WO2019044795A1 - Agent d'alignement de cristaux liquides, film d'alignement de cristaux liquides , et élément d'affichage à cristaux liquides - Google Patents

Agent d'alignement de cristaux liquides, film d'alignement de cristaux liquides , et élément d'affichage à cristaux liquides Download PDF

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WO2019044795A1
WO2019044795A1 PCT/JP2018/031670 JP2018031670W WO2019044795A1 WO 2019044795 A1 WO2019044795 A1 WO 2019044795A1 JP 2018031670 W JP2018031670 W JP 2018031670W WO 2019044795 A1 WO2019044795 A1 WO 2019044795A1
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Prior art keywords
liquid crystal
substrate
acid dianhydride
tetracarboxylic acid
aligning agent
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PCT/JP2018/031670
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English (en)
Japanese (ja)
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秀則 石井
達哉 名木
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日産化学株式会社
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Priority to JP2019539509A priority Critical patent/JP7196847B2/ja
Priority to KR1020207007943A priority patent/KR102635627B1/ko
Priority to CN201880070410.XA priority patent/CN111344630B/zh
Publication of WO2019044795A1 publication Critical patent/WO2019044795A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/1337—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
    • C08L79/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
    • C08L79/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • 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

Definitions

  • the present invention relates to a liquid crystal aligning agent, a liquid crystal alignment film, and a liquid crystal display element for producing a liquid crystal display element having excellent sticking characteristics.
  • Liquid crystal display devices are known as light-weight, thin and low power consumption display devices, and in recent years they have achieved remarkable development such as being used for large-sized television applications.
  • the liquid crystal display element is configured, for example, by sandwiching a liquid crystal layer by a pair of transparent substrates provided with electrodes. And in a liquid crystal display element, the organic film which consists of organic materials is used as a liquid crystal aligning film so that a liquid crystal may be in a desired orientation state between board
  • the liquid crystal alignment film is a component of the liquid crystal display element, and is formed on the surface of the substrate holding the liquid crystal in contact with the liquid crystal, and plays a role of orienting the liquid crystal in a certain direction between the substrates.
  • the liquid crystal alignment film may be required to control the pretilt angle of the liquid crystal, in addition to the function of aligning the liquid crystal in a fixed direction such as a direction parallel to the substrate.
  • alignment control ability The ability to control the alignment of liquid crystal (hereinafter referred to as alignment control ability) in such a liquid crystal alignment film is given by performing an alignment process on the organic film constituting the liquid crystal alignment film.
  • a rubbing method is conventionally known as an alignment treatment method of a liquid crystal alignment film for imparting alignment controllability.
  • the surface of the liquid crystal alignment film made of polyimide or the like is rubbed, generation of dust or static electricity may be a problem.
  • the surface of the liquid crystal alignment film can not be rubbed uniformly with a cloth, and is uniform. In some cases, alignment of the liquid crystal can not be realized.
  • the photo alignment method is actively examined as another alignment processing method of the liquid crystal aligning film which does not perform rubbing.
  • the anisotropy is formed in the organic film constituting the liquid crystal alignment film by the linearly polarized light or the collimated light, and the liquid crystal is aligned according to the anisotropy.
  • a decomposition type photoalignment method As a main photoalignment method, a decomposition type photoalignment method is known. For example, polarized ultraviolet light is irradiated to a polyimide film, and anisotropic decomposition is caused by utilizing the polarization direction dependency of the ultraviolet absorption of the molecular structure. Then, the liquid crystal is oriented by the polyimide left without being decomposed (see, for example, Patent Document 1).
  • photocrosslinking and photoisomerization photoalignment methods are also known. For example, using polyvinyl cinnamate, it is irradiated with polarized ultraviolet light to cause a dimerization reaction (crosslinking reaction) at the double bond portion of two side chains parallel to the polarized light. Then, the liquid crystal is aligned in a direction orthogonal to the polarization direction (see, for example, Non-Patent Document 1).
  • the liquid crystal cell of the lateral electric field type is excellent in viewing angle characteristics, a sufficient voltage can not be applied to the liquid crystal if the voltage holding ratio of the liquid crystal alignment film is weak because there are few electrodes formed in the substrate. Display contrast is reduced.
  • static electricity is likely to be accumulated in the liquid crystal cell, and charges are also accumulated in the liquid crystal cell by application of an asymmetric voltage generated by driving, and these accumulated charges (residual DC) cause disturbance in the alignment of the liquid crystal or residual image or It affects the display as burn-in and significantly reduces the display quality of the liquid crystal element.
  • the control of the liquid crystal molecules is not properly performed in the initial stage, and flicker or the like is generated.
  • the horizontal electric field method since the distance between the pixel electrode and the common electrode is shorter than that in the vertical electric field method, a strong electric field acts on the alignment film and the liquid crystal layer, and such a problem tends to be remarkable. there were.
  • Patent No. 3893659 Korean Patent Application Publication 10-2016-0042614 Korean Patent Application Publication 10-2017-0127966 Korean Patent Application Publication 10-2018-0020722
  • the photoalignment method eliminates the rubbing step itself as compared with the rubbing method conventionally used industrially as an alignment treatment method of liquid crystal display elements, and therefore has a great advantage. Then, as compared with the rubbing method in which the alignment control ability is substantially constant by rubbing, in the photo alignment method, the irradiation control amount of polarized light can be changed to control the alignment control ability.
  • the photoalignment method when it is intended to realize the same degree of alignment control ability as in the rubbing method, a large amount of polarized light irradiation may be required, or stable liquid crystal alignment may not be realized. .
  • liquid crystal alignment film As a measure against display burn-in caused by residual DC, when a liquid crystal alignment film is formed, as a component other than polyamic acid or polyimide to which the alignment control ability of liquid crystal is imparted by polarized ultraviolet irradiation, volume resistivity The technique of adding low polyamic acid to the orienting agent has been utilized. However, by storing the liquid crystal aligning agent in which two types of polyamic acid or polyimide are mixed at 23 ° C., the liquid crystal alignment stability may decrease with the passage of storage time. Therefore, there is a demand for a liquid crystal alignment film and a liquid crystal alignment agent that do not reduce liquid crystal alignment stability while eliminating display sticking due to residual DC.
  • the present invention provides a substrate having a liquid crystal alignment film for a liquid crystal display element for a lateral electric field drive type, which is highly efficiently imparted with an orientation controllability and excellent in burn-in characteristics due to liquid crystal alignment deviation and residual DC;
  • An object of the present invention is to provide a drive type liquid crystal display device.
  • polyamic acid or polyamic acid imidized polymer obtained from carboxylic acid dianhydride and diamine having a specific structure orientation controllability is imparted with high efficiency, and burn-in characteristics attributed to liquid crystal alignment deviation and residual DC
  • the present invention has been completed by finding that a liquid crystal alignment film excellent in
  • (Ab) A polyamic acid obtained by using a tetracarboxylic acid dianhydride component containing aliphatic tetracarboxylic acid dianhydride and a diamine component containing a diamine represented by the following formula (2), and the polyamic acid At least one polymer selected from imidized polymers, And an organic solvent, and the weight ratio of (A-a) to (A-b) is (A-a) :( A-b) 55: 45 to 90:10, preferably 60:40 to 90.
  • i is 0 or 1
  • X is a single bond, ether bond, carbonyl, ester bond, phenylene, linear alkylene having 1 to 20 carbon atoms, branched alkylene having 2 to 20 carbon atoms, A C 3 to C 12 cyclic alkylene, sulfonyl, amide bond or a combination thereof, wherein the C 1 to C 20 alkylene is interrupted by a bond selected from an ester bond and an ether bond And the carbon atoms of phenylene and alkylene may be substituted with one or more of the same or different substituents selected from halogen atoms, cyano groups, alkyl groups, haloalkyl groups, alkoxy groups and haloalkoxy groups .
  • the tetracarboxylic acid dianhydride represented by the above formula (1) is at least one selected from pyromellitic acid dianhydride and 3,3 ', 4,4'-biphenyltetracarboxylic acid dianhydride
  • the liquid crystal aligning agent as described in any one of the above. 6.
  • the liquid crystal alignment film obtained from the liquid crystal alignment agent of the present invention can align the liquid crystal with a small amount of polarized ultraviolet radiation, and the liquid crystal alignment film deteriorates in liquid crystal alignment stability even when stored at 23 ° C. It is possible to accelerate the alleviation of the residual DC accumulated by the DC voltage without causing the problem.
  • i is 0 or 1
  • X is a single bond, ether bond, carbonyl, ester bond, phenylene, linear alkylene having 1 to 20 carbon atoms, branched alkylene having 2 to 20 carbon atoms, A C 3 to C 12 cyclic alkylene, sulfonyl, amide bond or a combination thereof, wherein the C 1 to C 20 alkylene is interrupted by a bond selected from an ester bond and an ether bond And the carbon atoms of phenylene and alkylene may be substituted with one or more of the same or different substituents selected from halogen atoms, cyano groups, alkyl groups, haloalkyl groups, alkoxy groups and haloalkoxy groups .
  • substituents selected from halogen atoms, cyano groups, alkyl groups, haloalkyl groups, alkoxy groups and haloalkoxy groups .
  • the component (Aa) used for the liquid crystal aligning agent of the present invention can be obtained using a tetracarboxylic acid dianhydride component including the tetracarboxylic acid dianhydride represented by the above formula (1) and a diamine component. It is at least one polymer selected from polyamic acids and imidized polymers of the polyamic acids.
  • ⁇ Tetracarboxylic acid dianhydride component Although the following compounds are mentioned as a tetracarboxylic acid dianhydride represented by said Formula (1), It is not limited to these. In the following formulae, q represents an integer of 1 to 20.
  • the above formulas (1-1), (1-2), (1-3), ( 1-4), (1-5) and (1-7) are preferable, and in terms of stable supply, the above formulas (1-1) and (1-5) are particularly preferable.
  • the amount of the tetracarboxylic acid dianhydride represented by the formula (1) in the entire tetracarboxylic acid dianhydride component is too small, the effect of the present invention can not be obtained. Therefore, the amount of the tetracarboxylic acid dianhydride represented by the formula (1) is 30 to 100 mol% relative to 1 mol of all the tetracarboxylic acid dianhydrides used for the preparation of the component (Aa). Preferably, it is 50 to 100 mol%, more preferably 70 to 100 mol%.
  • the tetracarboxylic acid dianhydride represented by the formula (1) may be used alone or in combination of two or more, but also in this case, the tetracarboxylic acid dianhydride represented by the formula (1) It is preferred to use the above-mentioned preferred amounts as a total.
  • ⁇ Diamine component> As a diamine component used for manufacture of the (Aa) component of this invention, the diamine represented by following formula (5) is used.
  • W 2 in the formula (5) is a divalent organic group, and the structure is not particularly limited, and two or more types may be mixed. If specific examples are shown, structures represented by the following Formula [W 2 -1] to Formula [W 2 -152] can be mentioned.
  • R 1 and R 2 each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and a hydrogen atom or a methyl group is more preferable.
  • W2-49, W2-51, W2-65, W2-67, W2-68, W2-69, W2-70, W2-71, W2-142, W2-144, W2-148, W2-151 are preferred.
  • W2-65, W2-67, W2-68, W2-69, W2-70, W2-71, W2-142, W2-144, W2-148, and W2-151 are more preferable.
  • the component (Ab) used for the liquid crystal aligning agent of the present invention is a tetracarboxylic acid dianhydride component containing aliphatic tetracarboxylic acid dianhydride, and a diamine component containing a diamine represented by the above formula (2) And at least one polymer selected from the polyamic acid and the imidized polymer of the polyamic acid.
  • X 1 is any of the following (X-1) to (X-28).
  • R 3 to R 6 each independently represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a phenyl group, and a hydrogen atom or a methyl group is more preferable.
  • (X-1) most preferred in terms of light orientation is, as R 4 and R 6 R 3 and R 5 is a methyl group is a hydrogen atom (X-1), R 3 ⁇ A structure in which R 6 is a hydrogen atom is preferable, and a structure in which R 3 to R 6 are a hydrogen atom is particularly preferable.
  • the amount of aliphatic tetracarboxylic acid dianhydride is preferably 50 to 100 mol%, more preferably, 1 mol of all tetracarboxylic acid dianhydrides used for producing the component (Ab). It is 60 to 100 mol%, more preferably 80 to 100 mol%.
  • the proportion of the diamine represented by the formula (2) in the polyamic acid and the imidized polymer of the polyamic acid, which is the component (Ab) of the present invention is 1 mole of all diamines used in the production of the component (Ab). It is preferably 10 to 100% by mole, more preferably 30 to 100% by mole, and still more preferably 50 to 100% by mole.
  • the polyamic acid and the imidized polymer of the polyamic acid which are the (Ab) component contained in the liquid crystal aligning agent of the present invention have a surface represented by the above formula (5) in addition to the diamine represented by the above formula (2). May be used.
  • the effect of the present invention can be obtained by increasing the proportion of the diamine represented by the formula (5) in the polyamic acid and the imidized polymer of the polyamic acid which is the component (Ab) contained in the liquid crystal aligning agent of the present invention. It is not preferable because it may be damaged. Accordingly, the proportion of the diamine represented by the formula (5) is preferably 0 to 90% by mole, more preferably 0 to 70% by mole, still more preferably 0 to 50% by mole, relative to 1 mole of all diamines. .
  • the polyamic acid which is a polyimide precursor used for this invention can be synthesize
  • an organic solvent used for the above reaction is preferably N, N-dimethylformamide, N-methyl-2-pyrrolidone, ⁇ -butyrolactone, etc. in view of solubility of monomers and polymers, and one or more of these may be mixed You may use it.
  • the concentration of the polymer is preferably 1 to 30% by mass, and more preferably 5 to 20% by mass, from the viewpoint that precipitation of the polymer hardly occurs and a polymer can be easily obtained.
  • the polyamic acid obtained as described above can be recovered by precipitating a polymer by pouring the reaction solution into a poor solvent while well stirring it. Further, precipitation is carried out several times, and after washing with a poor solvent, it is possible to obtain a purified polyamic acid powder by normal temperature or heat drying.
  • the poor solvent is not particularly limited, and water, methanol, ethanol, 2-propanol, hexane, butyl cellosolve, acetone, toluene and the like can be mentioned, and water, methanol, ethanol, 2-propanol and the like are preferable.
  • the polyimide used in the present invention can be produced by imidizing the polyamic acid.
  • chemical imidization which adds a catalyst to the solution of the said polyamic acid obtained by reaction of a diamine component and tetracarboxylic dianhydride is simple.
  • Chemical imidization is preferable because the imidization reaction proceeds at a relatively low temperature, and molecular weight reduction of the polymer does not easily occur in the imidization process.
  • Chemical imidization can be carried out by stirring a polymer to be imidized in an organic solvent in the presence of a basic catalyst and an acid anhydride.
  • the solvent used at the time of the polymerization reaction mentioned above can be used.
  • basic catalysts include pyridine, triethylamine, trimethylamine, tributylamine and trioctylamine. Among them, pyridine is preferable because it has a suitable basicity to allow the reaction to proceed.
  • acid anhydride acetic anhydride, trimellitic anhydride, pyromellitic anhydride and the like can be mentioned, and it is preferable to use acetic anhydride among them because purification after completion of the reaction becomes easy.
  • the temperature at which the imidization reaction is carried out is -20 to 140 ° C, preferably 0 to 100 ° C, and the reaction time can be 1 to 100 hours.
  • the amount of basic catalyst is 0.5 to 30 times mol, preferably 2 to 20 times mol of polyamic acid group, and the amount of acid anhydride is 1 to 50 times mol, preferably 3 to 30 times mol of polyamic acid group. It is a mole.
  • the imidation ratio of the resulting polymer can be controlled by adjusting the amount of catalyst, temperature and reaction time. Since the added catalyst and the like remain in the solution after the imidization reaction of the polyamic acid, the obtained imidized polymer is recovered by the means described below, and redissolved in an organic solvent to obtain the present invention. It is preferable to use as the liquid crystal aligning agent of
  • the solution of the polyimide obtained as mentioned above can precipitate a polymer by inject
  • the poor solvent is not particularly limited, and methanol, 2-propanol, acetone, hexane, butyl cellosolve, heptane, methyl ethyl ketone, methyl isobutyl ketone, ethanol, toluene, benzene and the like can be mentioned, and methanol, ethanol, 2-propanol, Acetone is preferred.
  • the polyimide precursor used in the present invention is obtained from the reaction of a diamine component and a tetracarboxylic acid derivative, and examples thereof include polyamic acid and polyamic acid ester.
  • the polyamic acid ester which is a polyimide precursor to be used in the present invention can be produced by the following production method (1), (2) or (3).
  • Polyamic acid ester can be manufactured by esterifying the polyamic acid manufactured as mentioned above. Specifically, the polyamic acid and the esterifying agent are reacted in the presence of an organic solvent at -20 ° C to 150 ° C, preferably 0 ° C to 50 ° C, for 30 minutes to 24 hours, preferably 1 to 4 hours. It can be manufactured.
  • esterifying agent those which can be easily removed by purification are preferable, and N, N-dimethylformamide dimethyl acetal, N, N-dimethylformamide diethyl acetal, N, N-dimethylformamide dipropyl acetal, N, N-dimethylformamide Dineopentyl butyl acetal, N, N-dimethylformamide di-t-butyl acetal, 1-methyl-3-p-tolyltriazene, 1-ethyl-3-p-tolyltriazene, 1-propyl-3-p -Tolyltriazene, 4- (4,6-dimethoxy-1,3,5-triazin-2-yl) -4-methylmorpholinium chloride and the like.
  • the addition amount of the esterifying agent is preferably 2 to 6 molar equivalents with respect to 1 mole of the repeating unit of the polyamic acid.
  • organic solvent for example, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone or ⁇ -butyrolactone, N, N-dimethylformamide, N, N-dimethylacetamide, dimethyl sulfoxide or 1,3-dimethyl- And imidazolidinone.
  • solvent solubility of the polyimide precursor is high, methyl ethyl ketone, cyclohexanone, cyclopentanone, 4-hydroxy-4-methyl-2-pentanone, or the formula [D-1] to the formula [D-3] described later
  • the solvent shown by can be used. These solvents may be used alone or in combination.
  • the solvent used for the above reaction is preferably N, N-dimethylformamide, N-methyl-2-pyrrolidone, or ⁇ -butyrolactone in view of the solubility of the polymer, and these may be used alone or in combination of two or more. Good.
  • the concentration at the time of production is preferably 1 to 30% by mass, and more preferably 5 to 20% by mass, from the viewpoint that precipitation of a polymer hardly occurs and a polymer can be easily obtained.
  • Polyamic acid ester can be manufactured from tetracarboxylic-acid diester dichloride and diamine. Specifically, tetracarboxylic acid diester dichloride and diamine in the presence of a base and an organic solvent at -20 ° C to 150 ° C, preferably 0 ° C to 50 ° C, for 30 minutes to 24 hours, preferably 1 to 4 hours It can be produced by reacting.
  • a base pyridine, triethylamine, 4-dimethylaminopyridine and the like can be used, but pyridine is preferable because the reaction proceeds mildly.
  • the addition amount of the base is preferably 2 to 4 times the molar amount of the tetracarboxylic acid diester dichloride from the viewpoint of easy removal and high molecular weight.
  • the solvent used for the above reaction is preferably N-methyl-2-pyrrolidone or ⁇ -butyrolactone in view of the solubility of monomers and polymers, and these may be used alone or in combination of two or more.
  • the polymer concentration at the time of production is preferably 1 to 30% by mass, and more preferably 5 to 20% by mass from the viewpoint that precipitation of the polymer hardly occurs and a polymer can be easily obtained.
  • the solvent used for producing the polyamic acid ester is preferably dehydrated as much as possible, and it is preferable to prevent mixing of the outside air in a nitrogen atmosphere.
  • Polyamic acid ester can be manufactured by polycondensing tetracarboxylic acid diester and diamine. Specifically, a tetracarboxylic acid diester and a diamine in the presence of a condensing agent, a base and an organic solvent at 0 ° C. to 150 ° C., preferably 0 ° C. to 100 ° C., for 30 minutes to 24 hours, preferably 3 to 15 It can be produced by reacting for time.
  • the condensing agent examples include triphenyl phosphite, dicyclohexyl carbodiimide, 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide hydrochloride, N, N′-carbonyldiimidazole, dimethoxy-1,3,5-triadidi Nylmethylmorpholinium, O- (benzotriazol-1-yl) -N, N, N ', N'-tetramethyluronium tetrafluoroborate, O- (benzotriazol-1-yl) -N, N And N ′, N′-tetramethyluronium hexafluorophosphate, diphenyl (2,3-dihydro-2-thioxo-3-benzoxazolyl) phosphonate and the like can be used.
  • the addition amount of the condensing agent is preferably 2 to 3 moles per mol of the tetracarboxylic acid die
  • tertiary amines such as pyridine and triethylamine can be used.
  • the amount of the base added is preferably 2 to 4 moles per mole of the diamine component, in terms of easy removal and high molecular weight.
  • the reaction proceeds efficiently by adding a Lewis acid as an additive.
  • the Lewis acid lithium halides such as lithium chloride and lithium bromide are preferable.
  • the addition amount of the Lewis acid is preferably 0 to 1.0 times the molar amount with respect to the diamine component.
  • a high molecular weight polyamic acid ester can be obtained, and therefore the production method of the above (1) or the above (2) is particularly preferable.
  • the solution of the polyamic acid ester obtained as described above can precipitate the polymer by pouring it into a poor solvent while stirring well. Precipitation is carried out several times, and after washing with a poor solvent, it is possible to obtain a purified polyamic acid ester powder at room temperature or by heating and drying.
  • the poor solvent is not particularly limited, and water, methanol, ethanol, hexane, butyl cellosolve, acetone, toluene and the like can be mentioned.
  • the liquid crystal aligning agent used in the present invention has the form of a solution in which a polymer component is dissolved in an organic solvent.
  • the molecular weight of the polymer is preferably 2,000 to 500,000, more preferably 5,000 to 300,000, and still more preferably 10,000 to 100,000, in terms of weight average molecular weight.
  • the number average molecular weight is preferably 1,000 to 250,000, more preferably 2,500 to 150,000, and still more preferably 5,000 to 50,000.
  • the concentration of the polymer of the liquid crystal aligning agent used in the present invention can be appropriately changed by setting the thickness of the coating film to be formed, but from the point of forming a uniform and defect-free coating film, 1 mass % Or more, and in terms of storage stability of the solution, 10% by mass or less.
  • the particularly preferred concentration of the polymer is 2 to 8% by mass.
  • the organic solvent contained in the liquid crystal aligning agent used in the present invention is not particularly limited as long as the polymer component dissolves uniformly.
  • Specific examples thereof include N, N-dimethylformamide, N, N-diethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N-methylcaprolactam, Examples include 2-pyrrolidone, N-vinyl-2-pyrrolidone, dimethyl sulfoxide, dimethyl sulfone, ⁇ -butyrolactone, 1,3-dimethyl-imidazolidinone, 3-methoxy-N, N-dimethylpropanamide and the like. These may be used alone or in combination of two or more. Moreover, even if it is a solvent which can not melt
  • the organic solvent contained in a liquid crystal aligning agent uses the mixed solvent which used together the solvent which improves the surface smoothness of the coating property at the time of applying a liquid crystal aligning agent in addition to the above solvents and a liquid crystal aligning agent.
  • a mixed solvent is suitably used also in the liquid crystal aligning agent of the present invention.
  • ethanol isopropyl alcohol, 1-butanol, 2-butanol, isobutyl alcohol, tert-butyl alcohol, 1-pentanol, 2-pentanol, 3-pentanol, 2-methyl-1-butanol, isopentyl alcohol, tert-pentyl alcohol, 3-methyl-2-butanol, neopentyl alcohol, 1-hexanol, 2-methyl-1-pentanol, 2-methyl-2-pentanol, 2-ethyl-1-butanol, 1-heptanol 2-heptanol, 3-heptanol, 1-octanol, 2-octanol, 2-ethyl-1-hexanol, cyclohexanol, 1-methylcyclohexanol, 2-methylcyclohexanol, 3-methylcyclohexanol, 2,6- Dimethyl 4-heptanol, 1,2-ethanediol,
  • D 1 represents an alkyl group having 1 to 3 carbon atoms
  • D 2 represents an alkyl group having 1 to 3 carbon atoms
  • Formula [D-3] among, D 3 is an alkyl group having 1 to 4 carbon atoms.
  • additives may be added to the liquid crystal aligning agent of the present invention in order to increase the mechanical strength of the film.
  • the additive is preferably 0.1 to 30 parts by mass with respect to 100 parts by mass of the polymer component contained in the liquid crystal aligning agent. If the amount is less than 0.1 part by mass, no effect can be expected. If the amount is more than 30 parts by mass, the orientation of the liquid crystal is reduced.
  • the purpose is to change the electrical characteristics such as the dielectric constant and the conductivity of the polymer other than the polymer and the liquid crystal alignment film as long as the effects of the present invention are not impaired.
  • Dielectrics or conductive substances Dielectrics or conductive substances, silane coupling agents for the purpose of improving the adhesion between the liquid crystal alignment film and the substrate, crosslinkable compounds for the purpose of enhancing the hardness and density of the film when the liquid crystal alignment film is formed, and When firing the film, an imidization promoter may be added for the purpose of efficiently advancing imidization of polyamic acid.
  • the liquid crystal aligning film of this invention is a film
  • the substrate to which the liquid crystal alignment agent of the present invention is applied is not particularly limited as long as it is a highly transparent substrate, and plastic substrates such as glass substrates, silicon nitride substrates, acrylic substrates, and polycarbonate substrates can be used. It is preferable from the viewpoint of process simplification to use a substrate on which an ITO electrode or the like for the above is formed. Further, in the reflection type liquid crystal display device, an opaque material such as a silicon wafer can be used if it is only on one substrate, and in this case, a material that reflects light such as aluminum can also be used.
  • a spin coat method, the printing method, the inkjet method etc. are mentioned.
  • the drying and baking steps after the application of the liquid crystal aligning agent of the present invention can be performed at any temperature and time. Usually, drying is carried out at 50 ° C. to 120 ° C. for 1 minute to 10 minutes in order to sufficiently remove the contained organic solvent, followed by calcination at 150 ° C. to 300 ° C. for 5 minutes to 120 minutes.
  • the thickness of the coating after firing is not particularly limited, but if it is too thin, the reliability of the liquid crystal display element may be reduced, so it is 5 to 300 nm, preferably 10 to 200 nm.
  • the rubbing method As a method of carrying out the alignment process of the obtained liquid crystal aligning film, the rubbing method, the photo alignment treatment method, etc. are mentioned.
  • the rubbing process can be performed using an existing rubbing apparatus. Cotton, nylon, rayon etc. are mentioned as a material of the rubbing cloth in this case.
  • the conditions for the rubbing treatment generally, conditions of a rotational speed of 300 to 2000 rpm, a feed speed of 5 to 100 mm / s, and a pressing amount of 0.1 to 1.0 mm are used. After that, the residue generated by rubbing is removed by ultrasonic cleaning using pure water, alcohol or the like.
  • the coating film surface is irradiated with radiation deflected in a certain direction, and in some cases, heat treatment is performed at a temperature of 150 to 250 ° C. to impart liquid crystal alignment ability.
  • radiation ultraviolet light and visible light having a wavelength of 100 nm to 800 nm can be used. Among these, ultraviolet light having a wavelength of 100 nm to 400 nm is preferable, and one having a wavelength of 200 nm to 400 nm is particularly preferable.
  • radiation may be applied while heating the coated substrate at 50 to 250.degree.
  • Dose of the radiation is preferably 1 ⁇ 10,000mJ / cm 2, particularly preferably 100 ⁇ 5,000mJ / cm 2.
  • the liquid crystal alignment film produced as described above can stably align liquid crystal molecules in a certain direction.
  • the extinction ratio of the linearly polarized ultraviolet light is preferably 10: 1 or more, more preferably 20: 1 or more.
  • the film irradiated with polarized radiation may then be contact-treated with a solvent containing at least one selected from water and an organic solvent. It will not specifically limit, if it is a solvent which melt
  • the contact treatment between a film irradiated with polarized radiation and a solution containing an organic solvent is a treatment such as immersion treatment, spray treatment, etc., in which the film and the solution are preferably in sufficient contact. It takes place.
  • a method of immersing the membrane in a solution containing an organic solvent preferably for 10 seconds to 1 hour, more preferably for 1 to 30 minutes.
  • the contact treatment may be performed at normal temperature or may be heated, but is preferably performed at 10 to 80 ° C., more preferably 20 to 50 ° C.
  • means for enhancing contact such as ultrasonic waves can be provided as necessary.
  • a low boiling point solvent such as water, methanol, ethanol, 2-propanol, acetone, methyl ethyl ketone or drying, or both You may
  • the film which has been subjected to the above-mentioned solvent contact treatment may be heated at 150 ° C. or higher for the purpose of drying the solvent and reorientation of molecular chains in the film.
  • the heating temperature is preferably 150 to 300.degree. A higher temperature promotes reorientation of molecular chains, but too high a temperature may involve decomposition of molecular chains. Therefore, the heating temperature is more preferably 180 to 250 ° C., and particularly preferably 200 to 230 ° C. If the heating time is too short, the effect of molecular chain reorientation may not be obtained, and if it is too long, the molecular chain may be decomposed. 10 minutes is more preferable.
  • a method for producing a substrate having a liquid crystal alignment film of the present invention a method including the steps of the following [I] to [IV] is preferable.
  • [A] (Aa) A polyamic acid obtained by using a tetracarboxylic acid dianhydride component containing a tetracarboxylic acid dianhydride represented by the formula (1) and a diamine component, and imidization heavy weight of the polyamic acid Using at least one polymer selected from coalescence, a tetracarboxylic acid dianhydride component including (Ab) aliphatic tetracarboxylic acid dianhydride, and a diamine component including a diamine represented by formula (2) A liquid crystal aligning agent containing at least one polymer selected from polyamic acid and an imidized polymer of the polyamic acid, and an organic solvent, coated on a substrate having a conductive film for driving a horizontal electric field Forming a coating film; [II] a step of irradiating
  • a transverse electric field drive liquid crystal display element can be obtained by preparing a second substrate.
  • the second substrate uses the substrate having no conductive film for driving a lateral electric field instead of the substrate having a conductive film for driving a horizontal electric field, except that the above steps [I] to [III] (for In order to use a substrate having no conductive film, for convenience, a liquid crystal alignment film having an orientation control ability is provided by using steps [I ′] to [III ′] in the present application. Two substrates can be obtained.
  • the manufacturing method of the lateral electric field drive type liquid crystal display device is [IV] a step of obtaining a liquid crystal display element by opposingly arranging the first and second substrates obtained above so that the liquid crystal alignment films of the first and second substrates face each other via liquid crystal; Have. Thereby, a transverse electric field drive type liquid crystal display device can be obtained.
  • Step [I] a polymer composition containing a photosensitive main polymer and an organic solvent is coated on a substrate having a conductive film for driving a transverse electric field to form a coating film.
  • the substrate is not particularly limited, but in the case where the liquid crystal display device to be produced is of a transmission type, it is preferable to use a substrate with high transparency. In that case, there is no particular limitation, and a glass substrate or a plastic substrate such as an acrylic substrate or a polycarbonate substrate can be used. In addition, an opaque substrate such as a silicon wafer can be used in consideration of application to a reflective liquid crystal display device.
  • the substrate has a conductive film for driving a lateral electric field.
  • a conductive film for driving a lateral electric field.
  • the conductive film when the liquid crystal display element is of a transmission type, ITO (Indium Tin Oxide: Indium Tin Oxide), IZO (Indium Zinc Oxide: Indium Zinc Oxide), and the like can be mentioned, but it is not limited thereto.
  • examples of the conductive film include materials such as aluminum that reflect light, but the present invention is not limited thereto.
  • a conventionally known method can be used as a method of forming a conductive film on a substrate.
  • substrate which has a conductive film for horizontal electric field drive is not specifically limited.
  • the coating method is generally industrially performed by screen printing, offset printing, flexographic printing, an inkjet method or the like.
  • Other coating methods include a dip method, a roll coater method, a slit coater method, a spinner method (rotation coating method) or a spray method, and these may be used according to the purpose.
  • the polymer composition After the polymer composition is coated on a substrate having a conductive film for driving a transverse electric field, it is heated to 50 to 300 ° C., preferably 50 to 300 ° C. by heating means such as a hot plate, a heat circulating oven or an IR (infrared) oven.
  • the solvent can be evaporated at 180 ° C. to obtain a coating.
  • the drying temperature at this time is preferably lower than that in the step [III] from the viewpoint of liquid crystal alignment stability. If the thickness of the coating film is too thick, the power consumption of the liquid crystal display device will be disadvantageous, and if it is too thin, the reliability of the liquid crystal display device may be reduced, preferably 5 nm to 300 nm, more preferably 10 nm to 150 nm. It is. In addition, it is also possible to provide the process of cooling the board
  • the ultraviolet-ray which polarized to the coating film obtained at the process [I] is irradiated.
  • the substrate is irradiated with ultraviolet light polarized through a polarizing plate from a certain direction.
  • ultraviolet rays to be used ultraviolet rays in the wavelength range of 100 nm to 400 nm can be used.
  • the optimum wavelength is selected via a filter or the like depending on the type of coating film used.
  • ultraviolet rays in the wavelength range of 240 nm to 400 nm can be selected and used so that a photolytic reaction can be selectively induced.
  • the ultraviolet light for example, light emitted from a high pressure mercury lamp or a metal halide lamp can be used.
  • the dose of polarized UV light depends on the coating used.
  • the irradiation dose is a polarized UV light that achieves the maximum value of ⁇ A (hereinafter also referred to as ⁇ Amax), which is the difference between the UV absorbance in the direction parallel to the polarization direction of polarized UV light and the UV absorbance in the perpendicular direction.
  • ⁇ Amax the maximum value of ⁇ A
  • it is in the range of 1% to 70%, and more preferably in the range of 1% to 50%.
  • step [III] the coating film irradiated with ultraviolet light polarized in step [II] is heated.
  • the coating film can be provided with orientation controllability. Heating can be performed using a heating means such as a hot plate, a heat circulating oven, or an IR (infrared) oven.
  • the heating temperature can be determined in consideration of the temperature at which good liquid crystal alignment stability and electrical properties are exhibited in the used coating film.
  • the heating temperature is preferably in a temperature range in which the main chain polymer exhibits good liquid crystal alignment stability. If the heating temperature is too low, the amplification effect of thermal anisotropy or thermal imidization tends to be insufficient, and if the heating temperature is too high than the temperature range, the anisotropy imparted by polarized light exposure becomes It tends to disappear and in this case self-assembly may make it difficult to reorient in one direction.
  • the thickness of the coating film formed after heating is preferably 5 nm to 300 nm, more preferably 50 nm to 150 nm, for the same reason as described in step [I].
  • Step [IV] is the same as the step (I ') to [III'] in the same manner as the substrate (first substrate) having a liquid crystal alignment film on the conductive film for lateral electric field drive obtained in the step [III]. And a liquid crystal alignment film-provided substrate (second substrate) having no conductive film, and the liquid crystal alignment film facing each other with the liquid crystal interposed therebetween, and the liquid crystal is formed by a known method It is a process of producing a cell and producing a horizontal electric field drive type liquid crystal display element.
  • Steps [I '] to [III'] in place of the substrate having a conductive film for driving a horizontal electric field in Step [I], a substrate not having the conductive film for driving a horizontal electric field is used, It can be carried out in the same manner as steps [I] to [III]. Since the difference between steps [I] to [III] and steps [I '] to [III'] is only the presence or absence of the conductive film described above, the description of steps [I '] to [III'] is omitted. Do.
  • a substrate with a liquid crystal alignment film is obtained from the liquid crystal alignment agent of the present invention by the method for producing a liquid crystal alignment film, and then a liquid crystal cell is produced by a known method. It is used as a display element.
  • a liquid crystal cell manufacturing method a liquid crystal display element having a passive matrix structure will be described as an example. It may be a liquid crystal display element of an active matrix structure in which switching elements such as TFTs (Thin Film Transistors) are provided in respective pixel parts constituting an image display.
  • TFTs Thin Film Transistors
  • These electrodes can be, for example, ITO electrodes, and are patterned to provide a desired image display. Then, an insulating film is provided on each substrate so as to cover the common electrode and the segment electrode.
  • the insulating film can be, for example, a film made of SiO 2 -TiO 2 formed by a sol-gel method.
  • the liquid crystal alignment film of the present invention is formed on each substrate by the above method.
  • the other substrate is superimposed on one substrate so that the alignment film surfaces face each other, and the periphery is bonded with a sealing material.
  • spacers are mixed into the sealing material in order to control the substrate gap.
  • spacers for controlling the substrate gap be dispersed also in the in-plane portion where the sealing material is not provided.
  • an opening capable of being filled with liquid crystal from the outside is provided.
  • a liquid crystal material is injected into a space surrounded by the two substrates and the sealant through an opening provided in the sealant. Thereafter, the opening is sealed with an adhesive.
  • a vacuum injection method may be used, or a method utilizing capillary action in the atmosphere may be used.
  • the polarizing plate is installed. Specifically, a pair of polarizing plates is attached to the surface of the two substrates opposite to the liquid crystal layer.
  • the liquid crystal display element of the present invention can be obtained through the above steps.
  • the sealing agent for example, a resin which is cured by ultraviolet irradiation or heating having a reactive group such as an epoxy group, an acryloyl group, a methacryloyl group, a hydroxyl group, an allyl group or an acetyl group is used.
  • a cured resin system having reactive groups of both epoxy group and (meth) acryloyl group.
  • an inorganic filler may be blended for the purpose of improving adhesion and moisture resistance.
  • the inorganic filler that can be used is not particularly limited, and specific examples thereof include spherical silica, fused silica, crystalline silica, titanium oxide, titanium black, silicon carbide, silicon nitride, boron nitride, calcium carbonate, magnesium carbonate, barium sulfate, Calcium sulfate, mica, talc, clay, alumina, magnesium oxide, zirconium oxide, aluminum hydroxide, calcium silicate, aluminum silicate, lithium aluminum silicate, lithium aluminum silicate, zirconium silicate, barium titanate, glass fiber, carbon fiber, molybdenum disulfide, asbestos, etc.
  • the inorganic fillers may be used as a mixture of two or more.
  • the substrate for a lateral electric field drive type liquid crystal display device manufactured using the polymer of the present invention or the lateral electric field drive type liquid crystal display device having the substrate is an excellent liquid crystal with a small amount of polarized ultraviolet radiation. Since the alignment stability and the relaxation characteristics of residual DC are exhibited, it can be suitably used for a large screen and high definition liquid crystal television.
  • the liquid crystal alignment film manufactured by the method of the present invention is excellent in reliability, and can be used also for a variable phase shifter using liquid crystal, and this variable phase shifter can change, for example, a resonance frequency. It can be suitably used as an antenna or the like.
  • the viscosity of the solution of this polyamic acid-polyimide copolymer at a temperature of 25 ° C. was 178 mPa ⁇ s.
  • the liquid crystal aligning agent (A-1) was obtained.
  • Synthesis Example 2 5.10 g (12.6 mmol) of DA-1 and 1.32 g (5.40 mmol) of DA-3 are added to a 100 mL four-necked flask equipped with a stirrer and a nitrogen inlet tube, and 61.8 g of NMP is added. The mixture was stirred and dispersed while feeding nitrogen. While stirring this diamine solution under water cooling, 2.19 g (11.2 mmol) of CA-1 and 1.21 g (5.40 mmol) of CA-2 were added, and 26.5 g of NMP was further added, and the mixture was subjected to a nitrogen atmosphere. The mixture was stirred at 40 ° C. for 6 hours to obtain a polyamic acid-polyimide copolymer solution.
  • the viscosity of the solution of this polyamic acid-polyimide copolymer at a temperature of 25 ° C. was 193 mPa ⁇ s.
  • the liquid crystal aligning agent (A-2) was obtained.
  • Synthesis Example 6 Add 3.19 g (16.0 mmol) of DA-4, 0.977 g (4.00 mmol) of DA-3 to a 100 mL four-necked flask equipped with a stirrer and a nitrogen inlet tube, and add 41.0 g of NMP. The mixture was stirred and dissolved while feeding nitrogen. While stirring this diamine solution under water cooling, 1.65 g (8.40 mmol) of CA-1 is added, and after stirring for 4 hours at 23.degree. C. under a nitrogen atmosphere, 2.18 g (10.0 mmol) of CA-4. Then, 17.6 g of NMP was added, and the mixture was stirred at 50 ° C. for 18 hours under a nitrogen atmosphere to obtain a polyamic acid solution.
  • the viscosity of the solution of this polyamic acid at a temperature of 25 ° C. was 246 mPa ⁇ s.
  • This solution of polyamic acid is separated into 29.7 g in a 100 mL Erlenmeyer flask containing a stirrer, 25.7 g of NMP and 23.8 g of BCS are added, and stirred with a magnetic stirrer for 2 hours to obtain a liquid crystal aligning agent ( I got A-6).
  • Synthesis Example 7 In a 100 mL four-necked flask equipped with a stirrer and a nitrogen inlet tube, 3.97 g (20.0 mmol) of DA-7 was weighed, 49.1 g of NMP was added, and the mixture was stirred and dissolved while feeding nitrogen. While stirring the diamine solution under water cooling, 5.59 g (19.0 mmol) of CA-3 was added, 21.0 g of NMP was further added, and the solution of polyamic acid was stirred at 50 ° C. for 20 hours under a nitrogen atmosphere. Obtained. The viscosity of the solution of this polyamic acid at a temperature of 25 ° C. was 376 mPa ⁇ s.
  • Synthesis Example 8 8.07 g of the liquid crystal aligning agent (A-1) obtained in Synthesis Example 1 and 12.1 g of the liquid crystal aligning agent (A-3) obtained in Synthesis Example 3 were added to a 50 mL Erlenmeyer flask containing a stirrer. The resultant was stirred for 2 hours with a magnetic stirrer to obtain a liquid crystal aligning agent (A-8).
  • Synthesis Example 9 8.12 g of the liquid crystal aligning agent (A-1) obtained in Synthesis Example 1 and 12.2 g of the liquid crystal aligning agent (A-4) obtained in Synthesis Example 4 were added to a 50 mL Erlenmeyer flask containing a stirrer. The resultant was stirred for 2 hours with a magnetic stirrer to obtain a liquid crystal aligning agent (A-9).
  • Synthesis Example 10 8.21 g of the liquid crystal aligning agent (A-1) obtained in Synthesis Example 1 and 12.3 g of the liquid crystal aligning agent (A-5) obtained in Synthesis Example 5 were added to a 50 mL Erlenmeyer flask containing a stirrer. The resultant was stirred for 2 hours with a magnetic stirrer to obtain a liquid crystal aligning agent (A-10).
  • Synthesis Example 11 6.02 g of the liquid crystal aligning agent (A-2) obtained in Synthesis Example 2 and 14.0 g of the liquid crystal aligning agent (A-6) obtained in Synthesis Example 6 were added to a 50 mL Erlenmeyer flask containing a stirrer. The resultant was stirred for 2 hours with a magnetic stirrer to obtain a liquid crystal aligning agent (A-11).
  • Synthesis Example 12 6.11 g of the liquid crystal aligning agent (A-2) obtained in Synthesis Example 2 and 14.3 g of the liquid crystal aligning agent (A-7) obtained in Synthesis Example 7 were weighed in a 50 mL Erlenmeyer flask containing a stirrer. The resultant was stirred for 2 hours with a magnetic stirrer to obtain a liquid crystal aligning agent (A-12).
  • Synthesis Example 13 4.24 g of the liquid crystal aligning agent (A-1) obtained in Synthesis Example 1 and 16.96 g of the liquid crystal aligning agent (A-3) obtained in Synthesis Example 3 were added to a 50 mL conical flask containing a stirrer. The resultant was stirred for 2 hours with a magnetic stirrer to obtain a liquid crystal aligning agent (A-13).
  • the viscosity of the solution of this polyamic acid-polyimide copolymer at a temperature of 25 ° C. was 269 mPa ⁇ s. Separate 30.6 g of this polyamic acid-polyimide copolymer solution into a 100 mL Erlenmeyer flask containing a stirrer, add 17.0 g of NMP, and 20.4 g of BCS, and stir with a magnetic stirrer for 2 hours. The liquid crystal aligning agent (B-1) was obtained.
  • Comparative Synthesis Example 3 8.14 g of the liquid crystal aligning agent (B-1) obtained in Comparative Synthesis Example 1 and 12.2 g of the liquid crystal aligning agent (A-3) obtained in Synthesis Example 3 in a 50 mL Erlenmeyer flask containing a stirrer. The mixture was weighed and stirred with a magnetic stirrer for 2 hours to obtain a liquid crystal aligning agent (B-3).
  • Comparative Synthesis Example 4 6.07 g of the liquid crystal aligning agent (A-2) obtained in Synthesis Example 2 and 14.2 g of the liquid crystal aligning agent (B-2) obtained in Comparative Synthesis Example 2 in a 50 mL Erlenmeyer flask containing a stirrer. The mixture was weighed and stirred with a magnetic stirrer for 2 hours to obtain a liquid crystal aligning agent (B-4).
  • a liquid crystal cell having the configuration of a liquid crystal display element of the FFS system was manufactured.
  • a substrate with an electrode was prepared.
  • the substrate is a glass substrate of 30 mm ⁇ 35 mm in size and 0.7 mm in thickness.
  • a SiN (silicon nitride) film formed by a CVD method was formed on the first counter electrode.
  • the film thickness of the second SiN film is 500 nm and functions as an interlayer insulating film.
  • a comb-like pixel electrode formed by patterning an IZO film is disposed on the second layer SiN film, and two pixels of a first pixel and a second pixel are formed. .
  • the size of each pixel is 10 mm long and about 5 mm wide. At this time, the first opposing electrode and the third pixel electrode are electrically insulated by the action of the second SiN film.
  • the pixel electrode of the third layer is a comb-tooth formed by arranging a plurality of V-shaped electrode elements whose central portion is bent as in the case described in JP-A-2014-77845 (Japanese Patent Application Publication) It has a letter shape.
  • the width in the short direction of each electrode element is 3 ⁇ m, and the distance between the electrode elements is 6 ⁇ m. Since the pixel electrode forming each pixel is configured by arranging a plurality of bent, V-shaped electrode elements in the central portion, the shape of each pixel is not rectangular but is bent at the central portion like the electrode elements. , Bold, with a letter-like shape.
  • each pixel is divided up and down bordering on the central bending part, and has the 1st field of the upper part of a bending part, and the 2nd field of the lower side.
  • the forming directions of the electrode elements of the pixel electrodes constituting them are different. That is, when the polarization plane of polarized ultraviolet light described later is based on the direction of the line segment projected onto the substrate, in the first region of the pixel, the electrode element of the pixel electrode is formed to form an angle of + 10 ° (clockwise). In the second region of the pixel, the electrode element of the pixel electrode was formed to form an angle of -10 ° (clockwise).
  • the direction of the rotation operation (in-plane switching) in the substrate plane of the liquid crystal induced by the voltage application between the pixel electrode and the counter electrode is It comprised so that it might become mutually reverse direction.
  • the liquid crystal aligning agent obtained in Synthesis Examples 8 to 12 and Comparative Synthesis Examples 3 to 4 was filtered with a 1.0 ⁇ m filter, and then applied to the prepared electrode-equipped substrate by spin coating. . It was then dried for 90 seconds on a hot plate set at 70 ° C. Then, using an exposure apparatus: APL-L050121S1S-APW01 manufactured by Ushio Electric Co., Ltd., the substrate was irradiated with linearly polarized ultraviolet light through the wavelength selection filter and the polarizing plate from the vertical direction.
  • the polarization plane direction was set such that the direction of the line segment obtained by projecting the polarization plane of the polarized ultraviolet light onto the substrate was inclined by 10 ° with respect to the third layer IZO comb electrode.
  • baking was performed for 30 minutes in an IR (infrared) type oven set at 230 ° C., to obtain a substrate with a polyimide liquid crystal alignment film having a film thickness of 100 nm subjected to alignment treatment.
  • a substrate with a polyimide liquid crystal alignment film subjected to the alignment treatment in the same manner as described above was obtained also on a glass substrate having a columnar spacer with a height of 4 ⁇ m and having an ITO electrode on the back surface.
  • a sealing agent is printed on one of the two substrates with the liquid crystal alignment film with the liquid crystal injection port left, and the liquid crystal alignment film face of the other substrate faces the polarized ultraviolet light.
  • the polarization planes were pasted and crimped so that the directions of the line segments projected onto the substrate were parallel.
  • the sealing agent was cured to produce an empty cell having a cell gap of 4 ⁇ m.
  • a liquid crystal MLC-7026-100 (Melck negative liquid crystal) was injected into the empty cell by a pressure reduction injection method, and the injection port was sealed to obtain an FFS liquid crystal cell. Thereafter, the obtained liquid crystal cell was heated at 120 ° C. for 30 minutes, allowed to stand at 23 ° C. overnight, and then used for evaluation of liquid crystal alignment stability and relaxation property of residual DC.
  • the rotation angle when the liquid crystal cell is rotated from the angle at which the second region of the first pixel is the darkest to the angle at which the first region is the dark is calculated as the angle ⁇ .
  • the second area and the first area were compared, and the similar angle ⁇ was calculated.
  • the average value of the angle ⁇ values of the first pixel and the second pixel was calculated as the angle ⁇ of the liquid crystal cell.
  • the liquid crystal cell is disposed between two polarizing plates disposed so that the polarization axes are orthogonal to each other, and the pixel electrode and the counter electrode are short-circuited to have the same potential.
  • the backlight was illuminated, and the angle of the liquid crystal cell was adjusted so as to minimize the brightness of the LED backlight transmitted light measured on the two polarizing plates.
  • the VT characteristic voltage-transmittance characteristic
  • the AC voltage with a relative transmittance of 23% is measured. Calculated. Since this AC voltage corresponds to a region where the change in luminance with respect to the voltage is large, it is convenient to evaluate the residual DC through the luminance.
  • Example 1 A liquid crystal cell was prepared as described above using two types of liquid crystal aligning agent (A-8) obtained in Synthesis Example 8 stored at ⁇ 20 ° C. for 8 days and stored at 23 ° C. for 8 days. did.
  • the irradiation of polarized ultraviolet light was performed using a high pressure mercury lamp through a wavelength selection filter: 240 LCF and a polarizing plate of 254 nm type.
  • the irradiation amount of polarized ultraviolet light is measured by using an illuminance meter UVD-S254SB manufactured by Ushio Inc., and the irradiation amounts of 200, 300, 400, 600, 900, 1500 and 2000 mJ / cm 2 at a wavelength of 254 nm, respectively.
  • the polarized ultraviolet irradiation dose at which the angle ⁇ was the best is 300 mJ / cm 2
  • the angle ⁇ [1] is 0.18 °
  • the angle ⁇ [2] is The degree of deterioration of the angle ⁇ due to storage at 0.19 ° and 23 ° C. was 106, which was good.
  • the relaxation characteristics of the residual DC of the same polarized ultraviolet radiation dose, which was previously evaluated before the evaluation of the liquid crystal alignment stability is excellent with a relative transmittance of 26.1% after 30 minutes of DC voltage superposition.
  • Comparative Examples 1 to 3 The alignment stability of the liquid crystal and the relaxation characteristics of the residual DC were evaluated in the same manner as in Example 1 except that the liquid crystal aligning agent obtained in Comparative Synthesis Examples 3 to 5 was used.
  • the liquid crystal aligning agent used in Examples 1 to 6 and Comparative Examples 1 to 3 is a liquid crystal aligning agent containing the polymer represented by (A-a), and a liquid crystal containing the polymer represented by (A-b)
  • the weight% of each in the liquid crystal aligning agent containing the aligning agent and the polymer represented by (Aa) and (Ab) is shown in Table 1.
  • Table 2 when the liquid crystal aligning agents obtained in Examples 1 to 6 and Comparative Examples 1 to 3 were used, the amount of polarized ultraviolet light with the best angle ⁇ was evaluated as a result of evaluation of liquid crystal alignment stability, and residual DC The results of the evaluation of the relaxation characteristics of
  • the angle ⁇ which is the difference between the orientation azimuths before and after AC driving, was good at less than 0.4 °, and the liquid crystal aligning agent was stored at 23 ° C. for 8 days
  • the degree of deterioration of the angle ⁇ is also good at less than 150, and the angle ⁇ is best with a small polarized ultraviolet radiation dose of 300 mJ / cm 2 , and the relative transmittance after 30 minutes of DC voltage superposition showing relaxation characteristics of residual DC is Since it is favorable at less than 29.0% and all have good afterimage characteristics, it is excellent in the display quality improvement of a liquid crystal display element.
  • the substrate for a lateral electric field drive-type liquid crystal display device manufactured using the polymer of the present invention or the lateral electric field drive-type liquid crystal display device having the substrate has excellent liquid crystal alignment stability and residual DC with a small amount of polarized ultraviolet radiation. It is excellent in productivity and afterimage characteristics because it exhibits the relaxation characteristics of Therefore, it can be suitably used for a large screen and high definition liquid crystal television.

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Abstract

La présente invention concerne un substrat ayant un film d'alignement de cristaux liquides qui est destiné à un élément d'affichage à cristaux liquides de type à entraînement dans le plan, auquel il est donné la capacité à commander l'alignement à une efficacité élevée, et qui présente d'excellentes propriétés contre la combustion provoquée par un désalignement de cristaux liquides ou de CC résiduel, et un élément d'affichage à cristaux liquides de type à entraînement dans le plan ayant le substrat. La présente invention concerne un agent d'alignement de cristaux liquides contenant : (A-a) au moins un polymère choisi parmi les acides polyamiques obtenus en utilisant un constituant diamine et un constituant dianhydride d'acide tétracarboxylique comprenant un dianhydride d'acide tétracarboxylique représenté par la formule (1) (dans la formule (1), i représente 0 ou 1, et X représente une liaison simple, une liaison éther ou similaire), et des polymères imidisés des acides polyamiques ; (A-b) au moins un polymère choisi parmi les acides polyamiques obtenus en utilisant un constituant dianhydride d'acide tétracarboxylique comprenant un dianhydride d'acide tétracarboxylique aliphatique et un constituant diamine comprenant une diamine représentée par la formule (2), et des polymères imidisés des acides polyamiques ; et un solvant organique, le rapport en poids de (A-a) et (A-b) étant représenté comme (A-a) : (A-b) = 55 : 45 à 90 : 10.
PCT/JP2018/031670 2017-08-29 2018-08-28 Agent d'alignement de cristaux liquides, film d'alignement de cristaux liquides , et élément d'affichage à cristaux liquides WO2019044795A1 (fr)

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JPWO2019044795A1 (ja) 2020-10-15
CN111344630A (zh) 2020-06-26
TW201920630A (zh) 2019-06-01
CN111344630B (zh) 2023-04-04

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