WO2017126627A1 - 液晶配向剤、液晶配向膜及びそれを用いた液晶表示素子 - Google Patents
液晶配向剤、液晶配向膜及びそれを用いた液晶表示素子 Download PDFInfo
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- WO2017126627A1 WO2017126627A1 PCT/JP2017/001805 JP2017001805W WO2017126627A1 WO 2017126627 A1 WO2017126627 A1 WO 2017126627A1 JP 2017001805 W JP2017001805 W JP 2017001805W WO 2017126627 A1 WO2017126627 A1 WO 2017126627A1
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- liquid crystal
- crystal aligning
- group
- formula
- aligning agent
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- YXBIAYXZUDJVEB-UHFFFAOYSA-N Cc(cc1)c(C)cc1-c1ccc(C)c(C)c1 Chemical compound Cc(cc1)c(C)cc1-c1ccc(C)c(C)c1 YXBIAYXZUDJVEB-UHFFFAOYSA-N 0.000 description 1
- GLFKFHJEFMLTOB-UHFFFAOYSA-N Cc1c(C)cc(C(C(F)(F)F)(C(F)(F)F)c2cc(C)c(C)cc2)cc1 Chemical compound Cc1c(C)cc(C(C(F)(F)F)(C(F)(F)F)c2cc(C)c(C)cc2)cc1 GLFKFHJEFMLTOB-UHFFFAOYSA-N 0.000 description 1
- OKRNLSUTBJUVKA-UHFFFAOYSA-N OCCN(CCO)C(CCCCC(N(CCO)CCO)=O)=O Chemical compound OCCN(CCO)C(CCCCC(N(CCO)CCO)=O)=O OKRNLSUTBJUVKA-UHFFFAOYSA-N 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K19/00—Liquid crystal materials
- C09K19/52—Liquid crystal materials characterised by components which are not liquid crystals, e.g. additives with special physical aspect: solvents, solid particles
- C09K19/54—Additives having no specific mesophase characterised by their chemical composition
- C09K19/56—Aligning agents
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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
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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
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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
- G02F1/133711—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers by organic films, e.g. polymeric films
- G02F1/133723—Polyimide, polyamide-imide
Definitions
- the present invention relates to a liquid crystal aligning agent using a novel polymer, a liquid crystal aligning film, and a liquid crystal display element using the same.
- Liquid crystal display elements are widely used as display units for personal computers, mobile phones, smartphones, televisions and the like.
- the liquid crystal display element includes, for example, a liquid crystal layer sandwiched between an element substrate and a color filter substrate, a pixel electrode and a common electrode that apply an electric field to the liquid crystal layer, an alignment film that controls the alignment of liquid crystal molecules in the liquid crystal layer, A thin film transistor (TFT) for switching an electric signal supplied to the pixel electrode is provided.
- TFT thin film transistor
- As a driving method of liquid crystal molecules a vertical electric field method such as a TN method and a VA method, and a horizontal electric field method such as an IPS method and an FFS method are known.
- the horizontal electric field method in which an electrode is formed only on one side of the substrate and a voltage is applied in a direction parallel to the substrate is wider than the conventional vertical electric field method in which voltage is applied to the electrodes formed on the upper and lower substrates to drive the liquid crystal. It is known as a liquid crystal display element having viewing angle characteristics and capable of high-quality display.
- the horizontal electric field type liquid crystal cell is excellent in viewing angle characteristics, since there are few electrode portions formed in the substrate, if the voltage holding ratio is low, a sufficient voltage is not applied to the liquid crystal and the display contrast is lowered. Further, if the stability of the liquid crystal alignment is small, the liquid crystal does not return to the initial state when the liquid crystal is driven for a long time, which causes a decrease in contrast and an afterimage. Therefore, the stability of the liquid crystal alignment is important. Furthermore, static electricity is likely to be accumulated in the liquid crystal cell, and charges are accumulated in the liquid crystal cell even when a positive / negative asymmetric voltage generated by driving is applied, and these accumulated charges affect the display as a disorder of liquid crystal alignment or an afterimage. The display quality of the liquid crystal element is significantly reduced. In addition, charge is accumulated by irradiating the liquid crystal cell with backlight light immediately after driving, an afterimage is generated even in a short time driving, and the size of flicker (flicker) changes during driving, etc. It will cause problems.
- Patent Document 1 contains a specific diamine and an aliphatic tetracarboxylic acid derivative as a liquid crystal aligning agent that has excellent voltage holding ratio and reduced charge accumulation when used in such a horizontal electric field type liquid crystal display element.
- a liquid crystal aligning agent is disclosed.
- the characteristics required for the liquid crystal alignment film are becoming stricter, and it is difficult to sufficiently satisfy all the required characteristics with these conventional techniques.
- the present invention provides a liquid crystal aligning agent, a liquid crystal aligning film, and a liquid crystal display element that can obtain a liquid crystal aligning film that has an excellent voltage holding ratio, quickly reduces accumulated charges, and is less likely to flicker during driving. This is the issue.
- the present invention is based on this finding and has the following gist.
- the liquid crystal aligning agent characterized by including the polymer obtained from the diamine which has a structure represented by following formula (1), and an organic solvent.
- R 1 represents a hydrogen atom, a fluorine atom, a cyano group, a hydroxy group, or a monovalent organic group, and * represents a site bonded to another group. An arbitrary hydrogen atom of the benzene ring is converted to a monovalent organic group. May be substituted.
- the polymer is at least one selected from the group consisting of a polyimide precursor which is a polycondensate of a diamine having a structure represented by the formula (1) and a tetracarboxylic dianhydride and a poimide which is an imidized product thereof. 2.
- the liquid crystal aligning agent according to 1 above which is a seed polymer. 3. 3.
- R 1 is the same as that in formula (1), R 2 independently represents a single bond or the structure of the following formula (3), and n represents an integer of 1 to 3. Any hydrogen atom may be substituted with a monovalent organic group.
- R 3 is 2 selected from a single bond, —O—, —COO—, —OCO—, — (CH 2 ) 1 —, —O (CH 2 ) m O—, —CONH—, and —NHCO—.
- the liquid crystal aligning agent according to 4 wherein in the formula (6), the structure of X 1 is at least one selected from the group consisting of the structures of formulas (A-1) to (A-21) described later. 6). 6.
- the liquid crystal aligning agent according to 4 or 5 wherein the polymer having the structural unit represented by the formula (6) is contained in an amount of 10 mol% or more based on the total polymer contained in the liquid crystal aligning agent. 7).
- the organic solvent contains at least one selected from the group consisting of 4-hydroxy-4-methyl-2-pentanone and diethylene glycol diethyl ether. 8).
- a liquid crystal display device comprising the liquid crystal alignment film as described in 8 above. 10. 10. The liquid crystal display element as described in 9 above, wherein the liquid crystal display element is of a lateral electric field drive method. 11. At least 1 type of polymer chosen from the group which consists of the polyimide precursor which is a polycondensate of the diamine which has a structure represented by following formula (1), and tetracarboxylic dianhydride, and the polyimide which is the imidation thing. (R 1 and * are as defined in 1 above.) 12 The polymer according to 11 above, wherein the diamine is represented by the following formula (2). (R 1 , R 2 , and n are as described in 3 above.) 13.
- the structure of the above (1) possessed by the polymer contained in the liquid crystal aligning agent of the present invention has a conductive pyrrole structure and a conjugated structure, which promotes the movement of charges in, for example, a liquid crystal alignment film. It is considered that relaxation of accumulated charges can be promoted.
- the liquid crystal aligning agent of the present invention includes a polymer (also referred to as a specific polymer in the present invention) obtained from a diamine having a structure represented by the following formula (1) (also referred to as a specific diamine in the present invention), and an organic solvent. Containing.
- R 1 represents hydrogen, a fluorine atom, a cyano group, a hydroxy group, or a monovalent organic group
- * represents a site bonded to another group.
- the hydrogen atom may be optionally substituted with a monovalent organic group.
- the monovalent organic group include an alkyl group, an alkenyl group, an alkoxy group, a fluoroalkyl group, a fluoroalkenyl group, or a fluoroalkoxy group having 1 to 10 carbon atoms, preferably 1 to 3 carbon atoms.
- R 1 is preferably a hydrogen atom or a methyl group.
- the bonding position of the benzene ring to the pyrrole ring is the carbon atom adjacent to the nitrogen atom on the pyrrole ring as shown in the following formula (1-1) from the viewpoint of charge transfer. Is preferred.
- the specific diamine can be represented by, for example, the following formula (1-2), particularly preferably a diamine represented by the following formula (1-3), and further represented by the formula (1-4). Diamine is more preferred.
- R 1 is the same as in the case of the formula (1), and Q 1 and Q 2 are each independently a single bond or divalent It is an organic group, that is, Q 1 and Q 2 may have different structures. Further, the two Q 2 in the formula (1-4) may have different structures. Furthermore, any hydrogen atom of the benzene ring may be substituted with a monovalent organic group as in the case of the above formula (1).
- Preferable examples of the specific diamine include diamines represented by the following formula (2), more preferably diamines represented by the formula (2-1).
- R 1 in the above formulas (2) and (2-1) is the same as that in the above formula (1).
- Two R 2 s each independently represent a single bond or a structure of the following formula (3).
- any hydrogen atom in the benzene ring may be substituted with a monovalent organic group.
- R 3 represents a single bond, —O—, —COO—, —OCO—, — (CH 2 ) 1 —, —O (CH 2 ) m O—, —CONH—, and — It represents a divalent organic group selected from the group consisting of NHCO—, wherein l and m each represents an integer of 1 to 5.
- R 3 is preferably a single bond, —O—, —COO—, —OCO—, —CONH—, or —NHCO— from the viewpoint of relaxation of accumulated charge.
- diamine of the above formula (2) examples include the following, but are not limited thereto. Of these, (2-1-1), (2-1-2), (2-1-3), (2-1-5), and (2-1-8) from the viewpoint of relaxation of accumulated charges. , (2-1-9), (2-1-10), (2-1-11) or (2-1-12) are preferred, (2-1-1), (2-1-2) , (2-1-3), (2-1-11) or (2-1-12) are particularly preferred.
- the method for synthesizing the specific diamine is not particularly limited.
- the method of using the dinitro compound represented by following formula (4), and converting the nitro group which it has into an amino group by a reductive reaction is mentioned.
- the catalyst used for the above reduction reaction is preferably an activated carbon-supported metal available as a commercial product, and examples thereof include palladium-activated carbon, platinum-activated carbon, and rhodium-activated carbon. Further, palladium hydroxide, platinum oxide, Raney nickel, and the like can be used, and it is not always necessary to use an activated carbon-supported metal catalyst. Palladium-activated carbon, which is generally widely used, is preferred because good results are obtained.
- the amount of the solvent used is not particularly limited, but is 0.1 to 100 times the mass of the dinitro compound (4).
- the amount is preferably 0.5 to 30 times by mass, more preferably 1 to 10 times by mass.
- the reaction temperature is not particularly limited, but it is in the range from ⁇ 100 ° C. to the boiling point of the solvent used, preferably ⁇ 50 to 150 ° C.
- the reaction time is usually 0.05 to 350 hours, preferably 0.5 to 100 hours.
- any compound capable of reacting with amines may be used.
- examples thereof include acid halides, acid anhydrides, isocyanates, epoxy compounds, oxetanes, halogenated aryls, and halogenated alkyls.
- alcohols in which a hydroxyl group of alcohol is substituted with a leaving group such as OMs (mesyl group), OTf (triflate group), and OTs (tosyl group) can be used.
- R 1 When R 1 is introduced by reacting with an acid halide, it is preferably carried out in the presence of a base.
- acid halides include acetyl chloride, propionic acid chloride, methyl chloroformate, ethyl chloroformate, n-propyl chloroformate, i-propyl chloroformate, n-butyl chloroformate, i-butyl chloroformate, t-chloroformate.
- Examples include butyl, benzyl chloroformate, and 9-fluorenyl chloroformate.
- the base is not particularly limited as long as it can be synthesized.
- Inorganic bases such as potassium carbonate, sodium carbonate, cesium carbonate, sodium alkoxide, potassium alkoxide, sodium hydroxide, potassium hydroxide, sodium hydride, pyridine, dimethylamino Organic bases such as pyridine, trimethylamine, triethylamine and tributylamine can be used.
- the reaction solvent and reaction temperature are the same as in the reduction reaction of the nitro compound (4).
- R 1 When R 1 is introduced by reacting with an acid anhydride, examples of the acid anhydride include acetic anhydride, propionic anhydride, dimethyl dicarbonate, diethyl dicarbonate, di-tertiary butyl dicarbonate, dibenzyl dicarbonate, etc. Is mentioned.
- acetic anhydride propionic anhydride
- dimethyl dicarbonate diethyl dicarbonate
- di-tertiary butyl dicarbonate dibenzyl dicarbonate
- dibenzyl dicarbonate etc. Is mentioned.
- pyridine, collidine, N, N-dimethyl-4-aminopyridine and the like may be used as a catalyst.
- the amount of the catalyst is 0.0001 mol to 1 mol with respect to the compound (5).
- the reaction solvent and reaction temperature are the same as in the above acid halide.
- examples of isocyanates include methyl isocyanate, ethyl isocyanate, n-propyl isocyanate, and phenyl isocyanate.
- the reaction solvent and reaction temperature are the same as in the above acid halide.
- R 1 When R 1 is introduced by reacting an epoxy compound or an oxetane compound, examples of the epoxy compound or oxetane include ethylene oxide, propylene oxide, 1,2-butylene oxide, and trimethylene oxide.
- the reaction solvent and reaction temperature are the same as in the above acid halide.
- R 1 is introduced by reacting an alcohol in which a hydroxyl group of the alcohol is substituted with a leaving group such as OMs, OTf, or OTs
- the reaction is preferably performed in the presence of a base. Examples of the alcohols include methanol, ethanol, 1-propanol, and the like.
- OMs By reacting these alcohols with methanesulfonyl chloride, trifluoromethanesulfonyl chloride, paratoluenesulfonic acid chloride, and the like, OMs, Alcohols substituted with leaving groups such as OTf and OTs can be obtained.
- Examples of the base, reaction solvent, and reaction temperature are the same as in the above acid halide.
- R 1 When R 1 is introduced by reacting an alkyl halide, it is preferably carried out in the presence of a base.
- alkyl halides include methyl iodide, ethyl iodide, n-propyl iodide, methyl bromide, ethyl bromide, n-propyl bromide and the like.
- the base include metal alkoxides such as potassium tert-butoxide and sodium tert-butoxide in addition to the above-mentioned bases.
- the reaction solvent and reaction temperature are the same as in the above acid halide.
- the base used in the above reaction the base exemplified in the above acid halide can be used, and the reaction solvent and the reaction temperature are the same as described above.
- Zinc chloride, sodium iodide, potassium iodide, tetrabutylammonium iodide, or the like can be used for the purpose of accelerating the rate in the reaction.
- the corresponding halogenated pyrrole and the organometallic reagent are preferably obtained by a cross-coupling reaction using a metal catalyst.
- X represents Br, I, or OTf.
- M represents B (OH) 2 or 4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl.
- the cross coupling reaction (Suzuki-Miyaura reaction) preferably uses a metal complex and a ligand as a catalyst, but the reaction proceeds even without a catalyst.
- metal complexes include palladium acetate, palladium chloride, palladium chloride-acetonitrile complex, palladium-activated carbon, bis (dibenzylideneacetone) palladium, tris (dibenzylideneacetone) dipalladium, bis (acetonitrile) dichloropalladium, bis (benzo Nitrile) dichloropalladium, CuCl, CuBr, CuI, CuCN and the like.
- ligands include triphenylphosphine, tri-o-tolylphosphine, diphenylmethylphosphine, phenyldimethylphosphine, 1,2-bis (diphenylphosphino) ethane, 1,3-bis (diphenylphosphino) propane 1,4-bis (diphenylphosphino) butane, 1,1′-bis (diphenylphosphino) ferrocene, trimethyl phosphite, triethyl phosphite, triphenyl phosphite, tri-tert-butylphosphine and the like.
- the amount of the metal complex used may be a so-called catalytic amount, and 20 mol% or less is sufficient with respect to the substrate, preferably 10 mol% or less.
- the liquid crystal aligning agent of this invention is a polymer obtained using specific diamine.
- the polymer include polyamic acid, polyamic acid ester, polyimide, polyurea, polyamide and the like.
- X 1 is a tetravalent organic group derived from a tetracarboxylic acid derivative.
- Y 1 is a divalent organic group derived from a diamine containing the structure of formula (1).
- R 4 is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. R 4 is preferably a hydrogen atom, a methyl group or an ethyl group from the viewpoint of ease of imidization by heating.
- X 1 is a tetravalent organic group derived from a tetracarboxylic acid derivative.
- X 1 depends on the required properties such as solubility of the polymer in the solvent, coating property of the liquid crystal aligning agent, orientation of the liquid crystal when the liquid crystal aligning film is used, voltage holding ratio, accumulated charge, and the like. It is appropriately selected and one kind or two or more kinds may be used in the same polymer. Specific examples of X 1 include the structures of formulas (X-1) to (X-46) described on pages 13 to 14 of International Publication No. 2015/119168.
- (A-1) or (A-2) is particularly preferred from the standpoint of further improving rubbing resistance
- (A-4) is particularly preferred from the standpoint of further improving the rate of relaxation of accumulated charges
- (A-15) to (A-17) are particularly preferred from the standpoint of further improving the liquid crystal orientation and the rate of relaxation of accumulated charges.
- Y 1 may include a structure in which two amino groups are removed from the diamine of Formula (2).
- Y 1 represents the above formulas (2-1-1), (2-1-2), (2-1-3), (2-1-5), (2-1-8), (2 A structure in which two amino groups are removed from the structure of (-1-9), (2-1-10), (2-1-11), and (2-1-12) is more preferable, (2-1-1 ), (2-1-2), (2-1-3), (2-1-11), and (2-1-12), a structure obtained by removing two amino groups is particularly preferable.
- the liquid crystal aligning agent of this invention is from the polyimide which is a polyimide precursor which has a structural unit represented by following formula (7) other than the polyimide precursor which has a structural unit of said Formula (6), and its imidized substance. It may contain at least one polymer selected from the group consisting of
- X 2 is a tetravalent organic group derived from the tetracarboxylic acid derivatives.
- Y 2 is a divalent organic group derived from a diamine not having the structure of formula (1).
- R 4 has the same definition as in formula (6).
- R 5 represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. Moreover, it is preferable that at least one of two R ⁇ 5 > is a hydrogen atom.
- X 2 are the same as those exemplified for X 1 in formula (6), including preferred examples.
- Y 2 is selected according to properties such as solubility of the polymer in the solvent, coating property of the liquid crystal aligning agent, liquid crystal orientation when the liquid crystal alignment film is used, voltage holding ratio, accumulated charge, etc. However, two or more types may be used.
- Y 2 include the structure of Formula (2) published on page 4 of International Publication No. 2015/119168, and Formulas (Y-1) to (Y -97), structures of (Y-101) to (Y-118); a divalent organic group obtained by removing two amino groups from formula (2), published on page 6 of International Publication No. 2013/008906; Bivalent organic group obtained by removing two amino groups from Formula (1) published on page 8 of International Publication No. 2015/122413; Structure of Formula (3) published on page 8 of International Publication No.
- (B-28), (B-29) and the like are particularly preferable from the viewpoint of further improving the rubbing resistance, and (B-1) to (B-3) and the like are further improved in liquid crystal orientation.
- (B-14) to (B-18), (B-27) and the like are particularly preferable from the viewpoint of further improving the relaxation rate of accumulated charges, and (B-26) and the like are This is preferable from the viewpoint of further improving the voltage holding ratio.
- the liquid crystal aligning agent of this invention contains the polyimide precursor which has a structural unit of Formula (6), and the polyimide precursor which has a structural unit of Formula (7), the structural unit of Formula (6) is Formula (6).
- the formula (7) are preferably 10 mol% or more, more preferably 20 mol% or more, and particularly preferably 30 mol% or more.
- the molecular weight of the polyimide precursors of the above formulas (6) and (7) is preferably 2,000 to 500,000, more preferably 5,000 to 300,000, and still more preferably 10 in terms of weight average molecular weight. , 100,000 to 100,000.
- the polyimide having a divalent group represented by the formula (1) in the main chain include a polyimide obtained by ring-closing the polyimide precursor.
- the ring closure rate (also referred to as imidation rate) of the amic acid group is not necessarily 100%, and can be arbitrarily adjusted according to the use and purpose.
- Examples of the method for imidizing the polyimide precursor include thermal imidization in which the polyimide precursor solution is heated as it is, or catalytic imidization in which a catalyst is added to the polyimide precursor solution.
- the liquid crystal aligning agent of this invention contains the polymer (specific polymer) obtained from the diamine which has a structure represented by Formula (1), even if it contains 2 or more types of specific polymers of a different structure. Good. Moreover, in addition to a specific polymer, you may contain the other polymer, ie, the polymer which does not have a bivalent group represented by Formula (1).
- Other polymers include polyamic acid, polyimide, polyamic acid ester, polyester, polyamide, polyurea, polyorganosiloxane, cellulose derivative, polyacetal, polystyrene or derivatives thereof, poly (styrene-phenylmaleimide) derivative, poly (meth) acrylate Etc.
- the ratio of the specific polymer with respect to all polymer components is preferably 5% by mass or more, for example, 5 to 95% by mass.
- the liquid crystal aligning agent generally takes the form of a coating liquid from the viewpoint of forming a uniform thin film. It is preferable that the liquid crystal aligning agent of this invention is also a coating liquid containing the said polymer component and the organic solvent in which this polymer component is dissolved. At that time, the concentration of the polymer in the liquid crystal aligning agent can be appropriately changed by setting the thickness of the coating film to be formed. From the viewpoint of forming a uniform and defect-free coating film, it is preferably 1% by mass or more, and from the viewpoint of storage stability of the solution, it is preferably 10% by mass or less. A particularly preferred polymer concentration is 2 to 8% by mass.
- the organic solvent contained in the liquid crystal aligning agent is not particularly limited as long as the polymer component is uniformly dissolved.
- Specific examples are N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, dimethyl sulfoxide, ⁇ -butyrolactone, 1,3-dimethyl.
- -Imidazolidinone methyl ethyl ketone, cyclohexanone, cyclopentanone and the like.
- N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, or ⁇ -butyrolactone is preferably used.
- organic solvent contained in the liquid crystal aligning agent of the present invention can be used in combination with a solvent that improves the coating properties and the surface smoothness of the coating film when applying the liquid crystal aligning agent in addition to the above solvents.
- organic solvents are listed below, but are not limited to these.
- 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, 1,2- Ethane All, 1,2-propanediol, 1,3-propan
- D 1 represents an alkyl group having 1 to 3 carbon atoms
- D 2 represents an alkyl group having 1 to 3 carbon atoms
- D 3 represents an alkyl group having 1 to 4 carbon atoms.
- the kind and content of such a solvent are appropriately selected according to the application device, application conditions, application environment, and the like of the liquid crystal aligning agent.
- the liquid crystal aligning agent of the present invention may additionally contain components other than the polymer component and the organic solvent.
- additional components include an adhesion aid for increasing the adhesion between the liquid crystal alignment film and the substrate and the adhesion between the liquid crystal alignment film and the sealing material, a crosslinking agent for increasing the strength of the liquid crystal alignment film, and the liquid crystal alignment.
- additional components include dielectrics and conductive materials for adjusting the dielectric constant and electric resistance of the film. Specific examples of these additional components include those disclosed in International Publication No. 015/060357, page 53, paragraph 0105 to page 55, paragraph 0116.
- the liquid crystal aligning film of this invention is obtained from the said liquid crystal aligning agent.
- a liquid crystal aligning agent in the form of a coating solution is applied to a substrate, dried, and baked, and then the alignment treatment is performed by a rubbing treatment method or a photo-alignment treatment method.
- the method of giving is mentioned.
- the substrate to which the liquid crystal alignment agent is applied is not particularly limited as long as it is a highly transparent substrate, and a plastic substrate such as an acrylic substrate or a polycarbonate substrate can be used together with a glass substrate or a silicon nitride substrate.
- a substrate on which an ITO electrode or the like for driving the liquid crystal is used from the viewpoint of simplification of the process.
- an opaque object such as a silicon wafer can be used as long as only one substrate is used, and a material that reflects light such as aluminum can be used for the electrode in this case.
- the method for applying the liquid crystal aligning agent is not particularly limited, but industrially, screen printing, offset printing, flexographic printing, inkjet method, and the like are common. Other coating methods include a dipping method, a roll coater method, a slit coater method, a spinner method, and a spray method, and these may be used depending on the purpose.
- the solvent is evaporated and baked by a heating means such as a hot plate, a thermal circulation oven, an IR (infrared) oven, or the like.
- a heating means such as a hot plate, a thermal circulation oven, an IR (infrared) oven, or the like.
- Arbitrary temperature and time can be selected for the drying and baking steps after applying the liquid crystal aligning agent.
- the liquid crystal alignment film of the present invention is suitable for a horizontal electric field type liquid crystal display element such as an IPS mode or an FFS mode, and is particularly useful as a liquid crystal alignment film of an FFS mode liquid crystal display element.
- the liquid crystal display device of the present invention is a device in which a liquid crystal cell is prepared by a known method after obtaining a substrate with a liquid crystal alignment film obtained from the liquid crystal aligning agent, and the liquid crystal cell is used as an element.
- a liquid crystal display element having a passive matrix structure will be described as an example.
- an active matrix structure element in which a switching element such as a TFT (Thin Film Transistor) is provided in each pixel portion constituting the image display may be used.
- a transparent glass substrate is prepared, a common electrode is provided on one substrate, and a segment electrode is provided on the other substrate.
- These electrodes can be ITO electrodes, for example, and are patterned so as to display a desired image.
- 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.
- a liquid crystal alignment film is formed on each substrate under the above conditions.
- an ultraviolet curable sealing material is disposed at a predetermined position on one of the two substrates on which the liquid crystal alignment film is formed, and liquid crystals are disposed at predetermined positions on the liquid crystal alignment film surface.
- the other substrate is bonded and pressure-bonded so that the liquid crystal alignment film faces, and the liquid crystal is spread on the front surface of the liquid crystal alignment film, and then the entire surface of the substrate is irradiated with ultraviolet rays to cure the sealing material. Get a cell.
- an opening that can be filled with liquid crystal from the outside is provided when the sealing material is disposed at a predetermined position on one substrate, and the substrates are bonded together Thereafter, a liquid crystal material is injected into the liquid crystal cell through an opening provided in the sealing material, and then the opening is sealed with an adhesive to obtain a liquid crystal cell.
- the liquid crystal material may be injected by a vacuum injection method or a method utilizing capillary action in the atmosphere.
- the liquid crystal material examples include a nematic liquid crystal and a smectic liquid crystal. Among them, a nematic liquid crystal is preferable, and either a positive liquid crystal material or a negative liquid crystal material may be used.
- a polarizing plate is installed. Specifically, it is preferable to attach a pair of polarizing plates to the surfaces of the two substrates opposite to the liquid crystal layer.
- the liquid crystal alignment film and the liquid crystal display element of the present invention are not limited to the above description as long as the liquid crystal aligning agent of the present invention is used, and may be manufactured by other known methods. good. Processes from the liquid crystal aligning agent to obtaining a liquid crystal display element are disclosed in, for example, Japanese Unexamined Patent Publication No. 2015-135393, page 17, paragraph 0074 to page 19, paragraph 0081.
- Boc is a group represented by the following formula.
- ⁇ Viscosity measurement> The viscosity of the polyamic acid solution was measured using an E-type viscometer TVE-22H (manufactured by Toki Sangyo Co., Ltd.) at a temperature of 25 ° C. and a sample amount of 1.1 mL and a cone rotor TE-1 (1 ° 34 ′, R24). did.
- Zinc chloride (120.3 g, 882 mmol) was added to a 3 L (liter) four-necked flask, and the temperature was raised to 100 ° C., followed by vacuum drying for 1 hour with an oil pump. Then, at room temperature under nitrogen atmosphere, toluene (460 g), diethylamine (45.0 g, 615 mmol), t-butanol (46.4 g, 626 mmol), 2-bromo-4-nitroacetophenone (100.0 g, 410 mmol), And 4-nitroacetophenone (104.2 g, 631 mmol) were sequentially added, and the mixture was stirred at room temperature for 3 days.
- the precipitate was washed with methanol and dried under reduced pressure at 60 ° C. to obtain a polyimide powder.
- the imidation ratio of this polyimide was 75%.
- NMP586.7g was added to 80.0g of obtained polyimide powder, and it stirred for 20 hours and dissolved at 50 degreeC, and the polyimide solution (SPI-B8) was obtained.
- Examples 1 to 22 and [Comparative Examples 1 to 6] The polyamic acid solutions obtained in Synthesis Examples 1 to 16 and 18 and the polyimide solution obtained in Synthesis Example 17 were adjusted to the ratios of Polymer 1 and Polymer 2 shown in Table 2-1 and Table 2-2 below.
- Table 2-1 and Table 2 show NMP solutions containing 1% by weight of NMP, GBL, BCS, and LS-4668, and NMP solutions containing 3% by weight of AD-1.
- the liquid crystal aligning agents of Examples 1 to 22 and Comparative Examples 1 to 6 were obtained by adding the mixture so as to have the composition shown in -2 with stirring and further stirring at room temperature for 2 hours.
- a glass substrate with an electrode having a size of 30 mm ⁇ 35 mm and a thickness of 0.7 mm was prepared.
- an IZO electrode having a solid pattern constituting a counter electrode as a first layer is formed on the substrate.
- a SiN (silicon nitride) film formed by the CVD method is formed as the second layer.
- the second layer SiN film has a thickness of 500 nm and functions as an interlayer insulating film.
- a comb-like pixel electrode formed by patterning an IZO film as the third layer is arranged to form two pixels, a first pixel and a second pixel. ing.
- the size of each pixel is 10 mm long and about 5 mm wide.
- the first-layer counter electrode and the third-layer pixel electrode are electrically insulated by the action of the second-layer SiN film.
- the pixel electrode of the third layer is a comb formed by arranging a plurality of “U” -shaped electrode elements whose central portion is bent as shown in FIG. 3 described in Japanese Unexamined Patent Publication No. 2014-77845. It has a tooth shape. The width in the short direction of each electrode element is 3 ⁇ m, and the distance between the electrode elements is 6 ⁇ m.
- the pixel electrode forming each pixel is formed by arranging a plurality of bent “bow” -shaped electrode elements at the center, so the shape of each pixel is not rectangular but is the same as that of the electrode element. It has a shape that resembles a bold “Kugi” that bends in part.
- Each pixel is divided into upper and lower portions with a central bent portion as a boundary, and has a first region on the upper side of the bent portion and a second region on the lower side.
- the formation directions of the electrode elements of the pixel electrodes constituting them are different. That is, when the rubbing direction of the liquid crystal alignment film described later is used as a reference, the electrode element of the pixel electrode is formed to form an angle of + 10 ° (clockwise) in the first region of the pixel, and the pixel in the second region of the pixel.
- the electrode elements of the electrode are formed so as to form an angle of ⁇ 10 ° (clockwise).
- the directions of the rotation operation (in-plane switching) of the liquid crystal induced by the voltage application between the pixel electrode and the counter electrode in the substrate surface are mutually It is comprised so that it may become a reverse direction.
- the polyimide film surface is rubbed with a rayon cloth under the conditions of a roll diameter of 120 mm, a roller rotation speed of 500 rpm, a stage moving speed of 30 mm / sec, and a rubbing cloth indentation pressure of 0.3 mm, and then in pure water for 1 minute. Ultrasonic irradiation was performed, and drying was performed at 80 ° C. for 10 minutes. Using the two types of substrates with the above-mentioned liquid crystal alignment film, the rubbing directions were combined to be antiparallel, the periphery was sealed leaving the liquid crystal injection port, and an empty cell with a cell gap of 3.8 ⁇ m was produced. .
- a liquid crystal (MLC-3019, manufactured by Merck & Co., Inc.) was vacuum-injected into the empty cell at room temperature, and the injection port was sealed to obtain an anti-parallel alignment liquid crystal cell.
- the obtained liquid crystal cell comprised the FFS mode liquid crystal display element. Thereafter, the liquid crystal cell was heated at 120 ° C. for 1 hour and allowed to stand overnight before being used for each evaluation described below.
- the afterimage was evaluated using the following optical system and the like. That is, the prepared liquid crystal cell is placed between two polarizing plates arranged so that the polarization axes are orthogonal to each other, and the LED backlight is turned on with no voltage applied, so that the brightness of transmitted light is minimized. Further, the arrangement angle of the liquid crystal cell was adjusted. Next, a VT curve (voltage-transmittance curve) was measured while applying an AC voltage with a frequency of 30 Hz to the liquid crystal cell, and an AC voltage with a relative transmittance of 23% was calculated as a drive voltage.
- VT curve voltage-transmittance curve
- a DC voltage of 1 V was applied at the same time while driving the liquid crystal cell by applying an AC voltage of 30 Hz with a relative transmittance of 23%, and the liquid crystal cell was driven for 30 minutes. Thereafter, the applied DC voltage value was set to 0 V, and only the application of the DC voltage was stopped, and the device was further driven for 15 minutes in this state.
- the time during which the relative transmittance decreased to 30% or less by the time 30 minutes elapsed from the start of application of the DC voltage was quantified. Evaluation was made by defining “ ⁇ ” when the relative transmittance decreased to 30% or less within 5 minutes, and “ ⁇ ” when within 6 to 30 minutes. When it took 30 minutes or more before the relative transmittance decreased to 30% or less, the afterimage was not erased, and “x” was defined and evaluated. And the afterimage evaluation according to the method mentioned above was performed on the temperature conditions of the state whose temperature of a liquid crystal cell is 23 degreeC.
- the prepared liquid crystal cell is installed between two polarizing plates arranged so that the polarization axes are orthogonal to each other, and the LED backlight is turned on with no voltage applied, so that the brightness of transmitted light is minimized.
- the arrangement angle of the liquid crystal cell was adjusted.
- a VT curve voltage-transmittance curve
- the LED backlight that was turned on is temporarily turned off and left to block light for 72 hours, and then the LED backlight is turned on again.
- the frequency at which the relative transmittance becomes 23% at the same time when the backlight turns on is 30 Hz.
- the AC voltage was applied and the liquid crystal cell was driven for 60 minutes to track the flicker amplitude.
- the flicker amplitude is a data collection / data logger switch unit 34970A (Agilent technologies) that connects the transmitted light of the LED backlight that has passed through the two polarizing plates and the liquid crystal cell therebetween, via a photodiode and an IV conversion amplifier. ).
- z is a value obtained by reading the luminance when driven by an AC voltage with a frequency of 30 Hz with a relative transmittance of 23% by the data collection / data logger switch unit 34970A.
- the flicker level was evaluated as “ ⁇ ” when the flicker level was maintained at less than 3% by 60 minutes after the start of lighting of the LED backlight and application of the AC voltage. When the flicker level reached 3% or more in 60 minutes, it was evaluated as “x”.
- the evaluation of the flicker level according to the above-described method was performed under temperature conditions where the temperature of the liquid crystal cell was 23 ° C.
- Table 3 shows the evaluation results of the afterimage erasing time and the flicker level immediately after driving for the liquid crystal display elements using the liquid crystal aligning agents of Examples 1 to 22 and Comparative Examples 1 to 5. Show.
- the surface of the coating film was irradiated with 300 mJ / cm 2 of 254 nm linearly polarized ultraviolet light having an extinction ratio of 26: 1 through a polarizing plate.
- This substrate was heated on a hot plate at 230 ° C. for 30 minutes to obtain a substrate with a liquid crystal alignment film.
- the two substrates are combined as a set, a sealant is printed on the substrate, and the other substrate is bonded so that the liquid crystal alignment film faces and the alignment direction is 0 °, and then the sealant is added.
- An empty cell was produced by curing.
- Negative type liquid crystal MLC-7026-100 (manufactured by Merck & Co., Inc.) was injected into this empty cell by a reduced pressure injection method, and the injection port was sealed to obtain an FFS drive liquid crystal cell. Thereafter, the obtained liquid crystal cell was heated at 110 ° C. for 1 hour and allowed to stand overnight, and then used for each of the following evaluations.
- Table 4 shows the results of the evaluation of the afterimage erasing time and the evaluation of the flicker level immediately after driving for the liquid crystal display elements using the liquid crystal aligning agents obtained in Example 19 and Comparative Example 6.
- the liquid crystal display elements using the liquid crystal aligning agents of the examples of the present invention have a fast relaxation of accumulated charges and are less likely to cause a flicker shift that occurs immediately after the start of driving. I understand.
- the liquid crystal aligning agent using the novel polymer of the present invention is widely used for a liquid crystal display element of a vertical electric field method such as a TN method or a VA method, particularly a horizontal electric field method such as an IPS method or an FFS method.
- a vertical electric field method such as a TN method or a VA method
- a horizontal electric field method such as an IPS method or an FFS method.
Abstract
Description
2.前記重合体が、前記式(1)で表される構造を有するジアミンとテトラカルボン酸二無水物との重縮合物であるポリイミド前駆体及びそのイミド化物であるポイミドからなる群から選ばれる少なくとも1種の重合体である前記1に記載の液晶配向剤。
3.前記ジアミンが、下記の式(2)で表される前記1又は2に記載の液晶配向剤。
4.前記ポリイミド前駆体が、下記式(6)で表される前記1~3に記載の液晶配向剤。
5.前記式(6)中、X1の構造が、後記する式(A-1)~式(A-21)の構造からなる群から選ばれる少なくとも1種である前記4に記載の液晶配向剤。
6.前記式(6)で表される構造単位を有する重合体が、液晶配向剤に含有される全重合体に対して10モル%以上含有される前記4又は5に記載の液晶配向剤。
7.前記有機溶媒が4-ヒドロキシ-4-メチル-2-ペンタノン及びジエチレングリコールジエチルエーテルからなる群から選ばれる少なくとも1種を含有する、前記4~6に記載の液晶配向剤。
8.前記1~7のいずれかに記載の液晶配向剤を用いて得られる液晶配向膜。
9.前記8に記載の液晶配向膜を具備する液晶表示素子。
10.液晶表示素子が横電界駆動方式である前記9に記載の液晶表示素子。
11.下記式(1)で表される構造を有するジアミンとテトラカルボン酸二無水物との重縮合物であるポリイミド前駆体及びそのイミド化物であるポリイミドからなる群から選ばれる少なくとも1種の重合体。
12.上記ジアミンが、以下の式(2)で表される前記11に記載の重合体。
13.前記ポリイミド前駆体が、下記式(6)で表される前記11又は12に記載の重合体。
14.前記式(6)中、X1の構造が、後記する式(A-1)~式(A-21)の構造からなる群から選ばれる少なくとも1種である前記13に記載の重合体。
本発明の液晶配向剤に含有される重合体の有する上記(1)の構造は、導電性ピロール構造及び共役構造を有するが、これにより、例えば液晶配向膜中において、電荷の移動を促進させることができ、蓄積電荷の緩和を促進させることができるものと考えられる。
本発明の液晶配向剤は、下記式(1)の構造を有するジアミン(本発明では、特定ジアミンともいう。)から得られる重合体(本発明では、特定重合体ともいう。)と、有機溶媒とを含有する。
ここにおける一価の有機基としては、炭素数が1~10、好ましくは1~3を有する、アルキル基、アルケニル基、アルコキシ基、フルオロアルキル基、フルオロアルケニル基、又はフルオロアルコキシ基が挙げられる。なかでも、R1は、水素原子、又はメチル基が好ましい。
上記式(2)及び式(2-1)中のnは、1~3の整数を表す。好ましくは1又は2である。
上記特定ジアミンを合成する方法は特に限定されない。例えば、下記式(4)で表されるジニトロ化合物を使用し、その有するニトロ基を還元反応によりアミノ基に変換する方法が挙げられる。
反応温度は特に限定されないが、-100℃から使用する溶媒の沸点までの範囲、好ましくは、-50~150℃である。反応時間は、通常0.05~350時間、好ましくは0.5~100時間である。
イソシアネート類を反応させてR1を導入する場合、イソシアネート類の例としては、メチルイソシアネート、エチルイソシアネート、n-プロピルイソシアネート、フェニルイソシアネートなどが挙げられる。反応溶媒、反応温度は、上記酸ハライドにおける場合と同様である。
アルコールの水酸基をOMs、OTf、OTs等の脱離基に置換したアルコール類を反応させてR1を導入する場合、好ましくは塩基の存在下に行われる。上記アルコール類の例としては、メタノール、エタノール、1-プロパノールなどが挙げられ、これらのアルコール類と、メタンスルホニルクロリド、トリフルオロメタンスルホニルクロリド、パラトルエンスルホン酸クロリド等とを反応させることで、OMs、OTf、OTs等の脱離基に置換されたアルコールを得ることができる。塩基の例、反応溶媒、反応温度は、上記酸ハライドにおける場合と同様である。
式(5)の化合物を合成する方法に特に制限はないが、式(5)のピロール環上の置換位置が2位及び4位である場合は、例えば、下記反応式1で表すように、ニトロ基を有するα-ハロケトンとニトロ基を有するケトンとを、好ましくは塩基の存在下に反応させることにより得ることができる。反応式1において、Xは、Br、I又はOTfを表す。
上記反応における速度を促進する目的で、塩化亜鉛、ヨウ化ナトリウム、ヨウ化カリウム、ヨウ化テトラブチルアンモニウム等を用いることができる。
上記金属錯体の使用量は、いわゆる触媒量でよく、基質に対して20モル%以下で十分であり、好ましくは10モル%以下である。
本発明の液晶配向剤は、特定ジアミンを用いて得られる重合体である。重合体の具体例としては、ポリアミック酸、ポリアミック酸エステル、ポリイミド、ポリウレア、ポリアミドなどが挙げられる。なかでも、下記式(6)で表される構造単位を有するポリイミド前駆体、及びそのイミド化物であるポリイミドからなる群から選ばれる少なくとも1種である重合体が好ましい。
X1の具体例としては、国際公開公報2015/119168の13頁~14頁に掲載される、式(X-1)~(X-46)の構造などが挙げられる。
本発明の液晶配向剤は、上記式(6)の構造単位を有するポリイミド前駆体のほかに、下記式(7)で表される構造単位を有するポリイミド前駆体、及びそのイミド化物であるポリイミドからなる群から選ばれる少なくとも1種の重合体を含んでいてもよい。
本発明の液晶配向剤が、式(6)の構造単位を有するポリイミド前駆体と、式(7)の構造単位を有するポリイミド前駆体を含む場合、式(6)の構造単位は、式(6)と式(7)の合計に対して10モル%以上が好ましく、より好ましくは20モル%以上であり、特に好ましくは30モル%以上である。
式(1)で表される2価の基を主鎖に有するポリイミドとしては、前記ポリイミド前駆体を閉環させて得られるポリイミドが挙げられる。このポリイミドにおいては、アミド酸基の閉環率(イミド化率ともいう)は必ずしも100%である必要はなく、用途や目的に応じて任意に調整できる。
ポリイミド前駆体をイミド化させる方法としては、ポリイミド前駆体の溶液をそのまま加熱する熱イミド化、又はポリイミド前駆体の溶液に触媒を添加する触媒イミド化が挙げられる。
本発明の液晶配向剤は、式(1)で表される構造を有するジアミンから得られる重合体(特定重合体)を含有するが、異なる構造の特定重合体を2種以上含有していてもよい。また、特定重合体に加えて、その他の重合体、即ち式(1)で表される2価の基を有さない重合体を含有していてもよい。その他の重合体としては、ポリアミック酸、ポリイミド、ポリアミック酸エステル、ポリエステル、ポリアミド、ポリウレア、ポリオルガノシロキサン、セルロース誘導体、ポリアセタール、ポリスチレンまたはその誘導体、ポリ(スチレン-フェニルマレイミド)誘導体、ポリ(メタ)アクリレートなどが挙げられる。本発明の液晶配向剤がその他の重合体を含有する場合、全重合体成分に対する特定重合体の割合は5質量%以上でが好ましく、例えば5~95質量%が挙げられる。
なかでも、1-ヘキサノール、シクロヘキサノール、1,2-エタンジオール、1,2-プロパンジオール、プロピレングリコールモノブチルエーテル、ジエチレングリコールジエチルエーテル、4-ヒドロキシ-4-メチル-2-ペンタノン、エチレングリコールモノブチルエーテル又はジプロピレングリコールジメチルエーテルを用いることが好ましい。このような溶媒の種類及び含有量は、液晶配向剤の塗布装置、塗布条件、塗布環境などに応じて適宜選択される。
本発明の液晶配向膜は、前記液晶配向剤から得られる。液晶配向膜を得る方法の一例を挙げるなら、塗布液形態の液晶配向剤を基板に塗布し、乾燥し、焼成して得られた膜に対してラビング処理法又は光配向処理法で配向処理を施す方法が挙げられる。
液晶配向剤を塗布する基板としては、透明性の高い基板であれば特に限定されず、ガラス基板、窒化珪素基板とともに、アクリル基板やポリカーボネート基板などのプラスチック基板等を用いることもできる。その際、液晶を駆動させるためのITO電極などが形成された基板を用いると、プロセスの簡素化の点から好ましい。また、反射型の液晶表示素子では、片側の基板のみにならば、シリコンウエハーなどの不透明な物でも使用でき、この場合の電極にはアルミニウムなどの光を反射する材料も使用できる。
液晶配向剤を基板上に塗布した後は、ホットプレート、熱循環型オーブン、IR(赤外線)型オーブンなどの加熱手段により、溶媒を蒸発させ、焼成する。液晶配向剤を塗布した後の乾燥、焼成工程は、任意の温度と時間を選択できる。通常は、含有される溶媒を十分に除去するために、50~120℃で1~10分焼成し、その後、150~300℃で、5~120分焼成する条件が挙げられる。
本発明の液晶配向膜は、IPS方式やFFS方式などの横電界方式の液晶表示素子に好適であり、特に、FFS方式の液晶表示素子の液晶配向膜として有用である。
本発明の液晶表示素子は、上記液晶配向剤から得られる液晶配向膜付きの基板を得た後、既知の方法で液晶セルを作製し、該液晶セルを使用して素子としたものである。
液晶セルの作製方法の一例として、パッシブマトリクス構造の液晶表示素子を例にとり説明する。なお、画像表示を構成する各画素部分にTFT(Thin Film Transistor)などのスイッチング素子が設けられたアクティブマトリクス構造の素子であってもよい。
または、基板の上に液晶配向膜を形成した後、一方の基板上の所定の場所にシール材を配置する際に、外部から液晶を充填可能な開口部を設けておき、基板を貼り合わせた後、液晶材料をシール材に設けた開口部を通じて液晶セル内に注入し、次いで、この開口部を接着剤で封止して液晶セルを得る。液晶材料の注入は、真空注入法でもよいし、大気中で毛細管現象を利用した方法でもよい。
なお、本発明の液晶配向膜及び液晶表示素子は、本発明の液晶配向剤を用いている限り上記の記載に限定されるものでは無く、その他の公知の手法で作製されたものであっても良い。液晶配向剤から液晶表示素子を得るまでの工程は、例えば、日本国特開2015-135393号の17頁の段落0074~19頁の段落0081などに開示されている。
NMP:N-メチル-2-ピロリドン、GBL:γ―ブチロラクトン、
BCS:ブチルセロソルブ
<添加剤>
LS-4668:3-グリシドキシプロピルトリエトキシシラン
装置:Varian NMR system 400NB(400MHz)(Varian社製)、及びJMTC-500/54/SS(500MHz)(JEOL社製)
測定溶媒:CDCl3(重水素化クロロホルム),DMSO-d6(重水素化ジメチルスルホキシド)
基準物質:TMS(テトラメチルシラン)(δ:0.0ppm,1H)及びCDCl3(δ:77.0ppm,13C)
常温ゲル浸透クロマトグラフィー(GPC)装置(GPC-101)(昭和電工社製)、及びカラム(KD-803,KD-805)(Shodex社製)を用いて、以下のようにして測定した。
カラム温度:50℃
溶離液:N,N’-ジメチルホルムアミド(添加剤として、臭化リチウム-水和物(LiBr・H2O)が30mmol/L(リットル)、リン酸・無水結晶(o-リン酸)が30mmol/L、テトラヒドロフラン(THF)が10ml/L)
流速:1.0ml/分
検量線作成用標準サンプル:TSK 標準ポリエチレンオキサイド(分子量;約900,000、150,000、100,000、及び30,000、東ソー社製)及びポリエチレングリコール(分子量;約12,000、4,000、及び1,000、ポリマーラボラトリー社製)。
ポリアミック酸溶液の粘度は、E型粘度計TVE-22H(東機産業社製)を用い、温度25℃において、サンプル量1.1mL、コーンロータTE-1(1°34’、R24)で測定した。
1H-NMR(DMSO-d6):8.40-8.36(4H,m),8.28-8.24(4H,m),3.53(4H,s)
1H-NMR(DMSO-d6):11.8(1H,br),8.30-8.26(4H,m),8.11-8.07(4H,m),7.04(2H,s)
1H-NMR(DMSO-d6):10.6(1H,s),7.39-7.35(4H,m),6.57-6.53(4H,m),6.19(2H,s),5.01(4H,s)
撹拌装置付き及び窒素導入管付きの100mlの四つ口フラスコにDA-1を(2.49g,10.0mmol)加えた後、NMP29.0gを加え、窒素を送りながら撹拌し溶解させた。この溶液を撹拌しながら、CA-2を(0.98g,5.0mmol)、及びNMPを3.6g(表1中の追加量1)加えた後、25℃条件下にて1時間攪拌した。その後、CA-1を(0.87g,4.0mmol)加え、NMPを3.6g(表1中の追加量2)加えた後、さらに50℃条件下にて12時間攪拌することで樹脂固形分濃度12質量%のポリアミック酸溶液(PAA-A1)を得た。このポリアミック酸溶液の粘度は300mPa・sであった。
表1に示す、テトラカルボン酸酸二無水物成分、ジアミン成分、及びNMP量を使用し、それぞれ、表1に示す反応温度にせしめた他は、合成例1と同様に実施することにより、表1に示す固形分濃度及び粘度を有するポリアミック酸溶液(PAA-A2)~(PAA-A9)及びポリアミック酸溶液(PAA-B1)~((PAA-B7)を得た。
撹拌装置付き及び窒素導入管付きの200mlの四つ口フラスコにDA-6(4.03g,16.5mmol)、DA-7を(3.59g、9.0mmol)、及びDA-8を(2.50g、4.5mmol)加えた後、NMPを102.1g加え、窒素を送りながら撹拌し溶解させた。この溶液を撹拌しながらCA-4を(4.37g、19.5mmol)、及びNMPを12.8g加え、40℃条件下にて3時間攪拌した。その後、25℃条件下にてCA-2を(1.71g,8.7mmol)、及びNMPを12.8g加えた後、さらに12時間攪拌することで樹脂固形分濃度15質量%のポリアミック酸溶液を得た。このポリアミック酸溶液の粘度は820mPa・sであった。
このポリアミック酸溶液を80.0g分取し、NMPを70.0g加えた後、無水酢酸を6.8g、及びピリジンを1.8g加え、50℃で3時間反応させた。この反応溶液をメタノール555.0gに注ぎ、生成した沈殿物を濾別した。この沈殿物をメタノールで洗浄し、60℃で減圧乾燥しポリイミドの粉末を得た。このポリイミドのイミド化率は75%であった。得られたポリイミド粉末80.0gにNMP586.7gを加えて50℃にて20hr攪拌して溶解させることでポリイミド溶液(SPI-B8)を得た。
撹拌装置付き及び窒素導入管付きの100mlの四つ口フラスコにDA-6を(2.20g,9.0mmol)、DA-13を(1.62g,15.0mmol)、及びDA-14を(2.45g,6.0mmol)加えた後、NMPを81.8g加え、窒素を送りながら撹拌し溶解させた。この溶液を撹拌しながらCA-4を(6.52g,29.10mmol)加えNMPを9.1g加えた後、40℃条件下にて24時間攪拌することで樹脂固形分濃度12質量%のポリアミック酸溶液(PAA-B9)を得た。このポリアミック酸溶液の粘度は386mPa・sであった。
撹拌装置付き及び窒素導入管付きの200mlの四つ口フラスコにDA-1(2.62g,10.5mmol)、DA-2(1.39g,7.0mmol)、及びDA-3(3.49g,17.5mmol)を加えた後、NMP70.0gを加え、窒素を送りながら撹拌し溶解させた。この溶液を撹拌しながら、CA-2を(1.70g,8.7mmol)、及びNMPを9.5g加えた後、25℃条件下にて1時間攪拌した。その後、CA-3を(6.57g,26.3mmol)加え、NMPを9.5g加えた後、さらに50℃条件下にて12時間攪拌することで樹脂固形分濃度12質量%のポリアミック酸溶液(PAA-A10)を得た。このポリアミック酸溶液の粘度は375mPa・sであった。
撹拌装置付き及び窒素導入管付きの100mlの四つ口フラスコにDA-1(1.12g,4.5mmol)、DA-2(0.59g,3.0mmol)、及びDA-3(1.49g,7.5mmol)を加えた後、NMP:GBL=1:1混合溶媒31.0gを加え、窒素を送りながら撹拌し溶解させた。この溶液を撹拌しながら、CA-2を(1.15g,5.9mmol)、及びNMP:GBL=1:1混合溶媒を10.0g加えた後、25℃条件下にて1時間攪拌した。その後、CA-5を(2.60g,8.8mmol)加え、NMP:GBL=1:1混合溶媒を10.0g加えた後、さらに50℃条件下にて12時間攪拌することで樹脂固形分濃度12質量%のポリアミック酸溶液(PAA-A12)を得た。このポリアミック酸溶液の粘度は200mPa・sであった。
合成例1~16、18で得られたポリアミック酸溶液、及び合成例17で得られたポリイミド溶液を、下記の表2-1及び表2-2に示される、ポリマー1及びポリマー2の比率になるように混合して得られる溶液に対して、NMP、GBL、BCS、LS-4668を1重量%含むNMP溶液、及びAD-1を3重量%含むNMP溶液を、表2-1及び表2-2に示す組成になるように、攪拌しながら加え、更に室温で2時間撹拌することにより実施例1~22及び比較例1~6の液晶配向剤を得た。
30mm×35mmの大きさで、厚さが0.7mmの電極付きのガラス基板を準備した。基板上には第1層目として対向電極を構成する、ベタ状のパターンを備えたIZO電極が形成されている。第1層目の対向電極の上には第2層目として、CVD法により成膜されたSiN(窒化珪素)膜が形成されている。第2層目のSiN膜の膜厚は500nmであり、層間絶縁膜として機能する。第2層目のSiN膜の上には、第3層目としてIZO膜をパターニングして形成された櫛歯状の画素電極が配置され、第1画素及び第2画素の2つの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。このとき、第1層目の対向電極と第3層目の画素電極とは、第2層目のSiN膜の作用により電気的に絶縁されている。
上記液晶配向膜付きの2種類の基板を用いて、それぞれのラビング方向が逆平行になるように組み合わせ、液晶注入口を残して周囲をシールし、セルギャップが3.8μmの空セルを作製した。この空セルに液晶(メルク社製、MLC-3019、)を常温で真空注入した後、注入口を封止してアンチパラレル配向の液晶セルとした。得られた液晶セルは、FFSモード液晶表示素子を構成した。その後、液晶セルを120℃で1時間加熱し、一晩放置してから下記する各評価に使用した。
以下の光学系等を用いて残像の評価を行った。すなわち、作製した液晶セルを偏光軸が直交するように配置された2枚の偏光板の間に設置し、電圧無印加の状態でLEDバックライトを点灯させておき、透過光の輝度が最も小さくなるように、液晶セルの配置角度を調整した。次に、この液晶セルに周波数30Hzの交流電圧を印加しながらV-Tカーブ(電圧-透過率曲線)を測定し、相対透過率が23%となる交流電圧を駆動電圧として算出した。
残像評価では、相対透過率が23%となる周波数30Hzの交流電圧を印加して液晶セルを駆動させながら、同時に1Vの直流電圧を印加し、30分間駆動させた。その後、印加直流電圧値を0Vにして直流電圧の印加のみを停止し、その状態でさらに15分駆動した。
作製した液晶セルを偏光軸が直交するように配置された2枚の偏光板の間に設置し、電圧無印加の状態でLEDバックライトを点灯させておき、透過光の輝度が最も小さくなるように、液晶セルの配置角度を調整した。次に、この液晶セルに周波数30Hzの交流電圧を印加しながらV-Tカーブ(電圧-透過率曲線)を測定し、相対透過率が23%となる交流電圧を駆動電圧として算出した。
フリッカーレベル(%)={フリッカー振幅/(2×z)}×100
フリッカーレベルは、LEDバックライトの点灯及び交流電圧の印加を開始した時点から60分間が経過するまでに、フリッカーレベルが3%未満を維持した場合に「○」と評価した。60分間でフリッカーレベルが3%以上に達した場合に「×」と評価した。
そして、上述した方法に従うフリッカーレベルの評価は、液晶セルの温度が23℃の状態の温度条件下で行った。
上記実施例1~22、及び比較例1~5の各液晶配向剤を使用する液晶表示素子について、上記で実施した残像消去時間の評価、及び駆動直後のフリッカーレベルの評価の結果を表3に示す。
液晶配向剤を孔径1.0μmのフィルターで濾過した後、準備された上記電極付き基板と対向基板として裏面にITO膜が成膜されており、かつ高さ4μmの柱状のスペーサーを有するガラス基板のそれぞれにスピンコートした。次いで、80℃のホットプレート上で5分間乾燥後、230℃で30分間焼成して膜厚100nmの塗膜として、各基板上にポリイミド膜を得た。この塗膜面に偏光板を介して消光比26:1の直線偏光した波長254nmの紫外線を300mJ/cm2照射した。この基板を、230℃のホットプレート上で30分間加熱し、液晶配向膜付き基板を得た。上記、2枚の基板を一組とし、基板上にシール剤を印刷し、もう1枚の基板を、液晶配向膜面が向き合い配向方向が0°になるようにして張り合わせた後、シール剤を硬化させて空セルを作製した。この空セルに減圧注入法によって、ネガ型液晶のMLC-7026-100(メルク社製)を注入し、注入口を封止して、FFS駆動液晶セルを得た。その後、得られた液晶セルを110℃で1時間加熱し、一晩放置してから下記の各評価に使用した。
ラビング法による液晶表示素子の場合と同様にして、上記で作製した光配向法による液晶表示素子の光学系等を用いて残像の評価を行った。
なお、残像評価は、ラビング法による液晶表示素子の場合と異なり、直流電圧の印加を開始した時点から30分間が経過するまでに、相対透過率が23%に低下した時間を数値化した。5分以内に相対透過率が23%に低下した場合は「○」に、6~30分以内であれば「△」と定義した。相対透過率が23%に低下するまでに30分間以上を要した場合に、残像消去不可とし、「×」と定義した。
ラビング法による液晶表示素子の場合と同様にして、上記で作製した光配向法による液晶表示素子の光学系等を用いて残像の評価を行った。
上記実施例19及び比較例6で得られた液晶配向剤を使用する液晶表示素子について、上記で実施した残像消去時間の評価、及び駆動直後のフリッカーレベルの評価の結果を表4に示す。
なお、2016年1月22日に出願された日本特許出願2016-010996号及び2016年6月1日に出願された日本特許出願2016-110237号の明細書、特許請求の範囲、及び要約書の全内容をここに引用し、本発明の明細書の開示として、取り入れるものである。
Claims (14)
- 前記重合体が、前記式(1)で表される構造を有するジアミンとテトラカルボン酸二無水物との重縮合物であるポリイミド前駆体及びそのイミド化物であるポリイミドからなる群から選ばれる少なくとも1種の重合体である請求項1に記載の液晶配向剤。
- 前記式(6)で表される構造単位を有する重合体が、液晶配向剤に含有される全重合体に対して10モル%以上含有される請求項4又は5に記載の液晶配向剤。
- 前記有機溶媒が、4-ヒドロキシ-4-メチル-2-ペンタノン及びジエチレングリコールジエチルエーテルからなる群から選ばれる少なくとも1種を含有する請求項1~6のいずれか1項に記載の液晶配向剤。
- 請求項1~7のいずれか1項に記載の液晶配向剤から得られる液晶配向膜。
- 請求項8に記載の液晶配向膜を具備する液晶表示素子。
- 液晶表示素子が横電界駆動方式である請求項9に記載の液晶表示素子。
- 前記式(6)中、X1が請求項5に記載される式(A-1)~式(A-21)の構造からなる群から選ばれる少なくとも1種である請求項13に記載の重合体。
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CN103922989A (zh) * | 2014-04-29 | 2014-07-16 | 苏州海泰原新材料有限公司 | 含邻苯二甲腈结构的吡咯基芳香二胺及其制备方法和应用 |
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WO2020100918A1 (ja) * | 2018-11-14 | 2020-05-22 | 日産化学株式会社 | 液晶配向剤、液晶配向膜及びそれを用いた液晶表示素子 |
CN113015935A (zh) * | 2018-11-14 | 2021-06-22 | 日产化学株式会社 | 液晶取向剂、液晶取向膜及使用其的液晶表示元件 |
WO2023085390A1 (ja) * | 2021-11-12 | 2023-05-19 | 日産化学株式会社 | 液晶配向剤、液晶配向膜、及び液晶表示素子 |
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JPWO2017126627A1 (ja) | 2018-11-15 |
TW201736443A (zh) | 2017-10-16 |
JP2021101023A (ja) | 2021-07-08 |
TWI762464B (zh) | 2022-05-01 |
JP7173194B2 (ja) | 2022-11-16 |
JP6927050B2 (ja) | 2021-08-25 |
CN108885374A (zh) | 2018-11-23 |
CN108885374B (zh) | 2021-09-21 |
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