Classifications

• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D305/00—Heterocyclic compounds containing four-membered rings having one oxygen atom as the only ring hetero atoms
  • C07D305/02—Heterocyclic compounds containing four-membered rings having one oxygen atom as the only ring hetero atoms not condensed with other rings
  • C07D305/04—Heterocyclic compounds containing four-membered rings having one oxygen atom as the only ring hetero atoms not condensed with other rings having no double bonds between ring members or between ring members and non-ring members
  • C07D305/06—Heterocyclic compounds containing four-membered rings having one oxygen atom as the only ring hetero atoms not condensed with other rings having no double bonds between ring members or between ring members and non-ring members with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to the ring atoms
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
  • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
  • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
  • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
  • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
  • C08G73/1075—Partially aromatic polyimides
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
  • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
  • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
  • C08G73/1075—Partially aromatic polyimides
  • C08G73/1078—Partially aromatic polyimides wholly aromatic in the diamino moiety
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
  • C08L79/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
  • C08L79/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
  • C09K19/00—Liquid crystal materials
  • C09K19/52—Liquid crystal materials characterised by components which are not liquid crystals, e.g. additives with special physical aspect: solvents, solid particles
  • C09K19/54—Additives having no specific mesophase characterised by their chemical composition
  • C09K19/56—Aligning agents
• • G—PHYSICS
  • G02—OPTICS
  • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
  • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
  • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
  • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
  • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
  • G02F1/1333—Constructional arrangements; Manufacturing methods
  • G02F1/1337—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers
• • G—PHYSICS
  • G02—OPTICS
  • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
  • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
  • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
  • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
  • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
  • G02F1/1333—Constructional arrangements; Manufacturing methods
  • G02F1/1337—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers
  • G02F1/133711—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers by organic films, e.g. polymeric films
  • G02F1/133723—Polyimide, polyamide-imide
• • 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
  • C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
  • C08G2261/50—Physical properties
  • C08G2261/53—Physical properties liquid-crystalline

Definitions

• the present invention relates to a liquid crystal alignment treatment agent, a liquid crystal alignment film, and a liquid crystal display element used for 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 film used industrially is formed by applying a polyimide-based liquid crystal alignment treatment agent comprising a polyimide precursor, polyamic acid (also referred to as polyamic acid) or a polyimide solution, onto a substrate. It is made by filming.
• 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 liquid crystal alignment film is also used to control the angle of the liquid crystal with respect to the substrate, that is, the pretilt angle of the liquid crystal.
• the pretilt angle of the liquid crystal As the liquid crystal display element becomes more sophisticated and its range of use expands year by year, Not only can a predetermined pretilt angle be obtained, but also the stability of the pretilt angle has become increasingly important.
• a compound having two or more epoxy groups in the molecule is used as a polyimide-based liquid crystal for the purpose of obtaining a constant pretilt angle regardless of the rubbing conditions in the manufacturing process of the liquid crystal alignment film. It has been proposed to be included in an alignment treatment agent (see, for example, Patent Document 1).
• liquid crystal display elements in order to improve the alignment uniformity of the liquid crystal, the liquid crystal is sometimes isotropically treated by heat treatment after sealing the liquid crystal.
• the stability of the pretilt angle is low, there arises a problem that a pretilt angle having a target size cannot be obtained after this isotropic processing or the pretilt angle varies.
• liquid crystal display elements that use a backlight that generates a large amount of heat to obtain high brightness and liquid crystal display elements that are used in in-vehicle applications, such as car navigation systems and instrument panels, are used in high-temperature environments for long periods of time. Or it may be left unattended. Under such severe conditions, when the pretilt angle is gradually changed, problems such as inability to obtain initial display characteristics or occurrence of unevenness in display occur.
• liquid crystal display elements are used in harsh usage environments compared to liquid crystal display elements for monitors that mainly display characters and still images. Characteristics that can withstand long-term use are required. Therefore, the liquid crystal alignment film has been required to have higher reliability. In particular, when the voltage holding ratio, which is one of the electrical characteristics, is reduced, line sticking, which is a display defect of the liquid crystal display element, easily occurs, and a highly reliable liquid crystal display element cannot be obtained. Therefore, not only the initial characteristics are good, but also, for example, it is required that the initial characteristics are not easily lowered even after being exposed to a high temperature for a long time.
• the present invention has been made in view of the above circumstances, and the problem thereof is a liquid crystal alignment film that is excellent in stability of a pretilt angle even under a high temperature environment for a long time, and in which a decrease in voltage holding ratio is suppressed,
• the object is to provide a liquid crystal display element having the liquid crystal alignment film and a liquid crystal alignment treatment agent for forming the liquid crystal alignment film.
• a liquid crystal alignment treatment agent containing a polyamic acid using a specific diamine compound as a diamine component and / or a polyimide obtained by imidizing the polyamic acid has the above-mentioned purpose.
• the present invention has been found to be extremely effective for achieving the present invention, and has been completed.
• the said specific diamine compound contains the novel compound which literature has not been described.
• the present invention has the following gist. (1) From the group consisting of a polyamic acid obtained by reacting a diamine component containing the diamine compound represented by the formula [1] with tetracarboxylic dianhydride, and a polyimide obtained by dehydrating and ring-closing the polyamic acid.
• X 1 is —O—, —NH—, —N (CH 3 ) —, —CONH—, —NHCO—, —CH 2 O—, —COO—, —OCO—, —CON) (CH 3 ) — or —N (CH 3 ) CO—
• X 2 is a single bond, an aliphatic hydrocarbon group having 1 to 20 carbon atoms, a non-aromatic cyclic hydrocarbon group, or an aromatic hydrocarbon.
• X 3 is a single bond, —O—, —NH—, —N (CH 3 ) —, —CONH—, —NHCO—, —COO—, —OCO—, —CON (CH 3 ) —, —N (CH 3 ) CO— or —O (CH 2 ) m — (m is an integer of 1 to 5), X 4 represents an organic group having 1 to 20 carbon atoms, and n is 1 It is an integer of ⁇ 4.) (2) The liquid crystal aligning agent according to the above (1), wherein X 2 in the formula [1] is a single bond or an alkylene group having 1 to 5 carbon atoms.
• X 1 is —O—, —NH—, —N (CH 3 ) —, —CONH—, —NHCO—, —CH 2 O—, —COO—, —OCO—, —CON) (CH 3 ) — or —N (CH 3 ) CO—
• X 2 is a single bond, an aliphatic hydrocarbon group having 1 to 20 carbon atoms, a non-aromatic cyclic hydrocarbon group, or an aromatic hydrocarbon.
• X 3 is a single bond, —O—, —NH—, —N (CH 3 ) —, —CONH—, —NHCO—, —COO—, —OCO—, —CON (CH 3 ) —, —N (CH 3 ) CO— or —O (CH 2 ) m — (m is an integer of 1 to 5), X 4 represents an organic group having 1 to 20 carbon atoms, and n is 1 It is an integer of ⁇ 4.) (9) Polyamic acid obtained by reacting a diamine component containing the diamine compound represented by the formula [1] described in (8) above with tetracarboxylic dianhydride, or dehydrating and ring-closing the polyamic acid. Obtained polyimide.
• the liquid crystal alignment film obtained from the liquid crystal aligning agent of the present invention has excellent pretilt angle stability even under a high temperature environment for a long time, and can suppress a decrease in voltage holding ratio. Therefore, the liquid crystal display element having the liquid crystal alignment film is excellent in reliability.
• the novel diamine compound useful as raw materials such as a liquid-crystal aligning agent, is provided.
• a diamine compound having an oxetane group represented by the following formula [1] (hereinafter also referred to as a specific diamine compound) is used.
• X 1 is —O—, —NH—, —N (CH 3 ) —, —CONH—, —NHCO—, —CH 2 O—, —COO—, —OCO—, —CON) (CH 3 ) — or —N (CH 3 ) CO—
• X 2 is a single bond, an aliphatic hydrocarbon group having 1 to 20 carbon atoms, a non-aromatic cyclic hydrocarbon group, or an aromatic hydrocarbon.
• X 3 is a single bond, —O—, —NH—, —N (CH 3 ) —, —CONH—, —NHCO—, —COO—, —OCO—, —CON (CH 3 ) —, —N (CH 3 ) CO— or —O (CH 2 ) m — (m is an integer of 1 to 5), X 4 represents an organic group having 1 to 20 carbon atoms, and n is 1 It is an integer of ⁇ 4.)
• the polyamic acid obtained by the reaction of a diamine component containing a specific diamine compound and tetracarboxylic dianhydride, and the polyimide obtained by dehydrating and ring-closing the polyamic acid are collectively referred to as a polymer.
• the polymer obtained by using the specific diamine compound in the present invention has a side chain of the following formula [1a].
• X 1 , X 2 , X 3 and X 4 are the same as defined in the above formula [1].
• the oxetane group present at the end of the side chain of the formula [1a] reacts with a carboxyl group and / or a hydroxyl group under heating. Two oxetane groups also undergo addition polymerization with each other. These reactions form a structure in which a plurality of polymers are crosslinked. Since the oxetane group has higher nucleophilicity than the epoxy group, the reaction efficiency is high.
• the plurality of polymers having the side chain of the formula [1a] are more easily cross-linked, and a liquid crystal alignment film having a structure with a high cross-linking density is easily formed. Furthermore, since the oxetane group has a four-membered ring structure, when it reacts with a carboxyl group and / or a hydroxyl group, it contains one more methylene group at the binding site than an epoxy group that has a three-membered ring structure. In addition, because of the oxetane group present at the end of the side chain of the formula [1a], it is easy to obtain a liquid crystal alignment film having a high crosslink density structure and a high elongation and toughness.
• the oxetane group present at the end of the side chain of the formula [1a] can efficiently promote the crosslinking reaction, thereby reducing the characteristics of the liquid crystal display element when the crosslinking compound is added. There is no residue of unreacted crosslinkable compounds that cause it.
• the liquid crystal alignment film obtained from the liquid crystal alignment treatment agent of the present invention is more stable against heat of the pretilt angle than the liquid crystal alignment film containing no crosslinkable compound or the liquid crystal alignment film added with the crosslinkable compound.
• the decrease in voltage holding ratio can be suppressed in a high temperature environment. Therefore, line sticking, which is one of display defects, hardly occurs, so that a liquid crystal display element with excellent reliability can be obtained.
• the specific diamine compound of the present invention is a diamine compound having an oxetane group represented by the following formula [1].
• X 1 represents —O—, —NH—, —N (CH 3 ) —, —CONH—, —NHCO—, —CH 2 O—, —COO—, —OCO—, —CON ( A divalent organic group selected from CH 3 ) — and —N (CH 3 ) CO—.
• —O—, —NH—, —CONH—, —NHCO—, —CON (CH 3 ) —, —CH 2 O—, —COO—, or —OCO— is easy to synthesize diamine compounds. preferable.
• X 2 is a single bond, an aliphatic hydrocarbon group having 1 to 20 carbon atoms, a non-aromatic cyclic hydrocarbon group, or an aromatic hydrocarbon group.
• the aliphatic hydrocarbon group having 1 to 20 carbon atoms may be linear or branched. Moreover, you may have an unsaturated bond.
• non-aromatic hydrocarbon group examples include cyclopropane ring, cyclobutane ring, cyclopentane ring, cyclohexane ring, cycloheptane ring, cyclooctane ring, cyclononane ring, cyclodecane ring, cycloundecane ring, cyclododecane ring, cyclotridecane ring.
• Decane ring cyclotetradecane ring, cyclopentadecane ring, cyclohexadecane ring, cycloheptadecane ring, cyclooctadecane ring, cyclononadecane ring, cycloicosane ring, tricycloeicosane ring, tricyclodecosan ring, bicycloheptane ring, decahydronaphthalene ring , Norbornene ring, adamantane ring and the like.
• aromatic hydrocarbon group examples include a benzene ring, a naphthalene ring, a tetrahydronaphthalene ring, an azulene ring, an indene ring, a fluorene ring, an anthracene ring, a phenanthrene ring, and a phenalene ring.
• X 2 is preferably a single bond, an alkylene group having 1 to 10 carbon atoms, an unsaturated alkylene group having 1 to 10 carbon atoms, a cyclopropane ring, a cyclobutane ring, a cyclopentane ring, a cyclohexane ring, a cycloheptane ring, a norbornene ring, Adamantane ring, benzene ring, naphthalene ring, tetrahydronaphthalene ring, fluorene ring or anthracene ring, more preferably a single bond, an alkyl group having 1 to 10 carbon atoms, an unsaturated alkyl group having 1 to 10 carbon atoms, cyclohexane A ring, a norbornene ring, an adamantane ring, a benzene ring, a naphthalene ring, a fluorene
• X 3 represents a single bond, —O—, —NH—, —N (CH 3 ) —, —CONH—, —NHCO—, —COO—, —OCO—, —CON (CH 3 ).
• X 4 represents an organic group having 1 to 20 carbon atoms, and the organic group may contain a hetero atom (N, O, S, Si).
• An alkyl group having 1 to 10 carbon atoms is preferable, and an alkyl group having 1 to 5 carbon atoms is more preferable.
• n is an integer of 1 to 4. Preferably, it is 1 to 3 and more preferably 1, from the viewpoint of reactivity with tetracarboxylic dianhydride.
• the bonding position of the two amino groups (—NH 2 ) in the formula [1] is not limited. Specifically, with respect to the linking group (X 1 ) of the side chain, 2, 3 position, 2, 4 position, 2, 5 position, 2, 6 position, 3, 4 position on the benzene ring Position, 3, 5 positions. Among these, from the viewpoint of reactivity when synthesizing a polyamic acid, positions 2, 4, 2, 5, or 3, 5 are preferable. Considering the ease in synthesizing the diamine compound, the positions 2, 4 or 3, 5 are more preferable. It is particularly preferred that X 1 in the formula [1] is —O—, —CONH—, or —COO—, X 3 is a single bond or —O—, and n is 1.
• X 1 in the formula [1] is —O—, —CONH—, or —COO—
• X 2 is a single bond or an alkylene group having 1 to 5 carbon atoms
• X 3 is a single bond, or It is particularly preferred that —O—
• X 4 is an alkyl group having 1 to 5 carbon atoms
• n is 1.
• Preferred combinations of X 1 , X 2 , X 3 , X 4 and n in the formula [1] are as shown in Table 1 below.
• the method for producing the specific diamine compound represented by the formula [1] of the present invention is not particularly limited, but preferred methods include the following methods.
• the specific diamine compound of the present invention can be obtained by synthesizing a dinitro compound represented by the following formula [2], further reducing the nitro group, and converting it to an amino group.
• the method for reducing the dinitro group is not particularly limited, and usually palladium-carbon, platinum oxide, Raney nickel, platinum black, rhodium-alumina, platinum sulfide carbon, etc. are used as a catalyst, ethyl acetate, toluene, tetrahydrofuran, dioxane, There is a method in which hydrogen gas, hydrazine, hydrogen chloride, or the like is used in a solvent such as an alcohol solvent.
• the dinitro compound of the formula [2] can be obtained by a method in which —X 2 —X 3 is bonded to dinitrobenzene via X 1 .
• X 1 is —O— (ether bond), —NH— (amino bond), —N (CH 3 ) — (methylated amino bond), —CONH— (amide bond), —NHCO— (reverse amide bond), —CH 2 O— (methylene ether bond), —COO— (ester bond), —OCO— (reverse ester bond), —CON (CH 3 ) — (N-methylated amide bond), and —N (CH 3 ) CO— (N-methylated reverse amide bond).
• These linking groups can be formed by ordinary organic synthetic techniques.
• X 1 is an ether or methylene ether bond
• a corresponding dinitro group-containing halogen derivative is reacted with a hydroxyl group derivative containing X 2 , X 3 and X 4 in the presence of an alkali, or a dinitro group-containing hydroxyl group derivative
• a halogen-substituted derivative containing an oxetane group having X 2 , X 3 and X 4 in the presence of an alkali a halogen-substituted derivative containing an oxetane group having X 2 , X 3 and X 4 in the presence of an alkali.
• an amino bond a method of reacting a corresponding dinitro group-containing halogen derivative with an amino group-substituted derivative containing an oxetane group having X 2 , X 3 and X 4 in the presence of an alkali can be mentioned.
• the amide bond include a method of reacting a corresponding dinitro group-containing acid chloride and an amino group-substituted product containing an oxetane group having X 2 , X 3 and X 4 in the presence of an alkali.
• a reverse amide bond a method in which a corresponding dinitro group-containing amino group-substituted product and an acid chloride containing an oxetane group having X 2 , X 3 and X 4 are reacted in the presence of an alkali can be mentioned.
• an ester bond a method in which the corresponding dinitro group-containing acid chloride is reacted with a hydroxyl group-substituted derivative containing an oxetane group having X 2 , X 3 and X 4 in the presence of an alkali can be mentioned.
• dinitro group-containing halogen derivatives and dinitro group-containing derivatives include 3,5-dinitrochlorobenzene, 2,4-dinitrochlorobenzene, 2,4-dinitrofluorobenzene, 3,5-dinitrobenzoic acid chloride, 3,5 -Dinitrobenzoic acid, 2,4-dinitrobenzoic acid chloride, 2,4-dinitrobenzoic acid, 3,5-dinitrobenzyl chloride, 2,4-dinitrobenzyl chloride, 3,5-dinitrobenzyl alcohol, 2,4- Dinitrobenzyl alcohol, 2,4-dinitroaniline, 3,5-dinitroaniline, 2,6-dinitroaniline, 2,4-dinitrophenol, 2,5-dinitrophenol, 2,6-dinitrophenol, 2,4- And dinitrophenylacetic acid. In consideration of availability of raw materials and reaction, one or more kinds can be selected and used.
• diamine examples include a diamine having an alkyl group, a fluorine-containing alkyl group, an aromatic ring, an aliphatic ring, a heterocyclic ring, or a macrocyclic substituent composed of these in the diamine side chain.
• R 1 represents an alkyl group having 1 to 22 carbon atoms or a fluorine-containing alkyl group.
• R 2 represents —COO—, —OCO—, —CONH—, —NHCO—, —CH 2 —, —O—, —CO—, or —NH—.
• R 3 represents an alkyl group having 1 to 22 carbon atoms or a fluorine-containing alkyl group.
• R 4 represents —O—, —OCH 2 —, —CH 2 O—, —COOCH 2 —, or —CH 2 OCO—
• R 5 represents the number of carbon atoms. 1 to 22 alkyl groups, alkoxy groups, fluorine-containing alkyl groups or fluorine-containing alkoxy groups.
• R 6 represents —COO—, —OCO—, —CONH—, —NHCO—, —COOCH 2 —, —CH 2 OCO—, —CH 2 O—, — OCH 2 — or —CH 2 —
• 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.
• R 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 a fluorine group, a cyano group, a trifluoromethane group, a nitro group, an azo group, a formyl group, an acetyl group, an acetoxy group, or a 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.
• R 11 is an alkyl group having 3 to 12 carbon atoms, and the cis-trans isomerism of 1,4-cyclohexylene is a trans isomer.
• diaminosiloxanes represented by the following formula [DA33] can also be exemplified.
• a 4 represents an alkyl group having 3 to 20 carbon atoms which may be substituted with a fluorine atom
• a 3 represents a 1,4-cyclohexylene group or 1,4-phenylene.
• a 2 is an oxygen atom or —COO— * (where a bond marked with “*” is bonded to A 3 )
• a 1 is an oxygen atom or —COO— * (wherein And a bond marked with “*” binds to (CH 2 ) a2.)
• a 1 is 0 or an integer of 1
• a 2 is an integer of 2 to 10, and a 3 is 0. Or an integer of 1.
• the above-mentioned other diamine compounds can be used alone or in combination of two or more depending on the properties such as liquid crystal alignment properties, voltage holding properties, and accumulated charges when the liquid crystal alignment film is used.
• tetracarboxylic dianhydride used in the present invention is not particularly limited. Specific examples are given below.
• the tetracarboxylic dianhydride can be used singly or in combination of two or more according to properties such as liquid crystal alignment properties, voltage holding properties, and accumulated charges when formed into a liquid crystal alignment film.
• the polymer of the present invention is a polyamic acid using a specific diamine compound as a raw material or a polyimide obtained by dehydrating and ring-closing the polyamic acid.
• the stability of the pretilt angle to heat increases as the content ratio of the specific diamine compound in the diamine component increases.
• the diamine component is a specific diamine compound.
• 5 mol% or more of a diamine component is a specific diamine compound, More preferably, it is 10 mol% or more.
• 100 mol% of a diamine component may be a specific diamine compound, from the viewpoint of uniform coatability when applying a liquid crystal aligning agent, the specific diamine compound is preferably 80 mol% or less of the diamine component. Preferably it is 40 mol% or less.
• tetracarboxylic dianhydride In obtaining the polyamic acid of the present invention by the reaction of the diamine component and tetracarboxylic dianhydride, a known synthesis method can be used. In general, tetracarboxylic dianhydride and diamine are reacted in an organic solvent. The reaction of tetracarboxylic dianhydride and diamine 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 tetracarboxylic dianhydride and diamine is not particularly limited as long as the produced polyamic acid can be dissolved. Specific examples are given below. N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, N-methylcaprolactam, dimethylsulfoxide, tetramethylurea, pyridine, dimethylsulfone, hexamethylsulfoxide, ⁇ -butyrolactone, isopropyl alcohol, Methoxymethylpentanol, dipentene, ethyl amyl ketone, methyl nonyl ketone, methyl ethyl ketone, methyl isoamyl ketone, methyl isopropyl ketone, methyl cellosolve, ethyl cellosolve, methyl cellosolve acetate, ethyl cellosolve acetate, butyl carbito
• a solvent that does not dissolve the polyamic acid may be used by mixing with the above solvent as long as the produced polyamic acid does not precipitate.
• water in the organic solvent inhibits the polymerization reaction and further causes hydrolysis of the produced polyamic acid, it is preferable to use a dehydrated and dried organic solvent.
• the solution in which the diamine is dispersed or dissolved in the organic solvent is stirred, and the tetracarboxylic dianhydride is dispersed as it is or in the organic solvent.
• a method of adding after dissolving a method of adding diamine to a solution in which tetracarboxylic dianhydride is dispersed or dissolved in an organic solvent, a method of adding tetracarboxylic dianhydride and diamine alternately, etc. 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 to form a high molecular weight product.
• the temperature at which the tetracarboxylic dianhydride reacts with the diamine component 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 content 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 is a polyimide obtained by dehydrating and ring-closing the above polyamic acid, and is useful as a polymer for obtaining a liquid crystal alignment film.
• the dehydration cyclization rate (imidization rate) of the amic acid group is not necessarily 100%, and can be adjusted, for example, in the range of 45 to 85% depending on the application and purpose.
• 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 system.
• the catalytic imidation of the polyamic acid can be carried out by adding a basic catalyst and an acid anhydride to the 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 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 a 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 and the polyimide contained in the liquid crystal alignment treatment agent of the present invention is determined by considering the strength of the coating film obtained therefrom, the workability during coating film formation, and the uniformity of the coating film.
• the weight average molecular weight measured by 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 resin component for forming a resin film melt
• the said resin component is a resin component containing at least 1 type of polymer chosen from the polymer of this invention mentioned above.
• the content of the resin component 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 above resin components may be polymers used in the present invention, and other polymers may be mixed with the polymer of the present invention.
• the content of the other polymer in the resin component is 0.5 to 15% by mass, preferably 1 to 10% by mass.
• polystyrene resin examples include polyamic acid or polyimide obtained by using a diamine other than the specific diamine compound as a diamine component to be reacted with tetracarboxylic dianhydride.
• the organic solvent used for the liquid-crystal aligning agent of this invention will not be specifically limited if it is an organic solvent in which the resin component mentioned above is dissolved.
• the liquid crystal aligning agent of this invention may contain components other than the above. Examples thereof include solvents and compounds that improve the film thickness uniformity and surface smoothness when a liquid crystal alignment treatment agent is applied, and compounds that improve the adhesion between the liquid crystal alignment film and the substrate.
• the solvent that improves the uniformity of the film thickness and the surface smoothness include the following.
• the solvent for improving the uniformity of the film thickness and the surface smoothness may be used alone or in combination.
• the amount of the solvent used 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.
• the compound that improves the uniformity of the film thickness and the surface smoothness include a fluorine-based surfactant, a silicone-based surfactant, and a nonionic surfactant.
• 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. .
• the compound that improves the adhesion between the liquid crystal alignment film and the substrate include the following functional silane-containing compounds and epoxy group-containing compounds.
• the amount of the compound used is preferably 0.1 to 30 parts by mass with respect to 100 parts by mass of the resin component contained in the liquid crystal aligning agent, More preferably, it is 1 to 20 parts by mass. If the amount is less than 0.1 part by mass, the effect of improving the adhesion cannot be expected, and if it exceeds 30 parts by mass, the orientation of the liquid crystal may deteriorate.
• the liquid crystal alignment treatment agent of the present invention is a dielectric or conductive material for the purpose of changing the electrical properties such as the dielectric constant and conductivity of the liquid crystal alignment film as long as the effects of the present invention are not impaired. May be added.
• the liquid crystal alignment treatment agent of the present invention can be used as a liquid crystal alignment film without applying an alignment treatment after being applied and baked on a substrate and then subjected to an alignment treatment by rubbing treatment, light irradiation, or the like.
• the substrate to be used is not particularly limited as long as it is a highly transparent substrate, and a glass substrate, a plastic substrate such as an acrylic substrate or a polycarbonate substrate, or the like can be used.
• 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 alignment treatment agent is not particularly limited, but industrially, methods such as screen printing, offset printing, flexographic printing, and ink jet are generally used. Other coating methods include dip, roll coater, slit coater, spinner and the like, and these may be used depending on the purpose.
• Calcination after applying the liquid crystal aligning agent on the substrate can form a coating film by evaporating the solvent at 50 to 300 ° C., preferably 80 to 250 ° C., by a heating means such as a hot plate. If the thickness of the coating film after baking is too thick, it is disadvantageous in terms of power consumption of the liquid crystal display element, and if it is too thin, the reliability of the liquid crystal display element may be lowered. Therefore, it is preferably 5 to 300 nm, more preferably 10 to 100 nm. When the liquid crystal is horizontally or tilted, the fired coating film is treated by rubbing or irradiation with polarized ultraviolet rays.
• the liquid crystal display element of the present invention is a liquid crystal display element obtained by obtaining a substrate with a liquid crystal alignment film from the liquid crystal aligning agent of the present invention by the method described above, and then preparing a liquid crystal cell by a known method.
• liquid crystal cell production prepare a pair of substrates on which a liquid crystal alignment film is formed, spray spacers on the liquid crystal alignment film of one substrate, and make the liquid crystal alignment film surface inside.
• Examples include a method of bonding the other substrate and injecting the liquid crystal under reduced pressure, or a method of sealing the liquid crystal after dropping the liquid crystal on the liquid crystal alignment film surface on which the spacers are dispersed, and the like.
• the thickness of the spacer at this time is preferably 1 to 30 ⁇ m, more preferably 2 to 10 ⁇ m.
• 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.
• 3-methyl-3-oxetaneethanol (2) 14.95 g, 146.4 mmol
• triethylamine 16.29 g, 160.1 mmol
• tetrahydrofuran 150 ml
• a solution of 3,5-dinitrobenzoyl chloride (1) 33.70 g, 146.2 mmol
• tetrahydrofuran 40 ml
• the reaction solution was poured into 1 L of pure water, and the resulting crystals were filtered and washed with pure water.
• CBDA 1,2,3,4-cyclobutanetetracarboxylic dianhydride
• BODA bicyclo [3,3,0] octane-2,4,6,8-tetracarboxylic dianhydride
• p-PDA p-phenylenediamine
• PCH7DAB 1,3-diamino-4- [4- (trans-4-n-heptylcyclohexyl) phenoxy] benzene
• PBCH5DAB 1,3-diamino-4- ⁇ 4- [ Trans-4- (trans-4-n-pentylcyclohexyl) cyclohexyl] phenoxy ⁇ benzene
• m-PBCH5DAB 3,5-diamino- ⁇ 4- [trans-4- (trans-4-n-pentylcyclohexyl) ) Cyclohexyl] phenyl ⁇ benzoate
• the imidation rate is determined by determining a proton derived from a structure that does not change before and after imidation as a reference proton, and the peak integrated value of this proton and the proton peak derived from the NH group of amic acid that appears near 9.5 to 10.0 ppm. It calculated
• Imidization rate (%) (1 ⁇ ⁇ x / y) ⁇ 100
• x is a proton peak integrated value derived from NH group of amic acid
• y is a peak integrated value of reference proton
• ⁇ is one NH group proton of amic acid in the case of polyamic acid (imidation rate is 0%) Is the number ratio of the reference proton to.
• NMP was added to the polyamic acid (A) solution (20.0 g) obtained in the same manner as in Example 2 and diluted to a concentration of 6% by mass. Then, acetic anhydride (2.48 g), pyridine ( 1.90 g) was added and reacted at 80 ° C. for 4 hours. The reaction solution was poured into methanol (300 ml), and the produced precipitate was separated by filtration. The precipitate was washed with methanol and dried under reduced pressure at 100 ° C. to obtain a polyimide (B) powder. The imidation ratio of this polyimide was 53%, the number average molecular weight was 21,300, and the weight average molecular weight was 51,200.
• NMP was added to a solution (20.2 g) of the polyamic acid (C) obtained in the same manner as in Example 4 to dilute to 6% by mass, and then acetic anhydride (2.50 g), pyridine (1 .95 g) was added and reacted at 80 ° C. for 4 hours.
• the reaction solution was poured into methanol (300 ml), and the produced precipitate was separated by filtration. The precipitate was washed with methanol and dried under reduced pressure at 100 ° C. to obtain a polyimide (D) powder.
• the imidation ratio of this polyimide was 55%, the number average molecular weight was 22,400, and the weight average molecular weight was 52,500.
• Example 7 BODA (3.50 g, 14.0 mmol), PBCH5DAB (0.50 g, 1.16 mmol), p-PDA (1.89 g, 17.5 mmol), diamine (4) (1.10 g, 4.66 mmol) in NMP (14.9 g), and after reacting at 80 ° C. for 5 hours, CBDA (1.83 g, 9.33 mmol) and NMP (12.3 g) were added, and reacted at 40 ° C. for 6 hours to obtain polyamic acid. A solution (concentration 24.5% by mass) was obtained.
• NMP was added to a solution (20.0 g) of polyamic acid (I) obtained in the same manner as in Synthesis Example 1 and diluted to 6% by mass, and then acetic anhydride (2.48 g) and pyridine (1 .92 g) was added and reacted at 80 ° C. for 4 hours.
• the reaction solution was poured into methanol (290 ml), and the produced precipitate was filtered off. The precipitate was washed with methanol and dried under reduced pressure at 100 ° C. to obtain a polyimide (J) powder.
• the imidation ratio of this polyimide was 55%, the number average molecular weight was 22,300, and the weight average molecular weight was 56,300.
• a liquid crystal alignment treatment agent is spin-coated on the ITO surface of the substrate with 3 ⁇ 4 cm ITO electrodes, and heat-treated on a hot plate at 80 ° C. for 5 minutes and in a thermal circulation clean oven for 30 minutes at 210 ° C.
• a 100 nm polyimide coating was obtained.
• the surface of the coating film was rubbed with a roll diameter 120 mm, rayon cloth rubbing apparatus under the conditions of a rotation speed of 700 rpm, a moving speed of 40 mm / sec, and an indentation amount of 0.3 mm to obtain a substrate with a liquid crystal alignment film.
• the orientation uniformity of the liquid crystal was confirmed by polarizing microscope observation.
• the state in which the liquid crystal was uniformly aligned was evaluated as “ ⁇ ”, and the state in which the disorder of the liquid crystal was observed was evaluated as “ ⁇ ”.
• Example 10 A solution of the polyamic acid (A) (10.2 g), NMP (9.71 g) and BCS (20.0 g) obtained in the same manner as in Example 2 were mixed at 25 ° C. for 12 hours to conduct a liquid crystal alignment treatment. Agent (1) was obtained. Abnormalities such as turbidity and precipitation were not observed in this liquid crystal aligning agent, and it was confirmed that the liquid crystal aligning agent was a uniform solution.
• Example 11 Liquid crystal alignment treating agent obtained by mixing polyimide (B) powder (2.51 g), NMP (24.5 g) and BCS (11.6 g) obtained in the same manner as in Example 3 at 50 ° C. for 15 hours. (2) was obtained. Abnormalities such as turbidity and precipitation were not observed in this liquid crystal aligning agent, and it was confirmed that the liquid crystal aligning agent was a uniform solution.
• Example 12 A solution (10.5 g) of polyamic acid (C), NMP (11.6 g) and BCS (18.0 g) obtained in the same manner as in Example 4 were mixed at 25 ° C. for 12 hours to conduct liquid crystal alignment treatment. Agent (3) was obtained. Abnormalities such as turbidity and precipitation were not observed in this liquid crystal aligning agent, and it was confirmed that the liquid crystal aligning agent was a uniform solution.
• Example 13 A liquid crystal aligning agent obtained by mixing polyimide (D) powder (2.50 g), NMP (18.7 g) and BCS (17.3 g) obtained in the same manner as in Example 5 at 50 ° C. for 15 hours. (4) was obtained. Abnormalities such as turbidity and precipitation were not observed in this liquid crystal aligning agent, and it was confirmed that the liquid crystal aligning agent was a uniform solution.
• Example 14 Liquid crystal aligning agent by mixing polyimide (E) powder (2.55 g), NMP (26.9 g) and BCS (9.81 g) obtained in the same manner as in Example 6 at 50 ° C. for 15 hours. (5) was obtained. Abnormalities such as turbidity and precipitation were not observed in this liquid crystal aligning agent, and it was confirmed that the liquid crystal aligning agent was a uniform solution.
• Example 15 A polyimide (F) powder (2.48 g), NMP (16.6 g) and BCS (19.2 g) obtained in the same manner as in Example 7 were mixed at 50 ° C. for 15 hours to obtain a liquid crystal aligning agent. (6) was obtained. Abnormalities such as turbidity and precipitation were not observed in this liquid crystal aligning agent, and it was confirmed that the liquid crystal aligning agent was a uniform solution.
• Liquid crystal aligning agent obtained by mixing polyimide (G) powder (2.50 g), NMP (28.3 g) and BCS (7.69 g) obtained in the same manner as in Example 8 at 50 ° C. for 15 hours. (7) was obtained. Abnormalities such as turbidity and precipitation were not observed in this liquid crystal aligning agent, and it was confirmed that the liquid crystal aligning agent was a uniform solution.
• Example 17 Liquid crystal aligning agent by mixing polyimide (H) powder (2.50 g), NMP (22.6 g) and BCS (13.4 g) obtained in the same manner as in Example 9 at 50 ° C. for 15 hours. (8) was obtained. Abnormalities such as turbidity and precipitation were not observed in this liquid crystal aligning agent, and it was confirmed that the liquid crystal aligning agent was a uniform solution.
• the liquid crystal alignment films obtained from the liquid crystal aligning agents of Examples 10 to 17 show uniform alignment, improve the stability of the pretilt angle against heat, and are exposed to high temperatures for a long time. When this was done, the decrease in voltage holding ratio was suppressed.
• the liquid crystal alignment films obtained from the liquid crystal alignment treatment agents of Comparative Examples 5 to 7 the alignment disorder of the liquid crystal, which is considered to be caused by scratches due to rubbing, was observed.
• the pretilt angle significantly decreased after heat treatment at 120 ° C. for 5 hours (heat treatment 2).
• the liquid crystal alignment films obtained from the liquid crystal alignment treatment agents of Comparative Examples 8 to 11 had a large decrease in voltage holding ratio after standing at high temperature with respect to the initial voltage holding ratio.
• the liquid crystal alignment films obtained from the liquid crystal alignment treatment agents of the examples from the comparison between the examples 10 and 12 and the comparative example 5 and the comparison between the examples 11 and 13 to 17 and the comparative examples 6 and 7 In this case, there was no shaving associated with the rubbing treatment, and the stability of the pretilt angle against heat was greatly improved.
• the liquid crystal alignment film obtained from the liquid crystal alignment treatment agent of these examples provides a liquid crystal display element that does not cause display unevenness even under severe conditions such as being used or left in a high temperature environment for a long time. be able to.
• the liquid crystal aligning agent of the present invention is useful for TN elements, STN elements, TFT liquid crystal elements, and vertical alignment type liquid crystal display elements, and can be suitably used particularly for large-screen and high-definition liquid crystal televisions. .

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