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
  • 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
• • 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
• • 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
• • 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 alignment agent, a liquid crystal alignment film, and a liquid crystal display element.
• the liquid crystal display element is configured by sandwiching a liquid crystal layer between a pair of transparent substrates provided with electrodes. Then, in the liquid crystal display element, an organic film made of an organic material is used as the liquid crystal alignment film so that the liquid crystal is in a desired orientation state between the substrates. That is, the liquid crystal alignment film is a constituent member of the liquid crystal display element, is formed on the surface of the substrate that sandwiches the liquid crystal in contact with the liquid crystal, and plays a role of orienting the liquid crystal in a certain direction between the substrates. Furthermore, the pre-tilt angle of the liquid crystal can be controlled by the liquid crystal alignment film. A method of lowering the pretilt angle by mainly selecting a polyimide structure (see Patent Documents 1 and 2) is known.
• liquid crystal display elements In recent years, with the increasing performance of liquid crystal display elements, in addition to applications such as large-screen, high-definition liquid crystal televisions, in-vehicle applications such as car navigation systems, meter panels, surveillance cameras, and medical camera monitors.
• a liquid crystal display element is used, and due to the demand for viewing angle characteristics, even a rubbing alignment film is required to have a lower pretilt angle than before.
• the viewing angle dependence of the tint derived from the pretilt angle, so-called color shift has been pointed out as a problem, and in order to solve this problem, a liquid crystal alignment film having a pretilt angle of 1 degree or less has been proposed.
• the polyimide-based liquid crystal alignment agent an organic polar solvent having high hygroscopicity such as N-methyl-2-pyrrolidone is generally used. Therefore, when a coating film is obtained from the polyimide-based liquid crystal alignment agent containing the organic solvent, the obtained film tends to be easily affected by the environment in which the coating film is applied. In particular, when coating or the like is performed in a high humidity environment, there is a problem that the solubility of the polyimide decreases due to moisture absorption, the polyimide precipitates, and the film becomes white (moisture absorption whitening).
• the film that has undergone moisture absorption and whitening is dried or heated, there is a problem that the original characteristics of the liquid crystal alignment film cannot be obtained, and there is a problem that the surface of the obtained film is roughened.
• the polyimide component is precipitated on the flexographic plate to generate printing foreign matter, or the polyimide component is precipitated at the ejection head portion of the inkjet device. In some cases, it may lead to defects in the process, such as clogging of the head.
• an object of the present invention is to obtain a liquid crystal alignment film having a pretilt angle of 1 degree or less, and at the same time, the occurrence rate of display defects (line burn-in) is low even when a negative liquid crystal is used as the liquid crystal material.
• An object of the present invention is to provide a liquid crystal aligning agent from which a liquid crystal display element can be obtained.
• the hygroscopic whitening phenomenon can be suppressed, foreign matter and clogging are less likely to occur when the coating film is obtained, and the obtained film is less likely to cause surface roughness, and even if it is dried or heated, it can be dried or heated. It is an object of the present invention to provide a liquid crystal alignment agent capable of exhibiting the characteristics of the original liquid crystal alignment film.
• the present invention is based on the above findings and has the following gist.
• It is a liquid crystal aligning agent containing polyimide (A) obtained by imidizing a polyimide precursor which is a reaction product of a tetracarboxylic acid derivative component and a diamine component, and the tetracarboxylic acid derivative component is 1, 2, 3, 4 -A diamine containing at least one diamine selected from the following formulas (1a) to (1b) and containing a butanetetracarboxylic acid dianhydride or a derivative thereof, and a diamine represented by the following formula (2).
• D represents a divalent saturated hydrocarbon group having 1 to 20 carbon atoms, an unsaturated hydrocarbon group, an aromatic hydrocarbon group or a heterocycle, and D represents even if it has one or more substituents.
• E is a single-bonded or divalent saturated hydrocarbon group having 1 to 20 carbon atoms, an unsaturated hydrocarbon group, an aromatic hydrocarbon group or a heterocycle, and E has one or more substituents. You may.
• F represents a single bond, -O-, -OCO-, or -COO-.
• m is an integer of 0 or 1.
• A represents an organic group that can be desorbed by heat. The hydrogen atom of the benzene ring having amino groups at both ends may be substituted with one or more substituents.
• Boc represents a tert-butoxycarbonyl group.
• the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.
• liquid crystal alignment agent of the present invention By using the liquid crystal alignment agent of the present invention, a liquid crystal alignment film having a pretilt angle of 1 degree or less can be obtained, and a liquid crystal with a low occurrence rate of display defects (line burn-in) even when a negative liquid crystal is used as the liquid crystal material. A display element is obtained.
• the hygroscopic whitening phenomenon can be suppressed, foreign matter and clogging are less likely to occur when the coating film is obtained, and the obtained film is less likely to cause surface roughness, and even if it is dried or heated, it can be dried or heated. It is possible to obtain a liquid crystal alignment agent capable of exhibiting the characteristics of the original liquid crystal alignment film.
• the polyimide (A) (hereinafter, also referred to as a specific polymer) contained in the liquid crystal alignment agent of the present invention is a tetracarboxylic acid derivative component containing a specific tetracarboxylic acid dianhydride and a diamine component containing a specific diamine. It is obtained by imidizing the polyimide precursor obtained from.
• the polyimide (A) may be composed of one kind or two or more kinds. Examples of the polyimide precursor include polyamic acid or a derivative thereof (for example, polyamic acid ester). Specific examples of the materials used and manufacturing methods will be described in detail below.
• the tetracarboxylic acid derivative component used in the production of the specific polymer of the present invention is not only tetracarboxylic acid dianhydride, but also its derivatives, tetracarboxylic acid dihalide compound, tetracarboxylic acid dialkyl ester, and tetracarboxylic acid dialkyl ester. Dihalide can be used.
• the tetracarboxylic acid derivative component one kind of tetracarboxylic dianhydride or a derivative thereof may be used alone, or two or more kinds thereof may be used in combination.
• the tetracarboxylic acid derivative component contains 1,2,3,4-butanetetracarboxylic dianhydride or a derivative thereof.
• the preferable content of the above 1,2,3,4-butanetetracarboxylic dianhydride or a derivative thereof is preferably 50 to 100 mol% of the total tetracarboxylic acid derivative component, more preferably 50 to 95 mol%. It is preferable, and 50 to 90 mol% is more preferable.
• the tetracarboxylic acid derivative component used for producing the specific polymer contained in the liquid crystal alignment agent of the present invention is a required liquid crystal in addition to the above 1,2,3,4-butanetetracarboxylic acid dianhydride or a derivative thereof.
• Various tetracarboxylic acid derivative components can be used depending on the characteristics of the aligning agent or the liquid crystal alignment film. Specific examples thereof include acyclic aliphatic tetracarboxylic acid dianhydrides or derivatives thereof, alicyclic tetracarboxylic acid dianhydrides or derivatives thereof, aromatic tetracarboxylic acid dianhydrides or derivatives thereof. Can be mentioned.
• the aromatic tetracarboxylic dianhydride is an acid dianhydride obtained by intramolecular dehydration of four carboxy groups including at least one carboxy group bonded to the aromatic ring.
• the acyclic aliphatic tetracarboxylic dianhydride is an acid dianhydride obtained by intramolecular dehydration of four carboxy groups bonded to a chain hydrocarbon structure. However, it does not have to be composed of only a chain hydrocarbon structure, and a part thereof may have an alicyclic structure or an aromatic ring structure.
• the alicyclic tetracarboxylic dianhydride is an acid dianhydride obtained by intramolecular dehydration of four carboxy groups including at least one carboxy group bonded to the alicyclic structure. However, none of these four carboxy groups are bonded to the aromatic ring. Further, it is not necessary to have only an alicyclic structure, and a chain hydrocarbon structure or an aromatic ring structure may be partially provided.
• the tetracarboxylic acid derivative component those represented by the following formula (3) are preferable.
• the tetracarboxylic dianhydride represented by the following formula (3) or a derivative thereof may be used alone or in combination of two or more.
• X 1 has a structure selected from the following formulas (X1-1) to (X1-25).
• R 3 to R 23 independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, and an alkenyl group having 2 to 6 carbon atoms. It represents an alkynyl group having 2 to 6 carbon atoms, a monovalent organic group having 1 to 6 carbon atoms containing a fluorine atom, or a phenyl group. * Represents a bond. From the viewpoint of liquid crystal orientation, R 3 to R 23 are preferably a hydrogen atom, a halogen atom, a methyl group, or an ethyl group, and more preferably a hydrogen atom or a methyl group.
• j and k are integers of 0 or 1
• a 1 and A 2 are independently single-bonded, -O-, -CO-, respectively.
• a plurality of A 2 may be the same or different.
• formula (X1-1) include the following formulas (X1-1-1) to (X1-1-6).
• (X1-1-1) is particularly preferable from the viewpoint of enhancing the liquid crystal orientation. * Is synonymous with the above.
• the above X 1 is represented by the above formulas (X1-1) to (X1-3), (X1-5), (X1-7) to (X1-9), (X1-10).
• (X1-23) is preferable, and more preferably the above formulas (X1-1-1), (X1-1-2), (X1-2) to (X1-3), (X1-5), (X1). -7) to (X1-9), (X1-10) or (X1-23).
• the diamine component used for producing the polyimide (A) contained in the liquid crystal alignment agent of the present invention is represented by at least one diamine selected from the following formulas (1a) to (1b) and the following formula (2).
• Contains diamine The diamines represented by the following formulas (1a) to (1b) and the following formula (2) may be used alone or in combination of two or more.
• D represents a saturated hydrocarbon group having 1 to 20 divalent carbon atoms, an unsaturated hydrocarbon group, an aromatic hydrocarbon group or a heterocycle, and D has one or more substituents.
• E may be a single bond or a divalent saturated hydrocarbon group having 1 to 20 carbon atoms, an unsaturated hydrocarbon group, an aromatic hydrocarbon group or a heterocycle, and E may have one or more substituents. May have.
• F represents a single bond, -O-, -OCO-, or -COO-.
• M is an integer of 0 or 1.
• A represents an organic group that can be desorbed by heat. Both ends. The hydrogen atom of the benzene ring having an amino group of may be substituted with one or more substituents.
• Examples of the substituent of D or E include a halogen atom, an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, and a fluoroalkyl group having 1 to 10 carbon atoms. , Fluoroalkenyl group having 2 to 10 carbon atoms, fluoroalkoxy group having 1 to 10 carbon atoms, carboxy group, hydroxy group, alkyloxycarbonyl group having 1 to 10 carbon atoms, cyano group, nitro group and the like.
• the organic group that can be eliminated by heat is not particularly limited as long as it is an organic group in which -NHA is converted into an amino group by decomposition and elimination by heat.
• Examples of the structure of the organic group that can be desorbed by heat include a benzyloxycarbonyl group, a 9-fluorenylmethyloxycarbonyl group, an allyloxycarbonyl group, and a tertiary butoxycarbonyl group (tert-butoxycarbonyl group).
• Carbamate-based organic groups can be mentioned, but from the viewpoint of efficient desorption by heat, desorption at a relatively low temperature, and discharge as a harmless gas when desorbed, tertiary butoxycarbonyl. Groups are particularly preferred.
• the organic group is, for example, a hydrocarbon group which may have a nitrogen atom or an oxygen atom.
• the hydrogen atom of the benzene ring having amino groups at both ends may be substituted with a substituent, specifically, a halogen atom or an alkyl group having 1 to 5 carbon atoms.
• a substituent specifically, a halogen atom or an alkyl group having 1 to 5 carbon atoms.
• various selections are made depending on the availability of reagents and the like, but non-substituted ones are preferable.
• the substitution position of the amino group is not particularly limited, but the meta or para position is preferable from the viewpoint of synthesis difficulty and the availability of the reagent, and the para position is preferable from the viewpoint of liquid crystal orientation. Especially preferable.
• the meta or para position is preferable when the amide bond is used as a reference, and the meta position is preferable from the viewpoint of solubility. From the viewpoint of liquid crystal orientation, the para position is preferable.
• Examples of the saturated hydrocarbon group having 1 to 20 carbon atoms in D and E of the above formula (1a) or (1b) include -CH 2- or-(CH 2 ) m- (m is an integer of 2 to 20).
• Examples include groups substituted with cycloalkylene groups.
• Examples of the unsaturated hydrocarbon group include a group in which a part of the carbon-carbon bond of the saturated hydrocarbon group having 2 to 20 carbon atoms is replaced with a double bond or a triple bond.
• Examples of the aromatic hydrocarbon group include a benzene ring, a biphenyl structure or a naphthalene ring.
• heterocycle examples include pyrrol, imidazole, pyrazole, triazole, pyridine, pyrimidine, pyridazine, pyrazine, indole, benzimidazole, purine, quinoline, isoquinoline, naphthylidine, quinoxaline, phthalazine, triazine, carbazole, aclysine, piperazine and piperazin.
• Pyridazine hexamethyleneimine and other nitrogen atom-containing heterocycles.
• pyridine, pyrimidine, pyrazine, piperidine, piperazine, quinoline, carbazole or acridine are preferable.
• the diamine selected from the above formulas (1a) to (1b) is preferably a diamine selected from the following formulas (1-1) to (1-4).
• the content of at least one or more diamines selected from the above formulas (1a) to (1b) is preferably 5 to 50 mol% of the total diamine component, more preferably 10 to 50 mol%, and 10 to 40. More preferably mol%.
• the hydrogen atom of the benzene ring having amino groups at both ends may be substituted with a substituent, specifically, for example, a halogen atom or an alkyl group having 1 to 5 carbon atoms.
• a substituent specifically, for example, a halogen atom or an alkyl group having 1 to 5 carbon atoms.
• Various selections are made depending on availability and the like, but non-replacement ones are preferable.
• the diamine represented by the above formula (2) is preferably a diamine represented by the following formulas (2-1) to (2-2).
• the diamine content of the above formula (2) is preferably 50 to 95 mol%, more preferably 50 to 90 mol% of the total diamine component.
• the diamine component used for producing the polyimide (A) contained in the liquid crystal alignment agent of the present invention is various diamines (hereinafter, also referred to as other diamines) depending on the required characteristics of the liquid crystal alignment agent. .) Can be used.
• Other diamines include diamines (4) having the structure of the following formula (iv) in the molecule; diamines represented by the following formula (O); photoorienting groups such as 4,4'-diaminoazobenzene or diaminotran.
• Diamine having amide bond or urea bond such as diamine represented by the following formulas (h-1) to (h-6); 3,3'-diaminodiphenylmethane, 3,4'-diaminodiphenylmethane, 4 , 4'-diaminobenzophenone, 1,4-bis (4-aminophenyl) benzene, 1,3-bis (4-aminophenyl) benzene, 1,4-bis (4-aminobenzyl) benzene, the following formula (A) Diamine represented by -1) to (A-6); at least one nitrogen atom-containing structure selected from the group consisting of a nitrogen atom-containing heterocycle, a secondary amino group and a tertiary amino group (hereinafter, specified nitrogen).
• Diamine having an atom-containing structure Diamine having an atom-containing structure); 2,4-diaminophenol, 3,5-diaminophenol, 3,5-diaminobenzyl alcohol, 2,4-diaminobenzyl alcohol, 4,6-diaminoresorcinol; 4, 4'-diamino-3,3'-dihydroxybiphenyl, 2,4-diaminobenzoic acid, 2,5-diaminobenzoic acid, 3,5-diaminobenzoic acid and the following formulas (3b-1) to (3b-4)
• a diamine having a carboxy group such as a diamine represented by); 4- (2- (methylamino) ethyl) aniline, 4- (2-aminoethyl) aniline, 1- (4-aminophenyl) -1,3.
• D is an organic group that can be desorbed by heat. * Represents a bond, and at least one is bonded to an aliphatic hydrocarbon group.
• Ar represents a divalent benzene ring, biphenyl structure, or naphthalene ring.
• Two Ars may be the same or different, and any hydrogen atom on the benzene ring, biphenyl structure, or naphthalene ring is monovalent. It may be replaced with an organic group.
• P is an integer of 0 or 1.
• a 1 is a single bond, -CH 2 -, - C 2 H 4 -, - C (CH 3) 2 -, - CF 2 -, - C (CF 3) 2 -, -O-, -CO-, -NH-, -N (CH 3 )-, -CONH-, -NHCO-, -CH 2 O-, -OCH 2- , -COO-, -OCO-, -CON ( CH 3) -. or -N (CH 3) CO- indicates, m1 and m2 are each independently an integer of 0 to 4, and is m1 + m2 is an integer of 1 to 4.
• m3 and m4 are independently integers of 1 to 5.
• a 2 represents a linear or branched alkyl group having 1 to 5 carbon atoms
• m5 is 1 to 5.
• a 3 and a 4 are each independently a single bond, -CH 2 -., - C 2 H 4 -, - C (CH 3) 2 -, - CF 2- , -C (CF 3 ) 2- , -O-, -CO-, -NH-, -N (CH 3 )-, -CONH-, -NHCO-, -CH 2 O-, -OCH 2- , -COO -, - OCO -, - CON (CH 3) - or -N (CH 3) -CO- represents, m6 is an integer of 1-4).
• X v1 to X v4 and X p1 to X p2 are independently- (CH 2 ) a- (a is an integer of 1 to 15), -CONH-, -NHCO-, and -CON (CH). 3) -, - NH -, - O -, - CH 2 O -, - CH 2 OCO -, - COO-, or -OCO- represent, X v5 is -O -, - CH 2 O - , - CH 2 Represents OCO-, -COO-, or -OCO-.
• Xa is a single bond, -O-, -NH-, or -O- (CH 2 ) m- O- (m is an integer of 1 to 6).
• R v1 to R v4 and R 1a to R 1b independently represent an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, or an alkoxyalkyl group having 2 to 20 carbon atoms. The two ks may be the same or different.
• the diamine (4) having the structure of the above formula (iv) in the molecule specific examples of the organic group that can be desorbed by heat in D of the above formula (iv) are exemplified in the above A including a preferable embodiment. Can be mentioned. Further, the diamine (4) is more preferably an aromatic diamine having one or two benzene rings in the molecule from the viewpoint of reducing the occurrence rate of display defects (line burn-in).
• diamine (4) examples include diamines represented by the following formulas (4-1) to (4-5).
• the content of the diamine (4) having the structure of the above formula (iv) in the molecule is preferably 5 to 40 mol%, more preferably 5 to 35 mol%, and 5 to 30 mol% of the total diamine component. % Is more preferable.
• any hydrogen atom on the benzene ring, biphenyl structure, or naphthalene ring may be replaced with a monovalent organic group.
• the monovalent organic group include a halogen atom, an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, and a fluoroalkyl group having 1 to 10 carbon atoms.
• Fluoroalkenyl group having 2 to 10 carbon atoms Fluoroalkenyl group having 2 to 10 carbon atoms, fluoroalkoxy group having 1 to 10 carbon atoms, carboxy group, hydroxy group, alkyloxycarbonyl group having 1 to 10 carbon atoms, cyano group, nitro group and the like.
• the divalent organic group obtained by removing the two amino groups from the diamine represented by the above formula (O) is used as a preferable specific example of the divalent organic group obtained by removing the two amino groups from the diamine represented by the above formula (O).
• the group is mentioned. * Represents a bond.
• Examples of the nitrogen atom-containing heterocycle that the diamine having the specific nitrogen atom-containing structure may have include the heterocycle exemplified above. Of these, pyridine, pyrimidine, pyrazine, piperidine, piperazine, quinoline, carbazole or acridine are preferred.
• the secondary amino group and the tertiary amino group that the diamine having the specific nitrogen atom-containing structure may have are represented by, for example, the following formula (n).
• R represents a hydrogen atom or a monovalent hydrocarbon group having 1 to 10 carbon atoms.
• "*" Represents a bond that binds to a hydrocarbon group.
• Examples of the monovalent hydrocarbon group of R in the above formula (n) include an alkyl group such as a methyl group, an ethyl group and a propyl group; a cycloalkyl group such as a cyclohexyl group; and an aryl such as a phenyl group and a methylphenyl group.
• R is preferably a hydrogen atom or a methyl group.
• diamine having the specific nitrogen atom-containing structure examples include, for example, 2,6-diaminopyridine, 3,4-diaminopyridine, 2,4-diaminopyrimidine, 3,6-diaminocarbazole, and N-methyl-3.
• 6-Diaminocarbazole, 1,4-bis- (4-aminophenyl) -piperazin, 3,6-diaminoacridine, N-ethyl-3,6-diaminocarbazole, N-phenyl-3,6-diaminocarbazole examples thereof include diamines represented by the following formulas (Dp-1) to (Dp-8) and diamines represented by the following formulas (z-1) to (z-18).
• the liquid crystal alignment agent of the present invention is a polyimide precursor (B) which is a reaction product of a tetracarboxylic acid derivative component and a diamine component from the viewpoint of reducing the afterimage derived from residual DC (hereinafter, also referred to as a polymer (B)). May be contained.
• the polyimide precursor (B) may be composed of one kind or two or more kinds. Specific examples of the polyimide precursor (B) include polyamic acid or a derivative thereof (for example, polyamic acid ester), and polyamic acid is particularly preferable.
• Examples of the tetracarboxylic acid derivative component for obtaining the polymer (B) include acyclic aliphatic tetracarboxylic acid dianhydride, alicyclic tetracarboxylic acid dianhydride, aromatic tetracarboxylic acid dianhydride, or these. Derivatives can be mentioned. Specific examples of the acyclic aliphatic tetracarboxylic dianhydride, the alicyclic tetracarboxylic dianhydride, and the aromatic tetracarboxylic dianhydride include the tetracarboxylic dianhydride exemplified in the above-mentioned specific polymer. The derivative is mentioned.
• the preferable tetracarboxylic acid derivative component is selected from the group consisting of 1,2,3,4-butanetetracarboxylic acid dianhydride or a derivative thereof, a benzene ring, a cyclobutane ring structure, a cyclopentane ring structure and a cyclohexane ring structure. It is preferable to contain a tetracarboxylic acid dianhydride having at least one partial structure or a derivative thereof, and a 1,2,3,4-butanetetracarboxylic acid dianhydride, a compound represented by the above formula (3), or a compound represented by the above formula (3). These derivatives are more preferred.
• the tetracarboxylic acid derivative component one kind of tetracarboxylic dianhydride or a derivative thereof may be used alone, or two or more kinds may be used in combination.
• X is preferably X in the above formulas (X1-1) to (X1-10), (X1-21), (X1-23) to ( Examples thereof include tetracarboxylic acid dianhydride represented by the formula (3) selected from X1-25), 1,2,3,4-butanetetracarboxylic acid dianhydride, and derivatives thereof.
• the ratio of the tetracarboxylic acid dianhydride represented by the above formula (3), 1,2,3,4-butanetetracarboxylic acid dianhydride or derivatives thereof is used for the synthesis of the polymer (B). 1 to 100 mol% is preferable, 5 to 100 mol% is more preferable, and 10 to 100 mol% is further preferable with respect to 1 mol of the total tetracarboxylic acid derivative component.
• Examples of the diamine component for obtaining the polymer (B) include the diamine component exemplified in the above-mentioned specific polymer.
• a diamine having at least one group selected from the group consisting of a urea bond, an amide bond, a carboxy group and a hydroxy group in the molecule (hereinafter, also referred to as diamine (b1)) and the above-mentioned specific nitrogen atom-containing structure. It is preferable to contain at least one diamine selected from the group consisting of diamines having (hereinafter, also referred to as diamines (b2)).
• diamine component one kind of diamine may be used alone, or two or more kinds may be used in combination.
• the polymer (B) may be composed of one component or two or more components of a polyimide precursor.
• a more preferable specific embodiment of the polymer (B) is a group consisting of a polyimide precursor which is a reaction product of a diamine component containing the diamine (b1) and the diamine (b2) and a tetracarboxylic acid derivative component. It is selected from the group consisting of at least one polymer selected from the above (hereinafter, also referred to as a copolymer), a polyimide component which is a reaction product of the diamine component containing the diamine (b1) and the tetracarboxylic acid derivative component.
• a mixture with (B-p2) (hereinafter, also referred to as a polymer blend) can be mentioned.
• the above-mentioned copolymer or polymer blend may be used alone or in combination.
• the preferable amount of the diamine (b1) used is 30 to 100 mol%, more preferably 40 to 100 mol%, based on the total amount of the diamine component for producing the polymer (B). , More preferably 50-100 mol%.
• the preferable amount of the diamine (b2) used is 30 to 100 mol%, more preferably 40 to 100 mol%, based on the total amount of the diamine component for producing the polymer (B). , More preferably 50-100 mol%.
• the preferable amounts of diamine (b1) and diamine (b2) used are relative to the total amount of the diamine component for producing the polymer (B-p1) and the polymer (B-p2), respectively. , 20-100 mol%.
• a more preferable amount of the diamine (b1) is 20 to 90 mol%, more preferably 20 to 80 mol%, based on the total amount of the diamine component for producing the polymer (B-p1).
• a more preferable amount of the diamine (b2) is 20 to 80 mol%, more preferably 30 to 80 mol%, based on the total amount of the diamine component for producing the polymer (B-p2).
• diamine (b1) examples include diamines represented by the above formulas (1a) to (1b), diamines represented by the above formula (4-1), and the above formulas (h-1) to (h-).
• Diamine represented by 6 2,4-diaminophenol, 3,5-diaminophenol, 3,5-diaminobenzyl alcohol, 2,4-diaminobenzyl alcohol, 4,6-diaminoresorcinol, 4,4'- Diamino-3,3'-dihydroxybiphenyl, 2,4-diaminobenzoic acid, 2,5-diaminobenzoic acid or 3,5-diaminobenzoic acid or represented by the above formulas (3b-1) to (3b-4). Diamine is mentioned.
• diamine (b2) examples include the diamine exemplified in the specific polymer. Of these, diamines represented by the above formulas (Dp-1) to (Dp-8) and diamines represented by the above formulas (z-1) to (z-18) are preferable.
• the mass ratio of the content of the polymer (B-p1) to the content of the polymer (B-p2) is preferably 5/95 to 95/5, more preferably 10/90 to 90 /. It is 10.
• the content ratio of the specific polymer and the polymer (B) is 10/90 to 90/10 in terms of the mass ratio of [specific polymer] / [polymer (B)]. It is preferably 20/80 to 90/10, more preferably 20/80 to 80/20, and particularly preferably 20/80 to 80/20.
• the polyimide precursor used in the present invention can be synthesized, for example, by a known method as described in WO2013 / 157586.
• a polyimide can be obtained by ring-closing (imidizing) the above-mentioned polyimide precursor.
• the imidization rate as used herein is the ratio of the imide group to the total amount of the imide group derived from the tetracarboxylic acid dianhydride or its derivative and the carboxy group (or its derivative).
• the imidization ratio does not necessarily have to be 100%, and can be arbitrarily prepared according to the application and purpose.
• the imidization rate of the specific polymer used in the present invention, polyimide (A), is preferably 20 to 100%, more preferably 50 to 99%, still more preferably 70 to 70, from the viewpoint of reducing the occurrence rate of display defects. It is 99%.
• Examples of the method for imidizing the polyimide precursor include thermal imidization in which the solution of the polyimide precursor is heated as it is or catalytic imidization in which a catalyst is added to the solution of the polyimide precursor.
• the temperature at which the polyimide precursor is thermally imidized in the solution is preferably 100 to 400 ° C., more preferably 120 to 250 ° C., and it is preferable to remove the water generated by the imidization reaction from the outside of the system. ..
• the catalytic imidization of the polyimide precursor can be carried out by adding a basic catalyst and an acid anhydride to the solution of the polyimide precursor 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, the amount of the amic acid group, and the amount of the acid anhydride is 1 to 50 mol times, preferably 3 to 30 mol times the amic acid group. It is double.
• the basic catalyst include pyridine, triethylamine, trimethylamine, tributylamine, and trioctylamine. Among them, pyridine is preferable because it has an appropriate basicity for advancing the reaction.
• the acid anhydride examples include acetic anhydride, trimellitic anhydride, pyromellitic anhydride and the like. Among them, acetic anhydride is preferable because it facilitates purification after completion of the reaction.
• the imidization rate by catalytic imidization can be controlled by adjusting the amount of catalyst, the reaction temperature, and the reaction time.
• the reaction solution may be added to a solvent to precipitate.
• the solvent used for precipitation include methanol, ethanol, isopropyl alcohol, acetone, hexane, butyl cellsolve, heptane, methyl ethyl ketone, methyl isobutyl ketone, toluene, benzene, water and the like.
• the polymer which has been put into a solvent and precipitated can be collected by filtration and then dried at normal temperature or by heating under normal pressure or reduced pressure.
• the operation of redistributing the polymer recovered by precipitation in an organic solvent and repeating the operation of recovering the precipitate by reprecipitation is repeated 2 to 10 times, 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 the purification efficiency is further increased.
• the molecular weight of the polymer used in the present invention is a weight average molecular weight measured by a GPC (Gel Permeation Chromatography) method in consideration of the strength of the liquid crystal alignment film obtained from the polymer, the workability at the time of film formation, and the coating film property. It is preferably 5,000 to 1,000,000, more preferably 10,000 to 150,000.
• a terminal-modified polymer is synthesized by using an appropriate terminal modifier together with the tetracarboxylic acid derivative component and the diamine component as described above. May be good.
• the terminal-modified polymer has the effects of improving the film hardness of the liquid crystal alignment film obtained by the coating film and improving the adhesion characteristics between the sealant and the liquid crystal alignment film.
• Examples of the terminal of the specific polymer and the polymer (B) in the present invention include an amino group, a carboxy group, an acid anhydride group, an isocyanate group, and derivatives thereof.
• the amino group, carboxy group, acid anhydride group and isocyanate group can be obtained by a usual condensation reaction, and the derivative can be obtained by modifying the terminal with, for example, the following terminal modifier.
• terminal modifier examples include acetic anhydride, maleic anhydride, nagic anhydride, phthalic anhydride, itaconic anhydride, cyclohexanedicarboxylic acid anhydride, 3-hydroxyphthalic anhydride, trimellitic anhydride, and the following formula (m).
• the ratio of the terminal modifier used is preferably 0.01 to 20 mol parts, more preferably 0.01 to 10 mol parts, based on 100 mol parts of the total diamine component used.
• the liquid crystal alignment agent of the present invention contains a specific polymer and, if necessary, a polymer (B).
• the content of the polymer component contained in the liquid crystal alignment agent of the present invention is preferably 0.1 to 30% by mass, more preferably 3 to 10% by mass.
• the total content of the specific polymer and the polymer (B) contained in the liquid crystal alignment agent is preferably 1 to 9% by mass, more preferably 1.5 to 9% by mass. The total includes the case where one or two or more of the constituent unit elements are 0% by mass.
• the liquid crystal alignment agent of the present invention may contain other polymers in addition to the specific polymer and the polymer (B).
• polyimide (B) which is an imidized product of the polyimide precursor (B) (excluding polyimide (A), which is a specific polymer), polyester, polyamide, polyurea, and polyorganosiloxane.
• polyimide (B) which is an imidized product of the polyimide precursor (B) (excluding polyimide (A), which is a specific polymer)
• polyester polyamide
• polyurea polyurea
• polyorganosiloxane polyorganosiloxane
• the liquid crystal alignment agent is used for producing a liquid crystal alignment film, and takes the form of a coating liquid from the viewpoint of forming a uniform thin film.
• the liquid crystal alignment agent of the present invention is also preferably a coating liquid containing the above-mentioned polymer component and an organic solvent.
• the organic solvent contained in the liquid crystal alignment agent is not particularly limited as long as the polymer component is uniformly dissolved. Specific examples thereof include N, N-dimethylformamide, N, N-dimethylacetamide, N, N-dimethyllactamide, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, dimethylsulfoxide, and ⁇ -butyrolactone.
• ⁇ -Valerolactone 1,3-dimethyl-2-imidazolidinone, methylethylketone, cyclohexanone, cyclopentanone, 3-methoxy-N, N-dimethylpropanamide, 3-butoxy-N, N-dimethylpropanamide, N- (n-propyl) -2-pyrrolidone, N-isopropyl-2-pyrrolidone, N- (n-butyl) -2-pyrrolidone, N- (tert-butyl) -2-pyrrolidone, N- (n-pentyl) ) -2-Pyrrolidone, N-methoxypropyl-2-pyrrolidone, N-ethoxyethyl-2-pyrrolidone, N-methoxybutyl-2-pyrrolidone, N-cyclohexyl-2-pyrrolidone (collectively, "good solvent”) Also called).
• N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, 3-methoxy-N, N-dimethylpropanamide, 3-butoxy-N, N-dimethylpropanamide or ⁇ -butyrolactone are preferable.
• the content of the good solvent is preferably 20 to 99% by mass, more preferably 20 to 90% by mass, and particularly preferably 30 to 80% by mass, based on the total amount of the solvent contained in the liquid crystal alignment agent.
• the organic solvent contained in the liquid crystal aligning agent is a mixture of the above solvent and a solvent (also referred to as a poor solvent) that improves the coatability when the liquid crystal aligning agent is applied and the surface smoothness of the coating film.
• a solvent also referred to as a poor solvent
• the use of a solvent is preferred. Specific examples of the organic solvent used in combination are described below, but the present invention is not limited thereto.
• diisopropyl ether diisobutyl ether, diisobutylcarbinol (2,6-dimethyl-4-heptanol)
• ethylene glycol dimethyl ether ethylene glycol diethyl ether
• ethylene glycol dibutyl ether 1,2-butoxyethane
• diethylene glycol dimethyl ether diethylene glycol diethyl ether.
• diisobutylcarbinol diisobutylcarbinol, propylene glycol monobutyl ether, propylene glycol diacetate, diethylene glycol diethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol dimethyl ether, 4-hydroxy-4-methyl-2-pentanone, ethylene glycol monobutyl ether, ethylene.
• Glycol monobutyl ether acetate or diisobutyl ketone is preferred.
• Preferred solvent combinations of good and poor solvents include N-methyl-2-pyrrolidone, ⁇ -butyrolactone and ethylene glycol monobutyl ether acetate, N-ethyl-2-pyrrolidone and ethylene glycol monobutyl ether and ethylene glycol monobutyl ether acetate.
• N-Methyl-2-pyrrolidone and ethylene glycol monobutyl ether N-methyl-2-pyrrolidone and ⁇ -butyrolactone and ethylene glycol monobutyl ether, N-methyl-2-pyrrolidone and ⁇ -butyrolactone and propylene glycol monobutyl ether, N- Ethyl-2-pyrrolidone and propylene glycol monobutyl ether, N-methyl-2-pyrrolidone and ⁇ -butyrolactone and 4-hydroxy-4-methyl-2-pentanone and diethylene glycol diethyl ether, N-methyl-2-pyrrolidone and ⁇ -butyrolactone And Propylene Glycol Monobutyl Ether and 2,6-Dimethyl-4-Heptanone, N-Methyl-2-pyrrolidone and ⁇ -Butylollactone and Propylene Glycol Monobutyl Ether and Diisopropyl Ether, N-Met
• the content of the poor solvent is preferably 1 to 80% by mass, more preferably 10 to 80% by mass, and particularly preferably 20 to 70% by mass, based on the total amount of the solvent contained in the liquid crystal alignment agent.
• the type and content of the poor solvent are appropriately selected according to the coating apparatus for the liquid crystal alignment agent, coating conditions, coating environment, and the like.
• the liquid crystal alignment agent of the present invention may additionally contain a component other than the polymer component and the organic solvent (hereinafter, also referred to as an additive component).
• additive components include an adhesion aid for increasing the adhesion between the liquid crystal alignment film and the substrate and the adhesion between the liquid crystal alignment film and the sealant, and a compound for increasing the strength of the liquid crystal alignment film (hereinafter, (Also referred to as a crosslinkable compound), dielectrics and conductive substances for adjusting the dielectric constant and electrical resistance of the liquid crystal alignment film, imidization accelerators, and the like can be mentioned.
• the crosslinkable compound exhibits good resistance to AC afterimages (afterimages generated by a decrease in the alignment performance of the liquid crystal alignment film generated by long-term AC driving) and has a high improvement in film strength.
• it consists of a group consisting of an oxylanyl group, an oxetanyl group, a protected isocyanate group, a protected isothiocyanate group, a group containing an oxazoline ring structure, a group containing a meldric acid structure, a cyclocarbonate group and a group represented by the following formula (d).
• R 2 and R 3 are each independently a hydrogen atom, an alkyl group having 1 to 3 carbon atoms or "* -CH 2- OH". * Indicates a bond.
• A has an aromatic ring. It represents an organic group of (m + n) valence. M represents an integer of 1 to 6, n represents an integer of 0 to 4.
• the aromatic ring of A may be substituted with a monovalent group, and the monovalent group may be substituted. Specific examples of the group include monovalent organic groups represented by Ar substituents in the above formula (O) (excluding alkoxy groups having 1 to 10 carbon atoms).
• the compound having an oxylanyl group examples include the compound described in paragraph [0037] of JP-A-10-338880 and the compound having a triazine ring as a skeleton described in International Publication No. 2017/170483.
• Examples include compounds having more than one oxylanyl group.
• the compound having an oxetanyl group include the compounds having two or more oxetanyl groups described in paragraphs [0170] to [0175] of International Publication No. 2011/132751.
• the compound having a protected isocyanate group include the compounds having two or more protected isocyanate groups described in paragraphs [0046] to [0047] of Japanese Patent Application Laid-Open No. 2014-224978, International Publication No. 2015/141598.
• Examples of the compound having three or more protected isocyanate groups described in paragraphs [0119] to [0120] of the above, and the compound represented by the following formulas (bi-1) to (bi-3) may be used. ..
• Specific examples of the compound having a protected isothiocyanate group include compounds having two or more protected isothiocyanate groups described in Japanese Patent Application Laid-Open No. 2016-209488.
• Specific examples of the compound having a group containing an oxazoline ring structure include compounds containing two or more oxazoline structures described in paragraph [0115] of Japanese Patent Application Laid-Open No. 2007-286597.
• Specific examples of the compound having a group containing a Meldrum's acid structure include the compound having two or more Meldrum's acid structures described in International Publication No. 2012/091088.
• Examples of the alkyl group having 1 to 3 carbon atoms of the groups R 2 and R 3 represented by the above formula (d) include a methyl group, an ethyl group and a propyl group.
• the compound having a group represented by the above formula (d) include the above formula (d) described in International Publication No. 2015/072554 and paragraph [0058] of Japanese Patent Application Laid-Open No. 2016-118753.
• Examples thereof include compounds having two or more groups represented by, compounds described in Japanese Patent Application Laid-Open No. 2016-209488, and compounds represented by the following formulas (hd-1) to (hd-8). May be good.
• Examples of the (m + n) -valent organic group having an aromatic ring in A of the above formula (e) include an (m + n) -valent aromatic hydrocarbon group having 6 to 30 carbon atoms and an aromatic hydrocarbon group having 6 to 30 carbon atoms. Examples thereof include a (m + n) -valent organic group in which a hydrogen group is directly bonded or via a linking group, and a (m + n) -valent group having an aromatic heterocycle.
• Examples of the aromatic hydrocarbon include benzene and naphthalene.
• aromatic heterocycle examples include a pyrrole ring, an imidazole ring, a pyrazole ring, a pyridine ring, a pyrimidine ring, a quinoline ring, an isoquinoline ring, a carbazole ring, a pyridazine ring, a pyrazine ring, a benzimidazole ring, an indole ring, a quinoxaline ring, and an acridin ring. And so on.
• linking group examples include -NR- (R represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms), an alkylene group having 1 to 10 carbon atoms, or a group obtained by removing one hydrogen atom from the alkylene group. Examples thereof include a divalent or trivalent cyclohexane ring. Any hydrogen atom of the alkylene group may be substituted with an organic group such as a fluorine atom or a trifluoromethyl group. Specific examples include the compounds described in International Publication No. 2010/074269 and the compounds represented by the following formulas (e-1) to (e-10).
• the above compound is an example of a crosslinkable compound, and is not limited thereto.
• components other than the above disclosed in International Publication No. 2015/060357 on pages 53 [0105] to 55 [0116] can be mentioned.
• the content of the crosslinkable compound in the liquid crystal aligning agent of the present invention is preferably 0.5 to 20 parts by mass with respect to 100 parts by mass of the polymer component contained in the liquid crystal aligning agent, and the crosslinking reaction proceeds. From the viewpoint of exhibiting good resistance to AC afterimages, the amount is more preferably 1 to 15 parts by mass.
• adhesion aid examples include 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropyldiethoxymethylsilane, 2-aminopropyltrimethoxysilane, 2-aminopropyltriethoxysilane, and N.
• -Styryltrimethoxysilane 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyltrimethoxy Silane cups such as silane, tris- (trimethoxysilylpropyl) isocyanurate, 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-isocyanoxidetriethoxysilane, etc. Ring agent can be mentioned.
• silane coupling agent when used, it should be 0.1 to 30 parts by mass with respect to 100 parts by mass of the polymer component contained in the liquid crystal alignment agent from the viewpoint of exhibiting good resistance to AC afterimages. It is preferably 0.1 to 20 parts by mass.
• the solid content concentration in the liquid crystal alignment agent (the ratio of the total mass of the components other than the solvent of the liquid crystal alignment agent to the total mass of the liquid crystal alignment agent) is appropriately selected in consideration of viscosity, volatility, etc., but is preferable. It is in the range of 0.5 to 15% by mass, more preferably 1 to 10% by mass.
• the range of particularly preferable solid content concentration depends on the method used when applying the liquid crystal alignment agent to the substrate. For example, in the case of the spin coating method, the solid content concentration is particularly preferably in the range of 1.5 to 4.5% by mass.
• the solid content concentration is in the range of 3 to 9% by mass, and the solution viscosity is in the range of 12 to 50 mPa ⁇ s.
• the solid content concentration is in the range of 1 to 5% by mass and the solution viscosity is in the range of 3 to 15 mPa ⁇ s.
• the liquid crystal alignment film of the present invention is obtained from the above liquid crystal alignment agent.
• the liquid crystal alignment film of the present invention can be used for a horizontally oriented type or vertically oriented type (VA type) liquid crystal alignment film, and among them, a liquid crystal alignment suitable for a horizontally oriented liquid crystal display element such as an IPS system or an FFS system. It is a membrane.
• the liquid crystal display element of the present invention includes the liquid crystal alignment film.
• the liquid crystal display element of the present invention can be manufactured, for example, by a method including the following steps (1) to (3).
• the liquid crystal alignment agent of the present invention is applied to one surface of a substrate provided with a patterned transparent conductive film, for example, by a roll coater method, a spin coating method, a printing method, or an inkjet. Apply by an appropriate coating method such as the method.
• the substrate is not particularly limited as long as it is a highly transparent substrate, and a plastic substrate such as an acrylic substrate or a polycarbonate substrate can be used together with the glass substrate and the silicon nitride substrate.
• the reflective liquid crystal display element if only one side of the substrate is used, an opaque object such as a silicon wafer can be used, and in this case, a material that reflects light such as aluminum can also be used for the electrode.
• the prebake temperature is preferably 30 to 200 ° C, more preferably 40 to 150 ° C, and particularly preferably 40 to 100 ° C.
• the prebake time is preferably 0.25 to 10 minutes, more preferably 0.5 to 5 minutes.
• a heating (post-baking) step is further carried out.
• the post-bake temperature is preferably 80 to 300 ° C, more preferably 120 to 250 ° C.
• the post-bake time is preferably 5 to 200 minutes, more preferably 10 to 100 minutes.
• the film thickness of the film thus formed is preferably 5 to 300 nm, more preferably 10 to 200 nm.
• the coating film formed in the above step (1) can be used as it is as a liquid crystal alignment film, but the coating film may be subjected to an alignment ability imparting treatment.
• the alignment ability-imparting treatment includes a rubbing treatment in which the coating film is rubbed in a certain direction with a roll wrapped with a cloth made of fibers such as nylon, rayon, and cotton, and photoalignment in which the coating film is irradiated with polarized or unpolarized radiation. Processing etc. can be mentioned.
• the radiation to irradiate the coating film for example, ultraviolet rays including light having a wavelength of 150 to 800 nm and visible light can be used.
• the radiation when the radiation is polarized, it may be linearly polarized or partially polarized.
• the irradiation may be performed from a direction perpendicular to the substrate surface, may be performed from an oblique direction, or may be performed in combination thereof.
• the direction of irradiation is diagonal.
• the second method is a method called the ODF (One Drop Fill) method.
• ODF One Drop Fill
• an ultraviolet light-curable sealant is applied to a predetermined place on one of the two substrates on which the liquid crystal alignment film is formed, and the liquid crystal composition is further applied to a predetermined number of places on the liquid crystal alignment film surface. Is dropped. After that, the other substrate is attached so that the liquid crystal alignment films face each other, and the liquid crystal composition is spread over the entire surface of the substrate and brought into contact with the film surface. Next, the entire surface of the substrate is irradiated with ultraviolet light to cure the sealant.
• the two substrates are arranged so as to face each other so that the rubbing directions of the coating films are opposite to each other at a predetermined angle, for example, orthogonal or antiparallel.
• the sealing agent for example, an epoxy resin containing an aluminum oxide sphere as a curing agent and a spacer can be used.
• the liquid crystal include a nematic liquid crystal and a smectic liquid crystal, and among them, the nematic liquid crystal is preferable.
• a liquid crystal display element can be obtained by attaching a polarizing plate to the outer surface of the liquid crystal cell.
• a polarizing plate attached to the outer surface of the liquid crystal cell for example, a polarizing plate or H in which a polarizing film called "H film” in which polyvinyl alcohol is stretched and oriented and iodine is absorbed is sandwiched between cellulose acetate protective films.
• a polarizing plate made of the film itself can be mentioned.
• the liquid crystal display element of the present invention can be effectively applied to various devices, for example, a clock, a portable game, a word processor, a notebook computer, a car navigation system, a cam coder, a PDA, a digital camera, a mobile phone, a smartphone, and the like. It can be used for various display devices such as various monitors, liquid crystal televisions, and information displays.
• AD-1 3-glycidoxypropyltriethoxysilane
• AD-2 A compound represented by the following structural formula.
• the viscosity of the polymer solution was determined by using an E-type viscometer TVE-22H (manufactured by Toki Sangyo Co., Ltd.), a sample volume of 1.1 mL, a cone rotor TE-1 (1 ° 34', R24), and a temperature of 25. Measured at ° C.
• the imidization rate of polyimide in the synthetic example was measured as follows. 30 mg of polyimide powder is placed in an NMR (nuclear magnetic resonance) sample tube (NMR sampling tube standard, ⁇ 5 (manufactured by Kusano Kagaku Co., Ltd.)) and deuterated dimethyl sulfoxide (DMSO-d 6,0.05 mass% TMS (tetramethylsilane)). (Mixed product) (0.53 ml) was added and ultrasonically applied to completely dissolve. This solution was measured for proton NMR at 500 MHz with an NMR measuring machine (JNW-ECA500) (manufactured by JEOL Datum Ltd.).
• a solution of terminally modified polyamic acid (PAA-0-1) was obtained.
• PAA-0-1 terminally modified polyamic acid
• a 200 mL triangular flask containing a stirrer 100 g of the above solution (PAA-0-1) was taken, 66.7 g of NMP, 14.2 g of acetic anhydride, and 4.70 g of pyridine were added, and the mixture was added at room temperature for 30 minutes. After stirring, the reaction was carried out at 60 ° C. for 4 hours. This reaction solution was put into 650 g of methanol, and the obtained precipitate was filtered off. The precipitate was washed with methanol and then dried under reduced pressure at a temperature of 80 ° C.
• the method of manufacturing the liquid crystal display element for evaluating the pre-tilt angle and the voltage holding ratio is shown below.
• a substrate with electrodes was prepared.
• the substrate is a glass substrate having a size of 30 mm ⁇ 40 mm and a thickness of 1.1 mm.
• An ITO electrode having a film thickness of 35 nm is formed on the substrate, and the electrode has a stripe pattern of 40 mm in length and 10 mm in width.
• the liquid crystal alignment agent obtained above was filtered through a filter having a pore size of 1.0 ⁇ m, and then applied to the prepared substrate with electrodes by spin coating. After drying on a hot plate at 80 ° C.
• Two substrates with the liquid crystal alignment film are prepared, a spacer of 4 ⁇ m is sprayed on the surface of the liquid crystal alignment film, a sealant is printed on the substrate, and the rubbing direction of the other substrate is opposite. Then, after the film surfaces were bonded so as to face each other, the sealant was cured to prepare an empty cell.
• a negative type liquid crystal MLC-7026 (manufactured by Merck & Co., Inc.) was injected into this empty cell by a reduced pressure injection method, and the injection port was sealed to obtain a liquid crystal cell. Then, the obtained liquid crystal cell was heated at 120 ° C. for 1 hour, left at 23 ° C. overnight, and then used for each evaluation.
• ⁇ Pre-tilt angle> The pretilt angle in the liquid crystal display element was evaluated using an AxoScan Muller matrix polarimeter manufactured by Optometrics. The lower the value of the pretilt angle, the better.
• ⁇ Voltage retention rate> A voltage of 1 V was applied to the liquid crystal display element at a temperature of 60 ° C. for 60 ⁇ sec, the voltage after 500 msec was measured, and how much the voltage could be maintained was evaluated as the voltage retention rate. The higher the value of the voltage holding ratio, the better. It is known that when the voltage holding ratio, which is one of the electrical characteristics of the liquid crystal display element, increases, line burn-in, which is one of the display defects of the liquid crystal display element, is less likely to occur.
• Table 5 below shows the results of the pre-tilt angle evaluation and the voltage retention evaluation for the liquid crystal display elements having the liquid crystal alignment films obtained by using the liquid crystal alignment agents of Examples 1 to 6 and Comparative Examples 1 to 5. Shown in.
• liquid crystal alignment agent of the embodiment of the present invention By using the liquid crystal alignment agent of the embodiment of the present invention, a liquid crystal alignment film having a pretilt angle of 1 degree or less was obtained, and a liquid crystal display having a high voltage retention rate even when a negative liquid crystal was used as the liquid crystal material. An element (that is, a liquid crystal display element having a low occurrence rate of display defects (line burn-in)) was obtained. Further, by using the liquid crystal alignment agent of the embodiment of the present invention, the moisture absorption and whitening phenomenon can be suppressed, foreign matter and clogging are less likely to occur when obtaining a coating film, and the obtained film has a rough surface. It was possible to obtain a liquid crystal alignment agent that is less likely to occur and that can exhibit the characteristics of the original liquid crystal alignment film even when dried or heated.
• the liquid crystal display element manufactured by using the liquid crystal aligning agent of the present invention can be a liquid crystal display element having excellent display quality, and is typified by a horizontally oriented liquid crystal display element such as an IPS system or an FFS system. It is preferably used for a display element according to the above method.

Landscapes

• Physics & Mathematics (AREA)
• Chemical & Material Sciences (AREA)
• Nonlinear Science (AREA)
• Organic Chemistry (AREA)
• Crystallography & Structural Chemistry (AREA)
• Mathematical Physics (AREA)
• Polymers & Plastics (AREA)
• Spectroscopy & Molecular Physics (AREA)
• Health & Medical Sciences (AREA)
• Medicinal Chemistry (AREA)
• Chemical Kinetics & Catalysis (AREA)
• General Physics & Mathematics (AREA)
• Optics & Photonics (AREA)
• Engineering & Computer Science (AREA)
• Materials Engineering (AREA)
• Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
• Liquid Crystal (AREA)

Priority Applications (3)

Applications Claiming Priority (2)

Publications (1)

Family

ID=78024147

Family Applications (1)

Country Status (5)

Citations (3)

Family Cites Families (3)

• 2021
  • 2021-04-02 KR KR1020227033082A patent/KR20230002334A/ko active Search and Examination
  • 2021-04-02 WO PCT/JP2021/014272 patent/WO2021206003A1/ja active Application Filing
  • 2021-04-02 CN CN202180027287.5A patent/CN115380245A/zh active Pending
  • 2021-04-02 JP JP2022514451A patent/JPWO2021206003A1/ja active Pending
  • 2021-04-08 TW TW110112654A patent/TW202202605A/zh unknown

Patent Citations (3)

Also Published As

Similar Documents

Legal Events