WO2019004433A1 - Method for producing zero-azimuthal anchoring film, and liquid crystal display element - Google Patents
Method for producing zero-azimuthal anchoring film, and liquid crystal display element Download PDFInfo
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- WO2019004433A1 WO2019004433A1 PCT/JP2018/024824 JP2018024824W WO2019004433A1 WO 2019004433 A1 WO2019004433 A1 WO 2019004433A1 JP 2018024824 W JP2018024824 W JP 2018024824W WO 2019004433 A1 WO2019004433 A1 WO 2019004433A1
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- 0 **1CC*CC1 Chemical compound **1CC*CC1 0.000 description 5
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/04—Coating
- C08J7/043—Improving the adhesiveness of the coatings per se, e.g. forming primers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/12—Chemical modification
- C08J7/16—Chemical modification with polymerisable compounds
- C08J7/18—Chemical modification with polymerisable compounds using wave energy or particle radiation
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/04—Coating
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- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells
- G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
- G02F1/1333—Constructional arrangements; Manufacturing methods
- G02F1/1337—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers
Definitions
- the present invention 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.
- a zero plane anchor comprising a step of providing sufficient energy for causing a polymerization reaction of the radically polymerizable compound in a state where the liquid crystal composition containing the liquid crystal and the radically polymerizable compound is in contact with the radical generating film.
- Method of manufacturing ring film [2] The method according to [1], wherein the radical generating film of the first substrate is a uniaxially oriented radical generating film. [3] The method according to [1] or [2], wherein the step of applying energy is performed without an electric field. [4] The method according to any one of [1] to [3], wherein the radical generating film is a film formed by fixing 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 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 inducing the radical polymerization is an organic group represented by the following structures [X-1] to [X-18], [W], [Y] and [Z] [4] and [8] 6] and the method as described in any one of [7].
- R 9 and R 10 are alkyl groups, they may be bonded to each other at their ends to form a ring structure, and Q represents the following structure.
- 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.
- At least one of the radically polymerizable compounds is a compound having one polymerizable reactive group in one molecule, which is compatible with liquid crystal. Method described. [11] The method according to [10], wherein the polymerizable reactive group of the radically polymerizable compound is selected from the following structures. (Wherein, * represents a binding site to a moiety other than the polymerizable reactive group of the compound molecule.
- R b represents a linear alkyl group having 2 to 8 carbon atoms
- E represents a single bond
- -O-, -NR c represents a linking group selected from-, -S-, an ester bond and an amide bond
- R c represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.
- At least one of the radically polymerizable compounds is a compound having one polymerizable reactive group in one molecule, which is compatible with liquid crystal,
- R b represents a linear alkyl group having 2 to 8 carbon atoms
- E represents a single bond
- -O-, -NR c represents a linking group selected from-, -S-, an ester bond and an amide bond
- R c represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.
- 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 excellent characteristics such that the response speed of the liquid crystal at the time of Off is faster than the prior art, and the low driving voltage, no bright spot, and Vcom shift hardly occur. It is possible to provide a liquid crystal display element having the same.
- 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 cell having a liquid crystal composition containing a liquid crystal 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. And a step of providing the cell with sufficient energy to polymerize 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 and a radically 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-18], [W], [Y], and [Z].
- Be In formulas [X-1] to [X-18], * represents a binding site to a moiety other than the polymerizable reactive group of the compound molecule, and S 1 and S 2 are each independently —O— or —NR -, -S-, R represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, R 1 and R 2 each independently represent a hydrogen atom or a halogen Represents an alkyl group having 1 to 4 carbon atoms)
- Ar has an organic group and / or a halogen atom as a substituent
- R 9 and R 10 each independently represent an alkyl
- R 9 and R 10 are alkyl groups, they may be bonded to each other at their ends to form a ring structure, and Q represents the following structure.
- 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 23 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
- the size of the spacer used is usually 1 to 30 ⁇ m, preferably 2 to 10 ⁇ m.
- the rubbing direction of the first substrate can be used for IPS mode or FFS mode, and if arranged so that the rubbing direction is orthogonal, a twisted nematic mode It can be used for
- the method for injecting a liquid crystal and a liquid crystal composition containing a liquid crystal and a radically polymerizable compound is not particularly limited, and a vacuum method in which a mixture containing liquid crystal and a polymerizable compound is injected after reducing the pressure in the produced liquid crystal cell, liquid crystal and polymerization
- the dropping method etc. which seal after dripping the mixture containing an organic compound can be mentioned.
- 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 radically polymerizable compound, and for example, a compound having one or more polymerizable reactive groups in one molecule is there.
- it is a compound having one polymerizable reactive group in one molecule (hereinafter, it may be referred to as "a compound having a monofunctional polymerizable group", "a compound having a monofunctional polymerizable group”, etc.) .
- the polymerizable reactive group is preferably a radical polymerizable reactive group, 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 reactive group in one molecule, that is, a compound having a monofunctional radically polymerizable group.
- the polymeric group chosen from the following structures is preferable.
- * represents a binding site to a moiety other than the polymerizable reactive group of the compound molecule.
- R b represents a linear alkyl group having 2 to 8 carbon atoms
- E represents a single bond
- -O-, -NR c represents a linking group selected from-, -S-, an ester bond and an amide bond
- R c represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.
- liquid crystal composition containing the liquid crystal and the radically polymerizable compound it is preferable to contain a radically polymerizable compound in which the Tg of the polymer obtained by polymerizing the radically polymerizable compound is 100 ° C. or less.
- the compound having a monofunctional radically polymerizable group is a compound having a reactive group capable of performing radical polymerization in the presence of an organic radical, and examples thereof include t-butyl methacrylate, hexyl methacrylate, 2-ethylhexyl methacrylate and nonyl Methacrylate monomers such as 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-,
- R a and R b each independently represent a linear alkyl group having 2 to 8 carbon atoms
- E is a single bond, -O-, -NR c- , -S-, ester bond, amide Represents a linking group selected from a bond.
- R c represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.
- At least one of the radically polymerizable compounds is preferably a compound having compatibility with liquid crystal and having one polymerizable reactive group in one molecule, that is, a compound having a monofunctional radically polymerizable group.
- compounds having the following structures are preferable, but they are not particularly limited.
- R a and R b each independently represent a linear alkyl group having 2 to 8 carbon atoms.
- the content of the radically polymerizable compound in the liquid crystal composition is preferably 3% by mass or more, more preferably 5% by mass or more, and preferably 50% by mass or more, based on the total mass of the liquid crystal and the radically polymerizable compound.
- the following content is more preferably 20% by mass or less.
- 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 liquid crystal cell in which a mixture (liquid crystal composition) containing the liquid crystal and the radically polymerizable compound is introduced.
- 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.
- a chiral dopant may be introduced into the liquid crystal cell as necessary when used in the twisted nematic mode.
- 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, Preferably, it is 10 J or less, and a smaller amount of UV irradiation is preferable because it can suppress the decrease in reliability resulting from the destruction of the members constituting the liquid crystal display, and the tact upon manufacturing can be improved by reducing the UV irradiation time. It is.
- 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 100 ° C. or more and 150 ° 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 according to 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., Inc.) 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.
- 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
- Second step Synthesis of 2- (heptanoyloxymethyl) acrylic acid ethyl ester
- 19.9 g 152 g
- 2-hydroxymethyl acrylic acid obtained by the above method. .9 mmol
- Measure add 300 ml of THF and 23.2 g (229.3 mmol) of triethylamine, add 25.0 g (168.2 mmol) of heptanoyl chloride dropwise while keeping under 10 ° C.
- the precipitated triethylamine hydrochloride is removed by filtration, the reaction solution is concentrated, redissolved in 300 ml of ethyl acetate, and washed three times with 100 ml of 10% aqueous potassium carbonate solution, and 3 times with 50 ml of pure water. The mixture was washed several times, dried over anhydrous magnesium sulfate, filtered and concentrated to obtain a pale yellow viscous material.
- liquid crystal compositions LC-1 to LC-4 are obtained by adding the polymerizable compounds described in the following table to the MLC-3019 in the following amounts.
- liquid crystals (LC-1, LC-2) into which IDBu and IDHex have been introduced and the liquid crystals into which C2C6 and C4C6 have been introduced exhibited very good orientation even when performed at a relatively high degree of vacuum.
- 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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Abstract
Description
このような技術的課題を解決できればパネルメーカーとしても大きなコストメリットとなり、バッテリーの消費抑制や画質の向上等にもメリットとなることが考えられる。
本発明は、上記のような課題を解決するためになされたものであり、ゼロ面アンカリング膜を製造することが可能なポリマー安定化技術を応用した製造方法、及び、常温において、簡便且つ安価な方法で非接触配向と低駆動電圧化とOff時の応答速度も速くすることが同時に実現できる、横電界液晶表示素子およびその製造方法を提供することを目的とする。 On the other hand, there is a problem that occurs in principle in this technology, and firstly, in order to stably generate a polymer brush on a substrate, it is necessary to carry out under very delicate conditions, and considering mass production it is realistic Not to mention. Second, 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. By eliminating the resistance at the time of driving applied to the liquid crystal by making the alignment control force zero, it is expected that the luminance can be improved by the drastic drop of the threshold voltage and the decrease of the alignment failure area at the time of driving. As for 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.
[1] 液晶及びラジカル重合性化合物を含有する液晶組成物を、ラジカル発生膜に接触させた状態で、前記ラジカル重合性化合物を重合反応させるのに十分なエネルギーを与えるステップを含む、ゼロ面アンカリング膜の製造方法。
[2] 前記第一基板の有するラジカル発生膜が一軸配向処理されたラジカル発生膜である[1]に記載の方法。
[3] エネルギーを与えるステップを無電界で行う、[1]又は[2]に記載の方法。
[4] 前記ラジカル発生膜が、ラジカル重合を誘発する有機基が固定化されて成る膜であることを特徴とする[1]~[3]のいずれか一項に記載の方法。
[5] 前記ラジカル発生膜が、ラジカルを発生する基を有する化合物と重合体との組成物を塗布、硬化して膜を形成することにより膜中に固定化させて得られることを特徴とする[1]~[3]のいずれか一項に記載の方法。
[6] 前記ラジカル発生膜が、ラジカル重合を誘発する有機基を含有する重合体から成ることを特徴とする[1]~[3]のいずれか一項に記載の方法。
[7] 前記ラジカル重合を誘発する有機基を含有する重合体が、ラジカル重合を誘発する有機基を含有するジアミンを含むジアミン成分を用いて得られるポリイミド前駆体、ポリイミド、ポリウレアおよびポリアミドから選ばれる少なくとも一種の重合体であることを特徴とする[6]記載の方法。
[8] 前記ラジカル重合を誘発する有機基が下記構造[X-1]~[X-18]、[W]、[Y]、[Z]で表される有機基である[4]、[6]及び[7]のいずれか一項に記載の方法。
(式[X-1]~[X-18]中、*は化合物分子の重合性反応基以外の部分との結合部位を示し、S1、S2はそれぞれ独立して-O-、-NR-、-S-を表し、Rは水素原子、ハロゲン原子、炭素数1~10のアルキル基、炭素数1~10のアルコキシ基を表し、R1,R2はそれぞれ独立して水素原子、ハロゲン原子、炭素数1~4のアルキル基を表す)
(式[W]、[Y]、[Z]中、*は化合物分子の重合性反応基以外の部分との結合部位を示し、Arは有機基及び/又はハロゲン原子を置換基として有しても良いフェニレン、ナフチレン、及びビフェニレンからなる群より選ばれる芳香族炭化水素基を示し、R9及びR10は、それぞれ独立に、炭素数1~10のアルキル基又は炭素数1~10のアルコキシ基を表し、R9とR10がアルキル基の場合、末端で互いに結合し環構造を形成していても良い。Qは下記の構造を表す。
(式中、R11は-CH2-、-NR-、-O-、又は-S-を表し、Rは水素原子又は炭素原子数1~4のアルキル基を表し、*は化合物分子のQ以外の部分との結合部位を示す。)
R12は水素原子、ハロゲン原子、炭素数1~10のアルキル基又は炭素数1~10のアルコキシ基を表す。)
[9] 前記ラジカル重合を誘発する有機基を含有するジアミンが下記一般式(6)又は下記一般式(7)で表される構造を有するジアミンであることを特徴とする[7]記載の方法。
(式(6)中、R6は単結合、-CH2-、-O-、-COO-、-OCO-、-NHCO-、-CONH-、-NH-、-CH2O-、-N(CH3)-、-CON(CH3)-、又は-N(CH3)CO-を表し、
R7は単結合、又は非置換もしくはフッ素原子によって置換されている炭素数1~20のアルキレン基を表し、当該アルキレン基の任意の-CH2-又は-CF2-の1以上は、それぞれ独立に-CH=CH-、二価の炭素環、および二価の複素環から選ばれる基で置き換えられていてもよく、さらに、次に挙げるいずれかの基、すなわち、-O-、-COO-、-OCO-、-NHCO-、-CONH-、又は-NH-が互いに隣り合わないことを条件に、これらの基で置き換えられていてもよい;
R8は、下記式:
から選択されるラジカル重合反応性基を表す。
(式[X-1]~[X-18]中、*は化合物分子のラジカル重合反応性基以外の部分との結合部位を示し、S1、S2はそれぞれ独立して-O-、-NR-、-S-を表し、Rは水素原子、ハロゲン原子、炭素数1~10のアルキル基、炭素数1~10のアルコキシ基を表し、R1,R2はそれぞれ独立して水素原子、ハロゲン原子、炭素数1~4のアルキル基を表す))
(式(7)中、T1及びT2は、それぞれ独立に、単結合、-O-、-S-、-COO-、-OCO-、-NHCO-、-CONH-、-NH-、-CH2O-、-N(CH3)-、-CON(CH3)-、又は-N(CH3)CO-であり、
Sは単結合、又は非置換もしくはフッ素原子によって置換されている炭素数1~20のアルキレン基を表し、当該アルキレン基の任意の-CH2-又は-CF2-の1以上は、それぞれ独立に-CH=CH-、二価の炭素環、および二価の複素環から選ばれる基で置き換えられていてもよく、さらに、次に挙げるいずれかの基、すなわち、-O-、-COO-、-OCO-、-NHCO-、-CONH-、又は-NH-が互いに隣り合わないことを条件に、これらの基で置き換えられていてもよく、
Jは下記式で表される有機基であり、
(式[W]、[Y]、[Z]中、*はT2との結合箇所を表し、Arは有機基及び/又はハロゲン原子を置換基として有しても良いフェニレン、ナフチレン、及びビフェニレンからなる群より選ばれる芳香族炭化水素基を示し、R9及びR10は、それぞれ独立に、炭素数1~10のアルキル基又は炭素数1~10のアルコキシ基を表し、Qは下記の構造を表す。
(式中、R11は-CH2-、-NR-、-O-、又は-S-を表し、Rは水素原子又は炭素原子数1~4のアルキル基を表し、*は化合物分子のQ以外の部分との結合部位を示す。)
R12は水素原子、ハロゲン原子、炭素数1~10のアルキル基又は炭素数1~10のアルコキシ基を表す。))
[10] 前記ラジカル重合性化合物のうち少なくとも一種が、液晶と相溶性を有する、一分子中に一個の重合性反応基を有する化合物である、[1]~[9]のいずれか一項に記載の方法。
[11] 前記ラジカル重合性化合物の重合性反応基が以下の構造から選ばれる、[10]に記載の方法。
(式中、*は化合物分子の重合性反応基以外の部分との結合部位を示す。Rbは炭素数2~8の直鎖アルキル基を表し、Eは単結合、-O-、-NRc-、-S-、エステル結合及びアミド結合から選ばれる結合基を表す。Rcは水素原子、炭素数1~4のアルキル基を示す。)
[12] 前記液晶及びラジカル重合性化合物を含有する液晶組成物において、前記ラジカル重合性化合物を重合させて得られるポリマーのTgが100℃以下のものになるラジカル重合性化合物を含有する液晶組成物を用いることを特徴とする[1]~[11]のいずれか一項に記載の方法。
[13] ラジカル発生膜を有する第一基板と、ラジカル発生膜を有していてもよい第二基板とを用意するステップ、
第一基板上のラジカル発生膜が第二基板に対向するようにセルを作成するステップ、および、
第一基板と第二基板との間に、液晶及びラジカル重合性化合物を含有する液晶組成物を充填するステップを含み、
[1]~[12]のいずれか一項に記載の方法を用いる液晶セルの製造方法。
[14] 前記第二基板がラジカル発生膜を有さない第二基板である[13]に記載の液晶セルの製造方法。
[15] 前記第二基板が、一軸配向性を有する液晶配向膜がコーティングされた基板であることを特徴とする[14]に記載の液晶セルの製造方法。
[16] 前記一軸配向性を有する液晶配向膜が水平配向用の液晶配向膜であることを特徴とする[15]に記載の液晶セルの製造方法。
[17] 前記ラジカル発生膜を有する第一基板が櫛歯電極を有する基板である[13]~[16]のいずれか一項に記載の液晶セルの製造方法。
[18] 液晶及びラジカル重合性化合物を含有し、
前記ラジカル重合性化合物のうち少なくとも一種が、液晶と相溶性を有する、一分子中に一個の重合性反応基を有する化合物であり、
重合性反応基が以下の構造から選ばれる、液晶組成物。
(式中、*は化合物分子の重合性反応基以外の部分との結合部位を示す。Rbは炭素数2~8の直鎖アルキル基を表し、Eは単結合、-O-、-NRc-、-S-、エステル結合及びアミド結合から選ばれる結合基を表す。Rcは水素原子、炭素数1~4のアルキル基を示す。)
[19] [1]~[17]のいずれか一項に記載の方法を用いて得られたゼロ面アンカリング状態を作り出す膜を用いる液晶表示素子の製造方法。
[20] [19]記載の方法を用いて得られた液晶表示素子。
[21] 第一基板又は第二基板が電極を有する、[20]に記載の液晶表示素子。
[22] 低電圧駆動横電界液晶表示素子である、[20]又は[21]に記載の液晶表示素子。 That is, the present invention includes the following.
[1] A zero plane anchor comprising a step of providing sufficient energy for causing a polymerization reaction of the radically polymerizable compound in a state where the liquid crystal composition containing the liquid crystal and the radically polymerizable compound is in contact with the radical generating film. Method of manufacturing ring film.
[2] The method according to [1], wherein the radical generating film of the first substrate is a uniaxially oriented radical generating film.
[3] The method according to [1] or [2], wherein the step of applying energy is performed without an electric field.
[4] The method according to any one of [1] to [3], wherein the radical generating film is a film formed by fixing an organic group that induces radical polymerization.
[5] 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 [1] to [3].
[6] The method according to any one of [1] to [3], wherein the radical generating film comprises a polymer containing an organic group that induces radical polymerization.
[7] 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 method according to [6], which is at least one polymer.
[8] The organic group inducing the radical polymerization is an organic group represented by the following structures [X-1] to [X-18], [W], [Y] and [Z] [4] and [8] 6] and the method as described in any one of [7].
(In formulas [X-1] to [X-18], * represents a binding site to a moiety other than the polymerizable reactive group of the compound molecule, and S 1 and S 2 are each independently —O— or —NR -, -S-, R represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, R 1 and R 2 each independently represent a hydrogen atom or a halogen Represents an alkyl group having 1 to 4 carbon atoms)
(In the formulas [W], [Y] and [Z], * represents a binding site to a moiety other than the polymerizable reactive group of the compound molecule, Ar has an organic group and / or a halogen atom as a substituent R 9 and R 10 each independently represent an alkyl group having 1 to 10 carbon atoms or an alkoxy group having 1 to 10 carbon atoms, each of which is an aromatic hydrocarbon group selected from the group consisting of phenylene, naphthylene and biphenylene. When R 9 and R 10 are alkyl groups, they may be bonded to each other at their ends to form a ring structure, and Q represents the following structure.
(Wherein, R 11 represents —CH 2 —, —NR—, —O— or —S—, R represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and * 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. )
[9] The method according to [7], wherein 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) .
(In the formula (6), 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,
R 7 represents a single bond or an alkylene group having 1 to 20 carbon atoms which is unsubstituted or substituted by a fluorine atom, and one or more of any —CH 2 — or —CF 2 — of the alkylene group are each independently And may be substituted with a group selected from -CH = CH-, a divalent carbocycle, and a divalent heterocycle, and further, any of the following groups, ie, -O-, -COO- , -OCO-, -NHCO-, -CONH- or -NH- may be replaced by these groups, provided that they are not adjacent to each other;
R 8 has the following formula:
And a radical polymerization reactive group selected from
(In formulas [X-1] to [X-18], * represents a binding site to a moiety other than the radical polymerization reactive group of the compound molecule, and S 1 and S 2 are each independently —O—, — And R 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, and R 1 and R 2 each independently represent a hydrogen atom, Halogen atom, represents an alkyl group having 1 to 4 carbon atoms))
(In Formula (7), 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—,
S represents a single bond, or an alkylene group having 1 to 20 carbon atoms which is unsubstituted or substituted by a fluorine atom, and one or more of any —CH 2 — or —CF 2 — of the alkylene group are each independently It may be substituted by a group selected from -CH = CH-, a divalent carbocyclic ring, and a divalent heterocyclic ring, and further, any of the following groups, ie, -O-, -COO-, These groups may be substituted on the condition that -OCO-, -NHCO-, -CONH- or -NH- is not adjacent to each other,
J is an organic group represented by the following formula,
(In the formulas [W], [Y] and [Z], * represents a bonding site to T 2 , Ar represents an organic group and / or a phenylene, naphthylene, and biphenylene which may have a halogen atom as a substituent) And R 9 and R 10 each independently represent an alkyl group having 1 to 10 carbon atoms or an alkoxy group having 1 to 10 carbon atoms, and Q represents a structure shown below Represents
(Wherein, R 11 represents —CH 2 —, —NR—, —O— or —S—, R represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and * 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. )))
[10] In any one of [1] to [9], at least one of the radically polymerizable compounds is a compound having one polymerizable reactive group in one molecule, which is compatible with liquid crystal. Method described.
[11] The method according to [10], wherein the polymerizable reactive group of the radically polymerizable compound is selected from the following structures.
(Wherein, * represents a binding site to a moiety other than the polymerizable reactive group of the compound molecule. R b represents a linear alkyl group having 2 to 8 carbon atoms, E represents a single bond, -O-, -NR c represents a linking group selected from-, -S-, an ester bond and an amide bond, and R c represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.
[12] A liquid crystal composition containing a liquid crystal and a radical polymerizable compound, wherein the polymer obtained by polymerizing the radical polymerizable compound has a Tg of 100 ° C. or less. The method according to any one of [1] to [11], which is characterized in that
[13] preparing a first substrate having a radical generation film and a second substrate which may have the radical generation film;
Creating a cell such that the radical generating film on the first substrate faces the second substrate;
Filling the liquid crystal composition containing a liquid crystal and a radically polymerizable compound between the first substrate and the second substrate,
A method for producing a liquid crystal cell using the method according to any one of [1] to [12].
[14] The method for producing a liquid crystal cell according to [13], wherein the second substrate is a second substrate not having a radical generation film.
[15] The method for producing a liquid crystal cell according to [14], wherein the second substrate is a substrate coated with a liquid crystal alignment film having uniaxial orientation.
[16] The method for producing a liquid crystal cell according to [15], wherein the liquid crystal alignment film having uniaxial alignment property is a liquid crystal alignment film for horizontal alignment.
[17] The method for producing a liquid crystal cell according to any one of [13] to [16], wherein the first substrate having the radical generating film is a substrate having a comb electrode.
[18] containing a liquid crystal and a radically polymerizable compound,
At least one of the radically polymerizable compounds is a compound having one polymerizable reactive group in one molecule, which is compatible with liquid crystal,
A liquid crystal composition, wherein the polymerizable reactive group is selected from the following structures.
(Wherein, * represents a binding site to a moiety other than the polymerizable reactive group of the compound molecule. R b represents a linear alkyl group having 2 to 8 carbon atoms, E represents a single bond, -O-, -NR c represents a linking group selected from-, -S-, an ester bond and an amide bond, and R c represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.
[19] A method for producing a liquid crystal display device using a film that produces a zero plane anchoring state obtained by using the method according to any one of [1] to [17].
[20] A liquid crystal display device obtained by using the method described in [19].
[21] The liquid crystal display device according to [20], wherein the first substrate or the second substrate has an electrode.
[22] The liquid crystal display device according to [20] or [21], which is a low voltage drive horizontal electric field liquid crystal display device.
本発明に用いるラジカル発生膜を形成するためのラジカル発生膜形成組成物は、成分として、重合体を含有し、ラジカルを発生しうる基を含有する。その際、当該組成物は、ラジカルを発生しうる基が結合した重合体を含有するものであってもよいし、ラジカルを発生しうる基を有する化合物と、ベース樹脂となる重合体との組成物であってもよい。このような組成物を塗布、硬化して膜を形成することにより、ラジカルを発生しうる基が膜中に固定化されたラジカル発生膜を得ることができる。ラジカルを発生しうる基は、ラジカル重合を誘発する有機基であることが好ましい。 [Radical Generation Film Forming Composition]
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. At this time, 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. By applying such a composition and curing it to form a film, it is possible to obtain a radical generating film in which a group capable of generating radicals is immobilized in the film. The group capable of generating a radical is preferably an organic group that induces radical polymerization.
(式[X-1]~[X-18]中、*は化合物分子の重合性反応基以外の部分との結合部位を示し、S1、S2はそれぞれ独立して-O-、-NR-、-S-を表し、Rは水素原子、ハロゲン原子、炭素数1~10のアルキル基、炭素数1~10のアルコキシ基を表し、R1,R2はそれぞれ独立して水素原子、ハロゲン原子、炭素数1~4のアルキル基を表す)
(式[W]、[Y]、[Z]中、*は化合物分子の重合性反応基以外の部分との結合部位を示し、Arは有機基及び/又はハロゲン原子を置換基として有しても良いフェニレン、ナフチレン、及びビフェニレンからなる群より選ばれる芳香族炭化水素基を示し、R9及びR10は、それぞれ独立に、炭素数1~10のアルキル基又は炭素数1~10のアルコキシ基を表し、R9とR10がアルキル基の場合、末端で互いに結合し環構造を形成していても良い。Qは下記の構造を表す。
(式中、R11は-CH2-、-NR-、-O-、又は-S-を表し、Rは水素原子又は炭素原子数1~4のアルキル基を表し、*は化合物分子のQ以外の部分との結合部位を示す。)
R12は水素原子、ハロゲン原子、炭素数1~10のアルキル基又は炭素数1~10のアルコキシ基を表す。) Such organic groups that induce radical polymerization include organic groups represented by the following structures [X-1] to [X-18], [W], [Y], and [Z]. Be
(In formulas [X-1] to [X-18], * represents a binding site to a moiety other than the polymerizable reactive group of the compound molecule, and S 1 and S 2 are each independently —O— or —NR -, -S-, R represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, R 1 and R 2 each independently represent a hydrogen atom or a halogen Represents an alkyl group having 1 to 4 carbon atoms)
(In the formulas [W], [Y] and [Z], * represents a binding site to a moiety other than the polymerizable reactive group of the compound molecule, Ar has an organic group and / or a halogen atom as a substituent R 9 and R 10 each independently represent an alkyl group having 1 to 10 carbon atoms or an alkoxy group having 1 to 10 carbon atoms, each of which is an aromatic hydrocarbon group selected from the group consisting of phenylene, naphthylene and biphenylene. When R 9 and R 10 are alkyl groups, they may be bonded to each other at their ends to form a ring structure, and Q represents the following structure.
(Wherein, R 11 represents —CH 2 —, —NR—, —O— or —S—, R represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and * 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. )
(式(6)中、R6は単結合、-CH2-、-O-、-COO-、-OCO-、-NHCO-、-CONH-、-NH-、-CH2O-、-N(CH3)-、-CON(CH3)-、又は-N(CH3)CO-を表し、
R7は単結合、又は非置換もしくはフッ素原子によって置換されている炭素数1~20のアルキレン基を表し、当該アルキレン基の任意の-CH2-又は-CF2-の1以上は、それぞれ独立に-CH=CH-、二価の炭素環、および二価の複素環から選ばれる基で置き換えられていてもよく、さらに、次に挙げるいずれかの基、すなわち、-O-、-COO-、-OCO-、-NHCO-、-CONH-、又は-NH-が互いに隣り合わないことを条件に、これらの基で置き換えられていてもよい;
R8は、下記式:
から選択されるラジカル重合反応性基を表す。
(式[X-1]~[X-18]中、*は化合物分子のラジカル重合反応性基以外の部分との結合部位を示し、S1、S2はそれぞれ独立して-O-、-NR-、-S-を表し、Rは水素原子、ハロゲン原子、炭素数1~10のアルキル基、炭素数1~10のアルコキシ基を表し、R1,R2はそれぞれ独立して水素原子、ハロゲン原子、炭素数1~4のアルキル基を表す) Specifically, 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.
(In the formula (6), 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,
R 7 represents a single bond or an alkylene group having 1 to 20 carbon atoms which is unsubstituted or substituted by a fluorine atom, and one or more of any —CH 2 — or —CF 2 — of the alkylene group are each independently And may be substituted with a group selected from -CH = CH-, a divalent carbocycle, and a divalent heterocycle, and further, any of the following groups, ie, -O-, -COO- , -OCO-, -NHCO-, -CONH- or -NH- may be replaced by these groups, provided that they are not adjacent to each other;
R 8 has the following formula:
And a radical polymerization reactive group selected from
(In formulas [X-1] to [X-18], * represents a binding site to a moiety other than the radical polymerization reactive group of the compound molecule, and S 1 and S 2 are each independently —O—, — And R 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, and R 1 and R 2 each independently represent a hydrogen atom, Represents a halogen atom or an alkyl group having 1 to 4 carbon atoms)
(式中、J1は単結合、-O-、-COO-、-NHCO-、又は-NH-より選ばれる結合基であり、J2は単結合、又は非置換もしくはフッ素原子によって置換されている炭素数1~20のアルキレン基を表す。) Specific examples of the 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)
(式(7)中、T1及びT2は、それぞれ独立に、単結合、-O-、-S-、-COO-、-OCO-、-NHCO-、-CONH-、-NH-、-CH2O-、-N(CH3)-、-CON(CH3)-、又は-N(CH3)CO-であり、
Sは単結合、又は非置換もしくはフッ素原子によって置換されている炭素数1~20のアルキレン基を表し、当該アルキレン基の任意の-CH2-又は-CF2-の1以上は、それぞれ独立に-CH=CH-、二価の炭素環、および二価の複素環から選ばれる基で置き換えられていてもよく、さらに、次に挙げるいずれかの基、すなわち、-O-、-COO-、-OCO-、-NHCO-、-CONH-、又は-NH-が互いに隣り合わないことを条件に、これらの基で置き換えられていてもよく、
Jは下記式で表される有機基であり、
(式[W]、[Y]、[Z]中、*はT2との結合箇所を表し、Arは有機基及び/又はハロゲン原子を置換基として有しても良いフェニレン、ナフチレン、及びビフェニレンからなる群より選ばれる芳香族炭化水素基を示し、R9及びR10は、それぞれ独立に、炭素数1~10のアルキル基又は炭素数1~10のアルコキシ基を表し、Qは下記の構造を表す。
(式中、R11は-CH2-、-NR-、-O-、又は-S-を表し、Rは水素原子又は炭素原子数1~4のアルキル基を表し、*は化合物分子のQ以外の部分との結合部位を示す。)
R12は水素原子、ハロゲン原子、炭素数1~10のアルキル基又は炭素数1~10のアルコキシ基を表す。)) Examples of the diamine which is decomposed by irradiation with ultraviolet light and which has a site where a radical is generated as a side chain include, but not limited to, diamines represented by the following general formula (7).
(In Formula (7), 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—,
S represents a single bond, or an alkylene group having 1 to 20 carbon atoms which is unsubstituted or substituted by a fluorine atom, and one or more of any —CH 2 — or —CF 2 — of the alkylene group are each independently It may be substituted by a group selected from -CH = CH-, a divalent carbocyclic ring, and a divalent heterocyclic ring, and further, any of the following groups, ie, -O-, -COO-, These groups may be substituted on the condition that -OCO-, -NHCO-, -CONH- or -NH- is not adjacent to each other,
J is an organic group represented by the following formula,
(In the formulas [W], [Y] and [Z], * represents a bonding site to T 2 , Ar represents an organic group and / or a phenylene, naphthylene, and biphenylene which may have a halogen atom as a substituent) And R 9 and R 10 each independently represent an alkyl group having 1 to 10 carbon atoms or an alkoxy group having 1 to 10 carbon atoms, and Q represents a structure shown below Represents
(Wherein, R 11 represents —CH 2 —, —NR—, —O— or —S—, R represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and * 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. )))
(式中、nは2~8の整数である。) In particular, in view of easiness of synthesis, height of versatility, characteristics and the like, a structure represented by the following formula is most preferable, but is not limited thereto.
(Wherein n is an integer of 2 to 8)
脂肪族テトラカルボン酸ジエステルの具体的な例としては1,2,3,4-シクロブタンテトラカルボン酸ジアルキルエステル、1,2-ジメチル-1,2,3,4-シクロブタンテトラカルボン酸ジアルキルエステル、1,3-ジメチル-1,2,3,4-シクロブタンテトラカルボン酸ジアルキルエステル、1,2,3,4-テトラメチル-1,2,3,4-シクロブタンテトラカルボン酸ジアルキルエステル、1,2,3,4-シクロペンタンテトラカルボン酸ジアルキルエステル、2,3,4,5-テトラヒドロフランテトラカルボン酸ジアルキルエステル、1,2,4,5-シクロヘキサンテトラカルボン酸ジアルキルエステル、3,4-ジカルボキシ-1-シクロヘキシルコハク酸ジアルキルエステル、3,4-ジカルボキシ-1,2,3,4-テトラヒドロ-1-ナフタレンコハク酸ジアルキルエステル、1,2,3,4-ブタンテトラカルボン酸ジアルキルエステル、ビシクロ[3,3,0]オクタン-2,4,6,8-テトラカルボン酸ジアルキルエステル、3,3’,4,4’-ジシクロヘキシルテトラカルボン酸ジアルキルエステル、2,3,5-トリカルボキシシクロペンチル酢酸ジアルキルエステル、シス-3,7-ジブチルシクロオクタ-1,5-ジエン-1,2,5,6-テトラカルボン酸ジアルキルエステル、トリシクロ[4.2.1.0<2,5>]ノナン-3,4,7,8-テトラカルボン酸-3,4:7,8-ジアルキルエステル、ヘキサシクロ[6.6.0.1<2,7>.0<3,6>.1<9,14>.0<10,13>]ヘキサデカン-4,5,11,12-テトラカルボン酸-4,5:11,12-ジアルキルエステル、4-(2,5-ジオキソテトラヒドロフラン-3-イル)-1,2,3,4-テトラヒドロナフタレンー1,2-ジカルボンジアルキルエステルなどが挙げられる。 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 ester, 2,3,4,5-tetrahydrofuran tetracarboxylic acid dialkyl ester, 1,2,4,5-cyclohexane tetracarboxylic acid dialkyl ester, 3,4-dicarboxy-1 -Cyclohexyl succinic acid dialkyl ester, 3,4- dicarboxy- 2,2,3,4-Tetrahydro-1-naphthalenesuccinic acid dialkyl ester, 1,2,3,4-butanetetracarboxylic acid dialkyl ester, bicyclo [3,3,0] octane-2,4,6,8- Tetracarboxylic acid dialkyl ester, 3,3 ′, 4,4′-dicyclohexyltetracarboxylic acid dialkyl ester, 2,3,5-tricarboxycyclopentylacetic acid dialkyl ester, cis-3,7-dibutylcycloocta-1,5- Diene-1,2,5,6-tetracarboxylic acid dialkyl ester, tricyclo [4.2.1.0 <2,5>] nonane-3,4,7,8-tetracarboxylic acid-3,4: 7 , 8-dialkyl esters, hexacyclo [6.6.0.1 <2,7>. 0 <3, 6>. 1 <9, 14>. 0 <10, 13>] 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.
式中R22、R23は炭素数1~10の脂肪族炭化水素を表す。 There is no particular limitation on the diisocyanate to be reacted with the above-mentioned diamine component in the synthesis when the polymer is polyurea, and it can be used according to the availability etc. The specific structure of diisocyanate is shown below.
In the formula, R 22 and R 23 each represent an aliphatic hydrocarbon having 1 to 10 carbon atoms.
また、一部のジイソシアネートを上記で説明したテトラカルボン酸二無水物に置き換えることもでき、ポリアミック酸とポリウレアの共重合体のような形で使用しても良く、化学イミド化によってポリイミドとポリウレアの共重合体のような形で使用しても良い。 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. Particularly preferred. 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.
In addition, some of the 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.
本発明のラジカル発生膜は、上記ラジカル発生膜形成組成物を用いて得られる。例えば、本発明に用いるラジカル発生膜形成組成物を、基板に塗布した後、乾燥・焼成を行うことで得られる硬化膜を、そのままラジカル発生膜として用いることもできる。また、この硬化膜をラビングしたり、偏光又は特定の波長の光等を照射したり、イオンビーム等の処理をしたり、PSA用配向膜として液晶充填後の液晶表示素子にUVを照射することも可能である。 [Radical generation film]
The radical generating film of the present invention can be obtained using the above radical generating film forming composition. For example, after the composition for forming a radical generation film used in the present invention is applied to a substrate, 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.
具体例を挙げると、ガラス板、ポリカーボネート、ポリ(メタ)アクリレート、ポリエーテルサルホン、ポリアリレート、ポリウレタン、ポリサルホン、ポリエーテル、ポリエーテルケトン、トリメチルペンテン、ポリオレフィン、ポリエチレンテレフタレート、(メタ)アクリロニトリル、トリアセチルセルロース、ジアセチルセルロース、アセテートブチレートセルロースなどのプラスチック板などに透明電極が形成された基板を挙げることができる。 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.
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 There can be mentioned a substrate in which a transparent electrode is formed on a plastic plate of acetyl cellulose, diacetyl cellulose, acetate butyrate cellulose or the like.
また、TFT型の素子のような高機能素子においては、液晶駆動のための電極と基板の間にトランジスタの如き素子が形成されたものが用いられる。
透過型の液晶表示素子を意図している場合は、上記の如き基板を用いることが一般的であるが、反射型の液晶表示素子を意図している場合では、片側の基板のみにならばシリコンウエハー等の不透明な基板も用いることが可能である。その際、基板に形成された電極には、光を反射するアルミニウムの如き材料を用いることもできる。 As a substrate that can be used for a liquid crystal display element of the IPS system, 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.
In addition, as 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.
When a transmission type liquid crystal display device is intended, 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.
本発明の液晶セルは、上記の方法により、基板にラジカル発生膜を形成した後、当該ラジカル発生膜を有する基板(第一基板)と、公知の液晶配向膜を有する基板(第二基板)とを、ラジカル発生膜と液晶配向膜とが向かい合うように配置し、スペーサーを挟んで、シール剤で固定し、液晶及びラジカル重合性化合物を含有する液晶組成物を注入して封止することにより得られる。その際、用いるスペーサーの大きさは通常1~30μmであるが、好ましくは2~10μmである。また、第一基板のラビング方向と、第二基板のラビング方向とを平行にすることにより、IPSモードやFFSモードに使用することができ、ラビング方向が直交するように配置すれば、ツイストネマチックモードに使用することができる。
液晶及びラジカル重合性化合物を含有する液晶組成物を注入する方法は特に制限されず、作製した液晶セル内を減圧にした後、液晶と重合性化合物を含む混合物を注入する真空法、液晶と重合性化合物とを含む混合物を滴下した後に封止を行う滴下法などを挙げることができる。 <Liquid crystal cell>
In the liquid crystal cell of the present invention, after the radical generation film is formed on the substrate by the above method, a substrate (first substrate) having the radical generation film and a substrate (second substrate) having a known liquid crystal alignment film Obtained by arranging the radical generating film and the liquid crystal alignment film to face each other, fixing the spacer with a sealing agent with the spacer interposed therebetween, and injecting and sealing a liquid crystal composition containing a liquid crystal and a radically polymerizable compound. Be In this case, the size of the spacer used is usually 1 to 30 μm, preferably 2 to 10 μm. Also, by making the rubbing direction of the first substrate parallel to the rubbing direction of the second substrate, it can be used for IPS mode or FFS mode, and if arranged so that the rubbing direction is orthogonal, a twisted nematic mode It can be used for
The method for injecting a liquid crystal and a liquid crystal composition containing a liquid crystal and a radically polymerizable compound is not particularly limited, and a vacuum method in which a mixture containing liquid crystal and a polymerizable compound is injected after reducing the pressure in the produced liquid crystal cell, liquid crystal and polymerization The dropping method etc. which seal after dripping the mixture containing an organic compound can be mentioned.
本発明の液晶表示素子の作成において、液晶とともに用いる重合性化合物は、ラジカル重合性化合物であれば特に限定されないが、例えば、一分子中に一個又は二個以上の重合性反応基を有する化合物である。好ましくは一分子中に一個の重合性反応基を有する化合物である(以下、「一官能の重合性基を有する化合物」、「単官能の重合性基を有する化合物」等と称する場合がある)。重合性反応基は、好ましくはラジカル重合性反応基であり、例えばビニル結合である。 <Liquid Crystal Composition Containing Liquid Crystal and Radically Polymerizable Compound>
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 radically polymerizable compound, and for example, a compound having one or more polymerizable reactive groups in one molecule is there. Preferably, it is a compound having one polymerizable reactive group in one molecule (hereinafter, it may be referred to as "a compound having a monofunctional polymerizable group", "a compound having a monofunctional polymerizable group", etc.) . The polymerizable reactive group is preferably a radical polymerizable reactive group, such as a vinyl bond.
(式中、*は化合物分子の重合性反応基以外の部分との結合部位を示す。Rbは炭素数2~8の直鎖アルキル基を表し、Eは単結合、-O-、-NRc-、-S-、エステル結合及びアミド結合から選ばれる結合基を表す。Rcは水素原子、炭素数1~4のアルキル基を示す。) And as a polymeric group of the said radically polymerizable compound, the polymeric group chosen from the following structures is preferable.
(Wherein, * represents a binding site to a moiety other than the polymerizable reactive group of the compound molecule. R b represents a linear alkyl group having 2 to 8 carbon atoms, E represents a single bond, -O-, -NR c represents a linking group selected from-, -S-, an ester bond and an amide bond, and R c represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.
式(1)中、RaおよびRbはそれぞれ独立に炭素数2~8の直鎖アルキル基を表し、Eは単結合、-O-、-NRc-、-S-、エステル結合、アミド結合から選ばれる結合基を表す。文中Rcは水素原子、炭素数1~4のアルキル基を示す。 Moreover, as said radically polymerizable compound, the compound represented by following formula (1) is also preferable.
In formula (1), R a and R b each independently represent a linear alkyl group having 2 to 8 carbon atoms, and E is a single bond, -O-, -NR c- , -S-, ester bond, amide Represents a linking group selected from a bond. In the text, R c represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.
このようにして得られた液晶セルを用いて液晶表示素子を作製することができる。
例えば、この液晶セルに必要に応じて反射電極、透明電極、λ/4板、偏光膜、カラーフィルター層等を常法に従って設けることにより反射型液晶表示素子とすることができる。
また、この液晶セルに必要に応じてバックライト、偏光板、λ/4板、透明電極、偏光膜、カラーフィルター層等を常法に従って設けることにより透過型液晶表示素子とすることができる。 <Liquid crystal display element>
A liquid crystal display element can be manufactured using the liquid crystal cell obtained in this manner.
For example, a reflective liquid crystal display element can be obtained by providing a reflective electrode, a transparent electrode, a λ / 4 plate, a polarizing film, a color filter layer and the like according to a conventional method to the liquid crystal cell as necessary.
In addition, by providing a backlight, a polarizing plate, a λ / 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, a transmissive liquid crystal display device can be obtained.
GBL:γ―ブチルラクトン、
BCS:ブチルセロソルブ NMP: N-methyl-2-pyrrolidone,
GBL: γ-butyl lactone,
BCS: Butyl Cellosolve
ポリアミド酸溶液について、E型粘度計TVE-22H(東機産業社製)を用い、サンプル量1.1mL、コーンロータTE-1(1°34’、R24)にて25℃の粘度を測定した。 <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.) .
ポリイミド粉末20mgをNMRサンプル管(草野科学社製 NMRサンプリングチューブスタンダード φ5)に入れ、重水素化ジメチルスルホキシド(DMSO-d6、0.05質量%TMS(テトラメチルシラン)混合品)0.53mlを添加し、超音波をかけて完全に溶解させた。この溶液の500MHzのプロトンNMRを、測定装置(日本電子データム社製、JNW-ECA500)にて測定した。
イミド化率は、イミド化前後で変化しない構造に由来するプロトンを基準プロトンとして決め、このプロトンのピーク積算値と、9.5~10.0ppm付近に現れるアミド基のNHに由来するプロトンピーク積算値とを用い以下の式によって求めた。
イミド化率(%)=(1-α・x/y)×100
式中、xはアミド基のNH由来のプロトンピーク積算値、yは基準プロトンのピーク積算値、αはポリアミド酸(イミド化率が0%)の場合におけるアミド基のNHプロトン1個に対する基準プロトンの個数割合である。 <Measurement of imidation ratio>
20 mg of polyimide powder is placed in an NMR sample tube (NMR sampling tube standard φ5 manufactured by Kusano Science Co., Ltd.), and 0.53 ml of deuterated dimethyl sulfoxide (DMSO-d6, 0.05 mass% TMS (tetramethylsilane) mixed product) is added The solution was sonicated and completely dissolved. The 500 MHz proton NMR of this solution was measured by a measuring apparatus (JNW-ECA500 manufactured by Nippon Denshi Datum 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−α · x / y) × 100
In the formula, 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, and α is a reference proton for one NH proton of the amide group in the case of polyamic acid (imidation ratio is 0%) The percentage of
合成例1
TC-1、TC-2(50)/DA-1(50)、DA-2(50) ポリイミドの重合
窒素導入管、空冷管、メカニカルスターラーを備えた100mlの4口フラスコに、DA-1を1.62g(15.00mmol)、DA-2を3.96g(15.00mmol)測り取り、NMP48.2gを加え窒素雰囲気下で撹拌し、完全に溶解させた。溶解を確認した後、TC-2を3.75g(15.00mmol)加え、窒素雰囲気下60℃で3時間反応させ。再び室温に戻し、TC-1を2.71g(13.80mmol)を加え、窒素雰囲気下40℃で12時間反応させた。重合粘度を確認し、重合粘度が1000mPa・sになるように更にTC-1を添加し、ポリアミック酸濃度が20質量%の重合液を得た。
マグネティックスターラーを備えた200mlの三角フラスコに、上記で得られたポリアミック酸溶液60gを測り取り、NMPを111.4g加え、7質量%の溶液を調整し、撹拌しながら無水酢酸を9.10g(88.52mmol)、ピリジンを3.76g(47.53mmol)加え、室温で30分撹拌後、55℃で3時間撹拌し反応させた。反応終了後、溶液を室温に戻し、500mlのメタノール中に撹拌しながらこの反応溶液を注ぎ、固体を析出させた。個体をろ過により回収し、更に300mlのメタノール中に固体を投入し30分間撹拌洗浄を計2回行い、固体をろ過により回収し、風乾を行った後、真空オーブン60℃にて乾燥を行うことで数平均分子量は11300、重量平均分子量は32900、イミド化率が53%のポリイミド(PI-1)を得た。 <Polymerization of Polymer and Preparation of Radical Generating Film Forming Composition>
Synthesis example 1
Polymerization of TC-1, TC-2 (50) / DA-1 (50), DA-2 (50) Polyimide In a 100 ml four-necked flask equipped with a nitrogen inlet tube, air-cooled tube, and mechanical stirrer, DA-1 was added. 1.62 g (15.00 mmol) and 3.96 g (15.00 mmol) of DA-2 were weighed, 48.2 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, 2.71 g (13.80 mmol) of TC-1 was added, and 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.
Measure 60 g of the polyamic acid solution obtained above in a 200 ml Erlenmeyer flask equipped with a magnetic stirrer, add 111.4 g of NMP, prepare a 7% by mass solution, and 9.10 g of acetic anhydride while stirring 88.52 mmol) and 3.76 g (47.53 mmol) of pyridine were added and stirred at room temperature for 30 minutes and then reacted at 55 ° C. for 3 hours with stirring. After completion of the reaction, the solution was returned to room temperature, and the reaction solution was poured into 500 ml of methanol with stirring to precipitate a solid. 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.
TC-1、TC-2(50)/DA-1(50)、DA-3(50)ポリイミドの重合
窒素導入管、空冷管、メカニカルスターラーを備えた100mlの4口フラスコに、DA-1を1.62g(15.00mmol)、DA-3を4.96g(15.00mmol)測り取り、NMP51.90gを加え窒素雰囲気下で撹拌し、完全に溶解させた。溶解を確認した後、TC-2を3.75g(15.00mmol)加え、窒素雰囲気下60℃で3時間反応させ。再び室温に戻し、TC-1を2.64g(13.5mmol)加え、窒素雰囲気下40℃で12時間反応させた。重合粘度を確認し、重合粘度が1000mPa・sになるように更にTC-1を添加し、ポリアミック酸濃度が20質量%の重合液を得た。
マグネティックスターラーを備えた200mlの三角フラスコに、上記で得られたポリアミック酸溶液60gを測り取り、NMPを111.4g加え加え、7質量%の溶液を調整し、撹拌しながら無水酢酸を8.38g(81.4mmol)、ピリジンを3.62g(45.8mmol)加え、室温で30分撹拌後、55℃で3時間撹拌し反応させた。反応終了後、溶液を室温に戻し、500mlのメタノール中に撹拌しながらこの反応溶液を注ぎ、固体を析出させた。個体をろ過により回収し、更に300mlのメタノール中に固体を投入し30分間撹拌洗浄を計2回行い、固体をろ過により回収し、風乾を行った後、真空オーブン60℃にて乾燥を行うことで数平均分子量Mnは13100、重量平均分子量Mwは34000、イミド化率が55%のポリイミド(PI-2)を得た。 Synthesis example 2
Polymerization of TC-1, TC-2 (50) / DA-1 (50), DA-3 (50) Polyimide In a 100 ml 4-neck flask equipped with a nitrogen inlet tube, air-cooled tube, and mechanical stirrer, DA-1 was added. 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. 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, 2.64 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.
Measure 60 g of the polyamic acid solution obtained above into a 200 ml Erlenmeyer flask equipped with a magnetic stirrer, add 111.4 g of NMP, add a 7% by mass solution, and while stirring, 8.38 g of acetic anhydride (81.4 mmol) and 3.62 g (45.8 mmol) of pyridine were added and stirred at room temperature for 30 minutes and then reacted at 55 ° C. for 3 hours with stirring. After completion of the reaction, the solution was returned to room temperature, and the reaction solution was poured into 500 ml of methanol with stirring to precipitate a solid. 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.
TC-1、TC-2(50)/DA-1(50)、DA-4(50)ポリイミドの重合
窒素導入管、空冷管、メカニカルスターラーを備えた100mlの4口フラスコに、DA-1を1.62g(15.00mmol)、DA-4を5.65g(15.00mmol)測り取り、NMP55.4gを加え窒素雰囲気下で撹拌し、完全に溶解させた。溶解を確認した後、TC-2を3.75g(15.00mmol)加え、窒素雰囲気下60℃で3時間反応させ。再び室温に戻し、TC-1を2.82g(14.40mmol)加え、窒素雰囲気下40℃で12時間反応させた。重合粘度を確認し、重合粘度が1000mPa・sになるように更にTC-1を添加し、ポリアミック酸濃度が20質量%の重合液を得た。
マグネティックスターラーを備えた200mlの三角フラスコに、上記で得られたポリアミック酸溶液60gを測り取り、NMPを111.4g加え、7質量%の溶液を調整し、撹拌しながら無水酢酸を8.36g(81.2mmol)、ピリジンを3.65g(46.1mmol)加え、室温で30分撹拌後、55℃で3時間撹拌し反応させた。反応終了後、溶液を室温に戻し、500mlのメタノール中に撹拌しながらこの反応溶液を注ぎ、固体を析出させた。個体をろ過により回収し、更に300mlのメタノール中に固体を投入し30分間撹拌洗浄を計2回行い、固体をろ過により回収し、風乾を行った後、真空オーブン60℃にて乾燥を行うことで数平均分子量Mnは12900、重量平均分子量Mwは31000、イミド化率が51%のポリイミド(PI-3)を得た。 Synthesis example 3
Polymerization of TC-1, TC-2 (50) / DA-1 (50), DA-4 (50) Polyimide In a 100 ml 4-neck flask equipped with a nitrogen inlet tube, air-cooled tube, and mechanical stirrer, DA-1 was added. 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.
Measure 60 g of the polyamic acid solution obtained above in a 200 ml Erlenmeyer flask equipped with a magnetic stirrer, add 111.4 g of NMP, prepare a 7% by mass solution, and while stirring, 8.36 g of acetic anhydride ( 81.2 mmol) and 3.65 g (46.1 mmol) of pyridine were added, stirred at room temperature for 30 minutes and then reacted at 55 ° C. for 3 hours with stirring. After completion of the reaction, the solution was returned to room temperature, and the reaction solution was poured into 500 ml of methanol with stirring to precipitate a solid. 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.
マグネティックスターラーを備えた50ml三角フラスコに、合成例1で得られたポリイミド粉末(PI-1)を2.0g測り取り、NMPを18.0g加え、50℃で撹拌し、完全に溶解させた。更にNMPを6.7g、BCSを6.7g加え、更に3時間撹拌することで本発明に係るラジカル発生膜形成組成物:AL1(固形分:6.0質量%、NMP:66質量%、BCS:30質量%)を得た。 Preparation of Radical Generating Film-Forming Composition: Preparation of AL1 In a 50 ml Erlenmeyer flask equipped with a magnetic stirrer, 2.0 g of the polyimide powder (PI-1) obtained in Synthesis Example 1 was weighed out, 18.0 g of NMP was added, and the temperature was 50.degree. The solution was completely dissolved. Further, 6.7 g of NMP and 6.7 g of BCS are added, and the mixture is further stirred for 3 hours to form a radical generating film-forming composition according to the present invention: AL1 (solid content: 6.0 mass%, NMP: 66 mass%, BCS : 30% by mass) was obtained.
マグネティックスターラーを備えた50ml三角フラスコに、合成例2で得られたポリイミド粉末(PI-2)を2.0g測り取り、NMPを18.0g加え、50℃で撹拌し、完全に溶解させた。更にNMPを6.7g、BCSを6.7g加え、更に3時間撹拌することで本発明に係るラジカル発生膜形成組成物:AL2(固形分:6.0質量%、NMP:66質量%、BCS:30質量%)を得た。 Preparation of Radical-Generating Film-Forming Composition: Preparation of AL2 In a 50 ml Erlenmeyer flask equipped with a magnetic stirrer, 2.0 g of the polyimide powder (PI-2) obtained in Synthesis Example 2 was weighed out, 18.0 g of NMP was added, and 50 ° C. The solution was completely dissolved. Further, 6.7 g of NMP and 6.7 g of BCS are added, and the mixture is further stirred for 3 hours to form a radical generating film-forming composition according to the present invention: AL2 (solid content: 6.0 mass%, NMP: 66 mass%, BCS : 30% by mass) was obtained.
マグネティックスターラーを備えた50ml三角フラスコに、合成例3で得られたポリイミド粉末(PI-3)を2.0g測り取り、NMPを18.0g加え、50℃で撹拌し、完全に溶解させた。更にNMPを6.7g、BCSを6.7g加え、更に3時間撹拌することで比較対象とする非ラジカル発生膜形成組成物:AL3(固形分:6.0質量%、NMP:66質量%、BCS:30質量%)を得た。 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.
上記で得たAL1~AL3及び水平配向用の液晶配向剤であるSE-6414(日産化学工業株式会社製)を用い、表3に示す構成で液晶表示素子を作製した。 <Production of Liquid Crystal Display Element>
A liquid crystal display element was produced according to 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.
第一基板(以後IPS基板ともいう)は、30mm×35mmの大きさで、厚さが0.7mmの無アルカリガラス基板である。基板上には電極幅が10μm、電極と電極の間隔が10μmの櫛歯型パターンを備えたITO(Indium-Tin-Oxide)電極が形成され、画素を形成している。各画素のサイズは、縦10mmで横約5mmである。
AL1~AL3又はSE-6414は、1.0μmのフィルターで濾過した後、上記IPS基板の電極形成面にスピンコート法にて塗布し、80℃のホットプレート上で1分間乾燥させた。次いで、AL1~AL3は150℃で20分間、SE-6414は220℃で20分焼成し、焼成して、それぞれ膜厚100nmの塗膜とした。
ラビング処理「有り」では、ラビング方向が櫛歯電極と平行になるようにラビングした。ラビングは吉川化工製のレーヨン布:YA-20Rを用い、ロール径120mm、回転数300rpm、移動速度50mm/sec、押し込み量0.4mmの条件にて行った。ただし、SE-6414を塗布した膜のみ上記の回転数を1000rpmにした。ラビング処理後は、純水中にて1分間超音波照射を行い、80℃で10分間乾燥した。 (First board)
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 μm and an electrode-to-electrode distance of 10 μm 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.
After filtering through a 1.0 μm filter, 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. Subsequently, AL1 to AL3 were baked at 150 ° C. for 20 minutes, and SE-6414 was baked at 220 ° C. for 20 minutes, and baked to form a coating film having a film thickness of 100 nm.
In the rubbing process “present”, rubbing was performed so that the rubbing direction was parallel to the comb electrode. Rubbing was performed using Yoshikawa Kako Rayon cloth: YA-20R, under conditions of 120 mm roll diameter, 300 rpm rotation speed, 50 mm / sec moving speed, and 0.4 mm pushing amount. However, the above-mentioned rotational speed was set to 1000 rpm only for the film coated with SE-6414. After rubbing treatment, ultrasonic wave irradiation was performed in pure water for 1 minute, and dried at 80 ° C. for 10 minutes.
第二基板(裏面ITO基板ともいう)は、30mm×35mmの大きさで、厚さが0.7mmの無アルカリガラス基板であり、裏面(セルの外側を向く面)にITO膜が成膜されている。また、表面(セルの内側を向く面)には高さ4μmの柱状のスペーサーが形成されている。
AL1、AL2又はSE-6414は、1.0μmのフィルターで濾過した後、上記IPS基板の電極形成面にスピンコート法にて塗布し、80℃のホットプレート上で1分間乾燥させた。次いで、AL1、AL2は150℃で20分間、SE-6414は220℃で20分焼成し、焼成して、それぞれ膜厚100nmの塗膜とした後、ラビング処理を行った。ラビング処理は、吉川化工製のレーヨン布:YA-20Rを用い、ロール径120mm、回転数1000rpm、移動速度50mm/sec、押し込み量0.4mmの条件にてラビングを行った。ただし、AL1またはAL2を塗布した膜は上記の回転数を300rpmにした。ラビング処理後は、純水中にて1分間超音波照射を行い、80℃で10分間乾燥した。 (Second board)
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. In addition, columnar spacers having a height of 4 μm are formed on the surface (surface facing the inside of the cell).
After filtering AL1, AL2 or SE-6414 with a filter of 1.0 μm, it was applied by spin coating on the electrode formation surface of the IPS substrate and dried on a hot plate at 80 ° C. for 1 minute. Next, AL1 and AL2 were baked at 150 ° C. for 20 minutes, and 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. However, the film coated with AL1 or AL2 had the above-mentioned rotational speed of 300 rpm. After rubbing treatment, ultrasonic wave irradiation was performed in pure water for 1 minute, and dried at 80 ° C. for 10 minutes.
上記液晶配向膜付きの2種類の基板(第一基板及び第二基板)を用い、液晶注入口を残して周囲をシールし、セルギャップが約4μmの空セルを作製した。この際、第一基板がラビング処理していない場合は、第一基板の櫛歯電極の向きと第二基板のラビング方向が平行になるように組み合わせ、第一基板をラビング処理した場合は、第一基板と第二基板のラビング方向が逆平行になるように組み合わせた。
この空セルに、液晶(メルク社製MLC-3019にHMAを10wt%添加したもの)を常温で真空注入した後、注入口を封止して液晶セルとした。得られた液晶セルは、IPSモード液晶表示素子を構成する。その後、得られた液晶セルを120℃で20分加熱処理を行った。
UV処理ありでは、高圧水銀ランプを用い波長313nmのバンドパスフィルター介して露光量が1000mJとなるよう液晶セルに紫外線を照射した。 (Preparation of liquid crystal cell)
Using the two types of substrates (first and second substrates) with the liquid crystal alignment film, the periphery was sealed leaving a liquid crystal injection port, and a vacant cell having a cell gap of about 4 μm was produced. At this time, in the case where the first substrate is not subjected to the rubbing process, the first substrate is rubbed in combination such that the direction of the comb electrode of the first substrate and the rubbing direction of the second substrate become parallel. The rubbing directions of one substrate and the second substrate were combined so as to be antiparallel.
A liquid crystal (a product obtained by adding 10 wt% of HMA to MLC-3019 manufactured by Merck & Co., Inc.) 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.
クロスニコルにセットした偏光板を用いて液晶セルの配向性を確認した。欠陥無く配向しているものは○、軽微な配向欠陥のあるものは△、配向していないものは×とした。 <Evaluation of liquid crystal alignment>
The orientation of the liquid crystal cell was confirmed using the polarizing plate set in cross nicol. Those with no defects were rated ○, those with minor orientation defects were △, and those without orientation were x.
光軸が合うように白色LEDバックライトと輝度計をセットし、その間に、輝度が最も小さくなるように偏光板を取り付けた液晶セル(液晶表示素子)をセットし、1V間隔で8Vまで電圧を印加し、電圧における輝度を測定することでV-Tカーブの測定を行った。得られたV-Tカーブから駆動閾値電圧と輝度が最大になる電圧の値を見積もった。 <Measurement of 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.
上記V-Tカーブの測定で使用した装置を用い、輝度計をオシロスコープに接続し、最大輝度になる電圧を印加した際の応答速度(Ton)および電圧を0にした際の応答速度(Toff)を測定した。 <Evaluation of response speed of liquid crystal display>
Using the device used to measure the VT curve above, connect a luminance meter to an oscilloscope and respond speed (Ton) when applying a voltage that produces maximum luminance and response speed (Toff) when voltage is set to 0. Was measured.
2-(ヘプタノイルオキシメチル)アクリル酸 エチルエステルの合成
第1工程:2-ヒドロキシメチルアクリル酸エチルエステルの合成
窒素導入管を取り付けた500mlの四口フラスコに、4-メトキシフェノール10mg、DABCO(1,4-ジアザビシクロ[2.2.2]オクタン)21.88g(195.1mmol)を計り取り、純水を50ml加え、窒素雰囲気下で10℃以下で攪拌しながらパラホルムアルデヒド11.52g(390.1mmol)を加え、1時間攪拌した。スラリー状態から溶液状態に変化したのを確認し、アセトニトリルを300ml加え、アクリル酸エチル19.53g(195.1mmol)を滴下しながら加え、50℃で5時間反応させた。反応終了後、分液ロートに反応溶液を移し、n-ヘキサン50mlを加えた。3層に分かれたのを確認し、下の2層を回収し、この操作を3回行った。更にpHが4~5になるように塩酸を加え、酢酸エチルを用いて抽出を行った。抽出した溶液に無水硫酸マグネシウムを加え攪拌し乾燥させた後、濾過・濃縮を行い、無色透明のオイル状液体22.9g(175.6mmol、収率90%)を得た。構造は核磁気共鳴スペクトル(1H-NMRスペクトル)にて目的物であることを確認した。測定データを以下に示す。
1H NMR (400 MHz,CDCl3)δ:6.81(1H)、5.80(1H)、4.31(2H)、4.17(1H)、1.98(1H)、0.93(3H) Polymerizable Compound Synthesis Example 1
Synthesis of 2- (Heptanoyloxymethyl) acrylic acid ethyl ester
Step 1: Synthesis of 2-hydroxymethyl acrylic acid ethyl ester In a 500 ml four-necked flask fitted with a nitrogen introduction tube, 10 mg of 4-methoxyphenol, DABCO (1,4-diazabicyclo [2.2.2] octane) 21 .88 g (195.1 mmol) was weighed, 50 ml of pure water was added, and 11.52 g (390.1 mmol) of paraformaldehyde was added while stirring at 10 ° C. or less under a nitrogen atmosphere, and stirred for 1 hour. It was confirmed that the slurry state changed to a solution state, 300 ml of acetonitrile was added, 19.53 g (195.1 mmol) of ethyl acrylate was added dropwise, and the reaction was allowed to proceed at 50 ° C. for 5 hours. After completion of the reaction, the reaction solution was transferred to a separatory funnel, and 50 ml of n-hexane was added. It confirmed that it divided into 3 layers, 2 lower layers were collect | recovered, and this operation was performed 3 times. Further, hydrochloric acid was added so that the pH was 4-5, and extraction was performed using ethyl acetate. The extracted solution was added with anhydrous magnesium sulfate, stirred, dried, filtered and concentrated to obtain 22.9 g (175.6 mmol, yield 90%) of a colorless and transparent oily liquid. The structure was confirmed to be the desired product by nuclear magnetic resonance spectrum ( 1 H-NMR spectrum). The measurement data is shown below.
1 H NMR (400 MHz, CDCl 3 ) δ: 6.81 (1 H), 5.80 (1 H), 4.31 (2 H), 4.17 (1 H), 1.98 (1 H), 0.93 (3H)
窒素導入管を取り付けた500mlの4口フラスコに、上記方法にて得られた2-ヒドロキシメチルアクリル酸を19.9g(152.9mmol)計り取り、THF300ml、トリエチルアミン23.2g(229.3mmol)を加え、窒素雰囲気下10℃以下に保ちながらヘプタノイルクロリド25.0g(168.2mmol)を滴下しながら加え、6時間反応させた。反応終了後、析出したトリエチルアミン塩酸塩を濾過にて除去し、反応溶液を濃縮させ、酢酸エチル300mlにて再溶解させ、10%炭酸カリウム水溶液100mlにて3回洗浄し、純水50mlにて3回洗浄し、無水硫酸マグネシウムにて乾燥させた後、濾過・濃縮を行い薄黄色の粘体を得た。更にフラッシュカラムクロマトグラフィー(展開溶媒:酢酸エチル:n-ヘキサン=20:80)にて精製し、溶媒除去・真空乾燥を行うことで無色透明のオイル状液体32.2g(133.0mmol:収率87%)を得た。構造は核磁気共鳴スペクトル(1H-NMRスペクトル)にて目的物であることを確認した。測定データを以下に示す。
1H NMR (400 MHz,CDCl3)δ:6.37(1H)、5.80(1H)、3.80(2H)、4.23-4.21(2H)、2.39-2.37(2H)、1.64-1.58(2H)、1.30-1.27(9H)、0.86(3H) Second step: Synthesis of 2- (heptanoyloxymethyl) acrylic acid ethyl ester In a 500 ml four-necked flask equipped with a nitrogen introduction tube, 19.9 g (152 g) of 2-hydroxymethyl acrylic acid obtained by the above method. .9 mmol) Measure, add 300 ml of THF and 23.2 g (229.3 mmol) of triethylamine, add 25.0 g (168.2 mmol) of heptanoyl chloride dropwise while keeping under 10 ° C. under nitrogen atmosphere, and react for 6 hours The After completion of the reaction, the precipitated triethylamine hydrochloride is removed by filtration, the reaction solution is concentrated, redissolved in 300 ml of ethyl acetate, and washed three times with 100 ml of 10% aqueous potassium carbonate solution, and 3 times with 50 ml of pure water. The mixture was washed several times, dried over anhydrous magnesium sulfate, filtered and concentrated to obtain a pale yellow viscous material. Further, purification is conducted by flash column chromatography (developing solvent: ethyl acetate: n-hexane = 20: 80), and solvent removal and vacuum drying are carried out to obtain a colorless transparent oil 32.2 g (133.0 mmol: yield) 87%). The structure was confirmed to be the desired product by nuclear magnetic resonance spectrum ( 1 H-NMR spectrum). The measurement data is shown below.
1 H NMR (400 MHz, CDCl 3 ) δ: 6.37 (1 H), 5.80 (1 H), 3.80 (2 H), 4.23-4.21 (2 H), 2.39-2. 37 (2H), 1.64-1.58 (2H), 1.30-1.27 (9H), 0.86 (3H)
2-(ヘプタノイルオキシメチル)アクリル酸 ブチルエステルの合成
第1工程:2-ヒドロキシメチルアクリル酸ブチルエステルの合成
前記第1工程と同様の操作にて、エチルアクリレートをブチルアクリレートに変更し合成を行い、無色透明のオイル24.3gを得た(26.2g:収率85%)。構造は核磁気共鳴スペクトル(1H-NMRスペクトル)にて目的物であることを確認した。測定データを以下に示す。
1H NMR (400 MHz,CDCl3)δ:6.81(1H)、5.80(1H)、4.31(2H)、4.17(1H)、1.98(1H)、1.67-1.64(2H)、1.42-1.38(2H)、0.93(3H) Polymerizable Compound Synthesis Example 2
Synthesis of 2- (heptanoyloxymethyl) acrylic acid butyl ester
Step 1: Synthesis of 2-hydroxymethyl acrylic acid butyl ester In the same operation as the first step, ethyl acrylate was changed to butyl acrylate to carry out synthesis to obtain 24.3 g of a colorless and transparent oil (26. 2 g: yield 85%). The structure was confirmed to be the desired product by nuclear magnetic resonance spectrum ( 1 H-NMR spectrum). The measurement data is shown below.
1 H NMR (400 MHz, CDCl 3 ) δ: 6.81 (1 H), 5.80 (1 H), 4.31 (2 H), 4.17 (1 H), 1.98 (1 H), 1.67 -1.64 (2H), 1.42-1.38 (2H), 0.93 (3H)
前記第2工程の2-ヒドロキシメチルアクリル酸を上記方法にて得られた2-((ヘプタノイロキシ)メチル)アクリル酸 ブチルエステルに変えて、同様の操作にて合成を行い、無色透明のオイル状液体34.2g(126.7:収率82.8%)を得た。構造は核磁気共鳴スペクトル(1H-NMRスペクトル)にて目的物であることを確認した。測定データを以下に示す。
1H NMR (400 MHz,CDCl3)δ:6.36(1H)、5.81(1H)、4.80(2H)、4.19-4.16(2H)、2.35-2.31(2H)、1.64-1.58(4H)、1.40-1.25(8H)、0.96-0.83(6H) Second Step: Synthesis of 2- (Heptanoyloxymethyl) Acrylic Acid Butyl Ester The 2-hydroxymethyl acrylic acid of the second step is converted to the 2-((heptanoyloxy) methyl) acrylic acid butyl ester obtained by the above method. In the same manner, synthesis was carried out using the same procedure to obtain 34.2 g (126.7: yield 82.8%) of a colorless and transparent oily liquid. The structure was confirmed to be the desired product by nuclear magnetic resonance spectrum ( 1 H-NMR spectrum). The measurement data is shown below.
1 H NMR (400 MHz, CDCl 3 ) δ: 6.36 (1 H), 5.81 (1 H), 4.80 (2 H), 4.19-4.16 (2 H), 2.35-2. 31 (2H), 1.64-1.58 (4H), 1.40-1.25 (8H), 0.96-0.83 (6H)
イタコン酸ジヘキシルの合成
ディーンスターク管を取り付けた4口フラスコに、イタコン酸23.8g(182.9mmol)、1-ヘキサノール35.5g(347.5mmol)を計り取り、シクロヘキサン500ml、濃硫酸0.9g(9.1mmol)、ジブチルヒドロキシトルエン(BHT)0.04g(1.82mmol)を加え、窒素雰囲気にし、110℃にて24時間脱水縮合反応させた。反応終了後、反応溶液にn-ヘキサンを100ml加え、10%炭酸ナトリウム水溶液100gで3回、純水100mlにて3回洗浄し、無水硫酸マグネシウムで乾燥させた。濾過・濃縮後真空乾燥させることで無色透明のオイル状液体48.6g(162.8mmol:収率89%)を得た。構造は核磁気共鳴スペクトル(1H-NMRスペクトル)にて目的物であることを確認した。測定データを以下に示す。
1H NMR (400 MHz,CDCl3)δ:6.30(1H)、5.65(1H)、4.20―4.00(4H)、3.32(2H)、1.64-1.58(4H)、1.40-1.25(12H)、0.96-0.83(6H) Polymerizable Compound Synthesis Example 3
Synthesis of dihexyl itaconate
In a four-necked flask fitted with a Dean-Stark tube, 23.8 g (182.9 mmol) of itaconic acid and 35.5 g (347.5 mmol) of 1-hexanol were weighed, 500 ml of cyclohexane, 0.9 g (9.1 mmol) of concentrated sulfuric acid Then, 0.04 g (1.82 mmol) of dibutylhydroxytoluene (BHT) was added, and a nitrogen atmosphere was set, and a dehydration condensation reaction was performed at 110 ° C. for 24 hours. After completion of the reaction, 100 ml of n-hexane was added to the reaction solution, and the mixture was washed three times with 100 g of a 10% aqueous sodium carbonate solution and three times with 100 ml of pure water, and dried over anhydrous magnesium sulfate. After filtration and concentration, vacuum drying was carried out to obtain 48.6 g (162.8 mmol: yield 89%) of a colorless and transparent oily liquid. The structure was confirmed to be the desired product by nuclear magnetic resonance spectrum ( 1 H-NMR spectrum). The measurement data is shown below.
1 H NMR (400 MHz, CDCl 3 ) δ: 6.30 (1 H), 5.65 (1 H), 4.20 to 4.00 (4 H), 3.32 (2 H), 1.64-1. 58 (4H), 1.40-1.25 (12H), 0.96-0.83 (6H)
前記(液晶セルの作成)に準じて空セルを作成した後、この空セルに、液晶組成物LC-1~LC-4(メルク社製MLC-3019に上記重合性化合物をそれぞれの最適量にて添加したもの)を、室温下で約300Paほどの真空度にて真空注入を行ったものと、1Paほどの真空度で1時間脱気を行った後真空注入したものを作成し、注入口を封止して液晶セルとした。得られた液晶セルは、IPSモード液晶表示素子を構成する。その後、得られた液晶セルを120℃で10分加熱処理を行った。あとは、前記と同様に試験を行った。 (Preparation of liquid crystal cell)
After preparing an empty cell according to the above (preparation of liquid crystal cell), the above-mentioned polymerizable compounds are respectively added to the optimum amount of liquid crystal compositions LC-1 to LC-4 (Merck MLC-3019) in this empty cell. Added at a vacuum of about 300 Pa at room temperature, and after vacuum degassing at a vacuum of about 1 Pa for 1 hour, and then the injection port 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 10 minutes. The rest was tested in the same manner as described above.
次に、前記でゼロアンカリング配向した液晶を用いたセルのうち、ラジカル発生膜をラビングしていないものとしたものの駆動閾値電圧、最大輝度時の電圧、応答速度をまとめたものを以下に示す。
Next, among the cells using the liquid crystal with zero anchoring orientation described above, the driving threshold voltage, the voltage at the maximum luminance, and the response speed are summarized below although the radical generating film is not rubbed. .
よって、重合性化合物は高真空下でのゼロアンカリング化とラビングによる応答速度向上の効果が同時に得られることが分かった。 When the polymerizable compound was used, a decrease in driving voltage was confirmed regardless of the presence or absence of the rubbing treatment, and the response speed was also likely to be improved by performing the rubbing treatment.
Therefore, it was found that the polymerizable compound was able to simultaneously obtain the effects of zero anchoring under high vacuum and response speed improvement by rubbing.
Claims (22)
- 液晶及びラジカル重合性化合物を含有する液晶組成物を、ラジカル発生膜に接触させた状態で、前記ラジカル重合性化合物を重合反応させるのに十分なエネルギーを与えるステップを含む、ゼロ面アンカリング膜の製造方法。 A zero plane anchoring film comprising a step of providing sufficient energy for causing a polymerization reaction of the radical polymerizable compound in a state where the liquid crystal composition containing the liquid crystal and the radical polymerizable compound is in contact with the radical generating film. Production method.
- 前記第一基板の有するラジカル発生膜が一軸配向処理されたラジカル発生膜である請求項1に記載の方法。 The method according to claim 1, wherein the radical generating film of the first substrate is a uniaxially oriented radical generating film.
- エネルギーを与えるステップを無電界で行う、請求項1又は2に記載の方法。 The method according to claim 1 or 2, wherein the step of applying energy is performed without an electric field.
- 前記ラジカル発生膜が、ラジカル重合を誘発する有機基が固定化されて成る膜であることを特徴とする請求項1~3のいずれか一項に記載の方法。 The method according to any one of claims 1 to 3, wherein the radical generating film is a film in which an organic group that induces radical polymerization is immobilized.
- 前記ラジカル発生膜が、ラジカルを発生する基を有する化合物と重合体との組成物を塗布、硬化して膜を形成することにより膜中に固定化させて得られることを特徴とする請求項1~3のいずれか一項に記載の方法。 The radical generating film may be 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 to 3.
- 前記ラジカル発生膜が、ラジカル重合を誘発する有機基を含有する重合体から成ることを特徴とする請求項1~3のいずれか一項に記載の方法。 The method according to any one of claims 1 to 3, wherein the radical generating film comprises a polymer containing an organic group which induces radical polymerization.
- 前記ラジカル重合を誘発する有機基を含有する重合体が、ラジカル重合を誘発する有機基を含有するジアミンを含むジアミン成分を用いて得られるポリイミド前駆体、ポリイミド、ポリウレアおよびポリアミドから選ばれる少なくとも一種の重合体であることを特徴とする請求項6記載の方法。 The polymer containing an organic group that induces radical polymerization is at least one selected from a polyimide precursor, a polyimide, a polyurea and a polyamide obtained using a diamine component containing a diamine containing an organic group that induces radical polymerization The method according to claim 6, which is a polymer.
- 前記ラジカル重合を誘発する有機基が下記構造[X-1]~[X-18]、[W]、[Y]、[Z]で表される有機基である請求項4、6及び7のいずれか一項に記載の方法。
(式[X-1]~[X-18]中、*は化合物分子の重合性反応基以外の部分との結合部位を示し、S1、S2はそれぞれ独立して-O-、-NR-、-S-を表し、Rは水素原子、ハロゲン原子、炭素数1~10のアルキル基、炭素数1~10のアルコキシ基を表し、R1,R2はそれぞれ独立して水素原子、ハロゲン原子、炭素数1~4のアルキル基を表す)
(式[W]、[Y]、[Z]中、*は化合物分子の重合性反応基以外の部分との結合部位を示し、Arは有機基及び/又はハロゲン原子を置換基として有しても良いフェニレン、ナフチレン、及びビフェニレンからなる群より選ばれる芳香族炭化水素基を示し、R9及びR10は、それぞれ独立に、炭素数1~10のアルキル基又は炭素数1~10のアルコキシ基を表し、R9とR10がアルキル基の場合、末端で互いに結合し環構造を形成していても良い。Qは下記の構造を表す。
(式中、R11は-CH2-、-NR-、-O-、又は-S-を表し、Rは水素原子又は炭素原子数1~4のアルキル基を表し、*は化合物分子のQ以外の部分との結合部位を示す。)
R12は水素原子、ハロゲン原子、炭素数1~10のアルキル基又は炭素数1~10のアルコキシ基を表す。) The organic group which induces the radical polymerization is an organic group represented by the following structures [X-1] to [X-18], [W], [Y] and [Z]. The method according to any one of the preceding claims.
(In formulas [X-1] to [X-18], * represents a binding site to a moiety other than the polymerizable reactive group of the compound molecule, and S 1 and S 2 are each independently —O— or —NR -, -S-, R represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, R 1 and R 2 each independently represent a hydrogen atom or a halogen Represents an alkyl group having 1 to 4 carbon atoms)
(In the formulas [W], [Y] and [Z], * represents a binding site to a moiety other than the polymerizable reactive group of the compound molecule, Ar has an organic group and / or a halogen atom as a substituent R 9 and R 10 each independently represent an alkyl group having 1 to 10 carbon atoms or an alkoxy group having 1 to 10 carbon atoms, each of which is an aromatic hydrocarbon group selected from the group consisting of phenylene, naphthylene and biphenylene. When R 9 and R 10 are alkyl groups, they may be bonded to each other at their ends to form a ring structure, and Q represents the following structure.
(Wherein, R 11 represents —CH 2 —, —NR—, —O— or —S—, R represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and * 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. ) - 前記ラジカル重合を誘発する有機基を含有するジアミンが下記一般式(6)又は下記一般式(7)で表される構造を有するジアミンであることを特徴とする請求項7記載の方法。
(式(6)中、R6は単結合、-CH2-、-O-、-COO-、-OCO-、-NHCO-、-CONH-、-NH-、-CH2O-、-N(CH3)-、-CON(CH3)-、又は-N(CH3)CO-を表し、
R7は単結合、又は非置換もしくはフッ素原子によって置換されている炭素数1~20のアルキレン基を表し、当該アルキレン基の任意の-CH2-又は-CF2-の1以上は、それぞれ独立に-CH=CH-、二価の炭素環、および二価の複素環から選ばれる基で置き換えられていてもよく、さらに、次に挙げるいずれかの基、すなわち、-O-、-COO-、-OCO-、-NHCO-、-CONH-、又は-NH-が互いに隣り合わないことを条件に、これらの基で置き換えられていてもよい;
R8は、下記式:
から選択されるラジカル重合反応性基を表す。
(式[X-1]~[X-18]中、*は化合物分子のラジカル重合反応性基以外の部分との結合部位を示し、S1、S2はそれぞれ独立して-O-、-NR-、-S-を表し、Rは水素原子、ハロゲン原子、炭素数1~10のアルキル基、炭素数1~10のアルコキシ基を表し、R1,R2はそれぞれ独立して水素原子、ハロゲン原子、炭素数1~4のアルキル基を表す))
(式(7)中、T1及びT2は、それぞれ独立に、単結合、-O-、-S-、-COO-、-OCO-、-NHCO-、-CONH-、-NH-、-CH2O-、-N(CH3)-、-CON(CH3)-、又は-N(CH3)CO-であり、
Sは単結合、又は非置換もしくはフッ素原子によって置換されている炭素数1~20のアルキレン基を表し、当該アルキレン基の任意の-CH2-又は-CF2-の1以上は、それぞれ独立に-CH=CH-、二価の炭素環、および二価の複素環から選ばれる基で置き換えられていてもよく、さらに、次に挙げるいずれかの基、すなわち、-O-、-COO-、-OCO-、-NHCO-、-CONH-、又は-NH-が互いに隣り合わないことを条件に、これらの基で置き換えられていてもよく、
Jは下記式で表される有機基であり、
(式[W]、[Y]、[Z]中、*はT2との結合箇所を表し、Arは有機基及び/又はハロゲン原子を置換基として有しても良いフェニレン、ナフチレン、及びビフェニレンからなる群より選ばれる芳香族炭化水素基を示し、R9及びR10は、それぞれ独立に、炭素数1~10のアルキル基又は炭素数1~10のアルコキシ基を表し、Qは下記の構造を表す。
(式中、R11は-CH2-、-NR-、-O-、又は-S-を表し、Rは水素原子又は炭素原子数1~4のアルキル基を表し、*は化合物分子のQ以外の部分との結合部位を示す。)
R12は水素原子、ハロゲン原子、炭素数1~10のアルキル基又は炭素数1~10のアルコキシ基を表す。)) The method according to claim 7, wherein the diamine containing an organic group capable of inducing radical polymerization is a diamine having a structure represented by the following general formula (6) or the following general formula (7).
(In the formula (6), 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,
R 7 represents a single bond or an alkylene group having 1 to 20 carbon atoms which is unsubstituted or substituted by a fluorine atom, and one or more of any —CH 2 — or —CF 2 — of the alkylene group are each independently And may be substituted with a group selected from -CH = CH-, a divalent carbocycle, and a divalent heterocycle, and further, any of the following groups, ie, -O-, -COO- , -OCO-, -NHCO-, -CONH- or -NH- may be replaced by these groups, provided that they are not adjacent to each other;
R 8 has the following formula:
And a radical polymerization reactive group selected from
(In formulas [X-1] to [X-18], * represents a binding site to a moiety other than the radical polymerization reactive group of the compound molecule, and S 1 and S 2 are each independently —O—, — And R 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, and R 1 and R 2 each independently represent a hydrogen atom, Halogen atom, represents an alkyl group having 1 to 4 carbon atoms))
(In Formula (7), 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—,
S represents a single bond, or an alkylene group having 1 to 20 carbon atoms which is unsubstituted or substituted by a fluorine atom, and one or more of any —CH 2 — or —CF 2 — of the alkylene group are each independently It may be substituted by a group selected from -CH = CH-, a divalent carbocyclic ring, and a divalent heterocyclic ring, and further, any of the following groups, ie, -O-, -COO-, These groups may be substituted on the condition that -OCO-, -NHCO-, -CONH- or -NH- is not adjacent to each other,
J is an organic group represented by the following formula,
(In the formulas [W], [Y] and [Z], * represents a bonding site to T 2 , Ar represents an organic group and / or a phenylene, naphthylene, and biphenylene which may have a halogen atom as a substituent) And R 9 and R 10 each independently represent an alkyl group having 1 to 10 carbon atoms or an alkoxy group having 1 to 10 carbon atoms, and Q represents a structure shown below Represents
(Wherein, R 11 represents —CH 2 —, —NR—, —O— or —S—, R represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and * 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. ))) - 前記ラジカル重合性化合物のうち少なくとも一種が、液晶と相溶性を有する、一分子中に一個の重合性反応基を有する化合物である、請求項1~9のいずれか一項に記載の方法。 The method according to any one of claims 1 to 9, wherein at least one of the radically polymerizable compounds is a compound having one polymerizable reactive group in one molecule, which is compatible with liquid crystal.
- 前記ラジカル重合性化合物の重合性反応基が以下の構造から選ばれる、請求項10に記載の方法。
(式中、*は化合物分子の重合性反応基以外の部分との結合部位を示す。Rbは炭素数2~8の直鎖アルキル基を表し、Eは単結合、-O-、-NRc-、-S-、エステル結合及びアミド結合から選ばれる結合基を表す。Rcは水素原子、炭素数1~4のアルキル基を示す。) The method according to claim 10, wherein the polymerizable reactive group of the radically polymerizable compound is selected from the following structures.
(Wherein, * represents a binding site to a moiety other than the polymerizable reactive group of the compound molecule. R b represents a linear alkyl group having 2 to 8 carbon atoms, E represents a single bond, -O-, -NR c represents a linking group selected from-, -S-, an ester bond and an amide bond, and R c represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. - 前記液晶及びラジカル重合性化合物を含有する液晶組成物において、前記ラジカル重合性化合物を重合させて得られるポリマーのTgが100℃以下のものになるラジカル重合性化合物を含有する液晶組成物を用いることを特徴とする請求項1~11のいずれか一項に記載の方法。 A liquid crystal composition containing the liquid crystal and a radical polymerizable compound, wherein the polymer obtained by polymerizing the radical polymerizable compound has a Tg of 100 ° C. or less. A method according to any one of the preceding claims, characterized in that
- ラジカル発生膜を有する第一基板と、ラジカル発生膜を有していてもよい第二基板とを用意するステップ、
第一基板上のラジカル発生膜が第二基板に対向するようにセルを作成するステップ、および、
第一基板と第二基板との間に、液晶及びラジカル重合性化合物を含有する液晶組成物を充填するステップを含み、
請求項1~12のいずれか一項に記載の方法を用いる液晶セルの製造方法。 Preparing a first substrate having a radical generating film and a second substrate which may have a radical generating film;
Creating a cell such that the radical generating film on the first substrate faces the second substrate;
Filling the liquid crystal composition containing a liquid crystal and a radically polymerizable compound between the first substrate and the second substrate,
A method of manufacturing a liquid crystal cell using the method according to any one of claims 1 to 12. - 前記第二基板がラジカル発生膜を有さない第二基板である請求項13に記載の液晶セルの製造方法。 The method of manufacturing a liquid crystal cell according to claim 13, wherein the second substrate is a second substrate not having a radical generating film.
- 前記第二基板が、一軸配向性を有する液晶配向膜がコーティングされた基板であることを特徴とする請求項14に記載の液晶セルの製造方法。 The method for manufacturing a liquid crystal cell according to claim 14, wherein the second substrate is a substrate coated with a liquid crystal alignment film having uniaxial alignment property.
- 前記一軸配向性を有する液晶配向膜が水平配向用の液晶配向膜であることを特徴とする請求項15に記載の液晶セルの製造方法。 The method for producing a liquid crystal cell according to claim 15, wherein the liquid crystal alignment film having uniaxial alignment property is a liquid crystal alignment film for horizontal alignment.
- 前記ラジカル発生膜を有する第一基板が櫛歯電極を有する基板である請求項13~16のいずれか一項に記載の液晶セルの製造方法。 The method of manufacturing a liquid crystal cell according to any one of claims 13 to 16, wherein the first substrate having the radical generating film is a substrate having a comb electrode.
- 液晶及びラジカル重合性化合物を含有し、
前記ラジカル重合性化合物のうち少なくとも一種が、液晶と相溶性を有する、一分子中に一個の重合性反応基を有する化合物であり、
重合性反応基が以下の構造から選ばれる、液晶組成物。
(式中、*は化合物分子の重合性反応基以外の部分との結合部位を示す。Rbは炭素数2~8の直鎖アルキル基を表し、Eは単結合、-O-、-NRc-、-S-、エステル結合及びアミド結合から選ばれる結合基を表す。Rcは水素原子、炭素数1~4のアルキル基を示す。) Contains liquid crystal and radically polymerizable compounds,
At least one of the radically polymerizable compounds is a compound having one polymerizable reactive group in one molecule, which is compatible with liquid crystal,
A liquid crystal composition, wherein the polymerizable reactive group is selected from the following structures.
(Wherein, * represents a binding site to a moiety other than the polymerizable reactive group of the compound molecule. R b represents a linear alkyl group having 2 to 8 carbon atoms, E represents a single bond, -O-, -NR c represents a linking group selected from-, -S-, an ester bond and an amide bond, and R c represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. - 請求項1~17のいずれか一項に記載の方法を用いて得られたゼロ面アンカリング状態を作り出す膜を用いる液晶表示素子の製造方法。 A method of manufacturing a liquid crystal display device using a film that produces a zero plane anchoring state obtained by using the method according to any one of claims 1 to 17.
- 請求項19記載の方法を用いて得られた液晶表示素子。 The liquid crystal display element obtained using the method of Claim 19.
- 第一基板又は第二基板が電極を有する、請求項20に記載の液晶表示素子。 The liquid crystal display element according to claim 20, wherein the first substrate or the second substrate has an electrode.
- 低電圧駆動横電界液晶表示素子である、請求項20又は21に記載の液晶表示素子。 22. The liquid crystal display device according to claim 20, which is a low voltage drive horizontal electric field liquid crystal display device.
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