WO2018181818A1 - 液晶配向剤、液晶配向膜及び液晶表示素子 - Google Patents
液晶配向剤、液晶配向膜及び液晶表示素子 Download PDFInfo
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- WO2018181818A1 WO2018181818A1 PCT/JP2018/013467 JP2018013467W WO2018181818A1 WO 2018181818 A1 WO2018181818 A1 WO 2018181818A1 JP 2018013467 W JP2018013467 W JP 2018013467W WO 2018181818 A1 WO2018181818 A1 WO 2018181818A1
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- liquid crystal
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- 0 CN(C(C(*)C1(*)N(*)I)=O)C1=O Chemical compound CN(C(C(*)C1(*)N(*)I)=O)C1=O 0.000 description 1
- RVHVKTGUMPMVPC-UHFFFAOYSA-N Cc(cc1)ccc1C(Oc(cc1)ccc1C(Oc1ccc(C)cc1)=O)=O Chemical compound Cc(cc1)ccc1C(Oc(cc1)ccc1C(Oc1ccc(C)cc1)=O)=O RVHVKTGUMPMVPC-UHFFFAOYSA-N 0.000 description 1
- OXCHCYYHWJRQJA-UHFFFAOYSA-N Cc(cc1)ccc1C(Oc(cc1)ccc1OC(c1ccc(C)cc1)=O)=O Chemical compound Cc(cc1)ccc1C(Oc(cc1)ccc1OC(c1ccc(C)cc1)=O)=O OXCHCYYHWJRQJA-UHFFFAOYSA-N 0.000 description 1
- CJNXJWPAGDCOBK-UHFFFAOYSA-N Cc(cc1)ccc1C(Sc(cc1)ccc1C(Sc1ccc(C)cc1)=O)=O Chemical compound Cc(cc1)ccc1C(Sc(cc1)ccc1C(Sc1ccc(C)cc1)=O)=O CJNXJWPAGDCOBK-UHFFFAOYSA-N 0.000 description 1
- WTCJBHOWHJNGIL-UHFFFAOYSA-N Cc(cc1)ccc1OC(c(cc1)cc(cc2)c1cc2C(Oc1ccc(C)cc1)=O)=O Chemical compound Cc(cc1)ccc1OC(c(cc1)cc(cc2)c1cc2C(Oc1ccc(C)cc1)=O)=O WTCJBHOWHJNGIL-UHFFFAOYSA-N 0.000 description 1
- XOGHUKBCGNLXOX-UHFFFAOYSA-N Cc(cc1)ccc1OC(c(cc1)ccc1C(Oc1ccc(C)cc1)=O)=O Chemical compound Cc(cc1)ccc1OC(c(cc1)ccc1C(Oc1ccc(C)cc1)=O)=O XOGHUKBCGNLXOX-UHFFFAOYSA-N 0.000 description 1
- FKRLZXYFFYMGEN-UHFFFAOYSA-N Cc(cc1)ccc1OC(c1cc(C(Oc2ccc(C)cc2)=O)ccc1)=O Chemical compound Cc(cc1)ccc1OC(c1cc(C(Oc2ccc(C)cc2)=O)ccc1)=O FKRLZXYFFYMGEN-UHFFFAOYSA-N 0.000 description 1
- PRELWCYEOIVLBQ-JYFOCSDGSA-N Cc1ccc(/C=C/C(Oc(cc2)ccc2OC(/C=C/c2ccc(C)cc2)=O)=O)cc1 Chemical compound Cc1ccc(/C=C/C(Oc(cc2)ccc2OC(/C=C/c2ccc(C)cc2)=O)=O)cc1 PRELWCYEOIVLBQ-JYFOCSDGSA-N 0.000 description 1
- XIAAMHCLUJRZGF-JYFOCSDGSA-N Cc1ccc(/C=C/C(Oc2ccc(/C=C/C(Oc3ccc(C)cc3)=O)cc2)=O)cc1 Chemical compound Cc1ccc(/C=C/C(Oc2ccc(/C=C/C(Oc3ccc(C)cc3)=O)cc2)=O)cc1 XIAAMHCLUJRZGF-JYFOCSDGSA-N 0.000 description 1
- XCGIDGRJPRURKS-UHFFFAOYSA-N Cc1ccc(N(CC2)CCN2c2ncc(C)cc2)nc1 Chemical compound Cc1ccc(N(CC2)CCN2c2ncc(C)cc2)nc1 XCGIDGRJPRURKS-UHFFFAOYSA-N 0.000 description 1
- DRVIPZJZGKGMPJ-UHFFFAOYSA-N Cc1nccc(N(CC2)CCN2c2cc(C)ncc2)c1 Chemical compound Cc1nccc(N(CC2)CCN2c2cc(C)ncc2)c1 DRVIPZJZGKGMPJ-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
-
- 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
-
- 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
- C09K19/542—Macromolecular compounds
-
- 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/55—Design of synthesis routes, e.g. reducing the use of auxiliary or protecting groups
Definitions
- the present invention relates to a novel diamine compound (also referred to simply as “diamine” in the present specification) that is useful as a raw material for a polymer used in a liquid crystal alignment film, and a polymer (polyamic acid, polyamic acid) obtained using the diamine.
- a novel diamine compound also referred to simply as “diamine” in the present specification
- a polymer polyamic acid, polyamic acid obtained using the diamine.
- Acid ester, polyimide, etc. a liquid crystal aligning agent
- a liquid crystal aligning film a liquid crystal aligning film
- a liquid crystal display element a novel diamine compound that is useful as a raw material for a polymer used in a liquid crystal alignment film
- a polymer polyamic acid, polyamic acid obtained using the diamine.
- Acid ester, polyimide, etc. a liquid crystal aligning agent
- a liquid crystal aligning film a liquid crystal aligning film
- a liquid crystal display element a
- liquid crystal display elements have been widely used as display units for personal computers, mobile phones, television receivers, and the like.
- vertical electric field methods such as TN method and VA method, IPS method, and fringe.
- a lateral electric field method such as a field switching (hereinafter referred to as “FFS”) method is known.
- FFS field switching
- a vertical electric field that drives a liquid crystal by applying a voltage to electrodes formed on the upper and lower substrates.
- a liquid crystal display element capable of high-quality display such as having a wide viewing angle characteristic is easily obtained.
- a method for aligning the liquid crystal in a certain direction there is a method of performing a so-called rubbing process in which a polymer film such as polyimide is formed on a substrate and the surface is rubbed with a cloth.
- ion density and the like can be mentioned. If the ion density is excessively high, the voltage applied to the liquid crystal during the frame period is lowered, and as a result, the luminance is lowered, which may hinder normal gradation display. Moreover, even if the initial ion density is low, the ion density after the high-temperature acceleration test may increase. Such deterioration in long-term reliability and generation of afterimages accompanying residual charges and ionic impurities cause the display quality of the liquid crystal to deteriorate.
- a liquid crystal aligning agent containing a tertiary amine having a predetermined structure in addition to polyamic acid or an imide group-containing polyamic acid is used as a liquid crystal aligning film having a short time until an afterimage generated by a direct current voltage disappears
- a liquid crystal aligning agent containing a soluble polyimide using a predetermined diamine compound having a pyridine skeleton or the like as a raw material
- the rubbing treatment is widely used industrially as a method for aligning liquid crystals, but depending on the liquid crystal alignment film used, a phenomenon that the rubbing direction does not coincide with the alignment direction of the liquid crystal, a so-called twist angle may occur. That is, the horizontal electric field element displays black when no voltage is applied, but the luminance increases even when no voltage is applied due to this phenomenon, and as a result, the display contrast decreases. there were.
- the present invention can suppress the ion density in the liquid crystal display element and reduce the accumulated charge quickly, and suppresses the deviation between the rubbing direction and the alignment direction of the liquid crystal, which is a problem particularly in the lateral electric field driving method.
- An object of the present invention is to provide a liquid crystal alignment film that can be used.
- Another object of the present invention is to provide a diamine, a polymer, and a liquid crystal aligning agent from which such a liquid crystal aligning film can be obtained.
- an object of this invention is to provide the liquid crystal display element which comprises such a liquid crystal aligning film.
- the present inventors have introduced various structures by introducing a specific structure ("specific structure" will be described later) into the polymer contained in the liquid crystal aligning agent.
- the inventors have found that the characteristics are improved at the same time, and completed the present invention.
- the present invention is based on such knowledge and has the following gist.
- R represents a hydrogen atom or a monovalent organic group
- R 1 represents a hydrogen atom or a linear or branched alkyl group or aryl group having 1 to 5 carbon atoms, and there are two on the same maleimide ring R 1 may be the same as or different from each other, and two R 1 may be bonded to each other to form an alkylene having 3 to 6 carbon atoms
- W 1 represents a single bond or a divalent organic group.
- W 2 represents a divalent organic group
- Ar 1 represents an aromatic ring
- L 1 represents a single bond, carbonyl, sulfonyl or alkylene having 1 to 20 carbon atoms.
- Ar 1 is a 1,3-phenylene group or a 1,4-phenylene group. Liquid crystal aligning agent as described in.
- W 1 is a single bond Or 2.
- the polymer is at least one selected from a polyimide precursor containing a structural unit represented by the following formula (3) and a polyimide which is an imidized product thereof.
- X 1 represents a tetravalent organic group derived from a tetracarboxylic acid derivative
- Y 1 represents a divalent organic group derived from a diamine containing the structure of formula (1)
- R 4 represents a hydrogen atom or a carbon number of 1 Represents an alkyl group of ⁇ 5.
- the structure of X 1 is at least one selected from the following structures; Liquid crystal aligning agent as described in.
- the polymer is at least one selected from a polyimide precursor further containing a structural unit represented by the following formula (4) and a polyimide which is an imidized product thereof. ⁇ 5. Liquid crystal aligning agent as described in any one of these.
- X 2 represents a tetravalent organic group derived from a tetracarboxylic acid derivative
- Y 2 represents a divalent organic group derived from a diamine not containing the structure of formula (1) in the main chain direction
- R 14 is Each independently represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms
- each R 15 independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.
- Y 2 is represented by the following formula (11). Liquid crystal aligning agent as described in.
- R 32 represents a single bond or a divalent organic group
- R 33 represents a structure represented by — (CH 2 ) r —, r represents an integer of 2 to 10, and arbitrary —CH 2 — It may be replaced with an ether, ester, amide, urea, or carbamate bond under non-adjacent conditions
- R 34 represents a single bond or a divalent organic group, and any hydrogen atom on the benzene ring is a monovalent organic group May be replaced.
- the structural unit represented by the formula (3) is 10 mol% or more with respect to all the structural units of the polymer.
- the liquid crystal display element which comprises the liquid crystal aligning film of description.
- R represents a hydrogen atom or a monovalent organic group
- R 1 represents a hydrogen atom or an alkyl group or an aryl group which may be linear or branched having 1 to 5 carbon atoms, and 2 on the same maleimide ring.
- Two R 1 s may be the same or different from each other, and two R 1 s may be bonded to each other to form an alkylene having 3 to 6 carbon atoms
- W 1 is a single bond or a divalent organic group.
- W 2 represents a divalent organic group
- Ar 1 represents an aromatic ring
- L 1 represents a single bond, carbonyl, sulfonyl or alkylene having 1 to 20 carbon atoms.
- R represents a hydrogen atom or a monovalent organic group
- R 1 represents a hydrogen atom or an alkyl group or an aryl group which may be linear or branched having 1 to 5 carbon atoms, and 2 on the same maleimide ring.
- Two R 1 s may be the same or different from each other, and two R 1 s may be bonded to each other to form an alkylene having 3 to 6 carbon atoms
- W 1 is a single bond or a divalent organic group.
- W 2 represents a divalent organic group
- Ar 1 represents an aromatic ring
- L 1 represents a single bond, carbonyl, sulfonyl or alkylene having 1 to 20 carbon atoms.
- liquid crystal aligning agent of the present invention By using the liquid crystal aligning agent of the present invention, it is possible to keep the ion density in the liquid crystal display element low and to quickly relieve the accumulated charges, and particularly the rubbing direction and the liquid crystal are problematic in the lateral electric field driving method.
- a liquid crystal alignment film that can suppress the displacement of the alignment direction is obtained.
- the mechanism that can solve the above-described problems of the present invention is generally considered as follows.
- the structure of the above formula (1) contained in the polymer of the present invention has a nitrogen atom. Accordingly, for example, in the liquid crystal alignment film, the ability to supplement ionic impurities can be provided, the movement of charges can be promoted, and the relaxation of accumulated charges can be promoted.
- the polymer and the liquid crystal aligning agent can be obtained by using the diamine of the present invention. Further, by providing the liquid crystal alignment film of the present invention, such a liquid crystal display element excellent in various characteristics can be obtained.
- the liquid crystal aligning agent of the present invention includes a polymer (hereinafter also referred to as a specific polymer) obtained from a diamine having a structure represented by the above formula (1) (hereinafter also referred to as a specific structure).
- R represents a hydrogen atom or a monovalent organic group
- R 1 represents a hydrogen atom, a linear or branched alkyl group or aryl group having 1 to 5 carbon atoms
- Two R 1 on the maleimide ring may be the same or different from each other, and two R 1 may be bonded to each other to form an alkylene having 3 to 6 carbon atoms
- W 1 may be a single bond or A divalent organic group
- W 2 represents a divalent organic group
- Ar 1 represents an aromatic ring
- L 1 represents a single bond, carbonyl, sulfonyl or alkylene having 1 to 20 carbon atoms.
- R is preferably a hydrogen atom or a linear alkyl group having 1 to 3 carbon atoms, more preferably a hydrogen atom or a methyl group.
- R may be a protective group that undergoes a desorption reaction by heat and replaces a hydrogen atom. From the viewpoint of storage stability of the liquid crystal aligning agent, R does not desorb at room temperature, and preferably is desorbed by heat of 80 ° C. or higher. A protecting group which is released, and more preferably a protecting group which is released by heat at 100 ° C. or higher.
- Examples thereof include 1,1-dimethyl-2-chloroethoxycarbonyl group, 1,1-dimethyl-2-cyanoethoxycarbonyl group, and tert-butoxycarbonyl group, preferably tert-butoxycarbonyl group.
- R 1 is preferably a hydrogen atom, a methyl group, an ethyl group, an iso-propyl group, or a phenyl group, and more preferably a hydrogen atom, a methyl group, or a phenyl group.
- the alkylene having 3 to 6 carbon atoms formed by bonding two R 1 's to each other is preferably — (CH 2 ) 3 —, — (CH 2 ) 4 —, — (CH 2 ) 5 —. More preferably — (CH 2 ) 4 —.
- W 1 is a divalent bond selected from a single bond, —O—, —COO—, —OCO—, — (CH 2 ) p —, —O (CH 2 ) q O—, —CONH—, or —NHCO—.
- An organic group is preferred, p represents a natural number of 1 to 10, and q represents a natural number of 1 to 10.
- Ar 1 is preferably a 1,3-phenylene group or a 1,4-phenylene group.
- L 1 represents a single bond, carbonyl, sulfonyl or alkylene having 1 to 20 carbon atoms.
- the alkylene having 1 to 20 carbon atoms of L 1 may be linear or branched, and is linear alkylene represented by — (CH 2 ) n — (where n is 1 to 20).
- the divalent organic group W 2 is represented by the following formulas [W 2 -1] to [W 2 -152].
- W 2 ⁇ 7, W 2 ⁇ 20, W 2 ⁇ 21, W 2 ⁇ 23, W 2 ⁇ 26, W 2 ⁇ 39, and W 2 ⁇ 51 , W 2 -52, W 2 -53, W 2 -54, W 2 -55, W 2 -59, W 2 -60, W 2 -61, W 2 -64, W 2 -65, W 2 -67 , W 2 -68, W 2 -69, W 2 -70, and W 2 -71 are preferable.
- the method for synthesizing a diamine having a specific structure (sometimes referred to as “specific diamine” in the present specification) of the present invention is not particularly limited.
- a nitromaleimide compound represented by the following formula (A1) A method of reacting with a diamino compound represented by the following formula (B1) to obtain an aminonitro compound represented by the following formula (C1) and reducing this can be mentioned.
- R, R 1 , L 1 , Ar 1 , W 1 and W 2 are the same as in the above formula (1).
- the amount of the compound represented by the formula (B1) to be used is preferably 1 to 2 mol, preferably 1 to 1.2 mol, relative to 1 mol of the compound represented by the formula (A1). Further preferred. By using an excessive amount of the compound represented by the formula (B1), the reaction can proceed smoothly and by-products can be suppressed.
- a solvent does not react with each raw material, it can be used without a restriction
- aprotic polar organic solvents DMF, DMSO, DMAc, NMP, etc.
- ethers Et 2 O, i-Pr 2 O, TBME, CPME, THF, dioxane, etc.
- aliphatic hydrocarbons penentane, Hexane, heptane, petroleum ether, etc.
- aromatic hydrocarbons benzene, toluene, xylene, mesitylene, chlorobenzene, dichlorobenzene, nitrobenzene, tetralin, etc.
- halogenated hydrocarbons chloroform, dichloromethane, carbon tetrachloride, dichloroethane) Etc.
- lower fatty acid esters methyl acetate, ethyl acetate, butyl acetate, methyl
- solvents can be appropriately selected in consideration of the ease of reaction and the like, and can be used singly or in combination of two or more. If necessary, the solvent can be dried using a suitable dehydrating agent or desiccant and used as a non-aqueous solvent.
- the amount of solvent used is not particularly limited, but is 0.1 to 100 times by mass with respect to the bismaleimide compound. 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.
- This reaction can be carried out in the presence of an inorganic base or an organic base as necessary.
- the base used in the reaction include sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium hydrogen carbonate, potassium hydrogen carbonate, potassium phosphate, sodium carbonate, potassium carbonate, lithium carbonate, cesium carbonate and other inorganic bases; tert-butoxy Bases such as sodium, potassium tert-butoxy, sodium hydride and potassium hydride; amines such as trimethylamine, triethylamine, tripropylamine, triisopropylamine, tributylamine, diisopropylethylamine, pyridine, quinoline and collidine can be used.
- the amount of the base used is not particularly limited, but is 0 to 100 times by mass with respect to the bismaleimide compound.
- the amount is preferably 0 to 30 times by mass, and more preferably 0 to 10 times by mass.
- the conditions for producing the specific diamine represented by the formula (1) by reducing the compound represented by the formula (C1) are described below.
- a method for reducing the compound represented by the formula (C1) there is a reduction reaction performed in the presence of Fe, Sn, Zn, or a salt thereof and protons.
- the amount of Fe, Sn, Zn or a salt thereof used is preferably 1 to 100 equivalents, particularly preferably 3 to 50 equivalents, relative to the compound represented by the above formula (1).
- any solvent can be used as long as it does not interfere with the target reaction under the reaction conditions.
- water alcohol solvents such as methyl alcohol, ethyl alcohol, tert-butyl alcohol; aprotic polar organic solvents such as dimethylformamide, dimethyl sulfoxide, dimethylacetamide, N-methylpyrrolidone; diethyl ether, diisopropyl ether, tert-butyl Ethers such as methyl ether, cyclopentyl methyl ether, tetrahydrofuran and dioxane; aliphatic hydrocarbons such as pentane, hexane, heptane and petroleum ether; aromatic hydrocarbons such as benzene, toluene, xylene, mesitylene and tetralin, chloroform, dichloromethane, Halogenated hydrocarbons such as carbon tetrachloride and dichloroethane; lower
- solvents can be appropriately selected in consideration of the ease of reaction and the like, and can be used alone or in combination of two or more. Moreover, depending on the case, the said solvent can also be used as a solvent which does not contain water using a suitable dehydrating agent and a desiccant.
- the amount of the solvent used is not particularly limited, but is 0.1 to 100 times by mass with respect to the compound represented by the above formula (C1). The amount is preferably 0.5 to 50 times by mass, more preferably 3 to 30 times by mass.
- the reaction can be carried out under pressure in order to make the reaction proceed more effectively.
- the reaction in order to avoid the reduction of the benzene nucleus, the reaction is preferably carried out in a pressure range of about 20 atm (kgf), more preferably in a range up to 10 atm.
- acids such as hydrochloric acid, sulfuric acid, formic acid, acetic acid, and salts thereof may coexist.
- the amount of these used is not particularly limited, but is 0 to 10 times by mass with respect to the compound represented by the above formula (C1).
- the amount is preferably 0 to 5 times by mass, and more preferably 0 to 3 times by mass.
- the reaction temperature can be selected from a temperature range of preferably ⁇ 100 ° C. or higher to the boiling point of the reaction solvent to be used, more preferably ⁇ 50 to 150 ° C., particularly preferably 0 to 100 ° C. .
- the reaction time is 0.1 to 1000 hours, more preferably 1 to 200 hours.
- a hydrogenation reaction using palladium-activated carbon or platinum-activated carbon as a catalyst a reduction reaction using formic acid as a hydrogen source, or hydrazine as a hydrogen source. Reaction. These reactions can also be carried out in combination.
- the catalyst used for the 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 or the like is not necessarily an activated carbon-supported metal catalyst.
- Palladium-activated carbon and platinum-activated carbon which are generally widely used are preferable because good results can be obtained.
- the amount of these catalysts used may be a so-called catalytic amount, preferably 20 mol% or less, particularly preferably 10 mol% or less, relative to the compound represented by the above formula (C1).
- any solvent can be used as long as it does not interfere with the target reaction under the reaction conditions.
- alcohol solvents such as methyl alcohol, ethyl alcohol, tert-butyl alcohol; aprotic polar organic solvents such as dimethylformamide, dimethyl sulfoxide, dimethylacetamide, N-methylpyrrolidone; diethyl ether, isopropyl ether, tert-butyl methyl ether , Ethers such as cyclopentyl methyl ether, tetrahydrofuran and dioxane; aliphatic hydrocarbons such as pentane, hexane, heptane and petroleum ether; aromatic hydrocarbons such as benzene, toluene, xylene, mesitylene and tetralin, chloroform, dichloromethane and tetrachloride Halogen-based hydrocarbons such as carbon and dichloroethane; lower
- the amount of the solvent used is not particularly limited, but is 0.1 to 100 times by mass with respect to the compound represented by the above formula (C1). The amount is preferably 0.5 to 50 times by mass, more preferably 3 to 30 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.
- the reaction can be carried out in the presence of activated carbon.
- the amount of the activated carbon to be used is not particularly limited, but is preferably in the range of 1 to 30% by mass, more preferably 10 to 20% by mass with respect to the dinitro compound (C1).
- the reaction may be carried out under pressure. In this case, in order to avoid reduction of benzene nuclei, it is carried out in a pressure range up to 20 atm. The reaction is preferably carried out in the range up to 10 atm.
- a hydrogenation reaction in view of the structure of the compound represented by the formula (C1) and the reactivity of the reduction reaction.
- a maleimide compound represented by the following formula (A1) and an aminonitro compound represented by the following formula (B2) are reacted to form the following formula (C2).
- the method of obtaining the dinitro compound represented by these and reducing this can be mentioned.
- reaction conditions between the compound represented by the formula (B2) and the compound represented by the formula (A1) are the same as the reaction conditions between the compound represented by the formula (B1) and the compound represented by the formula (A1).
- reaction conditions for obtaining the diamine represented by the formula (1) by reducing the dinitro compound represented by the formula (C2) are the same as those obtained by reducing the compound represented by the formula (C1). According to the conditions for producing the specific diamine represented by
- a maleimide compound represented by the following formula (A2) and an aminonitro compound represented by the following formula (B2) are reacted to form the following formula (C3).
- reaction conditions between the compound represented by the formula (B2) and the compound represented by the formula (A2) are the same as the reaction conditions between the compound represented by the formula (B1) and the compound represented by the formula (A1).
- reaction conditions for obtaining the diamine represented by the formula (1) by reducing the aminonitro compound represented by the formula (C3) are the same as those obtained by reducing the compound represented by the formula (C1). According to the conditions for producing the specific diamine represented by 1).
- the maleimide compound represented by a following formula (A2) and the diamino compound represented by a following formula (B1) are made to react, and (1) is obtained.
- A2 and B1 are made to react, and (1) is obtained.
- reaction conditions between the compound represented by the formula (B1) and the compound represented by the formula (A2) conform to the reaction conditions between the compound represented by the formula (B1) and the compound represented by the formula (A1). .
- a compound in which R is a hydrogen atom in the dinitro compound represented by the above formula (C2) may be reacted with a compound capable of reacting with amines.
- a compound capable of reacting with amines include acid halides, acid anhydrides, isocyanates, epoxies, oxetanes, halogenated aryls, and halogenated alkyls.
- hydroxyl groups of alcohols can be OMs, OTf, OTs, and the like. Alcohols substituted with the leaving group can be used.
- the method of introducing a monovalent organic group into the NH group is not particularly limited, and a method of reacting an acid halide in the presence of a suitable base can be mentioned.
- 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. Butyl, benzyl chloroformate, and 9-fluorenyl chloroformate.
- the base the aforementioned bases can be used.
- the reaction solvent and reaction temperature are the same as described above.
- the NH group may be reacted with an acid anhydride to introduce a monovalent organic group.
- acid anhydrides include acetic anhydride, propionic anhydride, dimethyl dicarbonate, diethyl dicarbonate, ditertiary butyl dicarbonate. And dibenzyl dicarbonate.
- a catalyst may be added, and pyridine, collidine, N, N-dimethyl-4-aminopyridine and the like may be used.
- the amount of the catalyst is 0.0001 to 1 mol with respect to 1 mol of the compound in which R is a hydrogen atom in the dinitro compound represented by the above formula (C2).
- the reaction solvent and reaction temperature are the same as described above.
- a monovalent organic group may be introduced by reacting an isocyanate with an NH group, and examples of the isocyanate include methyl isocyanate, ethyl isocyanate, n-propyl isocyanate, and phenyl isocyanate.
- the reaction solvent and reaction temperature are the same as described above.
- a monovalent organic group may be introduced by reacting an NH group with an epoxy compound or oxetane compound.
- the epoxy compound and oxetane include ethylene oxide, propylene oxide, 1,2-butylene oxide, trimethylene. And oxides.
- the reaction solvent and reaction temperature are the same as described above.
- Monovalent organic groups may be introduced by reacting aryl halides with NH in the presence of a metal catalyst, a ligand and a base.
- aryl halides include iodobenzene, bromobenzene and chlorobenzene. Is mentioned.
- metal catalysts 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, but are not limited thereto.
- 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 base the aforementioned bases can be used.
- the reaction solvent and reaction temperature are the same as described above.
- a monovalent organic group may be introduced by reacting an alcohol in which a hydroxyl group of the alcohol is substituted with a leaving group such as OMs, OTf, OTs, etc. in the presence of a suitable base in the NH group. , Methanol, ethanol, 1-propanol and the like. By reacting these alcohols with methanesulfonyl chloride, trifluoromethanesulfonyl chloride, paratoluenesulfonic acid chloride, etc., elimination of OMs, OTf, OTs, etc. Alcohols substituted with groups can be obtained.
- the base the aforementioned bases can be used.
- the reaction solvent and reaction temperature are the same as described above.
- Monovalent organic groups may be introduced by reacting an alkyl halide with an NH group in the presence of a suitable base.
- alkyl halides include methyl iodide, ethyl iodide, and 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. Reaction conditions such as reaction solvent, reaction temperature and reaction time are the same as described above.
- the amount of the compound capable of reacting with the above amines is 1.0 to 3.0 with respect to 1.0 molar equivalent of the compound in which R is a hydrogen atom in the dinitro compound represented by the above formula (C2).
- the molar equivalent can be obtained.
- the range of 2.0 to 2.5 molar equivalent is preferred.
- the compound which can react with said amines can be used individually or in combination.
- each isomer and a mixture thereof are all represented by the diamine represented by Formula (1). included.
- the diamine compound represented by the formula (1) has a different substitution position of R 1 . All of these mixtures are also included in the diamine represented by the formula (1).
- the amount of the maleic anhydride derivative to be used is preferably 1 to 1.5 mol, more preferably 1 to 1.2 mol, per 1 mol of the nitroamine compound represented by the formula (D1). .
- This reaction is preferably performed in a solvent. Preferred solvents and reaction conditions are the same as the production conditions for the compound (1).
- the method for synthesizing the compound of the formula (A2) is not particularly limited.
- the diamine represented by the following formula (D2) is described in JP-A No. 2003-321531 or WO 2004/012735 pamphlet. And a method of reacting a maleic anhydride derivative under the conditions described above.
- the amount of the maleic anhydride derivative used is preferably 0.01 to 1 mol, more preferably 0.1 to 1.0 mol, relative to 1 mol of the diamine compound represented by the formula (D2). Further preferred.
- diamine (D2) By making diamine (D2) into an excessive amount, reaction can be advanced smoothly and a by-product can be suppressed.
- This reaction is preferably performed in a solvent.
- Preferred solvents and reaction conditions are the same as the production conditions for the compound (1).
- reaction conditions for obtaining the amine represented by the formula (A2) by reducing the nitro compound represented by the formula (A1) are the same as those obtained by reducing the compound represented by the formula (C1) above.
- a reduction reaction performed in the presence of Fe, Sn, Zn, or a salt thereof and a proton is preferable from the viewpoint of suppressing reduction of the double bond.
- the specific diamine of the present invention includes a maleimide compound represented by the following formula (A1) and ammonia, alkylamine, benzylamine and the like represented by a commercially available amino compound represented by the following formula (E).
- a maleimide compound represented by the following formula (A1) and ammonia, alkylamine, benzylamine and the like represented by a commercially available amino compound represented by the following formula (E).
- E a nitro compound represented by the following formula (F)
- nitrobenzyl chloride, nitrobenzoyl chloride, nitrobenzenesulfonyl chloride or nitrobenzene isocyanate represented by the following formula (G) 4- A method of reducing this by reacting with fluoronitrobenzene, 4-iodonitrobenzene or the like to obtain the following formula (C2) can be mentioned.
- reaction conditions between the compound represented by the formula (E) and the compound represented by the formula (A1) are the same as the reaction conditions between the compound represented by the formula (B1) and the compound represented by the formula (A1).
- a compound in which Z is OH and L 1 is carbonyl in the above formula (G) and a compound represented by the above formula (F) are used, if necessary, using a solvent inert to the reaction, and if necessary By reacting with a condensing agent in the presence of a base, a compound in which L 1 is carbonyl in the general formula (C2) can be obtained.
- As the amount of the reaction substrate 0.5 to 2 equivalents of the compound represented by the general formula (F) can be used with respect to 1 equivalent of the compound represented by the formula (G).
- the condensing agent is not particularly limited as long as it is used for ordinary amide synthesis.
- Mukaiyama reagent (2-chloro-N-methylpyridinium iodide), DCC (1,3-dicyclohexylcarbodiimide), WSC ( 1-ethyl-3- (3-dimethylaminopropyl) -carbodiimide hydrochloride), CDI (carbonyldiimidazole), dimethylpropynylsulfonium bromide, propargyltriphenylphosphonium bromide, DEPC (diethyl cyanophosphate), etc. 1) to 4 equivalents based on the compound in which Z is OH and L 1 is carbonyl.
- the solvent to be used is not particularly limited as long as it does not inhibit the progress of the reaction.
- aromatic hydrocarbons such as benzene, toluene and xylene
- aliphatic hydrocarbons such as hexane and heptane.
- Aliphatic halogenated hydrocarbons such as diethyl ether, 1,2-dimethoxyethane, tetrahydrofuran, ethers such as 1,4-dioxane, esters such as ethyl acetate and ethyl propionate, N, N-dimethylformamide, N, N-dimethylacetamide, N- Amides chill-2-pyrrolidone, triethylamine, tributylamine, N, N-amines dimethylaniline, pyridine, pyridine picoline, etc., include acetonitrile and dimethyl sulfoxide.
- a base for example, an alkali metal hydroxide such as sodium hydroxide or potassium hydroxide, an alkali metal carbonate such as sodium carbonate or potassium carbonate, sodium hydrogen carbonate, or potassium hydrogen carbonate.
- Alkali metal bicarbonates such as triethylamine, tributylamine, N, N-dimethylaniline, pyridine, 4- (dimethylamino) pyridine, imidazole, 1,8-diazabicyclo [5,4,0] -7-undecene, etc.
- An organic base or the like can be used in an amount of 1 to 4 equivalents with respect to the compound in which Z is OH and L 1 is carbonyl in the above formula (G).
- the reaction temperature can be set to any temperature from ⁇ 60 ° C. to the reflux temperature of the reaction mixture, and the reaction time varies depending on the concentration of the reaction substrate and the reaction temperature, but is usually arbitrary within the range of 5 minutes to 100 hours. Can be set.
- a compound in which Z is OH and L 1 is carbonyl or sulfonyl is reacted with a known method described in the literature, for example, with a chlorinating agent such as thionyl chloride, phosphorus pentachloride or oxalyl chloride. Or a method of reacting with an organic acid halide such as pivaloyl chloride or isobutyl chloroformate in the presence of a base, if necessary, or a method of reacting with carbonyldiimidazole or sulfonyldiimidazole.
- a chlorinating agent such as thionyl chloride, phosphorus pentachloride or oxalyl chloride.
- an organic acid halide such as pivaloyl chloride or isobutyl chloroformate in the presence of a base, if necessary, or a method of reacting with carbonyldiimidazole or sulfonyld
- the amount of the reaction substrate used is 0.5 to 2 equivalents of the compound represented by the above formula (F) with respect to 1 equivalent of the compound in which Z is Cl and L 1 is carbonyl or sulfonyl in the above formula (G). be able to.
- the solvent to be used is not particularly limited as long as it does not inhibit the progress of the reaction.
- aromatic hydrocarbons such as benzene, toluene and xylene
- aliphatic hydrocarbons such as hexane and heptane.
- a base for example, an alkali metal hydroxide such as sodium hydroxide or potassium hydroxide, an alkali metal carbonate such as sodium carbonate or potassium carbonate, sodium hydrogen carbonate, or potassium hydrogen carbonate.
- Alkali metal bicarbonates such as triethylamine, tributylamine, N, N-dimethylaniline, pyridine, 4- (dimethylamino) pyridine, imidazole, 1,8-diazabicyclo [5,4,0] -7-undecene, etc.
- An organic base or the like can be used in an amount of 1 to 4 equivalents with respect to the compound in which Z is Cl and L 1 is carbonyl or sulfonyl in the above formula (G).
- the reaction temperature can be set to any temperature from ⁇ 60 ° C. to the reflux temperature of the reaction mixture, and the reaction time varies depending on the concentration of the reaction substrate and the reaction temperature, but is usually arbitrary within the range of 5 minutes to 100 hours. Can be set.
- L 1 and W 1 are both a single bond, Z is F or Cl, and a NO 2 group is in the 2-position or 4-position with respect to Z.
- the compound represented by the formula (F) can be reacted to obtain the dinitro compound represented by the above formula (C2).
- Examples of the base used include inorganic bases such as sodium bicarbonate, potassium bicarbonate, potassium phosphate, sodium carbonate, potassium carbonate, lithium carbonate, cesium carbonate; trimethylamine, triethylamine, tripropylamine, triisopropylamine, tributylamine, diisopropyl Amines such as ethylamine, pyridine, quinoline and collidine; bases such as sodium hydride and potassium hydride; can be used.
- inorganic bases such as sodium bicarbonate, potassium bicarbonate, potassium phosphate, sodium carbonate, potassium carbonate, lithium carbonate, cesium carbonate
- trimethylamine, triethylamine, tripropylamine, triisopropylamine, tributylamine, diisopropyl Amines such as ethylamine, pyridine, quinoline and collidine
- bases such as sodium hydride and potassium hydride
- any solvent that does not react with the raw material can be used.
- aprotic polar organic solvents N, N-dimethylformamide, dimethyl sulfoxide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, etc.
- ethers Et 2 O, i-Pr 2 O, tert -Butyl methyl ether, cyclopentyl methyl ether, tetrahydrofuran, dioxane, etc.
- aliphatic hydrocarbons pentane, hexane, heptane, petroleum ether, etc.
- aromatic hydrocarbons benzene, toluene, xylene, mesitylene, chlorobenzene, di) Chlorobenzene, nitrobenzene, tetralin, etc.
- halogenated hydrocarbons chloroform, dichloromethane, carbon tetrachloride, dichloroethane
- the said solvent can be used individually by 1 type or in mixture of 2 or more types.
- the solvent may be dehydrated and dried using an appropriate dehydrating agent or desiccant.
- the reaction temperature is in the range from ⁇ 100 ° C. to the boiling point of the solvent used, and any temperature can be selected, but it is preferably in the range of ⁇ 50 to 150 ° C.
- the reaction time can be arbitrarily selected in the range of 0.1 to 1000 hours, but is preferably 0.1 to 100 hours.
- the NO 2 group may be in the 2nd , 3rd or 4th position with respect to X, and contains a suitable metal catalyst and ligand, and a CN crosslink in the presence of a base.
- a dinitro compound can be obtained by using a coupling reaction.
- metal catalysts 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, but are not limited thereto.
- 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. However, it is not limited to these.
- the aforementioned bases can be used.
- the reaction solvent and reaction temperature are the same as described above.
- the target product in each stage obtained by the above reactions may be purified by distillation, recrystallization, or column chromatography such as silica gel, or may be subjected to the next stage as it is without purification. it can.
- the reaction conditions for obtaining the diamine represented by the formula (1) by reducing the dinitro compound represented by the formula (C2) are the same as described above.
- the polymer of the present invention is obtained using the diamine.
- Specific examples include polyamic acid, polyamic acid ester, polyimide, polyurea, polyamide and the like.
- X 1 represents a tetravalent organic group derived from a tetracarboxylic acid derivative
- Y 1 represents a divalent organic group derived from a diamine containing the structure of formula (1)
- R 4 Represents 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 in the polyimide precursor is a required property such as solubility of the polymer in a solvent, application property of a liquid crystal aligning agent, liquid crystal alignment property when a liquid crystal alignment film is formed, voltage holding ratio, accumulated charge, and the like. Depending on the degree, it may be appropriately selected, and one type may be used in the same polymer, or two or more types may be mixed. If Specific examples of X 1 dare shown, is published in 13 pages to 14 pages of WO 2015/119168, the structure or the like of the formula (X-1) ⁇ (X -46) are mentioned. Below, shows the structure of a preferred X 1, the present invention is not limited thereto.
- (A-1) and (A-2) are particularly preferable from the viewpoint of further improving rubbing resistance, and (A-4) is particularly preferable from the viewpoint 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.
- the polyimide precursor containing the structural unit represented by the formula (3) is at least selected from the structural unit represented by the following formula (4) and a polyimide that is an imidized product thereof, as long as the effects of the present invention are not impaired.
- One kind may be included.
- X 2 represents a tetravalent organic group derived from a tetracarboxylic acid derivative
- Y 2 represents a divalent organic group derived from a diamine that does not include the structure of Formula (1) in the main chain direction.
- R 14 is the same as the definition of R 4 in the formula (3), and R 15 each independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.
- X 2 include the same structures as those exemplified for X 1 in formula (3), including preferred examples.
- Y 2 in the polyimide precursor is a divalent organic group derived from a diamine that does not include the structure of formula (1) in the main chain direction, and the structure is not particularly limited. Y 2 depends on the required properties such as the solubility of the polymer in the solvent, the coating property of the liquid crystal aligning agent, the orientation of the liquid crystal when it is used as the liquid crystal alignment film, the voltage holding ratio, the accumulated charge, etc. 1 type may be selected in the same polymer, and 2 or more types may be mixed.
- Y 2 include groups represented by the above formulas [W 2 -1] to [W 2 -152]. Also, the structure of formula (2) published on page 4 of International Publication No. 2015/119168, and formulas (Y-1) to (Y-97), (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; 8 of International Publication No. 2015/122413 A divalent organic group obtained by removing two amino groups from the formula (1) published on the page; the structure of the formula (3) published on page 8 of International Publication No.
- a preferable structure of Y 2 includes a structure of the following formula (11).
- R 32 is a single bond or a divalent organic group, and a single bond is preferable.
- R 33 is a structure represented by — (CH 2 ) r —. r is an integer of 2 to 10, preferably 3 to 7. Arbitrary —CH 2 — may be replaced with an ether, ester, amide, urea, or carbamate bond under the condition that they are not adjacent to each other.
- R 34 represents a single bond or a divalent organic group. Any hydrogen atom on the benzene ring may be replaced with a monovalent organic group, and a fluorine atom or a methyl group is preferred.
- Specific examples of the structure represented by the formula (11) include the following structures, but are not limited thereto.
- the structural unit represented by the formula (3) is preferably 1 to 80 mol%, more preferably 5 to 60 mol% based on the total of the formula (3) and the formula (4).
- the mol% is particularly preferably 10 to 40 mol%.
- amino group, imino group, and structures having at least one are selected from the group consisting of nitrogen-containing heterocyclic ring.
- a structure of Y 2 it has at least one structure selected from the group consisting of an amino group, an imino group, and a nitrogen-containing heterocyclic ring, or a thermal leaving group is substituted on the nitrogen atom.
- the structure is not particularly limited as long as it has at least one structure selected from an amino group, an imino group, and a nitrogen-containing heterocyclic ring.
- At least one selected from the group consisting of an amino group represented by the following formulas (YD-1) to (YD-5), an imino group, and a nitrogen-containing heterocyclic ring will be given.
- Examples thereof include a divalent organic group having a structure.
- a 1 represents a nitrogen atom-containing heterocyclic ring having 3 to 15 carbon atoms
- Z 1 represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms which may have a substituent.
- V 1 represents a hydrocarbon group having 1 to 10 carbon atoms
- a 2 is a monovalent organic group having 3 to 15 carbon atoms having a nitrogen atom-containing heterocyclic ring, or 1 carbon atom A disubstituted amino group substituted with an aliphatic group of ⁇ 6.
- V 2 represents a divalent organic group having 6 to 15 carbon atoms and 1 to 2 benzene rings
- V 3 represents alkylene or biphenylene having 2 to 5 carbon atoms
- Z 2 represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, a benzene ring, or a thermally leaving group
- a represents an integer of 0 to 1.
- a 3 represents a nitrogen atom-containing heterocycle having 3 to 15 carbon atoms.
- a 4 represents a nitrogen atom-containing heterocycle having 3 to 15 carbon atoms
- V 5 represents an alkylene having 2 to 5 carbon atoms.
- pyrrolidine, pyrrole, imidazole, pyrazole, oxazole, thiazole, piperidine, piperazine, pyridine, pyrazine, indole, benzimidazole, quinoline, isoquinoline are included, and piperazine, piperidine, indole, benzimidazole, imidazole, carbazole, and pyridine are included. More preferred.
- the thermally desorbable group may be any substituent that does not desorb at room temperature but desorbs when the alignment film is baked to replace a hydrogen atom.
- a tert-butoxycarbonyl group and a 9-fluoro group can be used.
- An oleenylmethoxycarbonyl group is mentioned.
- Y 2 examples include divalent organic groups having nitrogen atoms represented by the following formulas (YD-6) to (YD-52), which can suppress charge accumulation due to AC driving. Therefore, the formulas (YD-14) to (YD-21) are more preferable, and (YD-14) and (YD-18) are particularly preferable.
- j represents an integer of 0 to 3.
- j represents an integer of 0 to 3.
- n and n each represent an integer of 1 to 11, and m + n represents an integer of 2 to 12.
- the polyamic acid which is a polyimide precursor used in the present invention can be synthesized by the following method. Specifically, tetracarboxylic dianhydride and diamine are reacted in the presence of an organic solvent at ⁇ 20 to 150 ° C., preferably 0 to 70 ° C., for 30 minutes to 24 hours, preferably 1 to 12 hours. Can be synthesized.
- the organic solvent used in the above reaction is preferably N, N-dimethylformamide, N-methyl-2-pyrrolidone, ⁇ -butyrolactone, etc. in view of the solubility of the monomer and polymer, and these may be used alone or in combination. May be used.
- the concentration of the polymer is preferably 1 to 30% by mass, and more preferably 5 to 20% by mass from the viewpoint that polymer precipitation is difficult to occur and a high molecular weight product is easily obtained.
- the polyamic acid obtained as described above can be recovered by precipitating a polymer by pouring into a poor solvent while thoroughly stirring the reaction solution. Moreover, the powder of polyamic acid refine
- the poor solvent is not particularly limited, and examples thereof include water, methanol, ethanol, 2-propanol, hexane, butyl cellosolve, acetone, toluene and the like, 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 imidation which adds a catalyst to the solution of the said polyamic acid obtained by reaction with a diamine component and tetracarboxylic dianhydride is simple.
- Chemical imidization is preferable because the imidization reaction proceeds at a relatively low temperature and the molecular weight of the polymer does not easily decrease during the imidization process.
- Chemical imidation can be performed 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.
- the basic catalyst include pyridine, triethylamine, trimethylamine, tributylamine, trioctylamine and the like. Of these, pyridine is preferable because it has an appropriate basicity for proceeding with the reaction.
- the acid anhydride include acetic anhydride, trimellitic anhydride, pyromellitic anhydride and the like. Among them, use of acetic anhydride is preferable because purification after completion of the reaction is facilitated.
- the temperature for carrying out the imidization reaction is ⁇ 20 to 140 ° C., preferably 0 to 100 ° C., and the reaction time can be 1 to 100 hours.
- the amount of the basic catalyst is 0.5 to 30 times mol, preferably 2 to 20 times mol of the polyamic acid group, and the amount of acid anhydride is 1 to 50 times mol, preferably 3 to 30 times mol of the polyamic acid group. 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. It is preferable to use a liquid crystal aligning agent.
- the polyimide solution obtained as described above can be polymerized by pouring into a poor solvent while stirring well. Precipitation is performed several times, and after washing with a poor solvent, a polymer powder purified by drying at normal temperature or by heating can be obtained.
- the poor solvent include, but are not limited to, methanol, 2-propanol, acetone, hexane, butyl cellosolve, heptane, methyl ethyl ketone, methyl isobutyl ketone, ethanol, toluene, benzene, and the like. Methanol, ethanol, 2-propanol, Acetone is preferred.
- the polyamic acid ester which is a polyimide precursor 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. Can be manufactured.
- the esterifying agent is preferably one that can be easily removed by purification, 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 per 1 mol of the polyamic acid repeating unit.
- organic solvent examples include N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone or ⁇ -butyrolactone, N, N-dimethylformamide, N, N-dimethylacetamide, dimethyl sulfoxide or 1,3-dimethyl- Examples include imidazolidinone.
- solvent solubility of the polyimide precursor is high, methyl ethyl ketone, cyclohexanone, cyclopentanone, 4-hydroxy-4-methyl-2-pentanone, or the formulas [D-1] to [D-3] described later
- the solvent shown by can be used.
- solvents may be used alone or in combination. Furthermore, even if it is a solvent which does not dissolve a polyimide precursor, you may mix and use it for the said solvent in the range which the produced
- the solvent used in the above reaction is preferably N, N-dimethylformamide, N-methyl-2-pyrrolidone, or ⁇ -butyrolactone in view of polymer solubility. 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 polymer precipitation is unlikely to occur and a high molecular weight product is easily obtained.
- the 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 gently.
- 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 in the above reaction is preferably N-methyl-2-pyrrolidone or ⁇ -butyrolactone in view of the solubility of the monomer and polymer, and these may be used alone or in combination.
- the polymer concentration at the time of production is preferably 1 to 30% by mass, more preferably 5 to 20% by mass, from the viewpoint that polymer precipitation is unlikely to occur and a high molecular weight product is easily obtained.
- the solvent used for the production of the polyamic acid ester is preferably dehydrated as much as possible, and it is preferable to prevent mixing of outside air in a nitrogen atmosphere.
- Polyamic acid ester can be manufactured by polycondensing tetracarboxylic-acid diester and diamine. Specifically, tetracarboxylic acid diester and diamine are reacted in the presence of a condensing agent, a base, and an organic solvent at 0 to 150 ° C., preferably 0 to 100 ° C., for 30 minutes to 24 hours, preferably 3 to 15 hours. Can be manufactured.
- condensing agent examples include triphenyl phosphite, dicyclohexylcarbodiimide, 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide hydrochloride, N, N′-carbonyldiimidazole, dimethoxy-1,3,5-triazide.
- Nylmethylmorpholinium O- (benzotriazol-1-yl) -N, N, N ′, N′-tetramethyluronium tetrafluoroborate, O- (benzotriazol-1-yl) -N, N , N ′, N′-tetramethyluronium hexafluorophosphate, (2,3-dihydro-2-thioxo-3-benzoxazolyl) phosphonate diphenyl, and the like.
- the addition amount of the condensing agent is preferably 2 to 3 times the molar amount of the tetracarboxylic acid diester.
- tertiary amines such as pyridine and triethylamine can be used.
- the amount of the base added is preferably 2 to 4 times the mol of the diamine component from the viewpoint that it can be easily removed and a high molecular weight product can be easily obtained.
- the reaction proceeds efficiently by adding Lewis acid as an additive.
- 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 mol with respect to the diamine component.
- the production method (1) or (2) is particularly preferable.
- the polymer solution can be precipitated by injecting the polyamic acid ester solution obtained as described above into a poor solvent while stirring well. Precipitation is performed several times, and after washing with a poor solvent, a purified polyamic acid ester powder can be obtained at room temperature or by heating and drying.
- a poor solvent is not specifically limited, Water, methanol, ethanol, hexane, butyl cellosolve, acetone, toluene etc. are mentioned.
- the diamine represented by the formula (1) may be used as the diamine in the above production method.
- the molecular weight of the polyimide precursor or polyimide that is a polymer contained in the liquid crystal aligning agent of the present invention is such that when the liquid crystal aligning film is obtained from the liquid crystal aligning agent containing the polymer, the coating film (liquid crystal aligning film)
- the weight average molecular weight measured by GPC (Gel Permeation Chromatography) method is preferably 2,000 to 500,000, It is more preferably from 000 to 300,000, and even more preferably from 10,000 to 100,000.
- 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).
- polymer specific polymer obtained from the diamine which has a structure represented by Formula (1).
- two or more kinds of specific polymers having different structures may be included within the limit of achieving the effects described in the present invention.
- other polymers that is, a polymer having no divalent group represented by the formula (1) may be included.
- polystyrene-phenylmaleimide poly (meta ) Acrylate and the like.
- the ratio of the specific polymer to the total polymer components is preferably 5% by mass or more, and an example thereof is 5 to 95% by mass.
- the liquid crystal aligning agent is used for producing a liquid crystal aligning film, and generally takes the form of a coating liquid from the viewpoint of forming a uniform thin film. Also in the liquid crystal aligning agent of this invention, it is preferable that it is a coating liquid containing an above-described 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, the content 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.
- the organic solvent contained in the liquid crystal aligning agent should use the mixed solvent which used together the solvent which improves the applicability
- a mixed solvent is also preferably used in the liquid crystal aligning agent of the present invention. Specific examples of the organic solvent to be used in combination are listed below, but are not limited to these examples.
- 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- Etanji 1,2-propanediol, 1,3-propaned
- 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 suitably selected according to the coating device, coating conditions, coating environment, etc. 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 as long as the effects of the present invention are not impaired.
- 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.
- examples thereof include dielectrics and conductive materials for adjusting the dielectric constant and electrical resistance of the film. Specific examples of these additional components are as disclosed in various known literatures relating to liquid crystal alignment agents. For example, pages 53 [0105] to 55 of International Publication No. 2015/060357. Ingredients disclosed in [0116] can be mentioned.
- the liquid crystal aligning film of this invention is obtained from the said liquid crystal aligning agent. If an example of the method of obtaining a liquid crystal aligning film from a liquid crystal aligning agent is given, a liquid crystal aligning agent in the form of a coating solution is applied to a substrate, dried and baked on a film obtained by rubbing or photo-aligning. And a method of performing an alignment treatment.
- the substrate on which the liquid crystal aligning 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 formed in terms of simplification of the process.
- an opaque material such as a silicon wafer can be used as long as it is only on one side of the substrate, and a material that reflects light such as aluminum can be used for the electrode in this case.
- the application method of the liquid crystal aligning agent is not particularly limited, but industrially, screen printing, offset printing, flexographic printing, ink jet method and the like are common. As other coating methods, there are a dipping method, a roll coater method, a slit coater method, a spinner method, a spray method, and the like, and these may be used according to 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. Arbitrary temperature and time can be selected for the drying and baking steps after applying the liquid crystal aligning agent.
- the thickness of the liquid crystal alignment film after firing is not particularly limited, but if it is too thin, the reliability of the liquid crystal display element may be lowered, so that it is preferably 5 to 300 nm, more preferably 10 to 200 nm.
- the liquid crystal alignment film of the present invention is suitable as a liquid crystal alignment film of a liquid crystal display element of a horizontal electric field type such as an IPS mode or an FFS mode, and particularly useful as a liquid crystal alignment film of an FFS mode liquid crystal display element.
- the liquid crystal display element of the present invention can be obtained by using a liquid crystal cell by preparing a liquid crystal cell by a known method after obtaining a substrate with a liquid crystal alignment film obtained from the liquid crystal aligning agent.
- a liquid crystal display element having a passive matrix structure will be described as an example.
- the liquid crystal display element may be an active matrix structure in which switching elements such as TFTs (Thin Film Transistors) are provided in each pixel portion constituting the image display.
- TFTs Thin Film Transistors
- 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 crystal is 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 location on one substrate, and the liquid crystal is After the substrates are bonded without being arranged, 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.
- liquid crystal material examples include a nematic liquid crystal and a smectic liquid crystal.
- 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.
- liquid crystal aligning film and liquid crystal display element of this invention are not limited to said description, as long as the liquid crystal aligning agent of this invention is used, The thing produced by the other well-known method may be used. Processes for obtaining a liquid crystal display element from a liquid crystal aligning agent are also disclosed in a number of documents in addition to, for example, JP-A-2015-135393, page 17 [0074] to page 19 [0081].
- Viscosity measurement In the following examples or comparative examples, the viscosity of the polyamic acid solution was measured using an E-type viscometer TVE-22H (manufactured by Toki Sangyo Co., Ltd.), with a sample amount of 1.1 mL, cone rotor TE-1 (1 ° 34 ′, R24).
- Example 5 Synthesis of polyamic acid solution (PAA-2) After adding 2.36 g (7 mmol) of (DA-1-1) to a 50 ml four-necked flask equipped with a stirrer and a nitrogen inlet tube, 24.6 g of NMP was added, and nitrogen was added. The solution was stirred and dissolved while feeding. While stirring this diamine solution, 0.61 g (2.8 mmol) of CA-1 and 0.75 g (3.9 mmol) of CA-2 were added, and 2.7 g of NMP was added, and further, at 50 ° C. for 12 hours. A polyamic acid solution (PAA-2) was obtained by stirring. The viscosity of this polyamic acid solution at 25 ° C. was 230 mPa ⁇ s.
- Example 6 Preparation of Liquid Crystal Alignment Agent (Q-1) 7.5 g of the polyamic acid solution (PAA-1) obtained in Example 4 was collected and stirred with stirring, NMP 5.6 g, BCS 6.0 g, 3-aminopropyltriethoxy 0.9 g of NMP solution containing 1% by weight of silane was added and further stirred at room temperature for 2 hours to obtain a liquid crystal aligning agent (Q-1).
- Example 7 Preparation of Liquid Crystal Alignment Agent (Q-2) 7.5 g of the polyamic acid solution (PAA-2) obtained in Example 5 was collected and stirred while stirring 5.6 g of NMP, 6.0 g of BCS, 3-aminopropyltriethoxy 0.9 g of NMP solution containing 1% by weight of silane was added, and further stirred at room temperature for 2 hours to obtain a liquid crystal aligning agent (Q-2).
- This liquid crystal alignment film is rubbed (roller diameter: 120 mm, roller rotation speed: 1000 rpm, moving speed: 20 mm / sec, indentation length: 0.4 mm) with a rayon cloth (YA-20R, manufactured by Yoshikawa Chemical), and then into pure water.
- the substrate was cleaned by irradiating with ultrasonic waves for 1 minute, and after removing water droplets by air blow, it was dried at 80 ° C. for 15 minutes to obtain a substrate with a liquid crystal alignment film.
- a substrate with electrodes was prepared.
- the substrate is a glass substrate having a size of 30 mm ⁇ 35 mm and a thickness of 0.7 mm.
- 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 has a comb-like shape configured by arranging a plurality of dog-shaped electrode elements having a bent central portion, as in the drawing described in Japanese Patent Application Laid-Open No. 2014-77845. .
- 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-shaped electrode elements having a bent central portion, the shape of each pixel is not a rectangular shape, and the central portion is similar to the electrode element. It has a shape similar to that of a bold, bent, bent at 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). That is, in the first region and the second region of each pixel, 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 are mutually in the substrate plane. It is comprised so that it may become a reverse direction.
- the polyimide film is rubbed with a rayon cloth in a predetermined rubbing direction (roll diameter 120 mm, rotation speed 500 rpm, moving speed 30 mm / sec, pushing amount 0.3 mm), and then irradiated with ultrasonic waves in pure water for 1 minute. And dried at 80 ° C. for 10 minutes.
- 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 constitutes an FFS mode liquid crystal display element. Thereafter, the obtained liquid crystal cell was heated at 120 ° C. for 1 hour and allowed to stand overnight before being used for each evaluation.
- the rotation angle when the liquid crystal cell was rotated from the angle at which the second region of the first pixel became darkest to the angle at which the first region became darkest was calculated as an angle ⁇ .
- the second area was compared with the first area, and a 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.
- a liquid crystal cell having an angle ⁇ value of 0.15 ° or less was evaluated as good and a value higher than 0.15 ° was evaluated as defective.
- the liquid crystal cell is placed between two polarizing plates arranged so that their polarization axes are orthogonal to each other, and the pixel electrode and the counter electrode are short-circuited to be at the same potential, and the LED is displayed from under the two polarizing plates.
- the angle of the liquid crystal cell was adjusted so that the brightness of the LED backlight transmitted light measured on the two polarizing plates was minimized by irradiating the backlight.
- the VT characteristics voltage-transmittance characteristics
- an 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 accumulated charge via the luminance.
- a rectangular wave having an AC voltage with a relative transmittance of 23% and a frequency of 30 Hz was applied for 5 minutes, and then a +1.0 V DC voltage was superimposed and driven for 30 minutes. Thereafter, the DC voltage was turned off, and only a rectangular wave having an AC voltage with a relative transmittance of 23% and a frequency of 30 Hz was applied for 30 minutes.
- Examples 1 to 4 Using the liquid crystal aligning agents Q1 to Q4 of Examples 6 to 7 and Comparative Examples 3 to 4, ion density measurement, evaluation of stability of liquid crystal alignment, and evaluation of relaxation characteristics of accumulated charges were performed. The results are shown in Table 1. In the table, liquid crystal cells produced using the liquid crystal aligning agents Q1 to Q2 are designated as Examples 8 to 9, respectively, and liquid crystal cells produced using the liquid crystal aligning agents Q3 to Q4 are designated as Comparative Examples 5 to 6, respectively.
- the liquid crystal alignment film of the present invention can obtain display performance with excellent afterimage characteristics and contrast, particularly in an IPS drive type or FFS drive type liquid crystal display element that requires rubbing treatment. Therefore, it is particularly useful as a liquid crystal alignment film used in IPS drive type or FFS drive type liquid crystal display elements, multifunctional mobile phones (smartphones), tablet personal computers, liquid crystal televisions, and the like.
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Abstract
Description
上記式(1)中、Rは水素原子又は一価の有機基を示し、R1は水素原子又は炭素数1~5の直鎖又は分岐してもよい、アルキル基若しくはアリール基を示し、同じマレイミド環上に2つあるR1は互いに同一でも、異なっていてもよく、2つあるR1が互いに結合して炭素数3~6のアルキレンを形成してもよく、W1は単結合又は2価の有機基を示し、W2は2価の有機基を示し、Ar1は芳香族環を示し、L1は単結合、カルボニル、スルホニル又は炭素数1~20のアルキレンを示す。
本発明の、特定構造を有するジアミン(本明細書では「特定ジアミン」と称することがある)を合成する方法は特に限定されないが、例えば、下記式(A1)で表されるニトロマレイミド化合物と、下記式(B1)で表されるジアミノ化合物とを反応させて下記式(C1)で表されるアミノニトロ化合物を得て、これを還元する方法を挙げることができる。
式(A1)の化合物を合成する方法に特に制限はないが、例えば、下記式(D1)で表される市販のニトロアミンに、無水マレイン酸誘導体を反応させる方法が挙げられる。
式(A2)の化合物を合成する方法に特に制限はないが、例えば、下記式(D2)で表されるジアミンに、特開2003-321531号公報又は国際公開公報2004/012735号パンフレット等に記載されている条件下で、無水マレイン酸誘導体を反応させる方法が挙げられる。
本発明の重合体は、上記ジアミンを用いて得られる。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、ポリアミド等が挙げられるが、液晶配向剤としての使用の観点から、下記式(3)で表される構造単位を含む、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選ばれる少なくとも1種であるとより好ましい。
ポリイミド前駆体中のX1は、重合体の溶媒への溶解性や液晶配向剤の塗布性、液晶配向膜とした場合における液晶の配向性、電圧保持率、蓄積電荷等、必要とされる特性の程度に応じて適宜選択され、同一重合体中に1種であってもよく、2種以上が混在していてもよい。X1の具体例をあえて示すならば、国際公開公報2015/119168の13頁~14頁に掲載される、式(X-1)~(X-46)の構造等が挙げられる。以下に、好ましいX1の構造を示すが、本発明はこれらに限定されない。
式(3)で表される構造単位を含むポリイミド前駆体は、本発明の効果を損なわない範囲において、下記式(4)で表される構造単位、及びそのイミド化物であるポリイミドから選ばれる少なくとも1種を含んでいてもよい。
本発明に用いられるポリイミド前駆体であるポリアミック酸は、以下に示す方法により合成することができる。具体的には、テトラカルボン酸二無水物とジアミンとを有機溶媒の存在下で-20~150℃、好ましくは0~70℃において、30分~24時間、好ましくは1~12時間反応させることによって合成できる。上記の反応に用いる有機溶媒は、モノマー及び重合体の溶解性からN,N-ジメチルホルムアミド、N-メチル-2-ピロリドン、γ-ブチロラクトン等が好ましく、これらは1種又は2種以上を混合して用いてもよい。重合体の濃度は、重合体の析出が起こりにくく、かつ高分子量体が得やすいという観点から、1~30質量%が好ましく、5~20質量%がより好ましい。
本発明に用いられるポリイミドは、前記ポリアミック酸をイミド化することにより製造することができる。ポリアミック酸からポリイミドを製造する場合、ジアミン成分とテトラカルボン酸二無水物との反応で得られた前記ポリアミック酸の溶液に触媒を添加する化学的イミド化が簡便である。化学的イミド化は、比較的低温でイミド化反応が進行し、イミド化の課程で重合体の分子量低下が起こりにくいので好ましい。化学的イミド化は、イミド化させたい重合体を、有機溶媒中において塩基性触媒と酸無水物の存在下で攪拌することにより行うことができる。有機溶媒としては前述した重合反応時に用いる溶媒を使用することができる。塩基性触媒としてはピリジン、トリエチルアミン、トリメチルアミン、トリブチルアミン、トリオクチルアミン等を挙げることができる。中でもピリジンは反応を進行させるのに適度な塩基性を持つので好ましい。また、酸無水物としては無水酢酸、無水トリメリット酸、無水ピロメリット酸等を挙げることができ、中でも無水酢酸を用いると反応終了後の精製が容易となるので好ましい。
本発明に用いられるポリイミド前駆体であるポリアミック酸エステルは、以下に示す(1)、(2)又は(3)の製法で製造することができる。
ポリアミック酸エステルは、前記のように製造されたポリアミック酸をエステル化することによって製造できる。具体的には、ポリアミック酸とエステル化剤を有機溶剤の存在下で-20℃~150℃、好ましくは0℃~50℃において、30分~24時間、好ましくは1~4時間反応させることによって製造することができる。エステル化剤としては、精製によって容易に除去できるものが好ましく、N,N-ジメチルホルムアミドジメチルアセタール、N,N-ジメチルホルムアミドジエチルアセタール、N,N-ジメチルホルムアミドジプロピルアセタール、N,N-ジメチルホルムアミドジネオペンチルブチルアセタール、N,N-ジメチルホルムアミドジ-t-ブチルアセタール、1-メチル-3-p-トリルトリアゼン、1-エチル-3-p-トリルトリアゼン、1-プロピル-3-p-トリルトリアゼン、4-(4,6-ジメトキシ-1,3,5-トリアジンー2-イル)-4-メチルモルホリニウムクロリド等が挙げられる。エステル化剤の添加量は、ポリアミック酸の繰り返し単位1モルに対して、2~6モル当量が好ましい。
ポリアミック酸エステルは、テトラカルボン酸ジエステルジクロリドとジアミンから製造することができる。具体的には、テトラカルボン酸ジエステルジクロリドとジアミンとを塩基と有機溶剤の存在下で-20℃~150℃、好ましくは0℃~50℃において、30分~24時間、好ましくは1~4時間反応させることによって製造することができる。前記塩基には、ピリジン、トリエチルアミン、4-ジメチルアミノピリジン等が使用できるが、反応が穏和に進行するためにピリジンが好ましい。塩基の添加量は、除去が容易な量で、かつ高分子量体が得やすいという点から、テトラカルボン酸ジエステルジクロリドに対して、2~4倍モルであることが好ましい。
ポリアミック酸エステルは、テトラカルボン酸ジエステルとジアミンを重縮合することにより製造することができる。具体的には、テトラカルボン酸ジエステルとジアミンを縮合剤、塩基、及び有機溶剤の存在下で0~150℃、好ましくは0~100℃において、30分~24時間、好ましくは3~15時間反応させることによって製造することができる。前記縮合剤には、トリフェニルホスファイト、ジシクロヘキシルカルボジイミド、1-エチル-3-(3-ジメチルアミノプロピル)カルボジイミド塩酸塩、N,N’-カルボニルジイミダゾール、ジメトキシ-1,3,5-トリアジニルメチルモルホリニウム、O-(ベンゾトリアゾール-1-イル)-N,N,N’,N’-テトラメチルウロニウム テトラフルオロボラート、O-(ベンゾトリアゾール-1-イル)-N,N,N’,N’-テトラメチルウロニウムヘキサフルオロホスファート、(2,3-ジヒドロ-2-チオキソ-3-ベンゾオキサゾリル)ホスホン酸ジフェニル等が使用できる。縮合剤の添加量は、テトラカルボン酸ジエステルに対して2~3倍モルが好ましい。
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)を含む。また、本発明に記載の効果を奏する限度において、異なる構造の特定重合体を2種以上含んでいてもよい。また、特定重合体に加えて、その他の重合体、すなわち式(1)で表される2価の基を有さない重合体を含んでいてもよい。その他の重合体の種類としては、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、ポリスチレン又はその誘導体、ポリ(スチレン-フェニルマレイミド)誘導体、ポリ(メタ)アクリレート等を挙げることができる。本発明の液晶配向剤がその他の重合体を含む場合、全重合体成分に対する特定重合体の割合は5質量%以上であることが好ましく、その一例として5~95質量%が挙げられる。
本発明の液晶配向膜は、前記液晶配向剤から得られる。液晶配向剤から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等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電極等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、シリコンウエハー等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等の光を反射する材料も使用できる。
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得ることができる。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)等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液晶表示素子であってもよい。具体的には、透明なガラス製の基板を準備し、一方の基板の上にコモン電極を、他方の基板の上にセグメント電極を設ける。これらの電極は、例えばITO電極とすることができ、所望の画像表示ができるようパターニングされている。次いで、各基板の上に、コモン電極とセグメント電極を被覆するようにして絶縁膜を設ける。絶縁膜は、例えば、ゾル-ゲル法によって形成されたSiO2-TiO2からなる膜とすることができる。次に、前記のような条件で、各基板の上に液晶配向膜を形成する。
本実施例及び比較例で使用した化合物の略号、及び特性評価の方法は、以下のとおりである。
NMP:N-メチル-2-ピロリドン
BCS:ブチルセロソルブ
GBL:γ―ブチルラクトン
BCS:ブチルセロソルブ
DA-1-1:下記式DA-1-1で表される化合物
DA-2:下記式DA-2で表される化合物
DA-3:下記式DA-3で表される化合物
CA-1:下記式CA-1で表される化合物
CA-2:下記式CA-2で表される化合物
(DA-1-1)の合成
1H-NMR(D6-DMSO、δppm):8.36(d、2H)、7.61(d、2H)、6.88(d、2H)、6.49(d、2H)、4.84(brs、2H)、4.20-4.25(m、1H)、2.91-3.00(m、1H)、2.65-2.83(m、3H)、2.54-2.61(m、2H)、2.37(s、3H)
1H-NMR(D6-DMSO、δppm):6.87(d、2H)、6.81(d、2H)、6.58(d、2H)、6.48(d、2H)、5.30(brs、2H)、4.83(brs、2H)、4.06-4.12(m、1H)、2.81-2.90(m、1H)、2.60-2.73(m、3H)、2.52-2.59(m、2H)、2.31(s、3H)
(DA-1-2)の合成
1H-NMR(D6-DMSO、δppm):8.38(d、2H)、7.62(d、2H)、3.81-3.87(m、1H)、3.03-3.14(m、1H)、2.56-2.66(m、1H)、2.66(brs、1H)、2.42(s、3H)
1H-NMR(D6-DMSO、δppm):8.32-8.44(m、4H)、7.73-7.81(m、2H)、7.58-7.68(m、2H)、4.93-5.13(m、1H)、3.00-3.37(m+s、2H+3H)
1H-NMR(D6-DMSO、δppm):7.19-7.25(m、2H)、6.83-6.88(m、2H)、6.53-6.62(m、4H)、5.93(brs、2H)、5.31(brs、2H)、4.50-4.90(m、1H)、2.98-3.20(m、3H)、2.71-2.96(m、2H)
(DA-1-3)の合成
1H-NMR(D6-DMSO、δppm):8.43-8.8.48(m、2H)、8.34-8.41(m、2H)、8.12-8.17(m、2H)、7.57-7.63(m、2H)、5.48-5.55(m、1H)、3.04-3.14(m、1H)、2.91-3.02(m、1H)、2.86(s、3H)
1H-NMR(D6-DMSO、δppm):7.42-7.48(m、2H)、6.80-6.86(m、2H)、6.61-6.68(m、2H)、6.54-6.60(m、2H)、6.10(brs、2H)、5.32(brs、2H)、5.14-5.20(m、1H)、2.66-2.79(m、1H)、2.60(s、3H)、2.51-2.59(m、1H)
以下の実施例又は比較例において、ポリアミック酸溶液の粘度は、E型粘度計TVE-22H(東機産業社製)を用い、サンプル量1.1mL、コーンロータTE-1(1°34’、R24)で測定した。
ポリアミド酸溶液(PAA-1)の合成
撹拌装置付き及び窒素導入管付きの50ml四つ口フラスコに(DA-1-1)を2.36g(7mmol)を加えた後、NMP25.0gを加え、窒素を送りながら撹拌し溶解させた。このジアミン溶液を撹拌しながらCA-1 1.43g(6.58mmol)を加え、NMP2.8gを加えた後、更に50℃条件下にて12時間攪拌することでポリアミド酸溶液(PAA-1)を得た。このポリアミド酸溶液の25℃における粘度は250mPa・sであった。
ポリアミド酸溶液(PAA-2)の合成
撹拌装置付き及び窒素導入管付きの50ml四つ口フラスコに(DA-1-1)2.36g(7mmol)を加えた後、NMP24.6gを加え、窒素を送りながら撹拌し溶解させた。このジアミン溶液を撹拌しながらCA-1 0.61g(2.8mmol)、CA-2 0.75g(3.9mmol)を加え、NMP2.7gを加えた後、更に50℃条件下にて12時間攪拌することでポリアミド酸溶液(PAA-2)を得た。このポリアミド酸溶液の25℃における粘度は230mPa・sであった。
ポリアミド酸溶液(PAA-3)の合成
撹拌装置付き及び窒素導入管付きの100ml四つ口フラスコに(DA-2)5.73g(20mmol)を加え、NMP65.1gを加え、窒素を送りながら撹拌し溶解させた。このジアミン溶液を撹拌しながらCA-1 4.14g(19mmol)を加えた後、NMP7.2gを加えた後、更に室温条件下にて18時間攪拌することでポリアミド酸溶液(PAA-3)を得た。このポリアミド酸溶液の25℃における粘度は500mPa・sであった。
ポリアミド酸溶液(PAA-4)の合成
撹拌装置付き及び窒素導入管付きの50ml四つ口フラスコに(DA-3)1.98g(10mmol)を加えた後、NMP26.0gを加え、窒素を送りながら撹拌し溶解させた。このジアミン溶液を撹拌しながらCA-1 0.87g(4.0mmol)、CA-2 1.08g(5.5mmol)を加え、NMP2.9gを加えた後、更に50℃条件下にて12時間攪拌することでポリアミド酸溶液(PAA-4)を得た。このポリアミド酸溶液の25℃における粘度は300mPa・sであった。
液晶配向剤(Q-1)の作製
実施例4で得られたポリアミック酸溶液(PAA-1)7.5gを分取し、攪拌しながらNMP5.6g、BCS6.0g、3-アミノプロピルトリエトキシシランを1重量%含むNMP溶液0.9gを加え、更に室温で2時間撹拌し液晶配向剤(Q-1)を得た。
液晶配向剤(Q-2)の作製
実施例5で得られたポリアミック酸溶液(PAA-2)7.5gを分取し、攪拌しながらNMP5.6g、BCS6.0g、3-アミノプロピルトリエトキシシランを1重量%含むNMP溶液0.9gを加え、更に室温で2時間撹拌し液晶配向剤(Q-2)を得た。
液晶配向剤(Q-3)の作製
比較例1で得られたポリアミック酸溶液(PAA-3)7.5gを分取し、攪拌しながらNMP5.6g、BCS6.0g、3-アミノプロピルトリエトキシシランを1重量%含むNMP溶液0.9gを加え、更に室温で2時間撹拌し液晶配向剤(Q-3)を得た。
液晶配向剤(Q-4)の作製
比較例2で得られたポリアミック酸溶液(PAA-4)7.5gを分取し、攪拌しながらNMP5.6g、BCS6.0g、3-アミノプロピルトリエトキシシランを1重量%含むNMP溶液0.9gを加え、更に室温で2時間撹拌し液晶配向剤(Q-4)を得た。
液晶配向剤を1.0μmのフィルターで濾過した後、電極付き基板(横30mm×縦40mmの大きさで、厚さが1.1mmのガラス基板。電極は幅10mm×長さ40mmの矩形で、厚さ35nmのITO電極)に、スピンコート法により塗布した。50℃のホットプレート上で5分間乾燥させた後、230℃のIR式オーブンで20分間焼成を行い、膜厚100nmの塗膜を形成させて液晶配向膜付き基板を得た。この液晶配向膜をレーヨン布(吉川化工製YA-20R)でラビング(ローラー直径:120mm、ローラー回転数:1000rpm、移動速度:20mm/sec、押し込み長:0.4mm)した後、純水中にて1分間超音波照射をして洗浄を行い、エアブローにて水滴を除去した後、80℃で15分間乾燥して液晶配向膜付き基板を得た。
上記[イオン密度測定用液晶セルの作製]に記載の方法で作製した液晶セルについて、イオン密度の測定を行った。イオン密度の測定においては、液晶セルに電圧±10V、周波数0.01Hzの三角波を印加した時のイオン密度を測定した。測定温度は60℃で行った。測定装置は、東陽テクニカ社製6256型液晶物性評価装置を用いた。イオン密度の測定は液晶セル作製後及び、液晶セルを60℃、90%の高温高湿条件下で120時間エージングした後にて実施した。なお、イオン密度は、実施例6の液晶配向剤(Q-1)を用いて作製した液晶セルと、比較例3の液晶配向剤(Q-3)を用いて作製した液晶セルと、について測定した。
初めに電極付きの基板を準備した。基板は、30mm×35mmの大きさで、厚さが0.7mmのガラス基板である。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。
この液晶セルを用い、60℃の恒温環境下、周波数30Hzで10VPPの交流電圧を168時間印加した。その後、液晶セルの画素電極と対向電極との間を短絡させた状態にし、そのまま室温に一日放置した。放置の後、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。そして、第1画素の第2領域が最も暗くなる角度から第1領域が最も暗くなる角度まで液晶セルを回転させたときの回転角度を角度Δとして算出した。第2画素でも同様に、第2領域と第1領域とを比較し、同様の角度Δを算出した。そして、第1画素と第2画素の角度Δ値の平均値を液晶セルの角度Δとして算出した。この液晶セルの角度Δの値が0.15°以下のものを良好、0.15°より高いものを不良として評価した。
上記液晶セルを、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、画素電極と対向電極とを短絡して同電位にした状態で、2枚の偏光板の下からLEDバックライトを照射しておき、2枚の偏光板の上で測定するLEDバックライト透過光の輝度が最小となるように、液晶セルの角度を調節した。次に、この液晶セルに周波数30Hzの矩形波を印加しながら、23℃の温度下でのV-T特性(電圧-透過率特性)を測定し、相対透過率が23%となる交流電圧を算出した。この交流電圧は電圧に対する輝度の変化が大きい領域に相当するため、蓄積電荷を輝度を介して評価するのに都合がよい。
実施例6~7及び比較例3~4の液晶配向剤Q1~Q4を用いて、イオン密度測定、液晶配向の安定性評価及び蓄積電荷の緩和特性の評価を行った。結果を表1に示す。表中、液晶配向剤Q1~Q2を用いて作製した液晶セルを各々実施例8~9とし、液晶配向剤Q3~Q4を用いて作製した液晶セルを各々比較例5~6としてある。
Claims (12)
- 前記Ar1が1,3-フェニレン基又は1,4-フェニレン基である請求項1に記載の液晶配向剤。
- 前記W1が単結合である請求項1又は2に記載の液晶配向剤。
- 前記式(3)で表される構造単位が、前記重合体の全構造単位に対して10モル%以上である、請求項4~7のいずれか一項に記載の液晶配向剤。
- 請求項1~8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9に記載の液晶配向膜を具備する液晶表示素子。
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Patent Citations (3)
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JPS4867394A (ja) * | 1971-10-18 | 1973-09-14 | ||
JPS4941488A (ja) * | 1972-08-16 | 1974-04-18 | ||
JPS60152528A (ja) * | 1984-01-19 | 1985-08-10 | Hitachi Ltd | 熱硬化性樹脂組成物の製造方法 |
Non-Patent Citations (1)
Title |
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DEVENDRA KUMAR: "New Polypyromellitimide Films Based on Cyclotriphosphazene and Bisaspartimide Derived Diamines", JOURNAL OF POLYMER SCIENCE, POLYMER CHEMISTRY EDITION, vol. 22, 20 March 1984 (1984-03-20) - November 1984 (1984-11-01), pages 3439 - 3446, XP055612822 * |
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KR20190126881A (ko) | 2019-11-12 |
TWI773748B (zh) | 2022-08-11 |
CN110476114A (zh) | 2019-11-19 |
JPWO2018181818A1 (ja) | 2020-02-06 |
JP7100297B2 (ja) | 2022-07-13 |
TW201900728A (zh) | 2019-01-01 |
KR102588725B1 (ko) | 2023-10-12 |
JP2022109969A (ja) | 2022-07-28 |
JP7345724B2 (ja) | 2023-09-19 |
CN110476114B (zh) | 2022-04-19 |
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