Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
  • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
  • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
  • C08G73/1042—Copolyimides derived from at least two different tetracarboxylic compounds or two different diamino compounds
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
  • C09K19/00—Liquid crystal materials
  • C09K19/52—Liquid crystal materials characterised by components which are not liquid crystals, e.g. additives with special physical aspect: solvents, solid particles
  • C09K19/54—Additives having no specific mesophase characterised by their chemical composition
  • C09K19/56—Aligning agents

Definitions

• the present invention relates to a liquid crystal alignment treatment agent used for producing a liquid crystal alignment film and a liquid crystal display element using the same.
• liquid crystal alignment film of a liquid crystal display element a so-called polyimide liquid crystal alignment film obtained by applying and baking a liquid crystal alignment treatment agent mainly composed of a polyimide precursor such as polyamic acid or a soluble polyimide solution is mainly used. ing.
• the liquid crystal alignment film is used for the purpose of controlling the alignment state of the liquid crystal.
• the liquid crystal alignment film used has a higher voltage holding ratio and a DC voltage is applied from the viewpoint of suppressing the reduction in contrast of the liquid crystal display elements and reducing the afterimage phenomenon. The characteristic that the accumulated charge at the time is small or the relaxation of the charge accumulated by the DC voltage is fast becomes important.
• a liquid crystal alignment treatment agent containing a tertiary amine having a specific structure in addition to polyamic acid or an imide group-containing polyamic acid is assumed to have a short time until an afterimage generated by a DC voltage disappears.
• Known ones for example, see Patent Document 1 and those using a liquid crystal alignment treatment agent containing a soluble polyimide using a specific diamine having a pyridine skeleton as a raw material are known.
• one carboxylic acid group is contained in the molecule, assuming that the voltage holding ratio is high and the time until the afterimage generated by direct current voltage disappears is short.
• liquid crystal aligning agent containing a very small amount of a compound selected from a compound, a compound containing one carboxylic anhydride group in the molecule, and a compound containing one tertiary amino group in the molecule (For example, refer to Patent Document 3).
• the present invention has been made in view of the above circumstances, and in addition to the initial characteristics, even when exposed to light irradiation for a long time, it suppresses a decrease in voltage holding ratio and further accumulates charges accumulated by a DC voltage. It is an object of the present invention to provide a liquid crystal alignment treatment agent capable of forming a liquid crystal alignment film that can be quickly relaxed, and to provide a highly reliable liquid crystal display element that can withstand long-term use in harsh usage environments.
• the present inventors have found that a polyimide precursor having a specific structure and a liquid crystal alignment treatment agent containing a polyimide obtained by dehydrating and ring-closing the polyimide precursor are extremely suitable for achieving the above object.
• the present invention has been found to be effective. That is, the present invention has the following gist.
• a diamine component including a diamine compound represented by the following formula [1] (also referred to as a specific diamine compound) and a diamine compound represented by the following formula [2] (also referred to as a specific side chain diamine compound);
• X 1 is —O—, —CO—, —NH—, —N (CH 3 ) —, —CONH—, —NHCO—, —CH 2 O—, —OCO—, —CON (CH 3 ) — Or N (CH 3 ) CO—
• X 2 is an alkyl group having 1 to 5 carbon atoms or a non-aromatic heterocyclic ring containing a nitrogen atom
• X 3 is an alkyl group having 1 to 5 carbon atoms (It is a 5-membered or 6-membered aromatic heterocycle containing two optionally substituted nitrogen atoms.)
• (Y 1 is a single bond, — (CH 2 ) a — (a is an integer of 1 to 15), —O—, —CH 2 O—, —COO— or OCO—
• Y 2 is A single bond or (CH 2 ) b — (b is an integer of 1 to 15)
• Y 3 is a single
• the atom is substituted with an alkyl group having 1 to 3 carbon atoms, an alkoxyl group having 1 to 3 carbon atoms, a fluorine-containing alkyl group having 1 to 3 carbon atoms, a fluorine-containing alkoxyl group having 1 to 3 carbon atoms, or a fluorine atom.
• a divalent organic group selected from organic groups having 12 to 25 carbon atoms having a steroid skeleton.
• a group, Y 5 is a benzene ring, any hydrogen atom on the divalent cyclic group (these cyclic group selected from the group consisting of hexane ring and the heterocyclic cycloheteroalkyl represents an alkyl group having 1 to 3 carbon atoms N may be substituted with an alkoxyl group having 1 to 3 carbon atoms, a fluorine-containing alkyl group having 1 to 3 carbon atoms, a fluorine-containing alkoxyl group having 1 to 3 carbon atoms, or a fluorine atom).
• Y 6 is an alkyl group having 1 to 18 carbon atoms, a fluorine-containing alkyl group having 1 to 18 carbon atoms, an alkoxyl group having 1 to 18 carbon atoms, or a fluorine-containing alkoxyl group having 1 to 18 carbon atoms.
• m is an integer of 1 to 4.
• X 1 is —O—, —CO—, —NH—, —CONH—, —NHCO—, —CON (CH 3 ) — or CH 2 O— ) Liquid crystal aligning agent.
• X 2 is a liquid crystal alignment treating agent according to (1) or (2) a piperazine ring.
• X 3 is an imidazole ring, a pyrazine ring or a pyrimidine ring.
• the polymer is a polyamic acid obtained by reacting a diamine component and a tetracarboxylic dianhydride component and at least one heavy selected from the group consisting of polyimides obtained by dehydrating and ring-closing the polyamic acid.
• a liquid crystal display device having the liquid crystal alignment film according to (11).
• a liquid crystal composition having a liquid crystal layer between a pair of substrates provided with electrodes and including a polymerizable compound that is polymerized by at least one of active energy rays and heat is disposed between the pair of substrates.
• a liquid crystal display device comprising the liquid crystal alignment film according to (13).
• a liquid crystal layer is provided between a pair of substrates provided with the liquid crystal alignment film and the electrode according to (11) or (13), and active energy rays and heat are interposed between the pair of substrates.
• a liquid crystal alignment film having a liquid crystal layer between a pair of substrates provided with electrodes and including a polymerizable group that is polymerized by at least one of active energy rays and heat is disposed between the pair of substrates.
• a liquid crystal display device comprising the liquid crystal alignment film according to (16).
• the liquid crystal layer is provided between a pair of substrates provided with electrodes, and the polymerizable substrate is polymerized by at least one of active energy rays and heat between the pair of substrates.
• liquid crystal aligning agent of the present invention in addition to the initial characteristics, even when exposed to light irradiation for a long time, the decrease in the voltage holding ratio is suppressed, and further, the charge accumulated by the DC voltage is quickly relaxed. A liquid crystal alignment film can be obtained. Furthermore, a highly reliable liquid crystal display element that can withstand long-term use in a severe use environment can be provided.
• X 1 represents —O—, —CO—, —NH—, —N (CH 3 ) —, —CONH—, —NHCO—, —CH 2 O—, —OCO—, —CON. (CH 3 ) — or N (CH 3 ) CO—.
• —O—, —COO—, —NH—, —CONH—, —NHCO—, —CON (CH 3 ) —, —CH 2 O— or OCO— is preferable because a diamine compound can be easily synthesized.
• Particularly preferred is —O—, —CO—, —NH—, —CONH—, —NHCO—, —CON (CH 3 ) — or CH 2 O—.
• X 2 is a non-aromatic heterocyclic ring containing an alkyl group having 1 to 5 carbon atoms or a nitrogen atom.
• the alkyl group may be linear or branched.
• the alkyl group preferably has 1 to 3 carbon atoms.
• Examples of the case where X 2 is a non-aromatic heterocyclic ring containing a nitrogen atom include a pyrrolidine ring, piperidine ring, pyrazolidine ring, quinuclidine ring or imidazolidine ring.
• a non-aromatic heterocyclic ring having a 5-membered ring or a 6-membered ring is preferable because good alignment can be obtained when a liquid crystal alignment film is used.
• the non-aromatic heterocycle contains two nitrogen atoms
• ionic impurities in the liquid crystal are adsorbed at the liquid crystal alignment film interface, and the liquid crystal display device has good electrical characteristics. It is desirable to keep.
• a piperazine ring is particularly preferable as the non-aromatic heterocyclic ring containing a nitrogen atom.
• X 2 is bonded to the nitrogen atom in X 3 or the carbon atom adjacent to the nitrogen atom, the residual charge accumulated by the DC voltage is quickly relaxed when the liquid crystal display element is formed. It is preferable because of its excellent effect.
• X 3 is a 5-membered or 6-membered aromatic heterocyclic ring containing two nitrogen atoms which may be substituted with an alkyl group having 1 to 5 carbon atoms.
• the 5-membered or 6-membered aromatic heterocycle containing two nitrogen atoms include an imidazole ring, a pyrazole ring, a pyrazine ring, a pyrimidine ring, and a pyridazine ring. Of these, an imidazole ring, a pyrazine ring or a pyrimidine ring is preferable.
• n is an integer of 1 to 4. Among these, an integer of 1 or 2 is preferable.
• Preferred combinations of X 1 , X 2 , X 3 and n in the formula [1] are as shown in Tables 1 to 14.
• more preferable combinations are 1-1 to 1-6, 1-19 to 1-24, 1-43 to 1- 48, 1-61 to 1-66, 1-85 to 1-90, 1-103 to 1-108, 1-127 to 1-132, 1-145 to 1-150, 1-169 to 1-174, 1-187 to 1-192, 1-211 to 1-216, 1-229 to 1-234, 1-253 to 1-258, or 1-276.
• Particularly preferred combinations are 1-1, 1-3, 1-5, 1-19, 1-21, 1-23, 1-43, 1-45, 1-47, 1-61, 1-63, 1 -65, 1-85, 1-87, 1-89, 1-103, 1-105, 1-107, 1-127, 1-129, 1-131, 1-145, 1-147, 1-149 1-169, 1-171, 1-173, 1-187, 1-189, 1-191, 1-211, 1-213, 1-215, 1-229, 1-231, 1-233, 1 -253, 1-255, 1-257, 1-271, 273 or 1-275.
• the method for producing the specific diamine compound of the present invention is not particularly limited, but preferred methods include the following methods.
• the specific diamine compound of the present invention can be obtained by synthesizing a dinitro compound represented by the following formula [1a], and further reducing the nitro group of the dinitro compound and converting it to an amino group.
• the method for reducing the dinitro compound is not particularly limited, and usually palladium-carbon, platinum oxide, Raney nickel, platinum black, rhodium-alumina, platinum sulfide carbon, etc.
• the dinitro compound represented by the formula [1a] can be obtained by a method in which —X 2 —X 3 is bonded to dinitrobenzene via X 1 .
• X 1 is an —O— or CH 2 O— bond
• a corresponding dinitro group-containing halogen derivative is reacted with a hydroxyl group derivative containing X 2 and X 3 in the presence of an alkali, or a dinitro group-containing hydroxyl group
• Examples thereof include a method in which a derivative is reacted with a halogen-substituted derivative containing X 2 and X 3 in the presence of an alkali.
• halogen derivative containing dinitro group and the hydroxyl group derivative containing dinitro group include 3,5-dinitrochlorobenzene, 2,4-dinitrochlorobenzene, 2,4-dinitrofluorobenzene, 3,5-dinitrobenzoic acid chloride, 3,5-dinitrobenzoic acid, 2,4-dinitrobenzoic acid chloride, 2,4-dinitrobenzoic acid, 3,5-dinitrobenzyl chloride, 2,4-dinitrobenzyl chloride, 3,5-dinitrobenzyl alcohol, 2 , 4-dinitrobenzyl alcohol, 2,4-dinitroaniline, 3,5-dinitroaniline, 2,6-dinitroaniline, 2,4-dinitrophenol, 2,5-dinitrophenol, 2,6-dinitrophenol, , 4-dinitrophenylacetic acid. In consideration of availability of raw materials and reaction, one or more kinds can be selected and used.
• the specific side chain diamine compound of the present invention is a diamine compound represented by the following formula [2].
• Y 1 is a single bond, - (CH 2) a - (a is an integer of 1 ⁇ 15), - O - , - CH 2 O -, - COO- or OCO- .
• a single bond, — (CH 2 ) a — (a is an integer of 1 to 15), —O—, —CH 2 O— or COO— is preferable because a side chain structure is easily synthesized.
• Y 2 is a single bond or (CH 2 ) b — (b is an integer of 1 to 15).
• a single bond or (CH 2 ) b — (b is an integer of 1 to 10) is preferable.
• Y 3 is a single bond, — (CH 2 ) c — (c is an integer of 1 to 15), —O—, —CH 2 O—, —COO— or OCO—. .
• a single bond, — (CH 2 ) c — (c is an integer of 1 to 15), —O—, —CH 2 O—, —COO— or OCO— is preferable because they are easily synthesized. More preferably, they are a single bond, — (CH 2 ) c — (c is an integer of 1 to 10), —O—, —CH 2 O—, —COO— or OCO—.
• Y 4 is a divalent cyclic group selected from the group consisting of a benzene ring, a cyclohexane ring, and a heterocyclic ring, and any hydrogen atom on these cyclic groups has 1 carbon atom. It may be substituted with an alkyl group having 3 to 3, an alkoxyl group having 1 to 3 carbon atoms, a fluorine-containing alkyl group having 1 to 3 carbon atoms, a fluorine-containing alkoxyl group having 1 to 3 carbon atoms, or a fluorine atom. Y 4 is a divalent organic group having 12 to 25 carbon atoms having a steroid skeleton.
• Y 4 is preferably a C 12-25 organic group having a benzene ring, a cyclohexyl ring or a steroid skeleton.
• Y 5 is a divalent cyclic group selected from the group consisting of a benzene ring, a cyclohexyl ring and a heterocyclic ring, and any hydrogen atom on these cyclic groups has 1 carbon atom.
• alkyl group having 3 to 3 an alkoxyl group having 1 to 3 carbon atoms, a fluorine-containing alkyl group having 1 to 3 carbon atoms, a fluorine-containing alkoxyl group having 1 to 3 carbon atoms, or a fluorine atom.
• n is an integer of 0 to 4. Preferably, it is an integer of 0-2.
• Y 6 represents an alkyl group having 1 to 18 carbon atoms, a fluorine-containing alkyl group having 1 to 18 carbon atoms, an alkoxyl group having 1 to 18 carbon atoms, or a fluorine-containing alkoxyl group having 1 to 18 carbon atoms. is there. Of these, an alkyl group having 1 to 18 carbon atoms, a fluorine-containing alkyl group having 1 to 10 carbon atoms, an alkoxyl group having 1 to 18 carbon atoms, or a fluorine-containing alkoxyl group having 1 to 10 carbon atoms is preferable.
• m is an integer of 1 to 4.
• Y 1 , Y 2 , Y 3 , Y 4 , Y 5 , Y 6 , n and m in the formula [2] are as shown in Tables 15 to 44.
• more preferable combinations are 2-25 to 2-96, 2 to 145 to 2-168, 2-217 to 2-240, 2-268 to 2-315, 2-364 to 2-387, 2-436 to 2-483, 2-604 to 2-628, etc., and particularly preferred combinations Are 2-49 to 2-96, 2-145 to 2-168, 2-217 to 2-240, 2-604 to 2-612, and the like. More specifically, it is a diamine compound having a structure represented by the following formulas [2-1] to [2-31].
• R 1 represents —O—, —OCH 2 —, —CH 2 O—, —COOCH 2 — or CH 2 OCO—
• R 2 represents an alkyl group having 1 to 22 carbon atoms, an alkoxyl group, fluorine-containing An alkyl group or a fluorine-containing alkoxyl group.
• R 3 represents —COO—, —OCO—, —COOCH 2 —, —CH 2 OCO—, —CH 2 O—, —OCH 2 — or CH 2 —
• R 4 represents 1 to 22 carbon atoms.
• R 5 represents —COO—, —OCO—, —COOCH 2 —, —CH 2 OCO—, —CH 2 O—, —OCH 2 —, —CH 2 — or O—
• R 6 represents fluorine Group, cyano group, trifluoromethane group, nitro group, azo group, formyl group, acetyl group, acetoxy group or hydroxyl group.
• R 7 is an alkyl group having 3 to 12 carbon atoms, and the cis-trans isomerism of 1,4-cyclohexylene is a trans isomer.
• R 8 is an alkyl group having 3 to 12 carbon atoms, and the cis-trans isomerism of 1,4-cyclohexylene is a trans isomer.
• a 4 is an alkyl group having 3 to 20 carbon atoms which may be substituted with a fluorine atom, A 3 is a 1,4-cyclohexylene group or a 1,4-phenylene group, and A 2 is , An oxygen atom or COO- * (where a bond with “*” is bonded to A 3 ), and A 1 is an oxygen atom or COO— * (where a bond with “*” is (CH 2 ) a 2 )).
• a 1 is an integer of 0 or 1
• a 2 is an integer of 2 to 10
• a 3 is an integer of 0 or 1.
• diamine compounds having particularly preferred structures are represented by the formulas [2-1] to [2-6], the formulas [2-9] to the formulas [2-31]. 13], Formula [2-16], Formula [2-19], Formula [2-23], Formula [2-25], Formula [2-29], and the like.
• ⁇ Other diamine compounds> In this invention, unless the effect of this invention is impaired, other diamine compounds other than a specific diamine compound and a specific side chain type diamine compound can be used together as a diamine component. Specific examples are given below. p-phenylenediamine, 2,3,5,6-tetramethyl-p-phenylenediamine, 2,5-dimethyl-p-phenylenediamine, m-phenylenediamine, 2,4-dimethyl-m-phenylenediamine, 2, 5-diaminotoluene, 2,6-diaminotoluene, 2,5-diaminophenol, 2,4-diaminophenol, 3,5-diaminophenol, 3,5-diaminobenzyl alcohol, 2,4-diaminobenzyl alcohol, 4 , 6-diaminoresorcinol, 4,4′-diaminobiphenyl, 3,3′-dimethyl-4,4′-diamin
• diamine compound which has an alkyl group or a fluorine-containing alkyl group in a diamine side chain
• diamine compounds represented by the following formulas [DA1] to [DA12] can be exemplified.
• a 5 is an alkyl group having 1 to 22 carbon atoms or a fluorine-containing alkyl group.
• a 6 represents —COO—, —OCO—, —CONH—, —NHCO—, —CH 2 —, —O—, —CO— or NH—
• a 7 represents an alkyl having 1 to 22 carbon atoms. Group or fluorine-containing alkyl group.
• diamine compounds represented by the following formulas [DA13] to [DA20] can be used as long as the effects of the present invention are not impaired.
• a diamine compound having a carboxyl group in the molecule represented by the following formulas [DA21] to [DA25] can be used as long as the effects of the present invention are not impaired.
• M 1 is an integer of 1 to 4
• a 8 is a single bond, —CH 2 —, —C 2 H 4 —, —C (CH 3 ) 2 —, —CF 2 —, —C (CF 3 ) —, —O—, —CO—, —NH—, —N (CH 3 ) —, —CONH—, —NHCO—, —CH 2 O—, —OCH 2 —, —COO—, —OCO— , -CON (CH 3 )-or N (CH 3 ) CO-, m 2 and m 3 are each an integer of 0 to 4, and m 2 + m 3 is an integer of 1 to 4.
• m 4 and m 5 are each an integer of 1 to 5
• a 9 is a linear or branched alkyl group having 1 to 5 carbon atoms
• m 6 is an integer of 1 to 5.
• a 10 is Single bond, —CH 2 —, —C 2 H 4 —, —C (CH 3 ) 2 —, —CF 2 —, —C (CF 3 ) —, —O—, —CO—, —NH—, — N (C 3) -, - CONH -, - NHCO -, - CH 2 O -, - OCH 2 -, - COO -, - OCO -, - CON (CH 3) - or N (CH 3) a CO-, m 7 is an integer of 1 to 4.)
• the said other diamine compound can also be used 1 type or in mixture of 2 or more types according to characteristics, such as a liquid crystal aligning property at the time of setting it as a liquid crystal aligning
• tetracarboxylic dianhydride component In order to obtain the specific polymer of the present invention, it is preferable to use a tetracarboxylic dianhydride (also referred to as a specific tetracarboxylic dianhydride) represented by the following formula [3] as a part of the raw material.
• Z 1 is a tetravalent organic group having 4 to 13 carbon atoms and contains a non-aromatic cyclic hydrocarbon group having 4 to 10 carbon atoms. Specifically, it is a group having a structure represented by the following formulas [3a] to [3j].
• Z 2 to Z 5 are groups selected from a hydrogen atom, a methyl group, a chlorine atom or a benzene ring, and each may be the same or different.
• 6 and Z 7 are a hydrogen atom or a methyl group, and may be the same or different.
• a particularly preferred group of Z 1 is represented by the formula [3a], the formula [3c], the formula [3d], the formula [3e], the formula [3f] because of polymerization reactivity and ease of synthesis. Or it is Formula [3g].
• tetracarboxylic dianhydrides other tetracarboxylic dianhydrides other than the specific tetracarboxylic dianhydride (also referred to as other tetracarboxylic dianhydrides) can be used as long as the effects of the present invention are not impaired.
• examples of other tetracarboxylic dianhydrides include tetracarboxylic dianhydrides of the following tetracarboxylic acids.
• the specific polymer of the present invention is at least one polymer selected from the group consisting of a polyimide precursor and polyimide, and the polyimide precursor has a structure represented by the following formula [A].
• R 9 is a tetravalent organic group
• R 10 is a divalent organic group
• a 11 and A 12 are a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, and each is the same. Or n may be different, and n represents a positive integer.
• the specific polymer of the present invention is relatively easily obtained by using a diamine component represented by the following formula [B] and a tetracarboxylic dianhydride component represented by the following formula [C] as raw materials.
• a polyamic acid having a structural formula of a repeating unit represented by the following formula [D] or a polyimide obtained by imidizing the polyamic acid is preferable.
• R 9 and R 10 are synonymous with those defined in Formula [A].
• R 9 , R 10 and n have the same meaning as defined in formula [A].
• R 9 and R 10 may be one type each, or may be a combination of different types using different R 9 and R 10 as repeating units.
• the method for synthesizing the specific polymer is not particularly limited. Usually, it is obtained by reacting a diamine component with a tetracarboxylic dianhydride component. Generally, at least one tetracarboxylic acid component selected from the group consisting of tetracarboxylic acids and derivatives thereof is reacted with a diamine component consisting of one or more diamine compounds to obtain a polyamic acid.
• a method of converting the carboxyl group of the polyamic acid into an ester is used.
• the method of imidating the said polyamic acid or polyamic-acid alkylester to make a polyimide is used.
• the liquid crystal alignment film obtained using the specific polymer of the present invention increases the content ratio of the specific diamine compound in the diamine component, even after being exposed to backlight light for a long time in addition to the initial characteristics.
• the relaxation of the electric charge accumulated by the voltage holding ratio and the DC voltage is fast.
• the pretilt angle of a liquid crystal can be enlarged, so that the content rate of the specific side chain type diamine compound in a diamine component increases.
• the content of the specific side chain diamine compound in the diamine component is preferably 0.01 to 99 mol with respect to 1 mol of the specific diamine compound.
• tetracarboxylic dianhydride for the tetracarboxylic dianhydride component.
• 1 mol% or more of a tetracarboxylic dianhydride component is a specific tetracarboxylic dianhydride, More preferably, it is 5 mol% or more, More preferably, it is 10 mol% or more.
• 100 mol% of the tetracarboxylic dianhydride component may be a specific tetracarboxylic dianhydride.
• Reaction of a diamine component and a tetracarboxylic dianhydride component is normally performed in an organic solvent.
• the organic solvent used at that time is not particularly limited as long as the produced polyimide precursor is dissolved. Specific examples are given below.
• the solution in which the diamine component is dispersed or dissolved in the organic solvent is stirred and the tetracarboxylic dianhydride component is used as it is or in an organic solvent.
• a method of adding by dispersing or dissolving in a solvent, a method of adding a diamine component to a solution in which tetracarboxylic dianhydride is dispersed or dissolved in an organic solvent, and a tetracarboxylic dianhydride component and a diamine component may be used alternately, and any of these methods may be used.
• the polymerization temperature can be selected from -20 to 150 ° C., but is preferably in the range of ⁇ 5 to 100 ° C.
• the reaction can be carried out at any concentration, but if the concentration is too low, it will be difficult to obtain a specific polymer having a high molecular weight, and if the concentration is too high, the viscosity of the reaction solution will become too high and uniform stirring will occur. It becomes difficult. Therefore, it is preferably 1 to 50% by mass, more preferably 5 to 30% by mass.
• the initial stage of the reaction is carried out at a high concentration, and then an organic solvent can be added.
• the ratio of the total number of moles of the diamine component to the total number of moles of the tetracarboxylic dianhydride component is preferably 0.8 to 1.2. Similar to a normal polycondensation reaction, the molecular weight of the polyimide precursor produced increases as the molar ratio approaches 1.0.
• the polyimide of the present invention is a polyimide obtained by dehydrating and ring-closing the above polyimide precursor, and is useful as a polymer for obtaining a liquid crystal alignment film.
• the dehydration cyclization rate (imidation rate) of the amic acid group is not necessarily 100%, and can be arbitrarily adjusted according to the application and purpose.
• Examples of the method for imidizing the polyimide precursor include thermal imidization in which the polyimide precursor solution is heated as it is or catalyst imidization in which a catalyst is added to the polyimide precursor solution.
• the temperature at which the polyimide precursor is thermally imidized in the solution is 100 to 400 ° C., preferably 120 to 250 ° C., and it is preferable to carry out while removing water generated by the imidation reaction from the system.
• the catalytic imidation of the polyimide precursor can be carried out by adding a basic catalyst and an acid anhydride to the polyimide precursor solution and stirring at -20 to 250 ° C, preferably 0 to 180 ° C.
• the amount of the basic catalyst is 0.5 to 30 mol times, preferably 2 to 20 mol times of the amic acid group, and the amount of the acid anhydride is 1 to 50 mol times, preferably 3 to 30 mol of the amido acid group. Is double.
• the basic catalyst include pyridine, triethylamine, trimethylamine, tributylamine, trioctylamine and the like. Among them, pyridine is preferable because it has an appropriate basicity for proceeding with the reaction.
• the acid anhydride include acetic anhydride, trimellitic anhydride, pyromellitic anhydride, and the like. Among them, use of acetic anhydride is preferable because purification after completion of the reaction is facilitated.
• the imidization rate by catalytic imidation can be controlled by adjusting the amount of catalyst, reaction temperature, and reaction time.
• the reaction solution may be poured into a solvent and precipitated.
• the solvent used for precipitation include methanol, acetone, hexane, butyl cellosolve, heptane, methyl ethyl ketone, methyl isobutyl ketone, ethanol, toluene, benzene, and water.
• the polymer precipitated in the solvent can be collected by filtration, and then dried by normal temperature or reduced pressure at room temperature or by heating.
• impurities in the polymer can be reduced.
• the solvent at this time include alcohols, ketones, hydrocarbons and the like, and it is preferable to use three or more kinds of solvents selected from these because purification efficiency is further improved.
• the molecular weight of the specific polymer of the present invention was measured by a GPC (Gel Permeation Chromatography) method in consideration of the strength of the polymer film obtained therefrom, workability at the time of forming the polymer film, and uniformity of the polymer film.
• the weight average molecular weight is preferably 5,000 to 1,000,000, and more preferably 10,000 to 150,000.
• the liquid-crystal aligning agent of this invention is a coating liquid for forming a liquid crystal aligning film, and is a coating liquid containing a specific polymer and an organic solvent.
• the polymer component in the liquid crystal aligning agent of the present invention may all be a specific polymer used in the present invention, and other polymers may be mixed with the specific polymer of the present invention. . In that case, the content of the other polymer with respect to the specific polymer is 0.5 to 15% by mass, preferably 1 to 10% by mass.
• a polyimide precursor obtained from a diamine component not containing a specific diamine compound and a specific side chain diamine compound and a tetracarboxylic dianhydride component not containing a specific tetracarboxylic dianhydride or a polyimide obtained from the polyimide precursor.
• a polyimide precursor and a polymer other than polyimide specifically, an acrylic polymer, a methacrylic polymer, polystyrene, or polyamide are also included.
• the organic solvent in the liquid crystal aligning agent of the present invention preferably has an organic solvent content of 70 to 99% by mass from the viewpoint of forming a uniform polymer film by coating. This content can be appropriately changed depending on the film thickness of the target liquid crystal alignment film.
• the organic solvent in that case will not be specifically limited if it is an organic solvent in which the specific polymer mentioned above is dissolved.
• the liquid crystal aligning agent of the present invention is at least one selected from the group consisting of a crosslinkable compound having an epoxy group, an isocyanate group, an oxetane group or a cyclocarbonate group, a hydroxyl group or an alkoxyl group, unless the effects of the present invention are impaired.
• a crosslinkable compound having a substituent, a crosslinkable compound having a polymerizable unsaturated bond, and the like can also be contained.
• crosslinkable compound having an epoxy group or an isocyanate group examples include bisphenolacetone glycidyl ether, phenol novolac epoxy resin, cresol novolac epoxy resin, triglycidyl isocyanurate, tetraglycidylaminodiphenylene, tetraglycidyl-m-xylenediamine, tetra Glycidyl-1,3-bis (aminoethyl) cyclohexane, tetraphenyl glycidyl ether ethane, triphenyl glycidyl ether ethane, bisphenol hexafluoroacetodiglycidyl ether, 1,3-bis (1- (2,3-epoxypropoxy)- 1-trifluoromethyl-2,2,2-trifluoromethyl) benzene, 4,4-bis (2,3-epoxypropoxy) octafluorobiphenyl, Liglycidyl-p-a
• the crosslinkable compound having an oxetane group is a crosslinkable compound having at least two oxetane groups represented by the following formula [4]. Specifically, it is a crosslinkable compound represented by the following formulas [4a] to [4k].
• crosslinkable compound having a cyclocarbonate group examples include a crosslinkable compound having at least two cyclocarbonate groups represented by the following formula [5].
• n is an integer of 1 to 5
• n is an integer of 1 to 5
• n is 1 to 100
• n is an integer of 1 to 10.
• polysiloxanes having at least one structure represented by the following formulas [5-38] to [5-40] can also be mentioned.
• R 1 , R 2 , R 3 , R 4 and R 5 each independently represents a structure represented by the formula [5], a hydrogen atom, a hydroxyl group, An alkyl group having 1 to 10 carbon atoms, an alkoxyl group, an aliphatic ring or an aromatic ring, at least one of which is a structure represented by the formula [5]).
• compounds of the following formula [5-41] or formula [5-42] can be mentioned.
• n is an integer of 1 to 10).
• crosslinkable compound having at least one substituent selected from the group consisting of a hydroxyl group or an alkoxyl group include, for example, amino resins having a hydroxyl group or an alkoxyl group, such as melamine resin, urea resin, guanamine resin, glycoluril. -Formaldehyde resin, succinylamide-formaldehyde resin, ethyleneurea-formaldehyde resin and the like.
• a melamine derivative, a benzoguanamine derivative, or glycoluril in which a hydrogen atom of an amino group is substituted with a methylol group, an alkoxymethyl group, or both can be used.
• Melamine derivatives or benzoguanamine derivatives can also exist as dimers or trimers. These preferably have an average of 3 to 6 methylol groups or alkoxymethyl groups per triazine ring.
• Examples of such melamine derivatives or benzoguanamine derivatives include MX-750, which has an average of 3.7 substituted methoxymethyl groups per triazine ring, and an average of 5. methoxymethyl groups per triazine ring.
• Eight-substituted MW-30 (above, manufactured by Sanwa Chemical Co., Ltd.), Cymel 300, 301, 303, 350, 370, 771, 325, 327, 703, 712 and other methoxymethylated melamines, Cymel 235, 236 Methoxymethylated butoxymethylated melamine such as 238, 212, 253, 254, butoxymethylated melamine such as Cymel 506, 508, carboxymethyl-containing methoxymethylated isobutoxymethylated melamine such as Cymel 1141, methoxy such as Cymel 1123 Methylated ethoxyme Benzoguanamine, methoxymethylated butoxymethylated benzoguanamine such as Cymel 1123-10, butoxymethylated benzo
• Benzene having a hydroxyl group or an alkoxyl group, or a phenolic compound can also be exemplified as the crosslinkable compound.
• the crosslinkable compound For example, 1,3,5-tris (methoxymethyl) benzene, 1,2,4-tris (isopropoxymethyl) benzene, 1,4-bis (sec-butoxymethyl) benzene or 2,6-dihydroxymethyl-p -Tert-butylphenol and the like. More specifically, it is a crosslinkable compound represented by the following formulas [6-1] to [6-48].
• crosslinkable compound having a polymerizable unsaturated bond examples include trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, and tri (meth) acryloyloxyethoxytrimethylol.
• Crosslinkable compounds having three polymerizable unsaturated groups in the molecule such as propane or glycerin polyglycidyl ether poly (meth) acrylate; ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) ) Acrylate, polyethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, butylene glycol di ( ) Acrylate, neopentyl glycol di (meth) acrylate, ethylene oxide bisphenol A type di (meth) acrylate, propylene oxide bisphenol type di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, glycerin di ( (Meth) acrylate, pentaerythritol di (meth) acrylate, ethylene glycol diglycidy
• E 1 is a monovalent group consisting of a cyclohexane ring, a bicyclohexane ring, a benzene ring, a biphenyl ring, a terphenyl ring, a naphthalene ring, a fluorene ring, an anthracene ring or a phenanthrene ring
• E 2 is represented by the following formula [ 7a] or the formula [7b], and n is an integer of 1 to 4.
• the said compound is an example of a crosslinkable compound, It is not limited to these.
• the crosslinkable compound contained in the liquid crystal aligning agent of this invention may be one type, and may be combined two or more types.
• the content of the crosslinkable compound is preferably 0.1 to 150 parts by mass with respect to 100 parts by mass of the polymer component, and the crosslinking reaction proceeds to exhibit the desired effect.
• the amount is more preferably 0.1 to 100 parts by weight, particularly 1 to 50 parts by weight.
• a nitrogen-containing heterocyclic amine compound represented by the following formulas [M1] to [M156] is added as a compound that promotes charge transfer in the liquid crystal alignment film and promotes charge loss of a liquid crystal cell using the liquid crystal alignment film. It is preferable to do.
• the amine compound may be added directly to the solution of the specific polymer, but it is preferable to add the amine compound after making a solution with a concentration of 0.1 to 10% by mass, preferably 1 to 7% by mass with an appropriate solvent. .
• the solvent is not particularly limited as long as it is an organic solvent that dissolves the specific polymer described above.
• the liquid-crystal aligning agent of this invention is an organic solvent (it is also called a poor solvent) which improves the uniformity of the film thickness of a polymer film at the time of apply
• Examples of the compound that improves the uniformity of the film thickness and the surface smoothness include a fluorine-based surfactant, a silicone-based surfactant, and a nonionic surfactant. More specifically, for example, F-top EF301, EF303, EF352 (manufactured by Tochem Products), MegaFuck F171, F173, R-30 (manufactured by Dainippon Ink), Florard FC430, FC431 (manufactured by Sumitomo 3M), Asahi Guard AG710, Surflon S-382, SC101, SC102, SC103, SC104, SC105, SC106 (Asahi Glass Co., Ltd.) and the like.
• the use ratio of these surfactants is preferably 0.01 to 2 parts by mass, more preferably 0.01 to 1 part by mass with respect to 100 parts by mass of the polymer component contained in the liquid crystal aligning agent. is there.
• the compound that improves the adhesion between the liquid crystal alignment film and the substrate include the following functional silane-containing compounds and epoxy group-containing compounds.
• the amount is preferably 0.1 to 30 parts by mass, more preferably 1 to 100 parts by mass of the polymer component contained in the liquid crystal aligning agent. ⁇ 20 parts by mass. If it is less than 0.1 part by mass, the effect of improving the adhesion cannot be expected, and if it exceeds 30 parts by mass, the orientation of the liquid crystal may deteriorate.
• the dielectric constant and conductivity of the liquid crystal alignment film are within the range where the effects of the present invention are not impaired.
• a dielectric material or a conductive material for the purpose of changing the electrical characteristics such as property may be added.
• the liquid crystal alignment treatment agent of the present invention can be used as a liquid crystal alignment film after being applied and baked on a substrate and then subjected to alignment treatment by rubbing treatment or light irradiation. In the case of vertical alignment, etc., it can be used as a liquid crystal alignment film without alignment treatment.
• the substrate used at this time is not particularly limited as long as it is a highly transparent substrate.
• a plastic substrate such as an acrylic substrate or a polycarbonate substrate can also be used. From the viewpoint of simplification of the process, it is preferable to use a substrate on which an ITO electrode for driving a liquid crystal is formed.
• an opaque substrate such as a silicon wafer can be used if only one substrate is used, and a material that reflects light such as aluminum can be used as an electrode in this case.
• the method for applying the liquid crystal aligning agent is not particularly limited, but industrially, methods such as screen printing, offset printing, flexographic printing, and ink jet are generally used. Other coating methods include dip, roll coater, slit coater, spinner and the like, and these may be used depending on the purpose.
• the solvent can be evaporated at 50 to 300 ° C., preferably 80 to 250 ° C., by a heating means such as a hot plate to form a polymer film. If the thickness of the polymer film after baking is too thick, it is disadvantageous in terms of power consumption of the liquid crystal display element, and if it is too thin, the reliability of the liquid crystal display element may be lowered. Is 10 to 100 nm. When the liquid crystal is horizontally or tilted, the polymer film after baking is treated with rubbing or irradiation with polarized ultraviolet rays.
• the liquid crystal display element of the present invention is a liquid crystal display element obtained by obtaining a substrate with a liquid crystal alignment film from the liquid crystal alignment treatment agent of the present invention by the method described above, and then preparing a liquid crystal cell by a known method.
• a liquid crystal cell manufacturing method a pair of substrates on which a liquid crystal alignment film is formed are prepared, spacers are dispersed on the liquid crystal alignment film of one substrate, and the liquid crystal alignment film surface is on the inside, so that the other Examples include a method in which substrates are attached and liquid crystal is injected under reduced pressure, or a method in which liquid crystal is dropped onto a liquid crystal alignment film surface on which spacers are dispersed and then a substrate is attached and sealed.
• the liquid-crystal aligning agent of this invention has a liquid-crystal layer between a pair of board
• the liquid crystal composition is preferably used also for a liquid crystal display device manufactured through a step of polymerizing a polymerizable compound by at least one of irradiation with active energy rays and heating while applying a voltage between electrodes.
• ultraviolet rays are suitable as the active energy ray.
• the liquid crystal display element controls a pretilt angle of liquid crystal molecules by a PSA (Polymer Sustained Alignment) method.
• a PSA method a small amount of a photopolymerizable compound, for example, a photopolymerizable monomer is mixed in a liquid crystal material, and after assembling a liquid crystal cell, a predetermined voltage is applied to the liquid crystal layer and an ultraviolet ray is applied to the photopolymerizable compound.
• the pretilt angle of the liquid crystal molecules is controlled by the produced polymer. Since the alignment state of the liquid crystal molecules when the polymer is formed is stored even after the voltage is removed, the pretilt angle of the liquid crystal molecules can be adjusted by controlling the electric field formed in the liquid crystal layer. .
• the PSA method does not require a rubbing process and is suitable for forming a vertical alignment type liquid crystal layer in which it is difficult to control the pretilt angle by the rubbing process. That is, in the liquid crystal display element of the present invention, a liquid crystal cell is prepared after obtaining a substrate with a liquid crystal alignment film from the liquid crystal alignment treatment agent of the present invention by the above-described method, and a polymerizable compound is obtained by at least one of ultraviolet irradiation and heating. The orientation of liquid crystal molecules can be controlled by polymerizing.
• liquid crystal cell production prepare a pair of substrates on which a liquid crystal alignment film is formed, spread spacers on the liquid crystal alignment film of one substrate, and make the liquid crystal alignment film surface inside.
• Examples include a method in which the other substrate is attached and liquid crystal is injected under reduced pressure and sealing is performed, or a method in which liquid crystal is dropped on the liquid crystal alignment film surface on which spacers are dispersed and then the substrate is attached and sealed.
• a polymerizable compound that is polymerized by heat or ultraviolet irradiation is mixed.
• the polymerizable compound include compounds having at least one polymerizable unsaturated group such as an acrylate group or a methacrylate group in the molecule.
• the polymerizable compound is preferably 0.01 to 10 parts by mass, more preferably 0.1 to 5 parts by mass with respect to 100 parts by mass of the liquid crystal component.
• the polymerizable compound is less than 0.01 part by mass, the polymerizable compound is not polymerized and the orientation of the liquid crystal cannot be controlled, and when it exceeds 10 parts by mass, the amount of the unreacted polymerizable compound increases and the liquid crystal display element. The seizure characteristics of the steel deteriorate.
• the polymerizable compound is polymerized by irradiating heat or ultraviolet rays while applying an AC or DC voltage to the liquid crystal cell.
• the liquid crystal aligning agent of the present invention has a liquid crystal layer between a pair of substrates provided with electrodes, and is polymerized by at least one of active energy rays and heat between the pair of substrates. It is also preferably used for a liquid crystal display device manufactured through a step of disposing a liquid crystal alignment film containing a group and applying a voltage between the electrodes.
• ultraviolet rays are suitable as the active energy ray.
• a method of adding a compound containing the polymerizable group to a liquid crystal aligning agent A method using a coalescing component may be mentioned.
• the polymerizable group include polymerizable unsaturated groups such as an acryl group, a methacryl group, a vinyl group, and a maleimide group.
• the liquid crystal aligning agent of the present invention contains a specific amine compound having a double bond site that reacts by heat or ultraviolet irradiation
• the alignment of liquid crystal molecules is controlled by at least one of ultraviolet irradiation and heating. Can do. If an example of liquid crystal cell production is given, prepare a pair of substrates on which a liquid crystal alignment film is formed, spread spacers on the liquid crystal alignment film of one substrate, and make the liquid crystal alignment film surface inside, Examples include a method in which the other substrate is attached and liquid crystal is injected under reduced pressure and sealing is performed, or a method in which liquid crystal is dropped on the liquid crystal alignment film surface on which spacers are dispersed and then the substrate is attached and sealed.
• the orientation of the liquid crystal molecules can be controlled by irradiating heat or ultraviolet rays while applying an AC or DC voltage to the liquid crystal cell.
• the liquid crystal display device manufactured using the liquid crystal aligning agent of the present invention has excellent reliability and can be suitably used for a large-screen, high-definition liquid crystal television.
• Specific diamine compound Specific diamine compound (4): Specific diamine compound obtained by the synthesis route of Synthesis Example 1 Specific diamine compound (7): Specific diamine compound obtained by the synthesis route of Synthesis Example 2 Specific diamine compound (10): Synthesis Example 3 Specific diamine compound (specific side chain type diamine compound) obtained by the synthetic route of PCH7DAB: 1,3-diamino-4- [4- (trans-4-n-heptylcyclohexyl) phenoxy] benzene PBCH5DAB: 1,3-diamino-4- ⁇ 4- [trans-4- (trans-4 -N-pentylcyclohexyl) cyclohexyl] phenoxy ⁇ benzene m-PBCH5DABz: 1,3-diamino-5- ⁇ 4- [4- (trans-4-n-pentylcyclohexyl) phenyl] phenoxymethyl ⁇ benzene ColDAB -1: Specific side chain diamine compound represented
• Crosslinkable compound (1) YH-434L (manufactured by Toto Kasei) (epoxy-based crosslinkable compound)
• Crosslinkable compound (2) OXT-221 (manufactured by Toa Gosei Co., Ltd.) (oxetane-based crosslinkable compound)
• Crosslinkable compound (3) crosslinkable compound represented by the following formula (hydroxylated phenol-based crosslinkable compound) (Organic solvent)
• NMP N-methyl-2-pyrrolidone
• BCS Butyl cellosolve
• the molecular weight of polyimide in the synthesis example is as follows using a normal temperature gel permeation chromatography (GPC) apparatus (GPC-101) (manufactured by Showa Denko KK) and columns (KD-803, KD-805) (manufactured by Shodex). The measurement was performed as described above.
• GPC normal temperature gel permeation chromatography
• the imidation ratio of polyimide in the synthesis example was measured as follows. 20 mg of polyimide powder was put into an NMR sample tube (NMR sampling tube standard, ⁇ 5 (manufactured by Kusano Kagaku)), and deuterated dimethyl sulfoxide (0.05 mass% TMS (tetramethylsilane) in DMSO-d6) (0.005). 53 ml) was added and completely dissolved by sonication. This solution was measured for proton NMR at 500 MHz with an NMR measuring instrument (JNW-ECA500) (manufactured by JEOL Datum).
• the imidation rate is determined based on protons derived from structures that do not change before and after imidation as reference protons, and the peak integrated value of these protons and proton peaks derived from NH groups of amic acid appearing in the vicinity of 9.5 to 10.0 ppm. It calculated
• Imidization rate (%) (1 ⁇ ⁇ x / y) ⁇ 100
• x is a proton peak integrated value derived from NH group of amic acid
• y is a peak integrated value of reference proton
• ⁇ is one NH group proton of amic acid in the case of polyamic acid (imidation rate is 0%) Is the number ratio of the reference proton to.
• the reaction was performed for 4.5 hours. This reaction solution was put into methanol (350 ml), and the resulting precipitate was separated by filtration. This deposit was wash
• the imidation ratio of this polyimide was 52%, the number average molecular weight was 21,200, and the weight average molecular weight was 51,300.
• Preparation of liquid crystal cell and “Evaluation of electrical characteristics” are as follows. A liquid crystal cell was prepared using each of the liquid crystal alignment treatment agents obtained in Examples 1 to 13 and Comparative Examples 1 to 6, and the electrical characteristics of the obtained liquid crystal cell were evaluated.
• a liquid crystal alignment treatment agent is spin-coated on the ITO surface of a 30 ⁇ 40 mm ITO electrode substrate, and heated at 80 ° C. for 5 minutes on a hot plate and at 230 ° C. for 30 minutes in a heat-circulating clean oven.
• a substrate with a polyimide liquid crystal alignment film having a thickness of 100 nm was obtained.
• Two substrates with the obtained liquid crystal alignment film were prepared, combined with a 6 ⁇ m spacer sandwiched with the liquid crystal alignment film surface on the inside, and the periphery was adhered with a sealant to produce an empty cell.
• MLC-6608 manufactured by Merck Japan
• MLC-6608 manufactured by Merck Japan
• a DC voltage of 10 V was applied to the liquid crystal cell after measuring the voltage holding ratio for 30 minutes and short-circuited for 1 second, and then the potential generated in the liquid crystal cell was measured for 1800 seconds. The residual charges after 50 seconds and 1000 seconds were measured.
• a liquid crystal property evaluation apparatus (6254 type) manufactured by Toyo Technica Co., Ltd. was used.
• the liquid crystal cell in which the measurement of the voltage holding ratio and the residual charge was completed was irradiated with ultraviolet rays of 50 J / cm 2 in terms of 365 nm, and then the voltage holding ratio and the residual charge were measured under the same conditions as described above.
• the ultraviolet irradiation was performed using a desktop UV curing device (HCT3B28HEX-1) (SEN LIGHT CORPRATION).
• Example 1 The polyamic acid solution (A) (10.5 g), NMP (8.50 g), and BCS (24.6 g) having a resin solid content concentration of 24.9% by mass obtained in Synthesis Example 1 were added at 25 ° C. for 6 hours. By mixing, the liquid crystal aligning agent (1) was obtained. This liquid crystal aligning agent was confirmed to be a uniform solution without any abnormality such as turbidity or precipitation. Using the obtained liquid crystal aligning agent (1), production of a liquid crystal cell and evaluation of electric characteristics were performed under the above-described conditions. In Examples 2 to 13 and Comparative Examples 1 to 6, liquid crystal cells were prepared and electrical characteristics were evaluated using the produced liquid crystal alignment treatment agents in the same manner as in Example 1. The results are shown in Tables 48 to 51.
• Example 2 The polyimide powder (B) (2.52 g), NMP (22.3 g), and BCS (19.7 g) obtained in Synthesis Example 2 were mixed at 25 ° C. for 8 hours to obtain a liquid crystal aligning agent (2). Got. This liquid crystal aligning agent was confirmed to be a uniform solution without any abnormality such as turbidity or precipitation.
• Example 3 The polyimide powder (C) (2.50 g), NMP (24.0 g), and BCS (17.6 g) obtained in Synthesis Example 3 were mixed at 25 ° C. for 8 hours to obtain a liquid crystal aligning agent (3). Got. This liquid crystal aligning agent was confirmed to be a uniform solution without any abnormality such as turbidity or precipitation.
• Example 4 The polyimide powder (D) (2.51 g), NMP (26.1 g) and BCS (15.7 g) obtained in Synthesis Example 4 were mixed at 25 ° C. for 8 hours to obtain a liquid crystal aligning agent (4). Got. This liquid crystal aligning agent was confirmed to be a uniform solution without any abnormality such as turbidity or precipitation.
• Example 5 The polyimide powder (E) (2.50 g), NMP (29.9 g), and BCS (11.8 g) obtained in Synthesis Example 5 were mixed at 25 ° C. for 8 hours to obtain a liquid crystal alignment treatment agent (5). Got. This liquid crystal aligning agent was confirmed to be a uniform solution without any abnormality such as turbidity or precipitation.
• Example 6 The polyamic acid solution (F) (11.0 g), NMP (11.1 g) and BCS (23.7 g) having a resin solid content concentration of 25.0% by mass obtained in Synthesis Example 6 were added at 25 ° C. for 6 hours. By mixing, the liquid crystal aligning agent (6) was obtained. This liquid crystal aligning agent was confirmed to be a uniform solution without any abnormality such as turbidity or precipitation.
• Example 7 The polyimide powder (G) (2.51 g), NMP (30.0 g), and BCS (11.8 g) obtained in Synthesis Example 7 were mixed at 25 ° C. for 8 hours to obtain a liquid crystal alignment treatment agent (7). Got. This liquid crystal aligning agent was confirmed to be a uniform solution without any abnormality such as turbidity or precipitation.
• Example 8 The polyimide powder (H) (2.50 g), NMP (26.0 g), and BCS (15.7 g) obtained in Synthesis Example 8 were mixed at 25 ° C. for 8 hours to obtain a liquid crystal aligning agent (8). Got. This liquid crystal aligning agent was confirmed to be a uniform solution without any abnormality such as turbidity or precipitation.
• Example 9 The polyimide powder (I) obtained in Synthesis Example 9 (2.50 g), NMP (31.9 g) and BCS (9.80 g) were mixed at 25 ° C. for 8 hours to obtain a liquid crystal aligning agent (9). Got. This liquid crystal aligning agent was confirmed to be a uniform solution without any abnormality such as turbidity or precipitation.
• Example 10 The polyimide powder (J) (2.53 g), NMP (30.3 g) and BCS (11.9 g) obtained in Synthesis Example 10 were mixed at 25 ° C. for 8 hours to obtain a liquid crystal alignment treatment agent (10). Got. This liquid crystal aligning agent was confirmed to be a uniform solution without any abnormality such as turbidity or precipitation.
• Example 11 The polyimide powder (B) (2.50 g), NMP (22.1 g), BCS (19.6 g) and the crosslinkable compound (1) (0.25 g) obtained in Synthesis Example 2 were added at 25 ° C. It mixed for a time and the liquid-crystal aligning agent (11) was obtained. This liquid crystal aligning agent was confirmed to be a uniform solution without any abnormality such as turbidity or precipitation.
• Example 12 The polyimide powder (C) (2.50 g), NMP (24.0 g), BCS (17.6 g) and the crosslinkable compound (2) (0.50 g) obtained in Synthesis Example 3 were added at 25 ° C. It mixed for a time and the liquid-crystal aligning agent (12) was obtained. This liquid crystal aligning agent was confirmed to be a uniform solution without any abnormality such as turbidity or precipitation.
• Example 13 The polyimide powder (C) (2.51 g), NMP (24.1 g), BCS (17.7 g) and the crosslinkable compound (3) (0.25 g) obtained in Synthesis Example 3 were added at 25 ° C. It mixed for a time and the liquid-crystal aligning agent (13) was obtained. This liquid crystal aligning agent was confirmed to be a uniform solution without any abnormality such as turbidity or precipitation.
• the liquid crystal display element having the liquid crystal alignment film of the present invention has excellent reliability and is suitably used for a large-screen, high-definition liquid crystal television and the like, and also has a TN element, an STN element, a TFT liquid crystal element, particularly a vertical liquid crystal display element. This is useful for an alignment type liquid crystal display element.
• liquid crystal aligning film obtained from the liquid crystal aligning agent of this invention can be used for manufacture of the liquid crystal display element which has the process of irradiating an ultraviolet-ray, applying a voltage between electrodes.

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