Classifications

• • 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
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
  • C08L79/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
  • C08L79/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
• • G—PHYSICS
  • G02—OPTICS
  • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
  • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
  • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
  • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
  • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
  • G02F1/1333—Constructional arrangements; Manufacturing methods
  • G02F1/1337—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers
  • G02F1/133711—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers by organic films, e.g. polymeric films
  • G02F1/133723—Polyimide, polyamide-imide

Definitions

• the present invention relates to a liquid crystal aligning agent used for preparing a liquid crystal alignment film and a liquid crystal display element using the same.
• Liquid crystal display elements are currently widely used as display devices that are thin and light.
• a liquid crystal alignment film is used in order to determine the alignment state of the liquid crystal.
• Most of the liquid crystal alignment films, except for some vertical alignment type liquid crystal display elements, are produced by subjecting the surface of the polymer film formed on the electrode substrate to some alignment treatment.
• the most popular method at present is a method of performing a so-called rubbing process in which the surface of the film is rubbed with a cloth made of rayon or the like under pressure.
• a method of using a liquid crystal alignment treatment agent containing a specific thermally crosslinkable compound together with at least one polymer of polyamic acid or polyimide for example, A method for improving rubbing resistance by using a curing agent, such as a method using a liquid crystal aligning agent containing an epoxy group-containing compound (see, for example, Patent Document 2) has been proposed. Yes.
• the rubbing treatment is performed in a short time and under strong rubbing conditions for the purpose of shortening the manufacturing process time of the liquid crystal display element. Therefore, compared to the conventional case, there are cases in which a large amount of film scraps and scratches associated with the rubbing process occur, and these abnormalities deteriorate the characteristics of the liquid crystal display element, and further decrease the yield. Is one of the causes
• liquid crystal display elements are used for large-screen, high-definition liquid crystal televisions and in-vehicle applications such as car navigation systems and meter panels.
• a backlight with a large calorific value may be used.
• the liquid crystal alignment film is required to have high reliability from another point of view, that is, high stability to light from the backlight.
• the voltage holding ratio which is one of the electrical characteristics of the liquid crystal display element, decreases due to light irradiation from the backlight, a burn-in defect (line burn-in), which is one of the display defects of the liquid crystal display element, occurs.
• An object of the present invention is to provide a liquid crystal alignment film having the above characteristics. That is, the object of the present invention is to prevent film scraping and scratches associated with the rubbing process during the manufacturing process of the liquid crystal display element, and to reduce the voltage holding ratio even when exposed to light irradiation.
• An object of the present invention is to provide a suppressed liquid crystal alignment film, a liquid crystal alignment treatment agent capable of providing the liquid crystal alignment film, and a compound having a specific structure constituting the liquid crystal alignment treatment agent.
• the present inventor has found that a liquid crystal aligning agent containing a compound having a specific structure is extremely effective for achieving the above object, and has completed the present invention. That is, the present invention has the following gist. (1) At least one selected from the group consisting of a compound having a structure in which a group represented by the following formula [1], which is the component (A), is bonded, a polyimide precursor, and a polyimide, which is the component (B)
• a liquid crystal aligning agent characterized by comprising:
• X 1 represents an alkylene group having 1 to 3 carbon atoms
• X 2 represents a single bond, —O—, —CO—, —COO—, —OCO—, —NH—, —CONH— , —NHCO—, —CON (CH 3 ) —, or a nitrogen atom
• a is
• X 2 is —O—, —CO—, —COO—, —OCO—, —NH—, —CONH—, —NHCO 1 when-or CON (CH 3 )-, and 2 when X 2 is a nitrogen atom.
• X 1 and X 8 each independently represent an alkylene group having 1 to 3 carbon atoms
• X 2 and X 7 each independently represent a single bond, —O —, —CO—, —COO—, —OCO—, —NH—, —CONH—, —NHCO—, —CON (CH 3 ) —, or a nitrogen atom
• X 3 represents a single bond, an aromatic ring, A cyclohexane ring, or a trivalent organic group having a structure of any of the following formulas [X-1] to [X-4], or a tetravalent organic group having a structure of the following formula [X-5]:
• X 4 and X 6 each independently represent a single bond, an aromatic ring in which any hydrogen atom may be substituted with
• Y 1 is a single bond, — (CH 2 ) a — (a is an integer of 1 to 10), —O—, —CH 2 O—, —COO—, or OCO—.
• Y 2 is a single bond or a divalent organic group selected from (CH 2 ) b — (b is an integer of 1 to 10), and Y 3 is a single bond.
• Y 4 Is a cyclic group selected from the group consisting of a benzene ring, a cyclohexyl ring and a heterocyclic ring, wherein any hydrogen atom on these cyclic groups is an alkyl group having 1 to 3 carbon atoms, or 1 to 3 carbon atoms.
• Group substituted by 2 may be divalent organic group selected from the group, or a divalent organic group selected from an organic group having a carbon number of 12 to 25 having a steroid skeleton
• Y 5 is a benzene ring
• Y 6 is an alkyl group having 1 to 18 carbon atoms, a fluorine-containing alkyl group having 1 to 18 carbon atoms
• 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.
• the liquid crystal alignment film according to (12) which is used for a liquid crystal display device manufactured through a step of polymerizing the polymerizable compound while applying a voltage between the electrodes.
• a polymerizable compound that includes a liquid crystal layer between a pair of substrates including an electrode and the liquid crystal alignment film and that polymerizes at least one of active energy rays and heat between the pair of substrates.
• liquid crystal aligning agent of the present invention it is possible to obtain a liquid crystal aligning film with little film scraping due to rubbing treatment and small decrease in voltage holding ratio even after being exposed to a backlight for a long time.
• a liquid crystal display element having such a liquid crystal alignment film has excellent reliability and can be suitably used for a large-screen high-definition liquid crystal television.
• the liquid-crystal aligning agent of this invention contains the compound (it is also called a specific compound in this invention) which has the structure which group shown by following formula [1] couple
• the liquid crystal alignment film obtained from the liquid crystal alignment treatment agent of the present invention has less film abrasion due to the rubbing process and is exposed to the backlight for a long time as compared with the liquid crystal alignment film not containing the specific compound.
• the decrease in the voltage holding ratio is small.
• a compound having a structure in which a group represented by the following formula [1a] is bonded is preferable.
• X 1 is an alkylene group having 1 to 3 carbon atoms. Among these, an alkylene group having 1 or 2 carbon atoms is preferable from the viewpoint of crosslink density and ease of synthesis.
• X 2 is a single bond, —O—, —CO—, —COO—, —OCO—, —NH—, —CONH—, —NHCO—, —CON (CH 3 ) —, or a nitrogen atom, However, from the viewpoint of ease of synthesis, a single bond, —O—, —COO—, —OCO—, or a nitrogen atom is preferable.
• a is 1 when X 2 is —O—, —CO—, —COO—, —OCO—, —NH—, —CONH—, —NHCO—, or CON (CH 3 ) —, and X 2 2 when is a nitrogen atom.
• the specific compound is preferably at least one compound selected from the group consisting of compounds represented by the following formula [1b] and formula [1c].
• X 1 and X 8 are each independently an alkylene group having 1 to 3 carbon atoms.
• a C1-C2 alkylene group is preferable from a viewpoint of a crosslinking density and the ease of a synthesis
• X 2 and X 7 are each independently a single bond, —O—, —CO—, —COO—, —OCO—, —NH—, —CONH—, —NHCO—, —CON (CH 3 ) —, Or a nitrogen atom, and from the viewpoint of ease of synthesis, a single bond, —O—, —COO—, —OCO—, or a nitrogen atom is preferable. Particularly preferred is —COO—, —OCO—, or a nitrogen atom.
• X 3 is a single bond, an aromatic ring, a cyclohexane ring, a trivalent having a structure of any of the following formulas [X-1] to [X-4] An organic group or a tetravalent organic group having the structure of the following formula [X-5].
• aromatic ring examples include benzene ring, naphthalene ring, tetrahydronaphthalene ring, azulene ring, indene ring, fluorene ring, anthracene ring, phenanthrene ring, phenalene ring, pyrrole ring, imidazole ring, oxazole ring, thiazole ring, pyrazole ring Pyridine ring, pyrimidine ring, quinoline ring, pyrazoline ring, isoquinoline ring, carbazole ring, purine ring, thiadiazole ring, pyridazine ring, triazine ring, pyrazolidine ring, triazole ring, pyrazine ring, benzimidazole ring, benzimidazole ring, thionoline ring Phenanthroline ring, indole ring, quinoxaline ring, benzo
• more preferable aromatic rings include benzene ring, naphthalene ring, fluorene ring, anthracene ring, pyrrole ring, imidazole ring, pyrazole ring, pyridine ring, pyrimidine ring, quinoline ring, isoquinoline ring, carbazole ring, pyridazine ring, pyrazine. Ring, benzimidazole ring, benzimidazole ring, indole ring, quinoxaline ring, acridine ring and the like. More preferred is a benzene ring, naphthalene ring, pyridine ring or carbazole ring, and most preferred is a benzene ring or pyridine ring.
• X 4 and X 6 are each independently a single bond, an aromatic ring in which any hydrogen atom may be substituted with an alkyl group having 1 to 3 carbon atoms, or cyclohexane It is a ring.
• aromatic ring include those described above.
• X 5 represents a single bond, an alkylene group having 1 to 5 carbon atoms in which an arbitrary hydrogen atom may be substituted, an oxygen atom, an aromatic ring, a cyclohexane ring, or the following A divalent organic group having a structure of any one of formulas [X-6] to [X-13].
• a represents that X 2 is —O—, —CO—, —COO—, —OCO—, —NH—, —CONH—, —NHCO—, or CON (CH 3 )
• X 2 is a nitrogen atom, it is 2.
• b, c, and d are each independently an integer of 1 to 4.
• e is an integer of 1 to 10.
• More specific specific compounds include compounds of the following formulas [1-1] to [1-38].
• n is an integer of 1 to 5
• n is an integer of 1 to 5
• n is 1 to 100
• n is 1 to 10.
• R 1 , R 2 , R 3 , R 4 , and R 5 are each independently a group having a structure represented by the formula [1], a hydrogen atom, a hydroxyl group, an alkyl group having 1 to 10 carbon atoms, or an alkoxyl group. And at least one of R 1 and R 2 and at least one of R 3 and R 4 is a structure represented by the formula [1].
• each R 6 independently represents a group having the structure represented by the formula [1], a hydrogen atom, a hydroxyl group, an alkyl group having 1 to 10 carbon atoms, an alkoxyl group, an aliphatic ring, Or at least one is a structure represented by the formula [1], and in the formula [1-43], n is an integer of 1 to 10.
• the method for producing the specific compound of the present invention is not particularly limited, but preferred methods include the following methods.
• X 1 , X 2 , X 3 , X 4 , X 5 , X 6 , X 7 , X 8 , a, b, c, and d are , Formula [1b], and formula [1c].
• X 2 is —NH—
• a method of reacting a halogen derivative containing the formula [1] and X 1 with an amino group containing X 3 and a ring derivative in the presence of an alkali can be mentioned.
• X 2 is —CONH— or CON (CH 3 ) —
• X 2 is —NHCO—
• a method of reacting an amino group-substituted product containing formula [1] and X 2 with an acid chloride containing X 3 in the presence of an alkali can be mentioned.
• X 2 is —COO—
• a method of reacting an acid chloride containing formula [1] and X 2 with a hydroxyl group-containing derivative containing X 3 in the presence of an alkali can be mentioned.
• X 2 is —OCO—
• a method of reacting a hydroxyl group-containing derivative containing the formula [1] and X 2 with an acid chloride containing X 3 in the presence of an alkali can be mentioned.
• a basic compound In order to promote the reaction with the specific compound of the present invention and the specific polymer, that is, the carboxylic acid group or hydroxyl group contained in the polyamic acid or polyimide, it is preferable to add a basic compound.
• the basic compound is not particularly limited. Specific examples include alkali metal or alkaline earth metal hydroxides such as sodium hydroxide and potassium hydroxide, inorganic amine compounds such as ammonia, and organic amine compounds such as pyridine and triethylamine. Of these, organic amine compounds are preferred from the viewpoint of the electrical characteristics of the liquid crystal alignment film.
• examples of the organic amine compound include nitrogen-containing heterocyclic amine compounds represented by the following formulas [M1] to [M156]. These amine compounds may be added directly to the solution of the specific polymer, but may be added after a solution having a concentration of 0.1 to 10% by mass, preferably 1 to 7% by mass with an appropriate solvent. preferable.
• the solvent is not particularly limited as long as it is an organic solvent that dissolves the specific polymer of the present invention.
• More preferable organic amine compounds include M6, M7, M16, M17, M20, M35, M36, M40, M49, M50, M60 to M62, M69, M70, M76, M118 to M121, M135, or M140. Further preferred are M6, M16, M17, M35, M36, M40, M49, M50, M60, M61, M118, M120, M121, or M140. Most preferred is M6, M17, M35, M40, M61 or M118.
• the basic compound contained in the liquid-crystal aligning agent of this invention may be one type, and may combine two or more types.
• the content of the basic compound is preferably 0.1 to 100 parts by mass with respect to 100 parts by mass of the specific polymer, and the carboxylic acid contained in the polyamic acid or polyimide
• the amount is more preferably 0.1 to 50 parts by mass, particularly 1 to 30 parts by mass.
• the specific polymer is at least one polymer selected from the group consisting of a polyimide precursor and polyimide.
• the specific polymer is relatively easily obtained by polycondensing a diamine component represented by the following formula [A] and a tetracarboxylic dianhydride component represented by the following formula [B].
• a polyamic acid having a repeating unit represented by the formula [C]] and a polyimide obtained by imidizing this polyamic acid are preferred.
• R 1 represents a divalent organic group
• R 2 represents a tetravalent organic group
• R 1 and R 2 have the same meanings as defined in the formula [A] and the formula [B], and R 1 and R 2 are different even if each is one kind.
• a combination of a plurality of species may be used, and n represents a positive integer.
• a diamine compound represented by the following formula [2] (also referred to as a specific side chain diamine compound in the present invention).
• Y 1 is selected from a single bond, — (CH 2 ) a — (a is an integer of 1 to 15), —O—, —CH 2 O—, —COO—, or OCO—.
• a divalent organic group Among these, 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 can be easily synthesized. More preferably, they are a single bond, — (CH 2 ) a — (a is an integer of 1 to 10), —O—, —CH 2 O—, or COO—.
• Y 2 is a single bond or a divalent organic group selected from (CH 2 ) b — (b is an integer of 1 to 15). Among these, a single bond or (CH 2 ) b — (b is an integer of 1 to 10) is preferable.
• Y 3 represents a single bond, — (CH 2 ) c — (c is an integer of 1 to 15), —O—, —CH 2 O—, —COO—, or OCO—. It is.
• a single bond — (CH 2 ) c — (c is an integer of 1 to 10), —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 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 to 3 carbon atoms. It may be substituted with a group selected from the group consisting of an alkyl group, 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, and a fluorine atom.
• Y 5 is a 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 to 3 carbon atoms. It may be substituted with a group selected from the group consisting of an alkyl group, 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, and a fluorine atom. It is a divalent organic group.
• Y 6 is an alkyl group having 1 to 18, preferably 1 to 12, more preferably 1 to 9 carbon atoms, a fluorine-containing alkyl group having 1 to 18, preferably 1 to 12, more preferably 1 to 9 carbon atoms, An alkoxyl group having 1 to 18 carbon atoms, preferably 1 to 12 carbon atoms, more preferably 1 to 9 carbon atoms, or a fluorine-containing alkoxyl group having 1 to 18 carbon atoms, preferably 1 to 12 carbon atoms, more preferably 1 to 9 carbon atoms.
• n is an integer of 0 to 4, preferably 0 to 2.
• the organic group having 3 or more carbon atoms may have either a linear structure or a branched structure.
• m is an integer of 1 to 4, preferably 1 to 2.
• Preferred specific examples of the specific side chain type diamine compound of the present invention are those having structures 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 alkoxy group, fluorine-containing An alkyl group or a fluorine-containing alkoxy 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.
• 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 1 is an oxygen atom or COO- * (where a bond with “*” is bonded to (CH 2 ) a 2 )), and A 2 is an oxygen atom or COO — * ( However, a bond marked with “*” is bonded to A 3 ),
• a 3 is a 1,4-cyclohexylene group or a 1,4-phenylene group, and
• a 4 is a fluorine atom An alkyl group having 3 to 20 carbon atoms which may be substituted.
• 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 other than a specific side chain type diamine compound can be used as a diamine component.
• diamine component 2,3,5,6-tetramethyl-p-phenylenediamine, 2,5-dimethyl-p-phenylenediamine, m-phenylenediamine, 2,4-dimethyl-m-phenylenediamine, 2, 5-diaminotoluene, 2,6-diaminotoluene, 2,5-diaminophenol, 2,4-diaminophenol, 3,5-diaminophenol, 3,5-diaminobenzyl alcohol, 2,4-diaminobenzyl alcohol, 4 , 6-diaminoresorcinol, 4,4′-diaminobiphenyl, 3,3′-dimethyl-4,4′-diaminobiphenyl, 3,3′-dimethoxy-4,4′-
• a diamine compound having an alkyl group or a fluorine-containing alkyl group in the diamine side chain can be used.
• diamines represented by the following formulas [DA1] to [DA12] can be exemplified.
• a 1 is an alkyl group or a fluorine-containing alkyl group having 1 to 22 carbon atoms.
• a 2 represents —COO—, —OCO—, —CONH—, —NHCO—, —CH 2 —, —O—, —CO—, or NH—
• a 3 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 also be used.
• m is an integer of 0 to 3
• n is an integer of 1 to 5.
• a diamine compound having a carboxyl group in the molecule represented by the following formulas [DA21] to [DA25] can also be used.
• m 1 is an integer of 1 to 4
• a 4 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—, each of m 2 and m 3 independently represents an integer of 0 to 4, and m 2 + M 3 represents an integer of 1 to 4, m 4 and m 5 are each independently an integer of 1 to 5 in Formula [DA23], and in Formula [DA24], A 5 has 1 to 5 carbon atoms.
• m 6 is an integer of 1 to 5, wherein [DA25], a 6 represents 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—, and m 7 is an integer of 1 to 4.
• the specific side chain type diamine compound and the other diamine compound may be one kind or a mixture of two or more kinds depending on characteristics such as liquid crystal orientation, voltage holding ratio, and accumulated charge when the liquid crystal orientation film is used. It can also be used.
• a tetracarboxylic dianhydride represented by the following formula [3] (also referred to as a specific tetracarboxylic dianhydride in the present invention) is used as a part of the raw material. It is preferable.
• 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, preferably 4 to 6 carbon atoms.
• Z 1 is specifically an organic group having a structure of any one of the following formulas [3a] to [3j].
• Z 2 to Z 5 are each independently a group selected from a hydrogen atom, a methyl group, a chlorine atom, or a benzene ring.
• Z 6 and Z 7 are Each independently represents a hydrogen atom or a methyl group.
• a particularly preferable structure of Z 1 is represented by the formula [3a], the formula [3c], the formula [3d], the formula [3e], the formula [3f], or the formula [3g] because of polymerization reactivity and ease of synthesis. .
• tetracarboxylic dianhydrides other than the specific tetracarboxylic dianhydride can be used. Specific examples are given below. Pyromellitic acid, 2,3,6,7-naphthalenetetracarboxylic acid, 1,2,5,6-naphthalenetetracarboxylic acid, 1,4,5,8-naphthalenetetracarboxylic acid, 2,3,6,7 -Anthracene tetracarboxylic acid, 1,2,5,6-anthracene tetracarboxylic acid, 3,3 ', 4,4'-biphenyltetracarboxylic acid, 2,3,3', 4-biphenyltetracarboxylic acid, bis ( 3,4-dicarboxyphenyl) ether, 3,3 ′, 4,4′-benzophenonetetracarboxylic acid, bis (3,4-dicarboxyphenyl) sulfone, bis (3,4-dicarboxylicy
• the above-mentioned specific tetracarboxylic dianhydride and other tetracarboxylic dianhydrides may be one kind or two kinds depending on characteristics such as liquid crystal orientation, voltage holding ratio, accumulated charge, etc.
• the above can also be mixed and used.
• the liquid-crystal aligning agent of this invention contains at least one of the polyimide precursor obtained by reaction of a diamine component and a tetracarboxylic acid component, and the polyimide obtained by carrying out dehydration ring closure of this polyimide precursor.
• the polyimide precursor and the polyimide may be collectively referred to as a specific polymer.
• the polyimide precursor has a structure represented by the following formula [A].
• R 1 is a tetravalent organic group
• R 2 is a divalent organic group
• a 1 and A 2 are a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, They may be the same or different
• n represents a positive integer.
• the method for synthesizing the specific polymer is not particularly limited. Usually, it is obtained by reacting a diamine component and a tetracarboxylic acid 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 for obtaining polyamic acid by polycondensation of tetracarboxylic dianhydride and a diamine component a method for obtaining polyamic acid by dehydration polycondensation reaction of tetracarboxylic acid and a diamine component, or tetracarboxylic acid dihalide
• a method is used in which a polyamic acid is obtained by polycondensation of a diamine component and diamine component.
• polyamic acid alkyl ester a method of polycondensing a tetracarboxylic acid obtained by dialkyl esterifying a carboxylic acid group and a diamine component, a polycondensation of a tetracarboxylic acid dihalide obtained by dialkyl esterifying a carboxylic acid group and a diamine component.
• a method or a method of converting a carboxyl group of a polyamic acid into an ester is used.
• polyimide a method is used in which the polyamic acid or polyamic acid alkyl ester is cyclized to form polyimide.
• the liquid crystal alignment film obtained using the specific polymer of the present invention can increase the pretilt angle of the liquid crystal as the content ratio of the specific side chain diamine compound in the diamine component increases.
• 5 to 80 mol% of the diamine component is preferably a specific side chain diamine compound.
• 5 to 60 mol% of the diamine component is preferably a specific side chain diamine compound.
• 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. Further, 100 mol% of the tetracarboxylic dianhydride component may be a specific tetracarboxylic dianhydride.
• the reaction between the diamine component and the tetracarboxylic acid component is usually carried out 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. N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N-methylcaprolactam, dimethyl sulfoxide, tetramethyl urea, pyridine, dimethyl sulfone, hexamethyl sulfoxide , ⁇ -butyrolactone, isopropyl alcohol, methoxymethylpentanol, dipentene, ethyl amyl ketone, methyl nonyl ketone, methyl ethyl ketone, methyl isoamyl ketone, methyl isopropyl ketone, methyl cellosolve, ethyl cello
• a method of adding a diamine component to a solution in which a tetracarboxylic acid component is dispersed or dissolved in an organic solvent a method of alternately adding a tetracarboxylic acid component and a diamine component, and the like. Any method may be used.
• the diamine component or the tetracarboxylic acid component is composed of a plurality of types of compounds, they may be reacted in a premixed state, individually may be reacted sequentially, and further individually reacted low molecular weight substances. A specific reaction may be carried out by mixing reaction.
• 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 in a wide range of concentrations of the diamine component and the tetracarboxylic acid component, but if the concentration is too low, it is difficult to obtain a high molecular weight specific polymer, and if the concentration is too high, the viscosity of the reaction solution becomes too high, and uniform stirring becomes difficult.
• the concentration of the diamine component and the tetracarboxylic acid component is 1 to 50% by mass, more preferably 5 to 30% by mass, based on the entire reaction solution.
• the initial reaction can be 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 and the total number of moles of the tetracarboxylic acid component is preferably 0.8 to 1.2, more preferably 0.9 to 1.1. . Similar to a normal polycondensation reaction, the molecular weight of the polyimide precursor formed 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 (imidization rate) of the amic acid group is not necessarily 100%, and can be arbitrarily adjusted according to the application and purpose.
• the method for imidizing the polyimide precursor include thermal imidization in which the polyimide precursor solution is heated as it is, or catalytic 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, and trioctylamine. Among them, pyridine is preferable because it has an appropriate basicity for proceeding with the reaction.
• Examples of 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, reaction time, and the like.
• 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. Further, when the specific polymer collected by precipitation is redissolved in an organic solvent and reprecipitation and collection are repeated 2 to 10 times, impurities in the polymer can be reduced.
• the solvent at this time include alcohols, ketones, and hydrocarbons, 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 contained in the liquid crystal aligning agent of the present invention is GPC (Gel Permeation) in consideration of the strength of the coating film obtained therefrom, workability when forming the coating film, uniformity of the coating film, and the like.
• the weight average molecular weight measured by the Chromatography method is preferably 5,000 to 1,000,000, 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 compound, a specific polymer, and an organic solvent.
• the content of the specific compound is preferably 0.1 to 150 parts by mass with respect to 100 parts by mass of the specific polymer, and a desired film curability is obtained by the progress of the crosslinking reaction.
• the amount is more preferably 0.1 to 100 parts by weight, and particularly preferably 1 to 50 parts by weight, in order to express the liquid crystal and not to deteriorate the orientation of the liquid crystal.
• the specific polymer in the liquid crystal aligning agent of the present invention may all be the specific polymer of the present invention, and other polymers may be mixed with the specific polymer of the present invention.
• the content of the other polymer in the specific polymer is 0.5 to 15% by mass, preferably 1 to 10% by mass, based on the entire specific polymer.
• other polymers include polyimide precursors and polyimides obtained from diamine components and tetracarboxylic dianhydrides.
• a polyimide precursor and a polymer other than polyimide specifically, an acrylic polymer, a methacrylic polymer, polystyrene, polyamide, or the like can be given.
• the content of the organic solvent is 70 to 99% by mass of the entire liquid crystal aligning agent from the viewpoint of forming a uniform thin film by coating. preferable.
• the content of the organic solvent 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 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 and an alkoxyl group, unless the effects of the present invention are impaired. It can also contain a crosslinkable compound having one type of substituent, a crosslinkable compound having a polymerizable unsaturated bond, and the like.
• 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, Tetraglycidyl-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 Triglycidyl-p-aminophenol
• the crosslinkable compound having an oxetane group is a crosslinkable compound having at least two oxetane groups represented by the following formula [4].
• Examples of the crosslinkable compound having at least one substituent selected from the group consisting of a hydroxyl group and an alkoxyl group include an amino resin having a hydroxyl group or an alkoxyl group, such as a melamine resin, a urea resin, a guanamine resin, and a glycol. Examples include uril-formaldehyde resin, succinylamide-formaldehyde resin, and ethylene urea-formaldehyde resin.
• 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.
• the melamine derivative and benzoguanamine derivative can exist as a dimer or a trimer. 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 is an average of 3.7 substituted methoxymethyl groups per triazine ring, and an average of 5 methoxymethyl groups per triazine ring. .8 substituted MW-30 (manufactured by Sanwa Chemical Co., Ltd.), Cymel 300, 301, 303, 350, 370, 771, 325, 327, 703, 712 and other methoxymethylated melamines, Cymel 235, Of methoxymethylated butoxymethylated melamine such as 236, 238, 212, 253, 254, butoxymethylated melamine such as Cymel 506, 508, carboxyl group-containing methoxymethylated isobutoxymethylated melamine such as Cymel 1141, Cymel 1123 Methoxymethylated et Cymethylated benzoguanamine, methoxymethylated butoxymethylated benzoguanamine such as Cymel 1123-10, butoxymethylated benzoguanamine such as
• Examples of the benzene having a hydroxyl group or an alkoxyl group or a phenolic compound include 1,3,5-tris (methoxymethyl) benzene, 1,2,4-tris (isopropoxymethyl) benzene, 1,4- Examples thereof include bis (sec-butoxymethyl) benzene and 2,6-dihydroxymethyl-p-tert-butylphenol. More specifically, it is a crosslinkable compound represented by the following formulas [5-1] to [5-48].
• crosslinkable compound having a polymerizable unsaturated bond examples include trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, tri (meth) acryloyloxyethoxytrimethylolpropane, Or a crosslinkable compound having three polymerizable unsaturated groups in the molecule, such as 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 (meth) Chlorate, neopentyl glycol di (meth) acrylate
• a 1 is cyclohexyl ring, bicyclohexyl ring, a benzene ring, a biphenyl ring, a terphenyl ring, a naphthalene ring, a fluorene ring, an anthracene ring, or a group selected from a phenanthrene ring
• a 2 is the following formula [6a Or a group selected from formula [6b], 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 in the liquid crystal aligning agent of the present invention is preferably 0.1 to 150 parts by mass with respect to 100 parts by mass of the entire specific polymer, and the crosslinking reaction proceeds to achieve the desired effect. Is preferably 0.1 to 100 parts by mass, and more preferably 1 to 50 parts by mass, in order to exhibit the above-described properties and not to deteriorate the orientation of the liquid crystal.
• a nitrogen-containing heterocyclic amine compound can be added as a compound that promotes charge transfer in the liquid crystal alignment film and promotes charge release of a liquid crystal cell using the liquid crystal alignment film.
• the nitrogen-containing heterocyclic amine compound compounds represented by the above formulas [M1] to [M156] exemplified as the basic compound can be used.
• the amine compound may be added directly to the solution of the specific polymer, but it is preferable to add the amine compound in a suitable solvent at a concentration of 0.1 to 10% by mass, preferably 1 to 7% by mass.
• the solvent is not particularly limited as long as it is an organic solvent that dissolves the above-described resin component.
• the liquid crystal aligning agent of the present invention is an organic solvent (also referred to as a poor solvent) or a compound that improves the uniformity of the film thickness and surface smoothness when the liquid crystal aligning agent is applied, as long as the effects of the present invention are not impaired.
• substrate can be contained.
• poor solvents that improve film thickness uniformity and surface smoothness include the following.
• These poor solvents may be used alone or in combination.
• the above poor solvent it is preferably 5 to 80% by mass, more preferably 20 to 60% by mass, based on the whole organic solvent contained in the liquid crystal alignment treatment agent.
• the compound that improves film thickness uniformity and surface smoothness include fluorine-based surfactants, silicone-based surfactants, and nonionic surfactants.
• 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 high molecular weight compound component contained in the liquid crystal aligning agent. It is.
• 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 100 parts by mass of the entire specific polymer contained in the liquid crystal aligning agent. Is 1 to 20 parts by mass. If the amount 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 liquid crystal alignment treatment agent of the present invention is a dielectric or conductive material for the purpose of changing the electrical properties such as the dielectric constant and conductivity of the liquid crystal alignment film as long as the effects of the present invention are not impaired. May be added.
• the liquid crystal aligning agent of the present invention can be used as a liquid crystal aligning film after being applied on a substrate and baked, and then subjected to an alignment treatment by rubbing treatment or light irradiation. Moreover, in the case of vertical alignment use 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. In addition to a glass 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 coating film. If the thickness of the coating 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.
• the thickness of the coating film is preferably 5 to 300 nm, more preferably 10 to 100 nm.
• 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 method for manufacturing a liquid crystal cell prepare a pair of substrates on which a liquid crystal alignment film is formed, spray spacers on the liquid crystal alignment film of one substrate, and place the other side of the liquid crystal alignment film on the other side. And a method of sealing the substrate by injecting liquid crystal under reduced pressure, or a method of sealing the substrate by bonding the liquid crystal after dropping the liquid crystal on the liquid crystal alignment film surface on which the spacers are dispersed.
• the liquid-crystal aligning agent of this invention has a liquid-crystal layer between a pair of board
• the liquid crystal composition is also preferably used for a liquid crystal display element produced 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 above liquid crystal display element controls the 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. it can.
• 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.
• 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. It is possible to control the orientation of the liquid crystal molecules by polymerizing.
• a liquid crystal cell 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. A method of bonding the other substrate and injecting liquid crystal under reduced pressure, 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 bonded and sealed. It is done.
• 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. Thereby, the alignment of the liquid crystal molecules can be controlled.
• the liquid crystal display element produced using the liquid crystal aligning agent of this invention becomes the thing excellent in reliability, and can be utilized suitably for a large-screen, high-definition liquid crystal television.
• dichloromethane (200 g) was added to the crude product, followed by stirring at 20 ° C., and further compound (c) (12.1 g, 96.8 mmol), pyridine (13.93 g, 176 mmol), and dichloromethane (100 g). The solution was slowly added dropwise. After stirring for 1 hour, compound (c) (12.1 g, 96.8 mmol) and pyridine (13.93 g, 176 mmol) were further added. After completion of the reaction, the solvent was distilled off and washed with distilled water (144 g) to obtain a crude product.
• Tetrahydrofuran (144 g) was added to this crude product, dispersed and washed at 23 ° C., filtered, washed with tetrahydrofuran (130 g), distilled water (170 g), and methanol (150 g), and then dried to obtain the specific compound (2 (Yield: 17.72 g, Yield: 62%).
• p-PDA p-phenylenediamine
• m-PDA m-phenylenediamine
• DBA 3,5-diaminobenzoic acid
• DDM 4,4′-diaminodiphenylmethane
• Specific compounds Specific compound (1): Specific compound obtained by the synthetic route of Example 1
• Crosslinkable compound (1) YH-434L (manufactured by Toto Kasei) (epoxy-based crosslinkable compound)
• the imidation ratio of polyimide in the synthesis example was measured as follows. 20 mg of polyimide powder is put into an NMR sample tube (NMR sampling tube standard ⁇ 5 (manufactured by Kusano Kagaku)) and deuterated dimethyl sulfoxide (DMSO-d6, 0.05 mass% TMS (tetramethylsilane) mixed product) 0.53 ml. Was added and completely dissolved by sonication. A 500 MHz proton ( 1 H) NMR of this solution was measured with an NMR measuring device (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.
• This reaction solution was poured into methanol (330 ml), and the resulting precipitate was filtered off. This deposit was wash
• the imidation ratio of this polyimide was 50%, the number average molecular weight was 18,100, and the weight average molecular weight was 52,300.
• This reaction solution was put into methanol (370 ml), and the resulting precipitate was filtered off. This deposit was wash
• the imidation ratio of this polyimide was 51%, the number average molecular weight was 18,600, and the weight average molecular weight was 72,600.
• Table 43 shows the polyamic acid and polyimide of the present invention. * 1: Polyamic acid.
• a liquid crystal alignment treatment agent is spin-coated on the ITO surface of the substrate with 3 ⁇ 4 cm ITO electrode, and heat-treated at 80 ° C. for 5 minutes on a hot plate, and at 220 ° C. for 30 minutes in a thermal circulation clean oven, A substrate with a polyimide liquid crystal alignment film having a thickness of 100 nm was obtained.
• the surface of the liquid crystal alignment film in the vicinity of the center of the substrate after the rubbing treatment was randomly observed with a laser microscope set at a magnification of 100 times, and the rubbing scratches confirmed in an observation visual field of about 6.5 mm square,
• the rubbing treatment resistance was evaluated from the average value of rubbing shavings residue (adhered matter).
• the evaluation criteria were determined as follows. (Evaluation criteria) A: 20 or less rubbing scratches or rubbing scraps B: 20 to 40 rubbing scratches or rubbing scraps C: 40 to 60 rubbing scratches or rubbing scraps D: 60 or more rubbing scratches or rubbing scraps
• the liquid crystal cell for which the measurement of the voltage holding ratio was completed was irradiated with ultraviolet rays of 50 J / cm 2 in terms of 365 nm, and then VHR was measured under the same conditions.
• the ultraviolet irradiation was performed using a desktop UV curing device (HCT3B28HEX-1) (SEN LIGHT CORPRATION).
• NMP (48.8 g) was added to the polyimide powder (A) (10.0 g) obtained in Synthesis Example 1, and dissolved by stirring at 70 ° C. for 30 hours.
• an NMP solution of 3-API (10.0 g) NMP solution containing 5.0% by mass of 3-API
• NMP (14.5 g) NMP (14.5 g)
• BCS (75.0 g) BCS
• an NMP solution (10.0 g) of the specific compound (1) was added to this solution, and the mixture was stirred at 25 ° C. for 2 hours to obtain liquid crystal alignment.
• a treating agent (1) was obtained.
• This liquid crystal aligning agent was confirmed to be a uniform solution without any abnormality such as turbidity or precipitation.
• the rubbing treatment resistance was evaluated under the conditions described above.
• NMP 48.8 g was added to the polyimide powder (A) (10.0 g) obtained in Synthesis Example 1, and dissolved by stirring at 70 ° C. for 30 hours.
• an NMP solution of 3-API (10.0 g) NMP solution containing 5.0% by mass of 3-API
• NMP (14.5 g) NMP (14.5 g)
• BCS 75.0 g
• an NMP solution (10.0 g) of the specific compound (3) was added to this solution, and the mixture was stirred at 25 ° C. for 2 hours to obtain liquid crystal alignment.
• a treating agent (2) 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 (2), evaluation of rubbing treatment resistance and evaluation of electric characteristics were performed under the above-described conditions.
• NMP 48.8 g was added to the polyimide powder (A) (10.0 g) obtained in Synthesis Example 1, and dissolved by stirring at 70 ° C. for 30 hours.
• NMP solution of 3-AMP (10.0 g) NMP solution containing 5.0% by mass of 3-AMP
• NMP (14.5 g) NMP (14.5 g)
• BCS 75.0 g
• an NMP solution (10.0 g) of the specific compound (3) NMP solution containing 10.0% by mass of the specific compound (3)
• was added to this solution and the mixture was stirred at 25 ° C. for 2 hours to obtain liquid crystal alignment.
• a treating agent (3) 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 (3), evaluation of rubbing treatment resistance and evaluation of electric characteristics were performed under the above-described conditions.
• NMP (24.4 g) was added to the polyimide powder (A) (5.00 g) obtained in Synthesis Example 1 and dissolved by stirring at 70 ° C. for 30 hours.
• an NMP solution (10.0 g) of TEA NMP solution with TEA of 5.0% by mass
• NMP (5.60 g) NMP (5.60 g)
• BCS BCS (33.3 g) were added and stirred at 25 ° C. for 2 hours. did.
• an NMP solution (5.00 g) of the specific compound (3) (NMP solution containing 10.0% by mass of the specific compound (3)) was added to this solution, and the mixture was stirred at 25 ° C. for 2 hours to obtain liquid crystal alignment.
• a treating agent (4) 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 (4), the rubbing treatment resistance was evaluated under the conditions described above.
• NMP 48.8 g was added to the polyimide powder (A) (10.0 g) obtained in Synthesis Example 1, and dissolved by stirring at 70 ° C. for 30 hours.
• an NMP solution of 3-API (10.0 g) NMP solution containing 5.0% by mass of 3-API
• NMP (14.5 g) NMP (14.5 g)
• BCS 75.0 g
• an NMP solution (5.00 g) of the specific compound (4) NMP solution containing 10.0% by mass of the specific compound (4)
• was added to this solution and the mixture was stirred at 25 ° C. for 2 hours to obtain liquid crystal alignment.
• a treating agent (5) 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 (5), the rubbing resistance and the electrical characteristics were evaluated under the above-described conditions.
• NMP 48.8 g was added to the polyimide powder (A) (10.0 g) obtained in Synthesis Example 1, and dissolved by stirring at 70 ° C. for 30 hours.
• an NMP solution of 3-API (10.0 g) NMP solution containing 5.0% by mass of 3-API
• NMP (14.5 g) NMP (14.5 g)
• BCS 75.0 g
• an NMP solution (10.0 g) of the specific compound (4) NMP solution containing 10.0% by mass of the specific compound (4)
• was added to this solution and the mixture was stirred at 25 ° C. for 2 hours to obtain liquid crystal alignment.
• a treating agent (6) 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 (6), the rubbing resistance and the electrical characteristics were evaluated under the above-described conditions.
• Example 9 To the polyimide powder (A) (10.0 g) obtained in Synthesis Example 1, NMP (63.3 g) and BCS (75.0 g) were stirred at 50 ° C. for 15 hours. To this solution, an NMP solution (10.0 g) of the specific compound (2) (NMP solution containing 20.0% by mass of the specific compound (2)) was added and stirred for 2 hours at 25 ° C. (7) 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 (7), the rubbing resistance and the electrical characteristics were evaluated under the conditions described above.
• NMP 48.8 g was added to the polyimide powder (A) (10.0 g) obtained in Synthesis Example 1, and dissolved by stirring at 70 ° C. for 30 hours.
• an NMP solution of 3-API (10.0 g) NMP solution containing 5.0% by mass of 3-API
• NMP (14.5 g) NMP (14.5 g)
• BCS BCS (75.0 g)
• an NMP solution (10.0 g) of the specific compound (2) was added to this solution, and the mixture was stirred at 25 ° C. for 2 hours to obtain liquid crystal alignment.
• a treating agent (8) 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 (8), evaluation of rubbing treatment resistance and evaluation of electric characteristics were performed under the above-described conditions.
• NMP (48.8 g) was added to the polyimide powder (B) (10.0 g) obtained in Synthesis Example 2 and dissolved by stirring at 70 ° C. for 30 hours.
• an NMP solution of 3-API (10.0 g) NMP solution containing 5.0% by mass of 3-API
• NMP (14.5 g) NMP (14.5 g)
• BCS (75.0 g) BCS
• an NMP solution (10.0 g) of the specific compound (3) was added to this solution, and the mixture was stirred at 25 ° C. for 2 hours to obtain liquid crystal alignment.
• a treating agent (9) 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 (9), the rubbing resistance and the electrical characteristics were evaluated under the conditions described above.
• NMP (10.3 g) was added to the polyimide powder (D) (2.10 g) obtained in Synthesis Example 4, and dissolved by stirring at 70 ° C. for 30 hours.
• an NMP solution of 3-API (2.10 g) NMP solution containing 3-API of 5.0% by mass
• NMP (4.5 g) NMP (4.5 g)
• BCS (14.0 g) BCS (14.0 g) were added, and the mixture was heated to 50 ° C. And stirred for 15 hours.
• an NMP solution (2.10 g) of the specific compound (3) was added to this solution, and the mixture was stirred at 25 ° C. for 2 hours to obtain liquid crystal alignment.
• a treatment agent (10) 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 (10), the rubbing treatment resistance was evaluated under the conditions described above.
• NMP (48.8 g) was added to the polyimide powder (E) (10.0 g) obtained in Synthesis Example 5, and dissolved by stirring at 70 ° C. for 30 hours.
• an NMP solution of 3-API (10.0 g) NMP solution containing 5.0% by mass of 3-API
• NMP (14.5 g) NMP (14.5 g)
• BCS (75.0 g) BCS 75.0 g
• an NMP solution (10.0 g) of the specific compound (3) was added to this solution, and the mixture was stirred at 25 ° C. for 2 hours to obtain liquid crystal alignment.
• a treatment agent (11) was obtained.
• This liquid crystal aligning agent was confirmed to be a uniform solution without any abnormality such as turbidity or precipitation.
• the obtained liquid crystal aligning agent (11) the rubbing resistance and the electrical characteristics were evaluated under the conditions described above.
• Example 14 NMP (6.70 g) and 3-API NMP solution (2.30 g) were added to the polyamic acid solution (C) (15.0 g) having a resin solid content concentration of Synthesis Example 3 of 14.8% by mass. (3-MP NMP solution with 5.0 mass%), BCS (11.3 g), and NMP solution (2.30 g) of specific compound (3) (NMP with 10.0 mass% of specific compound (3)) Solution) was added and stirred at 25 ° C. for 2 hours to obtain a liquid crystal aligning agent (12). 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 (12), evaluation of rubbing treatment resistance and evaluation of electric characteristics were performed under the above-described conditions.
• Example 15 The polyamic acid solution (C) (15.0 g) having a resin solid concentration of 14.8% by mass obtained in Synthesis Example 3 was added to NMP (4.40 g) and 3-AMP in NMP (4.60 g). (3-MP NMP solution with 5.0 mass%), BCS (11.3 g), and NMP solution (2.30 g) of specific compound (3) (NMP with 10.0 mass% of specific compound (3)) Solution) and stirred at 25 ° C. for 2 hours to obtain a liquid crystal aligning agent (13). 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 (13), rubbing treatment resistance was evaluated under the conditions described above.
• Example 16> The polyamic acid solution (C) (15.0 g) having a resin solid content concentration obtained in Synthesis Example 3 was added to NMP (4.40 g), Hist. NMP solution (4.60 g) (NMP solution with Hist of 5.0% by mass), BCS (11.3 g), and NMP solution (2.30 g) of specific compound (3) (specific compound (3) is 10 0.0 mass% NMP solution) was added, and the mixture was stirred at 25 ° C. for 2 hours to obtain a liquid crystal aligning agent (14). 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 (14), the rubbing treatment resistance was evaluated under the conditions described above.
• the liquid crystal alignment film obtained from the liquid crystal alignment treatment agent of the example of the present invention is less rubbing scraped by rubbing than the liquid crystal alignment film obtained from the liquid crystal alignment treatment agent of the comparative example.
• the decrease in the voltage holding ratio was small even after being exposed to ultraviolet rays for a long time.
• Comparative Example 3 using the crosslinkable compound (1) the rubbing scrap due to the rubbing treatment was small, but the decrease in the voltage holding ratio after being exposed to ultraviolet rays for a long time was large.
• a liquid crystal display element having a liquid crystal alignment film obtained from 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 or the like.
• the liquid crystal alignment film obtained from the liquid crystal alignment treatment agent of the present invention is a liquid crystal display element that irradiates ultraviolet rays when controlling the alignment direction of the liquid crystal, that is, a liquid crystal layer between a pair of substrates provided with electrodes.
• a liquid crystal composition containing a polymerizable compound that is polymerized by at least one of active energy rays and heat between the pair of substrates, and polymerizing the polymerizable compound while applying a voltage between the electrodes It is also useful for liquid crystal display elements manufactured through the process.

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