Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
  • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
  • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
  • C08G73/1075—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
  • 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
  • C08G73/12—Unsaturated polyimide precursors
• • G—PHYSICS
  • G02—OPTICS
  • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
  • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
  • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
  • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
  • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
  • G02F1/1333—Constructional arrangements; Manufacturing methods
  • G02F1/1337—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers
• • 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
  • G02F1/1343—Electrodes
• • 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
  • G02F1/137—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 characterised by the electro-optical or magneto-optical effect, e.g. field-induced phase transition, orientation effect, guest-host interaction or dynamic scattering

Definitions

• the present invention is a manufacturing method applying a polymer stabilization technology capable of manufacturing a zero plane anchoring film in a cheap and complicated method, and a further low voltage using the manufacturing method.
• the present invention relates to a liquid crystal display element for realizing driving and a method of manufacturing the same.
• liquid crystal display devices have been widely used for displays of mobile phones, computers and televisions.
• Liquid crystal display devices have characteristics such as thinness, lightness, and low power consumption, and in the future, application to further contents such as VR and ultra high definition displays are expected.
• Various display modes such as TN (Twisted Nematic), IPS (In-Plane Switching), VA (Vertical Alignment), etc. have been proposed as display methods for liquid crystal displays, but in all modes, the liquid crystal is in a desired alignment state
• a film (a liquid crystal alignment film) that leads to
• FFS has a problem that the manufacturing cost of the substrate is larger than IPS, and a display defect specific to FFS mode called Vcom shift occurs.
• photoalignment there are advantages in that the size of the device that can be manufactured can be increased and the display characteristics can be greatly improved compared to the rubbing method.
• an isomerization type there is a problem such as burn-in due to lack of orientation.
• liquid crystal display element manufacturers and liquid crystal alignment film manufacturers are making various efforts to solve those problems.
• a liquid crystal alignment film having strong anchoring energy is used as the substrate on one side, and the substrate side provided with an electrode for generating one of the lateral electric fields has no ability to control the alignment of the liquid crystal at all. Treatment to make an IPS mode liquid crystal display element using them.
• the alignment film plays an important role such as suppression of image sticking, but it is difficult to control the required electric properties when using a polymer brush or the like.
• the third reason is that the response speed at the time of setting the voltage to Off in driving principle becomes very slow.
• the power of the liquid crystal to be returned depends on the elastic force of the liquid crystal, it is considered that the speed is greatly reduced as compared with the case where the alignment film is present. If such a technical problem can be solved, it will be a great cost advantage also as a panel maker, and it may be a merit also to the consumption control of a battery, the improvement of an image quality, etc.
• the present invention has been made to solve the above problems, and a manufacturing method applying a polymer stabilization technology capable of manufacturing a zero plane anchoring film, and a simple and inexpensive method at normal temperature. It is an object of the present invention to provide an in-plane switching mode liquid crystal display device and a method of manufacturing the same, which can simultaneously realize non-contact alignment, low driving voltage and high response speed at the time of Off.
• the present invention includes the following.
• a step of providing sufficient energy for causing a polymerization reaction of the radically polymerizable compound in a state where a liquid crystal composition containing a liquid crystal, a chiral dopant and a radically polymerizable compound is brought into contact with a radical generating film Method of manufacturing a zero plane anchoring membrane.
• the radical generating film of the first substrate is a radical generating film subjected to uniaxial alignment treatment.
• the step of applying energy is performed in the absence of an electric field. 4.
• the radical generating film is a film formed by immobilizing an organic group that induces radical polymerization.
• the radical generating film is characterized in that it is obtained by applying and curing a composition of a compound having a radical generating group and a polymer to form a film, thereby immobilizing the film in the film.
• the method according to any one of claims 1 to 3. 6.
• the method according to any one of claims 1 to 3, wherein the radical generating film comprises a polymer containing an organic group that induces radical polymerization.
• the polymer containing an organic group that induces radical polymerization is selected from polyimide precursors, polyimides, polyureas, and polyamides obtained using a diamine component containing a diamine containing an organic group that induces radical polymerization.
• the organic group that induces the radical polymerization is an organic group represented by the following structures [X-1] to [X-14], [W], [Y], and [Z]. And the method according to any one of 7.
• R 11 represents —CH 2 —, —NR—, —O— or —S—
• R represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms
• * represents Q of the compound molecule Indicates the binding site with other parts.
• R 12 represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms, or an alkoxy group having 1 to 10 carbon atoms.
• the diamine containing an organic group that induces radical polymerization is a diamine having a structure represented by the following general formula (6) or the following general formula (7) .
• R 6 represents a single bond, —CH 2 —, —O—, —COO—, —OCO—, —NHCO—, —CONH—, —NH—, —CH 2 O—, —N (CH 3) -, - CON (CH 3) -, or -N (CH 3) CO- represents
• liquid crystal alignment film having uniaxial alignment property is a liquid crystal alignment film for horizontal alignment.
• first substrate having a radical generating film is a substrate having a comb electrode.
• radically polymerizable compound containing liquid crystal, chiral dopant and radically polymerizable compound, At least one of the radically polymerizable compounds is a compound having one polymerizable unsaturated bond in one molecule, which is compatible with liquid crystal, A liquid crystal composition, wherein the polymerizable unsaturated bond is selected from the following structures.
• a zero plane anchoring film can be industrially produced with high yield.
• the method of the present invention it is possible to easily manufacture a liquid crystal display element similar to the zero plane anchoring IPS mode liquid crystal display element described in Patent Documents 1 and 2 by using inexpensive raw materials or existing manufacturing methods.
• the liquid crystal display device obtained by the manufacturing method of the present invention has a faster response speed of the liquid crystal at the time of Off than the prior art, low driving voltage, no bright spots, and can suppress Vcom shift in IPS mode. It is possible to provide a liquid crystal display element having such excellent characteristics that further high definition can be achieved in the mode.
• the present invention is a method for producing a zero plane anchoring film, which comprises polymerizing a polymerizable compound by UV or heat in a state in which a liquid crystal containing a specific polymerizable compound is in contact with a radical generating film. More specifically, a liquid crystal composition containing a liquid crystal, a chiral dopant and a radical polymerizable compound is provided between a first substrate having a radical generating film and a second substrate which may have a radical generating film.
• a method for producing a zero plane anchoring film comprising the steps of: preparing a cell; and providing the cell with sufficient energy to cause a polymerization reaction of the radically polymerizable compound.
• a method of manufacturing a liquid crystal cell comprising the step of filling a liquid crystal composition containing a liquid crystal, a chiral dopant and a radical polymerizable compound between one substrate and a second substrate.
• the second substrate does not have a radical generation film, and is a substrate having a liquid crystal alignment film subjected to uniaxial alignment processing, and the first substrate has a comb electrode. It is a creation method.
• the "zero-surface anchoring film” means that there is no alignment control force of liquid crystal molecules in the in-plane direction, or if any, it is weaker than the intermolecular force between liquid crystals.
• the zero plane anchoring film is not limited to a solid film, and includes a liquid film covering a solid surface. Normally, in the liquid crystal display element, a film that regulates the alignment of liquid crystal molecules, ie, a liquid crystal alignment film is used as a pair to align the liquid crystal, but even when this zero plane anchoring film and the liquid crystal alignment film are used as a pair It can be oriented.
• Horizontal alignment refers to a state in which the major axes of liquid crystal molecules are aligned substantially parallel to the liquid crystal alignment film surface, and inclined alignment of several degrees is included in the category of horizontal alignment.
• the composition for forming a radical generating film for forming a radical generating film used in the present invention contains a polymer as a component, and contains a group capable of generating a radical.
• the composition may contain a polymer to which a radical-generating group is bonded, or the composition of a compound having a radical-generating group and a polymer to be a base resin. It may be a thing.
• the group capable of generating a radical is preferably an organic group that induces radical polymerization.
• Such organic groups that induce radical polymerization include organic groups represented by the following structures [X-1] to [X-14], [W], [Y], and [Z].
• Be In formulas [X-1] to [X-14], * represents a binding site to a moiety other than the polymerizable unsaturated bond of the compound molecule, and S 1 and S 2 are each independently —O—, — NR- or -S- represents, R represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, R 12 represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms, or 1 to 10 carbon atoms R 1 and R 2 each independently represent a hydrogen atom, a halogen atom, or an alkyl group having 1 to 4 carbon atoms) (In the formulas [W], [Y] and [Z], * represents a bonding site to a moiety other than the polymerizable unsaturated bond of the compound molecule, Ar has an organic group and
• R 11 represents —CH 2 —, —NR—, —O— or —S—
• R represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms
• * represents Q of the compound molecule Indicates the binding site with other parts.
• R 12 represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms, or an alkoxy group having 1 to 10 carbon atoms.
• polyimide precursor for example, a polyimide precursor and at least one polymer selected from the group consisting of polyimide, polyurea, polyamide, polyacrylate, polymethacrylate and the like are preferable.
• a polymer having an organic group capable of inducing radical polymerization is used to obtain a radical generating film used in the present invention, to obtain a polymer having a group capable of generating a radical, a methacryl group as a monomer component,
• a monomer having a photoreactive side chain containing at least one selected from an acryl group, a vinyl group, an allyl group, a coumarin group, a styryl group and a cinnamoyl group, or a site which is decomposed by ultraviolet irradiation to generate a radical is a side chain It is preferable to manufacture using the monomer which it has.
• such a radical generation site-containing diamine is, for example, a diamine having a side chain capable of generating a radical and capable of polymerization, and examples thereof include diamines represented by the following general formula (6). Not limited to this.
• R 6 represents a single bond, —CH 2 —, —O—, —COO—, —OCO—, —NHCO—, —CONH—, —NH—, —CH 2 O—, —N (CH 3) -, - CON (CH 3) -, or -N (CH 3) CO- represents
• the bonding position of the two amino groups (-NH 2 ) in the formula (6) is not limited. Specifically, with respect to the linking group of the side chain, the 2, 3 positions, 2, 4 positions, 2, 5 positions, 2, 6 positions, 3, 4 positions, 3, 4 positions on the benzene ring There are 5 positions. Among them, from the viewpoint of reactivity when synthesizing a polyamic acid, the positions of 2, 4, 2, 5, or 3, 5 are preferable. The positions of 2, 4 or 3, 5 are more preferable in consideration of the ease of synthesis of the diamine.
• diamine having a photoreactive group containing at least one selected from the group consisting of methacryl group, acryl group, vinyl group, allyl group, coumarin group, styryl group and cinnamoyl group include the following: Compounds include but are not limited to these. (Wherein, J 1 is a bonding group selected from a single bond, -O-, -COO-, -NHCO-, or -NH-, and J 2 is a single bond, or unsubstituted or substituted by a fluorine atom) (C 1 to C 20 alkylene group)
• T 1 and T 2 are each independently a single bond, —O—, —S—, —COO—, —OCO—, —NHCO—, —CONH—, —NH—, — CH 2 O—, —N (CH 3 ) —, —CON (CH 3 ) — or —N (CH 3 ) CO—,
• T 1 and T 2 are each independently a single bond, —O—, —S—, —COO—, —OCO—, —NHCO—, —CONH
• the bonding position of the two amino groups (-NH 2 ) in the above formula (7) is not limited. Specifically, with respect to the linking group of the side chain, the 2, 3 positions, 2, 4 positions, 2, 5 positions, 2, 6 positions, 3, 4 positions, 3, 4 positions on the benzene ring There are 5 positions. Among them, from the viewpoint of reactivity when synthesizing a polyamic acid, the positions of 2, 4, 2, 5, or 3, 5 are preferable. The positions of 2, 4 or 3, 5 are more preferable in consideration of the ease of synthesis of the diamine.
• n is an integer of 2 to 8.
• the above diamines may be used alone or in combination of two or more, depending on the properties such as liquid crystal orientation when forming a radical generating film, sensitivity in polymerization reaction, voltage holding characteristics, and accumulated charge.
• the diamine having a site where such radical polymerization occurs is preferably used in an amount of 5 to 50% by mole based on the total of the diamine component used in the synthesis of the polymer contained in the radical generating film-forming composition, more preferably It is 10 to 40 mol%, particularly preferably 15 to 30 mol%.
• the polymer used for the radical generating film of the present invention is obtained from a diamine
• other diamines other than the diamine having a site where the radical is generated may be used as a diamine component as long as the effect of the present invention is not impaired. be able to.
• p-phenylenediamine 2,3,5,6-tetramethyl-p-phenylenediamine, 2,5-dimethyl-p-phenylenediamine, m-phenylenediamine, 2,4-dimethyl- m-phenylenediamine, 2,5-diaminotoluene, 2,6-diaminotoluene, 2,5-diaminophenol, 2,4-diaminophenol, 3,5-diaminophenol, 3,5-diaminobenzyl alcohol, 2, 4-diaminobenzyl alcohol, 4,6-diaminoresorcinol, 4,4'-diaminobiphenyl, 3,3'-dimethyl-4,4'-diaminobiphenyl, 3,3'-dimethoxy-4,4'-diaminobiphenyl , 3,3'-Dihydroxy-4,4'-diaminobiphenyl, 3,3'-dicarboxy
• the above-mentioned other diamines may be used alone or in combination of two or more according to the properties such as liquid crystal alignment, sensitivity in polymerization reaction, voltage holding property, and accumulated charge when forming a radical generating film. .
• tetracarboxylic acid dianhydride to be reacted with the above-mentioned diamine component in the synthesis when the polymer is a polyamic acid.
• tetracarboxylic acid dianhydride may be used alone or in combination depending on the properties such as liquid crystal alignment when used as a radical generating film, sensitivity in polymerization reaction, voltage holding characteristics, and accumulated charge. .
• the structure of the tetracarboxylic acid dialkyl ester to be reacted with the above diamine component is not particularly limited in the synthesis in the case where the polymer is a polyamic acid ester, but specific examples thereof will be given below.
• Specific examples of aliphatic tetracarboxylic acid diesters include 1,2,3,4-cyclobutane tetracarboxylic acid dialkyl ester, 1,2-dimethyl-1,2,3,4-cyclobutane tetracarboxylic acid dialkyl ester, 1 , 3-Dimethyl-1,2,3,4-cyclobutane tetracarboxylic acid dialkyl ester, 1,2,3,4-tetramethyl-1,2,3,4-cyclobutane tetracarboxylic acid dialkyl ester, 1,2,3,4-cyclobutane tetracarboxylic acid dialkyl ester 3,4-cyclopentane tetracarboxylic acid dialkyl este
• Hexadecane-4,5,11,12-tetracarboxylic acid-4,5 1,12-dialkyl ester, 4- (2,5-dioxotetrahydrofuran-3-yl) -1, 2,3,4-tetrahydronaphthalene-1,2-dicarboxylic dialkyl ester and the like.
• aromatic tetracarboxylic acid dialkyl ester pyromellitic acid dialkyl ester, 3,3 ′, 4,4′-biphenyl tetracarboxylic acid dialkyl ester, 2,2 ′, 3,3′-biphenyl tetracarboxylic acid dialkyl ester, 2,3,3 ', 4-biphenyltetracarboxylic acid dialkyl ester, 3,3', 4,4'-benzophenonetetracarboxylic acid dialkyl ester, 2,3,3 ', 4'-benzophenonetetracarboxylic acid dialkyl ester, Bis (3,4-dicarboxyphenyl) ether dialkyl ester, bis (3,4-dicarboxyphenyl) sulfone dialkyl ester, 1,2,5,6-naphthalene tetracarboxylic acid dialkyl ester, 2,3,6,7 -Naphthalenetetracarboxylic acid dial
• R 22 and R 33 each represent an aliphatic hydrocarbon having 1 to 10 carbon atoms.
• Aliphatic diisocyanates shown in K-1 to K-5 are inferior in reactivity but have the merit of improving solvent solubility, and aromatic diisocyanates such as K-6 to K-7 are rich in reactivity and heat resistance Although it has the effect of improving the solvent, it has the disadvantage of reducing the solvent solubility.
• Particularly preferred are K-1, K-7, K-8, K-9, and K-10 in terms of versatility and properties, K-12 in terms of added electrical characteristics, and K-13 in terms of liquid crystal alignment.
• Diisocyanate can be used in combination of one or more kinds, and it is preferable to apply variously according to the characteristics to be obtained.
• diisocyanates can be replaced with the tetracarboxylic acid dianhydride described above, and may be used in the form of a copolymer of polyamic acid and polyurea, and chemical imidation can be used to convert polyimide and polyurea. You may use in a form like a copolymer.
• the structure of the dicarboxylic acid to be reacted is not particularly limited, but it is as follows if a specific example is mentioned below.
• Specific examples of aliphatic dicarboxylic acids include malonic acid, oxalic acid, dimethylmalonic acid, succinic acid, fumaric acid, glutaric acid, adipic acid, muconic acid, 2-methyladipic acid, trimethyladipic acid, pimelic acid, 2, 2- Mention may be made of dicarboxylic acids such as dimethyl glutaric acid, 3,3-diethylsuccinic acid, azelaiic acid, sebacic acid and suberic acid.
• alicyclic dicarboxylic acid examples include 1,1-cyclopropanedicarboxylic acid, 1,2-cyclopropanedicarboxylic acid, 1,1-cyclobutanedicarboxylic acid, 1,2-cyclobutanedicarboxylic acid and 1,3-cyclobutanedicarboxylic acid Acid, 3,4-diphenyl-1,2-cyclobutanedicarboxylic acid, 2,4-diphenyl-1,3-cyclobutanedicarboxylic acid, 1-cyclobutene-1,2-dicarboxylic acid, 1-cyclobutene-3,4-dicarboxylic acid Acid, 1,1-cyclopentanedicarboxylic acid, 1,2-cyclopentanedicarboxylic acid, 1,3-cyclopentanedicarboxylic acid, 1,1-cyclohexanedicarboxylic acid, 1,2-cyclohexanedicarboxylic acid, 1,3-cyclohexane Dicarboxylic
• aromatic dicarboxylic acid o-phthalic acid, isophthalic acid, terephthalic acid, 5-methylisophthalic acid, 5-tert-butylisophthalic acid, 5-aminoisophthalic acid, 5-hydroxyisophthalic acid, 2,5-dimethylterephthalic acid Acid, tetramethylterephthalic acid, 1,4-naphthalenedicarboxylic acid, 2,5-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic acid, 1,4-anthracenedicarboxylic acid, 1,4 -Anthraquinonedicarboxylic acid, 2,5-biphenyldicarboxylic acid, 4,4'-biphenyldicarboxylic acid, 1,5-biphenylenedicarboxylic acid, 4,4 "-terphenyldicarboxylic acid, 4,4'-diphenylmethanedicarboxylic
• dicarboxylic acid containing a heterocyclic ring 1,5- (9-oxofluorene) dicarboxylic acid, 3,4-furandicarboxylic acid, 4,5-thiazoledicarboxylic acid, 2-phenyl-4,5-thiazoledicarboxylic acid, 1,2,5-Thiadiazole-3,4-dicarboxylic acid, 1,2,5-oxadiazole-3,4-dicarboxylic acid, 2,3-pyridinedicarboxylic acid, 2,4-pyridinedicarboxylic acid 2, 5-pyridinedicarboxylic acid, 2,6-pyridinedicarboxylic acid, 3,4-pyridinedicarboxylic acid, 3,5-pyridinedicarboxylic acid and the like can be mentioned.
• the various dicarboxylic acids described above may be acid dihalides or those of anhydrous structure. These dicarboxylic acids are preferably dicarboxylic acids that can give a polyamide having a particularly linear structure, from the viewpoint of maintaining the alignment of liquid crystal molecules.
• terephthalic acid isoterephthalic acid, 1,4-cyclohexanedicarboxylic acid, 4,4'-biphenyldicarboxylic acid, 4,4'-diphenylmethanedicarboxylic acid, 4,4'-diphenylethanedicarboxylic acid, 4,4 '-Diphenylpropanedicarboxylic acid, 4,4'-diphenylhexafluoropropanedicarboxylic acid, 2,2-bis (phenyl) propanedicarboxylic acid, 4,4-terphenyldicarboxylic acid, 2,6-naphthalenedicarboxylic acid, 2, 5-pyridinedicarboxylic acid or their acid dihalides are preferably used. Although some of these compounds have isomers, they may be a mixture containing them. Also, two or more compounds may be used in combination.
• the dicarboxylic acids used in the present invention are not limited to the above exemplified compounds.
• diamine which is a raw material (also described as “diamine component”) and tetracarboxylic acid dianhydride which is a raw material (also described as “tetracarboxylic acid dianhydride component”), tetracarboxylic acid diester, diisocyanate and dicarboxylic acid
• tetracarboxylic acid diester a raw material (also described as “tetracarboxylic acid dianhydride component”
• diisocyanate dicarboxylic acid
• the method is a method in which a diamine component and one or more components selected from tetracarboxylic acid dianhydride component, tetracarboxylic acid diester, diisocyanate and dicarboxylic acid are reacted in an organic solvent.
• reaction of the diamine component with the tetracarboxylic acid dianhydride component is advantageous in that it proceeds relatively easily in an organic solvent and no by-products are generated.
• the organic solvent used for the above reaction is not particularly limited as long as it can dissolve the produced polymer. Furthermore, even if it is an organic solvent in which a polymer does not melt
• organic solvent examples include N, N-dimethylformamide, N, N-dimethylacetamide, N, N-diethylformamide, N-methylformamide, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, 2 -Pyrrolidone, 1,3-dimethyl-2-imidazolidinone, 3-methoxy-N, N-dimethylpropanamide, N-methylcaprolactam, dimethylsulfoxide, tetramethylurea, pyridine, dimethylsulfone, hexamethylsulfoxide, ⁇ - Butyrolactone, isopropyl alcohol, methoxymethyl pentanol, dipentene, ethyl amyl ketone, methyl nonyl ketone, methyl ethyl ketone, methyl isoamyl ketone, methyl isopropyl ketone, methyl cellosolve, ethyl cellosolv
• a solution in which the diamine component is dispersed or dissolved in an organic solvent is stirred, and the tetracarboxylic acid dianhydride component is used as it is or as an organic solvent.
• a method of dispersing or dissolving in a solvent and adding it conversely, a method of adding a diamine component to a solution in which a tetracarboxylic acid dianhydride component is dispersed or dissolved in an organic solvent, a tetracarboxylic acid dianhydride component and a diamine component
• a method of alternately adding may be mentioned, and any of these methods may be used.
• the diamine component or the tetracarboxylic acid dianhydride component when the diamine component or the tetracarboxylic acid dianhydride component is composed of a plurality of types of compounds, it may be reacted in a mixed state in advance, or may be reacted separately one after another, and further it is a low molecular weight individually reacted.
• the body may be mixed and reacted to form a high molecular weight product.
• the temperature for reacting the diamine component and the tetracarboxylic acid dianhydride component can be selected arbitrarily, and is, for example, in the range of ⁇ 20 to 100 ° C., preferably ⁇ 5 to 80 ° C.
• the reaction can be carried out at any concentration, for example, the total amount of diamine component and tetracarboxylic acid dianhydride component is 1 to 50% by mass, preferably 5 to 30% by mass, based on the reaction solution. .
• the ratio of the total number of moles of tetracarboxylic acid dianhydride component to the total number of moles of diamine components in the above polymerization reaction can be selected to be any value depending on the molecular weight of the polyamic acid to be obtained. As in the conventional polycondensation reaction, the molecular weight of the formed polyamic acid increases as the molar ratio approaches 1.0. The preferred range is 0.8 to 1.2.
• the method of synthesizing the polymer used in the present invention is not limited to the above-mentioned method, and in the case of synthesizing a polyamic acid, the above-mentioned tetracarboxylic acid dianhydride may be used in the same manner as a general polyamic acid synthesis method.
• the corresponding polyamic acid can be obtained also by reacting using a tetracarboxylic acid or a tetracarboxylic acid derivative such as a tetracarboxylic acid dihalide having a corresponding structure by a known method.
• diamine and diisocyanate react when synthesize
• a component selected from a diamine, a tetracarboxylic acid diester and a dicarboxylic acid is induced to an acid halide in the presence of a known condensing agent or by a known method. And may be reacted with a diamine.
• the thermal imidization which heats the solution of polyamic acid as it is, the catalyst imidization which adds a catalyst to the solution of polyamic acid are mentioned.
• the imidation ratio from polyamic acid to polyimide is preferably 30% or more, and more preferably 30 to 99%, because the voltage holding ratio can be increased.
• 70% or less is preferable from the viewpoint of suppressing precipitation of the polymer in the varnish of whitening property. 40 to 80% is more preferable considering both properties.
• the temperature for thermally imidizing the polyamic acid in the solution is usually 100 to 400 ° C., preferably 120 to 250 ° C., and it is preferable to carry out while removing water generated by the imidization reaction out of the system.
• Catalytic imidization of polyamic acid can be carried out by adding a basic catalyst and an acid anhydride to a solution of polyamic acid and stirring at a temperature of generally ⁇ 20 to 250 ° C., preferably 0 to 180 ° C.
• the amount of basic catalyst is usually 0.5 to 30 times by mole, preferably 2 to 20 times by mole of the amic acid group, and the amount of acid anhydride is usually 1 to 50 times by mole of the amic acid group, preferably It is 3 to 30 molar times.
• the basic catalyst may, for example, be pyridine, triethylamine, trimethylamine, tributylamine or trioctylamine.
• pyridine is preferable because it has an adequate basicity to allow the reaction to proceed.
• acid anhydride acetic anhydride, trimellitic anhydride, pyromellitic anhydride and the like can be mentioned.
• acetic anhydride is preferable because it facilitates purification after completion of the reaction.
• the imidation ratio by catalytic imidation can be controlled by adjusting the amount of catalyst, reaction temperature, reaction time and the like.
• the reaction solution When the produced polymer is recovered from the reaction solution of the polymer, the reaction solution may be poured into a poor solvent to precipitate.
• the poor solvent used for precipitation include methanol, acetone, hexane, butyl cellosolve, heptane, methyl ethyl ketone, methyl isobutyl ketone, ethanol, toluene, benzene, water and the like.
• the polymer precipitated by charging into a poor solvent can be recovered by filtration and then dried by heating at normal temperature or under normal pressure or reduced pressure.
• impurities in the polymer can be reduced.
• a poor solvent for example, alcohols, ketones, hydrocarbons and the like can be mentioned, and it is preferable to use three or more poor solvents selected from these, because the efficiency of purification is further enhanced.
• the composition for forming a radical generating film used in the present invention is a polymer other than a polymer containing an organic group that induces radical polymerization. Other polymers may be contained. At that time, the content of the other polymer in the total components of the polymer is preferably 5 to 95% by mass, more preferably 30 to 70% by mass.
• the molecular weight of the polymer possessed by the radical generating film-forming composition is preferably GPC (per mass) in consideration of the strength of the radical generating film obtained by applying the radical generating film, the workability at the time of coating film formation, the uniformity of the coating film, etc.
• the weight average molecular weight measured by the gel permeation chromatography method is preferably 5,000 to 1,000,000, and more preferably 10,000 to 150,000.
• the radical generating film used in the present invention is obtained by applying and curing a composition of a compound having a radical generating group and a polymer to form a film and immobilizing it in the film
• at least one polymer obtained using a diamine component that is 0 mol% of the entire diamine component used for the synthesis of the polymer to be contained in the radical generating film-forming composition may be used.
• produces the radical which is added in that case, the following are mentioned.
• the compound that generates radicals by heat is a compound that generates radicals by heating to a temperature higher than the decomposition temperature.
• radical thermal polymerization initiators include ketone peroxides (methyl ethyl ketone peroxide, cyclohexanone peroxide etc.), diacyl peroxides (acetyl peroxide, benzoyl peroxide etc.), hydroperoxides (peroxide Hydrogen, tert-butyl hydroperoxide, cumene hydroperoxide etc., dialkyl peroxides (di-tert-butyl peroxide, dicumyl peroxide, dilauroyl peroxide etc), peroxy ketals (dibutyl peroxycyclohexane Etc.), alkyl peresters (peroxyneodecanoic acid-tert-butyl ester, peroxypivalic acid-tert-butyl ester, peroxy 2-ethyl cyclohex
• radical photopolymerization initiators benzophenone, Michler's ketone, 4,4'-bis (diethylamino) benzophenone, xanthone, thioxanthone, isopropyl xanthone, 2,4-diethylthioxanthone, 2-ethyl anthraquinone, acetophenone, 2-hydroxy -2-Methylpropiophenone, 2-hydroxy-2-methyl-4'-isopropylpropiophenone, 1-hydroxycyclohexyl phenyl ketone, isopropylbenzoin ether, isobutylbenzoin ether, 2,2-diethoxyacetophenone, 2,2 2-Dimethoxy-2-phenylacetophenone, camphorquinone, benzanthrone, 2-methyl
• the radical generating film is made of a polymer containing an organic group which induces radical polymerization
• the group which generates the above radical for the purpose of promoting radical polymerization when energy is given is You may contain the compound which it has.
• the radical generating film-forming composition can contain an organic solvent in which the polymer component and, if necessary, the radical generator and other components contained therein are dissolved or dispersed.
• an organic solvent for example, the organic solvent which was illustrated by the synthesis
• N-methyl-2-pyrrolidone, ⁇ -butyrolactone, N-ethyl-2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone, 3-methoxy-N, N-dimethylpropanamide, etc. have solubility. It is preferable from the viewpoint of In particular, N-methyl-2-pyrrolidone or N-ethyl-2-pyrrolidone is preferred, but two or more mixed solvents may be used.
• a solvent for improving the uniformity and smoothness of the coating film for example, isopropyl alcohol, methoxymethyl pentanol, methyl cellosolve, ethyl cellosolve, butyl cellosolve, methyl cellosolve acetate, butyl cellosolve acetate, ethyl cellosolve acetate, butyl carbitol, ethyl carbiol Toll, ethyl carbitol acetate, ethylene glycol, ethylene glycol monoacetate, ethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether, propylene glycol, propylene glycol monoacetate, propylene glycol monomethyl ether, propylene glycol monobutyl ether, propylene glycol tert-butyl ether , Dipropylene glycol monome Ether, diethylene glycol, diethylene glycol monoacetate, diethylene glycol dimethyl ether, diethylene glycol
• the radical generating film-forming composition may contain components other than the above. Examples thereof include a compound that improves the film thickness uniformity and surface smoothness when the radical generating film forming composition is applied, a compound that improves the adhesion between the radical generating film forming composition and the substrate, and a radical generating film formed. The compound etc. which further improve the film strength of a composition are mentioned.
• a fluorochemical surfactant silicone type surfactant, nonion type surfactant etc.
• F-top EF301, EF303, EF352 manufactured by Tochem Products
• Megafac F171, F173, R-30 manufactured by Dainippon Ink and Chemicals, Inc.
• Florard FC430, FC431 manufactured by Sumitomo 3M Limited
• Asahi Guard AG 710 Surfron S-382, SC101, SC102, SC103, SC104, SC105, SC106 (manufactured by Asahi Glass Co., Ltd.) and the like.
• these surfactants are used, their use ratio is preferably 0.01 to 2 parts by mass, more preferably 0 based on 100 parts by mass of the total amount of polymers contained in the radical generating film-forming composition. .01 to 1 part by mass.
• a functional silane containing compound, an epoxy group containing compound, etc. are mentioned.
• a phenol compound such as 2,2'-bis (4-hydroxy-3,5-dihydroxymethylphenyl) propane or tetra (methoxymethyl) bisphenol may be added. It is also good.
• the amount 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 total amount of polymers contained in the radical generating film-forming composition. It is.
• the composition for forming a radical generating film may be a dielectric or conductivity for the purpose of changing the electric characteristics such as the dielectric constant or conductivity of the radical generating film. Substances may be added.
• the radical generating film of the present invention can be obtained using the above radical generating film forming composition.
• a cured film obtained by drying and baking can be used as a radical generation film as it is.
• the cured film may be rubbed, irradiated with polarized light or light of a specific wavelength, or treated with an ion beam, or irradiated with UV to a liquid crystal display element filled with liquid crystal as an alignment film for PSA. Is also possible.
• the substrate on which the radical generating film-forming composition is applied is not particularly limited as long as it is a highly transparent substrate, but a substrate on which a transparent electrode for driving liquid crystal is formed is preferable.
• a substrate on which a transparent electrode for driving liquid crystal is formed is preferable.
• Specific examples include glass plate, polycarbonate, poly (meth) acrylate, polyether sulfone, polyarylate, polyurethane, polysulfone, polyether, polyether ketone, trimethyl pentene, polyolefin, polyethylene terephthalate, (meth) acrylonitrile, tri
• an electrode pattern such as a standard IPS comb electrode or a PSA fish bone electrode or a projection pattern such as MVA can be used.
• a highly functional element such as a TFT type element, one in which an element such as a transistor is formed between an electrode for driving liquid crystal and a substrate is used.
• a transmission type liquid crystal display device it is general to use a substrate as described above, but when a reflection type liquid crystal display device is intended, silicon is used if it is only on one side of the substrate.
• An opaque substrate such as a wafer can also be used. At that time, a material such as aluminum that reflects light can also be used for the electrode formed on the substrate.
• Examples of the method of applying the radical generating film-forming composition include spin coating method, printing method, ink jet method, spray method and roll coating method, but from the viewpoint of productivity, transfer printing method is widely used industrially. And are suitably used in the present invention.
• the step of drying after applying the radical generating film-forming composition is not necessarily required, but if the time from application to firing is not constant for each substrate, or if it is not fired immediately after application, drying is performed. It is preferable to include the process.
• the drying is not particularly limited as long as the solvent is removed to such an extent that the coating film shape is not deformed by the transport of the substrate and the like.
• a method of drying on a hot plate at a temperature of 40 ° C. to 150 ° C., preferably 60 ° C. to 100 ° C. for 0.5 to 30 minutes, preferably 1 to 5 minutes can be mentioned.
• the coating film formed by applying the radical generating film-forming composition by the above method can be fired to form a cured film.
• the calcination temperature can be performed usually at any temperature of 100 ° C. to 350 ° C., preferably 140 ° C. to 300 ° C., more preferably 150 ° C. to 230 ° C., further preferably 160 ° C. to 220 ° C. ° C.
• the firing can be carried out usually for any time of 5 minutes to 240 minutes. Preferably, it is 10 to 90 minutes, more preferably 20 to 90 minutes.
• the heating may be carried out by any known method, for example, a hot plate, a hot air circulating oven, an IR oven, a belt furnace or the like.
• the thickness of the cured film can be selected according to need, but is preferably 5 nm or more, more preferably 10 nm or more, since the reliability of the liquid crystal display element can be easily obtained.
• the thickness of the cured film is preferably 300 nm or less, more preferably 150 nm or less, the power consumption of the liquid crystal display element is not extremely large, which is preferable.
• the first substrate having a radical generation film can be obtained, but the radical generation film can be subjected to uniaxial alignment treatment.
• a method of performing uniaxial alignment processing a photo alignment method, an oblique deposition method, rubbing, uniaxial alignment processing by a magnetic field, etc. may be mentioned.
• the substrate is moved so that the rubbing cloth and the film come in contact with each other while rotating the rubbing roller around which the rubbing cloth is wound.
• the direction is selected depending on the electrical properties of the liquid crystal, but in the case of using liquid crystal having positive dielectric anisotropy, the rubbing direction is the comb electrode
• the direction is substantially the same as the direction in which the
• the second substrate of the present invention is the same as the first substrate except that it does not have a radical generating film. It is preferable to set it as the board
• a substrate (first substrate) having the radical generation film and a substrate (second substrate) having a known liquid crystal alignment film are arranged so that the radical generating film and the liquid crystal alignment film face each other, and are fixed with a sealing agent with the spacer interposed therebetween, and a liquid crystal composition containing a liquid crystal, a chiral dopant and a radical polymerizable compound is injected and sealed.
• the size of the spacer used is usually 1 to 30 ⁇ m, preferably 2 to 10 ⁇ m.
• the polymerizable compound used together with the liquid crystal in the preparation of the liquid crystal display device of the present invention is not particularly limited as long as it is a radical polymerizable compound, and for example, a compound having one or more polymerizable unsaturated bonds in one molecule It is.
• it is a compound having one polymerizable unsaturated bond in one molecule (hereinafter, it may be referred to as "compound having a monofunctional polymerizable group", “compound having a monofunctional polymerizable group”, etc. ).
• the polymerizable unsaturated bond is preferably a radically polymerizable unsaturated bond, such as a vinyl bond.
• At least one of the radically polymerizable compounds is preferably a compound having compatibility with liquid crystal and having one polymerizable unsaturated bond in one molecule, that is, a compound having a monofunctional radically polymerizable group. .
• the polymeric group chosen from the following structures is preferable. (Wherein * represents a binding site to a moiety other than the polymerizable unsaturated bond of the compound molecule)
• the polymer obtained by polymerizing the radically polymerizable compound contains a radically polymerizable compound having Tg of 100 ° C. or less. Is preferred.
• the compound having a monofunctional radically polymerizable group is one having an unsaturated bond capable of conducting radical polymerization in the presence of an organic radical, and examples thereof include t-butyl methacrylate, hexyl methacrylate, and 2-ethylhexyl methacrylate.
• Methacrylate monomers such as nonyl methacrylate, lauryl methacrylate and n-octyl methacrylate; acrylate monomers such as t-butyl acrylate, hexyl acrylate, 2-ethylhexyl acrylate, nonyl acrylate, benzyl acrylate, lauryl acrylate and n-octyl acrylate; styrene, Styrene derivatives (eg, o-, m-, p-methoxystyrene, o-, m-, p-t-butoxystyrene, o-, m-, p-chloromethylstyrene, etc.) Vinyl esters (eg, vinyl acetate, vinyl propionate, vinyl benzoate, vinyl acetate etc.), vinyl ketones (eg, vinyl methyl ketone, vinyl hexyl ketone, methyl isopropenyl
• the content of the radically polymerizable compound in the liquid crystal composition is preferably 0.1% by mass or more, more preferably 1% by mass or more, preferably 50% by mass, based on the total mass of the liquid crystal and the radically polymerizable compound. It is at most mass%, more preferably at most 20 mass%.
• the polymer obtained by polymerizing the radically polymerizable compound preferably has a Tg of 100 ° C. or less.
• the liquid crystal generally means a substance in a state showing both solid and liquid properties, and there are nematic liquid crystal and smectic liquid crystal as typical liquid crystal phases, but the liquid crystal usable in the present invention is not particularly limited.
• One example is 4-pentyl-4'-cyanobiphenyl.
• the chiral dopant refers to an optically active compound added in a small amount to nematic liquid crystal to obtain a cholesteric liquid crystal.
• the chiral dopant does not necessarily have to exhibit liquid crystallinity, but may have liquid crystallinity.
• chiral dopants create intermolecular forces that cause nematic liquid crystal molecules to align at a slight angle to one another.
• the helical pitch of the cholesteric liquid crystal can be varied depending on the structure and amount of the chiral dopant.
• non-polymerizable chiral compounds include, for example, R-811, S-811, R-1011, S-1011, R-2011, S-2011, R-3011, S-3011, R Standard chiral dopants such as -4011, S-4011, R-5011, S-5011, or CB15 (Merck), sorbitols as described in WO 98/00428 A1, described in GB 2,328,207 Hydrobenzoins, chiral binaphthols as described in WO 02/94805 A1, chiral binaphthol acetals as described in WO 02/34739 A1, chiral TADDOLs as described in WO 02/06265 A1, Or WO 02/06196 A1 or WO 02 / 6195A1 chiral compounds having fluorinated bridging group as described in.
• polymeric chiral compound polymeric chiral material Paliocolor (trademark) LC756 (BASF company) etc. are mentioned, for example.
• the amount of addition of the chiral dopant needs to be adjusted appropriately depending on the twist angle and twist pitch, but it is usually in the range of 0.001% by mass to 1% by mass.
• the liquid crystal cell in which the liquid crystal and the mixture (liquid crystal composition) containing a chiral dopant and a radical polymerizable compound are introduced is given sufficient energy to cause the radical polymerizable compound to undergo a polymerization reaction.
• This can be carried out, for example, by applying heat or UV irradiation, and the desired properties appear when the radically polymerizable compound is polymerized in situ.
• UV irradiation is preferable in that the use of UV enables orientation patterning and allows a polymerization reaction in a short time.
• the heating temperature at the time of UV irradiation is preferably a temperature range in which the introduced liquid crystal exhibits liquid crystallinity, and is usually 40 ° C. or higher, and heating below the temperature at which the liquid crystal is changed to an isotropic phase is preferable.
• the UV irradiation amount is usually 0.01 to 30 J / cm 2 .
• the UV irradiation amount is usually 0.01 to 30 J / cm 2 .
• the UV irradiation amount there is preferably 10 J / cm 2 or less, and the smaller the UV irradiation amount, the reduction in reliability due to the destruction of the members constituting the liquid crystal display can be suppressed, and the UV irradiation time can be reduced. It is preferable because tact improves. Irradiation may be performed for a long time in a wavelength range including 313 nm.
• heating in the case of polymerization by heating only, not UV irradiation is preferably performed at a temperature at which the polymerizable compound reacts and which is lower than the decomposition temperature of the liquid crystal.
• the temperature is 40 ° C. or more and 100 ° C. or less.
• a liquid crystal display element can be manufactured using the liquid crystal cell obtained in this manner.
• a reflective liquid crystal display element can be obtained by providing a reflective electrode, a transparent electrode, a ⁇ / 4 plate, a polarizing film, a color filter layer and the like according to a conventional method to the liquid crystal cell as necessary.
• a transmissive liquid crystal display device can be obtained by providing a backlight, a polarizing plate, a ⁇ / 4 plate, a transparent electrode, a polarizing film, a color filter layer, and the like according to a conventional method to the liquid crystal cell according to need.
• NMP N-methyl-2-pyrrolidone
• GBL ⁇ -butyl lactone
• BCS Butyl Cellosolve
• ⁇ Viscosity measurement> The viscosity of the polyamic acid solution was measured at 25 ° C. with a sample volume of 1.1 mL and cone rotor TE-1 (1 ° 34 ′, R24) using an E-type viscometer TVE-22H (manufactured by Toki Sangyo Co., Ltd.) .
• the imidation ratio is determined based on a proton derived from a structure which does not change before and after imidization as a reference proton, and a proton integrated value derived from the peak integrated value of this proton and NH of the amide group appearing in the vicinity of 9.5 to 10.0 ppm It calculated
• required by the following formula using value and. Imidation ratio (%) (1 ⁇ ⁇ x / y) ⁇ 100
• x is an integrated value of the proton peak derived from NH of the amide group
• y is a peak integrated value of the reference proton
• ⁇ is a reference proton for one NH proton of the amide group in the case of polyamic acid (imidation ratio is 0%)
• the solid is recovered by filtration, and the solid is further poured into 300 ml of methanol, stirred and washed for a total of 30 minutes twice, collected by filtration, air-dried, and then dried in a vacuum oven at 60 ° C.
• the polyimide (PI-1) having a number average molecular weight of 11,300, a weight average molecular weight of 32,900 and an imidization ratio of 53% was obtained.
• Synthesis example 2 Polymerization of TC-1, TC-2 (50) / DA-1 (50), DA-3 (50) Polyimide
• DA-1 was added in a 100 ml 4-neck flask equipped with a nitrogen inlet tube, air-cooled tube, and mechanical stirrer.
• 1.62 g (15.00 mmol) and 4.96 g (15.00 mmol) of DA-3 were weighed, 51.90 g of NMP was added, and the mixture was stirred under a nitrogen atmosphere and completely dissolved.
• 3.75 g (15.00 mmol) of TC-2 is added, and the mixture is reacted at 60 ° C. for 3 hours under a nitrogen atmosphere.
• the temperature was returned to room temperature again, 2.64 g (13.5 mmol) of TC-1 was added, and reacted at 40 ° C. for 12 hours under a nitrogen atmosphere.
• the polymerization viscosity was confirmed, and TC-1 was further added so that the polymerization viscosity was 1000 mPa ⁇ s, to obtain a polymerization solution having a polyamic acid concentration of 20% by mass.
• the solid is recovered by filtration, and the solid is further poured into 300 ml of methanol, stirred and washed for a total of 30 minutes twice, collected by filtration, air-dried, and then dried in a vacuum oven at 60 ° C.
• Polyimide (PI-2) having a number average molecular weight Mn of 13100, a weight average molecular weight Mw of 34000, and an imidation ratio of 55% was obtained.
• Synthesis example 3 Polymerization of TC-1, TC-2 (50) / DA-1 (50), DA-4 (50) Polyimide
• DA-1 was added in a 100 ml 4-neck flask equipped with a nitrogen inlet tube, air-cooled tube, and mechanical stirrer. 1.62 g (15.00 mmol) and 5.65 g (15.00 mmol) of DA-4 were weighed, 55.4 g of NMP was added, and the mixture was stirred under a nitrogen atmosphere and completely dissolved. After confirmation of dissolution, 3.75 g (15.00 mmol) of TC-2 is added, and the mixture is reacted at 60 ° C. for 3 hours under a nitrogen atmosphere.
• the temperature was returned to room temperature again, 2.82 g (14.40 mmol) of TC-1 was added, and the reaction was performed at 40 ° C. for 12 hours under a nitrogen atmosphere.
• the polymerization viscosity was confirmed, and TC-1 was further added so that the polymerization viscosity was 1000 mPa ⁇ s, to obtain a polymerization solution having a polyamic acid concentration of 20% by mass.
• the solid is recovered by filtration, and the solid is further poured into 300 ml of methanol, stirred and washed for a total of 30 minutes twice, collected by filtration, air-dried, and then dried in a vacuum oven at 60 ° C.
• Polyimide (PI-3) having a number average molecular weight Mn of 12,900, a weight average molecular weight Mw of 31,000 and an imidization ratio of 51% was obtained.
• non-radical generating film forming composition Preparation of non-radical generating film forming composition: AL3 Into a 50 ml Erlenmeyer flask equipped with a magnetic stirrer, 2.0 g of the polyimide powder (PI-3) obtained in Synthesis Example 3 was measured, and 18.0 g of NMP was added, 50 Stir at 0 C to dissolve completely. Further, 6.7 g of NMP and 6.7 g of BCS are added, and the non-radical generating film forming composition to be compared by stirring for 3 hours further: AL3 (solid content: 6.0 mass%, NMP: 66 mass%, BCS: 30% by mass was obtained.
• a liquid crystal display element was produced with the configuration shown in Table 3 using AL1 to AL3 obtained above and SE-6414 (manufactured by Nissan Chemical Industries, Ltd.) which is a liquid crystal aligning agent for horizontal alignment.
• the first substrate (hereinafter also referred to as an IPS substrate) is a non-alkali glass substrate having a size of 30 mm ⁇ 35 mm and a thickness of 0.7 mm.
• An ITO (Indium-Tin-Oxide) electrode having a comb-like pattern having an electrode width of 10 ⁇ m and an electrode-to-electrode distance of 10 ⁇ m is formed on the substrate to form a pixel.
• the size of each pixel is about 10 mm in height and about 5 mm in width.
• AL1 to AL3 or SE-6414 were applied by spin coating on the electrode-forming surface of the IPS substrate, and dried on a hot plate at 80 ° C. for 1 minute.
• the second substrate (also referred to as the back surface ITO substrate) is a non-alkali glass substrate of 30 mm ⁇ 35 mm in size and 0.7 mm in thickness, and an ITO film is formed on the back surface (surface facing the outside of the cell) ing.
• columnar spacers having a height of 4 ⁇ m are formed on the surface (surface facing the inside of the cell).
• SE-6414 was baked at 220 ° C. for 20 minutes, and baked to form a coating having a film thickness of 100 nm, and then rubbing was performed.
• the rubbing process was performed using Yoshikawa Kako Rayon cloth: YA-20R under the conditions of 120 mm roll diameter, 1000 rpm rotation speed, 50 mm / sec moving speed, and 0.4 mm pushing amount.
• the film coated with AL1 or AL2 had the above-mentioned rotational speed of 300 rpm.
• ultrasonic wave irradiation was performed in pure water for 1 minute, and dried at 80 ° C. for 10 minutes.
• a liquid crystal (a product obtained by adding 10 wt% of HMA to MLC-3019 manufactured by Merck Co., Ltd.) was vacuum injected into this empty cell at normal temperature, and then the inlet was sealed to form a liquid crystal cell.
• the obtained liquid crystal cell constitutes an IPS mode liquid crystal display element. Thereafter, the obtained liquid crystal cell was subjected to heat treatment at 120 ° C. for 20 minutes. In the presence of UV treatment, the liquid crystal cell was irradiated with ultraviolet light through a band pass filter with a wavelength of 313 nm using a high pressure mercury lamp so that the exposure amount would be 1000 mJ / cm 2 .
• VT curve and drive threshold voltage maximum luminance voltage evaluation>
• Set the white LED backlight and the luminance meter so that the optical axis is aligned, and set the liquid crystal cell (liquid crystal display element) attached with the polarizing plate between them so that the luminance is the smallest.
• the VT curve was measured by applying and measuring the luminance at the voltage. From the obtained VT curve, values of the driving threshold voltage and the voltage at which the luminance is maximum were estimated.
• a liquid crystal cell was prepared in which AL1 was used for both the back surface ITO substrate (second substrate) and the IPS substrate (first substrate) and both the first and second substrates were not rubbed.
• this liquid crystal cell alignment defects and bright spots (flow alignment) along the flow direction at the time of injection of liquid crystal were observed before UV irradiation, but after UV irradiation, the flow alignment disappeared completely, and domains derived from liquid crystal (Schlieren) was confirmed.
• the radical generating film loses the liquid crystal alignment control power by irradiating UV, and a zero plane anchoring film is formed on the radical generating film. It was suggested that
• a liquid crystal display element was produced with the configuration shown in Table 5 using AL1 to AL3 obtained above and SE-6414 (manufactured by Nissan Chemical Industries, Ltd.) which is a liquid crystal aligning agent for horizontal alignment.
• the first substrate (hereinafter also referred to as an FFS substrate) is a glass substrate having a size of 30 mm ⁇ 35 mm and a thickness of 0.7 mm.
• the IZO electrode which comprises a counter electrode as a 1st layer on the board
• a SiN (silicon nitride) film formed by the CVD method is formed on the first IZO electrode.
• the film thickness of the second SiN film is 500 nm and functions as an interlayer insulating film.
• a comb-like pixel electrode formed by patterning an IZO film as a third layer is disposed on the second-layer SiN film, and the size of the pixel is 10 mm long and about 10 mm wide. At this time, the first opposing electrode and the third pixel electrode are electrically insulated by the action of the second SiN film.
• the width in the short direction of the electrodes is 3 ⁇ m, and the distance between the electrodes is 6 ⁇ m.
• the second substrate (also referred to as the back surface ITO substrate) is a non-alkali glass substrate of 30 mm ⁇ 35 mm in size and 0.7 mm in thickness, and an ITO film is formed on the back surface (surface facing the outside of the cell) ing.
• columnar spacers having a height of 4 ⁇ m are formed on the surface (surface facing the inside of the cell).
• coat apply
• the obtained liquid crystal cell constitutes an FFS mode liquid crystal display element. Thereafter, the obtained liquid crystal cell was subjected to heat treatment at 120 ° C. for 20 minutes. In the presence of UV treatment, the liquid crystal cell was irradiated with ultraviolet light via a high-pass mercury lamp using a high-pressure mercury lamp so that the exposure amount was 5000 mJ / cm 2 in terms of energy at 365 nm through a high pass filter of wavelength 300 nm.
• VT curve and drive threshold voltage, brightness minimum voltage evaluation Set the white LED backlight and the luminance meter so that the optical axis is aligned, and set the liquid crystal cell (liquid crystal display element) attached with the polarizing plate between them so that the luminance is maximum.
• the VT curve was measured by applying and measuring the luminance at the voltage. From the obtained VT curve, the value of the voltage at which the driving threshold voltage and the brightness become minimum was estimated.
• the minimum luminance voltage was 10 V or more, and even if a voltage of 20 V or more was applied, a complete black display was not obtained.
• the zero plane anchoring film can be produced industrially with high yield from inexpensive raw materials.
• the liquid crystal display device obtained by the method of the present invention is useful as a vertical alignment liquid crystal display device such as a PSA type liquid crystal display or an SC-PVA type liquid crystal display.

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