Weakly anchored liquid crystal alignment agents, liquid crystal display elements, and polymers

Abstract

This invention provides a weakly anchored liquid crystal alignment agent, which is used in the formation of the liquid crystal alignment film in a liquid crystal cell having liquid crystal and a liquid crystal alignment film. The agent contains a graft copolymer, which has a dry polymer and a branch polymer that is bonded to the dry polymer as a side chain of the dry polymer. The branch polymer and the liquid crystal are mutually compatible, while the dry polymer is not mutually compatible with the liquid crystal or becomes immiscible with the liquid crystal due to calcination.

Description

Technical Field

[0001] The present invention relates to an organic film (weak anchoring film) exhibiting weak anchoring characteristics that can be manufactured in a low-cost and non-complex manner, thereby enabling liquid crystal display elements to achieve high brightness and low voltage driving, as well as weak anchoring liquid crystal alignment agents and polymers that can be used in such elements. Prior Technology

[0002] In recent years, liquid crystal display (LCD) elements have been widely used in mobile phones, computers, and television monitors. LCD elements are characterized by their thinness, light weight, and low power consumption, and are expected to be used in further applications such as VR (Virtual Reality) and ultra-high-resolution displays. Various display methods have been proposed for LCDs, including TN (Twisted Nematic), IPS (In-Plane Switching), and VA (Vertical Alignment), all of which utilize a film (liquid crystal alignment film) to induce the liquid crystals into a desired alignment state.

[0003] In particular, for products with touch panels such as tablet PCs, smartphones, and smart TVs, the ideal is an IPS display that is less prone to display confusion even when touched. In recent years, in order to improve contrast and viewing angle characteristics, liquid crystal display elements using FFS (Frind Field Switching) and liquid crystal alignment technology using photo-alignment have been used.

[0004] However, compared to IPS, FFS (Film-Free System) has higher substrate manufacturing costs and suffers from a unique display defect called Vcom misalignment. Furthermore, photoalignment, compared to rubbing alignment, is advantageous in terms of adaptability to larger components and significantly improved display characteristics, but it also has inherent problems (if photodecomposition materials are used, there will be undesirable light from the decomposed products; if isomerization materials are used, there will be burn-in due to insufficient alignment force). To address these issues, liquid crystal display element manufacturers and liquid crystal alignment film manufacturers have made various efforts.

[0005] On the other hand, in recent years, some researchers have proposed a weak-anchored IPS method using weak anchoring technology. Compared with conventional IPS methods, this method can achieve improved contrast ratio and significantly lower voltage driving (see Patent Document 1).

[0006] The weakly anchored IPS method is fabricated by using a liquid crystal alignment film with strong anchoring energy on one side of the substrate, and a thin film with no anchoring energy applied to the other side of the substrate (which has electrodes that generate a transverse electric field).

[0007] In recent years, a technical proposal has been put forward to create a weakly anchored IPS by directly setting a thick polymer brush on the substrate to achieve a weak anchoring state (see Patent Document 2). According to this technology, a significant improvement in contrast ratio and a significant reduction in driving voltage can be achieved.

[0008] Furthermore, regarding other methods, a technique for weakly anchored IPS has been proposed. This technique uses a liquid crystal alignment film that can generate photoradicals and a compound that can polymerize on free radicals. UV light is irradiated into the liquid crystal to induce a free radical reaction, thereby weakening its anchorage (see Patent Document 3). According to this technique, in addition to improving the contrast ratio and significantly reducing voltage driving through mass production methods, it can also achieve high-speed response and reduce burn-in. [Previous Technical Documents] [Patent Literature]

[0009] [Patent Document 1] Japanese Patent No. 4053530 [Patent Document 2] Japanese Patent Application Publication No. 2013-231757 [Patent Document 3] International Publication No. 2019 / 004433 Summary of the Invention

[0010] (The problem the invention aims to solve)

[0011] The method of directly applying a thick polymer brush to a substrate (Patent Document 2) requires a surface treatment step to create reaction sites on the substrate, and a step to allow the polymer to grow from these reaction sites on the substrate surface. This process is complex, and because it requires a high degree of deoxidation, the environment must be strictly controlled. Therefore, the technology is technically challenging and impractical from a mass production perspective. Another method has been proposed to coat a bottle brush polymer with anchoring sites on a substrate to obtain a weakly anchored IPS display element. However, the manufacturing of bottle brush polymers uses macromonomers with polymerization initiation sites, and all are manufactured using living radical polymerization, which presents a problem of difficulty in large-scale supply. Furthermore, bottle brush polymers have insufficient solvent selectivity, exhibiting low solubility for commonly used solvents such as N-methyl-2-pyrrolidone (NMP) and γ-butyrolactone (GBL). It is believed that this poses a significant challenge in conventional coating processes due to their structure, insufficient sealing, and inadequate adhesion to the substrate. Methods to address these issues need to be considered.

[0012] Furthermore, the method of weak anchoring using photoradical polymerization and compounds that can be polymerized by free radicals (Patent Document 3) is believed to have issues such as the volatilization of polymerizable additives during liquid crystal injection under high vacuum conditions, and the adverse effects on the liquid crystal composition caused by the ultraviolet irradiation step required after the liquid crystal element is manufactured.

[0013] If such technical challenges can be solved, even panel manufacturers can easily and with good yield produce weakly anchored IPS LCD display elements that offer benefits such as battery saving and improved image quality.

[0014] The present invention was developed to solve the problems mentioned above, and aims to provide a weakly anchored liquid crystal alignment agent that is easy to manufacture and has good coatability. It has good adhesion to the seal and does not produce a pretilt angle. It can obtain a weakly anchored liquid crystal alignment film that can achieve high-speed response when driving at low voltage and when the voltage is OFF, and provide a liquid crystal display element. (Methods for solving problems)

[0015] In order to solve the above-mentioned problems, the inventors of this case have made efforts to study and found that the above-mentioned problems can be solved, and thus completed the present invention having the following essential points. That is, the present invention includes the following key points. [1] A weakly anchored liquid crystal alignment agent, used in the formation of a liquid crystal alignment film in a liquid crystal cell having liquid crystal and a liquid crystal alignment film. It contains a graft copolymer, having a dry polymer and a branch polymer that is a side chain of the dry polymer and is bonded to the dry polymer. The polymer and the liquid crystal are mutually compatible. The dry polymer is incompatible with the liquid crystal or becomes incompatible with the liquid crystal due to calcination. [2] As in [1], a weakly anchored liquid crystal alignment agent, wherein the branch polymer is derived from a macromonomer represented by the following formula (1), [Chemistry 1] In formula (1), P represents a polymerizable group having a polymerizable unsaturated hydrocarbon group, Q represents a structure obtained by polymerizing at least one monomer from compounds containing the following formulas (2), (3), (5), and (7), and n is an integer from 1 to 2. When n is 2, the two Qs can be the same or different. [Chemistry 2] In formula (2), M represents a polymerizable group with a polymerizable unsaturated hydrocarbon group, X represents a single bond, ether bond, ester bond, amide bond, carbamate bond, urea bond, or thioether bond, R1 represents an alkyl group with 1 to 20 carbon atoms that may also have a bonding group inserted, and n is an integer from 1 to 2. When n is 2, the two X's and R1's can be the same or different. [Chemistry 3] In formula (3), M represents a polymerizable group with a polymerizable unsaturated hydrocarbon group, S represents a saturated hydrocarbon group with 1 to 6 carbons that has a single bond or can also have a bonded group inserted, T represents the organic group represented by formula (4) below, n is an integer from 1 to 2, when n is 2, the two Ts can be the same or different, but when n is 2, S represents a saturated hydrocarbon group with 1 to 6 carbons that can also have a bonded group inserted. [Chemistry 4] In formula (4), * represents the bonding site, X represents a bonding group selected from single bonds, ether bonds, ester bonds, amide bonds, carbamate bonds, urea bonds, thioether bonds, -Si(R1)(R2)- (R1 and R2 each independently represent alkyl groups bonded to Si), -Si(R3)(R4)-O- (R3 and R4 each independently represent alkyl groups bonded to Si), and -N(R5)- (R5 represents a hydrogen atom bonded to N or an alkyl group), and Cy represents a non-aromatic cyclic group with 6 to 20 members. [Chemistry 5] In formula (5), M represents a polymerizable group with a polymerizable unsaturated hydrocarbon group, R1 represents an aliphatic hydrocarbon group with a straight chain or branched structure having 1 to 10 carbon atoms, and each of the three X's independently represents a hydrogen atom or the following formula (6), except that at least one of the three X's represents formula (6). [Chemistry 6] In formula (6), Y represents a single bond, -O-, -S-, or -N(R)- (R represents a hydrogen atom bonded to N or an alkyl group with 1 to 4 carbon atoms), * represents the bonding site, and R2, R3, and R4 each independently represent an alkyl group with 1 to 6 carbon atoms or an aromatic hydrocarbon group that may also have substituents. [Chemistry 7] In formula (7), M represents a polymerizable group with a polymerizable unsaturated hydrocarbon group, R1 to R3 each independently represent a single bond or an alkyl group with 1 to 6 carbon atoms that may also have a bonding group inserted, Ar represents an aromatic hydrocarbon group that may also have a substituent, X1 and X2 each independently represent a hydrogen atom or an aromatic hydrocarbon group that may also have a substituent, and the carbon atoms bonded by R1X1 and R2X2 and R1X1 and R2X2 may also form a ring together, but the total number of carbon atoms of R1X1, R2X2 and R3 is 1 or more. [3] As in [1] or [2], a weakly anchored liquid crystal alignment agent, wherein the dry polymer contains a compound represented by formula (8) as a constituent component. [Chemistry 8] In equation (8), M represents a polymerizable group with a polymerizable unsaturated hydrocarbon group, n is an integer from 1 to 2, and Z represents the group represented by equation (9) below. When n is 2, the two Zs can be the same or different. [Chemistry 9] In formula (9), L represents a group selected from amino, protected amino, aniline, protected aniline, hydroxyl, protected hydroxyl, phenol, protected phenol, thiol, protected thiol, thiophenol, protected thiophenol, carboxyl, protected carboxyl, benzoic acid, protected benzoic acid, isocyanate, protected isocyanate, cyclic ether with 2-5 carbon atoms, maleimino, carboxylic anhydride, N-hydroxysuccinimino, acezolinyl, trialkoxysilyl, vinyl, olefin. The functional group can be propyl, styryl, α-hydroxyacetophenone, α-aminoalkylphenylphenone, oxime ester, acetophosphonium oxide, cinnamic acid, cinnamic acid ester, azophenyl, N-benzylaniline, stilbene, diphenylethynyl, phenylbenzoate, or aromatic hydrocarbon groups with 5-18 carbon atoms that may have a bonding group inserted, or aromatic heterocyclic groups with 5-18 carbon atoms that may have a bonding group inserted. J represents a single bond or an aliphatic hydrocarbon group with 1-6 carbon atoms. When K is bonded to an aromatic hydrocarbon group, it represents a linking group selected from single bonds, ether bonds, ester bonds, acetoamine bonds, urea bonds, carbamate bonds, and thioether bonds. In other cases, it represents a single bond. * indicates the bonding site. m is an integer from 1 to 3. When m is 2 or 3, multiple K and L can be the same or different. However, when J is a single bond, m is 1. [4] As in [2] or [3], weakly anchored liquid crystal alignment agents, wherein P in formula (1) and M in formulas (2), (3), (5), (7), and (8) each independently represent any of the following structures. [Chemistry 10] In the formula, R1 and R2 each independently represent a hydrogen atom or a straight-chain or branched alkyl group having 1 to 12 carbon atoms; X, Y, and Z each independently represent an oxygen atom or a sulfur atom; *, *1, and *2 represent bonding sites; one of *1 and *2 may also be replaced by a hydrogen atom or a straight-chain or branched alkyl group having 1 to 12 carbon atoms. n represents an integer from 1 to 5. [5] A weakly anchored liquid crystal alignment agent as described in any of [1] to [4], wherein the dry polymer contains at least one compound selected from the group consisting of compounds represented by formulas (B-1) to (B-9) as a constituent component. [Chemistry 11] [6] A weakly anchored liquid crystal alignment agent as described in any of [1] to [5], wherein the graft copolymer is obtained by free radical polymerization. [7] A graft copolymer, which is a graft copolymer contained in a liquid crystal alignment agent. It comprises a dry polymer and a branch polymer that is bonded to the dry polymer as a side chain. This branch polymer originates from the macromonomer represented by formula (1). [Chemistry 12] In formula (1), P represents a polymerizable group with a polymerizable unsaturated hydrocarbon group, Q is a structure obtained by polymerizing at least one monomer from compound 5 containing the following formulas (2), (3), (5), and (7), and n is an integer from 1 to 2. When n is 2, the two Qs can be the same or different. [Chemistry 13] In formula (1), M represents a polymerizable group with a polymerizable unsaturated hydrocarbon group, X represents a single bond, ether bond, ester bond, amide bond, carbamate bond, urea bond, or thioether bond, R1 represents an alkyl group with 1 to 20 carbon atoms that may also have a bonding group inserted, and n is an integer from 1 to 2. When n is 2, the two X's and R1's can be the same or different. [Chemistry 14] In formula (3), M represents a polymerizable group with a polymerizable unsaturated hydrocarbon group, S represents a saturated hydrocarbon group with 1 to 6 carbons that has a single bond or can also have a bonded group inserted, T represents the organic group represented by formula (4) below, and n is an integer from 1 to 2. When n is 2, the two Ts can be the same or different, but when n is 2, S represents a saturated hydrocarbon group with 1 to 6 carbons that can also have a bonded group inserted. [Chemistry 15] In formula (4), * represents the bonding site, X represents a bonding group selected from single bonds, ether bonds, ester bonds, amide bonds, carbamate bonds, urea bonds, thioether bonds, -Si(R1)(R2)- (R1 and R2 each independently represent alkyl groups bonded to Si), -Si(R3)(R4)-O- (R3 and R4 each independently represent alkyl groups bonded to Si), and -N(R5)- (R5 represents a hydrogen atom bonded to N or an alkyl group), and Cy represents a non-aromatic cyclic group with 6 to 20 members. [Chemistry 16] In formula (5), M represents a polymerizable group with a polymerizable unsaturated hydrocarbon group, R1 represents an aliphatic hydrocarbon group with a straight chain or branched structure having 1 to 10 carbon atoms, and each of the three X's independently represents a hydrogen atom or the following formula (6), except that at least one of the three X's represents formula (6). [Chemistry 17] In formula (6), Y represents a single bond, -O-, -S-, or -N(R)- (R represents a hydrogen atom bonded to N or an alkyl group with 1 to 4 carbon atoms), * represents the bonding site, and R2, R3, and R4 each independently represent an alkyl group with 1 to 6 carbon atoms or an aromatic hydrocarbon group that may also have substituents. [Chemistry 18] In formula (7), M represents a polymerizable group with a polymerizable unsaturated hydrocarbon group, R1 to R3 each independently represent a single bond or an alkyl group with 1 to 6 carbon atoms that may also have a bonding group inserted, Ar represents an aromatic hydrocarbon group that may also have a substituent, X1 and X2 each independently represent a hydrogen atom or an aromatic hydrocarbon group that may also have a substituent, and the carbon atoms bonded by R1X1 and R2X2 and R1X1 and R2X2 may also form a ring together, but the total number of carbon atoms of R1X1, R2X2 and R3 is 1 or more. [8] Graft copolymers as in [7], wherein the dry polymer contains a compound represented by formula (8) as a constituent component. [Chemistry 19] In equation (8), M represents a polymerizable group with a polymerizable unsaturated hydrocarbon group, and n is an integer from 1 to 2. Z represents the group represented by equation (9) below. When n is 2, the two Zs can be the same or different. [Chemistry 20] In formula (9), L represents a group selected from amino, protected amino, aniline, protected aniline, hydroxyl, protected hydroxyl, phenol, protected phenol, thiol, protected thiol, thiophenol, protected thiophenol, carboxyl, protected carboxyl, benzoic acid, protected benzoic acid, isocyanate, protected isocyanate, cyclic ether with 2-5 carbon atoms, maleimino, carboxylic anhydride, N-hydroxysuccinimino, acezolinyl, trialkoxysilyl, vinyl, allyl, styryl, α-hydroxyacetophenone, α-aminoalkylphenylphenone, oxime ester, acetophosphine oxide, etc. The functional group can be one of the following: cinnamyl group, cinnamic acid ester group, azophenyl group, N-benzylaniline group, stilbene group, diphenylethynyl group, phenylbenzoate group, aromatic hydrocarbon group with 5-18 carbon atoms that may have a bonding group inserted, or aromatic heterocyclic group with 5-18 carbon atoms that may have a bonding group inserted. J represents a single bond or an aliphatic hydrocarbon group with 1-6 carbon atoms. When K is bonded to an aromatic hydrocarbon group, it represents a linking group selected from single bonds, ether bonds, ester bonds, amide bonds, urea bonds, carbamate bonds, and thioether bonds. In other cases, it represents a single bond. * indicates the bonding site. m is an integer from 1 to 3. When m is 2 or 3, multiple K and L can be the same or different. However, when J is a single bond, m is 1. [9] Graft copolymers such as [7] or [8], wherein P in formula (1) and M in formulas (2), (3), (5), (7), and (8) each independently represent any of the following structures. [Chemistry 21] In the formula, R1 and R2 each independently represent a hydrogen atom or a straight-chain or branched alkyl group having 1 to 12 carbon atoms, X, Y, and Z each independently represent an oxygen atom or a sulfur atom, *, *1, and *2 represent bonding sites, one of *1 and *2 can also be replaced by a hydrogen atom or a straight-chain or branched alkyl group having 1 to 12 carbon atoms, and n represents an integer from 1 to 5.

[10] A graft copolymer of any one of [7] to [9], wherein the dry polymer contains at least one compound selected from the group consisting of compounds represented by formulas (B-1) to (B-9) as a constituent component. [Chemistry 22] .

[11] The graft copolymers of any of [7] to

[10] are obtained by free radical polymerization.

[12] A weakly anchored liquid crystal alignment agent containing a graft copolymer of any one of [7] to

[11] .

[13] A liquid crystal display element is obtained by using a weakly anchored liquid crystal alignment agent such as [1] to [6] and

[12] .

[14] The liquid crystal display element of

[13] is a transverse electric field liquid crystal display element. (Effects of the invention)

[0016] According to the present invention, a stable weakly anchored alignment film can be manufactured using a method that is far simpler than conventional techniques. In actual industrial production, the step load applied to the manufacturing of weakly anchored transverse electric field liquid crystal display elements can be reduced, improving yield. Furthermore, by using the materials and methods of the present invention, compared to conventional techniques, higher speed response at voltage OFF, reduced solder paste, high backlight transmittance in low-temperature environments, and low-voltage driving can be achieved. Therefore, materials and transverse electric field liquid crystal display elements that stably exhibit excellent characteristics can be provided. Simple Explanation of the Diagram

[0017] Figure 1 is a schematic cross-sectional view showing an example of the transverse electric field liquid crystal display element of the present invention. Figure 2 is a schematic cross-sectional view showing another example of the transverse electric field liquid crystal display element of the present invention. Implementation

[0018] (Weakly anchored, weakly anchored alignment film) In this invention, "weak anchoring" refers to a force that regulates the alignment of liquid crystal molecules relative to the substrate in the azimuth or polar direction, but without any anchoring energy (i.e., the interfacial elastic energy that maintains the position of liquid crystal molecules, or the energy that allows them to return to their original state even after an alignment change), or if present, it is weaker than the intermolecular forces between liquid crystal molecules. In this invention, weak anchoring refers to a situation where the azimuth anchoring strength (A²) is less than 10⁻⁵ [J / m²]. Furthermore, "weakly anchored alignment film" refers to a film that forms a weakly anchored state through contact with liquid crystal, and is not limited to solid films, but also includes liquid films coated on solid surfaces.

[0019] (Strong anchoring, strong anchoring alignment film) In this invention, "strong anchoring" refers to the alignment of liquid crystal molecules along a single axis, maintaining the liquid crystal alignment even when energy is applied externally, or possessing anchoring energy that allows the liquid crystal molecules to return to their original positions even if their alignment changes. In this invention, strong anchoring refers to an azimuth anchoring strength (A²) greater than 10⁻⁴ [J / m²]. Furthermore, "strongly anchored alignment film" refers to a film that forms a strongly anchored state upon contact with liquid crystal, and is not limited to solid films, but also includes liquid films coated on solid surfaces.

[0020] (Weakly anchored liquid crystal display element) By coating weakly anchored alignment films and strongly anchored alignment films, as defined above, onto a substrate with attached electrodes and bonding them in pairs, a weakly anchored liquid crystal display element can be fabricated. Because the azimuth anchoring strength of one of the liquid crystal alignment films in a weakly anchored liquid crystal display element is minimized, the alignment of the liquid crystal can be induced by a weak electric field or external field energy. This allows even normally stationary liquid crystal molecules to undergo alignment changes. Therefore, especially in display elements using comb-type electrodes such as IPS and FFS, liquid crystal molecules on electrodes with weak electric field strength can be driven. Compared to liquid crystal display elements composed of paired alignment films with strongly anchored alignment films, this results in higher transmittance and lower driving voltage.

[0021] Azimuth anchoring strength refers to the intensity of the interfacial elastic energy between liquid crystal molecules and the liquid crystal alignment film relative to the azimuth direction. Methods for calculating azimuth anchoring strength include the torque equalization method, the strong electric field method, the geometric method (external field application method), and the Frederick transfer method.

[0022] (graft copolymer) In this invention, one embodiment of the "graft copolymer" is a graft copolymer contained in a weakly anchored liquid crystal alignment agent. The weakly anchored liquid crystal alignment agent is used in the formation of a liquid crystal alignment film for use in liquid crystal display elements, i.e., the formation of a liquid crystal alignment film. Furthermore, the weakly anchored liquid crystal alignment agent is used in the formation of a liquid crystal alignment film having liquid crystal and liquid crystal alignment film cells. Graft copolymers have a dry polymer and a branch polymer that is a side chain of the dry polymer and is bonded to the dry polymer.

[0023] Graft copolymers are a general term for polymers with branched structures, referring to polymers that simultaneously possess a polymer corresponding to the "trunk" and polymers that are side chains bonded to the trunk. The liquid crystal alignment agent of this invention uses a graft copolymer. The graft copolymer of this invention is characterized by having a branch polymer that is compatible with the liquid crystal, and a dry polymer that is incompatible with the liquid crystal or becomes incompatible with the liquid crystal due to calcination. That is, the branch polymer that is compatible with the liquid crystal contributes to the formation of a weakly anchored state through its compatibility with and swelling of the liquid crystal, and the dry polymer prevents the graft copolymer from dissolving into the liquid crystal due to insolubility in the liquid crystal or insolubility in the liquid crystal due to calcination. Furthermore, through fixation to the substrate, cross-linking of the polymers, and cross-linking of the sealing components, a weakly anchored liquid crystal display element with excellent film hardness and sealing strength can be obtained.

[0024] International Publication No. 2019 / 004433 proposes a weakly anchored liquid crystal display element using a high-density graft copolymer (referred to as a polymer brush) derived from a living polymer. This polymer brush is synthesized using a grafting-from method, requiring living polymerization. Furthermore, attempts have been made to improve the adhesion between the substrate and the polymer by introducing groups that enhance adhesion to the substrate into the graft copolymer. However, increasing the amount introduced may compromise the weak anchoring properties. Moreover, the graft copolymer has a very high density, so solvation with solvents is considered unlikely to occur; in particular, it is believed to impair affinity for high-boiling-point and highly polar solvents such as NMP and γ-butyrolactone. The inventors of this case have explored using weakly anchored liquid crystal alignment agents, such as block copolymers obtained by living polymerization of polymer brushes, but all of these methods resulted in low solvent selectivity and low adhesion strength of the polymers. Polymer brushes are also believed to have the same problems as precisely synthesized polymers. These results are described in the examples.

[0025] The ideal form of the graft copolymer used in the weakly anchored liquid crystal alignment agent of this invention is characterized by using a polymerizable compound having a pre-polymerized polymer (hereinafter, a macromonomer) to synthesize a graft copolymer with low graft polymer density via free radical polymerization (grafting through method). This method involves introducing highly polar or rigid groups or crosslinking groups onto the dry polymer side, enabling simple manufacturing, high solvent selectivity, and excellent adhesion between films, seals, and substrates. However, methods using polymer reactions to form graft polymers (grafting to method) and the aforementioned grafting from method can synthesize the same polymer; therefore, the synthesis method is not particularly limited.

[0026] The graft copolymer of the present invention is characterized by having a branch polymer that is compatible with liquid crystals, and a dry polymer that is incompatible with liquid crystals or becomes incompatible with liquid crystals due to calcination. Furthermore, the graft copolymer is insoluble in liquid crystals due to the dry polymer or becomes insoluble in liquid crystals due to calcination.

[0027] There are no special restrictions on the structure of dendritic polymers that are compatible with liquid crystals, as long as they are soluble in liquid crystals. For example, dendritic polymers can come from the macromonomers represented by the following formula (1). [Chemistry 23] In formula (1), P represents a polymerizable group with a polymerizable unsaturated hydrocarbon group, Q is a structure obtained by polymerizing at least one monomer of compound 5 containing the following formulas (2), (3), (5) and (7), and n is an integer from 1 to 2. When n is 2, the two Qs can be the same or different. [Chemistry 24] In formula (2), M represents a polymerizable group with a polymerizable unsaturated hydrocarbon group, X represents a single bond, ether bond, ester bond, amide bond, carbamate bond, urea bond, or thioether bond, R1 represents an alkyl group with 1 to 20 carbon atoms that may also have a bonding group inserted, and n is an integer from 1 to 2. When n is 2, the two Xs and R1 can be the same or different. It can also insert a bonding group into an alkyl group with 1 to 20 carbon atoms, such as: ether bond, ester bond, amide bond, carbamate bond, urea bond, thioether bond, -Si(R 11)(R 12)- (R 11 and R 12 each independently represent an alkyl group bonded to Si.), -Si(R 13)(R 14)-O- (R 13 and R 14 each independently represent an alkyl group bonded to Si.), -N(R 15)- (R 15 represents a hydrogen atom bonded to N or an alkyl group.). Alkyl groups from R 11 to R 15, for example: alkyl groups with 1 to 6 carbon atoms. [Chemistry 25] In formula (3), M represents a polymerizable group with a polymerizable unsaturated hydrocarbon group, S represents a saturated hydrocarbon group with 1 to 6 carbons that has a single bond or can also have a bonded group inserted, T represents the organic group represented by formula (4) below, and n is an integer from 1 to 2. When n is 2, the two Ts can be the same or different. However, when n is 2, S represents a saturated hydrocarbon group with 1 to 6 carbons that can also have a bonded group inserted. [Chemistry 26] In formula (4), * indicates the bonding site. X is a bonding group selected from single bond, ether bond, ester bond, amide bond, carbamate bond, urea bond, thioether bond, -Si(R1)(R2)- (R1 and R2 each independently represent an alkyl group bonded to Si), -Si(R3)(R4)-O- (R3 and R4 each independently represent an alkyl group bonded to Si), and -N(R5)- (R5 represents a hydrogen atom or alkyl group bonded to N). Cy represents a non-aromatic cyclic group with 6 to 20 members.

[0028] In formula (3), the saturated hydrocarbon group in S refers to the n+1 valence group formed by removing n+1 hydrogen atoms from a saturated hydrocarbon (n is the same integer as n in formula (2)). When n is 1, the saturated hydrocarbon group is an alkyl group. In formula (3), S is a saturated hydrocarbon group with 1 to 6 carbon atoms that has a bonding group inserted. This is either an n+1 valence group with a bonding group inserted between carbon atoms in a saturated hydrocarbon group with 2 to 6 carbon atoms, or an n+1 valence group with a bonding group inserted between a saturated hydrocarbon group with 1 to 6 carbon atoms and its bonded atom (e.g., a carbon atom). In formula (3), the bonds in S can be, for example, carbon-carbon unsaturated bonds, ether bonds (-O-), ester bonds (-COO- or -OCO-), amide bonds (-CONH- or -NHCO-), etc. Carbon-carbon unsaturated bonds can be, for example, carbon-carbon double bonds, etc. However, it is preferable that the carbon-carbon double bond is inserted into a saturated hydrocarbon group with 1 to 6 carbons, rather than at its end, and that the carbon-carbon double bond is internal. When n is 1, alkyl groups with 1 to 6 carbon atoms that have a bonding group can also be inserted, such as alkyl groups with 1 to 6 carbon atoms, alkyl groups with 1 to 6 carbon atoms, etc. Alkyl groups having 1 to 6 carbon atoms can be straight-chain, branched, or cyclic.

[0029] In formula (4), R1 and R2 of -Si(R1)(R2)- are each independently alkyl groups bonded to Si, for example, alkyl groups with 1 to 6 carbon atoms. In formula (4), R3 and R4 of -Si(R3)(R4)-O- are each independently an alkyl group bonded to Si, for example, an alkyl group with 1 to 6 carbon atoms. In formula (4), the R5 in -N(R5)- is bonded to the hydrogen atom of N or an alkyl group. Alkyl groups, for example, are alkyl groups with 1 to 6 carbon atoms.

[0030] In formula (4), Cy is a non-aromatic cyclic group with 6 to 20 members, preferably a non-aromatic cyclic group with 8 to 18 members. Alternatively, Cy can be a non-aromatic cyclic group with 12 to 20 members. In formula (4), X is bonded to the atoms constituting the ring in Cy. The atoms that make up the ring in a non-aromatic cyclic group, such as carbon atoms, oxygen atoms, nitrogen atoms, silicon atoms, etc. The bonds between atoms that make up a ring can be single bonds, double bonds, or parabolic bonds, with single bonds being preferred. The ring in a non-aromatic cyclic group, such as cyclic alkanes, cyclic ethers, cyclic siloxanes, etc. Cyclic ethers, for example, crown ethers. For example, in 12-crown-4, the ring is composed of carbon and oxygen atoms, with a member number of 12. A ring can be a single ring or multiple rings. The number of rings in a multiple ring can be, for example, 2 to 4. In a multi-ring structure, the bonding methods between the rings include the following three types. • Contains 1 atom: e.g., spirocyclic compounds • Contains 2 atoms: Similar to decahydronaphthalene, the two rings contain a total of 2 atoms. • Bridging structure: Similar to norcamphene, it is considered as having two rings with a total of three or more atoms. Furthermore, in the case of polycyclic rings, the number of atoms constituting the ring is used as the ring member number. For example, norcamphene is a 7-membered ring. The atoms constituting the ring may not be bonded to hydrogen atoms, but rather to halogen atoms or alkyl groups having 1 to 6 carbon atoms. Halogen atoms include, for example, fluorine atoms and chlorine atoms.

[0031] [Chemistry 27] In formula (5), M represents a polymerizable group with a polymerizable unsaturated hydrocarbon group, R1 represents an aliphatic hydrocarbon group with a straight chain or branched structure having 1 to 10 carbon atoms, and each of the three X's independently represents a hydrogen atom or the following formula (6). Only at least one of the three X's represents formula (6).

[0032] [] [Chemistry 28] In formula (6), Y represents a single bond, -O-, -S-, or -N(R)- (R represents a hydrogen atom bonded to N or an alkyl group having 1 to 4 carbon atoms), and * represents the bonding site. R2, R3, and R4 each independently represent an alkyl group having 1 to 6 carbon atoms or an aromatic hydrocarbon group that may also have substituents.

[0033] In formula (5), the aliphatic hydrocarbon group in R1 has 1 to 10 carbons, or it can have 1 to 8 carbons, or it can have 1 to 6 carbons, or it can have 1 to 4 carbons.

[0034] In formula (6), the alkyl groups of R2, R3, and R4 that have 1 to 6 carbon atoms can be, for example, alkyl groups with 1 to 5 carbon atoms or alkyl groups with 1 to 4 carbon atoms. These alkyl groups can be straight-chain structures or branched structures.

[0035] In formula (6), the aromatic hydrocarbon groups in R2, R3 and R4 can be unsubstituted or have their hydrogen atoms substituted by substituents. Substituents may also be aromatic hydrocarbon groups with substituents, such as halogen atoms, alkyl groups with 1 to 4 carbon atoms, alkoxy groups with 1 to 4 carbon atoms, alkyl halides with 1 to 4 carbon atoms, and alkoxy halides with 1 to 4 carbon atoms. The halogenation in alkyl halides and alkoxy halides can be either full or partial halogenation. Halogen atoms may include, for example, fluorine atoms and chlorine atoms. It can also be an aromatic hydrocarbon group with substituents, such as phenyl or naphthyl. There is no particular restriction on the number of substituents in aromatic hydrocarbon groups.

[0036] In equation (5), equation (6) can be one or more, including one, two, or three. In equation (5), the three X's are independent. Therefore, in equation (5), when there are two or more equations (6), the two or more equations (6) can have the same structure or different structures.

[0037] In formula (6), at least one of R2, R3, and R4 can be an aromatic hydrocarbon group that may also have substituents. Therefore, in formula (6), one of R2, R3, and R4 can be an aromatic hydrocarbon group that may also have substituents, two of R2, R3, and R4 can be aromatic hydrocarbon groups that may also have substituents, or three of R2, R3, and R4 can be aromatic hydrocarbon groups that may also have substituents.

[0038] [Chemistry 29] In formula (7), M represents a polymerizable group with a polymerizable unsaturated hydrocarbon group; R1 to R3 each independently represent a single bond, or an alkyl group with 1 to 6 carbon atoms that may also have a bonding group inserted; Ar represents an aromatic hydrocarbon group that may also have a substituent; X1 and X2 each independently represent a hydrogen atom, or an aromatic hydrocarbon group that may also have a substituent; the carbon atoms bonded by R1X1 and R2X2 and R1X1 and R2X2 may also form a ring together. However, the total number of carbon atoms in R1X1, R2X2 and R3 must be 1 or more.

[0039] In formula (7), R1 to R3 are alkyl groups with 1 to 6 carbon atoms that have inserted bonding groups. This means that a divalent group of bonding groups has been inserted between carbon atoms in the alkyl groups with 1 to 6 carbon atoms, or a divalent group of bonding groups has been inserted between the alkyl groups with 1 to 6 carbon atoms and the carbon atoms to which they are bonded. Bonding groups, such as carbon-carbon unsaturated bonds, ether bonds (-O-), ester bonds (-COO- or -OCO-), amide bonds (-CONH- or -NHCO-), etc. Unsaturated bonds, such as carbon-carbon double bonds, etc., but it is preferable that the alkyl group with 1 to 6 carbon atoms inserted into the bonding group has a carbon-carbon double bond internally rather than at its end. It is also possible to insert a alkyl group with 1 to 6 carbon atoms, such as an alkyl group with 1 to 6 carbon atoms, an alkyl group with 1 to 6 carbon atoms, etc. The oxygen atom in the alkyl group with 1 to 6 carbon atoms is, for example, the carbon atom bonded by M, R1, R2 and R3 in formula (7). Alkyl groups with 1 to 6 carbon atoms can be straight-chain alkyl groups, branched alkyl groups, or cyclic alkyl groups.

[0040] In formula (7), X1 and X2 can also be aromatic hydrocarbon groups with substituents, such as phenyl, naphthyl, etc. Substituents, such as halogen atoms, alkyl groups with 1 to 4 carbon atoms, alkoxy groups with 1 to 4 carbon atoms, alkyl halides with 1 to 4 carbon atoms, alkoxy halides with 1 to 4 carbon atoms, etc. The halogenation in alkyl halides and alkoxy halides can be either full halogenation or partial halogenation. Halogen atoms, such as fluorine atoms, chlorine atoms, etc.

[0041] R1 in formula (7) can be, for example, a single bond, an alkyl group having 1 to 6 carbon atoms, etc. More specifically, an alkyl group having 1 to 6 carbon atoms can be, for example, a straight-chain alkyl group having 1 to 6 carbon atoms. R2 in formula (7) can be, for example, a single bond, an alkyl group having 1 to 6 carbon atoms, etc. More specifically, an alkyl group having 1 to 6 carbon atoms can be, for example, a straight-chain alkyl group having 1 to 6 carbon atoms. R3 in formula (7) can be, for example, a single bond, an alkyl group having 1 to 6 carbon atoms, etc. More specifically, an alkyl group having 1 to 6 carbon atoms can be a straight-chain alkyl group having 1 to 6 carbon atoms. In formula (7), X1 can be, for example, a hydrogen atom, a phenyl group, etc. In formula (7), X2 can be, for example, hydrogen atom, phenyl, etc. In formula (7), Ar can be, for example, phenyl.

[0042] If the total number of carbons of R1X1, R2X2 and R3 in formula (7) is 1 or more, it is not particularly limited, and it can also be 2 or more. Furthermore, the total number of carbons of R1, R2, and R3 in formula (7) can be, for example, less than 18, less than 15, or less than 10. Furthermore, when X1 and X2 in formula (7) are hydrogen atoms, the total number of carbon atoms of R1, R2 and R3 is not particularly limited if it is 1 or more, and can also be 2 or more. Furthermore, when at least one of X1 and X2 in formula (7) is an aromatic hydrocarbon group that may also have substituents, the total number of carbons of R1, R2 and R3 may also be 0.

[0043] In equation (7), the ring formed by the carbon atoms bonded to R1X1 and R2X2 together can also include, for example, a hydrocarbon ring with 3 to 13 carbon atoms that has a bonding group inserted. The bonding group is as described above.

[0044] The applicant in this case discovered free radical polymerizable monomers contained in the liquid crystal composition of a liquid crystal display element with a weakly anchored horizontal electric field that facilitate weak anchoring without pretilt angle, and discovered compounds represented by formula (2), formula (3), formula (5), and formula (7) (hereinafter referred to as specific compounds), and has filed patent applications (Japanese Patent Application 2020-134149, Japanese Patent Application 2020-163212, Japanese Patent Application 2021-041196, WO2019 / 004433, and PCT / JP2021 / 29199, which claims priority to Japanese Patent Application 2020-134149. By reference herein, the contents of these applications and publications are incorporated into this specification to the same extent as expressly stated.). By using these monomers, it is easy to achieve high-speed response at voltage OFF, reduced burn-in, high backlight transmittance in low-temperature environments, and low-voltage driving. Therefore, it can be said that the use of these monomers is useful.

[0045] The synthesis of branched polymers can utilize the aforementioned monomers as a single component or a combination of multiple monomers. Furthermore, other monomers capable of free radical polymerization, as described below, can also be used in combination.

[0046] In the graft copolymer used in the weakly anchored liquid crystal alignment agent of this invention, the graft polymer has a significant impact on the weak anchoring properties. The physical properties of the weakly anchored film vary depending on the molecular weight of the graft polymer, thus optimizing the molecular weight becomes important. From the viewpoint of forming a good weakly anchored film, the ideal molecular weight of the graft polymer is 1,000 to 100,000, more preferably 3,000 to 50,000, and the molecular weight distribution (PDI), expressed as the ratio of weight average molecular weight (Mw) to number average molecular weight (Mn), is preferably 3.0 or less, more preferably 2.0 or less. Furthermore, when the graft copolymer is synthesized using a copolymer grafting-through method employing macromonomers, the molecular weight referred to here corresponds to the molecular weight of the macromonomer.

[0047] The structure other than the end in the branch polymer (e.g., the structure of Q in formula (1)) can be a homopolymer structure using only one monomer represented by formulas (2), (3), (5), and (7) above, or a copolymer structure combining multiple monomers. When multiple monomers are combined with each other, it can be random copolymerization or block copolymerization. When monomers represented by formulas (2), (3), (5), and (7) above are combined with each other, the combination method is not limited, and the ratio is not particularly restricted. When combined with the liquid crystal insoluble compounds described below, from the point of view of maintaining properties, the ideal combination ratio of liquid crystal insoluble monomers is 30 mol% or less, more preferably 20 mol% or less, but not limited. Such synthesis methods, combined monomers, and combination ratios are preferably used within the range of obtaining the desired physical properties, display properties, electrical properties, etc.

[0048] The macromonomer represented by formula (1) for the raw material of the graft copolymer of the present invention can be obtained, for example, by a combination of living polymerization, chain transfer polymerization, and polymer end-modification reaction. Also, it has been reported that polymers with unsaturated bonds at the end groups having free radical polymerizability can be obtained by continuous bulk polymerization at high temperatures above 200°C (TREND 2002 No. 5 of East Asia Synthetic Research Annual Report). Living polymerization is a polymerization reaction that does not involve side reactions such as chain transfer or termination reactions, resulting in polymers with narrow molecular weight distributions and highly controlled structures. For example, one method involves introducing stable covalently bonded species called dormant species into the active polymerization sites, thereby inhibiting the deactivation of the active sites and preventing side reactions such as chain transfer and termination reactions. The active species used in living polymerization can be categorized as those using free radicals, cationic species, or anionic species; it is important to distinguish which species to use based on the structure and properties of the monomers employed. When obtaining the macromonomer used as a raw material for the graft copolymer of the weakly anchored alignment film of this invention, the polymerization method is not particularly limited. However, cationic polymerization and anionic polymerization often use alkali metals, metal complexes, and halogen compounds to generate active species. Since metal residues and halogen compounds may be mixed in with liquid crystal displays, causing burn-in and display defects, it is preferable to use free radical polymerization that does not use metals or halogen compounds. Examples of living free radical polymerization include: living free radical polymerization (NMP) using nitroxide free radicals as dormant species, atom-moving free radical polymerization (ATRP) using metal complexes, reversible addition-fragmentation chain transfer polymerization (RAFT polymerization) using sulfur compounds as dormant species, living free radical polymerization (TERP) using organotelluric compounds, and reversible mobile catalyst polymerization (RTCP) using iodinated alkyl compounds as dormant species and phosphorus compounds, alcohols, etc. as catalysts. Ideal polymerization methods include living free radical polymerization such as NMP, RTCP, and RAFT polymerization, with NMP or RAFT polymerization being particularly preferred. Alternatively, chain transfer polymerization is also ideal.

[0049] When using NMP, polymerization initiators such as 2,2'-azobis(isobutyronitrile), 2,2'-azobis(2,4-dimethylpentanonitrile), benzoyl peroxide, 1,1'-bis(tert-butylperoxide)cyclohexane, and hydrogen peroxide are used. The proportion of the polymerization initiator used relative to 1 mole of the monomer used is typically 0.000001 to 0.1 mol, preferably 0.00001 to 0.01 mol. Nitrogen oxide radicals, such as compounds represented by formulas (N-1) to (N-12), are also used. The proportion of nitroxide radicals used relative to 1 mole of the monomer used is typically 0.000001 to 0.1 mol, preferably 0.00001 to 0.01 mol. The reaction temperature in the above polymerization is preferably 20~200℃, more preferably 40~150℃, and the reaction time is preferably 1~168 hours, more preferably 8~72 hours.

[0050] [Chemistry 30]

[0051] When using RTCP, polymerization initiators used include, for example, 2,2'-azobis(isobutyronitrile), 2,2'-azobis(2,4-dimethylpentanonitrile), benzoyl peroxide, 1,1'-bis(tert-butylperoxide)cyclohexane, and hydrogen peroxide. The ratio of the polymerization initiator to 1 mole of monomer used is typically 0.000001 to 0.1 moles, preferably 0.00001 to 0.01 moles. Iodide catalysts, such as compounds represented by formulas (P-1) to (P-7), are used in a proportion of iodide catalyst relative to 1 mol of monomer used. This proportion is typically 0.000001 to 0.1 mol, preferably 0.00001 to 0.01 mol. Similarly, hydride catalysts, such as compounds represented by formulas (O-1) to (O-6), are used in a proportion of hydride catalyst relative to 1 mol of monomer used. This proportion is typically 0.000001 to 0.1 mol, preferably 0.00001 to 0.01 mol. The reaction temperature in the above polymerization is preferably 20 to 200°C, more preferably 40 to 150°C, and the reaction time is preferably 1 to 168 hours, more preferably 8 to 72 hours.

[0052] [Chemistry 31] [Chemistry 32]

[0053] When using RAFT polymerization, polymerization initiators such as 2,2'-azobis(isobutyronitrile), 2,2'-azobis(2,4-dimethylpentanonitrile), benzoyl peroxide, 1,1'-bis(tert-butylperoxide)cyclohexane, and hydrogen peroxide are used. The ratio of the polymerization initiator to 1 mole of monomer used is typically 0.000001 to 0.1 moles, preferably 0.00001 to 0.01 moles. Chain transfer agents (RAFT agents) are preferably trithiocarbonates, dithiobenzoates, dithiocarbamates, or xanthates, specifically, compounds represented by formulas (R-1) to (R-24). The ratio of the chain transfer agent to 1 mole of monomer used is typically 0.000001 to 0.1 moles, preferably 0.00001 to 0.01 moles. The reaction temperature in the above polymerization is preferably 20~200℃, more preferably 40~150℃, and the reaction time is preferably 1~168 hours, more preferably 8~72 hours.

[0054] [Chemistry 33] In formulas (R-1) to (R-24), Me represents methyl.

[0055] The RAFT polymerization exhibits active free radical properties because most active chains are dormant, there are compounds that can reversibly deactivate growing free radical species, and there is a rapid equilibrium between active and dormant chains.

[0056] By using RAFT polymerization, it is possible to control polymer ends, achieve a high degree of molecular weight control, and control molecular weight distribution.

[0057] To precisely synthesize functional polymers using RAFT polymerization, the reactivity of the monomers must be considered when selecting appropriate chain transfer agents.

[0058] In RAFT polymerization, the polymer ends can be controlled by thermal and chemical modification of the RAFT ends present at the growth ends. Thermal modification involves heating the RAFT agent above its thermal decomposition temperature to convert the ends into unsaturated hydrocarbon groups. Chemical modification involves contact with primary or secondary amines for aminolysis, which converts the ends into thiol bonds. Furthermore, contact with new monomers and free radical generators can introduce new block segments at the ends.

[0059] In RAFT polymerization, molecular weight can be controlled using the following formula (eq1). Specifically, since the number average molecular weight (Mn) changes linearly with the ratio of the molar concentration of the monomer to the molar concentration of the chain transfer agent, molecular weight control is possible. [Number 1]

[0060] In the above formula (eq1), Mn (theor) represents the molecular weight of the polymer, [Monomer] 0 represents the molar concentration of the monomer, [CTA] 0 represents the molar concentration of the chain transfer agent, M monomer represents the molecular weight of the monomer, conv. represents the polymerization conversion rate, and M CTA represents the molecular weight of the chain transfer agent.

[0061] When using chain transfer polymerization, polymerization initiators such as 2,2'-azobis(isobutyronitrile), 2,2'-azobis(2,4-dimethylpentanonitrile), benzoyl peroxide, 1,1'-bis(tert-butylperoxide)cyclohexane, and hydrogen peroxide are used. The ratio of the polymerization initiator to 1 mole of monomer used is typically 0.000001 to 0.1 moles, preferably 0.00001 to 0.01 moles. Thiols are preferred as chain transfer agents; specific examples include compounds represented by formulas (S-1) to (S-15). The ratio of the chain transfer agent to 1 mole of monomer used is typically 0.000001 to 0.1 moles, preferably 0.00001 to 0.01 moles. The preferred reaction temperature for the above polymerization is 20~200℃, more preferably 40~150℃, and the preferred reaction time is 1~168 hours, more preferably 8~72 hours.

[0062] [Chemistry 34] In formulas (S-1) to (S-15), Me represents methyl and Et represents ethyl.

[0063] There are no special restrictions on the organic solvents used in chain transfer polymerization reactions, as long as the resulting polymer will dissolve. Specific examples can be listed below. One type of organic solvent can be used alone, or two or more types can be mixed. Furthermore, even solvents that do not dissolve the generated polymer can be mixed with the aforementioned organic solvents and used within a range where the generated polymer does not precipitate. Furthermore, in chain transfer polymerization, oxygen in the organic solvent can hinder the polymerization reaction, so it is better to use organic solvents that are as degassed as possible.

[0064] By using chain transfer polymerization, polymer end control, molecular weight control, and molecular weight distribution control can be achieved.

[0065] In chain transfer polymerization, polymers are obtained through a competitive reaction involving chain transfer and growth. The molecular weight and molecular weight distribution of the polymer obtained by chain transfer polymerization are determined by the chain transfer constant (Cs), which is obtained by dividing the chain transfer rate constant (kc) by the growth rate constant (kp). Generally, chain transfer polymerization is best suited for compositions with Cs in the range of 1 to 60. The types of monomers used, the types of chain transfer agents, and their proper combination are crucial.

[0066] The chain transfer constant (Cs) varies greatly depending on the type of monomer and chain transfer agent used, and must be selected correctly.

[0067] Dry polymers, for example, contain compounds represented by the following formula (8) as constituent components. [Chemistry 35] In equation (8), M represents a polymerizable group with a polymerizable unsaturated hydrocarbon group, and n is an integer from 1 to 2. Z represents the group represented by equation (9) below. When n is 2, the two Zs can be the same or different. [Chemistry 36] In formula (9), L represents a group selected from amino, protected amino, aniline, protected aniline, hydroxyl, protected hydroxyl, phenol, protected phenol, thiol, protected thiol, thiophenol, protected thiophenol, carboxyl, protected carboxyl, benzoic acid, protected benzoic acid, isocyanate, protected isocyanate, cyclic ether with 2-5 carbon atoms, maleimino, carboxylic anhydride, N-hydroxysuccinimino, acezolinyl, trialkyloxy The functional group can be one of the following: alkylsilyl, vinyl, allyl, styryl, α-hydroxyacetophenone, α-aminoalkylphenylacetophenone, oxime ester, acetophosphonyl oxyacetyl, cinnamic acid, cinnamic ester, azophenyl, N-benzylaniline, stilbene, diphenylethynyl, phenylbenzoate, or aromatic hydrocarbon groups with 5-18 carbon atoms that may have a bonding group inserted, or aromatic heterocyclic groups with 5-18 carbon atoms that may have a bonding group inserted. J represents a single bond or an aliphatic hydrocarbon group with 1-6 carbon atoms. K, when bonded to an aromatic hydrocarbon group, represents a linking group selected from single bonds, ether bonds, ester bonds, acetylamine bonds, urea bonds, carbamate bonds, and thioether bonds; otherwise, it represents a single bond. * indicates the bonding site. m is an integer from 1 to 3. When m is 2 or 3, multiple K and L can be the same or different. However, when J is a single bond, m is 1.

[0068] For liquid crystal incompatible dry polymer structures, such as highly polar or rigid structures, calcination can alter the structure of liquid crystal incompatible dry polymers, for example, structures that react with heat to form covalent bonds, and structures where the functional groups of the substrate and sealing components react (these structures are also called thermosetting structures). Therefore, monomers constituting dry polymers (excluding macromonomers) are preferably monomers containing polymerizable unsaturated hydrocarbon groups capable of polymerization and highly polar structures, rigid structures, and polymerizable unsaturated hydrocarbon groups capable of polymerization and thermosetting structures. If a polymer contains such structures and is incompatible with liquid crystals, the dry polymer may also contain structures that do not have such structures, for example, it may also contain monomers of compounds represented by formulas (2), (3), (5) and (7), or general monomers as constituent components.

[0069] Specific examples of highly polar structures include, but are not limited to, the following structures. [Chemistry 37] X and Y each independently represent an oxygen atom or a sulfur atom. R1 and R2 each independently represent a single bond or an alkyl group having 1 to 18 carbon atoms. R3 represents an alkyl group having 1 to 18 carbon atoms. One of A1, A2, and A3 represents N, and the other two represent CH. One of A4 and A5 represents N, and the other one represents CH. * indicates a bonding site, and n represents an integer from 0 to 4 or an integer from 0 to 5.

[0070] Examples of rigid structures are shown below, but are not limited to these. [Chemistry 38] X, Y, and Z each independently represent an oxygen atom or a sulfur atom. R1 and R2 each independently represent a single bond or an alkyl group having 1 to 18 carbon atoms. R3 represents an alkyl group having 1 to 18 carbon atoms. * indicates a bonding site, and n represents an integer from 1 to 5.

[0071] Specific examples of thermosetting structures are shown below, but are not limited to these. [Chemistry 39] X, Y, and Z each independently represent an oxygen atom or a sulfur atom. R1, R2, and R3 each independently represent an alkyl group having 1 to 18 carbon atoms. R4 represents a single bond or an alkyl group having 1 to 18 carbon atoms. R5 represents an alkyl group having 1 to 18 carbon atoms. * indicates a bonding site, and n represents an integer from 0 to 5.

[0072] In order to obtain the graft copolymer of the present invention, the polymerizable group having a polymerizable unsaturated hydrocarbon group preferably has the following structure. [Chemistry 40] In the formula, R1 and R2 each independently represent a hydrogen atom or a straight-chain or branched alkyl group having 1 to 12 carbon atoms, and X, Y, and Z each independently represent an oxygen atom or a sulfur atom. *, *1, and *2 represent bonding sites, and one of *1 and *2 can also be replaced by a hydrogen atom or a straight-chain or branched alkyl group having 1 to 12 carbon atoms. n represents an integer from 1 to 5.

[0073] From the perspective of availability and weak anchoring characteristics, the graft copolymer used in the weak anchoring liquid crystal alignment agent of the present invention has a particularly ideal structure. The graft polymer is a macromonomer with a structure obtained by polymerizing the compound represented by the aforementioned formula (2) in formula (1), and the dry polymer is a structure obtained by using one or more monomers represented by the following compounds B-1 to B-9. [Chemistry 41] The main synthesis methods of the graft copolymer of the present invention can be listed as follows: grafting-to method, which involves directly introducing branch polymers into dry polymers; grafting-from method, which involves polymerizing monomers from macromolecular initiators (dry polymers with polymerizable active sites) and extending the branch polymers; and copolymer grafting-through method, which involves polymerizing macromonomers (polymers with polymerizable functional groups at one end). All of the above methods can be used, so there is no limitation on the synthesis method.

[0074] The method for manufacturing the graft copolymer used in this invention is not particularly limited, and can utilize commonly used industrial methods. Specifically, it can be manufactured using the aforementioned monomers and employing free radical polymerization, cationic polymerization, or anionic polymerization. Among these, free radical polymerization is particularly preferred from the viewpoint of ease of reaction control.

[0075] The polymerization initiators for free radical polymerization can be well-known compounds such as free radical polymerization initiators (free radical thermal polymerization initiators, free radical photopolymerization initiators) and reversible addition-crack chain transfer (RAFT) polymerization reagents.

[0076] Free radical thermal polymerization initiators are compounds that generate free radicals by heating them above their decomposition temperature. Examples of such free radical thermal polymerization initiators include: ketone peroxides (methyl ethyl ketone peroxide, cyclohexanone peroxide, etc.), diacyl peroxides (acetyl peroxide, benzoyl peroxide, etc.), hydrogen peroxides (hydrogen peroxide, tert-butyl hydrogen peroxide, cumene hydrogen peroxide, etc.), dialkyl peroxides (di-tert-butyl peroxide, diisopropylphenyl peroxide, lauryl peroxide, etc.), peroxy ketals (di-butyl peroxycyclohexane, etc.), alkyl peresters (tert-butyl peroxyneodecanoate, tert-butyl peroxytrimethylacetic acid, tert-pentyl peroxy2-ethylcyclohexanoate, etc.), persulfates (potassium persulfate, sodium persulfate, ammonium persulfate, etc.), and azo compounds (azobisisobutyronitrile, 2,2'-di(2-hydroxyethyl)azobisisobutyronitrile, etc.). Free radical thermal polymerization initiators can be used alone or in combination of two or more.

[0077] There are no special restrictions on free radical photopolymerization initiators, as long as they are compounds that begin free radical polymerization due to light irradiation. Examples of such free radical photopolymerization initiators include diphenyl ketone, milchnerone, 4,4'-bis(diethylamino)diphenyl ketone, xanthonone, thioxanthonone, isopropyl xanthonone, 2,4-diethylthioxanthonone, 2-ethylanthraquinone, acetophenone, 2-hydroxy-2-methylpropenylbenzene, 2-hydroxy-2-methyl-4'-isopropylpropenylbenzene, 1-hydroxycyclohexylphenyl ketone, isopropyl phenazine ether, isobutyl phenazine ether, 2,2-diethoxyacetophenone, 2,2-dimethoxy-2-phenylacetophenone, camphorquinone, benzoanthraquinone, 2-methyl-1-[4-(methylthio)phenyl]-2-dioxolinopropyl-1-one, and 2-benzyl-2-dimethylamino-1-(4-dioxolinophenyl)-1-butanone. 4-Dimethylaminobenzoate, 4-Dimethylaminobenzoate, 4,4'-Di(tert-butylperoxycarbonyl)diphenyl ketone, 3,4,4'-Tris(tert-butylperoxycarbonyl)diphenyl ketone, 2,4,6-Trimethylbenzoyldiphenylphosphine oxide, 2-(4'-methoxystyryl)-4,6-bis(trichloromethyl)-s-triphenyl, 2-(3',4'-dimethoxystyryl)-4,6-bis(trichloromethyl)-s-triphenyl, 2-(2',4'-dimethoxystyryl)-4,6-bis(trichloromethyl)-s-triphenyl, 2-(2'-methoxystyryl)-4,6-bis(trichloromethyl)-s-triphenyl, 2-(4'-pentyl) 4,6-bis(trichloromethyl)-s-triazine, 4-[p-N,N-di(ethoxycarbonylmethyl)]-2,6-bis(trichloromethyl)-s-triazine, 1,3-bis(trichloromethyl)-5-(2'-chlorophenyl)-s-triazine, 1,3-bis(trichloromethyl)-5-(4'-methoxyphenyl)-s-triazine, 2-(p-dimethylaminostyryl)benzo[a]azole, 2-(p-dimethylaminostyryl)benzo[a]thiazole, 2-mercaptobenzo[a]thiazole, 3,3'-carbonylbis(7-diethylaminocoumarin), 2-(o-chlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole, 2,2'-bis(2-chlorophenyl)-4,4 ',5,5'-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-dimethylaminopropyl)carbazole, 3,6-bis(2-methyl-2-hydroxylinopropyl)-9-dodecylcarbazole, 1-hydroxycyclohexylphenyl ketone, bis(5-2,4-cyclopentadien-1-yl)-bis(2,6-Difluoro-3-(1H-pyrrolo-1-yl)-phenyl)titanium, 3,3',4,4'-tetra(tert-butylperoxycarbonyl)diphenyl ketone, 3,3',4,4'-tetra(tert-hexylperoxycarbonyl)diphenyl ketone, 3,3'-bis(methoxycarbonyl)-4,4'-bis(tert-butylperoxycarbonyl)diphenyl ketone, 3,4'-bis(methoxycarbonyl)-4,3'-bis(tert-butylperoxycarbonyl)diphenyl ketone, 4,4'-bis(methoxycarbonyl)-3,3'-bis(tert-butylperoxycarbonyl)diphenyl ketone, 2-(3-methyl-3H-benzothiazol-2-ylidene)-1-naphth-2-yl-ethyl ketone, 2-(3-methyl-1,3-benzothiazol-2(3H)-ylidene)-1-(2-benzoyl)ethyl ketone, etc. Free radical photopolymerization initiators can be used alone or in combination of two or more.

[0078] Free radical polymerization has no special limitations and can use emulsion polymerization, suspension polymerization, dispersion polymerization, precipitation polymerization, bulk polymerization, solution polymerization, etc. There are no special restrictions on the organic solvents used in free radical polymerization reactions, as long as the resulting polymer can be dissolved. Specific examples include N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N-methyl-ε-caprolactone, dimethyl sulfoxide, tetramethylurea, pyridine, dimethyl sulfoxide, hexamethylphosphatidine, γ-butyrolactone, isopropanol, methoxymethylpentanol, dipentene, ethylpentanone, methyl nonyl ketone, methyl ethyl ketone, methyl isopentanone, methyl isopropyl ketone, methyl cyrrolidone, ethyl cyrrolidone, and so on. Cyclothose acetate, ethyl cyclothose acetate, butyl carbitol, ethyl carbitol, ethylene glycol, ethylene glycol monoacetate, ethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether (butyl cyclothose), propylene glycol, propylene glycol monoacetate, propylene glycol monomethyl ether, propylene glycol mono-tert-butyl ether, diethylene glycol, diethylene glycol monoacetate, diethylene glycol dimethyl ether, dipropylene glycol monoacetate monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monoacetate monoethyl ether, di... Propylene 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, 1,4-dimethyl ether, n-hexane, n-pentane, n-octane, diethyl ether, cyclohexanone, ethyl acetate, propyl acetate, methyl lactate, ethyl lactate, etc. Methyl acetate, ethyl acetate, n-butyl acetate, propylene glycol monoethyl ether, methyl pyruvate, ethyl pyruvate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, 3-ethoxypropionic acid, 3-methoxypropionic acid, propyl 3-methoxypropionate, butyl 3-methoxypropionate, dimethyl ether, 4-hydroxy-4-methyl-2-pentanone, 3-methoxy-N,N-dimethylpropionic acid, 3-ethoxy-N,N-dimethylpropionic acid, 3-butoxy-N,N-Dimethylpropionylamine, benzene, xylene, toluene, ethylbenzene, isopropylbenzene, tert-butylbenzene, tetrahydrofuran, cyclohexane, 2-ethyl-1-hexanol, propyl pyruvate, butyl pyruvate, amyl pyruvate, hexyl pyruvate, 2-ethylhexyl pyruvate, methyl acetate, ethyl acetate, propyl acetate, butyl acetate, amyl acetate, hexyl acetate, 2-ethylhexyl acetate Ethylhexyl acetate, methyl acetate, ethyl acetate, propyl acetate, butyl acetate, pentyl acetate, hexyl acetate, 2-ethylhexyl acetate, dimethyl malonate, dimethyl succinate, dimethyl glutarate, dimethyl adipate, dimethyl phthalate, dimethyl maleate, diethyl malonate, diethyl succinate, diethyl glutarate, diethyl adipate, phthalic acid Diethyl phthalate, diethyl maleate, dipropyl malonate, dipropyl succinate, dipropyl glutarate, dipropyl adipate, dipropyl phthalate, dipropyl maleate, dibutyl malonate, dibutyl succinate, dibutyl glutarate, dibutyl adipate, dibutyl phthalate, dibutyl maleate, dibutyl malonate, dibutyl succinate, dibutyl glutarate, dibutyl adipate, dibutyl phthalate Dipentyl maleate, dihexyl malonate, dihexyl succinate, dihexyl glutarate, dihexyl adipate, dihexyl phthalate, dihexyl maleate, di-2-ethylhexyl malonate, 2-ethylhexyl succinate, 2-ethylhexyl glutarate, 2-ethylhexyl adipate, 2-ethylhexyl phthalate, 2-ethylhexyl maleate (these are also referred to as "specific organic solvents"), etc. These organic solvents can be used alone or in mixtures of two or more.

[0079] Furthermore, even solvents in which the generated polymer does not dissolve can be mixed with the aforementioned organic solvents for use within a range where the generated polymer will not precipitate. Furthermore, oxygen in organic solvents during free radical polymerization can hinder the polymerization reaction; therefore, it is better to degas organic solvents as much as possible before use. Furthermore, when the graft copolymer obtained by the above polymerization has dissolved in the reaction solution, the reaction solution can be directly used for the preparation of liquid crystal alignment agent, or the graft copolymer contained in the reaction solution can be isolated and used for the preparation of liquid crystal alignment agent. The polymerization temperature for free radical polymerization can be selected from any temperature between 30 and 150°C, with a preferred range of 50 to 100°C. Furthermore, the reaction can be carried out at any concentration, but if the concentration is too low, it becomes difficult to obtain high molecular weight polymers; if the concentration is too high, the viscosity of the reaction solution becomes too high, making uniform stirring difficult. Therefore, the monomer concentration is preferably 1 to 50% by mass, more preferably 5 to 40% by mass. The reaction can initially proceed at a high concentration, followed by the addition of an organic solvent.

[0080] In the above-mentioned free radical polymerization reaction, if the ratio of the free radical polymerization initiator is higher than that of the monomer, the molecular weight of the obtained polymer will decrease; if it is lower, the molecular weight of the obtained polymer will increase. Therefore, the ratio of the free radical initiator to the monomer to be polymerized should preferably be 0.1~10 mol%. Furthermore, various monomer components, solvents, initiators, etc., can also be added during polymerization.

[0081] The polymer generated from the reaction solution obtained by the above reaction can be recovered by precipitating it in a poor solvent, but this reprecipitation process is not necessary. Poor solvents for precipitation include methanol, acetone, hexane, heptane, butylceryl ketone, heptane, methyl ethyl ketone, methyl isobutyl ketone, ethanol, toluene, benzene, diethyl ether, methyl ethyl ether, and water. The polymer precipitated in the poor solvent can be recovered by filtration and dried at room temperature or under reduced pressure. Alternatively, if the recovered polymer is redissolved in an organic solvent and reprecipitated, repeating this operation 2-10 times can reduce impurities in the polymer. Poor solvents in this case include, for example, alcohols, ketones, and hydrocarbons. Using three or more of these poor solvents will result in higher purification efficiency, which is ideal.

[0082] The graft copolymer used in this invention, considering the strength of the obtained coating, the workability during coating formation, and the uniformity of the coating, has a weight average molecular weight of 2,000 to 5,000,000 as determined by GPC (Gel Permeation Chromatography), with 5,000 to 2,000,000 being even more ideal.

[0083] The graft copolymers of this invention comprise graft polymers that are compatible with liquid crystals and dry polymers that are incompatible with liquid crystals or become incompatible due to heat, etc., characterized in that they are randomly linked by free radical polymerization. This results in high sealing performance, solvent selectivity, and coatability.

[0084] To ensure the coating properties, sealing performance, film strength, and good weak anchoring characteristics of the weakly anchored liquid crystal alignment film, the ratio of dendritic polymers to dry polymers is also an important factor. For example, dendritic polymers play a crucial role in the weak anchoring characteristics, and increasing their proportion can impair film strength or hinder thermosetting. Therefore, an appropriate amount of dendritic polymers must be considered. On the other hand, the amount and molecular weight of dry polymers do not affect the weak anchoring characteristics (the impact is small). Therefore, to balance the aforementioned characteristics, the ratio of the number of monomer molecules (represented by formula (8)) of dendritic polymers to the number of macromonomer molecules (represented by formula (1)) used in the synthesis of dry polymers should be smaller (the introduction ratio). The ideal introduction ratio (macromonomer represented by formula (1) / monomer represented by formula (8)) is 0.1 / 99.9~50 / 50 (moles / moles), and more preferably 0.2 / 99.8~30 / 70 (moles / moles).

[0085] (Weakly anchored liquid crystal alignment agent) In the liquid crystal alignment agent containing graft copolymers of the present invention, the components constituting the alignment film can be a single component of the graft copolymer or a composite material. The composite components other than the graft copolymer can be monomers or polymers. When a polymer is selected as the composite component, multiple polymers can be mixed. Furthermore, the composite polymer can contain polymers such as polyamide, polyimide, polyamide ester, polyamide, polyester, polyurea, polyacrylate, and polyorganosiloxane, as well as silane coupling agents and other additives. Considering the improvement of electrical properties and reliability, it is ideal to use components different from the aforementioned graft copolymers, especially polyamide and polyimide. There are no particular restrictions on the composite ratio of the polymers combined with the graft copolymers; however, considering optical properties and processability, the ideal composite ratio (the proportion of the composite component to the total of the graft copolymer and the composite component) is 99% by mass or less, more preferably 70% by mass or less. There are also no particular restrictions on the amount of additives added. When selecting monomers as composite components, most monomers can be used in combination. Furthermore, it is ideal to use polyfunctional (meth)acrylates, polyfunctional epoxides, polyfunctional ethylenes, etc., which exhibit thermosetting properties. The use of thermogenic acid generators, thermogenic alkali generators, and thermogenic free radical generators is also possible. There are no particular restrictions on the composite ratio of monomers in graft copolymers; however, considering optical properties and processability, a composite ratio of 99% by mass or less is preferred, and more preferably 70% by mass or less.

[0086] When polyamides and polyimides are used as composite components, the diamines used in the synthesis of polyamides and polyimides can be listed below. 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, and 3,3'-dicarboxyl-4,4'-diaminobiphenyl. 3,3'-Difluoro-4,4'-diaminobiphenyl, 3,3'-bis(trifluoromethyl)-4,4'-diaminobiphenyl, 3,4'-diaminobiphenyl, 3,3'-diaminobiphenyl, 2,2'-diaminobiphenyl, 2,3'-diaminobiphenyl, 4,4'-diaminodiphenylmethane, 3,3'-diaminodiphenylmethane, 3,4'-diaminodiphenylmethane, 2,2'-diaminodiphenylmethane, 2,3'-diaminodiphenylmethane, 4,4'-diaminodiphenyl ether, 3,3'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 2,2'-diaminodiphenyl ether, 2,3'-diaminodiphenyl ether, 4,4'-sulfonyldiphenylamine, 3,3'-sulfonyl Dimethyl-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, N-methyl(2,2'-diaminodiphenyl)amine, N-methyl(2,3'-diaminodiphenyl)amine, 4,4'-Diaminodiphenyl ketone, 3,3'-Diaminodiphenyl ketone, 3,4'-Diaminodiphenyl ketone, 2,2'-Diaminodiphenyl ketone, 2,3'-Diaminodiphenyl ketone, 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-extrinsylphenylbis(methylene)]diphenylamine, 4,4'-[1,3-extrinsylphenylbis(methylene)]diphenylamine, 3,4'-[1,4-extrinsylphenylbis(methylene)]diphenylamine, 3,4'-[1,3-extrinsylphenylbis(methylene)]diphenylamine, 3,3'-[1,3-extrinsylphenylbis(methylene)]diphenylamine, 3,3'-[1,3-extrinsylphenylbis(methylene)]diphenylamine, 3,3'-[1,3-extrinsylphenylbis(methylene)]diphenylamine, Diphenylamine, 1,4-Phenylbenzenebis[(4-aminophenyl) ketone], 1,4-Phenylbenzenebis[(3-aminophenyl) ketone], 1,3-Phenylbenzenebis[(4-aminophenyl) ketone], 1,3-Phenylbenzenebis[(3-aminophenyl) ketone], 1,4-Phenylbenzenebis(4-aminobenzoate), 1,4-Phenylbenzenebis(3-aminobenzoate), 1,3-Phenylbenzenebis(4-aminobenzoate), 1,3-Phenylbenzenebis(3-aminobenzoate), bis(4-aminophenyl) terephthalate, bis(3-aminophenyl) terephthalate, bis(4-aminophenyl) isophthalate, bis(3-aminophenyl) isophthalate, N,N'-(1,4-Phenylbenzene)bis(4-aminophenyl) Benzylamine), N,N'-(1,3-epenylphenyl)bis(4-aminobenzoylamine), N,N'-(1,4-epenylphenyl)bis(3-aminobenzoylamine), N,N'-(1,3-epenylphenyl)bis(3-aminobenzoylamine), N,N'-bis(4-aminophenyl)terephthalamide, N,N'-bis(3-aminophenyl)terephthalamide Amines, N,N'-bis(4-aminophenyl)m-phenylenediamine, N,N'-bis(3-aminophenyl)m-phenylenediamine, 9,10-bis(4-aminophenyl)anthracene, 4,4'-bis(4-aminophenoxy)diphenylamine, 2,2'-bis[4-(4-aminophenoxy)phenyl]propane, 2,2'-bis[4-(4-aminophenoxy)phenyl]propane Hexafluoropropane, 2,2'-bis(4-aminophenyl)hexafluoropropane, 2,2'-bis(3-aminophenyl)hexafluoropropane, 2,2'-bis(3-amino-4-methylphenyl)hexafluoropropane, 2,2'-bis(4-aminophenyl)propane, 2,2'-bis(3-aminophenyl)propane, 2,2'-bis(3-amino-4-methylphenyl)propane, trans-1,4-bis(4-aminophenyl)cyclohexane, 3,5-diaminobenzoic acid, 2,5-diaminobenzoic acid, bis(4-aminophenoxy)methane, 1,2-bis(4-aminophenoxy)ethane, 1,3-bis(4-aminophenoxy)propane, 1,3-bis(3-aminophenoxy)propane, 1,4-bis(4-aminophenoxy)butane, 1,4-bis(3-aminophenoxy)butane, 1,5-bis(4-aminophenoxy)pentane, 1,5-bis(3-aminophenoxy)pentane, 1,6-bis(4-aminophenoxy)hexane, 1,6-bis(3-aminophenoxy)hexane, 1,7-bis(4-aminophenoxy)heptane, 1,7-bis(3-aminophenoxy)heptane, 1,8-bis(4-aminophenoxy)octane, 1,8-bis(3-aminophenoxy)octane, 1,9- Aromatic diamines such as bis(4-aminophenoxy)nonane, 1,9-bis(3-aminophenoxy)nonane, 1,10-bis(4-aminophenoxy)decane, 1,10-bis(3-aminophenoxy)decane, 1,11-bis(4-aminophenoxy)undecane, 1,11-bis(3-aminophenoxy)undecane, 1,12-bis(4-aminophenoxy)dodecane, and 1,12-bis(3-aminophenoxy)dodecane; bis(4-aminocyclohexane) Alicyclic diamines such as bis(4-amino-3-methylcyclohexyl)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; 1,3-bis[2-(p-aminophenyl)] Diamines with a urea structure include ethyl urea and 1,3-bis[2-(p-aminophenyl)ethyl]-1-tert-butoxycarbonylurea; diamines with a nitrogen-containing unsaturated heterocyclic structure include N-p-aminophenyl-4-p-aminophenyl(tert-butoxycarbonyl)aminomethylpiperidine; and diamines with an N-Boc group (Boc represents tert-butoxycarbonyl) include N-tert-butoxycarbonyl-N-(2-(4-aminophenyl)ethyl)-N-(4-aminobenzyl)amine.

[0087] The above-mentioned diamines can be used in combination, either one or two or more. There are no particular limitations on the tetracarboxylic acid dianhydrides that react with the aforementioned diamine components. Specifically, examples include benzopyrene, 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'-diphenylketonetetracarboxylic acid, bis(3,4-dicarboxyphenyl) arsenate, 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. 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'-diphenyltristyrenetetracarboxylic acid, 3,4,9,10-perylenetetracarboxylic acid, 1,3-diphenyl-1,2,3,4-cyclobutanetetracarboxylic acid, oxydiphthaloyltetracarboxylic acid, 1,2,3,4-cyclobutanetetracarboxylic acid, 1,2,3,4-cyclopentanetetracarboxylic acid, 1,2,4,5-cyclohexanetetracarboxylic acid, 1,2,3,4-tetramethyl-1,2,3,4-cyclobutanetetracarboxylic acid, 1,2-dimethyl-1,2,3,4-cyclobutanetetracarboxylic acid Alkanetetracarboxylic 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] [0<2,6>] Undecane-3,5,9,11-tetracarboxylic acid, 1,2,3,4-butanetetracarboxylic acid, 4-(2,5-dioxytetrahydrofuran-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-dioxytetrahydrofuranyl)-3-methyl-3-cyclohexane-1,2-dicarboxylic acid, tetracyclo[6.2.1.1.0<2,7>] dodecacarbon-4,5,9,10-tetracarboxylic acid, 3,5,6-tricarboxylated norbornene-2:3,5:6 dicarboxylic acid, 1,2,4,5-cyclohexanetetracarboxylic acid, etc., are dianhydrides of tetracarboxylic acids.

[0088] Of course, one type of tetracarboxylic dianhydride or two or more types can be used together.

[0089] When the polymer is a polyamide ester, the synthesis is not particularly limited as long as the structure of the tetracarboxylic acid dialkyl ester that reacts with the above-mentioned diamine component is not particularly limited. Specific examples can be listed below. Specific examples of aliphatic tetracarboxylic acid diesters include 1,2,3,4-cyclobutanetetracarboxylic acid diester, 1,2-dimethyl-1,2,3,4-cyclobutanetetracarboxylic acid diester, 1,3-dimethyl-1,2,3,4-cyclobutanetetracarboxylic acid diester, 1,2,3,4-tetramethyl-1,2,3,4-cyclobutanetetracarboxylic acid diester, 1,2,3,4-cyclopentanetetracarboxylic acid diester, 2,3,4,5-tetrahydrofurantetracarboxylic acid diester, 1,2,4,5-cyclohexanetetracarboxylic acid diester, 3,4-dicarboxy-1-cyclohexylsuccinate diester, 3,4-dicarboxy-1,2,3,4-tetrahydro-1-naphthylsuccinate diester, 1,2,3,4-butanetetracarboxylic acid diester, and bicyclo[3.3.0]octane- Dialkyl 2,4,6,8-tetracarboxylate, dialkyl 3,3',4,4'-dicyclohexyltetracarboxylate, dialkyl 2,3,5-tricarboxylated cyclopentylacetate, dialkyl cis-3,7-dibutylcyclooctyl-1,5-diene-1,2,5,6-tetracarboxylate, tricyclo[4.2.1.0<2,5>]nonane-3,4,7,8-tetracarboxylate-3,4:7,8-dialkyl ester, tert-cyclo[6.6.0.1<2,7>.0<3,6>.1<9,14>.0<10,13>]hexadecane-4,5,11,12-tetracarboxylate-4,5:11,12-dialkyl ester, 4-(2,5-di-side-oxytetrahydrofuran-3-yl)-1,2,3,4-tetrahydronaphthalene-1,2-dicarboxylate, etc.

[0090] Aromatic tetracarboxylic acid dialkyl esters include benzopyrene dialkyl ester, 3,3',4,4'-biphenyltetracarboxylic acid dialkyl ester, 2,2',3,3'-biphenyltetracarboxylic acid dialkyl ester, 2,3,3',4-biphenyltetracarboxylic acid dialkyl ester, 3,3',4,4'-diphenylketone tetracarboxylic acid dialkyl ester, 2,3,3',4'-diphenylketone tetracarboxylic acid dialkyl ester, bis(3,4-dicarboxyphenyl) ether dialkyl ester, bis(3,4-dicarboxyphenyl) guanidine dialkyl ester, 1,2,5,6-naphthalenetetracarboxylic acid dialkyl ester, and 2,3,6,7-naphthalenetetracarboxylic acid dialkyl ester, etc.

[0091] In the synthesis of polyurea as the polymer of the composite component, there are no special restrictions on the diisocyanate reacting with the above-mentioned diamine component, and it can be used depending on availability, etc. The specific structure of the diisocyanate is shown below. [Chemistry 42] In the formula, R2 and R3 represent aliphatic hydrocarbon groups with 1 to 10 carbon atoms.

[0092] For example, aliphatic diisocyanates represented by formulas (K-1) to (K-5) have poor reactivity but improve solvent solubility. Aromatic diisocyanates represented by formulas (K-6) to (K-13) are highly reactive and improve heat resistance, but decrease solvent solubility. In terms of versatility and specific properties, formulas (K-1), (K-7), (K-8), (K-9), and (K-10) are more ideal. From an electrical property perspective, formula (K-12) is better, and from a liquid crystal alignment perspective, formula (K-13) is better. Two or more diisocyanates can also be used in combination; it is best to use various diisocyanates depending on the desired properties.

[0093] Alternatively, a portion of the diisocyanate can be replaced with the tetracarboxylic dianhydride described above, or it can be used in the form of a copolymer of polyamide and polyurea, or it can be used in the form of a copolymer of polyimide and polyurea by chemical imidization.

[0094] In the synthesis of polyamide as a composite component, the structure of the dicarboxylic acid to be reacted is not particularly limited. Specific examples are listed below.

[0095] Aliphatic dicarboxylic acids include malonic acid, oxalic acid, dimethylmalonic acid, succinic acid, fumaric acid, glutaric acid, adipic acid, mucoconic acid, 2-methyl adipic acid, trimethyl adipic acid, pimelic acid, 2,2-dimethylglutaric acid, 3,3-diethylsuccinic acid, azelaic acid, sebacic acid, and octanoic acid. 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, and 1,2-cyclohexanedicarboxylic acid. Dicarboxylic acids, 1,3-cyclohexanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, 1,4-(2-norcamphene)dicarboxylic acid, norcamphene-2,3-dicarboxylic acid, bicyclo[2.2.2]octane-1,4-dicarboxylic acid, bicyclo[2.2.2]octane-2,3-dicarboxylic acid, 2,5-dioxy-1,4-bicyclo[2.2.2]octanedicarboxylic acid, 1,3-adamantanedicarboxylic acid, 4,8-dioxy-1,3-adamantanedicarboxylic acid, 2,6-spiro[3.3]heptanedicarboxylic acid, 1,3-adamantanediacetic acid, camphoric acid, etc. 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'-biphenyl dicarboxylic acid, 1,5-biphenyl dicarboxylic acid, 4,4'-triphenyl dicarboxylic acid, 4,4'-diphenylmethane dicarboxylic acid, 4,4'-diphenylethane dicarboxylic acid, 4,4'-diphenylpropane dicarboxylic acid, and 4,4'-diphenylhexafluorodicarboxylic acid. Propane dicarboxylic acid, 4,4'-diphenyl ether dicarboxylic acid, 4,4'-bibenzyl dicarboxylic acid, 4,4'-stilbene dicarboxylic acid, 4,4'-diphenylacetyl dicarboxylic acid, 4,4'-carbonyl dibenzoic acid, 4,4'-sulfonyl dibenzoic acid, 4,4'-dithiodibenzoic acid, p-phenylenediacetic acid, 3,3'-p-phenylenediacetic acid, 4-carboxycinnamic acid, p-phenylenediacrylic acid, 3,3'-[4,4'-(methylene di-p-phenyl)]dipropionic acid, 4,4'-[4,4'-(oxy di-p-phenyl)]dipropionic acid, 4,4'-[4,4'-(oxy di-p-phenyl)]dibutyric acid, (isopropylidene di-p-phenylenediamine)dibutyric acid, bis(p-carboxyphenyl)dimethylsilane, and other dicarboxylic acids. Examples of heterocyclic dicarboxylic acids include 1,5-(9-sideoxygenase)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-diazole-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.

[0096] The aforementioned dicarboxylic acids can also have acetic acid dihalides or anhydrides. Among these dicarboxylic acids, those that can be given a linear structure, such as polyamide dicarboxylic acids, are particularly ideal in maintaining the orientation of liquid crystal molecules. Among these, terephthalic acid, isophthalic acid, 1,4-cyclohexanedicarboxylic acid, 4,4'-biphenyldicarboxylic acid, 4,4'-diphenylmethanedicarboxylic acid, 4,4'-diphenylethanedicarboxylic acid, 4,4'-diphenylpropanedicarboxylic acid, 4,4'-diphenylhexafluoropropanedicarboxylic acid, 2,2-bis(phenyl)propanedicarboxylic acid, 4,4'-triphenyl dicarboxylic acid, 2,6-naphthalenedicarboxylic acid, 2,5-pyridinedicarboxylic acid, or these acetic acid dihalides are preferred. These compounds may also have isomers, or mixtures containing them may be used. Furthermore, two or more compounds may be used in combination. The dicarboxylic acids used in this invention are not limited to the compounds illustrated above.

[0097] Polyamides, polyamide esters, polyureas, and polyamides can be obtained by reacting a diamine (also referred to as "diamine component") with a component selected from tetracarboxylic dianhydride (also referred to as "tetracarboxylic dianhydride component"), tetracarboxylic acid diester, diisocyanate, and dicarboxylic acid. Generally, a method is used to react the diamine component with one or more components selected from tetracarboxylic dianhydride component, tetracarboxylic acid diester, diisocyanate, and dicarboxylic acid in an organic solvent.

[0098] Ideally, a polyacrylate as a component of a composite material is a graft copolymer polyacrylate other than those described above. For example, a polymer obtained by polymerizing industrially available monomers capable of free radical polymerization using a common free radical generator.

[0099] Industrially available monomers that can undergo free radical polymerization include unsaturated carboxylic acids, acrylate compounds, methacrylate compounds, maleimide compounds, acrylonitrile, maleic anhydride, styrene compounds, and vinyl compounds.

[0100] Specific examples of unsaturated carboxylic acids include acrylic acid, methacrylic acid, itaconic acid, maleic acid, and fumaric acid.

[0101] Acrylic ester compounds, such as methyl acrylate, ethyl acrylate, isopropyl acrylate, benzyl acrylate, naphthyl acrylate, anthracene acrylate, anthracene methacrylate, phenyl acrylate, 2,2,2-trifluoroethyl acrylate, tributyl acrylate, cyclohexyl acrylate, isocamphene acrylate, 2-methoxyethyl acrylate, methoxytriethylene glycol acrylate, 2-ethoxyethyl acrylate, tetrahydrofuran methyl acrylate, 3-methoxybutyl acrylate, 2-methyl-2-adamantane acrylate, 2-propyl-2-adamantane acrylate, 8-methyl-8-tricyclodecyl acrylate, and 8-ethyl-8-tricyclodecyl acrylate, etc. Glycol acrylate, (3-methyl-3-epoxypropane) methyl acrylate, and (3-ethyl-3-epoxypropane) methyl acrylate, which have cyclic ether groups, may also be used.

[0102] Methacrylate compounds, such as methyl methacrylate, ethyl methacrylate, isopropyl methacrylate, benzyl methacrylate, naphthyl methacrylate, anthracene methacrylate, anthraceneyl methacrylate, phenyl methacrylate, 2,2,2-trifluoroethyl methacrylate, tributyl methacrylate, cyclohexyl methacrylate, isocamphenyl methacrylate, 2-methoxyethyl methacrylate, methoxytriethylene glycol methacrylate, 2-ethoxyethyl methacrylate, tetrahydrofuran methyl methacrylate, 3-methoxybutyl methacrylate, 2-methyl-2-adamantane methacrylate, 2-propyl-2-adamantane methacrylate, 8-methyl-8-tricyclodecyl methacrylate, and 8-ethyl-8-tricyclodecyl methacrylate, etc. Glycol methacrylate, (3-methyl-3-epoxypropane) methyl methacrylate, and (3-ethyl-3-epoxypropane) methyl methacrylate, which have cyclic ether groups, may also be used.

[0103] Vinyl compounds, such as vinyl ethers, methyl vinyl ethers, benzyl vinyl ethers, 2-hydroxyethyl vinyl ethers, phenyl vinyl ethers, and propyl vinyl ethers.

[0104] Styrene compounds, such as styrene, methylstyrene, chlorostyrene, bromostyrene, etc.

[0105] Maleimine compounds, such as maleimine, N-methylmaleimine, N-phenylmaleimine, and N-cyclohexylmaleimine.

[0106] In addition to the monomers that can be polymerized by free radicals and are available in industry, side-chain polymers with monomers having liquid crystal side-chain structures (hereinafter referred to as liquid crystal side-chain monomers) and photosensitive monomers with photosensitive groups (hereinafter referred to as photoreactive side-chain monomers) can also be used.

[0107] Liquid crystal side chain monomers refer to monomers from which polymers exhibit liquid crystal properties and which can form liquid crystal primordia at the side chain sites. More specific examples of liquid crystal side chain monomers are preferably those consisting of a polymerizable group composed of at least one of the group consisting of a free radical polymerizable group selected from hydrocarbons, (meth)acrylates, itaconic acid esters, fumarates, maleates, α-methylene-γ-butyrolactone, styrene, vinyl groups, maleimide, norcamphene, and a side chain having at least one liquid crystal atom.

[0108] For the liquid crystal side chain monomer, it is preferable to use monomers selected from formulas (LS-1) to (LS-13) whose liquid crystal side chains are bonded to a polymerizable group that can be polymerized on a free radical basis. Examples of polymerizable groups that can be polymerized on a free radical basis include polymerizable unsaturated hydrocarbon groups as illustrated in the description of the graft copolymer of the present invention. [Chemistry 43] [Chemistry 44] In formulas (LS-1) to (LS-13), A1 and A2 independently represent single bonds, -O-, -CH2-, -C(=O)-O-, -OC(=O)-, -C(=O)NH-, -NHC(=O)-, -CH=CH-C(=O)O-, or -OC(=O)-CH=CH-; R11 represents -NO2, -CN, halogen atoms, phenyl, naphthyl, biphenyl, furanyl, monovalent nitrogen-containing heterocyclic group, monovalent alicyclic hydrocarbon group with 5 to 8 carbons, alkyl group with 1 to 12 carbons, or alkoxy group with 1 to 12 carbons; R12 represents a group selected from the group consisting of phenyl, naphthyl, biphenyl, furanyl, monovalent nitrogen-containing heterocyclic group, monovalent alicyclic hydrocarbon group with 5 to 8 carbons, and groups obtained by combining them; R11 and R In R12, the hydrogen atoms bonded to them can also be replaced by -NO2, -CN, halogen atoms, alkyl groups with 1 to 5 carbon atoms, or alkoxy groups with 1 to 5 carbon atoms. R13 represents hydrogen atoms, -NO2, -CN, or -CH=C(CN). 2. -CH=CH-CN, halogen atom, phenyl, naphthyl, biphenyl, furanyl, monovalent nitrogen-containing heterocyclic group, monovalent alicyclic hydrocarbon group with 5-8 carbon atoms, alkyl group with 1-12 carbon atoms, or alkoxy group with 1-12 carbon atoms; E represents -C(=O)O- or -OC(=O)-; d represents an integer from 1 to 12; k1-k5 are each an integer from 0 to 2, but the sum of k1-k5 in each formula is 2 or more; k6 and k7 are each an integer from 0 to 2, but the sum of k6 and k7 in each formula is 1 or more; m1, m2, and m3 are each an integer from 1 to 3; n is 0 or 1; Z1 and Z2 each independently represent a single bond, -C(=O)-, -CH2O-, -CH=N-, or -CF2-. A dashed line represents an atomic bond.

[0109] In photoreactive side-chain monomers, the photosensitive side chain is bonded to the main chain. The photoreactive side-chain monomer system contains monomers with side chains that can undergo cross-linking, isomerization, or photofries rearrangement in response to light. The structure of the photosensitive side chain is not particularly limited, but it is preferable to have a structure that induces cross-linking or photofries rearrangement in response to light; a structure that induces cross-linking is preferred. In this case, even when exposed to external pressures such as heat, the achieved alignment control can be maintained stably for a long period. The structure of the photosensitive side-chain acrylic polymer exhibiting liquid crystal properties is not particularly limited as long as it meets these characteristics; however, a rigid liquid crystal component in the side chain structure is preferred.

[0110] The structure of the acrylic polymer can be, for example, the following: having a main chain and side chains bonded to the main chain, wherein the side chains have liquid crystal precursor components such as biphenyl, terphenyl, phenylcyclohexyl, phenylbenzoate, azophenyl, etc., and photosensitive groups bonded to the front end for photosensitive crosslinking and isomerization reactions; or having a main chain and side chains bonded to the main chain, wherein the side chains also become liquid crystal precursor components, and have phenylbenzoate groups for photoFries rearrangement reactions.

[0111] A more specific example of a side-chain acrylic polymer structure that exhibits liquid crystal-like photosensitive properties within a predetermined temperature range is preferably a main chain composed of at least one of the following groups of free radical polymerizable groups: hydrocarbon, (meth)acrylate, itaconic acid, fumarate, maleate, α-methylene-γ-butyrolactone, styrene, vinyl, maleimide, norcamphene, etc., and a side chain composed of at least one of the following formulas (31) to (35). [Chemistry 45] In the formula, Ar1 and Ar2 each independently represent a divalent organic group that has removed two hydrogen atoms from a benzene ring, naphthalene ring, pyrrole ring, furan ring, thiophene ring, or pyridine ring. One of q1 and q2 is 1, and the other is 0. Y1-Y2 represent CH=CH, CH=N, N=CH, or CC (except for carbon-carbon bonds, which are parametric bonds). S1 and S2 each independently represent a single bond, a linear or branched alkyl group having 1 to 18 carbon atoms, a cycloalkyl group having 5 to 8 carbon atoms, an alkylene group or an alkyl-binding group, or a bond selected from single bonds, ether bonds, ester bonds, amide bonds, urea bonds, carbamate bonds, -NR- (R represents a hydrogen atom or an alkyl group having 1 to 18 carbon atoms), and carbonyl groups, or combinations thereof, or a structure in which 2 to 10 sites selected from linear or branched alkyl groups having 1 to 18 carbon atoms, cycloalkyl groups having 5 to 8 carbon atoms, alkylene groups, alkyl-binding groups, or combinations thereof are linked together, with Ar1 and Ar2 linked together in multiples, separated by the aforementioned bonds. R represents a hydrogen atom, hydroxyl group, mercapto group, amino group, alkyl group with 1 to 10 carbon atoms, alkoxy group with 1 to 10 carbon atoms, alkylamino group with 1 to 8 carbon atoms, or dialkylamino group with 2 to 16 carbon atoms. The benzene ring and / or naphthyl ring in Ar 1, Ar 2, S 1, and S 2 may also be substituted by one or more substituents selected from halogen atoms, cyano, nitro, carboxyl, and alkoxycarbonyl groups having 2 to 11 carbon atoms, either the same or different. In this case, the alkyl group having 1 to 10 carbon atoms in the alkoxycarbonyl group having 2 to 11 carbon atoms may be linear, branched, cyclic, or a combination thereof, and the hydrogen atom in the alkyl group having 1 to 10 carbon atoms may also be substituted by a halogen atom.

[0112] There are no particular limitations on the manufacturing method of the aforementioned polyacrylates, and commonly used industrial methods can be employed. Specifically, cationic polymerization, free radical polymerization, and anionic polymerization of vinyl groups utilizing liquid crystal side-chain monomers or photoreactive side-chain monomers can be used. Among these, free radical polymerization is particularly preferred considering the ease of reaction control.

[0113] The polymerization initiators for free radical polymerization can be well-known free radical polymerization initiators such as AIBN (azobisisobutyronitrile), and well-known compounds such as reversible addition-crack chain transfer (RAFT) polymerization reagents.

[0114] Free radical polymerization has no special limitations and can use emulsion polymerization, suspension polymerization, dispersion polymerization, precipitation polymerization, bulk polymerization, solution polymerization, etc.

[0115] The organic solvent used in the polymerization reaction of photosensitive side-chain acrylic polymers that exhibit liquid crystal properties within a predetermined temperature range is not particularly limited as long as the resulting polymer can dissolve. Specific examples are listed below. N,N-Dimethylformamide, N,N-Dimethylacetamide, N-Methyl-2-pyrrolidone, N-Ethyl-2-pyrrolidone, N-Methyl-ε-caprolactam, Dimethyl sulfoxide, Tetramethylurea, Pyridine, Dimethyl sulfoxide, Hexamethylphosphatamide, γ-Butyrolactone, Isopropanol, Methoxymethylpentanol, Dipentene, Ethylpentanone, Methyl nonyl ketone, Methyl ethyl ketone, Methyl isopentanone, Methyl isopropyl ketone, Methyl cyrrolidone, Ethyl cyrrolidone, Methyl cyrrolidone acetic acid Ester, Ethyl ceroxose acetate, Butyl carbitol, Ethyl carbitol, Ethyl glycol, Ethyl glycol monoacetate, Ethyl glycol monoisopropyl ether, Ethyl glycol monobutyl ether, Propylene glycol, Propylene glycol monoacetate, Propylene glycol monomethyl ether, Propylene glycol-tert-butyl ether, Diethylene glycol, Diethylene glycol monoacetate, Diethylene glycol dimethyl 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 monoethyl ether Monopropyl ester 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, 1,4-dimethyl ether, n-hexane, n-pentane, n-octane, diethyl ether, cyclohexanone, ethyl acetate, propyl acetate, methyl lactate, ethyl lactate, methyl acetate, ethyl acetate, n-butyl acetate Ester, propylene glycol monoethyl ether, methyl pyruvate, ethyl pyruvate, methyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-methoxypropionate, 3-ethoxypropionic acid, 3-methoxypropionic acid, propyl 3-methoxypropionate, butyl 3-methoxypropionate, dimethyl ether, 4-hydroxy-4-methyl-2-pentanone, 3-methoxy-N,N-dimethylpropionic acid, 3-ethoxy-N,N-dimethylpropionic acid, 3-butoxy-N,N-Dimethylpropionamide, propyl pyruvate, butyl pyruvate, amyl pyruvate, hexyl pyruvate, 2-ethylhexyl pyruvate, methyl acetate, ethyl acetate, propyl acetate, butyl acetate, amyl acetate, hexyl acetate, 2-ethylhexyl acetate, methyl acetate, ethyl acetate, propyl acetate, acetyl... Butyl propionate, pentyl acetate, hexyl acetate, 2-ethylhexyl acetate, dimethyl malonate, dimethyl succinate, dimethyl glutarate, dimethyl adipate, dimethyl phthalate, dimethyl maleate, diethyl malonate, diethyl succinate, diethyl glutarate, diethyl adipate, diethyl phthalate, diethyl maleate, malonic acid Dipropyl phthalate, dipropyl succinate, dipropyl glutarate, dipropyl adipate, dipropyl phthalate, dipropyl maleate, dibutyl malonate, dibutyl succinate, dibutyl glutarate, dibutyl adipate, dibutyl phthalate, dibutyl maleate, dipentyl malonate, dipentyl succinate, dipentyl glutarate, dipentyl adipate, dipentyl phthalate Dihexyl maleate, dihexyl malonate, dihexyl succinate, dihexyl glutarate, dihexyl adipate, dihexyl phthalate, dihexyl maleate, di-2-ethylhexyl malonate, 2-ethylhexyl succinate, 2-ethylhexyl glutarate, 2-ethylhexyl adipate, 2-ethylhexyl phthalate, 2-ethylhexyl maleate, etc. These organic solvents can be used alone or in combination. Furthermore, even solvents that do not dissolve the generated polymer can still be used in combination with the aforementioned organic solvents, provided that the generated polymer does not precipitate. Furthermore, in free radical polymerization, oxygen in the organic solvent can hinder the polymerization reaction. Therefore, it is better to use organic solvents that have been degassed as much as possible.

[0116] The polymerization temperature for free radical polymerization can be selected from any temperature between 30 and 150°C, preferably within the range of 50 to 100°C. Furthermore, the reaction can be carried out at any concentration, but if the concentration is too low, it becomes difficult to obtain a high molecular weight polymer; if the concentration is too high, the viscosity of the reaction liquid becomes too high, making uniform stirring difficult. Therefore, the monomer concentration is preferably 1 to 50% by mass, more preferably 5 to 30% by mass. The reaction can be carried out at a high concentration initially, followed by the addition of an organic solvent. In the above-mentioned free radical polymerization reaction, if the ratio of free radical polymerization initiator to monomer is too high, the molecular weight of the obtained polymer will decrease; if it is too low, the molecular weight of the obtained polymer will increase. Therefore, the ratio of free radical initiator to monomer is preferably 0.1~10 mol%. Furthermore, various monomer components, solvents, initiators, etc., can also be added during polymerization.

[0117] When recovering the polymer from a reaction solution containing a photosensitive side-chain polymer exhibiting liquid crystal properties obtained from the above reaction, the reaction solution can be added to a poor solvent to precipitate the polymer. Examples of poor solvents for precipitation include methanol, acetone, hexane, heptane, butylceryl ketone, heptane, methyl ethyl ketone, methyl isobutyl ketone, ethanol, toluene, benzene, diethyl ether, methyl ethyl ether, 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, or by heating. Furthermore, if the recovered precipitated polymer is dissolved in an organic solvent and reprecipitated, repeating this operation 2 to 10 times, impurities in the polymer can be reduced. Ideally, three or more poor solvents, such as alcohols, ketones, and hydrocarbons, should be selected to improve purification efficiency.

[0118] The molecular weight of a side-chain acrylic polymer exhibiting liquid crystal properties within a predetermined temperature range is ideal when considering the strength of the obtained coating, the workability during coating formation, and the uniformity of the coating. The weight-average molecular weight determined by GPC is 2,000 to 1,000,000, and 5,000 to 100,000 is even more ideal.

[0119] Organic solvents used in liquid crystal alignment agents include, for example: 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, N-methyl-ε-caprolactone, dimethyl sulfoxide, tetramethylurea, pyridine, dimethyl sulfoxide, hexamethylphosphatidylamine, γ-butyrolactone, isopropanol, methoxymethylpentanol, dipentene, ethylpentanone, methyl nonyl ketone, methyl ethyl ketone, methyl isopentanone, methyl Isopropyl ketone, methyl cerroxine, ethyl cerroxine, methyl cerroxine acetate, butyl cerroxine acetate, ethyl cerroxine acetate, butyl carbitol, ethyl carbitol, ethylene glycol, ethylene glycol monoacetate, ethylene glycol monoisopropyl ether (butyl cerroxine), ethylene glycol monobutyl ether, propylene glycol, propylene glycol monoacetate, propylene glycol monomethyl ether, propylene glycol monobutyl ether, propylene glycol-tert-butyl ether, propylene glycol monomethyl ether acetate, diethylene glycol, diethylene glycol monoacetate, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, dipropylene glycol monoacetate monomethyl ether, dipropylene glycol monomethyl ether, di... Propylene 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, 1,4-dimethylbenzene, n-hexane, n-pentane, n-octane, cyclohexane, 2-ethyl-1-hexanol, benzene, xylene, toluene, ethylbenzene, isopropylbenzene, tert-butylbenzene, tetrahydrofuran Diethyl ether, cyclohexanone, ethyl acetate, propyl acetate, methyl lactate, ethyl lactate, methyl acetate, ethyl acetate, n-butyl acetate, propylene glycol monoethyl ether, methyl pyruvate, ethyl pyruvate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, 3-ethoxypropionic acid, 3-methoxypropionic acid, propyl 3-methoxypropionate, butyl 3-methoxypropionate, dimethyl ether, 4-hydroxy-4-methyl-2-pentanone, 3-methoxy-N,N-dimethylpropionic acid, 3-ethoxy-N,N-dimethylpropionic acid, 3-butoxy-N,N-Dimethylpropionamide, propyl pyruvate, butyl pyruvate, amyl pyruvate, hexyl pyruvate, 2-ethylhexyl pyruvate, methyl acetate, ethyl acetate, propyl acetate, butyl acetate, amyl acetate, hexyl acetate, 2-ethylhexyl acetate, methyl acetate, ethyl acetate, propyl acetate, acetyl... Butyl propionate, pentyl acetate, hexyl acetate, 2-ethylhexyl acetate, dimethyl malonate, dimethyl succinate, dimethyl glutarate, dimethyl adipate, dimethyl phthalate, dimethyl maleate, diethyl malonate, diethyl succinate, diethyl glutarate, diethyl adipate, diethyl phthalate, diethyl maleate, malonic acid Dipropyl phthalate, dipropyl succinate, dipropyl glutarate, dipropyl adipate, dipropyl phthalate, dipropyl maleate, dibutyl malonate, dibutyl succinate, dibutyl glutarate, dibutyl adipate, dibutyl phthalate, dibutyl maleate, dipentyl malonate, dipentyl succinate, dipentyl glutarate, dipentyl adipate, dipentyl phthalate Di(2-ethylhexyl) maleate, di(2-ethylhexyl) malonate, di(2-ethylhexyl) succinate, di(2-ethylhexyl) glutarate, di(2-ethylhexyl) adipate, di(2-ethylhexyl) phthalate, di(2-ethylhexyl) maleate, di-2-ethylhexyl malonate, 2-ethylhexyl succinate, 2-ethylhexyl glutarate, 2-ethylhexyl adipate, 2-ethylhexyl phthalate, 2-ethylhexyl maleate, etc. These organic solvents can be used alone or in combination.

[0120] Furthermore, it is ideal to use a solvent that improves the uniformity and smoothness of the coating by mixing it with a highly soluble organic solvent.

[0121] Solvents that improve the uniformity and smoothness of the coating film include: isopropanol, methoxymethylpentanol, methyl ceroxythione, ethyl ceroxythione, methyl ceroxythione acetate, butyl ceroxythione acetate, ethyl ceroxythione acetate, butyl carbitol, ethyl carbitol, ethyl carbitol acetate, ethylene glycol, ethylene glycol monoacetate, ethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether (butyl ceroxythione), propylene glycol, propylene glycol monoacetate, propylene glycol monomethyl ether, propylene glycol monobutyl ether, propylene glycol tributyl ether, diethylene glycol, diethylene glycol monoacetate, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, dipropylene glycol monoacetate monomethyl ether, dipropylene 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, ethyl 3-methoxypropionate, 3-ethoxypropionic acid, 3-methoxypropionic acid, propyl 3-methoxypropionate, butyl 3-methoxypropionate, 1- Methoxy-2-propanol, 1-ethoxy-2-propanol, 1-butoxy-2-propanol, 1-phenoxy-2-propanol, propylene glycol diacetate, propylene glycol-1-monomethyl ether-2-acetate, propylene glycol-1-monoethyl ether-2-acetate, dipropylene glycol, 2-(2-ethoxypropoxy)propanol, 2-ethyl-1-hexanol, 3-methoxy-N,N-dimethylpropionic acid, 3-ethoxy-N,N-dimethylpropionic acid, 3-butoxy-N,N-dimethylpropionic acid, 2-ethyl-1,3-hexanediol, ethylene glycol, propylene glycol (1,2-propanediol), 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 2,3-butanediol, 1,4-butanediol, 1,2-pentanediol, 1,3-pentanediol Alcohols, 1,4-pentanediol, 1,5-pentanediol, 2-methyl-2,4-pentanediol, 1,2-hexanediol, 1,3-hexanediol, 1,4-hexanediol, 1,5-hexanediol, 1,6-hexanediol, 2,3-hexanediol, 2,4-hexanediol, 2,5-hexanediol, 3,5-hexanediol, 1,2-heptanediol, 1,3 -Heptanediol, 1,4-Heptanediol, 1,5-Heptanediol, 1,6-Heptanediol, 1,7-Heptanediol, 1,2-Octanediol, 1,4-Octanediol, 1,8-Octanediol, 1,2-Nonanediol, 1,3-Nonanediol, 1,5-Nonanediol, 1,6-Nonanediol, 1,9-Nonanediol, 1,2-Decanediol, 1,5-Decanediol, 1,8-Decanediol, 1,10-Decanediol, 1,2-Cyclohexanediol, 1,3-Cyclohexanediol, 1,4-Cyclohexanediol, Diethylene glycol, Dipropylene glycol, Dibutyl glycol, Glycerin, Methyl pyruvate, Ethyl pyruvate, Propyl pyruvate, Butyl pyruvate, Amyl pyruvate, Hexyl pyruvate, 2-Ethylhexyl pyruvate, Methyl acetoacetate, Ethyl acetoacetate, Propyl acetoacetate Ester, butyl acetate, amyl acetate, hexyl acetate, 2-ethylhexyl acetate, methyl acetate, ethyl acetate, propyl acetate, butyl acetate, amyl acetate, hexyl acetate, 2-ethylhexyl acetate, dimethyl malonate, dimethyl succinate, dimethyl glutarate, dimethyl adipate, dimethyl phthalate, dimethyl maleate, diethyl malonate, succinate Diethyl succinate, diethyl glutarate, diethyl adipate, diethyl phthalate, diethyl maleate, dipropyl malonate, dipropyl succinate, dipropyl glutarate, dipropyl adipate, dipropyl phthalate, dipropyl maleate, dibutyl malonate, dibutyl succinate, dibutyl glutarate, dibutyl adipate, dibutyl phthalate, dibutyl maleate, dipentyl malonate, dipentyl succinate, glutaric acid Dipentyl acetate, dipentyl adipate, dipentyl phthalate, dipentyl maleate, dihexyl malonate, dihexyl succinate, dihexyl glutarate, dihexyl adipate, dihexyl phthalate, dihexyl maleate, di-2-ethylhexyl malonate, 2-ethylhexyl succinate, 2-ethylhexyl glutarate, 2-ethylhexyl adipate, 2-ethylhexyl phthalate, 2-ethylhexyl maleate, etc. These solvents can also be mixed in various ways. When using these solvents, it is preferable that the total amount of solvent contained in the liquid crystal alignment agent is 5-80% by mass, more preferably 20-60% by mass.

[0122] The weakly anchored liquid crystal alignment agent of the present invention may also contain components other than those mentioned above. Examples include compounds that improve the film thickness uniformity and surface smoothness during coating of the components contained in the weakly anchored liquid crystal alignment agent, compounds that improve the adhesion between the components contained in the weakly anchored liquid crystal alignment agent and the substrate, and compounds that improve the film strength of the components contained in the weakly anchored liquid crystal alignment agent.

[0123] Compounds that improve film thickness uniformity and surface smoothness include fluorinated surfactants, polysiloxane 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, Surflon S-382, SC101, SC102, SC103, SC104, SC105, SC106 (manufactured by AGC Corporation). When using these surfactants, the preferred proportion is 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 polymer content in the composition of the weakly anchored liquid crystal alignment agent.

[0124] Specific examples of compounds that improve the adhesion between components of weakly anchored liquid crystal alignment agents 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-ureapropyltrimethoxysilane, 3-ureapropyltriethoxysilane, N-ethoxycarbonyl-3-aminopropyltrimethoxysilane, N-ethoxycarbonyl-3-aminopropyltrimethoxysilane, and N-ethoxycarbonyl-3-aminopropyltriethoxysilane. Oxysilanes, N-(3-triethoxysilyl)propyltriethylenetetramine, N-(3-trimethoxysilyl)propyltriethylenetetramine, 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 Silane, N-phenyl-3-aminopropyltrimethoxysilane, N-phenyl-3-aminopropyltriethoxysilane, N-bis(oxoethyl)-3-aminopropyltrimethoxysilane, N-bis(oxoethyl)-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-tetracyclooxypropyl-2,4-hexanediol, N,N,N',N'-tetracyclooxypropyl-methylenediamine, 1,3-bis(N,N-dicyclooxypropylaminomethyl)cyclohexane, N,N,N',N'-tetracyclooxypropyl-4,4'-diaminodiphenylmethane, 3-(N-allyl-N-epoxypropyl)aminopropyltrimethoxysilane, 3-(N,N-dicyclooxypropyl)aminopropyltrimethoxysilane, etc.

[0125] Furthermore, to further improve the film strength of the weakly anchored liquid crystal alignment film, 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 total amount of polymer contained in the weakly anchored liquid crystal alignment agent is preferably 0.1 to 30 parts by mass per 100 parts by mass, and more preferably 1 to 20 parts by mass. Furthermore, in addition to the above, the composition of the weakly anchored liquid crystal alignment agent may also include dielectrics and conductive substances that change the dielectric constant, conductivity, and other electrical properties of the weakly anchored liquid crystal alignment film, without compromising the effect of the present invention.

[0126] (Strong anchoring alignment film) A strong anchoring horizontal alignment film needs to be provided on the substrate opposite to the substrate with a weak anchoring alignment film. The strong anchoring horizontal alignment film mentioned here refers to a liquid crystal alignment film that can make the liquid crystals uniformly aligned in the horizontal direction and maintain the force of the aligned liquid crystals, that is, a liquid crystal alignment film with sufficiently strong interface anchoring energy. Strongly anchored horizontal alignment films can be obtained by aligning polyamide, polyimide, polyamide ester, polyamide, polyester, polyacrylate, etc., as described above, along a uniaxial direction using methods such as friction treatment and photoalignment treatment. Strongly anchored horizontal alignment films can be obtained by combining the monomers described above.

[0127] (Weakly anchored alignment film and strong anchored alignment film) The weakly anchored alignment film of the present invention can be obtained by using the aforementioned weakly anchored liquid crystal alignment agent. For example, after coating the weakly anchored liquid crystal alignment agent used in the present invention onto a substrate, it is dried and calcined to obtain a hardened film that can be directly used as a weakly anchored alignment film. Furthermore, this hardened film can be aligned by rubbing, irradiating with polarized light or light of a specific wavelength, or by using an ion beam, and the liquid crystal display element after liquid crystal filling can also be irradiated with UV light.

[0128] Similarly, a strongly anchored alignment film can be obtained by coating a strongly anchored liquid crystal alignment agent onto a substrate, drying and calcining it, and then performing alignment treatment on the resulting hardened film.

[0129] In this invention, the first substrate is a substrate with comb-tooth electrodes, and the second substrate may also be a counter substrate. Furthermore, in this invention, the second substrate is a substrate with comb-tooth electrodes, and the first substrate may also be a counter substrate. The substrate on which the liquid crystal alignment films are coated is not particularly limited if it is a substrate with high transparency, but it is preferable to have a substrate on which transparent electrodes for driving the liquid crystal are formed.

[0130] Specific examples include substrates for transparent electrodes formed from glass plates, polycarbonate, poly(meth)acrylate, polyether ether, polyarylate, polyurethane, polyether, polyetherketone, trimethylpentene, polyolefin, polyethylene terephthalate, (meth)acrylonitrile, triacetyl cellulose, diacetyl cellulose, ethyl butyrate cellulose, and other plastic sheets. The substrates that can be used for IPS liquid crystal display elements can also use standard IPS comb electrodes, PSA (Polymer-Stabilized Alignment) herringbone electrodes, and MVA (Multi-domain Vertical Alignment) protrusion patterns.

[0131] Furthermore, it can be used in high-performance components such as TFT (Thin-Film-Transistor) devices, where a transistor-like element is formed between the electrode for liquid crystal driving and the substrate.

[0132] When fabricating transmissive liquid crystal display elements, substrates as described above are generally used. However, when fabricating reflective liquid crystal display elements, if a single-sided substrate is desired, 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 light-reflective materials such as aluminum. Methods for applying weakly anchored liquid crystal alignment agents include spin coating, printing, inkjet coating, spray coating, and roller coating. However, from a production perspective, transfer printing is widely used in industry, and this invention can also be ideally used.

[0133] A drying step after coating the liquid crystal alignment agent is not necessary. However, if the time from coating to calcination is not fixed to the substrate, or if calcination is not performed immediately after coating, a drying step is preferable. This drying only needs to remove the solvent to a level that will not cause deformation of the coating shape due to substrate transportation, etc. There are no special restrictions on the drying method. Ideal conditions for the drying step include drying on a hot plate at a temperature of 40~150℃, more preferably 60~100℃ for 0.5~30 minutes, and more preferably 1~5 minutes. The calcination step is preferably performed when the block segments that are not compatible with the liquid crystal are composed of thermosetting compounds, at a temperature above their curing temperature and below the thermal decomposition temperature of the polymer. Ideal conditions for the calcination step include calcination on a hot plate or in a thermal circulating oven at a temperature of 80~250℃, more preferably 100~230℃ for 1~120 minutes, and more preferably 5~30 minutes.

[0134] The thickness of this curing film can be selected as needed, preferably 5nm or more, and even more preferably 10nm or more, as this improves the reliability of the liquid crystal display element. Furthermore, a thickness of 300nm or less, and even more preferably 150nm or less, prevents an extreme increase in the power consumption of the liquid crystal display element.

[0135] The above methods can be used to obtain a first substrate with a weakly anchored alignment film and a second substrate with a strongly anchored alignment film. Methods for uniaxial alignment processing include photo-alignment, oblique evaporation, tactile alignment, and uniaxial alignment processing using a magnetic field.

[0136] When performing alignment processing using unidirectional friction, for example, the substrate can be moved while rotating a friction roller wound with friction cloth, so that the friction cloth contacts the film. When using photoalignment, the film can be fully irradiated with polarized UV light of a specific wavelength, and heated as needed, to perform alignment processing. When forming the first substrate of the present invention with comb electrodes, the direction is selected according to the electrical properties of the liquid crystal. However, when using liquid crystal with positive dielectric anisotropy, it is preferable that the rubbing direction is approximately the same as the direction in which the comb electrodes extend.

[0137] [Liquid crystal cell] The liquid crystal cell of the present invention is obtained by the above-described method, by arranging a substrate (e.g., a first substrate) having a weakly anchored alignment film obtained using the liquid crystal alignment agent of the present invention, and a substrate (e.g., a second substrate) having a known strongly anchored liquid crystal alignment film, with the weakly anchored alignment film and the strongly anchored alignment film facing each other, sandwiching a spacer, fixing it with a sealant, and injecting liquid crystal to seal it. The size of the spacer used is typically 1~30 μm, preferably 2~10 μm. Furthermore, by arranging the friction direction of the first substrate parallel to the friction direction of the second substrate, it can be used in IPS and FFS systems; if arranged with the friction directions perpendicular, it can be used in TN systems. Furthermore, the IPS substrate, which is a comb-tooth electrode substrate used in the IPS method, has: a substrate, a plurality of linear electrodes formed on the substrate and arranged in a comb-tooth shape, and a liquid crystal alignment film formed on the substrate in such a way as to cover the linear electrodes. Furthermore, the FFS substrate for use in the FFS method comprises: a substrate, a surface electrode formed on the substrate, an insulating film formed on the surface electrode, a plurality of linear electrodes formed on the insulating film and arranged in a comb-like pattern, and a liquid crystal alignment film formed on the insulating film in such a way as to cover the linear electrodes.

[0138] (Liquid crystal display element) A liquid crystal display element, for example, comprises a first substrate, a second substrate disposed facing the first substrate, and liquid crystal filling the space between the first substrate and the second substrate. Furthermore, the liquid crystal display element is manufactured by coating the weakly anchored liquid crystal alignment agent of the present invention into a film and using a first substrate or a second substrate having a weakly anchored alignment film, and a second substrate or a first substrate having a strongly anchored horizontal alignment film. Liquid crystal display elements can be manufactured in various ways. For example, a reflective liquid crystal display element can be manufactured by incorporating reflective electrodes, transparent electrodes, a λ / 4 plate, a polarizing film, and a color filter layer into the liquid crystal cells as required by conventional methods. Conversely, a transmissive liquid crystal display element can be manufactured by incorporating backlight, a polarizing plate, a λ / 4 plate, a transparent electrode, a polarizing film, and a color filter layer into the liquid crystal cells as required by conventional methods.

[0139] Figure 1 is a schematic cross-sectional view showing an example of a transverse electric field liquid crystal display element of the present invention, and is an example of an IPS-type liquid crystal display element. In the transverse electric field liquid crystal display element 1 illustrated in Figure 1, liquid crystal 3 is sandwiched between a comb electrode substrate 2 having a liquid crystal alignment film 2c and a counter substrate 4 having a liquid crystal alignment film 4a. The comb 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 weakly anchored liquid crystal alignment film or a strongly anchored horizontal alignment film (liquid crystal alignment film 4a) formed on the substrate 4b. The liquid crystal alignment film 2c, for example, is the weakly anchored alignment film or the strongly anchored horizontal alignment film of the present invention. The liquid crystal alignment films on the counter substrates are fabricated as a combination of strongly anchored alignment films and weakly anchored liquid crystal alignment films. In this transverse electric field liquid crystal display element 1, if a voltage is applied to the linear electrode 2b, an electric field will be generated between the linear electrodes 2b as shown by the electric field line L.

[0140] Figure 2 is a schematic cross-sectional view showing another example of the transverse electric field liquid crystal display element of the present invention, which is an example of an FFS liquid crystal display element. In the transverse electric field liquid crystal display element 1 illustrated in Figure 2, liquid crystal 3 is sandwiched between a comb electrode substrate 2 having a liquid crystal alignment film 2h and a counter substrate 4 having a liquid crystal alignment film 4a. The comb electrode substrate 2 includes: 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 arranged in a comb-like pattern on the insulating film 2f, and a liquid crystal alignment film 2h formed on the insulating film 2f in such a way as to cover the linear electrodes 2g. 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 4a is the same as the liquid crystal alignment film 4a in Figure 1 described above. The liquid crystal alignment film 2h is the same as the liquid crystal alignment film 2c in Figure 1 described above. If a voltage is applied to the surface electrode 2e and the linear electrode 2g of this transverse electric field liquid crystal display element 1, an electric field will be generated between the surface electrode 2e and the linear electrode 2g, as shown by the electric field line L. [Example]

[0141] The following examples illustrate the present invention in detail, but the invention is not limited to these examples. The abbreviations of the compounds and the methods for determining their properties are as follows.

[0142] (giant unit) The giant monomer (A-1) was synthesized and used in accordance with the following references. 1) Ito, K., Usami, N., Yamashita, Y.: Macromolecules, 13, 216 (1980). 2) Tsukahara, Y., Nakanishi, Y., Yamashita, Y., Ohtani,Y., Nakashima, Y., Luo, YF, Ando, ​​T., Tsuge, S.: Macromolecules, 24, 2493 (1991). 3) Tsukahara, Y., Katsuji, I., HAS-CHUAN, T., Yuya, Y.: J. Polym. Sci.: Part A: Polym. Chem., 27, 1099(1989).

[0143] (Free radical polymerizable monomers) [Chemistry 46]

[0144] (RAFT agent) [Chemistry 47]

[0145] (Chain transfer agent) [Chemistry 48]

[0146] (Thermal polymerization initiator) [Chemistry 49]

[0147] (Diamine) [Transformation 50]

[0148] (Tetracarboxylic acid dianhydride) [Chemistry 51]

[0149] (additive) [Chemistry 52]

[0150] (solvent) THF: Tetrahydrofuran NMP: N-methyl-2-pyrrolidone BCS: Dingji Sailusu PGMEA: Propylene Glycol Monomethyl Ether Acetate

[0151] (Viscosity Measurement) The viscosity of polyamide solutions, etc., was measured using a TVE-22H E-type viscometer (manufactured by Toki Sangyo Co., Ltd.), with a sample volume of 1.1 mL, using a conical rotor TE-1 (1°34', R24), at a temperature of 25°C.

[0152] (Determination of molecular weight) The molecular weights of polyimide precursors and other synthesized polymers were determined using a room-temperature gel permeation chromatography (GPC) apparatus (CBM-20A) (manufactured by Shimadzu Corporation) and a column (Shodex KF-804L and KF-803L in series) (manufactured by Showa Denko Corporation) in the following manner. Column temperature: 40℃ Dissolution solution: Tetrahydrofuran Flow rate: 1.0 mL / min Standard samples for making the calibration curve: Standard polystyrene (molecular weight: 197,000, 55,100, 12,800, 3,950, 1,260) (manufactured by Tosoh Corporation)

[0153] The molecular weights of the polyimide precursor and polyimide were determined using a room-temperature gel permeation chromatography (GPC) apparatus (GPC-101) (manufactured by Showa Denko Corporation) and a column (GPC KD-803 and GPC KD-805 in series) (manufactured by Showa Denko Corporation) in the following manner. Column temperature: 50℃ Dissolution solution: N,N-dimethylformamide (additives: lithium bromide monohydrate (LiBr·H₂O) 30 mmol / L, anhydrous phosphoric acid crystals (orthophosphoric acid) 30 mmol / L, tetrahydrofuran (THF) 10 mL / L) Flow rate: 1.0 mL / min Standard samples for the preparation of the calibration curve: TSK standard polyethylene oxide (molecular weight; about 900,000, 150,000, 100,000 and 30,000) (manufactured by Tosoh Corporation) and polyethylene glycol (molecular weight; about 12,000, 4,000 and 1,000) (manufactured by Polymer Laboratory Corporation).

[0154] (Determination of acetylation rate) 20 mg of polyimide powder was placed in an NMR sample tube (NMR standard sampling tube, φ5 (manufactured by Kusano Science Co., Ltd.)), and 1.0 mL of deuterated dimethyl monoxide (a mixture of [D6]-DMSO and 0.05% tetramethylsilane (TMS)) was added. The solution was then dissolved completely by ultrasound. Proton NMR of this solution was measured at 500 MHz using a Fourier transform superconducting nuclear magnetic resonance (FT-NMR) device, "AVANCE III" (manufactured by BRUKER Co., Ltd.). The chemiimidization rate is determined using a proton from a structure that remains unchanged before and after chemiimidization as a reference proton. The cumulative peak value of this proton, along with the cumulative peak value of protons from the NH group of acetic acid appearing around 9.5–10.0 ppm, is calculated using the following formula. In the formula, X represents the cumulative peak value of protons from the NH group of acetic acid, Y represents the cumulative peak value of the reference proton, and A represents the ratio of the number of reference protons to one proton from the NH group of acetic acid when the polyacetic acid (chemiimidization rate is 0%). Acrylimide rate (%) = (1 - A·X / Y) × 100

[0155] <Synthesis of Mega-Single> (Synthesis example 1) In a 100 ml round-bottom flask equipped with a stir bar and a nitrogen inlet tube, 10.00 g (78.0 mmol) of B-12, 0.216 g (2.34 mmol) of S-4, and 0.128 g (0.780 mmol) of AIBN were measured. 10.3 g of THF was added, and the mixture was stirred at room temperature until dissolved. Nitrogen was then substituted into the system, and the mixture was heated and stirred in an oil bath at 60 °C for 12 hours. After heating and stirring, cold methanol (30.0 g) was carefully added to the reaction solution while stirring, causing the solid to precipitate. The mixture was stirred for 30 minutes. The precipitate was collected by filtration and washed with cold methanol (30.0 g) for 30 minutes, repeating this process twice. The solid was then dried under vacuum at 50 °C to obtain the prepolymer. Mn: 6,000, Mw: 9,900. In a 100 ml flask equipped with a stir bar and a nitrogen inlet tube, the prepolymer synthesized by the above method (10.0 g, 1.67 mmol), B-9 (0.829 g, 5.83 mmol), Hydroquinone (8.1 mg), N,N-dimethyllaurylamine (2.0 mg), and Xylene (20.0 g) were added. The mixture was stirred at room temperature until dissolved, and then heated and stirred in an oil bath at 140 °C for 6 hours. After heating and stirring, methanol (50.0 g) was carefully added while stirring to precipitate the solid, and the mixture was stirred for 30 minutes. The precipitate was collected by filtration and washed twice with methanol (50.0 g) for 30 minutes each time. The solid was then dried under vacuum at 50 °C to obtain the giant monomer (A-1). Mn: 6,100, Mw: 9,900.

[0156] (Synthesis Examples 1-2~1-3) The types of raw materials (component B) and the molar ratio of raw materials and chain transfer agent (S-4) used [(raw material / S-4)] were changed as shown in Table 1. Otherwise, the same procedure as in Synthesis Example 1-1 was performed to obtain the macromonomers (A-2) to (A-3) shown in Table 1 below.

[0157] [Table 1]

[0158] Synthesis of Graft Copolymers (Synthesis example 2-1) In a 100 ml eggplant-shaped flask equipped with a stir bar and a nitrogen inlet tube, measure A-1 (1.00 g, 0.167 mmol), B-1 (4.10 g, 16.5 mmol), and AIBN (82.1 mg, 0.500 mmol), add THF (7.77 g), stir at room temperature to dissolve, then replace the system with nitrogen, and heat and stir in an oil bath set at 60 °C for 12 hours. After heating and stirring, carefully inject the reaction solution while stirring methanol (40 g) to precipitate solids, and stir for 30 minutes. Separate this precipitate by filtration, and wash it as a slurry with methanol (40 g) for 30 minutes, for a total of 2 times. Dry the solid in vacuo at 50 °C to obtain the graft copolymer (GP-1). Number average molecular weight (Mn): 92,200, weight average molecular weight (Mw): 196,600.

[0159] (Synthesis Examples 2-2 to 2-16) Replace the types, amounts, and polymerization concentrations of the raw materials (monomers) used with those shown in Table 2-1 or Table 2-2 below, and carry out the same procedure as in Synthesis Example 2-1 except for this. Obtain the graft copolymers (GP-2) to (GP-16) shown in Table 2-1 and Table 2-2 below.

[0160] [Table 2-1]

[0161] [[ID=,16]][Table 2-1]

[0162] [Synthesis of Homopolymer] (Synthesis Example 3-1) In a 100 ml eggplant-shaped flask equipped with a stir bar and a nitrogen inlet tube, measure B-7 (24.3 g, 106 mmol), R-3 (0.60 g, 1.49 mmol), and AIBN (0.12 g, 0.74 mmol), add THF (37.5 g), stir at room temperature to dissolve, then replace the system with nitrogen, and heat and stir in an oil bath set at 60 °C for 12 hours. After heating and stirring, carefully inject the reaction solution while stirring methanol (187 g) to precipitate solids, and stir for 30 minutes. Separate this precipitate by filtration, and wash it as a slurry with methanol (187.0 g) for 30 minutes, for a total of 2 times. Dry the solid in vacuo at 50 °C to obtain B-7mCTA. Mn: 8,600, Mw: 9,500.

[0163] [Synthesis of AB Block Polymer] (Synthesis example 3-2) In a 100 ml flask equipped with a stir bar and a nitrogen inlet tube, B-7mCTA (1.91 g, 0.222 mmol), B-3 (3.20 g, 12.7 mmol), and AIBN (18.3 mg, 0.111 mmol) obtained in Synthesis Example 3-1 were measured. THF (12.0 g) was added, and the mixture was stirred at room temperature until dissolved. Nitrogen was then substituted into the system, and the mixture was heated and stirred in an oil bath at 60°C for 12 hours. After heating and stirring, methanol (50.0 g) was carefully injected while stirring to precipitate the solid. The mixture was stirred for 30 minutes. The precipitate was collected by filtration and washed twice with methanol (50.0 g) for 30 minutes each time. The solid was then dried under vacuum at 50°C to obtain the block copolymer (BP-1). Mn: 17,400, Mw: 20,200.

[0164] <Synthesis of Bottle Brush Polymers> (Synthesis example 3-3) In a 100 ml round-bottom flask equipped with a stir bar and a nitrogen inlet tube, 5.00 g (17.91 mmol) of 2-((2-bromo-2-methylpropanoyl)oxy)ethyl methacrylate, 0.078 g (0.60 mmol), 0.72 g (1.80 mmol), and 0.09 g (0.54 mmol) of AIBN were measured. 10.2 g of THF was added, and the mixture was stirred at room temperature until dissolved. Nitrogen was then substituted into the system, and the mixture was heated and stirred in an oil bath at 60 °C for 12 hours. After heating and stirring, 50 g of methanol was carefully added while stirring to precipitate the solid. Stirring was continued for 30 minutes. The precipitate was collected by filtration and washed twice with 50 g of methanol for 30 minutes each time. The solid was then dried under vacuum at 50 °C to obtain the giant monomer (A-2). Mn: 45,300, Mw: 68,000. In a 50 ml flask equipped with a stir bar and a nitrogen inlet tube, the macromonomers synthesized by the aforementioned method (A-2: 2.00 g, 0.03 mmol), B-1 (0.43 g, 1.76 mmol), B-10 (3.00 g, 17.62 mmol), ethyl 2-bromoisobutyrate (0.012 g, 0.06 mmol), CuBr (0.03 g, 0.19 mmol), N,N,N',N'',N''-Pentamethyldiethylenetriamine (0.043 g, 0.25 mmol), and Anisole (7.5 g) were added. After dissolving by stirring at room temperature, the mixture was degassed three times by freezing and then heated and stirred in an oil bath at 90 °C for 6 hours. After heating and stirring, methanol (50.0 g) was carefully added to the reaction solution while stirring, causing the solid to precipitate. Stirring continued for 30 minutes. The precipitate was collected by filtration and then washed with methanol (50.0 g) for 30 minutes twice. The solid was then vacuum dried at 50°C to obtain the bottle brush polymer (BBP-1). Mn: 203,000, Mw: 384,000.

[0165] Synthesis of polyamides and polyimides (Synthesis Example 4-1) DA-5 (3.58 g: 12.0 mmol) and DA-6 (1.20 g: 8.00 mmol) were measured into a 100 mL four-necked flask equipped with a mechanical stirrer and a nitrogen inlet tube. NMP (48.0 g) was added, and the mixture was stirred under nitrogen to dissolve it. Then, TC-1 (3.70 g: 18.8 mmol) was added while maintaining the temperature below 10°C in an ice bath. The mixture was reacted at room temperature under nitrogen for 18 hours to obtain a polyacrylic acid (PAA-1) solution with a viscosity of approximately 740 mPa·s and a solid content concentration of 15% by mass. The molecular weight of this polyacrylic acid is Mn: 12,600 and Mw: 35,200.

[0166] (Synthesis Example 4-2) DA-7 (3.19 g: 16.0 mmol) and DA-8 (793 mg: 4.00 mmol) were measured into a 100 mL four-necked flask equipped with a mechanical stirrer and a nitrogen inlet tube. NMP (43.5 g) was added, and the mixture was stirred under nitrogen to dissolve it. The solution was then kept below 10°C in an ice bath, and TC-1 (3.69 g: 18.8 mmol) was added. The mixture was reacted at room temperature under nitrogen for 18 hours to obtain a polyacrylic acid (PAA-2) solution with a viscosity of approximately 70 mPa·s and a solid content concentration of 15% by mass. The molecular weight of this polyacrylic acid is Mn: 14,000 and Mw: 38,600.

[0167] (Synthesis Example 4-3) DA-1 (1.08 g: 10.0 mmol) and DA-3 (3.30 g: 10.0 mmol) were measured into a 100 mL four-necked flask equipped with a mechanical stirrer and a nitrogen inlet tube. NMP (24.9 g) was added, and the mixture was stirred under nitrogen to dissolve the DA-1. Then, TC-2 (2.50 g: 10.0 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 nitrogen. After returning to room temperature, TC-1 (1.84 g: 9.4 mmol) and NMP (10.0 g) were added, and the reaction was carried out at room temperature for 18 hours to obtain a polyacrylic acid (PAA-3) solution with a viscosity of approximately 1120 mPa·s and a solids content of 20% by mass. The molecular weight of this polyacrylic acid is Mn: 11,200 and Mw: 31,400. A solution (40.0 g) of the polyamide (PAA-3) obtained above was measured into a 300 mL flask equipped with a stir bar and a nitrogen inlet tube. NMP (74.3 g) was added, and the mixture was stirred at room temperature for a period of time. Acetic anhydride (5.61 g: 55.0 mmol) and pyridine (2.90 g, 36.7 mmol) were then added. The mixture was stirred at room temperature under nitrogen for 30 minutes, and then reacted at 50 °C under nitrogen for 3 hours. After the reaction was completed, the reaction solution was slowly injected into methanol (500 mL) cooled to below 10 °C while stirring, causing the solid to precipitate. The mixture was stirred for 10 minutes. The precipitate was separated by filtration and then washed with methanol (200 mL) for 30 minutes, twice in total. The solid was then dried under vacuum at 80 °C to obtain the desired polyamide powder (SPI-1) (7.04 g, yield 88%). The polyimide has an imidization rate of 57% and a molecular weight of Mn: 10,400 and Mw: 29,100.

[0168] (Synthesis Example 4-4) DA-2 (3.42 g: 14.0 mmol) and DA-4 (4.11 g: 6.00 mmol) were measured into a 100 mL four-necked flask equipped with a mechanical stirrer and a nitrogen inlet tube. NMP (56.8 g) was added, and the mixture was stirred under nitrogen to dissolve it. Then, TC-3 (4.26 g: 19.0 mmol) and NMP (10.0 g) were added while maintaining the temperature below 10°C in an ice bath. The mixture was allowed to react at room temperature for 24 hours to obtain a polyacrylic acid (PAA-4) solution with a viscosity of approximately 680 mPa·s and a solids content of 15% by mass. The molecular weight of this polyacrylic acid is Mn: 17,200 and Mw: 48,200.

[0169] The contents of the synthesized polyamides and polyimides are shown in Table 3.

[0170] [Table 3]

[0171] <Preparation of Weakly Anchored Liquid Crystal Alignment Agents> (Preparation Example 1) 0.9 g of GP-1 obtained in Synthesis Example 2-1 was measured into a 20 mL glass vial equipped with a stir bar, and 14.1 g of PGMEA was added. The mixture was stirred at room temperature for 1 hour to obtain a weakly anchored liquid crystal alignment agent (WAS-1).

[0172] (Preparation Examples 2-15) The polymers used were replaced with those shown in Table 4 below, and the same procedure as in Preparation Example 1 was performed to obtain the weakly anchored liquid crystal alignment agents (WAS-2)~(WAS-15), (WAS-20)~(WAS-21), (WAS-C1), and (WAS-C4)~(WAS-C5) shown in Table 4 below.

[0173] [Table 4]

[0174] (Preparation Example 16) GP-7 (0.81 g) and AD-1 (0.09 g) obtained in Synthesis Example 2-7 were measured into a 20 mL glass vial equipped with a stir bar, and PGMEA (14.1 g) was added. The mixture was stirred at room temperature for 1 hour to obtain a weakly anchored liquid crystal alignment agent (WAS-15).

[0175] (Preparation Example 17) Measure 0.18 g of GP-3 obtained in Synthesis Example 2-3 and 4.8 g of PAA-1 obtained in Synthesis Example 4-1 into a 20 mL glass vial equipped with a stir bar, add NMP (5.52 g) and BCS (4.5 g), and stir at room temperature for 1 hour to obtain a weakly anchored liquid crystal alignment agent (WAS-16).

[0176] (Preparation Examples 18-20) The polymers used were replaced with those shown in Table 5 below, and the same procedure as in Preparation Example 17 was performed to obtain the weakly anchored liquid crystal alignment agents (WAS-17) to (WAS-19) shown in Table 5 below. Furthermore, the mass concentration of the polymer in the weakly anchored liquid crystal alignment agents (WAS-17) to (WAS-19) is the same as the mass concentration of the polymer in the weakly anchored liquid crystal alignment agent (WAS-16).

[0177] (Preparation Example 21) BP-1 (0.9 g) obtained in Synthesis Example 3-2 was measured into a 20 mL glass vial equipped with a stir bar, and PGMEA (14.1 g) was added. The mixture was stirred at room temperature for 1 hour to obtain a weakly anchored liquid crystal alignment agent (WAS-C2).

[0178] (Preparation Example 22) BBP-1 (0.9 g) obtained in Synthesis Example 3-3 was added to a 20 mL glass vial equipped with a stir bar, and PGMEA (14.1 g) was added. The mixture was stirred at room temperature for 1 hour to obtain a weakly anchored liquid crystal alignment agent (WAS-C3).

[0179] [Table 5] In Table 5, the values ​​in parentheses for polymers represent the mass ratio of each polymer.

[0180] <Preparation of Free Radical-Generated Film-Forming Components> (Preparation Example 23) 2.0 g of polyimide powder (SPI-1) obtained in Synthesis Example 4-3 was measured into a 50 mL Erlenmeyer flask equipped with a stir bar, and NMP (18.0 g) was added. The mixture was stirred at room temperature for 12 hours to dissolve the solid. 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) used as a comparative example.

[0181] (Preparation Example 24) In a 50 mL Erlenmeyer flask equipped with a stir bar, a solution (15.0 g) of polyacrylic acid (PAA-4) obtained in Synthesis Example 4-4 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) used as a comparative example.

[0182] [Table 6]

[0183] (Fabrication of Liquid Crystal Display Components) The following describes a method for fabricating liquid crystal cells to evaluate liquid crystal alignment and electro-optical response. First, a substrate with electrodes is prepared. The substrate is an alkali-free glass substrate measuring 30mm × 35mm and 0.7mm thick. ITO (Indium Tin Oxide) electrodes with a 3μm wide electrode, a 6μm spacing between electrodes, and a comb-like pattern at a 10° angle relative to the long side of the substrate have been formed on the substrate, and pixels have been formed. Each pixel measures approximately 10mm vertically and 5mm horizontally. This substrate is referred to as the IPS substrate. Then, the weakly anchored liquid crystal alignment agents (WAS-1~WAS-21, WAS-C1~WAS-C5), free radical generating film forming components (AL-1, AL-2), and liquid crystal alignment agents for horizontal alignment (SE-6414, NRB-U973 (manufactured by Nissan Chemical Co., Ltd.)) obtained by the above method were filtered through filters with a pore size of 1.0 mm, and then coated and deposited by spin coating on the prepared IPS substrate and a glass substrate (hereinafter referred to as the opposing substrate) with an ITO film deposited on the back side and columnar spacers with a height of 3.0 μm. Then, after drying on a hot plate at 80°C for 2 minutes, the coating was calcined at 230°C for 30 minutes to obtain a coating with a thickness of 100 nm. The coating on the IPS substrate was aligned in the direction along the comb teeth, and the coating on the opposing substrate was aligned in the direction perpendicular to the comb teeth electrodes. Furthermore, regarding alignment treatment, the friction method was used for AL-1 and SE-6414, while the photoalignment method was used for AL-2 and NRB-U973. WAS-1 to WAS-21 and WAS-C1 to WAS-C5 did not undergo alignment treatment; the calcined substrates were used directly. The friction method utilized a friction device manufactured by iinuma-gauge, friction cloth (YA-20R) manufactured by Yoshikawa Chemical Co., Ltd., a friction roller (10.0 cm in diameter), a table conveying speed of 30 mm / s, a roller speed of 700 rpm, and a pushing pressure of 0.3 mm. The photoalignment method used a UV exposure device manufactured by USHIO Electric Co., Ltd., irradiating the polarized UV light with an extinction ratio of approximately 26:1 at a wavelength of 254 nm, with an irradiation dose of 300 mJ / cm², and heating at 230°C for 30 minutes to perform the alignment treatment. Then, using the two substrates described above, they were combined in the manner shown in Tables 8 and 10 below, with their respective alignment directions parallel. The liquid crystal injection port was retained and the surrounding area was sealed (sealant: XN-1500T (manufactured by Mitsui Chemicals)), creating empty cells with an intercellular gap of approximately 3.0 μm. Liquid crystal (MLC-3019 (manufactured by Merck)) was then vacuum-injected into these empty cells at room temperature, and the injection port was sealed to obtain antiparallel aligned liquid crystal cells. Furthermore, in some display elements (Comparative Examples 4 and 9, where the radical generation film forming composition was used on an IPS substrate), a liquid crystal composition mixed with 2.0% by mass of B-11 as an additive was vacuum-injected at room temperature, and the injection port was sealed to obtain antiparallel aligned liquid crystal cells. The obtained liquid crystal cells constitute an IPS-type liquid crystal display element. The obtained liquid crystal cells are then heat-treated at 120°C for 10 minutes to obtain a liquid crystal display element. Furthermore, as one of the comparative objects, a display element (Comparative Example 5) was obtained by irradiating it with UV (UV lamp: FLR40SUV32 / A-1) for 30 minutes using a TOSHIBALIGHTECH UV-FL irradiation apparatus without applying voltage after the heat treatment to obtain a liquid crystal display element.

[0184] (Evaluation of initial alignment) Using a polarizing microscope, with the polarizing plate set to orthogonal Nicol, and fixed at the minimum brightness of the liquid crystal cell, the liquid crystal cell is rotated 1° to observe the alignment state of the liquid crystal. When no misalignment such as unevenness or micro-regions is observed, or when it is very slight, it is rated as "good". When misalignment such as unevenness or micro-regions is clearly observed, it is rated as "poor".

[0185] (Evaluation of black brightness) A photodiode is installed on a polarizing microscope, and a current-to-voltage converter is connected to a potentiometer. The voltage at which the minimum brightness is achieved under orthogonal Nicol scales is monitored to measure the blackness.

[0186] (Measurement of VT curve and evaluation of driving threshold voltage, maximum luminance voltage, and transmittance) A white LED backlight and a luminance meter are installed, aligning the optical axes. A liquid crystal cell (liquid crystal display element) with a polarizing plate is placed between them, minimizing the brightness. A voltage is applied at 1V intervals up to 8V. The brightness at this voltage is measured to determine the VT curve. The voltage at which the brightness reaches its maximum (Vmax) is estimated from the obtained VT curve. Furthermore, a liquid crystal cell without applied voltage is used as a buffer, with the transmittance at parallel Nicol tubes taken as 100%, and the maximum transmittance on the VT curve is compared to estimate the maximum transmittance (Tmax).

[0187] (Measurement of response time (Ton, Toff)) Using the apparatus described above for measuring the VT curve, a luminance meter is connected to an oscilloscope to measure the response speed (Ton) when a voltage is applied to achieve maximum luminance and the response speed (Toff) when the voltage returns to 0V.

[0188] (Determination of azimuth anchorage strength (A2)) The azimuth anchoring strength A2, SA of strongly anchored alignment films AL-1, SE-6414, AL-2, and NRB-U973 was separately determined using the torque equalization method. The azimuth anchoring strength A2, WA of weakly anchored alignment films was calculated from the driving threshold voltage (Vth) obtained by measuring the VT curve of the liquid crystal cells prepared above, using the following formulas (eq2) and (eq3). Furthermore, an azimuth anchoring strength less than 10⁻⁵ [J / m²] is defined as a weakly anchored alignment film, and a strength greater than 10⁻⁴ [J / m²] is defined as a strongly anchored alignment film.

[0189] [Number 2]

[0190] [Number 3]

[0191] Here, Vth,SA represents the driving threshold voltage of a strongly anchored liquid crystal cell, Vth,WA represents the driving threshold voltage of a weakly anchored liquid crystal cell, l represents the distance between the comb electrodes, d represents the intercellular gap, K2 represents the torsional elastic constant of the liquid crystal, ε0 represents the dielectric constant of the liquid crystal in a vacuum, and Δε represents the anisotropy of the dielectric constant of the liquid crystal. The above formula eq3 was originally a formula for calculating the weak anchoring alignment film used on two substrates. Therefore, it cannot calculate the correct azimuth anchoring strength of the weak anchoring liquid crystal alignment film. It is used as an approximation of the azimuth anchoring strength of the weak anchoring alignment film.

[0192] (Solubility test for liquid crystals) A weakly anchored liquid crystal alignment agent was coated onto a glass substrate and calcined. The resulting weakly anchored film was then immersed in liquid crystal (MLC-3019 (Merck)) for 30 minutes, washed with hexane, and dried at 80°C for 15 minutes. The solubility in the liquid crystal was evaluated using the residual film rate calculated by the following formula. The evaluation criteria were: a residual film rate of 80% or higher was rated as "insoluble" (immiscible), and a residual film rate of less than 10% was rated as "soluble" (miscible). Residual film yield (%) = (film thickness after drying) / (film thickness before liquid crystal impregnation) × 100

[0193] (Regarding the solubility of liquid crystals)

[0194] [Table 7]

[0195] The weakly anchored liquid crystal alignment films shown in Preparation Examples 15 and 27-28, composed solely of macromonomers (A-1) to (A-3), are soluble in liquid crystals. However, the weakly anchored liquid crystal alignment films made from the graft copolymers shown in Preparation Examples 1-14, 16-20, and 25-26, and from composite materials using these copolymers, are insoluble in liquid crystals and are therefore suitable as coating-type weakly anchored liquid crystal alignment agents. Furthermore, the graft copolymers shown in Preparation Examples 1-14, 16-20, and 25-26 contain branch polymers derived from macromonomers (A-1) to (A-3) that are soluble in liquid crystals but insoluble in liquid crystals. Therefore, the dry polymers in these graft copolymers are either immiscible with liquid crystals or become immiscible with liquid crystals due to calcination.

[0196] <Using Optical Orientation for Cell Property Evaluation> (Example Content)

[0197] [Table 8] IPS substrate Opposing substrate Additives for liquid crystal components Example 1 WAS-1 NRB-U973 - Example 2 WAS-2 NRB-U973 - Example 3 WAS-3 NRB-U973 - Example 4 WAS-4 NRB-U973 - Example 5 WAS-5 NRB-U973 - Example 6 WAS-6 NRB-U973 - Example 7 WAS-7 NRB-U973 - Example 8 WAS-8 NRB-U973 - Example 9 WAS-9 NRB-U973 - Example 10 WAS-10 NRB-U973 - Example 11 WAS-11 NRB-U973 - Example 12 WAS-12 NRB-U973 - Example 13 WAS-13 NRB-U973 - Example 14 WAS-14 NRB-U973 - Example 15 WAS-15 NRB-U973 - Example 16 WAS-16 NRB-U973 - Example 17 WAS-17 NRB-U973 - Example 18 WAS-18 NRB-U973 - Example 19 WAS-19 NRB-U973 - Example 20 NRB-U973 WAS-1 - Comparative Example 1 WAS-C1 NRB-U973 - Comparative Example 2 WAS-C2 NRB-U973 - Comparative Example 3 WAS-C3 NRB-U973 - Comparative Example 4 AL-2 NRB-U973 B-11 Comparative Example 5 NRB-U973 NRB-U973 - Example 21 WAS-20 NRB-U973 - Example 22 WAS-21 NRB-U973 -

[0198] (Evaluation results of weakly anchored IPS characteristics) The evaluation results are shown in Table 9. Table 9 also shows the measurement results of the azimuth anchoring strength (A2).

[0199] [Table 9]

[0200] By using the graft copolymer of the present invention, compared with Comparative Example 5, the transmittance of each sample in Examples 1 to 22 is improved and the driving voltage is reduced. Furthermore, the azimuth anchoring energy is approximately 2.7 × 10⁻⁶. Therefore, it can be seen that good weak anchoring characteristics can be obtained by using the graft copolymer of the present invention. Moreover, by using the graft copolymer of the present invention, compared with the liquid crystal cell manufactured by the method described in Patent Document 3 (Comparative Example 4), there is an advantage in weak anchoring characteristics, achieving better alignment quality, black brightness, and high-speed response at voltage OFF. This indicates that no pretilt angle occurs when using the graft copolymer of the present invention.

[0201] Examples 1-4 all feature low-voltage driving and high transmittance, and also achieve good alignment quality, black brightness, and high-speed response. This demonstrates that, within an appropriate range, good weak anchoring characteristics can be obtained regardless of the ratio of macromonomers to free radical polymerizable monomers constituting the graft copolymer. If the macromonomer ratio is too low, the weak anchoring characteristics disappear; if it is too high, there is a concern about dissolution into the liquid crystal. Therefore, the ideal ratio of macromonomers to free radical polymerizable monomers (macromonomer / free radical polymerizable monomer (molar ratio)) is 0.1 / 99.9 to 50 / 50, more preferably 0.2 / 99.8 to 30 / 70.

[0202] Examples 1 and 5 both exhibit low-voltage drive and high transmittance, and also demonstrate good alignment quality, black brightness, and high-speed response. This indicates that, within an appropriate range, good weak anchoring characteristics can be obtained regardless of the molecular weight of the graft copolymer. Small molecular weight raises concerns about dissolution into the liquid crystal, while large molecular weight raises concerns about solubility. Therefore, the ideal range for the weight-average molecular weight of the graft copolymer is 10,000 to 5,000,000, more preferably 20,000 to 3,000,000.

[0203] In Examples 1, 6-14, and 21-22, good weak anchoring properties were obtained by using the graft copolymer of the present invention. However, when the macromonomer was used alone as the polymer for weak anchoring liquid crystal alignment (Comparative Example 1), poor driving was caused by the pretilt angle, and the desired properties were not obtained. This is because the coating composed solely of macromonomers will dissolve into the liquid crystal due to heat treatment or voltage driving of the liquid crystal cells. Therefore, it is important for the graft copolymer to have components that inhibit dissolution as dry polymers. Furthermore, it is also known that if the component can inhibit dissolution, the polymeric group of the compound constituting the dry polymer is not limited.

[0204] Examples 1 and 21-22 all show good weak anchoring characteristics, indicating that for liquid crystal compatibility components, the type of compound constituting the dendritic polymer and the polymeric group are not limited.

[0205] Examples 7 and 15 both exhibited good weak anchoring properties. This demonstrates that even with the addition of crosslinking additives to the graft copolymers of this invention, the properties remain unchanged. By using crosslinking additives, improvements in the film hardness of the weakly anchored alignment film, inhibition of liquid crystal dissolution, and high resistivity can be expected.

[0206] Examples 3 and 16-19 all exhibited good weak anchoring properties. This demonstrates that if a certain amount of graft copolymer is present, it can also be a composite material; within an appropriate range, the composite ratio is not critical.

[0207] Examples 1 and 20 demonstrate that high transmittance can be achieved by providing graft copolymers to the opposing substrate. This phenomenon suggests that by providing graft copolymers to the opposing substrate, a higher phase difference change is obtained before and after liquid crystal driving, due to the increased thickness of the driving liquid crystal's execution film. It is understood that, typically, to achieve high transmittance, the product of the complex refractive index difference (Δn) of the liquid crystal and the intercellular gap (D) is designed to be approximately 300 nm. However, the aforementioned value can still exhibit high transmittance even below 300 nm, achieving faster response times. Furthermore, it also has effects on burn-in and contrast improvement.

[0208] <Evaluation of Cell Properties Using Tribo-Oriented Integration> (Example Content)

[0209] [Table 10] First substrate (IPS substrate) Second substrate (backside ITO substrate) Additives for liquid crystal components Example 23 WAS-1 SE-6414 - Example 24 WAS-2 SE-6414 - Example 25 WAS-3 SE-6414 - Example 26 WAS-4 SE-6414 - Example 27 WAS-5 SE-6414 - Example 28 WAS-6 SE-6414 - Example 29 WAS-7 SE-6414 - Example 30 WAS-8 SE-6414 - Example 31 WAS-9 SE-6414 - Example 32 WAS-10 SE-6414 - Example 33 WAS-11 SE-6414 - Example 34 WAS-12 SE-6414 - Example 35 WAS-13 SE-6414 - Example 36 WAS-14 SE-6414 - Example 37 WAS-15 SE-6414 - Example 38 WAS-16 SE-6414 - Example 39 WAS-17 SE-6414 - Example 40 WAS-18 SE-6414 - Example 41 WAS-19 SE-6414 - Example 42 SE-6414 WAS-1 - Comparative Example 6 WAS-C1 SE-6414 - Comparative Example 7 WAS-C2 SE-6414 - Comparative Example 8 WAS-C3 SE-6414 - Comparative Example 9 AL-2 SE-6414 B-11 Comparative Example 10 SE-6414 SE-6414 - Example 43 WAS-20 SE-6414 - Example 44 WAS-21 SE-6414 -

[0210] (Evaluation results of weakly anchored IPS characteristics) The evaluation results are shown in Table 11. Table 11 also shows the measurement results of the azimuth anchoring strength (A2).

[0211] [Table 11]

[0212] By using the graft copolymer of the present invention, compared with Comparative Example 10, it can be seen that the transmittance of each sample in Examples 21-44 is improved and the driving voltage is reduced. Furthermore, the azimuth anchoring energy is approximately 2.7 × 10⁻⁶. Therefore, it can be seen that the graft copolymer of the present invention exhibits weak anchoring characteristics even when subjected to rubbing alignment treatment on substrates with which it is disposed (substrates coated with SE-6414 in Table 10), regardless of the alignment treatment method. Moreover, compared with the liquid crystal cell manufactured according to the method of Patent Document 3 (Comparative Example 9), the weak anchoring characteristics are advantageous, resulting in better display quality, black level, and high-speed response at voltage OFF. These phenomena demonstrate that by using the graft copolymer of the present invention, no pretilt angle occurs.

[0213] Examples 21-24 all exhibited good weak anchoring characteristics. This demonstrates that, if the frictional alignment is within an appropriate range, good weak anchoring characteristics can be obtained regardless of the ratio of macromonomers to monomers constituting the graft copolymer.

[0214] Examples 21 and 25 both exhibited good weak anchoring properties. This indicates that if the frictional alignment is within an appropriate range, good weak anchoring properties can be obtained regardless of the molecular weight of the graft copolymer.

[0215] Examples 21, 26-34, and 41-42 all exhibited good weak anchoring properties. This demonstrates that, in triboelectric alignment, the design of the types of compounds constituting the dry polymer can be similar to that in photoalignment, without being limited to any particular alignment method.

[0216] Examples 1 and 43-44 all exhibited good weak anchoring properties. This indicates that in triboelectric alignment, the types of compounds constituting the dendritic polymer and the design of the polymerizable groups can be the same as in photoalignment, without being limited by the alignment method.

[0217] Examples 27 and 35 both exhibited good weak anchoring properties. This demonstrates that good weak anchoring properties can be achieved in frictional alignment regardless of the presence or absence of crosslinking additives.

[0218] Examples 23 and 36-39 all exhibited good weak anchoring properties. This demonstrates that, in the frictional alignment method, weakly anchored liquid crystal alignment agents composed of graft copolymers and other composite materials can still achieve good weak anchoring properties.

[0219] From Examples 21 and 40, by providing graft copolymers on opposing substrates, higher transmittance can be obtained compared to providing them on IPS substrates. It can be seen that, like photo-alignment, tactile alignment has different characteristics and effects due to the substrate coated with a weakly anchored alignment film, and is not limited to alignment methods.

[0220] (Preparation of samples for adhesiveness evaluation) The liquid crystal alignment agent and NRB-U973 obtained in Examples 1-23 and 25-26 above were filtered through a 1.0 μm filter and then spin-coated onto a glass substrate with a transparent electrode. After drying on a hot plate at 80°C for 2 minutes, the coating was calcined at 230°C for 20 minutes to obtain a coating with a thickness of 100 nm. Similarly, NRB-U973 was formed on both opposing substrates. Two substrates were prepared, and 4 μm diameter bead spacers were dispersed on the liquid crystal alignment film surface of one substrate. A sealant (Mitsui Chemicals XN-1500T) was then added. The amount of sealant added was adjusted so that the diameter of the sealant after bonding was approximately 3 mm. The film surfaces were then bonded together so that the overlap width of the substrates was 1 cm. After fixing the bonded substrates with clamps, they were heat-cured at 120°C for 1 hour to produce a sample for adhesion evaluation.

[0221] (Measurement of Adhesion) The prepared samples were tested using a Shimadzu AGS-X 500N benchtop precision universal testing machine. After fixing the ends of the upper and lower substrates, the samples were pushed in from the upper part of the center of the substrate, and the pressure (N) during peeling was measured. Furthermore, the adhesion (also known as seal peel strength or seal tightness) was evaluated using the pressure (N / 3mm) when the diameter of the sealant was standardized to 3.0 mm. The results are shown in Table 12.

[0222] [Table 12] Orientation agent Seal peel strength (N) Example 45 WAS-1 15.2 Example 46 WAS-2 14.8 Example 47 WAS-3 11.1 Example 48 WAS-4 7.7 Example 49 WAS-5 15.8 Example 50 WAS-6 16.1 Example 51 WAS-7 19.8 Example 52 WAS-8 20.0 Example 53 WAS-9 15.8 Example 54 WAS-10 16.3 Example 55 WAS-11 24.4 Example 56 WAS-12 21.2 Example 57 WAS-13 22.3 Example 58 WAS-14 24.5 Example 59 WAS-15 24.8 Example 60 WAS-16 19.5 Example 61 WAS-17 17.6 Example 62 WAS-18 20.2 Example 63 WAS-19 18.0 Comparative Example 11 WAS-C1 1.2 Comparative Example 12 WAS-C2 3.3 Comparative Example 13 WAS-C3 8.7 Comparative Example 14 AL-1 20.4 Comparative Example 15 NRB-U973 21.3 Example 64 WAS-20 14.4 Example 65 WAS-21 15.1

[0223] Example 45 shows that the seal peel strength of the graft copolymer of the present invention is significantly improved compared to the coating-type weakly anchored liquid crystal alignment agent using AB block copolymer (BP-1) (Comparative Example 12), and shows the same level of value as the polyimide-based strongly anchored liquid crystal alignment agent (Comparative Example 15). This demonstrates that by using the graft copolymer of the present invention, the sealing performance of coating-type weakly anchored materials is significantly improved. On the other hand, the weakly anchored alignment film composed only of macromonomer (A-1) (Comparative Example 11) shows very low seal peel strength. This demonstrates the importance of producing graft copolymers.

[0224] From Examples 45-48, it is shown that the lower the proportion of macromonomers in the graft copolymers of the present invention, the greater the seal peel strength. Therefore, the seal tightness of the graft copolymer depends on the density of the graft polymer.

[0225] Examples 45 and 49 both exhibit good seal peel strength. Therefore, it can be said that the graft copolymer of the present invention, regardless of molecular weight, is a material capable of exhibiting good sealing and adhesion.

[0226] Examples 45 and 50-59 all exhibit good seal peel strength. This demonstrates that the graft copolymers of the present invention, regardless of the types of compounds constituting the dry polymer, exhibit high seal tightness. In particular, the graft copolymers shown in Examples 51-52 and 55-59 exhibit even better seal peel strength. This indicates that they achieve better seal tightness by selecting compounds that enhance the mechanical strength of the weakly anchored alignment film and compounds with high reactivity in the hardening components of the sealant, depending on the design of the dry polymer.

[0227] Examples 60-63 all exhibited very good seal peel strength. This demonstrates that composite materials containing graft copolymers also exhibit high sealing performance.

[0228] (Solubility evaluation of NMP and BCS) The polymers obtained in the above synthesis examples were each placed in a 20 mL glass vial and diluted to a solid content of 20% by mass with a mixed solvent of NMP only, NMP / BCS = 1 / 1 (mass ratio), or BCS only. The solutions were stirred at room temperature (25°C) for 12 hours. Alternatively, as in Examples 15-18, the polymers were mixed according to the mass ratios shown in parentheses in Table 13. The solutions were then placed in a freezer at -20°C for 12 hours, and the state of the solution was observed to evaluate the polymer solubility. Based on the evaluation criteria, those not dissolved at room temperature were rated "×", those dissolved at room temperature but precipitated upon freezing were rated "△", and those dissolved at room temperature and showed no precipitation upon freezing were rated "〇". The results are shown in Table 13.

[0229] (Copyability evaluation using NMP and BCS solvents) The polymers obtained in the above synthesis examples were each placed in a 20 mL glass vial and diluted to a solid content of 6% by mass with a mixed solvent of NMP only, NMP / BCS = 1 / 1 (mass ratio), or BCS only. The solutions were stirred at room temperature (25°C) for 12 hours. Alternatively, in Examples 15-18, the polymers were mixed according to the mass ratios shown in parentheses in Table 13. The obtained diluted solutions were spin-coated onto an alkali-free glass substrate and dried on a hot plate at 80°C for 2 minutes. The state of the organic film was then observed to evaluate its coatability. Based on the evaluation criteria, those with numerous defects, whitening, or streaks were rated "×"; those with uniform coating but minor defects were rated "△"; and those with uniform coating and no defects were rated "〇". The results are shown in Table 13.

[0230] [Table 13]

[0231] As can be seen from Examples 1-18, the graft copolymers of the present invention exhibit better solvent selectivity and coatability compared to AB block copolymers (Example 20), bottle brush polymers (Example 21), and polyimide polymers (Example 22). In particular, the graft copolymers shown in Examples 7-8 and 11-14 demonstrate even better solvent selectivity and coatability. These were achieved by selecting compounds that readily solubilize with coating solvents NMP and BCS in relation to the types of compounds constituting the dry polymer. It is evident that better solvent selectivity and coatability can be obtained depending on the design of the dry polymer. [Industrial applicability]

[0232] According to the present invention, a stable weak anchoring film can be manufactured in a much simpler way than conventional techniques. Therefore, the step load imposed on the manufacturing of weakly anchored IPS in actual industrial applications can be reduced, and the yield can be improved. Furthermore, by using the materials and methods of the present invention, the occurrence of pretilt angle associated with narrowing of cell gaps can be suppressed. Compared with conventional techniques, high-speed response at voltage OFF, reduced burn-in, high backlight transmittance in low-temperature environments, and low-voltage driving can be achieved. Therefore, materials and transverse electric field liquid crystal display elements with stable and excellent characteristics can be provided.

[0233] 1: Horizontal electric field liquid crystal display element 2: Comb-shaped electrode substrate 2a: Substrate 2b: Wire electrode 2c: Liquid crystal alignment film 2d: Substrate 2e: Surface electrode 2f: Insulating film 2g: Wire electrode 2h: Liquid crystal alignment film 3: LCD 4: Opposing substrate 4a: Liquid crystal alignment film 4b: Substrate L: Power line

Claims

1. A weakly anchored liquid crystal alignment agent used in the formation of a liquid crystal alignment film in a liquid crystal cell having a liquid crystal and a liquid crystal alignment film, comprising a graft copolymer having a dry polymer and a branch polymer bonded to the dry polymer as a side chain of the dry polymer, the branch polymer being miscible with the liquid crystal, the dry polymer being miscible with the liquid crystal or becoming miscible with the liquid crystal due to calcination, the ratio of the number of monomers used in the synthesis of the branch polymer to the number of macromonomers used in the synthesis of the branch polymer being 0.1 / 99.9 to 50 / 50 (moles / moles), the branch polymer being derived from a macromonomer represented by formula (1), and the dry polymer containing a compound represented by formula (8) as a constituent component. In formula (1), P represents a polymerizable group having a polymerizable unsaturated hydrocarbon group, Q represents a structure obtained by polymerizing at least one monomer from compounds containing formulas (2), (3), (5), and (7), and n is an integer from 1 to 2. When n is 2, the two Qs can be the same or different. In formula (2), M represents a polymerizable group having a polymerizable unsaturated hydrocarbon group, X represents a single bond, ether bond, ester bond, amide bond, carbamate bond, urea bond, or thioether bond, and R1 represents an alkyl group with 1 to 20 carbon atoms that may also have a bonding group inserted. n is an integer from 1 to 2. When n is 2, the two Xs and R1s can be the same or different. In formula (3), M represents a polymerizable group with a polymerizable unsaturated hydrocarbon group, S represents a saturated hydrocarbon group with 1 to 6 carbons that has a single bond or can also have a bonded group inserted, T represents the organic group represented by formula (4) below, n is an integer from 1 to 2, when n is 2, the two Ts can be the same or different, but when n is 2, S represents a saturated hydrocarbon group with 1 to 6 carbons that can also have a bonded group inserted. In formula (4), * represents the bonding site, X represents a bonding group selected from single bond, ether bond, ester bond, amide bond, carbamate bond, urea bond, thioether bond, -Si(R1)(R2)- (R1 and R2 each independently represent an alkyl group bonded to Si), -Si(R3)(R4)-O- (R3 and R4 each independently represent an alkyl group bonded to Si), and -N(R5)- (R5 represents a hydrogen atom or alkyl group bonded to N), Cy represents a non-aromatic cyclic group with 6 to 20 members. In formula (5), M represents a polymerizable group with a polymerizable unsaturated hydrocarbon group, R1 represents an aliphatic hydrocarbon group with a straight chain or branched structure having 1 to 10 carbon atoms, and each of the three X's independently represents a hydrogen atom or the following formula (6), except that at least one of the three X's represents formula (6). In formula (6), Y represents a single bond, -O-, -S-, or -N(R)- (R represents a hydrogen atom bonded to N or an alkyl group with 1 to 4 carbon atoms), * represents a bonding site, and R2, R3, and R4 each independently represent an alkyl group with 1 to 6 carbon atoms or an aromatic hydrocarbon group that may have substituents. In formula (7), M represents a polymerizable group with a polymerizable unsaturated hydrocarbon group, and R1 to R3 each independently represent a single bond or an alkyl group with 1 to 6 carbon atoms that may have a bonding group inserted.Ar represents an aromatic hydrocarbon group that may also have substituents. X1 and X2 each independently represent hydrogen atoms, or aromatic hydrocarbon groups that may also have substituents. The carbon atoms bonded to R1X1 and R2X2 and R1X1 and R2X2 can also form a ring together, provided that the total number of carbon atoms in R1X1, R2X2 and R3 is 1 or more. In formula (8), M represents a polymerizable group with a polymerizable unsaturated hydrocarbon group, n is an integer from 1 to 2, and Z represents the group represented by formula (9) below. When n is 2, the two Zs can be the same or different. In formula (9), L represents a group selected from amino, protected amino, aniline, protected aniline, hydroxyl, protected hydroxyl, phenol, protected phenol, thiol, protected thiol, thiophenol, protected thiophenol, carboxyl, protected carboxyl, benzoic acid, protected benzoic acid, isocyanate, protected isocyanate, cyclic ether with 2-5 carbon atoms, maleimino, carboxylic anhydride, N-hydroxysuccinimino, acezolinyl, trialkoxysilyl, vinyl, allyl, styryl, α-hydroxyacetophenone, α-aminoalkylacetophenone, oxime ester, acetophosphine oxide, cinnamic acid, cinnamic ester, azophenyl The functional group can be any of the following: N-benzylaniline, stilbene, diphenylethynyl, phenylbenzoate, aromatic hydrocarbon groups with 5-18 carbon atoms that may have a bonding group inserted, or aromatic heterocyclic groups with 5-18 carbon atoms that may have a bonding group inserted. J represents a single bond or an aliphatic hydrocarbon group with 1-6 carbon atoms. When K is bonded to an aromatic hydrocarbon group, it represents a linking group selected from single bonds, ether bonds, ester bonds, amide bonds, urea bonds, carbamate bonds, and thioether bonds. In other cases, it represents a single bond. * indicates the bonding site. m is an integer from 1 to 3. When m is 2 or 3, multiple K and L can be the same or different. However, when J is a single bond, m is 1.

2. As in claim 1, a weakly anchored liquid crystal alignment agent, wherein, In formula (1), P and in formulas (2), (3), (5), (7), and (8), M each independently represent any of the following structures: R1 and R2 each independently represent a hydrogen atom or a straight-chain or branched alkyl group having 1 to 12 carbon atoms; X, Y, and Z each independently represent an oxygen atom or a sulfur atom; *, *1, and *2 represent bonding sites; one of *1 and *2 may also be replaced by a hydrogen atom or a straight-chain or branched alkyl group having 1 to 12 carbon atoms; and n represents an integer from 1 to 5.

3. As in claim 1, a weakly anchored liquid crystal alignment agent, wherein, The dry polymer contains at least one of the compounds selected from the group consisting of compounds represented by formulas (B-1) to (B-9) as a constituent component.

4. As in claim 1, a weakly anchored liquid crystal alignment agent, wherein, The graft copolymer was obtained by free radical polymerization.

5. A graft copolymer, which is a graft copolymer contained in a liquid crystal alignment agent, having a dry polymer and a branch polymer bonded to the dry polymer as a side chain of the dry polymer, wherein the ratio of the number of macromonomers used in the synthesis of the branch polymer to the number of monomers used in the synthesis of the dry polymer is 0.1 / 99.9 to 50 / 50 (moles / moles), the branch polymer is derived from a macromonomer represented by formula (1), and the dry polymer contains a compound represented by formula (8) as a constituent component, wherein in formula (1), P represents a polymerizable group having a polymerizable unsaturated hydrocarbon group, Q is a structure obtained by polymerizing at least one of the monomers containing compounds 5 represented by formulas (2), (3), (5), and (7), and n is an integer from 1 to 2. When n is 2, the two Qs may be the same or different. In formula (2), M represents a polymerizable group with a polymerizable unsaturated hydrocarbon group, X represents a single bond, ether bond, ester bond, amide bond, carbamate bond, urea bond, or thioether bond, R1 represents an alkyl group with 1 to 20 carbon atoms that can also have a bonding group inserted, and n is an integer of 1 to 2. When n is 2, the two X and R1 can be the same or different. In formula (3), M represents a polymerizable group with a polymerizable unsaturated hydrocarbon group, S represents a single bond or a saturated hydrocarbon group with 1 to 6 carbon atoms that can also have a bonding group inserted, T represents the organic group represented by formula (4) below, and n is an integer of 1 to 2. When n is 2, the two T can be the same or different. However, when n is 2, S represents a saturated hydrocarbon group with 1 to 6 carbon atoms that can also have a bonding group inserted. In formula (4), * represents the bonding site, X represents a bonding group selected from single bond, ether bond, ester bond, amide bond, carbamate bond, urea bond, thioether bond, -Si(R1)(R2)- (R1 and R2 each independently represent an alkyl group bonded to Si), -Si(R3)(R4)-O- (R3 and R4 each independently represent an alkyl group bonded to Si), and -N(R5)- (R5 represents a hydrogen atom or alkyl group bonded to N), Cy represents a non-aromatic cyclic group with 6 to 20 members. In formula (5), M represents a polymerizable group with a polymerizable unsaturated hydrocarbon group, R1 represents an aliphatic hydrocarbon group with a straight chain or branched structure having 1 to 10 carbon atoms, and each of the three X's independently represents a hydrogen atom or the following formula (6), except that at least one of the three X's represents formula (6). In formula (6), Y represents a single bond, -O-, -S-, or -N(R)- (R represents a hydrogen atom bonded to N or an alkyl group with 1 to 4 carbon atoms), * represents a bonding site, R2, R3, and R4 each independently represent an alkyl group with 1 to 6 carbon atoms or an aromatic hydrocarbon group that may also have substituents, in formula (7), M represents a polymerizable group with a polymerizable unsaturated hydrocarbon group, R1 to R3 each independently represent a single bond or an alkyl group with 1 to 6 carbon atoms that may also have a bonding group inserted, Ar represents an aromatic hydrocarbon group that may also have substituents, X1 and X2 each independently represent a hydrogen atom or an aromatic hydrocarbon group that may also have substituents,The carbon atoms bonded to R1X1 and R2X2 can also form a ring together, provided that the total number of carbon atoms in R1X1, R2X2, and R3 is 1 or more. In equation (8), M represents a polymerizable group with a polymerizable unsaturated hydrocarbon group, n is an integer from 1 to 2, and Z represents the group represented by equation (9). When n is 2, the two Zs can be the same or different. In formula (9), L represents a group selected from amino, protected amino, aniline, protected aniline, hydroxyl, protected hydroxyl, phenol, protected phenol, thiol, protected thiol, thiophenol, protected thiophenol, carboxyl, protected carboxyl, benzoic acid, protected benzoic acid, isocyanate, protected isocyanate, cyclic ether with 2-5 carbon atoms, maleimino, carboxylic anhydride, N-hydroxysuccinimino, acezolinyl, trialkoxysilyl, vinyl, allyl, styryl, α-hydroxyacetophenone, α-aminoalkylacetophenone, oxime ester, acetophosphine oxide, cinnamic acid, cinnamic ester, azophenyl The functional group can be any of the following: N-benzylaniline, stilbene, diphenylethynyl, phenylbenzoate, aromatic hydrocarbon groups with 5-18 carbon atoms that may have a bonding group inserted, or aromatic heterocyclic groups with 5-18 carbon atoms that may have a bonding group inserted. J represents a single bond or an aliphatic hydrocarbon group with 1-6 carbon atoms. When K is bonded to an aromatic hydrocarbon group, it represents a linking group selected from single bonds, ether bonds, ester bonds, amide bonds, urea bonds, carbamate bonds, and thioether bonds. In other cases, it represents a single bond. * indicates the bonding site. m is an integer from 1 to 3. When m is 2 or 3, multiple K and L can be the same or different. However, when J is a single bond, m is 1.

6. The graft copolymer as claimed in claim 5, wherein, In formula (1), P and in formulas (2), (3), (5), (7), and (8), M each independently represent any of the following structures: R1 and R2 each independently represent a hydrogen atom or a straight-chain or branched alkyl group having 1 to 12 carbon atoms; X, Y, and Z each independently represent an oxygen atom or a sulfur atom; *, *1, and *2 represent bonding sites; one of *1 and *2 may also be replaced by a hydrogen atom or a straight-chain or branched alkyl group having 1 to 12 carbon atoms; and n represents an integer from 1 to 5.

7. The graft copolymer as claimed in claim 5, wherein, The dry polymer contains at least one of the compounds selected from the group consisting of compounds represented by formulas (B-1) to (B-9) as a constituent component.

8. The graft copolymer of claim 5 is obtained by free radical polymerization.

9. A weakly anchored liquid crystal alignment agent comprising the graft copolymer as claimed in claim 5.

10. A liquid crystal display element obtained using a weakly anchored liquid crystal alignment agent as claimed in any one of claims 1 to 4 and 9.

11. The liquid crystal display element of claim 10 is a horizontal electric field liquid crystal display element.

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