WO2013008906A1 - Liquid crystal aligning agent, liquid crystal alignment film, and liquid crystal display element - Google Patents
Liquid crystal aligning agent, liquid crystal alignment film, and liquid crystal display element Download PDFInfo
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- WO2013008906A1 WO2013008906A1 PCT/JP2012/067901 JP2012067901W WO2013008906A1 WO 2013008906 A1 WO2013008906 A1 WO 2013008906A1 JP 2012067901 W JP2012067901 W JP 2012067901W WO 2013008906 A1 WO2013008906 A1 WO 2013008906A1
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- liquid crystal
- diamine
- polyamic acid
- aligning agent
- crystal aligning
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- 0 CCNCc1cc(*)ccc1 Chemical compound CCNCc1cc(*)ccc1 0.000 description 4
- AWMZEKGTWKVJHE-UHFFFAOYSA-N CCNCCc(cc1)ccc1N Chemical compound CCNCCc(cc1)ccc1N AWMZEKGTWKVJHE-UHFFFAOYSA-N 0.000 description 1
- RBBFEQBVGNFDCI-UHFFFAOYSA-N CCNCc(cc1)ccc1N Chemical compound CCNCc(cc1)ccc1N RBBFEQBVGNFDCI-UHFFFAOYSA-N 0.000 description 1
- GWEBPSPLDWBTDH-UHFFFAOYSA-N CNCC(C=C1)=CCC1N Chemical compound CNCC(C=C1)=CCC1N GWEBPSPLDWBTDH-UHFFFAOYSA-N 0.000 description 1
- IDYZRZAXUUIAAT-UHFFFAOYSA-N CNCCC(C=CC1)=CC1N Chemical compound CNCCC(C=CC1)=CC1N IDYZRZAXUUIAAT-UHFFFAOYSA-N 0.000 description 1
- NNIPOYNUFNLQMO-UHFFFAOYSA-N CNCCc(cc1)ccc1N Chemical compound CNCCc(cc1)ccc1N NNIPOYNUFNLQMO-UHFFFAOYSA-N 0.000 description 1
- HBLPYXIZPMDWIO-UHFFFAOYSA-N CNCc1cc(N)ccc1 Chemical compound CNCc1cc(N)ccc1 HBLPYXIZPMDWIO-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
Definitions
- the present invention relates to a liquid crystal alignment agent, a liquid crystal alignment film, and a liquid crystal display element.
- Liquid crystal display elements are currently widely used as display devices.
- a liquid crystal alignment film which is a constituent member of a liquid crystal display element, is a film that uniformly arranges liquid crystals.
- display defects such as display unevenness and afterimages are liable to occur. Occurrence of display defects may involve ionic impurities in the liquid crystal, and as a method for reducing these impurities, a proposal as in Patent Document 1 has been made.
- liquid crystal alignment film an alignment process called rubbing is generally performed by rubbing the surface of the polymer film with a cloth.
- the rubbing resistance of the liquid crystal alignment film is insufficient, the film is scraped to generate scratches or dust, or the film itself is peeled off, thereby degrading the display quality of the liquid crystal display element.
- the liquid crystal alignment film is required to have high rubbing resistance, and methods as disclosed in Patent Documents 2 to 5 have been proposed.
- JP 2002-323701 A JP-A-7-120769 JP-A-9-146100 JP 2008-90297 A JP-A-9-258229 International Publication No. 2004/053583
- an object of the present invention is to provide a liquid crystal alignment film having good liquid crystal alignment and rubbing resistance, a low ion density, and a small accumulated charge in an FFS mode liquid crystal display element.
- Another object of the present invention is to provide a liquid crystal aligning agent capable of obtaining the liquid crystal aligning film.
- an object of the present invention is to provide a liquid crystal display element having excellent display quality.
- the present inventor has conducted extensive research. As a result, the tetracarboxylic dianhydride having an alicyclic structure or an aliphatic structure, a diamine having a urea structure, and 2 polymerization reaction sites are included. It has been found that the above object can be achieved by a liquid crystal aligning agent containing a polyamic acid obtained by using a diamine having a secondary amine.
- the present invention has the following gist. 1.
- a diamine containing a tetracarboxylic dianhydride component containing a tetracarboxylic dianhydride having an alicyclic structure or an aliphatic structure, a diamine having a urea structure, and a diamine having a secondary amine at the polymerization reaction site Liquid crystal aligning agent containing the polyamic acid obtained by reaction with a component.
- liquid crystal aligning agent according to 1, wherein the tetracarboxylic dianhydride component contains 50 mol% or more of a tetracarboxylic dianhydride having an alicyclic structure or an aliphatic structure.
- liquid crystal aligning agent according to any one of 1 to 3, wherein the diamine component contains 10 to 70 mol% of a diamine having a urea structure.
- liquid crystal aligning agent according to any one of 1 to 4, wherein the diamine having a secondary amine at the polymerization reaction site is a diamine represented by the following formula (1).
- X represents an aromatic ring
- R 1 represents an alkylene group having 1 to 5 carbon atoms
- R 2 represents an alkyl group having 1 to 4 carbon atoms.
- liquid crystal aligning agent according to any one of 1 to 5, wherein the diamine having a urea structure is a diamine represented by the following formula (2).
- Y represents an oxygen atom or a sulfur atom
- R 3 and R 4 each independently represents an alkylene group having 1 to 3 carbon atoms
- Z 1 and Z 2 each independently represents a single atom. Represents a bond, —O—, —S—, —OCO—, or —COO—.
- a liquid crystal display element comprising the liquid crystal alignment film of 8.7.
- the liquid crystal display device has a high alignment control function for liquid crystal, that is, has excellent liquid crystal alignment properties, high rubbing resistance, low ion density when used as a liquid crystal display device, and further FFS mode liquid crystal display.
- a liquid crystal aligning agent with little accumulated charge in the device
- a liquid crystal aligning film obtained using the liquid crystal aligning agent
- a liquid crystal display device comprising the liquid crystal aligning film.
- the liquid crystal aligning agent of the present invention contains a polyamic acid obtained by reacting a diamine component and a tetracarboxylic dianhydride component.
- the tetracarboxylic dianhydride component that is a raw material of polyamic acid contains a tetracarboxylic dianhydride having an alicyclic structure or an aliphatic structure, and is a diamine component that is a raw material of polyamic acid Contains a diamine having a urea structure and a diamine having a secondary amine at the polymerization reaction site.
- the tetracarboxylic dianhydride contained in the tetracarboxylic dianhydride component and the diamine contained in the diamine component may each be one kind or plural kinds.
- the diamine contained in the diamine component and the tetracarboxylic dianhydride contained in the tetracarboxylic dianhydride component will be described in detail.
- ⁇ Diamine having secondary amine at polymerization reaction site> As a specific example of a diamine having a secondary amine at a polymerization reaction site contained as an essential component in the diamine component which is a raw material of the polyamic acid contained in the liquid crystal aligning agent of the present invention, for example, it is represented by the following formula (1). Diamines. Of course, the diamine component is a secondary amine in the polymerization reaction site other than the diamine represented by the formula (1) in place of the diamine represented by the formula (1) or together with the diamine represented by the formula (1).
- the polymerization reaction site is a site that reacts with the tetracarboxylic dianhydride component, and a secondary amine of a diamine having a secondary amine at the polymerization reaction site, that is, —NH— is a tetracarboxylic dianhydride component. React with.
- X represents an aromatic ring
- R 1 represents an alkylene group having 1 to 5 carbon atoms
- R 2 represents an alkyl group having 1 to 4 carbon atoms.
- X in the formula is a site for giving an aromatic amine site to a diamine having a secondary amine at the polymerization reaction site, and is not particularly limited as long as it is an aromatic ring.
- X is preferably phenylene or naphthalene from the viewpoint of availability of raw materials, easiness of synthesis, liquid crystal orientation, and the like, and phenylene is particularly preferable from the viewpoint of versatility.
- the substitution position of R 1 is preferably a meta position or a para position.
- R 1 represents an alkylene group having 1 to 5 carbon atoms. From the viewpoint of imparting solubility of the polymer (polyamic acid), R 1 may be branched or have a ring structure within this carbon number range, but from the viewpoint of liquid crystal orientation and rubbing resistance, a linear structure From the viewpoint of availability of the reagent, an alkylene group having 1 or 2 carbon atoms is particularly preferable.
- R 2 represents an alkyl group having 1 to 4 carbon atoms and may have a linear or branched structure.
- a group as small as possible is preferable, and a methyl group or an ethyl group is particularly preferable.
- the content of the diamine having a secondary amine at the polymerization reaction site such as the diamine represented by the formula (1) is preferably 10 to 70 mol% of the total diamine component, but has a high rubbing resistance and a small accumulated charge amount. From the viewpoint of compatibility, it is more preferably 15 to 65 mol%, particularly preferably 20 to 60 mol%.
- diamine having a urea structure included as an essential component in the diamine component that is a raw material of the polyamic acid contained in the liquid crystal aligning agent of the present invention include diamines represented by the following formula (2).
- the diamine component contains a diamine having a urea structure other than the diamine represented by the formula (2) instead of the diamine represented by the formula (2) or together with the diamine represented by the formula (2). You may do it.
- Y represents an oxygen atom or a sulfur atom
- R 3 and R 4 each independently represents an alkylene group having 1 to 3 carbon atoms
- Z 1 and Z 2 each independently represents a single bond. , -O-, -S-, -OCO-, or -COO-.
- Y when Y is an oxygen atom, it is a urea group, and when Y is a sulfur atom, it is a thiourea group (hereinafter, the urea group and the thiourea group may be collectively referred to as (thio) urea group).
- the urea group and the thiourea group may be collectively referred to as (thio) urea group).
- a urea group or a thiourea group has a urea structure.
- both oxygen atoms and sulfur atoms are atoms with high electronegativity.
- two hydrogen atoms with high donor properties exist on the nitrogen atom. Therefore, the oxygen or sulfur atom of the (thio) urea group is relatively strongly self-assembled by non-covalent bonding with two hydrogen atoms of another (thio) urea group.
- the urea structure of a diamine having a urea structure is preferably a urea group
- Y in Formula (2) is preferably an oxygen atom. This is because the oxygen atom has a higher electronegativity than the oxygen atom and the sulfur atom, and therefore the urea structure is stronger and more likely to self-assemble than the thiourea structure.
- the liquid crystal aligning agent of this invention has (thio) urea group derived from diamine which has urea structures, such as diamine represented by Formula (2), in a polymer chain (polyamic acid chain). For this reason, rubbing tolerance can be improved by electrostatic interaction (non-covalent bond) between (thio) urea groups.
- the present invention is different from a method for improving rubbing resistance by connecting polymer chains generally used in the field of liquid crystal alignment films with a crosslinking agent.
- R 3 and R 4 each independently represent an alkylene group having 1 to 3 carbon atoms, and the structure thereof may be either linear or branched. Specific examples include methylene group, ethylene group, trimethylene group, 1-methylethylene group, 2-methylethylene group and the like. Among these, from the viewpoint of liquid crystal alignment and rubbing resistance, a structure having as many free rotation sites as possible and having a small steric hindrance is preferable, and specifically, a methylene group, an ethylene group, and a trimethylene group are preferable.
- Z 1 and Z 2 are each independently a single bond, —O—, —S—, —OCO—, or —COO—.
- the structures of Z 1 and Z 2 are preferably as flexible as possible and have as little steric hindrance as possible from the viewpoint of liquid crystal orientation and rubbing resistance, and are preferably a single bond, —O—, or —S—.
- the structure between the (thio) urea group and the benzene ring is preferably symmetrical about the (thio) urea group in the sense of forming a film having a high film density and forming a stronger liquid crystal alignment film.
- —R 3 —Z 1 — and —R 4 —Z 2 — preferably have the same structure.
- diamines represented by the formula (2) compounds represented by the following formulas (2-a) to (2-c) are preferable.
- R 11 and R 21 are both an alkylene group having 1 to 3 carbon atoms.
- R 12 and R 22 are alkylene groups having 1 to 3 carbon atoms which are different from each other.
- R 13 and R 23 are each independently an alkylene group having 1 to 3 carbon atoms.
- the bonding position of the amino group (—NH 2 ) on the benzene ring is not particularly limited, but is preferably a 3-aminophenyl structure or a 4-aminophenyl structure from the viewpoint of liquid crystal alignment.
- a 4-aminophenyl structure is preferred.
- the formula (2) is preferably any one of the following formulas (2-1), (2-2), and (2-3), and particularly preferably the formula (2-1).
- Z 1 , Z 2 , R 3, and R 4 have the same definitions as in the formula (2).
- formula (2) examples include compounds represented by formula (2-4) to formula (2-15). Among these, it is particularly preferable to use diamines represented by the above formulas (2-8) to (2-11).
- the content of the diamine represented by the formula (2) is preferably 10 to 70 mol% of the total diamine component, but is more preferably 15 to 65 mol% from the viewpoint of achieving both high rubbing resistance and a small amount of accumulated charge, 20 to 60 mol% is particularly preferable.
- a diamine component that is a raw material of polyamic acid in addition to a diamine having a secondary amine at the polymerization reaction site or a diamine having a urea structure, It is also possible to contain other diamine compounds. Specific examples of other diamine compounds are listed below.
- the other diamine compounds mentioned above are of one type depending on characteristics such as volume resistivity, rubbing resistance, ion density characteristics, transmittance, liquid crystal alignment characteristics, voltage holding characteristics and accumulated charges when used as a liquid crystal alignment film. Alternatively, two or more types can be mixed and used.
- the tetracarboxylic dianhydride having an alicyclic structure or an aliphatic structure contained as an essential component in the tetracarboxylic dianhydride component that is a raw material of the polyamic acid contained in the liquid crystal aligning agent of the present invention is, for example, It is a tetracarboxylic dianhydride represented by the formula (3).
- the tetracarboxylic dianhydride component is replaced with the tetracarboxylic dianhydride represented by the formula (3) or together with the tetracarboxylic dianhydride represented by the formula (3).
- the tetracarboxylic dianhydride which has alicyclic structure or aliphatic structure other than the tetracarboxylic dianhydride represented by this may be contained.
- a tetracarboxylic dianhydride having an alicyclic structure or an aliphatic structure and a tetracarboxylic dianhydride other than a tetracarboxylic dianhydride having an alicyclic structure or an aliphatic structure may be contained. Good.
- R 5 represents a tetravalent hydrocarbon group having an alicyclic structure or an aliphatic structure.
- the alicyclic structure is a structure having a carbocyclic ring having no aromaticity, such as cycloalkane or cycloalkene.
- the aliphatic structure is a chain hydrocarbon group such as a paraffin hydrocarbon group, an olefin hydrocarbon group, an acetylene hydrocarbon group (for example, the chain hydrocarbon group has a total of 4 carbon atoms).
- Specific examples of R 5 include tetravalent groups represented by the following formulas (3-1) to (3-30).
- the tetracarboxylic dianhydride component is represented by formulas (3-1) to (3-25) and R 5 having an alicyclic structure or an aliphatic structure such as formula (3-30) is preferred.
- R 5 is a group represented by the formula (3-1), the formula (3-2), the formula (3-6), the formula (3-25) and the formula (3-
- a tetracarboxylic dianhydride selected from the group consisting of 30 it is preferable because a liquid crystal alignment film with less accumulated charge can be obtained.
- the tetracarboxylic dianhydride component preferably contains an aromatic tetracarboxylic dianhydride.
- an aromatic tetracarboxylic dianhydride is preferably 50 mol% or less, more preferably 30 mol% or less, based on the total amount of the tetracarboxylic dianhydride component.
- aromatic tetracarboxylic dianhydride examples include tetracarboxylic dianhydrides represented by the following formula (4).
- R 6 is a group having an aromatic structure.
- the aromatic structure is a structure having an aromatic ring showing aromaticity such as a benzene ring.
- Specific examples of R 6 include tetravalent groups represented by the following formulas (3-31) to (3-47).
- the method for obtaining the polyamic acid contained in the liquid crystal aligning agent of the present invention by reacting the diamine component and the tetracarboxylic dianhydride component (hereinafter also simply referred to as tetracarboxylic dianhydride) is particularly limited.
- a known method can be applied.
- a diamine component and a tetracarboxylic dianhydride component are mixed in an organic solvent to cause a polymerization reaction to obtain a polyamic acid.
- the solution in which the diamine component is dispersed or dissolved in the organic solvent is stirred, and the tetracarboxylic dianhydride component is used as it is, or A method of adding by dispersing or dissolving in an organic solvent, a method of adding a diamine component to a solution in which a tetracarboxylic dianhydride component is dispersed or dissolved in an organic solvent, and alternating a tetracarboxylic dianhydride component and a diamine component And the like.
- the plurality of types of components may be preliminarily mixed and polymerized separately or sequentially. May be.
- the temperature at which the tetracarboxylic dianhydride component and the diamine component are subjected to a polymerization reaction in an organic solvent is usually 0 to 150 ° C., preferably 5 to 100 ° C., more preferably 10 to 80 ° C. The higher the temperature, the faster the polymerization reaction ends. However, when the temperature is too high, a high molecular weight polymer (polyamic acid) may not be obtained.
- the polymerization reaction can be carried out at any charge concentration, but if the charge concentration is too low, it will be difficult to obtain a high molecular weight polymer, and if the charge concentration is too high, the reaction solution will become too viscous and uniform.
- the amount is preferably 1 to 50% by mass, more preferably 5 to 30% by mass.
- the initial stage of the polymerization reaction may be performed at a high concentration, and then an organic solvent may be added.
- the charged concentration is the concentration of the total mass of the tetracarboxylic dianhydride component and the diamine component.
- the organic solvent used in the above reaction is not particularly limited as long as the generated polyamic acid is soluble.
- Specific examples include N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, N-methylcaprolactam, dimethyl sulfoxide, tetramethyl urea, pyridine, dimethyl sulfone, hexamethyl sulfoxide or and ⁇ -butyrolactone. These may be used alone or in combination.
- the solvent may be used by mixing with the above solvent as long as the produced polyamic acid does not precipitate.
- the ratio of the tetracarboxylic dianhydride component to the diamine component used in the polymerization reaction for obtaining the polyamic acid is preferably 1: 0.8 to 1: 1.2 in terms of molar ratio, and this molar ratio is 1: The closer to 1, the greater the molecular weight of the polyamic acid obtained. If the molecular weight of the polyamic acid is too small, the strength of the coating film obtained therefrom may be insufficient. Conversely, if the molecular weight of the polyamic acid is too large, the viscosity of the liquid crystal aligning agent produced therefrom will increase. Thus, workability during coating film formation and uniformity of the coating film may be deteriorated. Therefore, the weight average molecular weight of the polyamic acid used in the liquid crystal aligning agent of the present invention is preferably 2,000 to 500,000, more preferably 5,000 to 300,000.
- the liquid crystal aligning agent of this invention contains 1 or more types of polyamic acid obtained by making it above.
- a liquid crystal aligning agent containing a polyamic acid obtained by reaction of such a specific diamine component and a specific tetracarboxylic dianhydride component as shown in the examples described later, good liquid crystal alignment properties
- a liquid crystal alignment film having rubbing resistance, low ion density, and low accumulated charge in the FFS mode liquid crystal display element can be obtained.
- the liquid crystal aligning agent of the present invention is usually a coating solution in which the polyamic acid is dissolved in an organic solvent, but the liquid crystal aligning agent of the present invention can be used as long as a uniform thin film can be formed on the substrate. May take other forms.
- the liquid crystal aligning agent of the present invention contains a tetracarboxylic dianhydride containing the above-described tetracarboxylic dianhydride having an alicyclic structure or an aliphatic structure, as long as the effects of the present invention are not impaired.
- a polymer having another structure may be contained together with a polyamic acid obtained by a reaction between an anhydride component, a diamine having a urea structure and a diamine component having a diamine having a secondary amine at the polymerization reaction site.
- Examples of the polymer having another structure include a polyamic acid having a molecular structure different from the above-described polyamic acid, a polyamic acid ester, and the like.
- a tetracarboxylic dianhydride component containing the above-described tetracarboxylic dianhydride having an alicyclic structure or an aliphatic structure And a polyamic acid content obtained by a reaction between a diamine having a urea structure and a diamine component containing a diamine having a secondary amine at the polymerization reaction site, with respect to the total amount (100 mol%) of the polymer component, % To 80 mol% is preferred.
- the organic solvent contained in the liquid crystal aligning agent is not particularly limited as long as it contains a polymer component such as polyamic acid contained therein.
- Specific examples of the organic solvent include N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, N-methylcaprolactam, 2-pyrrolidone, N-ethylpyrrolidone, N-vinylpyrrolidone, dimethyl Examples thereof include sulfoxide, tetramethylurea, pyridine, dimethylsulfone, hexamethylsulfoxide, ⁇ -butyrolactone, and 1,3-dimethyl-imidazolidinone. You may use these 1 type or in mixture of 2 or more types.
- ethyl cellosolve, butyl cellosolve, ethyl carbitol, butyl carbitol, ethyl carbitol acetate ethylene glycol, 1-methoxy-2-propanol, 1-ethoxy-2-propanol, 1-butoxy-2-propanol, 1-phenoxy -2-propanol, propylene glycol monoacetate, propylene glycol diacetate, propylene glycol-1-monomethyl ether-2-acetate, propylene glycol-1-monoethyl ether-2-acetate, dipropylene glycol, 2- (2-ethoxy Propoxy) propanol, lactate methyl ester, lactate ethyl ester, lactate N-propyl ester, lactate N-butyl ester
- the amount of the solvent having a low surface tension is more preferably 5 to 80% by mass, and further preferably 20 to 60% by mass with respect to the total solvent contained in the liquid crystal aligning agent.
- the liquid crystal aligning agent of the present invention may contain various additives in addition to the polymer component and the organic solvent.
- a fluorine-based surfactant for example, as an additive for improving film thickness uniformity and surface smoothness, a fluorine-based surfactant, a silicone-based surfactant, a nonionic surfactant, and the like can be given.
- F-top EF301, EF303, EF352 manufactured by Tochem Products
- Megafac 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 polymer component contained in the liquid crystal aligning agent. is there.
- additives that improve the adhesion between the liquid crystal alignment film and the substrate include functional silane-containing compounds and epoxy group-containing compounds.
- the amount of these compounds added is preferably 0.1 to 30 parts by mass, more preferably 1 to 20 parts by mass with respect to 100 parts by mass of the polymer component contained in the liquid crystal aligning agent. If it 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 liquid crystal orientation may be deteriorated.
- a dielectric or conductive material can be added for the purpose of changing the electrical properties such as the dielectric constant and conductivity of the liquid crystal aligning film.
- a crosslinkable compound or the like may be added for the purpose of increasing the density.
- the concentration of the solid content in the liquid crystal aligning agent of the present invention can be appropriately changed depending on the film thickness of the target liquid crystal aligning film. Is preferably from 1 to 20% by mass, more preferably from 2 to 10% by mass.
- the liquid crystal aligning agent of the present invention is applied to a substrate and baked, and then subjected to an alignment treatment such as rubbing treatment or light irradiation, or when applied to a vertical alignment liquid crystal display element, without the alignment treatment.
- the substrate used in this case 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 and a polycarbonate substrate can be used, but ITO (Indium for driving liquid crystal) can be used. It is preferable to use a substrate on which (Tin Oxide) electrodes and the like are formed from the viewpoint of simplification of the process.
- an opaque substrate such as a silicon wafer can be used as long as the substrate is only on one side. In this case, a material that reflects light, such as aluminum, can be used as the electrode.
- the method for applying the liquid crystal aligning agent is not particularly limited, but industrially, a method of screen printing, offset printing, flexographic printing, inkjet, or the like is generally used. Other coating methods include a dipping method, a method using a roll coater, a slit coater, a spinner, or the like, and may be appropriately selected from these according to the purpose.
- the substrate coated with the liquid crystal aligning agent can be baked at an arbitrary temperature of 100 to 350 ° C., preferably 150 to 300 ° C., more preferably 180 to 250 ° C.
- the polyamic acid in the liquid crystal aligning agent and the polyamic acid ester contained as necessary change the conversion rate to polyimide depending on the firing temperature, but the liquid crystal aligning agent of the present invention does not necessarily need to be imidized 100%.
- the firing time can be set to an arbitrary time, but if the firing time is too short, display failure may occur due to the influence of the residual solvent. Therefore, it is preferably 5 to 60 minutes, more preferably 10 to 40 minutes. It is.
- the thickness of the coating film after baking is preferably 5 to 300 nm, more preferably 10 to 100 nm.
- 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 fabrication is as follows. First, a pair of substrates on which a liquid crystal alignment film is formed are prepared. Next, spacers are dispersed on the liquid crystal alignment film of one substrate, the other substrate is bonded so that the liquid crystal alignment film surface is on the inside, and then liquid crystal is injected under reduced pressure to seal. Alternatively, after the liquid crystal is dropped on the liquid crystal alignment film surface on which the spacers are dispersed, the substrate may be bonded to perform sealing.
- the thickness of the spacer at this time is preferably 1 to 30 ⁇ m, more preferably 2 to 10 ⁇ m.
- the liquid crystal display element produced using the liquid crystal aligning agent of the present invention is excellent in display quality and reliability, and can be suitably used for a large-screen high-definition liquid crystal television.
- the liquid crystal aligning agent of the present invention As described above, by using the liquid crystal aligning agent of the present invention, there are few scratches and scratches on the film surface during the rubbing treatment, the liquid crystal orientation is good, and the liquid crystal display element has a low ion density. An alignment film can be obtained.
- the liquid crystal alignment film obtained using the liquid crystal aligning agent of the present invention has a remarkably high volume resistivity as compared with a general polyamic acid because of the influence of the secondary amine structure and the urea structure. is doing.
- the value is equivalent to a soluble polyimide that is said to have a high volume resistivity.
- an FFS mode liquid crystal display element using a liquid crystal alignment film obtained by using the liquid crystal aligning agent of the present invention has a small amount of accumulated charge and can provide a high-quality liquid crystal display element having a low afterimage level.
- the liquid crystal alignment film obtained by using the liquid crystal aligning agent of the present invention has a high volume resistivity, but since the amount of accumulated charges is very small, it is possible to suppress the occurrence of afterimages, and it takes time to erase afterimages. It can be said that this problem does not occur.
- the liquid crystal alignment agent of the present invention can be used not only to form a liquid crystal alignment film that is aligned by rubbing, but also to form a photo-alignment liquid crystal alignment film, that is, a liquid crystal alignment film that is aligned by light irradiation. It is.
- CA-1 1,2,3,4-cyclobutanetetracarboxylic dianhydride
- CA-2 pyromellitic dianhydride
- CA-3 bicyclo [3,3,0] octane-2,4,6,8 -Tetracarboxylic dianhydride
- DA-1 4- (2- (methylamino) ethyl) aniline
- DA-2 1,3-bis (4-aminophenethyl) urea
- DA-3 3-((methylamino) Methyl) aniline
- DA-4 1,5-bis (4-aminophenoxy) pentane
- DA-5 p-phenylenediamine
- DA-6 4,4′-diaminodiphenylamine
- the viscosity of the polyamic acid solution was an E-type viscometer TVE-22H (manufactured by Toki Sangyo Co., Ltd.), sample volume 1.1 mL, cone rotor TE-1 (1 ° 34 ′, R24 ), Measured at a temperature of 25 ° C.
- Solid concentration measurement In the synthesis example or the comparative synthesis example, the solid content concentration of the polyamic acid solution was calculated as follows.
- the polyamic acid solution obtained in the synthesis example or the comparative synthesis example is filtered through a 1.0 ⁇ m filter, and then applied by spin coating on a glass substrate with an ITO solid electrode (ITO film is provided on the entire surface of the glass substrate). Then, after drying on a hot plate at 50 ° C. for 5 minutes, it was baked at 230 ° C. for 30 minutes to obtain a polyimide film having a thickness of 100 nm.
- the polyimide film is rubbed with a rayon cloth (roller diameter: 120 mm, roller rotation speed: 1000 rpm, moving speed: 20 mm / sec, indentation length: 0.3 mm), and then irradiated with ultrasonic waves in pure water for 1 minute. After washing and removing water droplets by air blow, drying was performed at 80 ° C. for 15 minutes to obtain a substrate with a liquid crystal alignment film. Two substrates with such a liquid crystal alignment film are prepared, a 6 ⁇ m spacer is set on the liquid crystal alignment film surface of one substrate, and then the rubbing directions of the two substrates are combined so that they are antiparallel. The periphery was sealed, and an empty cell with a cell gap of 6 ⁇ m was produced. Liquid crystal (MLC-2041, manufactured by Merck & Co., Inc.) was vacuum-injected into this cell at room temperature, and the inlet was sealed to obtain an anti-parallel liquid crystal cell.
- MLC-2041 manufactured by Merck & Co
- Voltage holding ratio measurement Using the vertical electric field liquid crystal cell produced as described above, measurement was performed with a VHR-1 type voltage holding ratio measurement system manufactured by Toyo Corporation. In the measurement, an AC voltage of ⁇ 4 V was applied for 60 ⁇ sec, and the voltage after 16.67 msec was measured, and the fluctuation from the initial value was calculated as the voltage holding ratio. During the measurement, the temperature of the liquid crystal cell was set to 60 ° C., 98% or more was “good”, and less than 98% was “bad”.
- the polyamic acid solution obtained in the synthesis example or the comparative synthesis example is filtered through a 1.0 ⁇ m filter, spin-coated on a glass substrate with an ITO transparent electrode, dried on a hot plate at 70 ° C. for 2 minutes, and 230 The film was baked at 15 ° C. for 15 minutes to form a coating film (liquid crystal alignment film) having a film thickness of about 220 nm.
- a coating film liquid crystal alignment film
- Aluminum was vapor-deposited on the surface of the coating film through a mask to form a 1.0 mm ⁇ upper electrode (aluminum electrode), which was used as a sample for volume resistivity measurement.
- a voltage of 5 V is applied between the ITO electrode and the aluminum electrode of this sample, the current value 180 seconds after the voltage application is measured, and the volume resistivity is calculated from the measured value of the electrode area and the film thickness. did.
- the first layer on the glass substrate is a 50 nm thick IZO (Indium Zinc Oxide) solid electrode, and the second layer is 500 nm thick.
- a silicon nitride insulating film is applied by spin coating onto a substrate capable of FFS mode driving having an IZO comb-teeth electrode (electrode width: 3 ⁇ m, electrode interval: 6 ⁇ m) having a thickness of 50 nm as the third layer, on a hot plate at 50 ° C. And then dried at 230 ° C.
- a polyimide film having a thickness of 100 nm.
- This polyimide film is rubbed with a rayon cloth (roller diameter: 120 mm, roller rotation speed: 500 rpm, moving speed: 30 mm / sec, indentation length: 0.3 mm, rubbing direction: inclined by 10 ° with respect to the third layer IZO comb-teeth electrode.
- the substrate was cleaned by irradiating with ultrasonic waves in pure water for 1 minute, and water droplets were removed by air blowing, followed by drying at 80 ° C. for 15 minutes to obtain a substrate with a liquid crystal alignment film.
- a liquid crystal alignment in which a polyimide film is formed in the same manner as described above on a glass substrate having a columnar spacer having a height of 4 ⁇ m on which an electrode is not formed as a counter substrate, and subjected to an alignment process in the same manner as described above.
- a substrate with a film was obtained.
- Liquid crystal ZLI-4792, manufactured by Merck & Co., Inc.
- this polyamic acid solution is placed in a 500 mL Erlenmeyer flask containing a stir bar, 55.1 g of N-methyl-2-pyrrolidone, and 1.0 mass% N-methyl-2-pyrrolidone solution of 3-aminopropyltriethoxysilane. 16.5 g and 60.0 g of butyl cellosolve were added and stirred for 2 hours to obtain a polyamic acid solution having a solid content concentration of 5.7% by mass.
- this polyamic acid solution is placed in a 500 mL Erlenmeyer flask containing a stir bar, 48.0 g of N-methyl-2-pyrrolidone, and 1.0% by mass of N-methyl-2-pyrrolidone solution of 3-aminopropyltriethoxysilane. 16.5 g and 60.0 g of butyl cellosolve were added and stirred for 2 hours to obtain a polyamic acid solution having a solid content concentration of 5.7% by mass.
- Methyl-2-pyrrolidone was added, and the mixture was stirred at room temperature for 5 hours under a nitrogen atmosphere to obtain a solution of polyamic acid (A-7).
- the viscosity of this polyamic acid solution at a temperature of 25 ° C. was 196 mPa ⁇ s.
- Table 1 shows the blending in the above synthesis examples and comparative synthesis examples.
- Example 1 As a result of each evaluation and measurement of the polyamic acid solution containing the polyamic acid (A-1) obtained in Synthesis Example 1, the rubbing resistance was “good”, the liquid crystal orientation was “good”, and the voltage holding ratio Is 98.8% “good”, the ion density is “good” at 6 pC / cm 2 , the volume resistivity is 1.9 ⁇ 10 15 ⁇ ⁇ cm, the residual DC is 1.05 V after 10 minutes, and 1 after 20 minutes. 0.08 V, 60 minutes later, 1.11 V, “good”.
- Example 2 As a result of each evaluation and measurement of the polyamic acid solution containing the polyamic acid (A-2) obtained in Synthesis Example 2, the rubbing resistance was “good”, the liquid crystal orientation was “good”, and the voltage holding ratio Is 98.7% “good”, the ion density is 0 pC / cm 2 “good”, and the residual DC is 10 minutes 0.87 V, 20 minutes 0.96 V, 60 minutes 0.99 V “good”. there were.
- Example 3 As a result of each evaluation and measurement of the polyamic acid solution containing the polyamic acid (A-3) obtained in Synthesis Example 3, the rubbing resistance was “good”, the liquid crystal orientation was “good”, and the voltage holding ratio Is 98.4% “good”, ion density is 59 pC / cm 2 “good”, residual DC is 0.69 V after 10 minutes, 0.74 V after 20 minutes, 0.81 V after 60 minutes, “good” there were.
- Example 4 As a result of each evaluation and measurement of the polyamic acid solution containing the polyamic acid (A-4) obtained in Synthesis Example 4, the rubbing resistance was “good”, the liquid crystal orientation was “good”, and the voltage holding ratio Is “good” at 98.1%, the ion density is “good” at 73 pC / cm 2 , and the residual DC is “good” at 1.03 V after 10 minutes, 1.06 V after 20 minutes, and 1.14 V after 60 minutes. there were.
- Example 5 As a result of each evaluation and measurement of the polyamic acid solution containing the polyamic acid (A-5) obtained in Synthesis Example 5, the rubbing resistance was “good”, the liquid crystal orientation was “good”, and the voltage holding ratio Is 99.1% “good”, the ion density is “good” at 2 pC / cm 2 , the residual DC is 0.38 V after 10 minutes, 0.52 V after 20 minutes, 0.65 V after 60 minutes, “good”. there were.
- Example 6 As a result of each evaluation and measurement of the polyamic acid solution containing the polyamic acid (A-6) obtained in Synthesis Example 6, the rubbing resistance was “good”, the liquid crystal orientation was “good”, and the voltage holding ratio Is “good” at 98.1%, the ion density is “good” at 13 pC / cm 2 , and the residual DC is “good” at 1.28 V after 10 minutes, 1.43 V after 20 minutes, and 1.50 V after 60 minutes. there were.
- Example 7 As a result of each evaluation and measurement of the polyamic acid solution containing the polyamic acid (A-7) obtained in Synthesis Example 7, the rubbing resistance was “good”, the liquid crystal orientation was “good”, and the voltage holding ratio 98.5% is “good”, the ion density is “good” at 8 pC / cm 2 , the residual DC is 0.61 V after 10 minutes, 0.71 V after 20 minutes, 0.79 V after 60 minutes and “good”. there were.
- Example 8> As a result of each evaluation and measurement of the polyamic acid solution containing the polyamic acid (A-8) obtained in Synthesis Example 8, the rubbing resistance was “good”, the liquid crystal orientation was “good”, and the voltage holding ratio Is “good” at 98.7%, the ion density is “good” at 0 pC / cm 2 , and the residual DC is “good” at 1.58 V after 10 minutes, 1.79 V after 20 minutes, and 1.88 V after 60 minutes. there were.
- Example 9 As a result of each evaluation and measurement of the polyamic acid solution containing the polyamic acid (A-9) obtained in Synthesis Example 9, the rubbing resistance was “good”, the liquid crystal orientation was “good”, and the voltage holding ratio Is “good” at 98.8%, the ion density is “good” at 0 pC / cm 2 , and the residual DC is “good” at 1.15 V after 10 minutes, 1.39 V after 20 minutes, and 1.51 V after 60 minutes. there were.
- Examples 1 to 10 using the liquid crystal aligning agent (polyamic acid solution) of the present invention were excellent in liquid crystal alignment, high rubbing resistance, and low ion density.
- the residual DC in the FFS mode is low, the accumulated charge in the liquid crystal display element is small.
- the voltage holding ratio was also good.
- Examples 2 to 10 using each of the polyamic acid solutions of Synthesis Examples 2 to 10 also had high volume resistivity.
- liquid crystal aligning agent of the present invention By using the liquid crystal aligning agent of the present invention, it is possible to obtain a liquid crystal aligning film having excellent rubbing resistance, good liquid crystal aligning property, high voltage holding ratio and low ion density when used as a liquid crystal display element. Moreover, since the liquid crystal alignment film of the present invention has a small amount of accumulated charge in the FFS mode liquid crystal display element, it can be used in an FFS mode liquid crystal display element that requires high display quality.
Abstract
Description
1.脂環式構造または脂肪族構造を有するテトラカルボン酸二無水物を含有するテトラカルボン酸二無水物成分と、ウレア構造を有するジアミン及び重合反応部位に2級アミンを有するジアミンを含有するジアミン成分との反応により得られるポリアミック酸を含有する液晶配向剤。 Thus, the present invention has the following gist.
1. A diamine containing a tetracarboxylic dianhydride component containing a tetracarboxylic dianhydride having an alicyclic structure or an aliphatic structure, a diamine having a urea structure, and a diamine having a secondary amine at the polymerization reaction site Liquid crystal aligning agent containing the polyamic acid obtained by reaction with a component.
本発明の液晶配向剤に含有されるポリアミック酸の原料であるジアミン成分に、必須成分として含まれる重合反応部位に2級アミンを有するジアミンの具体例として、例えば、下記式(1)で表されるジアミンが挙げられる。もちろん、ジアミン成分は、式(1)で表されるジアミンの代わりに、または、式(1)で表されるジアミンと共に、式(1)で表されるジアミン以外の重合反応部位に2級アミンを有するジアミンを含有していてもよい。なお、重合反応部位とは、テトラカルボン酸二無水物成分と反応する部位であり、重合反応部位に2級アミンを有するジアミンの2級アミン、すなわち-NH-が、テトラカルボン酸二無水物成分と反応する。 <Diamine having secondary amine at polymerization reaction site>
As a specific example of a diamine having a secondary amine at a polymerization reaction site contained as an essential component in the diamine component which is a raw material of the polyamic acid contained in the liquid crystal aligning agent of the present invention, for example, it is represented by the following formula (1). Diamines. Of course, the diamine component is a secondary amine in the polymerization reaction site other than the diamine represented by the formula (1) in place of the diamine represented by the formula (1) or together with the diamine represented by the formula (1). It may contain a diamine having The polymerization reaction site is a site that reacts with the tetracarboxylic dianhydride component, and a secondary amine of a diamine having a secondary amine at the polymerization reaction site, that is, —NH— is a tetracarboxylic dianhydride component. React with.
本発明の液晶配向剤に含有されるポリアミック酸の原料であるジアミン成分に、必須成分として含まれるウレア構造を有するジアミンの具体例として、下記式(2)で表されるジアミンが挙げられる。もちろん、ジアミン成分は、式(2)で表されるジアミンの代わりに、または、式(2)で表されるジアミンと共に、式(2)で表されるジアミン以外のウレア構造を有するジアミンを含有していてもよい。 <Diamine having a urea structure>
Specific examples of the diamine having a urea structure included as an essential component in the diamine component that is a raw material of the polyamic acid contained in the liquid crystal aligning agent of the present invention include diamines represented by the following formula (2). Of course, the diamine component contains a diamine having a urea structure other than the diamine represented by the formula (2) instead of the diamine represented by the formula (2) or together with the diamine represented by the formula (2). You may do it.
本発明の液晶配向剤は、本発明の効果を損なわない限りにおいて、ポリアミック酸の原料であるジアミン成分として、上記の重合反応部位に2級アミンを有するジアミンや、ウレア構造を有するジアミン以外に、その他のジアミン化合物を含有させることも可能である。その他のジアミン化合物の具体例を以下に挙げる。 <Other diamine compounds>
As long as the liquid crystal aligning agent of the present invention does not impair the effects of the present invention, as a diamine component that is a raw material of polyamic acid, in addition to a diamine having a secondary amine at the polymerization reaction site or a diamine having a urea structure, It is also possible to contain other diamine compounds. Specific examples of other diamine compounds are listed below.
本発明の液晶配向剤に含有されるポリアミック酸の原料であるテトラカルボン酸二無水物成分に、必須成分として含まれる脂環式構造または脂肪族構造を有するテトラカルボン酸二無水物は、例えば下記式(3)で表されるテトラカルボン酸二無水物である。もちろん、テトラカルボン酸二無水物成分は、式(3)で表されるテトラカルボン酸二無水物の代わりに、または、式(3)で表されるテトラカルボン酸二無水物と共に、式(3)で表されるテトラカルボン酸二無水物以外の脂環式構造または脂肪族構造を有するテトラカルボン酸二無水物を含有していてもよい。また、脂環式構造または脂肪族構造を有するテトラカルボン酸二無水物と共に、脂環式構造または脂肪族構造を有するテトラカルボン酸二無水物以外のテトラカルボン酸二無水物を含有していてもよい。 <Tetracarboxylic dianhydride having an alicyclic structure or an aliphatic structure>
For example, the tetracarboxylic dianhydride having an alicyclic structure or an aliphatic structure contained as an essential component in the tetracarboxylic dianhydride component that is a raw material of the polyamic acid contained in the liquid crystal aligning agent of the present invention is, for example, It is a tetracarboxylic dianhydride represented by the formula (3). Of course, the tetracarboxylic dianhydride component is replaced with the tetracarboxylic dianhydride represented by the formula (3) or together with the tetracarboxylic dianhydride represented by the formula (3). The tetracarboxylic dianhydride which has alicyclic structure or aliphatic structure other than the tetracarboxylic dianhydride represented by this may be contained. In addition, a tetracarboxylic dianhydride having an alicyclic structure or an aliphatic structure and a tetracarboxylic dianhydride other than a tetracarboxylic dianhydride having an alicyclic structure or an aliphatic structure may be contained. Good.
上記したジアミン成分とテトラカルボン酸二無水物成分(以下、単にテトラカルボン酸二無水物ともいう。)とを反応させて、本発明の液晶配向剤に含有されるポリアミック酸を得る方法は特に限定されず、公知の方法が適用できる。一般的には、有機溶剤中でジアミン成分とテトラカルボン酸二無水物成分を混合することにより重合反応をさせてポリアミック酸とすることができる。 <Polyamic acid polymerization>
The method for obtaining the polyamic acid contained in the liquid crystal aligning agent of the present invention by reacting the diamine component and the tetracarboxylic dianhydride component (hereinafter also simply referred to as tetracarboxylic dianhydride) is particularly limited. A known method can be applied. In general, a diamine component and a tetracarboxylic dianhydride component are mixed in an organic solvent to cause a polymerization reaction to obtain a polyamic acid.
本発明の液晶配向剤は、以上のようにして得られたポリアミック酸を1種類以上含有するものである。このような特定のジアミン成分と特定のテトラカルボン酸二無水物成分との反応により得られるポリアミック酸を含有する液晶配向剤とすることにより、後述する実施例に示すように、良好な液晶配向性及びラビング耐性を有し、イオン密度が小さく、且つ、FFSモード液晶表示素子における蓄積電荷が少ない液晶配向膜を得ることができる。なお、本発明の液晶配向剤は、通常は上記ポリアミック酸を有機溶媒に溶解させた塗布液とするが、基板上に均一な薄膜を形成することができるのであれば、本発明の液晶配向剤は他の形態であっても良い。 <Liquid crystal aligning agent>
The liquid crystal aligning agent of this invention contains 1 or more types of polyamic acid obtained by making it above. By using a liquid crystal aligning agent containing a polyamic acid obtained by reaction of such a specific diamine component and a specific tetracarboxylic dianhydride component, as shown in the examples described later, good liquid crystal alignment properties In addition, a liquid crystal alignment film having rubbing resistance, low ion density, and low accumulated charge in the FFS mode liquid crystal display element can be obtained. The liquid crystal aligning agent of the present invention is usually a coating solution in which the polyamic acid is dissolved in an organic solvent, but the liquid crystal aligning agent of the present invention can be used as long as a uniform thin film can be formed on the substrate. May take other forms.
本発明の液晶配向剤は、基板上に塗布し焼成した後、ラビング処理または光照射などで配向処理をして、あるいは、垂直配向性の液晶表示素子に適用する場合などでは、配向処理なしに液晶配向膜として用いられる。この際に用いる基板は、透明性の高い基板であれば特に限定されず、ガラス基板、または、アクリル基板およびポリカーボネート基板などのプラスチック基板などを用いることができるが、液晶駆動のためのITO(Indium Tin Oxide)電極などが形成された基板を用いることがプロセスの簡素化の観点から好ましい。また、反射型の液晶表示素子では、片側の基板のみにならばシリコンウェハなどの不透明な基板を使用することができる。尚、この場合の電極としては、アルミニウムなどの光を反射する材料も使用可能である。 <Liquid crystal alignment film>
The liquid crystal aligning agent of the present invention is applied to a substrate and baked, and then subjected to an alignment treatment such as rubbing treatment or light irradiation, or when applied to a vertical alignment liquid crystal display element, without the alignment treatment. Used as a liquid crystal alignment film. The substrate used in this case 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 and a polycarbonate substrate can be used, but ITO (Indium for driving liquid crystal) can be used. It is preferable to use a substrate on which (Tin Oxide) electrodes and the like are formed from the viewpoint of simplification of the process. In the reflective liquid crystal display element, an opaque substrate such as a silicon wafer can be used as long as the substrate is only on one side. In this case, a material that reflects light, such as aluminum, can be used as the electrode.
本発明の液晶表示素子は、上記した手法により本発明の液晶配向剤から液晶配向膜付き基板を得た後、公知の方法で液晶セルを作製し、液晶表示素子としたものである。 <Liquid crystal display element>
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.
CA-1:1,2,3,4-シクロブタンテトラカルボン酸二無水物
CA-2:ピロメリット酸二無水物
CA-3:ビシクロ[3,3,0]オクタン-2,4,6,8-テトラカルボン酸二無水物
DA-1:4-(2-(メチルアミノ)エチル)アニリン
DA-2:1,3-ビス(4-アミノフェネチル)ウレア
DA-3:3-((メチルアミノ)メチル)アニリン
DA-4:1,5-ビス(4-アミノフェノキシ)ペンタン
DA-5:p-フェニレンジアミン
DA-6:4,4’-ジアミノジフェニルアミン The abbreviations and structures of the compounds used in this synthesis example are shown below.
CA-1: 1,2,3,4-cyclobutanetetracarboxylic dianhydride CA-2: pyromellitic dianhydride CA-3: bicyclo [3,3,0] octane-2,4,6,8 -Tetracarboxylic dianhydride DA-1: 4- (2- (methylamino) ethyl) aniline DA-2: 1,3-bis (4-aminophenethyl) urea DA-3: 3-((methylamino) Methyl) aniline DA-4: 1,5-bis (4-aminophenoxy) pentane DA-5: p-phenylenediamine DA-6: 4,4′-diaminodiphenylamine
合成例または比較合成例において、ポリアミック酸溶液の粘度はE型粘度計TVE-22H(東機産業株式会社製)を用い、サンプル量1.1mL、コーンロータTE-1(1°34’、R24)、温度25℃で測定した。 [Viscosity measurement]
In the synthesis example or the comparative synthesis example, the viscosity of the polyamic acid solution was an E-type viscometer TVE-22H (manufactured by Toki Sangyo Co., Ltd.), sample volume 1.1 mL, cone rotor TE-1 (1 ° 34 ′, R24 ), Measured at a temperature of 25 ° C.
合成例または比較合成例において、ポリアミック酸溶液の固形分濃度の算出は以下のようにして行った。 [Solid concentration measurement]
In the synthesis example or the comparative synthesis example, the solid content concentration of the polyamic acid solution was calculated as follows.
合成例または比較合成例で得られたポリアミック酸溶液を1.0μmのフィルターで濾過した後、透明電極付きガラス基板上にスピンコートで塗布し、50℃のホットプレート上で5分間乾燥後、230℃で30分間焼成して、膜厚100nmのポリイミド膜を得た。このポリイミド膜をレーヨン布でラビング(ローラー直径120mm、ローラー回転数1000rpm、移動速度20mm/sec、押し込み長0.6mm)した。このポリイミド膜表面における傷の有無を、共焦点レーザ顕微鏡(倍率10倍)で観察した。傷が無いものを「良好」、傷が有るものを「不良」とした。 [Rubbing resistance evaluation]
After filtering the polyamic acid solution obtained in the synthesis example or the comparative synthesis example with a 1.0 μm filter, the solution was applied on a glass substrate with a transparent electrode by spin coating, dried on a hot plate at 50 ° C. for 5 minutes, and then 230 The polyimide film with a film thickness of 100 nm was obtained by baking at 30 ° C. for 30 minutes. This polyimide film was rubbed with a rayon cloth (roller diameter 120 mm, roller rotation speed 1000 rpm, moving speed 20 mm / sec, indentation length 0.6 mm). The presence or absence of scratches on the polyimide film surface was observed with a confocal laser microscope (magnification 10 times). A sample having no scratch was defined as “good”, and a sample having a scratch was defined as “bad”.
合成例または比較合成例で得られたポリアミック酸溶液を1.0μmのフィルターで濾過した後、ITOベタ電極付きガラス基板(ガラス基板上にITO膜を全面に設けたもの)上にスピンコートで塗布し、50℃のホットプレート上で5分間乾燥後、230℃で30分間焼成して膜厚100nmのポリイミド膜を得た。このポリイミド膜をレーヨン布でラビング(ローラー直径:120mm、ローラー回転数:1000rpm、移動速度:20mm/sec、押し込み長:0.3mm)した後、純水中にて1分間超音波照射をして洗浄を行い、エアブローにて水滴を除去した後、80℃で15分間乾燥して液晶配向膜付き基板を得た。このような液晶配向膜付き基板を2枚用意し、一方の基板の液晶配向膜面に6μmのスペーサを設置した後、2枚の基板のラビング方向が逆平行になるように組み合わせ、液晶注入口を残して周囲をシールし、セルギャップが6μmの空セルを作製した。このセルに液晶(MLC-2041、メルク社製)を常温で真空注入し、注入口を封止してアンチパラレル液晶セルとした。 [Vertical electric field liquid crystal cell fabrication]
The polyamic acid solution obtained in the synthesis example or the comparative synthesis example is filtered through a 1.0 μm filter, and then applied by spin coating on a glass substrate with an ITO solid electrode (ITO film is provided on the entire surface of the glass substrate). Then, after drying on a hot plate at 50 ° C. for 5 minutes, it was baked at 230 ° C. for 30 minutes to obtain a polyimide film having a thickness of 100 nm. The polyimide film is rubbed with a rayon cloth (roller diameter: 120 mm, roller rotation speed: 1000 rpm, moving speed: 20 mm / sec, indentation length: 0.3 mm), and then irradiated with ultrasonic waves in pure water for 1 minute. After washing and removing water droplets by air blow, drying was performed at 80 ° C. for 15 minutes to obtain a substrate with a liquid crystal alignment film. Two substrates with such a liquid crystal alignment film are prepared, a 6 μm spacer is set on the liquid crystal alignment film surface of one substrate, and then the rubbing directions of the two substrates are combined so that they are antiparallel. The periphery was sealed, and an empty cell with a cell gap of 6 μm was produced. Liquid crystal (MLC-2041, manufactured by Merck & Co., Inc.) was vacuum-injected into this cell at room temperature, and the inlet was sealed to obtain an anti-parallel liquid crystal cell.
上記のようにして作製した縦電界液晶セルの配向状態を偏光顕微鏡にて観察し、配向欠陥がないものを「良好」、配向欠陥があるものを「不良」とした。 [Liquid crystal orientation evaluation]
The alignment state of the vertical electric field liquid crystal cell produced as described above was observed with a polarizing microscope, and the sample having no alignment defect was defined as “good” and the sample having an alignment defect was defined as “bad”.
上記のようにして作製した縦電界液晶セルを用い、東陽テクニカ社製のVHR-1型電圧保持率測定システムにて測定を行った。測定は±4Vの交流電圧を60μ秒間印加し、16.67m秒後の電圧を測定することで、初期値からの変動を電圧保持率として計算した。測定の際、液晶セルの温度を60℃とし、98%以上を「良好」、98%未満を「不良」とした。 [Voltage holding ratio measurement]
Using the vertical electric field liquid crystal cell produced as described above, measurement was performed with a VHR-1 type voltage holding ratio measurement system manufactured by Toyo Corporation. In the measurement, an AC voltage of ± 4 V was applied for 60 μsec, and the voltage after 16.67 msec was measured, and the fluctuation from the initial value was calculated as the voltage holding ratio. During the measurement, the temperature of the liquid crystal cell was set to 60 ° C., 98% or more was “good”, and less than 98% was “bad”.
上記のようにして作製した縦電界液晶セルを用い、東陽テクニカ社製の6254型液晶物性評価システムにて測定を行った。測定は±10V、0.01Hzの三角波を印加し、得られた波形のイオン密度に相当する面積を三角形近似法により算出してイオン密度とした。測定の際、液晶セルの温度は23℃とし、100pC/cm2未満を「良好」、100pC/cm2以上を「不良」とした。 [Ion density measurement]
Using the vertical electric field liquid crystal cell produced as described above, measurement was performed with a 6254 type liquid crystal physical property evaluation system manufactured by Toyo Technica. In the measurement, a triangular wave of ± 10 V and 0.01 Hz was applied, and an area corresponding to the ion density of the obtained waveform was calculated by a triangle approximation method to obtain an ion density. At the time of measurement, the temperature of the liquid crystal cell was 23 ° C., “less than 100 pC / cm 2 ” was defined as “good”, and 100 pC / cm 2 or more was defined as “bad”.
合成例または比較合成例で得られたポリアミック酸溶液を1.0μmのフィルターで濾過した後、ITO透明電極付きガラス基板上にスピンコート塗布し、70℃のホットプレート上で2分間乾燥後、230℃で15分焼成し、膜厚約220nmの塗膜(液晶配向膜)を形成させた。この塗膜表面にマスクを介してアルミを蒸着させ、1.0mmφの上部電極(アルミ電極)を形成し体積抵抗率測定用の試料とした。この試料のITO電極とアルミ電極との間に5Vの電圧を印加し、電圧印加から180秒後の電流値を測定し、この値と電極面積、膜厚の測定値とから体積抵抗率を算出した。 [Measurement of volume resistivity]
The polyamic acid solution obtained in the synthesis example or the comparative synthesis example is filtered through a 1.0 μm filter, spin-coated on a glass substrate with an ITO transparent electrode, dried on a hot plate at 70 ° C. for 2 minutes, and 230 The film was baked at 15 ° C. for 15 minutes to form a coating film (liquid crystal alignment film) having a film thickness of about 220 nm. Aluminum was vapor-deposited on the surface of the coating film through a mask to form a 1.0 mmφ upper electrode (aluminum electrode), which was used as a sample for volume resistivity measurement. A voltage of 5 V is applied between the ITO electrode and the aluminum electrode of this sample, the current value 180 seconds after the voltage application is measured, and the volume resistivity is calculated from the measured value of the electrode area and the film thickness. did.
合成例または比較合成例で得られたポリアミック酸溶液を1.0μmのフィルターで濾過した後、ガラス基板上1層目に厚み50nmのIZO(Indium Zinc Oxide)ベタ電極、2層目に厚み500nmの窒化ケイ素絶縁膜、3層目に厚み50nmのIZO櫛歯電極(電極幅:3μm、電極間隔:6μm)を有するFFSモード駆動が可能な基板上にスピンコートで塗布し、50℃のホットプレート上で5分間乾燥後、230℃で30分間焼成して膜厚100nmのポリイミド膜を得た。このポリイミド膜をレーヨン布でラビング(ローラー直径:120mm、ローラー回転数:500rpm、移動速度:30mm/sec、押し込み長:0.3mm、ラビング方向:3層目IZO櫛歯電極に対して10°傾いた方向)した後、純水中にて1分間超音波照射をして洗浄を行い、エアブローにて水滴を除去した後、80℃で15分間乾燥して液晶配向膜付き基板を得た。また、対向基板として電極が形成されていない高さ4μmの柱状スペーサーを有するガラス基板上にも、上記と同様にしてポリイミド膜を形成し、上記と同様の手順で配向処理が施された液晶配向膜付き基板を得た。これら2枚の液晶配向膜付き基板を1組とし、2枚の基板のラビング方向が逆平行になるように組み合わせ、液晶注入口を残して周囲をシールし、セルギャップが4μmの空セルを作製した。このセルに液晶(ZLI-4792、メルク社製)を常温で真空注入し、注入口を封止してアンチパラレル液晶セルとした。 [FFS mode liquid crystal cell fabrication]
After the polyamic acid solution obtained in the synthesis example or the comparative synthesis example is filtered through a 1.0 μm filter, the first layer on the glass substrate is a 50 nm thick IZO (Indium Zinc Oxide) solid electrode, and the second layer is 500 nm thick. A silicon nitride insulating film is applied by spin coating onto a substrate capable of FFS mode driving having an IZO comb-teeth electrode (electrode width: 3 μm, electrode interval: 6 μm) having a thickness of 50 nm as the third layer, on a hot plate at 50 ° C. And then dried at 230 ° C. for 30 minutes to obtain a polyimide film having a thickness of 100 nm. This polyimide film is rubbed with a rayon cloth (roller diameter: 120 mm, roller rotation speed: 500 rpm, moving speed: 30 mm / sec, indentation length: 0.3 mm, rubbing direction: inclined by 10 ° with respect to the third layer IZO comb-teeth electrode Then, the substrate was cleaned by irradiating with ultrasonic waves in pure water for 1 minute, and water droplets were removed by air blowing, followed by drying at 80 ° C. for 15 minutes to obtain a substrate with a liquid crystal alignment film. Further, a liquid crystal alignment in which a polyimide film is formed in the same manner as described above on a glass substrate having a columnar spacer having a height of 4 μm on which an electrode is not formed as a counter substrate, and subjected to an alignment process in the same manner as described above. A substrate with a film was obtained. Combine these two substrates with a liquid crystal alignment film into a set so that the rubbing directions of the two substrates are antiparallel, seal the surroundings leaving the liquid crystal injection port, and create an empty cell with a cell gap of 4 μm did. Liquid crystal (ZLI-4792, manufactured by Merck & Co., Inc.) was vacuum-injected into this cell at room temperature, and the inlet was sealed to obtain an anti-parallel liquid crystal cell.
上記のようにして作製したFFSモード液晶セルを用い、東陽テクニカ社製の6254型液晶物性評価システムにて測定を行った。測定は+4Vの直流電圧を30分間印加した後、1秒間放電し、その後60分間の残留DC量を計測した。測定の際、液晶セルの温度は60℃とし、放電から60分後の残留DC量が2.0V未満を「良好」、2.0V以上を「不良」とした。 [Residual DC (dielectric absorption method) measurement]
Using the FFS mode liquid crystal cell produced as described above, measurement was performed with a 6254 type liquid crystal physical property evaluation system manufactured by Toyo Corporation. In the measurement, a DC voltage of +4 V was applied for 30 minutes and then discharged for 1 second, and then the amount of residual DC for 60 minutes was measured. At the time of measurement, the temperature of the liquid crystal cell was set to 60 ° C., and the residual DC amount after 60 minutes after the discharge was determined to be “good” when the amount was less than 2.0 V and “bad” when 2.0 V or more.
撹拌装置付きおよび窒素導入管付きの200mL四つ口フラスコにDA-1を2.83g(18.8mmol)、DA-2を5.61g(18.8mmol)、およびDA-4を2.70g(9.40mmol)取り、N-メチル-2-ピロリドン126gを加え、窒素を送りながら撹拌して溶解させた。このジアミン溶液を撹拌しながらCA-1を8.84g(45.1mmol)添加し、更に固形分濃度が10質量%になるようにN-メチル-2-ピロリドンを加え、窒素雰囲気下、室温で2時間撹拌してポリアミック酸(A-1)の溶液を得た。このポリアミック酸溶液の温度25℃における粘度は135mPa・sであった。 (Synthesis Example 1)
In a 200 mL four-necked flask equipped with a stirrer and a nitrogen inlet tube, 2.83 g (18.8 mmol) of DA-1, 5.61 g (18.8 mmol) of DA-2, and 2.70 g of DA-4 ( 9.40 mmol), 126 g of N-methyl-2-pyrrolidone was added, and the mixture was dissolved by stirring while feeding nitrogen. While stirring this diamine solution, 8.84 g (45.1 mmol) of CA-1 was added, N-methyl-2-pyrrolidone was further added so that the solid content concentration was 10% by mass, and at room temperature under a nitrogen atmosphere. The solution was stirred for 2 hours to obtain a solution of polyamic acid (A-1). The viscosity of this polyamic acid solution at a temperature of 25 ° C. was 135 mPa · s.
撹拌装置付きおよび窒素導入管付きの300mL四つ口フラスコにDA-1を3.55g(23.6mmol)、およびDA-2を10.6g(35.4mmol)取り、N-メチル-2-ピロリドン136gを加え、窒素を送りながら撹拌して溶解させた。このジアミン溶液を撹拌しながらCA-1を11.3g(57.6mmol)添加し、更に固形分濃度が10質量%になるようにN-メチル-2-ピロリドンを加え、窒素雰囲気下、室温で5時間撹拌してポリアミック酸(A-2)の溶液を得た。このポリアミック酸溶液の温度25℃における粘度は156mPa・sであった。 (Synthesis Example 2)
In a 300 mL four-necked flask equipped with a stirrer and a nitrogen inlet tube, 3.51 g (23.6 mmol) of DA-1 and 10.6 g (35.4 mmol) of DA-2 were taken, and N-methyl-2-pyrrolidone 136 g was added and dissolved by stirring while feeding nitrogen. While stirring the diamine solution, 11.3 g (57.6 mmol) of CA-1 was added, and N-methyl-2-pyrrolidone was further added so that the solid content concentration was 10% by mass. The solution was stirred for 5 hours to obtain a solution of polyamic acid (A-2). The viscosity of this polyamic acid solution at a temperature of 25 ° C. was 156 mPa · s.
撹拌装置付きおよび窒素導入管付きの5LセパラブルフラスコにDA-1を72.1g(480mmol)、DA-2を71.5g(240mmol)、およびDA-4を137g(480mmol)取り、N-メチル-2-ピロリドン3200gを加え、窒素を送りながら撹拌して溶解させた。このジアミン溶液を撹拌しながらCA-1を227g(1.16mol)添加し、更に固形分濃度が10質量%になるようにN-メチル-2-ピロリドンを加え、窒素雰囲気下、室温で1時間撹拌してポリアミック酸(A-3)の溶液を得た。このポリアミック酸溶液の温度25℃における粘度は155mPa・sであった。 (Synthesis Example 3)
In a 5 L separable flask with a stirrer and a nitrogen inlet tube, 72.1 g (480 mmol) of DA-1, 71.5 g (240 mmol) of DA-2, and 137 g (480 mmol) of DA-4 were taken, and N-methyl -2-Pyrrolidone 3200 g was added and dissolved by stirring while feeding nitrogen. While stirring this diamine solution, 227 g (1.16 mol) of CA-1 was added, N-methyl-2-pyrrolidone was further added so that the solid content concentration would be 10% by mass, and one hour at room temperature in a nitrogen atmosphere. By stirring, a solution of polyamic acid (A-3) was obtained. The viscosity of this polyamic acid solution at a temperature of 25 ° C. was 155 mPa · s.
撹拌装置付きおよび窒素導入管付きの300mL四つ口フラスコにDA-1を1.68g(11.2mmol)、DA-2を6.68g(22.4mmol)、およびDA-4を6.42g(22.4mmol)取り、N-メチル-2-ピロリドン157gを加え、窒素を送りながら撹拌して溶解させた。このジアミン溶液を撹拌しながらCA-1を10.6g(54.0mmol)添加し、更に固形分濃度が10質量%になるようにN-メチル-2-ピロリドンを加え、窒素雰囲気下、室温で5時間撹拌してポリアミック酸(A-4)の溶液を得た。このポリアミック酸溶液の温度25℃における粘度は148mPa・sであった。 (Synthesis Example 4)
1.68 g (11.2 mmol) of DA-1, 6.68 g (22.4 mmol) of DA-2, and 6.42 g of DA-4 in a 300 mL four-necked flask equipped with a stirrer and a nitrogen inlet tube 22.4 mmol), 157 g of N-methyl-2-pyrrolidone was added, and the mixture was dissolved by stirring while feeding nitrogen. While stirring this diamine solution, 10.6 g (54.0 mmol) of CA-1 was added, and N-methyl-2-pyrrolidone was further added so that the solid content concentration was 10% by mass. The solution was stirred for 5 hours to obtain a solution of polyamic acid (A-4). The viscosity of this polyamic acid solution at a temperature of 25 ° C. was 148 mPa · s.
撹拌装置付きおよび窒素導入管付きの300mL四つ口フラスコにDA-1を5.41g(36.0mmol)、DA-2を3.59g(12.0mmol)、およびDA-4を3.44g(12.0mmol)取り、N-メチル-2-ピロリドン151gを加え、窒素を送りながら撹拌して溶解させた。このジアミン溶液を撹拌しながらCA-1を11.5g(58.7mmol)添加し、更に固形分濃度が10質量%になるようにN-メチル-2-ピロリドンを加え、窒素雰囲気下、室温で2時間撹拌してポリアミック酸(A-5)の溶液を得た。このポリアミック酸溶液の温度25℃における粘度は159mPa・sであった。 (Synthesis Example 5)
In a 300 mL four-necked flask equipped with a stirrer and a nitrogen introduction tube, DA-1 (5.41 g, 36.0 mmol), DA-2 (3.59 g, 12.0 mmol), and DA-4 (3.44 g) 12.0 mmol), and 151 g of N-methyl-2-pyrrolidone was added and dissolved by stirring while feeding nitrogen. While stirring this diamine solution, 11.5 g (58.7 mmol) of CA-1 was added, and N-methyl-2-pyrrolidone was further added so that the solid content concentration would be 10% by mass. The solution was stirred for 2 hours to obtain a solution of polyamic acid (A-5). The viscosity of this polyamic acid solution at a temperature of 25 ° C. was 159 mPa · s.
撹拌装置付きおよび窒素導入管付きの500mL四つ口フラスコにDA-1を3.30g(22.0mmol)、DA-2を16.4g(55.0mmol)、およびDA-4を9.45g(33.0mmol)取り、N-メチル-2-ピロリドン229gを加え、窒素を送りながら撹拌して溶解させた。このジアミン溶液を撹拌しながらCA-1を15.1g(77.0mmol)、およびCA-3を7.79g(31.1mmol)添加し、更に固形分濃度が12質量%になるようにN-メチル-2-ピロリドンを加え、窒素雰囲気下、40℃で40時間撹拌してポリアミック酸(A-6)の溶液を得た。このポリアミック酸溶液の温度25℃における粘度は295mPa・sであった。 (Synthesis Example 6)
In a 500 mL four-necked flask equipped with a stirrer and a nitrogen inlet tube, DA-1 3.30 g (22.0 mmol), DA-2 16.4 g (55.0 mmol), and DA-4 9.45 g ( 33.0 mmol), 229 g of N-methyl-2-pyrrolidone was added, and the mixture was dissolved by stirring while feeding nitrogen. While stirring this diamine solution, 15.1 g (77.0 mmol) of CA-1 and 7.79 g (31.1 mmol) of CA-3 were added, and N— was added so that the solid content concentration became 12% by mass. Methyl-2-pyrrolidone was added and stirred at 40 ° C. for 40 hours under a nitrogen atmosphere to obtain a solution of polyamic acid (A-6). The viscosity of this polyamic acid solution at a temperature of 25 ° C. was 295 mPa · s.
撹拌装置付きおよび窒素導入管付きの100mL四つ口フラスコにDA-1を1.57g(10.4mmol)、およびDA-2を4.65g(15.6mmol)取り、N-メチル-2-ピロリドン57.9gを加え、窒素を送りながら撹拌して溶解させた。このジアミン溶液を撹拌しながらCA-1を3.44g(17.6mmol)、およびCA-2を1.70g(7.80mmol)添加し、更に固形分濃度が12質量%になるようにN-メチル-2-ピロリドンを加え、窒素雰囲気下、室温で5時間撹拌してポリアミック酸(A-7)の溶液を得た。このポリアミック酸溶液の温度25℃における粘度は196mPa・sであった。 (Synthesis Example 7)
In a 100 mL four-necked flask equipped with a stirrer and a nitrogen inlet tube, 1.51 g (10.4 mmol) of DA-1 and 4.65 g (15.6 mmol) of DA-2 were taken, and N-methyl-2-pyrrolidone was added. 57.9 g was added and dissolved by stirring while feeding nitrogen. While stirring this diamine solution, 3.41 g (17.6 mmol) of CA-1 and 1.70 g (7.80 mmol) of CA-2 were added, and N— was added so that the solid content concentration became 12% by mass. Methyl-2-pyrrolidone was added, and the mixture was stirred at room temperature for 5 hours under a nitrogen atmosphere to obtain a solution of polyamic acid (A-7). The viscosity of this polyamic acid solution at a temperature of 25 ° C. was 196 mPa · s.
撹拌装置付きおよび窒素導入管付きの200mL四つ口フラスコにDA-1を3.49g(23.2mmol)、DA-2を6.92g(23.2mmol)、およびDA-6を2.31g(11.6mmol)取り、N-メチル-2-ピロリドン125gを加え、窒素を送りながら撹拌して溶解させた。このジアミン溶液を撹拌しながらCA-1を9.10g(46.4mmol)、およびCA-3を2.57g(10.3mmol)添加し、更に固形分濃度が12質量%になるようにN-メチル-2-ピロリドンを加え、窒素雰囲気下、40℃で24時間撹拌してポリアミック酸(A-8)の溶液を得た。このポリアミック酸溶液の温度25℃における粘度は348mPa・sであった。 (Synthesis Example 8)
In a 200 mL four-necked flask equipped with a stirrer and a nitrogen inlet tube, 3.49 g (23.2 mmol) of DA-1, 6.92 g (23.2 mmol) of DA-2, and 2.31 g of DA-6 ( 11.6 mmol), 125 g of N-methyl-2-pyrrolidone was added, and the mixture was dissolved by stirring while feeding nitrogen. While stirring the diamine solution, 9.10 g (46.4 mmol) of CA-1 and 2.57 g (10.3 mmol) of CA-3 were added, and N— was added so that the solid content concentration became 12% by mass. Methyl-2-pyrrolidone was added and stirred at 40 ° C. for 24 hours under a nitrogen atmosphere to obtain a solution of polyamic acid (A-8). The viscosity of this polyamic acid solution at a temperature of 25 ° C. was 348 mPa · s.
撹拌装置付きおよび窒素導入管付きの100mL四つ口フラスコにDA-1を1.68g(11.2mmol)、DA-2を2.51g(8.40mmol)、およびDA-5を0.91g(8.40mmol)取り、N-メチル-2-ピロリドン43gを加え、窒素を送りながら撹拌して溶解させた。このジアミン溶液を撹拌しながらCA-1を5.30g(27.0mmol)添加し、更に固形分濃度が10質量%になるようにN-メチル-2-ピロリドンを加え、窒素雰囲気下、室温で2時間撹拌してポリアミック酸(A-9)の溶液を得た。このポリアミック酸溶液の温度25℃における粘度は125mPa・sであった。 (Synthesis Example 9)
In a 100 mL four-necked flask equipped with a stirrer and a nitrogen inlet tube, 1.68 g (11.2 mmol) of DA-1, 2.51 g (8.40 mmol) of DA-2, and 0.91 g of DA-5 ( 8.40 mmol), 43 g of N-methyl-2-pyrrolidone was added, and the mixture was dissolved by stirring while feeding nitrogen. While stirring this diamine solution, 5.30 g (27.0 mmol) of CA-1 was added, and N-methyl-2-pyrrolidone was further added so that the solid content concentration would be 10% by mass. The mixture was stirred for 2 hours to obtain a solution of polyamic acid (A-9). The viscosity of this polyamic acid solution at a temperature of 25 ° C. was 125 mPa · s.
撹拌装置付きおよび窒素導入管付きの100mL四つ口フラスコにDA-3を1.64g(12.0mmol)、およびDA-2を5.38g(18.0mmol)取り、N-メチル-2-ピロリドン64.7gを加え、窒素を送りながら撹拌して溶解させた。このジアミン溶液を撹拌しながらCA-1を5.68g(29.0mmol)を添加し、更に固形分濃度が12質量%になるようにN-メチル-2-ピロリドンを加え、窒素雰囲気下、室温で3.5時間撹拌してポリアミック酸(A-10)の溶液を得た。このポリアミック酸溶液の温度25℃における粘度は211mPa・sであった。 (Synthesis Example 10)
In a 100 mL four-necked flask equipped with a stirrer and a nitrogen inlet tube, 1.64 g (12.0 mmol) of DA-3 and 5.38 g (18.0 mmol) of DA-2 were taken, and N-methyl-2-pyrrolidone was added. 64.7 g was added and dissolved by stirring while feeding nitrogen. While stirring this diamine solution, 5.68 g (29.0 mmol) of CA-1 was added, and N-methyl-2-pyrrolidone was further added so that the solid content concentration was 12% by mass. And stirred for 3.5 hours to obtain a solution of polyamic acid (A-10). The viscosity of this polyamic acid solution at a temperature of 25 ° C. was 211 mPa · s.
撹拌装置付きおよび窒素導入管付きの2LセパラブルフラスコにDA-5を31.7g(294mmol)、およびDA-2を37.6g(126mmol)取り、N-メチル-2-ピロリドン864gを加え、窒素を送りながら撹拌して溶解させた。このジアミン溶液を撹拌しながらCA-1を78.2g(399mmol)添加し、更に固形分濃度が12質量%になるようにN-メチル-2-ピロリドンを加え、窒素雰囲気下、室温で6時間撹拌してポリアミック酸(B-1)の溶液を得た。このポリアミック酸溶液の温度25℃における粘度は308mPa・sであった。 (Comparative Synthesis Example 1)
In a 2 L separable flask equipped with a stirrer and a nitrogen inlet tube, 31.7 g (294 mmol) of DA-5 and 37.6 g (126 mmol) of DA-2 were added, and 864 g of N-methyl-2-pyrrolidone was added. Was dissolved by stirring while feeding. While stirring this diamine solution, 78.2 g (399 mmol) of CA-1 was added, N-methyl-2-pyrrolidone was further added so that the solid content concentration would be 12% by mass, and 6 hours at room temperature in a nitrogen atmosphere. By stirring, a solution of polyamic acid (B-1) was obtained. The viscosity of this polyamic acid solution at a temperature of 25 ° C. was 308 mPa · s.
撹拌装置付きおよび窒素導入管付きの100mL四つ口フラスコにDA-1を5.25g(35.0mmol)取り、N-メチル-2-ピロリドン60.5gを加え、窒素を送りながら撹拌して溶解させた。このジアミン溶液を撹拌しながらCA-1を6.79g(34.7mmol)添加し、更に固形分濃度が12質量%になるようにN-メチル-2-ピロリドンを加え、窒素雰囲気下、室温で4.5時間撹拌してポリアミック酸(B-2)の溶液を得た。このポリアミック酸溶液の温度25℃における粘度は275mPa・sであった。 (Comparative Synthesis Example 2)
Take DA25 (5.25 g, 35.0 mmol) in a 100 mL four-necked flask equipped with a stirrer and a nitrogen inlet tube, add 60.5 g of N-methyl-2-pyrrolidone, and dissolve by stirring while feeding nitrogen. I let you. While stirring this diamine solution, 6.79 g (34.7 mmol) of CA-1 was added, and N-methyl-2-pyrrolidone was further added so that the solid content concentration was 12% by mass. The solution was stirred for 4.5 hours to obtain a solution of polyamic acid (B-2). The viscosity of this polyamic acid solution at a temperature of 25 ° C. was 275 mPa · s.
撹拌装置付きおよび窒素導入管付きの100mL四つ口フラスコにDA-1を3.16g(21.0mmol)、およびDA-2を2.69g(9.00mmol)取り、N-メチル-2-ピロリドン62.3gを加え、窒素を送りながら撹拌して溶解させた。このジアミン溶液を撹拌しながらCA-2を6.28g(29.7mmol)添加し、更に固形分濃度が12質量%になるようにN-メチル-2-ピロリドンを加え、窒素雰囲気下、室温で5時間撹拌してポリアミック酸(B-3)の溶液を得た。このポリアミック酸溶液の温度25℃における粘度は65mPa・sであった。 (Comparative Synthesis Example 3)
In a 100 mL four-necked flask equipped with a stirrer and a nitrogen inlet tube, 3.16 g (21.0 mmol) of DA-1 and 2.69 g (9.00 mmol) of DA-2 were taken, and N-methyl-2-pyrrolidone 62.3 g was added and dissolved by stirring while feeding nitrogen. While stirring the diamine solution, 6.28 g (29.7 mmol) of CA-2 was added, and N-methyl-2-pyrrolidone was further added so that the solid content concentration was 12% by mass. The solution was stirred for 5 hours to obtain a solution of polyamic acid (B-3). The viscosity of this polyamic acid solution at a temperature of 25 ° C. was 65 mPa · s.
合成例1で得られたポリアミック酸(A-1)を含有するポリアミック酸溶液の各評価、および各測定を行った結果、ラビング耐性は「良好」、液晶配向性は「良好」、電圧保持率は98.8%で「良好」、イオン密度は6pC/cm2で「良好」、体積抵抗率は1.9×1015Ω・cm、残留DCは10分後1.05V、20分後1.08V、60分後1.11Vで「良好」であった。 <Example 1>
As a result of each evaluation and measurement of the polyamic acid solution containing the polyamic acid (A-1) obtained in Synthesis Example 1, the rubbing resistance was “good”, the liquid crystal orientation was “good”, and the voltage holding ratio Is 98.8% “good”, the ion density is “good” at 6 pC / cm 2 , the volume resistivity is 1.9 × 10 15 Ω · cm, the residual DC is 1.05 V after 10 minutes, and 1 after 20 minutes. 0.08 V, 60 minutes later, 1.11 V, “good”.
合成例2で得られたポリアミック酸(A-2)を含有するポリアミック酸溶液の各評価、および各測定を行った結果、ラビング耐性は「良好」、液晶配向性は「良好」、電圧保持率は98.7%で「良好」、イオン密度は0pC/cm2で「良好」、残留DCは10分後0.87V、20分後0.96V、60分後0.99Vで「良好」であった。 <Example 2>
As a result of each evaluation and measurement of the polyamic acid solution containing the polyamic acid (A-2) obtained in Synthesis Example 2, the rubbing resistance was “good”, the liquid crystal orientation was “good”, and the voltage holding ratio Is 98.7% “good”, the ion density is 0 pC / cm 2 “good”, and the residual DC is 10 minutes 0.87 V, 20 minutes 0.96 V, 60 minutes 0.99 V “good”. there were.
合成例3で得られたポリアミック酸(A-3)を含有するポリアミック酸溶液の各評価、および各測定を行った結果、ラビング耐性は「良好」、液晶配向性は「良好」、電圧保持率は98.4%で「良好」、イオン密度は59pC/cm2で「良好」、残留DCは10分後0.69V、20分後0.74V、60分後0.81Vで「良好」であった。 <Example 3>
As a result of each evaluation and measurement of the polyamic acid solution containing the polyamic acid (A-3) obtained in Synthesis Example 3, the rubbing resistance was “good”, the liquid crystal orientation was “good”, and the voltage holding ratio Is 98.4% “good”, ion density is 59 pC / cm 2 “good”, residual DC is 0.69 V after 10 minutes, 0.74 V after 20 minutes, 0.81 V after 60 minutes, “good” there were.
合成例4で得られたポリアミック酸(A-4)を含有するポリアミック酸溶液の各評価、および各測定を行った結果、ラビング耐性は「良好」、液晶配向性は「良好」、電圧保持率は98.1%で「良好」、イオン密度は73pC/cm2で「良好」、残留DCは10分後1.03V、20分後1.06V、60分後1.14Vで「良好」であった。 <Example 4>
As a result of each evaluation and measurement of the polyamic acid solution containing the polyamic acid (A-4) obtained in Synthesis Example 4, the rubbing resistance was “good”, the liquid crystal orientation was “good”, and the voltage holding ratio Is “good” at 98.1%, the ion density is “good” at 73 pC / cm 2 , and the residual DC is “good” at 1.03 V after 10 minutes, 1.06 V after 20 minutes, and 1.14 V after 60 minutes. there were.
合成例5で得られたポリアミック酸(A-5)を含有するポリアミック酸溶液の各評価、および各測定を行った結果、ラビング耐性は「良好」、液晶配向性は「良好」、電圧保持率は99.1%で「良好」、イオン密度は2pC/cm2で「良好」、残留DCは10分後0.38V、20分後0.52V、60分後0.65Vで「良好」であった。 <Example 5>
As a result of each evaluation and measurement of the polyamic acid solution containing the polyamic acid (A-5) obtained in Synthesis Example 5, the rubbing resistance was “good”, the liquid crystal orientation was “good”, and the voltage holding ratio Is 99.1% “good”, the ion density is “good” at 2 pC / cm 2 , the residual DC is 0.38 V after 10 minutes, 0.52 V after 20 minutes, 0.65 V after 60 minutes, “good”. there were.
合成例6で得られたポリアミック酸(A-6)を含有するポリアミック酸溶液の各評価、および各測定を行った結果、ラビング耐性は「良好」、液晶配向性は「良好」、電圧保持率は98.1%で「良好」、イオン密度は13pC/cm2で「良好」、残留DCは10分後1.28V、20分後1.43V、60分後1.50Vで「良好」であった。 <Example 6>
As a result of each evaluation and measurement of the polyamic acid solution containing the polyamic acid (A-6) obtained in Synthesis Example 6, the rubbing resistance was “good”, the liquid crystal orientation was “good”, and the voltage holding ratio Is “good” at 98.1%, the ion density is “good” at 13 pC / cm 2 , and the residual DC is “good” at 1.28 V after 10 minutes, 1.43 V after 20 minutes, and 1.50 V after 60 minutes. there were.
合成例7で得られたポリアミック酸(A-7)を含有するポリアミック酸溶液の各評価、および各測定を行った結果、ラビング耐性は「良好」、液晶配向性は「良好」、電圧保持率は98.5%で「良好」、イオン密度は8pC/cm2で「良好」、残留DCは10分後0.61V、20分後0.71V、60分後0.79Vで「良好」であった。 <Example 7>
As a result of each evaluation and measurement of the polyamic acid solution containing the polyamic acid (A-7) obtained in Synthesis Example 7, the rubbing resistance was “good”, the liquid crystal orientation was “good”, and the voltage holding ratio 98.5% is “good”, the ion density is “good” at 8 pC / cm 2 , the residual DC is 0.61 V after 10 minutes, 0.71 V after 20 minutes, 0.79 V after 60 minutes and “good”. there were.
合成例8で得られたポリアミック酸(A-8)を含有するポリアミック酸溶液の各評価、および各測定を行った結果、ラビング耐性は「良好」、液晶配向性は「良好」、電圧保持率は98.7%で「良好」、イオン密度は0pC/cm2で「良好」、残留DCは10分後1.58V、20分後1.79V、60分後1.88Vで「良好」であった。 <Example 8>
As a result of each evaluation and measurement of the polyamic acid solution containing the polyamic acid (A-8) obtained in Synthesis Example 8, the rubbing resistance was “good”, the liquid crystal orientation was “good”, and the voltage holding ratio Is “good” at 98.7%, the ion density is “good” at 0 pC / cm 2 , and the residual DC is “good” at 1.58 V after 10 minutes, 1.79 V after 20 minutes, and 1.88 V after 60 minutes. there were.
合成例9で得られたポリアミック酸(A-9)を含有するポリアミック酸溶液の各評価、および各測定を行った結果、ラビング耐性は「良好」、液晶配向性は「良好」、電圧保持率は98.8%で「良好」、イオン密度は0pC/cm2で「良好」、残留DCは10分後1.15V、20分後1.39V、60分後1.51Vで「良好」であった。 <Example 9>
As a result of each evaluation and measurement of the polyamic acid solution containing the polyamic acid (A-9) obtained in Synthesis Example 9, the rubbing resistance was “good”, the liquid crystal orientation was “good”, and the voltage holding ratio Is “good” at 98.8%, the ion density is “good” at 0 pC / cm 2 , and the residual DC is “good” at 1.15 V after 10 minutes, 1.39 V after 20 minutes, and 1.51 V after 60 minutes. there were.
合成例10で得られたポリアミック酸(A-10)を含有するポリアミック酸溶液の各評価、および各測定を行った結果、ラビング耐性は「良好」、液晶配向性は「良好」、電圧保持率は98.7%で「良好」、イオン密度は2pC/cm2で「良好」、残留DCは10分後0.19V、20分後0.27V、60分後0.43Vで「良好」であった。 <Example 10>
As a result of each evaluation and measurement of the polyamic acid solution containing the polyamic acid (A-10) obtained in Synthesis Example 10, the rubbing resistance was “good”, the liquid crystal orientation was “good”, and the voltage holding ratio Is 98.7% "good", the ion density is 2pC / cm 2 "good", the residual DC is 0.19V after 10 minutes, 0.27V after 20 minutes, 0.43V after 60 minutes, "good" there were.
比較合成例1で得られたポリアミック酸(B-1)を含有するポリアミック酸溶液の各評価、および各測定を行った結果、ラビング耐性は「良好」、液晶配向性は「良好」、電圧保持率は98.4%で「良好」、イオン密度は1pC/cm2で「良好」、残留DCは10分後1.99V、20分後2.07V、60分後2.12Vで「不良」であった。 <Comparative Example 1>
As a result of each evaluation and measurement of the polyamic acid solution containing the polyamic acid (B-1) obtained in Comparative Synthesis Example 1, the rubbing resistance was “good”, the liquid crystal orientation was “good”, and the voltage was maintained. The rate is “good” at 98.4%, the ion density is “good” at 1 pC / cm 2 , the residual DC is “bad” at 1.99 V after 10 minutes, 2.07 V after 20 minutes, and 2.12 V after 60 minutes. Met.
比較合成例2で得られたポリアミック酸(B-2)を含有するポリアミック酸溶液の各評価、および各測定を行った結果、ラビング耐性は「不良」、液晶配向性は「不良」、電圧保持率は99.0%で「良好」、イオン密度は0pC/cm2で「良好」、残留DCは10分後0.95V、20分後1.21V、60分後1.42Vで「良好」であった。 <Comparative example 2>
As a result of each evaluation and measurement of the polyamic acid solution containing the polyamic acid (B-2) obtained in Comparative Synthesis Example 2, the rubbing resistance was “poor”, the liquid crystal alignment was “poor”, and the voltage was maintained. The rate is “good” at 99.0%, the ion density is “good” at 0 pC / cm 2 , and the residual DC is “good” at 0.95 V after 10 minutes, 1.21 V after 20 minutes, and 1.42 V after 60 minutes. Met.
比較合成例3で得られたポリアミック酸(B-3)を含有するポリアミック酸溶液の各評価、および各測定を行った結果、ラビング耐性は「不良」、液晶配向性は「良好」、電圧保持率は98.8%で「良好」、イオン密度は3pC/cm2で「良好」、残留DCは10分後0.29V、20分後0.42V、60分後0.67Vで「良好」であった。 <Comparative Example 3>
As a result of each evaluation and measurement of the polyamic acid solution containing the polyamic acid (B-3) obtained in Comparative Synthesis Example 3, the rubbing resistance was “poor”, the liquid crystal orientation was “good”, and the voltage was maintained. The rate is “good” at 98.8%, the ion density is “good” at 3 pC / cm 2 , and the residual DC is “good” at 0.29 V after 10 minutes, 0.42 V after 20 minutes, and 0.67 V after 60 minutes. Met.
Claims (8)
- 脂環式構造または脂肪族構造を有するテトラカルボン酸二無水物を含有するテトラカルボン酸二無水物成分と、ウレア構造を有するジアミン及び重合反応部位に2級アミンを有するジアミンを含有するジアミン成分との反応により得られるポリアミック酸を含有することを特徴とする液晶配向剤。 A tetracarboxylic dianhydride component containing a tetracarboxylic dianhydride having an alicyclic structure or an aliphatic structure; a diamine component containing a diamine having a urea structure and a diamine having a secondary amine at the polymerization reaction site; The liquid crystal aligning agent characterized by including the polyamic acid obtained by reaction of this.
- テトラカルボン酸二無水物成分中、脂環式構造または脂肪族構造を有するテトラカルボン酸二無水物を50mol%以上含有することを特徴とする請求項1記載の液晶配向剤。 The liquid crystal aligning agent according to claim 1, wherein the tetracarboxylic dianhydride component contains 50 mol% or more of a tetracarboxylic dianhydride having an alicyclic structure or an aliphatic structure.
- ジアミン成分中、重合反応部位に2級アミンを有するジアミンを10~70mol%含有することを特徴とする請求項1または2に記載の液晶配向剤。 3. The liquid crystal aligning agent according to claim 1, wherein the diamine component contains 10 to 70 mol% of a diamine having a secondary amine at a polymerization reaction site.
- ジアミン成分中、ウレア構造を有するジアミンを10~70mol%含有することを特徴とする請求項1~3のいずれかに記載の液晶配向剤。 4. The liquid crystal aligning agent according to claim 1, wherein the diamine component contains 10 to 70 mol% of a diamine having a urea structure.
- 重合反応部位に2級アミンを有するジアミンが、下記式(1)で表されるジアミンであることを特徴とする請求項1~4のいずれかに記載の液晶配向剤。
- ウレア構造を有するジアミンが、下記式(2)で表されるジアミンであることを特徴とする請求項1~5のいずれかに記載の液晶配向剤。
- 請求項1~6のいずれかに記載の液晶配向剤を用いて得られることを特徴とする液晶配向膜。 A liquid crystal alignment film obtained by using the liquid crystal aligning agent according to any one of claims 1 to 6.
- 請求項7の液晶配向膜を具備することを特徴とする液晶表示素子。 A liquid crystal display element comprising the liquid crystal alignment film of claim 7.
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WO2014148440A1 (en) * | 2013-03-19 | 2014-09-25 | 日産化学工業株式会社 | Liquid crystal aligning agent for in-plane switching |
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---|---|
JPWO2013008906A1 (en) | 2015-02-23 |
TW201309784A (en) | 2013-03-01 |
CN103797409B (en) | 2017-05-24 |
JP5633714B2 (en) | 2014-12-03 |
TWI499656B (en) | 2015-09-11 |
KR101610559B1 (en) | 2016-04-07 |
CN103797409A (en) | 2014-05-14 |
KR20140041834A (en) | 2014-04-04 |
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