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

Abstract

A method for producing a liquid-crystal display element, the method including a step in which a liquid-crystal composition comprising a liquid crystal and a radial-polymerizable compound represented by formula (A) is brought into contact with a radical-generating film and the radical-polymerizable compound is polymerized while maintaining the contact. (In formula (A), M represents a radical-polymerizable group, R1 to R3 each independently represent a single bond or an alkylene group having 1-6 carbon atoms and optionally having a linking group inserted thereinto, Ar represents an optionally substituted aromatic hydrocarbon group, X1 and X2 each independently represent a hydrogen atom or an optionally substituted aromatic hydrocarbon group, and the R1X1 and R2X2 moieties and the carbon atom bonded to the R1X1 and R2X2 moieties may have together formed a ring, with the proviso that the total number of carbon atoms of R1X1, R2X2, and R3 is 1 or larger.)

Description

Technical Field

[0001] The present invention relates to a method for manufacturing a liquid crystal display element, a liquid crystal display element for realizing further low voltage driving, a liquid crystal composition and a radical polymerizable compound that can be used therein, which can manufacture a weak anchoring film by an inexpensive method without including a complicated process, and apply a technique for stabilizing a liquid crystal layer with a polymer.

Background Art

[0002] In recent years, liquid crystal display elements have been widely used in displays of mobile phones, computers, televisions, etc. Liquid crystal display elements have characteristics such as being thin, lightweight, and having low power consumption, and in the future, applications to further contents such as VR (Virtual Reality) and ultra-high definition displays are expected. Various display modes such as TN (Twisted Nematic), IPS (In-Plane Switching), and VA (Vertical Alignment) have been proposed for liquid crystal displays, and a film (liquid crystal alignment film) for inducing liquid crystal into a desired alignment state is used in all modes.

[0003] Particularly in products equipped with a touch panel such as a tablet PC, a smartphone, and a smart TV, the IPS mode in which the display is not easily disturbed even when touched is preferred. In recent years, liquid crystal display elements using FFS (Frindge Field Switching) and techniques using a non-contact technique using photo-alignment have been increasingly used in terms of improving contrast and viewing angle characteristics.

[0004] However, compared to IPS, FFS has a higher substrate manufacturing cost and has problems such as display defects specific to the FFS mode called Vcom shift. Regarding photo-alignment, compared to the rubbing method, there are advantages such as the ability to increase the size of the elements that can be manufactured and significantly improve the display characteristics. However, there are problems in the principle of photo-alignment (display defects derived from decomposition products in the case of the decomposition type, and image sticking due to insufficient alignment force in the case of the isomerization type). Currently, liquid crystal display element manufacturers and liquid crystal alignment film manufacturers are making various efforts to solve these problems.

[0005] On the other hand, in recent years, an IPS mode using weak anchoring has been proposed, and it has been reported that by using this method, it is possible to improve the contrast and achieve significant low-voltage driving compared to the conventional IPS mode (see Patent Document 1).

[0006] Specifically, a liquid crystal alignment film having strong anchoring energy is used on one side of the substrate, and the substrate side having the electrode for generating one of the transverse electric fields is subjected to a treatment such that it has no liquid crystal alignment regulating force at all, and an IPS mode liquid crystal display element is made using these.

[0007] In recent years, technical proposals for the weak anchoring IPS mode have been made using thick polymer brushes, etc. (see Patent Document 2). By this technology, a significant improvement in the contrast ratio and a significant reduction in the driving voltage have been realized.

[0008] On the other hand, there is a problem that the response speed, especially the response speed when the voltage is OFF, is significantly reduced. This is because the driving voltage is low, so it is due to the influence of responding with a weaker electric field compared to the normal driving method, and because the anchoring force of the alignment film is extremely small, it takes time for the liquid crystal to recover.

[0009] As a method to solve this, a method of making only the pixel electrode have weak anchoring has been proposed (see Patent Document 3). It has been reported that this enables both an improvement in brightness and a response speed.

Prior Art Documents

Patent Documents

[0010]

Patent Document 1

Patent Document 2

Patent Document 3

Summary of the Invention

Problems to be Solved by the Invention

[0011] By making the weak anchoring only on the electrodes of the IPS comb electrodes, the response speed delay during driving is suppressed. On the other hand, in order to make the weak anchoring state only on the electrodes, it is necessary to prepare difficult techniques such as applying different materials to very fine regions, which is considered to be a major problem in actual industrialization.

[0012] By another method, improving the response speed by narrowing the cell gap has been studied. Usually, in a liquid crystal display element, the response speed tends to increase as the cell gap becomes narrower. However, on the other hand, there is a problem that the transmittance decreases. To solve this, the use of a liquid crystal with a large birefringence difference (Δn) can be mentioned. By setting the product (retardation) of the cell gap D and Δn to be 300 nm to 400 nm (measurement wavelength 550 nm), the decrease in transmittance can be solved. However, when increasing Δn, basically, only that parameter cannot be changed, and parameters such as Δε (dielectric anisotropy) and elastic coefficient also change, so it is considered that the basic physical properties of the liquid crystal change greatly. For example, in the case of weak anchoring alignment, a case where the liquid crystal is aligned in the vertical direction may occur. Therefore, it becomes an important issue to obtain stable weak anchoring characteristics even when parameters such as Δn and Δε change.

[0013] Solving such technical problems would bring significant cost benefits to panel manufacturers and is also considered beneficial for suppressing battery consumption and improving image quality, etc.

[0014] The present invention has been made to solve the above problems, and in the case of reducing the cell gap, a stable weak anchoring horizontal electric field liquid crystal display element can be manufactured without generating a pretilt angle, and at the same time, it is possible to simultaneously achieve a lower driving voltage and a faster response speed in the off state. In addition, the present invention aims to provide a method for manufacturing a liquid crystal display element capable of manufacturing a horizontal electric field liquid crystal display element with less decrease in VHR (voltage holding ratio) even at high temperatures, and the liquid crystal display element, and a liquid crystal composition and a radical polymerizable compound that can be used therein.

Means for Solving the Problems

[0015] As a result of intensive studies to solve the above problems, the present inventors have found that the above problems can be solved and completed the present invention having the following gist.

[0016] That is, the present invention includes the following. [1] A method for manufacturing a liquid crystal display element, including a step of polymerizing the radical polymerizable compound in a state where a liquid crystal composition containing a liquid crystal and a radical polymerizable compound represented by the following formula (A) is in contact with a radical generating film.

Chemical Formula

Chemical formula

[10] The method for manufacturing a liquid crystal display element according to [9], wherein the organic group that induces the radical polymerization is an organic group represented by the following formulas [X-1] to [X-18], [W], [Y], or [Z]. [Chemical formula] (In formulas [X-1] to [X-18], * indicates the bonding site, S1 and S2 each independently represent -O-, -NR-, or -S-, R represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms (among the alkyl groups having 1 to 10 carbon atoms, a part of the -CH2- group of the alkyl group having 2 to 10 carbon atoms may be replaced by an oxygen atom. However, in S2R or NR, when a part of the -CH2- group of the alkyl group is replaced by an oxygen atom, the oxygen atom is not directly bonded to S2 or N). R1 and R2 each independently represent a hydrogen atom, a halogen atom, or an alkyl group having 1 to 4 carbon atoms.) [Chemical formula] (In formulas [W], [Y], and [Z], * indicates the bonding site, Ar represents an aromatic hydrocarbon group selected from the group consisting of phenylene, naphthylene, and biphenylylene which may have an organic group and / or a halogen atom as a substituent, R 9 and R 10 each independently represent an alkyl group having 1 to 10 carbon atoms or an alkoxy group having 1 to 10 carbon atoms, and when R 9 and R 10 are alkyl groups, they may be bonded to each other at the ends to form a ring structure. Q represents any of the following structures. [Chemical formula] (In the formula, R 11 represents -CH2-, -NR-, -O-, or -S-, R each independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and * indicates the bonding site.). 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 12represents 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 manufacturing a liquid crystal display element according to [9] or

[10] , wherein the diamine containing an organic group that induces the radical polymerization has a structure represented by the following formula (6), the following formula (7), or the following formula (7’). [Chemical formula] (In formula (6), R 6 represents a single bond, -CH2-, -O-, -COO-, -OCO-, -NHCO-, -CONH-, -NH-, -CH2O-, -N(CH3)-, -CON(CH3)-, or -N(CH3)CO-; R 7 represents a single bond, or an alkylene group having 1 to 20 carbon atoms which is unsubstituted or substituted by a fluorine atom. One or more of any -CH2- or -CF2- of the alkylene group may each independently be replaced by a group selected from -CH=CH-, a divalent carbocyclic ring, and a divalent heterocyclic ring. Further, on the condition that any of the following groups, namely, -O-, -COO-, -OCO-, -NHCO-, -CONH-, or -NH- do not adjoin each other, they may be replaced by these groups; R 8 represents a radical polymerization reactive group represented by a formula selected from the following formulas [X-1] to [X-18]. [Chemical formula] (In formulas [X-1] to [X-18], * indicates a bonding site, S1 and S2 each independently represent -O-, -NR-, or -S-, R represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms (among the alkyl groups having 1 to 10 carbon atoms, a part of the -CH2- group of the alkyl group having 2 to 10 carbon atoms may be replaced by an oxygen atom. However, in S2R or NR, when a part of the -CH2- group of the alkyl group is replaced by an oxygen atom, the oxygen atom is not directly bonded to S2 or N). R1 and R2 each independently represent a hydrogen atom, a halogen atom, or an alkyl group having 1 to 4 carbon atoms.))

Chemical formula

Chemical formula

[12] Preparing a first substrate having the radical generating film and a second substrate which may have a radical generating film; Oppositely disposing the first substrate and the second substrate such that the radical generating film on the first substrate faces the second substrate; Filling the liquid crystal composition between the first substrate and the second substrate; and Performing the polymerization reaction. The manufacturing method of the liquid crystal display element according to any one of [1] to

[11] , including

[13] The manufacturing method of the liquid crystal display element according to

[12] , wherein the second substrate is a second substrate having no radical generating film.

[14] The manufacturing method of the liquid crystal display element according to

[12] , wherein the second substrate is a substrate coated with a liquid crystal alignment film having uniaxial alignment property.

[15] The manufacturing method of the liquid crystal display element according to

[14] , wherein the liquid crystal alignment film having uniaxial alignment property is a liquid crystal alignment film for horizontal alignment.

[16] The manufacturing method of the liquid crystal display element according to any one of

[12] to

[15] , wherein either the first substrate or the second substrate is a substrate having comb electrodes.

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

Chemical formula

[18] The liquid crystal composition according to

[17] , wherein in formula (A), R3 is a linear alkylene group having 1 to 6 carbon atoms, and X1 and X2 are hydrogen atoms.

[19] The liquid crystal composition according to

[17] or

[18] , wherein M in formula (A) is selected from the following structures.

Chemical formula

[20] A liquid crystal display device having a first substrate, a second substrate disposed opposite to the first substrate, and a liquid crystal filled between the first substrate and the second substrate, wherein a liquid crystal composition containing the liquid crystal and a radically polymerizable compound represented by the following formula (A) is brought into contact with the radical generating film of the first substrate having a radical generating film, and the radically polymerizable compound is subjected to a polymerization reaction. [Chemical formula] (In formula (A), M represents a radically polymerizable polymerizable group, R1 to R3 each independently represent a single bond or an alkylene group having 1 to 6 carbon atoms in which a linking group may be inserted, Ar represents an aromatic hydrocarbon group which may have a substituent, X1 and X2 each independently represent a hydrogen atom or an aromatic hydrocarbon group which may have a substituent, and R1X1, R2X2, and the carbon atoms to which R1X1 and R2X2 are bonded may together form a ring. However, the total number of carbon atoms of R1X1, R2X2, and R3 is 1 or more.)

[21] The liquid crystal display device according to

[20] , wherein either one of the first substrate and the second substrate is a substrate having a comb-shaped electrode.

[22] The liquid crystal display device according to

[20] or

[21] , which is a low-voltage driving transverse electric field liquid crystal display device.

[23] A radically polymerizable compound characterized by being represented by the following formula (A). [Chemical formula] (In formula (A), M, R1, R2, R3, X1, X2, and Ar are any of the following combinations (i) to (v).) (i) M is the following structure (C), R1X1 is a 1-pentyl group, and R2 is a single bond 、A combination where X2 is a hydrogen atom, R3 is a single bond, and Ar is a phenyl group. (ii) M has the following structure (B), R1X1 is a 1-propyl group, and R2 is a single bond 、 A combination where X2 is a hydrogen atom, R3 is a single bond, and Ar is a phenyl group. (iii) M has the following structure (C), R1X1 is an ethyl group, and R2X2 is an ethyl group 、 A combination where R3 is a 1,2-ethylene group and Ar is a phenyl group. (iv) M has the following structure (C), R1X1 is a 1-propyl group, R2 is a single bond, and X2 is a hydrogen atom 、 A combination where R3 is a 1,2-ethylene group and Ar is a phenyl group. (v) M has the following structure (D), R1 is a single bond, and X1 is a hydrogen atom 、 R2 is a single bond and X2 is a hydrogen atom 、 A combination where R3 is a 1,2-ethylene group and Ar is a phenyl group. [Chemical formula] (In structures (B), (C), and (D), * indicates the bonding site.) [Advantages of the Invention]

[0017] According to the present invention, in the process of narrowing the cell gap, a weakly anchored transverse electric field liquid crystal display element can be stably fabricated without generating a pretilt angle. At the same time, it is possible to simultaneously achieve a lower driving voltage and a faster response speed in the off state. In addition, a transverse electric field liquid crystal display element with less reduction in VHR even at high temperatures can be manufactured. A method for manufacturing a liquid crystal display element, the liquid crystal display element, a liquid crystal composition and a radically polymerizable compound that can be used therein are provided. [Brief Description of the Drawings]

[0018]

Figure 1

Figure 2

Embodiments for Carrying Out the Invention

[0019] The present invention utilizes an additive (a radical polymerizable compound with a specific structure) that can suppress the manifestation of a pretilt angle associated with the formation of a weak anchoring film and can stably produce a highly reliable weak anchoring horizontal electric field liquid crystal display element even in the case of a narrow cell gap. For example, a step of preparing a cell having a liquid crystal composition containing a liquid crystal and a radical polymerizable compound with a specific structure between a first substrate having a radical generating film and a second substrate having a liquid crystal alignment film, and a step of applying sufficient energy to the cell to cause a polymerization reaction of the radical polymerizable compound are included in a method for manufacturing a weak anchoring horizontal electric field liquid crystal display element. Preferably, a step of preparing a first substrate having a radical generating film subjected to an alignment treatment by rubbing or photoalignment and a second substrate having a liquid crystal alignment film without a radical generating film, a step of creating a cell such that the respective substrates face each other, and a step of filling a liquid crystal composition containing a liquid crystal and a radical polymerizable compound with a specific structure between the first substrate and the second substrate are included in a method for manufacturing a liquid crystal cell. For example, it is a method for creating a low voltage driving horizontal electric field liquid crystal display element in which one substrate has a radical generating film subjected to an alignment treatment and the other substrate has a liquid crystal alignment film subjected to a uniaxial alignment treatment, and one of the substrates is a substrate having comb electrodes for driving the liquid crystal.

[0020] In the present invention, the "weak anchoring film" refers to a film that has no or, if any, an in-plane orientation regulating force of liquid crystal molecules weaker than the intermolecular force between liquid crystals, and that cannot uniaxially orient liquid crystal molecules in any direction by this film alone. Further, this weak anchoring film is not limited to a solid film and includes a liquid film covering the solid surface. Usually, in a liquid crystal display element, a film that regulates the orientation of liquid crystal molecules, that is, a liquid crystal alignment film, is used in pairs to align the liquid crystal. However, even when this weak anchoring film and the liquid crystal alignment film are used in pairs, the liquid crystal can be aligned. This is because the orientation regulating force of the liquid crystal alignment film is transmitted in the thickness direction of the liquid crystal layer by the intermolecular force between liquid crystal molecules, and as a result, the liquid crystal molecules close to the weak anchoring film are also aligned. Therefore, when a horizontal alignment liquid crystal alignment film is used as the liquid crystal alignment film, a horizontal alignment state can be created throughout the liquid crystal cell. Horizontal alignment refers to a state in which the long axes of liquid crystal molecules are arranged substantially parallel to the liquid crystal alignment film surface, and inclined alignment of about several degrees is also included in the category of horizontal alignment.

[0021] The applicant of the present application has proposed a method for manufacturing a zero-surface anchoring film, which includes a step of contacting a liquid crystal composition containing a liquid crystal and a radically polymerizable compound with a radical generating film and applying energy sufficient to cause a polymerization reaction of the radically polymerizable compound (see Claim 1 of International Publication No. 2019 / 004433). Examples of the radically polymerizable compound used in this proposal are given in

[0077] to

[0086] of International Publication No. 2019 / 004433. The inventors of the present invention utilized the above-proposed technology and found that in the case of a narrow cell gap, a weakly-anchored horizontal electric field liquid crystal display element can be stably fabricated without generating a pretilt angle, and at the same time, both a reduction in driving voltage and a fast response speed in the off state can be achieved. In addition, intensive studies were conducted to fabricate a horizontal electric field liquid crystal display element with little reduction in VHR even at high temperatures. As a result, by using a radical polymerizable compound having a specific structure among radical polymerizable compounds, in the case of a narrow cell gap, a weakly-anchored horizontal electric field liquid crystal display element can be stably fabricated without generating a pretilt angle, and at the same time, both a reduction in driving voltage and a fast response speed in the off state can be achieved. In addition, it has been found that a horizontal electric field liquid crystal display element with little reduction in VHR even at high temperatures can be manufactured. Here, the radical polymerizable compound having a specific structure is represented by the following formula (A). [Chemical formula] (In formula (A), M represents a polymerizable group capable of radical polymerization, R1 to R3 each independently represent a single bond or an alkylene group having 1 to 6 carbon atoms which may have a bonding group inserted therein, Ar represents an aromatic hydrocarbon group which may have a substituent, X1 and X2 each independently represent a hydrogen atom or an aromatic hydrocarbon group which may have a substituent, and R1X1, R2X2 and the carbon atoms to which R1X1 and R2X2 are bonded may form a ring together. However, the total number of carbon atoms of R1X1, R2X2 and R3 is 1 or more.)

[0022] In the method for manufacturing a liquid crystal display element of the present invention, a step of polymerizing a radical polymerizable compound is included in a state where a liquid crystal composition containing a liquid crystal and a radical polymerizable compound represented by formula (A) is brought into contact with a radical generating film. In this step, the inventors presume that if a change occurs on the surface of the radical generating film due to the polymerization reaction of the radical polymerizable compound using the radicals generated by the radical generating film, and a weak anchoring film is obtained. However, it is difficult to confirm whether the change on the surface of the radical generating film by such a step is a change in the radical generating film itself or a change due to the formation of a polymerization layer of the radical polymerizable compound on the radical generating film. Therefore, the result of such a step has not been specified yet.

[0023] In the present invention, by performing the above step, in reducing the cell gap, a pretilt angle does not occur, and a stable weak anchoring transverse electric field liquid crystal display element can be fabricated. At the same time, a reduction in driving voltage and a fast response speed in the off state can be realized. In addition, a transverse electric field liquid crystal display element with little reduction in VHR even at high temperatures can be manufactured. The inventors consider how the radical polymerizable compound represented by formula (A) contributes to this as follows. M of the radical polymerizable compound represented by formula (A) contributes to the radical polymerization of the radical polymerizable compound. Thereby, a weak anchoring film can be formed, and a reduction in driving voltage can be realized. In addition, the inventors presume that Ar (an aromatic hydrocarbon group which may have a substituent) of the radical polymerizable compound represented by formula (A) contributes to the suppression of the generation of the pretilt angle, the improvement of the response speed, and the high VHR at high temperatures. In addition, in formula (A), the inventors presume that M and Ar are not too close to each other and that the presence of a group [-C(R1X1)(R2X2)R3-] of a certain size between M and Ar has the effect of further increasing the response speed. In the present specification, a narrow cell gap means a cell gap of 3.5 μm or less.

[0024] [Radical Generation Film - Forming Composition] The radical generation film - forming composition for forming a radical generation film used in the present invention contains a polymer as a component and a group capable of generating radicals. At this time, the composition may contain a polymer to which a group capable of generating radicals is bonded, or may be a composition of a compound having a group capable of generating radicals and a polymer serving as a base resin. By applying and curing such a composition to form a film, a radical generation film in which a group capable of generating radicals is immobilized in the film can be obtained. The group capable of generating radicals is preferably an organic group that induces radical polymerization.

[0025] Examples of such organic groups that induce radical polymerization include organic groups represented by the following formulas [X - 1] to [X - 18], [W], [Y], and [Z]. [Chemical Formula] (In formulas [X - 1] to [X - 18], * represents a bonding site, S1 and S2 each independently represent -O-, -NR-, or -S-, R represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms (among the alkyl groups having 1 to 10 carbon atoms, a part of the -CH2 - group of the alkyl group having 2 to 10 carbon atoms may be replaced by an oxygen atom. However, in S2R or NR, when a part of the -CH2 - group of the alkyl group is replaced by an oxygen atom, the oxygen atom is not directly bonded to S2 or N). R1 and R2 each independently represent a hydrogen atom, a halogen atom, or an alkyl group having 1 to 4 carbon atoms.) [Chemical Formula] (In formulas [W], [Y], and [Z], * represents a bonding site, 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 9 and R 10 each independently represent an alkyl group having 1 to 10 carbon atoms or an alkoxy group having 1 to 10 carbon atoms, R 9 and R10 When it is an alkyl group, they may be bonded to each other at the ends to form a ring structure. Q represents any of the following structures.

Chemical formula

[0026] As the polymer, at least one polymer selected from the group consisting of a polyimide precursor, polyimide, polyurea, polyamide, polyacrylate, polymethacrylate, and polyorganosiloxane is preferable.

[0027] In order to obtain the radical generation film used in the present invention, when using a polymer having an organic group that induces the radical polymerization, in order to obtain a polymer having a group capable of generating radicals, as a monomer component, a monomer having a photoreactive side chain containing at least one selected from a methacryl group, an acrylic group, a vinyl group, an allyl group, a coumarin group, a styryl group, and a cinnamoyl group, or a monomer having a site that decomposes upon ultraviolet irradiation and generates radicals in the side chain is preferably used for production. On the other hand, a monomer that generates radicals has problems such as spontaneously polymerizing itself and becoming an unstable compound. Therefore, from the viewpoint of ease of synthesis, a polymer derived from a diamine having a radical generation site is preferable, and a polyimide precursor such as polyamic acid or polyamic acid ester, polyimide, polyurea, polyamide, etc. are more preferable.

[0028] The polymer containing an organic group that induces radical polymerization is preferably at least one polymer selected from a polyimide precursor, a polyimide, a polyurea, and a polyamide obtained using a diamine component containing a diamine having an organic group that induces radical polymerization. Specific examples of such a diamine containing an organic group that induces radical polymerization include, for example, a diamine having a side chain that generates radicals and is polymerizable, and a diamine having a structure represented by the following formula (6), but are not limited thereto.

Chemical formula

Chemical formula

[0029] The bonding positions of the two amino groups (-NH2) in formula (6) are not limited. Specifically, for the bonding group on the side chain, the 2,3 position, 2,4 position, 2,5 position, 2,6 position, 3,4 position, and 3,5 position on the benzene ring can be mentioned. Among them, from the perspective of reactivity when synthesizing polyamic acid, the 2,4 position, 2,5 position, or 3,5 position is preferable. Considering the ease of synthesizing diamine as well, the 2,4 position or 3,5 position is more preferable.

[0030] Specific examples of the diamine having a photoreactive group containing at least one selected from the group consisting of a methacryl group, an acrylic group, a vinyl group, an allyl group, a coumaril group, a styryl group, and a cinnamoyl group include, but are not limited to, the following compounds.

Chemical formula

[0031] Among diamines containing an organic group that induces radical polymerization, examples of diamines having a site that decomposes upon ultraviolet irradiation to generate radicals as a side chain include, but are not limited to, diamines having a structure represented by the following formula (7) or formula (7’).

Chemical formula

Chemical formula

Chemical formula

[0032] The bonding positions of the two amino groups (-NH2) in the above formula (7) are not limited. Specifically, for the bonding group on the side chain, the 2,3 position, 2,4 position, 2,5 position, 2,6 position, 3,4 position, and 3,5 position on the benzene ring can be mentioned. Among them, from the viewpoint of reactivity when synthesizing polyamic acid, the 2,4 position, 2,5 position, or 3,5 position is preferable.)

[0033] Especially in view of ease of synthesis, high versatility, properties, etc., the structure represented by the following formula is most preferable, but not limited thereto.) [Chemical formula] (In the formula, n is an integer of 2 to 8.)

[0034] In the diamines represented by Formula (7) and Formula (7’), in view of ease of synthesis, high versatility, properties, etc., the structure represented by the following formula is most preferable, but is not limited thereto. [Chemical Formula] (In the formula, n is an integer of 2 to 8, and E is a single bond, -O-, -C(CH3)2-, -NH-, -CO-, -NHCO-, -CONH-, -COO-, -OCO-, -(CH2) m -, -SO2-, -O-(CH2) m -O-, -O-C(CH3)2-, -C(CH3)2-O-, -CO-(CH2) m -,-(CH2) m -CO-,-NH-(CH2) m -,-(CH2) m -NH-,-SO2-(CH2) m -,-(CH2) m -SO2-,-CONH-(CH2) m -,-(CH2) m -NHCO-,-CONH-(CH2) m -NHCO- or -COO-(CH2) m -OCO-, and m is an integer of 1 to 8.)

[0035] The above diamines can also be used alone or in combination of two or more depending on properties such as liquid crystal alignment properties when used as a radical generation film, sensitivity in a polymerization reaction, voltage holding characteristics, and stored charge.

[0036] It is preferable to use the diamine containing an organic group that induces such radical polymerization in an amount of 5 to 50 mol% of the total diamine component used for the synthesis of the polymer contained in the radical generation film-forming composition, more preferably 10 to 40 mol%, and particularly preferably 15 to 30 mol%.

[0037] In addition, when obtaining the polymer used in the radical generating film of the present invention from diamine, as long as the effects of the present invention are not impaired, other diamines other than diamine containing an organic group that induces the radical polymerization can be used in combination as a diamine component. Specifically, 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-diaminophenol, 3,5-diaminobenzyl alcohol, 2,4-diaminobenzyl alcohol, 4,6-diaminoresorcinol, 4,4'-diaminobiphenyl, 3,3'-dimethyl-4,4'-diaminobiphenyl, 3,3'-dimethoxy-4,4'-diaminobiphenyl, 3,3'-dihydroxy-4,4'-diaminobiphenyl, 3,3'-dicarboxy-4,4'-diaminobiphenyl, 3,3'-difluoro-4,4'-diaminobiphenyl, 3,3'-bis(trifluoromethyl)-4,4'-diaminobiphenyl, 3,4'-diaminobiphenyl, 3,3'-diaminobiphenyl, 2,2'-diaminobiphenyl, 2,3'-diaminobiphenyl, 4,4'-diaminodiphenylmethane, 3,3'-diaminodiphenylmethane, 3,4'-diaminodiphenylmethane, 2,2'-diaminodiphenylmethane, 2,3'-diaminodiphenylmethane, 4,4'-diaminodiphenyl ether, 3,3'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 2,2'-diaminodiphenyl ether, 2,3'-diaminodiphenyl ether, 4,4'-sulfonyldianiline, 3,3'-sulfonyldianiline, bis(4-aminophenyl)silane, bis(3-aminophenyl)silane, dimethyl-bis(4-aminophenyl)silane, dimethyl-bis(3-aminophenyl)silane, 4,4'-thiodianiline, 3,3'-thiodianiline, 4,4'-diaminodiphenylamine, 3,3'-diaminodiphenylamine, 3,4'-diaminodiphenylamine, 2,2'-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, 3,3'-diaminobenzophenone, 3,4'-diaminobenzophenone, 2,2'-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, 4,4'-[1,4-phenylenebis(methylene)]dianiline, 4,4'-[1,3-phenylenebis(methylene)]dianiline, 3,4'-[1,4-phenylenebis(methylene)]dianiline, 3,4'-[1,3-phenylenebis(methylene)]dianiline, 3,3'-[1,4-phenylenebis(methylene)]dianiline, 3,3'-[1,3-phenylenebis(methylene)]dianiline, 1,4-phenylenebis[(4-aminophenyl)methanone], 1,4-phenylenebis[(3-aminophenyl)methanone], 1,3-phenylenebis[(4-aminophenyl)methanone], 1,3-phenylenebis[(3-aminophenyl)methanone], 1,4-phenylenebis(4-aminobenzoate), 1,4-phenylenebis(3-aminobenzoate), 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,N'-(1,4-phenylene)bis(4-aminobenzamide), N,N'-(1,3-phenylene)bis(4-aminobenzamide), N,N'-(1,4-phenylene)bis(3-aminobenzamide), N,N'-(1,3-phenylene)bis(3-aminobenzamide), N,N'-bis(4-aminophenyl)terephthalamide, N,N'-bis(3-aminophenyl)terephthalamide, N,N'-bis(4-aminophenyl)isophthalamide, N,N'-bis(3-aminophenyl)isophthalamide, 9,10-bis(4-aminophenyl)anthracene, 4,4'-bis(4-aminophenoxy)diphenyl sulfone, 2,2'-bis[4-(4-aminophenoxy)phenyl]propane, 2,2'-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane, 2,2'-bis(4-aminophenyl)hexafluoropropane, 2,2'-bis(3-aminophenyl)hexafluoropropane, 2,2'-bis(3-amino-4-methylphenyl)hexafluoropropane, 2,2'-bis(4-aminophenyl)propane, 2,2'-bis(3-aminophenyl)propane, 2,2'-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, 1,Aromatic diamines such as 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, 1,12-bis(3-aminophenoxy)dodecane; Alicyclic diamines such as bis(4-aminocyclohexyl)methane, 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-diamino-undecane, 1,12-diaminododecane; Diamines having a urea structure such as 1,3-bis[2-(p-aminophenyl)ethyl]urea, 1,3-bis[2-(p-aminophenyl)ethyl]-1-tert-butoxycarbonylurea; Diamines having a nitrogen-containing unsaturated heterocyclic structure such as N-p-aminophenyl-4-p-aminophenyl(tert-butoxycarbonyl)aminomethylpiperidine; Diamines having an N-Boc group (Boc represents a tert-butoxycarbonyl group) such as N-tert-butoxycarbonyl-N-(2-(4-aminophenyl)ethyl)-N-(4-aminobenzyl)amine, etc. may be mentioned.,

[0038] When using the above other diamines as a radical generation film, one kind or a mixture of two or more kinds can be used according to characteristics such as liquid crystal alignment properties, sensitivity in the polymerization reaction, voltage holding characteristics, and accumulated charge.,

[0039] In the synthesis when the polymer is polyamic acid, the tetracarboxylic dianhydride to be reacted with the above diamine component is not particularly limited. Specifically, pyromellitic acid, 2,3,6,7-naphthalenetetracarboxylic acid, 1,2,5,6-naphthalenetetracarboxylic acid, 1,4,5,8-naphthalenetetracarboxylic acid, 2,3,6,7-anthracenetetracarboxylic acid, 1,2,5,6-anthracenetetracarboxylic acid, 3,3’,4,4’-biphenyltetracarboxylic acid, 2,3,3’,4’-biphenyltetracarboxylic acid, bis(3,4-dicarboxyphenyl) ether, 3,3’,4,4’-benzophenonetetracarboxylic acid, bis(3,4-dicarboxyphenyl) sulfone, bis(3,4-dicarboxyphenyl) methane, 2,2-bis(3,4-dicarboxyphenyl) propane, 1,1,1,3,3,3-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, 3,3’,4,4’-diphenylsulfonetetracarboxylic acid, 3,4,9,10-perylenetetracarboxylic acid, 1,3-diphenyl-1,2,3,4-cyclobutanetetracarboxylic acid, oxydiphthalic tetracarboxylic acid, 1,2,3,4-cyclobutanetetracarboxylic acid, 1,2,3,4-cyclopentanetetracarboxylic acid, 1,2,4,5-cyclohexanetetracarboxylic 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-tetrahydrofuran tetracarboxylic acid, 3,4-dicarboxy-1-cyclohexyl succinic acid, 2,3,5-tricarboxycyclopentyl acetic acid, 3,4-dicarboxy-1,2,3,4-tetrahydro-1-naphthalene succinic acid, bicyclo[3,3,0]octane-2,4,6,8-tetracarboxylic acid, bicyclo[4,3,0]nonane-2,4,7,9-tetracarboxylic acid, bicyclo[4,4,0]decane-2,4,7,Dianhydrides of tetracarboxylic acids such as 9-tetracarboxylic acid, bicyclo[4,4,0]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, bicyclo[2,2,2]oct-7-ene-2,3,5,6-tetracarboxylic acid, 5-(2,5-dioxotetrahydrofuryl)-3-methyl-3-cyclohexane-1,2-dicarboxylic acid, tetracyclo[6,2,1,1,0<2,7>]dodeca-4,5,9,10-tetracarboxylic acid, 3,5,6-tricarboxynorbornane-2:3,5:6-dicarboxylic acid, 1,2,4,5-cyclohexanetetracarboxylic acid, etc. may be mentioned.,

[0040] Of course, the tetracarboxylic dianhydride may also be used alone or in combination of two or more kinds according to the properties such as the liquid crystal alignment property when used as a radical generating film, the sensitivity in the polymerization reaction, the voltage holding characteristic, and the accumulated charge.,

[0041] In the synthesis when the polymer is a polyamic acid ester, the structure of the tetracarboxylic acid dialkyl ester to be reacted with the above diamine component is not particularly limited, and specific examples thereof are given below.,

[0042] Specific examples of the aliphatic tetracarboxylic acid diester include 1,2,3,4-cyclobutanetetracarboxylic acid dialkyl ester, 1,2-dimethyl-1,2,3,4-cyclobutanetetracarboxylic acid dialkyl ester, 1,3-dimethyl-1,2,3,4-cyclobutanetetracarboxylic acid dialkyl ester, 1,2,3,4-tetramethyl-1,2,3,4-cyclobutanetetracarboxylic acid dialkyl ester, 1,2,3,4-cyclopentanetetracarboxylic acid dialkyl ester, 2,3,4,5-tetrahydrofuran tetracarboxylic acid dialkyl ester, 1,2,4,5-cyclohexanetetracarboxylic acid dialkyl ester, 3,4-dicarboxy-1-cyclohexyl succinic acid dialkyl ester, 3,4-dicarboxy-1,2,3,4-tetrahydro-1-naphthalene succinic acid dialkyl ester, 1,2,3,4-butanetetracarboxylic acid dialkyl ester, bicyclo[3.3.0]octane-2,4,6,8-tetracarboxylic acid dialkyl ester, 3,3’,4,4’-dicyclohexyltetracarboxylic acid dialkyl ester, 2,3,5-tricarboxycyclopentyl acetic acid dialkyl ester, cis-3,7-dibutylcycloocta-1,5-diene-1,2,5,6-tetracarboxylic acid dialkyl ester, tricyclo[4.2.1.0<2,5>]nonane-3,4,7,8-tetracarboxylic acid-3,4:7,8-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 ester, 4-(2,5-dioxotetrahydrofuran-3-yl)-1,2,3,4-tetrahydronaphthalene-1,2-dicarboxylic dialkyl ester, and the like.

[0043] Examples of the aromatic tetracarboxylic acid dialkyl esters include dialkyl pyromellitates, dialkyl 3,3’,4,4’-biphenyltetracarboxylates, dialkyl 2,2’,3,3’-biphenyltetracarboxylates, dialkyl 2,3,3’,4-biphenyltetracarboxylates, dialkyl 3,3’,4,4’-benzophenonetetracarboxylates, dialkyl 2,3,3’,4’-benzophenonetetracarboxylates, dialkyl bis(3,4-dicarboxyphenyl) ether esters, dialkyl bis(3,4-dicarboxyphenyl) sulfone esters, dialkyl 1,2,5,6-naphthalenetetracarboxylates, dialkyl 2,3,6,7-naphthalenetetracarboxylates, and the like.

[0044] In the synthesis when the polymer is a polyurea, there is no particular limitation on the diisocyanate to be reacted with the above diamine component, and it can be used according to availability and the like. The specific structure of the diisocyanate is shown below. [Chemical formula] In the formula, R2 and R3 represent aliphatic hydrocarbon groups having 1 to 10 carbon atoms.

[0045] The aliphatic diisocyanates shown as K-1 to K-5 have the disadvantage of poor reactivity but the merit of improving solvent solubility. The aromatic diisocyanates such as those shown as K-6 to K-13 are rich in reactivity and have the effect of improving heat resistance, but have the drawback of reducing solvent solubility. In terms of versatility and properties, K-1, K-7, K-8, K-9, and K-10 are preferable. From the viewpoint of electrical properties, K-12 is preferable, and from the viewpoint of liquid crystal alignment properties, K-13 is preferable. Two or more diisocyanates can also be used in combination, and it is preferable to apply them variously according to the desired properties.

[0046] In addition, some of the diisocyanates can be replaced with the tetracarboxylic dianhydrides described above, and they may be used in the form of a copolymer of polyamic acid and polyurea, or may be used in the form of a copolymer of polyimide and polyurea by chemical imidization.

[0047] In the synthesis when the polymer is polyamide, the structure of the dicarboxylic acid to be reacted is not particularly limited, but specific examples are as follows. Examples of aliphatic dicarboxylic acids include dicarboxylic acids such as malonic acid, oxalic acid, dimethylmalonic acid, succinic acid, fumaric acid, glutaric acid, adipic acid, muconic acid, 2-methyladipic acid, trimethyladipic acid, pimelic acid, 2,2-dimethylglutaric acid, 3,3-diethylsuccinic acid, azelaic acid, sebacic acid, and suberic acid.

[0048] Examples of alicyclic dicarboxylic acids include 1,1-cyclopropanedicarboxylic acid, 1,2-cyclopropanedicarboxylic acid, 1,1-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, 1,1-cyclopentanedicarboxylic acid, 1,2-cyclopentanedicarboxylic acid, 1,3-cyclopentanedicarboxylic acid, 1,1-cyclohexanedicarboxylic acid, 1,2-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, 1,4-(2-norbornene)dicarboxylic acid, norbornene-2,3-dicarboxylic acid, bicyclo[2.2.2]octane-1,4-dicarboxylic acid, bicyclo[2.2.2]octane-2,3-dicarboxylic acid, 2,5-dioxo-1,4-bicyclo[2.2.2]octanedicarboxylic acid, 1,3-adamantanedicarboxylic acid, 4,8-dioxo-1,3-adamantanedicarboxylic acid, 2,6-spiro[3.3]heptanedicarboxylic acid, 1,3-adamantanediacetic acid, camphoric acid, etc.

[0049] Examples of the aromatic dicarboxylic acid include dicarboxylic acids such as o-phthalic acid, isophthalic acid, terephthalic acid, 5-methylisophthalic acid, 5-tert-butylisophthalic acid, 5-aminoisophthalic acid, 5-hydroxyisophthalic acid, 2,5-dimethylterephthalic acid, tetramethylterephthalic acid, 1,4-naphthalenedicarboxylic acid, 2,5-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic acid, 1,4-anthracenedicarboxylic acid, 1,4-anthraquinonedicarboxylic acid, 2,5-biphenyldicarboxylic acid, 4,4'-biphenyldicarboxylic acid, 1,5-biphenylenedicarboxylic acid, 4,4''-terphenyldicarboxylic acid, 4,4'-diphenylmethanedicarboxylic acid, 4,4'-diphenylethanedicarboxylic acid, 4,4'-diphenylpropanedicarboxylic acid, 4,4'-diphenylhexafluoropropanedicarboxylic acid, 4,4'-diphenyletherdicarboxylic acid, 4,4'-bibenzyl dicarboxylic acid, 4,4'-stilbenedicarboxylic acid, 4,4'-transdicarboxylic acid, 4,4'-carbonyl dibenzoic acid, 4,4'-sulfonyldibenzoic acid, 4,4'-dithiodibenzoic acid, p-phenylenediacetic acid, 3,3'-p-phenylenedipropionic acid, 4-carboxycinnamic acid, p-phenylenediacrylic acid, 3,3'-[4,4'-(methylenedi-p-phenylene)]dipropionic acid, 4,4'-[4,4'-(oxydi-p-phenylene)]dipropionic acid, 4,4'-[4,4'-(oxydi-p-phenylene)]dibutyric acid, (isopropylidenedi-p-phenylene dioxy) dibutyric acid, bis(p-carboxyphenyl)dimethylsilane, etc.

[0050] Examples of the dicarboxylic acid containing a complex ring include 1,5-(9-oxofluorenyl)dicarboxylic acid, 3,4-furandicarboxylic acid, 4,5-thiazoledicarboxylic acid, 2-phenyl-4,5-thiazoledicarboxylic 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.

[0051] Each of the above-mentioned various dicarboxylic acids may have an acid dichloride or anhydride structure. These dicarboxylic acids are preferably those capable of giving a polyamide having a linear structure, since it is preferable for maintaining the orientation of liquid crystal molecules. Among these, terephthalic acid, isophthalic acid, 1,4-cyclohexanedicarboxylic acid, 4,4'-biphenyldicarboxylic acid, 4,4'-diphenylmethanedicarboxylic acid, 4,4'-diphenylethanedicarboxylic acid, 4,4'-diphenylpropanedicarboxylic acid, 4,4'-diphenylhexafluoropropanedicarboxylic acid, 2,2-bis(phenyl)propanedicarboxylic acid, 4,4'-terphenyldicarboxylic acid, 2,6-naphthalenedicarboxylic acid, 2,5-pyridinedicarboxylic acid, or acid dichlorides thereof, etc. are preferably used. Some of these compounds have isomers, and mixtures containing them may also be used. Further, two or more kinds of compounds may be used in combination. Note that the dicarboxylic acids used in the present invention are not limited to the exemplified compounds above.

[0052] In obtaining polyamic acid, polyamic acid ester, polyurea, and polyamide by the reaction of a diamine as a raw material (also referred to as "diamine component") with a tetracarboxylic dianhydride as a raw material (also referred to as "tetracarboxylic dianhydride component"), a tetra-carboxylic acid diester, a diisocyanate, and a component selected from dicarboxylic acids, known synthesis methods can be used. Generally, it is a method of reacting the diamine component with one or more components selected from the tetracarboxylic dianhydride component, the tetra-carboxylic acid diester, the diisocyanate, and the dicarboxylic acid in an organic solvent.

[0053] The reaction between the diamine component and the tetracarboxylic dianhydride component is advantageous in that it proceeds relatively easily in an organic solvent and no by-products are generated.

[0054] The organic solvent used in the above reaction is not particularly limited as long as the generated polymer can dissolve therein. Furthermore, even if it is an organic solvent in which the polymer does not dissolve, it may be mixed with the above solvent and used within the range where the generated polymer does not precipitate. Note that since the water in the organic solvent inhibits the polymerization reaction and furthermore causes hydrolysis of the generated polymer, it is preferable to use an organic solvent that has been dehydrated and dried.

[0055] Examples of the organic solvent include N,N-dimethylformamide, N,N-dimethylacetamide, N,N-diethylformamide, N-methylformamide, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, 2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone, 3-methoxy-N,N-dimethylpropanamide, N-methylcaprolactam, dimethyl sulfoxide, tetramethylurea, pyridine, dimethyl sulfone, hexamethyl sulfoxide, γ-butyrolactone, isopropyl alcohol, methoxymethyl pentanol, dipentene, ethyl amyl ketone, methyl nonyl ketone, methyl ethyl ketone, methyl isoamyl ketone, methyl isopropyl ketone, methyl cellosolve, ethyl cellosolve, methyl cellosolve acetate, butyl cellosolve acetate, ethyl cellosolve acetate, butyl carbitol, ethyl carbitol, ethylene glycol, ethylene glycol monoacetate, ethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether, propylene glycol, propylene glycol monoacetate, propylene glycol monomethyl ether, propylene glycol monobutyl ether, propylene glycol - tert-butyl ether, dipropylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, diethylene glycol, diethylene glycol monoacetate, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, dipropylene glycol monoacetate monomethyl ether, dipropylene glycol 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, ethyl isobutyl ether, diisobutylene, amyl acetate, butyl butyrate, butyl ether, diisobutyl ketone, methyl cyclohexene, 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-ethoxypropionate, 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, etc. can be mentioned. These organic solvents may be used alone or in combination.

[0056] When reacting the diamine component and the tetracarboxylic dianhydride component in an organic solvent, methods include stirring a solution in which the diamine component is dispersed or dissolved in the organic solvent and adding the tetracarboxylic dianhydride component as it is or dispersed or dissolved in the organic solvent; conversely, adding the diamine component to a solution in which the tetracarboxylic dianhydride component is dispersed or dissolved in the organic solvent; and adding the tetracarboxylic dianhydride component and the diamine component alternately. Any of these methods may be used. Also, when the diamine component or the tetracarboxylic dianhydride component consists of multiple types of compounds, they may be reacted in a pre-mixed state, reacted sequentially individually, or further, the low molecular weight bodies reacted individually may be mixed and reacted to form a high molecular weight body.

[0057] When reacting the diamine component and the tetracarboxylic dianhydride component, any temperature can be selected. For example, it is in the range of -20 to 100 °C, preferably -5 to 80 °C. Also, the reaction can be carried out at any concentration. For example, the total amount of the diamine component and the tetracarboxylic dianhydride component with respect to the reaction solution is 1 to 50% by mass, preferably 5 to 30% by mass.

[0058] In the above polymerization reaction, the ratio of the total molar number of the tetracarboxylic dianhydride component to the total molar number of the diamine component can be selected as an arbitrary value according to the molecular weight of the polyamic acid to be obtained. Similar to a normal polycondensation reaction, the closer this molar ratio is to 1.0, the larger the molecular weight of the resulting polyamic acid becomes. The preferable range is 0.8 to 1.2.

[0059] The method for synthesizing the polymer used in the present invention is not limited to the above method. When synthesizing polyamic acid, similar to the general method for synthesizing polyamic acid, instead of the above tetracarboxylic dianhydride, a tetracarboxylic acid derivative such as a tetracarboxylic acid or tetracarboxylic acid dihalide having a corresponding structure can be used, and the corresponding polyamic acid can also be obtained by reacting in a known method. Further, when synthesizing polyurea, a diamine and a diisocyanate may be reacted. When producing a polyamic acid ester or polyamide, a diamine and a component selected from tetracarboxylic acid diesters and dicarboxylic acids may be reacted in the presence of a known condensing agent or after being derived into acid halides by a known method and then reacted with the diamine.

[0060] Further, a polyimide can be obtained by subjecting the above polyamic acid to ring closure (imidization). Note that the imidization rate as used in this specification refers to the ratio of the imide group to the total amount of the imide group and carboxy group derived from the tetracarboxylic dianhydride. In the polyimide, the imidization rate does not necessarily have to be 100% and can be arbitrarily adjusted according to the use and purpose. The imidization rate of the polyimide in the present invention is preferably 30% or more because the voltage holding ratio can be increased. On the other hand, from the viewpoint of suppressing whitening characteristics, that is, precipitation of the polymer in the varnish, 80% or less is preferable.

[0061] Examples of the method for imidizing the above-described polyamic acid to obtain a polyimide include thermal imidization in which the solution of the polyamic acid is directly heated and catalytic imidization in which a catalyst is added to the solution of the polyamic acid. When thermally imidizing polyamic acid in a solution, the temperature is usually 100 to 400°C, preferably 120 to 250°C, and it is preferably carried out while removing the water generated by the imidization reaction outside the system.

[0062] Catalytic imidization of polyamic acid can be carried out by adding a basic catalyst and an acid anhydride to a solution of polyamic acid and stirring at a temperature of usually -20 to 250°C, preferably 0 to 180°C. The amount of the basic catalyst is usually 0.5 to 30 molar times, preferably 2 to 20 molar times, based on the amic acid group, and the amount of the acid anhydride is usually 1 to 50 molar times, preferably 3 to 30 molar times, based on the amic acid group. Examples of the basic catalyst include pyridine, triethylamine, trimethylamine, tributylamine, trioctylamine, etc. Among them, pyridine is preferable because it has an appropriate basicity to promote the reaction. Examples of the acid anhydride include acetic anhydride, trimellitic anhydride, pyromellitic anhydride, etc. Among them, acetic anhydride is preferable because it facilitates purification after the reaction. The imidization rate by catalytic imidization can be controlled by adjusting the amount of catalyst, reaction temperature, reaction time, etc.

[0063] When recovering the produced polymer from the reaction solution of the polymer, the reaction solution may be poured into a poor solvent to precipitate it. Examples of the poor solvent used for precipitation include methanol, acetone, hexane, butyl cellosolve, heptane, methyl ethyl ketone, methyl isobutyl ketone, ethanol, toluene, benzene, water, etc. The polymer precipitated by pouring into the poor solvent can be recovered by filtration and then dried at normal pressure or reduced pressure, at room temperature or by heating. Also, if the operation of redissolving the precipitated and recovered polymer in an organic solvent and reprecipitating and recovering it is repeated 2 to 10 times, the impurities in the polymer can be reduced. Examples of the poor solvent at this time include alcohols, ketones, hydrocarbons, etc. Using three or more types of poor solvents selected from these is preferable because the purification efficiency is further improved.

[0064] Also, when the radical generating film is made of a polymer containing an organic group that induces radical polymerization, the radical generating film-forming composition used in the present invention may contain a polymer other than the polymer containing an organic group that induces radical polymerization. At that time, the content of the other polymer in all the polymer components is preferably 5 to 95% by mass, more preferably 30 to 70% by mass.

[0065] When considering the strength of the radical generating film obtained by coating the radical generating film-forming composition, the workability during film formation, the uniformity of the coating film, etc., the molecular weight of the polymer contained in the radical generating film-forming composition is preferably 5,000 to 1,000,000 in terms of the weight average molecular weight measured by the GPC (Gel Permeation Chromatography) method, and more preferably 10,000 to 150,000.

[0066] When the radical generating film used in the present invention is obtained by coating and curing a composition of a compound having a radical-generating group and a polymer to form a film and immobilizing it in the film, examples of the polymer include a polyimide precursor produced according to the above production method, and a polymer selected from the group consisting of polyimide, polyurea, polyamide, polyacrylate, polymethacrylate, etc., and at least one polymer obtained using a diamine component in which the diamine containing the organic group that induces the above radical polymerization is 0 mol% of the total diamine component used in the synthesis of the polymer to be contained in the radical generating film-forming composition may be used. Examples of the compound having a radical-generating group added at that time include the following.

[0067] A compound that generates radicals upon heating is a compound that generates radicals by heating to a temperature equal to or higher than its decomposition temperature. Examples of such radical thermal polymerization initiators include ketone peroxides (such as methyl ethyl ketone peroxide, cyclohexanone peroxide, etc.), diacyl peroxides (such as acetyl peroxide, benzoyl peroxide, etc.), hydroperoxides (such as hydrogen peroxide, tert-butyl hydroperoxide, cumene hydroperoxide, etc.), dialkyl peroxides (such as di-tert-butyl peroxide, dicumyl peroxide, dilauroyl peroxide, etc.), peroxyketals (such as dibutyl peroxycyclohexane, etc.), alkyl peresters (such as tert-butyl peroxyneodecanoate, tert-butyl peroxypivalate, tert-amyl peroxy-2-ethylhexanoate, etc.), persulfates (such as potassium persulfate, sodium persulfate, ammonium persulfate, etc.), and azo compounds (such as azobisisobutyronitrile, and 2,2'-di(2-hydroxyethyl)azobisisobutyronitrile, etc.). Such radical thermal polymerization initiators can be used alone or in combination of two or more.

[0068] The compound that generates radicals with light is not particularly limited as long as it is a compound that initiates radical polymerization by light irradiation. Examples of such radical photoinitiators include benzophenone, Michler's ketone, 4,4'-bis(diethylamino)benzophenone, xanthone, thioxanthone, isopropylxanthone, 2,4-diethylthioxanthone, 2-ethylanthraquinone, acetophenone, 2-hydroxy-2-methylpropiophenone, 2-hydroxy-2-methyl-4'-isopropylpropiophenone, 1-hydroxycyclohexyl phenyl ketone, isopropyl benzoin ether, isobutyl benzoin ether, 2,2-diethoxyacetophenone, 2,2-dimethoxy-2-phenylacetophenone, camphorquinone, benzanthrone, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone-1, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, 4,4'-di(t-butylperoxycarbonyl)benzophenone, 3,4,4'-tri(t-butylperoxycarbonyl)benzophenone, 2,4,6-trimethylbenzoyldiphenylphosphine 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'-pentyloxystyryl)-4,6-bis(trichloromethyl)-s-triazine, 4-[p-N,N-di(ethoxycarbonylmethyl)]-2,6-di(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, 3,3'-Carbonylbis(7-diethylaminocoumarin), 2-(o-chlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetrakis(4-ethoxycarbonylphenyl)-1,2'-biimidazole, 2,2'-bis(2,4-dichlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole, 2,2'-bis(2,4-dibromophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole, 2,2'-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-hydroxycyclohexyl phenyl ketone, bis(5-2,4-cyclopentadien-1-yl)-bis(2,6-difluoro-3-(1H-pyrrol-1-yl)-phenyl)titanium, 3,3',4,4'-tetra(t-butylperoxycarbonyl)benzophenone, 3,3',4,4'-tetra(t-hexylperoxycarbonyl)benzophenone, 3,3'-di(methoxycarbonyl)-4,4'-di(t-butylperoxycarbonyl)benzophenone, 3,4'-di(methoxycarbonyl)-4,3'-di(t-butylperoxycarbonyl)benzophenone, 4,4'-di(methoxycarbonyl)-3,3'-di(t-butylperoxycarbonyl)benzophenone, 2-(3-methyl-3H-benzothiazol-2-ylidene)-1-naphthalen-2-yl-ethanone, or 2-(3-methyl-1,3-benzothiazol-2(3H)-ylidene)-1-(2-benzoyl)ethanone, etc. can be mentioned. These compounds may be used alone or two or more of them may be mixed and used.,

[0069] In addition, even when the radical generating film is composed of a polymer containing an organic group that induces radical polymerization, for the purpose of promoting radical polymerization when energy is applied, a compound having the above radical generating group may be contained.,

[0070] The radical generating film-forming composition can contain a polymer component, and an organic solvent that dissolves or disperses a radical generator and other optional components as required. There is no particular limitation on such an organic solvent, and examples thereof include the organic solvents exemplified in the synthesis of the above polyamic acid. Among them, N-methyl-2-pyrrolidone, γ-butyrolactone, N-ethyl-2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone, 3-methoxy-N,N-dimethylpropanamide, etc. are preferable from the viewpoint of solubility. In particular, N-methyl-2-pyrrolidone or N-ethyl-2-pyrrolidone is preferable, but a mixed solvent of two or more types may also be used.

[0071] Further, it is preferable to mix and use a solvent that improves the uniformity and smoothness of the coating film with an organic solvent having high solubility of the components contained in the radical generating film-forming composition.

[0072] As solvents for improving the uniformity and smoothness of the coating film, for example, isopropyl alcohol, methoxymethyl pentanol, methyl cellosolve, ethyl cellosolve, butyl cellosolve (ethylene glycol monobutyl ether), methyl cellosolve acetate, butyl cellosolve acetate, ethyl cellosolve acetate, butyl carbitol, ethyl carbitol, ethyl carbitol acetate, ethylene glycol, ethylene glycol monoacetate, ethylene glycol monoisopropyl ether, propylene glycol, propylene glycol monoacetate, propylene glycol monomethyl ether, propylene glycol monobutyl ether, propylene glycol - tert - butyl ether, dipropylene glycol monomethyl ether, diethylene glycol, 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, dipropylene glycol monopropyl ether, dipropylene glycol monoacetate monopropyl ether, 3 - methyl - 3 - methoxybutyl acetate, tripropylene glycol methyl ether, 3 - methyl - 3 - methoxybutanol, diisopropyl ether, ethyl isobutyl ether, diisobutylene, amyl acetate, butyl butyrate, butyl ether, diisobutyl ketone, methyl cyclohexene, 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 - ethoxypropionate, 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 can be mentioned. These solvents may be mixed in multiple types. When using these solvents, it is preferably 5 to 80% by mass, more preferably 20 to 60% by mass, of the total solvents contained in the radical generating film-forming composition.

[0073] The radical generating film-forming composition may contain components other than those described above. Examples thereof include compounds that improve the film thickness uniformity and surface smoothness when the radical generating film-forming composition is applied, compounds that improve the adhesion between the radical generating film-forming composition and the substrate, and compounds that further improve the film strength of the radical generating film-forming composition.

[0074] Examples of the compounds that improve the film thickness uniformity and surface smoothness include fluorine-based surfactants, silicone-based surfactants, and nonionic surfactants. More specifically, for example, F-Top EF301, EF303, EF352 (manufactured by Mitsubishi Materials Electronic Chemicals Co., Ltd.), Megafac F171, F173, R-30 (manufactured by DIC Corporation), Fluorad FC430, FC431 (manufactured by 3M Company), Asahi Guard AG710, Surflon S-382, SC101, SC102, SC103, SC104, SC105, SC106 (manufactured by AGC Inc.) and the like can be mentioned. When using these surfactants, the usage ratio is preferably 0.01 to 2 parts by mass, more preferably 0.01 to 1 part by mass, based on 100 parts by mass of the total amount of the polymers contained in the radical generating film-forming composition.

[0075] Specific examples of the compound for improving the adhesion between the radical generating film-forming composition and the substrate include a functional silane-containing compound and an epoxy group-containing compound, etc.For example, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 2-aminopropyltrimethoxysilane, 2-aminopropyltriethoxysilane, N-(2-aminoethyl)-3-aminopropyltrimethoxysilane, N-(2-aminoethyl)-3-aminopropylmethyldimethoxysilane, 3-ureidopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane, N-ethoxycarbonyl-3-aminopropyltrimethoxysilane, N-ethoxycarbonyl-3-aminopropyltriethoxysilane, N-triethoxysilylpropyltriethylenetriamine, N-trimethoxysilylpropyltriethylenetriamine, 10-trimethoxysilyl-1,4,7-triazadecane, 10-triethoxysilyl-1,4,7-triazadecane, 9-trimethoxysilyl-3,6-diazanonyl acetate, 9-triethoxysilyl-3,6-diazanonyl acetate, N-benzyl-3-aminopropyltrimethoxysilane, N-benzyl-3-aminopropyltriethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, N-phenyl-3-aminopropyltriethoxysilane, N-bis(oxyethylene)-3-aminopropyltrimethoxysilane, N-bis(oxyethylene)-3-aminopropyltriethoxysilane, 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, glycerin diglycidyl ether, 2,2-dibromoneopentyl glycol diglycidyl ether, 1,3,5,6-tetraglycidyl-2,4-hexanediol, N,N,N’,N’-tetraglycidyl-m-xylenediamine, 1,3-bis(N,N-diglycidylaminomethyl)cyclohexane, N,N,N’,N’-tetraglycidyl-4,4’-diaminodiphenylmethane, 3-(N-allyl-N-glycidyl)aminopropyltrimethoxysilane, 3-(N,N-diglycidyl)aminopropyltrimethoxysilane and the like can be mentioned.

[0076] Also, in order to further increase the film strength of the radical generating film, phenolic compounds such as 2,2'-bis(4-hydroxy-3,5-dihydroxymethylphenyl)propane and tetrakis(methoxymethyl)bisphenol may be added. When using these compounds, it is preferably 0.1 to 30 parts by mass, more preferably 1 to 20 parts by mass, based on 100 parts by mass of the total amount of the polymer contained in the radical generating film forming composition.

[0077] Furthermore, in addition to the above, dielectric materials or conductive substances for the purpose of changing electrical properties such as the dielectric constant and conductivity of the radical generating film may be added to the radical generating film forming composition as long as the effects of the present invention are not impaired.

[0078] [Radical generating film] The radical generating film of the present invention can be obtained, for example, using the above radical generating film forming composition. For example, the cured film obtained by applying the radical generating film forming composition used in the present invention to a substrate and then performing drying and baking can be used as the radical generating film as it is. In addition, this cured film can be subjected to an alignment treatment by rubbing, irradiating with polarized light or light of a specific wavelength, or treatment with an ion beam, and it is also possible to irradiate UV to the liquid crystal display element after filling with liquid crystal as an alignment film for PSA.

[0079] The substrate on which the radical generating film forming composition is applied is not particularly limited as long as it is a highly transparent substrate, but a substrate on which a transparent electrode for driving liquid crystal is formed on the substrate is preferred.

[0080] Specific examples include substrates on which transparent electrodes are formed on plastic plates such as glass plates, polycarbonate, poly(meth)acrylate, polyethersulfone, polyarylate, polyurethane, polysulfone, polyether, polyether ketone, trimethylpentene, polyolefin, polyethylene terephthalate, (meth)acrylonitrile, triacetyl cellulose, diacetyl cellulose, and acetate butyrate cellulose.

[0081] For the substrate that can be used in the liquid crystal display element of the IPS mode, electrode patterns such as standard IPS comb electrodes and PSA fishbone electrodes, and protrusion patterns such as those of MVA can also be used.

[0082] Also, in a high-functional element such as a TFT-type element, an element in which an element such as a transistor is formed between the electrode for liquid crystal driving and the substrate is used.

[0083] When intending a transmissive liquid crystal display element, it is common to use the substrate as described above. However, when intending a reflective liquid crystal display element, an opaque substrate such as a silicon wafer can also be used as long as it is only one side of the substrate. At that time, a material such as aluminum that reflects light can also be used for the electrode formed on the substrate.

[0084] Examples of the coating method of the radical generation film forming composition include spin coating method, printing method, inkjet method, spray method, roll coating method, etc. From the viewpoint of productivity, the transfer printing method is widely used industrially and is also preferably used in the present invention.

[0085] The drying step after applying the radical generation film forming composition is not necessarily required. However, when the time from application to firing is not constant for each substrate, or when firing is not performed immediately after application, it is preferable to include the drying step. This drying only needs to remove the solvent to such an extent that the coating film shape is not deformed by the conveyance of the substrate, etc., and the drying means is not particularly limited. For example, a method of drying on a hot plate at a temperature of 40 to 150 °C, preferably 60 to 100 °C for 0.5 to 30 minutes, preferably 1 to 5 minutes can be mentioned.

[0086] The coating film formed by applying the radical generating film forming composition by the above method can be baked to form a cured film. At that time, the baking temperature can usually be carried out at any temperature of 100 to 350 °C, preferably 140 to 300 °C, more preferably 150 to 230 °C, and still more preferably 160 to 220 °C. The baking time can usually be carried out for any time of 5 to 240 minutes. Preferably it is 10 to 90 minutes, and more preferably 20 to 90 minutes. Heating can usually be carried out by known methods, for example, using a hot plate, a hot air circulation oven, an IR (infrared) type oven, a belt furnace, etc.

[0087] The thickness of this cured film can be selected as needed, but preferably 5 nm or more, more preferably 10 nm or more. In this case, the reliability of the liquid crystal display element is improved, so it is suitable. Also, when the thickness of the cured film is preferably 300 nm or less, more preferably 150 nm or less, the power consumption of the liquid crystal display element does not become extremely large, so it is suitable.

[0088] As described above, the first substrate having a radical generating film can be obtained, and the radical generating film can be subjected to a uniaxial orientation treatment. Examples of the method for performing the uniaxial orientation treatment include an optical orientation method, an oblique evaporation method, rubbing, and a uniaxial orientation treatment by a magnetic field.

[0089] When performing the orientation treatment by rubbing in one direction, for example, while rotating a rubbing roller around which a rubbing cloth is wound, the substrate is moved so that the rubbing cloth and the film are in contact. When using the optical orientation method, the orientation treatment can be performed by irradiating the entire surface of the film with polarized UV of a specific wavelength and heating as needed. In the case of the first substrate of the present invention on which the comb-shaped electrodes are formed, the direction is selected according to the electrical physical properties of the liquid crystal. When using a liquid crystal having positive dielectric anisotropy, the rubbing direction is preferably substantially the same as the direction in which the comb-shaped electrodes extend.

[0090] As a process for creating a weak anchoring portion and a strong anchoring portion, there is a method of irradiating radiation in an arbitrary pattern through a photomask or the like. This is a process of irradiating the radical generating film with radiation in advance to eliminate the radical generating sites so as not to enter a weak anchoring state. Examples of the radiation used in this process include polarized light, light of a specific wavelength, and ion beams. It is particularly preferable to irradiate light having a wavelength at which the absorbance of the portion corresponding to the photo radical generating site is highest.

[0091] The second substrate of the present invention may or may not have a radical generating film. The second substrate is preferably a substrate having a conventionally known liquid crystal alignment film.

[0092] In the present invention, the first substrate may be a substrate having comb electrodes, and the second substrate may be a counter substrate. Also, in the present invention, the second substrate may be a substrate having comb electrodes, and the first substrate may be a counter substrate.

[0093] <Liquid crystal cell> The liquid crystal cell of the present invention is obtained by forming a radical generating film on a substrate by the above method, and then arranging a substrate (first substrate) having the radical generating film and a substrate (second substrate) having a known liquid crystal alignment film so that the radical generating film and the liquid crystal alignment film face each other, sandwiching spacers, fixing them with a sealant, and injecting and sealing a liquid crystal composition containing a liquid crystal and a radical polymerizable compound. At that time, the size of the spacers used is usually 1 to 30 μm, preferably 2 to 10 μm.

[0094] The method of injecting a liquid crystal composition containing a liquid crystal and a radical polymerizable compound is not particularly limited, and examples include a vacuum method in which the inside of the fabricated liquid crystal cell is depressurized and then a mixture containing a liquid crystal and a polymerizable compound is injected, and a dropping method in which a mixture containing a liquid crystal and a polymerizable compound is dropped and then sealed.

[0095] <Radical polymerizable compound, and liquid crystal composition> The radical polymerizable compound of the present invention is represented by the following formula (A). [Chemical formula] (In formula (A), M represents a polymerizable group capable of radical polymerization, R1 to R3 each independently represent a single bond or an alkylene group having 1 to 6 carbon atoms in which a linking group may be inserted, Ar represents an aromatic hydrocarbon group which may have a substituent, X1 and X2 each independently represent a hydrogen atom or an aromatic hydrocarbon group which may have a substituent, and R1X1, R2X2 and the carbon atom to which R1X1 and R2X2 are bonded may together form a ring. However, the total number of carbon atoms of R1X1, R2X2 and R3 is 1 or more.)

[0096] The alkylene group having 1 to 6 carbon atoms in which a linking group is inserted means a divalent group in which a linking group is inserted between carbon-carbon atoms in the alkylene group having 1 to 6 carbon atoms, or a divalent group in which a linking group is inserted between the alkylene group having 1 to 6 carbon atoms and the carbon atom bonded thereto. Examples of the linking group include a carbon-carbon unsaturated bond, an ether bond (-O-), an ester bond (-COO- or -OCO-), an amide bond (-CONH- or -NHCO-), etc. Examples of the unsaturated bond include a carbon-carbon double bond, etc. However, the alkylene group having 1 to 6 carbon atoms in which a carbon-carbon double bond is inserted preferably has the carbon-carbon double bond inside rather than at the terminal. Examples of the alkylene group having 1 to 6 carbon atoms in which a linking group may be inserted include an alkylene group having 1 to 6 carbon atoms, an oxyalkylene group having 1 to 6 carbon atoms, etc. The oxygen atom in the oxyalkylene group having 1 to 6 carbon atoms is bonded to, for example, the carbon atom bonded to M, R1, R2, and R3 in formula (A). The alkylene group having 1 to 6 carbon atoms may be a linear alkylene group, a branched alkylene group, or a cyclic alkylene group.

[0097] 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 halogenated alkyl group having 1 to 4 carbon atoms, and a halogenated alkoxy group having 1 to 4 carbon atoms. The halogenation in the halogenated alkyl group and the halogenated alkoxy group may be complete halogenation or partial halogenation. Examples of the halogen atom include a fluorine atom and a chlorine atom.

[0098] Examples of R1 include a single bond and an alkylene group having 1 to 6 carbon atoms. More specifically, the alkylene group having 1 to 6 carbon atoms is a linear alkylene group having 1 to 6 carbon atoms. Examples of R2 include a single bond and an alkylene group having 1 to 6 carbon atoms. More specifically, the alkylene group having 1 to 6 carbon atoms is a linear alkylene group having 1 to 6 carbon atoms. Examples of R3 include a single bond and an alkylene group having 1 to 6 carbon atoms. More specifically, the alkylene group having 1 to 6 carbon atoms is a linear alkylene group having 1 to 6 carbon atoms. Examples of X1 include a hydrogen atom and a phenyl group. Examples of X2 include a hydrogen atom and a phenyl group. A r Examples thereof include a phenyl group.

[0099] If the total carbon number of R1X1, R2X2 and R3 is 1 or more, it is not particularly limited, but it may be 2 or more. Also, the total carbon number of R1, R 2、 and R3 may be, for example, 18 or less, 15 or less, or 10 or less. Also, when X1 and X2 are hydrogen atoms, if the total carbon number of R1, R 2、 and R3 is 1 or more, it is not particularly limited, but it may be 2 or more. In the case where at least one of X1 and X2 is an aromatic hydrocarbon group which may have a substituent, the total number of carbon atoms of R1, R 2、 and R3 may be 0.

[0100] Examples of the ring formed by R1X1, R2X2 and the carbon atom to which R1X1 and R2X2 are attached together include a hydrocarbon ring having 3 to 13 carbon atoms in which a linking group may be inserted. The linking group is as described above.

[0101] Examples of the radically polymerizable compound represented by formula (A) include radically polymerizable compounds represented by the following formulas (A-1) to (A-3). [Chemical formula] In the formula, M represents a polymerizable group capable of radical polymerization, R1 to R3 each independently represent a single bond or an alkylene group having 1 to 6 carbon atoms in which a linking group may be inserted, Ar, Ar1 and Ar2 each independently represent an aromatic hydrocarbon group which may have a substituent, R 11 and R 12 each independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms in which a linking group may be inserted. In formula (A-1), R 11 and R 12 and R 11 and R 12 and the carbon atom to which they are attached may form a ring together. In formula (A-1), the total number of carbon atoms of R 11 , R 12 and R3 is 1 or more, and may be 2 or more. Also, the total number of carbon atoms may be 18 or less, may be 15 or less, or may be 10 or less. In formula (A-2), the total number of carbon atoms of R1, R 12 and R3 is not particularly limited and may be 0. The total number of carbon atoms may be, for example, 18 or less, may be 15 or less, or may be 10 or less. In formula (A-3), the total number of carbon atoms of R1, R2 and R3 is not particularly limited and may be 0. The total number of carbon atoms may be, for example, 18 or less, 15 or less, or 10 or less. Note that R 11 is the case where X1 is a hydrogen atom in R1X1. R 12 is the case where X2 is a hydrogen atom in R2X2.

[0102] And as the radically polymerizable polymerizable group M of the radically polymerizable compound, a polymerizable group selected from the following structures is preferable.

Chemical formula

[0103] Examples of the radically polymerizable compound contained in formula (A) and formula (A-1) include the following radically polymerizable compounds.

Chemical formula

[0104] (i) Add-1 corresponds to the combination in formula (A) where M is the following structure (C), R1X1 is a 1-pentyl group, R2 is a single bond 、 X2 is a hydrogen atom, R3 is a single bond, and Ar is a phenyl group. (ii) Add-3 corresponds to the combination in formula (A) where M is the following structure (B), R1X1 is a 1-propyl group, R2 is a single bond 、 X2 is a hydrogen atom, R3 is a single bond, and Ar is a phenyl group. (iii) Add-6 corresponds to the combination where, in formula (A), M has the following structure (C), R1X1 is an ethyl group, R2X2 is an ethyl group, 、 R3 is a 1,2-ethylene group, and Ar is a phenyl group. (iv) Add-8 corresponds to the combination where, in formula (A), M has the following structure (C), R1X1 is a 1-propyl group, R2 is a single bond, X2 is a hydrogen atom, 、 R3 is a 1,2-ethylene group, and Ar is a phenyl group. (v) Add-12 corresponds to the combination where, in formula (A), M has the following structure (D), R1 is a single bond, X1 is a hydrogen atom, 、 R2 is a single bond, X2 is a hydrogen atom, 、 R3 is a 1,2-ethylene group, and Ar is a phenyl group.

Chemical Structure

[0105] The liquid crystal composition contains at least a liquid crystal and the above radical polymerizable compound. The content of the above radical polymerizable compound in the liquid crystal composition is preferably 0.5% by mass or more, more preferably 1% by mass or more, and preferably 10% by mass or less, more preferably 5% by mass or less, based on the total mass of the liquid crystal and the radical polymerizable compound.

[0106] Also, in the liquid crystal composition, 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 with the above radical polymerizable compound.

[0107] Other radically polymerizable compounds are those having an unsaturated bond capable of undergoing radical polymerization in the presence of an organic radical. Examples thereof include methacrylate monomers such as t-butyl methacrylate, hexyl methacrylate, 2-ethylhexyl methacrylate, nonyl methacrylate, lauryl methacrylate, and n-octyl methacrylate; acrylate monomers such as tert-butyl acrylate, hexyl acrylate, 2-ethylhexyl acrylate, nonyl acrylate, lauryl acrylate, and n-octyl acrylate; styrene, styrene derivatives (e.g., o-, m-, p-methoxystyrene, o-, m-, p-tert-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.), (meth)acrylic acid derivatives (e.g., acrylonitrile, methacrylonitrile, acrylamide, isopropyl acrylamide, methacrylamide, etc.), vinyl halides (e.g., vinyl chloride, vinylidene chloride, tetrachloroethylene, hexachloroprene, vinyl fluoride, etc.), and other vinyl monomers, but are not limited thereto. Further, these preferably have compatibility with the liquid crystal.

[0108] In addition, as other radically polymerizable compounds, compounds represented by the following formula (1) are also preferable. [Chemical formula] (In formula (1), R a and R b each independently represent a linear alkyl group having 2 to 8 carbon atoms, and E represents a bonding group selected from a single bond, -O-, -NR c -, -S-, an ester bond, and an amide bond. R c represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.)

[0109] Among the radical polymerizable compounds contained in the liquid crystal composition, at least one kind is preferably a compound having a polymerizable unsaturated bond in one molecule and being compatible with the liquid crystal, that is, a compound having a monofunctional radical polymerizable group.

[0110] And, as the radical polymerizable compound represented by the formula (1), those in which E in the formula is an ester bond (a bond represented by -C(=O)-O- or -O-C(=O)-) are preferable from the viewpoints of ease of synthesis, compatibility with the liquid crystal, and polymerization reactivity. Specifically, compounds represented by the following structures are preferable, but are not particularly limited.

Chemical formula

[0111] These various radical polymerizable monomers may be used alone or in combination of two or more. Further, it is preferable that these are compatible with the liquid crystal.

[0112] The polymer obtained by polymerizing the radical polymerizable compound preferably has a Tg of 100°C or lower, more preferably 0°C or lower.

[0113] Note that the liquid crystal generally refers to a substance in a state showing properties of both a solid and a liquid. Typical liquid crystal phases include nematic liquid crystal and smectic liquid crystal, but the liquid crystal that can be used in the present invention is not particularly limited. For example, it is 4-pentyl-4'-cyanobiphenyl.

[0114] Next, sufficient energy is applied to the liquid crystal cell into which a mixture (liquid crystal composition) containing this liquid crystal and the radically polymerizable compound is introduced to cause a polymerization reaction of the radically polymerizable compound. This can be carried out, for example, by applying heat or irradiating with UV, and by polymerizing the radically polymerizable compound in situ, desired properties are exhibited. Among them, UV irradiation is preferable in that it enables patterning of the orientation and allows the polymerization reaction to be carried out in a shorter time.

[0115] Also, heating may be performed during UV irradiation. The heating temperature during UV irradiation is preferably in the temperature range in which the introduced liquid crystal exhibits liquid crystallinity, usually 40°C or higher, and heating below the temperature at which the liquid crystal changes to the isotropic phase is preferable.

[0116] Here, when performing UV irradiation, it is preferable to select the wavelength at which the reaction quantum yield of the polymerizable compound to react is the best. The irradiation amount of UV is usually 0.01 to 30 J / cm 2 However, preferably, it is 10 J / cm 2 or less. A smaller UV irradiation amount is preferable because it can suppress a decrease in reliability due to damage to the members constituting the liquid crystal display and can improve the tact in manufacturing by reducing the UV irradiation time.

[0117] Also, when polymerizing only by heating instead of UV irradiation, the heating is preferably carried out in a temperature range that is the reaction temperature of the polymerizable compound and is lower than the decomposition temperature of the liquid crystal. Specifically, it is 100 to 150°C.

[0118] When applying sufficient energy to cause a polymerization reaction of the radically polymerizable compound, it is preferable to be in a non-electric field state where no voltage is applied.

[0119] <Liquid crystal display element> A liquid crystal display element can be fabricated using the liquid crystal cell thus obtained. The liquid crystal display element has, 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. And the liquid crystal display element is formed by polymerizing a radical polymerizable compound in a state where a liquid crystal composition containing the liquid crystal and the radical polymerizable compound represented by formula (A) is brought into contact with the radical generating film of the first substrate having the radical generating film. The liquid crystal display element can be made into a reflective liquid crystal display element, for example, by providing a reflective electrode, a transparent electrode, a λ / 4 plate, a polarizing film, a color filter layer, etc. on the liquid crystal cell as needed according to a conventional method. Further, the liquid crystal cell can be made into a transmissive liquid crystal display element by providing a backlight, a polarizing plate, a λ / 4 plate, a transparent electrode, a polarizing film, a color filter layer, etc. on the liquid crystal cell as needed according to a conventional method.

[0120] FIG. 1 is a schematic cross-sectional view showing an example of the horizontal electric field liquid crystal display element of the present invention, and is an example of an IPS mode liquid crystal display element. In the horizontal electric field liquid crystal display element 1 illustrated in FIG. 1, liquid crystal 3 is sandwiched between a comb-shaped electrode substrate 2 having a liquid crystal alignment film 2c and a counter substrate 4 having a liquid crystal alignment film 4a. The comb-shaped 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 shape, and a liquid crystal alignment film 2c formed on the base material 2a so as to cover the linear electrodes 2b. The counter substrate 4 has a base material 4b and a liquid crystal alignment film 4a formed on the base material 4b. The liquid crystal alignment film 2c is, for example, a weak anchoring film obtained by chemically changing a radical generating film. The liquid crystal alignment film on the comb-shaped electrode substrate side is obtained, for example, by polymerizing a radical polymerizable compound 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. In this horizontal electric field liquid crystal display element 1, when a voltage is applied to the linear electrode 2b, an electric field is generated between the linear electrodes 2b as indicated by the electric force line L.

[0121] FIG. 2 is a schematic cross-sectional view showing another example of the horizontal electric field liquid crystal display element of the present invention, and is an example of an FFS mode liquid crystal display element. In the horizontal electric field liquid crystal display element 1 illustrated in FIG. 2, liquid crystal 3 is sandwiched between a comb-shaped electrode substrate 2 having a liquid crystal alignment film 2h and a counter substrate 4 having a liquid crystal alignment film 4a. The comb-shaped 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 shape, and a liquid crystal alignment film 2h formed on the insulating film 2f so as to cover the linear electrodes 2g. The counter substrate 4 includes a base material 4b and a liquid crystal alignment film 4a formed on the base material 4b. The liquid crystal alignment film 2h is, for example, a weak anchoring film obtained by chemically changing a radical generating film. The liquid crystal alignment film on the comb-shaped electrode substrate side is obtained, for example, by polymerizing a radical polymerizable compound 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. In this horizontal electric field liquid crystal display element 1, when a voltage is applied to the surface electrode 2e and the linear electrodes 2g, an electric field is generated between the surface electrode 2e and the linear electrodes 2g as indicated by the electric force lines L.

Example

[0122] The present invention will be specifically described below with reference to examples, but the present invention is not construed as being limited to these examples. The abbreviations of the compounds and the measurement methods of the respective properties are as follows.

[0123] (Diamine) DA-1 to DA-5: Compounds represented by the following formulas (DA-1) to (DA-5) respectively

Chemical formula

[0124] (Tetracarboxylic dianhydride) TC-1 to TC-3: Compounds represented by the following formulas (TC-1) to (TC-3) respectively

Chemical formula

[0125] (Additive) Add-1 to Add-12: Compounds represented by the following formulas (Add-1) to (Add-12), respectively Add-C1 to Add-C3: Compounds represented by the following formulas (Add-C1) to (Add-C3), respectively AD-1: Compound represented by the following formula (AD-1) [Chemical formula] [Chemical formula]

[0126] (Solvent) THF: Tetrahydrofuran CH2Cl2: Dichloromethane CHCl3: Chloroform NMP: N-Methyl-2-pyrrolidone BCS: Butyl cellosolve GBL: γ-Butyrolactone (Reaction reagent) TEA: Triethylamine DMAP: 4-Dimethylaminopyridine (Others) BHT: Dibutylhydroxytoluene

[0127] (Viscosity measurement) The viscosity of polyamic acid solution etc. was measured using an E-type viscometer TVE-22H (manufactured by Toki Sangyo Co., Ltd.) with a sample volume of 1.1 mL (milliliter), a cone rotor TE-1 (1°34’, R24), and a temperature of 25°C.

[0128] (Molecular weight measurement) The molecular weights of polyimide precursors and polyimides etc. were measured as follows using a normal temperature gel permeation chromatography (GPC) apparatus (GPC-101) (manufactured by Showa Denko KK) and columns (GPC KD-803, GPC KD-805) (manufactured by Showa Denko KK). Column temperature: 50°C Eluent: N,N-dimethylformamide (as additives, lithium bromide monohydrate (LiBr·H2O) is 30 mmol / L (liter), phosphoric acid·anhydrous crystal (o-phosphoric acid) is 30 mmol / L, and tetrahydrofuran (THF) is 10 mL / L) Flow rate: 1.0 mL / min Standard samples for calibration curve preparation: TSK standard polyethylene oxide (molecular weights: approximately 900,000, 150,000, 100,000, and 30,000) (manufactured by Tosoh Corporation) and polyethylene glycol (molecular weights: approximately 12,000, 4,000, and 1,000) (manufactured by Polymer Laboratories).

[0129] <Measurement of imidization rate> 20 mg of polyimide powder was placed in an NMR sample tube (NMR sampling tube standard φ5 manufactured by Kusano Kagaku), 1.0 mL of deuterated dimethyl sulfoxide (DMSO-d6, a mixture containing 0.05% by mass of tetramethylsilane (TMS)) was added, and ultrasonic waves were applied to completely dissolve it. The proton NMR of this solution was measured at 500 MHz using a Fourier transform superconducting nuclear magnetic resonance apparatus (FT-NMR) "AVANCE III" (manufactured by BRUKER). The chemical imidization rate was determined using protons derived from a structure that does not change before and after imidization as reference protons, and the peak integration value of these protons and the peak integration value of protons derived from the NH group of amic acid that appears around 9.5 - 10.0 ppm were used in the following formula. In the formula, x is the peak integration value of protons derived from the NH group of amic acid, y is the peak integration value of reference protons, and α is the ratio of the number of reference protons to one proton of the NH group of amic acid in the case of polyamic acid (imidization rate of 0%). Imidization rate (%) = (1 - α·x / y)×100

[0130] <<Synthesis example: Synthesis of additives for weak anchoring IPS>> The products described in the following synthesis examples were 1 Identified by 1H-NMR analysis (the analysis conditions are as follows). Apparatus: Fourier transform superconducting nuclear magnetic resonance apparatus (FT-NMR) "AVANCE III" (manufactured by BRUKER), 500 MHz. Solvent: CDCl3 (deuterated chloroform) or DMSO-d6 (deuterated dimethyl sulfoxide). Reference substance: Tetramethylsilane (TMS) (δ 0.0 ppm for 1 H).

[0131] <Synthesis of Synthesis Example 1 Add-1 (1-phenylhexyl methacrylate)>

Chemical Structure

[0132] A 500 mL four-necked flask equipped with a stir bar was weighed and dissolved with 1-phenyl-1-hexanol (25.0 g: 0.140 mol), TEA (21.3 g: 0.210 mol), and CH2Cl2 (300 mL). After cooling this solution to 0 °C in an ice bath, methacryloyl chloride (16.1 g: 0.155 mol) was gently added dropwise while maintaining the internal temperature at 5 °C or lower, and the mixture 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 this reaction solution, and it was washed three times with a 10% aqueous potassium carbonate solution (100 mL) and three times with pure water (100 mL) using a separatory funnel. After washing, it was dehydrated with magnesium sulfate, and the solvent was distilled off using a rotary evaporator to obtain a crude product. Purification was carried out by silica gel column chromatography (developing solvent: n-hexane / ethyl acetate = 8 / 2 (volume ratio)), and the solvent was distilled off and vacuum dried to obtain Add-1 (29.3 g: yield 82%, colorless transparent liquid). 1 It was confirmed to be the target product by 1H-NMR measurement. BHT (0.01 mol%) was added as a polymerization inhibitor and used. 1H-NMR (500 MHz) in DMSO-d6: 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]

[0133] <Synthesis Example 2 Synthesis of Add-2 (1-phenylbutyl methacrylate)>[ [Chemical formula]

[0134] 1-phenyl-1-butanol (25.0 g: 0.166 mol), TEA (25.3 g: 0.250 mol), and CH2Cl2 (300 mL) were weighed and dissolved in a 500 mL four-necked flask equipped with a stir bar. After cooling this solution to 0 °C in an ice bath, methacryloyl chloride (20.8 g: 0.199 mol) was gently added dropwise while maintaining the internal temperature at 5 °C or lower, and the mixture 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 this reaction solution, and it was washed three times with a 10% aqueous potassium carbonate solution (100 mL) and three times with pure water (100 mL) using a separatory funnel. After washing, it was dehydrated with magnesium sulfate, and the solvent was distilled off using a rotary evaporator to obtain a crude product. Purification was carried out by silica gel column chromatography (developing solvent: n-hexane / ethyl acetate = 8 / 2 (volume ratio)), and Add-2 (31.2 g: yield 86%, colorless transparent liquid) was obtained by distilling off the solvent and performing vacuum drying. 1 It was confirmed to be the target product by H-NMR measurement. BHT (0.01 mol%) was added as a polymerization inhibitor and used. 1 H-NMR (500 MHz) in DMSO-d6: 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]

[0135] <Synthesis Example 3 Synthesis of Add-3 (1-phenylbutyl acrylate)>

Chem.

[0136] A 500 mL four-necked flask equipped with a stir bar was charged with 1-phenyl-1-butanol (25.0 g: 0.166 mol), TEA (25.3 g: 0.250 mol), and THF (300 mL), and dissolved. After cooling this solution to 0 °C in an ice bath, acryloyl chloride (16.6 g: 0.183 mol) was gently added dropwise while maintaining the internal temperature at 5 °C or lower, and the mixture 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 this reaction solution, and it was washed three times with a 10% aqueous potassium carbonate solution (100 mL) and three times with pure water (100 mL) using a separatory funnel. After washing, it was dehydrated with magnesium sulfate, and the solvent was distilled off using a rotary evaporator to obtain a crude product. Purification was carried out by silica gel column chromatography (developing solvent: n-hexane / ethyl acetate = 8 / 2 (volume ratio)), and Add-3 (26.8 g: yield 79%, colorless transparent liquid) was obtained by distilling off the solvent and performing vacuum drying. 1 It was confirmed to be the target product by 1H-NMR measurement. BHT (0.01 mol%) was added as a polymerization inhibitor and used. 1 1H-NMR (500 MHz) in DMSO-d6: 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]

[0137] <Synthesis Example 4 Synthesis of Add-4 (2-methyl-1-phenylpropan-2-yl methacrylate)>

Chem.

[0138] In a 500 mL four-necked flask equipped with a stir bar, 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 CHCl3 (300 mL) were weighed and dissolved. After cooling this solution to 0 °C in an ice bath, methacryloyl chloride (26.0 g: 0.249 mol) was gently added dropwise. After stirring at 0 °C for 30 minutes, the reaction was carried out at 70 °C for 18 hours. After confirming the completion of the reaction by HPLC, ethyl acetate (200 mL) was added to this reaction solution, and the precipitated salt was removed by filtration. The solution was washed three times with a 10% aqueous potassium carbonate solution (100 mL) and three times with pure water (100 mL) using a separatory funnel. After washing, it was dehydrated with magnesium sulfate, and the solvent was distilled off using a rotary evaporator to obtain a crude product. Purification was carried out by silica gel column chromatography (developing solvent: n-hexane / ethyl acetate = 9 / 1 (volume ratio)), and solvent distillation and vacuum drying were performed to obtain Add-4 (21.6 g: yield 87%, colorless transparent liquid). 1 It was confirmed to be the target product by 1H-NMR measurement. BHT (0.01 mol%) was added as a polymerization inhibitor and used. 1 1H-NMR (500 MHz) in CDCl3: 7.32 - 7.22 (5H), 6.02 (1H), 5.50 (1H), 3.12 (2H), 1.92 (3H), 1.52 (6H) [ppm]

[0139] <Synthesis of Synthesis Example 5 Add-5 (2-methyl-4-phenylpropan-2-yl methacrylate)>

Chemical formula

[0140] A 500 mL four-necked flask equipped with a stir bar was charged with 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 CHCl3 (300 mL) and dissolved. After cooling this solution to 0 °C in an ice bath, methacryloyl chloride (23.8 g: 0.228 mol) was gently added dropwise. After stirring at 0 °C for 30 minutes, the reaction was carried out at 70 °C for 18 hours. After confirming the completion of the reaction by HPLC, ethyl acetate (200 mL) was added to this reaction solution, and the precipitated salt was removed by filtration. The solution was washed three times with a 10% aqueous potassium carbonate solution (100 mL) and three times with pure water (100 mL) using a separatory funnel. After washing, it was dehydrated with magnesium sulfate, and the solvent was distilled off using a rotary evaporator to obtain a crude product. Purification was carried out by silica gel column chromatography (developing solvent: n-hexane / ethyl acetate = 9 / 1 (volume ratio)), and solvent distillation and vacuum drying were performed to obtain Add-5 (29.0 g: yield 82%, colorless transparent liquid). 1 It was confirmed to be the target product by 1H-NMR measurement. BHT (0.01 mol%) was added as a polymerization inhibitor and used. 1 1H-NMR (500 MHz) in CDCl3: 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]

[0141] <Synthesis Example 6 Synthesis of Add-6 (3-ethyl-1-phenylpentan-3-yl methacrylate)>

Chemical formula

[0142] (Step 1) In a 1 L four-necked flask equipped with a stir bar, methyl 3-phenylpropanoate (25.0 g: 0.152 mol) and THF (500 mL) were weighed and dissolved. After cooling this solution to 0 °C in an ice bath, ethylmagnesium bromide (3.0 mol / L Ethyl Ether solution, 107 mL: 0.320 mol) was gently added dropwise. After stirring at 0 °C for 30 minutes, the reaction was carried out at room temperature for 6 hours. After confirming the completion of the reaction by HPLC, it was cooled again to 0 °C in an ice bath, and a 10% aqueous ammonium chloride solution (200 mL) was added little by little to quench the reaction while keeping the internal temperature from rising above 10 °C. This reaction solution was left standing for a while to allow the precipitate to settle, and then the supernatant was recovered by decantation. The residue was washed with ethyl acetate, and decantation was carried out several times in the same manner. The recovered solutions were combined, washed three times with pure water (200 mL) and once with saturated brine (200 mL) using a separatory funnel, dehydrated with anhydrous magnesium sulfate, and the solvent was distilled off using a rotary evaporator to obtain a crude product. Purification was carried out by silica gel column chromatography (developing solvent: ethyl acetate / n-hexane = 5 / 5 (volume ratio)), and solvent distillation and vacuum drying were performed to obtain Add-6a (27.2 g: yield 93%, colorless transparent liquid). 1 It was confirmed to be the target product by 1H-NMR measurement. 1 1H-NMR (500 MHz) in CDCl3: 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]

[0143] (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 CHCl3 (300 mL) were weighed and dissolved in a 500 mL four-necked flask equipped with a stir bar. After cooling this solution to 0 °C in an ice bath, methacryloyl chloride (20.9 g: 0.195 mol) was gently added dropwise. After stirring at 0 °C for 30 minutes, the reaction was carried out at 70 °C for 18 hours. After confirming the completion of the reaction by HPLC, ethyl acetate (200 mL) was added to this reaction solution, and the precipitated salt was removed by filtration. The solution was washed three times with 10% aqueous potassium carbonate solution (100 mL) and three times with pure water (100 mL) using a separatory funnel. After washing, it was dehydrated with magnesium sulfate, and the solvent was distilled off using a rotary evaporator to obtain a crude product. Purification was carried out by silica gel column chromatography (developing solvent: n-hexane / ethyl acetate = 9 / 1 (volume ratio)), and solvent distillation and vacuum drying were performed to obtain Add-6 (28.4 g: yield 84%, colorless transparent liquid). 1 It was confirmed to be the target product by 1H-NMR measurement. BHT (0.01 mol%) was added as a polymerization inhibitor and used. 1 1H-NMR (500 MHz) in CDCl3: 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]

[0144] <Synthesis Example 7 Synthesis of Add-7 (2-methyl-4-phenylbutan-2-yl acrylate)>

Chemical formula

[0145] In a 500 mL four-necked flask equipped with a stir bar, 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. After cooling this solution to 0 °C in an ice bath, acryloyl chloride (16.5 g: 0.182 mol) was gently added dropwise while maintaining the internal temperature at 5 °C or lower, and the mixture 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 this reaction solution, and it was washed three times with a 10% aqueous potassium carbonate solution (100 mL) and three times with pure water (100 mL) using a separatory funnel. After washing, it was dehydrated with magnesium sulfate, and the solvent was distilled off using a rotary evaporator to obtain a crude product. Purification was carried out by silica gel column chromatography (developing solvent: n-hexane / ethyl acetate = 9 / 1 (volume ratio)), and solvent distillation and vacuum drying were performed to obtain Add-7 (29.9 g: yield 90%, colorless transparent liquid). 1 It was confirmed to be the target product by 1H-NMR measurement. BHT (0.01 mol%) was added as a polymerization inhibitor and used. 1 1H-NMR (500 MHz) in DMSO-d6: 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]

[0146] <Synthesis Example 8 Synthesis of Add-8 (1-phenylhexan-3-yl methacrylate)>

Chemical formula

[0147] (First step) Hydrocinnamaldehyde (25.0 g: 0.186 mol) and THF (300 mL) were weighed and dissolved in a 500 mL four-necked flask equipped with a stir bar. After cooling this solution to -78 °C in a dry ice-methanol bath, n-propylmagnesium bromide (1.5 mol / L THF solution, 186 mL: 0.279 mol) was added dropwise so that the internal temperature did not exceed -70 °C. After completion of the addition, the mixture was returned to room temperature and stirred for 18 hours. After confirming the completion of the reaction by HPLC, the reaction solution was cooled to 0 °C, and 1 N aqueous hydrochloric acid solution (100 mL) was added for quenching. Ethyl acetate (200 mL) was added to this reaction solution, and it was washed three times with pure water (100 mL) using a separatory funnel. After washing, it was dehydrated with magnesium sulfate, and the solvent was distilled off using a rotary evaporator to obtain a crude product. Further vacuum drying was carried out to obtain Add-8a (30.0 g: yield 89%, colorless transparent liquid).

[0148] (Step 2) Add-8a (30.0 g: 0.168 mol), TEA (25.5 g: 0.252 mol), and THF (300 mL) were weighed and dissolved in a 500 mL four-necked flask equipped with a stir bar. After cooling this solution to 0 °C in an ice bath, methacryloyl chloride (21.1 g: 0.201 mol) was gently added dropwise while maintaining the internal temperature at 5 °C or lower. After returning to room temperature, it was stirred for 18 hours. After confirming the completion of the reaction by HPLC, ethyl acetate (200 mL) was added to this reaction solution, and it was washed three times with 10% aqueous potassium carbonate solution (100 mL) and three times with pure water (100 mL) using a separatory funnel. After washing, it was dehydrated with magnesium sulfate, and the solvent was distilled off using a rotary evaporator to obtain a crude product. Purification was carried out by silica gel column chromatography (developing solvent: n-hexane / ethyl acetate = 9 / 1 (volume ratio)), and solvent distillation and vacuum drying were carried out to obtain Add-8 (35.6 g: yield 86%, colorless transparent liquid). 1 It was confirmed to be the target product by 1H-NMR measurement. BHT (0.01 mol%) was added as a polymerization inhibitor and used. 1H-NMR (500 MHz) in DMSO-d6: 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]

[0149] <Synthesis Example 9 Synthesis of Add-9 (5-phenylpentyl methacrylate)>[[]]

Chemical Structure

[0150] 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 in a 500 mL four-necked flask equipped with a stir bar. After cooling this solution to 0 °C in an ice bath, methacryloyl chloride (19.1 g: 0.182 mol) was gently added dropwise while maintaining the internal temperature at 5 °C or lower, and the mixture 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 this reaction solution, and it was washed three times with a 10% aqueous potassium carbonate solution (100 mL) and three times with pure water (100 mL) using a separatory funnel. After washing, it was dehydrated with magnesium sulfate, and the solvent was distilled off using a rotary evaporator to obtain a crude product. Purification was carried out by silica gel column chromatography (developing solvent: n-hexane / ethyl acetate = 8 / 2 (volume ratio)), and Add-9 (31.8 g: yield 90%, colorless transparent liquid) was obtained by distilling off the solvent and performing vacuum drying.[[]] 1 1 It was confirmed to be the target product by H-NMR measurement. BHT (0.01 mol%) was added as a polymerization inhibitor and used.[[]] 1 H-NMR (500 MHz) in DMSO-d6: 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]

[0151] <Synthesis Example 10 Synthesis of Add-11 (3-methyl-1-phenylpentan-3-yl methacrylate)>

Chemical formula

[0152] 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 CHCl3 (300 mL) were weighed and dissolved in a 500 mL four-necked flask equipped with a stir bar. After cooling this solution to 0 °C in an ice bath, methacryloyl chloride (22.0 g: 0.210 mol) was gently added dropwise. After stirring at 0 °C for 30 minutes, the reaction was carried out at 70 °C for 18 hours. After confirming the completion of the reaction by HPLC, ethyl acetate (200 mL) was added to this reaction solution, and the precipitated salt was removed by filtration. The solution was washed three times with a 10% aqueous potassium carbonate solution (100 mL) and three times with pure water (100 mL) using a separatory funnel. After washing, it was dehydrated with magnesium sulfate, and the solvent was distilled off using a rotary evaporator to obtain a crude product. Purification was carried out by silica gel column chromatography (developing solvent: n-hexane / ethyl acetate = 9 / 1 (volume ratio)), and Add-11 (26.6 g: yield 77%, colorless transparent liquid) was obtained by distilling off the solvent and vacuum drying. 1 It was confirmed to be the target product by 1H-NMR measurement. BHT (0.01 mol%) was added as a polymerization inhibitor and used. 1 1H-NMR (500 MHz) in CDCl3: 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]

[0153] <Synthesis of Example 11 Add-12 (N-(3-phenylpropyl)-N-propylacrylamide)>

Chemical Structure

[0154] N-(3-phenylpropyl)-N-propylamine (20.0 g: 0.113 mol), TEA (22.8 g: 0.226 mol), and THF (250 mL) were weighed and dissolved in a 500 mL four-necked flask equipped with a stir bar. After cooling this solution to 0 °C in an ice bath, acryloyl chloride (12.3 g: 0.136 mol) was gently added dropwise. After stirring at 0 °C for 30 minutes, the reaction was carried out at room temperature for 18 hours. After confirming the completion of the reaction by HPLC, ethyl acetate (200 mL) was added to this reaction solution, and the precipitated salt was removed by filtration. The solution was washed three times with a 10% aqueous solution of potassium carbonate (100 mL) and three times with pure water (100 mL) using a separatory funnel. After washing, it was dehydrated with magnesium sulfate, and the solvent was distilled off using a rotary evaporator to obtain a crude product. Purification was carried out by silica gel column chromatography (developing solvent: n-hexane / ethyl acetate = 9 / 1 (volume ratio)), and Add-12 (18.2 g: yield 70%, colorless transparent liquid) was obtained by distilling off the solvent and vacuum drying. 1 It was confirmed to be the target product by 1H-NMR measurement. BHT (0.01 mol%) was added as a polymerization inhibitor and used. 1 1H-NMR (500 MHz) in DMSO-d6: 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]

[0155] <<Synthesis of Polyamic Acid and Polyimide>> <Synthesis Example 12> Weighed DA-1 (1.08 g: 10.00 mmol) and DA-3 (3.30 g: 10.00 mmol) into a 100 mL four-necked flask equipped with a mechanical stirrer and a nitrogen inlet tube, added NMP (24.9 g), stirred and dissolved it under a nitrogen atmosphere. Then, while maintaining the temperature below 10 °C in an ice bath, added TC-2 (2.50 g: 10.00 mmol) and reacted it at 50 °C for 6 hours under a nitrogen atmosphere. After returning to room temperature, added TC-1 (1.84 g: 9.40 mmol) and NMP (10.0 g), and reacted it at room temperature for 18 hours to obtain a polyamic acid solution (PAA-1) with a viscosity of about 1,120 mPa·s and a solid content concentration of 20% by mass. The molecular weight of this polyamic acid was number average molecular weight: 11,200, weight average molecular weight: 31,360. Weighed the polyamic acid solution (PAA-1) (40.0 g) obtained above into a 300 mL eggplant flask equipped with a stir bar and a nitrogen inlet tube, added NMP (74.3 g), stirred at room temperature for a while, then added acetic anhydride (5.61 g: 54.98 mmol) and pyridine (2.90 g, 36.65 mmol), stirred at room temperature for 30 minutes under a nitrogen atmosphere, and then reacted it at 50 °C for 3 hours under a nitrogen atmosphere. After the reaction was completed, slowly poured the reaction solution into methanol (500 mL) cooled to 10 °C or lower while stirring to precipitate a solid, and stirred for 10 minutes. This precipitate was separated by filtration, slurried and washed with methanol (200 mL) for 30 minutes twice again, and the solid was vacuum dried at 80 °C to obtain the target polyimide powder (SPI-1) (7.04 g, yield 88%). The imidization rate of this polyimide was 57%, and the molecular weight was number average molecular weight: 10,400, weight average molecular weight: 29,120.

[0156] <Synthesis Example 13> In a 100 mL four-necked flask equipped with a mechanical stirrer and a nitrogen inlet tube, DA-2 (3.42 g: 14.00 mmol) and DA-4 (4.11 g: 6.00 mmol) were weighed, NMP (56.8 g) was added, and the mixture was stirred and dissolved under a nitrogen atmosphere. Then, while maintaining the temperature at 10 °C or lower in an ice bath, TC-3 (4.26 g: 19.00 mol) and NMP (10.0 g) were added, and the reaction was carried out at room temperature for 24 hours to obtain a polyamic acid solution (PAA-2) with a viscosity of about 680 mPa·s and a solid content concentration of 15% by mass. The molecular weight of this polyamic acid was a number average molecular weight of 17,200 and a weight average molecular weight of 48,160.

[0157] <Synthesis Example 14> In a 100 mL 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, and the mixture was stirred and dissolved under a nitrogen atmosphere. Then, while maintaining the temperature at 10 °C or lower in an ice bath, TC-3 (4.21 g: 18.8 mmol) and NMP (10.0 g) were added, and the reaction was carried out at room temperature for 24 hours to obtain a polyamic acid solution (PAA-3) with a viscosity of about 710 mPa·s and a solid content concentration of 15% by mass. The molecular weight of this polyamic acid was a number average molecular weight of 15,500 and a weight average molecular weight of 41,800.

[0158] <<Preparation of Liquid Crystal Alignment Agent>> <Preparation Example 1 Preparation of Radical Generation Film-Forming Composition AL-1> In a 50 mL Erlenmeyer flask equipped with a stir bar, 2.0 g of the polyimide powder (SPI-1) obtained in Synthesis Example 12 above was weighed, NMP (18.0 g) was added, and the mixture was stirred at room temperature for 12 hours to dissolve. After confirming that all the solids had dissolved, NMP (8.0 g), BCS (12.0 g), and AD-1 (0.20 g) were added, and the mixture was stirred at room temperature for 1 hour to obtain the liquid crystal alignment agent and radical generation film-forming composition (AL-1) used in the present invention.

[0159] <Preparation Example 2 Preparation of Radical Generation Film-Forming Composition AL-2> 15.0 g of the polyamic acid solution (PAA-2) obtained in Synthesis Example 13 was weighed into a 50 mL Erlenmeyer flask equipped with a stir bar, NMP (16.5 g) and BCS (13.5 g) were added, and the mixture was stirred at room temperature for 1 hour to obtain a liquid crystal aligning agent and radical generating film forming composition (AL-2) used in the present invention.

[0160] <Preparation Example 3 Preparation of Liquid Crystal Aligning Agent AL-3> 15.0 g of the polyamic acid solution (PAA-3) obtained in Synthesis Example 14 was weighed into a 50 mL Erlenmeyer flask equipped with a stir bar, NMP (16.5 g) and BCS (13.5 g) were added, and the mixture was stirred at room temperature for 1 hour to obtain a liquid crystal aligning agent (AL-3) used in the present invention.

[0161] <Examples 1 to 24, Comparative Examples 1 to 8> <Fabrication of Liquid Crystal Display Element> The method for fabricating a liquid crystal cell for evaluating liquid crystal alignment and electro-optical response is shown below. First, a substrate with electrodes was prepared. The substrate is a non-alkali glass substrate with a size of 30 mm × 35 mm and a thickness of 0.7 mm. An ITO (Indium-Tin-Oxide) electrode having a comb-tooth pattern with an electrode width of 3 μm, a distance between electrodes of 6 μm, and an angle of 10° with respect to the long side of the substrate is formed on the substrate to form pixels. The size of each pixel is 10 mm in length and about 5 mm in width. Hereinafter, it is referred to as an IPS substrate. Next, the radical generation film-forming compositions AL-1, AL-2, and the liquid crystal aligning agent AL-3 obtained by the above method, and SE-6414 (manufactured by Nissan Chemical Industries, Ltd.), which is a liquid crystal aligning agent for horizontal alignment, were filtered through a filter with a pore size of 1.0 μm. Then, they were applied and formed into a film by spin coating on the prepared IPS substrate and a glass substrate (hereinafter referred to as the counter substrate) having an ITO film formed on the back surface and columnar spacers with a height of 3.0 μm. Subsequently, after drying on a hot plate at 80°C for 80 minutes, firing was performed at 230°C for 20 minutes to obtain a coating film with a thickness of 100 nm. For the polyimide film on the IPS substrate side, alignment treatment was performed in the direction following the direction of the comb teeth, and for the polyimide film on the counter substrate side, alignment treatment was performed in the direction perpendicular to the comb electrodes. In the alignment treatment, the rubbing method was used for AL-1 and SE-6414, and it was performed using a rubbing apparatus manufactured by Iinuma Gauge Co., Ltd., a rubbing cloth (YA-20R) manufactured by Yoshikawa Chemical Industry Co., Ltd., a rubbing roller (diameter 10.0 cm), a stage feed rate of 30 mm / s, a roller rotation speed of 700 rpm, and a pressing pressure of 0.3 mm. For both AL-2 and AL-3, a UV exposure apparatus manufactured by USHIO Inc. was used, and linearly polarized UV with an extinction ratio of approximately 26:1 was irradiated at a wavelength of 254 nm with an irradiation dose of 300 mJ / cm 2 so as to reach, and alignment treatment was performed by heating at 230°C for 20 minutes. Thereafter, regarding the display elements targeted in the examples and some of the display elements for comparison (Comparative Examples 2, 3, 4, 6, 7, 8) using the above two types of substrates, combinations were made using those provided with the radical generation alignment film AL-1 or AL-2 on the IPS substrate side and the liquid crystal alignment film SE-6414 or AL-3 on the counter substrate side. For some of the display elements for comparison (Comparative Examples 1 and 5), those using SE-6414 or AL-3 on both substrates were used. They were combined so that their respective alignment directions were parallel, the periphery was sealed leaving the liquid crystal injection port, and an empty cell with a cell gap of approximately 3.0 μm was fabricated. Into this empty cell, a liquid crystal mixture obtained in the above synthesis example with 2% by mass of (Add-1) to (Add-12) added, and as a comparison, a liquid crystal mixture without addition or a liquid crystal mixture with 2% by mass of (Add-C1) to (Add-C3) added were used, and after vacuum injecting them at room temperature respectively, the injection port was sealed to form a liquid crystal cell with anti-parallel alignment. The liquid crystal mixture used was LC-A (manufactured by DIC, Δn: 0.130, Δε: 4.4), and Add-10, Add-C1 to Add-C3 were purchased from Tokyo Chemical Industry and used respectively. The obtained liquid crystal cell constitutes an IPS mode liquid crystal display element. Thereafter, the obtained liquid crystal cell was heat-treated at 120 °C for 10 minutes, and irradiated with UV (UV lamp: FLR40SUV32 / A-1) for 30 minutes using a UV-FL irradiation device manufactured by Toshiba Lighting & Technology in a state where no voltage was applied to obtain a liquid crystal display element.

[0162] <Evaluation of liquid crystal alignment> Using a polarizing microscope, the polarizing plates were set to cross Nicol, fixed in a state where the luminance of the liquid crystal cell was minimized, and the liquid crystal cell was rotated by 1° therefrom to observe the alignment state of the liquid crystal. When no alignment defects such as unevenness or domains were observed or when they were very slight, it was rated as "good", and when they were clearly observed, it was rated as "bad" for evaluation. Also, a photodiode was attached to the same polarizing microscope, connected to an electrometer via a current-voltage conversion amplifier, and the black luminance (V: a.u.) was measured by monitoring the voltage under the condition where the luminance was minimized under cross Nicol.

[0163] <Measurement of the V-T Curve, Driving Threshold Voltage, Maximum Luminance Voltage, and Transmittance Evaluation> The white LED backlight and the luminance meter were set so that the optical axes were aligned. Between them, a liquid crystal cell (liquid crystal display element) with a polarizing plate attached so that the luminance was minimized was set. A voltage was applied up to 8V at 1V intervals, and the V-T curve was measured by measuring the luminance at each voltage. The value of the voltage (Vmax) at which the luminance was maximized was estimated from the obtained V-T curve. Also, with the liquid crystal cell without voltage applied, the transmitted luminance at parallel Nicol was set to 100%, and the maximum transmittance (Tmax) was estimated by comparing the maximum transmitted luminance in the V-T curve.

[0164] <Measurement of Response Time (Ton, Toff)> Using the apparatus used in the measurement of the above V-T curve, the luminance meter was connected to an oscilloscope, and the response speed (Ton) when the voltage at which the maximum luminance was obtained was applied and the response speed (Toff) when the voltage was returned to 0V were measured.

[0165] <Measurement of Voltage Holding Ratio (VHR)> The voltage holding ratio at room temperature was measured. A voltage of 4V was applied to the fabricated liquid crystal display element at a temperature of 23°C for 60 μs, and the voltage 16.7 ms later was measured. The voltage holding ratio was calculated to determine how well the voltage was retained. Also, the voltage holding ratio at high temperature was measured. A voltage of 1V was applied to the fabricated liquid crystal display element at a temperature of 70°C for 60 μs, and the voltage 1667 ms later was measured. The voltage holding ratio was calculated to determine how well the voltage was retained. Note that a VHR-1 voltage holding ratio measuring device manufactured by Toyo Technica Co., Ltd. was used for the measurement of the voltage holding ratio.

[0166] <Content of the Polymer> The compositions of the polymers synthesized in Synthesis Examples 11 to 13 are shown in Table 1.

[0167]

Table 1

[0168] <Content of the liquid crystal aligning agent or radical generating film forming composition> The compositions of the liquid crystal aligning agents or radical generating film forming compositions prepared in Preparation Examples 1 to 3 are shown in Table 2.

Table 2

[0169] <Content of the liquid crystal cell (rubbing)> The contents of the examples and comparative examples of the liquid crystal cells subjected to the alignment treatment by the rubbing method are shown in Table 3.

[0170]

Table 3

[0171] <Characteristic evaluation results> The characteristic evaluation results of the liquid crystal cells subjected to the alignment treatment by the rubbing method are shown in Tables 4-1 and 4-2.

[0172]

Table 4-1

[0173]

Table 4-2

[0174] In a weakly anchoring liquid crystal cell using the radical polymerizable compounds (Add-1) to (Add-12) of the present invention as additives, the alignment state and black luminance are good, Vmax is significantly lower than that of the strongly anchoring liquid crystal cell of Comparative Example 1, and the transmittance is significantly improved compared to Comparative Examples 1 to 3. On the other hand, in Comparative Examples 2 to 3, many rubbing streaks were confirmed in the liquid crystal display elements using Add-C1 or Add-C2 as additives, the black luminance was poor, and the alignment state showed a large birefringence. Also, in Comparative Examples 2 and 3, although Vmax was lower than that of the strongly anchoring liquid crystal cell of Comparative Example 1, a decrease in transmittance was confirmed. It was found that this is due to the generation of a pretilt angle associated with weak anchoring. In Examples 1 to 12, the pretilt angle was approximately 0°, while in Comparative Example 2, it was approximately 72°, and in Comparative Example 3, it was approximately 83°, indicating that a very large pretilt angle had occurred. Regarding the response speed, the response speed of the devices using the additives of Examples 1 to 12 was slightly slower than that of the strongly anchoring liquid crystal cell of Comparative Example 1, but it was still within an acceptable range and achieved a fast response speed, and it was found that it was significantly improved compared to Comparative Examples 2 and 3. In Comparative Example 4, weak anchoring characteristics were exhibited, and a good alignment state was shown, but the response speed was slow and the VHR was also poor. In the above Examples and Comparative Examples, when MLC-3019 (Δn: 0.104, Δε: 9.9) manufactured by Merck was used as the liquid crystal instead of LC-A, good weak anchoring IPS characteristics could be obtained even when Add-C1 or Add-C2 used in Comparative Examples 2 to 3 was used. However, when a liquid crystal with a large Δn or a small Δε like LC-A was used, good weak anchoring IPS characteristics could not be obtained. This means that, for example, when manufacturing a liquid crystal display element with a narrow cell gap (e.g., 3.5 μm or less), the additives used in Comparative Examples 2 to 3 cannot cope. With the additives of the present invention, good weak anchoring IPS characteristics can be obtained even when using such liquid crystals with a large Δn and a small Δε, and it becomes possible to improve the response speed by narrowing the cell gap. Also, regarding VHR, especially at high temperatures, it was found to be higher than that of Comparative Examples 1 to 4, and the reliability can be improved by using the additives of the present invention.

[0175] <Content of liquid crystal cell (photo-alignment)> Table 5 shows the content of examples and comparative examples of liquid crystal cells subjected to alignment treatment by the photo-alignment method.

[0176]

Table 5

[0177] <Characteristic evaluation results> Table 6 shows the characteristic evaluation results of liquid crystal cells subjected to alignment treatment by the photo-alignment method.

[0178]

Table 6

[0179] Even in the case of a weak anchoring IPS prepared using the photo-alignment method, when the radical polymerizable compounds (Add-1) to (Add-12) of the present invention were used as additives, it was confirmed that good characteristics similar to those of a weak anchoring IPS prepared using the rubbing method were obtained. On the other hand, when using (Add-C1) or (Add-C2) used in Comparative Examples 2 to 3, domains were generated and it became impossible to drive. In the case of photo-alignment, unlike the rubbing method, the anisotropy of the pretilt angle is not exhibited. Therefore, when a relatively large pretilt angle is generated by some method, the direction of the pretilt angle is not defined and it becomes a domain. When attempting to drive, it is presumed that the domain region expands due to the electric field and driving becomes impossible. Regarding Comparative Example 8, the response speed and VHR were poor, similar to those prepared by the rubbing method. When using the additive of the present invention, domains do not occur even when using the photo-alignment method, and good weak anchoring IPS characteristics can be obtained, so it was found to be very useful. Regarding VHR, it was also found that VHR is good at high temperatures, similar to the rubbing method, and it was found that using the radical polymerizable compound of the present invention as an additive for weak anchoring IPS is effective in improving reliability.

[0180] <Preparation Example 4: Preparation of Liquid Crystal Alignment Agent AL-4> Into a 50 mL Erlenmeyer flask equipped with a stir bar, 10.0 g each of the radical generating film-forming composition AL-2 prepared in Preparation Example 2 and the liquid crystal alignment agent AL-3 prepared in Preparation Example 3 were weighed, and stirred at room temperature for 1 hour to obtain a radical generating film-forming composition (AL-4).

[0181] <Examples 25 to 36, Comparative Examples 9 and 10> In Example 1, the liquid crystal alignment agent or radical generating film-forming composition applied to the IPS substrate and the counter substrate was changed to the liquid crystal alignment agent or radical generating film-forming composition described in Table 7 below. Furthermore, except that the additives described in Table 7 were used as additives for the liquid crystal mixture, a liquid crystal cell and a liquid crystal display element were fabricated in the same manner as in Example 1.

[0182] <Content of Liquid Crystal Cell> Examples and comparative examples of liquid crystal cells subjected to alignment treatment by the rubbing method are Examples 25 to 28 and Comparative Example 9. Examples and comparative examples of liquid crystal cells subjected to alignment treatment by the photo-alignment method are Examples 29 to 36 and Comparative Example 10.

[0183]

Table 7

[0184] <Characteristic Evaluation Results> The characteristic evaluation results are shown in Table 8.

Table 8

[0185] Examples 25 to 36 involve coating a radical generating film forming composition on a counter substrate and using a liquid crystal alignment film on an IPS substrate for a liquid crystal cell. Examples 25 to 28 relate to liquid crystal display elements fabricated using the rubbing method, and Examples 29 to 36 relate to liquid crystal display elements fabricated using the photoalignment method. Among Examples 29 to 36, Examples 33 to 36 use AL-4, which is a mixture of a radical generating film forming composition and a strong anchoring liquid crystal aligning agent, on the counter substrate. In any of Examples 25 to 36, compared with those in which a radical generating film forming composition is coated on an IPS substrate (for example, Examples 1, 13, etc.), Vmax tends to increase to a higher voltage, but it is sufficiently lower than that of the conventional strong anchoring liquid crystal cells shown in Comparative Examples 9 and 10, and a very high transmittance is obtained. Regarding the response speed, it can be seen that the difference between Ton and Toff is smaller compared with those in which a radical generating film forming composition is coated on an IPS substrate shown in the above examples. In addition, it can be seen that by using AL-4, which is a mixture of a radical generating film forming composition and a strong anchoring liquid crystal aligning agent, a fast response speed can be obtained while maintaining a high transmittance.

Industrial Applicability

[0186] According to the present invention, it is possible to provide a horizontal electric field liquid crystal display element that can realize a high backlight transmittance and a fast response speed without generating a pretilt angle or domains even when using a liquid crystal with a high Δn and a low Δε, and it is also possible to obtain a liquid crystal display element with good 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 horizontal electric field driving system.

Explanation of Reference Numerals

[0187] 1 Horizontal electric field liquid crystal display element 2 Comb electrode substrate 2a Substrate 2b Linear electrode 2c Liquid crystal alignment film 2d Substrate 2e Plane electrode 2f Insulating film 2g Linear electrode 2h Liquid crystal alignment film 3 Liquid crystal 4 Counter substrates 4a Liquid crystal alignment film 4b Substrate L Electric lines of force

Claims

1. A method for manufacturing a liquid crystal display element, comprising a step of polymerizing a radical polymerizable compound in a state where a liquid crystal composition containing a liquid crystal and a radical polymerizable compound represented by the following formula (A) is brought into contact with a radical generating film. 【Chemical 1】 (In formula (A), M represents a polymerizable group capable of radical polymerization, and R １ and R 2 each independently represent a single bond or an alkylene group having 1 to 6 carbon atoms in which a linking group may be inserted, R 3 represents a single bond or a linear alkylene group having 1 to 6 carbon atoms, Ar represents an aromatic hydrocarbon group which may have a substituent, X １ and X ２ represent a hydrogen atom, and R １ X １ and R ２ X ２ and R １ X １ and R ２ X ２ may together form a ring with the carbon atoms to which they are attached. However, the total number of carbon atoms of R １ X １ , R ２ X ２ and R ３ is 1 or more.)

2. The method for manufacturing a liquid crystal display element according to claim 1, wherein M in the formula (A) is selected from the following structures. 【Chemical 2】 (In the formula, * indicates a binding site. R ｂ represents a linear alkyl group having 2 to 8 carbon atoms, and E represents a single bond, -O-, -NR ｃ -, -S-, an ester bond, or an amide bond. 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.)

3. The method for manufacturing a liquid crystal display element according to any one of claims 1 or 2, wherein the radical generating film is a uniaxially oriented radical generating film.

4. The method for manufacturing a liquid crystal display element according to any one of claims 1 to 3, wherein the step of performing the polymerization reaction is carried out under non-electric field conditions.

5. The method for manufacturing a liquid crystal display element according to any one of claims 1 to 4, wherein the radical generating film is a film formed by immobilizing an organic group that induces radical polymerization.

6. The method for manufacturing a liquid crystal display element according to any one of claims 1 to 4, wherein the radical generating film is obtained by applying and curing a composition containing a compound having an organic group that generates radicals and a polymer to form a film, thereby immobilizing the organic group that generates radicals in the film.

7. The method for manufacturing a liquid crystal display element according to any one of claims 1 to 4, wherein the radical generating film is composed of a polymer containing an organic group that induces radical polymerization.

8. The method for manufacturing a liquid crystal display element according to claim 7, wherein the polymer containing an organic group that induces radical polymerization is at least one polymer selected from a polyimide precursor, polyimide, polyurethane, and polyamide obtained using a diamine component containing a diamine containing an organic group that induces radical polymerization.

9. The method for manufacturing a liquid crystal display element according to claim 8, wherein the organic group that induces radical polymerization is an organic group represented by the following formulas [X-1] to [X-18], [W], [Y], or [Z]. 【Chemical Formula 3】 (In Formulas [X-1] to [X-18], * indicates a bonding site, S １ , and S ２ each independently represents -O-, -NR-, or -S-, and R represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms (among the alkyl groups having 1 to 10 carbon atoms, a part of the -CH ２ - group of the alkyl group having 2 to 10 carbon atoms may be replaced by an oxygen atom. However, in S ２ R or NR, when a part of the -CH ２ - group of the alkyl group is replaced by an oxygen atom, the oxygen atom is not directly bonded to S ２ or N.). R １ , and R ２ each independently represents a hydrogen atom, a halogen atom, or an alkyl group having 1 to 4 carbon atoms.) 【Chemical Formula 4】 (In formulas [W], [Y], and [Z], * represents a bonding site, 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, and R ９ and R 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 １０ are alkyl groups, they may be bonded to each other at the ends to form a ring structure. Q represents any of the following structures.) 【Chemical Formula 5】 (In the formula, R １１ represents -CH ２ -, -NR-, -O-, or -S-, R each independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and * indicates a bonding site.). 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 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.).

10. The method for manufacturing a liquid crystal display element according to claim 8 or 9, 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 Formula 6] (In 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-, and R ７ represents a single bond or an alkylene group having 1 to 20 carbon atoms which is unsubstituted or substituted by a fluorine atom, and any -CH ２ - or -CF ２ - of these may each independently be replaced by a group selected from -CH=CH-, a divalent carbocyclic ring, and a divalent heterocyclic ring, and further, provided that any of the following groups, namely, -O-, -COO-, -OCO-, -NHCO-, -CONH-, or -NH- do not adjoin each other, they may be replaced by these groups; R ８ represents a radically polymerizable reactive group represented by a formula selected from the following formulas [X-1] to [X-18]. 【Chemical Formula 7】 (In formulas [X-1] to [X-18], * indicates a bonding site, S １ , and S ２ each independently represent -O-, -NR-, or -S-, and R represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms (among the alkyl groups having 1 to 10 carbon atoms, a part of the -CH ２ - group of the alkyl group having 2 to 10 carbon atoms may be replaced by an oxygen atom. However, in S ２ R or NR, when a part of the -CH ２ - group of the alkyl group is replaced by an oxygen atom, the oxygen atom is not directly bonded to S ２ or N.). R １ , and R ２ each independently represent a hydrogen atom, a halogen atom, or an alkyl group having 1 to 4 carbon atoms.)) 【Chemical 8】 【Chemical Formula 9】 (In formulas (7) and (7'), T １ and T ２ are each independently a single bond, -O-, -S-, -COO-, -OCO-, -NHCO-, -CONH-, -NH-, -CH ２ O-, -N(CH ３ ), -CON(CH ３ ), or -N(CH ３ CO-, and S represents a single bond or an alkylene group having 1 to 20 carbon atoms which is unsubstituted or substituted by a fluorine atom, and any —CH ２ — or —CF ２ — of one or more of them may each independently be replaced by a group selected from —CH═CH—, a divalent carbocyclic ring, and a divalent heterocyclic ring, and furthermore, on the condition that any of the following groups, namely, —O—, —COO—, —OCO—, —NHCO—, —CONH—, or —NH— do not adjoin each other, they may 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-, where m is an integer from 1 to 8, J is an organic group represented by a formula selected from the following formulas [W], [Y], and [Z]. 【Chemical Formula 10】 (In formulas [W], [Y], and [Z], * represents a bonding position with T ２ and Ar represents an aromatic hydrocarbon group selected from the group consisting of phenylene, naphthylene, and biphenylylene which may have an organic group and / or a halogen atom as a substituent, and R ９ and R １０ each independently represents an alkyl group having 1 to 10 carbon atoms or an alkoxy group having 1 to 10 carbon atoms, and Q represents any of the following structures. 【Chemical 11】 (wherein, R １１ represents -CH ２ -, -NR-, -O-, or -S-, R each independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and * indicates a bonding site.). 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 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 is each independently 0 or 1, at least one q is 1, and p represents an integer of 1 to 2.).

11. A step of preparing a first substrate having the radical generating film and a second substrate that may have a radical generating film. A step of oppositely disposing the first substrate and the second substrate such that the radical generation film on the first substrate faces the second substrate, A step of filling the liquid crystal composition between the first substrate and the second substrate, and A step of causing the polymerization reaction, The method for manufacturing a liquid crystal display element according to any one of claims 1 to 10, including these steps.

12. The method for manufacturing a liquid crystal display element according to claim 11, wherein the second substrate is a second substrate having no radical generation film.

13. The method for manufacturing a liquid crystal display element according to claim 11, wherein the second substrate is a substrate coated with a liquid crystal alignment film having uniaxial alignment properties.

14. The method for manufacturing a liquid crystal display element according to claim 13, wherein the liquid crystal alignment film having uniaxial alignment properties is a liquid crystal alignment film for horizontal alignment.

15. The method for manufacturing a liquid crystal display element according to any one of claims 11 to 14, wherein either the first substrate or the second substrate is a substrate having comb teeth electrodes.

16. A liquid crystal composition characterized by containing a liquid crystal and a radical polymerizable compound represented by the following formula (A). 【Chemical 12】 (In formula (A), M represents a polymerizable group capable of radical polymerization, and R １ and R 2 each independently represent a single bond or an alkylene group having 1 to 6 carbon atoms in which a bonding group may be inserted, R 3 represents a single bond or a linear alkylene group having 1 to 6 carbon atoms, Ar represents an aromatic hydrocarbon group which may have a substituent, X １ and X ２ represent a hydrogen atom, and R １ X １ and R ２ X ２ and R １ X １ and R ２ X ２ may combine with the carbon atoms to which they are attached to form a ring. However, the total number of carbon atoms of R １ X １ , R ２ X ２ and R ３ is 1 or more.)

17. The liquid crystal composition according to claim 16, wherein M in the formula (A) is selected from the following structures. 【Chemical Formula 13】 (In the formula, * indicates a binding site. R ｂ represents a linear alkyl group having 2 to 8 carbon atoms, and E represents a single bond, -O-, -NR ｃ -, -S-, an ester bond, or an amide bond. 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.)

18. A liquid crystal display element having a first substrate, a second substrate disposed opposite to the first substrate, and a liquid crystal filled between the first substrate and the second substrate, The liquid crystal display element is characterized in that a radical polymerizable compound is subjected to a polymerization reaction in a state where a liquid crystal composition containing the liquid crystal and a radical polymerizable compound represented by the following formula (A) is in contact with the radical generation film of the first substrate having the radical generation film. 【Chemical 14】 (In formula (A), M represents a polymerizable group capable of radical polymerization, and R １ and R 2 each independently represent a single bond or an alkylene group having 1 to 6 carbon atoms which may have a linking group inserted therein, R 3 represents a single bond or a linear alkylene group having 1 to 6 carbon atoms, Ar represents an aromatic hydrocarbon group which may have a substituent, X １ and X ２ represent a hydrogen atom, and R １ X １ and R ２ X ２ and R １ X １ and R ２ X ２ may together form a ring with the carbon atoms to which they are attached. However, the total number of carbon atoms of R １ X １ , R ２ X ２ and R ３ is 1 or more. )

19. The liquid crystal display element according to claim 18, wherein either the first substrate or the second substrate is a substrate having comb teeth electrodes.

20. The liquid crystal display element according to claim 18 or 19, which is a low voltage driving transverse electric field liquid crystal display element.

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