JP2012180484A - Liquid crystal aligning agent, liquid crystal alignment layer, liquid crystal display device, novel maleimide-based polymer, and novel bismaleimide - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a novel resin composition usable for formation of a liquid crystal alignment layer and the like having good characteristics, and containing a maleimide-based polymer; and to provide a liquid crystal alignment layer and the like, and a novel compound according to the same.SOLUTION: In the resin composition containing a maleimide-based polymer and a solvent, the maleimide-based polymer has a plurality of rigid linear structures intermittent in the main chain.

Description

  The present invention relates to a resin composition containing a maleimide polymer and a solvent by a Michael addition reaction, which is generated by polymerization of bismaleimide and a diamine, that is, an addition reaction of an amino group of diamine to an unsaturated bond of bismaleimide, and The present invention relates to a novel maleimide polymer and bismaleimide.

  One application field of the present invention is a liquid crystal display element. Liquid crystal display elements are used in various liquid crystal display devices such as monitors for notebook computers and desktop computers, video camera viewfinders, and projection displays. Recently, they have also been used as televisions. . Furthermore, liquid crystal display elements are also used as optoelectronic-related elements such as optical printer heads, optical Fourier transform elements, and light valves.

  The liquid crystal display element usually has 1) a pair of substrates arranged opposite to each other, 2) electrodes formed on one or both of the opposed surfaces of each of the pair of substrates, and 3) each of the pair of substrates. And 4) a liquid crystal layer formed between the pair of substrates.

As the liquid crystal display element, a display element using a nematic liquid crystal is mainly used. As the liquid crystal display element, for example, 1) a TN (twisted nematic) type liquid crystal display element twisted by 90 degrees, and 2) an STN twisted by 180 degrees or more are usually used. Super Twisted Nematic) type liquid crystal display element, 3) So-called TFT (Thin) using a thin film transistor
A film transistor type liquid crystal display element is known. Moreover, as a liquid crystal display element in which the viewing angle in these liquid crystal display elements is further improved, for example, 4) a TN-TFT type liquid crystal display element using an optical compensation film, and 5) a vertical alignment and an optical compensation film. VA (Vertical Alignment) type liquid crystal display element used, 6) MVA (Multi Domain Vertical) using both vertical alignment and protrusion structure technology
Alignment type liquid crystal display element, 7) In-plane switching type IPS (In-Plane Switching) type liquid crystal display element, 8) ECB (Electrically Controlled Birefringence) type liquid crystal display element, and 9) Optically Compensated Bend Optically
A self-compensated birefringence (OCB) type liquid crystal display element is known.

  The development of the technology of the liquid crystal display element is achieved not only by simply improving these driving methods and element structures, but also by improving the components used in the liquid crystal display element. Among the components used in the liquid crystal display element, the liquid crystal alignment film is one of the important elements related to the display quality of the liquid crystal display element. Roles are becoming important year after year.

  The liquid crystal alignment film is prepared from a liquid crystal aligning agent. As a typical liquid crystal aligning agent conventionally used, a polyamic acid or a soluble polyimide obtained by reacting a tetracarboxylic anhydride or a derivative thereof with a diamine or a derivative thereof is dissolved in an organic solvent. Solutions are known.

  On the other hand, in addition to polyimide (that is, polyamic acid or soluble polyimide), a maleimide polymer obtained by reacting bismaleimide and diamine is also a liquid crystal aligning agent that forms a liquid crystal aligning film having good electro-optical properties. It is known that it can be used (for example, refer patent document 1).

  The polyimide can form various types of molded products such as films, substrates, fibers, and particles by firing, and further add functionality as necessary to form adhesives and separation membranes. In addition, a functional film such as an electrolyte film can be formed. The maleimide polymer is also expected to be applied to such various uses.

Japanese Patent Laid-Open No. 07-110483

  The present invention provides a novel resin composition containing a maleimide polymer, and a liquid crystal alignment film, a liquid crystal display element, and a novel compound that can be used to form a liquid crystal alignment film having good characteristics. To do.

  The present inventors have intensively studied to solve the above problems. As a result, by using a rigid linear structure and a flexible structure in combination with the main chain of the maleimide polymer, the orientation of the maleimide polymer in the liquid crystal alignment film is improved when used as a liquid crystal alignment agent. The present invention was completed. The present invention has the following configuration.

[1] In a resin composition containing a maleimide polymer having a reaction product structure by Michael addition reaction of bismaleimide and diamine, and a solvent,
A resin composition having a plurality of rigid linear structures in which the maleimide polymer is intermittently connected to the main chain.

[2] The resin composition according to [1], wherein the maleimide polymer has a weight average molecular weight of 3,000 to 500,000.

[3] The bismaleimide includes a bismaleimide having a rigid linear structure,
The resin composition according to [1] or [2], wherein the bismaleimide having the rigid linear structure includes a bismaleimide represented by the following formula (MA).

In the formula (MA), X ¹³ independently represents a single bond or alkylene having 1 to 30 carbon atoms,
X ¹⁴ independently represents 1,4-phenylene, a condensed ring having 8 to 22 atoms constituting the ring, or 1,4-cyclohexylene,
X ¹⁵ independently represents a single bond or — (CH ₂ CH ₂ ) _ab2 —;
ab1 represents an integer of 0 to 4, and ab2 represents an integer of 0 to 4.
Provided that when ab1 is 0, X ¹⁴ represents a fused ring of the number of atoms constituting the ring 8 to 22.
-H on —CH═CH— of the maleimide group may be independently replaced by alkyl having 1 to 3 carbon atoms;
Is independently -NH - - -CH ₂ in the alkylene of X ^13, - NY ² -, or -Si (Y ²²⁾ ₂ - may be replaced by,
—CH ₂ CH ₂ — in the alkylene of X ¹³ may be independently replaced with —CH═CH—, —C≡C—,
—CH ₂ — that is not adjacent to the nitrogen atom of the maleimide group in the alkylene of X ¹³ may be independently replaced with —O—, —CO—, —S—, —SO—, or —SO ₂ —;
—CH ₂ CH ₂ — that is not adjacent to the nitrogen atom of the maleimide group in the alkylene of X ¹³ may be independently replaced by —N═N—,
Of _{^{X 15 - (CH 2 CH 2}} ) ab2 - -CH Medium ₂ - is independently -O -, - NH -, - CO -, - NY 2 -, - S -, - SO -, - SO _2- or -Si (Y ²² ) _2- may be substituted,
—CH ₂ CH ₂ — in — (CH ₂ CH ₂ ) _ab2 — in X ¹⁵ may be independently replaced with —CH═CH—, _—C≡C— , or —N═N—,
—H on X ¹³ alkylene or substituted alkylene, or X ¹⁵ — (CH ₂ CH ₂ ) _ab2 — or substituted — (CH ₂ CH ₂ ) _ab2 — is independently —F, —Cl , -Br, -C≡N, -OH, -COOH, -SO ₃ H, -PO ₃ H ₂ , an arbitrary -H having 1 to 20 carbon atoms optionally substituted with halogen, Or any -H may be independently replaced by an alkenyl having 2 to 20 carbon atoms which may be replaced by a halogen;
1,4-phenylene of X ¹⁴ , 1,4-cyclohexylene, and —H on the fused ring are each independently 1 carbon number in which arbitrary —H may be independently replaced by halogen. ˜3 alkyl, optional —H may be independently replaced by halogen, C 1-3 alkoxy, —F, —Cl, —Br, —C≡N, —OH, —COOH, — May be replaced by SO ₃ H, —PO ₃ H ₂ , or —N (Y ² ) ₂ ;
In the alkyl and alkoxy, —CH ₂ — may be independently replaced by —O—, —CO— or —S—,
In each group constituting (MA), Y ² independently represents —H, alkyl having 1 to 20 carbon atoms, or alkenyl having 2 to 20 carbon atoms, and Y ²² independently represents —H, carbon number 1 20 alkyl, alkenyl having 1 to 20 carbon atoms, or represents phenyl, -H on the phenyl are independently -F, -Cl, -Br, -C≡N, -OH, -COOH, -SO 3 H, —PO ₃ H ₂ , or alkyl having 1 to 30 carbon atoms may be substituted.

[4] The bismaleimide having the rigid linear structure is represented by the following formulas (MA-1-1-1), (MA-1-2-1), (MA-1-3-1), (MA-1- 4-1), (MA-1-5-1), (MA-2-1-1), (MA-2-1-2), (MA-2-1-4), (MA-2-1) 1-9), (MA-2-1-15), (MA-2-2-1), (MA-2-3-1), (MA-2-4-1), (MA-2-1) 5-1), (MA-2-6-1), (MA-2-7-1), (MA-2-8-1), (MA-2-9-1), (MA-3- 1-1), (MA-3-2-1), (MA-3-2-2), (MA-3-3-1), (MA-3-3-3), (MA-3- 3-4), (MA-3-4-1), (MA-3-5-1), (MA-3-11-3) to (MA-3-1) -14), (MA-4-1-1), (MA-4-2-1), (MA-4-11-1) to (MA-4-11-9), and (MA-5) The resin composition according to [3], comprising one or more selected from the group of 11-1).

[5] The bismaleimide having the rigid linear structure includes the formula (MA-2-1-2), (MA-2-1-4), or (MA-2-1-9) [4 ] The resin composition as described in.

[6] The resin composition according to [5], wherein the bismaleimide is a bismaleimide represented by the formula (MA-2-1-2).

[7] The resin composition according to any one of [1] to [6], wherein the diamine includes an aliphatic diamine.

[8] The diamine is represented by the following formulas (II-1-1) to (II-1-14), (II-1-21) to (II-1-30), (IV-1-1) to (IV). -1-4), one or more diamines selected from the group of (V-1-20) to (V-1-22) and (VI-1-40), [1] to [7 ] The resin composition as described in any one of.

[9] The resin composition according to [8], wherein the aliphatic diamine includes the formula (IV-1-1) or (II-1-22).

[10] The resin composition according to any one of [1] to [9], wherein the diamine includes one or both of a diamine having a rigid linear structure and an aliphatic diamine.

[11] The resin composition according to [10], wherein the diamine having a rigid linear structure includes a diamine represented by the following formula (VII-13).

In Formula (VII-13), X ¹¹ independently represents an alkylene having 1 to 12 carbons,
Ring R independently represents a ring in which the sum of the number of carbon, nitrogen, oxygen, sulfur, and silicon constituting the skeleton is 3 to 30, a is independently an integer of 0 to 4, and b is independently And represents an integer from 0 to 12,
—CH ₂ — in the alkylene in X ¹¹ may be independently replaced with —O—, —NH—, —CO—, —CHY ² —, —C (Y ² ) ₂ —, or —NY ² —. , -CH ₂ CH ₂ in the alkylene - independently -CH = CH -, - C≡C-, or -N = may be replaced by N-, -H on the alkylene or replaced alkylene May be independently substituted with alkyl of 1 to 20 carbons or alkenyl of 2 to 20 carbons;
The —CH ₂ — in the alkylene between the ring R and the amino group may be independently replaced by —NH—, —CHY ² —, —C (Y ² ) ₂ —, or —NY ² —. -CH ₂ CH ₂ in - may be replaced by -CH = CH- or -C≡C-, independently,
—CH ₂ — that is not adjacent to —NH _{2 in} alkylene may be independently replaced with —O— or —CO—;
-CH ₂ CH ₂ which is not adjacent to the -NH ₂ in the alkylene - may be replaced independently by -N = N-,
-H is independently -F on the alkylene or replaced alkylene, -Cl, -Br, -C≡N, -OH , -COOH, replaced by -SO ₃ H, or -PO ₃ H ₂ Often,
The —H of the amino group may be independently replaced with alkyl having 1 to 12 carbons, and —CH ₂ — in this alkyl is independently —NH—, —CHY ² —, —C (Y ² ) _2. -, or -NY ² - may be replaced by, -CH ₂ CH ₂ in the alkyl - may be replaced by -CH = CH- or -C≡C-, independently,
—CH ₂ — that is not adjacent to —NH _{2 in} alkyl may be independently replaced with —O— or —CO—;
—CH ₂ CH ₂ — that is not adjacent to —NH _{2 in} alkyl may be independently replaced by —N═N—,
-H is independently -F on the alkyl or replaced alkyl, -Cl, -Br, -C≡N, -OH , -COOH, replaced by -SO ₃ H, or -PO ₃ H ₂ Often,
In each group constituting the formula (VII-13), Y ² independently represents -H, alkyl having 1 to 20 carbons, or alkenyl having 2 to 20 carbons. However the -CHY ² - and -C (Y ^{₂₎ 2} - In, Y ² is not a -H.

[12] The resin according to [11], wherein the diamine having a rigid linear structure includes one or more diamines selected from the group of the following formulas (VII-13-1) to (VII-13-4): Composition.

[13] The resin composition according to any one of [10] to [12], wherein the diamine includes both a diamine having a rigid linear structure and another aliphatic diamine.

[14] The other aliphatic diamines are represented by the following formulas (II-1-1) to (II-1-14), (II-1-21) to (II-1-30), (IV-1- 1) one or more diamines selected from the group of (IV-1-4), (V-1-20) to (V-1-22), and (VI-1-40), 13].

[15] The resin composition according to [14], wherein the other aliphatic diamine includes the formula (IV-1-1) or (II-1-22).

[16] The maleimide polymer is obtained by polymerizing a monomer mixture containing the bismaleimide and diamine in a solvent containing at least one selected from the group consisting of a solvent having a hydroxyl group and a protic amide solvent. The resin composition according to any one of [1] to [16].

[17] The resin composition according to [16], wherein the solvent having a hydroxyl group is a solvent having an alcoholic hydroxyl group.

[18] The solvent having an alcoholic hydroxyl group is methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, t-butyl alcohol, 1-pentanol, 1-hexanol, 2-ethylhexanol. Aliphatic monoalcohols such as benzyl alcohol, (o-, m-, or p-) methylbenzyl alcohol, (o-, m-, or p-) methoxybenzyl alcohol, 1-phenylethyl alcohol, 2-phenylethyl Aromatic alcohols such as alcohol, aliphatic polyols such as ethylene glycol and glycerol, alkoxy monoalcohols such as 3-methyl-3-methoxybutanol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono- -Selected from the group consisting of butyl ether, diethylene glycol monoethyl ether, triethylene glycol monoalkyl ether, propylene glycol monobutyl ether, dipropylene glycol monomethyl ether, and 1) alcoholic hydroxyl groups, and 2) amides, esters, and cyclic ethers [17] The resin composition according to [17], which is any one or more selected from the group consisting of highly polar alcohols having any one or more groups.

[19] The highly polar alcohol is methyl lactate, ethyl lactate, propyl lactate, butyl lactate, methyl 2-hydroxybutyrate, ethyl 2-hydroxybutyrate, methyl 2-hydroxyisobutyrate, ethyl 2-hydroxyisobutyrate, 2-hydroxy -3- hydroxyl group-containing esters such as methyl butenoate, dimethyl malate, diethyl malate, dipropyl malate, dibutyl malate, and glycerol diacetate, and one or more represented by the following formulas (1) to (21) The resin composition according to [18], wherein the protic amide solvent is one or more represented by the following formulas (22) to (26).

[20] A polymerization solvent for the monomer of the maleimide polymer is methyl lactate, ethyl lactate, propyl lactate, butyl lactate, methyl 2-hydroxybutyrate, ethyl 2-hydroxybutyrate, methyl 2-hydroxyisobutyrate, 2-hydroxyiso Hydroxyl-containing esters such as ethyl butyrate, methyl 2-hydroxy-3-butenoate, dimethyl malate, diethyl malate, dipropyl malate, dibutyl malate, glycerol diacetate, and the above formulas (1) to (21) The resin composition according to [19], comprising any one or more selected from the group consisting of highly polar alcohols.

[21] The resin composition according to [20], wherein a polymerization solvent for the maleimide polymer monomer includes a highly polar alcohol represented by the formula (3).

[22] The solvent contains a solvent having a hydroxyl group or a protic amide solvent, [
The resin composition according to any one of [1] to [21].

[23] The solvent having a hydroxyl group is methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, t-butyl alcohol, 1-pentanol, 1-hexanol, 2-ethylhexanol, benzyl alcohol. , (O-, m-, or p-) methylbenzyl alcohol, (o-, m-, or p-) methoxybenzyl alcohol, 1-phenylethyl alcohol, 2-phenylethyl alcohol, ethylene glycol, glycerol, 3- Methyl-3-methoxybutanol, ethylene glycol monoethyl ether, ethylene glycol mono-n-butyl ether, diethylene glycol monoalkyl ether, triethylene glycol monoalkyl ether, propylene glycol mono-n-butyl ether Dipropylene glycol monomethyl ether, methyl lactate, ethyl lactate, propyl lactate, butyl lactate, methyl 2-hydroxybutyrate, ethyl 2-hydroxybutyrate, methyl 2-hydroxyisobutyrate, ethyl 2-hydroxyisobutyrate, 2-hydroxy- 3-methyl butenoate, dimethyl malate, diethyl malate, dipropyl malate, dibutyl malate, glycerol diacetate, and at least selected from the group consisting of the compounds represented by formulas (1) to (21) One,
The resin composition according to [22], wherein the protic amide solvent is at least one selected from the group consisting of compounds represented by the formulas (22) to (26).

[24] The resin composition according to [22] or [23], wherein the solvent further includes a polar solvent and a coating property improving solvent.

[25] The polar solvent is at least one selected from the group consisting of N-methyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide, and N, N′-dimethylimidazolidinone. The resin composition according to [24].

[26] The coating property improving solvent is methyl lactate, ethyl lactate, propyl lactate, butyl lactate, methyl 2-hydroxybutyrate, ethyl 2-hydroxybutyrate, methyl 2-hydroxyisobutyrate, ethyl 2-hydroxyisobutyrate, 2 -Methyl hydroxy-3-butenoate, dimethyl malate, diethyl malate, dipropyl malate, dibutyl malate, glycerol diacetate, solvents represented by the above formulas (1) to (17), 3-methyl-3- Methoxybutanol, tetralin, isophorone, ethylene glycol monoalkyl ether, diethylene glycol monoalkyl ether, ethylene glycol monoalkyl or phenyl acetate, triethylene glycol monoalkyl ether, propylene glycol monoalkyl ether, dialkyl malonate, Propylene glycol monoalkyl ether, and a solvent selected from the group consisting of ester compounds, resin composition according to [24] or [25].

[27] The resin according to any one of [22] to [26], wherein a content of the solvent having a hydroxyl group or a protic amide solvent is 20% by weight or more based on the total amount of the solvent. Composition.

[28] The resin composition according to any one of [1] to [27], wherein the maleimide polymer is manufactured by a method that does not include a step of solvent replacement after polymerization.

[29] The resin composition according to any one of [1] to [28], which is a liquid crystal aligning agent for IPS, wherein the diamine does not include a diamine having a side chain structure.

[30] The resin composition according to any one of [1] to [28], which is a liquid crystal aligning agent for TN, wherein the diamine further includes a diamine having a side chain structure.

[31] The resin composition according to any one of [1] to [28], which is a liquid crystal aligning agent for VA, further including a diamine having a side chain structure.

[32] A coating material containing the resin composition according to any one of [1] to [28].

[33] An insulating material containing the resin composition according to any one of [1] to [28].

[34] An adhesive containing the resin composition according to any one of [1] to [28].

[35] A sealing material containing the resin composition according to any one of [1] to [28].

[36] A printed wiring board material containing the resin composition according to any one of [1] to [28].

[37] A molding material containing the resin composition according to any one of [1] to [28].

[38] A material for a gas separation material formed from the resin composition according to any one of [1] to [28].

[39] A wire material formed from the resin composition according to any one of [1] to [28].

[40] A liquid crystal alignment film formed from the resin composition according to any one of [29] to [31].

[41] A liquid crystal display device having the liquid crystal alignment film according to [40].

[42] In a maleimide polymer having a reaction product structure by Michael addition reaction between bismaleimide and diamine,
The maleimide polymer has a plurality of rigid linear structures intermittent to the main chain, and the monomer mixture containing the bismaleimide and diamine is selected from the group consisting of a solvent having an alcoholic hydroxyl group and a protic amide solvent. A maleimide polymer which is polymerized in a solvent containing any one or more selected.

[43] The maleimide polymer according to [42], wherein the maleimide polymer has a weight average molecular weight of 3,000 to 500,000.

[44] The bismaleimide includes a bismaleimide having a rigid linear structure;
The maleimide polymer according to [42] or [43], wherein the bismaleimide having the rigid linear structure includes a bismaleimide represented by the formula (MA).

[45] The bismaleimide having the rigid linear structure is represented by the formula (MA-1-1-1), (MA-1-2-1), (MA-1-3-1), (MA-1- 4-1), (MA-1-5-1), (MA-2-1-1), (MA-2-1-2), (MA-2-1-4), (MA-2-1) 1-9), (MA-2-1-15), (MA-2-2-1), (MA-2-3-1), (MA-2-4-1), (MA-2-1) 5-1), (MA-2-6-1), (MA-2-7-1), (MA-2-8-1), (MA-2-9-1), (MA-3- 1-1), (MA-3-2-1), (MA-3-2-2), (MA-3-3-1), (MA-3-3-3), (MA-3- 3-4), (MA-3-4-1), (MA-3-5-1), (MA-
3-11-3) to (MA-3-11-14), (MA-4-1-1), (MA-4-2-1), (MA-4-11-1) to (MA- 4-11-9) and the maleimide polymer according to [44], comprising one or more selected from the group of (MA-5-11-1).

[46] The bismaleimide having the rigid linear structure is selected from the group of the formulas (MA-2-1-2), (MA-2-1-4), and (MA-2-1-9). The maleimide polymer according to [45], comprising one or more of the above.

[47] The maleimide polymer according to [46], wherein the bismaleimide is a bismaleimide represented by the formula (MA-2-1-2).

[48] The maleimide polymer according to any one of [42] to [47], wherein the diamine includes an aliphatic diamine.

[49] The aliphatic diamine is a compound represented by the formula (II-1-1) to (II-1-14), (II-1-2) to (II-1-30), (IV-1-1). Comprising one or more diamines selected from the group of (IV-1-4), (V-1-20) to (V-1-22), and (VI-1-40) [48] The maleimide polymer described in 1.

[50] The maleimide polymer according to [49], wherein the aliphatic diamine includes the formula (IV-1-1) or (II-1-22).

[51] The maleimide polymer according to any one of [42] to [50], wherein the diamine includes one or both of a diamine having a rigid linear structure and an aliphatic diamine.

[52] The maleimide polymer according to any one of [51], wherein the diamine having a rigid linear structure includes a diamine represented by the formula (VII-13).

[53] The maleimide according to [52], wherein the diamine having a rigid linear structure includes one or more diamines selected from the group of the formulas (VII-13-1) to (VII-13-4) Polymer.

[54] The maleimide polymer according to any one of [51] to [53], wherein the diamine includes both a diamine having a rigid linear structure and another aliphatic diamine.

[55] The other aliphatic diamines are represented by the formulas (II-1-1) to (II-1-14), (II-1-21) to (II-1-30), (IV-1- 1) one or more diamines selected from the group of (IV-1-4), (V-1-20) to (V-1-22), and (VI-1-40), 54].

[56] The maleimide polymer according to [55], wherein the aliphatic diamine other than fat includes the formula (IV-1-1) or (II-1-22).

[57] The maleimide polymer is methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, t-butyl alcohol, 1-pentanol, 1-hexanol, 2-ethylhexanol, benzyl. Alcohol, (o-, m-, or p-) methylbenzyl alcohol, (o-, m-, or p-) methoxybenzyl alcohol, 1-phenylethyl alcohol, 2-phenylethyl alcohol, ethylene glycol, glycerol, 3 -Methyl-3-methoxybutanol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono-n-butyl ether, diethylene glycol monoethyl ether, triethylene glycol monoalkyl ether, Highly polar alcohol having at least one group selected from the group consisting of propylene glycol monobutyl ether, dipropylene glycol monomethyl ether, 1) alcoholic hydroxyl group, and 2) amide, ester, and cyclic ether, and protic amide The maleimide polymer according to any one of [42] to [56], which is polymerized in a solvent containing any one or more selected from the group consisting of a solvent.

[58] The high polar alcohol is methyl lactate, ethyl lactate, propyl lactate, butyl lactate, methyl 2-hydroxybutyrate, ethyl 2-hydroxybutyrate, methyl 2-hydroxyisobutyrate, ethyl 2-hydroxyisobutyrate, 2-hydroxy -3-butenoate, dimethyl malate, diethyl malate, dipropyl malate, dibutyl malate, glycerol diacetate, and one or more of the above formulas (1) to (21), and the protic amide The maleimide polymer according to [57], wherein the system solvent is one or more represented by the formulas (22) to (26).

[59] The polymerization solvent for the monomer of the maleimide polymer includes any one or more selected from the group consisting of high polar alcohols represented by the formulas (1) to (21). Maleimide polymer.

[60] The maleimide polymer according to [59], wherein the maleimide polymer is polymerized in a solvent containing a highly polar alcohol represented by the formula (3).

[61]
The following formulas (MA-1-1) to (MA-1-3), (MA-2-2) to (MA-2-6), (MA-3-1), (MA-3-2), (MA-2-1-19) to (MA-2-1-27), (MA-2-7-2), (MA-2-7-3), (MA-1-4-2), And bismaleimide represented by any one of (MA-1-5-1).

Wherein (MA-1-1), R ¹¹¹ represents -H, -OH, or -F, R ¹¹² represents -OH, -F, or -Cl independently, a1 is an integer of 0 to 5 Represents. However when R ¹¹¹ represents -H, a1 represents an integer of 1 to 5.
In formula (MA-1-2), R ¹²¹ independently represents —CH ₃ , —OH, —OCH ₃ , —SCH ₃ , or —F, and a2 represents an integer of 1 to 5.
(In the formula (MA-1-3), R ¹³¹ and R ¹³² each represent —H, —CH ₃ , or —OH.
In the formula (MA-2-2), R ²²¹ independently represents -CH ₃ , -CF ₃ , -OH, -F, -Cl, or -OCH ₃ , and a4 is independently an integer of 0 to 4. Represents. However, the sum of a4 is 1 or more.
In formula (MA-2-3), R ²³¹ independently represents —CF ₃ , —OH, —F, or —OCH ₃ , and a5 independently represents an integer of 0 to 4. However, the sum of a5 is 1 or more.
In the formula (MA-2-4), R ²⁴¹ independently represents —CH ₃ , —CF ₃ , —OH, —Cl, —Br, —OCH ₃ , or —OCH ₂ CH ₃ , and R ²⁴² represents — H or linear alkyl having 1 to 3 carbon atoms is represented, and a6 independently represents an integer of 0 to 4. However when R ²⁴² represents a straight-chain alkyl of 1 to 3 carbon atoms, R ²⁴¹ is it may represent independently -H, sum of a6 is 1 or more.

In formula (MA-2-5), R ²⁵¹ independently represents -CH ₃ , -OH, -Cl, or -OCH ₃ , and a7 independently represents an integer of 0 to 4. However, the sum of a7 is 1 or more.
In formula (MA-2-6), R ²⁶¹ independently represents -CH ₃ , -CF ₃ , or -F, and a8 independently represents an integer of 0 to 10.
In formula (MA-3-1), R ³¹¹ independently represents —CH ₃ , —CF ₃ , —OH, —F, —Cl, or —OCH ₃ , and a9 is independently an integer of 0 to 4 Represents. However, the sum of a9 is 1 or more.
In formula (MA-3-2), R ³²¹ independently represents —CH ₃ or —CH (CH ₃ ) ₂ , R ³²² independently represents —CH ₃ or —CH ₂ CH ₃ , and a10 represents Independently represents an integer of 0 to 4.

  According to the present invention, since the maleimide polymer in the present invention has a rigid linear structure and a flexible structure alternately in the main chain of the maleimide polymer, the resin composition can be handled in a solution. A liquid crystal alignment film having good characteristics such as excellent rubbing resistance and alignment stability and no flow alignment when used in, for example, a liquid crystal alignment film. The liquid crystal display element which has these, the resin composition used as a liquid crystal aligning agent which forms such a film | membrane, and the novel maleimide type polymer used for such a resin composition can be provided. Moreover, according to this invention, the novel bismaleimide which comprises such a maleimide type polymer can be provided.

It is a figure which shows each IR spectrum of the film | membrane of PM2 of Example 2, and MA-2-1-2 obtained by manufacture example 1. FIG.

  The resin composition of the present invention contains a maleimide polymer having a plurality of rigid linear structures intermittently in the main chain and a solvent.

In the present invention, -CH ₂ in the alkylene - is -O -, - NH -, - CO -, - CHY 2 -, - C (Y 2) 2 -, - NY 2 -, - S -, - SO- , —SO ₂ —, or —Si (Y ²² ) ₂ —, in which —CH ₂ CH ₂ — in alkylene is —CH═CH—, —C≡C—, —Si (CH ₃ ). _When defined as _2- O-Si (CH ₃ ) _2- , or -N = N-, the following embodiments are included.

For example, when alkylene is — (CH ₂ ) ₄ —, one or more of —CH ₂ — is replaced with —O— to replace —O— (CH ₂ ) ₃ — or —O—CH ₂ —O—CH. ₂ may be substituted, and one or more of —CH ₂ CH ₂ — may be replaced by —CH═CH—, and —CH═CH— (CH ₂ ) ₂ — or —CH═CH—CH═CH— Or —CH ₂ — and —CH ₂ CH ₂ — may be simultaneously replaced with —O— and —CH═CH— to give —O—CH ₂ —CH═CH—.

The same applies to the case where alkylene is alkyl in the above example. For example, when alkyl is — (CH ₂ ) ₃ CH ₃ , one or more —CH ₂ — is replaced by —O— and —O— (CH ₂ ) ₂ CH ₃ — or —O—CH ₂ —O—CH ₃ , wherein one or more —CH ₂ CH ₂ — is replaced by —CH═CH—, and —CH═CH —CH ₂ —CH ₃ — or —CH═CH—CH═CH ₂ , or —CH ₂ — and —CH ₂ CH ₂ — may be replaced with —O— and —CH═CH— at the same time. It may be —O—CH ₂ —CH═CH ₂ .

In the case where —CH ₂ — or —CH ₂ CH ₂ — in the above alkylene may be substituted, or —CH ₂ — or —CH ₂ CH ₂ — in alkyl may be substituted, each group The same applies to the case where the number or type of group options that may be replaced by is different.

In the present invention, a group in which —CH ₂ — or —CH ₂ CH ₂ — in alkylene is replaced may be referred to as “substituted alkylene” in the present invention, and —CH ₂ — in the above alkyl or A group in which —CH ₂ CH ₂ — is replaced may be referred to as “substituted alkyl” in the present invention.

In the present invention, it is not preferable that two consecutive —CH ₂ — are replaced by —O— to form —O—O—.

The “rigid linear structure” in the present invention is a divalent group, and when it is a molded body after heat treatment such as a liquid crystal alignment film, two groups located at both ends of the rigid structure are: A structure that is opposed to each other in a uniform positional relationship through the structure between them. Examples of such rigid linear structures include cyclic structures such as biphenyl, terphenyl, tolan, naphthalene, anthracene, fluorene, and steroid skeletons, unsaturated groups and cyclic groups having double bonds and triple bonds, and the like. A unit structure selected from the group consisting of a single bond, —CH ₂ CH ₂ —, —COO—, trans—CH═CH—, —CH ₂ O—, —C≡C—, —CONH—, —N═ N— and a structure in which any —H on these groups is bonded by a unit structure selected from the group such as —F, —Cl, or a group in which an alkyl having 1 to 3 carbon atoms is substituted. And structures having liquid crystallinity or mesogenicity.

  The structure having liquid crystallinity or mesogenicity refers to a structure having a property of inducing a liquid crystal phase, for example, a rod-like, disc-like, or plate-like structure. Accordingly, in the present invention, examples of the compound having a rigid linear structure also include compounds having a structure having liquid crystallinity or mesogenicity. The compound having a structure having liquid crystallinity or mesogenicity refers to a compound having at least one structure having a property of inducing a liquid crystal phase, for example, a rod-like, disc-like, or plate-like structure in a molecule. Even if a compound having a rigid linear structure has a structure having liquid crystallinity or mesogenicity, the compound itself may not exhibit a liquid crystal phase.

  In the present invention, “having a plurality of rigid linear structures intermittently connected to the main chain” means that the rigid linear structures are not continuously arranged in the main chain, but via other structures than the rigid linear structure. Say that it is located in the main chain. Such an arrangement is preferable from the viewpoint of obtaining the effect of the present invention more strongly. However, the rigid linear structure and other structures may be continuously arranged in the main chain as long as the effects of the present invention are obtained.

  In the present invention, a bismaleimide having a rigid linear structure in the molecular structure is also referred to as a “bismaleimide having a rigid linear structure”, and a diamine having a rigid linear structure in the molecular structure is particularly referred to as a “rigid linear structure. Also called “having diamine”. In addition, a bismaleimide that does not have a rigid linear structure in the molecular structure is also referred to as “other bismaleimide”, and a diamine that does not have a rigid linear structure in the molecular structure is also referred to as “other diamine”.

  As combinations of bismaleimide and diamine constituting the maleimide polymer of the present invention, combinations shown in Table 1 can be mentioned.

  For example, combination number 8 is a bismaleimide having a rigid linear structure, a diamine having a rigid linear structure, other bismaleimides (bismaleimides other than bismaleimide having a rigid linear structure), and other diamines (rigid It represents a maleimide polymer of the present invention using a diamine other than a diamine having a linear structure.

The rigid linear structure is included in the maleimide polymer such that a ratio of the monomer having the rigid linear structure is 10 to 90 mol% with respect to all monomers forming the maleimide polymer. It is preferable that it is contained so that it may become 20-80 mol%, and it is further more preferable that it is contained so that it may become 30-70 mol%.

In the present invention, a group in which left and right are asymmetrical is defined as that the left and right may be oriented in either direction (for example, -COCH = CH- is "-COCH = CH-" or "-CH = CHCO- "). When —CH ₂ — in alkyl or alkylene is replaced by —O—, —O— is not consecutive. Alkyl or alkylene shall be either linear or branched. In the present invention, when the same symbols are used in the same general formula or different general formulas, the respective symbols have meanings independent from each other within the definition.

  The content of the maleimide polymer in the resin composition of the present invention can be determined from the range of 0.05 to 80% by weight depending on the solubility of the maleimide polymer in the solvent and the use of the resin composition. For example, when the resin composition is a liquid crystal aligning agent, the content of the maleimide polymer is preferably 0.1 to 40% by weight.

  The viscosity of the resin composition can be appropriately determined depending on various conditions such as the use and working means employed, the concentration of the maleimide polymer, the type of the maleimide polymer, the type and ratio of the solvent, and the like. For example, when the application of the resin composition is a liquid crystal aligning agent and a coating film is formed by a printing machine, from the viewpoint of obtaining a sufficient film thickness of the coating film and suppressing the occurrence of printing unevenness, the resin composition The viscosity is preferably 5 to 100 mPa · s, and more preferably 10 to 80 mPa · s. Moreover, when forming a coating film by spin coating, it is preferable that the viscosity of a resin composition is 5-200 mPa * s, and it is more preferable that it is 10-100 mPa * s.

  The viscosity of the resin composition can be measured by a rotational viscosity measurement method. For example, the viscosity can be measured at a measurement temperature of 25 ° C. using a rotational viscometer (TVE-20L type manufactured by Toki Sangyo Co., Ltd.).

  The maleimide polymer is a structure of a reaction product of bismaleimide and a diamine, and is not a polyamic acid that accompanies the opening of an imide ring of bismaleimide, but an amino acid of diamine to an unsaturated bond of bismaleimide. It has a polymer structure by Michael addition reaction, which is generated by group addition reaction.

  The weight average molecular weight of the maleimide polymer is 3,000 to 500,000 from the viewpoints of workability and quality (for example, solubility, stirrability, coatability, printability, etc.) when handling the resin composition. It is preferably 5,000 to 500,000, more preferably 8,000 to 250,000, still more preferably 10,000 to 200,000, and 20,000. Particularly preferred is ˜150,000.

  The weight average molecular weight was measured using Alliance 2695, manufactured by WATERS, 1% phosphoric acid-containing N, N-dimethylformamide as a developing solvent, (polystyrene) as a standard sample, and HSPgel (registered trademark) as a column. It can be measured by performing liquid chromatography analysis using RTMB-M manufactured by WATERS.

The maleimide polymer may have a polymer structure by addition reaction between a bismaleimide having a rigid linear structure and a diamine, or by addition reaction between a diamine having a rigid linear structure and bismaleimide. It may have a polymer structure. From the viewpoint of increasing the molecular weight, the maleimide polymer preferably has a large amount of polymer structure obtained by addition reaction of bismaleimide and diamine having a rigid linear structure. The maleimide polymer used in the present invention is a Michael polymer of bismaleimide and diamine, rather than a polymer having many units with remarkable branching, crosslinking, or coloring of the polymer chain due to the reaction between double bonds. A polymer having a large number of linear and less colored units (for example, 50 mol% or more based on the total amount of the maleimide polymer) by addition reaction is preferable.

  When the maleimide polymer is prepared by addition reaction between bismaleimide and diamine, side reaction during the reaction (polymerization) (reaction caused by branching or cross-linking of polymer chains due to reaction between double bonds) From the viewpoint of suppressing solidification, gelation, or coloring of the liquid, it is preferable to use a solvent having an alcoholic or phenolic hydroxyl group or a solvent containing a protic amide solvent as a solvent used during polymerization.

  The maleimide polymer obtained by using these solvents as a solvent used at the time of polymerization has a relatively narrow molecular weight distribution (dispersion degree: Mw / Mn). For example, there is a polymer having a molecular weight distribution of 1.0 to 3.0 when the weight average molecular weight is 20,000, and the molecular weight distribution (dispersion degree: Mw / Mn) when the weight average molecular weight is 200,000. Examples thereof include a polymer having a molecular weight of 1.0 to 5.0.

  Examples of the solvent having an alcoholic or phenolic hydroxyl group used as a solvent for polymerization include methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, t-butyl alcohol, 1-pentanol, 1 -Aliphatic monoalcohols such as hexanol and 2-ethylhexanol, benzyl alcohol, (o-, m-, or p-) methylbenzyl alcohol, (o-, m-, or p-) methoxybenzyl alcohol, 1-phenyl Aromatic alcohols such as ethyl alcohol and 2-phenylethyl alcohol, aliphatic polyols such as ethylene glycol and glycerol, alkoxy monoalcohols such as 3-methyl-3-methoxybutanol, and ethylene glycol monomethyl ether and ethylene glycol Ethylene glycol monoalkyl ethers such as ethyl ether and ethylene glycol monobutyl ether, diethylene glycol monoalkyl ethers such as diethylene glycol monoethyl ether, propylene glycol monoalkyl ethers such as triethylene glycol monoalkyl ether and propylene glycol monobutyl ether, dipropylene glycol monomethyl ether Phenols such as dipropylene glycol monoalkyl ether, phenol, (o-, m-, or p-) cresol and mixtures thereof, (o-, m-, or p-) chlorophenol and mixtures thereof, Alternatively, a highly polar alkyl having 1) an alcoholic hydroxyl group and 2) one or more groups selected from the group consisting of amides, esters, and cyclic ethers A solvent can be used such as containing Lumpur. Specific examples of the highly polar alcohol include methyl lactate, ethyl lactate, propyl lactate, butyl lactate, methyl 2-hydroxybutyrate, ethyl 2-hydroxybutyrate, methyl 2-hydroxyisobutyrate, ethyl 2-hydroxyisobutyrate, 2- Hydroxyl-containing esters such as methyl hydroxy-3-butenoate, dimethyl malate, diethyl malate, dipropyl malate, dibutyl malate and glycerol diacetate, and compounds represented by the following formulas (1) to (21) Can be mentioned.

  Specific examples of the protic amide solvent include compounds represented by the following formulas (22) to (26).

  When the solvent used at the time of polymerization is a solvent having an alcoholic or phenolic hydroxyl group or a protic amide solvent, the amount used is 10 to 100% by weight based on the total amount of the solvents used at the time of polymerization. It is preferable from the viewpoint of suppressing a side reaction (solidification or gelation or coloring of the reaction solution due to branching or cross-linking of polymer chains due to reaction between double bonds) during the reaction (polymerization). These solvents may be used alone or in combination of two or more. The reaction solution after the polymerization reaction is diluted with a solvent other than the alcoholic or phenolic hydroxyl group, or a solvent other than the protic amide solvent, and as a result, the solvent having the alcoholic or phenolic hydroxyl group in the solution, Or even if the protic amide solvent is less than 10% by weight based on the total amount of the solvents, there is no problem.

  Among the solvents, the use of a solvent containing a solvent having an alcoholic or phenolic hydroxyl group as a polymerization solvent is preferable from the viewpoint of suppressing solidification or gelation of a reaction solution due to a side reaction in the addition reaction.

  When the solvent having an alcoholic hydroxyl group or a protic amide solvent is used as the solvent used in the polymerization, it is preferable because it can be used as a resin composition while containing the solvent used in the polymerization because of less odor. When these solvents are used, it is also preferable from the viewpoint of suppressing side reactions (maleimide group ring opening) during the reaction (polymerization).

  When these solvents are used, a maleimide polymer having a high degree of polymerization can be obtained without using a catalyst such as a proton donor, a tertiary amine, or a combination thereof in the reaction system during the reaction (polymerization). Is preferable. Further, since it is not necessary to add a catalyst to the reaction system during the reaction (at the time of polymerization), a maleimide polymer with less impurities can be obtained, which is preferable in terms of quality. Furthermore, the step of purifying the maleimide polymer after polymerization is unnecessary, and the reaction solution after polymerization can be used for a desired application as it is, which is preferable in terms of man-hours.

  Examples of the proton donor include inorganic acids (for example, hydrogen chloride, sulfuric acid, phosphoric acid, or perchloric acid), carboxylic acids (for example, formic acid, acetic acid, propionic acid, benzoic acid, or trifluoroacetic acid), phenols ( Examples include phenol, cresols, chlorophenols, xylenols, or hydroquinone), or acidic salts (eg, ammonium chloride, ammonium sulfide, tributylammonium chloride, boron trifluoride monoethylamine, or aluminum chloride). Examples of the tertiary amines include triethylamine, pyridine, dimethylaminopyridine, diazabicycloundecene, and the like.

  When the high polar alcohol or the protic amide solvent is used as the solvent used in the polymerization, it is preferable because the polymer has high solubility and the operability during polymerization and the storage stability of the resin composition are good.

  When an aromatic alcohol such as benzyl alcohol or 2-phenylethyl alcohol is used as the solvent used during polymerization, the polymer has a high composition ratio with a high ratio of rigid structures, and the operability and resin composition during polymerization are high. Since the storage stability of the product is good, it is preferable when such a composition is used.

  When the solvent having the alcoholic or phenolic hydroxyl group or the protic amide solvent is used as the polymerization solvent, the amount used is the raw material relative to the sum of the bismaleimide and diamine which are raw materials in the addition reaction and the solvent. From the viewpoint of suppressing the solidification or gelation of the reaction solution in the addition reaction process, the concentration of is preferably from 0.5 to 70% by weight, and more preferably from 1 to 50% by weight. preferable.

  The reaction (polymerization) temperature for obtaining the maleimide polymer may be appropriately changed according to the reactivity of the monomer. Preferably, it is −50 ° C. to the boiling point of the solvent. More preferably, it is −20 ° C. to the boiling point of the solvent.

  The reaction time may be appropriately changed according to the reactivity of the monomer. Preferably it is 1 to 200 hours. More preferably, it is 2 to 100 hours. Moreover, it is preferable that it is a normal pressure as a pressure at the time of superposition | polymerization.

The maleimide polymer of the present invention can be obtained by using the bismaleimide and the diamine as raw materials in an equimolar ratio, thereby obtaining a composition containing the maleimide polymer as the polymer. The equimolar ratio referred to in the present invention is obtained by subjecting a raw material in which the molar ratio of bismaleimide and diamine in the raw material is in the ratio of 0.8: 1.2 to 1.2: 0.8 to the reaction. It is more preferable that the molar ratio of the raw materials is 0.9: 1.1 to 1.1: 0.9. When the molar ratio of bismaleimide and diamine in the raw material is an equimolar ratio or the number of moles of diamine is excessive, it is preferable because the stability of the produced polymer itself is good. In addition, when the molar ratio of bismaleimide and diamine in the raw material is excessive in the number of moles of bismaleimide, it is preferable when the produced polymer is further used as a polymerization material.

  The bismaleimide having a rigid linear structure has a rigid linear structure and maleimide groups bonded to both ends thereof. The bismaleimide having the rigid linear structure includes a bismaleimide represented by the following formula (MA). The bismaleimide having a rigid linear structure may be one type or two or more types.

In the formula (MA), X ¹³ independently represents a single bond or alkylene having 1 to 30 carbon atoms,
X ¹⁴ independently represents 1,4-phenylene, a condensed ring having 8 to 22 atoms constituting the ring, or 1,4-cyclohexylene,
X ¹⁵ independently represents a single bond or — (CH ₂ CH ₂ ) _ab2 —;
ab1 represents an integer of 0 to 4, and ab2 represents an integer of 0 to 4.
Provided that when ab1 is 0, X ¹⁴ represents a fused ring of the number of atoms constituting the ring 8 to 22.
-H on —CH═CH— of the maleimide group may be independently replaced by alkyl having 1 to 3 carbon atoms;
Is independently -NH - - -CH ₂ in the alkylene of X ^13, - NY ² -, or -Si (Y ²²⁾ ₂ - may be replaced by,
—CH ₂ CH ₂ — in the alkylene of X ¹³ may be independently replaced with —CH═CH— or —C≡C—;
—CH ₂ — that is not adjacent to the nitrogen atom of the maleimide group in the alkylene of X ¹³ may be independently replaced with —O—, —CO—, —S—, —SO—, or —SO ₂ —;
—CH ₂ CH ₂ — that is not adjacent to the nitrogen atom of the maleimide group in the alkylene of X ¹³ may be independently replaced by —N═N—,
Of _{^{X 15 - (CH 2 CH 2}} ) ab2 - -CH Medium ₂ - is independently -O -, - NH -, - CO -, - NY 2 -, - S -, - SO -, - SO _2- or -Si (Y ²² ) _2- may be substituted,
—CH ₂ CH ₂ — in — (CH ₂ CH ₂ ) _ab2 — in X ¹⁵ may be independently replaced with —CH═CH—, _—C≡C— , or —N═N—,
—H on X ¹³ alkylene or substituted alkylene, or X ¹⁵ — (CH ₂ CH ₂ ) _ab2 — or substituted — (CH ₂ CH ₂ ) _ab2 — is independently —F, —Cl , -Br, -C≡N, -OH, -COOH, -SO ₃ H, -PO ₃ H ₂ , an arbitrary -H having 1 to 20 carbon atoms optionally substituted with halogen, Or any -H may be independently replaced by an alkenyl having 2 to 20 carbon atoms which may be replaced by a halogen;
1,4-phenylene of X ¹⁴ , 1,4-cyclohexylene, and —H on the fused ring are each independently 1 carbon number in which arbitrary —H may be independently replaced by halogen. ~
3 alkyl, optionally -H may be independently replaced by halogen, C1-3 alkoxy, -F, -Cl, -Br, -C≡N, -OH, -COOH, -SO May be replaced by ₃ H, —PO ₃ H ₂ , or —N (Y ² ) ₂ ;
In the alkyl and alkoxy, —CH ₂ — may be independently replaced by —O—, —CO— or —S—,
In each group constituting (MA), Y ² independently represents —H, alkyl having 1 to 20 carbon atoms, or alkenyl having 2 to 20 carbon atoms, and Y ²² independently represents —H, carbon number 1 20 alkyl, alkenyl having 1 to 20 carbon atoms, or represents phenyl, -H on the phenyl are independently -F, -Cl, -Br, -C≡N, -OH, -COOH, -SO 3 H, —PO ₃ H ₂ , or alkyl having 1 to 30 carbon atoms may be substituted.

  A condensed ring having 8 to 22 atoms is a ring composed of one or both of a carbon atom and a heteroatom, and each of two or more rings shares one side with each adjacent ring. Examples of the hetero atom include a nitrogen atom, an oxygen atom, and a sulfur atom. Examples of the condensed ring include naphthalene, anthracene, phenanthrene, fluorene, coumarin, tetracene, chrysene, pyrene, pentacene, picene, perylene, and acridine.

In the present invention, the “substituent” means a hydrogen atom chemically bonded on an organic compound, for example, the “other group” in a state where —H in C—H is replaced with “another group”. means. Examples of the substituent of —H include alkyl such as —CH ₃ or halogen such as —F.

  As the bismaleimide having a rigid linear structure represented by the formula (MA), for example, the following formulas (MA-1-1) to (MA-1-3), (MA-2-2) to (MA-) 2-6), bismaleimides represented by (MA-3-1) and (MA-3-2).

Wherein (MA-1-1), R ¹¹¹ represents -H, -OH, or -F, R ¹¹² represents -OH, -F, or -Cl independently, a1 is an integer of 0 to 5 Represents. However when R ¹¹¹ represents -H, a1 represents an integer of 1 to 5.

In formula (MA-1-2), R ¹²¹ independently represents —CH ₃ , —OH, —OCH ₃ , —SCH ₃ , or —F, and a2 represents an integer of 1 to 5.

In formula (MA-1-3), R ¹³¹ and R ¹³² each represent —H, —CH ₃ , or —OH.

In the formula (MA-2-2), R ²²¹ independently represents -CH ₃ , -CF ₃ , -OH, -F, -Cl, or -OCH ₃ , and a4 is independently an integer of 0 to 4. Represents. However, the sum of a4 is 1 or more.

In formula (MA-2-3), R ²³¹ independently represents —CF ₃ , —OH, —F, or —OCH ₃ , and a5 independently represents an integer of 0 to 4. However, the sum of a5 is 1 or more.

In the formula (MA-2-4), R ²⁴¹ independently represents —CH ₃ , —CF ₃ , —OH, —Cl, —Br, —OCH ₃ , or —OCH ₂ CH ₃ , and R ²⁴² represents — H or linear alkyl having 1 to 3 carbon atoms is represented, and a6 independently represents an integer of 0 to 4. However when R ²⁴² represents a straight-chain alkyl of 1 to 3 carbon atoms, R ²⁴¹ is it may represent independently -H, sum of a6 is 1 or more.

In formula (MA-2-5), R ²⁵¹ independently represents -CH ₃ , -OH, -Cl, or -OCH ₃ , and a7 independently represents an integer of 0 to 4. However, the sum of a7 is 1 or more.

In formula (MA-2-6), R ²⁶¹ independently represents -CH ₃ , -CF ₃ , or -F, and a8 independently represents an integer of 0 to 10.

In formula (MA-3-1), R ³¹¹ independently represents —CH ₃ , —CF ₃ , —OH, —F, —Cl, or —OCH ₃ , and a9 is independently an integer of 0 to 4 Represents. However, the sum of a9 is 1 or more.

In formula (MA-3-2), R ³²¹ independently represents —CH ₃ or —CH (CH ₃ ) ₂ , R ³²² independently represents —CH ₃ or —CH ₂ CH ₃ , and a10 represents Independently represents an integer of 0 to 4.

  Examples of the bismaleimide having a rigid linear structure include the following formulas (MA-1-1-1) to (MA-1-1-7), (MA-1-2-1) to (MA-1). -2-12), (MA-1-3-1) to (MA-1-3-3), (MA-1-4-1), (MA-1-4-2), (MA-1 -5-1), (MA-2-1-1) to (MA-2-1-27), (MA-2-2-1) to (MA-2-2-10), (MA-2) -3-1) to (MA-2-3-5), (MA-2-4-1) to (MA-2-4-24), (MA-2-5-1) to (MA-2) -5-7), (MA-2-6-1) to (MA-2-6-7), (MA-2-7-1) to (MA-2-7-3), (MA-2) -8-1), (MA-2-9-1), (MA-3-1-1) to (MA-3-1-1-14) (MA-3-2-1) to (MA-3-2-2-6), (MA-3-3-1) to (MA-3-3-3-4), (MA-3-4-1), Examples thereof include bismaleimides represented by (MA-3-5-1), (MA-4-1-1), and (MA-4-2-1).

  Examples of the bismaleimide represented by the formula (MA-1-1) include bismaleimides represented by the formulas (MA-1-1-1) to (MA-1-1-7).

  Examples of the bismaleimide represented by the formula (MA-1-2) include bismaleimides represented by the formulas (MA-2-1-1) to (MA-1-2-12).

As the bismaleimide represented by the formula (MA-1-3), for example, the formula (MA-1)
-3-1) to (MA-1-3-3).

  Examples of the bismaleimide represented by the formula (MA-2-2) include bismaleimides represented by the formulas (MA-2-2-1) to (MA-2-2-2-10).

  Examples of the bismaleimide represented by the formula (MA-2-3) include bismaleimides represented by the formulas (MA-2-3-1) to (MA-2-3-5).

  Examples of the bismaleimide represented by the formula (MA-2-4) include bismaleimides represented by the formulas (MA-2-4-1) to (MA-2-4-24).

  Examples of the bismaleimide represented by the formula (MA-2-5) include bismaleimides represented by the formulas (MA-2-5-1) to (MA-2-5-7).

  Examples of the bismaleimide represented by the formula (MA-2-6) include bismaleimides represented by the formulas (MA-2-6-1) to (MA-2-6-7).

  Examples of the bismaleimide represented by the formula (MA-3-1) include bismaleimides represented by the formulas (MA-3-1-1) to (MA-3-1-14).

  Examples of the bismaleimide represented by the formula (MA-3-2) include bismaleimides represented by the formulas (MA-3-2-1) to (MA-3-2-6).

  Examples of the bismaleimide having a rigid linear structure include bismaleimide having a structure having an alkylene group and liquid crystallinity or mesogenicity. As such bismaleimides, the following formulas (MA-3-11-1) to (MA-3-11-14), (MA-4-11-1) to (MA-4-11-9), And bismaleimide represented by (MA-5-11-1).

The bismaleimide having a rigid linear structure is from the viewpoint of workability and quality when constituting a polymer (for example, solubility, rubbing resistance when used in a liquid crystal aligning agent, stability over time of retardation change, etc.). , The formula (MA-2-1-1), (MA-2-1-2), (MA-2-1-2)
1-4), (MA-2-1-9), (MA-2-1-15), (MA-3-1-1), (MA-2-2-1), (MA-2-1) 3-1), (MA-2-4-1), (MA-2-5-1), (MA-2-6-1), (MA-3-2-2), (MA-2- 7-2), (MA-3-3-1), (= MA-3-2-1), (MA-3-3-3), (MA-3-3-3), (MA-3 -4-1), (MA-4-1-1), (MA-2-8-1), (MA-4-2-1), (MA-3-5-1), (MA-2 -9-1), (MA-1-1-1), (MA-1-2-1), (MA-1-3-1), (MA-1-4-1), (MA-1 -5-1), (MA-3-11-3) to (MA-3-11-14), (MA-4-11-1) to (MA-4-11-9), and It is preferable that one or more selected from the group of MA-5-11-1) is included, and the formula (MA-2-1-2), (MA-2-1-4), or (MA-2- More preferably, it contains 1-9).

  The bismaleimide having a rigid linear structure is a commercially available product or a diamine having a rigid linear structure having the rigid linear structure described above and amino groups bonded to both ends thereof (having the rigid linear structure). A diamine obtained by replacing the maleimide group of bismaleimide with an amino group) and a maleic anhydride having a molar ratio of 2 moles or more to this diamine, followed by dehydration imidization in the presence of an acid, etc. It can be obtained by a method (for example, the method described in JP-A No. 05-140096) or a synthesis method according to the method.

  In the present invention, when a bismaleimide having a rigid linear structure is used for the bismaleimide, the bismaleimide is a bismaleimide other than the bismaleimide having the rigid linear structure as long as the effect of the present invention is obtained. The structural unit may be included. The other bismaleimide can be used in combination with the bismaleimide having the rigid linear structure as a kind of structural unit of the maleimide polymer. In the present invention, when the aliphatic diamine (VII-13) is used, in addition to or instead of the bismaleimide having a rigid linear structure in the bismaleimide, other bismaleimide-containing structural units are included. Also good. In these inventions, the other bismaleimide may be one kind or two or more kinds.

  Examples of the other bismaleimides include bismaleimides represented by the following formulas (m-1) to (m-6).

  The diamine may be either a primary amine or a secondary amine, and may be one kind or two or more kinds. Examples of the diamine include diamines represented by the following formula (I).

^{Y 20 -HN-X 1 -X 1} -X 1 -X 1 -X 1 -X 1 -X 1 -NH-Y 20 (I)

In the general formula (I), Y ²⁰ independently represents the following general formula (XXIV).
^{~A 1 -A 1 -A 1 -A 1} -A 1 -A 1 -A 2 (XXIV)

In general formula (XXIV),
A ¹ independently represents a single bond, alkylene having 1 to 12 carbons, or a ring having a sum of 3 to 30 of carbon, nitrogen, oxygen, sulfur and silicon constituting the skeleton,
When A ¹ is alkylene,
-CH ₂ in the alkylene - is independently ^{-NH -, - CHY 2 -,} - C (Y 2) 2 -, or -NY ² - may be replaced by,
-CH ₂ CH ₂ in the alkylene - may be replaced by -CH = CH-, or -C≡C-, independently,
—CH ₂ — not adjacent to —NH in alkylene may be independently replaced with —O— or —CO—,
—CH ₂ CH ₂ — not adjacent to —NH in alkylene may be independently replaced by —N═N—,
-H on alkylene or replaced alkylene is independently -F, -Cl, -Br, -C≡N, -OH, -COOH, -SO 3 H, or -PO ₃ H _2, or the following general formula (XXII) may be substituted,
When A ¹ is a ring,
-H on the ring is independently -F, -Cl, -Br, -C≡N, -OH, -COOH, -SO 3 H, -PO 3 H 2, -N (Y 2) 2, or below It may be replaced by general formula (XXII).
^{~A 3 -A 3 -A 3 -A 2} (XXII)

In general formula (XXII),
A ³ independently represents a single bond, a linear or branched alkylene having 1 to 30 carbon atoms, or a ring having a sum of 3 to 30 carbon, nitrogen, oxygen, sulfur and silicon constituting the skeleton;
When A ³ is alkylene,
-CH ₂ in the alkylene - -O is independently -, - NH -, - CO -, - CHY 2 -, - C (Y 2) 2 -, or -NY ² - may be replaced by,
-CH ₂ CH ₂ in the alkylene - independently -CH = CH -, - C≡C-, or -N = may be replaced by N-,
-H on alkylene or replaced alkylene is independently -F, -Cl, -Br, -C≡N, -OH, -COOH, -SO 3 H, or -PO ₃ H _2, 1~ carbon atoms May be substituted with 20 alkyls or alkenyls of 2 to 20 carbon atoms,
When A ³ is a ring,
—H on the ring is independently —F, —Cl, —Br, —C≡N, —CH ₃ , —OCH ₃ , —OCH ₂ F, —OCHF ₂ , —OCF ₃ , —OH, —COOH, It may be replaced by —SO ₃ H, —PO ₃ H ₂ , or —N (Y ² ) ₂ .

In general formula (XXIV) or general formula (XXII),
A ² independently represents —H, —F, —Cl, —Br, —C≡N, —OH, —COOH, —SO ₃ H, —PO ₃ H ₂ , or alkyl having 1 to 40 carbon atoms. ,
When A ² is alkyl, —CH ₂ — in alkyl may be independently replaced with —O—, —NH—, or —CO—, and —CH ₂ CH ₂ — in alkyl is independently -CH = CH-, -C≡C-, or -N = N- may be substituted, and -H on the alkyl or substituted alkyl is independently -F, -Cl, -Br, -C≡ It may be replaced with N, —OH, —COOH, —SO ₃ H, or —PO ₃ H ₂ .

In formula (I), X ¹ independently represents a single bond, alkylene having 1 to 30 carbon atoms, or a ring having 3 to 30 carbon atoms, nitrogen, oxygen, sulfur and silicon constituting the skeleton. It represents a divalent group. Provided that at least one of X ¹ represents the ring alkylene having 1 to 30 carbon atoms, or carbon atoms constituting the skeleton, nitrogen, oxygen, sulfur, and the sum of silicon atoms is 3-30.

  As the ring having 3 to 30 carbon atoms, the cycloalkane is preferably a cycloalkane having 3 to 10 carbon atoms. Specific examples include cyclopropane, cyclobutane, cyclopentane, cyclohexane, methylcyclopentane, cycloheptane, methylcyclohexane, cyclooctane, and dimethylcyclohexane.

  The cycloalkane containing a hetero atom as the ring having 3 to 30 carbon atoms is preferably a cycloalkane containing a hetero atom having 1 to 10 carbon atoms. Specific examples include, for example, oxirane, azetidine, oxetane, thietane, pyrrolidine, tetrahydrofuran, tetrahydropyran, oxazoline, oxazolidine, dioxooxazolidine, thiazoline, thiazolidine, dioxothiazolidine, morpholine, thiomorpholine, piperazine, pyrrolidine, piperidine, morpholine, Examples include thiomorpholine, 1,3-dioxane, 1,4-dioxane, and hexahydro-furo [3.2-b] furan.

  The aromatic hydrocarbon ring as the ring having 3 to 30 carbon atoms is preferably an aromatic hydrocarbon ring having 6 to 18 carbon atoms, more preferably an aromatic hydrocarbon ring having 6 to 14 carbon atoms, More preferred is an aromatic hydrocarbon ring having 6 to 12 carbon atoms.

  Specific examples of the aromatic hydrocarbon ring include benzene, which is a monocyclic aromatic hydrocarbon ring, naphthalene, which is a condensed bicyclic aromatic hydrocarbon ring, and anthracene, which is a condensed tricyclic aromatic hydrocarbon ring. Acenaphthylene, fluorene, phenalene, phenanthrene, condensed tetracyclic aromatic hydrocarbon rings such as triphenylene, pyrene, naphthacene, chrysene, and condensed pentacyclic aromatic hydrocarbon rings such as perylene, picene, and pentacene.

  As the ring having 3 to 30 carbon atoms, the heteroaromatic hydrocarbon ring is preferably a heteroaromatic hydrocarbon ring having 2 to 20 carbon atoms, more preferably a heteroaromatic hydrocarbon ring having 2 to 15 carbon atoms, particularly Preferably, a C2-C10 heteroaromatic hydrocarbon ring is mentioned. Further, examples include a heterocyclic group containing 1 to 5 heteroatoms selected from oxygen, sulfur and nitrogen in addition to carbon.

  Examples of the heteroaromatic hydrocarbon ring include furan, thiophene, pyran, chromene, isochromene, oxazole, isoxazole, thiazole, isothiazole, pyrrole, imidazole, pyrazole, oxadiazole, thiadiazole, triazole, tetrazole, pyrazole, pyridine , Pyrimidine, pyridazine, pyrazine, triazine, indole, isoindole, 1H-indazole, benzimidazole, benzoxazole, benzothiazole, 1H-benzotriazole, quinoline, isoquinoline, cinnoline, quinazoline, quinoxaline, phthalazine, naphthyridine, purine, pteridine, Carbazole, acridine, phenoxazine, phenothiazine, phenazine, indolizine, furazane, benzofuran, Sobenzofuran, 9H-xanthene, benzo [b] thiophene, phenoxathiin, and thianthrene like.

  In addition, these rings may be further combined with one or more rings or bridged to form a condensed ring, a spiro ring, a bicyclo ring, or the like. Examples of these rings include cyclopenta [a] phenanthrene (steroid), bicyclo [2.2.1] heptane, and bicyclo [2.2.2] octane.

—CH ₂ — in the alkylene having 1 to 30 carbon atoms in X ¹ is independently replaced with —NH—, —CHY ¹ —, —C (Y ¹ ) ₂ —, or —NY ¹ —. Well, —CH ₂ CH ₂ — in the alkylene may be independently replaced with —CH═CH—, —C≡C—,
—CH ₂ — that is not adjacent to —NHY ^{20 in} alkylene is independently replaced by —O—, —CO—, —S—, —SO—, —SO ₂ —, or —Si (Y ²² ) ₂ —. Y ²² independently represents —H, alkyl having 1 to 20 carbons, alkenyl having 1 to 20 carbons, or phenyl, and —H on phenyl independently represents —F, —Cl, —Br. , —C≡N, —OH, —COOH, —SO ₃ H, —PO ₃ H ₂ , or alkyl having 1 to 30 carbon atoms,
—CH ₂ CH ₂ — that is not adjacent to —NHY ^{20 in} alkylene may be independently replaced by —N═N—,
The alkylene or replaced is -H on alkylene independently -F, -Cl, -Br, -C≡N, -OH, -COOH, replaced by -SO ₃ H, or -PO ₃ H ₂ Good.

—H on a divalent group having a ring in which the sum of the number of carbon, nitrogen, oxygen, sulfur, and silicon constituting the skeleton in X ¹ is 3 to 30 is independently —F, —Cl, -Br, -C≡N, -OH, -COOH, -SO 3 H, or -PO ₃ H _2, or may be replaced by Y ^1.

Y ¹ is independently represented by —H, —F, —Cl, —Br, —C≡N, —OH, —COOH, —SO ₃ H, —PO ₃ H ₂ , or the following formula (XXI). Represents a group.

^{~A 1 -A 1 -A 1 -A 1} -A 1 -A 1 -A 2 (XXI)
In Formula (XXI), A ¹ independently represents a single bond, alkylene having 1 to 12 carbons, or a ring having 3 to 30 in total of carbon, nitrogen, oxygen, sulfur, and silicon constituting the skeleton. To express. In the alkylene having 1 to 12 carbon atoms in A ¹ , —CH ₂ — is independently —O—, —NH—, —CO—, —CHY ² —, —C (Y ² ) ₂ —, or —NY. ² — may be substituted, and —CH ₂ CH ₂ — may independently be replaced with —CH═CH—, —C≡C—, or —N═N—, on the alkylene or substituted alkylene. of -H is -F independently, -Cl, -Br, -C≡N, -OH , -COOH, -SO 3 H, or replaced with -PO ₃ H _2. -H on the ring in which the sum of the number of carbon, nitrogen, oxygen, sulfur, and silicon constituting the skeleton in A ¹ is 3 to 30 is independently -F, -Cl, -Br, -C≡N , —OH, —COOH, —SO ₃ H, —PO ₃ H ₂ , —N (Y ² ) ₂ , or a group represented by the following formula (XXII).

^{~A 3 -A 3 -A 3 -A 2} (XXII)
In the formula (XXII), A ³ independently represents a single bond, alkylene having 1 to 12 carbons, or a ring having 3 to 30 carbon atoms, nitrogen, oxygen, sulfur and silicon constituting the skeleton. To express. In the alkylene group having 1 to 12 carbon atoms of A ³ , —CH ₂ — is independently —O—, —NH—, —CO—, —CHY ² —, —C (Y ² ) ₂ —, or — NY ² — may be substituted, and —CH ₂ CH ₂ — may be independently replaced with —CH═CH—, —C≡C—, or —N═N—, and the alkylene or substituted alkylene -H above is independently -F, -Cl, -Br, -C≡N, -OH, -COOH, -SO 3 H, or -PO ₃ H _2, alkyl having 1 to 20 carbon atoms, or carbon It may be replaced by alkenyl having the number 2-20. -H on the ring in which the sum of the number of carbon, nitrogen, oxygen, sulfur and silicon constituting the skeleton of A ³ is 3 to 30 is independently -F, -Cl, -Br, -C≡N , —CH ₃ , —OCH ₃ , —OCH ₂ F, —OCHF ₂ , —OCF ₃ , —OH, —COOH, —SO ₃ H, —PO ₃ H ₂ , or —N (Y ² ) ₂ You can.

In Formula (XXI) and Formula (XXII), A ² is independently —H, —F, —Cl, —Br, —C≡N, —OH, —COOH, —SO ₃ H, —PO ₃ H. ₂ or alkyl having 1 to 40 carbon atoms. In the alkyl having 1 to 40 carbon atoms of A ² , —CH ₂ — may be independently replaced with —O—, —NH—, or —CO—, and —CH ₂ CH ₂ — is independently -CH = CH-, -C≡C-, or -N = N- may be substituted, and -H on said alkyl or substituted alkyl is independently -F, -Cl, -Br, -C It may be replaced with ≡N, —OH, —COOH, —SO ₃ H, or —PO ₃ H ₂ . Further, in each group constituting the formula (I), Y ² represents independently -H, alkyl having 1 to 20 carbon atoms, or an alkenyl having 2 to 20 carbon atoms. However the -CHY ² - and -C (Y ^{₂₎ 2} - In, Y ² is not a -H.

In the above formula (I), Y ²⁰ is a Y ²⁰ of the other amino group, or independently coupled to the X ¹ may form a ring.

  Examples of the diamine include diamines represented by the following formulas (II), (III), (IV), (V), (VI), (VII), (VIII), and (IX).

  In the present invention, “aliphatic diamine” refers to an amine in which an aliphatic group is directly bonded to an amino group. Examples of such aliphatic diamines include diamines represented by formulas (II) to (IV).

In said formula (II), X < ² > represents a C1-C12 alkylene independently. In the alkylene having 1 to 12 carbon atoms of X ² , —CH ₂ — may be independently replaced with —NH—, and —CH ₂ CH ₂ — is independently —CH═CH—, —C≡. May be replaced by C-
—CH ₂ — that is not adjacent to —NHY ^{21 in} alkylene may be independently replaced with —O— or —CO—.
—CH ₂ CH ₂ — that is not adjacent to —NHY ^{21 in} alkylene may be independently replaced by —N═N—,
The alkylene or replaced is -H on alkylene independently -F, -Cl, -Br, -C≡N, -OH, -COOH, -SO 3 H, -PO 3 H 2, or 1 carbon atoms May be substituted with from 10 to 10 alkyls.

In the formulas (II) to (VIII), Y ¹ is the same as Y ^{1 in the} formula (I).
In the formula (IX), Y ²² independently represents —H, alkyl having 1 to 20 carbons, alkenyl having 1 to 20 carbons, or phenyl, and —H on phenyl independently represents —F, — Cl, —Br, —C≡N, —OH, —COOH, —SO ₃ H, —PO ₃ H ₂ , or alkyl having 1 to 30 carbon atoms may be substituted.

In the formula (II), Y ²¹ independently represents -H, alkyl having 1 to 20 carbons, or alkylene having 1 to 20 carbons, and -CH _2- in the alkyl or alkylene is independently- NH—, —CHY ² —, —C (Y ² ) ₂ —, or —NY ² — may be substituted, and —CH ₂ CH ₂ — in alkyl or alkylene is independently —CH═CH—, or -C≡C- may be substituted,
-CH ₂ - not adjacent to the -NH- alkyl or alkylene - is independently -O-, or -CO- may be replaced by,
—CH ₂ CH ₂ — not adjacent to —NH— in alkyl or alkylene may be independently replaced by —N═N—,
The alkyl or alkylene, or replaced is -H on the alkyl or replaced alkylene independently -F, -Cl, -Br, -C≡N, -OH, -COOH, -SO 3 H, or - may be replaced by PO ₃ H _2, if Y ²¹ is the alkylene having 1 to 20 carbon atoms, Y ²¹ is a Y ²¹ of the other amino group, or independently bonded to Y ¹ Form a ring.

  In the formulas (II) to (VIII), a independently represents an integer of 0 to 4.

In the formulas (IV) and (VI) to (VIII), X ³ is independently a single bond, —O—, —S—, —SS—, —SO ₂ —, —CO—, — CONH -, - COO -, - NH -, - N (CH 3) - (CH 2) m -N (CH 3) -, - C (CH 3) 2 -, - C (CF 3) 2 -, - _{(CH 2) m -, -} O- (CH 2) m -O -, - S- (CH 2) m -S- (m represents an integer of 1~6), - COCH = CH - , - N = N- or -C≡C-.

In the formula (IX), X ⁴ independently represents an alkylene or phenylene having 1 to 6 carbon atoms, and l represents an integer of 1 to 10. -H on phenylene X ⁴ independently may be replaced by alkyl having 1 to 30 carbon atoms.

In the above formulas (III) to (IX), —NH ₂ may independently replace one —H of two —H with alkyl having 1 to 12 carbons.

—CH ₂ — in the alkyl may be independently replaced by —NH—, —CHY ² —, —C (Y ² ) ₂ —, or —NY ² —, and —CH ₂ CH ₂ — in the alkyl may be substituted. May be independently replaced with —CH═CH— or —C≡C—, and —CH ₂ — not adjacent to —NH— in alkyl is independently replaced with —O— or —CO—. And —CH ₂ CH ₂ — not adjacent to —NH— in the alkyl may be independently replaced by —N═N—, and —H on this alkyl or substituted alkyl is independently —F , —Cl, —Br, —C≡N, —OH, —COOH, —SO ₃ H, or —PO ₃ H ₂ .

  In the formulas (V) to (VIII), the benzene ring is independently a piperazine ring, piperidine ring, morpholine ring, pyrrole ring, furan ring, thiophene ring, imidazole ring, oxazole ring, thiazole ring, pyrazole ring, triazole ring. Pyridine ring, pyrazine ring, pyridazine ring, pyrimidine ring, triazine ring, pyrrolidine ring, 1H-1-pyridine ring, 1H-2-pyridine ring, indolizine ring, indole ring, isoindole ring, indazole ring, steroid ring, Bicyclo [2.2.1] heptane ring, bicyclo [2.2.2] octane ring, hexahydro-furo [3.2-b] furan ring, quinoline ring, isoquinoline ring, benzofuran ring, chromene ring, isochromene ring, 9H-xanthene ring, naphthalene ring, anthracene ring, phenanthrene ring, It may be replaced with fluorene ring.

In the formulas (III) to (VIII), —NH ₂ , a cyclohexane ring, a benzene ring, or a piperazine ring, a piperidine ring, a morpholine ring, a pyrrole ring, a furan ring, a thiophene ring, an imidazole ring, Oxazole ring, thiazole ring, pyrazole ring, triazole ring, pyridine ring, pyrazine ring, pyridazine ring, pyrimidine ring, triazine ring, pyrrolidine ring, 1H-1-pyridine ring, 1H-2-pyridine ring, indolizine ring, indole ring , Isoindole ring, indazole ring, steroid ring, bicyclo [2
. 2.1] heptane ring, bicyclo [2.2.2] octane ring, hexahydro-furo [3.2-b] furan ring, quinoline ring, isoquinoline ring, benzofuran ring, chromene ring, isochromene ring, 9H-xanthene ring , A single bond between a naphthalene ring, an anthracene ring, a phenanthrene ring, or a fluorene ring may be replaced with an alkylene having 1 to 12 carbons;
It is independently -NH - - -CH ₂ in the ^{alkylene, - CHY 2 -, - C} (Y 2) 2 -, or -NY ² - may be replaced by,
Y ² independently represents -H, alkyl having 1 to 20 carbons, or alkenyl having 2 to 20 carbons;
-CH ₂ CH ₂ in the alkylene - may be replaced by -CH = CH-, or -C≡C-, independently,
—CH ₂ — that is not adjacent to —NH _{2 in} alkylene may be independently replaced with —O— or —CO—;
-CH ₂ CH ₂ which is not adjacent to the -NH ₂ in the alkylene - may be replaced independently by -N = N-,
-H on alkylene or replaced alkylene is independently -F, -Cl, -Br, -C≡N, -OH, -COOH, -SO 3 H, or replaced with -PO ₃ H ₂ .

  Examples of the diamine represented by the formula (II) include diamines represented by the following formula (II-1).

In the formula (II-1), X ¹¹ represents an alkylene having 1 to 12 carbon atoms having as a substituent 0-4 Y ^3. —CH ₂ — in the aforementioned C 1-12 alkylene of X ¹¹ may be independently replaced with —NH—, —CHY ² —, —C (Y ² ) ₂ —, or —NY ² —.
Y ² is the same as Y ^{2 in the} formula (I).
-CH ₂ CH ₂ in the alkylene - may be replaced by -CH = CH-, or -C≡C-, independently,
—CH ₂ — that is not adjacent to —NHY ^{21 in} alkylene may be independently replaced with —O— or —CO—.
—CH ₂ CH ₂ — that is not adjacent to —NHY ^{21 in} alkylene may be independently replaced by —N═N—,
-H on the alkylene or substituted alkylene may be independently substituted with alkyl having 1 to 10 carbons.

In the formula (II-1), Y ³ is independently —H, —F, —Cl, —Br, —C≡N, —OH, —COOH, —SO ₃ H, or —PO ₃ H ₂ , Alternatively, it represents alkyl having 1 or 2 carbon atoms. In C 1 or C ₂ alkyl of Y ³ , —CH ₂ — may be independently replaced with —O—, —NH—, or —CO—, and —H on alkyl or substituted alkyl is independently to -F, -Cl, -Br, -C≡N, -OH, -COOH, -SO 3 H, or may be replaced with -PO ₃ H _2, a ring plurality of Y ³ bonded to each other It may be formed.

In formula (II-1), Y ²¹ independently represents -H, alkyl having 1 to 20 carbons, or alkylene having 1 to 20 carbons,
Said alkyl or -CH ₂ in the alkylene - independently ^{-NH -, - CHY 2 -,} - C (Y 2) 2 -, or -NY ² - may be replaced by,
-CH ₂ CH ₂ alkyl or alkylene - may be replaced by -CH = CH-, or -C≡C-, independently,
-CH ₂ - not adjacent to the -NH- alkyl or alkylene - is independently -O-, or -CO- may be replaced by,
-CH ₂ CH _2- not adjacent to -NH- in alkyl or alkylene may be independently replaced by -N = N-, or-on the alkyl or alkylene, or substituted alkyl or substituted alkylene. H may be independently replaced by -F, -Cl, -Br, -C≡N, -OH, -COOH, -SO ₃ H, or -PO ₃ H ₂ , and Y ²¹ may have the above carbon number of 1 If it is 20 alkylene is Y ²¹ is a Y ²¹ of the other amino group, or independently bonded to Y ³ to form a ring.

  In the formula (II-1), a represents an integer of 0 to 4.

  Examples of the diamine represented by the formula (III) include diamines represented by the following formula (III-1).

In the formula (III-1), Y ³ and a are the same as Y ³ and a in the formula (II-1).

  Examples of the diamine represented by the formula (IV) include diamines represented by the following formula (IV-1).

In the formula (IV-1), X ⁶ is independently a single bond, —O—, —S—, —S—S—, —SO ₂ —, —CO—, —CONH—, —COO—, — NH—, —C (CH ₃ ) ₂ —, —C (CF ₃ ) ₂ —, —COCH═CH—, —N═N—, —C≡C—, or 0 to 4 with Y ³ as a substituent. -N having _{(CH 3) - (CH 2} ) m -N (CH 3) -, - (CH 2) m -, - O- (CH 2) m -O-, or -S- (CH _{2) m} -S- (m represents an integer of 1 to 6). In the formula (IV-1), Y ³ and a are the same as Y ³ and a in the formula (II-1).

  Examples of the diamine represented by the formula (V) include diamines represented by the following formulas (V-1), (V-2), and (V-11).

In the formula (V-1), Y ⁴ is independently benzyl, —H, —F, —Cl, —OH, —COOH, —SO ₃ H, —PO ₃ H ₂ , —NHY ⁵ , or —N. (Y ⁵ ) ₂ is represented. In the formula (V-1), a is the same as a in the formula (II-1). Y ⁵ independently represents alkyl having 1 to 30 carbons or alkenyl having 2 to 30 carbons.

In the formula (V-2), X ¹⁰ is a single bond, —O—, —COO—, —CO—, —CONH—, — (CH ₂ ) _m — (m represents an integer of 1 to 6), —CHY ² —, —C (Y ² ) ₂ —, or —NY ² — is represented. Y ² is the same as Y ^{2 in the} formula (I).

In formula (V-2), Y ¹¹ represents a group having a steroid skeleton, a succinimide skeleton, or a phthalimide skeleton, or a group represented by the following formula (XXIII).

In the formula (XXIII), ring S is independently a cyclopentane ring, cyclohexane ring, 1,3-dioxane ring, piperidine ring, piperazine ring, pyrrolidine ring, phenylene ring, pyridine ring, pyrazine ring, pyridazine ring, pyrimidine ring. , Triazine ring, pyrrole ring, furan ring, thiophene ring, imidazole ring, oxazole ring, thiazole ring, triazole ring, naphthalene ring, anthracene ring, indole ring, steroid ring, or hexahydro-furo [3.2-b] furan ring Represents a group having -H on the ring S is independently -F, -Cl, -OH, -COOH, -SO 3 H, -PO 3 H 2, may be replaced alkyl having 1 to 30 carbon atoms, or phenyl, ring When —H on S is replaced by alkyl, —CH ₂ — in alkyl may be independently replaced by —O—, —NH—, or —CO—, and —CH ₂ CH _{2 in} alkyl -May be independently replaced by -CH = CH-, -C≡C-, or -N = N-, where -H on the alkyl or substituted alkyl is independently -F, -Cl,- It may be replaced with Br, —C≡N, —OH, —COOH, —SO ₃ H, or —PO ₃ H ₂ . Also, if the -H on the ring S is replaced by phenyl, -H on the phenyl are independently, -F, -Cl, -Br, -C≡N , -CH 3, -OCH 3, -OCH _It may be replaced with ₂ F, —OCHF ₂ , —OCF ₃ , —OH, —COOH, —SO ₃ H, or —PO ₃ H ₂ .

In the formula (XXIII), Y ¹² independently represents -F or -CH ₃ , or a group having a succinimide ring. In the formula (XXIII), Y ¹³ is —H, —F, —Cl, —Br, —C≡N, —OH, —COOH, —SO ₃ H, —PO ₃ H ₂ , or C 1-30. Represents alkyl. In the alkyl having 1 to 30 carbon atoms of Y ¹³ , —CH ₂ — may be independently replaced with —O—, —NH—, or —CO—, and —CH ₂ CH ₂ — is independently — CH = CH—, —C≡C—, —Si (CH ₃ ) ₂ —O—Si (CH ₃ ) ₂ — or —N═N— may be substituted, alkyl or —H on the substituted alkyl -F independently, -Cl, -Br, -C≡N, -OH , -COOH, -SO 3 H, or replaced with -PO ₃ H _2.

In formula (XXIII), A ⁴ independently represents a single bond or alkylene having 1 to 12 carbons. In the alkylene group having 1 to 12 carbon atoms of A ⁴ , —CH ₂ — may be independently replaced with —O—, —NH—, or —CO—, and —CH ₂ CH ₂ — is independently — CH = CH—, —C≡C—, or —N═N— may be substituted, and —H on alkylene or substituted alkylene is independently —F, —Cl, —Br, —C≡N _{, -OH, -COOH, -SO 3 H} , or replaced with -PO ₃ H _2.

  In the formula (XXIII), b independently represents an integer of 0 or 1, c, d, and e each represents an integer of 0 to 3, and f independently represents an integer of 0 to 4. However, c + d + e ≧ 1 and 6 ≧ b + c + d + e.

In the formula (V-11), Y ¹⁴ independently represents the formula (XXI). In the formula (V-11), a is the same as a in the formula (II-1).

  Examples of the diamine represented by the formula (VI) include diamines represented by the following formulas (VI-1) to (VI-3), (VI-11), and (VI-12).

In the formula (VI-1), X ⁶ is the same as X ⁶ in the formula (IV-1), Y ³ and a are the same as Y ³ and a in the formula (II-1).

In the formula (VI-2), X ⁶ is the same as X ⁶ in the formula (IV-1), Y ³ and a are the same as Y ³ and a in the formula (II-1). In the formula (VI-2), Y ⁷ independently represents alkyl having 1 to 30 carbons, cyclohexyl, or bicyclohexyl. -H on the cyclohexyl or bicyclohexyl of Y ⁷ may be independently replaced with alkyl having 1 to 30 carbons.

In the formula (VI-3), X ⁶ represents the above formula (IV-1) except that “having 0 to 4 as Y ³ as a substituent” is “having —Y ¹⁰ —Y ¹¹ as a substituent”. is the same as X ⁶ in, Y ³ and a are the same as Y ³ and a in the formula (II-1), X ¹⁰ and Y ¹¹ and X ¹⁰ and Y ¹¹ in the formula (V-2) The same.

In the formula (VI-11), X ⁶ is the same as X ^{6 in the} formula (IV-1) except that “having 0 to 4 as a substituent for Y ³ ”, and Y ³ and a are The same as Y ³ and a in formula (II-1). In the formula (VI-11), X ⁵ represents —COCH═CH—, —N═N—, or —C.
Represents ≡C-.

In the formula (VI-12), X ⁶ is the same as X ^{6 in the} formula (IV-1) except that “Y ³ ” is changed to “Y ¹⁴ ”, and Y ³ and a represent the formula (II). -1) is the same as the Y ³ and a, Y ¹⁴ is the same as Y ¹⁴ in the formula (V-11).

  Examples of the diamine represented by the formula (VII) are represented by the following formulas (VII-1) to (VII-3), (VII-11), (VII-12), and (VII-13). Examples include diamines.

In the formula (VII-1), X ⁶ is the same as X ^{6 in the} formula (IV-1) except that “having 0 to 4 as Y ³ is a substituent”, and Y ³ and a are The same as Y ³ and a in formula (II-1).

In the formula (VII-2), Y ¹⁷ is independently —H, —F, —Cl, —Br, —C≡N, —OH, —COOH, —SO ₃ H, —PO ₃ H ₂ , or Represents alkyl having 1 to 20 carbon atoms. In the alkyl having 1 to 20 carbon atoms of Y ¹⁷ , —CH ₂ — may be independently replaced with —O—, —NH—, or —CO—, and —CH ₂ CH ₂ — is independently — CH = CH-, -C≡C-, or -N = N- may be substituted, and -H on the alkyl or substituted alkyl is independently -F, -Cl, -Br, -C≡N _{, -OH, -COOH, -SO 3 H} , or replaced with -PO ₃ H _2. In the formula (VII-2), a is the same as a in the formula (II-1).

In the formula (VII-3), X ⁶ is the same as X ^{6 in the} formula (IV-1) except that “having 0 to 4 as Y ³ is a substituent”, and a is the formula (II). -1) is the same as the a, Y ² is the same as Y ² in the formula (I).

In the formula (VII-11), X ⁵ is the same as X ^{5 in the} formula (VI-11), and X ⁶ is the same as in the formula (except that it has 0 to 4 as Y ³ as a substituent). IV-1) is the same as X ⁶ in, Y ³ and a are the same as Y ³ and a in the formula (II-1).

In the formula (VII-12), X ⁶ is the same as X ^{6 in the} formula (IV-1) except that “having 0 to 4 as a substituent for Y ³ ”, and Y ³ and a are is the same as Y ³ and a in the formula (II-1), Y ¹⁴ is the same as Y ¹⁴ in the formula (V-11).

In the formula (VII-13), X ¹¹ independently represents an alkylene having 1 to 12 carbon atoms, and the ring R is independently a sum of the number of carbon, nitrogen, oxygen, sulfur, and silicon constituting the skeleton of 3 Represents a ring which is ˜30, a independently represents an integer of 0 to 4, and b independently represents an integer of 0 to 12;

—CH ₂ — in alkylene in X ¹¹ of formula (VII-13) is independently —O—, —NH—, —CO—, —CHY ² —, —C (Y ² ) ₂ —, or —NY. ² — may be substituted, and —CH ₂ CH ₂ — in the alkylene may be independently replaced with —CH═CH—, —C≡C—, or —N═N—. -H on the alkylene may be independently replaced by alkyl having 1 to 20 carbons or alkenyl having 2 to 20 carbons.

-CH ₂ in the alkylene between the ring R and an amino group of the formula (VII-13) - -NH independently ^{-, - CHY 2 -, -} C (Y 2) 2 -, or -NY ² - And —CH ₂ CH ₂ — in the alkylene may be independently replaced with —CH═CH— or —C≡C—,
—CH ₂ — that is not adjacent to —NH _{2 in} alkylene may be independently replaced with —O— or —CO—;
-CH ₂ CH ₂ which is not adjacent to the -NH ₂ in the alkylene - may be replaced independently by -N = N-,
-H is independently -F on the alkylene or replaced alkylene, -Cl, -Br, -C≡N, -OH , -COOH, replaced by -SO ₃ H, or -PO ₃ H ₂ Good.

Formula (VII-13) may is -H amino group is replaced by alkyl having 1 to 12 carbon atoms independently of, -CH ₂ in the alkyl - is independently -NH -, - CHY ² -, —C (Y ² ) ₂ — or —NY ² — may be substituted, and —CH ₂ CH ₂ — in the alkyl may be independently substituted with —CH═CH— or —C≡C—. ,
—CH ₂ — that is not adjacent to —NH _{2 in} alkyl may be independently replaced with —O— or —CO—;
—CH ₂ CH ₂ — that is not adjacent to —NH _{2 in} alkyl may be independently replaced by —N═N—,
-H is independently -F on the alkyl or replaced alkyl, -Cl, -Br, -C≡N, -OH , -COOH, replaced by -SO ₃ H, or -PO ₃ H ₂ Good.
In each group constituting the formula (VII-13), Y ² independently represents -H, alkyl having 1 to 20 carbons, or alkenyl having 2 to 20 carbons. However the -CHY ² - and -C (Y ^{₂₎ 2} - In, Y ² is not a -H.

Examples of the ring R of the formula (VII-13) include a cyclohexane ring, a benzene ring, a piperazine ring, a piperidine ring, a morpholine ring, a pyrrole ring, a furan ring, a thiophene ring, an imidazole ring, an oxazole ring, a thiazole ring, a pyrazole ring, and a triazole. Ring, pyridine ring, pyrazine ring, pyridazine ring, pyrimidine ring, triazine ring, pyrrolidine ring, 1H-1-pyridine ring, 1H-2-pyridine ring, indolizine ring, indole ring, isoindole ring, indazole ring, steroid ring , Bicyclo [2.2.1] heptane ring, bicyclo [2.2.2] octane ring, hexahydro-furo [3.2-b] furan ring, quinoline ring, isoquinoline ring, benzofuran ring, chromene ring, isochromene ring 9H-xanthene ring, naphthalene ring, anthracene ring, phen Ntoren ring, and and a fluorene ring.

  Examples of the diamine represented by the formula (VIII) include diamines represented by the following formulas (VIII-1) to (VIII-4) and (VIII-11).

In the formula (VIII-1), X ⁶ is the same as X ^{6 in the} formula (IV-1) except that “having 0 to 4 as Y ³ is a substituent”, and Y ³ and a are The same as Y ³ and a in formula (II-1).

In the formula (VIII-2), X ⁶ is the same as X ^{6 in the} formula (IV-1) except that “having 0 to 4 as Y ³ is a substituent”, and Y ³ and a are The same as Y ³ and a in formula (II-1). In the formula (VIII-2), X ⁸ represents a single bond or alkylene having 1 to 3 carbon atoms, and X ⁹ represents a single bond, 1,4-phenylene or 1,4-cyclohexylene. In the (VIII-2), Y ⁸ represents an alkyl -H or C1-30. In the alkyl having 1 to 30 carbon atoms represented by Y ⁸ , —CH ₂ — may be independently replaced by —O—, —NH—, or —CO—, and —CH ₂ CH ₂ — is independently — CH = CH-, -C≡C-, or -N = N- may be substituted, and -H on the alkyl or substituted alkyl is independently -F, -Cl, -Br, -C≡N _{, -OH, -COOH, -SO 3 H} , or replaced with -PO ₃ H _2.

In the formula (VIII-3), X ⁶ is the same as X ^{6 in the} formula (IV-1) except that “having 0 to 4 as Y ³ is a substituent”, and Y ³ and a are The same as Y ³ and a in formula (II-1). In the formula (VIII-3), Y ⁹ represents an alkyl having 6 to 30 carbon atoms, and Y ¹⁰ represents an alkyl having 1 to 30 carbon atoms.

In the formula (VIII-4), X ^6, except except "0-4 having a Y ³ as a substituent group" is the same as X ⁶ in the formula (IV-1), Y ² is the formula ( I) is the same as Y ² , and a is the same as a in the formula (II-1).

In the formula (VIII-11), X ⁵ is the same as X ^{5 in the} formula (VI-11), and X ⁶ is the same as in the formula (except that it has 0 to 4 as Y ³ as a substituent). IV-1) is the same as X ⁶ in, Y ³ and a are the same as Y ³ and a in the formula (II-1).

  Examples of the diamine represented by the formula (IX) include diamines represented by the following formula (IX-1).

In the formula (IX-1), X ⁷ independently represents alkylene having 1 to 6 carbons or phenylene. -H on phenylene in X ⁷ may be independently substituted with alkyl having 1 to 30 carbons. In the formula (IX-1), Y ⁶ independently represents alkyl having 1 to 3 carbon atoms or phenyl, and l represents an integer of 1 to 10.

Formula (III-1), (IV-1), (V-1), (V-2), (V-11), (VI-1), (VI-2), (VI-3), (VI-11), (VI-12), (VII-1), (VII-2), (VII-3), (VII-11), (VII-12), (VIII-1), (VIII -2), (VIII-3) , (VIII-4), (VIII-11), and (IX-1 in), -NH ₂ has one of -H of the two independently -H carbon It may be substituted with an alkyl of the number 1-12. In the alkyl having 1 to 12 carbon atoms on the —NH ₂ , —CH ₂ — is independently replaced with —NH—, —CHY ² —, —C (Y ² ) ₂ —, or —NY ² —. well Te, Y ² is the same as Y ² in the formula (I), the
—CH ₂ CH ₂ — may be independently replaced with —CH═CH—, or —C≡C—,
—CH ₂ — that is not adjacent to —NH _{2 in} alkyl may be independently replaced with —O— or —CO—;
—CH ₂ CH ₂ — that is not adjacent to —NH _{2 in} alkyl may be independently replaced by —N═N—,
—H on alkyl or substituted alkyl may be independently replaced with —F, —Cl, —Br, —C≡N, —OH, —COOH, —SO ₃ H, or —PO ₃ H _2. .

In addition, the formulas (III-1), (IV-1), (V-1), (V-2), (V-11), (VI-1), (VI-2), (VI-3) ), (VI-11), (VI-12), (VII-1), (VII-2), (VII-3), (VII-11), (VII-12), (VIII-1), (VIII-2), (VIII-3), (VIII-4), (VIII
−11) and (IX-1), one —NH ₂ and a cyclohexane ring, a benzene ring, or X ⁷ may be bonded via an alkylene having 1 to 12 carbon atoms.
-NH ₂ and a cyclohexane ring, a benzene ring, or a piperazine ring, piperidine ring, morpholine ring, pyrrole ring, furan ring, thiophene ring, imidazole ring, oxazole ring, thiazole ring, pyrazole ring, triazole ring in which the benzene ring is replaced Pyridine ring, pyrazine ring, pyridazine ring, pyrimidine ring, triazine ring, pyrrolidine ring, 1H-1-pyridine ring, 1H-2-pyridine ring, indolizine ring, indole ring, isoindole ring, indazole ring, steroid ring, Bicyclo [2.2.1] heptane ring, bicyclo [2.2.2] octane ring, hexahydro-furo [3.2-b] furan ring, quinoline ring, isoquinoline ring, benzofuran ring, chromene ring, isochromene ring, 9H-xanthene ring, naphthalene ring, anthracene ring, fluorine Single bond between Nantoren ring, or a fluorene ring can be substituted by an alkylene having 1 to 12 carbon atoms,
In the alkylene, —CH ₂ — may be independently replaced by —NH—, —CHY ² —, —C (Y ² ) ₂ —, or —NY ² —, and Y ² represents Y in the formula (I). Same as ² ,
-CH ₂ CH ₂ in the alkylene - may be replaced by -CH = CH-, or -C≡C-, independently,
—CH ₂ — that is not adjacent to —NH _{2 in} alkylene may be independently replaced with —O— or —CO—;
-CH ₂ CH ₂ which is not adjacent to the -NH ₂ in the alkylene - may be replaced independently by -N = N-,
-H on alkylene or replaced alkylene is independently -F, -Cl, -Br, -C≡N, -OH, -COOH, may be replaced by -SO ₃ H, or -PO ₃ H ₂ ,

  Examples of the diamine represented by the formula (II-1) include the following formulas (II-1-1) to (II-1-14) and (II-1-21) to (II-1-30). The diamine represented is mentioned.

  Examples of the diamine represented by the formula (III-1) include diamines represented by the following formulas (III-1-1) to (III-1-5).

  Examples of the diamine represented by the formula (IV-1) include diamines represented by the following formulas (IV-1-1) to (IV-1-4).

  Examples of the diamine represented by the formula (V-1) include diamines represented by the following formulas (V-1-1) to (V-1-22).

  Examples of the diamine represented by the formula (V-2) include diamines represented by the following general formulas (V-2-1) to (V-2-54).

In formulas (V-2-1) to (V-2-17) and (V-2-24) to (V-2-40), Y ² is the same as Y ^{2 in} formula (I). is there.

In formula (V-2-41), Y ⁵ represents alkyl having 1 to 30 carbons or alkenyl having 2 to 30 carbons.

In the formula (V-2-48) and formulas (V-2-50) to (V-2-52), Y ¹⁶ is independently —H, alkyl having 1 to 30 carbons, or 1 to 29 carbons. Represents alkoxy or alkenyl having 2 to 30 carbon atoms.

  Examples of the diamine represented by the formula (V-11) include diamines represented by the following formulas (V-11-1) to (V-11-19).

  Examples of the diamine represented by the formula (VI-1) include diamines represented by the following formulas (VI-1-1) to (VI-1-41).

  Examples of the diamine represented by the formula (VI-2) include diamines represented by the following formulas (VI-2-1) to (VI-2-8).

In formulas (VI-2-1) to (VI-2-4), Y ¹⁵ independently represents alkyl having 3 to 30 carbons, alkoxy having 3 to 29 carbons, or alkenyl having 3 to 30 carbons. To express. In the formulas (VI-2-5) to (VI-2-8), Y ¹⁶ represents any of the formulas (V-2-48) and (V-2-50) to (V-2-52). is the same as Y ^16.

  Examples of the diamine represented by the formula (VI-3) include diamines represented by the following formulas (VI-3-1) and (VI-3-2).

In the formula (VI-3-1), Y ¹⁵ is the same as Y ¹⁵ in the formula (VI-2-1) ~ (VI -2-4), in the formula (VI-3-2), Y ¹⁶ is the same as Y ¹⁶ in the formula (V-2-48) and formula (V-2-50) ~ (V -2-52).

  Examples of the diamine represented by the formula (VI-11) include diamines represented by the following formulas (VI-11-1) to (VI-11-16).

  Examples of the diamine represented by the formula (VI-12) include diamines represented by the following formula (VI-12-1).

  Examples of the diamine represented by the formula (VII-1) include diamines represented by the following formulas (VII-1-1) to (VII-1-6).

  Examples of the diamine represented by the formula (VII-2) include diamines represented by the following formulas (VII-2-1) to (VII-2-15).

  Examples of the diamine represented by the formula (VII-3) include diamines represented by the following formulas (VII-3-1) to (VII-3-4).

  Examples of the diamine represented by the formula (VII-11) include diamines represented by the following formulas (VII-11-1) to (VII-11-6).

  Examples of the diamine represented by the formula (VII-12) include diamines represented by the following formula (VII-12-1).

  Examples of the diamine represented by the formula (VII-13) include diamines represented by the following formulas (VII-13-1) to (VII-13-4).

  Examples of the diamine represented by the formula (VIII-1) include diamines represented by the following formulas (VIII-1-1) to (VIII-1-16).

  Examples of the diamine represented by the formula (VIII-2) include diamines represented by the following formulas (VIII-2-1) to (VIII-2-8).

In the formulas (VIII-2-1) to (VIII-2-8), Y ¹⁶ represents Y in the formulas (V-2-48) and (V-2-50) to (V-2-52). Same as ¹⁶ .

  Examples of the diamine represented by the formula (VIII-3) include diamines represented by the following formulas (VIII-3-1) to (VIII-3-3).

In the formulas (VIII-3-1) to (VIII-3-3), Y ¹⁶ represents Y in the formulas (V-2-48) and (V-2-50) to (V-2-52). ¹⁶ is the same as, Y ⁹ is the same as Y ⁹ of the formula (VIII-3).

  Examples of the diamine represented by the formula (VIII-4) include diamines represented by the following formulas (VIII-4-1) to (VIII-4-8).

  Examples of the diamine represented by the formula (VIII-11) include a diamine represented by the following formula (VIII-11-1).

  Examples of the diamine represented by the formula (IX-1) include diamines represented by the following formula (IX-1-1).

  Furthermore, examples of the diamine include naphthalene diamine having a naphthalene structure and fluorene diamine having a fluorene structure.

  As the diamine, a diamine having a rigid linear structure or another diamine can be appropriately used. Examples of such other diamines include diamines having a side chain structure. Examples of the diamine having a side chain structure include diamines represented by the following formula (II-2) and diamines represented by the following formula (V-3).

In the formula (II-2), X ¹¹ represents an alkylene having 1 to 12 carbons having one —X ¹² —Y ¹¹ as a substituent, and in the formula (V-3), X ¹¹ independently represents a carbon number. Represents an alkylene of 1 to 12, and —CH ₂ — in the alkylene of X ¹¹ may be independently replaced by —NH—, —CHY ² —, —C (Y ² ) ₂ —, or —NY ² —. ,
-CH ₂ CH ₂ in the alkylene - may be replaced by -CH = CH-, or -C≡C-, independently,
—CH ₂ — that is not adjacent to —NH _{2 in} alkylene may be independently replaced with —O— or —CO—;
-CH ₂ CH ₂ which is not adjacent to the -NH ₂ in the alkylene - may be replaced independently by -N = N-,
-H on alkylene or replaced alkylene of X ¹¹ may be replaced with independently alkyl having 1 to 10 carbon atoms.

In Formula (II-2), Y ¹¹ represents a group having a steroid skeleton, a succinimide skeleton, or a phthalimide skeleton, or a group represented by Formula (XXIII).
In formula (II-2), X ¹² represents a single bond or a divalent organic group.

In Formula (V-3), X ¹³ independently represents a single bond or alkylene having 1 to 30 carbon atoms, and when X ¹³ is alkylene, —CH ₂ — in the alkylene independently represents —O—. , -NH -, - CO -, - NY 2 -, - S -, - SO -, - SO 2 -, or -Si (Y ²²⁾ ₂ - may be replaced by, Y ²² is independently -H Represents alkyl having 1 to 20 carbons, alkenyl having 1 to 20 carbons, or phenyl, and -H on phenyl is independently -F, -Cl, -Br, -C≡N, -OH, -COOH. , —SO ₃ H, —PO ₃ H ₂ , or alkyl having 1 to 30 carbon atoms, —CH ₂ CH ₂ — in the alkylene of X ¹³ is independently —CH═CH—, -C≡C-, or -N = N- may be substituted, alkylene of X ¹³ or substituted alkylene -H above is independently -F, -Cl, -Br, -C≡N, -OH, -COOH, -SO 3 H, -PO 3 H 2, alkyl having 1 to 20 carbon atoms, or carbon atoms It may be replaced with 2-20 alkenyl.

In each group constituting Equation (II-2) and (V-3), Y ² represents independently -H, alkyl having 1 to 20 carbon atoms, or an alkenyl having 2 to 20 carbon atoms. However the -CHY ² - and -C (Y ^{₂₎ 2} - In, Y ² is not a -H.

  Examples of the diamine represented by the formula (II-2) include diamines represented by the following formulas (II-2-1) to (II-2-4). Moreover, as a diamine represented by a formula (V-3), the diamine represented, for example by a following formula (V-3-1) is mentioned.

  The diamine preferably contains an aliphatic diamine from the viewpoint of reactivity with bismaleimide. The aliphatic diamine is represented by the general formulas (II-1-1) to (II-1-30), (IV-1-1) to (IV-1-4) from the viewpoint of imparting appropriate flexibility to the polymer. ), (V-1-20) to (V-1-22), and (VI-1-40).

  In particular, when an aliphatic diamine is used as a diamine as a monomer constituting the maleimide polymer, a catalyst such as a proton donor, a tertiary amine, or a combination thereof is added to the reaction system during the reaction (polymerization). Even if not used, a maleimide polymer having a high degree of polymerization is obtained, which is preferable. Further, since it is not necessary to add a catalyst to the reaction system at the time of reaction (at the time of polymerization), a polymer with less impurities can be obtained, which is preferable in terms of quality. Furthermore, a step of purifying the polymer after the polymerization is unnecessary, and the reaction solution after the polymerization can be used for a desired application as it is, which is preferable in terms of man-hours. Or when forming a film using a polymer solution, since generation | occurrence | production of the vapor | steam with an odor, toxicity, or corrosiveness is suppressed, it is preferable.

  Examples of the proton donor include inorganic acids (for example, hydrogen chloride, sulfuric acid, phosphoric acid, or perchloric acid), carboxylic acids (for example, formic acid, acetic acid, propionic acid, benzoic acid, or trifluoroacetic acid), phenols ( For example, phenol, cresols, chlorophenols, xylenols, hydroquinone, etc.) or salts (eg, ammonium chloride, ammonium sulfide, tributylammonium chloride, boron trifluoride monoethylamine, aluminum chloride, etc.), etc. Examples of the primary amines include triethylamine, pyridine, dimethylaminopyridine, diazabicycloundecene, and the like.

  The aliphatic diamine preferably includes a diamine having the above-described rigid linear structure, for example, a diamine represented by the formula (VII-13), from the viewpoint of imparting rigidity to the polymer. Specifically, it preferably contains at least one of general formulas (VII-13-1) to (VII-13-4).

  The diamine can be appropriately used depending on the properties required for the liquid crystal aligning agent. For example, a diamine having no side chain structure is preferably used for a liquid crystal aligning agent for an IPS liquid crystal display element. On the other hand, it is preferable to use a diamine having a side chain structure as a liquid crystal aligning agent for a TN type or VA type liquid crystal display element. A diamine having an oriented side chain structure, for example, has a substituent (side chain) branched from the main chain when a divalent group connecting two amino groups is used as the main chain, It is a diamine having the property of developing vertical alignment or pretilt angle. The side chain may be appropriately selected according to the required orientation. Diamines corresponding to such properties can be used as one or more diamines as the constituent unit of the maleimide polymer.

  In the diamine, when two amino groups are bonded to carbon of the same six-membered ring, for example, when importance is given to the introduction of a rigid structure, it is preferable that they are bonded to each other with a flexible structure. When the introduction is regarded as important, it is preferable that they are bonded to each other, and can be appropriately selected according to the purpose.

  The diamine preferably contains an aliphatic diamine. Specifically, the diamine is represented by the general formulas (II-1-1) to (II-1-30), (IV-1-1) to (IV-1-4), (V-1-20) to It preferably contains one or more diamines selected from the group of (V-1-22), (VI-1-40), and (VII-13-1) to (VII-13-4). When the ratio of bismaleimide having a non-rigid structure is high, the diamine preferably contains one or more diamines selected from the group of (VII-13-1) to (VII-13-4).

  Examples of the diamine used for the liquid crystal aligning agent for the IPS liquid crystal display element include the formulas (II-1-1) to (II-1-30) and (IV-1-1) to (IV-1-). 4), diamines represented by (V-1-20) to (V-1-22), (VI-1-40), and (VII-13-1) to (VII-13-4). It is done.

  Examples of the diamine used for the liquid crystal aligning agent for the TN type liquid crystal display element include the formulas (formulas (II-1-1) to (II-1-30), (IV-1-1) to (IV) -1-4), (V-1-20) to (V-1-22), (VI-1-40), and (VII-13-1) to (VII-13-4)) Diamines), and diamines represented by (II-2-1) to (II-2-4) and (V-3-1) in addition thereto.

  Examples of the diamine used for the liquid crystal aligning agent for the VA liquid crystal display element include those represented by the above formulas (formulas (II-2-1) to (II-2-4) and (V-3-1)). And (II-1-1) to (II-1-30), (IV-1-1) to (IV-1-4), (V-1-20) to (II) V-1-22), (VI-1-40), and diamines represented by (VII-13-1) to (VII-13-4)).

  The maleimide polymer of the present invention can be obtained by reacting the bismaleimide and the diamine by a Michael addition reaction. A part of the bismaleimide is a bisvinylsulfone compound, and a part of the diamine is a bisthiol series. It may be replaced with a compound.

  Specific examples of the bisvinylsulfone compound include compounds represented by the following formulas (VS-1) and (VS-2).

  The addition amount of the bisvinylsulfone compound is preferably such that the molar ratio of bismaleimide / bisvinylsulfone compound is 100/0 to 10/90 from the viewpoint of obtaining a polymer having an appropriate molecular weight.

  Specific examples of the bisthiol-based compound include compounds represented by the following formulas (HS-1) and (HS-2).

  The addition amount of the bisthiol compound is preferably such that the molar ratio of the diamine / bisthiol compound is 100/0 to 50/50 from the viewpoint of obtaining a polymer having an appropriate molecular weight.

  The solvent used for the resin composition of the present invention may be one kind or a mixture of two or more kinds. The solvent can be appropriately selected from various viewpoints. For example, the solvent can be used from the viewpoints of adjusting physical properties such as the viscosity of the composition, ease of handling, and simplification of the process. Examples of the solvent include a solvent having a hydroxyl group and a protic amide solvent used for preparing the polymer used in the composition of the present invention. Among these, the resin composition has a high resin dissolving power, has an effect of suppressing side reactions (gelation, coloring) as a solvent used during polymerization, and contains a solvent used during polymerization because of less odor. It is preferable that the high polar alcohol or the protic amide solvent is included from the viewpoint that it can be used as a solvent. The highly polar alcohol has 1) an alcoholic hydroxyl group and 2) one or more groups selected from the group consisting of a cyclic amide, a chain ester, a chain amide, and a cyclic ether.

  The composition of the present invention preferably contains the maleimide polymer and a solvent having a hydroxyl group or a protic amide solvent, but may contain additional components in addition to or instead of them. Good. Such additional components include, for example, solvents and various additives.

  The solvent can be appropriately selected from various viewpoints. For example, the solvent can be used from the viewpoints of adjusting physical properties such as viscosity of the composition, ease of handling, and simplification of the process. One type of solvent may be used, or two or more types may be mixed and used. Examples of the solvent include a polar solvent having a high ability to dissolve the maleimide polymer, and a coatability improving solvent having a high ability to improve the coatability of the composition by changing the surface tension. It is also preferable that it is a mixed solvent. When using the composition of this invention as a composition for application | coating, the aspect which contains the said application | coating improvement solvent in the composition of this invention can illustrate preferably.

Examples of the polar solvent include the protic amide solvents, but other than that, N-methyl-2-pyrrolidone, N, N′-dimethylimidazolidinone, N-methylcaprolactam, N, N-dimethylpropion. Amide, N, N-dimethylacetamide, dimethyl sulfoxide, N, N-dimethylformamide, N, N-diethylformamide, N
, N-diethylacetamide, N, N, N ′, N′-tetramethylurea, γ-butyrolactone, γ-valerolactone, δ-valerolactone, and ε-caprolactone. The polar solvent is preferably one or more selected from the group consisting of N-methyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide, and N, N′-dimethylimidazolidinone. .

  Examples of the coating property-improving solvent include the high polar alcohols, but other than these, ethylene glycol monoalkyl ethers such as 3-methyl-3-methoxybutanol, tetralin, isophorone, ethylene glycol monobutyl ether, and diethylene glycol monoethyl ether. Such as diethylene glycol monoalkyl ether, ethylene glycol monoalkyl or phenyl acetate, propylene glycol monoalkyl ether such as triethylene glycol monoalkyl ether, propylene glycol monobutyl ether, dialkyl malonate such as diethyl malonate, dipropylene glycol monomethyl ether, etc. Examples include dipropylene glycol monoalkyl ether and ester compounds such as acetates thereof. It is. Examples of the coating property improving solvent include one or more selected from the group consisting of the highly polar alcohol, ethylene glycol monobutyl ether, diethylene glycol monoethyl ether, propylene glycol monobutyl ether, and dipropylene glycol monomethyl ether.

As the solvent, in addition to the polar solvent or the coating property improving solvent, the following examples can be given according to the structure.
Ether systems such as diethyl ether, methyl-t-butyl ether, diisopropyl ether, 1,4-dioxane, and tetrahydrofuran;
Chain ester systems such as ethyl acetate and butyl acetate,
Ketones such as acetone, methyl ethyl ketone, cyclopentanone, cyclohexanone,
Aromatics such as toluene and xylene.

  When the polar solvent and the coatability improving solvent are used in combination, the types and ratios of the polar solvent and the coatability improving solvent are appropriately determined in consideration of the printability, coatability, solubility, storage stability, and the like. Can be set to The polar solvent is relatively superior in the solubility of the polymer and the storage stability of the polymer solution relative to the coating property improving solvent. On the other hand, the coatability improving solvent is more excellent in printability and coatability than the polar solvent.

  The additive may be a component used for the purpose of improving specific properties when the resin composition is used in various applications, and may be used alone or in combination of two or more. Examples of the additive include a high molecular compound and a low molecular compound other than the maleimide polymer used in accordance with each purpose. Examples of the polymer compound include polyamide and polyimide. Moreover, as said low molecular weight compound, a silane coupling agent is mentioned, for example.

  The content of the highly polar alcohol with respect to the total weight of the solvent is preferably 1 to 100% by weight, and 2 to 100% by weight from the viewpoint of the balance of handleability (polymer solubility, coatability, etc.). More preferably, it is 4 to 100% by weight, more preferably 20 to 100% by weight.

  The content of the solvent having an alcoholic hydroxyl group with respect to the total weight of the solvent is preferably 0.5 to 70% by weight from the viewpoint of the balance of handleability (polymer solubility, coatability, etc.). It is more preferably ˜50% by weight, and further preferably 2˜50% by weight.

  Since the solvent having the phenolic hydroxyl group has a high ability to dissolve the maleimide polymer, it can be used when odor and toxicity are not a problem. When used, the content of the solvent having a phenolic hydroxyl group relative to the total weight of the solvent is preferably 0 to 100% by weight, and preferably 1 to 100% by weight, from the viewpoint of the ability to dissolve the polymer. More preferably, it is 10 to 100% by weight.

  The content of the polar solvent relative to the total weight of the solvent is preferably 0 to 95% by weight, more preferably 1 to 90% by weight, more preferably 5 to 80% from the viewpoint of the ability to dissolve the maleimide polymer. More preferably, it is% by weight.

  The content of the coatability improving solvent relative to the total weight of the solvent is preferably 5 to 95% by weight, more preferably 10 to 90% by weight, from the viewpoint of printability such as surface smoothness. More preferably, it is -80 weight%.

  From the viewpoint of workability, the content of the ether, ester, ketone, or aromatic solvent with respect to the total weight of the solvent is preferably 0 to 70% by weight based on the total amount of the solvent, 0.5 More preferably, it is -50 weight%, and it is further more preferable that it is 1-50 weight%.

  The resin composition of the present invention may further contain an additive according to the application in an appropriate amount according to the application. For example, the resin composition may further contain another maleimide polymer that does not include a plurality of the rigid linear structures intermittently in the main chain as long as the effect of the present invention is obtained.

  The liquid crystal alignment film of this invention is formed from the resin composition of this invention as a liquid crystal aligning agent mentioned above. The liquid crystal alignment film is a method similar to the production of a liquid crystal alignment film from a polyimide-based liquid crystal aligning agent, that is, a step of forming a coating film, a step of heat-treating the formed coating film, and an alignment treatment if necessary. It can be manufactured by a method including a process.

  The step of forming the coating film can be performed, for example, by applying the liquid crystal aligning agent of the present invention to a substrate for a liquid crystal display element or a measurement substrate such as calcium fluoride or silicon. Moreover, the said heat processing process can be performed by heating the obtained coating film to 50-400 degreeC, for example, Preferably it is 120-280 degreeC for 1 minute-3 hours, Preferably it is 1 minute-1 hour. Here, the film thickness of the liquid crystal alignment film is preferably 10 to 300 nm, and more preferably 30 to 100 nm.

  In addition, the production of the liquid crystal alignment film may include further steps depending on the application. As such a further process, for example, in the case of producing a liquid crystal alignment film for IPS type or a liquid crystal alignment film for TN type, one main chain of the polymer in the liquid crystal alignment film obtained by the heat treatment is used. A rubbing process for aligning in the direction may be mentioned.

  Further, the production of the liquid crystal alignment film may include a further process depending on the material. As such a further step, for example, when the maleimide polymer has a rigid linear structure containing a group having a photo-alignment property such as an azo group, a carbon-carbon double bond, or a carbon-carbon triple bond, There is a step of irradiating a coating film of a liquid crystal aligning agent containing a maleimide polymer with radiation such as ultraviolet rays to align the maleimide polymer in the coating film in one direction. As the liquid crystal aligning agent to which such a photo-alignment step can be applied, the maleimide-based high molecular weight ratio is 5% or more with respect to all the structural units of the maleimide-based polymer. Examples thereof include liquid crystal aligning agents containing molecules. Such a photo-alignment process can be performed as described in, for example, Japanese Patent Application Laid-Open Nos. 2007-248637 and 2007-296991.

  The film thickness of the liquid crystal alignment film can be adjusted by the viscosity of the liquid crystal aligning agent and the application method of the liquid crystal aligning agent. The film thickness of the liquid crystal alignment film can be measured by a known film thickness measuring device such as a step meter or an ellipsometer. Furthermore, the components in the liquid crystal alignment film can be analyzed using a normal analysis means such as IR or MS after performing a treatment such as hydrolysis as necessary.

  The liquid crystal display element of the present invention has the liquid crystal alignment film of the present invention described above. The configuration of the liquid crystal display element of the present invention is not particularly limited except that the liquid crystal alignment film is the liquid crystal alignment film of the present invention described above.

  For example, in the liquid crystal display element, a pair of substrates arranged opposite to each other, electrodes formed on one or both of the opposed surfaces of the pair of substrates, and the pair of substrates are opposed to each other. A liquid crystal alignment film of the present invention formed on the surface and a liquid crystal layer formed between the pair of substrates.

  The pair of substrates with electrodes arranged opposite to each other is preferably a transparent substrate (for example, a glass substrate).

  An electrode is provided on the surface of at least one or both of the pair of substrates according to the form of the liquid crystal display element. The electrode is not particularly limited as long as it is an electrode formed on one surface of the substrate. Examples of such electrodes include ITO and metal vapor deposition films. The electrode may be formed on the entire surface of the substrate, or may be formed in a predetermined shape that is patterned, for example. Further, the electrode may be provided on only one of the pair of substrates, or may be provided on both.

  The liquid crystal alignment film of the present invention is formed on the surface of the electrode or the surface of the substrate. The formation of the liquid crystal alignment film of the present invention is as described above.

  The liquid crystal layer sandwiched between the pair of substrates includes a liquid crystal composition. Here, the liquid crystal composition is not particularly limited, and either a liquid crystal composition having a positive dielectric anisotropy or a liquid crystal composition having a negative dielectric anisotropy may be used depending on the driving mode. it can. One or more optically active compounds may be added to the liquid crystal composition having a positive or negative dielectric anisotropy.

  Of course, the liquid crystal display element of the present invention may have other members.

  The liquid crystal display element of the present invention can be manufactured by any method. For example, the above-described methods can be summarized as follows: 1) a step of applying a liquid crystal aligning agent on the two transparent substrates (coating film forming step), 2) A step of drying the applied liquid crystal aligning agent by heat treatment, 3) a step of aligning the obtained liquid crystal alignment film as necessary, and 4) a liquid crystal composition between the two substrates after being bonded together Or a step of dropping a liquid crystal composition onto one substrate and then bonding to the other substrate.

  As a coating method in the step of applying the liquid crystal aligning agent, a spinner method, a printing method, a dipping method, a dropping method, an ink jet method and the like are generally known. These methods are also applicable in the present invention.

Moreover, as a method for performing the heat treatment step, a method of heat treatment in an oven or an infrared furnace, a method of heat treatment on a hot plate, and the like are generally known. These methods are also applicable in the present invention. The heat treatment may be any of a method that is performed once, a method that is performed in a plurality of times, and a method that is performed while gradually increasing the temperature, but drying at a low temperature to prevent foaming and for sufficiently removing the solvent A method of combining drying at high temperature is preferred. That is, the first heat treatment step is preferably performed at a relatively low temperature (50 to 140 ° C.) within a range in which the solvent can be gradually evaporated. The second heat treatment step is preferably performed at a relatively high temperature (140 to 400 ° C.) for the purpose of removing the remaining solvent as much as possible. Also preferred is a method in which the heat treatment is started at a relatively low temperature (50 to 140 ° C.), and then the temperature is gradually increased and the heat treatment is terminated at a relatively high temperature (140 to 400 ° C.).

  In the alignment treatment step, for example, a rubbing treatment is performed on the IPS liquid crystal display element or the TN liquid crystal display element.

  Next, an adhesive is applied onto one substrate, and the liquid crystal is injected in a vacuum. In the case of the dropping injection method, the liquid crystal composition is dropped on a substrate before bonding, and then bonded on the other substrate. The liquid crystal display element of the present invention is produced by curing the adhesive used for bonding with heat or ultraviolet rays.

  A polarizing plate (polarizing film), a wave plate, a light scattering film, a driving circuit, and the like may be mounted on the liquid crystal display element of the present invention.

  The resin composition of the present invention can be used as it is, or other known components can be added and used as a coating material, an insulating material, a printed wiring board material, or a gas separation material using a conventionally known method. it can. Examples of the coating material include coating agents such as paints, printing inks, and surface protection materials. When the composition is used in such applications, the content of the maleimide polymer in the composition is 0.5 to 50% by weight based on the total amount of materials for each application, although it varies depending on each application. It is preferable that

  When it is used as a coating material, an insulating material, a printed wiring board material, or a gas separation material, for example, a colorant, mineral oil, filler, elastomer, antioxidant, stabilizer, Add defoamer, extender, plasticizer, catalyst, pigment, pigment paste, reinforcement, flow control agent, leveling agent, thickener, flame retardant, curing agent, curable compound, other resin Can do. Examples of other resins include polyamide and polyimide.

  These materials preferably contain 0.5 to 50% by weight of the maleimide polymer in the composition with respect to the total amount of the material from the viewpoint of workability. In addition, these materials can be obtained by using the composition as a raw material, for example, after adding each material and then performing stirring and kneading operations.

  The maleimide polymer of the present invention has a structure of a reaction product of bismaleimide and diamine represented by the formula (MA). Alternatively, the maleimide polymer of the present invention has a structure of a reaction product of the diamine represented by the above formula (MA) or another bismaleimide and the above formula (VII-13).

  Examples of the maleimide polymer of the present invention include bismaleimide represented by the above formula (MA-2-1-2) and bis (4-aminocyclohexyl) represented by the above formula (IV-1-1). And maleimide polymers having a structure of a reaction product with methane or N, N′-dimethyl-1,6-diaminohexane represented by the formula (II-1-22).

The maleimide polymer of the present invention can be produced by the aforementioned addition reaction between the corresponding bismaleimide and diamine. The bismaleimide as a raw material can be produced by the oxidation-reduction reaction and dehydration condensation reaction between the diamine and maleic anhydride described above.
In addition, the maleimide polymer of the present invention can be confirmed using ordinary analysis means such as NMR, IR, and MS.

  The bismaleimide of the present invention has the formulas (MA-1-1) to (MA-1-3), (MA-2-2) to (MA-2-6), (MA-3-1), ( MA-3-2), (MA-2-1-19) to (MA-2-1-27), (MA-2-7-2), (MA-2-7-3), (MA- 1-4-1) and (MA-1-5-1). The bismaleimide of the present invention can be produced by addition reaction of the above-described diamine and maleic anhydride, followed by dehydration imidization in the presence of an acid. In addition, the bismaleimide of the present invention can be confirmed using ordinary analysis means such as NMR, IR, and MS.

EXAMPLES Hereinafter, although an Example demonstrates this invention, this invention is not limited to these Examples. The compounds used in the examples are as follows.
Bismaleimide 3,3′-dimethyl-4,4′-bismaleimide biphenyl: (MA-2-1-2)
Bis (4-maleimido-3-methyl-5-ethylphenyl) methane: (m-2) (manufactured by Daiwa Kasei Kogyo Co., Ltd.)
Diamine bis (4-aminocyclohexyl) methane: (IV-1-1)
N, N′-dimethyl-1,6-diaminohexane: (II-1-22)
Piperazine: (II-1-24)
3,3′-dimethylbiphenyl-4,4′-diamine: (VI-1-41)
Solvent tetrahydrofurfuryl alcohol: S1
N-methyl-2-pyrrolidone: S2
Butyl cellosolve (ethylene glycol monobutyl ether): S3

[Production Example 1] Production of (MA-2-1-2) 100 mL of S2 and (VI-1-41) in a 500 mL four-necked flask equipped with a thermometer, a stirrer, a raw material inlet and a nitrogen gas inlet Of 18.362 g (86.495 mmol) was added and stirred and dissolved in a dry nitrogen stream. Next, 18.659 g (190.29 mmol) of maleic anhydride was added to the obtained solution under ice cooling, and the mixture was reacted at room temperature for 3 hours. When the reaction temperature rose during the reaction, the reaction temperature was kept at about 70 ° C. or lower for the reaction. After 3 hours, a solution in which 3.0 g of p-toluenesulfonic acid was dissolved in 300 mL of xylene was added to the reaction solution, and the mixture was gradually heated and heated. When refluxing started, the reaction was continued for 7 hours while removing the produced water out of the system. After completion of the reaction, the reaction mixture was cooled to room temperature, and the precipitated solid was collected by filtration. The solid was washed with water and recrystallized using S2, to obtain 19.325 g (51.897 mmol, yield 60%) of (MA-2-1-2).

[Example 1] Production of maleimide polymer solution PM1 In a 100 mL four-necked flask equipped with a thermometer, stirrer, raw material inlet and nitrogen gas inlet, 1.591 g (7. 565 mmol) and 23.5 g of S1 were added and stirred and dissolved in a dry nitrogen stream. Next, 4.409 g (7.565 mmol) of (MA-2-1-2) and 23.5 g of S1 were added to the obtained solution and reacted for 24 hours in a room temperature environment. After 24 hours, 47.0 g of S2 was added to the reaction solution and stirred until uniform to obtain a maleimide polymer solution having a concentration of 6% by weight. This polymer solution is designated as PM1. Table 1 shows the composition and physical properties of PM1.

  The viscosity of PM1 was measured by a rotational viscosity measurement method. More specifically, the viscosity of PM1 was measured at 25 ° C. using a rotational viscometer (TVE-20L type manufactured by Toki Sangyo). The weight average molecular weight Mw of PM1 was measured using Alliance 2695, manufactured by WATERS, 1% phosphoric acid-containing N, N-dimethylformamide as a developing solvent, (polystyrene) as a standard sample, and HSPgel as a column. (Trademark) It measured by performing a liquid chromatography analysis using RTMB-M, the product made from WATERS.

[Example 2] Production of maleimide polymer solution PM2 (II-1-22) was added to 1.191 g (8. 8) in a 100 mL four-necked flask equipped with a thermometer, a stirrer, a raw material inlet and a nitrogen gas inlet. 253 mmol) and 23.5 g of S1 were added and stirred and dissolved in a dry nitrogen stream. Next, 4.809 g (8.253 mmol) of (MA-2-1-2) and 23.5 g of S1 were added to the obtained solution, and the mixture was reacted for 24 hours in a room temperature environment. After 24 hours, 47.0 g of S2 was added to the reaction solution and stirred until uniform to obtain a maleimide polymer solution having a concentration of 6% by weight. This polymer solution is designated as PM2. Further, the physical properties of PM2 were measured in the same manner as PM1. The composition and physical properties of PM2 are shown in Table 1.

[Comparative Example 1] Production of maleimide polymer solution PM3 In a 100 mL four-necked flask equipped with a thermometer, a stirrer, a raw material inlet and a nitrogen gas inlet, 0.978 g (11. 35 mmol) and 23.5 g of S1, were stirred and dissolved in a dry nitrogen stream. Next, 5.022 g (11.35 mmol) of (m-2) and 23.5 g of S1 were added to the obtained solution, and the mixture was reacted for 24 hours in a room temperature environment. After 24 hours, 47.0 g of S2 was added to the reaction solution and stirred until uniform to obtain a maleimide polymer solution having a concentration of 6% by weight. This polymer solution is designated as RPM1. Furthermore, the physical properties of RPM1 were measured in the same manner as PM1. Table 2 shows the composition and physical properties of PM3.

  In Examples 1 and 2, a high molecular weight maleimide polymer was obtained by liquid chromatography analysis, and its peak was single and had a narrow molecular weight distribution (low dispersion).

[Example 3] Preparation of liquid crystal aligning agent To the 6 wt% polymer solution PM1 obtained in Example 1, a mixed solvent of S2 / S3 = 1/1 (weight ratio) was added, and the whole was made of polymer. The liquid crystal aligning agent A was obtained by diluting to a concentration of 4% by weight.

[Comparative Example 2]
A liquid crystal aligning agent B was obtained in the same manner as in Example 3 except that the polymer solution RPM1 was used instead of the polymer solution PM1.

Example 4 Production of Liquid Crystal Alignment Film and Liquid Crystal Display Element Liquid crystal alignment agent A was applied to two glass substrates with ITO electrodes by a spinner to form a film having a thickness of 70 nm. After coating, the film was heated and dried at 80 ° C. for about 5 minutes, and then heat-treated at 210 ° C. for 20 minutes to form liquid crystal alignment film A.

  Next, the surface of the substrate on which the liquid crystal alignment film was formed was rubbed with a rubbing apparatus to perform the alignment treatment. First, the obtained liquid crystal alignment film A was rubbed with a rubbing treatment device manufactured by Iinuma Gauge Co., Ltd., and the amount of push of the rubbing cloth (hair length 1.8 mm: rayon) was 0.40 mm, and the stage moving speed was 60 mm. / Sec, and a rubbing treatment was performed at a roller rotation speed of 1,000 rpm. Thereafter, the liquid crystal alignment film was ultrasonically cleaned in ultrapure water for 5 minutes and then dried in an oven at 120 ° C. for 30 minutes.

  One glass substrate was sprayed with a 7 μm gap material, and the surface on which the liquid crystal alignment film was formed was placed inside so as to face each other so that the rubbing direction was anti-parallel, and then sealed with an epoxy curing agent, and the gap was 7 μm. A parallel cell was produced. The liquid crystal composition shown below was injected into the cell, and the injection port was sealed with a photocuring agent. Next, heat treatment was performed at 110 ° C. for 30 minutes, and a liquid crystal display element A was produced.

<Evaluation of rubbing resistance>
The surface of the liquid crystal alignment film A formed on the surface of the substrate was rubbed with a rubbing apparatus, and scratches on the surface were visually observed. It can be said that the rubbing resistance is good when there is no scratch. The results are shown in Table 3.

<Evaluation of orientation (confirmation of fluid orientation)>
The liquid crystal display element A is sandwiched between polarizing plates arranged in crossed Nicols, and as a kind of display failure of the liquid crystal panel that occurs in the manufacturing process of the liquid crystal panel, when liquid crystal molecules are injected into the liquid crystal panel, It was visually confirmed whether or not fluid orientation, which is a fixed phenomenon, was observed. The results are shown in Table 3.

  Furthermore, in order to measure retardation, the substrate for retardation measurement was produced. First, the liquid crystal aligning agent A was apply | coated with the spinner on the transparent glass substrate. The coating conditions were 2,000 rpm and 15 seconds. After the coating, the first stage heat treatment is performed at 80 ° C. for about 3 minutes, and then the second stage heat treatment is performed at 210 ° C. for 20 minutes to form a liquid crystal alignment film A ′ having a thickness of about 70 nm. did. Using the rubbing treatment apparatus manufactured by Iinuma Gauge Co., Ltd., the obtained liquid crystal alignment film A ′ was 0.40 mm in the amount of pushing the rubbing cloth (hair length 1.8 mm: rayon), and the stage moving speed was 60 mm / The substrate was rubbed under the conditions of 1000 rpm for a roller rotation speed of 1,000 rpm to obtain a retardation measurement substrate A.

Using a spectroscopic ellipsometer M-2000U (manufactured by JA Woollam Co. Inc.), the retardation (R) of the alignment film of the retardation measurement substrate A was determined. As the value of R is larger, the liquid crystal alignment film is stretched in the rubbing direction and has higher uniaxial orientation, and as a result, it can be said that black display is better. In the test method of the example of the present invention, the retardation is preferably 0.1 nm or more. The results are shown in Table 3.

  Further, after the retardation measurement substrate A was stored at 100 ° C. for 500 hours, the measurement was performed in the same manner to determine the stability over time. Stability over time (%) was calculated by the formula of (retardation value after storage for 500 hours) / (initial retardation value) × 100. It is preferable that there is little change with time. The results are shown in Table 3.

[Comparative Example 3]
A liquid crystal alignment film, a liquid crystal display element, and a retardation measurement substrate were prepared in the same manner as in Example 4 except that RPM1 was used instead of the maleimide polymer solution PM1, and evaluated in the same manner as in Example 4. The results are shown in Table 3.

  As can be seen from Table 3, the liquid crystal alignment film of the present invention is excellent in rubbing resistance, flow alignment resistance, and retardation stability over time.

[Reference Example 1]
<Measurement of IR (infrared absorption) spectrum>
The 6 wt% polymer solution PM2 obtained in Example 2 was applied to a glass substrate with a spinner to form a film. After the coating, the film was obtained after heating and drying at 80 ° C. for about 5 minutes. The IR spectrum of the obtained film was measured by the KBr tablet method. The measurement was performed using a FT-IR apparatus (JASCO FT-IR610) at a measurement temperature of 25 ° C. and a total of 100 times.

[Reference Example 2]
Using the MA-2-1-2 obtained in Production Example 1, the IR spectrum was measured by the KBr tablet method. The measurement was performed under the same conditions as in Reference Example 1. The IR spectra of Reference Example 1 and Reference Example 2 are shown in FIG.

As shown in FIG. 1, in PM2 (Reference Example 1) which is a polymer of the present invention, MA-2-1-2 (Reference Example 2) which is a monomer before polymerization has around 3,100 cm ^−1. The absorption due to the C—H stretching of the alkene disappears, while the absorption due to the C═O stretching of the imide group is observed in the vicinity of 1,710 cm ⁻¹ and 1,780 cm ⁻¹ . From this analysis result, the polymer of the present invention was obtained by polymerizing by the addition reaction of the amino group to the double bond of bismaleimide (Michael addition reaction) while retaining the imide ring during the reaction. It can be seen that it is.

Since the maleimide polymer is formed by the addition reaction of bismaleimide and diamine, it is possible to realize a structure that is difficult to form with a polyimide polymer derived from polyamic acid using tetracarboxylic dianhydride as a raw material. . Therefore, in functional materials, further improvement of functions and the emergence of new functions are expected, and further diversification of functional materials that can be realized only from polyimide polymers in the past is expected.

  In particular, maleimide polymer is different from polyimide, and when forming a molded product, firing at high temperature for imidization, strict control of firing conditions to obtain a desired imidization rate, or soluble polyimide A complicated process such as an imidization reaction in a solution for obtaining the above is unnecessary. For this reason, for example, by using a maleimide polymer instead of polyimide, shortening of the process, shortening of working time, improvement of ease of working, or improvement of quality stabilization, etc. are expected, and further improvements are expected. As a result, effects such as reduction in energy required for production or cost reduction are also expected.

Claims (61)

In a resin composition containing a maleimide polymer having a reaction product structure by Michael addition reaction of bismaleimide and diamine, and a solvent,
A resin composition having a plurality of rigid linear structures in which the maleimide polymer is intermittently connected to the main chain.   The resin composition according to claim 1, wherein the maleimide polymer has a weight average molecular weight of 3,000 to 500,000. The bismaleimide comprises a bismaleimide having a rigid linear structure;
The resin composition according to claim 1 or 2, wherein the bismaleimide having the rigid linear structure includes a bismaleimide represented by the following formula (MA).
(In formula (MA), X ¹³ independently represents a single bond or alkylene having 1 to 30 carbon atoms,
X ¹⁴ independently represents 1,4-phenylene, a condensed ring having 8 to 22 atoms constituting the ring, or 1,4-cyclohexylene,
X ¹⁵ independently represents a single bond or — (CH ₂ CH ₂ ) _ab2 —;
ab1 represents an integer of 0 to 4, and ab2 represents an integer of 0 to 4.
Provided that when ab1 is 0, X ¹⁴ represents a fused ring of the number of atoms constituting the ring 8 to 22.
-H on —CH═CH— of the maleimide group may be independently replaced by alkyl having 1 to 3 carbon atoms;
Is independently -NH - - -CH ₂ in the alkylene of X ^13, - NY ² -, or -Si (Y ²²⁾ ₂ - may be replaced by,
—CH ₂ CH ₂ — in the alkylene of X ¹³ may be independently replaced with —CH═CH— or —C≡C—;
—CH ₂ — that is not adjacent to the nitrogen atom of the maleimide group in the alkylene of X ¹³ may be independently replaced with —O—, —CO—, —S—, —SO—, or —SO ₂ —;
—CH ₂ CH ₂ — that is not adjacent to the nitrogen atom of the maleimide group in the alkylene of X ¹³ may be independently replaced by —N═N—,
Of _{^{X 15 - (CH 2 CH 2}} ) ab2 - -CH Medium ₂ - is independently -O -, - NH -, - CO -, - NY 2 -, - S -, - SO -, - SO _2- or -Si (Y ²² ) _2- may be substituted,
—CH ₂ CH ₂ — in — (CH ₂ CH ₂ ) _ab2 — in X ¹⁵ may be independently replaced with —CH═CH—, _—C≡C— , or —N═N—,
—H on X ¹³ alkylene or substituted alkylene, or X ¹⁵ — (CH ₂ CH ₂ ) _ab2 — or substituted — (CH ₂ CH ₂ ) _ab2 — is independently —F, —Cl , -Br, -C≡N, -OH, -COOH, -SO ₃ H, -PO ₃ H ₂ , an arbitrary -H having 1 to 20 carbon atoms optionally substituted with halogen, Or any -H may be independently replaced by an alkenyl having 2 to 20 carbon atoms which may be replaced by a halogen;
1,4-phenylene of X ¹⁴ , 1,4-cyclohexylene, and —H on the fused ring are each independently 1 carbon number in which arbitrary —H may be independently replaced by halogen. ˜3 alkyl, optional —H may be independently replaced by halogen, C 1-3 alkoxy, —F, —Cl, —Br, —C≡N, —OH, —COOH, — May be replaced by SO ₃ H, —PO ₃ H ₂ , or —N (Y ² ) ₂ ;
In the alkyl and alkoxy, —CH ₂ — may be independently replaced by —O—, —CO— or —S—,
In each group constituting (MA), Y ² independently represents —H, alkyl having 1 to 20 carbon atoms, or alkenyl having 2 to 20 carbon atoms, and Y ²² independently represents —H, carbon number 1 20 alkyl, alkenyl having 1 to 20 carbon atoms, or represents phenyl, -H on the phenyl are independently -F, -Cl, -Br, -C≡N, -OH, -COOH, -SO 3 H, —PO ₃ H ₂ , or alkyl having 1 to 30 carbon atoms may be substituted. ) The bismaleimide having the rigid linear structure is represented by the following formulas (MA-1-1-1), (MA-1-2-1), (MA-1-3-1), (MA-1-4-1). ), (MA-1-5-1), (MA-2-1-1), (MA-2-1-2), (MA-2-1-4), (MA-2-1-9) ), (MA-2-1-15), (MA-2-2-1), (MA-2-3-1), (MA-2-4-1), (MA-2-5-1) ), (MA-2-6-1), (MA-2-7-1), (MA-2-8-1), (MA-2-9-1), (MA-3-1-1) ), (MA-3-2-1), (MA-3-2-2), (MA-3-3-1), (MA-3-3-3), (MA-3-3-3-4) ), (MA-3-4-1), (MA-3-5-1), (MA-3-11-3) to (MA-3-11-14) , (MA-4-1-1), (MA-4-2-1), (MA-4-11-1) to (MA-4-11-9), and (MA-5-11-1). The resin composition according to claim 3, comprising at least one selected from the group of
  The bismaleimide having the rigid linear structure includes the formula (MA-2-1-2), (MA-2-1-4), or (MA-2-1-9). Resin composition.   The resin composition according to claim 5, wherein the bismaleimide is a bismaleimide represented by the formula (MA-2-1-2). The resin composition according to any one of claims 1 to 6, wherein the diamine includes an aliphatic diamine. Diamines are represented by the following formulas (II-1-1) to (II-1-14), (II-1-21) to (II-1-30), (IV-1-1) to (IV-1-). 4) One or more diamines selected from the group of (V-1-20) to (V-1-22) and (VI-1-40) are included. The resin composition according to item.
  The resin composition according to claim 8, wherein the aliphatic diamine comprises the formula (IV-1-1) or (II-1-22).   The resin composition according to any one of claims 1 to 9, wherein the diamine includes a diamine having a rigid linear structure. The resin composition according to claim 10, wherein the diamine having a rigid linear structure includes a diamine represented by the following formula (VII-13).
(In Formula (VII-13), X ¹¹ independently represents an alkylene having 1 to 12 carbon atoms,
Ring R independently represents a ring in which the sum of the number of carbon, nitrogen, oxygen, sulfur, and silicon constituting the skeleton is 3 to 30, a is independently an integer of 0 to 4, and b is independently And represents an integer from 0 to 12,
—CH ₂ — in the alkylene in X ¹¹ may be independently replaced with —O—, —NH—, —CO—, —CHY ² —, —C (Y ² ) ₂ —, or —NY ² —. , -CH ₂ CH ₂ in the alkylene - independently -CH = CH -, - C≡C-, or -N = may be replaced by N-,
-H on the alkylene or substituted alkylene may be independently substituted with alkyl having 1 to 20 carbons or alkenyl having 2 to 20 carbons;
The —CH ₂ — in the alkylene between the ring R and the amino group may be independently replaced by —NH—, —CHY ² —, —C (Y ² ) ₂ —, or —NY ² —. -CH ₂ CH ₂ in - may be replaced by -CH = CH- or -C≡C-, independently,
—CH ₂ — that is not adjacent to —NH _{2 in} alkylene may be independently replaced with —O— or —CO—;
-CH ₂ CH ₂ which is not adjacent to the -NH ₂ in the alkylene - may be replaced independently by -N = N-,
-H is independently -F on the alkylene or replaced alkylene, -Cl, -Br, -C≡N, -OH , -COOH, replaced by -SO ₃ H, or -PO ₃ H ₂ Often,
The —H of the amino group may be independently replaced with alkyl having 1 to 12 carbons, and —CH ₂ — in this alkyl is independently —NH—, —CHY ² —, —C (Y ² ) _2. -, or -NY ² - may be replaced by, -CH ₂ CH ₂ in the alkyl - may be replaced by -CH = CH- or -C≡C-, independently,
—CH ₂ — that is not adjacent to —NH _{2 in} alkyl may be independently replaced with —O— or —CO—;
—CH ₂ CH ₂ — that is not adjacent to —NH _{2 in} alkyl may be independently replaced by —N═N—,
-H is independently -F on the alkyl or replaced alkyl, -Cl, -Br, -C≡N, -OH , -COOH, replaced by -SO ₃ H, or -PO ₃ H ₂ Often,
In each group constituting the formula (VII-13), Y ² independently represents -H, alkyl having 1 to 20 carbons, or alkenyl having 2 to 20 carbons. However the -CHY ² - and -C (Y ^{₂₎ 2} - In, Y ² is not a -H. ) The resin composition according to claim 11, wherein the diamine having a rigid linear structure includes one or more diamines selected from the group of the following formulas (VII-13-1) to (VII-13-4).
  The resin composition as described in any one of Claims 10-12 in which the said diamine contains both the diamine which has a rigid linear structure, and another aliphatic diamine.   The other aliphatic diamines are represented by the formulas (II-1-1) to (II-1-14), (II-1-21) to (II-1-30), (IV- 1-1)-containing one or more diamines selected from the group of (IV-1-4), (V-1-20)-(V-1-22), and (VI-1-40) The resin composition according to claim 13.   The resin composition according to claim 14, wherein the other aliphatic diamine comprises the formula (IV-1-1) or (II-1-22).   The maleimide polymer is obtained by polymerizing a monomer mixture containing the bismaleimide and diamine in a solvent containing at least one selected from the group consisting of a solvent having a hydroxyl group and a protic amide solvent. The resin composition as described in any one of Claims 1-15 which exists.   The resin composition according to claim 16, wherein the solvent having a hydroxyl group is a solvent having an alcoholic hydroxyl group.   The solvent having an alcoholic hydroxyl group is methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, t-butyl alcohol, 1-pentanol, 1-hexanol, 2-ethylhexanol, benzyl alcohol. , (O-, m-, or p-) methylbenzyl alcohol, (o-, m-, or p-) methoxybenzyl alcohol, 1-phenylethyl alcohol, 2-phenylethyl alcohol, ethylene glycol, glycerol, 3- Methyl-3-methoxybutanol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono-n-butyl ether, diethylene glycol monoethyl ether, triethylene glycol monoalkyl ether Propylene glycol monobutyl ether, dipropylene glycol monomethyl ether, and 1) alcoholic hydroxyl group, and 2) high polarity alcohol having at least one group selected from the group consisting of amide, ester, and cyclic ether The resin composition according to claim 17, which is at least one selected from the group. The highly polar alcohol is methyl lactate, ethyl lactate, propyl lactate, butyl lactate, methyl 2-hydroxybutyrate, ethyl 2-hydroxybutyrate, methyl 2-hydroxyisobutyrate, ethyl 2-hydroxyisobutyrate, 2-hydroxy-3- Methyl butenoate, dimethyl malate, diethyl malate, dipropyl malate, dibutyl malate, glycerol diacetate, and one or more represented by the following formulas (1) to (21), wherein the protic amide solvent is The resin composition of Claim 18 which is one or more represented by following formula (22)-(26).
  A polymerization solvent for the maleimide polymer monomer is methyl lactate, ethyl lactate, propyl lactate, butyl lactate, methyl 2-hydroxybutyrate, ethyl 2-hydroxybutyrate, methyl 2-hydroxyisobutyrate, ethyl 2-hydroxyisobutyrate, The group consisting of methyl 2-hydroxy-3-butenoate, dimethyl malate, diethyl malate, dipropyl malate, dibutyl malate, glycerol diacetate, and a highly polar alcohol represented by the above formulas (1) to (21) The resin composition according to claim 19, comprising at least one selected from the group consisting of:   The resin composition according to claim 20, wherein a polymerization solvent for the monomer of the maleimide polymer contains a highly polar alcohol represented by the formula (3).   The resin composition according to any one of claims 1 to 21, wherein the solvent contains a solvent having a hydroxyl group or a protic amide solvent. A solvent having a hydroxyl group is methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, t-butyl alcohol, 1-pentanol, 1-hexanol, 2-ethylhexanol, benzyl alcohol, (o -, M-, or p-) methylbenzyl alcohol, (o-, m-, or p-) methoxybenzyl alcohol, 1-phenylethyl alcohol, 2-phenylethyl alcohol, ethylene glycol, glycerol, 3-methyl-3 -Methoxybutanol, ethylene glycol monoethyl ether, ethylene glycol mono-n-butyl ether, diethylene glycol monoalkyl ether, triethylene glycol monoalkyl ether, propylene glycol mono-n-butyl ether, dip Pyrene glycol monomethyl ether, methyl lactate, ethyl lactate, propyl lactate, butyl lactate, methyl 2-hydroxybutyrate, ethyl 2-hydroxybutyrate, methyl 2-hydroxyisobutyrate, ethyl 2-hydroxyisobutyrate, 2-hydroxy-3-butene At least one selected from the group consisting of methyl acid, dimethyl malate, diethyl malate, dipropyl malate, dibutyl malate, glycerol diacetate, and compounds represented by the following formulas (1) to (21) Yes,
The resin composition according to claim 22, wherein the protic amide solvent is at least one selected from the group consisting of compounds represented by the following formulas (22) to (26).
  The resin composition according to claim 22 or 23, wherein the solvent further comprises a polar solvent and a coatability improving solvent.   The polar solvent is at least one selected from the group consisting of N-methyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide, and N, N′-dimethylimidazolidinone. The resin composition according to claim 24. The coating property improving solvent is methyl lactate, ethyl lactate, propyl lactate, butyl lactate, methyl 2-hydroxybutyrate, ethyl 2-hydroxybutyrate, methyl 2-hydroxyisobutyrate, ethyl 2-hydroxyisobutyrate, 2-hydroxy- Methyl 3-butenoate, dimethyl malate, diethyl malate, dipropyl malate, dibutyl malate, glycerol diacetate, solvents represented by the following formulas (1) to (17), 3-methyl-3-methoxybutanol, Tetralin, isophorone, ethylene glycol monoalkyl ether, diethylene glycol monoalkyl ether, ethylene glycol monoalkyl or phenyl acetate, triethylene glycol monoalkyl ether, propylene glycol monoalkyl ether, dialkyl malonate, dipropylene Glycol monoalkyl ether, and a solvent selected from the group consisting of ester compounds, resin composition according to claim 24 or 25.
  27. The resin composition according to any one of claims 22 to 26, wherein a content of the solvent having a hydroxyl group or a protic amide solvent is 20% by weight or more based on the total amount of the solvent.   The resin composition according to any one of claims 1 to 27, wherein the maleimide polymer is produced by a method that does not include a step of solvent substitution after polymerization.   The resin composition according to any one of claims 1 to 28, which is a liquid crystal aligning agent for IPS, wherein the diamine does not include a diamine having a side chain structure.   The resin composition according to any one of claims 1 to 28, which is a liquid crystal aligning agent for TN, wherein the diamine further includes a diamine having a side chain structure.   The resin composition according to any one of claims 1 to 28, which is a VA liquid crystal aligning agent further including a diamine having a side chain structure.   The coating material containing the resin composition as described in any one of Claims 1-28.   The insulating material containing the resin composition as described in any one of Claims 1-28.   The adhesive agent containing the resin composition as described in any one of Claims 1-28.   The sealing material containing the resin composition as described in any one of Claims 1-28.   The printed wiring board material containing the resin composition as described in any one of Claims 1-28.   A molding material containing the resin composition according to any one of claims 1 to 28.   A gas separation material formed from the resin composition according to any one of claims 1 to 28.   A wire material formed from the resin composition according to any one of claims 1 to 28.   The liquid crystal aligning film formed from the resin composition as described in any one of Claims 29-31.   The liquid crystal display element which has a liquid crystal aligning film of Claim 40. In a maleimide polymer having a reaction product structure by Michael addition reaction between bismaleimide and diamine,
The maleimide polymer has a plurality of rigid linear structures intermittent to the main chain, and the monomer mixture containing the bismaleimide and diamine is selected from the group consisting of a solvent having an alcoholic hydroxyl group and a protic amide solvent. A maleimide polymer which is polymerized in a solvent containing any one or more selected.   43. The maleimide polymer according to claim 42, wherein the maleimide polymer has a weight average molecular weight of 3,000 to 500,000. The bismaleimide comprises a bismaleimide having a rigid linear structure;
44. The maleimide polymer according to claim 42 or 43, wherein the bismaleimide having a rigid linear structure includes a bismaleimide represented by the following formula (MA).
(In formula (MA), X ¹³ independently represents a single bond or alkylene having 1 to 30 carbon atoms,
X ¹⁴ independently represents 1,4-phenylene, a condensed ring having 8 to 22 atoms constituting the ring, or 1,4-cyclohexylene,
X ¹⁵ independently represents a single bond or — (CH ₂ CH ₂ ) _ab2 —;
ab1 represents an integer of 0 to 4, and ab2 represents an integer of 0 to 4.
Provided that when ab1 is 0, X ¹⁴ represents a fused ring of the number of atoms constituting the ring 8 to 22.
-H on —CH═CH— of the maleimide group may be independently replaced by alkyl having 1 to 3 carbon atoms;
Is independently -NH - - -CH ₂ in the alkylene of X ^13, - NY ² -, or -Si (Y ²²⁾ ₂ - may be replaced by,
—CH ₂ CH ₂ — in the alkylene of X ¹³ may be independently replaced with —CH═CH— or —C≡C—;
—CH ₂ — that is not adjacent to the nitrogen atom of the maleimide group in the alkylene of X ¹³ may be independently replaced with —O—, —CO—, —S—, —SO—, or —SO ₂ —;
—CH ₂ CH ₂ — that is not adjacent to the nitrogen atom of the maleimide group in the alkylene of X ¹³ may be independently replaced by —N═N—,
Of _{^{X 15 - (CH 2 CH 2}} ) ab2 - -CH Medium ₂ - is independently -O -, - NH -, - CO -, - NY 2 -, - S -, - SO -, - SO _2- or -Si (Y ²² ) _2- may be substituted,
—CH ₂ CH ₂ — in — (CH ₂ CH ₂ ) _ab2 — in X ¹⁵ may be independently replaced with —CH═CH—, _—C≡C— , or —N═N—,
—H on X ¹³ alkylene or substituted alkylene, or X ¹⁵ — (CH ₂ CH ₂ ) _ab2 — or substituted — (CH ₂ CH ₂ ) _ab2 — is independently —F, —Cl , -Br, -C≡N, -OH, -COOH, -SO ₃ H, -PO ₃ H ₂ , an arbitrary -H having 1 to 20 carbon atoms optionally substituted with halogen, Or any -H may be independently replaced by an alkenyl having 2 to 20 carbon atoms which may be replaced by a halogen;
1,4-phenylene of X ¹⁴ , 1,4-cyclohexylene, and —H on the fused ring are each independently 1 carbon number in which arbitrary —H may be independently replaced by halogen. ˜3 alkyl, optional —H may be independently replaced by halogen, C 1-3 alkoxy, —F, —Cl, —Br, —C≡N, —OH, —COOH, — May be replaced by SO ₃ H, —PO ₃ H ₂ , or —N (Y ² ) ₂ ;
In the alkyl and alkoxy, —CH ₂ — may be independently replaced by —O—, —CO— or —S—,
In each group constituting (MA), Y ² independently represents —H, alkyl having 1 to 20 carbon atoms, or alkenyl having 2 to 20 carbon atoms, and Y ²² independently represents —H, carbon number 1 20 alkyl, alkenyl having 1 to 20 carbon atoms, or represents phenyl, -H on the phenyl are independently -F, -Cl, -Br, -C≡N, -OH, -COOH, -SO 3 H, —PO ₃ H ₂ , or alkyl having 1 to 30 carbon atoms may be substituted. ) The bismaleimide having the rigid linear structure is represented by the following formulas (MA-1-1-1), (MA-1-2-1), (MA-1-3-1), (MA-1-4-1). ), (MA-1-5-1), (MA-2-1-1), (MA-2-1-2), (MA-2-1-4), (MA-2-1-9) ), (MA-2-1-15), (MA-2-2-1), (MA-2-3-1), (M
A-2-4-1), (MA-2-5-1), (MA-2-6-1), (MA-2-7-1), (MA-2-8-1), ( MA-2-9-1), (MA-3-1-1), (MA-3-2-1), (MA-3-2-2), (MA-3-3-1), ( MA-3-3-3), (MA-3-3-3), (MA-3-4-1), (MA-3-5-1), (MA-3-11-3) to ( MA-3-11-14), (MA-4-1-1), (MA-4-2-1), (MA-4-11-1) to (MA-4-11-9), and 45. The maleimide polymer according to claim 44, comprising one or more selected from the group of (MA-5-11-1).
  One or more bismaleimides having the rigid linear structure are selected from the group of the formulas (MA-2-1-2), (MA-2-1-4), and (MA-2-1-9) The maleimide polymer according to claim 45, comprising:   The maleimide polymer according to claim 46, wherein the bismaleimide is a bismaleimide represented by the formula (MA-2-1-2).   The maleimide polymer according to any one of claims 42 to 47, wherein the diamine comprises an aliphatic diamine. The aliphatic diamine is represented by the following formulas (II-1-1) to (II-1-14), (II-1-21) to (II-1-30), (IV-1-1) to (IV 49. The composition of claim 48, comprising one or more diamines selected from the group of -1-4), (V-1-20) to (V-1-22), and (VI-1-40). Maleimide polymer.
  The maleimide polymer according to claim 49, wherein the aliphatic diamine comprises the formula (IV-1-1) or (II-1-22).   The maleimide polymer according to any one of claims 42 to 50, wherein the diamine includes a diamine having a rigid linear structure. The maleimide polymer according to claim 51, wherein the diamine having a rigid linear structure includes a diamine represented by the following formula (VII-13).
(In Formula (VII-13), X ¹¹ independently represents an alkylene having 1 to 12 carbon atoms,
Ring R independently represents a ring in which the sum of the number of carbon, nitrogen, oxygen, sulfur, and silicon constituting the skeleton is 3 to 30, a is independently an integer of 0 to 4, and b is independently And represents an integer from 0 to 12,
—CH ₂ — in the alkylene in X ¹¹ may be independently replaced with —O—, —NH—, —CO—, —CHY ² —, —C (Y ² ) ₂ —, or —NY ² —. , -CH ₂ CH ₂ in the alkylene - independently -CH = CH -, - C≡C-, or -N = may be replaced by N-,
-H on the alkylene or substituted alkylene may be independently substituted with alkyl having 1 to 20 carbons or alkenyl having 2 to 20 carbons;
The —CH ₂ — in the alkylene between the ring R and the amino group may be independently replaced by —NH—, —CHY ² —, —C (Y ² ) ₂ —, or —NY ² —. -CH ₂ CH ₂ in - may be replaced by -CH = CH- or -C≡C-, independently,
—CH ₂ — that is not adjacent to —NH _{2 in} alkylene may be independently replaced with —O— or —CO—;
-CH ₂ CH ₂ which is not adjacent to the -NH ₂ in the alkylene - may be replaced independently by -N = N-,
-H is independently -F on the alkylene or replaced alkylene, -Cl, -Br, -C≡N, -OH , -COOH, replaced by -SO ₃ H, or -PO ₃ H ₂ Often,
The —H of the amino group may be independently replaced with alkyl having 1 to 12 carbons, and —CH ₂ — in this alkyl is independently —NH—, —CHY ² —, —C (Y ² ) _2. -, or -NY ² - may be replaced by, -CH ₂ CH ₂ in the alkyl - may be replaced by -CH = CH- or -C≡C-, independently,
—CH ₂ — that is not adjacent to —NH _{2 in} alkyl may be independently replaced with —O— or —CO—;
—CH ₂ CH ₂ — that is not adjacent to —NH _{2 in} alkyl may be independently replaced by —N═N—,
-H is independently -F on the alkyl or replaced alkyl, -Cl, -Br, -C≡N, -OH , -COOH, replaced by -SO ₃ H, or -PO ₃ H ₂ Often,
In each group constituting the formula (VII-13), Y ² independently represents -H, alkyl having 1 to 20 carbons, or alkenyl having 2 to 20 carbons. However the -CHY ² - and -C (Y ^{₂₎ 2} - In, Y ² is not a -H. ) 53. The maleimide polymer according to claim 52, wherein the diamine having a rigid linear structure includes one or more diamines selected from the group of the following formulas (VII-13-1) to (VII-13-4): .
  54. The maleimide polymer according to any one of claims 51 to 53, wherein the diamine includes both a diamine having a rigid linear structure and other aliphatic diamines. The other aliphatic diamines are represented by the following formulas (II-1-1) to (II-1-14), (II-1-21) to (II-1-30), (IV-1-1) to 55. comprising one or more diamines selected from the group of (IV-1-4), (V-1-20) to (V-1-22), and (VI-1-40). The maleimide polymer described.
  The maleimide polymer according to claim 55, wherein the other aliphatic diamine includes the formula (IV-1-1) or (II-1-22).   The maleimide polymer is methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, t-butyl alcohol, 1-pentanol, 1-hexanol, 2-ethylhexanol, benzyl alcohol, o-, m-, or p-) methylbenzyl alcohol, (o-, m-, or p-) methoxybenzyl alcohol, 1-phenylethyl alcohol, 2-phenylethyl alcohol, ethylene glycol, glycerol, 3-methyl- 3-methoxybutanol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono-n-butyl ether, diethylene glycol monoethyl ether, triethylene glycol monoalkyl ether, propylene Recall monobutyl ether, dipropylene glycol monomethyl ether, 1) alcoholic hydroxyl group, and 2) high polar alcohol having at least one group selected from the group consisting of amide, ester, and cyclic ether, and protic amide system 57. The maleimide polymer according to any one of claims 42 to 56, which is polymerized in a solvent containing any one or more selected from the group consisting of solvents. The highly polar alcohol is methyl lactate, ethyl lactate, propyl lactate, butyl lactate, methyl 2-hydroxybutyrate, ethyl 2-hydroxybutyrate, methyl 2-hydroxyisobutyrate, ethyl 2-hydroxyisobutyrate, 2-hydroxy-3- Methyl butenoate, dimethyl malate, diethyl malate, dipropyl malate, dibutyl malate, glycerol diacetate, and one or more represented by the following formulas (1) to (21), wherein the protic amide solvent is 58. The maleimide polymer according to claim 57, which is one or more represented by the following formulas (22) to (26).
  A polymerization solvent for the maleimide polymer monomer is methyl lactate, ethyl lactate, propyl lactate, butyl lactate, methyl 2-hydroxybutyrate, ethyl 2-hydroxybutyrate, methyl 2-hydroxyisobutyrate, ethyl 2-hydroxyisobutyrate, The group consisting of methyl 2-hydroxy-3-butenoate, dimethyl malate, diethyl malate, dipropyl malate, dibutyl malate, glycerol diacetate, and a highly polar alcohol represented by the above formulas (1) to (21) 59. The maleimide polymer according to claim 58, comprising at least one selected from the group consisting of:   60. The maleimide polymer according to claim 59, wherein a polymerization solvent for the monomer of the maleimide polymer contains a highly polar alcohol represented by the formula (3). The following formulas (MA-1-1) to (MA-1-3), (MA-2-2) to (MA-2-6), (MA-3-1), (MA-3-2), (MA-2-1-19) to (MA-2-1-27), (MA-2-7-2), (MA-2-7-3), (MA-1-4-2), And (MA
A bismaleimide represented by any one of -1-5-1).
(In the formula (MA-1-1), R ¹¹¹ represents —H, —OH, or —F, R ¹¹² independently represents —OH, —F, or —Cl, and a1 is 0 to 5. Represents an integer, provided that when R ¹¹¹ represents -H, a1 represents an integer of 1 to 5.)
(In formula (MA-1-2), R ¹²¹ independently represents —CH ₃ , —OH, —OCH ₃ , —SCH ₃ , or —F, and a 2 represents an integer of 1 to 5.)
(In formula (MA-1-3), R ¹³¹ and R ¹³² each represent —H, —CH ₃ , or —OH.)
(In Formula (MA-2-2), R ²²¹ independently represents -CH ₃ , -CF ₃ , -OH, -F, -Cl, or -OCH ₃ , and a4 is independently 0-4. Represents an integer, where the sum of a4 is 1 or more.)
(In formula (MA-2-3), R ²³¹ independently represents —CF ₃ , —OH, —F, or —OCH ₃ , and a5 independently represents an integer of 0 to 4, provided that a5 The sum is 1 or more.)
(In the formula (MA-2-4), R ²⁴¹ is independently —CH ₃ , —CF ₃ , —OH, —Cl, —Br.
, —OCH ₃ , or —OCH ₂ CH ₃ , R ²⁴² represents —H or linear alkyl having 1 to 3 carbon atoms, and a6 independently represents an integer of 0 to 4. However when R ²⁴² represents a straight-chain alkyl of 1 to 3 carbon atoms, R ²⁴¹ is it may represent independently -H, sum of a6 is 1 or more. )
(In the formula (MA-2-5), R ²⁵¹ independently represents —CH ₃ , —OH, —Cl, or —OCH ₃ , and a7 independently represents an integer of 0 to 4, provided that a7 The sum is 1 or more.)
(In the formula (MA-2-6), R ²⁶¹ independently represents -CH ₃ , -CF ₃ , or -F, and a8 independently represents an integer of 0 to 10.)
(In formula (MA-3-1), R ³¹¹ independently represents -CH ₃ , -CF ₃ , -OH, -F, -Cl, or -OCH ₃ , and a9 is independently 0-4. Represents an integer, provided that the sum of a9 is 1 or more.)
(In Formula (MA-3-2), R ³²¹ independently represents —CH ₃ or —CH (CH ₃ ) ₂ , R ³²² independently represents —CH ₃ or —CH ₂ CH ₃ , and a10 Independently represents an integer of 0 to 4.)