Classifications

• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D251/00—Heterocyclic compounds containing 1,3,5-triazine rings
  • C07D251/02—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings
  • C07D251/12—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members
  • C07D251/26—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members with only hetero atoms directly attached to ring carbon atoms
  • C07D251/30—Only oxygen atoms
  • C07D251/34—Cyanuric or isocyanuric esters
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D251/00—Heterocyclic compounds containing 1,3,5-triazine rings
  • C07D251/02—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings
  • C07D251/12—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members
  • C07D251/26—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members with only hetero atoms directly attached to ring carbon atoms
  • C07D251/38—Sulfur atoms
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D251/00—Heterocyclic compounds containing 1,3,5-triazine rings
  • C07D251/02—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings
  • C07D251/12—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members
  • C07D251/26—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members with only hetero atoms directly attached to ring carbon atoms
  • C07D251/40—Nitrogen atoms
  • C07D251/48—Two nitrogen atoms
  • C07D251/52—Two nitrogen atoms with an oxygen or sulfur atom attached to the third ring carbon atom
• • 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
• • 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

Definitions

• the present invention relates to a liquid crystal aligning agent, a liquid crystal aligning film obtained from the liquid crystal aligning agent, a liquid crystal display element comprising the liquid crystal aligning film, and a novel diamine and polymer suitable for them.
• Liquid crystal display elements are widely used, from small applications such as mobile phones and smartphones to relatively large applications such as televisions and monitors.
• a liquid crystal display element is generally constructed by arranging a pair of electrode substrates so as to face each other with a predetermined gap (several ⁇ m) and sealing liquid crystal between the electrode substrates. By applying a voltage between the transparent conductive films forming the respective electrodes of the electrode substrate, the display on the liquid crystal display element is performed.
• These liquid crystal display elements have liquid crystal alignment films that are indispensable for controlling the alignment state of liquid crystal molecules.
• Patent Document 1 discloses a polyimide alignment film obtained by using a diamine compound having a specific structure containing a triazine ring as a liquid crystal alignment film in which the pretilt angle of liquid crystal molecules can be easily adjusted.
• liquid crystal display element various drive systems having different electrode structures, different physical properties of liquid crystal molecules to be used, etc. have been developed. For example, various modes such as TN (Twisted Nematic) method, STN (Super Twisted Nematic) method, VA (Vertical Alignment) method, IPS (In-Plane Switching) method, and FFS (Fringe Field Switching) method are known. .
• TN Transmission Nematic
• STN Super Twisted Nematic
• VA Very Alignment
• IPS In-Plane Switching
• FFS Frringe Field Switching
• VA vertical alignment liquid crystal display elements have a wide viewing angle, fast response speed, high contrast, and can eliminate the need for rubbing in the production process. It is widely used mainly for monitors and monitors (Patent Documents 2 and 3).
• the above-mentioned transparent conductive film in the liquid crystal display element is usually formed of a composition (ITO) in which indium oxide is the main component and is doped with several percent of tin oxide (ITO). Unlike the refractive index, it has a high value. Therefore, when the light from the display light source is transmitted through the electrode substrate, the light is reflected at the interface between the transparent conductive film and the liquid crystal alignment film in each electrode substrate. As a result, a sufficient light transmittance of the electrode substrate cannot be obtained, resulting in a problem of reduced display brightness. In particular, in recent years, ultra-high-definition panels such as 4K and 8K have been developed. It is important to improve the transmittance of the display section.
• the present inventors have proposed the formation of the liquid crystal alignment film in order to increase the refractive index.
• a material for forming the liquid crystal alignment film polyamic acid or polyimide, which is one of its derivatives, is widely known.
• the use of a diamine having a triazine skeleton as a raw material diamine component for a polyimide liquid crystal alignment film is proposed in Patent Document 1, for example.
• the method using a diamine having a long-chain alkyl group or a polycyclic structure such as cholesterol and having a triazine skeleton which is specifically disclosed in Patent Document 1, has a refractive index. It was found that there is room for improvement in terms of increasing the rate. Specifically, in order to increase the refractive index of the liquid crystal alignment film, various types of polymers contained in the liquid crystal alignment agent forming the liquid crystal alignment film were searched.
• a liquid crystal alignment film formed from a liquid crystal alignment agent containing a polymer having a coloring property has low light transmittance, leading to a decrease in display brightness, and as a result, the above object cannot be achieved.
• an object of the present invention is to provide a liquid crystal aligning agent that forms a liquid crystal aligning film having a high light transmittance because it has a high refractive index but does not have coloring properties, and a liquid crystal aligning agent obtained from the liquid crystal aligning agent.
• An object of the present invention is to provide a film and a liquid crystal display element having the liquid crystal alignment film.
• a liquid crystal aligning agent containing a partially novel polymer having a specific structure is effective for achieving the above object. and completed the present invention.
• the present invention is selected from the group consisting of a polyimide precursor obtained using a diamine component containing a diamine (0) having a partial structure represented by the following formula (D T ) and a polyimide that is an imidized product of the polyimide precursor.
• R represents a hydrogen atom, a hydroxy group, a cyano group, a halogen atom, or a monovalent organic group having 1 to 4 carbon atoms; * represents a bond; hydrogen atoms may be replaced by monovalent groups, L 1 and L 2 are each independently a single bond, -(CH 2 ) n - (n is an integer of 1 to 6), -NR'-, -(CH 2 ) n -NR'- (n is an integer of 1 to 6), -O-, -S-, -O-CO-, or -CO-O-, and R' represents a hydrogen atom or a monovalent organic group.
• halogen atoms include fluorine, chlorine, bromine, and iodine atoms
• * represents a bond.
• the present invention it is possible to obtain a liquid crystal aligning agent that forms a liquid crystal alignment film having a high light transmittance because it has a high refractive index and does not have coloring properties. Since the liquid crystal alignment film on which such a liquid crystal alignment agent is formed has a high refractive index, it is possible to reduce the difference between the refractive index of the transparent conductive film and the refractive index of the liquid crystal alignment film in the liquid crystal display element. Since it does not have coloring properties, it is possible to obtain a liquid crystal display element with high light transmittance and high display luminance.
• the liquid crystal aligning agent of the present invention is, as described above, a polyimide obtained using a diamine component containing a diamine (0) having a partial structure represented by the following formula (D T ) (hereinafter also referred to as a specific diamine) It is characterized by containing at least one polymer (P) selected from the group consisting of a precursor and a polyimide which is an imidized product of the polyimide precursor.
• D T a diamine component containing a diamine (0) having a partial structure represented by the following formula (D T ) (hereinafter also referred to as a specific diamine) It is characterized by containing at least one polymer (P) selected from the group consisting of a precursor and a polyimide which is an imidized product of the polyimide precursor.
• D T a diamine component containing a diamine (0) having a partial structure represented by the following formula (D T ) (hereinafter also referred to as a specific diamine) It is characterized
• the monovalent organic group having 1 to 4 carbon atoms for R in the above formula (D T ) includes, for example, a hydrocarbon group having 1 to 4 carbon atoms, and at least between the carbon-carbon bonds of the hydrocarbon group or at the terminal
• the monovalent organic group (E) is a heteroatom-containing group or a carbon atom possessed by a hydrocarbon group.
• R′′ represents a monovalent organic group such as a hydrogen atom or a methyl group.
• hydrocarbon groups having 1 to 4 carbon atoms include carbon atoms such as methyl, ethyl, propyl, and butyl groups.
• Alkynyl groups having 2 to 4 carbon atoms such as alkyl groups having 1 to 4 carbon atoms, alkenyl groups having 2 to 4 carbon atoms such as vinyl groups and propenyl groups, and alkynyl groups having 2 to 4 carbon atoms such as ethynyl groups are mentioned.
• a part of the hydrogen atoms of the hydrogen group or the monovalent organic group (E) may be substituted with a substituent, and examples of the substituent include a halogen atom, a hydroxy group, and a cyano group.
• the halogen atom for R also has the same structure as described above.
• * in the formula (D T ) represents a bond, and any hydrogen atom of the benzene ring bonded to * may be replaced with a monovalent group.
• Specific examples of the monovalent group include methyl groups, ethyl groups, methoxy groups, and the like.
• the monovalent organic group having 1 to 4 carbon atoms in R in the above formula (D T ) is at least one selected from the group consisting of a halogen atom, an oxygen atom, a nitrogen atom, and a sulfur atom, from the viewpoint of increasing the refractive index. It is preferred to have seeds.
• R in the formula (D T ) include a fluorine atom, a chlorine atom, a methoxy group, an ethoxy group, a methylthio group, an ethylthio group, a trifluoromethylthio group, a dimethylamino group, a methyl group, an ethyl group, and a vinyl group, allyl group, methoxymethyl group, 2-methoxyethoxymethyl group, acetyl group, and hydroxy group.
• L 1 and L 2 in the above formula (D T ) are each independently a single bond, —(CH 2 ) n — (n is an integer of 1 to 6), from the viewpoint of suitably obtaining the effects of the present invention. ), -NR'-, -(CH 2 ) n -NR'- (n is an integer of 1 to 6.), -S-, or -O- is preferred, and -S-, -NH - or -O- is more preferred, and -S- is particularly preferred.
• R' represents a hydrogen atom or a monovalent organic group, and examples of the monovalent organic group include a methyl group, a tert-butoxycarbonyl group, an ethyl group and a propyl group.
• R' is preferably a hydrogen atom, a methyl group, or a tert-butoxycarbonyl group.
• the carbon atom adjacent to the carbon atom constituting the benzene ring bonded to L 1 and the benzene ring bonded to L 2 in the above formula (D T ) At least one selected from the group consisting of carbon atoms adjacent to the carbon atom is preferably bonded to a group capable of hydrogen bonding with the nitrogen atom of the triazine ring.
• a hydrogen atom is preferable as the hydrogen-bondable group.
• the group capable of hydrogen bonding is a hydrogen atom, it is possible to form a bond such as the following formula (M), and a stacking effect is obtained, which is more effective in increasing the refractive index.
• Preferable examples of the partial structure represented by the above formula (D T ) include the following formulas (d T ⁇ 1) to (d T ⁇ 3).
• R and * in the above formulas (d T -1) to (d T -3) are synonymous with R and * in the above formula (D T ), respectively.
• diamine (0) examples include diamines having the structure of the following formula (d 0 ).
• X represents the structure represented by the formula (D T )
• Ar and Ar′ each independently represent a divalent aromatic ring group.
• Specific examples of the aromatic ring in the divalent aromatic ring group include benzene ring, naphthalene ring, anthracene ring, pyridine ring, pyrimidine ring, pyrazine ring, pyridazine ring, triazine ring, pyrrole ring, imidazole ring, pyrazole ring, quinoline ring, isoquinoline ring, carbazole ring, benzimidazole ring, indole ring, quinoxaline ring and acridine ring.
• a hydrogen atom of the aromatic ring may be substituted with a monovalent group.
• the monovalent group include the structures exemplified for the monovalent group in the above formula (D T ).
• L d and L d ' are each independently a single bond, -(CH 2 ) n - (n is an integer of 1 to 6), -NR'-, - (CH 2 ) n —NR′— (n is an integer of 1 to 6), —O—, —S—, —O—CO—, or —CO—O—, where R′ is a hydrogen atom or represents a monovalent organic group.
• each of Ar and Ar′ independently has a benzene ring, naphthalene ring, anthracene ring, pyridine ring, pyrimidine ring, pyrazine ring, pyridazine ring, triazine ring, or carbazole ring.
• a benzene ring, a naphthalene ring, an anthracene ring, or a triazine ring is more preferred.
• Ld and Ld' are each independently preferably -NR'-, -O-, -S-, -O-CO- or -CO-O-, -NR'-, -O- or - S- is more preferred.
• R' is preferably a hydrogen atom, a methyl group, or a tert-butoxycarbonyl group.
• m and m' are each independently an integer of 0 to 2, preferably 0 or 1. When a plurality of Ar, Ar', L d and L d ' exist, the plurality of Ar, Ar', L d and L d ' may be the same or different.
• Examples of the diamine having the structure of formula (d 0 ) include diamines having a structure represented by the following formula (D TS ).
• D TS diamines having a structure represented by the following formula (D TS ).
• R represents a hydrogen atom, a hydroxy group, a cyano group, a halogen atom, or a monovalent organic group having 1 to 4 carbon atoms. Any hydrogen atom of the benzene ring bonded to the amino group may be replaced by a monovalent group.
• Preferred specific examples of the above formula (d 0 ) include diamines represented by the following formulas (d 0 -1) to (d 0 -9). Diamines of the formulas (d 0 -3), (d 0 -6) and (d 0 -9) are more preferred. (In the above formula, R has the same definition as R in the above formula (D T ).)
• the polymer (P) contained in the liquid crystal aligning agent of the present invention is from the group consisting of a polyimide precursor obtained using a diamine component containing the diamine (0) and a polyimide that is an imidized product of the polyimide precursor. At least one polymer is selected.
• the polyimide precursor is a polymer from which a polyimide can be obtained by imidating polyamic acid, polyamic acid ester, or the like.
• a polyamic acid (P′), which is a polyimide precursor of the polymer (P) can be obtained by a polymerization reaction between a diamine component containing the diamine (0) and a tetracarboxylic acid component.
• the diamine (0) may be used alone or in combination of two or more.
• the amount of diamine (0) used is preferably 5 mol % or more, more preferably 10 mol % or more, and even more preferably 20 mol % or more, based on the total diamine component.
• the diamine component used for producing the polyamic acid (P') may contain diamines other than diamine (0) (hereinafter also referred to as other diamines).
• diamine (0) diamine (0)
• the amount of the diamine (0) used is preferably 90 mol % or less, more preferably 80 mol % or less, relative to the diamine component. Examples of other diamines are listed below, but the present invention is not limited to these.
• the other diamines may be used singly or in combination of two or more.
• Diamines represented by the following formula (d1) or formula (d2) p-phenylenediamine, m-phenylenediamine, 4-(2-(methylamino)ethyl)aniline, 2,4-diaminobenzoic acid, 2,5 -diaminobenzoic acid, 3,5-diaminobenzoic acid, diamines having a carboxyl group such as diamine compounds represented by the following formulas (3b-1) to (3b-4), the following formulas (g-1) to (g) -6) having a photoalignable group such as diamines, 4,4′-diaminodiphenylmethane, 3,3′-diaminodiphenylmethane, 4,4′-diaminodiphenyl ether, 3,3′-diaminodiphenyl ether, 1,2-bis(4-aminophenyl)ethane, 1,3-bis(4-aminophenyl)propane, 1,4
• D is preferably a tert-butoxycarbonyl group.
• group "*-LOD" (* represents a bond with a nitrogen atom.
• L represents an alkylene group having 1 to 5 carbon atoms.
• D is a protecting group that is eliminated by heating and replaced with a hydrogen atom.
• D is preferably a tert-butoxycarbonyl group.), 1,3-bis(3-aminopropyl)-tetramethyldisiloxane, diamines represented by the following formula (Ds-1), etc.
• Diamines having a siloxane bond diamines having an oxazoline structure such as the following formulas (Ox-1) to (Ox-2), 1,1-meta-xylylenediamine, 1,3-propanediamine, tetramethylenediamine, pentamethylenediamine , hexamethylenediamine; cycloaliphatic diamines such as 1,4-diaminocyclohexane, 4,4'-methylenebis(cyclohexylamine), 1,3-bis(aminomethyl)cyclohexane.
• oxazoline structure such as the following formulas (Ox-1) to (Ox-2), 1,1-meta-xylylenediamine, 1,3-propanediamine, tetramethylenediamine, pentamethylenediamine , hexamethylenediamine; cycloaliphatic diamines such as 1,4-diaminocyclohexane, 4,4'-methylenebis
• X is a single bond, —O—, —C(CH 3 ) 2 —, —NH—, —CO—, —(CH 2 ) m —, —SO 2 —, —O -(CH 2 ) m -O-, -OC(CH 3 ) 2 -, -CO-(CH 2 ) m -, -NH-(CH 2 ) m -, -SO 2 -(CH 2 ) m -, -CONH-(CH 2 ) m -, -CONH-(CH 2 ) m -NHCO-, or -COO-(CH 2 ) m -OCO-, where m is an integer of 1 to 8.
• Y represents a structure represented by any one of the following formulas (S1) to (S2) In formula (d2), two Y's are the same may or may not be the same.
• X 1 is a single bond, —(CH 2 ) a — (a is an integer of 1 to 15), —CONH—, —NHCO—, —CO—N(CH 3 )-, -NH-, -O-, -COO-, -OCO- or -((CH 2 ) a1 -A 1 ) m1 - (a1 is an integer of 1 to 15, A 1 is an oxygen atom or - represents COO-, and m 1 is an integer of 1 to 2.
• m 1 is 2, multiple a 1 and A 1 each independently have the above definition).
• G 1 represents a divalent cyclic group selected from a divalent aromatic hydrocarbon group having 6 to 12 carbon atoms and a divalent alicyclic hydrocarbon group having 4 to 8 carbon atoms. Any hydrogen atom on the cyclic group is an alkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, a fluorine-containing alkyl group having 1 to 3 carbon atoms, or a fluorine-containing alkoxy group having 1 to 3 carbon atoms. Alternatively, it may be substituted with a fluorine atom.
• m is an integer of 1-4. When m is 2 or more, multiple X 1 and G 1 each independently have the above definition.
• R 1 is a fluorine atom, a fluorine-containing alkyl group having 1 to 10 carbon atoms, a fluorine-containing alkoxy group having 1 to 10 carbon atoms, an alkyl group having 3 to 10 carbon atoms, an alkoxy group having 3 to 10 carbon atoms, or 3 carbon atoms. represents an alkoxyalkyl group of ⁇ 10.
• X 2 represents -CONH-, -NHCO-, -O-, -CH 2 O-, -OCH 2 -, -COO- or -OCO-.
• G 2 represents a steroid skeleton.
• At least one of the hydrogen atoms of the structure having a steroid skeleton is a halogen atom, a halogen-containing alkyl group, a halogen-containing alkoxy group, an alkyl group having 3 to 10 carbon atoms, an alkyl group having 3 to 10 carbon atoms, Alkoxy groups, alkenyl groups having 3 to 10 carbon atoms, and the above halogen-containing alkyl groups, halogen-containing alkoxy groups, alkyl groups having 3 to 10 carbon atoms, alkoxy groups having 3 to 10 carbon atoms, and alkenyl groups having 3 to 10 carbon atoms Any carbon-carbon bond of the group may be substituted with a substituent selected from the group consisting of heteroatom-containing groups interrupted by oxygen atoms.)
• 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-, -CO- N(CH 3 )— or —N(CH 3 )—CO—, m1 and m2 each independently represent an integer of 0 to 4, and m1+m2 represents an integer of 1 to 4.
• Formula (3b) -2), m3 and m4 each independently represent an integer of 1 to 5.
• A2 represents a linear or branched alkyl group having 1 to 5 carbon atoms, and m5 is represents an integer of 1 to 5.
• a 3 and A 4 each independently represent 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-, -CO-N(CH 3 )- or -N(CH 3 )-CO-, and m6 is an integer of 1 to 4.
• L is a single bond, an alkylene group having 1 to 15 carbon atoms, or between the carbon-carbon bonds of the alkylene group and at least one of the terminals of the alkylene group, - represents a divalent organic group into which O-, -COO-, -NH-, -NHCO- or -CON(CH 3 )- is inserted (provided that the above divalent organic group is an ester bond adjacent to L ),
• X 1 , G 1 , and R 1 are the same as defined in the above formula (S1)
• m is an integer of 0 to 4
• m is 2 or more , a plurality of X 1 and G 1 each independently have the above definition
• the hydrogen atom on the benzene ring is an alkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, or a carbon It may be substituted with a fluorine-containing alkyl group having 1 to 3 carbon atoms,
• n1 is an integer of 2 to 12.
• n is an integer of 1 to 6.
• Boc represents a tert-butoxycarbonyl group.
• examples of the divalent cyclic group for G 1 include a cyclopropylene group, a cyclohexylene group, and a phenylene group. Any hydrogen atom on these cyclic groups may be an alkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, a fluorine-containing alkyl group having 1 to 3 carbon atoms, or a fluorine-containing alkoxy group having 1 to 3 carbon atoms. may be substituted with groups or fluorine atoms.
• the structure having a steroid skeleton in G2 is preferably a structure containing a cholestanyl group, a cholesteryl group, or a lanostanyl group.
• Preferable examples of the diamine represented by the above formula (d1) include the following formulas (d1-1) to (d1-6).
• Preferable examples of the diamine represented by the above formula (d2) include the following formulas (d2-1) to (d2-6).
• diamines include diamines represented by formula (d1) or formula (d2), p-phenylenediamine, 3,5-diaminobenzoic acid, 4,4'- Diaminodiphenylmethane, 4,4'-diaminobenzophenone, 2,2'-dimethyl-4,4'-diaminobiphenyl, 4,4'-diamino-2,2'-bis(trifluoromethyl)biphenyl, the photo-orientation diamine having a group, diamine having a radical initiation function, diamine having a photopolymerizable group at the end, diamines represented by the above formulas (z-1) to (z-13), the above formulas (5-1) to ( 5-13) and the diamines represented by the above formulas (Ox-1) to (Ox-2) are preferred.
• diamines represented by formula (d1) or formula (d2) p-phenylenediamine, 3,5-diaminobenzoic acid, 4,4'-
• the amount of the other diamines used is preferably 10 to 90 mol% with respect to the total diamine components used in the production of the polymer (P). and more preferably 20 to 80 mol %.
• the tetracarboxylic acid component to be reacted with the diamine component is not only tetracarboxylic dianhydride, but also tetracarboxylic acid, tetracarboxylic acid dihalide, tetracarboxylic acid dialkyl ester, or tetracarboxylic acid.
• tetracarboxylic dianhydrides such as carboxylic acid dialkyl ester dihalides can also be used.
• the tetracarboxylic dianhydride or derivative thereof is an acyclic aliphatic tetracarboxylic dianhydride or derivative thereof, an alicyclic tetracarboxylic dianhydride or derivative thereof, or an aromatic tetracarboxylic dianhydride or Derivatives thereof may be mentioned.
• the tetracarboxylic acid component that can be used for synthesizing the polyimide precursor is preferably a tetracarboxylic dianhydride represented by the following formula (T) or a derivative thereof.
• tetracarboxylic dianhydride derivatives include tetracarboxylic acid dihalides, tetracarboxylic acid dialkyl esters, and tetracarboxylic acid dialkyl ester dihalides.
• the tetracarboxylic dianhydrides or derivatives thereof may be used singly or in combination of two or more.
• X represents a structure selected from any of the following formulas (x-1) to (x-13).
• R 1 to R 4 each independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, represents an alkynyl group of 6, a monovalent organic group having 1 to 6 carbon atoms containing a fluorine atom, or a phenyl group
• R 5 and R 6 each independently represent hydrogen represents an atom or a methyl group
• j and k are integers of 0 or 1
• a 1 and A 2 each independently represent a single bond, —O—, —CO—, —COO—, phenylene group, sulfonyl group, or amide group
• *1 is bound to one acid anhydride group.
• *2 is a bond that bonds to
• Preferred specific examples of the above formula (x-1) include the following formulas (X1-1) to (X1-6).
• tetracarboxylic dianhydride represented by the formula (T) or a derivative thereof include the above formulas (x-1) to (x-7), (x-11) to (x-13).
• ) is a tetracarboxylic dianhydride represented by the formula (T) or a derivative thereof, more preferably a tetracarboxylic dianhydride represented by the formula (T) (x-1) to (x-6) and derivatives thereof.
• the ratio of the tetracarboxylic acid dianhydride represented by the formula (T) or a derivative thereof is preferably 10 mol% or more, more preferably 20 mol% or more, relative to 1 mol of the total tetracarboxylic acid component used. Preferably, 50 mol % or more is more preferable.
• the tetracarboxylic dianhydride and its derivative used for producing the polyamic acid (P') may contain a tetracarboxylic dianhydride other than the formula (T) or a derivative thereof.
• Synthesis of polyamic acid is carried out by reacting a diamine component containing the diamine and a tetracarboxylic acid component containing the tetracarboxylic dianhydride or its derivative in an organic solvent.
• the ratio of the tetracarboxylic dianhydride and the diamine used in the synthetic reaction of the polyamic acid is such that the acid anhydride group of the tetracarboxylic dianhydride is 0.5 to 2 per equivalent of the amino group of the diamine.
• a ratio that provides equivalents is preferred, and a ratio that provides 0.8 to 1.2 equivalents is more preferred.
• the reaction temperature in the polyamic acid synthesis reaction is preferably -20 to 150°C, more preferably 0 to 100°C.
• the reaction time is preferably 0.1 to 24 hours, more preferably 0.5 to 12 hours.
• the polyamic acid synthesis reaction can be carried out at any concentration, but the concentration of the polyamic acid in the reaction solution is preferably 1 to 50% by mass, more preferably 5 to 30% by mass.
• the initial stage of the reaction can be carried out at a high concentration, and then the solvent can be added.
• organic solvent examples include cyclohexanone, cyclopentanone, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, ⁇ -butyrolactone, N,N-dimethylformamide, N,N-dimethylacetamide, dimethyl sulfoxide, 1,3-dimethyl-2-imidazolidinone.
• the polymer has high solvent solubility, methyl ethyl ketone, cyclohexanone, cyclopentanone, 4-hydroxy-4-methyl-2-pentanone, or the following formulas [D-1] to [D-3] Any of the indicated solvents can be used.
• D 1 represents an alkyl group having 1 to 3 carbon atoms
• D 2 represents an alkyl group having 1 to 3 carbon atoms
• D 3 represents an alkyl group having 1 to 4 carbon atoms.
• solvents represented by formulas [D-1] to [D-3] above include propylene glycol monomethyl ether, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, diethylene glycol monomethyl ether, and diethylene glycol. monoethyl ether and the like.
• Polyamic acid esters are produced by, for example, [I] a method of reacting the polyamic acid obtained by the above method with an esterifying agent, [II] a method of reacting a tetracarboxylic acid diester with a diamine, [III] a tetracarboxylic acid It can be obtained by a known method such as a method of reacting a diester dihalide and a diamine.
• a polyimide can be obtained by ring-closing (imidating) a polyimide precursor such as the above polyamic acid or polyamic acid ester.
• the imidization ratio as used herein means the ratio of imide groups to the total amount of imide groups derived from tetracarboxylic dianhydride or derivatives thereof and carboxy groups (or derivatives thereof).
• the imidization rate does not necessarily have to be 100%, and can be arbitrarily adjusted according to the application and purpose.
• Examples of methods for imidizing the polyimide precursor include thermal imidization in which the solution of the polyimide precursor is heated as it is, and catalytic imidization in which a catalyst is added to the solution of the polyimide precursor.
• the temperature is preferably 100 to 400° C., more preferably 120 to 250° C., and water produced by the imidization reaction is removed from the system. is preferred.
• 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 times the molar amount of the amic acid group, preferably 2 to 20 times the molar amount, and the amount of the acid anhydride is 1 to 50 times the molar amount of the amic acid group, preferably 3 to 30 times the molar amount.
• the basic catalyst include pyridine, triethylamine, trimethylamine, tributylamine, trioctylamine, etc. Among them, pyridine is preferable because it has appropriate basicity for advancing the reaction.
• Examples of the acid anhydride include acetic anhydride, trimellitic anhydride, and pyromellitic anhydride. Among them, acetic anhydride is preferably used because it facilitates purification after the reaction is completed.
• the imidization rate by catalytic imidization can be controlled by adjusting the catalyst amount, reaction temperature, and reaction time.
• the reaction solution may be put into a solvent to precipitate.
• Solvents used for precipitation include methanol, ethanol, isopropyl alcohol, acetone, hexane, butyl cellosolve, heptane, methyl ethyl ketone, methyl isobutyl ketone, toluene, benzene, and water.
• the polymer precipitated by adding it to the solvent can be filtered and recovered, and then dried at room temperature or under heat under normal pressure or reduced pressure.
• the impurities in the polymer can be reduced by redissolving the precipitated and recovered polymer in an organic solvent and repeating the operation of reprecipitating and recovering 2 to 10 times.
• Solvents in this case include, for example, 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 improved.
• a tetracarboxylic acid component containing a tetracarboxylic acid dianhydride or a derivative thereof, and a diamine component containing the diamine, together with an appropriate terminal blocker to end block It is also possible to synthesize a polymer of the type
• the end-blocking polymer has effects of improving the film hardness of the alignment film obtained by the coating film and improving the adhesion properties between the sealant and the alignment film.
• the terminal of the polyimide precursor or polyimide in the present invention include an amino group, a carboxyl group, an acid anhydride group, or a group derived from a terminal blocking agent to be described later.
• An amino group, a carboxyl group, and an acid anhydride group can be obtained by a normal condensation reaction, or can be obtained by terminal blocking using the following terminal blocking agents.
• Terminal blockers include, for example, acetic anhydride, maleic anhydride, nadic anhydride, phthalic anhydride, itaconic anhydride, cyclohexanedicarboxylic anhydride, 3-hydroxyphthalic anhydride, trimellitic anhydride, 3-( Acids such as 3-trimethoxysilyl)propyl-3,4-dihydrofuran-2,5-dione, 4,5,6,7-tetrafluoroisobenzofuran-1,3-dione, 4-ethynylphthalic anhydride anhydride; dicarbonic acid diester compounds such as di-tert-butyl dicarbonate and diallyl dicarbonate; acryloyl chloride, methacryloyl chloride, chlorocarbonyl compounds such as nicotinic acid chloride; aniline, 2-aminophenol, 3-aminophenol, 4- aminosalicylic acid, 5-aminosalicylic acid, 6-aminosalicylic acid,
• the proportion of the end blocking agent used is preferably 0.01 to 20 mol parts, more preferably 0.01 to 10 mol parts, per 100 mol parts in total of the diamine components used.
• the polystyrene equivalent weight average molecular weight (Mw) measured by gel permeation chromatography (GPC) of the polyimide precursor and polyimide is preferably 1,000 to 500,000, more preferably 2,000 to 300,000. is.
• the molecular weight distribution (Mw/Mn) represented by the ratio of the above Mw to the polystyrene equivalent number average molecular weight (Mn) measured by GPC is preferably 15 or less, more preferably 10 or less.
• the liquid crystal aligning agent of the present invention is a liquid composition in which the polymer (P) and optionally other components are preferably dispersed or dissolved in a suitable solvent.
• the liquid crystal aligning agent of the present invention may contain other polymers other than the polymer (P).
• other polymers include at least one polymer selected from the group consisting of polyimide precursors other than the polymer (P) and polyimides that are imidized products of the polyimide precursors, polysiloxanes, and polyesters.
• poly(styrene-maleic anhydride) copolymers include SMA1000, SMA2000, SMA3000 (manufactured by Cray Valley), GSM301 (manufactured by Gifu Shellac Manufacturing Co., Ltd.) and the like.
• Anhydride) copolymers include Isoban-600 (manufactured by Kuraray Co., Ltd.), and specific examples of poly(vinyl ether-maleic anhydride) copolymers include Gantrez AN-139 (methyl vinyl ether anhydride). maleic acid resin, manufactured by Ashland).
• polymers include polyimide precursors obtained using a diamine component containing a diamine represented by the above formula (d1) or (d2), and imidized products of the polyimide precursors, from the viewpoint of enhancing vertical alignment properties. At least one polymer selected from the group consisting of polyimides is preferred. Other polymers may be used singly or in combination of two or more. The content of the other polymer is preferably 90 parts by mass or less, more preferably 10 to 90 parts by mass, and further 20 to 80 parts by mass with respect to the total 100 parts by mass of the polymer contained in the liquid crystal aligning agent. preferable.
• the liquid crystal aligning agent of this invention may contain the component other than the above as needed.
• Such components include, for example, a crosslinkable compound having at least one substituent selected from an epoxy group, an isocyanate group, an oxetanyl group, a cyclocarbonate group, a blocked isocyanate group, a hydroxy group and an alkoxy group, and a polymerizable unsaturated group.
• a crosslinkable compound having at least one substituent selected from an epoxy group, an isocyanate group, an oxetanyl group, a cyclocarbonate group, a blocked isocyanate group, a hydroxy group and an alkoxy group, and a polymerizable unsaturated group At least one compound selected from the group consisting of crosslinkable compounds having a functional silane compound, a metal chelate compound, a curing accelerator, a surfactant, an antioxidant, a sensitizer, an antiseptic, a dielectric of the liquid crystal alignment film Compounds
• crosslinkable compound examples include compounds represented by the following formulas (CL-1) to (CL-11).
• the compounds represented by the following formulas (CL-1) to (CL-11) are examples of crosslinkable compounds and are not limited to these.
• the crosslinkable compound used for the liquid crystal aligning agent of this invention may be one type, or may combine 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 50 parts by mass, more preferably 1 to 50 parts by mass, and 1 to 30 parts by mass with respect to 100 parts by mass of all polymer components. Parts by mass are more preferred.
• Compounds for adjusting the dielectric constant and electric resistance of the liquid crystal alignment film include monoamines having a nitrogen-containing aromatic heterocycle such as 3-picolylamine.
• organic solvent used in the liquid crystal aligning agent of the present invention examples include N-methyl-2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone, N-ethyl-2-pyrrolidone and N-(n-propyl).
• the solid content concentration in the liquid crystal aligning agent (ratio of the total mass of components other than the solvent of the liquid crystal aligning agent to the total mass of the liquid crystal aligning agent) is appropriately selected in consideration of viscosity, volatility, etc., but preferably It is in the range of 1 to 10% by mass. From the viewpoint of forming a uniform and defect-free coating film, it is preferably 1% by mass or more, and from the viewpoint of storage stability of the solution, it is preferably 10% by mass or less. A particularly preferred polymer concentration is 2 to 8% by weight.
• 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 horizontal alignment type or a vertical alignment type liquid crystal alignment film.
• a liquid crystal suitable for a vertical alignment type liquid crystal display element such as a VA mode or a PSA (Polymer Sustained Alignment) mode. It is an alignment film.
• the liquid crystal display element of the present invention comprises the liquid crystal alignment film.
• the liquid crystal aligning agent of the present invention has a liquid crystal layer between a pair of substrates provided with electrodes, and a liquid crystal composition containing a polymerizable compound polymerized by at least one of active energy rays and heat between the pair of substrates. It is also preferably used for a liquid crystal display element manufactured through a process of polymerizing a polymerizable compound by at least one of irradiation with an active energy ray and heating while placing a substance and applying a voltage between electrodes.
• the liquid crystal display device of the present invention can be manufactured, for example, by performing the following steps (1) to (3) or steps (1) to (4) in this order.
• the liquid crystal aligning agent of the present invention is coated on one surface of the substrate by an appropriate coating method such as a roll coater method, a spin coat method, a printing method, an ink jet method, or the like to prepare a coating film.
• the substrate is not particularly limited as long as it is highly transparent, and in addition to a glass substrate and a silicon nitride substrate, a plastic substrate such as an acrylic substrate or a polycarbonate substrate can also be used.
• a plastic substrate such as an acrylic substrate or a polycarbonate substrate can also be used.
• an opaque material such as a silicon wafer can be used, and in this case, a light-reflecting material such as aluminum can be used for the electrodes.
• the coating film is baked for the purpose of preventing dripping of the applied aligning agent.
• preheating is performed first.
• the prebaking temperature is preferably 30 to 200°C, more preferably 40 to 150°C, and particularly preferably 40 to 100°C.
• the pre-baking time is preferably 0.25-10 minutes, more preferably 0.5-5 minutes.
• a heating (post-baking) step is preferably performed.
• the post-bake temperature is preferably 80-300°C, more preferably 120-250°C.
• the post-bake time is preferably 5-200 minutes, more preferably 10-100 minutes.
• the 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 steps (1) and (2) 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.
• Alignment imparting treatment includes rubbing treatment in which the coating film is rubbed in a fixed direction with a roll wrapped with a cloth made of fibers such as nylon, rayon, cotton, etc., and photo-alignment treatment in which the coating film is irradiated with polarized or non-polarized radiation. processing and the like.
• ultraviolet rays and visible rays including light having a wavelength of 150 to 800 nm can be used as the radiation to irradiate the coating film.
• the radiation When the radiation is polarized, it may be linearly polarized or partially polarized. Further, when the radiation used is linearly polarized or partially polarized, the irradiation may be performed from a direction perpendicular to the substrate surface, from an oblique direction, or a combination thereof. When non-polarized radiation is applied, the direction of irradiation is oblique.
• Step of forming a liquid crystal layer between the pair of substrates to produce a liquid crystal cell (3-1) When manufacturing a VA liquid crystal display element Two substrates having the liquid crystal alignment film of the present invention formed on at least one of them are prepared, and a liquid crystal is arranged between the two substrates facing each other. Specifically, the following two methods are mentioned.
• the first method is a conventionally known method. First, two substrates are arranged to face each other with a gap (cell gap) interposed therebetween so that the respective liquid crystal alignment films face each other.
• a sealant is applied to the periphery of the two substrates and attached to each other, and a liquid crystal composition is injected and filled into the cell gap defined by the substrate surface and the sealant to contact the film surface, and then the injection hole is opened. Seal.
• the second method is a method called ODF (One Drop Fill) method.
• ODF One Drop Fill
• a predetermined place on one of the two substrates on which the liquid crystal alignment film is formed is coated with, for example, an ultraviolet light-curing sealant, and a liquid crystal composition is applied to several predetermined places on the surface of the liquid crystal alignment film. drip.
• 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.
• the entire surface of the substrate is irradiated with ultraviolet light to cure the sealant.
• liquid crystal composition is not particularly limited, and various liquid crystal compositions containing at least one liquid crystal compound (liquid crystal molecule) and having positive or negative dielectric anisotropy can be used.
• a liquid crystal composition with a positive dielectric anisotropy is also referred to as a positive liquid crystal
• a liquid crystal composition with a negative dielectric anisotropy is also referred to as a negative liquid crystal.
• the above liquid crystal composition contains a fluorine atom, a hydroxy group, an amino group, a fluorine atom-containing group (e.g., trifluoromethyl group), a cyano group, an alkyl group, an alkoxy group, an alkenyl group, an isothiocyanate group, a heterocyclic ring, a cycloalkane,
• a liquid crystal compound having a cycloalkene, a steroid skeleton, a benzene ring, or a naphthalene ring may be included, and a compound having two or more rigid sites (mesogenic skeleton) exhibiting liquid crystallinity in the molecule (for example, two rigid biphenyl structures or terphenyl structures linked by alkyl groups).
• the liquid crystal composition may be a liquid crystal composition exhibiting a nematic phase, a liquid crystal composition exhibiting a smectic phase, or a liquid crystal composition exhibiting a cholesteric phase.
• the liquid crystal composition may further contain an additive from the viewpoint of improving liquid crystal orientation.
• additives include photopolymerizable monomers such as compounds having a polymerizable group described below; optically active compounds (eg, S-811 manufactured by Merck Co., Ltd.); antioxidants; UV absorbers; dyes; antifoaming agents; polymerization initiators; or polymerization inhibitors.
• Positive liquid crystals include ZLI-2293, ZLI-4792, MLC-2003, MLC-2041, and MLC-7081 manufactured by Merck.
• Negative liquid crystals include, for example, MLC-6608, MLC-6609, MLC-6610, and MLC-7026-100 manufactured by Merck.
• MLC-3023 manufactured by Merck Co., Ltd. can be used as a liquid crystal containing a compound having a polymerizable group.
• the compound having a polymerizable group is a compound having one or more polymerizable unsaturated groups such as an acrylate group or a methacrylate group in the molecule as represented by the above formulas (M-1) to (M-6).
• the content is preferably 0.1 to 30 parts by mass, more preferably 1 to 20 parts by mass, based on 100 parts by mass of all polymer components.
• the polymerizable group may be present in the polymer used for the liquid crystal alignment agent, and such a polymer includes, for example, a diamine component containing a diamine having a photopolymerizable group at the end thereof, which is used in the reaction.
• a diamine component containing a diamine having a photopolymerizable group at the end thereof which is used in the reaction.
• the polymer obtained is mentioned.
• Step of irradiating the liquid crystal cell with light The liquid crystal cell is irradiated with light while a voltage is applied between the conductive films of the pair of substrates obtained in (3-2) or (3-3) above.
• the voltage applied here can be, for example, 5 to 50 V direct current or alternating current.
• As the light for irradiation for example, ultraviolet light containing light with a wavelength of 150 to 800 nm and visible light can be used, but ultraviolet light containing light with a wavelength of 300 to 400 nm is preferable.
• a low-pressure mercury lamp, a high-pressure mercury lamp, a deuterium lamp, a metal halide lamp, an argon resonance lamp, a xenon lamp, an excimer laser, or the like can be used as the light source for the irradiation light.
• the irradiation amount of light is preferably 1,000 to 200,000 J/m 2 , more preferably 1,000 to 100,000 J/m 2 .
• a liquid crystal display element can be obtained by bonding a polarizing plate to the outer surface of the liquid crystal cell.
• a polarizing plate As the polarizing plate to be attached to the outer surface of the liquid crystal cell, a polarizing film called "H film” in which polyvinyl alcohol is stretched and oriented while absorbing iodine is sandwiched between cellulose acetate protective films, or the H film itself.
• a polarizing plate consisting of
• the liquid crystal display device of the present invention can be effectively applied to various devices such as watches, portable games, word processors, notebook computers, car navigation systems, camcorders, PDAs, digital cameras, mobile phones, smart phones, It can be used for various display devices such as various monitors, liquid crystal televisions, and information displays.
• the polymer composition contained in the liquid crystal aligning agent is a liquid crystal alignment film for a retardation film, a liquid crystal alignment film for a scanning antenna or a liquid crystal array antenna, or a liquid crystal alignment film for a transmission scattering type liquid crystal light control element, Alternatively, it can also be used for applications other than these, such as protective films for color filters, gate insulating films for flexible displays, and substrate materials.
• DC-1 to DC-2 compounds represented by the following formulas (DC-1) to (DC-2), respectively
• Molecular weights (number average molecular weights) of polyimide precursors and polyimides are measured using a room temperature gel permeation chromatography (GPC) device (GPC-101) (manufactured by Showa Denko), a column (GPC KD-803, GPC KD-805 in series). (manufactured by Showa Denko Co., Ltd.) and measured under the following conditions.
• GPC room temperature gel permeation chromatography
• the refractive index can be obtained by the following calculation formula (1) (Lorentz-Lorenz formula) from the polarizability obtained by optimizing the structure obtained by molecular orbital calculation for the target molecule.
• calculation formula (1) Lientz-Lorenz formula
• B3LYP was used as a functional and 6-31G* was used as a basis function.
• the refractive index is calculated at 550 nm.
• the UV spectrum is calculated using TD-B3LYP as the functional and 6-31G* as the basis function.
• Gaussian09 Revision C.01, M.J.
• Table 1 shows the calculation results.
• molecules (A) to (C) derived from specific diamines (DA-1) to (DA-3) are molecules (D) to (E) having no triazine ring and It exhibited a higher refractive index than the molecules (F) to (G) in which the side chain group bonded to the triazine ring had a long-chain alkyl group or a polycyclic structure such as cholesterol.
• DA-1-1 (16.7 g, 43.3 mmol, yield 87.0%, white solid) was obtained.
• THF 314 g
• 5% palladium carbon manufactured by NE Chemcat, 50 mass% water content, 1.57 g
• the precipitated solid was separated by filtration, and the cake was washed three times with a mixed solvent of water (72.0 g) and methanol (72.0 g) each heated to 50°C.
• Acetonitrile (404 g) was added to the washed solid to dissolve the solid under reflux conditions, and the insoluble component was removed by filtration.
• Methanol (100 g) was added to the crude product obtained by concentrating the obtained filtrate, and the mixture was stirred under heating conditions of 60° C. for 1 hour.
• the precipitated solid was collected by filtration and vacuum dried at 40° C. to obtain DA-2 (14.9 g, 46.2 mmol, yield 46.2%, pink solid). .
• DA-3 A diamine (DA-3) was synthesized according to the route shown below. Acetone (125 g) was added to 2,4-dichloro-6-methoxy-1,3,5-triazine (12.5 g, 69.6 mmol) and cooled to 0°C. Aminothiophenol (19.2 g, 153 mmol), acetone (115 g), and 20% by weight aqueous sodium hydroxide solution (30.6 g) were added to form a homogeneous solution, and the solution cooled to 0° C. was added dropwise. After stirring at 0° C.
• Liquid crystal aligning agents (PAA-2) to (PAA-5) shown in Table 3 below were obtained by carrying out in the same manner as in Example 1 except that the polyamic acid solution was changed to that shown in Table 3 below.
• solid content concentration represents the ratio with respect to the whole liquid crystal aligning agent other than the solvent component contained in a liquid crystal aligning agent.
• Examples 4 to 6 and Comparative Example 3 The mass ratio of the liquid crystal aligning agent (PAA-1) obtained in Example 1 and the liquid crystal aligning agent (PAA-5) obtained in Comparative Example 2 is 3:7 (PAA-5:PAA-1 ) and stirred at room temperature for 3 hours to prepare a liquid crystal aligning agent (PAA-b-1) of Example 4. Further, by carrying out in the same manner as in Example 4 except that the combination of the liquid crystal aligning agents used was changed to those shown in Table 4 below, Examples 5 to 6 and Comparative Example 3 shown in Table 4 below were obtained. Liquid crystal aligning agents (PAA-b-2) to (PAA-b-4) were prepared.
• a measurement cell was fabricated using two quartz substrates.
• the liquid crystal alignment agents prepared in Examples 1 to 3 and Comparative Example 1 were spin-coated on a quartz substrate, dried on a hot plate at 70°C for 90 seconds, and then baked in a hot air circulation oven at 230°C for 20 minutes. , to form a liquid crystal alignment film having a thickness of 100 nm.
• a quartz substrate on which no liquid crystal alignment film was formed was bonded together with the surface on which the liquid crystal alignment film was formed inside.
• a refractive liquid contact liquid manufactured by Shimadzu Device Manufacturing Co., Ltd.
• Refractive liquids were selected from among 11 types of 1.60 to 1.70 in increments of 0.01, and used according to each refractive index.
• a UV-visible spectrophotometer (Shimadzu Corporation UV-2600) was used to measure the transmittance at a wavelength of 380 to 800 nm for the prepared measurement cell.
• Table 5 shows the results. Table 5 shows the average values of transmittance at wavelengths from 380 to 800 nm. As evaluation criteria, the case where the transmittance is greater than 99.90% is “excellent", the case where the transmittance is 99.90% or less and greater than 99.0% is “acceptable”, and the case where the transmittance is 99.0% or less is “improper”. evaluated as
• the liquid crystal alignment film obtained from the liquid crystal alignment agent using the specific diamines (DA-1) to (DA-3) is a liquid crystal alignment agent composed of a diamine component that does not contain a specific diamine. It exhibited a higher refractive index than the resulting liquid crystal alignment film. Further, the liquid crystal alignment films obtained from the liquid crystal alignment agents using the specific diamines (DA-1) to (DA-3) showed high light transmittance.
• liquid crystal aligning agent is spin-coated on the ITO surface of an ITO electrode substrate on which an ITO electrode pattern having a pixel size of 100 ⁇ m ⁇ 300 ⁇ m and a line/space of 5 ⁇ m is formed, and dried on a hot plate at 70 ° C. for 90 seconds. and 230° C. in a hot air circulation oven for 30 minutes to form a liquid crystal alignment film with a thickness of 100 nm.
• the liquid crystal aligning agent is spin-coated on the ITO surface on which the electrode pattern is not formed, dried on a hot plate at 70 ° C.
• a liquid crystal alignment film was formed. After spraying 4 ⁇ m bead spacers on the liquid crystal alignment film of one of the two substrates, a sealant (XN-1500T manufactured by Mitsui Chemicals, Inc.) was printed thereon. Next, the surface of the other substrate on which the liquid crystal alignment film was formed was turned inside, and after bonding with the previous substrate, the sealant was thermally cured to prepare an empty cell.
• a sealant XN-1500T manufactured by Mitsui Chemicals, Inc.
• a liquid crystal containing a polymerizable compound for PSA (MLC-3023, manufactured by Merck Ltd., negative type liquid crystal) was injected into this empty cell by a vacuum injection method to prepare a liquid crystal cell. After that, while a DC voltage of 15 V was applied to the liquid crystal cell, ultraviolet rays of 10 J/cm 2 were irradiated from the outside of the liquid crystal cell through a filter that cuts wavelengths of 325 nm or less. The ultraviolet illuminance was measured using UV-MO3A manufactured by ORC. After that, for the purpose of deactivating the unreacted polymerizable compound remaining in the liquid crystal cell, ultraviolet rays (UV lamp: FLR40SUV32/A-1) was irradiated for 30 minutes.
• Table 6 shows the evaluation of the vertical alignment property of each liquid crystal cell produced as described above.
• the evaluation method is as follows. Each liquid crystal cell was sandwiched between crossed nicol polarizing plates, and the liquid crystal cell was rotated in a state in which a backlight was applied from the rear, and whether or not the liquid crystal was vertically aligned was visually observed by changes in brightness. As the evaluation criteria, "O” indicates that the liquid crystal is vertically aligned, and "X” indicates that the liquid crystal is not vertically aligned. Results are shown in Table 6. As shown in Table 6, the liquid crystal alignment films obtained from the liquid crystal alignment agents using the specific diamines (DA-1) to (DA-3) exhibited good vertical alignment properties.

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