WO2014119682A1 - 液晶配向処理剤、液晶配向膜及び液晶表示素子 - Google Patents
液晶配向処理剤、液晶配向膜及び液晶表示素子 Download PDFInfo
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- WO2014119682A1 WO2014119682A1 PCT/JP2014/052157 JP2014052157W WO2014119682A1 WO 2014119682 A1 WO2014119682 A1 WO 2014119682A1 JP 2014052157 W JP2014052157 W JP 2014052157W WO 2014119682 A1 WO2014119682 A1 WO 2014119682A1
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- 0 C*CCC(C)(C)*CNC(C)(C)* Chemical compound C*CCC(C)(C)*CNC(C)(C)* 0.000 description 16
- VSTAOWNYNUTGOM-UHFFFAOYSA-N CCC1C(C)C(C)CC1C Chemical compound CCC1C(C)C(C)CC1C VSTAOWNYNUTGOM-UHFFFAOYSA-N 0.000 description 2
- WZCQRUWWHSTZEM-UHFFFAOYSA-N Nc1cc(N)ccc1 Chemical compound Nc1cc(N)ccc1 WZCQRUWWHSTZEM-UHFFFAOYSA-N 0.000 description 2
- BQLXCWZMPJMYIN-UHFFFAOYSA-N CC(CC1C)C2C1C(C)CC2C Chemical compound CC(CC1C)C2C1C(C)CC2C BQLXCWZMPJMYIN-UHFFFAOYSA-N 0.000 description 1
- NXWCEMULDKLEDF-UHFFFAOYSA-N CC(CCC=C(C)C)C(CC1)C2(C)C1C1C=CC(CC(CC3)Oc(ccc(N)c4)c4N)C3(C)C1CC2 Chemical compound CC(CCC=C(C)C)C(CC1)C2(C)C1C1C=CC(CC(CC3)Oc(ccc(N)c4)c4N)C3(C)C1CC2 NXWCEMULDKLEDF-UHFFFAOYSA-N 0.000 description 1
- INYXDKODFMWKER-UHFFFAOYSA-N CC1C(C)C(C)C(C)C1 Chemical compound CC1C(C)C(C)C(C)C1 INYXDKODFMWKER-UHFFFAOYSA-N 0.000 description 1
- VWWAILZUSKHANH-UHFFFAOYSA-N CC1C(C)CC(C)C(C)C1 Chemical compound CC1C(C)CC(C)C(C)C1 VWWAILZUSKHANH-UHFFFAOYSA-N 0.000 description 1
- VLVCDUSVTXIWGW-UHFFFAOYSA-N Nc(cc1)ccc1I Chemical compound Nc(cc1)ccc1I VLVCDUSVTXIWGW-UHFFFAOYSA-N 0.000 description 1
- YGYCECQIOXZODZ-UHFFFAOYSA-N O=C(C(C1C2C(O3)=O)C2C3=O)OC1=O Chemical compound O=C(C(C1C2C(O3)=O)C2C3=O)OC1=O YGYCECQIOXZODZ-UHFFFAOYSA-N 0.000 description 1
- ILOCNLYUKFZVBP-UHFFFAOYSA-N O=C(C(CC12)C(C(C3)C(O4)=O)C1C3C4=O)OC2=O Chemical compound O=C(C(CC12)C(C(C3)C(O4)=O)C1C3C4=O)OC2=O ILOCNLYUKFZVBP-UHFFFAOYSA-N 0.000 description 1
- QVEIRZNRYOJFCL-UHFFFAOYSA-N O=C(CC(C(C1)C(O2)=O)C3C1C2=O)OC3=O Chemical compound O=C(CC(C(C1)C(O2)=O)C3C1C2=O)OC3=O QVEIRZNRYOJFCL-UHFFFAOYSA-N 0.000 description 1
- JYCTWJFSRDBYJX-UHFFFAOYSA-N O=C(CC1C(CC(C2C(O3)=O)C3=O)c3c2cccc3)OC1=O Chemical compound O=C(CC1C(CC(C2C(O3)=O)C3=O)c3c2cccc3)OC1=O JYCTWJFSRDBYJX-UHFFFAOYSA-N 0.000 description 1
Classifications
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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
- G02F1/133719—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers by organic films, e.g. polymeric films with coupling agent molecules, e.g. silane
Definitions
- the present invention relates to a liquid crystal alignment treatment agent used in a liquid crystal display element, a liquid crystal alignment film obtained from the liquid crystal alignment treatment agent, and a liquid crystal display element equipped with the liquid crystal alignment film.
- a film made of an organic material such as a polymer material is widely used as an interlayer insulating film, a protective film, or the like in an electronic device for reasons of ease of formation and insulation performance.
- an organic film made of polyimide is used as a liquid crystal alignment film.
- the liquid crystal alignment film is used for the purpose of controlling the alignment state of the liquid crystal.
- liquid crystal alignment films are required to reduce the contrast of liquid crystal display elements and to suppress display defects associated with long-term use as the liquid crystal display elements become higher in definition.
- the liquid crystal alignment film using polyimide it is formed by using a liquid crystal alignment treatment agent to which an alkoxysilane compound is added as a technique for enhancing liquid crystal alignment and making display defects less likely to occur at the periphery of the liquid crystal display screen.
- a liquid crystal alignment film has been proposed (see, for example, Patent Document 1 or Patent Document 2).
- liquid crystal display elements have been used for mobile applications such as smartphones and mobile phones.
- the width of the sealing agent used for bonding the substrates of the liquid crystal display elements narrower than in the past.
- the drawing position of the sealing agent is also required to be in a position in contact with the end of the liquid crystal alignment film having weak adhesion to the sealing agent or on the liquid crystal alignment film.
- use under high-temperature and high-humidity conditions makes it easy for water to enter from between the sealing agent and the liquid crystal alignment film, resulting in display unevenness near the frame of the liquid crystal display element.
- Patent Document 2 discloses a technique of adding an alkoxysilane compound to a liquid crystal alignment treatment agent in order to improve the adhesion between the sealant and the liquid crystal alignment film.
- an alkoxysilane compound is added to the liquid crystal aligning agent, the adhesion between the sealing agent and the liquid crystal aligning film can be improved, but condensation of alkoxy groups in the alkoxysilane compound during storage of the liquid crystal aligning agent.
- the storage stability of the liquid crystal aligning agent is deteriorated due to the progress of the reaction, such as an increase in the viscosity of the liquid crystal aligning agent and the generation of a gelled product.
- an object of the present invention is a liquid crystal that has excellent storage stability, enhances the adhesion between the sealant and the liquid crystal alignment film, and can suppress the occurrence of display unevenness near the frame of the liquid crystal display element under high temperature and high humidity conditions.
- An object of the present invention is to provide a liquid crystal alignment treatment agent capable of forming an alignment film, and to provide a liquid crystal display element including the liquid crystal alignment film having the above-described performance.
- the present inventor has at least one selected from the group consisting of a silane compound having a specific structure, an amine compound having a specific structure, and a polyimide precursor and a polyimide obtained by imidizing the polyimide precursor.
- the present inventors have found that a liquid crystal aligning agent containing a polymer is extremely effective for achieving the above object, and have completed the present invention.
- a liquid crystal aligning agent comprising the following component (A), component (B) and component (C).
- Component (A) A silane compound represented by the following formula [a].
- a 1 represents a C 2-12 organic group having a vinyl group, an epoxy group, an amino group, a mercapto group, an isocyanate group, a methacryl group, an acrylic group, a ureido group or a cinnamoyl group.
- 2 represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms
- a 3 represents an alkyl group having 1 to 5 carbon atoms
- m represents an integer of 1 or 2
- n represents an integer of 0 to 2
- p represents an integer of 0 to 3 where m + n + p represents an integer of 4.
- a group A 1 has the formula [a] is an epoxy group, an amino group, a liquid crystal alignment treating agent according to the above (1) is a methacryl group or an acryl group.
- X 1 represents a divalent organic group having an aliphatic hydrocarbon group or a non-aromatic cyclic hydrocarbon group
- X 2 represents a nitrogen-containing aromatic heterocyclic ring.
- Y 1 represents a single bond, — (CH 2 ) a — (a is an integer of 1 to 15), —O—, —CH 2 O—, —COO— or OCO—, wherein Y 2 is a single bond or (CH 2 ) b — (B is an integer of 1 to 15), Y 3 is a single bond, — (CH 2 ) c — (c is an integer of 1 to 15), —O—, —CH 2 O—, — Represents COO— or OCO—, Y 4 represents a divalent cyclic group selected from a benzene ring, a cyclohexane ring and a heterocyclic ring, or a divalent organic group having 12 to 25 carbon atoms and having a steroid skeleton,
- the above arbitrary hydrogen atoms include an alkyl group having 1 to 3 carbon atoms, an alkoxyl group having 1 to 3 carbon atoms, a fluorine
- N represents an integer of 0 to 4.
- Y 6 represents an alkyl group having 1 to 18 carbon atoms, a fluorine-containing alkyl group having 1 to 18 carbon atoms, an alkoxyl group having 1 to 18 carbon atoms, or fluorine having 1 to 18 carbon atoms.
- Y 7 represents —O—, —CH 2 O—, —COO—, —OCO—, —CONH— or NHCO—
- Y 8 represents 8 carbon atoms.
- Y 9 and Y 10 each independently represent a hydrocarbon group having 1 to 12 carbon atoms, and in formula [2-6], Y 11 represents one having 1 to 5 carbon atoms. Represents an alkyl group.
- the component (D) contains at least one solvent selected from the group consisting of N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone and ⁇ -butyrolactone.
- the liquid-crystal aligning agent in any one.
- the above component (E) containing at least one solvent selected from the group consisting of solvents represented by the following formula [E-1], formula [E-2] and formula [E-3] ( The liquid crystal aligning agent according to any one of 1) to (7).
- E 1 represents an alkyl group having 1 to 3 carbon atoms.
- E 2 represents an alkyl group having 1 to 3 carbon atoms.
- E 3 represents an alkyl group having 1 to 4 carbon atoms.
- component (F) at least one solvent selected from the group consisting of 1-hexanol, cyclohexanol, 1,2-ethanediol, 1,2-propanediol, propylene glycol monobutyl ether and ethylene glycol monobutyl ether.
- the liquid crystal aligning agent according to any one of (1) to (8), which is contained.
- (11) A liquid crystal alignment film obtained by an ink jet method using the liquid crystal aligning agent according to any one of (1) to (9).
- (12) A liquid crystal display device having the liquid crystal alignment film according to (10) or (11).
- (13) A liquid crystal composition having a liquid crystal layer between a pair of substrates provided with electrodes and including a polymerizable compound that is polymerized by at least one of active energy rays and heat is disposed between the pair of substrates.
- a liquid crystal alignment film having a liquid crystal layer between a pair of substrates provided with electrodes and including a polymerizable group that is polymerized by at least one of active energy rays and heat is disposed between the pair of substrates.
- the liquid crystal alignment treatment agent of the present invention is excellent in storage stability of the liquid crystal alignment treatment agent, has high adhesion between the sealing agent and the liquid crystal alignment film, and displays unevenness in the vicinity of the frame of the liquid crystal display element under high temperature and high humidity conditions. It is possible to form a liquid crystal alignment film that can suppress the occurrence of the above. In particular, even a liquid crystal alignment agent using a polyamic acid or a solvent-soluble polyimide obtained by using a diamine compound having a side chain can provide a liquid crystal alignment film excellent in these characteristics. In addition, a liquid crystal display element having the above liquid crystal alignment film can be provided.
- a 1 is an organic group having 2 to 12 carbon atoms having a vinyl group, an epoxy group, an amino group, a mercapto group, an isocyanate group, an acrylic (acryloyl) group, a methacrylic (acryloyl) group, a ureido group or a cinnamoyl group. It is a group.
- the group that the organic group A 1 has is preferably a vinyl group, an epoxy group, an amino group, a methacryl group, an acrylic group, or a ureido group. More preferably, they are an epoxy group, an amino group, a methacryl group or an acrylic group.
- the organic group A 1 preferably has 2 to 10 carbon atoms.
- a 2 is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. Of these, a hydrogen atom or an alkyl group having 1 to 3 carbon atoms is preferable.
- a 3 is an alkyl group having 1 to 5 carbon atoms. Of these, alkyl groups having 1 to 3 carbon atoms are preferred from the viewpoint of polycondensation reactivity.
- m is an integer of 1 or 2. Of these, 1 is preferable from the viewpoint of ease of synthesis.
- n is an integer of 0-2.
- p is an integer of 0 to 3. Among these, an integer of 1 to 3 is preferable from the viewpoint of polycondensation reactivity. More preferably, it is 2 or 3. Note that m + n + p is an integer of 4.
- silane represented by the formula [a] examples include allyltriethoxysilane, allyltrimethoxysilane, diethoxymethylvinylsilane, dimethoxymethylvinylsilane, triethoxyvinylsilane, vinyltrimethoxysilane, vinyltris (2-methoxyethoxy) silane.
- the amine compound (hereinafter also referred to as a specific amine compound) as the component (B) of the present invention has one amino group and a nitrogen-containing aromatic heterocyclic ring in the molecule, and the amino group is divalent. It is an amine compound bonded to an aliphatic hydrocarbon group or a non-aromatic cyclic hydrocarbon group. Since this specific amine compound has only one amino group in the molecule, problems such as polymer precipitation and gelation may occur when the liquid crystal aligning agent is produced or during storage of the liquid crystal aligning agent. Sex can be suppressed.
- the amino group contained in the specific amine compound is a non-aromatic group that does not contain a divalent aliphatic hydrocarbon group or aromatic hydrocarbon in the molecule from the viewpoint of easy salt formation and a binding reaction with the specific polymer. It must be bonded to a cyclic hydrocarbon group.
- divalent aliphatic hydrocarbon group examples include a linear alkylene group, an alkylene group having a branched structure, or a divalent hydrocarbon group having an unsaturated bond.
- the number of carbon atoms of the aliphatic hydrocarbon group is preferably 1-20, more preferably 1-15, still more preferably 1-10.
- divalent non-aromatic cyclic hydrocarbon group examples include cyclopropane ring, cyclobutane ring, cyclopentane ring, cyclohexane ring, cycloheptane ring, cyclooctane ring, cyclononane ring, cyclodecane ring, cycloundecane ring, cyclododecane Ring, cyclotridecane ring, cyclotetradecane ring, cyclopentadecane ring, cyclohexadecane ring, cycloheptadecane ring, cyclooctadecane ring, cyclononadecane ring, cycloicosane ring, tricycloeicosan ring, tricyclodecosan ring, bicycloheptane ring, Examples include a decahydronaphthalene ring, a norbornene ring
- it is a ring having 3 to 20 carbon atoms, more preferably a ring having 3 to 15 carbon atoms, and still more preferably a non-aromatic cyclic hydrocarbon group having 3 to 10 carbon atoms. It is.
- the nitrogen-containing aromatic heterocyclic ring contained in the specific amine compound contains at least one structure selected from the group consisting of the following formula [1-a], formula [1-b] and formula [1-c]. Nitrogen-containing aromatic heterocycle. (In the formula [1-c], M represents a linear or branched alkyl group having 1 to 5 carbon atoms.)
- nitrogen-containing aromatic heterocycle examples include pyrrole ring, imidazole ring, oxazole ring, thiazole ring, pyrazole ring, pyridine ring, pyrimidine ring, quinoline ring, pyrazoline ring, isoquinoline ring, carbazole ring, purine ring, thiadiazole ring , Pyridazine ring, pyrazoline ring, triazine ring, pyrazolidine ring, triazole ring, pyrazine ring, benzimidazole ring, thionoline ring, phenanthroline ring, indole ring, quinoxaline ring, benzothiazole ring, phenothiazine ring, oxadiazole ring, acridine ring, etc. Can be mentioned. Furthermore, the carbon atom of these nitrogen-containing aromatic heterocycles may have a substituent containing a heteroatom.
- More preferable specific amine compounds include amine compounds represented by the following formula [1].
- X 1 represents a divalent organic group having an aliphatic hydrocarbon group or a non-aromatic cyclic hydrocarbon group
- X 2 represents a nitrogen-containing aromatic heterocyclic ring.
- X 1 is preferably a divalent organic group having one selected from an aliphatic hydrocarbon group having 1 to 20 carbon atoms and a non-aromatic cyclic hydrocarbon group having 3 to 20 carbon atoms.
- Examples of the non-aromatic cyclic hydrocarbon group include the structures described above.
- it is an aliphatic hydrocarbon group having 1 to 15 carbon atoms, cyclopropane ring, cyclobutane ring, cyclopentane ring, cyclohexane ring, cycloheptane ring, cyclooctane ring, cyclononane ring, cyclodecane ring, cycloundecane ring, cyclododecane ring.
- Particularly preferred is a linear or branched alkyl group having 1 to 10 carbon atoms.
- —CH 2 — in any aliphatic hydrocarbon group or non-aromatic cyclic hydrocarbon group not adjacent to the amino group contained in X 1 is —O—, —NH—, —CO—O—, —O—CO—, —CO—NH—, —NH—CO—, —CO—, —S—, —S (O) 2 —, —CF 2 —, —C (CF 3 ) 2 —, —C (CH 3 ) 2 —, —Si (CH 3 ) 2 —, —O—Si (CH 3 ) 2 —, —Si (CH 3 ) 2 —O—, —O—Si (CH 3 ) 2 —O—, —O—Si (CH 3 ) 2 —O— It may be replaced with a divalent cyclic hydrocarbon group or a divalent heterocyclic ring.
- a hydrogen atom bonded to an arbitrary carbon atom is a linear or branched alkyl group having 1 to 20 carbon atoms, a cyclic hydrocarbon group, a fluorine-containing alkyl group having 1 to 10 carbon atoms, a heterocyclic ring, a fluorine atom or It may be replaced with a hydroxyl group.
- divalent cyclic hydrocarbon group examples include benzene ring, naphthalene ring, tetrahydronaphthalene ring, azulene ring, indene ring, fluorene ring, anthracene ring, phenanthrene ring, phenalene ring, cyclopropane ring, cyclobutane ring, cyclopentane.
- divalent heterocyclic ring examples include pyrrole ring, imidazole ring, oxazole ring, thiazole ring, pyrazole ring, pyridine ring, pyrimidine ring, quinoline ring, pyrazoline ring, isoquinoline ring, carbazole ring, purine ring, thiadiazole.
- X 2 in the formula [1] is a nitrogen-containing aromatic heterocycle, and is selected from the group consisting of the formula [1-a], the formula [1-b] and the formula [1-c] as described above. And a nitrogen-containing aromatic heterocycle containing at least one structure. As a specific example, the structure mentioned above can be mentioned.
- pyrrole ring imidazole ring, pyrazole ring, pyridine ring, pyrimidine ring, pyridazine ring, triazine ring, triazole ring, pyrazine ring, benzimidazole ring, quinoxaline ring, azepine ring, diazepine ring, naphthyridine ring, phenazine ring or A phthalazine ring is preferred.
- X 1 is formula contained in X 2 [1-a ], A substituent that is not adjacent to the formula [1-b] or the formula [1-c] is preferable.
- the carbon atom of the nitrogen-containing aromatic heterocyclic ring which is X 2 in the formula [1] may have a halogen atom or an organic group substituent.
- the organic group may contain a hetero atom such as an oxygen atom, a sulfur atom or a nitrogen atom.
- a preferred combination of X 1 and X 2 in the formula [1] is a compound in which X 1 is selected from an aliphatic hydrocarbon group having 1 to 20 carbon atoms and a non-aromatic cyclic hydrocarbon group having 3 to 20 carbon atoms.
- X 2 is a pyrrole ring, an imidazole ring, a pyrazole ring, a pyridine ring, a pyrimidine ring, a pyridazine ring, a triazine ring, a triazole ring, a pyrazine ring, a benzimidazole ring, a quinoxaline ring, azepine ring, diazepine It is selected from a ring, a naphthyridine ring, a phenazine ring and a phthalazine ring.
- the carbon atoms of the nitrogen-containing aromatic heterocycle X 2 may have a substituent halogen atom or an organic group.
- the organic group may contain a hetero atom such as an oxygen atom, a sulfur atom or a nitrogen atom.
- a more preferable specific amine compound is an amine compound represented by the following formula [1a].
- X 3 represents a divalent aliphatic hydrocarbon group or a non-aromatic cyclic hydrocarbon group having 1 to 10 carbon atoms.
- X 4 represents a single bond, —O—, —NH—, —S—, —SO 2 — or a divalent organic group having 1 to 19 carbon atoms, and the total carbon number of X 3 and X 4 is 1 to 20.
- X 5 is a nitrogen-containing aromatic. Indicates a heterocyclic ring.
- X 3 represents a divalent aliphatic hydrocarbon group having 1 to 10 carbon atoms or a non-aromatic cyclic hydrocarbon group. Specific examples thereof include a linear or branched alkylene group having 1 to 10 carbon atoms, an unsaturated alkylene group having 1 to 10 carbon atoms, a cyclopropane ring, a cyclobutane ring, a cyclopentane ring, a cyclohexane ring, a cycloheptane ring, a cyclo Octane ring, cyclononane ring, cyclodecane ring, cycloundecane ring, cyclododecane ring, cyclotridecane ring, cyclotetradecane ring, cyclopentadecane ring, cyclohexadecane ring, cycloheptadecane ring, cyclooctadecane ring
- it is a linear or branched alkyl group having 1 to 10 carbon atoms, cyclopropane ring, cyclobutane ring, cyclopentane ring, cyclohexane ring, cycloheptane ring, cyclooctane ring, cyclononane ring, cyclodecane ring, cycloundecane ring, cyclododecane And a ring, a cyclotridecane ring, a cyclotetradecane ring, a norbornene ring, and an adamantane ring.
- Particularly preferred is a linear or branched alkylene group having 1 to 10 carbon atoms.
- —CH 2 — in any aliphatic hydrocarbon group or non-aromatic cyclic hydrocarbon group not adjacent to the amino group contained in X 3 is —O—, —NH—, —CO—O—, —O —CO—, —CO—NH—, —NH—CO—, —CO—, —S—, —S (O) 2 —, —CF 2 —, —C (CF 3 ) 2 —, —C (CH 3 ) 2 —, —Si (CH 3 ) 2 —, —O—Si (CH 3 ) 2 —, —Si (CH 3 ) 2 —O—, —O—Si (CH 3 ) 2 —O—, 2 A valent cyclic hydrocarbon group or a divalent heterocyclic ring may be substituted.
- a hydrogen atom bonded to an arbitrary carbon atom is a linear or branched alkyl group having 1 to 20 carbon atoms, a cyclic hydrocarbon group, a fluorine-containing alkyl group having 1 to 10 carbon atoms, a heterocyclic ring, a fluorine atom or It may be replaced with a hydroxyl group.
- the cyclic hydrocarbon group and the heterocycle mentioned here have the same meanings as defined for X 1 in the formula [1].
- X 4 is a single bond, —O—, —NH—, —S—, —SO 2 — or a divalent organic group having 1 to 19 carbon atoms.
- the divalent organic group having 1 to 19 carbon atoms is a divalent organic group having 1 to 19 carbon atoms, and may contain an oxygen atom, a nitrogen atom, a sulfur atom, a silicon atom, or the like. Specific examples of X 4 below.
- X 5 is a nitrogen-containing aromatic heterocycle and has the same meaning as defined for X 2 in formula [1]. Specific examples may include the same structure as the X 2 described above. Among these, pyrrole ring, imidazole ring, pyrazole ring, pyridine ring, pyrimidine ring, pyridazine ring, triazine ring, triazole ring, pyrazine ring, benzimidazole ring, quinoxaline ring, azepine ring, diazepine ring, naphthyridine ring, phenazine ring, A phthalazine ring is preferred.
- X 4 is a formula [1-a] contained in X 5 .
- it is preferably bonded to a carbon atom that is not adjacent to the formula [1-b] or the formula [1-c].
- the carbon atom of the nitrogen-containing aromatic heterocyclic ring as X 5 in the formula [1a] may have a halogen atom or an organic group substituent.
- the organic group may contain a hetero atom such as an oxygen atom, a sulfur atom or a nitrogen atom.
- Specific examples of the specific amine compound of the present invention include nitrogen-containing compounds represented by the formulas [M1] to [M156], which are described on pages 69 to 73 of International Publication WO2011 / 132751 (published 2011.10.27). Examples include heterocyclic amine compounds.
- the formula [M1], the formula [M7], the formula [M16] to the formula [20], the formula [M24], the formula [M35], the formula [M36], the formula [M40], the formula [M49], the formula [ M50], Formula [M52], Formula [M60] to Formula [M62], Formula [M68], Formula [M69], Formula [M76], Formula [M77], Formula [M82], Formula [M100], Formula [M M101], Formula [M108], Formula [M109], Formula [M118] to Formula [M121], Formula [M128], Formula [M134] to Formula [136], or Formula [M140] are preferable.
- the polymer (hereinafter also referred to as a specific polymer) which is the component (C) of the present invention is a polyimide precursor obtained by reacting a diamine component and a tetracarboxylic acid component, and a polyimide obtained by imidizing the polyimide precursor. To be elected.
- the polyimide precursor has a structure represented by the following formula [A].
- R 1 is a tetravalent organic group
- R 2 is a divalent organic group
- a 1 and A 2 represent a hydrogen atom or an alkyl group having 1 to 8 carbon atoms
- a 3 and A 4 each represent a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or an acetyl group, and may be the same or different
- n is a positive integer. Show.
- the weight average molecular weight of the polyimide precursor [A] is 5,000 to 1,000,000, preferably 10,000 to 150,000. A method for measuring the weight average molecular weight will be described later.
- the diamine component for forming the polyimide precursor include diamine compounds having two primary or secondary amino groups in the molecule.
- a tetracarboxylic acid component for forming a polyimide precursor a tetracarboxylic acid compound, a tetracarboxylic dianhydride, a tetracarboxylic acid dihalide compound, a tetracarboxylic acid dialkyl ester compound or a tetracarboxylic acid dialkyl ester dihalide compound Is mentioned.
- a tetracarboxylic dianhydride represented by the following formula [B] and a diamine compound represented by the following formula [C] are preferable because they can be obtained relatively easily.
- R 1 and R 2 are the same as those defined in Formula [A].
- R 1 and R 2 have the same meaning as defined in formula [A].
- the polymer of the formula [D] obtained above may be substituted with an alkyl group having 1 to 8 carbon atoms represented by A 1 and A 2 of the formula [A], or A 3 and A 4 of the formula [A].
- the indicated alkyl group having 1 to 5 carbon atoms or acetyl group can also be introduced by a usual synthesis method.
- ⁇ Diamine component> As the diamine component for forming the specific polymer which is the component (C) of the present invention, a known diamine compound can be used. Especially, it is preferable to use the diamine which has a structure shown by following formula [2]. (In the formula [2], Y represents the following formula [2-1], formula [2-2], formula [2-3], formula [2-4], formula [2-5] and formula [2- 6] represents a substituent having at least one structure selected from the group consisting of 6], and m represents an integer of 1 to 4.
- a represents an integer of 0 to 4.
- 0 or 1 is preferable from the viewpoint of availability of raw materials and ease of synthesis.
- b represents an integer of 0 to 4.
- the integer of 0 or 1 is preferable from the point of the availability of a raw material or the ease of a synthesis
- Y 1 represents a single bond, — (CH 2 ) a — (a is an integer of 1 to 15), —O—, —CH 2 O—, —COO— or OCO—. Show.
- a single bond — (CH 2 ) a — (a is an integer of 1 to 15), —O—, —CH 2 O— or COO— Is preferred. More preferred is a single bond, — (CH 2 ) a — (a is an integer of 1 to 10), —O—, —CH 2 O— or COO—.
- Y 2 represents a single bond or — (CH 2 ) b — (b is an integer of 1 to 15). Among these, a single bond or — (CH 2 ) b — (b is an integer of 1 to 10) is preferable.
- Y 3 represents a single bond, — (CH 2 ) c — (c is an integer of 1 to 15), —O—, —CH 2 O—, —COO— or OCO—. Of these, a single bond, — (CH 2 ) c — (c is an integer of 1 to 15), —O—, —CH 2 O— or COO— is preferable from the viewpoint of ease of synthesis.
- Y 4 is a divalent cyclic group selected from a benzene ring, a cyclohexane ring or a heterocyclic ring, and any hydrogen atom on these cyclic groups is an alkyl group having 1 to 3 carbon atoms or an alkoxyl having 1 to 3 carbon atoms.
- Y 4 may be a divalent organic group selected from organic groups having 12 to 25 carbon atoms having a steroid skeleton. Of these, an organic group having 12 to 25 carbon atoms having a benzene ring, a cyclohexane ring or a steroid skeleton is preferable from the viewpoint of ease of synthesis.
- Y 5 represents a divalent cyclic group selected from a benzene ring, a cyclohexane ring or a heterocyclic ring, and an arbitrary hydrogen atom on these cyclic groups is an alkyl group having 1 to 3 carbon atoms or an alkoxyl having 1 to 3 carbon atoms.
- n represents an integer of 0 to 4. Among these, 0 to 3 are preferable from the viewpoint of availability of raw materials and ease of synthesis. More preferred is 0-2.
- Y 6 represents an alkyl group having 1 to 18 carbon atoms, a fluorine-containing alkyl group having 1 to 18 carbon atoms, an alkoxyl group having 1 to 18 carbon atoms, or a fluorine-containing alkoxyl group having 1 to 18 carbon atoms.
- an alkyl group having 1 to 18 carbon atoms, a fluorine-containing alkyl group having 1 to 10 carbon atoms, an alkoxyl group having 1 to 18 carbon atoms, or a fluorine-containing alkoxyl group having 1 to 10 carbon atoms is preferable. More preferably, it is an alkyl group having 1 to 12 carbon atoms or an alkoxyl group having 1 to 12 carbon atoms. Particularly preferred is an alkyl group having 1 to 9 carbon atoms or an alkoxyl group having 1 to 9 carbon atoms.
- Y 7 represents —O—, —CH 2 O—, —COO—, —OCO—, —CONH— or NHCO—. Of these, —O—, —CH 2 O—, —COO— or CONH— is preferable. More preferred is —O—, —COO— or CONH—.
- Y 8 represents an alkyl group having 8 to 22 carbon atoms. An alkyl group having 8 to 18 carbon atoms is preferred.
- Y 9 and Y 10 each independently represent a hydrocarbon group having 1 to 12 carbon atoms. A hydrocarbon group having 1 to 8 carbon atoms is preferred.
- Y 11 represents an alkyl group having 1 to 5 carbon atoms. An alkyl group having 1 to 2 carbon atoms is preferred.
- the method to manufacture the diamine compound shown by Formula [2] of this invention is not specifically limited, What is shown below is mentioned as a preferable method.
- the diamine compound represented by the formula [2] can be obtained by synthesizing a dinitro compound represented by the following formula [2-A] and further reducing the nitro group to convert it to an amino group.
- Y represents Formula [2-1], Formula [2-2], Formula [2-3], Formula [2-4], Formula [2-5], and Formula [2].
- -6] represents a substituent having at least one structure selected from the group consisting of m), m represents an integer of 1 to 4.
- the method for reducing the nitro group of the dinitro compound represented by the formula [2-A] is not particularly limited, and usually in a solvent such as ethyl acetate, toluene, tetrahydrofuran, dioxane, alcohol solvent, palladium-carbon, There is a method in which platinum oxide, Raney nickel, platinum black, rhodium-alumina, platinum sulfide carbon or the like is used as a catalyst and reacted in hydrogen gas, hydrazine, or hydrogen chloride.
- a solvent such as ethyl acetate, toluene, tetrahydrofuran, dioxane, alcohol solvent, palladium-carbon
- platinum oxide, Raney nickel, platinum black, rhodium-alumina, platinum sulfide carbon or the like is used as a catalyst and reacted in hydrogen gas, hydrazine, or hydrogen chloride.
- diamine compound shown by Formula [2] of this invention is not limited to these examples. 2,4-dimethyl-m-phenylenediamine, 2,6-diaminotoluene, 2,4-diaminobenzoic acid, 3,5-diaminobenzoic acid, 2,4-diaminophenol, 3,5-diaminophenol, 3,
- diamine compounds having structures represented by the following formulas [2-7] to [2-47] can be exemplified. .
- a 1 represents an alkyl group having 1 to 22 carbon atoms or a fluorine-containing alkyl group.
- R 1 represents —O—, —OCH 2 —, —CH 2 O—, —COOCH 2 — or CH 2 OCO—.
- R 2 represents carbon. Represents an alkyl group, an alkoxy group, a fluorine-containing alkyl group or a fluorine-containing alkoxy group of formula 1 to 22.
- R 3 represents —COO—, —OCO—, —COOCH 2 —, —CH 2 OCO—, —CH 2 O—, —OCH 2 — or CH 2- represents R 4 represents an alkyl group having 1 to 22 carbon atoms, an alkoxy group, a fluorine-containing alkyl group or a fluorine-containing alkoxy group.
- R 5 represents —COO—, —OCO—, —COOCH 2 —, —CH 2 OCO—, —CH 2 O—, —OCH 2 —, — CH 2 -or O- represents R 6 represents a fluorine group, a cyano group, a trifluoromethane group, a nitro group, an azo group, a formyl group, an acetyl group, an acetoxy group or a hydroxyl group.
- R 7 represents an alkyl group having 3 to 12 carbon atoms.
- the cis-trans isomerism of 1,4-cyclohexylene is the trans isomer. preferable.
- R 8 represents an alkyl group having 3 to 12 carbon atoms.
- the cis-trans isomerism of 1,4-cyclohexylene is the trans isomer. preferable.
- B 4 represents an alkyl group having 3 to 20 carbon atoms which may be substituted with a fluorine atom.
- B 3 represents a 1,4-cyclohexylene group or a 1,4-phenylene group.
- B 2 represents an oxygen atom or COO- * (where a bond marked with “*” is bonded to B 3 )
- B 1 represents an oxygen atom or COO— * (where “*” is attached) bond that represents the (CH 2) coupled to a 2).
- a 1 represents an integer of 0 or 1
- a 2 represents an integer of 2 ⁇ 10
- a 3 a is an integer of 0 or 1 Show.
- the substituent Y in the formula [2] is obtained from a specific polymer using a diamine compound having a structure represented by the formula [2-3].
- the agent can increase the pretilt angle of the liquid crystal when the liquid crystal alignment film is used.
- the diamines represented by the formulas [2-29] to [2-40] or the formulas [2-43] to [2-47] are used. It is preferable to use a compound. More preferred are diamine compounds represented by the formulas [2-25] to [2-40] or the formulas [2-43] to [2-47].
- these diamine compounds are 5 mol% or more and 80 mol% or less of the whole diamine component. More preferably, these diamine compounds are 5 mol% or more and 60 mol% or less of the whole diamine component from the point of the applicability
- the diamine compound represented by the formula [2] includes the solubility and coating properties of the specific polyimide polymer of the present invention in a solvent, the orientation of liquid crystal when it is used as a liquid crystal alignment film, voltage holding ratio, accumulated charge, and the like. Depending on the characteristics, one kind or a mixture of two or more kinds can be used.
- diamine component for forming the specific polymer of the present invention a diamine compound other than the diamine compound represented by the formula [2] (also referred to as other diamine compound) can be used as the diamine component.
- diamine compound represented by the formula [2] also referred to as other diamine compound
- Specific examples of other diamine compounds are shown below, but are not limited to these examples.
- diamine compound examples include those having an alkyl group, a fluorine-containing alkyl group, an aromatic ring, an aliphatic ring or a heterocyclic ring in the diamine side chain, and those having a macrocyclic substituent composed of these. .
- diamine compounds represented by the following formulas [DA1] to [DA7] can be exemplified.
- a 1 represents —COO—, —OCO—, —CONH—, —NHCO—, —CH 2 —, —O—, —CO— or NH—.
- 2 represents a linear or branched alkyl group having 1 to 22 carbon atoms or a linear or branched fluorine-containing alkyl group having 1 to 22 carbon atoms.
- diamine compounds represented by the following formulas [DA8] to [DA13] can also be used as other diamine compounds.
- n represents an integer of 1 to 5
- diamine compounds represented by the following formulas [DA14] to [DA17] can also be used.
- a 1 is a single bond, —CH 2 —, —C 2 H 4 —, —C (CH 3 ) 2 —, —CF 2 —, —C (CF 3 ) 2 —, —O —, —CO—, —NH—, —N (CH 3 ) —, —CONH—, —NHCO—, —CH 2 O—, —OCH 2 —, —COO—, —OCO—, —CON (CH 3 )-Or N (CH 3 ) CO—, each of m 1 and m 2 represents an integer of 0 to 4, and m 1 + m 2 represents an integer of 1 to 4.
- m 3 And m 4 each represents an integer of 1 to 5.
- a 2 represents a linear or branched alkyl group having 1 to 5 carbon atoms
- m 5 represents an integer of 1 to 5.
- a 3 is a single bond, -CH 2 -, - C 2 H 4 -, - C (CH 3) 2 -, - CF 2 -, - C (CF 3) 2 -, O -, - CO -, - NH -, - N (CH 3) -, - CONH -, - NHCO -, - CH 2 O -, - OCH 2 -, - COO -, - OCO -, - CON (CH 3 ) — or N (CH 3 ) CO—, and m 6 represents an integer of 1 to 4.
- diamine compounds represented by the following formulas [DA18] and [DA19] can also be used.
- the above-mentioned other diamine compounds depend on properties such as solubility of a polyimide-based specific polymer in a solvent, coating properties of the composition, liquid crystal alignment in the case of a liquid crystal alignment film, voltage holding ratio, accumulated charge, etc.
- One type or a mixture of two or more types can also be used.
- Z 1 is a group having a structure selected from the following formulas [3a] to [3j].
- Z 2 to Z 5 represent a hydrogen atom, a methyl group, a chlorine atom or a benzene ring, and may be the same or different.
- Z 6 and Z 7 represent a hydrogen atom or a methyl group, and may be the same or different.
- Z 1 is represented by the formula [3a], from the viewpoint of ease of synthesis and polymerization reactivity when producing a polymer.
- a structure represented by the formula [3c], the formula [3d], the formula [3e], the formula [3f], or the formula [3g] is preferable. More preferred is a structure represented by formula [3a], formula [3e], formula [3f] or formula [3g], and particularly preferred is formula [3e], formula [3f] or formula [3g]. It is.
- the specific tetracarboxylic acid component of this invention is 1 mol% or more in all the tetracarboxylic acid components. More preferably, it is 5 mol% or more, more preferably 10 mol% or more, and particularly preferably 10 to 100 mol%. Moreover, when using the specific tetracarboxylic acid component of the structure of Formula [3e], Formula [3f], or Formula [3g], it is preferable that the usage-amount shall be 20 mol% or more of the whole tetracarboxylic acid component. More preferably, it is 30 mol% or more. Further, all of the tetracarboxylic acid component may be a tetracarboxylic acid component having a structure of the formula [3e], the formula [3f], or the formula [3g].
- tetracarboxylic acid components other than a specific tetracarboxylic acid component can be used for the specific polyimide-type polymer of this invention.
- examples of other tetracarboxylic acid components include the following tetracarboxylic acid compounds, tetracarboxylic dianhydrides, tetracarboxylic acid dihalide compounds, tetracarboxylic acid dialkyl ester compounds, and tetracarboxylic acid dialkyl ester dihalide compounds.
- tetracarboxylic acid components include pyromellitic acid, 2,3,6,7-naphthalenetetracarboxylic acid, 1,2,5,6-naphthalenetetracarboxylic acid, 1,4,5,8-naphthalenetetracarboxylic acid Acid, 2,3,6,7-anthracenetetracarboxylic acid, 1,2,5,6-anthracenetetracarboxylic acid, 3,3 ′, 4,4′-biphenyltetracarboxylic acid, 2,3,3 ′, 4-biphenyltetracarboxylic acid, bis (3,4-dicarboxyphenyl) ether, 3,3 ′, 4,4′-benzophenonetetracarboxylic acid, bis (3,4-dicarboxyphenyl) sulfone, bis (3 4-dicarboxyphenyl) methane, 2,2-bis (3,4-dicarboxyphenyl) propane, 1,1,1,3,3,3-hexafluoro
- the specific tetracarboxylic acid component and other tetracarboxylic acid components are the solubility of the specific polyimide polymer of the present invention in the solvent, the coating property of the composition, the liquid crystal alignment property, and the voltage holding ratio when used as a liquid crystal alignment film. Depending on the characteristics such as accumulated charge, one kind or a mixture of two or more kinds may be used.
- the method for synthesizing the specific polymer is not particularly limited. Usually, it is obtained by reacting a diamine component and a tetracarboxylic acid component. Generally, at least one tetracarboxylic acid component selected from the group consisting of tetracarboxylic acids and derivatives thereof is reacted with a diamine component consisting of one or more diamine compounds to obtain a polyamic acid.
- a method of obtaining a polyamic acid by polycondensation of a tetracarboxylic dianhydride and a primary or secondary diamine compound a dehydration polycondensation reaction of a tetracarboxylic acid and a primary or secondary diamine compound
- a method of obtaining a polyamic acid by polycondensation of a tetracarboxylic acid dihalide and a primary or secondary diamine compound a method of obtaining a polyamic acid by polycondensation of a tetracarboxylic acid dihalide and a primary or secondary diamine compound.
- a method of polycondensing a tetracarboxylic acid obtained by dialkyl esterifying a carboxylic acid group with a primary or secondary diamine compound, a tetracarboxylic acid dihalide obtained by dialkyl esterifying a carboxylic acid group and 1 A method of polycondensation with a secondary or secondary diamine compound, a method of converting a carboxyl group of polyamic acid into an ester, and the like are used.
- polyimide a method is used in which the polyamic acid or polyamic acid alkyl ester is cyclized to form polyimide.
- the reaction of the diamine component and the tetracarboxylic acid component is usually performed in an organic solvent.
- the organic solvent used at that time is not particularly limited as long as the produced polyimide precursor is dissolved.
- organic solvent used in the above reaction examples include N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone or ⁇ -butyrolactone, N, N-dimethylformamide, N, N-dimethylacetamide, dimethyl sulfoxide, 1,3-dimethyl-imidazolidinone, methyl ethyl ketone , Cyclohexanone, cyclopentanone and 4-hydroxy-4-methyl-2-pentanone.
- solvents represented by the following formulas [E-1] to [E-3] can be used.
- E 1 represents an alkyl group having 1 to 3 carbon atoms.
- E 2 represents an alkyl group having 1 to 3 carbon atoms.
- Formula [E-3 In the formula, E 3 represents an alkyl group having 1 to 4 carbon atoms.
- a method of adding a diamine component to a solution obtained by dispersing or dissolving a tetracarboxylic acid component in an organic solvent a method of alternately adding a diamine component and a tetracarboxylic acid component, etc. Any of these methods may be used.
- reacting using a plurality of diamine components or tetracarboxylic acid components they may be reacted in a premixed state, individually or sequentially, or further individually reacted low molecular weight substances. May be mixed and reacted to form a polymer.
- the polymerization temperature can be selected from -20 to 150 ° C, preferably -5 to 100 ° C.
- the reaction can be carried out at any concentration, but if the concentration is too low, it is difficult to obtain a high molecular weight polymer, and if the concentration is too high, the viscosity of the reaction solution becomes too high and uniform stirring is difficult. It becomes. Therefore, it is preferably 1 to 50% by mass, more preferably 5 to 30% by mass.
- the initial stage of the reaction is carried out at a high concentration, and then an organic solvent can be added.
- the ratio of the total number of moles of the diamine component to the total number of moles of the tetracarboxylic acid component is preferably 0.8 to 1.2. Similar to a normal polycondensation reaction, the molecular weight of the polyimide precursor produced increases as the molar ratio approaches 1.0.
- the polyimide of the present invention is a polyimide obtained by ring closure of the polyimide precursor, and in this polyimide, the ring closure rate of the amic acid group (also referred to as imidization rate) is not necessarily 100%. It can be arbitrarily adjusted according to the purpose.
- the method for imidizing the polyimide precursor include thermal imidization in which the polyimide precursor solution is heated as it is or catalyst imidization in which a catalyst is added to the polyimide precursor solution.
- the temperature is 100 to 400 ° C., preferably 120 to 250 ° C., and a method is preferably performed while removing water generated by the imidation reaction from the system.
- the catalytic imidation of the polyimide precursor can be carried out by adding a basic catalyst and an acid anhydride to the polyimide precursor solution and stirring at -20 to 250 ° C, preferably 0 to 180 ° C.
- the amount of the basic catalyst is 0.5 to 30 mol times, preferably 2 to 20 mol times the amic acid group.
- the amount of the acid anhydride is 1 to 50 mol times, preferably 3 to 30 mol times the amic acid group.
- Examples of the basic catalyst include pyridine, triethylamine, trimethylamine, tributylamine, and trioctylamine. 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. Of these, use of acetic anhydride is preferred because purification after completion of the reaction is facilitated.
- the imidization rate by catalytic imidation can be controlled by adjusting the amount of catalyst, reaction temperature, and reaction time.
- the reaction solution may be poured into a solvent and precipitated.
- the solvent used for precipitation include methanol, ethanol, isopropyl alcohol, acetone, hexane, butyl cellosolve, heptane, methyl ethyl ketone, methyl isobutyl ketone, toluene, benzene, and water.
- the polymer that has been introduced into the solvent and precipitated can be recovered by filtration, and then dried at normal temperature or under reduced pressure at room temperature or by heating.
- the impurities in the polymer can be reduced.
- the solvent at this time include alcohols, ketones, and hydrocarbons. It is preferable to use three or more kinds of solvents selected from these because purification efficiency is further improved.
- the molecular weight of the specific polymer of the present invention is a weight average molecular weight measured by a GPC (Gel Permeation Chromatography) method in consideration of the strength of the liquid crystal alignment film obtained therefrom, workability at the time of film formation, and coating properties. It is preferably 5,000 to 1,000,000, more preferably 10,000 to 150,000.
- the liquid crystal aligning agent of this invention is a solution for forming a liquid crystal aligning film (it is also called a resin film), and contains a specific silane compound, a specific amine compound, a specific polymer, and a solvent.
- the content of the specific silane compound in the liquid crystal aligning agent of the present invention is 0.1 to 15 parts by mass with respect to 100 parts by mass of the specific polymer. Among these, 0.5 to 10 parts by mass is preferable, and 1 to 10 parts by mass is particularly preferable. Further, the content of the specific amine compound in the liquid crystal aligning agent of the present invention is 0.1 to 20 parts by mass with respect to 100 parts by mass of the specific polymer. Among these, 0.1 to 15 parts by mass is preferable, and 1 to 10 parts by mass is particularly preferable.
- All the polymer components in the liquid crystal aligning agent of the present invention may all be the specific polymer of the present invention, or other polymers may be mixed.
- the content of the other polymer is 0.5 to 15 parts by mass, preferably 1 to 10 parts by mass with respect to 100 parts by mass of the specific polymer of the present invention.
- examples of other polymers include a diamine compound represented by the formula [2] and a polyimide polymer that does not use the specific tetracarboxylic acid component.
- other polymers specifically, cellulosic polymers, acrylic polymers, methacrylic polymers, polystyrenes, polyamides, polysiloxanes and the like can be mentioned.
- the solvent in the liquid crystal aligning agent of the present invention is preferably 70 to 99.9% by mass of the solvent in the liquid crystal aligning agent from the viewpoint of forming a uniform liquid crystal alignment film by coating, More preferably, it is 85 to 99% by mass. This content can be appropriately changed depending on the film thickness of the target liquid crystal alignment film.
- the solvent used for the liquid crystal aligning agent of the present invention is not particularly limited as long as it is a solvent (also referred to as a good solvent) that dissolves the specific silane compound, the specific amine compound, and the specific polymer.
- N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, ⁇ -butyrolactone, solvents represented by the above formulas [E-1] to [E-3], and the like can be given. These may be used alone or in combination.
- N-methyl-2-pyrrolidone N-ethyl-2-pyrrolidone, ⁇ -butyrolactone (also referred to as component (D) above) and the like.
- the solvents represented by the above formulas [E-1] to [E-3] it is preferable to use
- the good solvent in the liquid crystal aligning agent of the present invention is preferably 10 to 100% by mass of the total solvent contained in the liquid crystal aligning agent. Of these, 20 to 90% by mass is preferable. More preferred is 30 to 80% by mass.
- the liquid-crystal aligning agent of this invention contains the solvent (it is also called a poor solvent) which improves the coating property and surface smoothness of a liquid-crystal aligning film at the time of apply
- a poor solvent is 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-hexanol, cyclohexanol, 1,2-ethanediol, 1,2-propanediol, propylene glycol monobutyl ether or ethylene glycol monobutyl ether (hereinafter also referred to as component (F)), or the above-described formula [
- component (F) propylene glycol monobutyl ether or ethylene glycol monobutyl ether
- component (F) propylene glycol monobutyl ether or ethylene glycol monobutyl ether
- the liquid crystal alignment treatment agent of the present invention comprises a crosslinkable compound having an epoxy group, an isocyanate group, an oxetane group or a cyclocarbonate group, a hydroxyl group, a hydroxyalkyl group, and a lower alkoxyalkyl group unless the effects of the present invention are impaired.
- a crosslinkable compound having at least one substituent selected from the group or a crosslinkable compound having a polymerizable unsaturated bond can also be contained. Two or more of these substituents and polymerizable unsaturated bonds need to be contained in the crosslinkable compound.
- crosslinkable compound having an epoxy group or an isocyanate group examples include bisphenolacetone glycidyl ether, phenol novolac epoxy resin, cresol novolac epoxy resin, triglycidyl isocyanurate, tetraglycidylaminodiphenylene, tetraglycidyl-m-xylenediamine, tetra Glycidyl-1,3-bis (aminoethyl) cyclohexane, tetraphenyl glycidyl ether ethane, triphenyl glycidyl ether ethane, bisphenol hexafluoroacetodiglycidyl ether, 1,3-bis (1- (2,3-epoxypropoxy)- 1-trifluoromethyl-2,2,2-trifluoromethyl) benzene, 4,4-bis (2,3-epoxypropoxy) octafluorobiphenyl Triglycidyl-p-amin
- the crosslinkable compound having an oxetane group is a crosslinkable compound having at least two oxetane groups represented by the following formula [4]. Specific examples include crosslinkable compounds represented by the formulas [4a] to [4k] described on pages 58 to 59 of International Publication No. WO2011 / 132751 (published 2011.10.27).
- the crosslinkable compound having a cyclocarbonate group is a crosslinkable compound having at least two cyclocarbonate groups represented by the following formula [5]. Specifically, the crosslinkable compounds represented by the formulas [5-1] to [5-42] described on pages 76 to 82 of International Publication No. WO2012 / 014898 (published on 2012.2.2) Can be mentioned.
- Examples of the crosslinkable compound having at least one substituent selected from the group consisting of a hydroxyl group and an alkoxyl group include an amino resin having a hydroxyl group or an alkoxyl group, such as a melamine resin, urea resin, guanamine resin, glycoluril. -Formaldehyde resin, succinylamide-formaldehyde resin, ethyleneurea-formaldehyde resin and the like.
- a melamine derivative, a benzoguanamine derivative, or glycoluril in which a hydrogen atom of an amino group is substituted with a methylol group, an alkoxymethyl group, or both can be used.
- the melamine derivative or benzoguanamine derivative can exist as a dimer or a trimer. These preferably have an average of 3 to 6 methylol groups or alkoxymethyl groups per triazine ring.
- Examples of such melamine derivatives or benzoguanamine derivatives include MX-750, which has an average of 3.7 substituted methoxymethyl groups per triazine ring, and an average of 5. methoxymethyl groups per triazine ring.
- MX-750 which has an average of 3.7 substituted methoxymethyl groups per triazine ring, and an average of 5. methoxymethyl groups per triazine ring.
- MW-30 manufactured by Sanwa Chemical Co., Ltd.
- glycoluril examples include butoxymethylated glycoluril such as Cymel 1170, methylolated glycoluril such as Cymel 1172, and methoxymethylolated glycoluril such as Powderlink 1174.
- benzene or phenolic compounds having a hydroxyl group or an alkoxyl group include 1,3,5-tris (methoxymethyl) benzene, 1,2,4-tris (isopropoxymethyl) benzene, 1,4-bis (sec- Butoxymethyl) benzene, 2,6-dihydroxymethyl-p-tert-butylphenol and the like.
- International Publication WO2011 / 132751 examples thereof include crosslinkable compounds represented by the formulas [6-1] to [6-48] published on pages 62 to 66 of (2011.10.20).
- crosslinkable compound having a polymerizable unsaturated bond examples include trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, and tri (meth) acryloyloxyethoxytrimethylol.
- Crosslinkable compounds having three polymerizable unsaturated groups in the molecule such as propane and glycerin polyglycidyl ether poly (meth) acrylate, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, tetraethylene glycol di (meta ) Acrylate, polyethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, butylene glycol di (me ) Acrylate, neopentyl glycol di (meth) acrylate, ethylene oxide bisphenol A type di (meth) acrylate, propylene oxide bisphenol type di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, glycerin di (meth) ) Acrylate, pentaerythritol di (meth) acrylate, ethylene glycol diglycid
- E 1 represents a cyclohexane ring, bicyclohexane ring, a benzene ring, a biphenyl ring, a terphenyl ring, a naphthalene ring, a fluorene ring, a group selected from the group consisting of an anthracene ring and phenanthrene ring
- E 2 Represents a group selected from the following formulas [7a] and [7b], and n represents an integer of 1 to 4.
- the said compound is an example of a crosslinkable compound, It is not limited to these.
- the crosslinkable compound contained in the liquid crystal aligning agent of this invention may be one type, and may be combined two or more types.
- the content of the crosslinkable compound in the liquid crystal aligning agent of the present invention is preferably 0.1 to 150 parts by mass with respect to 100 parts by mass of all polymer components.
- the amount is more preferably 0.1 to 100 parts by weight, and most preferably 1 to 50 parts by weight with respect to 100 parts by weight of all polymer components.
- the liquid-crystal aligning agent of this invention can contain the compound which improves the uniformity of the film thickness of liquid crystal aligning film at the time of apply
- the compound that improves the film thickness uniformity and surface smoothness of the liquid crystal alignment film include fluorine-based surfactants, silicone-based surfactants, and nonionic surfactants.
- F Top EF301, F Top EF303, F Top EF352 (above, manufactured by Tochem Products), MegaFuck F171, MegaFuck F173, MegaFuck R-30 (above, manufactured by Dainippon Ink, Inc.) Fluorard FC430, Fluorard FC431 (above, manufactured by Sumitomo 3M), Asahi Guard AG710, Surflon S-382, Surflon SC101, Surflon SC102, Surflon SC103, Surflon SC104, Surflon SC105, Surflon SC106 (above, manufactured by Asahi Glass) Can be mentioned.
- the content of these surfactants is preferably 0.01 to 2 parts by mass, more preferably 0.01 to 1 part by mass with respect to 100 parts by mass of all the polymer components contained in the liquid crystal aligning agent. It is.
- the liquid crystal alignment treatment agent of the present invention impairs the effects of the present invention in addition to the above-mentioned poor solvent, crosslinkable compound, and a compound that improves the film thickness uniformity and surface smoothness of the resin film or liquid crystal alignment film. If it is within such a range, a dielectric or conductive material for changing the electrical characteristics such as the dielectric constant or conductivity of the liquid crystal alignment film may be added.
- the liquid crystal aligning agent of the present invention can be used as a liquid crystal aligning film after being applied on a substrate and baked, and then subjected to an alignment treatment by rubbing treatment or light irradiation. Moreover, in the case of vertical alignment use etc., it can be used as a liquid crystal alignment film without alignment treatment.
- the substrate is not particularly limited as long as it is a highly transparent substrate. In addition to a glass substrate, a plastic substrate such as an acrylic substrate or a polycarbonate substrate can also be used. From the viewpoint of simplification of the process, it is preferable to use a substrate on which an ITO electrode for driving a liquid crystal is formed.
- an opaque substrate such as a silicon wafer can be used if only one substrate is used, and a material that reflects light such as aluminum can be used as an 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.
- After applying the liquid crystal aligning agent on the substrate it is preferably 30 to 300 ° C., depending on the solvent used for the liquid crystal aligning agent, by a heating means such as a hot plate, a thermal circulation oven, or an IR (infrared) oven.
- the liquid crystal alignment film can be obtained by evaporating the solvent at a temperature of 30 to 250 ° C. If the thickness of the liquid crystal alignment film after baking is too thick, it is disadvantageous in terms of power consumption of the liquid crystal display element, and if it is too thin, the reliability of the liquid crystal display element may be lowered. Is 10 to 100 nm.
- the liquid crystal display element of the present invention is a liquid crystal display element obtained by obtaining a substrate with a liquid crystal alignment film from the liquid crystal alignment treatment agent of the present invention by the above-described method and then preparing a liquid crystal cell by a known method.
- a method for manufacturing a liquid crystal cell prepare a pair of substrates on which a liquid crystal alignment film is formed, spray spacers on the liquid crystal alignment film on one substrate, and place the liquid crystal alignment film surface on the other side. And a method of sealing the substrate by injecting liquid crystal under reduced pressure, a method of bonding the substrate after dropping the liquid crystal on the surface of the liquid crystal alignment film on which the spacers are dispersed, and the like.
- the liquid-crystal aligning agent of this invention has a liquid-crystal layer between a pair of board
- the liquid crystal composition is preferably used also for a liquid crystal display device manufactured through a step of polymerizing a polymerizable compound by at least one of irradiation with active energy rays and heating while applying a voltage between electrodes.
- the active energy ray ultraviolet rays are preferable.
- the wavelength of ultraviolet rays is 300 to 400 nm, preferably 310 to 360 nm.
- the heating temperature is 40 to 120 ° C, preferably 60 to 80 ° C. Moreover, you may perform an ultraviolet-ray and a heating simultaneously.
- the above liquid crystal display element controls the pretilt of liquid crystal molecules by a PSA (Polymer Sustained Alignment) method.
- a PSA method a small amount of a photopolymerizable compound, for example, a photopolymerizable monomer is mixed in a liquid crystal material, and after assembling a liquid crystal cell, a predetermined voltage is applied to the liquid crystal layer and an ultraviolet ray is applied to the photopolymerizable compound.
- the pretilt of the liquid crystal molecules is controlled by the produced polymer. Since the alignment state of the liquid crystal molecules when the polymer is formed is stored even after the voltage is removed, the pretilt of the liquid crystal molecules can be adjusted by controlling the electric field formed in the liquid crystal layer.
- the PSA method does not require a rubbing process and is suitable for forming a vertical alignment type liquid crystal layer in which it is difficult to control the pretilt by the rubbing process. That is, in the liquid crystal display element of the present invention, after obtaining a substrate with a liquid crystal alignment film from the liquid crystal alignment treatment agent of the present invention by the above-described method, a liquid crystal cell is prepared and polymerizable by at least one of ultraviolet irradiation and heating. By polymerizing the compound, the orientation of the liquid crystal molecules can be controlled.
- a pair of substrates on which a liquid crystal alignment film is formed is prepared, spacers are dispersed on the liquid crystal alignment film of one substrate, and the liquid crystal alignment film surface is on the inside. Then, the other substrate is bonded, the liquid crystal is injected under reduced pressure and sealed, the liquid crystal is dropped on the liquid crystal alignment film surface on which the spacers are dispersed, and then the substrate is bonded and sealed. .
- the liquid crystal is mixed with a polymerizable compound that is polymerized by heat or ultraviolet irradiation.
- the polymerizable compound include compounds having at least one polymerizable unsaturated group such as an acrylate group or a methacrylate group in the molecule.
- the content of the polymerizable compound is preferably 0.01 to 10 parts by mass, more preferably 0.1 to 5 parts by mass with respect to 100 parts by mass of the liquid crystal component.
- the polymerizable compound is less than 0.01 part by mass, the polymerizable compound is not polymerized and the alignment of the liquid crystal cannot be controlled. The seizure characteristics of the steel deteriorate.
- the polymerizable compound is polymerized by irradiating heat or ultraviolet rays while applying an AC or DC voltage to the liquid crystal cell.
- the liquid crystal aligning agent of the present invention has a liquid crystal layer between a pair of substrates provided with electrodes, and is polymerized by at least one of active energy rays and heat between the pair of substrates. It is also preferably used for a liquid crystal display device manufactured through a step of arranging a liquid crystal alignment film containing a group and applying a voltage between the electrodes.
- the active energy ray ultraviolet rays are preferable.
- the wavelength of ultraviolet rays is 300 to 400 nm, preferably 310 to 360 nm.
- the heating temperature is 40 to 120 ° C, preferably 60 to 80 ° C.
- a method of adding a compound containing this polymerizable group to a liquid crystal aligning agent A method containing a coalescing component is exemplified. Since the liquid crystal aligning agent of the present invention contains a specific compound having a double bond site that reacts by irradiation with heat or ultraviolet rays, the alignment of liquid crystal molecules is controlled by at least one of ultraviolet irradiation and heating. Can do.
- liquid crystal display element manufactured using the liquid crystal aligning agent of the present invention has excellent reliability, and is suitable for a large-screen, high-definition liquid crystal television.
- This reaction solution was poured into methanol (900 ml), and the resulting precipitate was separated by filtration. This deposit was wash
- the imidation ratio of this polyimide was 78%, the number average molecular weight was 17,900, and the weight average molecular weight was 39,900.
- This reaction solution was put into methanol (700 ml), and the resulting precipitate was separated by filtration. This deposit was wash
- the imidation ratio of this polyimide was 53%, the number average molecular weight was 18,000, and the weight average molecular weight was 40,900.
- Examples 1 to 20 and Comparative Examples 1 to 12 are production examples of liquid crystal aligning agents.
- the obtained liquid crystal aligning agent was also used for various characteristic evaluations.
- Tables 2 to 4 show the ratio of each component used in the production of each liquid crystal alignment treatment agent.
- Tables 5 to 7 show the results obtained in Examples and Comparative Examples. In the table, turbidity and precipitates were not observed, and the solution was a uniform solution, and turbidity and precipitates were observed as x.
- a liquid crystal alignment treatment agent stored at ⁇ 15 ° C. for 48 hours was washed with pure water and IPA on a substrate with an ITO (indium tin oxide) electrode (length 40 mm ⁇ width 30 mm, thickness 0.7 mm).
- the ITO surface was spin-coated and heat-treated at 100 ° C. for 5 minutes on a hot plate to produce an ITO substrate with a liquid crystal alignment film.
- the pinholes of the obtained substrate with a liquid crystal alignment film were evaluated.
- the pinhole was evaluated by visually observing the substrate under a sodium lamp. Specifically, the number of pinholes observed on the substrate with a liquid crystal alignment film was counted, and the smaller the number of pinholes, the fewer precipitates in the liquid crystal alignment treatment agent, and the better this evaluation was. Note that * 11 and * 12 in Tables 5 and 6 are the results of “B: Evaluation of Ink-jet Coating Property of Liquid Crystal Alignment Treatment Agent”, which will be described below and shown again in Table 8. .
- the liquid crystal aligning agent solution was spin-coated on the ITO surface of a substrate with an ITO electrode (40 mm long ⁇ 30 mm wide, 0.7 mm thick) washed with pure water and IPA, and 100% on a hot plate.
- An ITO substrate with a polyimide liquid crystal alignment film having a film thickness of 100 nm was obtained by heat treatment at 230 ° C. for 30 minutes in a heat-circulating clean oven at 5 ° C.
- liquid crystal aligning agent (7), (10), and (18) apply
- ITO substrate was obtained.
- the coated surface of the ITO substrate was rubbed using a rayon cloth with a rubbing apparatus having a roll diameter of 120 mm under the conditions of a roll rotation speed of 1000 rpm, a roll progression speed of 50 mm / sec, and an indentation amount of 0.1 mm.
- nematic liquid crystal (MLC-2003, manufactured by Merck Japan) was used as the liquid crystal.
- liquid crystal cell using the liquid crystal alignment agents (4) to (20) and (27) to (32) nematic liquid crystal (MLC-6608, manufactured by Merck Japan) was used as the liquid crystal.
- the obtained liquid crystal cell (ordinary cell) was visually observed using a polarizing plate and a backlight to evaluate the liquid crystal orientation in the vicinity of the sealant. All the liquid crystal cells obtained in Examples and Comparative Examples showed uniform liquid crystal alignment. Thereafter, the liquid crystal cell was stored in a high-temperature and high-humidity tank having a temperature of 80 ° C. and a relative humidity of 90% for 144 hours, and the liquid crystal orientation in the vicinity of the sealant was evaluated under the same conditions as described above. Specifically, it was determined that the evaluation in which the disorder of the liquid crystal orientation was not observed in the vicinity of the sealant was excellent in this evaluation.
- the evaluation of the liquid crystal orientation in the vicinity of the sealant after storage at high temperature and high humidity was evaluated as the display unevenness characteristic in the vicinity of the frame of the liquid crystal cell.
- Tables 5 to 8 show the evaluation results of the liquid crystal orientation (display unevenness characteristics in the vicinity of the frame of the liquid crystal cell) obtained after storage at high temperature and high humidity.
- surface the thing in which disorder of liquid crystal orientation was not seen was set to (circle), and the thing in which disorder of liquid crystal orientation was seen was set to x.
- a voltage of 1 V is applied to the liquid crystal cell not subjected to the high temperature and high humidity test at a temperature of 80 ° C. for 60 ⁇ s, and the voltage after 50 ms is measured. ).
- the measurement was performed using a voltage holding ratio measuring device (VHR-1, manufactured by Toyo Technica Co., Ltd.) with settings of Voltage: ⁇ 1 V, Pulse Width: 60 ⁇ s, and Frame Period: 50 ms.
- VHR-1 voltage holding ratio measuring device
- the liquid crystal cell for which the measurement of the voltage holding ratio was completed was stored in a high temperature and high humidity tank having a temperature of 80 ° C. and a relative humidity of 90% for 48 hours, and the voltage holding ratio was measured again under the same conditions as described above.
- Tables 5 to 8 show the measurement results of the voltage holding ratio immediately after the production of the liquid crystal cell and after storage at high temperature and high humidity.
- the solution stored for 48 hours was washed with pure water and IPA, and a 10 mm ⁇ 10 mm ITO electrode substrate with a pattern spacing of 20 ⁇ m (length 40 mm ⁇ width 30 mm, thickness 0.7 mm) and a center 10 mm ⁇ 40 mm Spin coating is applied to the ITO surface of a substrate with an ITO electrode with a pattern interval of 20 ⁇ m (length 40 mm ⁇ width 30 mm, thickness 0.7 mm), and heat treatment is performed at 100 ° C. for 5 minutes on a hot plate, and the film thickness is 100 nm. A polyimide coating was obtained. After the coated surface was washed with pure water, it was heat-treated at 100 ° C. for 15 minutes in a heat circulation type clean oven to obtain a substrate with a liquid crystal alignment film.
- the response speed of the liquid crystal before and after the ultraviolet irradiation of the liquid crystal cell was measured.
- the response speed was measured for T90 ⁇ T10 from 90% transmittance to 10% transmittance.
- the obtained PSA cell had a faster response speed of the liquid crystal cell after the ultraviolet irradiation than the response speed of the liquid crystal cell before the ultraviolet irradiation, and it was confirmed that the alignment direction of the liquid crystal was controlled. Further, in any liquid crystal cell, it was confirmed by observation with a polarizing microscope (ECLIPSE E600WPOL, manufactured by Nikon Corp.) that the liquid crystal was uniformly aligned.
- Examples 1 to 20 and Comparative Examples 1 to 12 Examples 1 to 20 and Comparative Examples 1 to 12 will be described below.
- the content ratios of the liquid crystal aligning agents in each example are summarized in Tables 2 to 4.
- * 2 to * 10 represent the following meanings.
- * 2, * 5, * 8 represent the content of component (A) with respect to 100 parts by mass of the specified polymer
- * 3, * 6, * 9 indicate the content of component (B) with respect to 100 parts by mass of the specified polymer.
- * 4, * 7, and * 10 represent the total content (mass%) of the component (A), the component (B), and the component (C) in the liquid crystal aligning agent.
- Example 1 The 25 mass% polyamic acid solution (1) (10.5 g) obtained in Synthesis Example 1 was added to a 10 mass% NMP solution (0.26 g) of NMP (18.0 g), BCS (15.9 g), and A1. ) And a 10% by mass NMP solution (0.79 g) of B1 were added and stirred at 50 ° C. for 15 hours to obtain a liquid crystal aligning agent (1).
- This liquid crystal aligning agent was confirmed to be a uniform solution without any abnormality such as turbidity or precipitation.
- Example 2 A 25% by mass polyamic acid solution (2) (10.0 g) obtained in Synthesis Example 2 was added to a 10% by mass NMP solution (1.25 g) of NMP (15.0 g), PB (18.0 g), and A2. ) And a 10% by mass NMP solution (0.75 g) of B1 were added and stirred at 50 ° C. for 15 hours to obtain a liquid crystal aligning agent (2).
- This liquid crystal aligning agent was confirmed to be a uniform solution without any abnormality such as turbidity or precipitation.
- Example 4 The 25 mass% polyamic acid solution (4) (10.0 g) obtained in Synthesis Example 4 was added to a 10 mass% NEP solution (1.25 g) of NEP (12.7 g), PB (20.6 g), and A2. ) And a 10% by mass NEP solution (1.25 g) of B1 were added and stirred at 50 ° C. for 15 hours to obtain a liquid crystal aligning agent (4).
- This liquid crystal aligning agent was confirmed to be a uniform solution without any abnormality such as turbidity or precipitation.
- Example 5 The 25 mass% polyamic acid solution (4) (10.2 g) obtained in Synthesis Example 4 was added to NEP (15.3 g), BCS (4.63 g), PB (13.9 g), and 10 mass% of A2. Of NEP solution (1.79 g) and a B2 10 mass% NEP solution (0.51 g) were added, and the mixture was stirred at 50 ° C. for 15 hours to obtain a liquid crystal aligning agent (5). This liquid crystal aligning agent was confirmed to be a uniform solution without any abnormality such as turbidity or precipitation.
- Example 6 To the polyimide powder (5) (2.50 g) obtained in Synthesis Example 5, NMP (7.35 g), NEP (12.9 g), PB (21.0 g), and 10 wt% NMP solution of A1 (1 .75 g) and a 10 mass% NEP solution (1.25 g) of B1 were added and stirred at 50 ° C. for 24 hours to obtain a liquid crystal aligning agent (6).
- This liquid crystal aligning agent was confirmed to be a uniform solution without any abnormality such as turbidity or precipitation.
- Example 7 NMP (8.11 g), NEP (14.2 g), PB (20.9 g), and 10 mass% NMP solution of A1 (1) were added to the polyimide powder (5) (1.45 g) obtained in Synthesis Example 5. 0.02 g) and a 10 mass% NEP solution (0.73 g) of B1 were added and stirred at 50 ° C. for 24 hours to obtain a liquid crystal aligning agent (7).
- This liquid crystal aligning agent was confirmed to be a uniform solution without any abnormality such as turbidity or precipitation.
- Example 8 NMP (18.1 g), PCS (8.80 g), BCS (8.73 g), PB (4.37 g), 10 of A1 were added to the polyimide powder (6) (2.50 g) obtained in Synthesis Example 6. A mass% NMP solution (0.50 g) and a B2 10 mass% NMP solution (0.75 g) were added, and the mixture was stirred at 50 ° C. for 24 hours to obtain a liquid crystal aligning agent (8). This liquid crystal aligning agent was confirmed to be a uniform solution without any abnormality such as turbidity or precipitation.
- Example 9 To the polyimide powder (7) (2.50 g) obtained in Synthesis Example 7, ⁇ -BL (15.9 g), DEEE (4.40 g), BCS (19.9 g), 10% by mass of ⁇ - A BL solution (1.25 g) and a 10% by mass ⁇ -BL solution (0.25 g) of B1 were added and stirred at 50 ° C. for 24 hours to obtain a liquid crystal aligning agent (9).
- This liquid crystal aligning agent was confirmed to be a uniform solution without any abnormality such as turbidity or precipitation.
- Example 10 To the polyimide powder (7) (1.55 g) obtained in Synthesis Example 7, ⁇ -BL (23.3 g), PGME (9.30 g), PB (11.6 g), 10% by mass of ⁇ - A BL solution (0.47 g) and a 10% by mass ⁇ -BL solution (0.31 g) of B1 were added and stirred at 50 ° C. for 24 hours to obtain a liquid crystal aligning agent (10).
- This liquid crystal aligning agent was confirmed to be a uniform solution without any abnormality such as turbidity or precipitation.
- Example 11 NMP (7.37 g), NEP (14.7 g), PB (18.3 g), and 10 mass% NMP solution of A1 (1) were added to the polyimide powder (8) (2.45 g) obtained in Synthesis Example 8. .72 g) and a 10 mass% NEP solution (1.23 g) of B1 were added and stirred at 50 ° C. for 24 hours to obtain a liquid crystal aligning agent (11).
- This liquid crystal aligning agent was confirmed to be a uniform solution without any abnormality such as turbidity or precipitation.
- Example 12 To the polyimide powder (9) (2.53 g) obtained in Synthesis Example 9, NEP (18.2 g), BCS (22.9 g), a 10 mass% NEP solution (1.27 g) of A1, and B2 10 A mass% NEP solution (0.89 g) was added and stirred at 50 ° C. for 24 hours to obtain a liquid crystal aligning agent (12).
- This liquid crystal aligning agent was confirmed to be a uniform solution without any abnormality such as turbidity or precipitation.
- Example 13 To the polyimide powder (10) (2.50 g) obtained in Synthesis Example 10, NMP (17.7 g), PCS (9.60 g), PB (14.4 g), and a 10% NMP solution of A1 (2 .50 g) and a 10% by mass NMP solution (1.25 g) of B1 were added and stirred at 50 ° C. for 24 hours to obtain a liquid crystal aligning agent (13).
- This liquid crystal aligning agent was confirmed to be a uniform solution without any abnormality such as turbidity or precipitation.
- Example 14 To the polyimide powder (10) (2.50 g) obtained in Synthesis Example 10, NEP (20.1 g), DEEE (4.70 g), PB (16.5 g), and 10% NEP solution of A2 (2 .50 g) and a 10% by mass NEP solution (0.75 g) of B2 were added and stirred at 50 ° C. for 24 hours to obtain a liquid crystal aligning agent (14).
- This liquid crystal aligning agent was confirmed to be a uniform solution without any abnormality such as turbidity or precipitation.
- Example 15 The polyimide powder (11) (2.50 g) obtained in Synthesis Example 11 was added to a 10% by mass ⁇ -BL solution (0.75 g) of ⁇ -BL (20.3 g), PB (19.7 g), and A1. And a 10 mass% ⁇ -BL solution of B1 (0.50 g) were added and stirred at 50 ° C. for 24 hours to obtain a liquid crystal aligning agent (15).
- This liquid crystal aligning agent was confirmed to be a uniform solution without any abnormality such as turbidity or precipitation.
- Example 16 The 25 mass% polyamic acid solution (12) (10.0 g) obtained in Synthesis Example 12 was added to a 10 mass% NEP solution (1.75 g) of NEP (17.3 g), BCS (16.3 g), and A2. ) And a 10% by mass NEP solution (1.25 g) of B1 were added and stirred at 50 ° C. for 15 hours to obtain a liquid crystal aligning agent (16).
- This liquid crystal aligning agent was confirmed to be a uniform solution without any abnormality such as turbidity or precipitation.
- Example 17 To the polyimide powder (13) (2.55 g) obtained in Synthesis Example 13, NMP (7.67 g), NEP (15.3 g), PB (19.6 g), and 10% NMP solution of A2 (2 .55 g) and a 10% by mass NEP solution (1.28 g) of B2 were added and stirred at 50 ° C. for 24 hours to obtain a liquid crystal aligning agent (17).
- This liquid crystal aligning agent was confirmed to be a uniform solution without any abnormality such as turbidity or precipitation.
- Example 18 To the polyimide powder (13) (1.45 g) obtained in Synthesis Example 13, NMP (8.33 g), NEP (16.7 g), PB (19.1 g), and an A2 10 mass% NMP solution (1 .45 g) and a 10% by mass NEP solution (0.73 g) of B2 were added and stirred at 50 ° C. for 24 hours to obtain a liquid crystal aligning agent (18).
- This liquid crystal aligning agent was confirmed to be a uniform solution without any abnormality such as turbidity or precipitation.
- Example 19 To the polyimide powder (14) (2.50 g) obtained in Synthesis Example 14, NEP (20.2 g), BCS (11.7 g), PB (9.33 g), and 10 mass% NEP solution of A1 (1 .75 g) and a 10 mass% NEP solution (1.25 g) of B1 were added and stirred at 50 ° C. for 24 hours to obtain a liquid crystal aligning agent (19).
- This liquid crystal aligning agent was confirmed to be a uniform solution without any abnormality such as turbidity or precipitation.
- Example 20 To the polyimide powder (14) (2.50 g) obtained in Synthesis Example 14, NMP (18.0 g), PCS (4.50 g), BCS (18.0 g), and 10% NMP solution of A2 (1 .25 g) and a 10% by mass NMP solution (0.75 g) of B1 were added, and the mixture was stirred at 50 ° C. for 24 hours to obtain a liquid crystal aligning agent (20).
- This liquid crystal aligning agent was confirmed to be a uniform solution without any abnormality such as turbidity or precipitation.
- the liquid crystal aligning agent of an Example was excellent in storage stability compared with the liquid crystal aligning agent of a comparative example. Also, by using the liquid crystal alignment treatment agent of the example, a liquid crystal alignment film was obtained in which the liquid crystal alignment in the vicinity of the sealant of the liquid crystal cell was not disturbed even when the liquid crystal cell was stored at high temperature and high humidity for a long time. . Furthermore, even when the liquid crystal cell was stored at high temperature and high humidity for a long period of time, a liquid crystal alignment film capable of suppressing a decrease in voltage holding ratio was obtained.
- the liquid crystal alignment treatment agent of the present invention is a liquid crystal that has excellent storage stability and can suppress the occurrence of display unevenness near the frame of the liquid crystal display element and the decrease in voltage holding ratio under high temperature and high humidity conditions. It was found that an alignment film can be formed.
- the liquid crystal aligning agent of these comparative examples is compared with the comparative example containing no specific silane compound.
- the liquid crystal cell is stored for a long time under high-temperature and high-humidity conditions, it is possible to suppress the disorder of the liquid crystal orientation and the decrease in the voltage holding ratio in the vicinity of the sealant of the liquid crystal cell. I got worse.
- the liquid crystal alignment treatment agent of the present invention is excellent in storage stability, has high adhesion to a sealant, and suppresses the occurrence of display unevenness near the frame even under high temperature and high humidity conditions. It is possible to form a liquid crystal alignment film that can also suppress degradation, and a liquid crystal display element having a liquid crystal alignment film obtained from the liquid crystal alignment treatment agent of the present invention has excellent reliability and a large screen. It is suitable for a high-definition liquid crystal television and the like, and is useful as a TN element, STN element, TFT liquid crystal element, particularly as a vertical alignment type liquid crystal display element. Furthermore, the liquid crystal alignment film obtained from the liquid crystal aligning agent of the present invention is also useful in the production of a liquid crystal display element that needs to be irradiated with ultraviolet rays when producing a display element.
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Abstract
Description
これらに対して、ポリイミドを用いた液晶配向膜において、液晶配向性を高め、液晶表示画面周辺部に表示不良が生じにくくする手法として、アルコキシシラン化合物を添加した液晶配向処理剤を用いて形成された液晶配向膜が提案されている(例えば、特許文献1又は特許文献2を参照)。
(1)下記の成分(A)、成分(B)及び成分(C)を含有することを特徴とする液晶配向処理剤。
成分(A):下記の式[a]で示されるシラン化合物。
成分(B):分子内にアミノ基を1個と窒素含有芳香族複素環とを有し、かつ前記アミノ基が2価の脂肪族炭化水素基又は非芳香族環式炭化水素基に結合しているアミン化合物。
成分(C):ジアミン成分とテトラカルボン酸成分とを反応させて得られるポリイミド前駆体及び前記ポリイミド前駆体をイミド化した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。
(3)前記成分(B)が、下記の式[1]で示される化合物である上記(1)又は(2)に記載の液晶配向処理剤。
(8)成分(E)として、下記の式[E-1]、式[E-2]及び式[E-3]で示される溶媒からなる群から選ばれる少なくとも1つの溶媒を含有する上記(1)~(7)のいずれかに記載の液晶配向処理剤。
(9)成分(F)として、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及びエチレングリコールモノブチルエーテルからなる群から選ばれる少なくとも1つの溶媒を含有する上記(1)~(8)のいずれかに記載の液晶配向処理剤。
(11)上記(1)~(9)のいずれかに記載の液晶配向処理剤を用いて、インクジェット法にて得られる液晶配向膜。
(12)上記(10)又は(11)に記載の液晶配向膜を有する液晶表示素子。
(13)電極を備えた一対の基板の間に液晶層を有してなり、前記一対の基板の間に活性エネルギー線及び熱の少なくとも一方により重合する重合性化合物を含む液晶組成物を配置し、前記電極間に電圧を印加しつつ、前記重合性化合物を重合させる工程を経て製造される液晶表示素子に用いられる上記(10)又は(11)に記載の液晶配向膜。
(14)上記(13)に記載の液晶配向膜を有する液晶表示素子。
(15)電極を備えた一対の基板の間に液晶層を有してなり、前記一対の基板の間に活性エネルギー線及び熱の少なくとも一方により重合する重合性基を含む液晶配向膜を配置し、前記電極間に電圧を印加しつつ、前記重合性基を重合させる工程を経て製造される液晶表示素子に用いられることを特徴とする上記(10)又は(11)に記載の液晶配向膜。
(16)上記(13)に記載の液晶配向膜を有する液晶表示素子。
本発明の成分(A)であるシラン化合物(以下、特定シラン化合物ともいう)は、下記の式[a]で示される。
A3は炭素数1~5のアルキル基である。なかでも、重縮合の反応性の点から、炭素数1~3のアルキル基が好ましい。
mは1又は2の整数である。なかでも、合成のし易さの点から、1が好ましい。
nは0~2の整数である。
pは0~3の整数である。なかでも、重縮合の反応性の点から、1~3の整数が好ましい。より好ましくは、2又は3である。
なお、m+n+pは4の整数である。
上記の式[a]で示される特定シラン化合物は、液晶配向膜とした際の液晶配向性、電圧保持率、蓄積電荷などの特性に応じて、1種類又は2種類以上を混合して使用することもできる。
本発明の成分(B)であるアミン化合物(以下、特定アミン化合物ともいう)は、分子内にアミノ基を1個と窒素含有芳香族複素環とを有し、かつ前記アミノ基が2価の脂肪族炭化水素基又は非芳香族環式炭化水素基に結合しているアミン化合物である。
この特定アミン化合物は、分子内に含まれるアミノ基が1個のみであるので、液晶配向処理剤を製造する際や液晶配向処理剤の保存中に、ポリマーの析出やゲル化といった問題が起こる可能性を抑えることができる。
特定アミン化合物に含まれるアミノ基は、特定重合体との塩形成や結合反応のしやすさの観点から、分子内において2価の脂肪族炭化水素基又は芳香族炭化水素を含まない非芳香族環式炭化水素基に結合している必要がある。
具体例としては、上述した構造を挙げることができる。これらのうち、ピロール環、イミダゾール環、ピラゾール環、ピリジン環、ピリミジン環、ピリダジン環、トリアジン環、トリアゾール環、ピラジン環、ベンゾイミダゾール環、キノキサリン環、アゼピン環、ジアゼピン環、ナフチリジン環、フェナジン環又はフタラジン環が好ましい。
さらに、式[1]のX2である窒素含有芳香族複素環の炭素原子は、ハロゲン原子又は有機基の置換基を有していてもよい。該有機基は酸素原子、硫黄原子又は窒素原子などのヘテロ原子を含有してもよい。
また、窒素含有芳香族複素環と特定ポリイミド中のカルボキシル基との塩形成や水素結合といった静電的相互作用のしやすさの観点から、X4はX5に含まれる式[1-a]、式[1-b]又は式[1-c]と隣り合わない炭素原子と結合していることが好ましい。
本発明の特定アミン化合物の具体例としては、国際公開公報WO2011/132751(2011.10.27公開)の69頁~73頁に掲載される、式[M1]~[M156]で示される窒素含有複素環アミン化合物が挙げられる。
なかでも、式[M1]、式[M7]、式[M16]~式[20]、式[M24]、式[M35]、式[M36]、式[M40]、式[M49]、式[M50]、式[M52]、式[M60]~式[M62]、式[M68]、式[M69]、式[M76]、式[M77]、式[M82]、式[M100]、式[M101]、式[M108]、式[M109]、式[M118]~式[M121]、式[M128]、式[M134]~式[136]または式[M140]が好ましい。
本発明の成分(C)である重合体(以下、特定重合体ともいう)は、ジアミン成分とテトラカルボン酸成分とを反応させて得られるポリイミド前駆体及び前記ポリイミド前駆体をイミド化したポリイミドから選ばれる。
ポリイミド前駆体は、下記の式[A]で示される構造である。
ポリイミド前駆体を形成するためのジアミン成分としては、分子内に1級又は2級のアミノ基を2個有するジアミン化合物が挙げられる。
また、ポリイミド前駆体を形成するためのテトラカルボン酸成分としては、テトラカルボン酸化合物、テトラカルボン酸二無水物、テトラカルボン酸ジハライド化合物、テトラカルボン酸ジアルキルエステル化合物又はテトラカルボン酸ジアルキルエステルジハライド化合物が挙げられる。
さらに、上記で得られた式[D]の重合体に、式[A]のA1及びA2で示される炭素数1~8のアルキル基や、式[A]のA3及びA4で示される炭素数1~5のアルキル基若しくはアセチル基を、通常の合成手法で導入することもできる。
本発明の成分(C)である特定重合体を形成するためのジアミン成分としては、公知のジアミン化合物を用いることができる。
なかでも、下記の式[2]で示される構造を有するジアミンを用いることが好ましい。
式[2-2]中、bは0~4の整数を示す。なかでも、原料の入手性や合成の容易さの点から、0又は1の整数が好ましい。
式[2-3]中、Y1は単結合、-(CH2)a-(aは1~15の整数である)、-O-、-CH2O-、-COO-又はOCO-を示す。なかでも、原料の入手性や合成の容易さの点から、単結合、-(CH2)a-(aは1~15の整数である)、-O-、-CH2O-又はCOO-が好ましい。より好ましいのは、単結合、-(CH2)a-(aは1~10の整数である)、-O-、-CH2O-又はCOO-である。
Y3は単結合、-(CH2)c-(cは1~15の整数である)、-O-、-CH2O-、-COO-又はOCO-を示す。なかでも、合成の容易さの点から、単結合、-(CH2)c-(cは1~15の整数である)、-O-、-CH2O-又はCOO-が好ましい。より好ましいのは、単結合、-(CH2)c-(cは1~10の整数である)、-O-、-CH2O-又はCOO-である。
Y4はベンゼン環、シクロヘキサン環又は複素環から選ばれる2価の環状基であり、これらの環状基上の任意の水素原子は、炭素数1~3のアルキル基、炭素数1~3のアルコキシル基、炭素数1~3のフッ素含有アルキル基、炭素数1~3のフッ素含有アルコキシル基又はフッ素原子で置換されていてもよい。さらに、Y4は、ステロイド骨格を有する炭素数12~25の有機基から選ばれる2価の有機基であってもよい。なかでも、合成の容易さの点から、ベンゼン環、シクロへキサン環又はステロイド骨格を有する炭素数12~25の有機基が好ましい。
nは0~4の整数を示す。なかでも、原料の入手性や合成の容易さの点から、0~3が好ましい。より好ましいのは、0~2である。
Y8は炭素数8~22のアルキル基を示す。好ましくは炭素数8~18のアルキル基である。
式[2-5]中、Y9及びY10はそれぞれ独立して、炭素数1~12の炭化水素基を示す。好ましくは炭素数1~8の炭化水素基である。
式[2-6]中、Y11は炭素数1~5のアルキル基を示す。好ましくは炭素数1~2のアルキル基である。
一例として、式[2]で示されるジアミン化合物は、下記の式[2-A]で示されるジニトロ体化合物を合成し、さらにそのニトロ基を還元してアミノ基に変換することで得られる。
式[2-A]で示されるジニトロ体化合物のニトロ基を還元する方法には、特に制限はなく、通常、酢酸エチル、トルエン、テトラヒドロフラン、ジオキサン、アルコール系溶剤などの溶媒中、パラジウム-炭素、酸化白金、ラネーニッケル、白金黒、ロジウム-アルミナ、硫化白金炭素などを触媒として用いて、水素ガス、ヒドラジン、塩化水素下で反応させる方法がある。
2,4-ジメチル-m-フェニレンジアミン、2,6-ジアミノトルエン、2,4-ジアミノ安息香酸、3,5-ジアミノ安息香酸、2,4-ジアミノフェノール、3,5-ジアミノフェノール、3,5-ジアミノベンジルアルコール、2,4-ジアミノベンジルアルコール、4,6-ジアミノレゾルシノールの他に、下記の式[2-7]~[2-47]で示される構造のジアミン化合物を挙げることができる。
本発明の成分(C)である特定重合体を形成するためのテトラカルボン酸成分としては、下記の式[3]で示されるテトラカルボン酸二無水物や、そのテトラカルボン酸誘導体であるテトラカルボン酸、テトラカルボン酸ジハライド化合物、テトラカルボン酸ジアルキルエステル化合物又はテトラカルボン酸ジアルキルエステルジハライド化合物(すべてを総称して特定テトラカルボン酸成分ともいう)を用いることが好ましい。
式[3g]中、Z6及びZ7は水素原子又はメチル基を示し、それぞれ同じであっても異なってもよい。
また、式[3e]、式[3f]又は式[3g]の構造の特定テトラカルボン酸成分を用いる場合、その使用量は、テトラカルボン酸成分全体の20モル%以上とすることが好ましい。より好ましくは、30モル%以上である。さらに、テトラカルボン酸成分のすべてが、式[3e]、式[3f]又は式[3g]の構造のテトラカルボン酸成分であってもよい。
その他のテトラカルボン酸成分としては、以下に示すテトラカルボン酸化合物、テトラカルボン酸二無水物、テトラカルボン酸ジハライド化合物、テトラカルボン酸ジアルキルエステル化合物又はテトラカルボン酸ジアルキルエステルジハライド化合物が挙げられる。
本発明において、特定重合体を合成する方法は特に限定されない。通常、ジアミン成分とテトラカルボン酸成分とを反応させて得られる。一般的には、テトラカルボン酸及びその誘導体からなる群から選ばれる少なくとも1種のテトラカルボン酸成分と、1種又は複数種のジアミン化合物からなるジアミン成分とを反応させて、ポリアミド酸を得る。具体的には、テトラカルボン酸二無水物と1級又は2級のジアミン化合物とを重縮合させてポリアミド酸を得る方法、テトラカルボン酸と1級又は2級のジアミン化合物とを脱水重縮合反応させてポリアミド酸を得る方法、テトラカルボン酸ジハライドと1級又は2級のジアミン化合物とを重縮合させてポリアミド酸を得る方法等が用いられる。
ポリイミドを得るには、前記のポリアミド酸又はポリアミド酸アルキルエステルを閉環させてポリイミドとする方法が用いられる。
ジアミン成分とテトラカルボン酸成分との反応は、通常、有機溶媒中で行う。その際に用いる有機溶媒としては、生成したポリイミド前駆体が溶解するものであれば特に限定されない。
例えば、N-メチル-2-ピロリドン、N-エチル-2-ピロリドン又はγ-ブチロラクトン、N,N-ジメチルホルムアミド、N,N-ジメチルアセトアミド、ジメチルスルホキシド、1,3-ジメチル-イミダゾリジノン、メチルエチルケトン、シクロヘキサノン、シクロペンタノンおよび4-ヒドロキシ-4-メチル-2-ペンタノンが挙げられる。さらに、本発明の特定重合体の溶媒への溶解性が高い場合は、下記の式[E-1]~式[E-3]で示される溶媒などを用いることができる。
これらは単独で使用しても、混合して使用してもよい。
ジアミン成分とテトラカルボン酸成分とを有機溶媒中で反応させる際には、ジアミン成分を有機溶媒に分散あるいは溶解させた溶液を攪拌させ、テトラカルボン酸成分をそのまま、又は有機溶媒に分散あるいは溶解させて添加する方法、逆にテトラカルボン酸成分を有機溶媒に分散、あるいは溶解させた溶液にジアミン成分を添加する方法、ジアミン成分とテトラカルボン酸成分とを交互に添加する方法などが挙げられ、これらのいずれの方法を用いてもよい。また、ジアミン成分又はテトラカルボン酸成分を、それぞれ複数種用いて反応させる場合は、あらかじめ混合した状態で反応させてもよく、個別に順次反応させてもよく、さらに個別に反応させた低分子量体を混合反応させ重合体としてもよい。
また、反応は任意の濃度で行うことができるが、濃度が低すぎると高分子量の重合体を得ることが難しくなり、濃度が高すぎると反応液の粘性が高くなり過ぎて均一な攪拌が困難となる。そのため、好ましくは1~50質量%、より好ましくは5~30質量%である。反応初期は高濃度で行い、その後、有機溶媒を追加することができる。
ポリイミド前駆体の重合反応においては、ジアミン成分の合計モル数とテトラカルボン酸成分の合計モル数との比は0.8~1.2であることが好ましい。通常の重縮合反応同様、このモル比が1.0に近いほど生成するポリイミド前駆体の分子量は大きくなる。
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。
ポリイミド前駆体の触媒イミド化は、ポリイミド前駆体の溶液に、塩基性触媒と酸無水物とを添加し、-20~250℃、好ましくは0~180℃で攪拌することにより行うことができる。
酸無水物の量は、アミド酸基の1~50モル倍、好ましくは3~30モル倍である。
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、トリブチルアミン又はトリオクチルアミンなど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。
酸無水物としては、無水酢酸、無水トリメリット酸又は無水ピロメリット酸などを挙げることができる。なか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。触媒イミド化によるイミド化率は、触媒量と反応温度、反応時間を調節することにより制御することができる。
本発明の液晶配向処理剤は、液晶配向膜(樹脂被膜ともいう)を形成するための溶液であり、特定シラン化合物、特定アミン化合物、特定重合体及び溶媒を含有する。
本発明の液晶配向処理剤における特定シラン化合物の含有量は、特定重合体100質量部に対して、0.1~15質量部である。なかでも、0.5~10質量部が好ましく、特に好ましいのは、1~10質量部である。
また、本発明の液晶配向処理剤における特定アミン化合物の含有量は、特定重合体100質量部に対して、0.1~20質量部である。なかでも、0.1~15質量部が好ましく、特に好ましいのは、1~10質量部である。
それ以外の他の重合体としては、前記式[2]で示されるジアミン化合物及び特定テトラカルボン酸成分を用いていないポリイミド系重合体が挙げられる。さらには、それ以外の重合体、具体的には、セルロース系重合体、アクリルポリマー、メタクリルポリマー、ポリスチレン、ポリアミド、ポリシロキサンなどが挙げられる。
本発明の液晶配向処理剤に用いる溶媒は、特定シラン化合物、特定アミン化合物及び特定重合体を溶解させる溶媒(良溶媒ともいう)であれば特に限定されない。
例えば、N,N-ジメチルホルムアミド、N,N-ジメチルアセトアミド、N-メチル-2-ピロリドン、N-エチル-2-ピロリドン、ジメチルスルホキシド、γ-ブチロラクトン、1,3-ジメチル-イミダゾリジノン、メチルエチルケトン、シクロヘキサノン、シクロペンタノン又は4-ヒドロキシ-4-メチル-2-ペンタノンなどである。なかでも、N-メチル-2-ピロリドン、N-エチル-2-ピロリドン、γ-ブチロラクトン、上述した前記式[E-1]~式[E-3]で示される溶媒などを挙げることができる。これらは単独で使用しても、混合して使用してもよい。
本発明の液晶配向処理剤における良溶媒は、液晶配向処理剤に含まれる溶媒全体の10~100質量%であることが好ましい。なかでも、20~90質量%が好ましい。より好ましいのは、30~80質量%である。
例えば、エタノール、イソプロピルアルコール、1-ブタノール、2-ブタノール、イソブチルアルコール、tert-ブチルアルコール、1-ペンタノール、2-ペンタノール、3-ペンタノール、2-メチル-1-ブタノール、イソペンチルアルコール、tert-ペンチルアルコール、3-メチル-2-ブタノール、ネオペンチルアルコール、1-ヘキサノール、2-メチル-1-ペンタノール、2-メチル-2-ペンタノール、2-エチル-1-ブタノール、1-ヘプタノール、2-ヘプタノール、3-ヘプタノール、1-オクタノール、2-オクタノール、2-エチル-1-ヘキサノール、シクロヘキサノール、1-メチルシクロヘキサノール、2-メチルシクロヘキサノール、3-メチ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、1,3-プロパンジオール、1,2-ブタンジオール、1,3-ブタンジオール、1,4-ブタンジオール、2,3-ブタンジオール、1,5-ペンタンジオール、2-メチル-2,4-ペンタンジオール、2-エチル-1,3-ヘキサンジオール、ジプロピルエーテル、ジブチルエーテル、ジヘキシルエーテル、ジオキサン、エチレングリコールジメチルエーテル、エチレングリコールジエチルエーテル、エチレングリコールジブチルエーテル、1,2-ブトキシエタン、ジエチレングリコールジメチルエーテル、ジエチレングリコールジエチルエーテル、ジエチレングリコールメチルエチルエーテル、ジエチレングリコールジブチルエーテル、2-ペンタノン、3-ペンタノン、2-ヘキサノン、2-ヘプタノン、4-ヘプタノン、3-エトキシブチルアセタート、1-メチルペンチルアセタート、2-エチルブチルアセタート、2-エチルヘキシルアセタート、エチレングリコールモノアセタート、エチレングリコールジアセタート、プロピレンカーボネート、エチレンカーボネート、2-(メトキシメトキシ)エタノール、エチレングリコールモノブチルエーテル、エチレングリコールモノイソアミルエーテル、エチレングリコールモノヘキシルエーテル、2-(ヘキシルオキシ)エタノール、フルフリルアルコール、ジエチレングリコール、プロピレングリコール、プロピレングリコールモノブチルエーテル、1-(ブトキシエトキシ)プロパノール、プロピレングリコールモノメチルエーテルアセタート、ジプロピレングリコール、ジプロピレングリコールモノメチルエーテル、ジプロピレングリコールモノエチルエーテル、トリプロピレングリコールモノメチルエーテル、エチレングリコールモノメチルエーテルアセタート、エチレングリコールモノエチルエーテルアセタート、エチレングリコールモノブチルエーテルアセタート、エチレングリコールモノアセタート、エチレングリコールジアセタート、ジエチレングリコールモノエチルエーテルアセタート、ジエチレングリコールモノブチルエーテルアセタート、2-(2-エトキシエトキシ)エチルアセタート、ジエチレングリコールアセタート、トリエチレングリコール、トリエチレングリコールモノメチルエーテル、トリエチレングリコールモノエチルエーテル、乳酸メチル、乳酸エチル、酢酸メチル、酢酸エチル、酢酸n-ブチル、酢酸プロピレングリコールモノエチルエーテル、ピルビン酸メチル、ピルビン酸エチル、3-メトキシプロピオン酸メチル、3-エトキシプロピオン酸メチルエチル、3-メトキシプロピオン酸エチル、3-エトキシプロピオン酸、3-メトキシプロピオン酸、3-メトキシプロピオン酸プロピル、3-メトキシプロピオン酸ブチル、乳酸メチルエステル、乳酸エチルエステル、乳酸n-プロピルエステル、乳酸n-ブチルエステル、乳酸イソアミルエステル、前記式[E-1]~式[E-3]で示される溶媒など。
これら貧溶媒は、液晶配向処理剤に含まれる溶媒全体の1~70質量%であることが好ましい。なかでも、1~60質量%が好ましい。より好ましいのは5~60質量%である。
ヒドロキシル基又はアルコキシル基を有するベンゼン若しくはフェノール性化合物としては、1,3,5-トリス(メトキシメチル)ベンゼン、1,2,4-トリス(イソプロポキシメチル)ベンゼン、1,4-ビス(sec-ブトキシメチル)ベンゼン、2,6-ジヒドロキシメチル-p-tert-ブチルフェノール等が挙げられる。
具体的には、国際公開公報WO2011/132751.(2011.10.27公開)の62~66頁に掲載の式[6-1]~式[6-48]で示される架橋性化合物が挙げられる。
本発明の液晶配向処理剤における、架橋性化合物の含有量は、すべての重合体成分100質量部に対して、0.1~150質量部であることが好ましい。架橋反応が進行し目的の効果を発現させるためには、すべての重合体成分100質量部に対して0.1~100質量部がより好ましく、1~50質量部が最も好ましい。
液晶配向膜の膜厚の均一性や表面平滑性を向上させる化合物としては、フッ素系界面活性剤、シリコーン系界面活性剤、ノ二オン系界面活性剤などが挙げられる。
本発明の液晶配向処理剤は、基板上に塗布し、焼成した後、ラビング処理や光照射などで配向処理をして、液晶配向膜として用いることができる。また、垂直配向用途などの場合では、配向処理なしでも液晶配向膜として用いることができる。
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、ガラス基板の他、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なども用いることができる。プロセスの簡素化の観点からは、液晶駆動のためのITO電極などが形成された基板を用いることが好ましい。
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ェハなどの不透明な基板も使用でき、この場合の電極としてはアルミなどの光を反射する材料も使用できる。
液晶配向処理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、液晶配向処理剤に用いる溶媒に応じて、30~300℃、好ましくは30~250℃の温度で溶媒を蒸発させて液晶配向膜とすることができる。
焼成後の液晶配向膜の厚みは、厚すぎると液晶表示素子の消費電力の面で不利となり、薄すぎると液晶表示素子の信頼性が低下する場合があるので、好ましくは5~300nm、より好ましくは10~100nmである。
本発明の液晶表示素子は、上記した手法により、本発明の液晶配向処理剤から液晶配向膜付き基板を得た後、公知の方法で液晶セルを作製して液晶表示素子としたものである。
液晶セルの作製方法としては、液晶配向膜の形成された一対の基板を用意し、片方の基板の液晶配向膜上にスペーサを散布し、液晶配向膜面が内側になるようにして、もう片方の基板を貼り合わせ、液晶を減圧注入して封止する方法、スペーサを散布した液晶配向膜面に液晶を滴下した後に基板を貼り合わせて封止を行う方法などが例示できる。
活性エネルギー線としては、紫外線が好適である。紫外線としては、波長が300~400nm、好ましくは310~360nmである。
すなわち、本発明の液晶表示素子においては、上記した手法により本発明の液晶配向処理剤から液晶配向膜付き基板を得た後、液晶セルを作製し、紫外線の照射及び加熱の少なくとも一方により重合性化合物を重合することで、液晶分子の配向を制御することができる。
重合性化合物の含有量は、液晶成分の100質量部に対して0.01~10質量部であることが好ましく、より好ましくは0.1~5質量部である。重合性化合物が0.01質量部未満であると、重合性化合物が重合せずに液晶の配向制御できなくなり、10質量部よりも多くなると、未反応の重合性化合物が多くなって液晶表示素子の焼き付き特性が低下する。
加えて、本発明の液晶配向処理剤は、電極を備えた一対の基板の間に液晶層を有してなり、前記一対の基板の間に活性エネルギー線及び熱の少なくとも一方により重合する重合性基を含む液晶配向膜を配置し、電極間に電圧を印加する工程を経て製造される液晶表示素子にも好ましく用いられる。
活性エネルギー線としては、紫外線が好適である。紫外線としては、波長が300~400nm、好ましくは310~360nmである。
活性エネルギー線及び熱の少なくとも一方により重合する重合性基を含む液晶配向膜を得るためには、この重合性基を含む化合物を液晶配向処理剤中に添加する方法や、重合性基を含む重合体成分を含有する方法が挙げられる。
本発明の液晶配向処理剤は、熱や紫外線の照射により、反応する2重結合部位を持つ特定化合物を含んでいるため、紫外線の照射及び加熱の少なくとも一方により、液晶分子の配向を制御することができる。
液晶セルを作製した後は、液晶セルに交流又は直流の電圧を印加しながら、熱や紫外線を照射することで、液晶分子の配向を制御することができる。
以上のようにして、本発明の液晶配向処理剤を用いて作製された液晶表示素子は、信頼性に優れたものとなり、大画面で高精細の液晶テレビなどに好適である。
合成例、実施例及び比較例で用いる化合物の略語は、以下の通りである。
(特定シラン化合物(成分(A))
A1:3-アミノプロピルジエトキシメチルシラン
A2:(3-グリシジルオキシプロピル)トリエトキシシラン
B1:3-ピコリルアミン
B2:1-(3-アミノプロピル)イミダゾール
(ジアミン化合物(式[2]のジアミン))
C1:1,3-ジアミノ-4-〔4-(トランス-4-n-ヘプチルシクロへキシル)フェノキシ〕ベンゼン(下記式[C1])
C2:1,3-ジアミノ-4-〔4-(トランス-4-n-ヘプチルシクロへキシル)フェノキシメチル〕ベンゼン(下記式[C2])
C3:1,3-ジアミノ-4-{4-〔トランス-4-(トランス-4-n-ペンチルシクロへキシル)シクロへキシル〕フェノキシ}ベンゼン(下記式[C3])
C4:下記式[C4]で示されるジアミン化合物
C5:3,5-ジアミノ安息香酸(下記式[C5])
C6:1,3-ジアミノ-4-オクタデシルオキシベンゼン(下記式[C6])
C7:下記式[C7]で示されるジアミン化合物
C8:p-フェニレンジアミン
C9:m-フェニレンジアミン
(テトラカルボン酸成分)
D1:1,2,3,4-シクロブタンテトラカルボン酸二無水物(下記式[D1])
D2:ビシクロ[3,3,0]オクタン-2,4,6,8-テトラカルボン酸二無水物(下記式[D2])
D3:下記式[D3]で示されるテトラカルボン酸二無水物
D4:下記式[D4]で示されるテトラカルボン酸二無水物
NMP:N-メチル-2-ピロリドン
NEP:N-エチル-2-ピロリドン
γ-BL:γ-ブチロラクトン
(溶媒(成分(E)))
PGME:プロピレングリコールモノメチルエーテル(式[E-1]で示される溶媒)
PCS:エチレングリコールモノプロピルエーテル(式[E-2]で示される溶媒)
DEEE:ジエチレングリコールモノエチルエーテル(式[E-3]で示される溶媒)
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)、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)。
ポリイミド粉末20mgをNMR(核磁気共鳴)サンプル管(NMRサンプリングチューブスタンダード,φ5(草野科学社製))に入れ、重水素化ジメチルスルホキシド(DMSO-d6,0.05質量%TMS(テトラメチルシラン)混合品)(0.53ml)を添加し、超音波をかけて完全に溶解させた。この溶液をNMR測定機(「JNW-ECA500」)(日本電子データム社製)にて500MHzのプロトンNMRを測定した。イミド化率は、イミド化前後で変化しない構造に由来するプロトンを基準プロトンとして決め、このプロトンのピーク積算値と、9.5~10.0ppm付近に現れるアミド酸のNH基に由来するプロトンピーク積算値とを用い以下の式によって求めた。
イミド化率(%)=(1-α・x/y)×100
上記式において、xはアミド酸のNH基由来のプロトンピーク積算値、yは基準プロトンのピーク積算値、αはポリアミド酸(イミド化率が0%)の場合におけるアミド酸のNH基プロトン1個に対する基準プロトンの個数割合である。
<合成例1>
D1(3.50g,17.8mmol)、C5(1.36g,8.94mmol)及びC8(0.96g,8.88mmol)をNMP(17.5g)中で混合し、40℃で8時間反応させ、25質量%のポリアミド酸溶液(1)を得た。このポリアミド酸の数平均分子量は、28,900、重量平均分子量は、82,100であった。
D2(10.4g,41.6mmol)、C5(4.53g,29.8mmol)及びC9(3.22g,29.8mmol)をNMP(35.7g)中で混合し、80℃で5時間反応させた後、D1(3.50g,17.8mmol)とNMP(29.2g)を加え、40℃で6時間反応させ、が25質量%のポリアミド酸溶液(2)を得た。このポリアミド酸の数平均分子量は、26,500、重量平均分子量は、77,400であった。
合成例2で得られたポリアミド酸溶液(2)(30.0g)に、NMPを加え6質量%に希釈した後、イミド化触媒として無水酢酸(3.75g)及びピリジン(2.85g)を加え、80℃で4時間反応させた。この反応溶液をメタノール(600ml)中に投入し、得られた沈殿物を濾別した。この沈殿物をメタノールで洗浄し、100℃で減圧乾燥しポリイミド粉末(3)を得た。このポリイミドのイミド化率は65%であり、数平均分子量は22,900、重量平均分子量は51,200であった。
D2(8.68g,34.7mmol)、C1(8.25g,21.7mmol)及びC5(3.30g,21.7mmol)をNEP(36.2g)中で混合し、80℃で5時間反応させた後、D1(1.70g,8.67mmol)とNEP(29.6g)を加え、40℃で8時間反応させ、が25質量%のポリアミド酸溶液(4)を得た。このポリアミド酸の数平均分子量は、24,200、重量平均分子量は、70,800であった。
合成例4で得られたポリアミド酸溶液(4)(30.0g)に、NEPを加え6質量%に希釈した後、イミド化触媒として無水酢酸(3.55g)及びピリジン(2.80g)を加え、80℃で4時間反応させた。この反応溶液をメタノール(700ml)中に投入し、得られた沈殿物を濾別した。この沈殿物をメタノールで洗浄し、100℃で減圧乾燥しポリイミド粉末(5)を得た。このポリイミドのイミド化率は56%であり、数平均分子量は19,900、重量平均分子量は44,200であった。
D2(2.81g,11.2mmol)、C2(3.54g,8.97mmol)、C5(0.68g,4.47mmol)、C7(1.37g,6.74mmol)及びC8(0.24g,2.22mmol)をNMP(17.9g)中で混合し、80℃で5時間反応させた後、D1(2.20g,11.2mmol)とNMP(14.6g)を加え、40℃で6時間反応させ、が25質量%のポリアミド酸溶液を得た。
得られたポリアミド酸溶液(30.0g)に、NMPを加え6質量%に希釈した後、イミド化触媒として無水酢酸(3.65g)及びピリジン(2.81g)を加え、80℃で4.5時間反応させた。この反応溶液をメタノール(700ml)中に投入し、得られた沈殿物を濾別した。この沈殿物をメタノールで洗浄し、100℃で減圧乾燥しポリイミド粉末(6)を得た。このポリイミドのイミド化率は60%であり、数平均分子量は18,600、重量平均分子量は42,300であった。
D2(1.15g,4.60mmol)、C3(2.98g,6.89mmol)、C7(1.87g,9.20mmol)及びC9(0.74g,6.84mmol)をNMP(17.1g)中で混合し、80℃で5時間反応させた後、D1(3.60g,18.4mmol)とNMP(14.0g)を加え、40℃で6時間反応させ、が25質量%のポリアミド酸溶液を得た。
得られたポリアミド酸溶液(30.0g)に、NMPを加え6質量%に希釈した後、イミド化触媒として無水酢酸(6.65g)及びピリジン(4.75g)を加え、90℃で3時間反応させた。この反応溶液をメタノール(900ml)中に投入し、得られた沈殿物を濾別した。この沈殿物をメタノールで洗浄し、100℃で減圧乾燥しポリイミド粉末(7)を得た。このポリイミドのイミド化率は81%であり、数平均分子量は18,200、重量平均分子量は40,500であった。
D2(4.02g,16.1mmol)、C4(1.70g,3.45mmol)及びC5(2.97g,19.5mmol)をNMP(16.6g)中で混合し、80℃で6時間反応させた後、D1(1.35g,6.88mmol)とNMP(13.5g)を加え、40℃で6時間反応させ、が25質量%のポリアミド酸溶液を得た。
得られたポリアミド酸溶液(30.0g)に、NMPを加え6質量%に希釈した後、イミド化触媒として無水酢酸(3.55g)及びピリジン(2.81g)を加え、80℃で4時間反応させた。この反応溶液をメタノール(700ml)中に投入し、得られた沈殿物を濾別した。この沈殿物をメタノールで洗浄し、100℃で減圧乾燥しポリイミド粉末(8)を得た。このポリイミドのイミド化率は52%であり、数平均分子量は16,300、重量平均分子量は39,000であった。
D2(2.68g,10.7mmol)、C5(0.33g,2.17mmol)、C6(3.23g,8.58mmol)及びC7(2.18g,10.7mmol)をNMP(17.3g)中で混合し、80℃で6時間反応させた後、D1(2.10g,10.7mmol)とNMP(14.2g)を加え、40℃で6時間反応させ、が25質量%のポリアミド酸溶液を得た。
得られたポリアミド酸溶液(30.0g)に、NMPを加え6質量%に希釈した後、イミド化触媒として無水酢酸(3.60g)及びピリジン(2.80g)を加え、80℃で4時間反応させた。この反応溶液をメタノール(700ml)中に投入し、得られた沈殿物を濾別した。この沈殿物をメタノールで洗浄し、100℃で減圧乾燥しポリイミド粉末(9)を得た。このポリイミドのイミド化率は55%であり、数平均分子量は17,900、重量平均分子量は40,200であった。
D3(5.00g,22.3mmol)、C3(2.89g,6.68mmol)及びC5(2.38g,15.6mmol)をNMP(30.9g)中で混合し、40℃で5時間反応させ、が25質量%のポリアミド酸溶液を得た。
得られたポリアミド酸溶液(30.0g)にNMPを加え、6質量%に希釈した後、イミド化触媒として無水酢酸(6.70g)及びピリジン(4.81g)を加え、90℃で3時間反応させた。この反応溶液をメタノール(900ml)中に投入し、得られた沈殿物を濾別した。この沈殿物をメタノールで洗浄し、100℃で減圧乾燥しポリイミド粉末(10)を得た。このポリイミドのイミド化率は78%であり、数平均分子量は17,900、重量平均分子量は39,900であった。
D3(5.00g,22.3mmol)、C4(2.20g,4.46mmol)、C5(1.02g,6.70mmol)、C7(1.36g,6.69mmol)及びC8(0.48g,4.44mmol)をNMP(30.2g)中で混合し、40℃で5時間反応させ、が25質量%のポリアミド酸溶液を得た。
得られたポリアミド酸溶液(30.0g)にNMPを加え、6質量%に希釈した後、イミド化触媒として無水酢酸(3.55g)及びピリジン(2.85g)を加え、80℃で4時間反応させた。この反応溶液をメタノール(700ml)中に投入し、得られた沈殿物を濾別した。この沈殿物をメタノールで洗浄し、100℃で減圧乾燥しポリイミド粉末(11)を得た。このポリイミドのイミド化率は53%であり、数平均分子量は18,000、重量平均分子量は40,900であった。
D4(6.89g,22.9mmol)、C1(8.73g,22.9mmol)、C7(2.80g,13.8mmol)及びC9(0.99g,9.15mmol)をNEP(39.5g)中で混合し、80℃で5時間反応させた後、D1(4.50g,22.9mmol)とNEP(32.3g)を加え、40℃で5時間反応させ、樹脂固形分濃度が25質量%のポリアミド酸溶液(12)を得た。このポリアミド酸の数平均分子量は、23,200、重量平均分子量は、66,200であった。
合成例12で得られたポリアミド酸溶液(12)(30.0g)に、NEPを加え6質量%に希釈した後、イミド化触媒として無水酢酸(3.65g)及びピリジン(2.90g)を加え、80℃で4時間反応させた。この反応溶液をメタノール(700ml)中に投入し、得られた沈殿物を濾別した。この沈殿物をメタノールで洗浄し、100℃で減圧乾燥しポリイミド粉末(13)を得た。このポリイミドのイミド化率は61%であり、数平均分子量は18,100、重量平均分子量は41,200であった。
D4(1.97g,6.56mmol)、C3(3.02g,7.65mmol)及びC5(2.16g,14.2mmol)をNMP(16.7g)中で混合し、80℃で5時間反応させた後、D1(3.00g,15.3mmol)とNMP(13.7g)を加え、40℃で5時間反応させ、が25質量%のポリアミド酸溶液を得た。
表1には、合成例で得られた(C)成分である特定重合体の合成に用いた各成分の組成、イミド化率等をまとめて示した。なお、表1のイミド化率の欄中の※1は、ポリアミド酸のため、イミド化率はないことを示す。
実施例1~20、及び比較例1~12は、液晶配向処理剤の製造例である。得られた液晶配向処理剤は、各種の特性評価にも使用した。
表2~表4には、各液晶配向処理剤の製造において用いた各成分の比率等を示す。
実施例及び比較例の液晶配向処理剤を用い、A:液晶配向処理剤の保存安定性試験の評価、B:液晶配向処理剤のインクジェット塗布性の評価、C:高温高湿保管前及び高温高湿保管後の額縁付近の表示ムラ特性の評価(通常液晶セル)、D:通常の液晶セルの作製直後及び高温高湿保管後の電圧保持率の評価(通常液晶セル)、及びE:PSA液晶セルの液晶配向性の評価を行った。
A:液晶配向処理剤の保存安定性試験の評価
実施例である、液晶配向処理剤(1)~(6)、(8)、(9)、(11)~(17)、(19)、(20)、及び比較例である、液晶配向処理剤(21)~(32)(以上比較例)のそれぞれを、細孔径1μmのメンブランフィルタで加圧濾過し、-15℃にて48時間保管した。その後、目視観察にて、液晶配向処理剤中の濁りや析出物の発生を確認した。
また、-15℃にて48時間保管した液晶配向処理剤を、純水及びIPAにて洗浄を行ったITO(酸化インジウムスズ)電極付き基板(縦40mm×横30mm、厚さ0.7mm)のITO面にスピンコートし、ホットプレート上にて100℃で5分間加熱処理をして、液晶配向膜付きのITO基板を作製した。得られた液晶配向膜付き基板のピンホールの評価を行った。
ピンホールの評価は、この基板をナトリウムランプの下で目視観察することで行った。具体的には、液晶配向膜付き基板上で観察されたピンホールの数を数え、ピンホールの数が少ないものほど、液晶配向処理剤中の析出物が少なく、本評価に優れるとした。
なお、表5、表6中の※11、※12は、「B:液晶配向処理剤のインクジェット塗布性の評価」の結果であり、これらについては、下記に説明するとともに、表8で改めて示す。
実施例である、液晶配向処理剤(7)、(10)、及び(18)のそれぞれを、細孔径1μmのメンブランフィルタで加圧濾過し、-15℃にて48時間保管した溶液を用いて、インクジェット塗布性の評価を行った。
インクジェット塗布機には、HIS-200(日立プラントテクノロジー社製)を用いた。
得られた液晶配向膜付き基板上のピンホールの数の評価を、「液晶配向処理剤の保存安定性試験」と同様の条件で行い、便宜的に、インクジェット塗布性の評価とした。
表8にピンホールの数(インクジェット塗布性)の評価結果を示す。
実施例である、液晶配向処理剤(1)~(20)、及び比較例である、液晶配向処理剤(21)~(32)のそれぞれを、細孔径1μmのメンブランフィルタで加圧濾過し、-15℃にて48時間保管した溶液を用いて、以下のように液晶セル(通常セル)を作製した。
なお、液晶配向処理剤(7)、(10)、及び(18)は、前記の液晶配向処理剤のインクジェット塗布性の評価と同様の方法で、液晶配向剤の塗布を行った。その際、液晶配向膜の焼成は、ホットプレート上にて100℃で5分間、熱循環型クリーンオーブンにて230℃で30分間加熱処理にて行い、膜厚が100nmのポリイミド液晶配向膜付きのITO基板を得た。
このITO基板の塗膜面を、ロール径が120mmのラビング装置でレーヨン布を用いて、ロール回転数が1000rpm、ロール進行速度が50mm/sec、押し込み量が0.1mmの条件でラビング処理した。
また、液晶配向処理剤(4)~(20)及び(27)~(32)を用いた液晶セルには、液晶にネマティック液晶(MLC-6608、メルク・ジャパン社製)を用いた。
その後、液晶セルを温度80℃、相対湿度90%の高温高湿槽内に144時間保管し、上記と同様の条件でシール剤付近の液晶配向性の評価を行った。具体的には、シール剤付近に液晶配向性の乱れが見られていないものほど、本評価に優れるとした。
表5~8に得られた高温高湿保管後の液晶配向性(液晶セルの額縁付近の表示ムラ特性)の評価結果を示す。
なお、表中、液晶配向性の乱れが見られなかったものを○とし、液晶配向性の乱れが見られたものを×とした。
実施例である、液晶配向処理剤(1)~(20)、及び比較例である、液晶配向処理剤(21)~(32)(以上比較例)のそれぞれを用いて、上記Cの「高温高湿保管後の液晶セルの額縁付近の表示ムラ特性の評価」と同様にして液晶セルを作製した。
さらに、電圧保持率の測定が終わった液晶セルを温度80℃、相対湿度90%の高温高湿槽内に48時間保管し、再度、上記と同様の条件で電圧保持率の測定を行った。
表5~表8に、液晶セルの作製直後、及び高温高湿保管後の電圧保持率の測定結果を示す。
実施例である、液晶配向処理剤(6)、(11)、及び(19)のそれぞれを、細孔径1μmのメンブランフィルタで加圧濾過し、-15℃にて48時間保管した溶液を用いて、液晶セルの作製及び液晶配向性の評価(PSAセル)を行った。
上記48時間保管した溶液を、純水及びIPAにて洗浄した中心に10mm×10mmのパターン間隔20μmのITO電極付き基板(縦40mm×横30mm、厚さ0.7mm)と中心に10mm×40mmのパターン間隔20μmのITO電極付き基板(縦40mm×横30mm、厚さ0.7mm)のITO面にスピンコートし、ホットプレート上にて100℃で5分間加熱処理をして、膜厚が100nmのポリイミド塗膜を得た。塗膜面を純水にて洗浄した後、熱循環型クリーンオーブン中にて100℃で15分間加熱処理をして、液晶配向膜付き基板を得た。
得られたPSAセルは、紫外線照射前の液晶セルの応答速度に比べて、紫外線照射後の液晶セルの応答速度が早くなっており、液晶の配向方向が制御されたことを確認できた。また、いずれの液晶セルとも、偏光顕微鏡(ECLIPSE E600WPOL、ニコン社製)での観察により、液晶は均一に配向していることを確認した。
以下に、実施例1~20及び比較例1~12について説明するが、各例における液晶配向処理剤の含有成分比率については、表2~表4にまとめて示した。なお、表2~表4における、※2~※10は、以下の意味を表す。※2、※5、※8は、特定重合体100質量部対する(A)成分の含有量を表し、※3、※6、※9は、特定重合体100質量部対する(B)成分の含有量を表し、※4、※7、※10は、液晶配向処理剤中の(A)成分、(B)成分及び(C)成分の合計含有量(質量%)を表す。
また、実施例1~20及び比較例1~12で得られた液晶配向処理剤を用いた上記A~Eの評価の結果は、表5~表8にまとめて示した。
合成例1で得られた25質量%のポリアミド酸溶液(1)(10.5g)に、NMP(18.0g)、BCS(15.9g)、A1の10質量%のNMP溶液(0.26g)及びB1の10質量%のNMP溶液(0.79g)を加え、50℃で15時間攪拌して、液晶配向処理剤(1)を得た。この液晶配向処理剤に、濁りや析出などの異常は見られず、均一な溶液であることが確認された。
合成例2で得られた25質量%のポリアミド酸溶液(2)(10.0g)に、NMP(15.0g)、PB(18.0g)、A2の10質量%のNMP溶液(1.25g)及びB1の10質量%のNMP溶液(0.75g)を加え、50℃で15時間攪拌して、液晶配向処理剤(2)を得た。この液晶配向処理剤に、濁りや析出などの異常は見られず、均一な溶液であることが確認された。
合成例3で得られたポリイミド粉末(3)(2.55g)に、NMP(20.6g)、BCS(7.00g)、PB(14.0g)、A1の10質量%のNMP溶液(1.28g)及びB2の10質量%のNMP溶液(1.28g)を加え、50℃で24時間攪拌して、液晶配向処理剤(3)を得た。この液晶配向処理剤に、濁りや析出などの異常は見られず、均一な溶液であることが確認された。
合成例4で得られた25質量%のポリアミド酸溶液(4)(10.0g)に、NEP(12.7g)、PB(20.6g)、A2の10質量%のNEP溶液(1.25g)及びB1の10質量%のNEP溶液(1.25g)を加え、50℃で15時間攪拌して、液晶配向処理剤(4)を得た。この液晶配向処理剤に、濁りや析出などの異常は見られず、均一な溶液であることが確認された。
合成例4で得られた25質量%のポリアミド酸溶液(4)(10.2g)に、NEP(15.3g)、BCS(4.63g)、PB(13.9g)、A2の10質量%のNEP溶液(1.79g)及びB2の10質量%のNEP溶液(0.51g)を加え、50℃で15時間攪拌して、液晶配向処理剤(5)を得た。この液晶配向処理剤に、濁りや析出などの異常は見られず、均一な溶液であることが確認された。
合成例5で得られたポリイミド粉末(5)(2.50g)に、NMP(7.35g)、NEP(12.9g)、PB(21.0g)、A1の10質量%のNMP溶液(1.75g)及びB1の10質量%のNEP溶液(1.25g)を加え、50℃で24時間攪拌して、液晶配向処理剤(6)を得た。この液晶配向処理剤に、濁りや析出などの異常は見られず、均一な溶液であることが確認された。
合成例5で得られたポリイミド粉末(5)(1.45g)に、NMP(8.11g)、NEP(14.2g)、PB(20.9g)、A1の10質量%のNMP溶液(1.02g)及びB1の10質量%のNEP溶液(0.73g)を加え、50℃で24時間攪拌して、液晶配向処理剤(7)を得た。この液晶配向処理剤に、濁りや析出などの異常は見られず、均一な溶液であることが確認された。
合成例6で得られたポリイミド粉末(6)(2.50g)に、NMP(18.1g)、PCS(8.80g)、BCS(8.73g)、PB(4.37g)、A1の10質量%のNMP溶液(0.50g)及びB2の10質量%のNMP溶液(0.75g)を加え、50℃で24時間攪拌して、液晶配向処理剤(8)を得た。この液晶配向処理剤に、濁りや析出などの異常は見られず、均一な溶液であることが確認された。
合成例7で得られたポリイミド粉末(7)(2.50g)に、γ-BL(15.9g)、DEEE(4.40g)、BCS(19.9g)、A2の10質量%のγ-BL溶液(1.25g)及びB1の10質量%のγ-BL溶液(0.25g)を加え、50℃で24時間攪拌して、液晶配向処理剤(9)を得た。この液晶配向処理剤に、濁りや析出などの異常は見られず、均一な溶液であることが確認された。
合成例7で得られたポリイミド粉末(7)(1.55g)に、γ-BL(23.3g)、PGME(9.30g)、PB(11.6g)、A2の10質量%のγ-BL溶液(0.47g)及びB1の10質量%のγ-BL溶液(0.31g)を加え、50℃で24時間攪拌して、液晶配向処理剤(10)を得た。この液晶配向処理剤に、濁りや析出などの異常は見られず、均一な溶液であることが確認された。
合成例8で得られたポリイミド粉末(8)(2.45g)に、NMP(7.37g)、NEP(14.7g)、PB(18.3g)、A1の10質量%のNMP溶液(1.72g)及びB1の10質量%のNEP溶液(1.23g)を加え、50℃で24時間攪拌して、液晶配向処理剤(11)を得た。この液晶配向処理剤に、濁りや析出などの異常は見られず、均一な溶液であることが確認された。
合成例9で得られたポリイミド粉末(9)(2.53g)に、NEP(18.2g)、BCS(22.9g)、A1の10質量%のNEP溶液(1.27g)及びB2の10質量%のNEP溶液(0.89g)を加え、50℃で24時間攪拌して、液晶配向処理剤(12)を得た。この液晶配向処理剤に、濁りや析出などの異常は見られず、均一な溶液であることが確認された。
合成例10で得られたポリイミド粉末(10)(2.50g)に、NMP(17.7g)、PCS(9.60g)、PB(14.4g)、A1の10質量%のNMP溶液(2.50g)及びB1の10質量%のNMP溶液(1.25g)を加え、50℃で24時間攪拌して、液晶配向処理剤(13)を得た。この液晶配向処理剤に、濁りや析出などの異常は見られず、均一な溶液であることが確認された。
合成例10で得られたポリイミド粉末(10)(2.50g)に、NEP(20.1g)、DEEE(4.70g)、PB(16.5g)、A2の10質量%のNEP溶液(2.50g)及びB2の10質量%のNEP溶液(0.75g)を加え、50℃で24時間攪拌して、液晶配向処理剤(14)を得た。この液晶配向処理剤に、濁りや析出などの異常は見られず、均一な溶液であることが確認された。
合成例11で得られたポリイミド粉末(11)(2.50g)に、γ-BL(20.3g)、PB(19.7g)、A1の10質量%のγ-BL溶液(0.75g)及びB1の10質量%のγ-BL溶液(0.50g)を加え、50℃で24時間攪拌して、液晶配向処理剤(15)を得た。この液晶配向処理剤に、濁りや析出などの異常は見られず、均一な溶液であることが確認された。
合成例12で得られた25質量%のポリアミド酸溶液(12)(10.0g)に、NEP(17.3g)、BCS(16.3g)、A2の10質量%のNEP溶液(1.75g)及びB1の10質量%のNEP溶液(1.25g)を加え、50℃で15時間攪拌して、液晶配向処理剤(16)を得た。この液晶配向処理剤に、濁りや析出などの異常は見られず、均一な溶液であることが確認された。
合成例13で得られたポリイミド粉末(13)(2.55g)に、NMP(7.67g)、NEP(15.3g)、PB(19.6g)、A2の10質量%のNMP溶液(2.55g)及びB2の10質量%のNEP溶液(1.28g)を加え、50℃で24時間攪拌して、液晶配向処理剤(17)を得た。この液晶配向処理剤に、濁りや析出などの異常は見られず、均一な溶液であることが確認された。
合成例13で得られたポリイミド粉末(13)(1.45g)に、NMP(8.33g)、NEP(16.7g)、PB(19.1g)、A2の10質量%のNMP溶液(1.45g)及びB2の10質量%のNEP溶液(0.73g)を加え、50℃で24時間攪拌して、液晶配向処理剤(18)を得た。この液晶配向処理剤に、濁りや析出などの異常は見られず、均一な溶液であることが確認された。
合成例14で得られたポリイミド粉末(14)(2.50g)に、NEP(20.2g)、BCS(11.7g)、PB(9.33g)、A1の10質量%のNEP溶液(1.75g)及びB1の10質量%のNEP溶液(1.25g)を加え、50℃で24時間攪拌して、液晶配向処理剤(19)を得た。この液晶配向処理剤に、濁りや析出などの異常は見られず、均一な溶液であることが確認された。
合成例14で得られたポリイミド粉末(14)(2.50g)に、NMP(18.0g)、PCS(4.50g)、BCS(18.0g)、A2の10質量%のNMP溶液(1.25g)及びB1の10質量%のNMP溶液(0.75g)を加え、50℃で24時間攪拌して、液晶配向処理剤(20)を得た。この液晶配向処理剤に、濁りや析出などの異常は見られず、均一な溶液であることが確認された。
合成例2で得られた25質量%のポリアミド酸溶液(2)(10.0g)に、NMP(15.0g)及びPB(16.7g)を加え、25℃で8時間攪拌して、液晶配向処理剤(21)を得た。この液晶配向処理剤に、濁りや析出などの異常は見られず、均一な溶液であることが確認された。
合成例2で得られた25質量%のポリアミド酸溶液(2)(10.5g)に、NMP(15.8g)、PB(18.0g)及びB1の10質量%のNMP溶液(0.79g)を加え、50℃で15時間攪拌して、液晶配向処理剤(22)を得た。この液晶配向処理剤に、濁りや析出などの異常は見られず、均一な溶液であることが確認された。
合成例2で得られた25質量%のポリアミド酸溶液(2)(10.5g)に、NMP(15.8g)、PB(18.4g)及びA2の10質量%のNMP溶液(1.31g)を加え、50℃で15時間攪拌して、液晶配向処理剤(23)を得た。この液晶配向処理剤に、濁りや析出などの異常は見られず、均一な溶液であることが確認された。
合成例3で得られたポリイミド粉末(3)(2.50g)に、NMP(20.4g)、BCS(6.27g)及びPB(12.5g)を加え、50℃で24時間攪拌して、液晶配向処理剤(24)を得た。この液晶配向処理剤に、濁りや析出などの異常は見られず、均一な溶液であることが確認された。
合成例3で得られたポリイミド粉末(3)(2.50g)に、NMP(20.3g)、BCS(6.57g)、PB(13.1g)及びB2の10質量%のNMP溶液(1.25g)を加え、50℃で24時間攪拌して、液晶配向処理剤(25)を得た。この液晶配向処理剤に、濁りや析出などの異常は見られず、均一な溶液であることが確認された。
合成例3で得られたポリイミド粉末(3)(2.50g)に、NMP(20.3g)、BCS(6.57g)、PB(13.1g)及びA1の10質量%のNMP溶液(1.25g)を加え、50℃で24時間攪拌して、液晶配向処理剤(26)を得た。この液晶配向処理剤に、濁りや析出などの異常は見られず、均一な溶液であることが確認された。
合成例4で得られた25質量%のポリアミド酸溶液(4)(11.0g)に、NEP(14.2g)及びPB(20.6g)を加え、25℃で8時間攪拌して、液晶配向処理剤(27)を得た。この液晶配向処理剤に、濁りや析出などの異常は見られず、均一な溶液であることが確認された。
合成例4で得られた25質量%のポリアミド酸溶液(4)(11.0g)に、NEP(14.1g)、PB(21.7g)及びB1の10質量%のNEP溶液(1.38g)を加え、50℃で15時間攪拌して、液晶配向処理剤(28)を得た。この液晶配向処理剤に、濁りや析出などの異常は見られず、均一な溶液であることが確認された。
合成例4の合成手法で得られた25質量%のポリアミド酸溶液(4)(11.5g)に、NEP(14.7g)、PB(22.6g)及びA2の10質量%のNEP溶液(1.44g)を加え、50℃で15時間攪拌して、液晶配向処理剤(29)を得た。この液晶配向処理剤に、濁りや析出などの異常は見られず、均一な溶液であることが確認された。
合成例5で得られたポリイミド粉末(5)(2.55g)に、NMP(7.56g)、NEP(13.2g)及びPB(19.1g)を加え、50℃で24時間攪拌して、液晶配向処理剤(30)を得た。この液晶配向処理剤に、濁りや析出などの異常は見られず、均一な溶液であることが確認された。
合成例5で得られたポリイミド粉末(5)(2.55g)に、NMP(7.56g)、NEP(13.2g)、PB(20.1g)及びB1の10質量%のNEP溶液(1.28g)を加え、50℃で24時間攪拌して、液晶配向処理剤(31)を得た。この液晶配向処理剤に、濁りや析出などの異常は見られず、均一な溶液であることが確認された。
合成例5で得られたポリイミド粉末(5)(2.55g)に、NMP(7.56g)、NEP(13.2g)、PB(20.1g)及びA1の10質量%のNEP溶液(1.79g)を加え、50℃で24時間攪拌して、液晶配向処理剤(32)を得た。この液晶配向処理剤に、濁りや析出などの異常は見られず、均一な溶液であることが確認された。
また、実施例の液晶配向処理剤を用いることにより、液晶セルを高温高湿下で、長期間保管しても、液晶セルのシール剤付近の液晶配向性が乱れない液晶配向膜が得られた。さらに、液晶セルを高温高湿下で長期間保管しても、電圧保持率の低下を抑制することができる液晶配向膜が得られた。
すなわち、本発明の液晶配向処理剤は、保存安定性に優れ、かつ、高温高湿条件下において、液晶表示素子の額縁付近の表示ムラの発生と電圧保持率の低下を抑制することができる液晶配向膜の形成を可能とすることが分かった。
さらに、本発明の液晶配向処理剤から得られた液晶配向膜は、表示素子を作製する際に、紫外線を照射する必要がある液晶表示素子の作製においても有用である。
Claims (16)
- 下記の成分(A)、成分(B)及び成分(C)を含有することを特徴とする液晶配向処理剤。
成分(A):下記の式[a]で示されるシラン化合物。
成分(B):分子内にアミノ基を1個と窒素含有芳香族複素環とを有し、かつ前記アミノ基が2価の脂肪族炭化水素基又は非芳香族環式炭化水素基に結合しているアミン化合物。
成分(C):ジアミン成分とテトラカルボン酸成分とを反応させて得られるポリイミド前駆体及び前記ポリイミド前駆体をイミド化した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。
- 前記式[a]A1が有する基が、エポキシ基、アミノ基、メタクリル基又はアクリル基である請求項1に記載の液晶配向処理剤。
- 前記成分(C)の重合体におけるジアミン成分が、下記の式[2]で示される構造のジアミン化合物を含む請求項1~4のいずれか一項に記載の液晶配向処理剤。
- 成分(D)として、N-メチル-2-ピロリドン、N-エチル-2-ピロリドン及びγ-ブチロラクトンからなる群から選ばれる少なくとも1つの溶媒を含有する請求項1~6のいずれか一項に記載の液晶配向処理剤。
- 成分(F)として、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及びエチレングリコールモノブチルエーテルからなる群から選ばれる少なくとも1つの溶媒を含有する請求項1~8のいずれか一項に記載の液晶配向処理剤。
- 請求項1~9のいずれか一項に記載の液晶配向処理剤を用いて得られる液晶配向膜。
- 請求項1~9のいずれか一項に記載の液晶配向処理剤を用いて、インクジェット法にて得られる液晶配向膜。
- 請求項10又は11に記載の液晶配向膜を有する液晶表示素子。
- 電極を備えた一対の基板の間に液晶層を有してなり、前記一対の基板の間に活性エネルギー線及び熱の少なくとも一方により重合する重合性化合物を含む液晶組成物を配置し、前記電極間に電圧を印加しつつ、前記重合性化合物を重合させる工程を経て製造される液晶表示素子に用いられる請求項10又は11に記載の液晶配向膜。
- 請求項13に記載の液晶配向膜を有する液晶表示素子。
- 電極を備えた一対の基板の間に液晶層を有してなり、前記一対の基板の間に活性エネルギー線及び熱の少なくとも一方により重合する重合性基を含む液晶配向膜を配置し、前記電極間に電圧を印加しつつ、前記重合性基を重合させる工程を経て製造される液晶表示素子に用いられることを特徴とする請求項10又は11に記載の液晶配向膜。
- 請求項13に記載の液晶配向膜を有する液晶表示素子。
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