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

Abstract

A method for manufacturing a liquid crystal display element includes the following steps: In a state where a liquid crystal composition containing liquid crystal and a free radical polymerizable compound represented by formula (A) is in film contact with free radicals, the free radical polymerizable compound is subjected to a polymerization reaction. (In formula (A), M represents a polymerizable group capable of free radical polymerization; R1 to R3 each independently represent a single bond or an alkylene group with 1 to 6 carbon atoms that can be inserted into a bonding group; Ar represents an aromatic hydrocarbon group that may have substituents; X1 and X2 each independently represent a hydrogen atom or an aromatic hydrocarbon group that may have substituents; R1X1, R2X2 and the carbon atoms bonded to R1X1 and R2X2 may form a ring together, but the total number of carbon atoms in R1X1, R2X2 and R3 is 1 or more.)

Description

Technical Field

[0001] The present invention relates to a method for manufacturing liquid crystal display elements that employ a polymer-based liquid crystal layer stabilization technique, capable of producing weakly anchored films using inexpensive methods and without complex processes, and liquid crystal display elements for achieving further low-voltage driving, as well as liquid crystal compositions and free radical polymerizable compounds that can be used therein. Background Technology

[0002] In recent years, liquid crystal display (LCD) elements have been widely used in mobile phones, computers, and television displays. LCD elements are characterized by their thinness, light weight, and low power consumption, and are expected to find applications in VR (Virtual Reality), ultra-high-resolution displays, and more in the future. Among the display methods of LCDs, various display modes have been proposed, including TN (Twisted Nematic), IPS (In-Plane Switching), and VA (Vertical Alignment). All modes use a film (liquid crystal alignment film) to guide the liquid crystal to the desired alignment state.

[0003] Especially in products with touch panels such as tablet PCs, smartphones, and smart TVs, the IPS mode is preferred because the display is less prone to distortion even when touched. In recent years, to improve contrast and viewing angle characteristics, liquid crystal display elements using FFS (Frindfield Switching) and non-contact technologies using light orientation have gradually been applied.

[0004] However, compared to IPS, FFS has higher substrate manufacturing costs and produces display defects unique to the FFS mode, known as Vcom offset. Furthermore, regarding photoalignment, compared to the rubbing method, it has advantages such as increasing the size of manufacturable elements and significantly improving display characteristics; however, there are inherent technical problems with the principle of photoalignment (if it is a decomposition type, there are display defects originating from decomposition products; if it is an isomerization type, there are sintering problems due to insufficient alignment force, etc.). To solve these technical problems, liquid crystal display element manufacturers and liquid crystal alignment film manufacturers are currently conducting various researches.

[0005] On the other hand, in recent years, IPS modes utilizing weak anchoring technology have been proposed. According to reports, by using this method, the contrast can be improved and the voltage drive can be significantly reduced compared with existing IPS modes (see Patent Document 1).

[0006] Specifically, the method is as follows: on a single-sided substrate, a liquid crystal alignment film with strong anchoring energy is used to process the other substrate side, which has an electrode that generates a lateral electric field, so that it has no liquid crystal alignment constraint force at all. Using these processes, an IPS-mode liquid crystal display element is fabricated.

[0007] In recent years, a technical solution for weakly anchored IPS modes has been proposed, which uses a thick polymer brush to create a weak state (see Patent Document 2). This technology achieves a significant increase in contrast ratio and a significant reduction in driving voltage.

[0008] On the other hand, there is a technical problem of significantly reduced response speed, especially when the voltage is off. This is because the driving voltage is lower, resulting in a weaker electric field than usual, and the anchoring force of the alignment film is very small, thus the liquid crystal recovery takes longer.

[0009] As a solution to this problem, a method of weakly anchoring only the pixel electrode has been proposed (see Patent Document 3). It is reported that this achieves a balance between increased brightness and faster response time.

[0010] Existing technical documents

[0011] Patent documents

[0012] Patent Document 1: Patent No. 4053530

[0013] Patent Document 2: Japanese Patent Application Publication No. 2013-231757

[0014] Patent Document 3: Japanese Patent Application Publication No. 2017-211566 Summary of the Invention

[0015] The technical problem that the invention aims to solve

[0016] While suppressing the response speed delay during driving by weakly anchoring only on the electrodes of the IPS comb electrode, the state of weak anchoring only on the electrode requires difficult techniques such as coating different materials separately on very small areas, which is considered to be a major technical problem in actual industrialization.

[0017] Different methods were also investigated, such as narrowing the cell gap to improve response speed. Generally, liquid crystal display elements tend to have faster response speeds with narrower cell gaps. However, this leads to a decrease in transmittance. To address this, a liquid crystal with a large birefringence difference (Δn) can be used. By setting the product of the cell gap D and Δn (retardation) to 300 nm–400 nm (measurement wavelength 550 nm), the decrease in transmittance can be resolved. However, increasing Δn is not simply a matter of changing this parameter alone; parameters such as Δε (dielectric constant anisotropy) and elastic modulus also change, leading to a significant alteration in the fundamental properties of the liquid crystal. For example, in cases of weak anchoring orientation, it is considered possible for the liquid crystal to align along the vertical direction. Therefore, obtaining stable weak anchoring characteristics even with changes in parameters such as Δn and Δε has become an important technical challenge.

[0018] It is believed that if such technical problems can be solved, panel manufacturers will have a significant cost advantage, as well as advantages in areas such as reducing battery consumption and improving image quality.

[0019] The present invention was made to solve the aforementioned technical problems, and its object is to provide a method for manufacturing a liquid crystal display element, the liquid crystal display element, and liquid crystal compositions and free radical polymerizable compounds that can be used therein. Using the above-mentioned method for manufacturing a liquid crystal display element, a liquid crystal display element with a weak anchored lateral electric field can be stably manufactured without pretilt angle in narrow cell spacing. It is possible to manufacture a lateral electric field liquid crystal display element that simultaneously achieves fast response speed when low driving voltage is applied and when off, and has a small decrease in VHR (voltage holding rate) even at high temperatures.

[0020] Means for solving technical problems

[0021] In order to solve the above-mentioned technical problems, the inventors conducted in-depth research and found that the above-mentioned technical problems could be solved, thereby completing the present invention with the following main purpose.

[0022] That is, the present invention includes the following.

[0023] [1] A method for manufacturing a liquid crystal display element, comprising the following steps: in a state in which a liquid crystal composition containing liquid crystal and a free radical polymerizable compound represented by the following formula (A) is in contact with a free radical to form a film, the free radical polymerizable compound is subjected to a polymerization reaction.

[0024] [Chemistry 1]

[0025]

[0026] (In formula (A), M represents a polymerizable group capable of free radical polymerization; R1 to R3 each independently represent a single bond or an alkylene group with 1 to 6 carbon atoms that can be inserted into a bonding group; Ar represents an aromatic hydrocarbon group that can have substituents; X1 and X2 each independently represent a hydrogen atom or an aromatic hydrocarbon group that can have substituents; R1X1, R2X2 and the carbon atoms bonded to R1X1 and R2X2 can form a ring together, but the total number of carbon atoms in R1X1, R2X2 and R3 is 1 or more.)

[0027] [2] According to the manufacturing method of the liquid crystal display element described in [1], in the formula (A), R3 is a straight-chain alkylene group with 1 to 6 carbon atoms, and X1 and X2 are hydrogen atoms.

[0028] [3] The manufacturing method of the liquid crystal display element according to [1] or [2], wherein M in the formula (A) is selected from the following structures.

[0029] [Chemistry 2]

[0030]

[0031] (In the formula, * indicates the bonding site. R) b It indicates a straight-chain alkyl group with 2 to 8 carbon atoms, and E indicates that it is selected from single bonds, -O-, and -NR. c -, -S-, ester bonds, and amide bonds containing bonding groups. c Represents an alkyl group having 1 to 4 hydrogen atoms or carbon atoms. R d (This refers to an alkyl group having 1 to 6 hydrogen atoms or carbon atoms.)

[0032] [4] The method for manufacturing a liquid crystal display element according to any one of [1] to [3], wherein the free radical generating film is a free radical generating film subjected to uniaxial orientation treatment.

[0033] [5] The method for manufacturing a liquid crystal display element according to any one of [1] to [4], wherein the polymerization reaction step is carried out under conditions without an electric field.

[0034] [6] A method for manufacturing a liquid crystal display element according to any one of [1] to [5], wherein the free radical generating film is a film formed by immobilizing organic groups that induce free radical polymerization.

[0035] [7] A method for manufacturing a liquid crystal display element according to any one of [1] to [5], wherein a composition containing a compound and a polymer having free radical generating groups is coated and cured to form a film, thereby immobilizing the free radical generating organic groups in the film, thereby obtaining the free radical generating film.

[0036] [8] A method for manufacturing a liquid crystal display element according to any one of [1] to [5], wherein the free radical generating film comprises: a polymer containing organic groups that induce free radical polymerization.

[0037] [9] According to the method for manufacturing a liquid crystal display element as described in [8], wherein the polymer containing organic groups that induce free radical polymerization is at least one polymer selected from polyimide precursor, polyimide, polyurea and polyamide, wherein the polyimide precursor, polyimide, polyurea and polyamide are obtained by using a diamine component containing a diamine containing organic groups that induce free radical polymerization.

[0038]

[10] According to the method for manufacturing a liquid crystal display element as described in [9], wherein the organic group that induces free radical polymerization is an organic group represented by the following formula [X-1] to [X-18], [W], [Y] or [Z].

[0039] [Chemistry 3]

[0040]

[0041] (In formulas [X-1] to [X-18], * indicates a bonding site; S1 and S2 independently represent -O-, -NR-, or -S-; R represents a hydrogen atom or an alkyl group with 1 to 10 carbon atoms (among the alkyl groups with 1 to 10 carbon atoms, a portion of the -CH2- group of the alkyl group with 2 to 10 carbon atoms may be replaced by an oxygen atom. However, in S2R or NR, if a portion 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 independently represent a hydrogen atom, a halogen atom, or an alkyl group with 1 to 4 carbon atoms.)

[0042] [Chemistry 4]

[0043]

[0044] (In formulas [W], [Y], and [Z], * indicates a bonding site, Ar represents an aromatic hydrocarbon group selected from the group consisting of phenylene, naphthylene, and biphenylene, which may have organic groups and / or halogen atoms as substituents; 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 When the alkyl group is present, they can bond to each other at the ends to form a ring structure; Q represents any of the following structures.

[0045] [Chemistry 5]

[0046]

[0047] (where R is in the formula) 11 The symbols -CH2-, -NR-, -O-, or -S- represent different groups of atoms, where R independently represents a hydrogen atom or an alkyl group with 1 to 4 carbon atoms; * indicates the bonding site. S 3 It can represent a single bond, -O-, -NR- (R represents an alkyl group with 1 to 14 hydrogen atoms), or -S-. 12 This refers to 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.

[0048]

[11] In the method of manufacturing a liquid crystal display element according to [9] or

[10] , the diamine containing an organic group that induces free radical polymerization is a diamine having a structure represented by the following formula (6), the following formula (7) or the following formula (7′).

[0049] [Chemistry 6]

[0050]

[0051] (In equation (6), R) 6 This indicates a single bond, -CH2-, -O-, -COO-, -OCO-, -NHCO-, -CONH-, -NH-, -CH2O-, -N(CH3)-, -CON(CH3)-, or -N(CH3)CO-.

[0052] R 7 The alkylene group represents a single bond, or an alkylene group with 1 to 20 carbon atoms that are either unsubstituted or substituted with fluorine atoms. Any one or more -CH2- or -CF2- atoms of the alkylene group can be independently replaced by a group selected from -CH=CH-, a divalent carbon ring, and a divalent heterocycle. Furthermore, any of the groups listed below, namely -O-, -COO-, -OCO-, -NHCO-, -CONH-, or -NH-, can be replaced by these groups if they are not adjacent to each other.

[0053] R 8 It represents a free radical polymerization reactive group selected from the following formulas [X-1] to [X-18].

[0054] [Chemistry 7]

[0055]

[0056] (In formulas [X-1] to [X-18], * indicates a bonding site; S1 and S2 independently represent -O-, -NR-, or -S-; R represents a hydrogen atom or an alkyl group with 1 to 10 carbon atoms (among the alkyl groups with 1 to 10 carbon atoms, a portion of the -CH2- group of the alkyl group with 2 to 10 carbon atoms may be replaced by an oxygen atom. However, in S2R or NR, if a portion 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 independently represent a hydrogen atom, a halogen atom, or an alkyl group with 1 to 4 carbon atoms.)

[0057] [Chemistry 8]

[0058]

[0059] [Chemistry 9]

[0060]

[0061] In equations (7) and (7′), T 1 and T 2 Each can be independently a single bond, -O-, -S-, -COO-, -OCO-, -NHCO-, -CONH-, -NH-, -CH2O-, -N(CH3)-, -CON(CH3)-, or -N(CH3)CO-.

[0062] S represents a single bond, or an alkylene group with 1 to 20 carbon atoms that is either unsubstituted or substituted with fluorine atoms. Any one or more -CH2- or -CF2- atoms in this alkylene group can be independently replaced by a group selected from -CH=CH-, a divalent carbocyclic ring, and a divalent heterocyclic ring. Furthermore, it can be replaced by any of the groups listed below—namely -O-, -COO-, -OCO-, -NHCO-, -CONH-, or -NH-—provided that they are not adjacent to each other.

[0063] E can be a single bond, -O-, -C(CH3)2-, -NH-, -CO-, -NHCO-, -COO-, or -(CH2). m -, -SO2-, -O-(CH2) m -O-, -OC(CH3)2-, -CO-(CH2) m -、-NH-(CH2) m -, -SO2-(CH2) m -、-CONH-(CH2) m -、-CONH-(CH2) m -NHCO- or -COO-(CH2) m -OCO-, where m is an integer from 1 to 8.

[0064] J is an organic group selected from the formulas [W], [Y] and [Z] below.

[0065] [Chemistry 10]

[0066]

[0067] (In formulas [W], [Y], and [Z], * indicates a relationship with T) 2 The bonding site; Ar represents an aromatic hydrocarbon group selected from the group consisting of phenylene, naphthylene, and biphenylene, which may have organic groups and / or halogen atoms as substituents; R 9 and R 10 Each of the following can be independently represented as an alkyl group having 1 to 10 carbon atoms or an alkoxy group having 1 to 10 carbon atoms; Q represents any of the following structures.

[0068] [Chemistry 11]

[0069]

[0070] (where R is in the formula) 11 -CH2-, -NR-, -O-, or -S-; R independently represents an alkyl group with 1 to 4 hydrogen atoms; * indicates a bonding site. S 3 It can represent a single bond, -O-, -NR- (R represents an alkyl group with 1 to 14 hydrogen atoms), or -S-. 12 This 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 formula (7′), each q is independently 0 or 1, with at least one q being 1, and p represents an integer from 1 to 2.

[0071]

[12] A method for manufacturing a liquid crystal display element according to any one of [1] to

[11] , comprising the following steps:

[0072] Prepare a first substrate having the free radical generating membrane and a second substrate that may have the free radical generating membrane;

[0073] The first substrate and the second substrate are arranged opposite each other such that the free radical generating film of the first substrate is opposite to the second substrate;

[0074] The liquid crystal composition is filled between the first substrate and the second substrate; and

[0075] The polymerization reaction is carried out.

[0076]

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

[12] , the second substrate is a second substrate without a free radical generating film.

[0077]

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

[12] , the second substrate is a substrate covered with a liquid crystal alignment film having uniaxial orientation.

[0078]

[15] In the method for manufacturing a liquid crystal display element according to

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

[0079]

[16] A method for manufacturing a 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.

[0080]

[17] A liquid crystal composition, characterized in that it contains a liquid crystal and a free radical polymerizable compound represented by the following formula (A).

[0081] [Chemistry 12]

[0082]

[0083] (In formula (A), M represents a polymerizable group capable of free radical polymerization; R1 to R3 each independently represent a single bond or an alkylene group with 1 to 6 carbon atoms that can be inserted into a bonding group; Ar represents an aromatic hydrocarbon group that can have substituents; X1 and X2 each independently represent a hydrogen atom or an aromatic hydrocarbon group that can have substituents; R1X1, R2X2 and the carbon atoms bonded to R1X1 and R2X2 can form a ring together, but the total number of carbon atoms in R1X1, R2X2 and R3 is 1 or more.)

[0084]

[18] The liquid crystal composition according to

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

[0085]

[19] In the liquid crystal composition according to

[17] or

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

[0086] [Chemistry 13]

[0087]

[0088] (In the formula, * indicates the bonding site. R) b It indicates a straight-chain alkyl group with 2 to 8 carbon atoms; E indicates a group selected from single bonds, -O-, and -NR. c -, -S-, ester bonds, and amide bonds containing bonding groups. c Represents an alkyl group having 1 to 4 hydrogen atoms or carbon atoms. R d (This refers to an alkyl group having 1 to 6 hydrogen atoms or carbon atoms.)

[0089]

[20] A liquid crystal display element, characterized in that it comprises a first substrate, a second substrate disposed opposite to the first substrate, and liquid crystal filling the space between the first substrate and the second substrate.

[0090] With the liquid crystal composition containing the liquid crystal and the free radical polymerizable compound represented by formula (A) in contact with the free radical generating film of the first substrate having a free radical generating film, the free radical polymerizable compound is subjected to a polymerization reaction to form the liquid crystal display element.

[0091] [Chemistry 14]

[0092]

[0093] (In formula (A), M represents a polymerizable group capable of free radical polymerization; R1 to R3 each independently represent a single bond or an alkylene group with 1 to 6 carbon atoms that can be inserted into a bonding group; Ar represents an aromatic hydrocarbon group that can have substituents; X1 and X2 each independently represent a hydrogen atom or an aromatic hydrocarbon group that can have substituents; R1X1, R2X2 and the carbon atoms bonded to R1X1 and R2X2 can form a ring together, but the total number of carbon atoms in R1X1, R2X2 and R3 is 1 or more.)

[0094]

[21] According to the liquid crystal display element of

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

[0095]

[22] The liquid crystal display element according to

[20] or

[21] , wherein the liquid crystal display element is a low voltage driven lateral electric field liquid crystal display element.

[0096]

[23] A free radical polymerizable compound, characterized by being represented by the following formula (A).

[0097] [Chemistry 15]

[0098]

[0099] (In formula (A), M, R1, R2, R3, X1, X2, and Ar are any of the combinations of (i) to (v) below.)

[0100] (i) M is a combination of the following structures (C), R1X1 is 1-pentyl, R2 is a single bond, X2 is a hydrogen atom, R3 is a single bond, and Ar is a phenyl group.

[0101] (ii) M is a combination of the following structures (B): R1X1 is 1-propyl, R2 is a single bond, X2 is a hydrogen atom, R3 is a single bond, and Ar is a phenyl group.

[0102] (iii) M is a combination of the following structures (C), R1X1 is ethyl, R2X2 is ethyl, R3 is 1,2-ethylidene, and Ar is phenyl.

[0103] (iv) M is a combination of the following structures (C): R1X1 is 1-propyl, R2 is a single bond, X2 is a hydrogen atom, R3 is 1,2-ethylene, and Ar is a phenyl group.

[0104] (v)M is a combination of the following structures (D), R1 is a single bond, X1 is a hydrogen atom, R2 is a single bond, X2 is a hydrogen atom, R3 is 1,2-ethylene, and Ar is a phenyl group.

[0105] [Chemistry 16]

[0106]

[0107] (In structures (B), (C), and (D), * indicates a bonding site.)

[0108] Invention Effects

[0109] According to the present invention, a method for manufacturing a liquid crystal display element, the liquid crystal display element, and liquid crystal compositions and free radical polymerizable compounds that can be used therein are provided. Using the above-described method for manufacturing a liquid crystal display element, a liquid crystal display element with a weak anchored lateral electric field can be stably manufactured without pretilt angle in narrow cell spacing. It is possible to manufacture a liquid crystal display element with a lateral electric field that simultaneously achieves a fast response speed when the driving voltage is low and when it is off, and has a small decrease in VHR even at high temperatures. Attached Figure Description

[0110] Figure 1 This is a schematic cross-sectional view illustrating an example of the transverse electric field liquid crystal display element of the present invention.

[0111] Figure 2 This is a schematic cross-sectional view illustrating other examples of the lateral electric field liquid crystal display element of the present invention. Detailed Implementation

[0112] This invention utilizes an additive (a free radical polymerizable compound with a specific structure) capable of suppressing the appearance of pretilt angles associated with the formation of a weak anchoring film, and enabling the stable fabrication of highly reliable weakly anchored lateral electric field liquid crystal display elements even in narrow cell spacing. For example, a method for manufacturing a weakly anchored lateral electric field liquid crystal display element includes the following steps: preparing a unit having a liquid crystal composition containing liquid crystal and a free radical polymerizable compound with a specific structure disposed between a first substrate having a free radical generating film and a second substrate having a liquid crystal alignment film; and applying sufficient energy to the unit to cause the free radical polymerizable compound to undergo a polymerization reaction. Preferably, a method for manufacturing a liquid crystal unit includes the following steps: preparing a first substrate having a free radical generating film that has been aligned by friction or photo-alignment, and a second substrate having a liquid crystal alignment film but not a free radical generating film; fabricating a unit with the respective substrates facing each other; and filling the space between the first and second substrates with a liquid crystal composition containing liquid crystal and a free radical polymerizable compound with a specific structure. For example, a method for manufacturing a low-voltage driven lateral electric field liquid crystal display element includes a free radical generating film that has undergone orientation treatment on one substrate and a liquid crystal alignment film that has undergone uniaxial orientation treatment on another substrate, wherein either substrate has a comb electrode for driving the liquid crystal.

[0113] In this invention, a "weak anchoring film" refers to a film that has no orientation-restricting force on liquid crystal molecules in the in-plane direction; or a film where even if there is an orientation-restricting force, it is weaker than the intermolecular forces between liquid crystal molecules, and the film alone cannot achieve uniaxial alignment of liquid crystal molecules in any direction. Furthermore, this weak anchoring film is not limited to solid films, but also includes liquid films covering solid surfaces. Typically, in liquid crystal display elements, liquid crystal alignment films, which restrict the orientation of liquid crystal molecules, are used in pairs to align the liquid crystals. However, liquid crystal alignment can also be achieved by using a weak anchoring film and a liquid crystal alignment film in pairs. This is because the orientation-restricting force of the liquid crystal alignment film is transmitted along the thickness direction of the liquid crystal layer through the intermolecular forces between liquid crystal molecules, resulting in the alignment of liquid crystal molecules near the weak anchoring film. Therefore, when a horizontal alignment liquid crystal alignment film is used, a horizontally aligned state can be fabricated as a whole within the liquid crystal cell. Horizontal alignment refers to a state in which the long axis of the liquid crystal molecules is arranged approximately parallel to the surface of the liquid crystal alignment film; tilting orientations of a few degrees are also included in the scope of horizontal alignment.

[0114] The applicant of this application proposes a method for manufacturing a zero-plane anchoring film, comprising the following steps: while a liquid crystal composition containing liquid crystal and a free radical polymerizable compound is in contact with a free radical to form a film, sufficient energy is applied to cause the free radical polymerizable compound to undergo a polymerization reaction (refer to claim 1 of International Publication No. 2019 / 004433). The free radical polymerizable compound used in this proposal is illustrated in

[0077] to

[0086] of International Publication No. 2019 / 004433.

[0115] In order to utilize the technology proposed above, the inventors conducted in-depth research to stably fabricate a weakly anchored lateral electric field liquid crystal display element without generating a pretilt angle in narrow cell spacing, and to fabricate a lateral electric field liquid crystal display element that simultaneously achieves faster response speeds when low driving voltage is applied and when off, and exhibits less VHR reduction even at high temperatures. The results showed that by using a free radical polymerizable compound with a specific structure, it is possible to stably fabricate a weakly anchored lateral electric field liquid crystal display element without generating a pretilt angle in narrow cell spacing, and to manufacture a lateral electric field liquid crystal display element that simultaneously achieves faster response speeds when low driving voltage is applied and when off, and exhibits less VHR reduction even at high temperatures.

[0116] Here, a free radical polymerizable compound with a specific structure is represented by the following formula (A).

[0117] [Chemistry 17]

[0118]

[0119] (In formula (A), M represents a polymerizable group capable of free radical polymerization; R1 to R3 each independently represent a single bond or an alkylene group with 1 to 6 carbon atoms that can be inserted into a bonding group; Ar represents an aromatic hydrocarbon group that can have substituents; X1 and X2 each independently represent a hydrogen atom or an aromatic hydrocarbon group that can have substituents; R1X1, R2X2 and the carbon atoms bonded to R1X1 and R2X2 can form a ring together, but the total number of carbon atoms in R1X1, R2X2 and R3 is 1 or more.)

[0120] The method for manufacturing a liquid crystal display element according to the present invention includes the following step: subjecting the free radical polymerizing compound to a polymerization reaction while contacting a liquid crystal composition containing liquid crystal and a free radical polymerizing compound represented by formula (A) with a free radical generating film. The inventors hypothesize that in this step, by utilizing the polymerization reaction of the free radical polymerizing compound with free radicals generated by the free radical generating film, a change occurs on the surface of the free radical generating film, resulting in a weakly anchored film. However, it is difficult to confirm whether the change on the surface of the free radical generating film in this step is a change in the free radical generating film itself or a change caused by the formation of a polymer layer of the free radical polymerizing compound on the free radical generating film. Therefore, the result of this step has not yet been determined.

[0121] In this invention, by performing the above steps, a weakly anchored lateral electric field liquid crystal display element can be stably fabricated without generating a pretilt angle during narrow cell spacing. This allows for the manufacture of a lateral electric field liquid crystal display element that simultaneously achieves low driving voltage and fast response speed at off, and exhibits minimal VHR reduction even at high temperatures. Regarding how the free radical polymerizable compound represented by formula (A) contributes to this, the inventors have determined as follows.

[0122] The M in the radical polymerizable compound represented by formula (A) facilitates the radical polymerization of the compound. This allows for the formation of a weakly anchored film, enabling the achievement of low driving voltage.

[0123] Furthermore, the inventors speculate that the Ar (which may have substituents) of the free radical polymerizable compound represented by formula (A) helps to suppress the generation of pretilt angle, improve response speed, and achieve high VHR at high temperatures.

[0124] Furthermore, the inventors speculate that in formula (A), M and Ar are not too close together, and the presence of a group [-C(R1X1)(R2X2)R3-] of a certain size between M and Ar has the effect of further accelerating the response speed.

[0125] It should be noted that in this specification, the term "narrow element gap" refers to an element gap of 3.5 μm or less.

[0126] [Free radical generating film forming composition]

[0127] The free radical generating membrane forming composition used in this invention comprises a polymer and, as components, groups capable of generating free radicals. This composition can be a composition of a polymer bonded together with groups capable of generating free radicals, or it can be a composition of a compound having groups capable of generating free radicals and a polymer as a base resin. By coating such a composition and allowing it to cure, a membrane is formed, thereby obtaining a free radical generating membrane in which groups capable of generating free radicals are immobilized. The groups capable of generating free radicals are preferably organic groups that induce free radical polymerization.

[0128] Organic groups that can induce free radical polymerization include those represented by the following formulas [X-1] to [X-18], [W], [Y], and [Z].

[0129] [Chemistry 18]

[0130]

[0131] (In formulas [X-1] to [X-18], * indicates a bonding site; S1 and S2 independently represent -O-, -NR-, or -S-; R represents a hydrogen atom or an alkyl group with 1 to 10 carbon atoms (among the alkyl groups with 1 to 10 carbon atoms, a portion of the -CH2- group of the alkyl group with 2 to 10 carbon atoms may be replaced by an oxygen atom. However, in S2R or NR, when a portion 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 independently represent a hydrogen atom, a halogen atom, or an alkyl group with 1 to 4 carbon atoms.)

[0132] [Chemistry 19]

[0133]

[0134] (In formulas [W], [Y], and [Z], * indicates a bonding site, Ar represents an aromatic hydrocarbon group selected from the group consisting of phenylene, naphthylene, and biphenylene, which may have organic groups and / or halogen atoms as substituents; 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 When the alkyl group is present, they can bond to each other at the ends to form a ring structure; Q represents any of the following structures.

[0135] [Chemistry 20]

[0136]

[0137] (where R is in the formula) 11-CH2-, -NR-, -O-, or -S-; R independently represents an alkyl group with 1 to 4 hydrogen atoms; * indicates a bonding site. S 3 It can represent a single bond, -O-, -NR- (R represents an alkyl group with 1 to 14 hydrogen atoms), or -S-. 12 This refers to 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.

[0138] The polymer is preferably at least one polymer selected from the group consisting of polyimide precursors, polyimides, polyureas, polyamides, polyacrylates, polymethacrylates, and polysiloxanes.

[0139] To obtain the free radical generating membrane used in this invention, when using the polymer having organic groups that induce free radical polymerization, it is preferable to use the following monomers as monomer components to obtain a polymer having groups capable of generating free radicals: the monomer having a photoreactive side chain containing at least one selected from methacrylyl, propenyl, vinyl, allyl, coumarinyl, styryl, and cinnamoyl; or a monomer having a free radical generating site on its side chain that decomposes upon ultraviolet irradiation. On the other hand, it is recognized that free radical generating monomers themselves have problems such as spontaneous polymerization, which can lead to the formation of unstable compounds. Therefore, in terms of ease of synthesis, polymers derived from diamines having free radical generating sites are preferred, and more preferably polyimide precursors such as polyamic acid and polyamic acid esters, polyimides, polyureas, and polyamides.

[0140] The polymer containing organic groups that induce free radical polymerization is preferably selected from at least one polymer selected from polyimide precursors, polyimides, polyureas, and polyamides obtained using a diamine component, wherein the diamine component comprises a diamine containing organic groups that induce free radical polymerization.

[0141] Specifically, such diamines containing organic groups that induce free radical polymerization are, for example, diamines with side chains that are capable of generating free radicals and undergoing polymerization. Examples of diamines with the structure represented by the following formula (6) are given, but are not limited thereto.

[0142] [Chemistry 21]

[0143] FP225170JP

[0144]

[0145] (In equation (6), R) 6This indicates a single bond, -CH2-, -O-, -COO-, -OCO-, -NHCO-, -CONH-, -NH-, -CH2O-, -N(CH3)-, -CON(CH3)-, or -N(CH3)CO-.

[0146] R 7 The alkylene group represents a single bond, or an alkylene group with 1 to 20 carbon atoms that are either unsubstituted or substituted with fluorine atoms. Any one or more -CH2- or -CF2- atoms of the alkylene group can be independently replaced by a group selected from -CH=CH-, a divalent carbon ring, and a divalent heterocycle. Furthermore, any of the groups listed below, namely -O-, -COO-, -OCO-, -NHCO-, -CONH-, or -NH-, can be replaced by these groups if they are not adjacent to each other.

[0147] R 8 It represents a free radical polymerization reactive group selected from the following formulas [X-1] to [X-18].

[0148] [Chemistry 22]

[0149]

[0150] (In formulas [X-1] to [X-18], * indicates a bonding site; S1 and S2 independently represent -O-, -NR-, or -S-; R represents a hydrogen atom or an alkyl group with 1 to 10 carbon atoms (among the alkyl groups with 1 to 10 carbon atoms, a portion of the -CH2- group of the alkyl group with 2 to 10 carbon atoms may be replaced by an oxygen atom. However, in S2R or NR, if a portion 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 independently represent a hydrogen atom, a halogen atom, or an alkyl group with 1 to 4 carbon atoms.)

[0151] The bonding positions of the two amino groups (-NH2) in formula (6) are not limited. Specifically, relative to the bonding groups on the side chain, positions 2,3, 2,4, 2,5, 2,6, 3,4, and 3,5 on the benzene ring can be cited. Among these, positions 2,4, 2,5, or 3,5 are preferred from the viewpoint of reactivity during the synthesis of polyamic acid. If the ease of synthesis of diamine is also considered, positions 2,4 or 3,5 are more preferred.

[0152] As a diamine having at least one photoreactive group selected from the group consisting of methacryl, propenyl, vinyl, allyl, coumarin, styryl and cinnamoyl, examples include, but are not limited to, the following compounds.

[0153] [Chemistry 23]

[0154]

[0155] (where J is in the formula) 1 J is a bonding group selected from single bonds, -O-, -COO-, -NHCO-, and -NH-. 2 This refers to an alkylene group with 1 to 20 carbon atoms, either single-bonded or unsubstituted or substituted with fluorine atoms.

[0156] Among diamines containing organic groups that induce free radical polymerization, diamines with a site that generates free radicals by decomposition under ultraviolet irradiation as a side chain can be exemplified by diamines having the structure represented by the following formula (7) or formula (7′), but are not limited thereto.

[0157] [Chemistry 24]

[0158]

[0159] [Chemistry 25]

[0160]

[0161] In equations (7) and (7′), T 1 and T 2 Each can be independently a single bond, -O-, -S-, -COO-, -OCO-, -NHCO-, -CONH-, -NH-, -CH2O-, -N(CH3)-, -CON(CH3)-, or -N(CH3)CO-.

[0162] S represents a single bond, or an alkylene group with 1 to 20 carbon atoms that is either unsubstituted or substituted with fluorine atoms. Any one or more -CH2- or -CF2- atoms in this alkylene group can be independently replaced by a group selected from -CH=CH-, a divalent carbocyclic ring, and a divalent heterocyclic ring. Furthermore, it can be replaced by any of the groups listed below—namely -O-, -COO-, -OCO-, -NHCO-, -CONH-, or -NH-—provided that they are not adjacent to each other.

[0163] E can be a single bond, -O-, -C(CH3)2-, -NH-, -CO-, -NHCO-, -COO-, or -(CH2). m -, -SO2-, -O-(CH2) m -O-, -OC(CH3)2-, -CO-(CH2) m -、-NH-(CH2) m -, -SO2-(CH2) m -、-CONH-(CH2) m -、-CONH-(CH2)m -NHCO- or -COO-(CH2) m -OCO-, where m is an integer from 1 to 8.

[0164] J is an organic group selected from the formulas [W], [Y], and [Z] below.

[0165] [Chemistry 26]

[0166]

[0167] (In formulas [W], [Y], and [Z], * indicates a relationship with T) 2 The bonding site; Ar represents an aromatic hydrocarbon group selected from the group consisting of phenylene, naphthylene, and biphenylene, which may have organic groups and / or halogen atoms as substituents; R 9 and R 10 Each of the following can be independently represented as an alkyl group having 1 to 10 carbon atoms or an alkoxy group having 1 to 10 carbon atoms; Q represents any of the following structures.

[0168] [Chemistry 27]

[0169]

[0170] (where R is in the formula) 11 -CH2-, -NR-, -O-, or -S-; R independently represents an alkyl group with 1 to 4 hydrogen atoms; * indicates a bonding site. S 3 It can represent a single bond, -O-, -NR- (R represents an alkyl group with 1 to 14 hydrogen atoms), or -S-. 12 This 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 formula (7′), each q is independently 0 or 1, with at least one q being 1, and p represents an integer from 1 to 2.

[0171] The bonding positions of the two amino groups (-NH2) in formula (7) above are not limited. Specifically, relative to the bonding groups on the side chain, positions 2,3, 2,4, 2,5, 2,6, 3,4, and 3,5 on the benzene ring can be cited. Among these, from the viewpoint of reactivity during the synthesis of polyamic acid, positions 2,4, 2,5, or 3,5 are preferred.

[0172] In particular, considering the ease of synthesis, high versatility, and properties, the structure represented by the following formula is preferred, but it is not limited to this.

[0173] [Chemistry 28]

[0174]

[0175] (In the formula, n is an integer from 2 to 8.)

[0176] Among the diamines represented by formulas (7) and (7′), the structure represented by the following formula is preferred, especially in terms of ease of synthesis, high versatility, and properties, but is not limited thereto.

[0177] [Chemistry 29]

[0178]

[0179] (In the formula, n is an integer from 2 to 8, and E represents a single bond, -O-, -C(CH3)2-, -NH-, -CO-, -NHCO-, -CONH-, -COO-, -OCO-, or -(CH2). m -, -SO2-, -O-(CH2) m -O-, -OC(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-, where m is an integer from 1 to 8.

[0180] Depending on the properties of the diamines used to form free radical generating films, such as liquid crystal orientation, sensitivity in polymerization reactions, voltage retention characteristics, and charge accumulation, one or more types of diamines can be used, or two or more types can be used in combination.

[0181] The amount of such diamine containing organic groups that induce free radical polymerization is preferably 5 to 50 mol% of the total diamine component for polymer synthesis contained in the free radical generating film forming composition, more preferably 10 to 40 mol%, and particularly preferably 15 to 30 mol%.

[0182] It should be noted that when the polymer used in the free radical generating membrane of the present invention is obtained from diamines, other diamines besides the diamines containing organic groups that induce free radical polymerization can be used as diamine components, as long as the effect of the present invention is not impaired. Specifically, examples include: 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 Diphenyl ether, 4,4′-sulfonyl diphenylamine, 3,3′-sulfonyl diphenylamine, bis(4-aminophenyl)silane, bis(3-aminophenyl)silane, dimethyl-bis(4-aminophenyl)silane, dimethyl-bis(3-aminophenyl)silane, 4,4′-thiodiphenylamine, 3,3′-thiodiphenylamine, 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 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)]diphenylamine, 4,4′-[1,3-phenylenebis(methylene)]diphenylamine, 3,4′-[1,4-phenylenebis(methylene)]diphenylamine, 3,4′-[1,3-phenylenebis(methylene)]diphenylamine, Diphenylamine, 3,3′-[1,4-phenylbis(methylene)]diphenylamine, 3,3′-[1,3-phenylbis(methylene)]diphenylamine, 1,4-phenylbis[(4-aminophenyl) ketone], 1,4-phenylbis[(3-aminophenyl) ketone], 1,3-phenylbis[(4-aminophenyl) ketone], 1,3-phenylbis[(3-aminophenyl) ketone], 1,4-phenylbis(4-aminobenzoate), 1,4-phenylbis(3-aminobenzoate), 1,3-phenylbis(4-aminobenzoate), 1,3-phenylbis(3-aminobenzoate), bis(4-aminophenyl) terephthalate, bis(3-aminophenyl) terephthalate, bis(4-aminophenyl) terephthalate, bis(4-aminophenyl) terephthalate 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-Di(3-aminophenoxy)propane, 1,4-Di(4-aminophenoxy)butane, 1,4-Di(3-aminophenoxy)butane, 1,5-Di(4-aminophenoxy)pentane, 1,5-Di(3-aminophenoxy)pentane, 1,6-Di(4-aminophenoxy)hexane, 1,6-Di(3-aminophenoxy)hexane, 1,7-Di(4-aminophenoxy)heptane, 1,7-Di(3-aminophenoxy)heptane, 1,8-Di(4-aminophenoxy)propane 1,8-bis(3-aminophenoxy)octane, 1,9-bis(4-aminophenoxy)nonane, 1,9-bis(3-aminophenoxy)nonane, 1,10-bis(4-aminophenoxy)decane, 1,10-bis(3-aminophenoxy)decane, 1,11-bis(4-aminophenoxy)undecane, 1,11-bis(3-aminophenoxy)undecane, 1,12-bis(4-aminophenoxy)dodecane, 1,12-bis(3-aminophenoxy)undecane Aromatic diamines such as (oxy)dodecane; alicyclic diamines such as bis(4-aminocyclohexyl)methane and bis(4-amino-3-methylcyclohexyl)methane; alicyclic diamines such as 1,3-diaminopropane, 1,4-diaminobutane, 1,5-diaminopentane, 1,6-diaminohexane, 1,7-diaminoheptane, 1,8-diaminooctane, 1,9-diaminononane, 1,10-diaminodecane, 1,11-diaminoundecane, and 1,12-diaminododecane; 1 Diamines with a urea structure, such as 3-bis[2-(p-aminophenyl)ethyl]urea and 1,3-bis[2-(p-aminophenyl)ethyl]-1-tert-butoxycarbonylurea; diamines with a nitrogen-containing unsaturated heterocyclic structure, such as N-p-aminophenyl-4-p-aminophenyl(tert-butoxycarbonyl)aminomethylpiperidine; and diamines with an N-Boc group (Boc represents tert-butoxycarbonyl) such as N-tert-butoxycarbonyl-N-(2-(4-aminophenyl)ethyl)-N-(4-aminobenzyl)amine.

[0183] The other diamines mentioned above can also be used in combination, depending on their properties such as liquid crystal orientation when forming free radical generating films, sensitivity in polymerization reactions, voltage retention characteristics, and charge accumulation.

[0184] In the synthesis of polyamic acid polymers, the tetracarboxylic acid dianhydride reacting with the aforementioned diamine component is not particularly limited. Specifically, examples include pyromellitic acid, 2,3,6,7-naphthalenetetracarboxylic acid, 1,2,5,6-naphthalenetetracarboxylic acid, 1,4,5,8-naphthalenetetracarboxylic acid, 2,3,6,7-anthracitetetracarboxylic acid, 1,2,5,6-anthracitetetracarboxylic 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, and 1,1,1,3,3,3-hexafluoro-2,2-bis(3,4-dicarboxyphenyl)propane. Alkane, 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, oxydi-phthalic 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-cyclohexanetetracarboxylic acid Butanetetracarboxylic acid, 1,3-dimethyl-1,2,3,4-cyclobutanetetracarboxylic acid, 1,2,3,4-cycloheptanetetracarboxylic acid, 2,3,4,5-tetrahydrofurantetracarboxylic acid, 3,4-dicarboxy-1-cyclohexylsuccinic acid, 2,3,5-tricarboxycyclopentylacetic acid, 3,4-dicarboxy-1,2,3,4-tetrahydro-1-naphthoussuccinic 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-2,4,7,9-tetracarboxylic acid, bicyclo[4,4,0]decane-2,4,8,10-tetracarboxylic acid, tricyclo[6.3.0. The dianhydrides of tetracarboxylic acids, including 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-dioxotetrahydrofuranyl)-3-methyl-3-cyclohexane-1,2-dicarboxylic acid, tetracyclo[6,2,1,1,0<2,7>]dodecane-4,5,9,10-tetracarboxylic acid, 3,5,6-tricarboxynorbornane-2:3,5:6-dicarboxylic acid, and 1,2,4,5-cyclohexanetetracarboxylic acid.

[0185] Of course, depending on the liquid crystal orientation when the tetracarboxylic acid dianhydride is made into a free radical generating film, the sensitivity in the polymerization reaction, the voltage holding characteristics, the charge accumulation characteristics, etc., one or more types can be used or two or more types can be used in combination.

[0186] In the synthesis of polyamic acid esters, the structure of the tetracarboxylic acid dialkyl ester that reacts with the above-mentioned diamine component is not particularly limited, and specific examples are listed below.

[0187] Specific examples of aliphatic tetracarboxylic acid diesters 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-tetrahydrofurantetracarboxylic acid dialkyl ester, 1,2,4,5-cyclohexanetetracarboxylic acid dialkyl ester, 3,4-dicarboxy-1-cyclohexylsuccinate dialkyl ester, 3,4-dicarboxy-1,2,3,4-tetrahydro-1-naphthylsuccinate dialkyl ester, 1,2,3,4-butanetetracarboxylic acid dialkyl ester, and bicyclo[3,3,0] Octane-2,4,6,8-tetracarboxylic acid dialkyl ester, 3,3′,4,4′-dicyclohexyltetracarboxylic acid dialkyl ester, 2,3,5-tricarboxylic acid dialkyl ester, cis-3,7-dibutylcyclooctyl-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 acid dialkyl ester, etc.

[0188] Examples of aromatic tetracarboxylic acid dialkyl esters include pyromellitic tetracarboxylate, 3,3',4,4'-biphenyltetracarboxylate, 2,2',3,3'-biphenyltetracarboxylate, 2,3,3',4-biphenyltetracarboxylate, 3,3',4,4'-benzophenone tetracarboxylate, 2,3,3',4'-benzophenone tetracarboxylate, bis(3,4-dicarboxyphenyl) ether dialkyl ester, bis(3,4-dicarboxyphenyl) sulfone dialkyl ester, 1,2,5,6-naphthalenetetracarboxylate, and 2,3,6,7-naphthalenetetracarboxylate.

[0189] In the synthesis of polyurea as the polymer, there are no particular limitations on the diisocyanate that reacts with the aforementioned diamine component, and it can be used depending on availability, etc. The specific structure of the diisocyanate is shown below.

[0190] [Chemistry 30]

[0191]

[0192] In the formula, R2 and R3 represent aliphatic hydrocarbon groups with 1 to 10 carbon atoms.

[0193] Aliphatic diisocyanates, represented by K-1 to K-5, have poor reactivity but offer the advantage of improved solvent solubility. Aromatic diisocyanates, represented by K-6 to K-13, are highly reactive and improve heat resistance, but suffer from reduced solvent solubility. In terms of versatility and specific properties, K-1, K-7, K-8, K-9, and K-10 are preferred; from an electrical property perspective, K-12 is preferred; and from a liquid crystal orientation perspective, K-13 is preferred. Two or more diisocyanates can also be used in combination, preferably for various applications based on the desired properties.

[0194] Alternatively, a portion of the diisocyanate can be replaced with the tetracarboxylic dianhydride described above, and it can be used in the form of a copolymer of polyamic acid and polyurea, or it can be used in the form of a copolymer of polyimide and polyurea through chemical imidization.

[0195] In the synthesis of polymers that are polyamides, the structure of the dicarboxylic acid involved in the reaction is not particularly limited, but specific examples are listed below. Examples of aliphatic dicarboxylic acids include: malonic acid, oxalic acid, dimethylmalonic acid, succinic acid, fumaric acid, glutaric acid, adipic acid, adipate, 2-methyl adipic acid, trimethyl adipic acid, pimelic acid, 2,2-dimethylglutaric acid, 3,3-diethylsuccinic acid, azelaic acid, sebacic acid, and octanoic acid.

[0196] 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-cyclopropanedicarboxylic acid, 1,3-cyclopentanedicarboxylic acid, 1,1-cyclohexanedicarboxylic acid, 1,2-cyclopropanedicarboxylic acid, 1,3-cyclopentanedicarboxylic acid, 1,1-cyclohexanedicarboxylic acid, 1,2-cyclopropanedicarboxylic acid, 1,3-cyclopentanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, 1,2-cyclopropanedicarboxylic acid, 1,3-cyclopropanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, 1,3 ...propanedicarboxylic acid, 1,3-cycloprop Hexanedicarboxylic 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.

[0197] Examples of aromatic dicarboxylic acids include: 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-anthraquinone dicarboxylic acid, 1,4-anthraquinone dicarboxylic acid, 2,5-biphenyl dicarboxylic acid, 4,4 4,4′-Biphenyl dicarboxylic acid, 1,5-Biphenylene dicarboxylic acid, 4,4″-Triphenyl dicarboxylic acid, 4,4′-Diphenylmethane dicarboxylic acid, 4,4′-Diphenylethane dicarboxylic acid, 4,4′-Diphenylpropane dicarboxylic acid, 4,4′-Diphenylhexafluoropropane dicarboxylic acid, 4,4′-Diphenyl ether dicarboxylic acid, 4,4′-Bibenzyl dicarboxylic acid, 4,4′-Stilbene dicarboxylic acid, 4,4′-Diphenylacetylene dicarboxylic acid (4,4′-tolandicarboxylic acid) dicarboxylic acids, including 4,4′-carbonyldibenzoic acid, 4,4′-sulfonyldibenzoic acid, 4,4′-dithiodibenzoic acid, p-phenylene diacetic acid, 3,3′-p-phenylene dipropionic acid, 4-carboxycinnamic acid, p-phenylene diacrylic acid, 3,3′-[4,4′-(methylene dip-phenylene)]dipropionic acid, 4,4′-[4,4′-(oxodip-phenylene)]dipropionic acid, 4,4′-[4,4′-(oxodip-phenylene)]dibutyric acid, (isopropylidene dip-phenylenedioxy)dibutyric acid, and bis(p-carboxyphenyl)dimethylsilane.

[0198] Examples of heterocyclic dicarboxylic acids include: 1,5-(9-oxofluorene)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, and 3,5-pyridinedicarboxylic acid.

[0199] The various dicarboxylic acids described above can be substances with the structure of acid dihalides or anhydrides. From the perspective of maintaining the orientation of liquid crystal molecules, these dicarboxylic acids are particularly preferred to be dicarboxylic acids capable of imparting a linear structure to polyamides. 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-triphenyldicarboxylic acid, 2,6-naphthalenedicarboxylic acid, 2,5-pyridinedicarboxylic acid, or their acid dihalides are preferred. These compounds sometimes exist as isomers and can be mixtures comprising them. Furthermore, two or more compounds can be used together. It should be noted that the dicarboxylic acids used in this invention are not limited to the compounds exemplified above.

[0200] Polyamic acid, polyamic acid ester, polyurea, and polyamide can be obtained by reacting a diamine (also referred to as "diamine component") as a starting material with a component selected from tetracarboxylic dianhydride (also referred to as "tetracarboxylic dianhydride component"), tetracarboxylic acid diester, diisocyanate, and dicarboxylic acid as a starting material using known synthetic methods. Generally, the method involves reacting the diamine component with one or more components selected from tetracarboxylic dianhydride component, tetracarboxylic acid diester, diisocyanate, and dicarboxylic acid in an organic solvent.

[0201] The reaction between the diamine component and the tetracarboxylic acid dianhydride component is relatively easy to carry out in organic solvents and does not produce byproducts, which is advantageous in this respect.

[0202] The organic solvent used in the above reaction is not particularly limited as long as it dissolves the polymer formed. Furthermore, even organic solvents that do not dissolve the polymer can be mixed with the above solvents as long as the polymer formed does not precipitate. It should be noted that water in the organic solvent can hinder the polymerization reaction and thus become a cause of hydrolysis of the polymer formed; therefore, it is preferable to use an organic solvent that has been dehydrated and dried.

[0203] Examples of organic solvents 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-imidazolinone, 3-methoxy-N,N-dimethylpropaneamide, N-methylcaprolactam, dimethyl sulfoxide, tetramethylurea, pyridine, dimethyl sulfone, hexamethyl sulfoxide, γ-butyrolactone, isopropanol, methoxymethylpentanol, and dipentene. Ethylpentyl ketone, methyl nonyl ketone, methyl ethyl ketone, methyl isopentyl 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 Ester, 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, methylcyclohexene, propyl ether, dihexyl ether, dioxane, n-hexane, n- Pentane, n-octane, diethyl ether, cyclohexanone, ethylene carbonate, propylene carbonate, methyl lactate, ethyl lactate, methyl acetate, ethyl acetate, n-butyl acetate, propylene glycol monoethyl ether, methyl pyruvate, ethyl pyruvate, methyl 3-methoxypropionate, methyl ethyl 3-ethoxypropionate, ethyl 3-methoxypropionate, 3-ethoxypropionic acid, 3-methoxypropionic acid, propyl 3-methoxypropionate, butyl 3-methoxypropionate, diethylene glycol dimethyl ether, 4-hydroxy-4-methyl-2-pentanone, 2-ethyl-1-hexanol, etc. These organic solvents can be used alone or in mixtures.

[0204] When reacting a diamine with a tetracarboxylic dianhydride in an organic solvent, the following methods can be used: stirring a solution obtained by dispersing or dissolving the diamine in an organic solvent, and then adding the tetracarboxylic dianhydride directly or by dispersing or dissolving it in an organic solvent; conversely, adding the diamine to a solution obtained by dispersing or dissolving the tetracarboxylic dianhydride in an organic solvent; or adding the tetracarboxylic dianhydride and diamine alternately. Any of these methods can be used. Furthermore, when the diamine or tetracarboxylic dianhydride contains multiple compounds, they can be reacted in a pre-mixed state, reacted separately and sequentially, or further mixed to produce a high molecular weight compound.

[0205] The temperature at which the diamine and tetracarboxylic dianhydride react can be selected arbitrarily, for example, from -20 to 100°C, preferably from -5 to 80°C. Furthermore, the reaction can be carried out at any concentration; for example, the combined amount of the diamine and tetracarboxylic dianhydride relative to the reaction solution is 1 to 50% by mass, preferably 5 to 30% by mass.

[0206] In the above polymerization reaction, the ratio of the total molar number of tetracarboxylic dianhydride components to the total molar number of diamine components can be selected as any value depending on the desired molecular weight of the polyamic acid. Similar to typical polycondensation reactions, the closer this molar ratio is to 1.0, the larger the molecular weight of the resulting polyamic acid. A preferred range is 0.8 to 1.2.

[0207] The method for synthesizing the polymers used in this invention is not limited to the methods described above. In the case of synthesizing polyamic acid, similar to the conventional method for synthesizing polyamic acid, a tetracarboxylic acid derivative such as a tetracarboxylic acid or a tetracarboxylic acid dihalide is used instead of the aforementioned tetracarboxylic acid dianhydride, and the reaction is carried out using a known method, thereby obtaining the corresponding polyamic acid. Furthermore, in the case of synthesizing polyurea, a diamine is reacted with a diisocyanate. In the manufacture of polyamic acid esters or polyamides, a diamine is reacted with a component selected from tetracarboxylic acid diesters and dicarboxylic acids in the presence of a known condensing agent or by a known method to derivatize into an acid halide, and then reacted with the diamine.

[0208] Furthermore, polyimide can be obtained by cyclizing (imidizing) the aforementioned polyamic acid. It should be noted that the imidization rate referred to in this specification refers to the proportion of imide groups in the total amount of imide groups and carboxyl groups derived from tetracarboxylic dianhydride. The imidization rate of the polyimide does not necessarily need to be 100% and can be adjusted arbitrarily according to the application and purpose. From the perspective of improving voltage retention rate, the imidization rate of the polyimide in this invention is preferably 30% or more; on the other hand, from the viewpoint of suppressing whitening characteristics, i.e., the precipitation of polymers in the varnish, it is preferably 80% or less.

[0209] Examples of methods for imidizing the above-mentioned polyamic acid to form polyimide include thermal imidization by directly heating a solution of polyamic acid and catalytic imidization by adding a catalyst to a solution of polyamic acid.

[0210] The temperature for thermal imidization of polyamic acid in solution is typically 100–400°C, preferably 120–250°C, and preferably carried out while removing water generated by the imidization reaction from the system.

[0211] Catalytic imidization of polyamic acid can be carried out by adding a basic catalyst and an acid anhydride to a solution of polyamic acid, typically at -20 to 250°C, preferably 0 to 180°C, with stirring. The amount of basic catalyst is typically 0.5 to 30 molar times that of the amic acid groups, preferably 2 to 20 molar times, and the amount of acid anhydride is typically 1 to 50 molar times that of the amic acid groups, preferably 3 to 30 molar times. Examples of basic catalysts include pyridine, triethylamine, trimethylamine, tributylamine, and trioctylamine, among which pyridine is preferred due to its suitable basicity for the reaction. Examples of acid anhydrides include acetic anhydride, trimellitic anhydride, and pyromellitic anhydride, among which acetic anhydride is preferred because it facilitates purification after the reaction. The imidization rate based on catalyst imidization can be controlled by adjusting the amount of catalyst, reaction temperature, and reaction time.

[0212] In recovering the polymer from the reaction solution, the reaction solution can be simply precipitated in a poor solvent. Examples of poor solvents for precipitation include methanol, acetone, hexane, butyl cellosolve, heptane, methyl ethyl ketone, methyl isobutyl ketone, ethanol, toluene, benzene, and water. The polymer precipitated in the poor solvent can be recovered by filtration and then dried at room temperature or under normal or reduced pressure. Furthermore, repeating the process 2 to 10 times to redissolve the precipitated polymer in an organic solvent and then precipitate it again reduces impurities in the polymer. Examples of poor solvents in this process include alcohols, ketones, and hydrocarbons. Using three or more poor solvents selected from these is preferred as it further improves purification efficiency.

[0213] Furthermore, when the free radical generating membrane comprises a polymer containing organic groups that induce free radical polymerization, the free radical generating membrane forming composition used in this invention may contain polymers other than the polymer containing organic groups that induce free radical polymerization. In this case, the content of other polymers in the total polymer composition is preferably 5-95% by mass, more preferably 30-70% by mass.

[0214] Taking into account the strength of the free radical generating film obtained by coating, the operability during film formation, and the uniformity of the film, the molecular weight of the polymer in the free radical generating film forming composition, measured by weight-average molecular weight using GPC (gel permeation chromatography), is preferably 5,000 to 1,000,000, more preferably 10,000 to 150,000.

[0215] A free radical generating membrane for use in this invention is obtained by coating a composition of a compound and a polymer having free radical generating groups onto a substrate and then curing it to form a film, thereby immobilizing the substrate within the film. The polymer used in this process can be a polymer selected from the group consisting of a polyimide precursor manufactured according to the above-described manufacturing method, polyimide, polyurea, polyamide, polyacrylate, polymethacrylate, etc. The polymer is at least one type obtained by using a diamine containing the organic groups of the free radical-inducing polymer described above as a 0 mol% diamine component in the synthesis of the polymer contained in the free radical generating membrane forming composition. Examples of compounds having free radical generating groups added at this time include the following substances.

[0216] Compounds that generate free radicals through heat are those that generate free radicals when heated to temperatures above their decomposition temperature. Examples of such free radical thermal polymerization initiators include: peroxide ketones (methyl ethyl ketone peroxide, cyclohexanone peroxide, etc.), peroxide diacyls (acetyl peroxide, benzoyl peroxide, etc.), hydroperoxides (hydrogen peroxide, tert-butyl hydroperoxide, cumene hydroperoxide, etc.), dialkyl peroxides (di-tert-butyl peroxide, dicumyl peroxide, dilauryl peroxide, etc.), peroxide ketals (dibutyl peroxycyclohexane, etc.), alkyl peresters (tert-butyl peroxyneodecanate, tert-butyl peroxynepentanoate, tert-pentyl peroxy2-ethylcyclohexanoate, etc.), persulfates (potassium persulfate, sodium persulfate, ammonium persulfate, etc.), and azo compounds (azobisisobutyronitrile, and 2,2'-di(2-hydroxyethyl)azobisisobutyronitrile, etc.). Such free radical thermal polymerization initiators can be used alone or in combination of two or more.

[0217] As compounds that generate free radicals through light, there are no particular limitations as long as the compound initiates free radical polymerization upon light irradiation. Examples of such free radical photopolymerization initiators include: benzophenone, milchone, 4,4'-bis(diethylamino)benzophenone, xanthonone, thioxanthonone, isopropyl xanthonone, 2,4-diethylthioxanthonone, 2-ethylanthraquinone, acetophenone, 2-hydroxy-2-methylphenylacetone, 2-hydroxy-2-methyl-4'-isopropylphenylacetone, 1-hydroxycyclohexylphenyl ketone, isopropyl benzoin ether, isobutyl benzoin ether, 2,2-diethoxyacetophenone, 2,2-dimethoxy-2-phenylacetophenone, camphorquinone, benzanthrone, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholino-1-propanone, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl) 4,4'-Butanone-1,4-Dimethylaminobenzoate, 4-Dimethylaminobenzoate isoamyl ester, 4,4'-Di(tert-butylperoxycarbonyl)benzophenone, 3,4,4'-Tris(tert-butylperoxycarbonyl)benzophenone, 2,4,6-Trimethylbenzoyl diphenylphosphine oxide, 2-(4'-methoxystyryl)-4,6-bis(trichloromethyl)-triazine, 2-(3',4'-dimethoxystyryl)-4,6-bis(trichloromethyl)-triazine, 2-(2',4'-dimethoxystyryl)-4,6-bis(trichloromethyl)-triazine, 2-(2'-methoxystyryl)-4,6-bis(trichloromethyl)-triazine, 2-(4'-pentane 4,6-bis(trichloromethyl)-triazine, 4-[p-N,N-di(ethoxycarbonylmethyl)]-2,6-bis(trichloromethyl)-triazine, 1,3-bis(trichloromethyl)-5-(2'-chlorophenyl)-triazine, 1,3-bis(trichloromethyl)-5-(4'-methoxyphenyl)-triazine, 2-(p-dimethylaminostyryl)benzoxazole, 2-(p-dimethylaminostyryl)benzothiazole, 2-mercaptobenzothiazole, 3,3'-carbonylbis(7-diethylaminecoumarin), 2-(o-chlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole, 2,2'-bis(2-chlorophenyl)-4,4',5 5'-Tetra(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-dodecylcarbazole, 1-hydroxycyclohexylphenyl ketone, bis(5-2,4-cyclopentyldien-1-yl)-bis(2,6-Difluoro-3-(1H-pyrrolo-1-yl)-phenyl)titanium, 3,3',4,4'-tetra(tert-butylperoxycarbonyl)benzophenone, 3,3',4,4'-tetra(tert-hexylperoxycarbonyl)benzophenone, 3,3'-di(methoxycarbonyl)-4,4'-di(tert-butylperoxycarbonyl)benzophenone, 3,4'-di(methoxycarbonyl)-4,3'-di(tert-butylperoxycarbonyl)benzophenone, 4,4'-di(methoxycarbonyl)-3,3'-di(tert-butylperoxycarbonyl)benzophenone, 2-(3-methyl-3H-benzothiazol-2-ylidene)-1-naphth-2-yl-ethyl ketone, or 2-(3-methyl-1,3-benzothiazol-2(3H)-ylidene)-1-(2-benzoyl)ethyl ketone, etc. These compounds can be used alone or in combination of two or more.

[0218] It should be noted that even when the free radical generating membrane contains a polymer with organic groups that induce free radical polymerization, it may also contain the aforementioned compounds with free radical generating groups in order to promote free radical polymerization when energy is applied.

[0219] The free radical generating film-forming composition may contain an organic solvent that dissolves or disperses the polymer components and, if desired, other components besides a free radical generator. Such an organic solvent is not particularly limited, and examples include those exemplified in the synthesis of the polyamic acid described above. From a solubility point of view, N-methyl-2-pyrrolidone, γ-butyrolactone, N-ethyl-2-pyrrolidone, 1,3-dimethyl-2-imidazolinone, 3-methoxy-N,N-dimethylpropaneamide, etc., are preferred. N-methyl-2-pyrrolidone or N-ethyl-2-pyrrolidone are particularly preferred, and mixtures of two or more solvents may also be used.

[0220] In addition, it is preferable to use a solvent that improves the uniformity and smoothness of the coating film in combination with an organic solvent that has high solubility of the components contained in the free radical generating film forming composition.

[0221] Solvents used to improve the uniformity and smoothness of coatings include, for example: isopropanol, methoxymethylpentanol, 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, etc. Diethylene 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, methylcyclohexene, propyl ether, dihexyl ether, n-hexane, n-pentane, n-octane, diethyl ether, methyl lactate, ethyl lactate, n-propyl lactate, n-butyl lactate, isoamyl lactate, methyl acetate, ethyl acetate, n-butyl acetate, propylene glycol monoethyl ether, methyl pyruvate, ethyl pyruvate, methyl 3-methoxypropionate, methyl 3-ethoxypropionate, 3-methyl... Ethyl oxypropionate, 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, etc. These solvents can be mixed in multiples. When using these solvents, it is preferable that the total amount of solvent contained in the free radical generating film forming composition is 5 to 80% by mass, more preferably 20 to 60% by mass.

[0222] The free radical generating film forming composition may contain components other than those mentioned above. Examples include compounds that improve the uniformity of film thickness and surface smoothness when the free radical generating film forming composition is coated, compounds that improve the adhesion between the free radical generating film forming composition and the substrate, and compounds that further improve the film strength of the free radical generating film forming composition.

[0223] Compounds used to improve film thickness uniformity and surface smoothness include fluorinated surfactants, silicone surfactants, and nonionic surfactants. More specifically, examples include: EFTOP EF301, EF303, EF352 (manufactured by Mitsubishi Materials Electronics & Chemicals Co., Ltd.), MEGAFAC F171, F173, R-30 (manufactured by DIC Corporation), Fluorad FC430, FC431 (manufactured by 3M Corporation), AsahiGuard AG710, SURFION S-382, SC101, SC102, SC103, SC104, SC105, SC106 (manufactured by AGC Corporation). When using these surfactants, the proportion used is preferably 0.01 to 2 parts by mass, more preferably 0.01 to 1 part by mass, relative to 100 parts by mass of the total amount of polymer contained in the free radical generating film forming composition.

[0224] Specific examples of compounds that improve the adhesion between the free radical generating film-forming composition and the substrate include compounds containing functional silanes and compounds containing epoxy groups. Examples include: 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 2-aminopropyltrimethoxysilane, 2-aminopropyltriethoxysilane, N-(2-aminoethyl)-3-aminopropyltrimethoxysilane, N-(2-aminoethyl)-3-aminopropylmethyldimethoxysilane, 3-ureopropyltrimethoxysilane, 3-ureopropyltriethoxysilane, N-ethoxycarbonyl-3-aminopropyltrimethoxysilane, N-ethoxycarbonyl-3-aminopropyltriethoxysilane. 10-Trimethoxysilylpropyltrivinyltriamine, 10-Trimethoxysilyl-1,4,7-triazadecane, 10-Triethoxysilyl-1,4,7-triazadecane, 9-Trimethoxysilyl-3,6-diazanonylacetate, 9-Triethoxysilyl-3,6-diazanonylacetate, N-Benzyl-3-aminopropyltrimethoxysilane, N-Benzyl-3-aminopropyltriethoxysilane Alkane, N-phenyl-3-aminopropyltrimethoxysilane, N-phenyl-3-aminopropyltriethoxysilane, N-di(oxyvinyl)-3-aminopropyltrimethoxysilane, N-di(oxyvinyl)-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, glycerol diglycidyl ether, 2 2-Dibromoneopentyl glycol diglycidyl ether, 1,3,5,6-tetraglycidyl-2,4-hexanediol, N,N,N′,N′-tetraglycidyl-m-phenylenediamine, 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, etc.

[0225] In addition, to further improve the membrane strength of the free radical generating membrane, phenolic compounds such as 2,2'-bis(4-hydroxy-3,5-dihydroxymethylphenyl)propane and tetra(methoxymethyl)bisphenol can be added. When using these compounds, the amount is preferably 0.1 to 30 parts by mass, more preferably 1 to 20 parts by mass, relative to 100 parts by mass of the total amount of polymer contained in the free radical generating membrane forming composition.

[0226] Furthermore, in addition to the above, in the free radical generating film forming composition, dielectrics and conductive substances that change the electrical properties such as dielectric constant and conductivity of the free radical generating film may be added, provided that the effect of the present invention is not impaired.

[0227] [Free radical generation membrane]

[0228] The free radical generating film of the present invention can be obtained, for example, using the above-described free radical generating film forming composition. For example, after coating the free radical generating film forming composition used in the present invention onto a substrate, it is dried and sintered to obtain a cured film, or the cured film can be used directly as a free radical generating film. In addition, the cured film can be oriented by irradiation with friction, polarized light or light of a specific wavelength, ion beam or the like, and then irradiated with UV light onto a liquid crystal display element filled with liquid crystal after it is made into an alignment film for PSA.

[0229] As a substrate for coating free radicals to generate film forming composition, there are no particular limitations as long as the substrate has high transparency, but a substrate with transparent electrodes for driving liquid crystals formed on it is preferred.

[0230] If specific examples are given, substrates on which transparent electrodes are formed are provided on glass plates, polycarbonate, poly(meth)acrylate, polyethersulfone, polyarylate, polyurethane, polysulfone, polyether, polyetherketone, trimethylpentene, polyolefin, polyethylene terephthalate, (meth)acrylonitrile, triacetylcellulose, diacetylcellulose, cellulose acetate butyrate, and other plastic plates.

[0231] In IPS-type liquid crystal display elements, the substrates that can be used can also use standard IPS comb electrodes, PSA fishbone electrodes, and MVA protrusion patterns.

[0232] In addition, in high-function components such as TFT-type components, components in which transistors are formed between the electrodes used for liquid crystal driving and the substrate can be used.

[0233] When the target is a transmissive liquid crystal display element, a substrate as described above is typically used. However, when the target is a reflective liquid crystal display element, if only a single-sided substrate is required, an opaque substrate such as a silicon wafer can also be used. In this case, the electrodes formed on the substrate can also be made of a material such as aluminum, which reflects light.

[0234] Examples of coating methods for free radical generating film forming compositions include spin coating, printing, inkjet coating, spray coating, and roller coating. From a productivity perspective, transfer printing is widely used in industry and is also suitable for use in this invention.

[0235] A drying process after coating the free radical-generated film composition is not necessarily required, but it is preferable to include a drying process when the time from coating to sintering is not fixed on each substrate, or when sintering is not performed immediately after coating. This drying only needs to remove the solvent to the extent that the shape of the coating film is not deformed due to substrate transport, etc., and there are no particular limitations on the drying method. For example, the following method can be used: drying on a hot plate at a temperature of 40–150°C, preferably 60–100°C, for 0.5–30 minutes, preferably 1–5 minutes.

[0236] The coating formed by applying the free radical-generating film-forming composition using the above method can be sintered to form a cured film. The sintering temperature can typically be any temperature between 100 and 350°C, preferably 140 to 300°C, more preferably 150 to 230°C, and even more preferably 160 to 220°C. The sintering time can typically be any time between 5 and 240 minutes, preferably 10 to 90 minutes, more preferably 20 to 90 minutes. Heating can be performed using commonly known methods, such as hot plates, hot air circulating ovens, IR (infrared) ovens, belt furnaces, etc.

[0237] The thickness of the cured film can be selected as needed, but it is preferably 5 nm or more, and more preferably 10 nm or more, as this improves the reliability of the liquid crystal display element. Furthermore, when the thickness of the cured film is preferably 300 nm or less, and more preferably 150 nm or less, the power consumption of the liquid crystal display element will not increase drastically, which is also preferable.

[0238] A first substrate having a free radical generating film can be obtained in the manner described above, but the free radical generating film can also be subjected to a uniaxial orientation process. Examples of methods for performing the uniaxial orientation process include photo-orientation, tilting evaporation, rubbing, and uniaxial orientation based on a magnetic field.

[0239] In the case of alignment processing by rubbing in one direction, for example, a substrate is moved so that the rubbing cloth contacts the film while a rubbing roller wound with rubbing cloth is rotated. In the case of using photoalignment, the entire surface of the film can be irradiated with polarized UV light of a specific wavelength and heated as needed, thereby performing alignment processing.

[0240] In the case of the first substrate of the present invention having comb-tooth electrodes, the direction can be selected according to the electrical properties of the liquid crystal, but when using a liquid crystal with positive dielectric anisotropy, it is preferable that the rubbing direction is approximately the same as the direction in which the comb-tooth electrodes extend.

[0241] As a step in creating weak and strong anchoring regions, one method is to irradiate the area with radiation in an arbitrary pattern using a photomask or similar means. This method involves pre-irradiating the free radical generation film with radiation to eliminate the free radical generation sites and prevent the formation of a weak anchoring state. Examples of radiation used in this step include polarized light, light of a specific wavelength, and ion beams. Light with the wavelength that maximizes the absorbance of the corresponding portion of the photofree radical generation site is particularly preferred.

[0242] The second substrate of the present invention may or may not have a free radical generating film. The second substrate is preferably a conventionally known substrate having a liquid crystal alignment film.

[0243] In this invention, the first substrate may be a substrate with comb-tooth electrodes, and the second substrate may be an opposing substrate. Alternatively, in this invention, the second substrate may be a substrate with comb-tooth electrodes, and the first substrate may be an opposing substrate.

[0244] <Liquid Crystal Unit>

[0245] After forming a free radical generating film on a substrate using the above method, the liquid crystal cell of the present invention is arranged with a substrate having the free radical generating film (first substrate) and a known substrate having a liquid crystal alignment film (second substrate) with the free radical generating film and the liquid crystal alignment film facing each other. A spacer is clamped between the two substrates, and the mixture is fixed with a sealant. A liquid crystal composition containing liquid crystal and a free radical polymerizable compound is then injected and sealed to obtain the product. The size of the spacer used is typically 1 to 30 μm, preferably 2 to 10 μm.

[0246] There are no particular limitations on the method of injecting a liquid crystal composition containing liquid crystal and free radical polymerizable compound. Examples include: vacuum method, in which a mixture containing liquid crystal and polymerizable compound is injected into a liquid crystal cell after depressurization; drop addition method, in which a mixture containing liquid crystal and polymerizable compound is added dropwise and then sealed.

[0247] <Free radical polymerizable compounds and liquid crystal compositions>

[0248] The free radical polymerizable compound of the present invention is represented by the following formula (A).

[0249] [Chemistry 31]

[0250]

[0251] (In formula (A), M represents a polymerizable group capable of free radical polymerization; R1 to R3 each independently represent a single bond or an alkylene group with 1 to 6 carbon atoms that can be inserted into a bonding group; Ar represents an aromatic hydrocarbon group that can have substituents; X1 and X2 each independently represent a hydrogen atom or an aromatic hydrocarbon group that can have substituents; R1X1, R2X2 and the carbon atoms bonded to R1X1 and R2X2 can form a ring together, but the total number of carbon atoms in R1X1, R2X2 and R3 is 1 or more.)

[0252] The term "alkylene group with 1 to 6 carbon atoms with inserted bonding groups" refers to a divalent group with inserted bonding groups between carbon atoms in an alkylene group with 1 to 6 carbon atoms, or a divalent group with inserted bonding groups between an alkylene group with 1 to 6 carbon atoms and the carbon atom to which it is bonded.

[0253] Examples of bonding groups include carbon-carbon unsaturated bonds, ether bonds (-O-), ester bonds (-COO- or -OCO-), and amide bonds (-CONH- or -NHCO-). Examples of unsaturated bonds include carbon-carbon double bonds, but alkylene groups with 1 to 6 carbon atoms inserted into the carbon-carbon double bond preferably have a carbon-carbon double bond internally rather than at their ends.

[0254] Examples of alkylene groups having 1 to 6 carbon atoms that can be inserted into bonding groups include alkylene groups having 1 to 6 carbon atoms and oxoalkylene groups having 1 to 6 carbon atoms. The oxygen atom in an oxoalkylene group having 1 to 6 carbon atoms is bonded, for example, to the carbon atoms bonded to M, R1, R2, and R3 in formula (A).

[0255] Alkylenes with 1 to 6 carbon atoms can be straight-chain alkylenes, branched alkylenes, or cyclic alkylenes.

[0256] Examples of aromatic hydrocarbon groups that can have substituents include phenyl and naphthyl groups.

[0257] Examples of substituents include halogen atoms, alkyl groups with 1 to 4 carbon atoms, alkoxy groups with 1 to 4 carbon atoms, haloalkyl groups with 1 to 4 carbon atoms, and haloalkoxy groups with 1 to 4 carbon atoms. The halogenation in haloalkyl and haloalkoxy groups can be either full halogenation or partial halogenation. Examples of halogen atoms include fluorine atoms and chlorine atoms.

[0258] Examples of R1 include single bonds and alkylene groups having 1 to 6 carbon atoms. More specifically, examples of alkylene groups having 1 to 6 carbon atoms include straight-chain alkylene groups having 1 to 6 carbon atoms.

[0259] Examples of R2 include single bonds and alkylene groups having 1 to 6 carbon atoms. More specifically, examples of alkylene groups having 1 to 6 carbon atoms include straight-chain alkylene groups having 1 to 6 carbon atoms.

[0260] Examples of R3 include single bonds and alkylene groups having 1 to 6 carbon atoms. More specifically, examples of alkylene groups having 1 to 6 carbon atoms include straight-chain alkylene groups having 1 to 6 carbon atoms.

[0261] Examples of X1 include hydrogen atoms, phenyl groups, etc.

[0262] Examples of X2 include hydrogen atoms and phenyl groups.

[0263] A r Examples include phenyl groups.

[0264] There is no special restriction on the total number of carbon atoms in R1X1, R2X2, and R3, as long as it is 1 or more; it can be 2 or more.

[0265] In addition, the total number of carbon atoms in R1, R2 and R3 can be less than 18, less than 15, or less than 10.

[0266] Furthermore, if X1 and X2 are hydrogen atoms, there is no special restriction as long as the total number of carbon atoms in R1, R2 and R3 is 1 or more, and it can be 2 or more.

[0267] It should be noted that if at least one of X1 and X2 is an aromatic hydrocarbon group that can have substituents, the total number of carbon atoms in R1, R2 and R3 can be 0.

[0268] Examples of rings formed by R1X1, R2X2, and the carbon atoms bonded to R1X1 and R2X2 include hydrocarbon rings with 3 to 13 carbon atoms into which the bonding groups can be inserted. The bonding groups are as described above.

[0269] Examples of free radical polymerizable compounds represented by formula (A) include those represented by formulas (A-1) to (A-3).

[0270] [Chemistry 32]

[0271]

[0272] In the formula, M represents a polymerizable group capable of free radical polymerization.

[0273] R1 to R3 each independently represent a single bond, or an alkylene group with 1 to 6 carbon atoms into which a bonding group can be inserted.

[0274] Ar, Ar1, and Ar2 each independently represent aromatic hydrocarbon groups that can have substituents.

[0275] R 11 and R 12 Each can independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms into which a bonding group can be inserted.

[0276] In equation (A-1), R 11 R 12 and bonded to R 11 and R 12 Carbon atoms can form rings together.

[0277] In equation (A-1), R 11 R 12 The total number of carbon atoms in the compound and R3 can be 1 or more, or 2 or more. Alternatively, the total number of carbon atoms can be less than 18, less than 15, or less than 10.

[0278] In equation (A-2), R1 and R 12 There is no particular limitation on the total number of carbon atoms of R and R3; it can be 0. For example, the total number of carbon atoms can be less than 18, less than 15, or less than 10.

[0279] In formula (A-3), the total number of carbon atoms of R1, R2, and R3 is not particularly limited and can be 0. For example, the total number of carbon atoms can be less than 18, less than 15, or less than 10.

[0280] It should be noted that R 11 This refers to the case where X1 in R1X1 is a hydrogen atom. R 12 This refers to the case where X2 in R2X2 is a hydrogen atom.

[0281] Furthermore, the polymerizable group M, which is capable of free radical polymerization, as the free radical polymerizable compound, is preferably selected from polymerizable groups in the following structures.

[0282] [Chemistry 33]

[0283]

[0284] (In the formula, * indicates the bonding site. R) b It indicates a straight-chain alkyl group with 2 to 8 carbon atoms, and E indicates that it is selected from single bonds, -O-, and -NR. c -, -S-, ester bonds, and amide bonds containing bonding groups. c Represents an alkyl group having 1 to 4 hydrogen atoms or carbon atoms. R d (This refers to an alkyl group having 1 to 6 hydrogen atoms or carbon atoms.)

[0285] Examples of free radical polymerizable compounds contained in formulas (A) and (A-1) include the following free radical polymerizable compounds.

[0286] [Chemistry 34]

[0287]

[0288] (i)Add-1 is equivalent to the combination of M in formula (A) as the following structure (C), R1X1 as 1-pentyl, R2 as a single bond, X2 as a hydrogen atom, R3 as a single bond, and Ar as a phenyl group.

[0289] (ii) Add-3 is equivalent to the combination of M in formula (A) as the following structure (B), R1X1 as 1-propyl, R2 as a single bond, X2 as a hydrogen atom, R3 as a single bond, and Ar as a phenyl group.

[0290] (iii) Add-6 is equivalent to the combination of M in formula (A) which is the following structure (C), R1X1 is ethyl, R2X2 is ethyl, R3 is 1,2-ethylidene, and Ar is phenyl.

[0291] (iv) Add-8 is equivalent to the combination of M in formula (A) as the following structure (C), R1X1 as 1-propyl, R2 as a single bond, X2 as a hydrogen atom, R3 as 1,2-ethylene, and Ar as phenyl.

[0292] (v)Add-12 is equivalent to the combination of M in formula (A) as the following structure (D), R1 as a single bond, X1 as a hydrogen atom, R2 as a single bond, X2 as a hydrogen atom, R3 as 1,2-ethylene, and Ar as a phenyl group.

[0293] [Chemistry 35]

[0294]

[0295] (In structures (B), (C), and (D), * indicates a bonding site.)

[0296] The liquid crystal composition contains at least liquid crystal and the above-mentioned free radical polymerizable compound.

[0297] The content of the free radical polymerizable compound in the liquid crystal composition is preferably 0.5% by mass or more, more preferably 1% by mass or more, more preferably 10% by mass or less, and more preferably 5% by mass or less, relative to the total mass of the liquid crystal and the free radical polymerizable compound.

[0298] In addition, in the liquid crystal composition, multiple other compounds having monofunctional free radical polymerizable groups (hereinafter sometimes referred to as "other free radical polymerizable compounds") may be used in combination with the above-mentioned free radical polymerizable compounds.

[0299] Other free radical polymerizable compounds possess unsaturated bonds that enable free radical polymerization in the presence of organic free radicals. Examples include: methacrylate monomers such as tert-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; and styrene and styrene derivatives (e.g., o-, m-, and p-methoxystyrene, o-, m-, and p-tert-butoxystyrene, o-, m-, and p-chloromethylstyrene). Vinyl monomers, including but not limited to, 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-vinylpyrrolidone, N-vinylpyrrole, N-vinylcarbazole, N-vinylindole, etc.), (meth)acrylic acid derivatives (e.g., acrylonitrile, methacrylonitrile, acrylamide, isopropylacrylamide, methacrylamide, etc.), and halogenated vinyl compounds (e.g., vinyl chloride, vinylidene chloride, tetrachloroethylene, hexachlorobutadiene, vinyl fluoride, etc.). Furthermore, these compounds are preferably compatible with liquid crystals.

[0300] In addition, the compound represented by the following formula (1) is preferred as another free radical polymerizable compound.

[0301] [Chemistry 36]

[0302]

[0303] (In equation (1), R) a and R b Each of these terms independently represents a straight-chain alkyl group having 2 to 8 carbon atoms, and E indicates a group selected from single bonds, -O-, and -NR. c -, -S-, ester bonds, and amide bonds containing bonding groups. c This refers to alkyl groups having 1 to 4 hydrogen atoms or carbon atoms.

[0304] The free radical polymerizable compound contained in the liquid crystal composition is preferably a compound that is compatible with liquid crystal and has a polymerizable unsaturated bond in one molecule, i.e. a compound having a monofunctional free radical polymerizable group.

[0305] Furthermore, as the free radical polymerizable compound represented by the formula (1), there is no particular limitation. From the viewpoint of ease of synthesis, compatibility with liquid crystals, and polymerization reactivity, it is preferred to be a compound in which E is an ester bond (represented by -C(=O)-O- or -OC(=O)-). Specifically, it is preferred to be a compound represented by the following structure.

[0306] [Chemistry 37]

[0307]

[0308] Furthermore, the liquid crystal composition preferably contains a free radical polymerizing compound whose Tg is below 100°C, which is the polymer obtained by polymerizing a free radical polymerizing compound.

[0309] These various free radical polymerizable monomers can be used individually or in combination of two or more. Furthermore, these monomers are preferably compatible with liquid crystals.

[0310] The Tg of the polymer obtained by polymerizing a free radical polymerizable compound is preferably below 100°C, and more preferably below 0°C.

[0311] It should be noted that liquid crystals generally refer to substances that exhibit both solid and liquid properties. Representative liquid crystal phases include nematic liquid crystals and smectic liquid crystals. The liquid crystals that can be used in this invention are not particularly limited. For example, 4-pentyl-4′-cyanobiphenyl.

[0312] Next, sufficient energy is applied to the liquid crystal cell containing the mixture of the liquid crystal and the free radical polymerizable compound (liquid crystal composition) to cause the free radical polymerizable compound to undergo a polymerization reaction. This can be carried out, for example, by applying heat or by UV irradiation. By causing the free radical polymerizable compound to polymerize under these conditions, the desired properties are exhibited. Among these methods, UV irradiation is preferred from the perspective of enabling oriented patterning and thus allowing the polymerization reaction to occur in a short time.

[0313] Alternatively, heating can be performed during UV irradiation. The preferred heating temperature during UV irradiation is within the temperature range where the introduced liquid crystal exhibits liquid crystal properties, typically above 40°C, and preferably below the temperature at which the liquid crystal becomes an isotropic phase.

[0314] Here, the UV irradiation wavelength is preferably selected to achieve the best reaction quantum yield for the polymerizable compound, and the UV irradiation dose is typically 0.01–30 J / cm². 2 Preferably 10 J / cm 2 The following is preferred because a low UV irradiation level can suppress the decrease in reliability caused by damage to components constituting the liquid crystal display, and the manufacturing cycle can be improved by reducing the UV irradiation time.

[0315] Furthermore, for polymerization processes that are carried out solely by heating without UV irradiation, it is preferable to conduct the polymerization within a temperature range that is within the reaction temperature of the polymerizable compound and lower than the decomposition temperature of the liquid crystal. Specifically, this ranges from 100°C to 150°C.

[0316] When sufficient energy is applied to enable free radical polymerizable compounds to undergo polymerization, a field-free state without applied voltage is preferred.

[0317] Liquid crystal display element

[0318] Liquid crystal display elements can be fabricated using liquid crystal cells obtained in the manner described above.

[0319] A liquid crystal display element, for example, includes a first substrate, a second substrate disposed opposite to the first substrate, and liquid crystal filling the space between the first substrate and the second substrate. Furthermore, the liquid crystal display element is formed by polymerizing the free radical polymerizing compound while the liquid crystal composition containing the liquid crystal and the free radical polymerizing compound represented by formula (A) is in contact with the free radical generating film of the first substrate having a free radical generating film.

[0320] For liquid crystal display elements, for example, a reflective liquid crystal display element can be manufactured by conventionally incorporating reflective electrodes, transparent electrodes, a λ / 4 plate, a polarizing film, a color filter layer, etc., into the liquid crystal cell as needed. Alternatively, a transmissive liquid crystal display element can be manufactured by conventionally incorporating backlight, a polarizer, a λ / 4 plate, a transparent electrode, a polarizing film, a color filter layer, etc., into the liquid crystal cell as needed.

[0321] Figure 1 This is a schematic cross-sectional view showing an example of a lateral electric field liquid crystal display element of the present invention, which is an example of an IPS mode liquid crystal display element.

[0322] exist Figure 1 In the illustrated lateral electric field liquid crystal display element 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 includes: a substrate 2a, a plurality of linear electrodes 2b formed on the substrate 2a and arranged in a comb-like pattern, and a liquid crystal alignment film 2c formed on the substrate 2a to cover the linear electrodes 2b. The counter substrate 4 includes a substrate 4b and a liquid crystal alignment film 4a formed on the substrate 4b. The liquid crystal alignment film 2c is, for example, a weakly anchoring film obtained by chemically changing a free radical generating film. The liquid crystal alignment film on the comb-shaped electrode substrate side is, for example, obtained by polymerizing a free radical polymerizing compound while a liquid crystal composition containing liquid crystal and a free radical polymerizing compound is in contact with the free radical generating film.

[0323] In this transverse electric field liquid crystal display element 1, if a voltage is applied to the linear electrode 2b, an electric field is generated between the linear electrodes 2b as shown by the electric field line L.

[0324] Figure 2This is a schematic cross-sectional view illustrating another example of the lateral electric field liquid crystal display element of the present invention, which is an example of an FFS mode liquid crystal display element.

[0325] exist Figure 2 In the illustrated lateral electric field liquid crystal display element 1, 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 has a substrate 2d, a surface electrode 2e formed on the substrate 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-like pattern, and a liquid crystal alignment film 2h formed on the insulating film 2f to cover the linear electrodes 2g. The counter substrate 4 has a substrate 4b and a liquid crystal alignment film 4a formed on the substrate 4b. The liquid crystal alignment film 2h is, for example, a weakly anchoring film obtained by chemically changing a free radical generating film. The liquid crystal alignment film on the comb-shaped electrode substrate side is, for example, obtained by polymerizing a free radical polymerizing compound while a liquid crystal composition containing liquid crystal and a free radical polymerizing compound is in contact with the free radical generating film.

[0326] In this transverse electric field liquid crystal display element 1, if a voltage is applied to the surface electrode 2e and the linear electrode 2g, an electric field is generated between the surface electrode 2e and the linear electrode 2g, as shown by the electric field line L.

[0327] Example

[0328] The present invention will be specifically described below with reference to examples, but the invention shall not be construed as limited by these examples. The abbreviations of the compounds and the methods for determining their properties are described below.

[0329] (Diamine)

[0330] DA-1 to DA-5: Compounds represented by the formulas (DA-1) to (DA-5) below.

[0331] [Chemistry 38]

[0332]

[0333] (Tetracarboxylic acid dianhydride)

[0334] TC-1 to TC-3: Compounds represented by the formulas (TC-1) to (TC-3) below.

[0335] [Chemistry 39]

[0336]

[0337] (additive)

[0338] Add-1 to Add-12: These are the compounds represented by the formulas (Add-1) to (Add-12) below.

[0339] Add-C1 to Add-C3: These are the compounds represented by the formulas (Add-C1) to (Add-C3) below.

[0340] AD-1: The compound represented by the following formula (AD-1)

[0341] [Chemistry 40]

[0342]

[0343] [Chemistry 41]

[0344]

[0345] (solvent)

[0346] THF: Tetrahydrofuran

[0347] CH2Cl2: Dichloromethane

[0348] CHCl3: Chloroform

[0349] NMP: N-methyl-2-pyrrolidone

[0350] BCS: Butyl Solvent

[0351] GBL: γ-Butyrolactone

[0352] (Reaction reagents)

[0353] TEA: Triethylamine

[0354] DMAP: 4-Dimethylaminopyridine

[0355] (other)

[0356] BHT: Butylated hydroxytoluene

[0357] <Viscosity Measurement>

[0358] For the viscosity of polyamic acid solutions, etc., the viscosity was measured using an E-type viscometer TVE-22H (manufactured by Toki Sangyo Co., Ltd.) under the following conditions: sample volume 1.1 mL, conical rotor TE-1 (1°34′, R24), and temperature 25°C.

[0359] <Determination of molecular weight>

[0360] The molecular weights of polyimide precursors and polyimides were determined using a room-temperature gel permeation chromatography (GPC) apparatus (GPC-101) (manufactured by Showa Denko Corporation) and columns (GPC KD-803, GPC KD-805) (manufactured by Showa Denko Corporation) as follows.

[0361] Column temperature: 50℃

[0362] Eluent: N,N-dimethylformamide (as additives, lithium bromide monohydrate (LiBr·H2O) 30 mmol / L, phosphoric acid·anhydrous crystals (orthophosphoric acid) 30 mmol / L, tetrahydrofuran (THF) 10 mL / L)

[0363] Flow rate: 1.0 mL / min

[0364] Standard samples used for preparing the standard curve: TSK standard polyethylene oxide (molecular weight: approximately 900,000, 150,000, 100,000 and 30,000) (manufactured by Tosoh Corporation) and polyethylene glycol (molecular weight: approximately 12,000, 4,000 and 1,000) (manufactured by Polymer Laboratories).

[0365] <Determination of imidization rate>

[0366] Place 20 mg of polyimide powder into an NMR sample tube (manufactured by Kusano Science Co., Ltd., NMR sampling tube specifications). To the solution, 1.0 mL of deuterated dimethyl sulfoxide (DMSO-d6, 0.05% by mass tetramethylsilane (TMS) mixture) was added and sonicated until completely dissolved. The solution was then subjected to proton NMR measurements at 500 MHz using a Fourier transform superconducting nuclear magnetic resonance (FT-NMR) device, "AVANCE III" (BRUKER manufactured).

[0367] The chemical imidization rate is determined using protons derived from structures that remain unchanged before and after imidization as reference protons. It is calculated using the cumulative peak value of this proton and the cumulative peak value of protons from the NH groups of the amic acid appearing around 9.5–10.0 ppm, by the following formula. It should be noted that in the formula, x is the cumulative peak value of protons from the NH groups of the amic acid, y is the cumulative peak value of the reference proton, and α is the ratio of the reference protons to one proton of the NH groups of the amic acid when the polyamic acid (imidization rate is 0%).

[0368] Imidification rate (%) = (1 - α·x / y) × 100

[0369] <<Synthesis Example: Synthesis of Additives for Weakly Anchored IPS>>

[0370] The products described in the following synthetic examples are obtained through... 1 H-NMR analysis for identification (analytical conditions as follows).

[0371] Apparatus: Fourier transform superconducting nuclear magnetic resonance (FT-NMR) device "AVANCE III" (BRUKER) 500MHz.

[0372] Solvents: CDCl3 (deuterated chloroform) or DMSO-d6 (deuterated dimethyl sulfoxide).

[0373] Reference material: Tetramethylsilane (TMS) (δ 0.0 ppm for 1 H).

[0374] <Synthetic Example 1 Add-1 (Synthesis of 1-phenylhexyl methacrylate)>

[0375] [Chemistry 42]

[0376]

[0377] In a 500 mL four-necked flask equipped with a stir bar, 1-phenyl-1-hexanol (25.0 g: 0.140 mol), TEA (21.3 g: 0.210 mol), and CH2Cl2 (300 mL) were weighed and dissolved. The solution was cooled to 0 °C in an ice bath, and then methacryloyl chloride (16.1 g: 0.155 mol) was slowly added dropwise while maintaining the internal temperature below 5 °C. The mixture was then brought to room temperature and stirred for 18 hours. After confirming the completion of the reaction by HPLC, ethyl acetate (200 mL) was added to the reaction solution. The solution was washed three times with a 10% potassium carbonate aqueous solution (100 mL) using a separatory funnel, and then three times with pure water (100 mL). After washing, the solution was dehydrated with magnesium sulfate, and the solvent was removed by rotary evaporation to obtain the crude product. Purification was performed using silica gel column chromatography (developing solvent: n-hexane / ethyl acetate = 8 / 2 (volume ratio)), followed by solvent distillation and vacuum drying to give Add-1 (29.3 g: 82% yield, colorless transparent liquid). 1 H-NMR analysis confirmed it as the target compound. BHT (0.01 mol%) was added as a polymerization inhibitor.

[0378] 1H-NMR(500MHz)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]

[0379] <Synthetic Example 2: Synthesis of Add-2 (1-phenylbutyl methacrylate)>

[0380] [Chemistry 43]

[0381]

[0382] Weigh 1-phenyl-1-butanol (25.0 g: 0.166 mol), TEA (25.3 g: 0.250 mol), and CH2Cl2 (300 mL) into a 500 mL four-necked flask equipped with a stir bar and dissolve them. Cool the solution to 0 °C in an ice bath, then slowly add methacryloyl chloride (20.8 g: 0.199 mol) dropwise while maintaining the internal temperature below 5 °C. The mixture is then brought to room temperature and stirred for 18 hours. After confirming the completion of the reaction by HPLC, ethyl acetate (200 mL) is added to the reaction solution. The solution is washed three times with 10% potassium carbonate aqueous solution (100 mL) using a separatory funnel, and then three times with pure water (100 mL). After washing, the solution is dehydrated with magnesium sulfate, and the solvent is removed by rotary evaporation to obtain the crude product. Purification was performed using silica gel column chromatography (developing solvent: n-hexane / ethyl acetate = 8 / 2 (volume ratio)), followed by solvent distillation and vacuum drying to give Add-2 (31.2 g: 86% yield, colorless transparent liquid). 1 H-NMR analysis confirmed it as the target compound. BHT (0.01 mol%) was added as a polymerization inhibitor.

[0383] 1 H-NMR(500MHz)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]

[0384] <Synthetic Example 3: Synthesis of Add-3 (1-phenylbutyl acrylate)>

[0385] [Chemistry 44]

[0386]

[0387] Weigh and dissolve 1-phenyl-1-butanol (25.0 g: 0.166 mol), TEA (25.3 g: 0.250 mol), and THF (300 mL) in a 500 mL four-necked flask equipped with a stir bar. Cool the solution to 0 °C in an ice bath, then slowly add acryloyl chloride (16.6 g: 0.183 mol) dropwise while maintaining the internal temperature below 5 °C. The mixture is then brought to room temperature and stirred for 18 hours. After confirming the reaction is complete using HPLC, ethyl acetate (200 mL) is added to the reaction solution. The solution is washed three times with 10% potassium carbonate aqueous solution (100 mL) using a separatory funnel, and then three times with pure water (100 mL). After washing, the solution is dehydrated with magnesium sulfate, and the solvent is removed by rotary evaporation to obtain the crude product. Purification was performed using silica gel column chromatography (developing solvent: n-hexane / ethyl acetate = 8 / 2 (volume ratio)), followed by solvent distillation and vacuum drying to give Add-3 (26.8 g: 79% yield, colorless transparent liquid). 1 H-NMR analysis confirmed it as the target compound. BHT (0.01 mol%) was added as a polymerization inhibitor.

[0388] 1 H-NMR(500MHz)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]

[0389] <Synthetic Example 4: Synthesis of Add-4 (2-methyl-1-phenylpropan-2-yl methacrylate)>

[0390] [Chemistry 45]

[0391]

[0392] Weigh and dissolve 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) in a 500 mL four-necked flask equipped with a stir bar. Cool the solution to 0 °C in an ice bath, then slowly add methacryloyl chloride (26.0 g: 0.249 mol). After stirring at 0 °C for 30 minutes, react the solution at 70 °C for 18 hours. After confirming the reaction is complete using HPLC, add ethyl acetate (200 mL) to the reaction solution. Remove the precipitated salt by filtration. Wash the solution three times with a 10% potassium carbonate aqueous solution (100 mL) using a separatory funnel, and then three times with pure water (100 mL). After washing, the product was dehydrated with magnesium sulfate, followed by solvent distillation using a rotary evaporator to obtain the crude product. Purification was performed using silica gel column chromatography (developing solvent: n-hexane / ethyl acetate = 9 / 1 (volume ratio)), by solvent distillation and vacuum drying to give Add-4 (21.6 g: 87% yield, colorless transparent liquid). 1 H-NMR analysis confirmed it as the target compound. BHT (0.01 mol%) was added as a polymerization inhibitor.

[0393] 1 H-NMR(500MHz)in CDCl3: 7.32-7.22(5H), 6.02(1H), 5.50(1H), 3.12(2H), 1.92(3H), 1.52(6H)[ppm]

[0394] <Synthetic Example 5 Add-5 (Synthesis of 2-methyl-4-phenylpropan-2-yl methacrylate)>

[0395] [Chemistry 46]

[0396]

[0397] Weigh and dissolve 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) in a 500 mL four-necked flask equipped with a stir bar. Cool the solution to 0°C in an ice bath, then slowly add methacryloyl chloride (23.8 g: 0.228 mol). After stirring at 0°C for 30 minutes, react the solution at 70°C for 18 hours. After confirming the reaction is complete using HPLC, add ethyl acetate (200 mL) to the reaction solution. Remove the precipitated salt by filtration. Wash the solution three times with a 10% potassium carbonate aqueous solution (100 mL) using a separatory funnel, and then three times with pure water (100 mL). After washing, the product was dehydrated with magnesium sulfate, followed by solvent distillation using a rotary evaporator to obtain the crude product. Purification was performed using silica gel column chromatography (developing solvent: n-hexane / ethyl acetate = 9 / 1 (volume ratio)), by solvent distillation and vacuum drying to give Add-5 (29.0 g: 82% yield, colorless transparent liquid). 1 H-NMR analysis confirmed it as the target compound. BHT (0.01 mol%) was added as a polymerization inhibitor.

[0398] 1 H-NMR (500MHz) in CDC13: 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].

[0399] <Synthetic Example 6: Synthesis of Add-6 (3-ethyl-1-phenylpentan-3-yl methacrylate)>

[0400] [Chemistry 47]

[0401]

[0402] (First process)

[0403] In a 1L four-necked flask equipped with a stir bar, weigh 25.0 g of methyl 3-phenylpropanoate (0.152 mol) and 500 mL of THF and dissolve them. Cool the solution to 0°C in an ice bath, then slowly add ethylmagnesium bromide (3.0 mol / L diethyl ether solution, 107 mL: 0.320 mol). Stir at 0°C for 30 minutes, then allow the reaction to proceed at room temperature for 6 hours. After confirming the reaction is complete using HPLC, cool the flask again to 0°C in an ice bath, and quench the reaction by adding 200 mL of 10% ammonium chloride aqueous solution little by little, ensuring the internal temperature does not exceed 10°C.

[0404] The reaction solution was allowed to stand for a short time to allow the precipitate to settle. The supernatant was then recovered by decantation, and the residue was washed with ethyl acetate. This process was repeated several times. The recovered solutions were combined and washed three times with pure water (200 mL) using a separatory funnel, and once with saturated saline solution (200 mL). The solution was then dehydrated with anhydrous magnesium sulfate, and the solvent was removed by rotary evaporation to obtain the crude product. Purification was performed using silica gel column chromatography (developing solvent: ethyl acetate / n-hexane = 5 / 5 (volume ratio)). Solvent removal and vacuum drying yielded Add-6a (27.2 g: 93% yield, colorless transparent liquid). 1 H-NMR analysis confirmed it as the target analyte.

[0405] 1 H-NMR(500MHz)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]

[0406] (Second process)

[0407] Weigh and dissolve 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) in a 500 mL four-necked flask equipped with a stir bar. Cool the solution to 0 °C in an ice bath, then slowly add methacryloyl chloride (20.9 g: 0.195 mol). Stir at 0 °C for 30 minutes, then react at 70 °C for 18 hours. After confirming the reaction is complete by HPLC, add ethyl acetate (200 mL) to the reaction solution. Remove the precipitated salt by filtration. Wash three times with 10% potassium carbonate aqueous solution (100 mL) using a separatory funnel, and then three times with pure water (100 mL). After washing, dehydrate with magnesium sulfate and distill off the solvent using a rotary evaporator to obtain the crude product. Purification was performed using silica gel column chromatography (developing solvent: n-hexane / ethyl acetate = 9 / 1 (volume ratio)), followed by solvent distillation and vacuum drying to give Add-6 (28.4 g: 84% yield, colorless transparent liquid). 1 H-NMR analysis confirmed it as the target compound. BHT (0.01 mol%) was added as a polymerization inhibitor.

[0408] 1 H-NMR(500MHz)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]

[0409] <Synthetic Example 7 Add-7 (Synthesis of 2-methyl-4-phenylbutan-2-yl acrylate)>

[0410] [Chemistry 48]

[0411]

[0412] Weigh 2-methyl-4-phenyl-2-butanol (25.0 g: 0.152 mol), TEA (23.1 g: 0.228 mol), and THF (300 mL) into a 500 mL four-necked flask equipped with a stir bar and dissolve them. Cool the solution to 0°C in an ice bath, then slowly add acryloyl chloride (16.5 g: 0.182 mol) dropwise while maintaining the internal temperature below 5°C. The mixture was then brought to room temperature and stirred for 18 hours. After confirming the reaction was complete using HPLC, ethyl acetate (200 mL) was added to the reaction solution. The solution was washed three times with a 10% potassium carbonate aqueous solution (100 mL) using a separatory funnel, and then three times with pure water (100 mL). After washing, the solution was dehydrated with magnesium sulfate, and the solvent was removed by rotary evaporation to obtain the crude product. Purification was performed using silica gel column chromatography (developing solvent: n-hexane / ethyl acetate = 9 / 1 (volume ratio)), followed by solvent distillation and vacuum drying to give Add-7 (29.9 g: 90% yield, colorless, transparent liquid). 1 H-NMR analysis confirmed it as the target compound. BHT (0.01 mol%) was added as a polymerization inhibitor.

[0413] 1 H-NMR (500MHz) 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]

[0414] <Synthetic Example 8: Synthesis of Add-8 (1-phenylhexan-3-ylmethacrylate)>

[0415] [Chemistry 49]

[0416]

[0417] (First process)

[0418] 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. The solution was cooled to -78 °C using a dry ice-methanol bath. Then, n-propylmagnesium bromide (1.5 mol / L THF solution, 186 mL: 0.279 mol) was added dropwise, ensuring the internal temperature did not exceed -70 °C. After the addition was complete, the mixture was brought back to room temperature and stirred for 18 hours. The reaction was confirmed by HPLC. The reaction solution was then cooled to 0 °C and quenched with a specified amount of hydrochloric acid aqueous solution (100 mL). Ethyl acetate (200 mL) was added to the reaction solution, and the mixture was washed three times with pure water (100 mL) using a separatory funnel. After washing, the solution was dehydrated with magnesium sulfate, and the solvent was removed by rotary evaporation to obtain the crude product. Further vacuum drying yielded Add-8a (30.0 g: 89% yield, colorless and transparent liquid).

[0419] (Second process)

[0420] Weigh Add-8a (30.0 g: 0.168 mol), TEA (25.5 g: 0.252 mol), and THF (300 mL) into a 500 mL four-necked flask equipped with a stir bar and dissolve them. Cool the solution to 0 °C in an ice bath, then slowly add methacryloyl chloride (21.1 g: 0.201 mol) dropwise while maintaining the internal temperature below 5 °C. The mixture was then brought to room temperature and stirred for 18 hours. After confirming the completion of the reaction by HPLC, ethyl acetate (200 mL) was added to the reaction solution. The solution was washed three times with a 10% potassium carbonate aqueous solution (100 mL) using a separatory funnel, and then three times with pure water (100 mL). After washing, the solution was dehydrated with magnesium sulfate, and the solvent was removed by rotary evaporation to obtain the crude product. Purification was performed using silica gel column chromatography (developing solvent: n-hexane / ethyl acetate = 9 / 1 (volume ratio)), followed by solvent distillation and vacuum drying to give Add-8 (35.6 g: 86% yield, colorless transparent liquid). 1 H-NMR analysis confirmed it as the target compound. BHT (0.01 mol%) was added as a polymerization inhibitor.

[0421] 1H-NMR(500MHz)in DMSO-d6: 7.28-7.15(5H), 6.02(1H), 5.64(1H), 4.90-4.88(1H), 2.62-2.55(2 H), 1.90-1.85(2H+3H), 1.59-1.54(2H), 1.30-1.28(2H), 0.88-0.86(3H)[ppm]

[0422] <Synthetic Example 9: Synthesis of Add-9 (5-phenylpentyl methacrylate)>

[0423] [Transformation 50]

[0424]

[0425] Weigh 5-phenyl-1-pentanol (25.0 g: 0.152 mol), TEA (23.1 g: 0.228 mol), and THF (300 mL) into a 500 mL four-necked flask equipped with a stir bar and dissolve them. Cool the solution to 0°C in an ice bath, then slowly add methacryloyl chloride (19.1 g: 0.182 mol) dropwise while maintaining the internal temperature below 5°C. The mixture was then brought to room temperature and stirred for 18 hours. After confirming the completion of the reaction by HPLC, ethyl acetate (200 mL) was added to the reaction solution. The solution was washed three times with 10% potassium carbonate aqueous solution (100 mL) using a separatory funnel, and then three times with pure water (100 mL). After washing, the solution was dehydrated with magnesium sulfate, and the solvent was removed by rotary evaporation to obtain the crude product. Purification was performed using silica gel column chromatography (developing solvent: n-hexane / ethyl acetate = 8 / 2 (volume ratio)), followed by solvent distillation and vacuum drying to give Add-9 (31.8 g: 90% yield, colorless transparent liquid). 1 H-NMR analysis confirmed it as the target compound. BHT (0.01 mol%) was added as a polymerization inhibitor.

[0426] 1 H-NMR (500MHz) 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]

[0427] <Synthetic Example 10 Add-11 (Synthesis of 3-methyl-1-phenylpentan-3-yl methacrylate)>

[0428] [Chemistry 51]

[0429]

[0430] Weigh and dissolve 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) in a 500 mL four-necked flask equipped with a stir bar. Cool the solution to 0°C in an ice bath, then slowly add methacryloyl chloride (22.0 g: 0.210 mol). After stirring at 0°C for 30 minutes, react the solution at 70°C for 18 hours. After confirming the reaction is complete using HPLC, add ethyl acetate (200 mL) to the reaction solution. Remove the precipitated salt by filtration. Wash the solution three times with a 10% potassium carbonate aqueous solution (100 mL) using a separatory funnel, and then three times with pure water (100 mL). After washing, the product was dehydrated with magnesium sulfate, followed by solvent distillation using a rotary evaporator to obtain the crude product. Purification was performed using silica gel column chromatography (developing solvent: n-hexane / ethyl acetate = 9 / 1 (volume ratio)), by solvent distillation and vacuum drying to give Add-11 (26.6 g: 77% yield, colorless transparent liquid). 1 H-NMR analysis confirmed it as the target compound. BHT (0.01 mol%) was added as a polymerization inhibitor.

[0431] 1 H-NMR(500MHz)in CDCl3:7.32-7.19(5H)

[0432] 6.06(1H), 5.52(1H), 2.68-2.62(2H)

[0433] 2.71-2.21(1H), 2.12-2.00(2H), 1.95(3H)

[0434] 1.92-1.86(4H), 1.86(3H), 0.96-0.93(3H)[ppm]

[0435] <Synthetic Example 11: Synthesis of Add-12 (N-(3-phenylpropyl)-N-propylacrylamide)>

[0436] [Chemistry 52]

[0437]

[0438] Weigh and dissolve N-(3-phenylpropyl)-N-propylamine (20.0 g: 0.113 mol), TEA (22.8 g: 0.226 mol), and THF (250 mL) in a 500 mL four-necked flask equipped with a stir bar. Cool the solution to 0 °C in an ice bath, then slowly add acryloyl chloride (12.3 g: 0.136 mol). Stir at 0 °C for 30 minutes, and then react at room temperature for 18 hours. After confirming the completion of the reaction by HPLC, add ethyl acetate (200 mL) to the reaction solution. Remove the precipitated salt by filtration. Wash three times with 10% potassium carbonate aqueous solution (100 mL) using a separatory funnel, and then three times with pure water (100 mL). After washing, dehydrate with magnesium sulfate and distill off the solvent using a rotary evaporator to obtain the crude product. Purification was performed using silica gel column chromatography (developing solvent: n-hexane / ethyl acetate = 9 / 1 (volume ratio)), followed by solvent distillation and vacuum drying to give Add-12 (18.2 g: 70% yield, colorless transparent liquid). 1 H-NMR analysis confirmed it as the target compound. BHT (0.01 mol%) was added as a polymerization inhibitor.

[0439] 1 H-NMR(500MHz)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]

[0440] <<Synthesis of Polyamic Acid / Polyimide>>

[0441] <Synthesis Example 12>

[0442] In a 100 mL four-necked flask equipped with a mechanical stirrer and a nitrogen inlet tube, DA-1 (1.08 g: 10.00 mmol) and DA-3 (3.30 g: 10.00 mmol) were measured, and NMP (24.9 g) was added. The mixture was stirred under a nitrogen atmosphere until dissolved, and then TC-2 (2.50 g: 10.00 mmol) was added while maintaining the temperature below 10°C in an ice bath. The reaction was carried out at 50°C for 6 hours under a nitrogen atmosphere. After returning to room temperature, TC-1 (1.84 g: 9.40 mmol) and NMP (10.0 g) were added, and the reaction was carried out at room temperature for 18 hours, thus obtaining a polyamic acid solution (PAA-1) with a viscosity of approximately 1,120 mPa·s and a solids content of 20% by mass. The polyamic acid has a number average molecular weight of 11,200 and a weight average molecular weight of 31,360.

[0443] In a 300 mL flask equipped with a stir bar and a nitrogen inlet tube, 40.0 g of the polyamic acid solution (PAA-1) obtained above was measured, and 74.3 g of NMP was added. After stirring briefly at room temperature, acetic anhydride (5.61 g: 54.98 mmol) and pyridine (2.90 g, 36.65 mmol) were added. The mixture was stirred at room temperature for 30 minutes under a nitrogen atmosphere, and then reacted at 50 °C for 3 hours under a nitrogen atmosphere. After the reaction was completed, the reaction solution was slowly injected into 500 mL of methanol cooled to below 10 °C while stirring to precipitate the solid. The mixture was stirred for 10 minutes. The precipitate was separated by filtration and washed twice with methanol (200 mL) for 30 minutes each time. The solid was then dried under vacuum at 80 °C to obtain the target polyimide powder (SPI-1) (7.04 g, yield 88%). The polyimide has an imidization rate of 57% and a molecular weight of 10,400 (number average) and 29,120 (weight average).

[0444] <Synthesis Example 13>

[0445] 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 measured, and NMP (56.8 g) was added. The mixture was stirred under a nitrogen atmosphere until dissolved. Then, while maintaining the temperature below 10°C in an ice bath, TC-3 (4.26 g: 19.00 mol) and NMP (10.0 g) were added. The reaction was carried out at room temperature for 24 hours, resulting in a polyamic acid solution (PAA-2) with a viscosity of approximately 680 mPa·s and a solids content of 15% by mass. The polyamic acid had a number average molecular weight of 17,200 and a weight average molecular weight of 48,160.

[0446] <Synthesis Example 14>

[0447] 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 measured, and NMP (42.0 g) was added. The mixture was stirred under a nitrogen atmosphere until dissolved. Then, while maintaining the temperature below 10°C in an ice bath, TC-3 (4.21 g: 18.8 mmol) and NMP (10.0 g) were added. The reaction was carried out at room temperature for 24 hours, resulting in a polyamic acid solution (PAA-3) with a viscosity of approximately 710 mPa·s and a solids content of 15% by mass. The polyamic acid had a number average molecular weight of 15,500 and a weight average molecular weight of 41,800.

[0448] <<Preparation of Liquid Crystal Alignment Agents>>

[0449] <Preparation Example 1: Preparation of Free Radical Generating Film Forming Composition AL-1>

[0450] 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 measured, and NMP (18.0 g) was added. The mixture was stirred at room temperature for 12 hours to dissolve the powder. After confirming that the solid had completely 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 free radical generating film forming composition (AL-1) that also serves as a liquid crystal alignment agent used in this invention.

[0451] <Preparation Example 2: Preparation of Free Radical Generating Film-Forming Composition AL-2>

[0452] In a 50 mL Erlenmeyer flask equipped with a stir bar, 15.0 g of the polyamic acid solution (PAA-2) obtained in Synthesis Example 13 above was measured, and NMP (16.5 g) and BCS (13.5 g) were added. The mixture was stirred at room temperature for 1 hour to obtain the free radical generating film forming composition (AL-2) that also serves as a liquid crystal alignment agent used in this invention.

[0453] <Preparation Example 3: Preparation of Liquid Crystal Alignment Agent AL-3>

[0454] In a 50 mL Erlenmeyer flask equipped with a stir bar, 15.0 g of the polyamic acid solution (PAA-3) obtained in Synthesis Example 14 above was measured, and NMP (16.5 g) and BCS (13.5 g) were added. The mixture was stirred at room temperature for 1 hour to obtain the liquid crystal alignment agent (AL-3) used in this invention.

[0455] <Examples 1-24, Comparative Examples 1-8>

[0456] <Fabrication of Liquid Crystal Display Components>

[0457] The following describes a method for fabricating a liquid crystal cell used to evaluate liquid crystal alignment and electro-optic response.

[0458] First, prepare a substrate with electrodes. The substrate is an alkali-free glass substrate measuring 30mm × 35mm and 0.7mm thick. ITO (Indium Tin Oxide) electrodes with a width of 3μm, an electrode spacing of 6μm, and a comb-like pattern at a 10° angle relative to the long side of the substrate are formed on the substrate to form pixels. Each pixel measures approximately 10mm vertically and 5mm horizontally. This substrate will be referred to as the IPS substrate.

[0459] Next, the free radical generating film forming compositions AL-1, AL-2, liquid crystal alignment agent AL-3, and SE-6414 (manufactured by Nissan Chemical Co., Ltd.) obtained by the above method were filtered through a 1.0 μm pore size filter. The resulting film was then coated onto the prepared IPS substrate and glass substrate (hereinafter referred to as the opposing substrate) using spin coating. The glass substrate has an ITO film on its back side and columnar spacers with a height of 3.0 μm. The coating was then dried on a hot plate at 80°C for 80 minutes and sintered at 230°C for 20 minutes to obtain a coating with a thickness of 100 nm. The polyimide film on the IPS substrate side was oriented in the direction along the comb teeth; the polyimide film on the opposing substrate side was oriented in a direction orthogonal to the comb teeth electrodes. It should be noted that in the orientation process, the friction method was used in cases AL-1 and SE-6414, using a friction device manufactured by Iinuma GAUGE Co., Ltd., a friction cloth (YA-20R) manufactured by Yoshikawa Chemical Co., Ltd., a friction roller (diameter 10.0 cm), a platform feed speed of 30 mm / s, a roller speed of 700 rpm, and an indentation pressure of 0.3 mm. In cases AL-2 and AL-3, a UV exposure device manufactured by USHIO Electric Co., Ltd. was used, with linearly polarized UV light of approximately 26:1 extinction ratio, based on a wavelength of 254 nm, and an irradiation dose of 300 mJ / cm². 2 The orientation process involves irradiating the object with polarized UV light and heating it at 230°C for 20 minutes.

[0460] Then, using the two substrates described above, for the display element as the subject of the embodiment and the partial display elements as the comparative objects (Comparative Examples 2, 3, 4, 6, 7, 8), display elements were fabricated by combining elements obtained by setting a free radical generation alignment film AL-1 or AL-2 on the IPS substrate side and a liquid crystal alignment film SE-6414 or AL-3 on the opposing substrate side. In the case of the partial display elements as the comparative objects (Comparative Examples 1 and 5), display elements using SE-6414 or AL-3 on both substrates were used. The elements were combined in a parallel manner with their respective alignment directions, and the liquid crystal injection port was retained while the surrounding area was sealed to create empty cells with a cell gap of approximately 3.0 μm. In these empty cells, liquid crystal mixtures with 2% by mass of the (Add-1) to (Add-12) obtained in the above synthesis examples were added. As comparative objects, liquid crystal mixtures without additives or liquid crystal mixtures with 2% by mass of (Add-C1) to (Add-C3) were used. After vacuum injection at room temperature, the injection port was sealed to create anti-parallel aligned liquid crystal cells. It should be noted that the liquid crystal mixture used is LC-A (manufactured by DIC Corporation, Δn: 0.130, Δε: 4.4), and Add-10, Add-C1 to Add-C3 are products purchased from Tokyo Kasei Corporation.

[0461] The obtained liquid crystal cells constitute an IPS-mode liquid crystal display element. Then, the obtained liquid crystal cells are heated at 120°C for 10 minutes, and then irradiated with UV (UV lamp: FLR40SUV32 / A-1) for 30 minutes using a UV-FL irradiation device manufactured by Toshiba Lighting Co., Ltd. without applying voltage, to obtain the liquid crystal display element.

[0462] <Evaluation of Liquid Crystal Orientation>

[0463] Using a polarizing microscope, the polarizer is set to orthogonal Nicol, and the liquid crystal cell is fixed in a state where the brightness is minimized. From this state, the liquid crystal cell is rotated by 1°, and the alignment state of the liquid crystal is observed. If no alignment defects such as inhomogeneity or abnormal areas are observed, or if they are very slight, the result is evaluated as "good." If they are clearly observed, they are defined as "bad."

[0464] In addition, a photodiode is installed on the polarizing microscope and connected to an electrometer via a current-to-voltage converter. The black brightness (V: au) is measured by monitoring the voltage under the condition that the brightness becomes the minimum under orthogonal Nicol.

[0465] <Measurement of VT curves and evaluation of driving threshold voltage, maximum luminance voltage, and transmittance>

[0466] A white LED backlight and a luminance meter are mounted along the same optical axis. During this process, a liquid crystal cell (liquid crystal display element) equipped with a polarizer is mounted with the brightness reduced to its minimum. Voltages are applied in 1V increments up to 8V, and the brightness within each voltage is measured to determine the VT curve. The voltage at which the brightness reaches its maximum (Vmax) is estimated based on the obtained VT curve. Additionally, with the transmitted brightness set to 100% when parallel to the Nicoler display via a liquid crystal cell without applied voltage, the maximum transmitted brightness in the VT curve is compared to estimate the maximum transmittance (Tmax).

[0467] <Determination of response time (Ton, Toff)>

[0468] Using the apparatus used in the above VT curve measurement, the luminance meter was connected to an oscilloscope to measure the response speed (Ton) when a voltage of maximum luminance was applied and the response speed (Toff) when the voltage returned to 0V.

[0469] <Determination of Voltage Retention Rate (VHR)>

[0470] Voltage holding rate was measured at room temperature. A 4V voltage was applied to the fabricated liquid crystal display element for 60μs at 23℃, and the voltage was measured after 16.7ms. The voltage holding rate was calculated based on how much of the voltage could be held.

[0471] In addition, voltage retention rate was measured at high temperatures. A 1V voltage was applied to the fabricated liquid crystal display element for 60μs at 70°C, and the voltage was measured after 1667ms. The voltage retention rate was calculated based on how much of the voltage could be maintained.

[0472] It should be noted that the voltage holding rate was measured using a VHR-1 voltage holding rate measuring device manufactured by Toyo Tecnica Co., Ltd.

[0473] <Polymer Contents>

[0474] The compositions of the polymers synthesized in Synthesis Examples 11 to 13 are shown in Table 1.

[0475] [Table 1]

[0476] polymer composition imidization rate SPI-1 TC-1, TC-2(50) / DA-1, DA-3(50) 57％ PAA-2 TC-3 / DA-2, DA-4(30) - PAA-3 TC-3 / DA-2, DA-5(30) -

[0477] <Contents of liquid crystal alignment agent or free radical generating film forming composition>

[0478] The compositions of the liquid crystal alignment agents or free radical generating film forming compositions prepared in Preparation Examples 1 to 3 are shown in Table 2.

[0479] [Table 2]

[0480]

[0481] <Liquid Crystal Cell Contents (Friction)>

[0482] Table 3 shows the contents of embodiments and comparative examples of liquid crystal cells that have undergone alignment processing using the rubbing method.

[0483] [Table 3]

[0484] Example IPS substrate Opposite substrate additive Example 1 AL-1 SE-6414 Add-1 Example 2 AL-1 SE-6414 Add-2 Example 3 AL-1 SE-6414 Add-3 Example 4 AL-1 SE-6414 Add-4 Example 5 AL-1 SE-6414 Add-5 Example 6 AL-1 SE-6414 Add-6 Example 7 AL-1 SE-6414 Add-7 Example 8 AL-1 SE-6414 Add-8 Example 9 AL-1 SE-6414 Add-9 Example 10 AL-1 SE-6414 Add-10 Example 11 AL-1 SE-6414 Add-11 Example 12 AL-1 SE-6414 Add-12 Comparative Example 1 SE-6414 SE-6414 No additives Comparative Example 2 AL-1 SE-6414 Add-C1 Comparative Example 3 AL-1 SE-6414 Add-C2 Comparative Example 4 AL-1 SE-6414 Add-C3

[0485] <Characteristic Evaluation Results>

[0486] The performance evaluation results of the liquid crystal cells that underwent alignment treatment using the rubbing method are shown in Tables 4-1 and 4-2.

[0487] [Table 4-1]

[0488]

[0489] [Table 4-2]

[0490]

[0491] It can be seen that in the weakly anchored liquid crystal cells using the free radical polymerizable compounds (Add-1) to (Add-12) of the present invention as additives, the orientation state and black brightness are good, and Vmax is significantly reduced compared with the strongly anchored liquid crystal cell of Comparative Example 1, while the transmittance is significantly improved compared with Comparative Examples 1 to 3. On the other hand, in Comparative Examples 2 and 3, most liquid crystal display elements using Add-C1 or Add-C2 as additives showed friction stripes, poor black brightness, and an orientation state with increased birefringence. In addition, it was confirmed that compared with the strongly anchored liquid crystal cell of Comparative Example 1, Comparative Examples 2 and 3 showed a decrease in Vmax, but a decrease in transmittance. It can be seen that this is due to the generation of a pretilt angle associated with weak anchoring. The pretilt angle of Examples 1 to 12 is almost 0°, while in contrast, a pretilt angle of about 72° was generated in Comparative Example 2, and a very large pretilt angle of about 83° was generated in Comparative Example 3. On the other hand, regarding the response speed, it can be seen that the response speed is slightly slower when using the additives of Examples 1 to 12 compared to the strongly anchored liquid crystal cell of Comparative Example 1. However, even so, a faster response speed can be achieved within an acceptable range, which is a significant improvement compared to Comparative Examples 2 and 3. Comparative Example 4 exhibits weak anchoring characteristics and shows a good alignment state, but this is a result of slow response speed and poor VHR. In the above examples and comparative examples, when using MLC-3019 (Δn: 0.104, Δε: 9.9) manufactured by Merck instead of LC-A in the liquid crystal, good weak anchoring IPS characteristics can be obtained even when using Add-C1 or Add-C2 used in Comparative Examples 2 to 3. However, if a liquid crystal with a large Δn or a small Δε, such as LC-A, is used, good weak anchoring IPS characteristics cannot be obtained. This means that, for example, when manufacturing liquid crystal display elements by narrowing the cell gap (e.g., setting it to 3.5 μm or less), the additives used in Comparative Examples 2 to 3 cannot cope with the situation. With the additive of the present invention, even when using liquid crystals with such large Δn and small Δε, good weakly anchored IPS characteristics can be obtained, and the response speed can be improved by narrowing the cell gap. Furthermore, it is known that the VHR, especially at high temperatures, is higher than that of Comparative Examples 1-4, and reliability can be improved by using the additive of the present invention.

[0492] <Liquid Crystal Cell Content (Optical Orientation)>

[0493] Table 5 shows the contents of embodiments and comparative examples of liquid crystal cells that have undergone alignment processing using the photo-alignment method.

[0494] [Table 5]

[0495] Example IPS substrate Opposite substrate additive Example 13 AL-2 AL-3 Add-1 Example 14 AL-2 AL-3 Add-2 Example 15 AL-2 AL-3 Add-3 Example 16 AL-2 AL-3 Add-4 Example 17 AL-2 AL-3 Add-5 Example 18 AL-2 AL-3 Add-6 Example 19 AL-2 AL-3 Add-7 Example 20 AL-2 AL-3 Add-8 Example 21 AL-2 AL-3 Add-9 Example 22 AL-2 AL-3 Add-10 Example 23 AL-2 AL-3 Add-11 Example 24 AL-2 AL-3 Add-12 Comparative Example 5 AL-3 AL-3 No additives Comparative Example 6 AL-2 AL-3 Add-C1 Comparative Example 7 AL-2 AL-3 Add-C2 Comparative Example 8 AL-2 AL-3 Add-C3

[0496] <Characteristic Evaluation Results>

[0497] The performance evaluation results of the liquid crystal cells that underwent alignment processing using the photo-alignment method are shown in Table 6.

[0498] [Table 6]

[0499]

[0500] For weakly anchored IPS fabricated using the photo-orientation method, when using the free radical polymerizable compounds (Add-1) to (Add-12) of the present invention as additives, it was confirmed that the same good properties as those obtained by the tribological method were obtained. On the other hand, when using (Add-C1) or (Add-C2) used in Comparative Examples 2 and 3, anomalies were generated, resulting in an undriveable state. In the case of photo-orientation, unlike the tribological method, no anisotropy of the pretilt angle is exhibited. Therefore, it is speculated that when a relatively large pretilt angle is generated in some methods, the direction of the pretilt angle is not defined, resulting in anomalies. If driveable, the range of the anomaly region expands due to the electric field, thus making driveable impossible. Regarding Comparative Example 8, the same result as in the case of fabrication using the tribological method resulted in poor response speed and VHR. When using the additives of the present invention, it is known that even when using the photo-orientation method, no anomalies are generated, and good weakly anchored IPS properties can be obtained, which is very useful. It can be seen that, regarding VHR, the VHR is as good as that of the friction method at high temperature, indicating that the use of the free radical polymerizable compound of the present invention as an additive for weakly anchored IPS is effective in improving reliability.

[0501] <Preparation Example 4: Preparation of Liquid Crystal Alignment Agent AL-4>

[0502] In a 50 mL Erlenmeyer flask equipped with a stir bar, 10.0 g of the free 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 measured and stirred at room temperature for 1 hour to obtain the free radical generating film forming composition (AL-4).

[0503] <Examples 25-36, Comparative Examples 9 and 10>

[0504] In Example 1, the liquid crystal alignment agent or free radical generating film forming composition coated on the IPS substrate and the opposing substrate was changed to the liquid crystal alignment agent or free radical generating film forming composition described in Table 7 below. Furthermore, the additives described in Table 7 were used as additives for the liquid crystal mixture. Otherwise, the liquid crystal cell and liquid crystal display element were manufactured in the same manner as in Example 1.

[0505] <Liquid Crystal Unit Contents>

[0506] Examples and comparative examples of liquid crystal cells that have undergone alignment processing by rubbing are Examples 25 to 28 and Comparative Example 9.

[0507] Examples and comparative examples of liquid crystal cells that have undergone alignment processing by photo-alignment are Examples 29 to 36 and Comparative Example 10.

[0508] [Table 7]

[0509] Example IPS substrate Opposite substrate additive Example 25 SE-6414 AL-1 Add-3 Example 26 SE-6414 AL-1 Add-5 Example 27 SE-6414 AL-1 Add-7 Example 28 SE-6414 AL-1 Add-8 Example 29 AL-3 AL-2 Add-3 Example 30 AL-3 AL-2 Add-5 Example 31 AL-3 AL-2 Add-7 Example 32 AL-3 AL-2 Add-8 Example 33 AL-3 AL-4 Add-3 Example 34 AL-3 AL-4 Add-5 Example 35 AL-3 AL-4 Add-7 Example 36 AL-3 AL-4 Add-8 Comparative Example 9 SE-6414 SE-6414 No additives Comparative Example 10 AL-3 AL-3 No additives

[0510] <Characteristic Evaluation Results>

[0511] The results of the characteristic evaluation are shown in Table 8.

[0512] [Table 8]

[0513]

[0514] Examples 25-36 describe liquid crystal cells in which a radical generation film forming composition is coated on an opposing substrate and a liquid crystal alignment film is used in an IPS substrate. Examples 25-28 relate to liquid crystal display elements fabricated using a rubbing method, and Examples 29-36 relate to liquid crystal display elements fabricated using a photoalignment method. Among Examples 29-36, Examples 33-36 describe the use of AL-4, a mixture of the radical generation film forming composition and a strong anchoring liquid crystal alignment agent, in an opposing substrate. In any of Examples 25-36, compared to examples where the radical generation film forming composition is coated on an IPS substrate (e.g., Examples 1, 13, etc.), Vmax tends to be slightly higher, but is sufficiently low compared to the conventional strongly anchoring liquid crystal cells shown in Comparative Examples 9 and 10, resulting in very high transmittance. Regarding response speed, it is observed that the difference between Ton and Toff is smaller compared to the case where the radical generation film forming composition is coated on an IPS substrate as shown in the examples. Furthermore, it is known that by using AL-4, which is a mixture of a free radical generating film forming composition and a strongly anchoring liquid crystal alignment agent, a faster response speed can be obtained while maintaining high transmittance.

[0515] Industrial availability

[0516] According to the present invention, a lateral electric field liquid crystal display element can be provided that does not produce pretilt angle or abnormal regions even when using liquid crystals with high Δn and low Δε, achieving high backlight transmittance and fast response speed, and providing 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 driven by a lateral electric field.

[0517] Explanation of reference numerals in the attached figures

[0518] 1. Lateral electric field liquid crystal display element

[0519] 2. Comb-shaped electrode substrate

[0520] 2a Substrate

[0521] 2b Wire electrode

[0522] 2c liquid crystal alignment film

[0523] 2D substrate

[0524] 2e surface electrode

[0525] 2f insulating film

[0526] 2g linear electrode

[0527] 2h liquid crystal alignment film

[0528] 3 LCD

[0529] 4 Opposite substrates

[0530] 4a Liquid crystal alignment film

[0531] 4b Substrate

[0532] L power line

Claims

1. A method for manufacturing a liquid crystal display element, wherein, The process includes the following steps: In a state where a liquid crystal composition containing a liquid crystal and a free radical polymerizable compound represented by formula (A) is in contact with a free radical to form a film, the free radical polymerizable compound is subjected to a polymerization reaction. ； In formula (A), M represents a polymerizable group capable of free radical polymerization; R1 to R3 each independently represent a single bond, or an alkylene group with 1 to 6 carbon atoms, with or without inserted bonding groups; Ar represents an aromatic hydrocarbon group with or without substituents; X1 and X2 each independently represent a hydrogen atom, or an aromatic hydrocarbon group with or without substituents; R1X1, R2X2 and the carbon atoms bonded to R1X1 and R2X2 may or may not form a ring; wherein, the total number of carbon atoms in R1X1, R2X2 and R3 is 1 or more; M is selected from the following structures: ； In the formula, Indicates the bonding site, R d It represents an alkyl group having 1 to 6 hydrogen atoms or carbon atoms.

2. The method for manufacturing a liquid crystal display element according to claim 1, wherein, In formula (A), R3 is a straight-chain alkylene group with 1 to 6 carbon atoms, and X1 and X2 are hydrogen atoms.

3. The method for manufacturing a liquid crystal display element according to claim 1 or 2, wherein, The free radical generating membrane is a free radical generating membrane that has undergone uniaxial orientation treatment.

4. The method for manufacturing a liquid crystal display element according to claim 1 or 2, wherein, The polymerization reaction is carried out under conditions without an electric field.

5. The method for manufacturing a liquid crystal display element according to claim 1 or 2, wherein, The free radical generating membrane is a membrane formed by immobilizing organic groups that induce free radical polymerization.

6. The method for manufacturing a liquid crystal display element according to claim 1 or 2, wherein, A free radical generating membrane is obtained by coating and curing a composition containing a compound and a polymer having free radical generating organic groups in the membrane, thereby immobilizing the free radical generating organic groups in the membrane.

7. The method for manufacturing a liquid crystal display element according to claim 1 or 2, wherein, The free radical generating membrane comprises a polymer containing organic groups that induce free radical polymerization.

8. The method for manufacturing a liquid crystal display element according to claim 7, wherein, The polymer containing organic groups that induce free radical polymerization is at least one polymer selected from polyimide precursors, polyimides, polyureas, and polyamides, wherein the polyimide precursors, polyimides, polyureas, and polyamides are obtained using a diamine component, wherein the diamine component comprises a diamine containing organic groups that induce free radical polymerization.

9. The method for manufacturing a liquid crystal display element according to claim 8, wherein, The organic group that induces free radical polymerization is an organic group represented by the following formulas: [X-1] to [X-18], [W], [Y], or [Z]. ； In formulas [X-1] to [X-18], Indicates the bonding site. S1 and S2 independently represent -O-, -NR-, or -S-, and R represents a hydrogen atom or an alkyl group with 1 to 10 carbon atoms; among the alkyl groups with 1 to 10 carbon atoms, a portion of the -CH2- group of the alkyl group with 2 to 10 carbon atoms may or may not be replaced by an oxygen atom; however, in S2R or NR, if a portion 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. ； 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 biphenylene, with or without organic groups and / or halogen atoms as substituents. 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 When the alkyl group is alkyl, the two groups may bond at the ends to form a ring structure or not. Q represents any of the following structures. ； In the formula, R 11 It can represent -CH2-, -NR-, -O-, or -S-; R independently represents either a hydrogen atom or an alkyl group having 1 to 4 carbon atoms; Indicates the bonding site. S 3 Indicates a single bond, -O-, -NR-, or -S-, where R represents a hydrogen atom or an alkyl group having 1 to 14 carbon atoms. R 12 It can represent 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, wherein, The diamine containing the organic group that induces free radical polymerization is a diamine having the structure represented by formula (6), formula (7), or formula (7′). ； In equation (6), R 6 This indicates a single bond, -CH2-, -O-, -COO-, -OCO-, -NHCO-, -CONH-, -NH-, -CH2O-, -N(CH3)-, -CON(CH3)-, or -N(CH3)CO-. R 7 This refers to an alkylene group with 1 to 20 carbon atoms, either a single bond or unsubstituted or substituted with fluorine atoms, wherein any one or more -CH2- or -CF2- atoms of the alkylene group are independently substituted by or not substituted by a group selected from -CH=CH-, a divalent carbocyclic ring, and a divalent heterocyclic ring. Furthermore, the substitution is conditional on the condition that any of the groups listed below, namely -O-, -COO-, -OCO-, -NHCO-, -CONH-, or -NH-, are not adjacent to each other. R 8 This represents a free radical polymerization reactive group selected from the following formulas [X-1] to [X-18]. ； 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, wherein in the alkyl group having 1 to 10 carbon atoms, a portion of the -CH2- group of the alkyl group having 2 to 10 carbon atoms may or may not be replaced by an oxygen atom, but in S2R or NR, if a portion 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. ； ； In equations (7) and (7′), T 1 and T 2 Each can be independently a single bond, -O-, -S-, -COO-, -OCO-, -NHCO-, -CONH-, -NH-, -CH2O-, -N(CH3)-, -CON(CH3)-, or -N(CH3)CO-. S represents a single bond, or an alkylene group with 1 to 20 carbon atoms that is either unsubstituted or substituted with a fluorine atom, wherein any one or more -CH2- or -CF2- atoms of the alkylene group are independently substituted by or not substituted by a group selected from -CH=CH-, a divalent carbocyclic ring, and a divalent heterocyclic ring. Furthermore, the substitution is conditional on the condition that any of the groups listed below, namely -O-, -COO-, -OCO-, -NHCO-, -CONH-, or -NH-, are not adjacent to each other. E can be a single bond, -O-, -C(CH3)2-, -NH-, -CO-, -NHCO-, -COO-, or -(CH2). m -, -SO2-, -O-(CH2) m -O-, -OC(CH3)2-, -CO-(CH2) m -、-NH-(CH2) m -, -SO2-(CH2) m -、-CONH-(CH2) m -、-CONH-(CH2) m -NHCO- or -COO-(CH2) m -OCO-, where m is an integer from 1 to 8. J is an organic group selected from the formulas [W], [Y], and [Z] below. ； In formulas [W], [Y], and [Z], Indicates with T 2 The bonding sites; Ar represents an aromatic hydrocarbon group selected from the group consisting of phenylene, naphthylene, and biphenylene, with or without organic groups and / or halogen atoms as substituents; R 9 and R 10 Each can independently represent an alkyl group having 1 to 10 carbon atoms or an alkoxy group having 1 to 10 carbon atoms; Q represents any of the following structures. ； In the formula, R 11 It can represent -CH2-, -NR-, -O-, or -S-; R independently represents either a hydrogen atom or an alkyl group having 1 to 4 carbon atoms; Indicates the bonding site. S 3 It represents a single bond, -O-, -NR-, or -S-, where R represents a hydrogen atom or an alkyl group having 1 to 14 carbon atoms; R 12 It 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 equation (7′), each q is 0 or 1 independently, at least one q is 1, and p represents an integer from 1 to 2.

11. The method for manufacturing a liquid crystal display element according to claim 1 or 2, wherein, Includes the following steps: Prepare a first substrate having the free radical generating membrane and a second substrate having or not having the free radical generating membrane; The first substrate and the second substrate are arranged opposite each other such that the free radical generating film of the first substrate is opposite to the second substrate; The liquid crystal composition is filled between the first substrate and the second substrate; and The polymerization reaction is carried out.

12. The method for manufacturing a liquid crystal display element according to claim 11, wherein, The second substrate is a second substrate that does not have a free radical generating film.

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

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

15. The method for manufacturing a liquid crystal display element according to claim 11, wherein, Either the first substrate or the second substrate is a substrate having comb-tooth electrodes.

16. A liquid crystal composition, characterized in that, Contains liquid crystal and a free radical polymerizable compound represented by formula (A) below. ； In formula (A), M represents a polymerizable group capable of free radical polymerization; R1 to R3 each independently represent a single bond, or an alkylene group with 1 to 6 carbon atoms, with or without inserted bonding groups; Ar represents an aromatic hydrocarbon group with or without substituents; X1 and X2 each independently represent a hydrogen atom, or an aromatic hydrocarbon group with or without substituents; R1X1, R2X2 and the carbon atoms bonded to R1X1 and R2X2 may or may not form a ring; wherein, the total number of carbon atoms in R1X1, R2X2 and R3 is 1 or more; M is selected from the following structures: ； In the formula, Indicates the bonding site, R d It represents an alkyl group having 1 to 6 hydrogen atoms or carbon atoms.

17. The liquid crystal composition according to claim 16, wherein, In formula (A), R3 is a straight-chain alkylene group with 1 to 6 carbon atoms, and X1 and X2 are hydrogen atoms.

18. A liquid crystal display element, characterized in that, The device comprises a first substrate, a second substrate disposed opposite to the first substrate, and liquid crystal filling the space between the first substrate and the second substrate. With the liquid crystal composition containing the liquid crystal and the free radical polymerizable compound represented by formula (A) in contact with the free radical generating film of the first substrate having a free radical generating film, the free radical polymerizable compound is subjected to a polymerization reaction to form the liquid crystal display element. ； In formula (A), M represents a polymerizable group capable of free radical polymerization; R1 to R3 each independently represent a single bond, or an alkylene group with 1 to 6 carbon atoms, with or without inserted bonding groups; Ar represents an aromatic hydrocarbon group with or without substituents; X1 and X2 each independently represent a hydrogen atom, or an aromatic hydrocarbon group with or without substituents; R1X1, R2X2 and the carbon atoms bonded to R1X1 and R2X2 may or may not form a ring; wherein, the total number of carbon atoms in R1X1, R2X2 and R3 is 1 or more; M is selected from the following structures: ； In the formula, Indicates the bonding site, R d It represents an alkyl group having 1 to 6 hydrogen atoms or carbon atoms.

19. The liquid crystal display element according to claim 18, wherein, Either the first substrate or the second substrate is a substrate with comb-tooth electrodes.

20. The liquid crystal display element according to claim 18 or 19, wherein, The liquid crystal display element is a low-voltage driven lateral electric field liquid crystal display element.

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