Liquid crystal aligning agent, liquid crystal alignment film, liquid crystal display device, and diamine

Abstract

To provide a liquid crystal alignment film that exhibits excellent adhesion (close adhesion) between the polyimide-based liquid crystal alignment film and a sealing agent or a substrate; a liquid crystal aligning agent therefor; and a liquid crystal display device provided with the liquid crystal alignment film.SOLUTION: Provided are a diamine having a structure represented by the following formula, a polymer obtained therefrom, and a liquid crystal aligning agent containing the polymer. Refer to the specification for symbols in the formula.SELECTED DRAWING: None

Description

[Technical field]

[0001] The present invention relates to a polymer having a protecting group which is substituted with a hydrogen atom by heat, which is used in a liquid crystal display element, a liquid crystal aligning agent, a liquid crystal alignment film and a liquid crystal display element using the same, and a novel diamine used therein. [Background technology]

[0002] Various driving methods have been developed for liquid crystal display elements, which differ in electrode structure, physical properties of the liquid crystal molecules used, manufacturing process, etc., and known liquid crystal display elements include the TN (twisted nematic) type, STN (super-twisted nematic) type, VA (vertical alignment) type, MVA (multi-domain vertical alignment) type, IPS (in-plane switching) type, FFS (fringe field switching) type, and PSA (polymer-sustained alignment) type. These liquid crystal display elements are provided with a liquid crystal alignment film to align the liquid crystal molecules. The material for the liquid crystal alignment film is generally a coating made of a polymer such as polyamic acid, polyimide, or polysiloxane, because these have various good properties such as heat resistance, mechanical strength, and affinity with liquid crystal.

[0003] As liquid crystal display elements become higher definition, there are demands for suppressing the decrease in contrast of liquid crystal display elements and reducing the afterimage phenomenon, and in addition to excellent liquid crystal alignment properties and stable pretilt angles, properties such as a high voltage holding ratio, suppression of afterimages caused by AC driving, small residual charge when a DC voltage is applied, and / or rapid relaxation of residual charge accumulated by a DC voltage are becoming increasingly important for liquid crystal alignment films.Various proposals have been made for polyimide-based liquid crystal alignment films to meet the above demands (see Patent Documents 1 to 5). [Prior art documents] [Patent documents]

[0004] [Patent Document 1] Japanese Patent Application Publication No. 9-316200 [Patent Document 2] Japanese Patent Application Publication No. 10-104633 [Patent Document 3] Japanese Patent Application Publication No. 8-76128 [Patent Document 4] Japanese Patent Application Publication No. 9-138414 [Patent Document 5] Japanese Patent Application Publication No. 11-38415 Summary of the Invention [Problem to be solved by the invention]

[0005] In recent liquid crystal display elements, in order to expand the effective pixel area, it is required to make the so-called frame area, where pixels are not formed at the peripheral edge of the substrate, smaller and smaller. As the frame of the panel becomes narrower, the sealant used when bonding two substrates to produce a liquid crystal display element is applied onto a polyimide liquid crystal alignment film. However, since there is no polar group on polyimide, covalent bonds are not formed between the sealant and the liquid crystal alignment film surface, resulting in insufficient adhesion between the substrates. Therefore, the challenge is to improve the adhesion (adhesion) between the polyimide liquid crystal alignment film and the sealant or substrate. [Means for solving the problem]

[0006] As a result of intensive research to solve the above problems, the present inventors have found that various properties can be improved simultaneously by introducing a specific structure into a polymer contained in a liquid crystal alignment agent, and have completed the present invention. The present invention is based on this finding and has the following gist. 1. A liquid crystal aligning agent comprising a polymer obtained from a diamine represented by the following general formula (1) and an organic solvent. [ka] (In formula (1), T 1 and T 2are each independently a single bond, -O-, -COO-, -OCO-, -NHCO-, -CONH-, -NH-, -N(CH3)-, -CON(CH3)-, or -N(CH3)CO-; W is a single bond or a divalent organic group (provided that T 1 or T 2 is a single bond, W is a single bond), and Q represents a substituent represented by the following formula (2). Two Q's in a molecule may be the same or different. [ka] In formula (2), X is a single bond, -O-, -COO-, -OCO-, or -S-; R 1 is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, A is a protecting group which is substituted with a hydrogen atom by heat, and n is an integer of 1 to 6. Effect of the Invention

[0007] According to the liquid crystal aligning agent of the present invention, a liquid crystal display element having excellent adhesion (tightness) between a polyimide-based liquid crystal alignment film and a sealing agent or a substrate, and a liquid crystal alignment film which gives such a liquid crystal display element can be obtained.

[0008] According to the liquid crystal alignment agent of the present invention, a liquid crystal alignment film having excellent adhesion to a sealant can be obtained. By using this liquid crystal alignment film, a liquid crystal display element having excellent adhesion between substrates and high resistance to impact can be obtained. Although the mechanism by which the adhesion to the sealant is improved is not necessarily clear, it is believed that when the A group is eliminated from the NA group of the diamine and replaced with a hydrogen atom due to the group having an NA structure being located at a predetermined position of the benzene ring, intramolecular cyclization is suppressed. As a result, the amino group generated by elimination of the protective group by heating is exposed on the surface of the liquid crystal alignment film, and it is believed that the adhesion between the liquid crystal alignment film and the sealant is improved due to the interaction between the group and the functional group in the sealant. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0009] The liquid crystal aligning agent of the present invention is a liquid crystal aligning agent containing a polymer (hereinafter also referred to as a specific polymer) obtained from a diamine having a structure (hereinafter also referred to as a specific structure) represented by the above formula (1). Each condition will be described in detail below.

[0010] <Diamine having a specific structure> In the above formula (1), T 1 , T 2 , W, and Q have the meanings as described above. In the above formula (1), T 1 and T 2 are preferably each independently a single bond, -O-, -COO-, -OCO-, -NHCO-, -CONH-, -NH-, or -N(CH3)-, and W is preferably a single bond or a hydrocarbon group having a linear, branched, or cyclic structure. The number of carbon atoms in the hydrocarbon group is preferably 1 to 20, and a part of the hydrocarbon group may be substituted with -O-, -COO-, or -OCO-. Preferable specific examples of the cyclic structure include a phenylene group and a cyclohexylene group. In the above formula (2), X is preferably any one of a single bond, -O-, -COO-, and -OCO-, and R 1 is preferably a hydrogen atom. A is preferably a tert-butoxycarbonyl group, and n is preferably an integer of 1 to 6. Specific examples of the diamine of the above formula (1) include, but are not limited to, the diamines represented by the following formulas DA-1 to DA-4, in which Boc represents a tert-butoxycarbonyl group. [ka]

[0011] <Polymer> The polymer of the present invention is a polymer obtained by using the above diamine. Specific examples include polyamic acid, polyamic acid ester, polyimide, polyurea, polyamide, etc., but from the viewpoint of use as a liquid crystal alignment agent, it is more preferable to use at least one selected from a polyimide precursor having a structural unit represented by the following formula (3) and a polyimide which is an imidized product thereof. [ka] However, X 1 is a tetravalent organic group derived from a tetracarboxylic acid derivative, and Y 1 is a divalent organic group derived from a diamine having a structure represented by the above formula (1), and R 2 R is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. 2 From the viewpoint of ease of imidization by heating, R is preferably a hydrogen atom, a methyl group, or an ethyl group. 2 may be the same or different from each other.

[0012] <Tetracarboxylic acid dianhydride> X1 is a tetravalent organic group derived from a tetracarboxylic acid derivative, and its structure is not particularly limited. X1 in the polyimide precursor is appropriately selected depending on the degree of required properties, such as the solubility of the polymer in a solvent, the applicability of the liquid crystal alignment agent, the alignment of the liquid crystal when made into a liquid crystal alignment film, the voltage holding ratio, the stored charge, etc., and one type of X1 may be present in the same polymer, or two or more types may be present in the same polymer.

[0013] Specific examples of X1 include structures of formulas (X-1) to (X-46) shown in pages 13 and 14 of WO 2015 / 119168.

[0014] Preferred structures of X1 are shown below, but the present invention is not limited to these. [ka]

[0015] [ka]

[0016] Of the above structures, (A-1) and (A-2) are particularly preferred from the viewpoint of photoalignment, (A-4) is particularly preferred from the viewpoint of further improving the relaxation speed of the accumulated charge, and (A-15) to (A-17) and the like are particularly preferred from the viewpoint of further improving the liquid crystal alignment and the relaxation speed of the accumulated charge.

[0017] <Polymers (other structural units)> The polyimide precursor having the structural unit represented by formula (3) may further have at least one selected from the structural unit represented by the following formula (4) and its imidized structure, within the range not impairing the effects of the present invention. [ka] In formula (4), X2 is a tetravalent organic group derived from a tetracarboxylic acid derivative, Y2 is a divalent organic group derived from a diamine that does not contain the structure of formula (1) in the main chain direction, R5 is defined as R2 in formula (3), and R6 represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. At least one of the two R6s is preferably a hydrogen atom. The two R5s and R6s may be the same or different from each other.

[0018] Specific examples of X2 include the same structures as those exemplified for X1 in formula (3), including preferred examples. Y2 in the polyimide precursor is a divalent organic group derived from a diamine that does not contain the structure of formula (1) in the main chain direction, and its structure is not particularly limited. Y2 is appropriately selected depending on the degree of required properties, such as the solubility of the polymer in a solvent, the coatability of the liquid crystal alignment agent, the alignment of the liquid crystal when made into a liquid crystal alignment film, the voltage holding rate, and the accumulated charge, and may be one type in the same polymer, or two or more types may be mixed.

[0019] Specific examples of Y2 include the structure of formula (2) described in paragraph 4 of WO 2015 / 119168, and the structures of formulae (Y-1) to (Y-97) and (Y-101) to (Y-118) described in paragraphs 8 to 12; a divalent organic group obtained by removing two amino groups from formula (2) described in paragraph 6 of WO 2013 / 008906; a divalent organic group obtained by removing two amino groups from formula (1) described in paragraph 8 of WO 2015 / 060360; a divalent organic group obtained by removing two amino groups from formula (1) described in paragraph 8 of JP 2012-173514; and a divalent organic group obtained by removing two amino groups from formulas (A) to (F) described in paragraph 9 of WO 2010-050523.

[0020] Preferred structures of Y2 are shown below, but the present invention is not limited to these. [ka]

[0021] [ka]

[0022] [ka]

[0023] [ka]

[0024] Of the above structures, (B-28) and (B-29) are particularly preferred from the viewpoint of further improving film hardness, (B-1) to (B-3) are particularly preferred from the viewpoint of further improving liquid crystal alignment, (B-14) to (B-18) and (B-27) are particularly preferred from the viewpoint of further improving the relaxation rate of accumulated charges, and (B-26) is preferred from the viewpoint of further improving the voltage holding ratio. In (B-28) to (B-30), the two n's may be the same or different.

[0025] <Diamines with specific side chain structures> Also, Y 2 It is also preferable to use a diamine having a specific side chain structure as the diamine. The diamine having a specific side chain structure is represented by, for example, the following formulas [1] and [2]. [ka] In the above formula [2], X is a single bond, -O-, -C(CH3)2-, -NH-, -CO-, -NHCO-, -COO-, -(CH2) m It represents a divalent organic group consisting of -, -SO2-, or any combination thereof. Among them, X is a single bond, -O-, -NH-, -O-(CH2) m As "any combination thereof", -O-(CH2) m -O-, -OC(CH3)2-, -CO-(CH2) m -, -NH-(CH2) m -, -SO2-(CH2) m -, -CONH-(CH2) m -, -CONH-(CH2) m -NHCO-, -COO-(CH2) m Examples of the aryl group include, but are not limited to, -OCO-, and the like. m is an integer of 1 to 8. In the above formulas [1] and [2], Y each independently represents at least one selected from the side chain structures represented by formulas [S1] to [S3]. In the above formula [2], the two Y's may be the same or different. The details of the side chain structures represented by formulas [S1] to [S3] will be described later.

[0026] In addition, in the above formula [2], Y may be in the meta position or the ortho position relative to the position of X, but is preferably in the ortho position. That is, the above formula [2] is preferably the following formula [2']. [ka]

[0027] In the above formula [2], the positions of the two amino groups (-NH2) may be any positions on the benzene ring, but the positions represented by the following formulas [2]-a1 to [2]-a3 are preferred, and the following formula [2]-a1 is more preferred. In the following formulas, X is the same as in the above formula [2]. Note that the following formulas [2]-a1 to [2]-a3 explain the positions of the two amino groups, and the notation of Y represented in the above formula [2] is omitted.

[0028] [ka]

[0029] Therefore, based on the above formulas [2'] and [2]-a1 to [1]-a3, the above formula [2] is preferably any structure selected from the following formulas [2]-a1-1 to [2]-a3-2, and more preferably the structure represented by the following formula [2]-a1-1, in which X and Y are the same as in formula [2].

[0030] [ka]

[0031] These two-chain diamines represented by the above formula [2] can be used alone or in combination of two or more. Depending on the properties required for the liquid crystal alignment film or liquid crystal display element, it is appropriate to appropriately adjust whether to use one alone or in combination of two or more, and when to use in combination of two or more, the ratio, etc.

[0032] In the above formulas [1] and [2], Y represents a specific side chain structure selected from the group represented by the following formulas [S1] to [S3]. Hereinafter, the specific side chain structure will be described in the order of formulas [S1] to [S3].

[0033] An example of the specific side chain structure is a diamine having a specific side chain structure represented by the following formula [S1]. [ka] In the above formula [S1], X 1 and X 2 are each independently a single bond, -(CH2) a -(a is an integer of 1 to 15), -CONH-, -NHCO-, -CON(CH3)-, -NH-, -O-, -COO-, -OCO- or -((CH2) a1 -A1) m1 In this, a1's each independently represent an integer of 1 to 15, a1's each independently represent an oxygen atom or -COO-, and m1 is 1 to 2.

[0034] Among them, from the viewpoints of availability of raw materials and ease of synthesis, X 1 and X 2 are each independently a single bond, -(CH2) a - (where a is an integer of 1 to 15), -O-, -CH2O- or -COO- is preferred. More preferred is X 1 and X 2 are each independently a single bond, -(CH2) a -(a is an integer of 1 to 10), -O-, -CH2O- or -COO-.

[0035] In addition, in the above formula [S1], G 1 and G 2 each independently represents a divalent cyclic group selected from a divalent aromatic group having 6 to 12 carbon atoms or a divalent alicyclic group having 3 to 8 carbon atoms. Any hydrogen atom on the cyclic group may be substituted with an alkyl group having 1 to 3 carbon atoms, an alkoxyl group having 1 to 3 carbon atoms, a fluorine-containing alkyl group having 1 to 3 carbon atoms, a fluorine-containing alkoxyl group having 1 to 3 carbon atoms, or a fluorine atom. m and n each independently represent an integer of 0 to 3, and the sum of m and n is 1 to 4. X 1 , X 2 , G 1 and G 2 If there are multiple X 1 , X 2 , G 1 and G 2may be the same or different from each other.

[0036] In addition, in the above formula [S1], R 1 represents an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, or an alkoxyalkyl group having 2 to 20 carbon atoms; R 1 Any hydrogen atom forming the group may be substituted with fluorine. Examples of the divalent aromatic group having 6 to 12 carbon atoms include phenylene, biphenylene, and naphthalene. Examples of the divalent alicyclic group having 3 to 8 carbon atoms include cyclopropylene and cyclohexylene.

[0037] Therefore, preferred specific examples of the above formula [S1] include the following formulas [S1-x1] to [S1-x7], but are not limited thereto.

[0038] [ka] In the above formula [S1-x1] to [S1-x7], R 1 is the same as in the above formula [S1]. p is -(CH2) a A1 represents an oxygen atom or -COO-* (the bond marked with "*" is (CH2)), -(a is an integer of 1 to 15), -CONH-, -NHCO-, -CON(CH3)-, -NH-, -O-, -CHO-, -COO- or -OCO-. a2 A2 represents an oxygen atom or *-COO- (the bond marked with "*" is (CH2) a2 a1 is an integer of 0 or 1, and a2 is an integer of 2 to 10. Cy, that is, a group in which "Cy" is written in a cyclohexane ring, represents a 1,4-cyclohexylene group or a 1,4-phenylene group.

[0039] Moreover, an example of the specific side chain structure is the specific side chain structure represented by the following formula [S2]. [ka] In the above formula [S2], X 3represents a single bond, -CONH-, -NHCO-, -CON(CH3)-, -NH-, -O-, -CHO-, -COO- or -OCO-. 3 is preferably -CONH-, -NHCO-, -O-, -CHO-, -COO- or -OCO-. 2 represents an alkyl group having 1 to 20 carbon atoms or an alkoxyalkyl group having 2 to 20 carbon atoms; R 2 Any hydrogen atom forming the group may be substituted with fluorine. 2 is preferably alkyl having 3 to 20 carbon atoms or alkoxyalkyl having 2 to 20 carbon atoms.

[0040] Further, an example of the specific side chain structure is the specific side chain structure represented by the following formula [S3]. [ka] In the above formula [S3], X 4 represents -CONH-, -NHCO-, -O-, -COO- or -OCO-. 3 represents a structure having a steroid skeleton. The steroid skeleton here has a skeleton represented by the following formula (st) in which three six-membered rings and one five-membered ring are bonded.

[0041] [ka]

[0042] An example of the above formula [S3] is the following formula [S3-x], but is not limited thereto. [ka] In the formula [S3-x], X represents the formula [X1] or [X2]. Col represents a group selected from the group consisting of the formulas [Col1] to [Col3], and G represents a group selected from the group consisting of the formulas [G1] to [G4]. * represents a site for bonding to another group.

[0043] In the above formula [S3-x], preferred examples of the combination of X, Col and G include the combination of formula [X1] with formula [Col1] and [G2], the combination of formula [X1] with formula [Col2] and [G2], the combination of formula [X2] with formula [Col1] and [G2], the combination of formula [X2] with formula [Col2] and [G2], and the combination of formula [X1] with formula [Col3] and [G1].

[0044] Specific examples of the above formula [S3] include a structure obtained by removing a hydroxyl group (hydroxy group) from a steroid compound described in paragraph

[0024] of JP-A-4-281427, a structure obtained by removing an acid chloride group from a steroid compound described in paragraph

[0030] of the same publication, a structure obtained by removing an amino group from a steroid compound described in paragraph

[0038] of the same publication, a structure obtained by removing a halogen group from a steroid compound described in paragraph

[0042] of the same publication, and structures described in paragraphs

[0018] to

[0022] of JP-A-8-146421.

[0045] These diamines having specific side chain structures represented by the above formulas [S1] to [S3] can be used alone or in combination of two or more. Depending on the properties required for the liquid crystal alignment film or liquid crystal display element, it is possible to appropriately adjust whether to use one type alone or in combination of two or more types, and when using two or more types in combination, the ratio, etc.

[0046] Among these, examples of diamines having a side chain structure selected from the group represented by the above formulas [S1] to [S3] include diamines having structures of the following formulas [1-S1] to [1-S3] and [2-S1] to [1-S3], respectively. [ka]

[0047] In the above formulas [1-S1] and [2-S1], X 1 , X 2 , G 1 , G 2 , R 1 , m and n are the same as those in the above formula [S1]. In the above formula [1-S2], X 3and R 2 is the same as in the above formula [S2]. In the above formula [1-S3], X 4 and R 3 is the same as in the above formula [S3]. In the above formulas [1-S1] and [2-S1] to [2-S3], X 1 , X 2 , G 1 , G 2 , X 3 , R 2 , X 4 , R 3 , m and n are multiple, then multiple X 1 , X 2 , G 1 , G 2 , X 3 , R 2 , X 4 , R 3 , m and n may be the same or different.

[0048] Among these, examples of the diamines represented by the above formulas [1-S1] to [1-S3] include specific structures as shown below, but are not limited thereto. [ka]

[0049] Examples of the diamines represented by the above formulas [2-S1] to [2-S3] include specific structures as shown below, but are not limited thereto. [ka]

[0050] <Other diamines: diamines having photoreactive side chains> Also, Y 2 It is also preferable to use a diamine having a photoreactive side chain as the photopolymer. When the diamine component contains a diamine having a photoreactive side chain, it becomes possible to introduce a photoreactive side chain into the specific polymer or other polymers.

[0051] Examples of diamines having a photoreactive side chain include, but are not limited to, those represented by the following formulas [VIII] and [IX]. [ka]

[0052] [ka]

[0053] In the above formulas [VIII] and [IX], the positions of the two amino groups (-NH2) may be any positions on the benzene ring, for example, the 2,3 positions, the 2,4 positions, the 2,5 positions, the 2,6 positions, the 3,4 positions, or the 3,5 positions on the benzene ring relative to the side chain bonding group. From the viewpoint of reactivity in synthesizing polyamic acid, the 2,4 positions, the 2,5 positions, or the 3,5 positions are preferred. Taking into consideration the ease of synthesizing diamine, the 2,4 positions or the 3,5 positions are more preferred.

[0054] In addition, in the above formula [VIII], R 8 represents a single bond, -CH2-, -O-, -COO-, -OCO-, -NHCO-, -CONH-, -NH-, -CHO-, -N(CH3)-, -CON(CH3)- or -N(CH3)CO-. In particular, R 8 is preferably a single bond, -O-, -COO-, -NHCO- or -CONH-.

[0055] In addition, in the above formula [VIII], R 9 represents a single bond or an alkylene group having 1 to 20 carbon atoms which may be substituted with a fluorine atom. Here, -CH2- in the alkylene group may be arbitrarily substituted with -CF2- or -CH=CH-, and may be substituted with any of the following groups when they are not adjacent to each other: -O-, -COO-, -OCO-, -NHCO-, -CONH-, -NH-, or a divalent carbocyclic or heterocyclic ring.

[0056] Of the above, specific examples of the divalent carbocyclic or heterocyclic ring include structures selected from the following formula (1a), but are not limited thereto. [ka]

[0057] In addition, in the above formula [VIII], R 9 can be formed by a typical organic synthesis method, but from the viewpoint of ease of synthesis, a single bond or an alkylene group having 1 to 12 carbon atoms is preferred.

[0058] In addition, in the above formula [VIII], R 10 represents a photoreactive group selected from the group consisting of the following formula (1b): 10 From the viewpoint of photoreactivity, a methacryl group, an acrylic group or a vinyl group is preferred. [ka]

[0059] In the formula [IX], Y1 represents -CH2-, -O-, -CONH-, -NHCO-, -COO-, -OCO-, -NH- or -CO-. Y2 represents an alkylene group having 1 to 30 carbon atoms, or a divalent carbocyclic ring or heterocyclic ring. In the alkylene group, divalent carbocyclic ring or heterocyclic ring, one or more hydrogen atoms may be substituted with a fluorine atom or an organic group. In Y2, -CH2- may be substituted with the following groups when they are not adjacent to each other: -O-, -NHCO-, -CONH-, -COO-, -OCO-, -NH-, -NHCONH-, -CO-. Examples of the organic group include a substituent selected from the group consisting of a halogen atom-containing alkyl group, a halogen atom-containing alkoxy group, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an alkenyl group having 1 to 10 carbon atoms, and a heteroatom-containing group in which a carbon-carbon bond of any methylene group of the halogen atom-containing alkyl group, halogen atom-containing alkoxy group, alkyl group, alkoxy group, and alkenyl group is interrupted by an oxygen atom.

[0060] In the formula [IX], Y3 represents -CH2-, -O-, -CONH-, -NHCO-, -COO-, -OCO-, -NH-, -CO-, or a single bond. Y4 represents a cinnamoyl group. Y5 represents a single bond, an alkylene group having 1 to 30 carbon atoms, or a divalent carbocyclic ring or heterocyclic ring. In the alkylene group, the divalent carbocyclic ring, or the heterocyclic ring, one or more hydrogen atoms may be substituted with a fluorine atom or an organic group. In Y5, when the following groups are not adjacent to each other, -CH2- may be substituted with these groups: -O-, -NHCO-, -CONH-, -COO-, -OCO-, -NH-, -NHCONH-, -CO-. Y6 represents a photopolymerizable group such as an acrylic group or a methacrylic group. Examples of the organic group include a substituent selected from the group consisting of a halogen atom-containing alkyl group, a halogen atom-containing alkoxy group, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an alkenyl group having 1 to 10 carbon atoms, and a heteroatom-containing group in which a carbon-carbon bond of any methylene group of the halogen atom-containing alkyl group, halogen atom-containing alkoxy group, alkyl group, alkoxy group, and alkenyl group is interrupted by an oxygen atom.

[0061] Specific examples of such diamines having a photoreactive side chain represented by the above formula [VIII] or [IX] include diamines selected from the following formula (1c), but are not limited thereto. [ka] In the above formula (1c), X 9 and X 10 each independently represents a single bond, -O-, -COO-, -NHCO- or -NH-. Y represents an alkylene group having 1 to 20 carbon atoms which may be substituted with a fluorine atom.

[0062] The diamine having a photoreactive side chain may be represented by the following formula [VII]. The diamine of formula [VII] has a moiety having a radical generating structure in the side chain. The radical generating structure is decomposed by irradiation with ultraviolet light to generate radicals. [ka] In the above formula [VII], Ar represents at least one aromatic hydrocarbon group selected from the group consisting of phenylene, naphthylene, and biphenylene, and the hydrogen atom of the aromatic hydrocarbon group may be substituted with a halogen atom. Since Ar with carbonyl bonded is involved in the absorption wavelength of ultraviolet light, in the case of increasing the wavelength, a structure with a long conjugation length such as naphthylene or biphenylene is preferable. On the other hand, when Ar has a structure such as naphthylene or biphenylene, the solubility may be deteriorated, and in this case, the difficulty of synthesis increases. If the wavelength of ultraviolet light is in the range of 250 nm to 380 nm, sufficient characteristics can be obtained even with a phenyl group, so Ar is most preferably a phenyl group.

[0063] In the above Ar, the aromatic hydrocarbon group may have a substituent other than a halogen atom. Preferred examples of the substituent include electron-donating organic groups such as alkyl groups, hydroxyl groups, alkoxy groups, and amino groups.

[0064] In the above formula [VII], R1 and R2 each independently represent an alkyl group, an alkoxy group, a benzyl group, or a phenethyl group having 1 to 10 carbon atoms. In the case of an alkyl group or an alkoxy group, R1 and R2 may form a ring.

[0065] In addition, in the above formula [VII], T1 and T2 each independently represent a single bond, or a bonding group such as -O-, -COO-, -OCO-, -NHCO-, -CONH-, -NH-, -CHO-, -N(CH)-, -CON(CH)-, or -N(CH)CO-.

[0066] In formula [VII], S represents a single bond, or an alkylene group having 1 to 20 carbon atoms which is unsubstituted or substituted with a fluorine atom. Here, -CH2- or -CF2- in the alkylene group may be optionally substituted with -CH=CH-, and may be substituted with any of the following groups when they are not adjacent to each other: -O-, -COO-, -OCO-, -NHCO-, -CONH-, -NH-, a divalent carbocyclic ring, or a divalent heterocyclic ring.

[0067] In addition, in formula [VII], Q represents a structure selected from the following formula (1d). [ka] In the above formula (1d), R represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. R3 represents -CH2-, -NR-, -O-, or -S-. The two R's may be the same or different.

[0068] In the above formula [VII], Q is preferably an electron-donating organic group, and is preferably a hydroxyl group, an alkoxy group, an amino group, etc., as mentioned in the above examples of Ar. When Q is an amino derivative, a carboxylic acid group generated during polymerization of a polyamic acid, which is a precursor of a polyimide, and an amino group may form a salt, which may cause other problems. Therefore, a hydroxyl group or an alkoxy group is more preferable.

[0069] In addition, in the above formula [VII], the positions of the two amino groups (-NH2) may be any of o-phenylenediamine, m-phenylenediamine, and p-phenylenediamine, but from the viewpoint of reactivity with acid dianhydrides, m-phenylenediamine and p-phenylenediamine are preferred.

[0070] Therefore, a preferred specific example of the above formula [VII] is the following formula, from the standpoint of ease of synthesis, versatility, properties, etc. In the following formula, n is an integer of 2-8. [ka]

[0071] The diamines having photoreactive side chains represented by the above formulas [VII], [VIII], or [IX] may be used alone or in combination of two or more. Whether they are used alone or in combination of two or more, and when they are used in combination of two or more, the ratio, etc., may be appropriately adjusted depending on the liquid crystal alignment property, pretilt angle, voltage retention property, stored charge property, etc., when used as a liquid crystal alignment film, and the response speed of the liquid crystal when used as a liquid crystal display element.

[0072] When a polyimide precursor having a structural unit represented by formula (3) simultaneously has a structural unit represented by formula (4), the structural unit represented by formula (3) preferably accounts for 10 mol % or more, more preferably 15 mol % or more, and particularly preferably 20 mol % or more, of the total of formulas (3) and (4).

[0073] The molecular weight of the polyimide precursor used in the present invention is preferably 2,000 to 500,000, more preferably 5,000 to 300,000, and further preferably 10,000 to 100,000, in terms of weight average molecular weight.

[0074] The polyimide having the divalent group represented by formula (1) in the main chain may be a polyimide obtained by ring-closing the polyimide precursor. In this polyimide, the ring-closing rate of the amic acid group (also called the imidization rate) does not necessarily have to be 100% and can be adjusted as desired depending on the application or purpose. Methods for imidizing the polyimide precursor include thermal imidization, in which a solution of the polyimide precursor is heated as is, and catalytic imidization, in which a catalyst is added to a solution of the polyimide precursor.

[0075] The liquid crystal aligning agent of the present invention is a composition containing the above-mentioned specific polymer and an organic solvent, and may contain two or more specific polymers having different structures. In addition, the liquid crystal aligning agent of the present invention may contain a polymer other than the specific polymer (hereinafter also referred to as a second polymer) and various additives to the extent that the effects described in the present invention are achieved.

[0076] When the liquid crystal aligning agent of the present invention contains a second polymer, the ratio of the specific polymer to the total polymer components is preferably 5% by mass or more, and an example thereof is 5 to 95% by mass.

[0077] Examples of the second polymer include polyamic acid, polyimide, polyamic acid ester, polyester, polyamide, polyurea, polyorganosiloxane, cellulose derivatives, polyacetal, polystyrene or its derivatives, poly(styrene-phenylmaleimide) derivatives, and poly(meth)acrylates.

[0078] In particular, a polyamic acid obtained from a tetracarboxylic dianhydride component and a diamine component (hereinafter also referred to as a second polyamic acid) is preferable as the second polymer.

[0079] An example of a tetracarboxylic dianhydride component for obtaining the second polyamic acid is a compound represented by the following formula (11). The dianhydride component may be composed of one type of compound or two or more types of compounds. [ka] In formula (11), A is a tetravalent organic group, preferably a tetravalent organic group having 4 to 30 carbon atoms.

[0080] Specific examples of A, including preferred examples, include the same structures as those exemplified for X1 in formula (3).

[0081] The diamine component for obtaining the second polyamic acid can be appropriately determined depending on the purpose, and for example, a diamine represented by the following formula (12) can be used. [ka] (Y9 represents a divalent organic group. A9 are each independently a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, an alkenyl group having 2 to 5 carbon atoms, or an alkynyl group having 2 to 5 carbon atoms, and may be the same or different. From the viewpoint of liquid crystal alignment, A9 is preferably a hydrogen atom or a methyl group.)

[0082] The structures of Y9 in formula (12), which are preferably used as the diamine component for obtaining the second polyamic acid, are shown below, but the present invention is not limited thereto. [ka]

[0083] For the purpose of improving electrical properties and relaxation properties, Y9 is preferably a divalent organic group having a tertiary nitrogen atom, or a divalent organic group having -NH-CO-NH- in the molecule. Specific examples of formula (12) when Y9 is a divalent organic group having a tertiary nitrogen atom include diamines having a pyrrole structure described in International Publication WO2017 / 126627, preferably diamines having a structure represented by the following formula (pr):

[0084] [ka] (R 1 represents a hydrogen atom, hydrogen, a fluorine atom, a cyano group, a hydroxyl group, or a methyl group, and R 2 are each independently a single bond or a group "*1-R 3 -Ph-*2" and R 3 is a single bond, -O-, -COO-, -OCO-, -(CH2) l -, -O(CH2) m represents a divalent organic group selected from -O-, -CONH-, and -NHCO- (l and m represent integers of 1 to 5), *1 represents a site bonded to the benzene ring in formula (pr), *2 represents a site bonded to the amino group in formula (pr); Ph represents a phenylene group; n represents 1 to 3; R 1 and R 2 If there are two or more, then there are two or more R 1 and R 2may be the same or different from each other.), a diamine having a pyrrole structure as described in International Publication WO2018 / 062197, preferably a diamine having a structure represented by the following formula (pn):

[0085] [ka] (R 1 and R 2 each independently represents a hydrogen atom or a methyl group; R 3 is a single bond or a group "*1-R 4 -Ph-*2" and R 4 is a single bond, -O-, -COO-, -OCO-, -(CH2) l -, -O(CH2) m represents a divalent organic group selected from -O-, -CONH-, and -NHCO- (l and m represent integers of 1 to 5), *1 represents a site bonded to the benzene ring in formula (pn), *2 represents a site bonded to the amino group in formula (pn). Ph represents a phenylene group. n represents 1 to 3. R 1 , R 2 and R 3 If there are two or more, then there are two or more R 1 , R 2 and R 3 may be the same or different from each other.), a diamine having a carbazole structure described in International Publication WO2018 / 110354, preferably a diamine having a structure represented by the following formula (cz):

[0086] [ka] (R 1 represents a hydrogen atom or a methyl group, R 2 represents a methyl group.), diamines having a nitrogen-containing heterocycle described in paragraphs

[0173] to

[0188] of International Publication WO2015 / 046374, diamines having a nitrogen-containing structure described in paragraph

[0050] of JP2016-218149A, and diamines represented by the following formula (BP):

[0087] [ka] (X is a biphenyl ring or a fluorene ring; Y is a benzene ring, a biphenyl ring, or a group selected from -phenylene-Z-phenylene-; Z is a divalent group represented by -O-, -NH-, -CH2-, -SO2-, -C(CH3)2-, or -C(CF3)2-; A and B are each independently a hydrogen atom or a methyl group), 2,3-diaminopyridine, 2,6-diaminopyridine, 3,4-diaminopyridine, Lysine, 2,4-diaminopyrimidine, 5,6-diamino-2,3-dicyanopyrazine, 5,6-diamino-2,4-dihydroxypyrimidine, 2,4-diamino-6-dimethylamino-1,3,5-triazine, 1,4-bis(3-aminopropyl)piperazine, 4,4'-[4,4'-propane-1,3-diylbis(piperidine-1,4-diyl)]dianiline, 2,4-diamino-6-isopropoxy-1 ,3,5-triazine, 2,4-diamino-6-methoxy-1,3,5-triazine, 2,4-diamino-6-phenyl-1,3,5-triazine, 2,4-diamino-6-methyl-s-triazine, 2,4-diamino-1,3,5-triazine, 4,6-diamino-2-vinyl-s-triazine, 3,5-diamino-1,2,4-triazole, 6,9-diamino-2-ethoxyacridine lactate, 3,8- Examples of the diamino-6-phenylphenanthridine include diamino-6-phenylphenanthridine, 1,4-diaminopiperazine, 3,6-diaminoacridine, bis(4-aminophenyl)phenylamine, 4,4'-diphenylmethylamine, 4,4'-diphenylamine, 3,6-diaminocarbazole, 9-methyl-3,6-diaminocarbazole, 9-ethyl-3,6-diaminocarbazole, and diamines represented by the following formulas (w1) to (w2).

[0088] [ka] (Sp represents phenylene, pyrrolidine, piperidine, piperazine, a divalent chain hydrocarbon group having 2 to 20 carbon atoms, or a group in which -CH2- of the divalent chain hydrocarbon group is substituted with a group selected from -O-, -CO-, -CO-O-, -NRCO- (R represents a hydrogen atom or a methyl group), -NRCOO- (R represents a hydrogen atom or a methyl group), -CONR- (R represents a hydrogen atom or a methyl group), -COS-, -NR- (R represents a methyl group), pyrrolidine, piperidine, and piperazine.)

[0089] Specific examples of the formula (12) in which Y9 in the formula (12) is a divalent organic group having -NH-CO-NH- in the molecule include diamines in which A1 in the above formula (4) is -NH-CO-NH-, a group in which at least one -CH2- in a chain hydrocarbon group having 2 to 20 carbon atoms is substituted with -NH-CO-NH-, or a group in which at least one -CH2- in a chain hydrocarbon group having 2 to 20 carbon atoms is substituted with -NH-CO-NH- and at least one other -CH2- is substituted with a group selected from -O-, -CO-, -CO-O-, -NRCO- (R represents a hydrogen atom or a methyl group), -NRCOO- (R represents a hydrogen atom or a methyl group), -CONR- (R represents a hydrogen atom or a methyl group), -COS-, and -NR- (R represents a methyl group). More preferred specific examples of diamines include diamines represented by the following formulas (U-1) to (U-9). [ka]

[0090] Preferred specific examples of the diamines represented by the above formulas (w1) to (w2) include diamines represented by the following formulas (n3-1) to (n3-7) and diamines represented by the following formulas (n4-1) to (n4-6). [ka]

[0091] [ka]

[0092] For the purpose of improving printability, diamine compounds having a carboxy group (-COOH group) or a hydroxy group (-OH group) can also be used. Specifically, 2,4-diaminophenol, 3,5-diaminophenol, 3,5-diaminobenzyl alcohol, 2,4-diaminobenzyl alcohol, 4,6-diaminoresorcinol, 2,4-diaminobenzoic acid, 2,5-diaminobenzoic acid, or 3,5-diaminobenzoic acid can be mentioned. Among them, 2,4-diaminobenzoic acid, 2,5-diaminobenzoic acid, or 3,5-diaminobenzoic acid is preferable. In addition, diamine compounds represented by the following formulas [3b-1] to [3b-4] and diamine compounds in which the amino group is a secondary amino group can also be used.

[0093] [ka] (In formula [3b-1], Q 1 represents a single bond, -CH2-, -C2H4-, -C(CH3)2-, -CF2-, -C(CF3)2-, -O-, -CO-, -NH-, -N(CH3)-, -CONH-, -NHCO-, -CHO-, -OCH2-, -COO-, -OCO-, -CON(CH3)- or -N(CH3)CO-; m1 and m2 each independently represent an integer of 0 to 4, and m1+m2 represents an integer of 1 to 4; in formula [3b-2], m3 and m4 each independently represent an integer of 1 to 5; in formula [3b-3], Q 2 represents a linear or branched alkyl group having 1 to 5 carbon atoms, m5 represents an integer of 1 to 5, and in formula [3b-4], Q 3 and Q 4 each independently represents a single bond, -CH2-, -C2H4-, -C(CH3)2-, -CF2-, -C(CF3)2-, -O-, -CO-, -NH-, -N(CH3)-, -CONH-, -NHCO-, -CHO-, -OCH2-, -COO-, -OCO-, -CON(CH3)- or -N(CH3)CO-, and m6 represents an integer of 1 to 4.

[0094] As the diamine component for obtaining the second polyamic acid, in addition to the above, the diamine used in the specific polymer or a known diamine can be used, but the present invention is not limited thereto. The diamine component for obtaining the second polyamic acid may be one kind of diamine, or two or more kinds of diamines may be used in combination.

[0095] <Methods of producing polyamic acid, polyamic acid ester, and polyimide> The polyimide precursors, ie, polyamic acid ester, polyamic acid and polyimide, used in the present invention can be synthesized by known methods such as those described in International Publication WO2013 / 157586.

[0096] <Liquid crystal alignment agent> The liquid crystal alignment agent of the present invention contains a specific polymer. The liquid crystal alignment agent of the present invention may contain other polymers in addition to the specific polymer and, if desired, a second polymer. Examples of the other polymers include polyamic acid, polyimide, polyamic acid ester, polyester, polyamide, polyurea, polyorganosiloxane, cellulose derivatives, polyacetal, polystyrene or its derivatives, poly(styrene-phenylmaleimide) derivatives, and poly(meth)acrylates.

[0097] The liquid crystal aligning agent is used to prepare a liquid crystal alignment film, and takes the form of a coating liquid from the viewpoint of forming a uniform thin film. The liquid crystal aligning agent of the present invention is also preferably a coating liquid containing a polymer component containing a specific polymer and an organic solvent. In this case, the concentration of the polymer in the liquid crystal aligning agent can be appropriately changed depending on the thickness of the coating film to be formed. From the viewpoint of forming a uniform and defect-free coating film, it is preferably 1% by mass or more, and from the viewpoint of storage stability of the solution, it is preferably 10% by mass or less. A particularly preferred polymer concentration is 2 to 8% by mass.

[0098] The organic solvent contained in the liquid crystal alignment agent is not particularly limited as long as the polymer component is dissolved uniformly. Specific examples thereof include N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, dimethylsulfoxide, γ-butyrolactone, 1,3-dimethyl-2-imidazolidinone, methyl ethyl ketone, cyclohexanone, cyclopentanone, 3-methoxy-N,N-dimethylpropanamide, 3-butoxy-N,N-dimethylpropanamide (collectively referred to as "good solvent"). Among them, it is preferable to use N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, 3-methoxy-N,N-dimethylpropanamide, 3-butoxy-N,N-dimethylpropanamide, or γ-butyrolactone. The good solvent in the liquid crystal aligning agent of the present invention is preferably 20 to 99 mass %, more preferably 20 to 90 mass %, and particularly preferably 30 to 80 mass % of the total solvent contained in the liquid crystal aligning agent.

[0099] In addition, the organic solvent contained in the liquid crystal alignment agent is preferably a mixed solvent containing the above-mentioned solvent and a solvent (also called a poor solvent) that improves the coating property and the surface smoothness of the coating film when the liquid crystal alignment agent is applied. Specific examples of the organic solvent to be used in combination are listed below, but are not limited to these examples. For example, diisopropyl ether, diisobutyl ether, diisobutyl carbinol (2,6-dimethyl-4-heptanol), ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol dibutyl ether, 1,2-butoxyethane, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, 4-hydroxy-4-methyl-2-pentanone, diethylene glycol methyl ethyl ether, diethylene glycol dibutyl ether, 3-ethoxybutyl acetate, 1-methylpentyl acetate, 2-ethylbutyl acetate, 2-ethylhexyl acetate, ethylene glycol monoacetate, ethylene glycol diacetate, propylene carbonate, ethylene carbonate, ethylene glycol monobutyl ether, ethylene glycol monoisoamyl ether, ethylene glycol monohexyl ether, propylene glycol monobutyl ether, 1-(2-butoxyethoxy)-2-propanol, 2-(2-butoxy)-2-propanol, Examples of the ethoxy)-1-propanol, propylene glycol monomethyl ether acetate, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol dimethyl ether, ethylene glycol monobutyl ether acetate, ethylene glycol monoacetate, ethylene glycol diacetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, 2-(2-ethoxyethoxy)ethyl acetate, diethylene glycol acetate, propylene glycol diacetate, n-butyl acetate, propylene glycol monoethyl ether acetate, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, ethyl 3-methoxypropionate, propyl 3-methoxypropionate, butyl 3-methoxypropionate, n-butyl lactate, isoamyl lactate, diethylene glycol monoethyl ether, diisobutyl ketone (2,6-dimethyl-4-heptanone), and the like.

[0100] Of these, it is preferable to use diisobutyl carbinol, propylene glycol monobutyl ether, propylene glycol diacetate, diethylene glycol diethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol dimethyl ether, 4-hydroxy-4-methyl-2-pentanone, ethylene glycol monobutyl ether, ethylene glycol monobutyl ether acetate, and diisobutyl ketone.

[0101] Preferred combinations of good and poor solvents include N-methyl-2-pyrrolidone and ethylene glycol monobutyl ether, N-methyl-2-pyrrolidone, γ-butyrolactone and ethylene glycol monobutyl ether, N-methyl-2-pyrrolidone, γ-butyrolactone and propylene glycol monobutyl ether, N-ethyl-2-pyrrolidone and propylene glycol monobutyl ether, N-methyl-2-pyrrolidone, γ-butyrolactone, 4-hydroxy-4-methyl-2-pentanone and diethylene glycol diethyl ether, and N-methyl-2-pyrrolidone and γ-butyrolactone. Examples of poor solvents include propylene glycol monobutyl ether and 2,6-dimethyl-4-heptanone, N-methyl-2-pyrrolidone, γ-butyrolactone, propylene glycol monobutyl ether and diisopropyl ether, N-methyl-2-pyrrolidone, γ-butyrolactone, propylene glycol monobutyl ether and 2,6-dimethyl-4-heptanol, N-methyl-2-pyrrolidone, γ-butyrolactone and dipropylene glycol dimethyl ether, and N-methyl-2-pyrrolidone, propylene glycol monobutyl ether and dipropylene glycol dimethyl ether. These poor solvents are preferably 1 to 80% by mass, more preferably 10 to 80% by mass, and particularly preferably 20 to 70% by mass of the total solvent contained in the liquid crystal alignment agent. The type and content of such solvents are appropriately selected depending on the coating device, coating conditions, coating environment, etc. of the liquid crystal alignment agent.

[0102] The liquid crystal alignment agent of the present invention may additionally contain components other than the polymer component and the organic solvent. Such additional components include an adhesion assistant for increasing the adhesion between the liquid crystal alignment film and the substrate or between the liquid crystal alignment film and the sealant, a compound for increasing the strength of the liquid crystal alignment film (hereinafter also referred to as a crosslinking compound), a dielectric or conductive material for adjusting the dielectric constant or electrical resistance of the liquid crystal alignment film, etc.

[0103] As the crosslinkable compound, from the viewpoints of generating less AC afterimages and having a high effect of improving film strength, a compound having at least one group selected from the group consisting of an oxiranyl group, an oxetanyl group, a protected isocyanate group, a protected isothiocyanate group, a group containing an oxazoline ring structure, a group containing a Meldrum's acid structure, a cyclocarbonate group, and a group represented by the following formula (d), or a compound selected from compounds represented by the following formula (e) (hereinafter these are also collectively referred to as compound (C)). [ka] (In formula (d), R2 and R3 each independently represent a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, or "*-CH2-OH". * represents a bond. In formula (e), A represents an (m+n)-valent organic group having an aromatic ring, R and R' represent a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, m represents an integer of 1 to 6, and n represents an integer of 0 to 4. Any hydrogen atom in the aromatic ring may be replaced with a halogen atom, an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a fluoroalkyl group having 1 to 10 carbon atoms, a fluoroalkenyl group having 2 to 10 carbon atoms, or a fluoroalkoxy group having 1 to 10 carbon atoms.)

[0104] Specific examples of compounds having an oxiranyl group include compounds having two or more oxiranyl groups, such as the compounds described in paragraph

[0037] of JP-A-10-338880 and compounds having a triazine ring skeleton described in International Publication WO2017 / 170483. Among these, compounds containing nitrogen atoms, such as N,N,N',N'-tetraglycidyl-m-xylylenediamine, 1,3-bis(N,N-diglycidylaminomethyl)cyclohexane, N,N,N',N'-tetraglycidyl-4,4'-diaminodiphenylmethane, N,N,N',N'-tetraglycidyl-p-phenylenediamine, and compounds represented by the following formulas (r-1) to (r-3), are particularly preferred. [ka]

[0105] Specific examples of the compound having an oxetanyl group include compounds having two or more oxetanyl groups described in paragraphs

[0170] to

[0175] of WO 2011 / 132751.

[0106] Specific examples of the compound having a protected isocyanate group include the compounds having two or more protected isocyanate groups described in paragraphs

[0046] to

[0047] of JP 2014-224978 A, and the compounds having three or more protected isocyanate groups described in paragraphs

[0119] to

[0120] of WO 2015 / 141598 A. Among these, the compounds represented by the following formulae (bi-1) to (bi-3) are preferred. [ka]

[0107] Specific examples of compounds having a protected isothiocyanate group include compounds having two or more protected isothiocyanate groups, as described in JP-A-2016-200798.

[0108] Specific examples of the compound having a group containing an oxazoline ring structure include compounds containing two or more oxazoline structures, as described in paragraph

[0115] of JP-A-2007-286597.

[0109] Specific examples of the compound having a group containing a Meldrum's acid structure include compounds having two or more Meldrum's acid structures, as described in International Publication WO2012 / 091088.

[0110] Specific examples of the compound having a cyclocarbonate group include compounds described in International Publication WO2011 / 155577.

[0111] Examples of the alkyl group having 1 to 3 carbon atoms for R2 and R3 in the group represented by formula (d) include the groups exemplified in the above formulae (l) and (n).

[0112] Specific examples of the compound having a group represented by the formula (d) include compounds having two or more groups represented by the formula (d) described in International Publication WO2015 / 072554 and paragraph

[0058] of JP2016-118753A, compounds described in JP2016-200798A, etc. Among these, compounds represented by the following formulas (hd-1) to (hd-8) are preferred. [ka]

[0113] Examples of the (m+n)-valent organic group having an aromatic ring in A of the formula (e) include an (m+n)-valent aromatic hydrocarbon group having 5 to 30 carbon atoms, an (m+n)-valent organic group to which an aromatic hydrocarbon group having 5 to 30 carbon atoms is bonded directly or via a linking group, and an (m+n)-valent group having an aromatic heterocycle. Examples of the aromatic hydrocarbon group include benzene and naphthalene. Examples of the aromatic heterocycle include a pyrrole ring, an imidazole ring, a pyrazole ring, a pyridine ring, a pyrimidine ring, a quinoline ring, an isoquinoline ring, a carbazole ring, a pyridazine ring, a pyrazine ring, a benzimidazole ring, a benzimidazole ring, an indole ring, a quinoxaline ring, and an acridine ring. Examples of the linking group include an alkylene group having 1 to 10 carbon atoms, a group obtained by removing one hydrogen atom from the alkylene group, and a divalent or trivalent cyclohexane ring. Any hydrogen atom of the alkylene group may be substituted with an organic group such as a fluorine atom or a trifluoromethyl group. Specific examples include compounds described in International Publication WO2010 / 074269. Preferred specific examples include the following formulae (e-1) to (e-10). [ka]

[0114] The above compounds are examples of crosslinkable compounds, and are not limited thereto. For example, components other than those described above disclosed on pages 53

[0105] to 55

[0116] of International Publication No. 2015 / 060357 can be mentioned. In addition, the crosslinkable compound contained in the liquid crystal aligning agent of the present invention may be one type, or two or more types may be combined. The content of the crosslinkable compound in the liquid crystal aligning agent of the present invention is preferably 0.5 to 20 parts by mass relative to 100 parts by mass of the polymer component contained in the liquid crystal aligning agent, and more preferably 1 to 15 parts by mass from the viewpoints of proceeding with the crosslinking reaction to exhibit the intended effect and minimizing the occurrence of AC afterimages.

[0115] Examples of the adhesion aid include 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropyldiethoxymethylsilane, 2-aminopropyltrimethoxysilane, 2-aminopropyltriethoxysilane, N-(2-aminoethyl)-3-aminopropyltrimethoxysilane, N-(2-aminoethyl)-3-aminopropylmethyldimethoxysilane, 3-ureidopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane, N-ethoxycarbonyl-3-aminopropyltrimethoxysilane, N-ethoxycarbonyl-3-aminopropyltriethoxysilane, N-triethoxysilylpropyltriethylenetriamine, N-trimethoxy ... triethylenetriamine, 10-trimethoxysilyl-1,4,7-triazadecane, 10-triethoxysilyl-1,4,7-triazadecane, 9-trimethoxysilyl-3,6-diazanonyl acetate, 9-triethoxysilyl-3,6-diazanonyl acetate, N-benzyl-3-aminopropyltrimethoxysilane, N-benzyl-3-aminopropyltriethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, N-phenyl-3-aminopropyltriethoxysilane, N-bis(oxyethylene)-3-aminopropyltrimethoxysilane, N-bis(oxyethylene)-3-aminopropyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, 2-(3,Examples of silane coupling agents include 4-epoxycyclohexyl)ethyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane, p-styryltrimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, tris-(trimethoxysilylpropyl)isocyanurate, 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropyltrimethoxysilane, and 3-isocyanatepropyltriethoxysilane. When using these silane coupling agents, the amount is preferably 0.1 to 30 parts by mass, more preferably 0.1 to 20 parts by mass, per 100 parts by mass of the polymer component contained in the liquid crystal alignment agent, from the viewpoint of reducing the occurrence of AC afterimages.

[0116] <Liquid crystal alignment film / Liquid crystal display element> A liquid crystal alignment film can be manufactured by using the liquid crystal alignment agent. The liquid crystal display element according to the present invention includes a liquid crystal alignment film formed by using the liquid crystal alignment agent. The operation mode of the liquid crystal display element according to the present invention is not particularly limited, and it can be applied to various operation modes such as TN (Twisted Nematic) type, STN type, vertical alignment type (including VA-MVA type, VA-PVA type, etc.), in-plane switching type (IPS type), FFS (Fringe Field Switching) type, and optical compensation bend type (OCB type).

[0117] The liquid crystal display element according to the present invention can be manufactured, for example, by the following steps (1-1) to (1-3). In step (1-1), different substrates are used depending on the desired operation mode. Steps (1-2) and (1-3) are common to each operation mode.

[0118] [Step (1-1): Formation of coating film] First, the liquid crystal aligning agent of the present invention is applied onto a substrate, and then the applied surface is heated to form a coating film on the substrate.

[0119] (1-1A) For example, when manufacturing a TN-type, STN-type or VA-type liquid crystal display element, first, two substrates each having a patterned transparent conductive film are used as a pair, and the liquid crystal alignment agent prepared above is applied to the transparent conductive film-formed surface of each substrate, preferably by offset printing, spin coating, roll coating or inkjet printing. As the substrate, for example, a transparent substrate made of glass such as float glass or soda glass; or a plastic such as polyethylene terephthalate, polybutylene terephthalate, polyethersulfone, polycarbonate or poly(alicyclic olefin) can be used. As the transparent conductive film provided on one side of the substrate, a NESA film (registered trademark of PPG, USA) made of tin oxide (SnO2), an ITO film made of indium oxide-tin oxide (In2O3-SnO2), or the like can be used. To obtain a patterned transparent conductive film, for example, a method of forming a pattern by photo-etching after forming a patternless transparent conductive film; a method of using a mask having a desired pattern when forming a transparent conductive film; or the like can be used. When applying the liquid crystal alignment agent, in order to further improve the adhesion between the substrate surface and the transparent conductive film and the coating film, the surface of the substrate on which the coating film is to be formed may be pretreated by applying a functional silane compound, a functional titanium compound, or the like.

[0120] After the liquid crystal alignment agent is applied, preheating (prebaking) is preferably performed for the purpose of preventing dripping of the applied liquid crystal alignment agent. The prebaking temperature is preferably 30 to 200°C, more preferably 40 to 150°C, and particularly preferably 40 to 100°C. The prebaking time is preferably 0.25 to 10 minutes, more preferably 0.5 to 5 minutes. Thereafter, the solvent is completely removed, and a baking (postbaking) step is performed for the purpose of thermally imidizing the amic acid structure present in the polymer as necessary. The baking temperature (postbaking temperature) at this time is preferably 80 to 300°C, more preferably 120 to 250°C. The postbaking time is preferably 5 to 200 minutes, more preferably 10 to 100 minutes. The film thickness of the film thus formed is preferably 0.001 to 1 μm, more preferably 0.005 to 0.5 μm.

[0121] (1-1B) When manufacturing an IPS or FFS type liquid crystal display element, a liquid crystal alignment agent is applied to the electrode forming surface of a substrate having an electrode made of a transparent conductive film or a metal film patterned into a comb-tooth shape and to one surface of an opposing substrate having no electrode, and then each applied surface is heated to form a coating film. The materials of the substrate and transparent conductive film used in this case, the coating method, the heating conditions after coating, the patterning method of the transparent conductive film or the metal film, the pretreatment of the substrate, and the preferred thickness of the coating film to be formed are the same as those in (1-1A) above. As the metal film, for example, a film made of a metal such as chromium can be used.

[0122] In both of the above (1-1A) and (1-1B), a liquid crystal alignment film or a coating film to be a liquid crystal alignment film is formed by applying the liquid crystal alignment agent onto a substrate and then removing the organic solvent. At this time, the coating film may be further heated after the coating film is formed to advance the dehydration ring-closing reaction of the polyamic acid, polyamic acid ester, and polyimide blended in the liquid crystal alignment agent according to the present invention, to form a more imidized coating film.

[0123] [Step (1-2): Treatment for imparting alignment ability] When manufacturing a TN-type, STN-type, IPS-type or FFS-type liquid crystal display element, a treatment is carried out to impart liquid crystal alignment ability to the coating film formed in the above step (1-1). This imparts the alignment ability of liquid crystal molecules to the coating film, forming a liquid crystal alignment film. Examples of the alignment ability imparting treatment include a rubbing treatment in which the coating film is rubbed in a certain direction with a roll wrapped with a cloth made of fibers such as nylon, rayon or cotton, and a photoalignment treatment in which the coating film is irradiated with polarized or non-polarized radiation. On the other hand, when manufacturing a VA-type liquid crystal display element, the coating film formed in the above step (1-1) can be used as it is as a liquid crystal alignment film, but the coating film may also be subjected to an alignment ability imparting treatment.

[0124] When the coating film is given liquid crystal alignment ability by photo-alignment treatment, ultraviolet light and visible light containing light with a wavelength of 150 to 800 nm can be used as radiation to be irradiated to the coating film. When the radiation is polarized, it may be linearly polarized or partially polarized. When the radiation used is linearly polarized or partially polarized, the radiation may be applied from a direction perpendicular to the substrate surface, from an oblique direction, or a combination of these. When applying non-polarized radiation, the radiation is applied in an oblique direction.

[0125] Examples of light sources that can be used include low-pressure mercury lamps, high-pressure mercury lamps, deuterium lamps, metal halide lamps, argon resonance lamps, xenon lamps, and excimer lasers. Ultraviolet rays in a preferred wavelength range can be obtained by using a light source in combination with, for example, a filter, a diffraction grating, and the like. The radiation dose is preferably 10 to 5,000 mJ / cm. 2 and more preferably 30 to 2,000 mJ / cm 2 It is.

[0126] The coating film may be irradiated with light while being heated in order to enhance reactivity. The temperature during heating is usually 30 to 250°C, preferably 40 to 200°C, and more preferably 50 to 150°C.

[0127] When ultraviolet light containing light having a wavelength of 150 to 800 nm is used, the light-irradiated film obtained in the above process can be used as a liquid crystal alignment film as it is, but the light-irradiated film may be baked, washed with water or an organic solvent, or a combination of these. The baking temperature is preferably 80 to 300°C, more preferably 80 to 250°C. The baking time is preferably 5 to 200 minutes, more preferably 10 to 100 minutes. The baking may be performed once or twice or more. The photo-alignment treatment here corresponds to a treatment of light irradiation in a state where the film is not in contact with the liquid crystal layer.

[0128] The organic solvent used for the washing is not particularly limited, but specific examples include water, methanol, ethanol, 2-propanol, acetone, methyl ethyl ketone, 1-methoxy-2-propanol, 1-methoxy-2-propanol acetate, butyl cellosolve, ethyl lactate, methyl lactate, diacetone alcohol, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, propyl acetate, butyl acetate, and cyclohexyl acetate.

[0129] The liquid crystal alignment film after the rubbing treatment may be further subjected to a treatment to change the pretilt angle of a part of the liquid crystal alignment film by irradiating a part of the liquid crystal alignment film with ultraviolet light, or a treatment to form a resist film on a part of the surface of the liquid crystal alignment film and then perform a rubbing treatment in a direction different from that of the previous rubbing treatment, followed by removing the resist film, so that the liquid crystal alignment film has different liquid crystal alignment capabilities for each region. In this case, it is possible to improve the visibility characteristics of the resulting liquid crystal display element. The liquid crystal alignment film suitable for VA type liquid crystal display elements can also be suitably used for PSA (polymer sustained alignment) type liquid crystal display elements.

[0130] [Step (1-3): Construction of liquid crystal cell] (1-3A) Two substrates on which a liquid crystal alignment film is formed are prepared as described above, and a liquid crystal is disposed between the two substrates arranged opposite to each other to manufacture a liquid crystal cell. There are, for example, two methods for manufacturing a liquid crystal cell. The first method is a conventionally known method. First, two substrates are arranged opposite to each other with a gap (cell gap) between them so that the liquid crystal alignment films face each other, the peripheries of the two substrates are bonded together with a sealant, and liquid crystal is injected and filled into the substrate surfaces and the cell gap partitioned by the sealant, and then the injection hole is sealed to manufacture a liquid crystal cell. The second method is a technique called the ODF (One Drop Fill) method. For example, an ultraviolet light curable sealant is applied to a predetermined location on one of the two substrates on which a liquid crystal alignment film is formed, and liquid crystal is further dropped at several predetermined locations on the liquid crystal alignment film surface, and then the other substrate is bonded so that the liquid crystal alignment films face each other, and the liquid crystal is spread over the entire surface of the substrate, and then ultraviolet light is irradiated over the entire surface of the substrate to cure the sealant, thereby manufacturing a liquid crystal cell. Regardless of which method is used, it is desirable to further heat the liquid crystal cell produced as described above to a temperature at which the liquid crystal used assumes an isotropic phase, and then slowly cool it to room temperature to remove the flow orientation that occurs during liquid crystal filling.

[0131] The sealing agent may be, for example, an epoxy resin containing a hardener and aluminum oxide spheres as spacers.

[0132] Examples of liquid crystals include nematic liquid crystals and smectic liquid crystals, among which nematic liquid crystals are preferred. For example, Schiff base liquid crystals, azoxy liquid crystals, biphenyl liquid crystals, phenylcyclohexane liquid crystals, ester liquid crystals, terphenyl liquid crystals, biphenylcyclohexane liquid crystals, pyrimidine liquid crystals, dioxane liquid crystals, bicyclooctane liquid crystals, cubane liquid crystals, etc. can be used. In addition, these liquid crystals may be used by adding cholesteric liquid crystals such as cholestyl chloride, cholesteryl nonaate, and cholesteryl carbonate; chiral agents such as those sold under the trade names "C-15" and "CB-15" (manufactured by Merck); and ferroelectric liquid crystals such as p-decyloxybenzylidene-p-amino-2-methylbutylcinnamate. The liquid crystal may also contain an anisotropic dye. The term "dye" may refer to a material capable of intensively absorbing or transforming light in at least a part or the entire visible light range, for example, a wavelength range of 400 nm to 700 nm, and the term "anisotropic dye" may refer to a material capable of anisotropically absorbing light in at least a part or the entire visible light range. The color of the liquid crystal cell can be adjusted by using such dyes. The type of anisotropic dye is not particularly limited, and for example, a black dye or a color dye can be used. The ratio of the anisotropic dye to the liquid crystal is appropriately selected within a range that does not impair the desired physical properties, and for example, the anisotropic dye can be included in a ratio of 0.01 to 5 parts by weight with respect to 100 parts by weight of the liquid crystal compound, but the ratio can be changed to an appropriate range as necessary.

[0133] (1-3B) When producing a PSA type liquid crystal display element, a liquid crystal cell is constructed in the same manner as in (1-3A) above, except that a photopolymerizable compound such as any of the following formulae (w-1) to (w-5) is injected or dropped together with the liquid crystal. [ka]

[0134] Thereafter, the liquid crystal cell is irradiated with light while a voltage is applied between the conductive films of the pair of substrates. The voltage applied here can be, for example, 5 to 50 V DC or AC. The light to be irradiated can be, for example, ultraviolet light and visible light containing light with a wavelength of 150 to 800 nm, but ultraviolet light containing light with a wavelength of 300 to 400 nm is preferred. The light source for the irradiated light can be, for example, a low pressure mercury lamp, a high pressure mercury lamp, a deuterium lamp, a metal halide lamp, an argon resonance lamp, a xenon lamp, an excimer laser, or the like. The ultraviolet light in the above-mentioned preferred wavelength range can be obtained by using the light source in combination with, for example, a filter diffraction grating. The light irradiation dose is preferably 100 mJ / cm. 2 More than 30,000mJ / cm 2 More preferably, it is 100 to 20,000 mJ / cm 2 It is.

[0135] (1-3C) When a coating film is formed on a substrate using a liquid crystal alignment agent containing a compound (polymer or additive) having a photopolymerizable group, a liquid crystal cell may be constructed in the same manner as in (1-3A) above, and then a liquid crystal display element may be manufactured by going through a process of irradiating the liquid crystal cell with light while applying a voltage between the conductive films of a pair of substrates. According to this method, the advantages of the PSA mode can be realized with a small amount of light irradiation. The light irradiation to the liquid crystal cell may be performed in a state where the liquid crystal is driven by applying a voltage, or may be performed in a state where a low voltage is applied so that the liquid crystal is not driven. The voltage to be applied may be, for example, 0.1 to 30 V DC or AC. The explanation in (1-3B) above can be applied to the conditions of the light to be irradiated. The light irradiation treatment here corresponds to the light irradiation treatment in a state where the liquid crystal layer is in contact with the liquid crystal layer.

[0136] The liquid crystal display element according to the present invention can be obtained by attaching a polarizing plate to the outer surface of the liquid crystal cell. Examples of the polarizing plate to be attached to the outer surface of the liquid crystal cell include a polarizing film called an "H film" made by absorbing iodine while stretching and aligning polyvinyl alcohol, sandwiched between cellulose acetate protective films, and a polarizing plate made of the H film itself.

[0137] The liquid crystal display element according to the present invention can be effectively applied to various devices, and can be used in various display devices such as watches, portable games, word processors, notebook computers, car navigation systems, camcorders, PDAs, digital cameras, mobile phones, smartphones, various monitors, liquid crystal televisions, and information displays. EXAMPLES

[0138] The present invention will be described in more detail below with reference to examples. However, the present invention is not limited to these examples. In the following, the abbreviations of the compounds and the measurement methods of the respective properties are as follows. (acid dianhydride) DC-1 to DC-3: Compounds represented by the following formulas (DC-1) to (DC-3), respectively (Diamine) DA-1 to DA-10: Compounds represented by the following formulas (DA-1) to (DA-10), respectively. (solvent) NMP: N-methyl-2-pyrrolidone BCS: Butyl cellosolve [ka] (Boc represents a tert-butoxycarbonyl group.)

[0139] The methods for measuring the various characteristics and the methods for preparing the measurement samples therefor are as follows. <Viscosity measurement> The viscosity of the polyamic acid solution was measured using an E-type viscometer TVE-22H (manufactured by Toki Sangyo Co., Ltd.) with a sample amount of 1.1 mL (milliliters), a cone rotor TE-1 (1°34', R24), and a temperature of 25°C.

[0140] <Molecular weight measurement> The molecular weights of the polyimide precursor and polyimide were measured using a room temperature gel permeation chromatography (GPC) apparatus (GPC-101) (Showa Denko K.K.) and columns (KD-803, KD-805) (Showa Denko K.K.) as follows. Column temperature: 50℃ Eluent: N,N-dimethylformamide (additives: lithium bromide monohydrate (LiBr·H2O) 30 mmol / L, phosphoric acid anhydrous crystal (o-phosphoric acid) 30 mmol / L, tetrahydrofuran (THF) 10 ml / L) Flow rate: 1.0ml / min Standard samples for preparing a calibration curve: TSK standard polyethylene oxide (molecular weight: approximately 900,000, 150,000, 100,000, and 30,000) (manufactured by Tosoh Corporation) and polyethylene glycol (molecular weight: approximately 12,000, 4,000, and 1,000) (manufactured by Polymer Laboratory Co., Ltd.).

[0141] <Measurement of imidization rate> 20 mg of polyimide powder was placed in an NMR (nuclear magnetic resonance) sample tube (NMR sampling tube standard, φ5 (Kusano Scientific Co., Ltd.)), deuterated dimethyl sulfoxide (DMSO-d6, 0.05 mass% TMS (tetramethylsilane) mixture) (0.53 mL) was added, and ultrasonic waves were applied to completely dissolve the powder. This solution was measured by 500 MHz proton NMR using an NMR measurement device (JNW-ECA500) (JEOL Datum Co., Ltd.). The imidization rate was calculated by the following formula using the proton peak integrated value of this proton and the proton peak integrated value of the proton peak derived from the NH group of the amic acid that appears around 9.5 to 10.0 ppm. Imidization rate (%) = (1-α·x / y) × 100 In the above formula, x is the integrated value of the proton peak derived from the NH group of the amic acid, y is the integrated value of the peak of the reference proton, and α is the ratio of the number of reference protons to one NH group proton of the amic acid in the case of polyamic acid (imidization rate 0%).

[0142] DA-1 to DA-4 are new compounds that have not been published in the literature, and their synthesis methods are described in detail below.

[0143] The products described in the following Synthesis Examples 1 to 4 are 1 The product was identified by H-NMR analysis (analysis conditions are as follows). Equipment:BRUKER ADVANCE III-500MHz Measurement solvent: DMSO-d6 Reference material: Tetramethylsilane (TMS) (δ0.0 ppm for 1 H)

[0144] (Synthesis Example 1: Synthesis of DA-1) DA-1 was synthesized according to the following procedure. [ka]

[0145] <Synthesis of compound [1]> (4,4'-dinitro-[1,1'-biphenyl]-2,2'-diyl)dimethanol (120g, 0.394mol) was charged with chloroform (720g) and thionyl chloride (117g, 0.986mol), pyridine (1mL) was added, and the mixture was stirred at 50°C for 19 hours. After the reaction was completed, water (720g) was added to the reaction solution for liquid separation and washing, and chloroform (720g) was added for liquid separation and extraction. The obtained organic phase was concentrated, and the crystals were slurry washed with hexane (20.0g) and filtered. The obtained crystals were dried to obtain compound [1] (yield: 115g, 0.337mol, 85% yield). 1H-NMR(500MHz) in DMSO-d6:8.59(d,J=3.0Hz,2H),8.36-8.32(m,2H),7.63(m,2H),4.69(d,J=15.0Hz,2H),4.48(d,J=14.5Hz,2H).

[0146] <Synthesis of compound [2]> Compound [1] (115g, 0.337mol) was charged with N,N-dimethylformamide (460g) and potassium phthalimide (131g, 0.708mol) and stirred at 25℃ for 19 hours. After the reaction was completed, ethyl acetate (960g) and water (960g) were added, and white crystals were precipitated. These were filtered, washed with water (600g), and the obtained crystals were dried to obtain compound [2] (yield: 125g, 0.222mol, 66% yield). 1 H-NMR(500MHz) in DMSO-d6:8.26(d,J=2.5Hz,2H),8.17-8.14(m,2H),7.85-7.80(m,8H),7.56(d,J=10.5Hz,2H),4.74-4.62(m,4H).

[0147] <Synthesis of compound [3]> Compound [2] (119g, 0.212mol) was charged with tetrahydrofuran (595g) and hydrazine monohydrate (79%) (174g, 4.29mol) and stirred at 65℃ for about 3 days. After the reaction was completed, white crystals precipitated outside the system, which were removed by filtration, and the filtrate was concentrated and dried to obtain crude compound [3] (yield: 65.6g). The compound obtained was used as it was in the next step. 1 H-NMR(500MHz) in DMSO-d6:8.55(d,J=2.4Hz,2H),8.18-8.15(m,2H),7.41(d,J=8.4Hz,2H),3.50-3.38(m,4H),3.26(br,4H).

[0148] <Synthesis of compound [4]> To the crude product of compound [3] (50.0 g, 0.165 mol), methanol (300 g) was charged, and the mixture was stirred while cooling in an ice bath. Di-tert-butyl dicarbonate (74.0 g, 0.339 mol) diluted with methanol (50.0 g) was added dropwise while paying attention to exotherm, and after the addition was completed, the mixture was stirred at 25 °C for 3 hours. Since white crystals precipitated outside the system, these were filtered, the cake was washed with methanol (150 g), and the obtained crystals were dried to obtain compound [4] (yield: 65.7 g, 0.131 mol, yield 79%). 1 H-NMR (500 MHz) in DMSO-d6: 8.27 (s, 2H), 8.22 (d, J = 10.0 Hz, 2H), 7.47 - 7.37 (m, 4H), 3.95 - 3.76 (m, 4H), 1.36 (s, 18H).

[0149] <Synthesis of DA-1> To compound [4] (50.0 g, 0.0995 mol), tetrahydrofuran (300 g) and methanol (60.0 g) were added. After nitrogen substitution, 5% palladium carbon (hydrous product) (4.00 g) was added and nitrogen substitution was carried out again. A hydrogen Tedlar bag was attached and the mixture was stirred at 25 °C for 24 hours. After the reaction was completed, the mixture was passed through a membrane filter to remove palladium carbon, and then the filtrate was concentrated and dried to obtain DA-1 (yield: 42.9 g, 0.0969 mol, yield 97%). 1 H-NMR (500 MHz) in DMSO-d6: 6.95 (t, J = 5.0 Hz, 2H), 6.66 (d, J = 10.0 Hz, 2H), 6.56 (s, 2H), 6.44 (m, 2H), 4.97 (s, 4H), 3.82 - 3.74 (m, 8H), 1.38 (s, 18H).

[0150] (Synthesis Example 2: Synthesis of DA-2) DA-2 was synthesized by the following procedure.

Chemical formula

[0151] (Synthesis of compound [5]) 2-Chloroethylamine hydrochloride (51.9g, 0.447mol) and triethylamine (49.6g, 0.490mol) were added to methanol (204g) and stirred under ice-cooled conditions in a nitrogen atmosphere. Di-tert-butyl dicarbonate (117g, 0.536mol) dissolved in methanol (102g) was added dropwise while being careful not to generate heat, and when the heat generation ceased, the mixture was stirred at 25°C for 15 hours. After the reaction was completed, 4-dimethylaminopyridine (0.543g, 4.44mmol) was added and the mixture was stirred at 60°C for 1 hour to react the excess di-tert-butyl dicarbonate with methanol, and the reaction solution was concentrated. Ethyl acetate (300g) was added to the concentrated crude product, which was washed with pure water (300g x 3 times), and the organic phase was concentrated under reduced pressure and dried to obtain crude compound [5] (yield: 77.8g). The obtained compound was used as it was in the next step.

[0152] <Synthesis of compound [6]> 2-Amino-5-nitrophenol (54.8g, 0.356mol), potassium carbonate (61.8g, 0.447mol), potassium iodide (5.90g, 0.0355mol) were added to N,N-dimethylacetamide (210g) and the mixture was heated to 100℃. Compound [5] crude (77.8g) dissolved in N,N-dimethylacetamide (70.0g) was added dropwise and stirred at 100℃ for 21 hours. Ethyl acetate (280g) and pure water (280g) were added to the reaction solution, and the precipitated crystals were separated by filtration to obtain compound [6] crude. The filtrate was concentrated, ethyl acetate (90.0g) and methanol (340g) were added, and the mixture was stirred to precipitate crystals, which were then filtered. The obtained crystals were washed with methanol (140g) to obtain compound [6] crude. The crude products obtained in the above two steps were combined and crystallized with ethyl acetate (480 g) and toluene (480 g). The crystals were filtered and dried to obtain compound [6] (yield: 63.3 g, 0.213 mol). 1H-NMR (500 MHz) in DMSO-d6: 7.74 (dd, 1H, J = 8.8 Hz, 2.4 Hz), 7.53 (d, 1H, J = 2.4 Hz), 6.64 (d, 1H, J = 8.8 Hz), 7.20 (t, 1H, J = 6.0 Hz), 4.00 - 3.97 (m, 2H), 6.54 (br, 2H), 3.39 - 3.34 (m, 2H), 1.93 (s, 9H).

[0153] <Synthesis of Compound [7]> To compound [6] (15.0 g, 0.0505 mol), tetrahydrofuran (90.0 g) and pyridine (4.28 g, 0.0541 mol) were charged, and the mixture was stirred while cooling to 5 °C in an ice bath. Adipic acid dichloride (4.50 g, 0.0246 mol) diluted with tetrahydrofuran (15.0 g) was added dropwise. After completion of the dropwise addition, the mixture was stirred at 25 °C for 19 hours. After completion of the reaction, water (105 g) was added to the reaction solution, methanol (315 g) was added, and the mixture was stirred for 40 minutes to precipitate crystals. These were filtered, and the obtained crystals were dried to obtain compound [7] (yield: 15.6 g, 0.0221 mol, yield 90%). 1 H-NMR (500 MHz) in DMSO-d6: 9.23 (s, 2H), 8.49 (d, J = 9.0 Hz, 2H), 7.90 - 7.87 (m, 2H), 7.77 (s, 2H), 7.23 (t, J = 5.5 Hz, 2H), 4.14 (br, 4H), 3.40 (br, 4H), 2.59 (br, 4H), 1.70 (br, 4H), 1.42 (s, 18H).

[0154] <Synthesis of DA-2> To compound [7] (15.5 g, 0.0220 mol), N,N-dimethylformamide (465 g) was added. After nitrogen substitution, 5% palladium carbon (hydrous product) (1.24 g) was added, followed by nitrogen substitution. A hydrogen Tedlar bag was attached, and the mixture was stirred at 50 °C for 5 days. After completion of the reaction, the mixture was passed through a membrane filter to remove palladium carbon. Then, ethyl acetate (930 g) was added to the filtrate, and the mixture was washed by liquid separation with water (800 g) three times. The organic phase was concentrated and dried to obtain DA-2 (yield: 9.41 g, 0.0146 mol, yield 66%). 1H-NMR(500MHz) in DMSO-d6: 8.54(s, 2H), 7.46(d, J = 8.5Hz, 2H), 7.05(t, J = 5.5Hz, 2H), 6.20(d, J = 2.0Hz, 2H), 6.09 - 6.07(m, 2H), 4.90(s, 4H), 3.83(t, J = 5.5Hz, 4H), 3.30(br, 4H), 2.33(br, 4H), 1.62(br, 4H), 1.42(s, 18H).

[0155] (Synthesis Example 3: Synthesis of DA-3) DA-3 was synthesized according to the following procedure.

Chemical Structure

[0156] (Synthesis of Compound [8]) To compound [6] (15.0 g, 0.0505 mol), tetrahydrofuran (90.0 g) and pyridine (4.28 g, 0.0541 mol) were charged, and the mixture was stirred while cooling to 5 °C in an ice bath. Terephthaloyl chloride (5.00 g, 0.0246 mol) diluted with tetrahydrofuran (15.0 g) was added dropwise. After the addition was complete, the mixture was stirred at 25 °C for 20 hours. After completion of the reaction, water (105 g) was added to the reaction solution, methanol (315 g) was added, and the mixture was stirred for 40 minutes to precipitate crystals. These were filtered, and the obtained crystals were dried to obtain compound [8] (yield: 14.4 g, 0.0198 mol, yield 81%). 1 H-NMR(500MHz) in DMSO-d6: 9.80(s, 2H), 8.49(d, J = 9.0Hz, 2H), 8.17(s, 4H), 7.98 - 7.96(m, 2H), 7.87(d, J = 2.0Hz, 2H), 7.21(t, J = 5.5Hz, 2H), 4.24 - 4.22(m, 4H), 3.47 - 3.46(m, 4H), 1.27(s, 18H).

[0157] (Synthesis of DA-3) Compound [8] (14.3 g, 0.0203 mol) was mixed with N,N-dimethylformamide (489 g), substituted with nitrogen, then 5% palladium carbon (wet product) (1.14 g) was added and substituted with nitrogen, and a hydrogen Tedlar bag was attached and stirred at 50 ° C for about 5 days. After the reaction was completed, the mixture was passed through a membrane filter to remove the palladium carbon, and ethyl acetate (978 g) was added to the filtrate, which was then washed three times with water (800 g). The organic phase was concentrated and dried to obtain crude DA-3 crystals. This was crystallized with ethyl acetate and hexane, filtered, and the obtained crystals were dried to obtain DA-3 (yield: 10.0 g, 0.0151 mol, 74% yield). 1 H-NMR(500MHz) in DMSO-d6:9.30(s,2H),8.05(s,4H),7.44(d,J=8.5Hz,2H),7.01(t,J=5.5Hz,2H),6.29(d,J=1.5Hz,2 H),6.18-6.16(m,2H),5.06(s,4H),3.91(t,J=5.0Hz,4H),3.33(br,4H),1.62(br,4H),1.42(s,18H).

[0158] (Synthesis Example 4: Synthesis of DA-4) DA-4 was synthesized according to the following procedure. [ka]

[0159] <Synthesis of compound [9]> Ethylene glycol (13.7g, 0.221mol) was charged with N,N-dimethylacetamide (150g) and potassium carbonate (67.0g, 0.485mol), and the mixture was heated and stirred at an internal temperature of 100℃. 2-Fluoro-5-nitrobenzonitrile (76.0g, 0.458mol) dissolved in N,N-dimethylacetamide (300g) was added dropwise over 50 minutes using a dropping funnel, and the mixture was heated and stirred for 6 hours from the end of the dropwise addition. After the reaction was completed, the reaction solution was cooled and then poured into stirred water (2250g) for water-diluted crystallization. This mixture was filtered, and tetrahydrofuran (100g) was added to the obtained wet crystals and stirred, and a mixed solvent of concentrated hydrochloric acid / methanol = 1 / 1 (100g) was added and filtered. The filtered crystals were dried to obtain compound [9] (yield: 54.6g, 0.700mol, 70% yield).

[0160] <Synthesis of compound

[10] > Compound [9] (30.5g, 0.0861mol) was added with tetrahydrofuran (305g) and substituted with nitrogen, and borane-tetrahydrofuran complex (287mL, 0.9mol / L solution: 0.258mol) was added dropwise at 25℃. After the dropwise addition, the mixture was heated to 65℃ under reflux for 17 hours. After the reaction, methanol was added to quench the excess borane, and concentrated hydrochloric acid / methanol = 1 / 1 mixed solvent (400g) was added and stirred at 25℃ for 14 hours. This was filtered using a Buchner filter, washed with tetrahydrofuran, and then dried to obtain compound

[10] (yield: 19.3g, 0.0443mol, 51% yield).

[0161] <Synthesis of compound

[11] > To compound

[10] (19.3 g, 0.0443 mol), methanol (77.2 g) and triethylamine (10.3 g, 0.0976 mol) were added, and the mixture was stirred under ice-cooling conditions in a nitrogen atmosphere. Di-tert-butyl dicarbonate (21.3 g, 0.0976 mol) dissolved in methanol (19.3 g) was added dropwise, and the mixture was stirred at 45 °C for 15 hours. After completion of the reaction, the reaction solution was poured into water (96.5 g) for dilution crystallization. After further adding methanol (128 g), sticky yellow crystals were obtained by filtration. These were washed with tetrahydrofuran / methanol to remove stickiness, and yellow crystals (11A) were collected by filtration. The filtrate was concentrated, washed in the same manner with tetrahydrofuran / methanol, and yellow crystals (11B) were collected by filtration. The obtained crystals (11A, 11B) were dried to obtain compound

[11] (yield: 17.1 g, 0.0304 mol, yield 69%). 1 H-NMR (500 MHz) in DMSO-d6: 8.23 - 8.18 (m, 2H), 8.02 (d, J = 1.0 Hz, 2H), 7.39 (br, 2H), 7.31 (d, J = 9.0 Hz, 2H), 4.61 (s, 4H), 4.12 (d, J = 6.0 Hz, 4H), 1.41 (s, 18H).

[0162] <Synthesis of DA-4> To compound

[12] (27.0 g, 0.0480 mol), tetrahydrofuran (459 g) and methanol (27 g) were added. After nitrogen substitution, 5% palladium carbon (hydrous) (2.16 g) was added, followed by nitrogen substitution again. A hydrogen Tedlar bag was attached and the mixture was stirred at 25 °C for 3 days. Since the reaction did not proceed completely, after removing palladium carbon by passing through a membrane filter, 5% palladium carbon (hydrous) (2.16 g) was added again, nitrogen substitution was carried out, a hydrogen Tedlar bag was attached, and the mixture was stirred at 45 °C for 2 days to complete the reaction. After completion of the reaction, palladium carbon was removed by passing through a membrane filter, the filtrate was concentrated, and the crude product was purified by column chromatography (ethyl acetate / hexane = 2 / 1 (volume ratio)) to obtain DA-4 (yield: 13.7 g, 0.0273 mol, yield 57%). 1H-NMR(500MHz) in DMSO-d6:6.93(t,J=5.5Hz,2H),6.71(d,J=8.5Hz,2H),6.44(s,2H),6.41-6 .39(m,2H),4.63(s,4H),4.11(s,4H),4.06(d,J=6.0Hz,4H),1.34(s,18H).

[0163] "Synthesis of polyamic acid" (Synthesis Example 5) In a 50mL four-necked flask equipped with a stirrer, 1.62g (2.2mmol) of 60wt% NMP solution of DA-1, 1.43g (13.2mmol) of DA-7, and 2.51g (6.6mmol) of DA-8 were weighed out, 19.7g of NMP was added, and the mixture was stirred to dissolve. While stirring this diamine solution, 2.75g (11.0mmol) of DC-1 was added, and 11.0g of NMP was further added, and the mixture was stirred at 60°C for 3 hours. Next, while stirring this solution, 1.94g (9.89mmol) of DC-2 was added, and 7.06g of NMP was further added, and the mixture was stirred at 40°C for 15 hours to obtain a polyamic acid solution (A-1, viscosity: 721mPa·s, number average molecular weight: 10,143).

[0164] (Synthesis Examples 6 to 9) Except for changing the diamine component and the acid dianhydride component to those shown in the table below, the same procedure as in Synthesis Example 5 was carried out to obtain polyamic acid solutions (A-2) to (A-5) shown in Table 1 below. The viscosity and molecular weight of the obtained polyamic acid are shown in Table 1 below. [Table 1]

[0165] "Synthesis of soluble polyimides" (Synthesis Example 10) The polyamic acid solution (A-1) (25 g) obtained in Synthesis Example 5 was diluted to 6.5 mass% with NMP, and then acetic anhydride (5.76 g) and pyridine (1.79 g) were added as imidization catalysts and reacted at 50 ° C for 3 hours. This reaction solution was poured into methanol (300 mL), and the resulting precipitate was filtered off. This precipitate was washed with methanol and dried under reduced pressure at 100 ° C to obtain polyimide powder (A-1-PI). The imidization rate of this polyimide was 52%. NMP (21.6 g) was added to the polyimide powder (A-1-PI) obtained above (2.4 g), and the mixture was stirred at 80 ° C for 20 hours to dissolve, obtaining a soluble polyimide (A-1-PI) solution.

[0166] (Synthesis Examples 11 to 14) Soluble polyimide solutions (A-2-PI) to (A-5-PI) shown in Table 2 were obtained by carrying out the same procedure as in Synthesis Example 10, except that the polyamic acid solution was changed to that shown in Table 2. The imidization ratios of the obtained soluble polyimides are shown in Table 2. [Table 2]

[0167] "Preparation of liquid crystal alignment agent" Example 1 NMP (6.0 g) and BCS (8.0 g) were added to the polyamic acid (A-1) solution (6.0 g) obtained in Synthesis Example 5, and the mixture was stirred at room temperature for 10 hours to obtain a liquid crystal alignment agent (PAA-1) containing 6 mass % of polyamic acid (A-1), 54 mass % of NMP, and 40 mass % of BCS.

[0168] Example 2 BCS (16.0 g) was added to the soluble polyimide (A-1-PI) solution (24.0 g) obtained in Synthesis Example 10, and the mixture was stirred at room temperature for 10 hours to obtain a liquid crystal alignment agent (SPI-1) containing 6 mass % of soluble polyimide (A-1-PI), 54 mass % of NMP, and 40 mass % of BCS.

[0169] (Examples 3 to 6 and Comparative Examples 1 to 4) Except for changing the polyamic acid solution or the soluble polyimide solution to those shown in Table 3 below, the same procedure as in Example 1 or Example 2 was carried out to obtain liquid crystal alignment agents (PAA-2) to (PAA-5) and (SPI-2) to (SPI-5). [Table 3]

[0170] "Preparation of samples for evaluating seal adhesion" The liquid crystal alignment agents prepared in Examples 1 to 6 and Comparative Examples 1 to 4 above were spin-coated onto a rectangular glass substrate with transparent electrodes measuring 30 mm in length, 40 mm in width, and 1.1 mm in thickness, and then dried on a hot plate at 70°C for 90 seconds. After that, the substrate was baked in a hot air circulating oven at 230°C for 20 minutes to form a liquid crystal alignment film with a thickness of 100 nm. The two substrates thus obtained were prepared, and 4 μm bead spacers were applied to the liquid crystal alignment film surface of one of the substrates, followed by application of a sealant (723K1 manufactured by Kyoritsu Chemical Industry Co., Ltd.). Next, these substrates were laminated together so that the liquid crystal alignment film surfaces faced each other and the overlap width of the substrates was 1 cm. At this time, the amount of sealant dispensed was adjusted so that the diameter of the sealant after lamination was 3 mm. The two laminated substrates were then fixed with clips, and 4 J / cm was applied at a wavelength of 365 nm. 2 The adhesive was irradiated with ultraviolet light of 1000 ohms and then thermally cured at 120° C. for 1 hour to prepare a sample for evaluating adhesion.

[0171] "Seal adhesion measurement" The adhesion was evaluated using a desktop precision universal testing machine (AGS-X 500N) (manufactured by Shimadzu Corporation). After fixing the edges of the top and bottom substrates of the obtained evaluation sample, the substrates were pressed from the top of the center and the strength (N) at the time of peeling was measured. The pressure (N) was then normalized by the measured diameter (mm) of the sealant to evaluate the seal adhesion (N / mm). The results are shown in Table 4. As a result, Examples 1 to 6 obtained from diamines DA-1, DA-2, and DA-3 having two Boc amino groups had higher seal adhesion than Comparative Examples 1 to 2 obtained from diamine DA-6 having one Boc amino group. Also, Examples 1 to 6 had higher seal adhesion than Comparative Examples 3 to 4 in which the Boc amino groups contained in the composition were unified to the same mol % as Examples 1 to 6. [Table 4]

[0172] "Synthesis of polyamic acid" (Synthesis Examples 15 to 17) Using the diamine components and acid dianhydride components shown in Table 5 below, all of the diamine components were dissolved in NMP, and the acid dianhydride components were added thereto and stirred at 40°C for 15 hours to obtain polyamic acid solutions (A-6) to (A-8). In Table 5, the numbers in parentheses indicate the blending ratio (parts by mole) of each compound relative to 100 parts by mole of the total amount of diamines used in the synthesis for the diamine components, the blending ratio (parts by mole) of each compound relative to 100 parts by mole of the total amount of dianhydrides used in the synthesis for the diamine components, and the blending ratio (parts by mole) of each compound relative to 100 parts by mole of the total amount of dianhydrides used in the synthesis for the organic solvents. [Table 5]

[0173] "Preparation of liquid crystal alignment agent" (Example 7 and Comparative Examples 5 to 6) Except for changing the polyamic acid solution to that shown in Table 6 below, the same procedure as in Example 1 was carried out to obtain liquid crystal alignment agents (PAA-6) to (PAA-8). [Table 6]

[0174] "Preparation of samples for evaluating seal adhesion" The liquid crystal alignment agents obtained in Example 7 and Comparative Examples 5 to 6 were filtered through a filter with a pore size of 1.0 μm, and then spin-coated onto a rectangular ITO substrate with dimensions of 30 mm length × 40 mm width × 1.1 mm thickness. The substrate was dried on a hot plate at 80°C for 2 minutes, and then baked in a hot air circulating oven at 230°C for 30 minutes to form a coating film with a thickness of 100 nm. Linearly polarized ultraviolet light with an extinction ratio of 26:1 and a wavelength of 254 nm was irradiated on the coating surface through a polarizer at a rate of 200 mJ / cm. 2 This substrate was heated on a hot plate at 230° C. for 30 minutes to obtain a substrate with a liquid crystal alignment film. After applying 4 μm bead spacers onto the liquid crystal alignment film surface of the substrate thus obtained, a sealant (XN-1500T manufactured by Kyoritsu Chemical Industry Co., Ltd.) was dropped at a position 5 mm from the short side of the substrate. At that time, the amount of the sealant dropped was adjusted so that the diameter of the sealant after lamination was 3 mm. Next, an ITO substrate of the same size as above, which was not applied with the liquid crystal alignment agent, was prepared and laminated so that the overlap width of the substrates was 1 cm. The two laminated substrates were fixed with clips and then thermally cured at 150° C. for 1 hour to prepare a sample for adhesion evaluation.

[0175] "Seal adhesion measurement" The seal adhesion (N / mm) was evaluated in the same manner as above, and the results are shown in Table 7. As a result, Example 7 obtained from diamine DA-4 having two Boc amino groups had higher seal adhesion than Comparative Example 6 obtained from diamine DA-6 having one Boc amino group. Also, Example 7 obtained from diamine DA-4 having a substituent having a Boc amino group substituted at the meta position of the amino group had higher seal adhesion than Comparative Example 5 obtained from diamine DA-5 having a substituent having a Boc amino group substituted at the ortho position of the amino group. [Table 7]

[0176] As can be seen from the above results, in the adhesion evaluation, the liquid crystal alignment film obtained from the liquid crystal alignment agent using the diamine compound DA-1, DA-2, DA-3 or DA-4 was found to have higher adhesion than the liquid crystal alignment film obtained from the liquid crystal alignment treatment agent using the diamine compound DA-5 or DA-6. Specifically, this is shown in the comparison between Examples 1 to 6 and Comparative Examples 1 to 4 shown in Table 4, and the comparison between Example 7 and Comparative Examples 5 to 6 in Table 7.

[0177] From the above, by using the diamine represented by the formula (1) of the present invention, it is possible to improve the seal adhesion. [Industrial Applicability]

[0178] The liquid crystal display element using the liquid crystal alignment film obtained from the liquid crystal alignment agent of the present invention can be suitably used as a liquid crystal display element. These elements are also useful in liquid crystal displays for display purposes, and further in light control windows and light shutters for controlling the transmission and blocking of light.

[0179] The entire contents of the specification, claims and abstract of Japanese Patent Application No. 2020-23546, filed on February 14, 2020, are hereby incorporated by reference as the disclosure of the specification of the present invention.

Claims

1. A diamine represented by the following general formula (1): 【Chemistry 1】 (In formula (1), T １ and T ２ each independently represents a single bond, —O—, —COO—, —OCO—, —NHCO—, —CONH—, —NH—, or —N(CH ３ )-,-CON(CH ３ )-, and -N(CH ３ )CO-, and W is a single bond or a divalent organic group (provided that T １ Or T ２ is a single bond, W is a single bond, and Q represents a substituent represented by the following formula (2). Two Q's in a molecule may be the same or different. 【Chemistry 2】 (In formula (2), X is any one of a single bond, —O—, —COO—, —OCO—, and —S—; R １ is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, A is a protecting group which is substituted with a hydrogen atom by heat, and n is an integer of 1 to 6.

2. A polymer obtained from the diamine according to claim 1.

3. The polymer according to claim 2, wherein the polymer is at least one polymer selected from the group consisting of a polyimide precursor having a structural unit represented by the following formula (3) and a polyimide which is an imidized product thereof: 【Chemistry 3】 However, X １ is a tetravalent organic group derived from a tetracarboxylic acid derivative, Y １ is a divalent organic group derived from the diamine represented by the formula (1), R ２ is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms.

4. In the formula (3), X １ The polymer according to claim 3, wherein the structure is at least one selected from the following structures: 【Chemistry 4】 【Chemistry 5】

5. 5. The polymer according to claim 3, wherein the structural unit represented by the formula (3) accounts for 10 mol % or more of all structural units of the polymer.

6. The diamine according to claim 1, represented by any one of DA-1 to DA-4 below. 【Chemistry 6】 (Boc represents a tert-butoxycarbonyl group.)

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