Classifications

• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C271/00—Derivatives of carbamic acids, i.e. compounds containing any of the groups, the nitrogen atom not being part of nitro or nitroso groups
  • C07C271/06—Esters of carbamic acids
  • C07C271/08—Esters of carbamic acids having oxygen atoms of carbamate groups bound to acyclic carbon atoms
  • C07C271/26—Esters of carbamic acids having oxygen atoms of carbamate groups bound to acyclic carbon atoms with the nitrogen atom of at least one of the carbamate groups bound to a carbon atom of a six-membered aromatic ring
  • C07C271/28—Esters of carbamic acids having oxygen atoms of carbamate groups bound to acyclic carbon atoms with the nitrogen atom of at least one of the carbamate groups bound to a carbon atom of a six-membered aromatic ring to a carbon atom of a non-condensed six-membered aromatic ring
• • 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
  • G02F1/133711—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers by organic films, e.g. polymeric films
• • 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
  • G02F1/13378—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers by treatment of the surface, e.g. embossing, rubbing or light irradiation
  • G02F1/133784—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers by treatment of the surface, e.g. embossing, rubbing or light irradiation by rubbing

Definitions

• the present invention relates to a novel diamine, a polymer, a liquid crystal aligning agent used for a liquid crystal display element, a liquid crystal alignment film, and a liquid crystal display element.
• a liquid crystal alignment film plays a role of aligning liquid crystals in a certain direction.
• the main liquid crystal alignment films that are industrially used are formed by applying a polyimide liquid crystal aligning agent consisting of a polyimide precursor polyamic acid (also called polyamic acid) or a polyimide solution to a substrate. It is produced by doing.
• a surface stretching process is further performed by rubbing after film formation.
• a method using an anisotropic photochemical reaction by irradiation with polarized ultraviolet rays has been proposed, and in recent years, studies for industrialization have been performed.
• the structure of the polyamic acid and polyimide is changed and optimized, blended with resins with different characteristics, and additives are added to improve liquid crystal alignment.
• Various techniques have been proposed for improving the display characteristics by controlling the pretilt angle and improving the electrical characteristics. For example, in order to obtain a high voltage holding ratio, it has been proposed to use a polyimide resin having a specific repeating structure (see Patent Document 1). Further, it has been proposed to shorten the time until the afterimage is erased by using soluble polyimide having a nitrogen atom in addition to the imide group for the afterimage phenomenon (see Patent Document 2, etc.).
• a polyamic acid obtained from a specific diamine containing an oxazole or imidazole skeleton and tetracarboxylic dianhydride or a derivative thereof has been proposed (see Patent Document 3).
• liquid crystal display elements have increased, the area has been increased, and the power consumption of display devices has progressed.
• the liquid crystal display elements can be used in various environments, and the characteristics required for liquid crystal alignment films are severe. It has become a thing.
• a liquid crystal aligning agent is applied to a substrate, printing failure due to precipitation or whitening due to a long tact time, increase in ion density due to long-term use of liquid crystal display elements, burn-in due to accumulated charges, etc. This problem is a problem, and it is difficult to solve both of these problems simultaneously with the conventional technology.
• a liquid crystal aligning agent using a diamine containing an alkylamine protected with a tert-butoxycarbonyl group (hereinafter also referred to as a Boc group) has been proposed (see Patent Document 4).
• a polyimide precursor or a polyimide coating film having a primary or secondary aliphatic amine protected with a Boc group is formed, and then a primary or secondary aliphatic amine having high reactivity during firing. To generate a polyimide film having excellent mechanical strength.
• liquid crystal display elements are used for large-screen, high-definition liquid crystal televisions and in-vehicle applications such as car navigation systems and meter panels.
• a backlight with a large calorific value may be used.
• the liquid crystal alignment film is required to have high reliability from another point of view, that is, high stability to light from the backlight.
• the voltage holding ratio which is one of the electrical characteristics, decreases due to light irradiation from the backlight, a seizure defect (linear seizure) that is one of the display defects of the liquid crystal display element is likely to occur.
• the liquid crystal alignment film in addition to good initial characteristics, for example, it is also required that the voltage holding ratio does not easily decrease even after being exposed to light irradiation for a long time.
• An object of the present invention is to provide a diamine that can produce a liquid crystal aligning agent that can produce a film and has good printability (solubility of a polymer in a solvent) on a substrate or the like. That is, it aims at providing the diamine which can obtain the polyamide, polyamic acid, polyamic acid ester, and polyimide which have these characteristics, and also providing a liquid crystal aligning agent, a liquid crystal aligning film, and a liquid crystal display element using the same. To do.
• the diamine component includes a polyamide, polyamic acid, polyamic acid ester, or a liquid crystal aligning agent containing polyimide, which uses a specific diamine represented by the following formula (1). It has been found that it is extremely effective for achieving the object, and the present invention has been completed.
• the diamine represented by Formula (1) is a novel compound which has not been published in the literature.
• A represents an organic group which can be removed by heat.
• B represents —CH 2 —, —O—, —S— or —NH—.
• X represents a single bond or a divalent organic group.
• Y represents a single bond, —O—, —CONH—, —NHCO—, —OCO—, —COO—, —HN—CO—NH—, —NHCOO— or —OCONH—, and Z represents a single bond or the number of carbon atoms.
• R 1 represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms
• R 2 represents an —NH—A group when Y is —CONH— or —OCO—.
• it represents a hydrogen atom, a halogen atom or an alkyl group having 1 to 5 carbon atoms
• k1 represents an integer of 0 to 3
• R 3 represents a halogen atom or an alkyl group having 1 to 5 carbon atoms.
• - (R 3) k1 represents that the substituent R 3 is (k1), where If 1 is 2 or more, two or more R 3 may respectively be the same or different .
• k2 represents an integer of 0 ⁇ 3
• R 4 is a halogen atom or an alkyl group
• - (R 4) k2 Represents that there are k2 substituents R 4 , provided that when k2 is 2 or more, 2 or more R 4 s may be the same or different.
• A is a tert-butoxycarbonyl group. The diamine described.
• B is -NH-. Or 2. The diamine described.
• X represents 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 heterocyclic ring
• Y represents a single bond, —O—, —OCO— or — 1. represents COO- ⁇ 3.
• the diamine in any one of.
• X represents a divalent saturated hydrocarbon group having 1 to 20 carbon atoms, an unsaturated hydrocarbon group, an aromatic hydrocarbon group or a heterocyclic ring
• Y is —CONH— (where C ⁇ O is bonded to X
• R 2 is a —NH—A group.
• the diamine in any one of.
• the diamine component contains 5 to 100 mol% of the diamine represented by the formula (1).
• the diamine component contains 5 to 50 mol% of a diamine represented by the following formula (2). Or 7. The polymer described.
• P 1 represents a single bond, —O—, —CH 2 O—, —CONH—, —NHCO—, —OCO—, —COO—, —HN—CO—NH—, —NHCOO— or OCONH—
• Q 1 , Q 2 , and Q 3 each independently represent a divalent benzene ring or a cyclohexane ring
• p, q, and r each independently represent an integer of 0 or 1
• P 2 represents hydrogen Represents an atom, an alkyl group having 1 to 22 carbon atoms, or a divalent organic group having 12 to 25 carbon atoms having a steroid skeleton.
• Liquid crystal aligning agent characterized by including the polymer as described in any one of these.
• a liquid crystal display element comprising the liquid crystal alignment film described above.
• the liquid crystal aligning agent of the present invention contains a polymer using a diamine having a specific structure represented by the above formula (1), the printability is good.
• the liquid crystal alignment film obtained from the liquid crystal aligning agent of the present invention reacts with an amino group from which a protective group derived from the diamine having a specific structure represented by the above formula (1) is removed during coating film baking. Since it forms a cyclized structure and reacts between molecules, it has excellent rubbing resistance and good liquid crystal orientation, RDC does not accumulate easily, and it is exposed to light irradiation conditions such as long-time high-temperature and high-humidity environments and backlights. Even underneath, the voltage holding ratio is unlikely to decrease. Therefore, a liquid crystal display element having such a liquid crystal alignment film is excellent in reliability.
• the diamine of the present invention is a diamine represented by the above formula (1).
• the organic group A that can be eliminated by heat in the formula (1) is not particularly limited as long as it is an organic group in which —NHA is converted into an amino group by decomposing and removing by heat. Of course, in the state of having A, the reactivity of the amino group is lowered.
• the structure of A, which is an organic group that can be removed by heat, includes benzyloxycarbonyl group, 9-fluorenylmethyloxycarbonyl group, allyloxycarbonyl group, tertiary butoxycarbonyl group (tert-butoxycarbonyl group), etc.
• the representative carbamate-based organic groups are listed, but from the viewpoint that the efficiency of desorption by heat is good, desorbs at a relatively low temperature, and is discharged as a harmless gas upon desorption.
• a carbonyl group is particularly preferred.
• the organic group is a hydrocarbon group which may have N or O, for example.
• D represents a divalent saturated hydrocarbon group having 1 to 20 carbon atoms, an unsaturated hydrocarbon group, an aromatic hydrocarbon group, or a heterocyclic ring, and D has various substituents. Also good. E is 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 heterocyclic ring, and F is a single bond or an ether bond (—O -) Represents an ester bond (-OCO-, -COO-). m is 1 or 0.
• the hydrogen atom of the benzene ring having an amino group in the above formula (3) may be substituted with an organic group, specifically, for example, R 3 or R 4 in formula (1). Although various selections are made, unsubstituted ones are preferred. Further, the substitution position of the amino group is not particularly limited, but from the viewpoint of the difficulty of synthesis and the availability of reagents, the position of meta or para is preferable based on the amide bond, and the position of para is preferable from the viewpoint of liquid crystal alignment. Particularly preferred. Similarly, in aminobenzene having no protected amino group (that is, —NHA), 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 position of para is preferable.
• D in the formula (3) is not limited, and various structures can be selected depending on the structure of the dicarboxylic acid or tetracarboxylic dianhydride used as the raw material of the diamine represented by the formula (3).
• D is preferably a divalent hydrocarbon group from the viewpoint of solubility, and preferred examples include a linear alkylene group and a cyclic alkylene group, and this hydrocarbon group may have an unsaturated bond.
• a divalent aromatic hydrocarbon group, a heterocyclic ring, and the like are preferable. From the viewpoint of liquid crystal orientation, it is preferable that D has no substituent, but from the viewpoint of solubility, it is preferable that D be substituted with a carboxylic acid group or a fluorine atom.
• Preferred D is the same as above, and preferred E is also the above. It is the same as preferable D of these.
• the diamine represented by Formula (4) the compound whose E and F are both a single bond is also preferable.
• the diamine represented by the formula (1) of the present invention contains an aromatic amino group protected with an organic group A that can be removed by heat, such as a tertiary butoxycarbonyl group (hereinafter also referred to as a Boc group). It is characterized by.
• an amino group is a highly reactive organic group, so it is difficult to apply as it is as a part of the side chain of a diamine.
• the amino group is protected by an organic group that can be removed by heat such as a Boc group.
• the amino group protected by the organic group A that can reduce the reactivity of the group and can be removed by heat such as the Boc group can be removed by the heat such as the Boc group when heated at about 150 ° C. or higher. Can be deprotected and converted to an amino group.
• the side chain of diamine is a structure branched from a structure connecting two amino groups of diamine.
• the Boc group has a bulky tertiary butyl group
• the solubility of the monomer (diamine represented by the formula (1)) can be improved.
• the monomer (expressed by the formula (1)) can be improved.
• the polymer produced by using the diamine) can also improve the solubility. Therefore, the liquid crystal aligning agent containing the polymer (polyamic acid, polyamic acid ester, polyimide) obtained using this monomer (diamine represented by the formula (1)) has good printability.
• the solubility of the obtained polymer is remarkably compared with the polymer obtained using the diamine represented by the formula (1) of the present invention. Since it is low, polyimide (solvent soluble polyimide) or polyamide soluble in a solvent such as ⁇ -butyrolactone used for the liquid crystal aligning agent could not be obtained.
• An amino group is a highly reactive organic group, and is known to react with various sites such as unsaturated bonds, carboxylic acids, carboxylic anhydrides, epoxy compounds, and carbonyls.
• an amino group protected with an organic group A that can be removed by heat is placed close to a bonding group containing a carbonyl group such as an amide bond or an ester bond, as shown in the figure below, Rather than within the molecule, it can be induced, for example, to benzimidazole [scheme-1].
• the diamine of the present invention is intended to form a heterocyclic ring by reacting an amino group generated by calcination in a molecule.
• the liquid crystal alignment film obtained from polyamic acid, polyamic acid ester, polyimide or polyamide using the diamine represented by the formula (1) of the present invention is less susceptible to film scraping during rubbing treatment and has excellent lavink resistance. It has been found from this study that the effect of making the voltage holding ratio less likely to occur even when exposed to high temperatures and high humidity for long periods of time or to backlights.
• the liquid crystal orientation also changes to a favorable structure, so that both rubbing resistance and liquid crystal orientation can be achieved.
• the structure of the benzimidazole and the like produced by firing becomes an electrochemically active structure by acquiring aromaticity, so that it contributes to low RDC and liquid crystal alignment in which RDC does not easily accumulate.
• a membrane can be obtained.
• both the aromatic tetracarboxylic dianhydride and the diamine represented by the formula (1) of the present invention are used as raw materials, it is considered that the mutual interaction is strong, and a liquid crystal alignment film that is very difficult to accumulate RDC is obtained. I can do it.
• the diamine of formula (1) of the present invention is synthesized, for example, by dinitro compound or mononitro compound having a protective group removable in the reduction process through each step described below, and the nitro group is converted into an amino group by a commonly used reduction reaction. It can be obtained by conversion.
• the method for synthesizing the dinitro or mononitro compound that is the precursor of the diamine represented by the formula (1) is not particularly limited.
• a diaminobenzene derivative in which two amino groups are close to each other tertiary butyl dicarbonate, etc.
• a method of reacting a protective reagent capable of thermal deprotection for example, in the case of 4-nitro-o-phenylenediamine, a method represented by the following reaction formula is exemplified.
• the above reaction can be carried out in the presence of a base as necessary.
• the base to be used is not particularly limited as long as it can be synthesized.
• potassium carbonate, sodium carbonate, cesium carbonate, sodium alkoxide, potassium alkoxide, sodium hydroxide, potassium hydroxide, sodium hydride and other inorganic bases pyridine, dimethylamino Examples thereof include organic bases such as pyridine, trimethylamine, triethylamine, and tributylamine.
• two protecting groups may be substituted for one amino group, so it is necessary to select a base as appropriate.
• a base such as sodium hydride is preferable because it can efficiently extract hydrogen of the amino group, but synthesis is not particularly limited because synthesis is possible by other methods.
• this dicarboxylic acid is derived from 1 equivalent of dicarboxylic acid halide or tetracarboxylic dianhydride derived from thionyl chloride or oxalyl chloride.
• a diamine precursor (dinitro form) represented by the above formula (3) can be synthesized.
• the precursor (dinitro body) of the diamine represented by the above formula (3) can also be synthesized by reacting a dicarboxylic acid, a condensing agent, and a base with a protected diaminobenzene derivative.
• dicarboxylic acid tetracarboxylic dianhydride and the like which can be used in these reactions, those exemplified for polyamide, polyamic acid, polyamic acid ester and polyimide described later can be used as they are.
• D is the same as D in formula (3), and D ′ is a tetravalent group obtained by removing two hydrogen atoms from D.
• the diaminobenzene derivative protected by the above method is reduced to 1 equivalent or less, and a monocarboxylic acid or dicarboxylic anhydride is added.
• a monocarboxylic acid or dicarboxylic anhydride is added.
• it can be obtained by reacting a mononitrobenzene derivative having a group capable of reacting with carboxylic acid.
• it can be obtained by reacting a carboxylic acid or dicarboxylic acid anhydride having nitrobenzene with a protected diaminobenzene derivative, but various synthetic methods can be selected depending on the kind of compound to be obtained.
• the method for reducing the dinitro compound which is a precursor of the diamine represented by the formula (1) of the present invention is not particularly limited, and is usually palladium-carbon, platinum oxide, Raney nickel, platinum black, rhodium-alumina, sulfide.
• platinum carbon or the like is used as a catalyst and reduction is performed with hydrogen gas, hydrazine, hydrogen chloride, or the like in a solvent such as ethyl acetate, toluene, tetrahydrofuran, dioxane, or alcohol. You may use an autoclave etc. as needed.
• an unsaturated bond site is included in the structure, if palladium carbon or platinum carbon is used, the unsaturated bond site may be reduced, resulting in a saturated bond.
• Reduction conditions using a transition metal such as tin or tin chloride as a catalyst are preferred.
• a diamine represented by the formula (1) of the present invention can be obtained by deprotecting from a diaminobenzene derivative protected with a benzyl group or the like in the same reduction step.
• the diamine component containing the diamine represented by the formula (1) and the dicarboxylic acid halide are reacted in the presence of a base, or the dicarboxylic acid and the diamine component are reacted in the presence of a suitable condensing agent and a base. It is a polyamide obtained by reacting.
• the polyamic acid of this invention is a polyamic acid obtained by reaction of the diamine component containing the diamine represented by Formula (1), and tetracarboxylic dianhydride.
• the polyamic acid ester of the present invention is obtained by reacting a diamine component containing the diamine represented by the formula (1) with a tetracarboxylic acid diester dichloride in the presence of a base, or reacting the tetracarboxylic acid diester and the diamine component with an appropriate condensing agent or base. It is a polyamic acid ester obtained by making it react in presence of this. In addition, polyamic acid ester is obtained also by the method of converting the carboxyl group of polyamic acid into ester.
• the polyimide of the present invention is a polyimide obtained by dehydrating and ring-closing (imidizing) this polyamic acid or by heating and ring-closing (imidizing) a polyamic acid ester. Any of such polyamide, polyamic acid, polyamic acid ester, and polyimide is useful as a polymer for obtaining a liquid crystal alignment film.
• the diamine represented by the formula (1) contained in the diamine component may be one kind or two or more kinds, and the diamine component is one kind of diamine other than the diamine represented by the formula (1). Or two or more types may be included.
• the diamine represented by the above formula (1) is preferably 5 to 100 mol%, more preferably 20 to 100 mol%, based on the total amount of the diamine component. In the present specification, unless otherwise specified, the ratio is based on the number of moles.
• Examples of the diamine other than the diamine represented by the formula (1) that may be contained in the diamine component include the diamine represented by the above formula (2).
• the diamine represented by the above formula (2) contributes to increasing the pretilt angle of the liquid crystal.
• Examples of these diamines include long-chain alkyl groups, perfluoroalkyl groups, aromatic cyclic groups, and aliphatic groups.
• a diamine having a cyclic group, a substituent obtained by combining these groups, a steroid skeleton group, or the like is preferable.
• pretilt angle varies depending on the mode, but a preferred pretilt angle can be obtained by variously selecting the structure and amount of the diamine.
• the tilt expression ability is relatively high.
• Diamines with low side chains (-P 1- (Q 1 ) p- (Q 2 ) q- (Q 3 ) r -P 2 ) are preferred.
• P 1 is preferably —O—, —NHCO—, or —CONH—, wherein p is 0 to 1, q is 0 to 1, and r is preferably 0.
• P 2 is preferably a linear alkyl group having 1 to 12 carbon atoms
• P 2 is a linear alkyl group having 10 to 22 carbon atoms or a steroid
• a divalent organic group selected from organic groups having 12 to 25 carbon atoms having a skeleton is preferable.
• Specific structures of the side chain diamine having a small tilting ability are shown in Table 1, but are not limited thereto.
• long-chain alkyl side chains such as [2-1] to [2-3] in Table 1 are preferred, and [2-25] in Table 1 from the viewpoint of liquid crystal orientation and pretilt stability.
• Diamines represented by [2-27] are preferred.
• the VA mode vertical alignment method, vertical alignment
• P 1 is preferably —O—, —COO—, or —CH 2 O—
• p is 0 to 1
• q is 0 to 1
• r is 0 to 1
• P 2 is preferably 2 to 22.
• P 2 is preferably a linear alkyl group having 18 to 22 carbon atoms or a divalent organic group that is an organic group having 12 to 25 carbon atoms having a steroid skeleton.
• Specific structures of side chain diamines having a high tilting ability are shown in Tables 2-1 and 2-2.
• diamines have a high tilting ability and are preferable when used in the VA mode.
• diamines such as [2-43] and [2-92] are preferable because they have a high tilting ability and exhibit vertical alignment with a relatively small amount of side chains, and are particularly preferable as [2-52] and [2-101].
• Diamine is preferable in terms of printability of the liquid crystal aligning agent because it has a very high ability to develop a tilt and can obtain vertical alignment with a very small amount of side chain.
• P 1 is preferably —NHCO—
• P 2 is preferably an alkyl group having 1 to 16 carbon atoms, preferably 3 to 10 carbon atoms.
• Q 1 , Q 2 , Q 3 and p, q, r are appropriately combined.
• the position of each substituent on the benzene ring is not particularly limited, but the positional relationship between the two amino groups is preferably meta or para.
• Examples of diamines represented by the above formula (2) include diamines represented by the following formula (5).
• n1 is an integer of 0 to 21, preferably an integer of 0 to 15.
• n2 is an integer from 0 to 19.
• the pretilt angle does not appear, and when n2 is large, the vertical alignment property is easily developed, but the coating property of the liquid crystal aligning agent is deteriorated. Therefore, the preferable range of n2 is 2 to 15, more preferably 4 to 10.
• the content of the diamine represented by the above formula (2) is preferably 5 to 50 mol% with respect to the total amount of the diamine component, and particularly preferably 5 to 30 mol% from the viewpoint of uniformity of pretilt and printability. .
• the diamine represented by the formula (2) is preferably contained in an amount of 0.1 to 1.2 mol, more preferably 0.3 to 1. mol per 1 mol of the diamine represented by the formula (1). 0 mole. When the diamine of the formula (2) is within this range, an appropriate pretilt angle can be obtained, and better liquid crystal orientation can be obtained.
• Examples of other diamines other than the diamine represented by the formula (1) that may be contained in the diamine component include the following diamines in addition to the diamine represented by the formula (2).
• alicyclic diamines examples include 1,4-diaminocyclohexane, 1,3-diaminocyclohexane, 4,4′-diaminodicyclohexylmethane, 4,4′-diamino-3,3′-dimethyldicyclohexylamine, isophorone Examples include diamines.
• aromatic diamines examples include o-phenylenediamine, m-phenylenediamine, p-phenylenediamine, 2,4-diaminotoluene, 2,5-diaminotoluene, 3,5-diaminotoluene, 1,4-diamino -2-methoxybenzene, 2,5-diamino-p-xylene, 1,3-diamino-4-chlorobenzene, 3,5-diaminobenzoic acid, 1,4-diamino-2,5-dichlorobenzene, 4,4 '-Diamino-1,2-diphenylethane, 4,4'-diamino-2,2'-dimethylbibenzyl, 4,4'-diaminodiphenylmethane, 3,3'-diaminodiphenylmethane, 3,4'-diaminodiphenylmethane 4,4′-diamin
• aromatic-aliphatic diamines include 3-aminobenzylamine, 4-aminobenzylamine, 3-amino-N-methylbenzylamine, 4-amino-N-methylbenzylamine, 3-aminophenethylamine, 4-aminobenzylamine, Aminophenethylamine, 3-amino-N-methylphenethylamine, 4-amino-N-methylphenethylamine, 3- (3-aminopropyl) aniline, 4- (3-aminopropyl) aniline, 3- (3-methylaminopropyl) Aniline, 4- (3-methylaminopropyl) aniline, 3- (4-aminobutyl) aniline, 4- (4-aminobutyl) aniline, 3- (4-methylaminobutyl) aniline, 4- (4-methyl Aminobutyl) aniline, 3- (5-aminopentyl) aniline, 4- (5-aminopentyl) Aniline, 3- (5-methyl)
• heterocyclic diamines examples include 2,6-diaminopyridine, 2,4-diaminopyridine, 2,4-diamino-1,3,5-triazine, 2,7-diaminodibenzofuran, 3,6-diamino
• examples thereof include carbazole, 2,4-diamino-6-isopropyl-1,3,5-triazine, 2,5-bis (4-aminophenyl) -1,3,4-oxadiazole.
• aliphatic diamines examples include 1,2-diaminoethane, 1,3-diaminopropane, 1,4-diaminobutane, 1,5-diaminopentane, 1,6-diaminohexane, 1,7-diaminoheptane 1,8-diaminooctane, 1,9-diaminononane, 1,10-diaminodecane, 1,3-diamino-2,2-dimethylpropane, 1,6-diamino-2,5-dimethylhexane, 1,7 -Diamino-2,5-dimethylheptane, 1,7-diamino-4,4-dimethylheptane, 1,7-diamino-3-methylheptane, 1,9-diamino-5-methylheptane, 1,12-diamino Examples include dodecane, 1,18-diaminoocta
• the diamine component may contain a diamine having an alkyl group, a fluorine-containing alkyl group, an aromatic ring, an aliphatic ring, a heterocyclic ring, and a macrocyclic substituent composed thereof in the side chain.
• diamines represented by the following formulas [DA-1] to [DA-30] can be exemplified.
• R 6 represents an alkyl group having 1 to 22 carbon atoms or a fluorine-containing alkyl group.
• S 5 represents —COO—, —OCO—, —CONH—, —NHCO—, —CH 2 —, —O—, —CO—, or —NH—, wherein R 6 represents an alkyl group having 1 to 22 carbon atoms or a fluorine-containing alkyl group.
• S 6 represents —O—, —OCH 2 —, —CH 2 O—, —COOCH 2 —, or —CH 2 OCO—
• R 7 is an alkyl group having 1 to 22 carbon atoms, an alkoxy group, a fluorine-containing alkyl group or a fluorine-containing alkoxy group.
• S 7 represents —COO—, —OCO—, —CONH—, —NHCO—, —COOCH 2 —, —CH 2 OCO—, —CH 2 O—, —OCH 2 —, or —CH 2 —, wherein R 8 is an alkyl group having 1 to 22 carbon atoms, an alkoxy group, a fluorine-containing alkyl group, or a fluorine-containing alkoxy group.
• S 8 represents —COO—, —OCO—, —CONH—, —NHCO—, —COOCH 2 —, —CH 2 OCO—, —CH 2 O—, —OCH 2 —, —CH 2 —, —O—, or —NH—, wherein R 9 is fluorine, cyano, trifluoromethane, nitro, azo, formyl, acetyl, acetoxy Group or hydroxyl group.
• R 10 is an alkyl group having 3 to 12 carbon atoms, and the cis-trans isomerism of 1,4-cyclohexylene is a trans isomer.
• a more stable pretilt can be obtained by using the diamine represented by the general formula (1) and the diamines of the above [DA-1] to [DA-26]. .
• More preferred diamines that can be used in combination are those represented by the formulas [DA-10] to [DA-26], and more preferred are diamines of [DA-10] to [DA-16].
• the preferred content of these diamines is not particularly limited, but is preferably 5 to 50 mol% with respect to the total amount of the diamine component, and is preferably 5 to 30 mol% from the viewpoint of printability.
• diamine component may contain the following diamine.
• n is an integer from 1 to 5.
• the introduction of [DA-31] and [DA-32] can further improve the VHR (voltage holding ratio), and [DA-33] to [DA-38] are more effective in reducing the accumulated charge. Because there is, it is preferable.
• the diamine component may contain diaminosiloxane as shown by the following formula [DA-39].
• n is an integer of 1 to 10.
• diamines may be used alone or in combination of two or more depending on the liquid crystal alignment properties, voltage holding characteristics, accumulated charge, and the like when the liquid crystal alignment film is formed.
• the tetracarboxylic dianhydride that is reacted with the diamine component to obtain the polyamic acid of the present invention is not particularly limited. Specific examples are given below.
• Examples of the tetracarboxylic dianhydride having an alicyclic structure or an aliphatic structure include 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2-dimethyl-1,2,3,4-cyclobutane.
• Tetracarboxylic dianhydride 1,3-dimethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2,3,4-tetramethyl-1,2,3,4-cyclobutanetetra Carboxylic dianhydride, 1,2,3,4-cyclopentanetetracarboxylic dianhydride, 2,3,4,5-tetrahydrofurantetracarboxylic dianhydride, 1,2,4,5-cyclohexanetetracarboxylic Acid dianhydride, 3,4-dicarboxy-1-cyclohexylsuccinic dianhydride, 3,4-dicarboxy-1,2,3,4-tetrahydro-1-naphthalene succinic dianhydride, 1, , 3,4-Butanetetracarboxylic dianhydride, bicyclo [3.3.0] octane-2,4,6,8-tetracarboxylic dianhydride, 3,3 ′, 4,4′-dicyclo
• the liquid crystal alignment is further improved and the accumulated charge of the liquid crystal cell is increased. Can be reduced, which is preferable.
• Aromatic tetracarboxylic dianhydrides include pyromellitic dianhydride, 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride, 2,2 ′, 3,3′-biphenyltetracarboxylic acid Dianhydride, 2,3,3 ′, 4-biphenyltetracarboxylic dianhydride, 3,3 ′, 4,4′-benzophenonetetracarboxylic dianhydride, 2,3,3 ′, 4-benzophenonetetra Carboxylic dianhydride, bis (3,4-dicarboxyphenyl) ether dianhydride, bis (3,4-dicarboxyphenyl) sulfone dianhydride, 1,2,5,6-naphthalenetetracarboxylic dianhydride And 2,3,6,7-naphthalenetetracarboxylic dianhydride and the like.
• the tetracarboxylic acid diester that is reacted with the diamine component to obtain the polyamic acid ester of the present invention is not particularly limited. Specific examples are given below.
• aliphatic tetracarboxylic acid diester examples include 1,2,3,4-cyclobutanetetracarboxylic acid dialkyl ester, 1,2-dimethyl-1,2,3,4-cyclobutanetetracarboxylic acid dialkyl ester, 1 , 3-Dimethyl-1,2,3,4-cyclobutanetetracarboxylic acid dialkyl ester, 1,2,3,4-tetramethyl-1,2,3,4-cyclobutanetetracarboxylic acid dialkyl ester, 1,2, 3,4-cyclopentanetetracarboxylic acid dialkyl ester, 2,3,4,5-tetrahydrofurantetracarboxylic acid dialkyl ester, 1,2,4,5-cyclohexanetetracarboxylic acid dialkyl ester, 3,4-dicarboxy-1 -Cyclohexyl succinic acid dialkyl ester, 3,4-dicarboxy- , 2,3,4-Tetrahydro-1-na
• aromatic tetracarboxylic acid diester examples include pyromellitic acid dialkyl ester, 3,3 ′, 4,4′-biphenyltetracarboxylic acid dialkyl ester, 2,2 ′, 3,3′-biphenyltetracarboxylic acid dialkyl ester, 2 , 3,3 ′, 4-biphenyltetracarboxylic acid dialkyl ester, 3,3 ′, 4,4′-benzophenone tetracarboxylic acid dialkyl ester, 2,3,3 ′, 4-benzophenone tetracarboxylic acid dialkyl ester, bis ( 3,4-dicarboxyphenyl) ether dialkyl ester, bis (3,4-dicarboxyphenyl) sulfone dialkyl ester, 1,2,5,6-naphthalene tetracarboxylic acid dialkyl ester, 2,3,6,7-naphthalene Tetracarboxylic acid dialky
• the dicarboxylic acid to be reacted with the diamine component to obtain the polyamide of the present invention is not particularly limited.
• Specific examples of the dicarboxylic acid or its aliphatic dicarboxylic acid include malonic acid, succinic acid, dimethylmalonic acid, succinic acid, fumaric acid, glutaric acid, adipic acid, muconic acid, 2-methyladipic acid, trimethyladipic acid, pimeline
• dicarboxylic acids such as acids, 2,2-dimethylglutaric acid, 3,3-diethylsuccinic acid, azelaic acid, sebacic acid and suberic acid.
• Examples of the alicyclic dicarboxylic acid include 1,1-cyclopropanedicarboxylic acid, 1,2-cyclopropanedicarboxylic acid, 1,1-cyclobutanedicarboxylic acid, 1,2-cyclobutanedicarboxylic acid, and 1,3-cyclobutanedicarboxylic acid.
• aromatic dicarboxylic acids o-phthalic acid, isophthalic acid, terephthalic acid, 5-methylisophthalic acid, 5-tert-butylisophthalic acid, 5-aminoisophthalic acid, 5-hydroxyisophthalic acid, 2,5-dimethylterephthalic acid Acid, tetramethylterephthalic acid, 1,4-naphthalenedicarboxylic acid, 2,5-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic acid, 1,4-anthracenedicarboxylic acid, 1,4 -Anthraquinone dicarboxylic acid, 2,5-biphenyl dicarboxylic acid, 4,4'-biphenyl dicarboxylic acid, 1,5-biphenylene dicarboxylic acid, 4,4 "-terphenyl dicarboxylic acid, 4,4'-diphenylmethane dicarboxylic
• dicarboxylic acid containing a heterocyclic ring examples include 1,5- (9-oxofluorene) dicarboxylic acid, 3,4-furandicarboxylic acid, 4,5-thiazole dicarboxylic acid, 2-phenyl-4,5-thiazole dicarboxylic acid, 1,2,5-thiadiazole-3,4-dicarboxylic acid, 1,2,5-oxadiazole-3,4-dicarboxylic acid, 2,3-pyridinedicarboxylic acid, 2,4-pyridinedicarboxylic acid, 2, Examples include 5-pyridinedicarboxylic acid, 2,6-pyridinedicarboxylic acid, 3,4-pyridinedicarboxylic acid, and 3,5-pyridinedicarboxylic acid.
• dicarboxylic acids may be acid dihalides or anhydrous structures. These dicarboxylic acids are preferably dicarboxylic acids that can give a polyamide having a linear structure, from the viewpoint of maintaining the orientation of liquid crystal molecules.
• terephthalic acid isoterephthalic acid, 1,4-cyclohexanedicarboxylic acid, 4,4′-biphenyldicarboxylic acid, 4,4′-diphenylmethanedicarboxylic acid, 4,4′-diphenylethanedicarboxylic acid, 4,4 '-Diphenylpropanedicarboxylic acid, 4,4'-diphenylhexafluoropropanedicarboxylic acid, 2,2-bis (phenyl) propanedicarboxylic acid, 4,4-tert-phenyldicarboxylic acid, 2,6-naphthalenedicarboxylic acid, 2 , 5-pyridinedicarboxylic acid or acid dihalides
• tetracarboxylic dianhydrides tetracarboxylic acid diesters
• tetracarboxylic acid diester dichlorides dicarboxylic acids, dicarboxylic acid halides, etc.
• characteristics such as liquid crystal orientation, voltage holding characteristics, accumulated charges, etc.
• one type or two or more types can be used in combination.
• tetracarboxylic dianhydride In obtaining the polyamic acid of the present invention by reaction of tetracarboxylic dianhydride and a diamine component, a known synthesis method can be used. In general, tetracarboxylic dianhydride and a diamine component are reacted in an organic solvent. The reaction between the tetracarboxylic dianhydride and the diamine component is advantageous in that it proceeds relatively easily in an organic solvent and no by-product is generated.
• the organic solvent used for the reaction between the tetracarboxylic dianhydride and the diamine component is not particularly limited as long as the generated polyamic acid dissolves. Specific examples are given below.
• the solution in which the diamine component is dispersed or dissolved in the organic solvent is stirred, and the tetracarboxylic dianhydride is used as it is or in an organic solvent.
• a method of adding by dispersing or dissolving a method of adding a diamine component to a solution in which tetracarboxylic dianhydride is dispersed or dissolved in an organic solvent, and alternately adding a tetracarboxylic dianhydride and a diamine component. Any of these methods may be used.
• tetracarboxylic dianhydride or diamine component when they are composed of a plurality of types of compounds, they may be reacted in a premixed state, may be individually reacted sequentially, or may be further reacted individually. May be mixed and reacted to form a high molecular weight product.
• the polymerization temperature at that time can be selected from -20 ° C. to 150 ° C., but is preferably in the range of ⁇ 5 ° C. to 100 ° C.
• the reaction can be carried out at any concentration, but if the concentration is too low, it is difficult to obtain a high molecular weight polymer, and if the concentration is too high, the viscosity of the reaction solution becomes too high and uniform stirring is difficult. Therefore, the total concentration of the tetracarboxylic dianhydride and the diamine component in the reaction solution is preferably 1 to 50% by mass, more preferably 5 to 30% by mass.
• the initial stage of the reaction is carried out at a high concentration, and then an organic solvent can be added.
• the ratio of the total number of moles of tetracarboxylic dianhydride to the total number of moles of the diamine component is preferably 0.8 to 1.2. Similar to the normal polycondensation reaction, the closer the molar ratio is to 1.0, the higher the molecular weight of the polyamic acid produced.
• the polyimide of the present invention can be obtained by dehydrating and ring-closing the polyamic acid.
• the dehydration cyclization rate (imidization rate) of the amic acid group is not necessarily 100%, and can be arbitrarily adjusted in the range of 0% to 100% depending on the application and purpose. .
• Examples of the method for imidizing the polyamic acid include thermal imidization in which the polyamic acid solution is heated as it is, and catalytic imidization in which a catalyst is added to the polyamic acid solution.
• the temperature at which the polyamic acid is thermally imidized in the solution is 100 ° C. to 400 ° C., preferably 120 ° C. to 250 ° C., and it is preferable to carry out while removing water generated by the imidation reaction from the outside of the system.
• the catalytic imidation of polyamic acid can be carried out by adding a basic catalyst and an acid anhydride to a polyamic acid solution and stirring at -20 to 250 ° C., preferably 0 to 180 ° C.
• the amount of the basic catalyst is 0.5 to 30 mol times, preferably 2 to 20 mol times of the amic acid group, and the amount of the acid anhydride is 1 to 50 mol times, preferably 3 to 30 mol of the amido acid group. Is double.
• the basic catalyst include pyridine, triethylamine, trimethylamine, tributylamine, trioctylamine and the like. Among them, pyridine is preferable because it has an appropriate basicity for proceeding with the reaction.
• Examples of the acid anhydride include acetic anhydride, trimellitic anhydride, pyromellitic anhydride, and the like. Among them, use of acetic anhydride is preferable because purification after completion of the reaction is facilitated.
• the imidization rate by catalytic imidation can be controlled by adjusting the amount of catalyst, reaction temperature, and reaction time.
• the polyamic acid ester is synthesized by reacting the tetracarboxylic acid diester dichloride with the diamine component, or reacting the tetracarboxylic acid diester with the diamine component in the presence of an appropriate condensing agent or base. Is mentioned. Alternatively, it can also be obtained by polymerizing a polyamic acid in advance and esterifying the carboxylic acid in the amic acid using a polymer reaction.
• tetracarboxylic acid diester dichloride and diamine in the presence of a base and an organic solvent at ⁇ 20 ° C. to 150 ° C., preferably 0 ° C. to 50 ° C., for 30 minutes to 24 hours, preferably 1 to 4 hours. It can be synthesized by reacting.
• pyridine triethylamine, 4-dimethylaminopyridine can be used, but pyridine is preferable because the reaction proceeds gently.
• the addition amount of the base is preferably 2 to 4 times the molar amount of the tetracarboxylic acid diester dichloride from the viewpoint of easy removal and high molecular weight.
• the reaction proceeds efficiently by adding Lewis acid as an additive.
• Lewis acid lithium halides such as lithium chloride and lithium bromide are preferable.
• the amount of Lewis acid added is preferably 0.1 to 1.0 times the molar amount of the tetracarboxylic acid diester.
• the solvent used in the above reaction can be the solvent used when polymerizing the polyamic acid shown above, but N-methyl-2-pyrrolidone and ⁇ -butyrolactone are preferred from the solubility of the monomer and polymer. These may be used alone or in combination of two or more.
• the concentration at the time of synthesis is preferably 1 to 30% by mass, and more preferably 5 to 20% by mass from the viewpoint that polymer precipitation is unlikely to occur and a high molecular weight product is easily obtained.
• the solvent used for the synthesis of the polyamic acid ester is preferably dehydrated as much as possible, and it is preferable to prevent mixing of outside air in a nitrogen atmosphere.
• Polyamide can be synthesized in the same manner as polyamic acid ester.
• the reaction solution may be poured into a poor solvent and precipitated.
• the poor solvent used for precipitation include methanol, acetone, hexane, butyl cellosolve, heptane, methyl ethyl ketone, methyl isobutyl ketone, ethanol, toluene, benzene, and water.
• the polymer precipitated in the poor solvent and collected by filtration can be dried by normal temperature or reduced pressure at room temperature or by heating.
• the polymer collected by precipitation is redissolved in an organic solvent and reprecipitation and collection is repeated 2 to 10 times, impurities in the polymer can be reduced.
• the poor solvent at this time include alcohols, ketones, hydrocarbons and the like, and it is preferable to use three or more kinds of poor solvents selected from these because purification efficiency is further improved.
• the molecular weight of the polyamic acid, polyamic acid ester, polyimide and polyamide of the present invention is the strength of the coating film obtained when used as a liquid crystal aligning agent, the workability during coating film formation, and the uniformity of the coating film,
• the weight average molecular weight measured by GPC (Gel Permeation Chromatography) method is preferably 5,000 to 1,000,000, and more preferably 10,000 to 150,000.
• the liquid crystal aligning agent of this invention is a coating liquid for forming a liquid crystal aligning film, and is a solution which the polymer component for forming a polymer film melt
• the polymer component is at least one heavy selected from polyamic acid, polyamic acid ester, polyimide and polyamide obtained by using the diamine represented by the formula (1) which is the polymer of the present invention described above. Includes coalescence.
• the content of the polymer component contained in the liquid crystal aligning agent is preferably 1% by mass to 20% by mass, more preferably 3% by mass to 15% by mass, and particularly preferably 3% by mass to 10% by mass.
• all of the polymer components may be the polymer of the present invention, and other polymers may be mixed with the polymer of the present invention.
• the content of the polymer other than the polymer of the present invention in the polymer component is 0.5 mass% to 15 mass%, preferably 1 mass% to 10 mass%.
• Such other polymer is, for example, a polyamic acid, a polyamic acid ester, a polyimide or a polyamic acid obtained by using a diamine other than the diamine represented by the formula (1) as a diamine component to be reacted with a tetracarboxylic dianhydride component.
• a diamine other than the diamine represented by the formula (1) as a diamine component to be reacted with a tetracarboxylic dianhydride component.
• examples thereof include polyamide.
• the organic solvent (solvent) used in the liquid crystal aligning agent of the present invention is not particularly limited as long as it is an organic solvent that dissolves the polymer component. Specific examples are given below.
• the liquid crystal aligning agent of the present invention may contain components other than the above polymer components. Examples thereof include solvents and compounds that improve the film thickness uniformity and surface smoothness when a liquid crystal aligning agent is applied, and compounds that improve the adhesion between the liquid crystal aligning film and the substrate.
• solvents that improve film thickness uniformity and surface smoothness include the following.
• These poor solvents may be used alone or in combination.
• the above solvent it is preferably 5 to 80% by mass, more preferably 20 to 60% by mass, based on the total amount of the solvent contained in the liquid crystal aligning agent.
• Examples of compounds that improve film thickness uniformity and surface smoothness include fluorine-based surfactants, silicone-based surfactants, and nonionic surfactants.
• F-top EF301, EF303, EF352 manufactured by Tochem Products
• MegaFuck F171, F173, R-30 manufactured by Dainippon Ink
• Florard FC430, FC431 manufactured by Sumitomo 3M
• Asahi Guard AG710 Surflon S-382, SC101, SC102, SC103, SC104, SC105, SC106 (manufactured by Asahi Glass Co., Ltd.).
• the use ratio of these surfactants is preferably 0.01 to 2 parts by mass, more preferably 0.01 to 1 part by mass with respect to 100 parts by mass of the resin component contained in the liquid crystal aligning agent.
• Specific examples of the compound that improves the adhesion between the liquid crystal alignment film and the substrate include the following functional silane-containing compounds and epoxy group-containing compounds.
• the following phenoplast-based additives may be introduced for the purpose of further preventing deterioration of electrical characteristics due to the backlight.
• Specific phenoplast additives are shown below, but are not limited to this structure.
• the amount used is preferably 0.1 to 30 parts by mass with respect to 100 parts by mass of the polymer component contained in the liquid crystal aligning agent.
• the amount is preferably 1 to 20 parts by mass. If the amount used is less than 0.1 parts by mass, the effect of improving the adhesion cannot be expected, and if it exceeds 30 parts by mass, the liquid crystal orientation may be deteriorated.
• the liquid crystal aligning agent of the present invention has a dielectric or conductive material for the purpose of changing the electrical properties such as the dielectric constant and conductivity of the liquid crystal aligning film, as long as the effects of the present invention are not impaired.
• a crosslinkable compound for the purpose of increasing the hardness and density of the liquid crystal alignment film may be added.
• the liquid crystal aligning agent of the present invention can be used as a liquid crystal alignment film after being applied and baked on a substrate or the like and then subjected to alignment treatment by rubbing treatment or light irradiation or without alignment treatment in vertical alignment applications.
• the substrate to be used is not particularly limited as long as it is a highly transparent substrate, and a glass substrate or a plastic substrate such as an acrylic substrate or a polycarbonate substrate can be used.
• a substrate on which an ITO (Indium Tin Oxide) electrode or the like for driving a liquid crystal is formed from the viewpoint of simplification of the process.
• an opaque material such as a silicon wafer can be used as long as the substrate is only on one side, and in this case, a material that reflects light such as aluminum can be used.
• the method for applying the liquid crystal aligning agent is not particularly limited, but industrially, methods such as screen printing, offset printing, flexographic printing, and inkjet are generally used. Other coating methods include dip, roll coater, slit coater, spinner and the like, and these may be used depending on the purpose. Since the solubility of the polymer obtained using the diamine represented by formula (1) contained in the solvent is good, the liquid crystal aligning agent of the present invention is excellent in printability. Therefore, precipitation and whitening (that is, generation of agglomerates) are suppressed when applied to a substrate or the like, and coating / film forming properties are improved. In addition, a liquid crystal alignment film having excellent uniformity and transparency can be produced even if the standing time after application to a substrate or the like is increased.
• the baking after applying the liquid crystal aligning agent on the substrate can be carried out by heating means such as a hot plate at 50 to 300 ° C., preferably 80 to 250 ° C., and the solvent can be evaporated to form a coating film.
• the organic group A that can be desorbed by the heat derived from the diamine represented by the formula (1) is desorbed from the polyamic acid, polyamic acid ester, polyimide or polyamide, and the cyclization reaction or intermolecular reaction described above. Is spent. Therefore, the obtained liquid crystal alignment film is less susceptible to film scraping during the rubbing treatment and excellent in rubbing resistance, and the voltage holding ratio is less likely to be lowered even when exposed to a high temperature and high humidity or a backlight for a long time.
• the structure of the polymer after baking becomes an electrochemically active structure, it is possible to obtain a liquid crystal alignment film in which RDC hardly accumulates. If the thickness of the coating film formed after baking is too thick, it is disadvantageous in terms of power consumption of the liquid crystal display element, and if it is too thin, the reliability of the liquid crystal display element may be lowered.
• the thickness is preferably 10 to 100 nm.
• the liquid crystal display element of the present invention is a liquid crystal display element obtained by obtaining a substrate with a liquid crystal alignment film from the liquid crystal aligning agent of the present invention by the method described above, and then producing a liquid crystal cell by a known method.
• the two substrates disposed so as to face each other, the liquid crystal layer provided between the substrates, and the liquid crystal aligning agent of the present invention provided between the substrate and the liquid crystal layer.
• a liquid crystal display device comprising a liquid crystal cell having a liquid crystal alignment film.
• a liquid crystal display device of the present invention a twisted nematic (TN) method, a vertical alignment (VA) method, a horizontal alignment (IPS) method, an OCB alignment (OCB: There are various types such as Optically (Compensated Bend).
• a pair of substrates on which a liquid crystal alignment film is formed are prepared, spacers are scattered on the liquid crystal alignment film of one substrate, and the liquid crystal alignment film surface is on the inside
• Examples include a method of bonding substrates and injecting liquid crystal under reduced pressure, or a method of sealing by bonding a substrate after dropping the liquid crystal on the liquid crystal alignment film surface on which spacers are dispersed.
• the thickness of the spacer at this time is preferably 1 to 30 ⁇ m, more preferably 2 to 10 ⁇ m.
• liquid crystal examples include a positive liquid crystal having a positive dielectric anisotropy and a negative liquid crystal having a negative dielectric anisotropy.
• a positive liquid crystal having a positive dielectric anisotropy examples include MLC-2003, MLC-6608, MLC-6609 manufactured by Merck & Co., Inc. Etc. can be used.
• the liquid crystal display device manufactured using the liquid crystal aligning agent of the present invention has excellent reliability and can be suitably used for a large-screen high-definition liquid crystal television.
• MW represents a molecular weight
• Boc represents a tert-butoxycarbonyl group (—COO—C (CH 3 )).
• Table 3 shows a list of polyamic acids (PAA) synthesized in Examples and Comparative Examples
• Table 4 shows a list of solvent-soluble polyimides (SPI) synthesized in Examples and Comparative Examples.
• Table 5 shows a list of liquid crystal aligning agents (AL) prepared in Examples and Comparative Examples
• Table 6 shows printability, rubbing resistance, cell display characteristics of the liquid crystal aligning agents in Examples and Comparative Examples. An evaluation result is shown and the characteristic evaluation result of the liquid crystal cell using the liquid crystal aligning agent of an Example and a comparative example is shown in Table 7.
• ⁇ Tetracarboxylic dianhydride> A-1: 1,2,3,4-cyclobutanetetracarboxylic dianhydride (MW196) A-2: 3,4-dicarboxy-1,2,3,4-tetrahydro-1-naphthalene succinic dianhydride (MW300) A-3: Pyromellitic dianhydride (MW218) A-4: Adipoyl chloride (MW183) A-5: Terephthaloyl chloride (MW203)
• B-1 1,4-phenylenediamine (MW108)
• B-2 3-Aminobenzylamine (MW122)
• B-3 4,4-Diaminodiphenylmethane (MW198)
• B-4 4-Hexadecyloxy-1,3-diaminobenzene (MW348)
• B-5 4- (trans-4-heptylcyclohexyl) benzamide-2 ′, 4′-phenylenediamine (MW407)
• B-6 N1, N4-bis (2-tert-butoxycarbonylamino-4-aminophenyl) succinamide (MW528)
• B-7 N1, N4-bis (2-tert-butoxycarbonylamino-4-aminophenyl) adipamide (MW556)
• B-8 N1, N4-bis (2-tert-butoxycarbonylamino-4-aminophenyl) terephthalamide (MW576)
• B-9 4-Amino-N- (2-tert-butoxycarbonylamino-4-aminophenyl) benzamide (MW342)
• GPC device manufactured by Shodex (GPC-101) Column: manufactured by Shodex (series of KD803 and KD805) Column temperature: 50 ° C Eluent: N, N-dimethylformamide (as additive, lithium bromide-hydrate (LiBr ⁇ H 2 O) 30 mmol / L, phosphoric acid / anhydrous crystal (o-phosphoric acid) 30 mmol / L , Tetrahydrofuran (THF) at 10 ml / L) Flow rate: 1.0 ml / min Standard sample for preparing a calibration curve: TSK standard polyethylene oxide (molecular weight: about 900,000, 150,000, 100,000, 30,000) manufactured by Tosoh Corporation, and polyethylene glycol manufactured by Polymer Laboratories ( Molecular weight about 12,000, 4,000, 1,000).
• the imidation ratio of polyimide was measured as follows. 20 mg of polyimide powder was put into an NMR sample tube, and 0.53 ml of deuterated dimethyl sulfoxide (DMSO-d 6 , 0.05% TMS mixed product) was added and completely dissolved. This solution was measured for proton NMR at 500 MHz with an NMR measuring instrument (JNM-ECA500) manufactured by JEOL Datum. The imidization rate was calculated by the following formula. In addition, the imidation rate of the polyimide which does not use the diamine represented by Formula (1) was calculated by setting the value of “Formula (1) Introduction amount of diamine during polyamic acid polymerization” in the following formula to zero.
• Imidization rate (%) (100-polyamic acid polymerization formula (1) introduction amount of diamine (mol%) / 2) ⁇ ⁇
• ⁇ is a proton derived from a structure that does not change before and after imidation as a reference proton, and a proton peak integrated value and a proton peak derived from the NH group of an amic acid that appears in the vicinity of 9.5 to 10.0 ppm. It calculated
• ⁇ (1 ⁇ ⁇ x / y)
• x is the proton peak integrated value derived from the NH group of the amic acid
• y is the peak integrated value of the reference proton
• ⁇ is one NH group proton of the amic acid in the case of polyamic acid (imidation rate is 0%). The number ratio of the reference protons.
• a liquid crystal aligning agent is spin-coated on a glass substrate with a transparent electrode, dried on a hot plate having a temperature of 80 ° C. for 70 seconds, and then baked in a nitrogen atmosphere using a 220 ° C. IR oven for 10 minutes to obtain a film thickness of 100 nm.
• the coating film was formed.
• This coating surface was rubbed with a cotton cloth (YA-25C, manufactured by Yoshikawa) using a rubbing machine with a roll diameter of 120 mm under the conditions of a roll rotation speed of 1000 rpm, a roll traveling speed of 50 mm / sec, and an indentation amount of 0.4 mm, and liquid crystal alignment A substrate with a film was obtained.
• Two substrates are prepared, a 6 ⁇ m spacer is sprayed on the surface of one liquid crystal alignment film, and a sealant (Sumitomo Chemical Co., Ltd., NX-1500T) is printed thereon with a seal dispenser.
• a sealant Suditomo Chemical Co., Ltd., NX-1500T
• the sealing agent was cured (temporary curing: 80 ° C. for 30 minutes, main curing: 150 ° C. for 1 hour) to produce an empty cell.
• Liquid crystal MLC-2003 manufactured by Merck Japan
• was injected into this empty cell by a reduced pressure injection method was sealed to obtain a twisted nematic liquid crystal cell.
• the prepared liquid crystal aligning agent was subjected to a flexographic printing on a cleaned Cr plate using an alignment film printing machine (“Angstromer” manufactured by Nissha Printing Co., Ltd.) to perform a coating property test. About 1.0 mL of the liquid crystal aligning agent was dropped onto the anilox roll, and the blanking operation was performed 10 times. Then, the printing machine was stopped for 10 minutes, and the printing plate was dried. Thereafter, printing was performed on one Cr substrate, and the printed substrate was left on a hot plate at 70 ° C. for 5 minutes, the coating film was temporarily dried, and the film state was observed. The observation was performed by visual observation and an optical microscope (“ECLIPSE ME600” manufactured by Nikon Corporation) at 50 times, and mainly the film thickness unevenness and the film thickness unevenness of the edge portion were observed.
• an optical microscope (“ECLIPSE ME600” manufactured by Nikon Corporation) at 50 times, and mainly the film thickness unevenness and the film thickness unevenness of the edge portion were observed.
• ⁇ Liquid crystal orientation evaluation> The initial alignment state of the antiparallel liquid crystal cell for evaluating liquid crystal alignment was visually observed through a polarizing plate. The evaluation criteria are shown below. The results are shown in Table 6. Good: Oriented well. Defect: Many light spots and alignment defects are observed.
• ⁇ Measurement of pretilt angle> A liquid crystal cell obtained in the same manner as in the above ⁇ Preparation of liquid crystal cell> was heated at 105 ° C. for 10 minutes, and then the pretilt angle was measured. For the measurement, an Axo Scan Mueller matrix polarimeter manufactured by Optometrics was used.
• VHR voltage holding ratio
• the VHR was measured by the same method as the initial VHR (after exposure to backlight aging). VHR).
• the results are shown in the “Backlight Aging” column of Table 7.
• the liquid crystal cell on which the VHR measurement after the backlight aging exposure was performed was allowed to stand for 240 hours in an environment of 70 ° C. and a relative humidity of 70%, and then the VHR was measured by the same method as the initial VHR (high temperature / high humidity). VHR after aging). The results are shown in the “high temperature / high humidity aging” column of Table 7.
• Step-1 Synthesis of 4-nitro 2-tertbutoxycarbonylaminoaniline [NB-NA]
• 1 L of THF and 300 mL of DMF were added and heated to about 60 ° C. in a nitrogen atmosphere to dissolve, and 285.2 g (1.44 mol) of tertbutyl dicarbonate was added over 2 hours using a dropping funnel. It was slowly added dropwise and refluxed for 4 hours.
• reaction solution is concentrated on a rotary evaporator, and the resulting residue is dissolved in THF, poured into a mixed solvent of ethyl acetate: n-hexane (volume ratio 7: 3), and recrystallized to give a yellow solid. 248 g (yield about 75%) was obtained.
• the resulting solid was 4-nitro-2-tertbutoxycarbonylaminoaniline.
• the structure was confirmed by 1 H-NMR spectrum which is a nuclear magnetic resonance spectrum of an intramolecular hydrogen atom. The measurement data is shown below.
• Step-2 N1, N4-bis [(2-tert-butoxycarbonylamino) -4-nitrophenyl] fuscinamide 20.0 g (78.2) of 4-nitro-2-tertbutoxycarbonylaminoaniline in a 500 mL four-necked flask. 97 mmol) and 15.6 g (197.43 mmol) of pyridine (also referred to as “Py”), dissolved in 300 ml of dehydrated THF, and 5.51 g of succinic dichloride in a nitrogen atmosphere while maintaining the temperature at 10 ° C. or lower in an ice bath.
• pyridine also referred to as “Py”
• Step-3 [B-6] 10.0 g of N1, N4-bis [(2-tert-butoxycarbonylamino) -4-nitrophenyl] succinamide and palladium were added to a 300 mL four-necked flask equipped with a three-way cock and a stirrer. 1.0 g of carbon (10 wt%) was weighed, 200 ml of DMF was added, vacuum degassing and hydrogen substitution were performed, and the reaction was allowed to proceed at room temperature for 48 hours.
• Example 5 Polymerization of polyamic acid [PAA-1: A-1 / B-6] and preparation of liquid crystal aligning agent [AL-1]
• B- 2.64 g (5.00 mmol) of 6 was measured, 20.3 g of NMP was added and dissolved, cooled to about 10 ° C. under a nitrogen atmosphere, 0.93 g (4.75 mmol) of A-1 was added little by little, The mixture was returned to room temperature and reacted for 6 hours to obtain a 15% by mass solution of polyamic acid (PAA-1).
• PAA-1 had a number average molecular weight of 11,300 and a weight average molecular weight of 24,500.
• Example 6 Polymerization of Polyamic Acid [PAA-2: A-1 / B-7] and Preparation of Liquid Crystal Alignment Agent [AL-2]
• B- 7.78 g (5.00 mmol) of 7 was measured, 21.1 g of NMP was added and dissolved, cooled to about 10 ° C. under a nitrogen atmosphere, 0.93 g (4.75 mmol) of A-1 was added little by little, The mixture was returned to room temperature and reacted for 6 hours to obtain a 15% by weight polyamic acid (PAA-2) solution.
• PAA-2 had a number average molecular weight of 13,400 and a weight average molecular weight of 30,100.
• Example 7 Polymerization of polyamic acid [PAA-3: A-1 / B-8] and preparation of liquid crystal aligning agent [AL-3]
• B- 2.88 g (5.00 mmol) of 8 was measured, 21.1 g of NMP was added and dissolved, cooled to about 10 ° C. under a nitrogen atmosphere, 0.93 g (4.75 mmol) of A-1 was added little by little, The mixture was returned to room temperature and reacted for 6 hours to obtain a 15% by weight polyamic acid (PAA-3) solution.
• the obtained PAA-3 had a number average molecular weight of 10,700 and a weight average molecular weight of 25,200.
• Example 8 Polymerization of polyamic acid [PAA-4: A-1 / B-9] and preparation of liquid crystal aligning agent [AL-4]
• B- 1.71 g (5.00 mmol) of 9 was measured, 15.00 g of NMP was added and dissolved, cooled to about 10 ° C. under a nitrogen atmosphere, 0.93 g (4.75 mmol) of A-1 was added little by little, The mixture was returned to room temperature and reacted for 6 hours to obtain a 15% by mass solution of polyamic acid (PAA-4).
• the obtained PAA-4 had a number average molecular weight of 11,100 and a weight average molecular weight of 23,500.
• a liquid crystal aligning agent [AL-4] having a mass% of NMP of 64% by mass and a BCS of 30% by mass was obtained.
• Example 9 Polymerization of Polyamic Acid [PAA-5: A-3 / B-6] and Preparation of Liquid Crystal Alignment Agent [AL-5]
• B- 2.64 g (5.00 mmol) of 6 was measured, 20.7 g of NMP was added and dissolved, cooled to about 10 ° C. under a nitrogen atmosphere, 1.01 g (4.65 mmol) of A-3 was added little by little, The mixture was returned to room temperature and reacted for 6 hours to obtain a 15% by mass solution of polyamic acid (PAA-5).
• the obtained PAA-5 had a number average molecular weight of 10,800 and a weight average molecular weight of 22,300.
• Example 10 Polymerization of polyamic acid [PAA-6: A-3 / B-7] and preparation of liquid crystal aligning agent [AL-6]
• B- 2.78 g (5.00 mmol) of 7 was measured, 21.5 g of NMP was added and dissolved, cooled to about 10 ° C. under a nitrogen atmosphere, 1.01 g (4.65 mmol) of A-3 was added little by little, The mixture was returned to room temperature and reacted for 6 hours to obtain a 15% by weight polyamic acid (PAA-6) solution.
• the obtained PAA-6 had a number average molecular weight of 11,900 and a weight average molecular weight of 24,900.
• Example 11 Polymerization of polyamic acid [PAA-7: A-1 / B-1, B-7 (30), B-4 (10)] and preparation of liquid crystal aligning agent [AL-7]
• Nitrogen introduction tube In a 50 ml four-necked flask equipped with a mechanical stirrer, 0.64 g (6.00 mmol) of B-1, 1.67 g (3.00 mmol) of B-7, and 0.35 g (1.00 mmol) of B-4 Weighed and dissolved 25.89 g of NMP, cooled to about 10 ° C.
• PAA-7 polyamic acid
• a liquid crystal aligning agent [AL-7] having a mass% of NMP of 64% by mass and a BCS of 30% by mass was obtained.
• PAA-10 polyamic acid
• Example 15 Preparation of Liquid Crystal Alignment Agent [AL-9]
• 20.00 g of the polyimide solution [SPI-2S] obtained in Example 13 was obtained in Example 14.
• 80.00 g of the obtained polyamic acid solution [PAA-10S] was weighed and stirred at room temperature for 24 hours to obtain a liquid crystal aligning agent [AL-9].
• Example 16 Polymerization of Polyamide [PA-1: A-4, A-1 / B-6] and Preparation of Liquid Crystal Alignment Agent [AL-10]
• A-1 10.00 mmol
• B-6 16.7 g
• NMP 1.98 g
• pyridine 1.98 g
• A-1 (1.02 g, 5.00 mmol) was added, and the mixture was returned to room temperature and reacted for 24 hours under a nitrogen atmosphere to obtain a polyamide (PA-1) solution having a concentration of 20% by mass.
• VHR measurement was performed in the order of initial stage, backlight aging, and high temperature / high humidity aging.
• * 3 RDC measurement is performed after initial VHR measurement, AC voltage: V50 (approximately 4.8 to 5.0 Vp-p), DC voltage: 5.0 V, DC application time: 1 hour, DC application 1 hour later RDC was performed by the flicker reference method.
• Comparative Examples 1 to 4 that do not use the diamine represented by the formula (1) of the present invention, the rubbing resistance, liquid crystal orientation, RDC, backlight resistance and high temperature and high humidity resistance of the liquid crystal alignment film, and the liquid crystal aligning agent It was not possible to satisfy all the characteristics of printability.
• the liquid crystal aligning agent of the present invention is resistant to film peeling and scraping during rubbing, does not easily accumulate initial charge even when a DC voltage is applied, and is resistant to voltage even when exposed to high temperatures and high humidity for a long period of time. A liquid crystal alignment film in which the retention rate is unlikely to decrease is obtained. Therefore, the liquid crystal display element produced using the liquid crystal aligning agent of this invention can be made into a highly reliable liquid crystal display element, TN liquid crystal display element, STN liquid crystal display element, TFT liquid crystal display element, VA liquid crystal display element. And IPS liquid crystal display elements, OCB liquid crystal display elements, and the like.

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