Liquid crystal alignment agent, liquid crystal alignment film and liquid crystal display element

Abstract

The present invention provides a liquid crystal alignment agent, which forms a liquid crystal alignment film having a high refractive index and a high light transmittance due to its non-coloring property, and a liquid crystal alignment agent that forms a liquid crystal alignment film having a high vertical alignment property in addition to the above characteristics. The liquid crystal alignment agent of the present invention contains the following (A) component and (B) component. (A) component: at least one polymer (A) selected from the group consisting of a polyimide precursor and a polyimide as an imide product of the polyimide precursor, (B) component: a polymer (B) characterized by comprising a repeating unit structure represented by the following formula (1), having at least one triazine ring end, at least a portion of which is terminated by an aromatic amino group having a crosslinking group.

Description

Technical Field

[0001] The present invention relates to a liquid crystal alignment agent, a liquid crystal alignment film obtained from the liquid crystal alignment agent, and a liquid crystal display element having the liquid crystal alignment film. Background Art

[0002] Various driving methods have been developed for liquid crystal display elements, such as the electrode structure and the physical properties of the liquid crystal molecules used. For example, various display elements are known, such as TN (Twisted Nematic) type or STN (super-twisted nematic) type, VA (vertical alignment) type, IPS (in-plane switching) type, FFS (fringe field switching) type, etc.

[0003] As for the liquid crystal display element, it is usually configured to arrange a pair of electrode substrates in a manner of facing each other with a predetermined gap (several μm) and to seal the liquid crystal between the electrode substrates. And, by applying a voltage between the transparent conductive films of the electrodes constituting the electrode substrates, the display in the liquid crystal display element is performed. In addition, these liquid crystal display elements have a liquid crystal alignment film for orienting the liquid crystal molecules. As the material of the liquid crystal alignment film, for example, polyamic acid (Polyamide acid), polyamic acid ester, polyimide, etc. are known (see Patent Document 1, etc.).

[0004] Prior art literature

[0005] Patent Literature

[0006] Patent Document 1: International Publication No. 2016-080458 Summary of the invention

[0007] Problems to be solved by the invention

[0008] The transparent conductive film in the liquid crystal display element is usually formed by a composition (ITO) with indium oxide as the main component and several % of tin oxide doped therein, and its refractive index is different from that of the liquid crystal alignment film and has a high value. Therefore, when it is desired to transmit light from the display light source to the electrode substrate, the light will be reflected at the boundary surface of the transparent conductive film and the liquid crystal alignment film in each electrode substrate. As a result, the transmittance of the electrode substrate cannot be fully obtained, and the display brightness is reduced.

[0009] In particular, in recent years, ultra-high-definition panels such as 4K and 8K have been developed. The occupancy rate of the black matrix (BM), TFT (Thin Film Transistor, thin film field effect transistor), etc. in these panels has increased, and the aperture ratio of the panel has decreased, so improving the transmittance of the display part has received attention.

[0010] Therefore, based on the view that the above-mentioned undesirable condition can be eliminated by reducing the difference between the refractive index of the transparent conductive film and the refractive index of the liquid crystal alignment film, the inventors have conducted various studies on the materials for forming the liquid crystal alignment film in order to increase the refractive index of the liquid crystal alignment film. Specifically, various explorations have been conducted on the types of polymers contained in the liquid crystal alignment agent forming the liquid crystal alignment film in order to increase the refractive index of the liquid crystal alignment film.

[0011] The results clearly show that by selecting a specific polymer, a liquid crystal alignment film with a high refractive index close to that of a transparent conductive film can be obtained. On the other hand, when there are many polymers forming a liquid crystal alignment film with a high refractive index, it has colorability. The liquid crystal alignment film formed by a liquid crystal alignment agent containing a polymer with colorability has a reduced light transmittance due to its reasons, resulting in a reduction in display brightness, and as a result, the above-mentioned purpose cannot be achieved. In addition, it is clear that a liquid crystal alignment film with high vertical orientation is not easy to obtain a high refractive index due to the influence of the side chain structure, and a liquid crystal alignment film with a high refractive index and vertical orientation is required.

[0012] In view of the above, the object of the present invention is to provide a liquid crystal alignment agent for forming a liquid crystal alignment film having a high refractive index and a high light transmittance due to non-coloring, a liquid crystal alignment film obtained from the liquid crystal alignment agent, and a liquid crystal display element having the liquid crystal alignment film. Further, a liquid crystal alignment agent for forming a liquid crystal alignment film having high vertical alignment in addition to the above characteristics, a liquid crystal alignment film obtained from the liquid crystal alignment agent, and a liquid crystal display element having the liquid crystal alignment film are provided.

[0013] Solutions for solving problems

[0014] The present inventors have conducted intensive studies to achieve the above-mentioned problems, and as a result, have found that a liquid crystal aligning agent containing a specific polymer is effective for achieving the above-mentioned purpose, thereby completing the present invention.

[0015] The present invention includes the following aspects.

[0016] [1] A liquid crystal aligning agent comprising the following (A) component and (B) component.

[0017] (A) Component: at least one polymer (A) selected from the group consisting of a polyimide precursor and a polyimide which is an imidation product of the polyimide precursor.

[0018] Component (B): a polymer (B) characterized by comprising a repeating unit structure represented by the following formula (1), having at least one triazine ring terminal, at least a part of which is terminated with an aromatic amino group having a crosslinking group.

[0019]

[0020] (R and R' independently represent a hydrogen atom, an alkyl group, an alkoxy group, an aryl group or an aralkyl group, and Ar represents at least one selected from the group represented by formulae (2) to (12).)

[0021]

[0022] (Any hydrogen atom on the aromatic ring of formula (2) to (12) is optionally substituted, R 12 represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, W 1 and W 2 Independently represent single bonds, -CR 95 R 96 -(R 95 and R 96 Each independently represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms (wherein R 95 and R 96 Optionally, they may form a ring together)), -C(=O)-, -O-, -S-, -S(=O)-, -SO 2 -, or -NR 97 -(R 97 represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or a phenyl group), X 1 and X 2 each independently represents a single bond, an alkylene group having 1 to 10 carbon atoms, or -Y 1 -Ph-Y 2 -(Ph represents a phenylene group, any hydrogen atom on the phenylene group is optionally substituted, Y 1 and Y 2 Each of them independently represents a single bond or an alkylene group having 1 to 10 carbon atoms).

[0023] Effects of the Invention

[0024] According to the present invention, a liquid crystal alignment agent for forming a liquid crystal alignment film having a high refractive index and a high light transmittance due to non-coloring, a liquid crystal alignment film obtained from the liquid crystal alignment agent, and a liquid crystal display element having the liquid crystal alignment film can be provided. Furthermore, a liquid crystal alignment agent for forming a liquid crystal alignment film having high vertical alignment in addition to the above characteristics, a liquid crystal alignment film obtained from the liquid crystal alignment agent, and a liquid crystal display element having the liquid crystal alignment film can be provided. BRIEF DESCRIPTION OF THE DRAWINGS

[0025] Figure 1 is the compound T-1 synthesized in the example 1 This is a graph showing the measurement results of H-NMR spectrum.

[0026] Figure 2 is the compound T-2 synthesized in the example 1 This is a graph showing the measurement results of H-NMR spectrum. DETAILED DESCRIPTION

[0027] Hereinafter, the liquid crystal aligning agent of the present invention, the liquid crystal aligning film obtained from the liquid crystal aligning agent, and the liquid crystal display element having the liquid crystal aligning film are described in detail. The description of the constituent elements described below is an example of an embodiment of the present invention and is not limited to these contents.

[0028] (Liquid Crystal Alignment Agent)

[0029] The liquid crystal aligning agent of this invention contains the following (A) component and (B) component.

[0030] (A) Component: at least one polymer (A) selected from the group consisting of a polyimide precursor and a polyimide which is an imidation product of the polyimide precursor.

[0031] Component (B): a polymer (B) characterized by comprising a repeating unit structure represented by the above formula (1), having at least one triazine ring terminal, at least a part of which is terminated with an aromatic amino group having a crosslinking group.

[0032] The polymer (A) as the component (A) and the polymer (B) as the component (B) are described in detail below.

[0033] <Polymer (A)>

[0034] The liquid crystal aligning agent of the present invention contains at least one polymer (A) selected from the group consisting of a polyimide precursor and a polyimide which is an imide product of the polyimide precursor. The polymer constituting the component (A) may be composed of one or more polymers.

[0035] In addition, as a polyimide precursor, a polyamic acid, a polyamic acid ester, or a polyamic acid-polyamic acid ester copolymer etc. are mentioned, and it is preferable that the said polyimide precursor is obtained by making a diamine component and a tetracarboxylic acid component polymerize-react.

[0036] <<Diamine component>>

[0037] Examples of the diamine component include diamine (a) having at least one selected from the group consisting of structures represented by the following formulae (S1) to (S3), p-phenylenediamine, m-phenylenediamine, 4-(2-(methylamino)ethyl)aniline, 2,4-diaminobenzoic acid, 2,5-diaminobenzoic acid, 3,5-diaminobenzoic acid, or diamine compounds represented by the following formulae (3b-1) to (3b-4), diamines having a carboxyl group, such as 4,4'-diaminodiphenylmethane, 3,3'-diaminodiphenylmethane, 4,4'-diaminodiphenyl ether, 3,3'-diaminodiphenyl ether, 1,2-bis(4-aminophenyl)ethane, 1,3-bis(4-aminophenyl)propane, 1,4-bis(4-aminophenyl)propane, 1,4-bis(4-aminophenoxy)benzene, 1,3-bis(4-aminophenoxy)benzene, 1,2-bis(4-aminophenoxy)ethane, 1,2-bis(4-amino-2-methylphenoxy)ethane, 1,3-bis(4-aminophenoxy)propane, 1,4-bis(4-aminophenoxy)butane, 1,5-bis(4-aminophenoxy)pentane, 1,6-bis(4-aminophenoxy)hexane, 4-(2-(4-aminophenoxy)ethoxy)-3-fluoroaniline, di(2-(4-aminophenoxy)ethyl)ether, 4-amino-4'-(2-(4-aminophenoxy)ethoxy)biphenyl, 2,2'-dimethyl-4,4'-diaminobiphenyl, 3, 3'-dimethyl-4,4'-diaminobiphenyl, 4,4'-diamino-2,2'-bis(trifluoromethyl)biphenyl, 1,4-diaminonaphthalene, 1,5-diaminonaphthalene, 2,6-diaminonaphthalene, 2,7-diaminonaphthalene, 2,2'-bis[4-(4-aminophenoxy)phenyl]propane, 2,2'-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane, 2,2'-bis(4-aminophenyl)propane, 1,3-bis(4-aminophenethyl)urea and other diamines having a urea bond, 2-(2,4-diaminophenoxy)ethyl methacrylate, 2,4-diamino-N,N-diallylaniline and other diamines having a photopolymerizable group at the end, and the following formulas (R1) to (R5) and the like Diamines having a radical initiating function, diamines having a photosensitizing function that exhibits a sensitizing effect upon light irradiation, such as 4,4'-diaminobenzophenone, 3,3'-diaminobenzophenone, and 9,9-bis(4-aminophenyl)fluorene, 2,6-diaminopyridine, 3,4-diaminopyridine, 2,4-diaminopyrimidine, 3,6-diaminocarbazole, N-methyl-3,6-diaminocarbazole, diamines having a heterocyclic ring such as the following formulas (z-1) to (z-18), diamines having a diphenylamine skeleton such as the following formulas (Dp-1) to (Dp-9), and diamines having a group "-N(D)-" (D represents a protecting group that is detached by heating and replaced by a hydrogen atom, preferably a tert-butyloxycarbonyl group) such as the following formulas (5-1) to (5-10).), diamines having an oxazoline structure such as the following formulas (Ox-1) to (Ox-2), etc., but the present invention is not limited thereto. The diamine component may be composed of one or more diamines.

[0038]

[0039] (X 1 and X 2 Each independently represents a single bond, -(CH 2 ) a -(a is an integer of 1 to 15), -CONH-, -NHCO-, -CON(CH 3 )-, -NH-, -O-, -COO-, -OCO- or -((CH 2 ) a1 -A 1 ) m1 -(a1 is an integer from 1 to 15, A 1 represents oxygen atom or -COO-, m 1 is an integer from 1 to 2. 1 When it is 2, multiple a1 and A 1 G 1 and G 2 Each independently represents a divalent cyclic group selected from a divalent aromatic group having 6 to 12 carbon atoms and a divalent alicyclic group having 3 to 8 carbon atoms. Any hydrogen atom on the cyclic group is optionally substituted by an alkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, an alkyl group containing fluorine atoms having 1 to 3 carbon atoms, an alkoxy group containing fluorine atoms having 1 to 3 carbon atoms, or a fluorine atom. m and n are each independently an integer of 0 to 3, and m+n is an integer of 1 to 6, preferably an integer of 1 to 4. 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, forming R 1 Any hydrogen atom of is optionally substituted by a fluorine atom. )

[0040] -X 3 -R 2 (S2)

[0041] (X 3 Indicates a single bond, -CONH-, -NHCO-, -CON(CH 3 )-, -NH-, -O-, -CH 2 O-, -COO- or -OCO-. 2 represents an alkyl group having 1 to 20 carbon atoms or an alkoxyalkyl group having 2 to 20 carbon atoms, forming R 2 Any hydrogen atom of is optionally substituted by a fluorine atom. )

[0042] -X 4 -R 3 (S3)

[0043] (X 4 Indicates -CONH-, -NHCO-, -O-, -CH 2 O-, -COO- or -OCO-. 3 Indicates a structure with a steroidal skeleton.)

[0044]

[0045] (In formula (3b-1), A 1 Represents a single bond, -CH 2 -, -C 2 H 4 -, -C(CH 3 ) 2 -, -CF 2 -, -C(CF 3 ) 2 -, -O-, -CO-, -NH-, -N(CH 3 )-, -CONH-, -NHCO-, -CH 2 O-、-OCH 2 -, -COO-, -OCO-, -CON(CH 3 )-or-N(CH 3 )CO-, m1 and m2 are each independently an integer of 0 to 4, and m1+m2 is an integer of 1 to 4. In formula (3b-2), m3 and m4 are each independently an integer of 1 to 5. In formula (3b-3), A 2 represents a linear or branched alkyl group having 1 to 5 carbon atoms, and m5 is an integer of 1 to 5. In formula (3b-4), A 3 and A 4 Each independently represents a single bond, -CH 2 -, -C 2 H 4 -, -C(CH 3 ) 2 -, -CF 2 -, -C(CF 3 ) 2 -, -O-, -CO-, -NH-, -N(CH 3 )-, -CONH-, -NHCO-, -CH 2 O-、-OCH 2 -, -COO-, -OCO-, -CON(CH 3 )-or-N(CH 3 )CO-, m6 is an integer from 1 to 4. )

[0046]

[0047]

[0048] (In (R3) to (R5), n is an integer of 1 to 6.)

[0049]

[0050]

[0051] (Boc represents tert-butyloxycarbonyl.)

[0052]

[0053] As diamine (a), it is preferable that it has at least one benzene ring. As a more preferable specific example, the diamine represented by the following formula (d1) or formula (d2) can be mentioned.

[0054]

[0055] (X represents a single bond, -O-, -C(CH 3 ) 2 -, -NH-, -CO-, -(CH 2 ) m -、-SO 2 -、-O-(CH 2 ) m -O-, -O-C(CH 3 ) 2 -、-CO-(CH 2 ) m -、-NH-(CH 2 ) m -、-SO 2 -(CH 2 ) m -、-CONH-(CH 2 ) m -、-CONH-(CH 2 ) m -NHCO- or -COO-(CH 2 ) m -OCO-. m is an integer of 1 to 8. Y represents any structure in the above formulae (S1) to (S3). In formula (d2), two Ys may be the same or different from each other.

[0056] Preferred examples of the diamine represented by the above formula (d1) include the following formulas (d1-1) to (d1-7). Preferred examples of the diamine represented by the above formula (d2) include the following formulas (d2-1) to (d2-6).

[0057]

[0058]

[0059] (X v1 ~X v4 , X p1 ~X p8 Respectively independently represent -(CH 2 ) a -(a is an integer of 1 to 15), -CONH-, -NHCO-, -CON(CH 3 )-, -NH-, -O-, -CH 2 O-、-CH 2 -OCO-, -COO- or -OCO-, X V5 ~X V6 , X s1 ~X s4 Each independently represents -O-, -CH 2 O-, -COO- or -OCO-. X v7 Indicates -O-, -CH 2 O-、-CH 2 -OCO-, -COO- or -OCO-. X a ~X f Indicates a single bond, -O-, -NH-, -O-(CH 2 ) m -O-(m is an integer from 1 to 8), R v1 ~R v4 , R 1a ~R 1h Represented independently -C n H 2n+1 (n is an integer from 1 to 20), -O-C n H 2n+1 (n is an integer from 2 to 20.)

[0060] From the perspective of improving the response speed of liquid crystal display elements such as PSA (polymer-sustained alignment) type liquid crystal display elements and SC-PVA mode liquid crystal display elements, the above-mentioned diamines having a free radical initiating function or a photosensitizing function that shows a sensitization effect by light irradiation can be used alone or in combination when manufacturing the polymer (A).

[0061] As the diamine component, from the viewpoint of preferably obtaining the effect of the present invention, preferred are p-phenylenediamine, 3,5-diaminobenzoic acid, 4,4'-diaminodiphenylmethane, 4,4'-diaminobenzophenone, 2,2'-dimethyl-4,4'-diaminobiphenyl, 2-(2,4-diaminophenoxy)ethyl methacrylate, 2,4-diamino-N,N-diallylaniline, diamines represented by the above formulae (R1) to (R5), diamines represented by the above formulae (z-1) to (z-18), diamines represented by the above formulae (Dp-1) to (Dp-9), and diamines represented by the above formulae (Ox-1) to (Ox-2).

[0062] Examples of the diamine component include aliphatic diamines such as meta-xylene diamine, alicyclic diamines such as 4,4-methylenebis(cyclohexylamine), and diamines described in International Publication No. 2016 / 125870.

[0063] <<Tetracarboxylic acid component>>

[0064] The tetracarboxylic acid component refers to a component containing at least one selected from tetracarboxylic acids and tetracarboxylic acid derivatives. As tetracarboxylic acid derivatives, tetracarboxylic acid dihalides, tetracarboxylic dianhydrides, tetracarboxylic acid diester dichlorides, tetracarboxylic acid diesters, etc. can be listed. The tetracarboxylic acid component can be composed of one or more tetracarboxylic acids and tetracarboxylic acid derivatives.

[0065] The tetracarboxylic acid components used to manufacture polymer (A) can be listed as: aromatic tetracarboxylic dianhydride, aliphatic tetracarboxylic dianhydride, alicyclic tetracarboxylic dianhydride, or their derivatives. Here, aromatic tetracarboxylic dianhydride refers to an acid dianhydride obtained by intramolecular dehydration of four carboxyl groups including at least one carboxyl group bonded to an aromatic ring. Aliphatic tetracarboxylic dianhydride refers to an acid dianhydride obtained by intramolecular dehydration of four carboxyl groups bonded to a chain hydrocarbon structure. Among them, it is not necessary to be composed only of a chain hydrocarbon structure, and a part of it may also have an alicyclic structure or an aromatic ring structure. Alicyclic tetracarboxylic dianhydride refers to an acid dianhydride obtained by intramolecular dehydration of four carboxyl groups including at least one carboxyl group bonded to an alicyclic structure. Among them, none of these four carboxyl groups are bonded to an aromatic ring. In addition, it is not necessary to be composed only of an alicyclic structure, and a part of it may also have a chain hydrocarbon structure or an aromatic ring structure.

[0066] It is preferable that the tetracarboxylic acid component contains tetracarboxylic dianhydride represented by the following formula (S4).

[0067]

[0068] (X represents a structure selected from the group consisting of the following (x-1) to (x-13).)

[0069]

[0070] (R 1 ~R 4 R each independently represents a hydrogen atom, a methyl group, an ethyl group, a propyl group, a chlorine atom, a monovalent organic group having 1 to 6 carbon atoms and containing a fluorine atom, or a phenyl group. 5 and R 6 Each independently represents a hydrogen atom or a methyl group. j and k are integers 0 or 1, A 1 and A 2 Each independently represents a single bond, -O-, -CO-, -COO-, a phenylene group, a sulfonyl group, or an amide bond. *1 is a bond to one of the acid anhydride groups, and *2 is a bond to the other of the acid anhydride groups.)

[0071] More preferable specific examples of the above formula (x-1) include the following formulas (X1-1) to (X1-6): In the formulas, * represents a bonding bond.

[0072]

[0073] Preferred specific examples of (x-12) and (x-13) include the following formulae (x-14) to (x-29). In the formulae, "*" represents a bonding bond.

[0074]

[0075] Preferred examples of tetracarboxylic dianhydride or a derivative thereof represented by the above formula (S4) include tetracarboxylic dianhydride or a derivative thereof represented by formula (3) wherein X is the above formulas (x-1) to (x-7) and (x-11) to (x-13).

[0076] <Method for producing polymer (A)>

[0077] The polymer (A) used in the present invention can be synthesized by a known method such as described in International Publication No. WO2013 / 157586.

[0078] The polyimide can be obtained by ring-closing (imidizing) the polyimide precursor obtained in the polymer (A). The imidization ratio in this specification refers to the ratio of the imide group to the total amount of the imide group and the carboxyl group (or its derivative) derived from tetracarboxylic dianhydride or its derivative.

[0079] The molecular weight of the polymer (A) used in the present invention is preferably 5,000 to 1,000,000, more preferably 10,000 to 150,000, as measured by a weight average molecular weight by GPC (Gel Permeation Chromatography) method, taking into account the strength of the liquid crystal alignment film obtained later, workability during film formation, and coating properties.

[0080] <Polymer (B)>

[0081] The liquid crystal aligning agent of the present invention contains a polymer (B) characterized by comprising a repeating unit structure represented by the following formula (1), having at least one triazine ring terminal, at least a portion of which is terminated by an aromatic amino group having a crosslinking group. The polymer constituting the component (B) may be composed of one or more polymers.

[0082]

[0083] (R and R' independently represent a hydrogen atom, an alkyl group, an alkoxy group, an aryl group or an aralkyl group, and Ar represents at least one selected from the group represented by formulae (2) to (12).)

[0084]

[0085] (Any hydrogen atom on the aromatic ring of formula (2) to (12) is optionally substituted, R 12 represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, W 1 and W 2 Independently represent single bonds, -CR 95 R 96 -(R 95 and R 96 Each independently represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms (wherein R 95 and R 96 Optionally, they may form a ring together)), -C(=O)-, -O-, -S-, -S(=O)-, -SO 2 -, or -NR 97 -(R 97 represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or a phenyl group), X 1 and X 2 each independently represents a single bond, an alkylene group having 1 to 10 carbon atoms, or -Y 1 -Ph-Y 2 -(Ph represents a phenylene group, any hydrogen atom on the phenylene group is optionally substituted, Y 1 and Y 2 Each of them independently represents a single bond or an alkylene group having 1 to 10 carbon atoms).

[0086] In the above formula (1), R and R' independently represent a hydrogen atom, an alkyl group, an alkoxy group, an aryl group or an aralkyl group, and preferably both are hydrogen atoms from the viewpoint of further increasing the refractive index.

[0087] In the present invention, the number of carbon atoms of the alkyl group as R and R' in the above formula (1) is not particularly limited, but is preferably 1 to 20. In consideration of further improving the heat resistance of the polymer, the number of carbon atoms is more preferably 1 to 10, and further preferably 1 to 3. In addition, the structure may be any of chain, branched, and cyclic.

[0088] Specific examples of the alkyl group for R and R' in the above formula (1) include methyl, ethyl, n-propyl, isopropyl, cyclopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, cyclobutyl, 1-methyl-cyclopropyl, 2-methyl-cyclopropyl, n-pentyl, 1-methyl-n-butyl, 2-methyl-n-butyl, 3-methyl-n-butyl, 1,1-dimethyl-n-propyl, 1,2-dimethyl-n-propyl, 2,2-dimethyl-n-propyl, 1-ethyl-n-propyl, cyclopentyl, 1-methyl-cyclobutyl , 2-methyl-cyclobutyl, 3-methyl-cyclobutyl, 1,2-dimethyl-cyclopropyl, 2,3-dimethyl-cyclopropyl, 1-ethyl-cyclopropyl, 2-ethyl-cyclopropyl, n-hexyl, 1-methyl-n-pentyl, 2-methyl-n-pentyl, 3-methyl-n-pentyl, 4-methyl-n-pentyl, 1,1-dimethyl-n-butyl, 1,2-dimethyl-n-butyl, 1,3-dimethyl-n-butyl, 2,2-dimethyl-n-butyl, 2,3-dimethyl-n-butyl, 3,3-dimethyl-n-butyl , 1-ethyl-n-butyl, 2-ethyl-n-butyl, 1,1,2-trimethyl-n-propyl, 1,2,2-trimethyl-n-propyl, 1-ethyl-1-methyl-n-propyl, 1-ethyl-2-methyl-n-propyl, cyclohexyl, 1-methyl-cyclopentyl, 2-methyl-cyclopentyl, 3-methyl-cyclopentyl, 1-ethyl-cyclobutyl, 2-ethyl-cyclobutyl, 3-ethyl-cyclobutyl, 1,2-dimethyl-cyclobutyl, 1,3-dimethyl-cyclobutyl, 2,2-dimethyl-cyclobutyl, 2,3 -dimethyl-cyclobutyl, 2,4-dimethyl-cyclobutyl, 3,3-dimethyl-cyclobutyl, 1-n-propyl-cyclopropyl, 2-n-propyl-cyclopropyl, 1-isopropyl-cyclopropyl, 2-isopropyl-cyclopropyl, 1,2,2-trimethyl-cyclopropyl, 1,2,3-trimethyl-cyclopropyl, 2,2,3-trimethyl-cyclopropyl, 1-ethyl-2-methyl-cyclopropyl, 2-ethyl-1-methyl-cyclopropyl, 2-ethyl-2-methyl-cyclopropyl, 2-ethyl-3-methyl-cyclopropyl, etc.

[0089] The number of carbon atoms of the alkoxy group of R or R' in the above formula (1) is not particularly limited, but is preferably 1 to 20. In order to further improve the heat resistance of the polymer, it is more preferably 1 to 10, and even more preferably 1 to 3. The structure of the alkyl portion may be any of chain, branched, or cyclic.

[0090] Specific examples of the alkoxy groups of R and R' in the above formula (1) include methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy, tert-butoxy, n-pentoxy, 1-methyl-n-butoxy, 2-methyl-n-butoxy, 3-methyl-n-butoxy, 1,1-dimethyl-n-propoxy, 1,2-dimethyl-n-propoxy, 2,2-dimethyl-n-propoxy, 1-ethyl-n-propoxy, n-hexyloxy, 1-methyl-n-pentoxy, 2-methyl-n-pent ...,2-dimethyl-n-propoxy, 2,2-dimethyl-n-propoxy, 1,2-dimethyl-n-propoxy, 2,2-dimethyl-n-propoxy, 1,2-dimethyl-n-propoxy, 2,2-dimethyl-n-propoxy, 1,2-dimethyl-n-propoxy, 1,2-dimethyl-n-propoxy, 1,2-dimethyl-n-propoxy, 1,2-dimethyl-n-propoxy, 1,2-dimethyl-n-propoxy, 1,2-dimethyl-n-propoxy, 1,2-dimethyl-n-propoxy, 1,2-dimethyl-n-propoxy, 1,2-dimethyl-n-propoxy, 1,2-dimethyl 4-Methyl-n-pentoxy, 1,1-dimethyl-n-butoxy, 1,2-dimethyl-n-butoxy, 1,3-dimethyl-n-butoxy, 2,2-dimethyl-n-butoxy, 2,3-dimethyl-n-butoxy, 3,3-dimethyl-n-butoxy, 1-ethyl-n-butoxy, 2-ethyl-n-butoxy, 1,1,2-trimethyl-n-propoxy, 1,2,2-trimethyl-n-propoxy, 1-ethyl-1-methyl-n-propoxy, 1-ethyl-2-methyl-n-propoxy, etc.

[0091] The number of carbon atoms of the aryl group of R or R' in the above formula (1) is not particularly limited, but is preferably 6 to 40. In consideration of further improving the heat resistance of the polymer, the number of carbon atoms is more preferably 6 to 16, and even more preferably 6 to 13.

[0092] Specific examples of the aryl group represented by R and R' in the above formula (1) include phenyl, o-chlorophenyl, m-chlorophenyl, p-chlorophenyl, o-fluorophenyl, p-fluorophenyl, o-methoxyphenyl, p-methoxyphenyl, p-nitrophenyl, p-cyanophenyl, α-naphthyl, β-naphthyl, o-biphenyl, m-biphenyl, p-biphenyl, 1-anthryl, 2-anthryl, 9-anthryl, 1-phenanthryl, 2-phenanthryl, 3-phenanthryl, 4-phenanthryl, 9-phenanthryl and the like.

[0093] The number of carbon atoms in the aralkyl group of R and R' in the above formula (1) is not particularly limited, but is preferably 7 to 20 carbon atoms, and the alkyl portion may be linear, branched, or cyclic.

[0094] Specific examples thereof include benzyl, p-methylphenylmethyl, m-methylphenylmethyl, o-ethylphenylmethyl, m-ethylphenylmethyl, p-ethylphenylmethyl, 2-propylphenylmethyl, 4-isopropylphenylmethyl, 4-isobutylphenylmethyl, and α-naphthylmethyl.

[0095] Any hydrogen atom on the aromatic ring in the above formulae (2) to (12) is optionally substituted by a halogen atom, a carboxyl group, a sulfo group, an alkyl group optionally having a branched structure with 1 to 10 carbon atoms, a halogenated alkyl group optionally having a branched structure with 1 to 10 carbon atoms, or an alkoxy group optionally having a branched structure with 1 to 10 carbon atoms.

[0096] Examples of the halogen atom as a substituent on the aromatic ring in the above formulae (2) to (12) include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.

[0097] Examples of the alkyl group and alkoxy group as substituents on the aromatic ring in the above formulae (2) to (12) include the same groups as those exemplified in the above formula (1).

[0098] The halogenated alkyl group having 1 to 10 carbon atoms as a substituent on the aromatic ring in the above formulae (2) to (12) is a group in which at least one hydrogen atom in the alkyl group optionally having a branched structure having 1 to 10 carbon atoms is substituted with a halogen atom. Specific examples thereof include trifluoromethyl, 2,2,2-trifluoroethyl, perfluoroethyl, 3,3,3-trifluoropropyl, 2,2,3,3,3-pentafluoropropyl, 2,2,3,3-tetrafluoropropyl, 2,2,2-trifluoro-1-(trifluoromethyl)ethyl, perfluoropropyl, 4, 4,4-trifluorobutyl, 3,3,4,4,4-pentafluorobutyl, 2,2,3,3,4,4,4-heptafluorobutyl, perfluorobutyl, 2,2,3,3,4,4,5,5,5-nonafluoropentyl, 2,2,3,3,4,4,5,5-octafluoropentyl, perfluoropentyl, 2,2,3,3,4,4,5,5,6,6,6-undecafluorohexyl, 2,2,3,3,4,4,5,5,6,6-decafluorohexyl, 3,3,4,4,5,5,6,6,6-nonafluorohexyl and perfluorohexyl.

[0099] As X in the above formula (11) 1 , X 2 The alkylene group having 1 to 10 carbon atoms in the group includes a methylene group, an ethylene group, a propylene group, a trimethylene group, a tetramethylene group, a pentamethylene group and the like.

[0100] The above group “-Y 1 -Ph-Y 2 Any hydrogen atom on the phenylene group in "-" may be substituted by a halogen atom, a carboxyl group, a sulfone group, an alkyl group optionally having a branched structure with 1 to 10 carbon atoms, a haloalkyl group optionally having a branched structure with 1 to 10 carbon atoms, or an alkoxy group optionally having a branched structure with 1 to 10 carbon atoms.

[0101] Any hydrogen atom and group "-Y" on the aromatic ring in the above formulas (2) to (12)1 -Ph-Y 2 When any hydrogen atom on the phenylene group in "-" is substituted, among the above examples, preferably, it is a halogen atom, a sulfo group, an alkyl group optionally having a branched structure with 1 to 5 carbon atoms, a haloalkyl group optionally having a branched structure with 1 to 5 carbon atoms, or an alkoxy group optionally having a branched structure with 1 to 5 carbon atoms.

[0102] Ar in the above formula (1) is preferably at least one of the formulas (2), (5) to (12), and more preferably at least one of the formulas (2), (5), (7), (8), (11) to (12). Specific examples of the aryl group represented by the above formulas (2) to (12) include, but are not limited to, the following formulas (1-1) to (1-25). In the formula, Ph represents a phenyl group.

[0103]

[0104] Furthermore, from the viewpoint of obtaining a polymer with a higher refractive index, an aryl group represented by the above formulae (1-1), (1-2), (1-5) to (1-15), (1-18) to (1-21), and (1-23) to (1-25) is more preferable.

[0105] In particular, in view of further improving the solubility of the polymer in an organic solvent, Ar is preferably a m-phenylene group represented by the formula (21-a).

[0106]

[0107] Furthermore, the polymer (B) of the present invention has at least one triazine ring terminal, and at least a part of the triazine ring terminal is capped with an aromatic amino group having a crosslinking group.

[0108] It should be noted that the polymer (B) of the present invention has at least one triazine ring terminal, and the triazine ring at the terminal generally has two halogen atoms that can be substituted with the above-mentioned arylamino group having a crosslinking group. Therefore, the above-mentioned arylamino group having a crosslinking group can be bonded to the same triazine ring terminal, and in the case of having multiple triazine ring terminals, they can also be bonded to different triazine ring terminals respectively.

[0109] Examples of the aryl group of the arylamino group having a crosslinking group include the same groups as described above, and a phenyl group is particularly preferred.

[0110] Examples of the crosslinking group include: a hydroxyl-containing group, a vinyl-containing group, an epoxy-containing group, an oxetane-containing group, a carboxyl-containing group, a sulfone-containing group, a thiol-containing group, a (meth)acryloyl-containing group, and the like. In consideration of improving the heat resistance of the polymer (B), a hydroxyl-containing group and a (meth)acryloyl-containing group are preferred.

[0111] Examples of the hydroxyl group-containing group include a hydroxyl group and a hydroxyalkyl group, etc. Preferably, it is a hydroxyl group or a hydroxyalkyl group, and more preferably, it is a hydroxyalkyl group having 1 to 10 carbon atoms.

[0112] Examples of the hydroxyalkyl group having 1 to 10 carbon atoms include hydroxymethyl, 2-hydroxyethyl, 3-hydroxypropyl, 4-hydroxybutyl, 5-hydroxypentyl, 6-hydroxyhexyl, 7-hydroxyheptyl, 8-hydroxyoctyl, 9-hydroxynonyl, 10-hydroxydecyl, 2-hydroxy-1-methylethyl, 2-hydroxy-1,1-dimethylethyl, 3-hydroxy-1-methylpropyl, 3-hydroxy-2-methylpropyl, 3-hydroxy-1,1-dimethylpropyl, 3-hydroxy-1,2-dimethylpropyl, 3-hydroxy-2,2-dimethylpropyl, 3-hydroxy-1,1-dimethylpropyl, 3-hydroxy-1,2-dimethylpropyl, 3-hydroxy-2,2-dimethylpropyl, 3-hydroxy-2,2-dimethylpropyl, 3-hydroxy-1,1-dimethylpropyl, 3-hydroxy-2,2-dimethylpropyl, 3-hydroxy-1,2-dimethylpropyl, 3-hydroxy-2,2-dimethylpropyl, 3-hydroxy-2,2-dimethylethyl, 3-hydroxy-1-methylpropyl, 3-hydroxy-2,2-dimethylpropyl, 3-hydroxy-1,1-dimethylpropyl, 3-hydroxy-1,2-dimethylpropyl, 3-hydroxy-2,2-dimethylethyl, 3-hydroxy-1-methylethyl, 2-hydroxy-1,1-dimethylethyl, 3-hydroxy-1-methylpropyl, 3-hydroxy-2,2-dimethylpropyl, 3-hydroxy-2,2-dimethylpropyl, 3-hydroxy-2,2-dimethylethyl, 3-hydroxy-1,2-dimethylpropyl, 3-hydroxy-2,2-dimethylethyl, 3-hydroxy-1-methylpropyl, 3-hydroxy-2,2-dimethylethyl, 3-hydroxy-1,2-dimethylpropyl, 3-hydroxy-2 Groups in which the carbon atom to which the hydroxyl group is bonded is a primary carbon atom, such as methylpropyl, 4-hydroxy-1-methylbutyl, 4-hydroxy-2-methylbutyl, and 4-hydroxy-3-methylbutyl; groups in which the carbon atom to which the hydroxyl group is bonded is a secondary or tertiary carbon atom, such as 1-hydroxyethyl, 1-hydroxypropyl, 2-hydroxypropyl, 1-hydroxybutyl, 2-hydroxybutyl, 1-hydroxyhexyl, 2-hydroxyhexyl, 1-hydroxyoctyl, 2-hydroxyoctyl, 1-hydroxydecyl, 2-hydroxydecyl, 1-hydroxy-1-methylethyl, and 2-hydroxy-2-methylpropyl.

[0113] In particular, in consideration of improving heat resistance and high-temperature and high-humidity resistance, a group in which the carbon atom to which the hydroxyl group is bonded is a primary carbon atom is preferred, among which a hydroxyalkyl group having 1 to 5 carbon atoms is more preferred, a hydroxyalkyl group having 1 to 3 carbon atoms is further preferred, a hydroxymethyl group and a 2-hydroxyethyl group are further preferred, and a 2-hydroxyethyl group is most preferred.

[0114] Examples of the group containing a (meth)acryloyl group include a (meth)acryloyl group, a (meth)acryloyloxyalkyl group, and a group represented by the following formula (i). A (meth)acryloyloxyalkyl group having an alkyl group having 1 to 10 carbon atoms and a group represented by the following formula (i) are preferred, and a group represented by the following formula (i) is more preferred.

[0115]

[0116] (In the formula, A 1 represents an alkylene group having 1 to 10 carbon atoms, A 2 represents a single bond or a group represented by the following formula (j), A 3represents a divalent or trivalent aliphatic hydrocarbon group optionally substituted by a hydroxyl group, A 4 represents a hydrogen atom or a methyl group, a represents 1 or 2, and * represents a bonding bond. )

[0117]

[0118] (* indicates a bond.)

[0119] Examples of the alkyl group contained in the (meth)acryloyloxyalkyl group having an alkyl group having 1 to 10 carbon atoms include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, and n-decyl. In view of improving heat resistance and high temperature and humidity resistance, a group having an alkyl group having 1 to 5 carbon atoms is preferred, a group having an alkyl group having 1 to 3 carbon atoms is preferred, and a group having an alkyl group having 1 or 2 carbon atoms is more preferred.

[0120] Specific examples of the (meth)acryloyloxyalkyl group include a (meth)acryloyloxymethyl group, a 2-(meth)acryloyloxyethyl group, a 3-(meth)acryloyloxypropyl group, and a 4-(meth)acryloyloxybutyl group.

[0121] In formula (i), A 1 The alkylene group has 1 to 10 carbon atoms, preferably has 1 to 5 carbon atoms, and more preferably is methylene and ethylene. Examples of the alkylene group having 1 to 10 carbon atoms include methylene, ethylene, propylene, trimethylene, tetramethylene, and pentamethylene.

[0122] A 2 represents a single bond or a group represented by formula (j), and preferably a group represented by formula (j).

[0123] A 3 A is a divalent or trivalent aliphatic hydrocarbon group optionally substituted with a hydroxyl group, and specific examples thereof include an alkylene group having 1 to 5 carbon atoms and groups represented by the following formulae (k-1) to (k-3). An alkylene group having 1 to 5 carbon atoms is preferred, an alkylene group having 1 to 3 carbon atoms is more preferred, and a methylene group and an ethylene group are further preferred. 3 The alkylene group includes A 1 The alkylene groups exemplified are those having 1 to 5 carbon atoms.

[0124]

[0125] (In the formula, * is the same as above.)

[0126] In formula (i), a represents 1 or 2, and preferably 1.

[0127] As a preferred embodiment of the group represented by formula (i), a group represented by the following formula (i-1) is also exemplified.

[0128]

[0129] (In the formula, A 1 , A 3 , A 4 and *Same as above. )

[0130] As more preferred embodiments of the group represented by formula (i), groups represented by the following formulae (i-2) to (i-3) are mentioned.

[0131]

[0132] (In the formula, * is the same as above.)

[0133] Examples of the vinyl group include alkenyl groups having 2 to 10 carbon atoms and having a vinyl group at the terminal, and specific examples include vinyl, 1-propenyl, allyl, isopropenyl, 1-butenyl, 2-butenyl, and 2-pentenyl.

[0134] Examples of the epoxy group-containing group include epoxy group, glycidyl group, glycidyl alkyl group, glycidyloxy group, etc. Specific examples include glycidyl methyl group, 2-glycidyl ethyl group, 3-glycidyl propyl group, 4-glycidyl butyl group, etc.

[0135] Examples of the oxetane-containing group include oxetane-3-yl, (oxetane-3-yl)methyl, 2-(oxetane-3-yl)ethyl, 3-(oxetane-3-yl)propyl, and 4-(oxetane-3-yl)butyl.

[0136] Examples of the carboxyl group-containing group include a carboxyl group and a carboxylalkyl group having 1 to 10 carbon atoms. As the carboxylalkyl group having 1 to 10 carbon atoms, a group in which the carbon atom to which the carboxyl group is bonded is preferably a primary carbon atom, and specific examples thereof include a carboxylmethyl group, a 2-carboxyethyl group, a 3-carboxypropyl group, and a 4-carboxybutyl group.

[0137] Examples of the sulfo group-containing group include a sulfo group and a sulfoalkyl group having 1 to 10 carbon atoms. As the sulfoalkyl group having 1 to 10 carbon atoms, a group in which the carbon atom to which the sulfo group is bonded is preferably a primary carbon atom, and specific examples thereof include a sulfomethyl group, a 2-sulfoethyl group, a 3-sulfopropyl group, and a 4-sulfobutyl group.

[0138] Examples of the thiol group-containing group include thiol groups and mercaptoalkyl groups having 1 to 10 carbon atoms. As the mercaptoalkyl group having 1 to 10 carbon atoms, the carbon atom to which the thiol group is bonded is preferably a primary carbon atom, and specific examples thereof include mercaptomethyl, 2-mercaptoethyl, 3-mercaptopropyl, and 4-mercaptobutyl.

[0139] The number of the crosslinking groups is not particularly limited and may be any number that can substitute on the aryl group, but is preferably 1 to 4, more preferably 1 to 2, and even more preferably 1.

[0140] Preferred examples of the arylamino group having a crosslinking group include a group represented by formula (15), and a group represented by formula (16) having a crosslinking group at the para position relative to the amino group is particularly preferred.

[0141]

[0142] (Where R 15 Indicates a cross-linking group. *Indicates a bonding bond. )

[0143]

[0144] (Where R 15 Has the same meaning as above. * indicates a bonding bond. )

[0145] Specific examples of the arylamino group having a crosslinking group include groups represented by the following formulae (16-1) to (16-13), but the present invention is not limited thereto. In the formulae, * represents a bonding bond.

[0146]

[0147] In addition, the arylamino group having a hydroxyalkyl group can be introduced by using a corresponding hydroxyalkyl-substituted arylamino compound in the production method described later.

[0148] Specific examples of the hydroxyalkyl-substituted arylamino compound include (4-aminophenyl)methanol and 2-(4-aminophenyl)ethanol.

[0149] The arylamino group having a (meth)acryloyloxyalkyl group can be introduced by the following methods: a method of using a corresponding (meth)acryloyloxyalkyl group to replace the arylamino compound; a method of introducing an arylamino group having a hydroxyalkyl group into the polymer (B) and then further allowing (meth)acryloyl halide or glycidyl (meth)acrylate to act on the hydroxyl group contained in the above hydroxyalkyl group.

[0150] The aromatic amino group having a group represented by formula (i) can be introduced by the following methods: a method using an aromatic amino compound having a target crosslinking group; a method in which an aromatic amino group having a hydroxyalkyl group is introduced into a polymer (B) and then a (meth)acrylate compound having an isocyanate group represented by the following formula (i') is allowed to act on the hydroxyl group contained in the above-mentioned hydroxyalkyl group.

[0151]

[0152] (In the formula, A 3 , A 4 and a is the same as above. )

[0153] Specific examples of the (meth)acryloyloxyalkyl-substituted arylamino compound include ester compounds obtained by allowing (meth)acryloyl halide or glycidyl (meth)acrylate to act on a hydroxyl group of the above-mentioned hydroxyalkyl-substituted arylamino compound.

[0154] Examples of the (meth)acrylic acid halide include (meth)acrylic acid chloride, (meth)acrylic acid bromide, and (meth)acrylic acid iodide.

[0155] Specific examples of the (meth)acrylate compound having an isocyanate group represented by the formula (i′) include 2-isocyanateethyl acrylate, 2-isocyanateethyl methacrylate, and 1,1-(bisacryloyloxymethyl)ethyl isocyanate.

[0156] In the present invention, particularly preferred polymers (B) include those containing repeating units represented by formulae (18) to (21).

[0157]

[0158] (In the formula, R, R' and R 15 Means the same as above. 1 ~R 4 represents a hydrogen atom, a halogen atom, a carboxyl group, a sulfo group, an alkyl group optionally having a branched structure with 1 to 10 carbon atoms, a haloalkyl group optionally having a branched structure with 1 to 10 carbon atoms, or an alkoxy group optionally having a branched structure with 1 to 10 carbon atoms. Except for the case where both R and R' are hydrogen atoms.)

[0159]

[0160] (Where R 15 Means the same as above. 1 ~R 4 has the same meaning as in the above formula (18). 1 ~R4 Except when all atoms are hydrogen.)

[0161]

[0162] (Where R 15 Means the same as above.)

[0163]

[0164] (Where R 15 Means the same as above.)

[0165] The weight average molecular weight of the polymer (B) in the present invention is not particularly limited, but is preferably 500 to 500,000, more preferably 500 to 100,000. From the perspective of further improving heat resistance and reducing shrinkage, it is preferably 2,000 or more. From the perspective of further improving solubility and reducing the viscosity of the resulting solution, it is preferably 50,000 or less, more preferably 30,000 or less, further preferably 15,000 or less, and particularly preferably 10,000 or less.

[0166] In addition, the weight average molecular weight in the present invention is an average molecular weight calculated in terms of standard polystyrene analyzed by gel permeation chromatography (hereinafter referred to as GPC).

[0167] The polymer (B) (hyperbranched polymer) of the present invention can be produced according to the method disclosed in International Publication No. 2010 / 128661.

[0168] That is, the polymer (B) of the present invention can be obtained by reacting a trihalotriazine compound with an aryl diamino compound in an organic solvent, and then reacting the compound with at least one aryl amino compound selected from the group consisting of an aryl amino compound having a hydroxyalkyl group (a hydroxyl-containing group), an aryl amino compound having an acryloyloxyalkyl group (an acryloyl-containing group), and an aryl amino compound having a group represented by formula (i) (an acryloyl-containing group) as a capping agent.

[0169] For example, as shown in the following Scheme 1, a polymer (B) (20') can be obtained by reacting a triazine compound (22) with an aromatic diamino compound (23) in an appropriate organic solvent, and then reacting the triazine compound (22) with at least one aromatic amino compound (24) selected from an aromatic amino compound having a hydroxyalkyl group and an aromatic amino compound having a group represented by formula (i) as a capping agent.

[0170]

[0171] (wherein, X independently represents a halogen atom, Ra represents a hydroxyalkyl group or a group represented by formula (i).

[0172] In the above reaction, the charging ratio of the aryl diamino compound (23) is arbitrary as long as the target polymer can be obtained, but the aryl diamino compound (23) is preferably 0.01 to 10 equivalents, more preferably 1 to 5 equivalents, based on 1 equivalent of the triazine compound (22).

[0173] The aryl diamino compound (23) may be added neat or as a solution dissolved in an organic solvent. The latter method is preferred in view of ease of handling, ease of reaction control, and the like.

[0174] The reaction temperature may be appropriately set within the range from the melting point to the boiling point of the solvent used, and is particularly preferably about -30°C to 150°C, more preferably -10°C to 100°C.

[0175] As another scheme, there can be cited the method shown in the following scheme 2. In this method, the polymer (B) (20') can be obtained by reacting a triazine compound (22) and an aromatic diamino compound (23) in a suitable organic solvent, and then reacting with an aromatic amino compound (24') having a hydroxyalkyl group as a capping agent to obtain a polymer (B) (20") (first stage), and then further allowing a (meth) acrylate compound having an isocyanate group represented by formula (i') to act on the hydroxyl group of the hydroxyalkyl group contained in the polymer (B) (20") (second stage).

[0176] In addition, when the polymer (B) (20") is used as the target product, the second stage reaction is not carried out and the first stage reaction may be completed.

[0177]

[0178] (Where R a1 represents hydroxyalkyl, X, A 3 , A 4 , R a and a have the same meaning as above. )

[0179] In the above reaction, the charging ratio and addition method of the aryl diamino compound (23) in the first stage and the reaction temperature in the reaction until the polymer (B) (20") is obtained can be the same as those described in Scheme 1.

[0180] Furthermore, in the second stage, the charging ratio of the (meth)acrylate compound having an isocyanate group represented by formula (i') to the polymer (B) (20") can be arbitrarily set according to the ratio of the hydroxyalkyl group to the group represented by formula (i), and is preferably 0.1 to 10 equivalents, more preferably 0.5 to 5 equivalents, further preferably 0.7 to 3 equivalents, and further preferably 0.9 to 1.5 equivalents, relative to 1 equivalent of the aromatic amino compound having a hydroxyalkyl group used. For example, when all the hydroxyalkyl groups contained in the polymer (B) (20") are groups represented by formula (i), the charging ratio of the (meth)acrylate compound is preferably 1.0 to 10 equivalents, more preferably 1.0 to 5 equivalents, further preferably 1.0 to 3 equivalents, and further preferably 1.0 to 1.5 equivalents, relative to 1 equivalent of the aromatic amino compound having a hydroxyalkyl group used.

[0181] The reaction temperature in the reaction is the same as the reaction temperature in the reaction for obtaining the polymer (B)(20"), and is preferably 30°C to 80°C, more preferably 40°C to 70°C, and even more preferably 50°C to 60°C in order to prevent the (meth)acryloyl group from being polymerized during the reaction.

[0182] As the organic solvent, various solvents commonly used in such reactions can be used, for example, tetrahydrofuran (THF), 1,4-dioxane, dimethyl sulfoxide; amide solvents such as N,N-dimethylformamide, N-methyl-2-pyrrolidone, tetramethylurea, hexamethylphosphoramide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, N,N-dimethylethyleneurea, N,N,N',N'-tetramethylmalonamide, N-methyl-ε-caprolactam, N-acetylpyrrolidine, N,N-diethylacetamide, N-ethyl-2-pyrrolidone, N,N-dimethylpropionamide, N,N-dimethylisobutylamide, N-methylformamide, N,N'-dimethylpropyleneurea, and mixed solvents thereof.

[0183] Among them, N,N-dimethylformamide, dimethyl sulfoxide, N-methyl-2-pyrrolidone, N,N-dimethylacetamide, and mixtures thereof are preferred, and N,N-dimethylacetamide and N-methyl-2-pyrrolidone are particularly preferred.

[0184] In the first-stage reaction of the above scheme 1, various bases commonly used may be added during or after the polymerization.

[0185] Specific examples of the base include potassium carbonate, potassium hydroxide, sodium carbonate, sodium hydroxide, sodium bicarbonate, sodium ethoxide, sodium acetate, lithium carbonate, lithium hydroxide, lithium oxide, potassium acetate, magnesium oxide, calcium oxide, barium hydroxide, trilithium phosphate, trisodium phosphate, tripotassium phosphate, cesium fluoride, aluminum oxide, ammonia, n-propylamine, trimethylamine, triethylamine, diisopropylamine, diisopropylethylamine, N-methylpiperidine, 2,2,6,6-tetramethyl-N-methylpiperidine, pyridine, 4-dimethylaminopyridine, and N-methylmorpholine.

[0186] The amount of the base added is preferably 1 to 100 equivalents, more preferably 1 to 10 equivalents, based on 1 equivalent of the triazine compound (22). These bases may be used in the form of aqueous solutions.

[0187] It is preferred that no raw material components remain in the obtained polymer, but a part of the raw material may remain unless the effects of the present invention are impaired.

[0188] After the reaction is completed, the product can be easily purified by reprecipitation or the like.

[0189] As the end-capping method using the aromatic amino compound having a crosslinking group, a known method may be adopted.

[0190] In this case, the amount of the end-capping agent used is preferably about 0.05 to 10 equivalents, more preferably 0.1 to 5 equivalents, and further preferably 0.5 to 2 equivalents, based on 1 equivalent of the halogen atoms derived from the remaining triazine compound not used in the polymerization reaction.

[0191] The reaction solvent and reaction temperature may be the same as those described in the first-stage reaction of the above Scheme 1. The end-capping agent may be charged simultaneously with the aryldiamino compound (23).

[0192] It should be noted that an unsubstituted arylamino compound having no crosslinking group may be used and end-capped with two or more groups. Examples of the aryl group of the unsubstituted arylamino compound include the same groups as described above.

[0193] Specific examples of the unsubstituted arylamino group include groups represented by the following formula (26), but are not limited thereto.

[0194]

[0195] In addition, the unsubstituted arylamino group can be introduced using a corresponding unsubstituted arylamino compound in the production method described later.

[0196] Specific examples of the unsubstituted arylamino compound include aniline and the like.

[0197] Furthermore, when an unsubstituted arylamino group is introduced, the ratio of the arylamino compound having a cross-linking group to the unsubstituted arylamino compound is preferably 0.1 mol to 1.0 mol, more preferably 0.1 mol to 0.5 mol, and even more preferably 0.1 mol to 0.3 mol, relative to 1 mol of the arylamino compound having a cross-linking group, from the viewpoint of achieving a good balance between solubility in an organic solvent and yellowing resistance.

[0198] (Liquid Crystal Alignment Agent)

[0199] The liquid crystal alignment agent is a substance used to make a liquid crystal alignment film, and from the viewpoint of forming a uniform film, it adopts the form of a coating liquid. In the liquid crystal alignment agent of the present invention, a coating liquid containing the above-mentioned polymer component and an organic solvent is also preferred. At this time, the concentration of the polymer component in the liquid crystal alignment agent can be appropriately changed according to the setting of the thickness of the coating film to be formed. From the perspective of forming a uniform and defect-free coating film, it is preferably 0.5% by mass or more, and from the perspective of the storage stability of the solution, it is preferably 15% by mass or less. The concentration of the polymer component is particularly preferably 1 to 10% by mass.

[0200] From the viewpoint of improving the liquid crystal orientation, the content ratio of the component (A) and the component (B) contained in the liquid crystal aligning agent of the present invention can be 10 / 90 to 90 / 10, 20 / 80 to 90 / 10, or 20 / 80 to 80 / 20 in terms of the mass ratio of [component (A)] / [component (B)].

[0201] In addition, in the liquid crystal alignment agent for manufacturing the liquid crystal alignment film, the polymer component is polymer (A) and polymer (B), and other polymers other than these may also be mixed. At this time, the content of other polymers is 0.5% to 15% by mass of the total amount of the polymer component, preferably 1% to 10% by mass. As other polymers other than these, acrylic polymers, methacrylic polymers, polystyrene, polyamides or polysiloxanes can be listed.

[0202] The solvent contained in the liquid crystal alignment agent is not particularly limited as long as it can dissolve the polymer (A) and the polymer (B), and examples thereof include: lactone solvents such as γ-valerolactone and γ-butyrolactone; γ-butyrolactam, N-n-propyl-2-pyrrolidone, N-isopropyl-2-pyrrolidone, N-n-butyl-2-pyrrolidone, N-tert-butyl-2-pyrrolidone, N-n-pentyl-2-pyrrolidone, N-methoxypropyl-2-pyrrolidone, N-ethoxyethyl-2-pyrrolidone, N-methoxybutyl-2-pyrrolidone, N-cyclohexyl- 2-pyrrolidone, N-ethyl-2-pyrrolidone, N-methyl-2-pyrrolidone and other lactam solvents; N,N-dimethylformamide, N,N-dimethylacetamide, N,N-dimethyllactamide, 3-butoxy-N,N-dimethylpropionamide, 3-methoxy-N,N-dimethylpropionamide, 3-hexyloxy-N,N-dimethylpropionamide, isopropoxy-N-isopropyl-propionamide, n-butoxy-N-isopropyl-propionamide and other amide solvents; 4-hydroxy-4-methyl-2-pentanone, 2,6-dimethyl-4-heptanone (diisopropylpropionamide) ketone), methyl lactate, ethyl lactate, n-propyl lactate, n-butyl lactate, isoamyl lactate, n-butyl acetate, propylene glycol monoethyl acetate, methyl pyruvate, ethyl pyruvate, methyl methoxypropionate, ethyl ethoxypropionate, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, ethylene glycol monopropyl ether, ethylene glycol monoisopropyl ether, ethylene glycol mono-n-butyl ether (butyl cellosolve), ethylene glycol dimethyl ether, ethylene glycol ethyl ether acetate, ethylene glycol monobutyl ether acetate, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol mono Methyl ether, diethylene glycol monoethyl ether, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monobutyl ether, propylene glycol diacetate, dipropylene glycol, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol dimethyl ether, tripropylene glycol monomethyl ether, isoamyl propionate, isoamyl isobutyrate, diisopropyl ether, diisoamyl ether; carbonate solvents such as ethylene carbonate and propylene carbonate, 1-hexanol, cyclohexanol, 1,2-ethylene glycol, 2,6-dimethyl-4-heptanol (diisobutylcarbinol), etc. These may be used alone or in combination of two or more.

[0203] Preferred combinations of 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; N-ethyl-2-pyrrolidone, N-methyl-2-pyrrolidone and 4-hydroxy-4-methyl-2-pentanone; N-methyl-2-pyrrolidone, 4-hydroxy-4-methyl-2-pentanone and diisobutyl ketone; N-methyl-2-pyrrolidone, 4-hydroxy-4-methyl-2-pentanone and dipropylene glycol monomethyl ether; N-methyl-2-pyrrolidone, 4-Hydroxy-4-methyl-2-pentanone and propylene glycol monobutyl ether; N-methyl-2-pyrrolidone, 4-hydroxy-4-methyl-2-pentanone and propylene glycol diacetate; γ-butyrolactone, 4-hydroxy-4-methyl-2-pentanone and diisobutyl ketone; γ-butyrolactone, 4-hydroxy-4-methyl-2-pentanone and propylene glycol diacetate; N-methyl-2-pyrrolidone, γ-butyrolactone, propylene glycol diacetate alcohol monobutyl ether and diisobutyl ketone; N-methyl-2-pyrrolidone, γ-butyrolactone, propylene glycol monobutyl ether and diisopropyl ether; N-methyl-2-pyrrolidone, γ-butyrolactone, propylene glycol monobutyl ether and diisobutyl carbinol; N-methyl-2-pyrrolidone, γ-butyrolactone and dipropylene glycol dimethyl ether; N-methyl-2-pyrrolidone, propylene glycol monobutyl ether and dipropylene glycol dimethyl ether, etc. The type and content of such solvents can be appropriately selected according to the coating device, coating conditions, coating environment, etc. of the liquid crystal alignment agent.

[0204] <Other ingredients>

[0205] To the liquid crystal aligning agent of the present invention, other components other than those described above, for example, a crosslinking compound, a functional silane compound, a surfactant, a compound having a photopolymerizable group, etc. may be added as necessary.

[0206] In order to improve the strength of the liquid crystal alignment film, a crosslinking compound can be used. Examples of the crosslinking compound include compounds having an isocyanate group or a cyclocarbonate group as described in paragraphs

[0109] to

[0113] of International Publication WO2016 / 047771, or compounds having at least one group selected from the group consisting of a lower alkoxyalkyl group, and compounds having a blocked isocyanate group.

[0207] The blocked isocyanate compound is commercially available, and for example, Coronate AP StableM, Coronate 2503, 2515, 2507, 2513, 2555, Millionate MS-50 (all manufactured by Tosoh Corporation), TAKENATE B-830, B-815N, B-820NSU, B-842N, B-846N, B-870N, B-874N, B-882N (all manufactured by Mitsui Chemicals, Inc.) and the like are preferably used.

[0208] Specific examples of preferred crosslinking compounds include compounds represented by the following formulae (CL-1) to (CL-11).

[0209]

[0210] The above is an example of the crosslinking compound, but the invention is not limited thereto. Moreover, the crosslinking compound used for the liquid crystal aligning agent of the present invention may be one kind or a combination of two or more kinds.

[0211] Content of other crosslinking compounds in the liquid crystal aligning agent of this invention is 0.1-150 mass parts, or 0.1-100 mass parts, or 1-50 mass parts with respect to 100 mass parts of all polymer components.

[0212] For the purpose of improving the adhesion between the liquid crystal alignment film and the base substrate, a functional silane compound can be used. As a specific example, the silane compound described in paragraph

[0019] of International Publication Gazette 2014 / 119682 can be cited. The content of the functional silane compound is preferably 0.1 to 30 parts by mass, more preferably 0.5 to 20 parts by mass, relative to 100 parts by mass of the total polymer components.

[0213] For the purpose of improving the uniformity of the film thickness and the surface smoothness of the liquid crystal alignment film, a surfactant can be used. As a surfactant, a fluorine-based surfactant, a silicone-based surfactant, a nonionic surfactant, etc. can be listed. These specific examples can list the surfactants described in paragraph

[0117] of the International Publication WO2016 / 047771. As for the amount of the surfactant used, it is preferably 0.01 to 2 parts by mass, more preferably 0.01 to 1 part by mass, relative to 100 parts by mass of all polymer components contained in the liquid crystal alignment agent.

[0214] Examples of the compound having a photopolymerizable group include compounds having one or more polymerizable unsaturated groups such as an acrylate group or a methacrylate group in the molecule, for example, compounds represented by the following formulae (M-1) to (M-7).

[0215]

[0216] Furthermore, in the liquid crystal aligning agent of the present invention, as a compound that promotes charge transfer in the liquid crystal aligning film and charge release of the element, a nitrogen-containing heterocyclic amine compound represented by formula [M1] to formula [M156] listed in paragraphs

[0194] to

[0200] of International Publication WO2011 / 132751 (published on October 27, 2011) can be added, and 3-aminomethylpyridine and 4-aminomethylpyridine are more preferably added. The amine compound can be directly added to the liquid crystal aligning agent, but it is preferably added after making a solution with a concentration of 0.1 to 10% by mass, preferably 1 to 7% by mass. The solvent is not particularly limited as long as it dissolves the polymer component.

[0217] In order to efficiently carry out imidization by heating when baking a coating film, an imidization accelerator etc. can be added to the liquid crystal aligning agent of this invention.

[0218] The solid content concentration in the liquid crystal aligning agent (the ratio of the total mass of the components other than the solvent of the liquid crystal aligning agent to the total mass of the liquid crystal aligning agent) is appropriately selected in consideration of viscosity, volatility, etc., and is preferably in the range of 0.5 to 15 mass %, and more preferably in the range of 1 to 10 mass %.

[0219] The range of particularly preferred solid content concentration varies depending on the method used when applying the liquid crystal alignment agent to the substrate. For example, in the case of spin coating, the solid content concentration is particularly preferably in the range of 1.5 to 4.5% by mass. In the case of printing, it is particularly preferred to set the solid content concentration in the range of 3 to 9% by mass, thereby setting the solution viscosity in the range of 12mPa·s to 50mPa·s. In the case of inkjet method, it is particularly preferred to set the solid content concentration in the range of 1 to 5% by mass, thereby setting the solution viscosity in the range of 3mPa·s to 15mPa·s.

[0220] (Liquid crystal alignment film, liquid crystal display element)

[0221] The liquid crystal alignment film of the present invention is obtained from the above-mentioned liquid crystal alignment agent. The liquid crystal alignment film of the present invention can be used for a horizontal alignment type or a vertical alignment type liquid crystal alignment film, wherein it is preferably used for a liquid crystal alignment film of a vertical alignment type liquid crystal display element such as a VA type liquid crystal display element or a PSA type liquid crystal display element. The liquid crystal display element of the present invention has the above-mentioned liquid crystal alignment film. The liquid crystal display element of the present invention can be manufactured, for example, by a method comprising the following steps (1) to (3) or steps (1) to (4). In addition, the liquid crystal alignment film of the present invention can be preferably used for a liquid crystal display element obtained by the following method for manufacturing a liquid crystal display element, that is, the manufacturing method is to form a coating film by coating on a pair of substrates having a conductive film, and the coating film is arranged in a manner opposite to each other with a layer of liquid crystal molecules therebetween to form a liquid crystal box, and the liquid crystal box is irradiated with light while a voltage is applied between the conductive films of the pair of substrates. More specifically, it is a PSA type liquid crystal display element and a liquid crystal display element for SC-PVA mode described later.

[0222] (1) Process of applying a liquid crystal alignment agent on a substrate

[0223] For example, the liquid crystal alignment agent of the present invention is applied to one side of a substrate provided with a patterned transparent conductive film by a suitable coating method such as a roller coating method, a spin coating method, a printing method, an inkjet method, etc. Here, as a substrate, there is no particular limitation as long as it is a substrate with high transparency, and a plastic substrate such as an acrylic substrate, a polycarbonate substrate, etc. can be used together with a glass substrate or a silicon nitride substrate. In addition, in a reflective liquid crystal display element, if it is only a single-sided substrate, an opaque object such as a silicon wafer can also be used, and in this case, a material reflecting light such as aluminum can also be used in the electrode.

[0224] (2) Process of firing the coating

[0225] After the liquid crystal alignment agent is applied, it is preferred to preheat (pre-bake) in advance for the purpose of preventing the liquid of the applied alignment agent from dripping. The pre-bake temperature is preferably 30°C to 200°C, more preferably 40°C to 150°C, and particularly preferably 40°C to 100°C. The pre-bake time is preferably 0.25 minutes to 10 minutes, and more preferably 0.5 minutes to 5 minutes. Moreover, in order to completely remove the solvent, it is further preferred to implement a heating (post-bake) process.

[0226] The post-baking temperature is preferably 80° C. to 300° C., more preferably 120° C. to 250° C. The post-baking time is preferably 5 minutes to 200 minutes, more preferably 10 minutes to 100 minutes. The film thickness of the film formed in this way is preferably 5 nm to 300 nm, more preferably 10 nm to 200 nm.

[0227] The coating film formed in the above step (1) can be used as a liquid crystal alignment film as it is, or the coating film can be subjected to a treatment to impart an alignment ability. Examples of the treatment to impart an alignment ability include: a brushing treatment in which a roll of cloth made of fibers such as nylon, rayon, and cotton is wound around the coating film and rubbed in a certain direction; and a photo-alignment treatment in which the coating film is irradiated with polarized or non-polarized radiation.

[0228] In the photo-alignment treatment, as the radiation irradiated to the coating film, for example, ultraviolet rays and visible light containing a wavelength of 150nm to 800nm ​​can be used. In the case where the radiation is polarized, it can be linearly polarized or partially polarized. In addition, in the case where the radiation used is linearly polarized or partially polarized, the irradiation can be performed from a direction perpendicular to the substrate surface, from an oblique direction, or a combination thereof. In the case of irradiating non-polarized radiation, the irradiation direction is set to an oblique direction.

[0229] (3) Step of forming a liquid crystal layer

[0230] (3-1) Case of VA-type liquid crystal display element

[0231] Prepare two substrates with liquid crystal alignment films formed as described above, and arrange the liquid crystal between the two opposing substrates. Specifically, the following two methods can be listed. The first method is a known method. First, two substrates are arranged opposite to each other in such a way that each liquid crystal alignment film is opposite to each other with a gap (unit gap) between them. Next, a sealant is used to bond the peripheral portions of the two substrates, and a liquid crystal composition is injected into the unit gap divided by the substrate surface and the sealant, and after contacting the film surface, the injection hole is sealed.

[0232] In addition, the second method is a method called ODF (One Drop Fill: liquid crystal dripping) method. A sealant such as a UV-curable sealant is applied at a predetermined position on one of the two substrates on which a liquid crystal alignment film is formed, and a liquid crystal composition is further dripped onto several predetermined positions on the surface of the liquid crystal alignment film. After that, the other substrate is bonded in a manner that the liquid crystal alignment film is opposite, and the liquid crystal composition is extended to the entire surface of the substrate and contacts the film surface. Then, ultraviolet light is irradiated on the entire surface of the substrate to cure the sealant. In the case of using any method, it is expected that the liquid crystal composition used is further heated to a temperature at which it becomes isotropic, and then slowly cooled to room temperature, thereby removing the flow orientation during liquid crystal filling.

[0233] (3-2) Manufacturing of PSA Type Liquid Crystal Display Element

[0234] The same procedure as in the above (3-1) is carried out except that a liquid crystal composition containing a polymerizable compound is injected or dropped. Examples of the polymerizable compound include polymerizable compounds represented by the above formulae (M-1) to (M-7).

[0235] (3-3) When a coating film is formed on a substrate using a liquid crystal aligning agent containing a compound having a polymerizable group (LCD element for SC-PVA mode)

[0236] After the same process as in (3-1) above, a method for manufacturing a liquid crystal display element by irradiating ultraviolet rays described later can be adopted. According to this method, a liquid crystal display element with excellent response speed under a small amount of light irradiation can be obtained, as in the case of manufacturing the above-mentioned PSA type liquid crystal display element. The compound having a polymerizable group can be a compound having one or more polymerizable unsaturated groups such as acrylate groups and methacrylate groups in the molecule as shown in the above-mentioned formulas (M-1) to (M-7), and its content is preferably 0.1 to 30 parts by mass, and more preferably 1 to 20 parts by mass, relative to 100 parts by mass of all polymer components. In addition, the above-mentioned polymerizable group may be present in a polymer used for a liquid crystal aligning agent, and as such a polymer, for example, a polymer obtained by using a diamine component containing a diamine having the above-mentioned photopolymerizable group at the end in a reaction.

[0237] (4) Ultraviolet irradiation process

[0238] The liquid crystal box is irradiated with light while a voltage is applied between the conductive films of a pair of substrates obtained in (3-2) or (3-3) above. The voltage applied here can be set to, for example, a direct current or alternating current of 5V to 50V. In addition, as the irradiation light, for example, ultraviolet rays and visible rays containing wavelengths of 150nm to 800nm ​​can be used, but ultraviolet rays containing wavelengths of 300nm to 400nm are preferred. As the light source of the irradiation light, 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, etc. can be used. The irradiation amount of light is preferably 1000J / m 2 ~200000J / m 2 , more preferably 1000 J / m 2 ~100000J / m 2 .

[0239] Furthermore, a liquid crystal display element can be obtained by attaching a polarizing plate to the outer surface of the liquid crystal cell. Examples of the polarizing plate attached to the outer surface of the liquid crystal cell include a polarizing plate formed by sandwiching a polarizing film called an "H film" between cellulose acetate protective films, or a polarizing plate composed of the H film itself, wherein the H film is formed by absorbing iodine while stretching and orienting polyvinyl alcohol.

[0240] The liquid crystal display element of the present invention can be effectively applied to various devices, for example, clocks, portable game consoles, word processors, notebook computers, car navigation systems, portable cameras, PDAs (Personal Digital Assistants), digital cameras, mobile phones, smart phones, various monitors, liquid crystal televisions, information displays and other display devices.

[0241] Example

[0242] The present invention will be described in further detail below with reference to Examples, but the present invention is not limited thereto. The abbreviations of the compounds used in the Examples have the following meanings.

[0243] (Specific diamine)

[0244] DA-1 to DA-5: compounds represented by the following formulas [DA-1] to [DA-5], respectively.

[0245]

[0246] (Tetracarboxylic acid component)

[0247] D1: 1,2,3,4-cyclobutanetetracarboxylic dianhydride.

[0248] D2: Bicyclo[3,3,0]octane-2,4,6,8-tetracarboxylic dianhydride.

[0249] D3: Benzene-1,2,4,5-tetracarboxylic anhydride.

[0250]

[0251] (Additive ingredients)

[0252] A-1: A compound represented by the following formula [A-1].

[0253]

[0254] (Triazine ring-containing polymer)

[0255] T-1: A compound having a repeating unit structure represented by the following formula [T-1].

[0256] T-2: A compound having a repeating unit structure represented by the following formula [T-2].

[0257]

[0258] (Solvent)

[0259] NMP: N-methyl-2-pyrrolidone.

[0260] BCS: ethylene glycol monobutyl ether.

[0261] THF: tetrahydrofuran.

[0262] DMAc: N,N-dimethylacetamide.

[0263] (Determination of Molecular Weight of Polymer (A)).

[0264] The molecular weight of the polymer (A) in the synthesis example was measured as follows using a room temperature gel permeation chromatography (GPC) apparatus (SSC-7200) manufactured by Senshu Scientific Co., Ltd. and a column (KD-803, KD-805) manufactured by Shodex Corporation.

[0265] Column temperature: 50°C.

[0266] Eluent: N, N-dimethylformamide (as an additive, lithium bromide monohydrate (LiBr·H 2 O) is 30mmol / L, phosphoric acid / anhydrous crystals (o-phosphoric acid) is 30mmol / L, and tetrahydrofuran (THF) is 10ml / L).

[0267] Flow rate: 1.0 ml / min.

[0268] Standard samples for preparing the calibration curve: TSK standard polyethylene oxide manufactured by Tosoh Corporation (molecular weight: about 900,000, 150,000, 100,000, 30,000), and polyethylene glycol manufactured by Polymer Laboratory (molecular weight: about 12,000, 4,000, 1,000).

[0269] (Synthesis of polymer (A))

[0270] <Synthesis example 1>

[0271] D2 (15.01 g) as tetracarboxylic dianhydride, DA-1 (15.65 g, 0.3 molar ratio to total diamine components), DA-2 (8.33 g, 0.35 molar ratio to total diamine components), DA-3 (5.95 g, 0.2 molar ratio to total diamine components), and DA-4 (5.81 g, 0.15 molar ratio to total diamine components) as diamine components were mixed in NMP solvent (203.00 g), and reacted at 60° C. for 3 hours, and then D1 (11.30 g) as tetracarboxylic dianhydride and NMP (44.24 g) were added and mixed, and reacted at 40° C. for 12 hours to obtain a polyamic acid solution (A). The number average molecular weight of the polyamic acid polymer was 9600, and the weight average molecular weight was 22900.

[0272] <Synthesis example 2>

[0273] D1 (14.43 g) as tetracarboxylic dianhydride, DA-2 (9.12 g, 0.4 molar ratio to the total diamine components), DA-3 (8.36 g, 0.3 molar ratio to the total diamine components), and DA-5 (14.16 g, 0.3 molar ratio to the total diamine components) as diamine components were mixed in an NMP solvent (221.94 g), and reacted at room temperature for 1 hour, and then D3 (7.52 g) as tetracarboxylic dianhydride and NMP (81.79 g) were added and mixed, and reacted at room temperature for 12 hours to obtain a polyamic acid solution (B). The number average molecular weight of the polyamic acid polymer was 10,800, and the weight average molecular weight was 32,500.

[0274] (Synthesis of polymer (B))

[0275] <Preparation of triazine ring-containing polymer solution>

[0276] <Synthesis example 3>

[0277]

[0278] In a 1000 mL four-necked flask, 1,3-phenylenediamine [2] (42.22 g, 0.390 mol, manufactured by Amino-Chem) and DMAc (672.62 g, manufactured by Kanto Chemical Co., Ltd.) were added, and after nitrogen substitution, 1,3-phenylenediamine [2] was dissolved in DMAc by stirring. Then, the flask was cooled to -10°C in an ethanol-dry ice bath, and 2,4,6-trichloro-1,3,5-triazine [1] (60.00 g, 0.325 mol, manufactured by Tokyo Chemical Industry Co., Ltd.) was added while confirming that the internal temperature did not exceed 0°C. After stirring for 30 minutes, the oil bath was set to 90°C to 100°C, and the temperature of the reaction solution was raised so that the internal temperature became 85±5°C. After stirring at an internal temperature of 85°C for 1 hour, aniline [6] (18.18 g, 0.195 mol, manufactured by Tokyo Chemical Industry Co., Ltd.) and 2-(4-aminophenyl)ethanol [3] (26.78 g, 0.195 mol, manufactured by Oakwood Co., Ltd.) previously dissolved in DMAc (42.93 g) were added dropwise, and stirred for 3 hours. Thereafter, 2-aminoethanol (59.62 g, manufactured by Tokyo Chemical Industry Co., Ltd.) was added dropwise, the temperature was lowered to room temperature, and stirring was stopped after 30 minutes. THF (369 g), ammonium acetate (415 g) and ion exchange water (415 g) were added to the reaction solution, and stirring was continued for 30 minutes. After stopping stirring, the solution was transferred to a separating funnel, separated into an organic layer and an aqueous layer, and the organic layer was recovered. The recovered organic layer was added dropwise to a mixed solution of methanol (461 g) and ion exchange water (1845 g) to reprecipitate. The obtained precipitate was filtered and dried at 120°C for 8 hours using a reduced pressure dryer to obtain 89.3 g of the target polymer compound

[10] (hereinafter referred to as T-1). 1 The results of H-NMR spectrum are shown in Figure 1 .

[0279] The weight average molecular weight Mw of the compound T-1 measured by GPC in terms of polystyrene was 23350, and the polydispersity coefficient Mw / Mn was 6.5.

[0280] The triazine ring-containing polymer (T-1) (5.00 g) and NMP solvent (20.0 g) were stirred at 40° C. for 12 hours to dissolve them, thereby obtaining a triazine ring-containing polymer solution (C).

[0281] <Synthesis example 4>

[0282]

[0283] In a 1000 mL four-necked flask, 1,3-phenylenediamine [2] (45.15 g, 0.418 mol) and DMAc (685.16 g) were added, and after nitrogen substitution, 1,3-phenylenediamine [2] was dissolved in DMAc by stirring. Then, the mixture was cooled to -10°C in an ethanol-dry ice bath, and 2,4,6-trichloro-1,3,5-triazine [1] (70.00 g, 0.380 mol) was added while confirming that the internal temperature did not exceed 0°C. After stirring for 30 minutes, each reaction vessel was transferred to an oil bath set at 90°C to 110°C, and the reaction solution was heated to an internal temperature of 85±5°C. After stirring for 1 hour, 3-aminophenol [3] (49.71 g, 0.456 mol, manufactured by Tokyo Chemical Industry Co., Ltd.) dissolved in DMAc (120.91 g) was added dropwise, and stirred for 3 hours. Then, 2-aminoethanol (69.56 g, manufactured by Tokyo Chemical Industry Co., Ltd.) was added dropwise, and after stirring for 30 minutes, stirring was stopped. THF (416 g), ammonium acetate (468.2 g) and ion exchange water (468.2 g) were added to the reaction solution and stirred for 30 minutes. After stirring was stopped, the solution was transferred to a separatory funnel, separated into an organic layer and an aqueous layer, and the organic layer was recovered. The recovered organic layer was added dropwise to a mixed solution of methanol (1040 g) and ion exchange water (1561 g) to reprecipitate. The obtained precipitate was filtered and dried at 120°C for 8 hours using a reduced pressure dryer to obtain 95.1 g of the target polymer compound [5] (hereinafter referred to as T-2).

[0284] The weight average molecular weight Mw of compound T-2 measured by GPC in terms of polystyrene was 12384, and the polydispersity coefficient Mw / Mn was 3.3. 1 The results of H-NMR spectrum are shown in Figure 2 .

[0285] The triazine ring-containing polymer (T-2) (5.00 g) and NMP solvent (20.0 g) were stirred at 40° C. for 12 hours to dissolve them, thereby obtaining a triazine ring-containing polymer solution (D).

[0286] <Preparation of Liquid Crystal Alignment Agent>

[0287] <Example 1>

[0288] NMP (3.88 g) and BCS (10.0 g) were added to the polyamic acid solution (A) (1.8 g) obtained in Synthesis Example 1, the triazine ring-containing polymer solution (C) (4.2 g) obtained in Synthesis Example 3, and the additive [A-1] (0.12 g), and stirred for 5 hours to obtain the liquid crystal aligning agent [1] of Example 1. No abnormalities such as turbidity and precipitation were observed in the liquid crystal aligning agent, and it was confirmed that the resin component was uniformly dissolved.

[0289] <Examples 2 to 6, Comparative Examples 1 and 2>

[0290] In Example 1, except that the compounding amounts described in the following Table 1 were changed, liquid crystal aligning agents [2] to [6] of Examples 2 to 6 and liquid crystal aligning agents [7] and [8] of Comparative Examples 1 and 2 were obtained according to the method of Example 1. Abnormalities such as turbidity and precipitation were not observed in these liquid crystal aligning agents, and it was confirmed that the resin component was uniformly dissolved.

[0291] [Table 1]

[0292]

[0293] (Determination of refractive index)

[0294] The liquid crystal alignment agents of Examples 1 to 6 and Comparative Examples 1 and 2 obtained above were spin-coated on a silicon substrate, fired on a hot plate at 70°C for 90 seconds, and then fired in an infrared heating furnace at 230°C for 20 minutes to prepare a liquid crystal alignment agent-coated Si substrate with a film thickness of 100 nm.

[0295] Next, the refractive index was measured using M-2000 manufactured by JA Woollam Japan Co., Ltd., and the refractive index at 550 nm was compared.

[0296] The measurement results of the refractive index in Examples 1 to 6 and Comparative Examples 1 and 2 are shown in Table 2 below.

[0297] (Measurement of transmittance)

[0298] The liquid crystal alignment agents of Examples 1 to 6 and Comparative Examples 1 and 2 obtained above were spin-coated on a quartz substrate, fired on a hot plate at 70°C for 90 seconds, and then fired in an infrared heating furnace at 230°C for 20 minutes to prepare a liquid crystal alignment agent-coated quartz substrate with a film thickness of 100 nm.

[0299] Next, the transmittance in the visible light region (380 nm to 780 nm) was measured using a UV-2600 manufactured by Shimadzu Corporation, using the quartz substrate before the liquid crystal alignment agent was applied as a reference. Then, the average transmittance Y in the XYZ colorimetric system determined by CIE was calculated as the average visible light transmittance.

[0300] The measurement results of the transmittance in Examples 1 to 6 and Comparative Examples 1 and 2 are shown in Table 2 below.

[0301] [Table 2]

[0302]

[0303] As shown in Table 2, it was confirmed that the refractive index was 1.64 or less in Comparative Examples 1 and 2, whereas the refractive index was 1.66 or more in Examples 1 to 6. It was also confirmed that in Examples 1 to 6, the high refractive index was maintained and the average light transmittance was 95% or more.

[0304] (Evaluation of voltage holding ratio)

[0305] <Preparation of a liquid crystal cell for voltage holding ratio evaluation>

[0306] The liquid crystal alignment agents of Examples 1 to 6 and Comparative Examples 1 and 2 obtained above were spin-coated on the ITO surface of a glass substrate (30 mm long, 40 mm wide, and 0.7 mm thick) with ITO that had been cleaned with pure water and IPA (isopropyl alcohol), and then fired at 70°C for 90 seconds using a hot plate and then fired in an infrared heating furnace at 230°C for 20 minutes to produce a polyimide-coated substrate with a film thickness of 100 nm.

[0307] Two liquid crystal alignment agent coated substrates were prepared by the above method. After 4 μm bead spacers were spread on the liquid crystal alignment film surface of one substrate, a thermosetting sealant (XN-1500T manufactured by Kyoritsu Chemical Industry Co., Ltd.) was printed thereon. Next, the surface of the other substrate on which the liquid crystal alignment film was formed was set to the inner side, and after it was bonded to the previous substrate, the sealant was cured to produce an empty box. Liquid crystal MLC-3023 (manufactured by MERCK Co., Ltd.) containing a polymerizable compound for PSA was injected into the empty box by the reduced pressure injection method to produce a liquid crystal box. The voltage holding rate of the liquid crystal box was measured.

[0308] Next, a DC voltage of 15 V was applied to the liquid crystal cell, and 10 J / cm 2 UV that has passed through a 325 nm cutoff filter (also referred to as primary PSA treatment). The UV illuminance was measured using UV-MO3A manufactured by ORC Corporation.

[0309] Then, in order to deactivate the unreacted polymerizable compound remaining in the liquid crystal cell, UV (UV lamp: FLR40SUV32 / A-1) was irradiated for 30 minutes using a UV-FL irradiation device manufactured by Toshiba Lighttech Co., Ltd. (referred to as secondary PSA treatment) without applying voltage. Then, the voltage holding ratio was measured.

[0310] <Determination of voltage holding ratio>

[0311] Using the liquid crystal cell prepared above, a voltage of 1V was applied for 60μs in a hot air circulation oven at 60°C, and the voltage was measured after 1667msec. The voltage was maintained to calculate the voltage holding ratio (VHR). The voltage holding ratio was measured using VHR-1 manufactured by Toyo Technology Co., Ltd.

[0312] The measurement results of the voltage holding ratios in Examples 1 to 6 and Comparative Examples 1 and 2 are shown in Table 3 below.

[0313] [Table 3]

[0314]

[0315] As shown in Table 3, it was confirmed that the VHR after the secondary PSA treatment in Examples 1 to 6 was approximately 90% in all cases, which was equivalent to that in the comparative example.

[0316] It was confirmed that the liquid crystal elements of Examples 1 to 6 are elements showing a practically good voltage holding ratio.

[0317] (Evaluation of pretilt angle)

[0318] <Preparation of a liquid crystal cell for pretilt angle evaluation>

[0319] The liquid crystal alignment agents of Examples 1 to 6 and Comparative Examples 1 and 2 obtained above were spin-coated on an ITO electrode substrate (35 mm long, 30 mm wide, 0.5 mm thick) washed with pure water and IPA (isopropyl alcohol) and having an ITO electrode pattern with a pixel size of 200 μm × 600 μm and a line width / line spacing of 3 μm, and an ITO surface of a patterned glass substrate with ITO (35 mm long, 30 mm wide, 0.7 mm thick) having an optical spacer with a height of 3.2 μm, and then fired at 70°C using a hot plate for 90 seconds and then fired in an infrared heating furnace at 230°C for 20 minutes or 60 minutes to produce a polyimide-coated substrate with a film thickness of 100 nm.

[0320] It should be noted that the ITO electrode substrate on which the ITO electrode pattern is formed is divided into four cross checker (grid) patterns, and can be driven separately for each of the four regions.

[0321] Two polyimide-coated substrates were prepared by the above method, and a thermosetting sealant (XN-1500T manufactured by Kyoritsu Chemical Industry Co., Ltd.) was printed thereon. Next, the surface of the other substrate on which the liquid crystal alignment film was formed was set as the inner side, and after being bonded to the previous substrate, the sealant was cured to produce an empty box. Liquid crystal MLC-3023 (manufactured by Merck) containing a polymerizable compound for PSA was injected into the empty box by a reduced pressure injection method to produce a liquid crystal box. The voltage holding ratio of the liquid crystal box was measured.

[0322] Next, a DC voltage of 15 V was applied to the liquid crystal cell, and 10 J / cm 2 UV that has passed through a 325 nm cutoff filter (also referred to as primary PSA treatment). The UV illuminance was measured using UV-MO3A manufactured by ORC Corporation.

[0323] Then, in order to deactivate the unreacted polymerizable compound remaining in the liquid crystal cell, UV (UV lamp: FLR40SUV32 / A-1) was irradiated for 30 minutes using a UV-FL irradiation device manufactured by Toshiba Lighttech without applying voltage (referred to as secondary PSA treatment). Then, the pretilt angle was measured.

[0324] <Measurement of pretilt angle>

[0325] The pretilt angle of the liquid crystal box prepared above for pretilt angle evaluation was measured using an LCD analyzer (LCA-LUV42A manufactured by Meiryo Technica). The pretilt angle measured using the polyimide coated substrate sintered in an infrared heating furnace at 230°C for 20 minutes was subtracted from the pretilt angle measured using the polyimide coated substrate sintered for 60 minutes, and the obtained value was taken as the pretilt angle difference.

[0326] The measurement results of the pretilt angles in Examples 1 to 6 and Comparative Examples 1 and 2 are shown in Table 4 below.

[0327] [Table 4]

[0328]

[0329] As shown in Table 4, it was confirmed that Examples 1 to 6 showed the same tilt angle characteristics as Comparative Examples 1 and 2, and showed good vertical alignment.

Claims

1. A liquid crystal alignment agent, It is characterized in that Contains the following components (A) and (B), (A) component: at least one polymer (A) selected from the group consisting of a polyimide precursor and a polyimide as an imide product of the polyimide precursor, the polymer (A) being obtained using a diamine component containing an aromatic diamine and a tetracarboxylic acid component containing a tetracarboxylic dianhydride represented by the following formula (S4) or a derivative thereof, Component (B): a polymer (B) characterized by comprising a repeating unit structure represented by the following formula (1), having at least one triazine ring terminal, at least a portion of which is capped with an aromatic amino group having a crosslinking group, In formula (1), R and R' independently represent a hydrogen atom, an alkyl group, an alkoxy group, an aryl group or an aralkyl group; Ar represents at least one selected from the group represented by formulae (2) to (12), In the formula, any hydrogen atom on the aromatic ring of formula (2) to (12) is optionally substituted, R 12 represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, W 1 and W 2 Independently represent single bonds, -CR 95 R 96 -, -C(=O)-, -O-, -S-, -S(=O)-, -SO 2 -or-NR 97 -; described -CR 95 R 96 - Middle, R 95 and R 96 Each independently represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, wherein R 95 and R 96 Optionally together to form a ring; said -NR 97 - Middle, R 97 represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or a phenyl group, X 1 and X 2 each independently represents a single bond, an alkylene group having 1 to 10 carbon atoms, or -Y 1 -Ph-Y 2 - shown in the group, said -Y 1 -Ph-Y 2 -, Ph represents a phenylene group, and any hydrogen atom on the phenylene group is optionally substituted; Y 1 and Y 2 each independently represents a single bond or an alkylene group having 1 to 10 carbon atoms, In formula (S4), X represents a structure selected from the group consisting of the following (x-1) to (x-13), In formulas (x-1) to (x-13), R 1 ~R 4 R each independently represents a hydrogen atom, a methyl group, an ethyl group, a propyl group, a chlorine atom, a monovalent organic group having 1 to 6 carbon atoms and containing a fluorine atom, or a phenyl group; 5 and R 6 represents a hydrogen atom or a methyl group; j and k are integers 0 or 1, A 1 and A 2 Each independently represents a single bond, -O-, -CO-, -COO-, a phenylene group, a sulfonyl group or an amide bond; *1 is a bond to one of the acid anhydride groups, and *2 is a bond to the other of the acid anhydride groups.

2. The liquid crystal alignment agent according to claim 1, in, The aromatic amino group having a crosslinking group of the polymer (B) is represented by formula (15), In formula (15), R 15 Represents a cross-linking group.

3. The liquid crystal aligning agent according to claim 1 or 2, in, The crosslinking group of the polymer (B) is a hydroxyl group or a (meth)acryloyl group.

4. The liquid crystal alignment agent according to claim 1 or 2, in, The crosslinking group of the polymer (B) is one or more selected from the group consisting of a hydroxyl group, a hydroxymethyl group, a 2-hydroxyethyl group, a (meth)acryloyloxymethyl group, a (meth)acryloyloxyethyl group, and a group represented by the following formula (i-2) to (i-3), 5. The liquid crystal aligning agent according to claim 1 or 2, in, A part of the triazine ring terminals of the polymer (B) are also capped with unsubstituted aromatic amino groups.

6. The liquid crystal aligning agent according to claim 1 or 2, in, The aromatic diamine has at least one selected from the group consisting of structures represented by the following formulae (S1) to (S3), In formula (S1), X 1 and X 2 Each independently represents a single bond, -(CH 2 ) a -, -CONH-, -NHCO-, -CON(CH 3 )-, -NH-, -O-, -COO-, -OCO- or -((CH 2 ) a1 -A 1 ) m1 -, said - (CH 2 ) a -, a is an integer from 1 to 15, and the -((CH 2 ) a1 -A 1 ) m1 -, a1 is an integer from 1 to 15, A 1 represents oxygen atom or -COO-, m 1 is an integer from 1 to 2, in m 1 When it is 2, multiple a1 and A 1 Each independently has the above definition; G 1 and G 2 Each independently represents a divalent cyclic group selected from a divalent aromatic group having 6 to 12 carbon atoms and a divalent alicyclic group having 3 to 8 carbon atoms; any hydrogen atom on the cyclic group is optionally substituted by an alkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, an alkyl group containing fluorine atoms having 1 to 3 carbon atoms, an alkoxy group containing fluorine atoms having 1 to 3 carbon atoms, or a fluorine atom; m and n are each independently an integer of 0 to 3, and m+n is an integer of 1 to 6; 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, forming R 1 Any hydrogen atom of is optionally substituted by a fluorine atom, —X 3 -R 2 (S2) In formula (S2), X 3 Indicates a single bond, -CONH-, -NHCO-, -CON(CH 3 )-, -NH-, -O-, -CH 2 O-, -COO- or -OCO-; R 2 represents an alkyl group having 1 to 20 carbon atoms or an alkoxyalkyl group having 2 to 20 carbon atoms, forming R 2 Any hydrogen atom of is optionally substituted by a fluorine atom, —X 4 -R 3 (S3) In formula (S3), X 4 Indicates -CONH-, -NHCO-, -O-, -CH 2 O-, -COO- or -OCO-; R 3 It indicates a structure having a steroidal skeleton.

7. The liquid crystal aligning agent according to claim 1 or 2, in, The aromatic diamine is a diamine represented by the following formula (d1) or formula (d2), In the formula, X represents a single bond, -O-, -C(CH 3 ) 2 -, -NH-, -CO-, -(CH 2 ) m -、-SO 2 -、-O-(CH 2 ) m -O-, -O-C(CH 3 ) 2 -、-CO-(CH 2 ) m -、-NH-(CH 2 ) m -、-SO 2 -(CH 2 ) m -、-CONH-(CH 2 ) m -、-CONH-(CH 2 ) m -NHCO- or -COO-(CH 2 ) m -OCO-; m is an integer of 1 to 8; Y represents any structure in the formulae (S1) to (S3); in formula (d2), two Ys are optionally the same or different from each other.

8. The liquid crystal alignment agent according to claim 1, in, The tetracarboxylic dianhydride or its derivative represented by the formula (S4) is a tetracarboxylic dianhydride or its derivative wherein X is one of the formulas (x-1) to (x-7) and (x-11) to (x-13).

9. The liquid crystal alignment agent according to claim 1 or 2, in, The content ratio of the component (A) to the component (B) is 10 / 90 to 90 / 10 in terms of the mass ratio of [component (A)] / [component (B)]. 10 . A liquid crystal alignment film formed using the liquid crystal aligning agent according to claim 1 . 11 . A liquid crystal display element comprising the liquid crystal alignment film according to claim 10 . 12 . A method for producing a liquid crystal display element, comprising the step of applying the liquid crystal aligning agent according to claim 1 onto a substrate.

13. The method for manufacturing a liquid crystal display element according to claim 12, in, A liquid crystal alignment agent as described in any one of claims 1 to 9 is applied onto a pair of substrates having a conductive film to form a coating film, the coating films are arranged opposite to each other with a layer of liquid crystal molecules therebetween to form a liquid crystal box, and light is irradiated to the liquid crystal box while a voltage is applied between the conductive films of the pair of substrates.

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