC, ethyl acetate (200 mL) was added to the reaction solution, which was washed 3 times with a 10% aqueous solution of potassium carbonate (100 mL) using a separating funnel, and 3 times with pure water (100 mL). After washing, dehydration was performed with magnesium sulfate, and solvent was distilled off using a rotary evaporator, whereby a crude product was obtained. Purification was performed by silica gel column chromatography (developing solvent: n-hexane/ethyl acetate=8/2 (capacity ratio)), and Add-3 (26.8 g: yield 79%, colorless transparent liquid) was obtained by solvent distillation and vacuum drying. By passing through ¹ H-NMR measurement was confirmed to be the target. BHT (0.01 mol% in the polymerization inhibitor) was added.

¹ H-NMR(500MHz)in DMSO-d ₆ ：7.36-7.28(5H)、6.38-6.34(1H)、6.24-6.19(1H)、5.96-5.94(1H)、5.79-5.76(1H)、1.89-1.85(2H)、1.77-1.74(2H)、1.37-1.22(1H)、0.89-0.86(3H)[ppm]

Synthesis example 4 Synthesis of Add-4 (2-methyl-1-phenylpropane-2-yl methacrylate)

[ 45]

2-methyl-1-phenyl-2-propanol (2-methyl-1-phenyl-2-propanol) (25.0 g:0.166 mol), TEA (33.7 g:0.333 mol), DMAP (2.0 g:0.017 mol) and CHCl were weighed in a 500mL four-necked flask equipped with a stirrer ₃ (300 mL) and allowed to dissolve. After cooling the solution to 0℃in an ice bath, methacryloyl chloride (methacryloyl chloride) (26.0 g: 0.247 mol) was slowly added dropwise, and after stirring at 0℃for 30 minutes, the reaction was carried out at 70℃for 18 hours. Confirmation of the reaction by HPLCAfter completion of this reaction, ethyl acetate (200 mL) was added to the reaction solution, and precipitated salts were removed by filtration, and the solution was washed 3 times with a 10% aqueous solution of potassium carbonate (100 mL) using a separating funnel and 3 times with pure water (100 mL). After washing, dehydration was performed with magnesium sulfate, and solvent was distilled off using a rotary evaporator, whereby a crude product was obtained. Purification was performed by silica gel column chromatography (developing solvent: n-hexane/ethyl acetate=9/1 (capacity ratio)), and Add-4 (21.6 g: yield 87%, colorless transparent liquid) was obtained by solvent distillation and vacuum drying. By passing through ¹ H-NMR measurement was confirmed to be the target. BHT (0.01 mol% in the polymerization inhibitor) was added.

¹ H-NMR(500MHz)in CDCl ₃ ：7.32-7.22(5H)、6.02(1H)、5.50(1H)、3.12(2H)、1.92(3H)、1.52(6H)[ppm]

Synthesis example 5 Synthesis of Add-5 (2-methyl-4-phenylpropane-2-yl methacrylate)

[ chemical 46]

2-methyl-4-phenyl-2-butanol (25.0 g:0.152 mol), TEA (30.8 g:0.304 mol), DMAP (1.8 g:0.015 mol) and CHCl were weighed into a 500mL four-necked flask equipped with a stirrer ₃ (300 mL) and allowed to dissolve. After cooling the solution to 0℃in an ice bath, methacryloyl chloride (methacryloyl chloride) (23.8 g:0.228 mol) was slowly added dropwise, and after stirring at 0℃for 30 minutes, the reaction was carried out at 70℃for 18 hours. After confirming the completion of the reaction by HPLC, ethyl acetate (200 mL) was added to the reaction solution, precipitated salts were removed by filtration, and the mixture was washed 3 times with a 10% aqueous solution of potassium carbonate (100 mL) using a separating funnel and 3 times with pure water (100 mL). After washing, dehydration was performed with magnesium sulfate, and solvent was distilled off using a rotary evaporator, whereby a crude product was obtained. Purification was performed by silica gel column chromatography (developing solvent: n-hexane/ethyl acetate=9/1 (capacity ratio)), and Add-5 (29.0 g: yield) was obtained by solvent distillation and vacuum drying 82%, colorless transparent liquid). By passing through ¹ H-NMR measurement was confirmed to be the target. BHT (0.01 mol% in the polymerization inhibitor) was added.

¹ H-NMR(500MHz)in CDCl ₃ ：7.32-7.19(5H)、6.05(1H)、5.52(1H)、2.71-2.68(2H)、2.14-2.11(2H)、1.95(3H)、1.58(6H)[ppm]。

Synthesis example 6 Synthesis of Add-6 (3-ethyl-1-phenylpentan-3-yl methacrylate (3-methyl-1-phenylpentan-3-yl methacrylate))

[ 47]

(first step)

Methyl 3-phenylpropionate (25.0 g:0.152 mol) and THF (500 mL) were weighed and dissolved in a 1L four-necked flask equipped with a stirrer. After cooling the solution to 0℃in an ice bath, ethyl magnesium bromide (ethylmagnesium bromide) (3.0 mol/L diethyl ether (Ethylether) solution, 107mL:0.320 mol) was slowly added dropwise, and after stirring at 0℃for 30 minutes, the mixture was reacted at room temperature for 6 hours. After confirming the completion of the reaction by HPLC, the reaction mixture was cooled again to 0℃with an ice bath, and a 10% aqueous solution (200 mL) of ammonium chloride was added little by little so that the internal temperature was not higher than 10℃and quenched.

After the reaction solution was allowed to stand for a while to settle the precipitate, the supernatant was collected by decantation, and the residue was washed with ethyl acetate, and the same was repeated for several times. The recovered solutions were combined, washed 3 times with pure water (200 mL) using a separating funnel, and washed 1 time with saturated brine (200 mL), dehydrated with anhydrous magnesium sulfate, and solvent-distilled off using a rotary evaporator, whereby a crude product was obtained. Purification was performed by silica gel column chromatography (developing solvent: ethyl acetate/n-hexane=5/5 (capacity ratio)), and Add-6a (27.2 g: yield 93%, colorless transparent liquid) was obtained by solvent distillation and vacuum drying. By passing through ¹ H-NMR measurement was confirmed to be the target.

¹ H-NMR(500MHz)in CDCl ₃ ：7.29-7.16(5H)、2.65-2.61(2H)、1.74-1.70(2H)、1.56-1.52(4H)、1.15(1H)、0.95-0.89(6H)[ppm]

(second step)

Add-6a (25.0 g:0.130 mol), TEA (26.3 g:0.260 mol), DMAP (11.6 g:0.013 mol) and CHCl were weighed into a 500mL four-necked flask equipped with a stirrer ₃ (300 mL) and allowed to dissolve. After cooling the solution to 0℃in an ice bath, methacryloyl chloride (methacryloyl chloride) (20.9 g:0.195 mol) was slowly added dropwise, and after stirring at 0℃for 30 minutes, the reaction was carried out at 70℃for 18 hours. After confirming the completion of the reaction by HPLC, ethyl acetate (200 mL) was added to the reaction solution, precipitated salts were removed by filtration, and the mixture was washed 3 times with a 10% aqueous solution of potassium carbonate (100 mL) using a separating funnel and 3 times with pure water (100 mL). After washing, dehydration was performed with magnesium sulfate, and solvent was distilled off using a rotary evaporator, whereby a crude product was obtained. Purification was performed by silica gel column chromatography (developing solvent: n-hexane/ethyl acetate=9/1 (capacity ratio)), and Add-6 (28.4 g: yield 84%, colorless transparent liquid) was obtained by solvent distillation and vacuum drying. By passing through ¹ H-NMR measurement was confirmed to be the target. BHT (0.01 mol% in the polymerization inhibitor) was added.

¹ H-NMR(500MHz)in CDCl ₃ ：7.28-7.16(5H)、6.04(1H)、5.48(1H)、2.59-2.55(2H)、2.17-2.13(2H)、2.01-1.90(4H+3H)、0.90-0.87(6H)[ppm]

Synthesis example 7 Synthesis of Add-7 (2-methyl-4-phenylbutan-2-yl acrylate)

[ 48]

2-methyl-4-phenyl-2-butanol (2-methyl-4-phenyl-2-butanol) (25.0 g:0.152 mol), TEA (23.1 g:0.228 mol) and THF (300 mL) were weighed and dissolved in a 500mL four-necked flask equipped with a stirrer. After the solution was cooled to 0℃in an ice bath, acryloyl chloride (acryloyl chloride) (16.5 g:0.182 mol) was slowly added dropwise while keeping the internal temperature below 5℃to recoverReturn to room temperature and stir for 18 hours. After confirming the completion of the reaction by HPLC, ethyl acetate (200 mL) was added to the reaction solution, which was washed 3 times with a 10% aqueous solution of potassium carbonate (100 mL) using a separating funnel, and 3 times with pure water (100 mL). After washing, dehydration was performed with magnesium sulfate, and solvent was distilled off using a rotary evaporator, whereby a crude product was obtained. Purification was performed by silica gel column chromatography (developing solvent: n-hexane/ethyl acetate=9/1 (capacity ratio)), and Add-7 (29.9 g: yield 90%, colorless transparent liquid) was obtained by solvent distillation and vacuum drying. By passing through ¹ H-NMR measurement was confirmed to be the target. BHT (0.01 mol% in the polymerization inhibitor) was added.

¹ H-NMR(500MHz)in DMSO-d ₆ ：7.29-7.15(5H)、6.27-6.23(1H)、6.11-6.06(1H)、5.86-5.84(1H)、2.62-2.58(2H)、2.07-2.03(2H)、1.49(6H)[ppm]

Synthesis example 8 Synthesis of Add-8 (1-phenylhexane-3-yl methacrylate)

[ 49]

(first step)

In a 500mL four-necked flask equipped with a stirrer, phenylpropionaldehyde (25.0 g:0.186 mol) and THF (300 mL) were weighed and dissolved. After the solution was cooled to-78℃with a dry ice-methanol bath, n-propylmagnesium bromide (n-propylmagnesium bromide) (1.5 mol/L THF solution, 186mL:0.279 mol) was added dropwise so that the internal temperature did not reach-70℃or higher, and the mixture was allowed to return to room temperature after the completion of the addition and stirred for 18 hours. After confirming the completion of the reaction by HPLC, the reaction solution was cooled to 0℃and quenched by addition of 1 prescribed amount of aqueous hydrochloric acid (100 mL). To the reaction solution was added ethyl acetate (200 mL), and the mixture was washed 3 times with pure water (100 mL) using a separating funnel. After washing, dehydration was performed with magnesium sulfate, and solvent was distilled off using a rotary evaporator, whereby a crude product was obtained. Further vacuum drying was conducted, whereby Add-8a (30.0 g: yield 89%, colorless transparent liquid) was obtained.

(second step)

Add-8a (30.0 g:0.168 mol), TEA (25.5 g:0.252 mol) and THF (300 mL) were weighed into a 500mL four-necked flask equipped with a stirrer and dissolved. After cooling the solution to 0℃in an ice bath, methacryloyl chloride (methacryloyl chloride) (21.1 g:0.201 mol) was slowly added dropwise while keeping the internal temperature below 5℃and the mixture was allowed to return to room temperature and stirred for 18 hours. After confirming the completion of the reaction by HPLC, ethyl acetate (200 mL) was added to the reaction solution, which was washed 3 times with a 10% aqueous solution of potassium carbonate (100 mL) using a separating funnel, and 3 times with pure water (100 mL). After washing, dehydration was performed with magnesium sulfate, and solvent was distilled off using a rotary evaporator, whereby a crude product was obtained. Purification was performed by silica gel column chromatography (developing solvent: n-hexane/ethyl acetate=9/1 (capacity ratio)), and Add-8 (35.6 g: yield 86%, colorless transparent liquid) was obtained by solvent distillation and vacuum drying. By passing through ¹ H-NMR measurement was confirmed to be the target. BHT (0.01 mol% in the polymerization inhibitor) was added.

¹ H-NMR(500MHz)in DMSO-d ₆ ：7.28-7.15(5H)、6.02(1H)、5.64(1H)、4.90-4.88(1H)、2.62-2.55(2H)、1.90-1.85(2H+3H)、1.59-1.54(2H)、1.30-1.28(2H)、0.88-0.86(3H)[ppm]

Synthesis example 9 Synthesis of Add-9 (5-phenylpentanylmethacrylate (5-phenylpentyl methacrylate))

[ 50]

In a 500mL four-necked flask equipped with a stirrer, 5-phenyl-1-pentanol (5-phenyl-1-pentanol) (25.0 g:0.152 mol), TEA (23.1 g:0.228 mol) and THF (300 mL) were weighed and dissolved. After cooling the solution to 0℃in an ice bath, methacryloyl chloride (methacryloyl chloride) (19.1 g:0.182 mol) was slowly added dropwise while keeping the internal temperature below 5℃and the mixture was allowed to return to room temperature and stirred for 18 hours. After confirming the completion of the reaction by HPLC, ethyl acetate (200 mL) was added to the reaction solution, and the mixture was used in a separating funnelPotassium carbonate 10% aqueous solution (100 mL) was washed 3 times, and washed 3 times with pure water (100 mL). After washing, dehydration was performed with magnesium sulfate, and solvent was distilled off using a rotary evaporator, whereby a crude product was obtained. Purification was performed by silica gel column chromatography (developing solvent: n-hexane/ethyl acetate=8/2 (capacity ratio)), and Add-9 (31.8 g: yield 90%, colorless transparent liquid) was obtained by solvent distillation and vacuum drying. By passing through ¹ H-NMR measurement was confirmed to be the target. BHT (0.01 mol% in the polymerization inhibitor) was added.

¹ H-NMR(500MHz)in DMSO-d ₆ ：7.28-7.14(5H)、6.00(1H)、5.64(1H)、4.08(2H)、2.59-2.56(2H)、1.87(3H)、1.67-1.57(4H)、1.38-1.32(2H)[ppm]

Synthesis example 10 Synthesis of Add-11 (3-methyl-1-phenylpentan-3-yl methacrylate))

[ 51]

3-methyl-1-phenyl-3-pentanol (3-methyl-1-phenyl-3-pentanol) (25.0 g:0.140 mol), TEA (28.4 g:0.280 mol), DMAP (1.4 g:0.014 mol) and CHCl were weighed into a 500mL four-necked flask equipped with a stirrer ₃ (300 mL) and allowed to dissolve. After cooling the solution to 0℃in an ice bath, methacryloyl chloride (methacryloyl chloride) (22.0 g:0.210 mol) was slowly added dropwise, and after stirring at 0℃for 30 minutes, the reaction was carried out at 70℃for 18 hours. After confirming the completion of the reaction by HPLC, ethyl acetate (200 mL) was added to the reaction solution, precipitated salts were removed by filtration, and the mixture was washed 3 times with a 10% aqueous solution of potassium carbonate (100 mL) using a separating funnel and 3 times with pure water (100 mL). After washing, dehydration was performed with magnesium sulfate, and solvent was distilled off using a rotary evaporator, whereby a crude product was obtained. Purification was performed by silica gel column chromatography (developing solvent: n-hexane/ethyl acetate=9/1 (capacity ratio)), and Add-11 (26.6 g: yield 77%) was obtained by solvent distillation and vacuum drying. By passing through ¹ H-NMR measurement confirmed to be the target. BHT (0.01 mol% in the polymerization inhibitor) was added.

¹ H-NMR(500MHz)in CDCl ₃ ：7.32-7.19(5H)

6.06(1H)、5.52(1H)、2.68-2.62(2H)

2.71-2.21(1H)、2.12-2.00(2H)、1.95(3H)

1.92-1.86(4H)、1.86(3H)、0.96-0.93(3H)[ppm]

Synthesis example 11 Synthesis of Add-12 (N- (3-phenylpropyl) -N-propylacrylamide)

[ 52]

N- (3-phenylpropyl) -N-propylamine (N- (3-phenylpropyl) -N-propylamine) (20.0 g:0.113 mol), TEA (22.8 g:0.226 mol) and THF (250 mL) were weighed into a 500mL four-necked flask equipped with a stirrer and dissolved. After cooling the solution to 0℃in an ice bath, acryloyl chloride (Acryloyl chloride) (12.3 g:0.136 mol) was slowly added dropwise thereto, and the mixture was stirred at 0℃for 30 minutes and then reacted at room temperature for 18 hours. After confirming the completion of the reaction by HPLC, ethyl acetate (200 mL) was added to the reaction solution, precipitated salts were removed by filtration, and the mixture was washed 3 times with a 10% aqueous solution of potassium carbonate (100 mL) using a separating funnel and 3 times with pure water (100 mL). After washing, dehydration was performed with magnesium sulfate, and solvent was distilled off using a rotary evaporator, whereby a crude product was obtained. Purification was performed by silica gel column chromatography (developing solvent: n-hexane/ethyl acetate=9/1 (capacity ratio)), and Add-12 (18.2 g: yield 70%, colorless transparent liquid) was obtained by solvent distillation and vacuum drying. By passing through ¹ H-NMR measurement was confirmed to be the target. BHT (0.01 mol% in the polymerization inhibitor) was added.

¹ H-NMR(500MHz)in DMSO-d ₆ ：7.27-7.18(5H)、6.74-6.66(1H)、6.15-6.10(1H)、5.65-5.62(1H)、3.39-3.20(4H)、2.55(2H)、1.80-1.78(2H)、1.49-1.48(2H)、0.89-0.78(3H)[ppm]

Synthesis of Polyamic acid/polyimide

Synthesis example 12

DA-1 (1.08 g:10.00 mmol) and DA-3 (3.30 g:10.00 mmol) were weighed into a 100mL four-necked flask equipped with a mechanical stirrer and a nitrogen inlet tube, NMP (24.9 g) was added thereto, and after dissolving the mixture by stirring under a nitrogen atmosphere, TC-2 (2.50 g:10.00 mmol) was added thereto while maintaining the temperature in an ice bath at 10℃or lower, and the mixture was reacted under a nitrogen atmosphere at 50℃for 6 hours. After the reaction was returned to room temperature, TC-1 (1.84 g:9.40 mmol) and NMP (10.0 g) were added and reacted at room temperature for 18 hours, whereby a polyamic acid solution (PAA-1) having a viscosity of about 1,120 mPas and a solid content concentration of 20% by mass was obtained. The molecular weight of the polyamic acid is the number average molecular weight: 11,200, weight average molecular weight: 31,360.

In a 300mL eggplant-shaped flask equipped with a stirrer and a nitrogen inlet tube, the polyamic acid solution (PAA-1) (40.0 g) obtained above was measured, NMP (74.3 g) was added, and after stirring at room temperature for a while, acetic anhydride (5.61 g:54.98 mmol) and pyridine (2.90 g,36.65 mmol) were added, and after stirring at room temperature for 30 minutes under a nitrogen atmosphere, the mixture was reacted at 50℃for 3 hours under a nitrogen atmosphere. After the completion of the reaction, the reaction solution was slowly poured into methanol (500 mL) cooled to 10 ℃ or lower while stirring, and the solid was precipitated and stirred for 10 minutes. The precipitate was collected by filtration, washed again with methanol (200 mL) for 2 times 30 minutes to give a solid which was dried at 80 ℃ under vacuum to give the objective polyimide powder (SPI-1) (7.04 g, yield 88%). The polyimide had an imidization rate of 57% and a molecular weight of a number average molecular weight: 10,400, weight average molecular weight: 29,120.

Synthesis example 13 >

DA-2 (3.42 g:14.00 mmol) and DA-4 (4.11 g:6.00 mmol) were weighed into a 100mL four-necked flask equipped with a mechanical stirrer and a nitrogen inlet tube, NMP (56.8 g) was added thereto and dissolved by stirring under a nitrogen atmosphere, and then TC-3 (4.26 g:19.00 mol) and NMP (10.0 g) were added thereto while maintaining the temperature at 10℃or lower in an ice bath, and reacted at room temperature for 24 hours to obtain a polyamic acid solution (PAA-2) having a viscosity of about 680 mPas and a solid content concentration of 15% by mass. The molecular weight of the polyamic acid is the number average molecular weight: 17,200 weight average molecular weight: 48,160.

Synthesis example 14

In a 100mL four-necked flask equipped with a mechanical stirrer and a nitrogen inlet tube, DA-2 (3.42 g:14.00 mmol) and DA-5 (1.55 g:6.00 mmol) were weighed, NMP (42.0 g) was added thereto and dissolved by stirring under a nitrogen atmosphere, and then TC-3 (4.21 g:18.8 mmol) and NMP (10.0 g) were added thereto while maintaining the temperature at 10℃or lower in an ice bath, and reacted at room temperature for 24 hours to obtain a polyamic acid solution (PAA-3) having a viscosity of about 710 mPas and a solid content concentration of 15% by mass. The molecular weight of the polyamic acid is the number average molecular weight: 15,500, weight average molecular weight: 41,800.

Preparation of liquid Crystal alignment agent

PREPARATION EXAMPLE 1 preparation of radical-generating film-forming composition AL-1

In a 50mL Erlenmeyer flask equipped with a stirrer, 2.0g of the polyimide powder (SPI-1) obtained in Synthesis example 12 was weighed, NMP (18.0 g) was added thereto, and the mixture was stirred at room temperature for 12 hours to dissolve the polyimide powder. After confirming that the solid was completely dissolved, NMP (8.0 g), BCS (12.0 g) and AD-1 (0.20 g) were added and stirred at room temperature for 1 hour, thereby obtaining a radical generating film forming composition (AL-1) which also serves as a liquid crystal aligning agent used in the present invention.

PREPARATION EXAMPLE 2 preparation of free radical generating film Forming composition AL-2

In a 50mL Erlenmeyer flask equipped with a stirrer, 15.0g of the polyamic acid solution (PAA-2) obtained in the above-mentioned synthetic example 13 was measured, NMP (16.5 g) and BCS (13.5 g) were added, and the mixture was stirred at room temperature for 1 hour, whereby the radical generating film-forming composition (AL-2) serving as a liquid crystal aligning agent used in the present invention was obtained.

PREPARATION EXAMPLE 3 preparation of liquid Crystal alignment agent AL-3

In a 50mL Erlenmeyer flask equipped with a stirrer, 15.0g of the polyamic acid solution (PAA-3) obtained in the above-mentioned Synthesis example 14 was measured, NMP (16.5 g) and BCS (13.5 g) were added, and the mixture was stirred at room temperature for 1 hour, thereby obtaining a liquid crystal aligning agent (AL-3) used in the present invention.

Examples 1 to 24 and comparative examples 1 to 8 >, respectively

< manufacturing of liquid Crystal display element >)

Hereinafter, a method for manufacturing a liquid crystal cell for evaluating liquid crystal alignment and electro-optical response will be described.

First, a substrate with electrodes is prepared. The substrate was an alkali-free glass substrate having a size of 30mm×35mm and a thickness of 0.7 mm. An ITO (Indium-Tin-Oxide) electrode having an electrode width of 3 μm and an electrode-electrode spacing of 6 μm and having a comb-tooth pattern forming an angle of 10 ° with respect to the long side of the substrate was formed on the substrate, and a pixel was formed. The size of each pixel is about 10mm in the longitudinal direction and about 5mm in the transverse direction. Hereinafter referred to as IPS substrate.

Subsequently, the radical generating film forming compositions AL-1 and AL-2, the liquid crystal aligning agent AL-3, and SE-6414 (manufactured by hitachi chemical Co., ltd.) as a liquid crystal aligning agent for horizontal alignment obtained by the above-described method were filtered by a filter having a pore diameter of 1.0 μm, and then coated and formed on the prepared IPS substrate and glass substrate (hereinafter referred to as a counter substrate) having an ITO film formed on the back surface and having a columnar spacer having a height of 3.0 μm by spin coating. Then, the resultant was dried on a hot plate at 80℃for 80 minutes, and then sintered at 230℃for 20 minutes to obtain a coating film having a film thickness of 100 nm. In the polyimide film on the IPS substrate side, alignment treatment is performed in a direction along the comb-teeth direction; in the polyimide film on the opposite substrate side, alignment treatment is performed in a direction orthogonal to the comb-teeth electrodes. In the alignment treatment, the rubbing method was used in the cases of AL-1 and SE-6414, and the alignment treatment was performed with a rubbing device manufactured by GAUGE Co., ltd., a rubbing cloth (YA-20R) manufactured by Jichuang chemical Co., ltd., a rubbing roller (diameter: 10.0 cm), a platen feed speed of 30mm/s, a roller rotation speed of 700rpm, and a press-in pressure of 0.3 mm. In the case of both AL-2 and AL-3, the extinction ratio was set to about 26 using a UV exposure device manufactured by USHIO Motor Co., ltd.): 1, and the irradiation amount of the linearly polarized light UV reaches 300mJ/cm based on 254nm wavelength ² The alignment treatment was performed by irradiating polarized light UV and heating at 230℃for 20 minutes.

Then, with respect to the display element to be the example and the partial display element to be the comparative example (comparative examples 2, 3, 4, 6, 7, 8), the display element manufactured by combining the elements obtained by providing the radical generating alignment film AL-1 or AL-2 on the IPS substrate side and providing the liquid crystal alignment film SE-6414 or AL-3 on the counter substrate side was used, and in the case of the partial display elements to be the comparative examples (comparative examples 1 and 5), the display element using SE-6414 or AL-3 in the substrates of both was used. The above-described liquid crystal cells were combined so that the alignment directions were parallel to each other, and the periphery thereof was sealed while leaving the liquid crystal injection port, whereby empty cells having a cell gap of about 3.0 μm were produced. The empty cell was prepared by using a liquid crystal mixture of (Add-1) to (Add-12) obtained in the above synthesis example, using a liquid crystal mixture without addition or a liquid crystal mixture of (Add-C1) to (Add-C3) with addition of 2% by mass as a comparison object, vacuum-injecting the mixture at room temperature, and sealing the injection port. The liquid crystal mixtures used were LC-A (Deltan: 0.130, deltaepsilon: 4.4, manufactured by DIC Co., ltd.) and products purchased from Tokyo were used for Add-10 and Add-C1 to Add-C3, respectively.

The resulting liquid crystal cell constitutes an IPS mode liquid crystal display element. Then, the obtained liquid crystal cell was subjected to heat treatment at 120℃for 10 minutes, and under the condition that no voltage was applied, UV (UV lamp: FLR40SUV 32/A-1) was irradiated for 30 minutes using a UV-FL irradiation device manufactured by Toshiba Lighting Co., ltd.

< evaluation of liquid Crystal orientation >)

Using a polarized light microscope, the polarizing plate was set to crossed nicols, and the polarizing plate was fixed in a state where the brightness of the liquid crystal cell was minimized, and the liquid crystal cell was rotated by 1 ° from this state, so that the alignment state of the liquid crystal was observed. The evaluation was performed by evaluating "good" when no orientation failure such as unevenness (japanese: in the united states) or abnormal regions (japanese in the united states) was observed or by evaluating "poor" when the orientation failure was observed clearly.

A photodiode was attached to the polarized light microscope, and the polarized light microscope was connected to an electrometer via a current-voltage conversion amplifier, and the voltage under the condition that the luminance became minimum in the crossed nicols was monitored to measure the black luminance (V: a.u.).

Determination of the V-T curve and drive threshold voltage, maximum luminance voltage, transmittance evaluation >

The white LED backlight and the luminance meter were mounted so that the optical axis was the same, and during this period, a liquid crystal cell (liquid crystal display element) having a polarizing plate was mounted so that the luminance became minimum, and a voltage was applied at 1V intervals up to 8V, and the luminance in the voltage was measured, whereby the V-T curve was measured. The value of the voltage (Vmax) at which the luminance becomes maximum is estimated from the obtained V-T curve. Further, the maximum transmittance (Tmax) was estimated by comparing the maximum transmittance in the V-T curve with the transmittance at parallel nicol being 100% via the liquid crystal cell to which no voltage was applied.

< determination of response time (Ton, toff >)

Using the apparatus used for the measurement of the V-T curve, a luminance meter was connected to an oscilloscope, and the response speed (Ton) when a voltage that is the maximum luminance was applied and the response speed (Toff) when the voltage was returned to 0V were measured.

< measurement of Voltage Holding Rate (VHR) >)

The voltage holding ratio was measured at normal temperature. The voltage of 4V was applied to the fabricated liquid crystal display element at a temperature of 23 ℃ for 60 μs, and the voltage after 16.7ms was measured, whereby the voltage was calculated as the voltage holding ratio.

In addition, the voltage holding ratio was measured at a high temperature. The voltage of 1V was applied to the fabricated liquid crystal display element at a temperature of 70 ℃ for 60 μs, and the voltage after 1667ms was measured, whereby the voltage was calculated as the voltage holding ratio.

The voltage holding ratio was measured using a VHR-1 voltage holding ratio measuring device manufactured by Tokyo Technika Co.

< content of Polymer >

The compositions of the polymers synthesized in Synthesis examples 11 to 13 are shown in Table 1.

TABLE 1

Polymer	Composition of the composition	Imidization ratio
			SPI-1	TC-1、TC-2(50)/DA-1、DA-3(50)	57％
PAA-2	TC-3/DA-2、DA-4(30)	-
			PAA-3	TC-3/DA-2、DA-5(30)	-

< content of liquid Crystal alignment agent or free radical Forming film Forming composition >

The compositions of the liquid crystal aligning agents or the radical generating film forming compositions prepared in preparation examples 1 to 3 are shown in table 2.

TABLE 2

< liquid Crystal cell content (rubbing) >)

Table 3 shows the contents of examples and comparative examples of the liquid crystal cell subjected to the alignment treatment by the rubbing method.

TABLE 3

Examples	IPS substrate	Counter substrate	Additive agent
				Example 1	AL-1	SE-6414	Add-1
Example 2	AL-1	SE-6414	Add-2
				Example 3	AL-1	SE-6414	Add-3
Example 4	AL-1	SE-6414	Add-4
				Example 5	AL-1	SE-6414	Add-5
Example 6	AL-1	SE-6414	Add-6
				Example 7	AL-1	SE-6414	Add-7
Example 8	AL-1	SE-6414	Add-8
				Example 9	AL-1	SE-6414	Add-9
Example 10	AL-1	SE-6414	Add-10
				Example 11	AL-1	SE-6414	Add-11
Example 12	AL-1	SE-6414	Add-12
				Comparative example 1	SE-6414	SE-6414	No addition
Comparative example 2	AL-1	SE-6414	Add-C1
				Comparative example 3	AL-1	SE-6414	Add-C2
Comparative example 4	AL-1	SE-6414	Add-C3

< results of evaluation of Properties >

The results of evaluating the characteristics of the liquid crystal cell subjected to the alignment treatment by the rubbing method are shown in tables 4-1 and 4-2.

[ Table 4-1]

[ Table 4-2]

It was found that in the weakly anchored liquid crystal cells using the radically polymerizable compounds (Add-1) to (Add-12) of the present invention as additives, the alignment state and black brightness were good, vmax was also significantly reduced as compared with the strongly anchored liquid crystal cell of comparative example 1, and the transmittance was significantly improved as compared with comparative examples 1 to 3. On the other hand, in comparative examples 2 to 3, the liquid crystal display elements using Add-C1 or Add-C2 as an additive often had streaks of rubbing, and also had poor black brightness, and exhibited an alignment state in which birefringence became large. In addition, the behavior of reducing the Vmax but the transmittance of comparative examples 2 and 3 was confirmed as compared with the strongly anchored liquid crystal cell of comparative example 1. It is found that this is caused by the occurrence of the pretilt angle accompanied by weak anchoring, whereas the pretilt angles of examples 1 to 12 were almost 0 °, the pretilt angle of about 72 ° was generated in comparative example 2, and the very large pretilt angle of about 83 ° was generated in comparative example 3. On the other hand, it is found that the response speed was slightly lower when the additives of examples 1 to 12 were used than in the strongly anchored liquid crystal cell of comparative example 1, but nevertheless, a faster response speed could be achieved within the allowable range, and the response speed was significantly improved as compared with comparative examples 2 and 3. In comparative example 4, although the weak anchoring property was exhibited and the alignment state was good, the response speed was slow and VHR was also poor. In the above examples and comparative examples, in place of LC-A, when MLC-3019 (Δn:0.104, Δε: 9.9) made by Merck was used as se:Sub>A liquid crystal, good weak anchoring IPS characteristics could be obtained even when Add-C1 or Add-C2 used in comparative examples 2 to 3 were used, but good weak anchoring IPS characteristics could not be obtained if liquid crystals with se:Sub>A large Δn or liquid crystals with se:Sub>A small Δε were used as in LC-A. This means that, for example, when a liquid crystal display element is produced by narrowing the cell gap (for example, 3.5 μm or less), the additives used in comparative examples 2 to 3 cannot be handled. In the case of the additive of the present invention, even when such a large Δn and small Δε liquid crystal is used, favorable characteristics of weakly anchored IPS can be obtained, and the response speed can be improved by narrowing the cell gap. It is also found that the use of the additive of the present invention can improve the reliability of VHR, which is higher than that of comparative examples 1 to 4, particularly at high temperatures.

< content of liquid Crystal cell (photo-alignment) >)

Table 5 shows the contents of examples and comparative examples of the liquid crystal cell subjected to the alignment treatment by the photo-alignment method.

TABLE 5

Examples	IPS substrate	Counter substrate	Additive agent
				Example 13	AL-2	AL-3	Add-1
Example 14	AL-2	AL-3	Add-2
				Example 15	AL-2	AL-3	Add-3
Example 16	AL-2	AL-3	Add-4
				Example 17	AL-2	AL-3	Add-5
Example 18	AL-2	AL-3	Add-6
				Example 19	AL-2	AL-3	Add-7
Example 20	AL-2	AL-3	Add-8
				Example 21	AL-2	AL-3	Add-9
Example 22	AL-2	AL-3	Add-10
				Example 23	AL-2	AL-3	Add-11
Example 24	AL-2	AL-3	Add-12
				Comparative example 5	AL-3	AL-3	No addition
Comparative example 6	AL-2	AL-3	Add-C1
				Comparative example 7	AL-2	AL-3	Add-C2
Comparative example 8	AL-2	AL-3	Add-C3

< results of evaluation of Properties >

Table 6 shows the results of evaluating the characteristics of the liquid crystal cell subjected to the alignment treatment by the photo-alignment method.

TABLE 6

In the case of using the radically polymerizable compounds (Add-1) to (Add-12) of the present invention as additives, it was confirmed that good characteristics similar to those of weakly anchored IPS produced by the rubbing method were obtained. On the other hand, when (Add-C1) or (Add-C2) used in comparative examples 2 to 3 is used, an abnormal region is generated, and the driving is disabled. In the case of photo-alignment, unlike the rubbing method, since anisotropy of the pretilt angle is not exhibited, it is presumed that in some methods, when a relatively large pretilt angle is generated, the direction of the pretilt angle is not defined and becomes an abnormal region, and if driving is performed, the range of the abnormal region is widened by an electric field, and thus driving is not performed. Comparative example 8 had a response speed and a VHR difference similar to those obtained by the friction method. When the additive of the present invention is used, it is found that no abnormal region is generated even when the photoalignment method is used, and good weak anchoring IPS characteristics can be obtained, and thus it is very useful. It is found that VHR is excellent at high temperature as in the friction method, and it is found that the use of the radically polymerizable compound of the present invention as an additive for weakly anchored IPS is effective in improving reliability.

PREPARATION EXAMPLE 4 preparation of liquid Crystal alignment agent AL-4

10.0g of the radical generating film forming composition AL-2 prepared in the above preparation example 2 and the liquid crystal aligning agent AL-3 prepared in the above preparation example 3 were separately weighed in a 50mL Erlenmeyer flask equipped with a stirrer, and stirred at room temperature for 1 hour, thereby obtaining a radical generating film forming composition (AL-4).

Examples 25 to 36, comparative examples 9 and 10 >, respectively

A liquid crystal cell and a liquid crystal display element were produced in the same manner as in example 1 except that the liquid crystal aligning agent or the radical generating film forming composition applied to the IPS substrate and the counter substrate in example 1 was changed to the liquid crystal aligning agent or the radical generating film forming composition described in table 7 below, and the additive described in table 7 was used as the additive of the liquid crystal mixture.

< content of liquid Crystal cell >)

Examples and comparative examples of the liquid crystal cell subjected to the alignment treatment by the rubbing method are examples 25 to 28 and comparative example 9.

Examples and comparative examples of the liquid crystal cells subjected to the alignment treatment by the photo-alignment method are examples 29 to 36 and comparative example 10.

TABLE 7

Examples	IPS substrate	Counter substrate	Additive agent
				Example 25	SE-6414	AL-1	Add-3
Example 26	SE-6414	AL-1	Add-5
				Example 27	SE-6414	AL-1	Add-7
Example 28	SE-6414	AL-1	Add-8
				Example 29	AL-3	AL-2	Add-3
Example 30	AL-3	AL-2	Add-5
				Example 31	AL-3	AL-2	Add-7
Example 32	AL-3	AL-2	Add-8
				Example 33	AL-3	AL-4	Add-3
Example 34	AL-3	AL-4	Add-5
				Example 35	AL-3	AL-4	Add-7
Example 36	AL-3	AL-4	Add-8
				Comparative example 9	SE-6414	SE-6414	No addition
Comparative example 10	AL-3	AL-3	No addition

< results of evaluation of Properties >

The results of the characteristic evaluation are shown in table 8.

TABLE 8

Examples 25 to 36 are the contents of liquid crystal cells in which a radical generating film forming composition was applied to a counter substrate and a liquid crystal alignment film was used for an IPS substrate. Examples 25 to 28 relate to liquid crystal display elements produced by a rubbing method, and examples 29 to 36 relate to liquid crystal display elements produced by a photo-alignment method. Examples 29 to 36 examples 33 to 36 were those in which AL-4 obtained by mixing a radical generating film-forming composition with a strongly anchored liquid crystal aligning agent was used for the counter substrate. In any of examples 25 to 36, vmax tends to be slightly higher in voltage than in the examples (for example, examples 1 and 13, etc.) in which the radical generating film forming composition was applied to the IPS substrate, but is sufficiently lower than in the conventional strongly anchored liquid crystal cells shown in comparative examples 9 and 10, and extremely high transmittance was obtained. Regarding the response speed, it is known that the difference between Ton and Toff becomes smaller than the case of coating the radical generating film forming composition on the IPS substrate shown in the above-described embodiment. It is also found that a faster response speed can be obtained while maintaining a high transmittance by using AL-4 in which a radical generating film forming composition is mixed with a strongly anchored liquid crystal aligning agent.

Industrial applicability

According to the present invention, a transverse electric field liquid crystal display device can be provided which does not generate a pretilt angle or an abnormal region even when liquid crystals having a high Δn or a low Δε are used, which can realize a high back light transmittance and a high response speed, and which can provide a liquid crystal display device having excellent reliability. Therefore, the liquid crystal display element obtained by the method of the present invention is useful as a liquid crystal display element of a transverse electric field driving system.

Description of the reference numerals

1. Transverse electric field liquid crystal display element

2. Comb electrode substrate

2a substrate

2b Linear electrode

2c liquid crystal alignment film

2d substrate

2e surface electrode

2f insulating film

2g linear electrode

2h liquid crystal alignment film

3. Liquid crystal

4. Counter substrate

4a liquid crystal alignment film

4b substrate

L power line

Claims

1. A method of manufacturing a liquid crystal display element, comprising the steps of: polymerizing a radical polymerizable compound in a state in which a liquid crystal composition containing a liquid crystal and the radical polymerizable compound represented by the following formula (A) is brought into contact with a radical generating film,

in the formula (A), M represents a polymerizable group capable of radical polymerization; r is R ₁ ～R ₃ Each independently represents a single bond or an alkylene group having 1 to 6 carbon atoms with or without a bonding group inserted therein; ar represents an aromatic hydrocarbon group having a substituent or not; x is X ₁ X is X ₂ Each independently represents a hydrogen atom or an aromatic hydrocarbon group having or not having a substituent; r is R ₁ X ₁ 、R ₂ X ₂ And R is equal to ₁ X ₁ R is R ₂ X ₂ The bonded carbon atoms together form a ring or not; wherein R is ₁ X ₁ 、R ₂ X ₂ And R is ₃ The total number of carbon atoms is 1 or more.

2. The method for manufacturing a liquid crystal display element according to claim 1, wherein in the formula (A), R ₃ Is a straight-chain alkylene group having 1 to 6 carbon atoms, X ₁ And X ₂ Is a hydrogen atom.

3. The method for manufacturing a liquid crystal display element according to claim 1 or 2, wherein M in the formula (A) is selected from the following structures,

in the method, in the process of the invention,

* The bonding site is indicated as being the bonding site,

R ^b represents a linear alkyl group having 2 to 8 carbon atoms,

e represents a single bond selected from the group consisting of, -O-, -NR ^c -, -S-, bond groups in ester and amide linkages, wherein R ^c Represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms,

R ^d represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.

4. The method for producing a liquid crystal display element according to any one of claims 1 to 3, wherein the radical generating film is a uniaxially oriented radical generating film.

5. The method for manufacturing a liquid crystal display element according to any one of claims 1 to 4, wherein the step of polymerizing is performed under an electric field-free condition.

6. The method for manufacturing a liquid crystal display element according to any one of claims 1 to 5, wherein the radical generating film is a film obtained by immobilizing an organic group which induces radical polymerization.

7. The method for producing a liquid crystal display element according to any one of claims 1 to 5, wherein a composition containing a polymer and a compound having a radical-generating organic group is applied and cured to form a film, whereby the radical-generating organic group is immobilized in the film, and the radical-generating film is obtained.

8. The method for manufacturing a liquid crystal display element according to any one of claims 1 to 5, wherein the radical generating film comprises: polymers containing organic groups that induce free radical polymerization.

9. The method for manufacturing a liquid crystal display element according to claim 8, wherein the polymer containing an organic group that induces radical polymerization is at least one polymer selected from polyimide precursors, polyimides, polyureas, and polyamides, which are obtained using a diamine component containing a diamine containing an organic group that induces radical polymerization.

10. The method for manufacturing a liquid crystal display element according to claim 9, wherein the radical polymerization-inducing organic group is an organic group represented by the following formulas [ X-1] to [ X-18], [ W ], [ Y ] or [ Z ],

in the formulas [ X-1] to [ X-18],

* The bonding site is indicated as being the bonding site,

S ₁ and S is ₂ Each independently represents-O-, -NR-or-S-, R represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms; of the alkyl groups having 1 to 10 carbon atoms, the-CH group of the alkyl group having 2 to 10 carbon atoms ₂ -a part of the groups is or is not replaced by oxygen atoms; but at S ₂ R or NR in the alkyl radical-CH ₂ In the case where a part of the radicals is replaced by oxygen atoms, said oxygen atoms are not directly bonded to S ₂ Or on the N-side of the substrate,

R ₁ and R is ₂ Each independently represents a hydrogen atom, a halogen atom, or an alkyl group having 1 to 4 carbon atoms,

in the formulae [ W ], [ Y ] and [ Z ],

* The bonding site is indicated as being the bonding site,

ar represents an aromatic hydrocarbon group selected from the group consisting of phenylene, naphthylene and biphenylene with or without an organic group and/or a halogen atom as a substituent,

R ⁹ and R is ¹⁰ Each independently represents an alkyl group having 1 to 10 carbon atoms or an alkoxy group having 1 to 10 carbon atoms; when R is ⁹ And R is ¹⁰ In the case of an alkyl group, the terminal groups may be bonded to each other to form a ring structure or may not form a ring structure,

Q represents any one of the structures described below,

＊-OR

in the method, in the process of the invention,

R ¹¹ represents-CH ₂ -, -NR-, -O-; or-S-;

r independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms;

* The bonding site is indicated as being the bonding site,

S ³ represents a single bond, -O-, -NR-, or-S-, wherein R represents a hydrogen atom or an alkyl group having 1 to 14 carbon atoms,

R ¹² represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms, or an alkoxy group having 1 to 10 carbon atoms.

11. The method for producing a liquid crystal display element according to claim 9 or 10, wherein the diamine containing an organic group that induces radical polymerization is a diamine having a structure represented by the following formula (6), the following formula (7) or the following formula (7'),

in the formula (6), the amino acid sequence of the compound,

R ⁶ represents a single bond, -CH ₂ -、-O-、-COO-、-OCO-、-NHCO-、-CONH-、-NH-、-CH ₂ O-、-N(CH ₃ )-、-CON(CH ₃ ) -or-N (CH) ₃ )CO-，

R ⁷ Represents a single bond or an alkylene group having 1 to 20 carbon atoms which is unsubstituted or substituted with a fluorine atom, and at least 1-CH of the alkylene group ₂ -or-CF ₂ Each independently substituted or not with a group selected from the group consisting of-ch=ch-, a 2-membered carbocyclic ring, and a 2-membered heterocyclic ring, and, in turn, any of the groups listed below, namely-O-, -COO-, -OCO-, -NHCO-, -CONH-or-NH-is replaced by these groups, or not replaced by these groups, provided that they are not adjacent to each other,

R ⁸ represents a compound selected from the following formula [ X-1 ] ]～[X-18]A radical polymerization reactive group represented by the formula (I),

in the formulas [ X-1] to [ X-18],

* Represents a bonding site;

S ₁ and S is ₂ Each independently represents-O-, -NR-, or-S-; r represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, wherein the alkyl group having 1 to 10 carbon atoms has a-CH group of an alkyl group having 2 to 10 carbon atoms ₂ Part of the radicals being replaced by oxygen atoms or not, but in S ₂ R or NR in the alkyl radical-CH ₂ In the case where a part of the radicals is replaced by oxygen atoms, said oxygen atoms are not directly bonded to S ₂ Or on N;

R ₁ r is R ₂ Each independently represents a hydrogen atom, a halogen atom, or an alkyl group having 1 to 4 carbon atoms,

in the formula (7) and (7'),

T ¹ t and T ² Each independently is a single bond, -O-, -S-, -COO-, -OCO-, -NHCO-, -CONH-, -NH-, -CH ₂ O-、-N(CH ₃ )-、-CON(CH ₃ ) -or-N (CH) ₃ )CO-，

S represents a single bond or an alkylene group having 1 to 20 carbon atoms which is unsubstituted or substituted with a fluorine atom, and at least 1-CH of the alkylene group ₂ -or-CF ₂ Each independently substituted or not with a group selected from the group consisting of-ch=ch-, a 2-membered carbocyclic ring, and a 2-membered heterocyclic ring, and, in turn, any of the groups listed below, namely-O-, -COO-, -OCO-, -NHCO-, -CONH-or-NH-is replaced by these groups, or not replaced by these groups, provided that they are not adjacent to each other,

E is a single bond, -O-, -C (CH) ₃ ) ₂ -、-NH-、-CO-、-NHCO-、-COO-、-(CH ₂ ) _m -、-SO ₂ -、-O-(CH ₂ ) _m -O-、-O-C(CH ₃ ) ₂ -、-CO-(CH ₂ ) _m -、-NH-(CH ₂ ) _m -、-SO ₂ -(CH ₂ ) _m -、-CONH-(CH ₂ ) _m -、-CONH-(CH ₂ ) _m NHCO-, or-COO- (CH) ₂ ) _m -OCO-, wherein m is an integer from 1 to 8,

in the formulas [ W ], [ Y ], [ Z ],

* Representation and T ² Is a bonding site of (2);

ar represents an aromatic hydrocarbon group selected from the group consisting of phenylene, naphthylene and biphenylene with or without an organic group and/or a halogen atom as a substituent;

R ⁹ and R is ¹⁰ Each independently represents an alkyl group having 1 to 10 carbon atoms or an alkoxy group having 1 to 10 carbon atoms;

q represents any one of the structures described below,

＊-OR

in the method, in the process of the invention,

R ¹¹ represents-CH ₂ -, -NR-, -O-; or-S-;

* The bonding site is indicated as being the bonding site,

S ³ represents a single bond, -O-, -NR-, or-S-, wherein R represents a hydrogen atom or an alkyl group having 1 to 14 carbon atoms;

R ¹² represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms, or an alkoxy group having 1 to 10 carbon atoms;

in the formula (7'), q are each independently 0 or 1, at least 1 q is 1, and p represents an integer of 1 to 2.

12. The method for manufacturing a liquid crystal display element according to any one of claims 1 to 11, comprising the steps of:

preparing a first substrate having the radical generating film and a second substrate having or not having the radical generating film;

The polymerization reaction is carried out.

13. The method for manufacturing a liquid crystal display element according to claim 12, wherein the second substrate is a second substrate having no radical generating film.

14. The method for manufacturing a liquid crystal display element according to claim 12, wherein the second substrate is a substrate coated with a liquid crystal alignment film having uniaxial alignment.

15. The method for manufacturing a liquid crystal display element according to claim 14, wherein the liquid crystal alignment film having uniaxial alignment is a liquid crystal alignment film for horizontal alignment.

16. The method for manufacturing a liquid crystal display element according to any one of claims 12 to 15, wherein any one of the first substrate and the second substrate is a substrate having comb-teeth electrodes.

17. A liquid crystal composition comprising a liquid crystal and a radical polymerizable compound represented by the following formula (A),

18. The liquid crystal composition according to claim 17, wherein in the formula (a), R ₃ Is a straight-chain alkylene group having 1 to 6 carbon atoms, X ₁ And X ₂ Is hydrogen sourceAnd (5) a seed.

19. The liquid crystal composition according to claim 17 or 18, wherein M in the formula (A) is selected from the following structures,

in the method, in the process of the invention,

* The bonding site is indicated as being the bonding site,

R ^b represents a linear alkyl group having 2 to 8 carbon atoms,

R ^d represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.

20. A liquid crystal display element is characterized by comprising a first substrate, a second substrate arranged opposite to the first substrate, and liquid crystal filled between the first substrate and the second substrate,

The liquid crystal display element is formed by polymerizing a radical polymerizable compound in a state in which a liquid crystal composition containing the liquid crystal and the radical polymerizable compound represented by the following formula (A) is brought into contact with the radical generating film of the first substrate having the radical generating film,

in the formula (A), M represents a polymerizable group capable of radical polymerization; r is R ₁ ～R ₃ Each independently represents a single bond or an alkylene group having 1 to 6 carbon atoms with or without a bonding group inserted therein; ar represents an aromatic hydrocarbon group having a substituent or not; x is X ₁ X is X ₂ Each independently represents a hydrogen atom, or with or without a bondAromatic hydrocarbon groups of the substituents; r is R ₁ X ₁ 、R ₂ X ₂ And R is equal to ₁ X ₁ R is R ₂ X ₂ The bonded carbon atoms together form a ring, or do not form a ring; wherein R is ₁ X ₁ 、R ₂ X ₂ And R is ₃ The total number of carbon atoms is 1 or more.

21. The liquid crystal display element according to claim 20, wherein any one of the first substrate and the second substrate is a substrate having comb-teeth electrodes.

22. The liquid crystal display element according to claim 20 or 21, wherein the liquid crystal display element is a low-voltage-driven transverse electric field liquid crystal display element.

23. A radically polymerizable compound represented by the following formula (A),

M, R in the formula (A) ₁ 、R ₂ 、R ₃ 、X ₁ 、X ₂ And Ar is any one of the following combinations (i) - (v):

(i) M is the following structure (C), R ₁ X ₁ Is 1-amyl, R ₂ Is a single bond, X ₂ Is a hydrogen atom, R ₃ A combination of a single bond, ar being phenyl;

(ii) M is the following structure (B), R ₁ X ₁ Is 1-propyl, R ₂ Is a single bond, X ₂ Is a hydrogen atom, R ₃ A combination of a single bond, ar being phenyl;

(iii) M is the following structure (C), R ₁ X ₁ Is ethyl, R ₂ X ₂ Is ethyl, R ₃ A combination of 1, 2-ethylene, ar being phenyl;

(iv) M is the following structure (C), R ₁ X ₁ Is 1-propyl, R ₂ Is a single bond,X ₂ Is a hydrogen atom, R ₃ A combination of 1, 2-ethylene, ar being phenyl;

(v) M is the following structure (D), R ₁ Is a single bond, X ₁ Is a hydrogen atom, R ₂ Is a single bond, X ₂ Is a hydrogen atom, R ₃ A combination of 1, 2-ethylene, ar being phenyl;

in structures (B), (C) and (D), the bonding sites are represented.