WO2011132752A1 - 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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- WO2011132752A1 WO2011132752A1 PCT/JP2011/059868 JP2011059868W WO2011132752A1 WO 2011132752 A1 WO2011132752 A1 WO 2011132752A1 JP 2011059868 W JP2011059868 W JP 2011059868W WO 2011132752 A1 WO2011132752 A1 WO 2011132752A1
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- liquid crystal
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- carbon atoms
- fluorine
- aligning agent
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- 0 *C(c1cc(N)cc(N)c1)O* Chemical compound *C(c1cc(N)cc(N)c1)O* 0.000 description 5
- LPXMMWJBPSYBHF-UHFFFAOYSA-N O=CC(C(C12)C1(CC(C1)=O)C1=O)OC2=O Chemical compound O=CC(C(C12)C1(CC(C1)=O)C1=O)OC2=O LPXMMWJBPSYBHF-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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1042—Copolyimides derived from at least two different tetracarboxylic compounds or two different diamino compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1075—Partially aromatic polyimides
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1075—Partially aromatic polyimides
- C08G73/1078—Partially aromatic polyimides wholly aromatic in the diamino moiety
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
- C08L79/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
- C08L79/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
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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
- G02F1/13378—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers by treatment of the surface, e.g. embossing, rubbing or light irradiation
- G02F1/133788—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers by treatment of the surface, e.g. embossing, rubbing or light irradiation by light irradiation, e.g. linearly polarised light photo-polymerisation
Definitions
- the present invention relates to a liquid crystal alignment treatment agent used for producing a liquid crystal alignment film and a liquid crystal display element using the same.
- an MVA (Multi-domain Vertical Alignment) mode that provides a wide viewing angle is known.
- MVA mode a liquid crystal having negative dielectric anisotropy, a liquid crystal alignment film for vertically aligning the liquid crystal, and an alignment control structure for controlling the alignment direction of the liquid crystal are used.
- the liquid crystal is tilted in a vertical direction along the alignment control structure.
- the aperture ratio is lower than that of the TN mode or the like, and the light transmittance from the backlight is lowered.
- Patent Document 1 a method of controlling the alignment direction of the liquid crystal during driving using a polymer.
- a liquid crystal material in which a liquid crystal is mixed with a polymerizable compound (also referred to as a monomer) that is polymerized by heat or ultraviolet irradiation is used.
- a polymer is formed by polymerizing a monomer by heat or ultraviolet irradiation under a state in which liquid crystal molecules are inclined by applying a voltage between substrates.
- pretilt angle a predetermined tilt angle
- the liquid crystal alignment film used in this method needs to be more reliable than the conventional MVA mode. Therefore, the electrical characteristics of the liquid crystal alignment film, that is, the voltage holding ratio, are required not only to have good initial characteristics, but also to be difficult to decrease even after heat or ultraviolet irradiation. When this voltage holding ratio is greatly reduced, line burn-in, which is a display defect of the liquid crystal display element, is likely to occur, and a highly reliable liquid crystal display element cannot be obtained.
- the present invention has been made in view of the above circumstances, and the problem is that polymerization is performed while applying a voltage to a liquid crystal layer using a liquid crystal material in which a polymerizable compound that is polymerized by heat or ultraviolet irradiation is mixed with liquid crystal.
- Liquid crystal alignment treatment with excellent reliability that does not decrease the voltage holding ratio even with heat or ultraviolet irradiation in a liquid crystal display element obtained by polymerizing a photosensitive compound and controlling the alignment direction of the liquid crystal during driving It is in providing an agent, a liquid crystal aligning film, and a liquid crystal display element.
- a liquid crystal alignment treatment agent comprising at least one of a polyimide precursor having a specific side chain structure and a polyimide obtained by dehydrating and ring-closing the polyimide precursor is The present invention has been found to be extremely effective for achieving the above.
- the present invention has the following gist.
- Liquid crystal alignment treatment used for a liquid crystal display device obtained by a method for controlling the alignment direction and containing a polyimide precursor having a side chain represented by the following formula [1] and at least one polymer of polyimides Agent.
- X 1 is —O—, —CH 2 O—, —COO—, — (CH 2 ) a — (a is an integer of 1 to 10), —NH—, —N (X 3 is a divalent organic group selected from CH 3 ) —, —CONH—, —NHCO—, —OCO—, —CON (CH 3 ) —, —N (CH 3 ) CO—, or a single bond.
- a valent cyclic group or a divalent organic group having 12 to 25 carbon atoms having a steroid skeleton, and an arbitrary hydrogen atom on these cyclic groups is an alkyl group having 1 to 3 carbon atoms, 3 may be substituted with an alkoxyl
- X 1 is —O—, —CH 2 O—, —COO—, — (CH 2 ) a — (a is an integer of 1 to 10), —NH—, —N (X 3 is a divalent organic group selected from CH 3 ) —, —CONH—, —NHCO—, —OCO—, —CON (CH 3 ) —, —N (CH 3 ) CO—, or a single bond.
- X 3 is a single bond, — (CH 2 ) c — (c is 1 Is an integer of ⁇ 10), —O—, —NH—, —N (CH 3 ) —, —CONH—, —NHCO—, —CH 2 O—, —COO—, —OCO—, —CON (CH 3 ) — or a divalent organic group selected from —N (CH 3 ) CO—
- X 4 is selected from a benzene ring, a cyclohexyl ring, or a heterocyclic ring.
- X 5 is a cyclohexyl ring, benzene, or an alkenyl group, a fluorine-containing alkyl group having 1 to 3 carbon atoms, a fluorine-containing alkoxyl group having 1 to 3 carbon atoms, or a fluorine atom.
- a divalent cyclic group selected from a ring or a heterocyclic ring, and an arbitrary hydrogen atom on these cyclic groups is an alkyl group having 1 to 3 carbon atoms, an alkoxyl group having 1 to 3 carbon atoms, or 1 to 3 carbon atoms 3 is a fluorine-containing alkyl group, or a fluorine-containing alkoxyl group having 1 to 3 carbon atoms, which may be substituted with one selected from fluorine atoms, n is an integer of 0 to 4, and X 6 is 1 to 3 carbon atoms.
- alkyl groups 1 to carbon atoms 8 fluorine-containing alkyl group, an alkoxyl group having 1 to 18 carbon atoms, a fluorine-containing alkoxyl group or a hydrogen atom having 1 to 18 carbon atoms, m is an integer of 1-4).
- Y 1 is a tetravalent organic group having 4 to 13 carbon atoms and contains a non-aromatic cyclic hydrocarbon group having 4 to 6 carbon atoms).
- Y 2 to Y 5 are groups selected from a hydrogen atom, a methyl group, a chlorine atom, or a benzene ring, which may be the same or different, and in Formula [2g] Y 6 and Y 7 are a hydrogen atom or a methyl group, and may be the same or different.
- the liquid crystal aligning agent of description a crosslinkable compound having at least one substituent selected from the group consisting of an epoxy group, an oxetane group, an isocyanate group and a cyclocarbonate group, a hydroxyl group, a hydroxyalkyl group, an alkoxyl group, and Any one of the above (1) to (6) having a crosslinkable compound having at least one substituent selected from the group consisting of lower alkoxyalkyl groups or a crosslinkable compound
- liquid crystal aligning agent according to any one of (1) to (7) above, wherein the polymer in the liquid crystal aligning agent is a polyimide obtained by dehydrating and ring-closing polyamic acid.
- liquid crystal aligning agent according to any one of (1) to (8), wherein the liquid crystal aligning agent contains 5 to 60% by mass of a poor solvent.
- liquid crystal alignment treatment agent of the present invention it is possible to obtain a liquid crystal alignment film that does not decrease the voltage holding ratio even under heat or ultraviolet irradiation, and the liquid crystal display element having this liquid crystal alignment film has excellent reliability. It becomes.
- the present invention is a polymer obtained by polymerizing a liquid crystal layer by applying a voltage to a liquid crystal layer using a liquid crystal material in which a polymerizable compound that is polymerized by heat or ultraviolet irradiation is mixed with the liquid crystal.
- the liquid crystal aligning agent used for the liquid crystal display element obtained by the method of controlling, the liquid crystal aligning film obtained using this liquid crystal aligning agent, and also the liquid crystal display element which has this liquid crystal aligning film.
- the liquid-crystal aligning agent in this invention is at least 1 type (generic name) chosen from the polyimide precursor obtained by reaction of a diamine component and tetracarboxylic dianhydride, and the polyimide obtained by carrying out dehydration ring closure of this polyimide precursor. And also referred to as a polymer).
- the polymer of the present invention that is, at least one selected from the polyimide precursor obtained by the reaction of the diamine component and tetracarboxylic dianhydride and the polyimide obtained by dehydrating and ring-closing the polyimide precursor has the following formula: It has a side chain (also referred to as a specific side chain structure) represented by [1].
- X 1 is —O—, —CH 2 O—, —COO—, — (CH 2 ) a — (a is an integer of 1 to 10), —NH—, —N (X 3 is a divalent organic group selected from CH 3 ) —, —CONH—, —NHCO—, —OCO—, —CON (CH 3 ) —, —N (CH 3 ) CO—, or a single bond.
- a divalent cyclic group selected from a ring or a heterocyclic ring, and an arbitrary hydrogen atom on these cyclic groups is an alkyl group having 1 to 3 carbon atoms, an alkoxyl group having 1 to 3 carbon atoms, or 1 to 3 carbon atoms 3 may be substituted with one selected from a fluorine-containing alkyl group, a fluorine-containing alkoxyl group having 1 to 3 carbon atoms, and a fluorine atom, n is an integer of 0 to 4, and X 6 has 1 to 18 carbon atoms.
- Alkyl group having 1 to 18 carbon atoms Fluorine-containing alkyl group, an alkoxyl group having 1 to 18 carbon atoms, a fluorine-containing alkoxyl group or a hydrogen atom having 1 to 18 carbon atoms).
- the specific side chain structure of the present invention has a cyclic group selected from a benzene ring, a cyclohexyl ring and a heterocyclic ring, or a steroid skeleton in the side chain portion.
- the specific side chain structure of the present invention is a structure represented by the following formula [1].
- X 1 is a single bond, — (CH 2 ) a — (a is an integer of 1 to 10), —O—, —NH—, —N (CH 3 ) —, —CONH— , —NHCO—, —CH 2 O—, —COO—, —OCO—, —CON (CH 3 ) —, or —N (CH 3 ) CO—.
- a single bond, — (CH 2 ) a — (a is an integer of 1 to 10), —O—, —CONH—, —CH 2 O—, or —COO— synthesizes a side chain structure. It is preferable because it is easy to do.
- it is a single bond, — (CH 2 ) a — (a is an integer of 1 to 10), —O—, —CONH—, —CH 2 O—, or —COO—. More preferably, it is a single bond, — (CH 2 ) a — (a is an integer of 1 to 10), —O—, —CH 2 O—, or —COO—.
- X 2 is a single bond or a divalent organic group selected from — (CH 2 ) b — (b is an integer of 1 to 10). Among these, a single bond or — (CH 2 ) b — (b is an integer of 1 to 10) is preferable.
- X 3 is a single bond, — (CH 2 ) c — (c is an integer of 1 to 10), —O—, —NH—, —N (CH 3 ) —, —CONH— , —NHCO—, —CH 2 O—, —COO—, —OCO—, —CON (CH 3 ) —, or —N (CH 3 ) CO—.
- a single bond, — (CH 2 ) c — (c is an integer of 1 to 10), —O—, —CH 2 O—, —COO—, or —OCO— is preferable because they are easy to synthesize.
- they are a single bond, — (CH 2 ) c — (c is an integer of 1 to 10), —O—, —CH 2 O—, —COO—, or —OCO—.
- X 4 represents a divalent cyclic group selected from a benzene ring, a cyclohexyl ring, or a heterocyclic ring, or a divalent organic group having 12 to 25 carbon atoms and having a steroid skeleton.
- Arbitrary hydrogen atom on the cyclic group is an alkyl group having 1 to 3 carbon atoms, an alkoxyl group having 1 to 3 carbon atoms, a fluorine-containing alkyl group having 1 to 3 carbon atoms, or a fluorine-containing alkoxyl group having 1 to 3 carbon atoms And may be substituted with one selected from fluorine atoms.
- a benzene ring, a cyclohexyl ring, that is, a phenylene group, a cyclohexylene group, or an organic group having 12 to 25 carbon atoms having a steroid skeleton is preferable.
- X 5 represents a divalent cyclic group selected from a benzene ring, a cyclohexyl ring, or a heterocyclic ring, and an arbitrary hydrogen atom on these cyclic groups is an alkyl having 1 to 3 carbon atoms.
- a benzene ring or a cyclohexyl ring is preferable.
- X 6 represents a hydrogen atom or 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 atom having 1 to 18 carbon atoms.
- An alkoxyl group Among these, 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.
- it is an alkyl group having 1 to 12 carbon atoms or an alkoxyl group having 1 to 12 carbon atoms. More preferably, it is an alkyl group having 1 to 9 carbon atoms or an alkoxyl group having 1 to 9 carbon atoms.
- n is an integer of 0 to 4. Preferably, it is an integer of 0-2.
- Preferred combinations of X 1 , X 2 , X 3 , X 4 , X 5 , X 6 , and n in Formula [1] are as shown in 1-1 to 1-629 shown in Tables 1 to 42 below.
- the polymer of the present invention that is, a specific side chain structure as at least one selected from a polyimide precursor obtained by reaction of a diamine component and tetracarboxylic dianhydride and a polyimide obtained by dehydrating and ring-closing the polyimide precursor
- a diamine compound represented by the following formula [1a] also referred to as a specific diamine compound
- X 1 is a single bond, — (CH 2 ) a — (a is an integer of 1 to 10), —O—, —NH—, —N (CH 3 ) —, —CONH— , —NHCO—, —CH 2 O—, —COO—, —OCO—, —CON (CH 3 ) —, or —N (CH 3 ) CO—.
- a single bond, — (CH 2 ) a — (a is an integer of 1 to 10), —O—, —CONH—, —CH 2 O—, or —COO— synthesizes a side chain structure. It is preferable because it is easy to do.
- it is a single bond, — (CH 2 ) a — (a is an integer of 1 to 10), —O—, —CONH—, —CH 2 O—, or —COO—. More preferably, it is a single bond, — (CH 2 ) a — (a is an integer of 1 to 10), —O—, —CH 2 O—, or —COO—.
- X 2 is a single bond or a divalent organic group selected from — (CH 2 ) b — (b is an integer of 1 to 10). Among these, a single bond or — (CH 2 ) b — (b is an integer of 1 to 10) is preferable.
- X 3 is a single bond, — (CH 2 ) c — (c is an integer of 1 to 10), —O—, —NH—, —N (CH 3 ) —, —CONH— , —NHCO—, —CH 2 O—, —COO—, —OCO—, —CON (CH 3 ) —, or —N (CH 3 ) CO—.
- a single bond, — (CH 2 ) c — (c is an integer of 1 to 10), —O—, —CH 2 O—, —COO—, or —OCO— is preferable because they are easy to synthesize.
- they are a single bond, — (CH 2 ) c — (c is an integer of 1 to 10), —O—, —CH 2 O—, —COO—, or —OCO—.
- X 4 represents a divalent cyclic group selected from a benzene ring, a cyclohexyl ring, or a heterocyclic ring, or a divalent organic group having 12 to 25 carbon atoms and having a steroid skeleton
- Arbitrary hydrogen atom on the cyclic group is an alkyl group having 1 to 3 carbon atoms, an alkoxyl group having 1 to 3 carbon atoms, a fluorine-containing alkyl group having 1 to 3 carbon atoms, or a fluorine-containing alkoxyl group having 1 to 3 carbon atoms
- an organic group having 12 to 25 carbon atoms having a benzene ring, a cyclohexyl ring or a steroid skeleton is preferable.
- X 5 represents a divalent cyclic group selected from a benzene ring, a cyclohexyl ring, or a heterocyclic ring, and an arbitrary hydrogen atom on these cyclic groups is an alkyl having 1 to 3 carbon atoms.
- a benzene ring or a cyclohexyl ring is preferable.
- X 6 represents a hydrogen atom or 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 atom having 1 to 18 carbon atoms.
- An alkoxyl group Among these, 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.
- it is an alkyl group having 1 to 12 carbon atoms or an alkoxyl group having 1 to 12 carbon atoms. More preferably, it is an alkyl group having 1 to 9 carbon atoms or an alkoxyl group having 1 to 9 carbon atoms.
- n is an integer of 0 to 4. Preferably, it is an integer of 0-2.
- m is an integer of 1 to 4. Preferably, it is an integer of 1 to 2.
- the structure is represented by the following formula [1a-1] to [1a-32].
- R 1 represents —O—, —OCH 2 —, —CH 2 O—, —COOCH 2 —, —CH 2 OCO—
- R 2 Is an alkyl group having 1 to 22 carbon atoms, an alkoxy group, a fluorine-containing alkyl group or a fluorine-containing alkoxy group).
- R 3 represents —COO—, —OCO—, —CONH—, —NHCO—, —COOCH 2 —, —CH 2 OCO—, —CH 2 O—, —OCH 2 —, or —CH 2 —, wherein R 4 is 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—, —CONH—, —NHCO—, —COOCH 2 —, —CH 2 OCO—, —CH 2 O—, —OCH 2 —, —CH 2 —, —O—, or —NH—, wherein R 6 is fluorine, cyano, trifluoromethane, nitro, azo, formyl, acetyl, acetoxy Group or hydroxyl group).
- R 7 is an alkyl group having 3 to 12 carbon atoms, and the cis-trans isomerism of 1,4-cyclohexylene is a trans isomer. is there).
- R 8 is an alkyl group having 3 to 12 carbon atoms, and the cis-trans isomerism of 1,4-cyclohexylene is a trans isomer. is there).
- a 4 is an alkyl group having 3 to 20 carbon atoms which may be substituted with a fluorine atom
- a 3 is a 1,4-cyclohexylene group or 1, 4 -Phenylene group
- a 2 is an oxygen atom or —COO— * (where a bond marked with “*” is bonded to A 3 )
- a 1 is an oxygen atom or —COO— * (However, the bond marked with “*” binds to (CH 2 ) a 2.
- a 1 is an integer of 0 or 1
- a 2 is an integer of 2 to 10.
- a 3 is an integer of 0 or 1).
- diamines having an alkyl group or a fluorine-containing alkyl group in the diamine side chain can be exemplified, and specific examples include diamines represented by the following formulas [DA1] to [DA12].
- a 1 is 1 or more carbon atoms 22 an alkyl group, or a fluorine-containing alkyl group).
- a 2 represents —COO—, —OCO—, —CONH—, —NHCO—, —CH 2 —, —O—, —CO—, or —NH—.
- a 3 represents an alkyl group having 1 to 22 carbon atoms or a fluorine-containing alkyl group).
- p is an integer of 1 to 10).
- the above-mentioned other diamine compounds may be used alone or in combination of two or more depending on the properties such as liquid crystal orientation, voltage holding ratio, and accumulated charge when the liquid crystal alignment film is used.
- tetracarboxylic dianhydride represented by the following formula [2] (also referred to as a specific tetracarboxylic dianhydride) as a part of the raw material.
- Y 1 is a tetravalent organic group having 4 to 13 carbon atoms and contains a non-aromatic cyclic hydrocarbon group having 4 to 6 carbon atoms.
- Y 1 is a tetravalent group represented by, for example, the following formulas [2a] to [2j].
- Y 2 to Y 5 are groups selected from a hydrogen atom, a methyl group, a chlorine atom, or a benzene ring, which may be the same or different, and in the formula [2g], Y 2 6 and Y 7 are a hydrogen atom or a methyl group, and may be the same or different.
- Y 1 particularly preferred structure of Y 1 is represented by formula [2a], formula [2c], formula [2d], formula [2e], formula [2f], or from the viewpoint of polymerization reactivity and ease of synthesis.
- Formula [2g] particularly preferred structure of Y 1 is represented by formula [2a], formula [2c], formula [2d], formula [2e], formula [2f], or from the viewpoint of polymerization reactivity and ease of synthesis.
- the above-mentioned other tetracarboxylic dianhydrides can be used alone or in combination of two or more depending on the properties such as liquid crystal alignment properties, voltage holding ratio, accumulated charge, etc. when the liquid crystal alignment film is formed.
- the polymer used in the present invention is a polyimide precursor having a specific side chain structure represented by the above formula [1] or a polyimide obtained by dehydrating and ring-closing the polyimide precursor.
- the method for synthesizing the polymer of the present invention is not particularly limited, but a method of reacting a diamine component with tetracarboxylic dianhydride, as in a general polyimide precursor (for example, polyamic acid) or polyimide synthesis method. Can be used. At that time, tetracarboxylic acid derivatives such as tetracarboxylic acid or tetracarboxylic acid dihalide can also be used.
- the liquid crystal alignment film obtained by using the polymer of the present invention can obtain a liquid crystal alignment film whose voltage holding ratio does not decrease even with heat or ultraviolet irradiation as the content ratio of the specific diamine compound in the diamine component increases.
- the liquid crystal display element having this liquid crystal alignment film is excellent in reliability.
- the diamine component is a specific diamine compound.
- 5 mol% or more of a diamine component is a specific diamine compound, More preferably, it is 10 mol% or more.
- 100 mol% of a diamine component may be a specific diamine compound, from the viewpoint of uniform coatability when applying a liquid crystal aligning agent, the specific diamine compound is preferably 80 mol% or less of the diamine component. Preferably it is 40 mol% or less.
- the specific tetracarboxylic dianhydride represented by the above formula [2] is used as the tetracarboxylic dianhydride.
- 1 mol% or more of tetracarboxylic dianhydrides are specific tetracarboxylic dianhydrides.
- 5 mol% or more of the tetracarboxylic dianhydride is a specific tetracarboxylic dianhydride, and more preferably 10 mol% or more.
- specific tetracarboxylic dianhydride may be sufficient as 100 mol% of tetracarboxylic dianhydride.
- the polyimide precursor of the present invention by a reaction between a diamine component and tetracarboxylic dianhydride, a known synthesis method can be used.
- the diamine component and tetracarboxylic dianhydride are reacted in an organic solvent.
- the reaction between the diamine component and tetracarboxylic dianhydride is advantageous in that it proceeds relatively easily in an organic solvent and no by-products are generated.
- the organic solvent used for the reaction between the diamine component and tetracarboxylic dianhydride is not particularly limited as long as the generated polyimide precursor is soluble. Specific examples are given below.
- the solution in which the diamine component is dispersed or dissolved in the organic solvent is stirred, and the tetracarboxylic dianhydride is used as it is or in an organic solvent.
- a method of adding by dispersing or dissolving a method of adding a diamine component to a solution in which tetracarboxylic dianhydride is dispersed or dissolved in an organic solvent, and alternately adding a tetracarboxylic dianhydride and a diamine component. Any of these methods may be used.
- the diamine component or tetracarboxylic dianhydride when they are composed of a plurality of types of compounds, they may be reacted in a premixed state, may be individually reacted sequentially, or may be further reacted individually. May be mixed and reacted to form a high molecular weight product.
- the polymerization temperature at that time can be selected from -20 ° C. to 150 ° C., but is preferably in the range of ⁇ 5 ° C. to 100 ° C.
- the reaction can be carried out at any concentration, but if the concentration is too low, it will be difficult to obtain a high molecular weight copolymer, and if the concentration is too high, the viscosity of the reaction solution will become too high and uniform stirring will occur. Since it becomes difficult, 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 and the total number of moles of tetracarboxylic dianhydride 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 dehydrating and ring-closing the polyamic acid which is the polyimide precursor, and is useful as a polymer for obtaining a liquid crystal alignment film.
- the dehydration cyclization rate (imidation rate) of the amic acid group is not necessarily 100%, and can be arbitrarily adjusted according to the application and purpose.
- Examples of the method for imidizing the polyimide precursor include thermal imidization in which the polyimide precursor solution is heated as it is, and catalyst imidization in which a catalyst is added to the polyimide precursor solution.
- the temperature is 100 ° C. to 400 ° C., preferably 120 ° C. to 250 ° C., and it is preferable to carry out while removing water generated by the imidation reaction from the system.
- the catalyst imidation of the polyimide precursor can be performed 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 of the amic acid group, and the amount of the acid anhydride is 1 to 50 mol times, preferably 3 to 30 mol of the amido acid group. Is double.
- the basic catalyst include pyridine, triethylamine, trimethylamine, tributylamine, trioctylamine and the like. Among them, pyridine is preferable because it has an appropriate basicity for proceeding with the reaction.
- Examples of the acid anhydride include acetic anhydride, trimellitic anhydride, pyromellitic anhydride, and the like. Among them, use of acetic anhydride is preferable because purification after completion of the reaction is facilitated.
- the 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 poor solvent and precipitated.
- the poor solvent used for precipitation include methanol, acetone, hexane, butyl cellosolve, heptane, methyl ethyl ketone, methyl isobutyl ketone, ethanol, toluene, benzene, and water.
- the polymer precipitated in a poor solvent and collected by filtration can be dried by normal temperature or reduced pressure at room temperature or by heating.
- the polymer collected by precipitation is redissolved in an organic solvent and reprecipitation and collection is repeated 2 to 10 times, impurities in the polymer can be reduced.
- the poor solvent at this time include alcohols, ketones, hydrocarbons and the like, and it is preferable to use three or more kinds of poor solvents selected from these because purification efficiency is further improved.
- the molecular weight of the polyimide precursor or polyimide contained in the liquid crystal aligning agent of the present invention is determined by considering the strength of the coating film obtained therefrom, the workability at the time of coating film formation, and the uniformity of the coating film.
- the weight average molecular weight measured by Gel Permeation Chromatography is preferably 5,000 to 1,000,000, and more preferably 10,000 to 150,000.
- the liquid crystal aligning agent of this invention is a coating liquid for forming a liquid crystal aligning film, and is a solution which the resin component for forming a resin film melt
- the resin component includes the above-described polymer of the present invention, that is, the resin component containing at least one polymer selected from the polyimide precursor having the specific side chain structure represented by the formula [1] and the polyimide. It is. In that case, the content of the resin component is preferably 1% by mass to 20% by mass, more preferably 3% by mass to 15% by mass, and particularly preferably 3% by mass to 10% by mass.
- all of the resin components may be the polymer of the present invention, and other polymers may be mixed with the polymer of the present invention.
- the content of the resin component other than the polymer of the present invention is 0.5 to 15% by mass, preferably 1 to 10% by mass.
- polyimide precursors or polyimides that do not have a specific side chain structure examples include polyimide precursors or polyimides that do not have a specific side chain structure.
- a crosslinkable compound that is a compound that crosslinks a polymer for the purpose of obtaining a liquid crystal alignment film whose voltage holding ratio does not decrease even under heat or ultraviolet irradiation
- 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, and tetraglycidyl.
- the crosslinkable compound having an oxetane group is a crosslinkable compound having at least two oxetane groups represented by the following formula [3].
- Examples of the crosslinkable compound having at least one substituent selected from the group consisting of a hydroxyl group, a hydroxyalkyl group and a lower alkoxyalkyl group include an amino resin having a hydroxyl group, an alkoxyl group or a lower alkoxyalkyl group, such as melamine Examples thereof include resins, urea resins, guanamine resins, glycoluril-formaldehyde resins, succinylamide-formaldehyde resins, and ethyleneurea-formaldehyde resins.
- the lower alkoxyalkyl group is, for example, an alkoxyalkyl group having 1 to 4 carbon atoms.
- crosslinkable compound for example, a melamine derivative, a benzoguanamine derivative or glycoluril in which a hydrogen atom of an amino group is substituted with a methylol group or an alkoxymethyl group or both can be used.
- the melamine derivative and benzoguanamine derivative may 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.
- Eight-substituted MW-30 (from Sanwa Chemical Co., Ltd.), methoxymethylated melamines such as Cymel 300, 301, 303, 350, 370, 771, 325, 327, 703, 712, Cymel 235, 236 Methoxymethylated butoxymethylated melamine such as 238, 212, 253, 254, butoxymethylated melamine such as Cymel 506, 508, carboxyl group-containing methoxymethylated isobutoxymethylated melamine such as Cymel 1141, Cymel 1123 and the like Methoxymethylated etoxy Methylated benzoguanamine, methoxymethylated butoxymethylated benzoguanamine such as Cymel 1123-10, butoxymethylated benzogu
- benzene or phenolic compounds having a hydroxyl group or an alkoxyl group examples 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.
- crosslinkable compound having a polymerizable unsaturated bond examples include trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, tri (meth) acryloyloxyethoxytrimethylolpropane, Crosslinkable compounds having three polymerizable unsaturated groups in the molecule such as 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,
- Z 1 is an n-valent group selected from a cyclohexyl ring, a bicyclohexyl ring, a benzene ring, a biphenyl ring, a terphenyl ring, a naphthalene ring, a fluorene ring, an anthracene ring, or a phenanthrene ring
- Z 2 is a group selected from the following formula [4a] or [4b]
- n is an integer of 1 to 4.
- 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 is preferably 0.1 to 150 parts by mass with respect to 100 parts by mass of the polymer of the present invention made of a polyimide precursor or polyimide.
- the amount is more preferably 0.1 to 100 parts by weight, particularly 1 to 50 parts by weight, so that the crosslinking reaction proceeds and the desired effect is exhibited and the orientation of the liquid crystal is not lowered.
- the organic solvent used in the liquid crystal aligning agent of the present invention is not particularly limited as long as it is an organic solvent that dissolves the above-described resin component. Examples thereof include N-methyl-2-pyrrolidone and butyl cellosolve.
- the liquid crystal aligning agent of the present invention preferably contains a poor solvent.
- the poor solvent refers to a solvent that improves film thickness uniformity and surface smoothness when a liquid crystal alignment treatment agent is applied. Specific examples of the poor solvent include the following.
- solvents may be used alone or in combination.
- the above poor solvent it is preferably 5 to 80% by mass, more preferably 20 to 60% by mass, based on the total amount of the solvent contained in the liquid crystal aligning agent.
- the liquid crystal aligning agent of the present invention may contain components other than those described above. Examples thereof include compounds that improve the film thickness uniformity and surface smoothness when a liquid crystal alignment treatment agent is applied, and compounds that improve the adhesion between the liquid crystal alignment film and the substrate.
- Examples of compounds that improve film thickness uniformity and surface smoothness include fluorine-based surfactants, silicone-based surfactants, and nonionic surfactants.
- F-top EF301, EF303, EF352 manufactured by Tochem Products
- MegaFuck F171, F173, R-30 manufactured by Dainippon Ink
- Florard FC430, FC431 manufactured by Sumitomo 3M
- Asahi Guard AG710 Surflon S-382, SC101, SC102, SC103, SC104, SC105, SC106 (manufactured by Asahi Glass) and the like.
- the use ratio 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 the resin component contained in the liquid crystal aligning agent.
- Specific examples of the compound that improves the adhesion between the liquid crystal alignment film and the substrate include the following functional silane-containing compounds and epoxy group-containing compounds.
- the amount is preferably 0.1 to 30 parts by mass, more preferably 1 to 20 parts by mass with respect to 100 parts by mass of the resin component contained in the liquid crystal aligning agent. It is. If it is less than 0.1 part by mass, the effect of improving the adhesion cannot be expected, and if it exceeds 30 parts by mass, the orientation of the liquid crystal may deteriorate.
- the liquid crystal alignment treatment agent of the present invention is a dielectric or conductive material for the purpose of changing the electrical properties such as the dielectric constant and conductivity of the liquid crystal alignment film as long as the effects of the present invention are not impaired. May be added.
- the liquid crystal alignment treatment agent of the present invention is a polymer obtained by polymerizing a polymerizable compound while applying a voltage to a liquid crystal layer using a liquid crystal material in which a polymerizable compound that is polymerized by heat or ultraviolet irradiation is mixed with liquid crystal,
- the present invention can be applied to a liquid crystal alignment film used in a liquid crystal display element obtained by a method for controlling the alignment direction of liquid crystal during driving.
- the substrate to be used is not particularly limited as long as it is a highly transparent substrate, and a glass substrate, a plastic substrate such as an acrylic substrate, a polycarbonate substrate, or the like can be used. Further, a substrate on which electrodes such as ITO and aluminum are formed for driving the liquid crystal is used on the substrate.
- the method for applying the liquid crystal alignment treatment agent is not particularly limited, but industrially, methods such as screen printing, offset printing, flexographic printing, and ink jet are generally used. Other coating methods include dip, roll coater, slit coater, spinner and the like, and these may be used depending on the purpose.
- Calcination after applying the liquid crystal aligning agent on the substrate can form a coating film by evaporating the solvent at 50 to 300 ° C., preferably 80 to 250 ° C., by a heating means such as a hot plate. If the thickness of the coating 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. Therefore, it is preferably 5 to 300 nm, more preferably 10 to 100 nm.
- 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 method described above, prepares a liquid crystal cell, polymerizes a polymerizable compound by irradiation with heat and ultraviolet rays, A liquid crystal display element in which the orientation of the liquid crystal is controlled is obtained.
- liquid crystal cell production prepare a pair of substrates on which a liquid crystal alignment film is formed, spray spacers on the liquid crystal alignment film of one substrate, and make the liquid crystal alignment film surface inside.
- Examples include a method of bonding the other substrate and injecting the liquid crystal under reduced pressure, or a method of sealing the liquid crystal after dropping the liquid crystal on the liquid crystal alignment film surface on which the spacers are dispersed, and the like.
- the thickness of the spacer at this time is preferably 1 to 30 ⁇ m, more preferably 2 to 10 ⁇ m.
- the liquid crystal used in this case 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 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 When 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, and when it exceeds 10 parts by mass, the amount of the unreacted polymerizable compound increases, and the liquid crystal display element The seizure characteristics of the steel deteriorate.
- the orientation of the liquid crystal can be controlled by polymerizing the polymerizable compound by irradiating the liquid crystal cell with heat or ultraviolet rays while applying an AC or DC voltage.
- the liquid crystal display device manufactured using the liquid crystal aligning agent of the present invention has excellent reliability and can be suitably used for a large-screen, high-definition liquid crystal television.
- Crosslinkable compound Crosslinkable compound (1): YH-434L (manufactured by Tohto Kasei) (epoxy-based crosslinkable compound) Crosslinkable compound (2): OXT-221 (manufactured by Toa Gosei) (oxetane-based crosslinkable compound) Crosslinkable compound (3): Cymel 303 (Mitsui Cytec) (methoxymethylated melamine-based crosslinkable compound) Crosslinkable compound (4): Crosslinkable compound represented by the following formula (hydroxylated phenol-based crosslinkable compound) Crosslinkable compound (5): KAYARADPDPHA-40H (manufactured by Nippon Kayaku) (unsaturated bond group-based crosslinkable compound)
- the molecular weight of polyimide in the synthesis example is as follows using a normal temperature gel permeation chromatography (GPC) apparatus (GPC-101) (manufactured by Showa Denko) and columns (KD-803, KD-805) (manufactured by Shodex). Measured.
- GPC gel permeation chromatography
- the imidation ratio of polyimide in the synthesis example was measured as follows. Add 20 mg of polyimide powder to an NMR sample tube (NMR sampling tube standard ⁇ 5 (Kusano Kagaku)) and add 0.53 ml of deuterated dimethyl sulfoxide (DMSO-d6, 0.05% TMS (tetramethylsilane) mixture) Then, it was completely dissolved by applying ultrasonic waves. This solution was measured for proton NMR at 500 MHz with an NMR measuring instrument (JNW-ECA500) (manufactured by JEOL Datum).
- JNW-ECA500 deuterated dimethyl sulfoxide
- the imidation rate is determined by determining a proton derived from a structure that does not change before and after imidation as a reference proton, and the peak integrated value of this proton and the proton peak derived from the NH group of amic acid that appears near 9.5 to 10.0 ppm. It calculated
- Imidization rate (%) (1 ⁇ ⁇ x / y) ⁇ 100
- x is a proton peak integrated value derived from NH group of amic acid
- y is a peak integrated value of reference proton
- ⁇ is one NH group proton of amic acid in the case of polyamic acid (imidation rate is 0%) Is the number ratio of the reference proton to.
- Tables 43 and 44 show the polyamic acid and polyimide of the present invention.
- a liquid crystal aligning agent is spin-coated on the ITO surface of a substrate with an ITO electrode having a pattern spacing of 10 ⁇ m at the center and 10 ⁇ m in the center and a substrate with an ITO electrode having a center of 10 ⁇ 40 mm at the center, and on a hot plate at 80 ° C. for 5 minutes. Then, heat treatment was performed at 210 ° C. for 30 minutes in a heat circulation type clean oven to obtain a polyimide coating film having a thickness of 100 nm. The coating surface was washed with pure water, and then heat-treated at 100 ° C. for 15 minutes in a heat-circulating clean oven to obtain a substrate with a liquid crystal alignment film.
- This substrate with a liquid crystal alignment film was sandwiched and combined with a 6 ⁇ m spacer with the liquid crystal alignment film surface facing inward, and the periphery was adhered with a sealant to produce an empty cell.
- a polymerizable compound (1) represented by the following formula was added to MLC-6608 (manufactured by Merck Japan) by a reduced pressure injection method into this empty cell, and the polymerizable compound was added to 100% by mass of MLC-6608. Liquid crystal mixed with 3% by mass was injected, and the injection port was sealed to obtain a liquid crystal cell.
- the wavelength of 350 nm or less was cut and irradiated with 20 J / cm 2 of ultraviolet rays in terms of 365 nm, and the alignment direction of the liquid crystal was obtained.
- the temperature in the irradiation apparatus when the liquid crystal cell was irradiated with ultraviolet rays was 50 ° C.
- Example 1 The polyamic acid solution (1) (10.5 g), NMP (11.8 g) and BCS (22.3 g) having a resin solid content concentration of 25.5% by mass obtained in Synthesis Example 1 were added at 25 ° C. at 8 ° C. By mixing for a time, a liquid crystal aligning agent (1) was obtained. This liquid crystal aligning agent was confirmed to be a uniform solution without any abnormality such as turbidity or precipitation.
- Example 2 The polyamic acid solution (2) (10.0 g), NMP (11.0 g), and BCS (21.0 g) having a resin solid concentration of 25.2% by mass obtained in Synthesis Example 2 were added at 25 ° C. at 8 ° C. By mixing for a time, a liquid crystal aligning agent (2) was obtained. This liquid crystal aligning agent was confirmed to be a uniform solution without any abnormality such as turbidity or precipitation.
- Example 3 The polyamide acid solution (3) (11.0 g), NMP (12.0 g), and BCS (23.0 g) having a resin solid content concentration of 25.1% by mass obtained in Synthesis Example 3 were added at 25 ° C. at 8 ° C. By mixing for a time, a liquid crystal aligning agent (3) was obtained. This liquid crystal aligning agent was confirmed to be a uniform solution without any abnormality such as turbidity or precipitation.
- Example 4 The polyimide powder (4) (2.50 g), NMP (18.3 g), and BCS (20.8 g) obtained in Synthesis Example 4 were mixed at 25 ° C. for 12 hours to obtain a liquid crystal aligning agent (4). Got. This liquid crystal aligning agent was confirmed to be a uniform solution without any abnormality such as turbidity or precipitation.
- Example 5 The polyimide powder (5) (2.51 g), NMP (22.6 g), and BCS (16.7 g) obtained in Synthesis Example 5 were mixed at 25 ° C. for 12 hours to obtain a liquid crystal aligning agent (5). Got. This liquid crystal aligning agent was confirmed to be a uniform solution without any abnormality such as turbidity or precipitation.
- Example 6 The polyimide powder (6) (2.48 g), NMP (18.2 g), and BCS (20.7 g) obtained in Synthesis Example 6 were mixed at 25 ° C. for 12 hours to obtain a liquid crystal aligning agent (6). Got. This liquid crystal aligning agent was confirmed to be a uniform solution without any abnormality such as turbidity or precipitation.
- Example 7 The polyimide powder (7) (2.50 g), NMP (22.5 g), and BCS (16.7 g) obtained in Synthesis Example 7 were mixed at 25 ° C. for 12 hours to obtain a liquid crystal aligning agent (7). Got. This liquid crystal aligning agent was confirmed to be a uniform solution without any abnormality such as turbidity or precipitation.
- Example 8 The polyimide powder (8) (2.50 g), NMP (18.3 g), and BCS (20.8 g) obtained in Synthesis Example 8 were mixed at 25 ° C. for 12 hours to obtain a liquid crystal aligning agent (8). Got. This liquid crystal aligning agent was confirmed to be a uniform solution without any abnormality such as turbidity or precipitation.
- Example 9 The polyimide powder (9) (2.51 g), NMP (24.7 g), and BCS (14.6 g) obtained in Synthesis Example 9 were mixed at 25 ° C. for 12 hours to obtain a liquid crystal aligning agent (9). Got. This liquid crystal aligning agent was confirmed to be a uniform solution without any abnormality such as turbidity or precipitation.
- Example 10 The polyimide powder (10) (2.50 g), NMP (24.6 g), and BCS (14.6 g) obtained in Synthesis Example 10 were mixed at 25 ° C. for 12 hours to obtain a liquid crystal aligning agent (10). Got. This liquid crystal aligning agent was confirmed to be a uniform solution without any abnormality such as turbidity or precipitation.
- Example 11 The polyamic acid solution (11) (10.5 g), NMP (11.5 g), and BCS (22.0 g) having a resin solid concentration of 25.1% by mass obtained in Synthesis Example 11 were added at 25 ° C. at 8 ° C. It mixed for a time and the liquid-crystal aligning agent (11) was obtained. This liquid crystal aligning agent was confirmed to be a uniform solution without any abnormality such as turbidity or precipitation.
- Example 12 The polyimide powder (12) (2.51 g), NMP (22.6 g), and BCS (16.7 g) obtained in Synthesis Example 12 were mixed at 25 ° C. for 12 hours to obtain a liquid crystal aligning agent (12). Got. This liquid crystal aligning agent was confirmed to be a uniform solution without any abnormality such as turbidity or precipitation.
- Example 13 The polyimide powder (13) (2.50 g), NMP (18.3 g), and BCS (20.8 g) obtained in Synthesis Example 13 were mixed at 25 ° C. for 12 hours to obtain a liquid crystal aligning agent (13). Got. This liquid crystal aligning agent was confirmed to be a uniform solution without any abnormality such as turbidity or precipitation.
- Example 14 The polyimide powder (14) (2.50 g), NMP (18.3 g), and BCS (20.8 g) obtained in Synthesis Example 14 were mixed at 25 ° C. for 12 hours to obtain a liquid crystal aligning agent (14). Got. 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 (15) (2.41 g), NMP (21.7 g), and BCS (16.1 g) obtained in Synthesis Example 15 were mixed at 25 ° C. for 12 hours to obtain a liquid crystal aligning agent (15). Got. This liquid crystal aligning agent was confirmed to be a uniform solution without any abnormality such as turbidity or precipitation.
- Example 16 The polyimide powder (16) (2.50 g), NMP (16.3 g), and BCS (22.9 g) obtained in Synthesis Example 16 were mixed at 25 ° C. for 12 hours to obtain a liquid crystal aligning agent (16). Got. This liquid crystal aligning agent was confirmed to be a uniform solution without any abnormality such as turbidity or precipitation.
- Example 17 The polyimide powder (17) (2.47 g), NMP (18.1 g), and BCS (20.6 g) obtained in Synthesis Example 17 were mixed at 25 ° C. for 12 hours to obtain a liquid crystal aligning agent (17). Got. This liquid crystal aligning agent was confirmed to be a uniform solution without any abnormality such as turbidity or precipitation.
- Example 18 The polyimide powder (18) (2.50 g), NMP (18.3 g), and BCS (20.8 g) obtained in Synthesis Example 18 were mixed at 25 ° C. for 12 hours to obtain a liquid crystal aligning agent (18). Got. This liquid crystal aligning agent was confirmed to be a uniform solution without any abnormality such as turbidity or precipitation.
- Example 19 The polyimide powder (19) (2.50 g), NMP (18.3 g), and BCS (20.8 g) obtained in Synthesis Example 19 were mixed at 25 ° C. for 12 hours to obtain a liquid crystal aligning agent (19). Got. This liquid crystal aligning agent was confirmed to be a uniform solution without any abnormality such as turbidity or precipitation.
- Example 20 The polyimide powder (20) (2.46 g), NMP (22.1 g), and BCS (16.4 g) obtained in Synthesis Example 20 were mixed at 25 ° C. for 12 hours to obtain a liquid crystal aligning agent (20). Got. This liquid crystal aligning agent was confirmed to be a uniform solution without any abnormality such as turbidity or precipitation.
- Example 21 The polyimide powder (21) (2.50 g), NMP (18.3 g), and BCS (20.8 g) obtained in Synthesis Example 21 were mixed at 25 ° C. for 12 hours to obtain a liquid crystal aligning agent (21). Got. This liquid crystal aligning agent was confirmed to be a uniform solution without any abnormality such as turbidity or precipitation.
- Example 22 Polyamide acid solution (2) (10.5 g), NMP (11.6 g), BCS (22.1 g), and crosslinkable compound (1) having a resin solid content concentration of 25.2% by mass obtained in Synthesis Example 2 (0.27 g) was mixed at 25 ° C. for 12 hours to obtain a liquid crystal aligning agent (22).
- This liquid crystal aligning agent was confirmed to be a uniform solution without any abnormality such as turbidity or precipitation.
- Example 23 Polyamide acid solution (2) (10.0 g), NMP (11.0 g), BCS (21.0 g), and crosslinkable compound (4) having a resin solid content concentration of 25.2% by mass obtained in Synthesis Example 2 (0.25 g) was mixed at 25 ° C. for 12 hours to obtain a liquid crystal aligning agent (23).
- This liquid crystal aligning agent was confirmed to be a uniform solution without any abnormality such as turbidity or precipitation.
- Example 24 Polyimide powder (4) (2.50 g), NMP (18.3 g), BCS (20.8 g), and crosslinkable compound (2) (0.50 g) obtained in Synthesis Example 4 were added at 25 ° C.
- the liquid crystal aligning agent (24) was obtained by mixing for 15 hours. This liquid crystal aligning agent was confirmed to be a uniform solution without any abnormality such as turbidity or precipitation.
- Example 25 The polyimide powder (4) (2.51 g), NMP (18.4 g), BCS (20.9 g), and crosslinkable compound (4) (0.50 g) obtained in Synthesis Example 4 were added at 25 ° C.
- the liquid crystal aligning agent (25) was obtained by mixing for 15 hours. This liquid crystal aligning agent was confirmed to be a uniform solution without any abnormality such as turbidity or precipitation.
- Example 26 The polyimide powder (7) (2.50 g), NMP (18.3 g), BCS (20.8 g), and crosslinkable compound (2) (0.25 g) obtained in Synthesis Example 7 were added at 25 ° C. The mixture was mixed for 15 hours to obtain a liquid crystal aligning agent (26). This liquid crystal aligning agent was confirmed to be a uniform solution without any abnormality such as turbidity or precipitation.
- Example 27 The polyimide powder (7) (2.50 g), NMP (18.3 g), BCS (20.8 g), and crosslinkable compound (4) (0.25 g) obtained in Synthesis Example 7 were added at 25 ° C. It mixed for 15 hours and obtained the liquid-crystal aligning agent (27). This liquid crystal aligning agent was confirmed to be a uniform solution without any abnormality such as turbidity or precipitation.
- Example 28 The polyimide powder (9) (2.50 g), NMP (18.3 g), BCS (20.8 g), and crosslinkable compound (1) (0.25 g) obtained in Synthesis Example 9 were added at 25 ° C. The mixture was mixed for 15 hours to obtain a liquid crystal aligning agent (28). This liquid crystal aligning agent was confirmed to be a uniform solution without any abnormality such as turbidity or precipitation.
- Example 29 The polyimide powder (9) (2.47 g), NMP (18.1 g), BCS (20.6 g), and crosslinkable compound (4) (0.47 g) obtained in Synthesis Example 9 were added at 25 ° C. The mixture was mixed for 15 hours to obtain a liquid crystal aligning agent (29). This liquid crystal aligning agent was confirmed to be a uniform solution without any abnormality such as turbidity or precipitation.
- Example 30 The polyimide powder (15) (2.50 g), NMP (18.3 g), BCS (20.8 g), and crosslinkable compound (3) (0.08 g) obtained in Synthesis Example 15 were added at 25 ° C.
- the liquid crystal aligning agent (30) was obtained by mixing for 15 hours. This liquid crystal aligning agent was confirmed to be a uniform solution without any abnormality such as turbidity or precipitation.
- Example 31 The polyimide powder (17) (2.49 g), NMP (18.3 g), BCS (20.8 g) obtained in Synthesis Example 17 and the crosslinkable compound (5) (0.08 g) were added at 25 ° C.
- the liquid crystal aligning agent (31) was obtained by mixing for 15 hours. This liquid crystal aligning agent was confirmed to be a uniform solution without any abnormality such as turbidity or precipitation.
- Example 22 to Example 31 the liquid crystal alignment film obtained from the liquid crystal aligning agent containing a crosslinkable compound was able to further suppress the decrease in voltage holding ratio due to ultraviolet irradiation.
- the liquid crystal alignment treatment agent of the present invention is a polymer obtained by polymerizing a polymerizable compound while applying a voltage to a liquid crystal layer using a liquid crystal material in which a polymerizable compound that is polymerized by heat or ultraviolet irradiation is mixed with liquid crystal, It can be used in a liquid crystal display element obtained by a method of controlling the alignment direction of liquid crystal during driving. Moreover, the liquid crystal aligning film obtained from the liquid-crystal aligning agent of this invention can suppress the fall of the voltage holding rate by ultraviolet irradiation. Therefore, the liquid crystal display element having this liquid crystal alignment film has excellent reliability and can be suitably used for a large-screen high-definition liquid crystal television.
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Abstract
Description
(1)液晶に熱や紫外線照射により重合する重合性化合物を混合した液晶材料を用いて、液晶層に電圧を印加しながら前記重合性化合物を重合させて得られるポリマーで、駆動時の液晶の配向方向を制御する方法により得られる液晶表示素子に用い、且つ、下記の式[1]で示される側鎖を有するポリイミド前駆体及びポリイミドの内の少なくとも1種の重合体を含有する液晶配向処理剤。
本発明の特定側鎖構造は、下記の式[1]で示される構造である。
本発明の重合体、すなわち、ジアミン成分とテトラカルボン酸二無水物との反応によって得られるポリイミド前駆体及び該ポリイミド前駆体を脱水閉環させて得られるポリイミドから選ばれる少なくとも1種に特定側鎖構造を導入する方法としては、下記の式[1a]で示されるジアミン化合物(特定ジアミン化合物ともいわれる)を原料の一部に用いることが好ましい。
本発明においては、本発明の効果を損なわない限りにおいて、特定ジアミン化合物以外のその他のジアミン化合物を、ジアミン成分として併用することができる。その具体例を以下に挙げる。
本発明の重合体を得るためには、下記の式[2]で示されるテトラカルボン酸二無水物(特定テトラカルボン酸二無水物ともいわれる)を原料の一部に用いることが好ましい。
本発明においては、本発明の効果を損なわない限りにおいて、特定テトラカルボン酸二無水物以外のその他のテトラカルボン酸二無水物を併用することができる。その具体例は以下の化合物の二無水物である。
本発明で用いる重合体は、上述したように、上記式[1]で示される特定側鎖構造を有するポリイミド前駆体や、該ポリイミド前駆体を脱水閉環させて得られるポリイミドである。
本発明の液晶配向処理剤は、液晶配向膜を形成するための塗布液であり、樹脂被膜を形成するための樹脂成分が有機溶媒に溶解した溶液である。ここで、前記の樹脂成分は、上記した本発明の重合体、すなわち、上記式[1]で示される特定側鎖構造を有するポリイミド前駆体及びポリイミドから選ばれる少なくとも一種の重合体を含む樹脂成分である。その際、樹脂成分の含有量は1質量%~20質量%が好ましく、より好ましくは3質量%~15質量%、特に好ましくは3質量%~10質量%である。
本発明の液晶配向処理剤は、液晶に熱や紫外線照射により重合する重合性化合物を混合した液晶材料を用いて、液晶層に電圧を印加しながら重合性化合物を重合させて得られるポリマーで、駆動時の液晶の配向方向を制御する方法により得られる液晶表示素子に用いられる液晶配向膜に適用することができる。
(テトラカルボン酸二無水物)
CBDA:1,2,3,4-シクロブタンテトラカルボン酸二無水物
BODA: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
TCA:2,3,5-トリカルボキシシクロペンチル酢酸―1,4:2,3-二無水物
TDA:3,4-ジカルボキシ-1,2,3,4-テトラヒドロ-1-ナフタレンコハク酸二無水物
PCH7DAB: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
PBCH5DAB: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
m-PBCH5DABz:1,3-ジアミノ-5-{4-〔4-(トランス-4-n-ペンチルシクロヘキシル)シクロヘキシル〕フェノキシメチル}ベンゼン
ColDAB-1:下記の式で示される特定ジアミン化合物
ColDAB-2:下記の式で示される特定ジアミン化合物
p-PDA:p-フェニレンジアミン
m-PDA:m-フェニレンジアミン
DBA:3,5-ジアミノ安息香酸
AP18:1,3-ジアミノ-4-オクタデシルオキシベンゼン
架橋性化合物(1):YH-434L(東都化成製)(エポキシ系架橋性化合物)
架橋性化合物(2):OXT-221(東亜合成製)(オキセタン系架橋性化合物)
架橋性化合物(3):サイメル303(三井サイテック製)(メトキシメチル化メラミン系架橋性化合物)
架橋性化合物(4):下記の式で示される架橋性化合物(ヒドロキシル化フェノール系架橋性化合物)
架橋性化合物(5):KAYARADDPHA-40H(日本化薬製)(不飽和結合基系架橋性化合物)
NMP:N-メチル-2-ピロリドン
BCS:ブチルセロソルブ
合成例におけるポリイミドの分子量は、常温ゲル浸透クロマトグラフィー(GPC)装置(GPC-101)(昭和電工製)、カラム(KD-803、KD-805)(Shodex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、30,000)(東ソー製)、及びポリエチレングリコール(分子量 約12,000、4,000、1,000)(ポリマーラボラトリー製)。
合成例におけるポリイミドのイミド化率は次のようにして測定した。ポリイミド粉末20mgをNMRサンプル管(NMRサンプリングチューブスタンダード φ5(草野科学製))に入れ、重水素化ジメチルスルホキシド(DMSO-d6、0.05%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から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。
CBDA(4.90g,25.0mmol)、PCH7DAB(4.76g,12.5mmol)、p-PDA(1.35g,12.5mmol)をNMP(32.1g)中で混合し、40℃で6時間反応させ、樹脂固形分濃度が25.5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27,900、重量平均分子量は76,900であった。
BODA(4.38g,17.5mmol)、PCH7DAB(4.76g,12.5mmol)、p-PDA(1.35g,12.5mmol)をNMP(19.5g)中で混合し、80℃で5時間反応させた後、CBDA(1.47g,7.50mmol)とNMP(16.0g)を加え、40℃で6時間反応させ、樹脂固形分濃度が25.2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25,400、重量平均分子量は61,800であった。
BODA(5.25g,21.0mmol)、PCH7DAB(5.71g,15.0mmol)、DBA(2.28g,15.0mmol)をNMP(24.6g)中で混合し、80℃で4時間反応させた後、CBDA(1.76g,8.97mmol)とNMP(20.2g)を加え、40℃で6時間反応させ、樹脂固形分濃度が25.1質量%のポリアミド酸溶液(3)を得た。このポリアミド酸の数平均分子量は22,400、重量平均分子量は59,200であった。
合成例3で得られた樹脂固形分濃度が25.1質量%のポリアミド酸溶液(3)(20.0g)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(2.49g)、ピリジン(1.91g)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(300ml)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(4)を得た。このポリイミドのイミド化率は58%であり、数平均分子量は21,100、重量平均分子量は50,100であった。
BODA(4.00g,16.0mmol)、PCH7DAB(2.28g,6.00mmol)、DBA(2.13g,14.0mmol)をNMP(15.1g)中で混合し、80℃で5時間反応させた後、CBDA(0.78g,4.00mmol)とNMP(12.4g)を加え、40℃で6時間反応させ、樹脂固形分濃度が25.0質量%のポリアミド酸溶液を得た。
BODA(3.50g,14.0mmol)、PBCH5DAB(2.60g,6.00mmol)、p-PDA(1.51g,14.0mmol)をNMP(14.4g)中で混合し、80℃で5時間反応させた後、CBDA(1.18g,6.02mmol)とNMP(11.7g)を加え、40℃で6時間反応させ、樹脂固形分濃度が25.2質量%のポリアミド酸溶液を得た。
BODA(3.00g,12.0mmol)、PBCH5DAB(3.46g,8.00mmol)、DBA(1.83g,12.0mmol)をNMP(16.5g)中で混合し、80℃で5時間反応させた後、CBDA(1.57g,8.01mmol)とNMP(13.5g)を加え、40℃で6時間反応させ、樹脂固形分濃度が24.7質量%のポリアミド酸溶液を得た。
BODA(3.00g,12.0mmol)、m-PBCH5DABz(3.57g,7.99mmol)、DBA(1.83g,12.0mmol)をNMP(16.5g)中で混合し、80℃で5時間反応させた後、CBDA(1.57g,8.01mmol)とNMP(13.5g)を加え、40℃で6時間反応させ、樹脂固形分濃度が24.9質量%のポリアミド酸溶液を得た。
BODA(4.38g,17.5mmol)、ColDAB-1(2.61g,4.99mmol)、m-PDA(2.16g,20.0mmol)をNMP(17.5g)中で混合し、80℃で6時間反応させた後、CBDA(1.47g,7.50mmol)とNMP(14.3g)を加え、40℃で8時間反応させ、樹脂固形分濃度が25.0質量%のポリアミド酸溶液を得た。
BODA(3.50g,14.0mmol)、ColDAB-2(1.97g,4.00mmol)、DBA(2.43g,16.0mmol)をNMP(15.0g)中で混合し、80℃で6時間反応させた後、CBDA(1.18g,6.02mmol)とNMP(12.3g)を加え、40℃で8時間反応させ、樹脂固形分濃度が25.0質量%のポリアミド酸溶液を得た。
TCA(4.48g,20.0mmol)、PCH7DAB(3.81g,10.0mmol)、DBA(1.52g,9.99mmol)をNMP(29.3g)中で混合し、40℃で6時間反応させ、樹脂固形分濃度が25.1質量%のポリアミド酸溶液(11)を得た。このポリアミド酸の数平均分子量は24,700、重量平均分子量は61,200であった。
TCA(4.48g,20.0mmol)、PCH7DAB(3.04g,8.00mmol)、m-PDA(1.30g,12.0mmol)をNMP(26.5g)中で混合し、40℃で6時間反応させ、樹脂固形分濃度が25.0質量%のポリアミド酸溶液を得た。
TCA(4.48g,20.0mmol)、PBCH5DAB(2.60g,6.01mmol)、DBA(2.13g,14.0mmol)をNMP(27.0g)中で混合し、40℃で8時間反応させ、樹脂固形分濃度が25.4質量%のポリアミド酸溶液を得た。
TCA(4.48g,20.0mmol)、ColDAB-1(1.57g,3.00mmol)、DBA(2.59g,17.0mmol)をNMP(25.7g)中で混合し、40℃で8時間反応させ、樹脂固形分濃度が25.2質量%のポリアミド酸溶液を得た。
BODA(4.38g,17.5mmol)、PCH7DAB(4.76g,12.5mmol)、DBA(1.90g,12.5mmol)をNMP(20.9g)中で混合し、80℃で5時間反応させた後、TCA(1.68g,7.49mmol)とNMP(17.1g)を加え、40℃で6時間反応させ、樹脂固形分濃度が25.1質量%のポリアミド酸溶液を得た。
BODA(3.75g,15.0mmol)、PBCH5DAB(3.24g,7.49mmol)、DBA(2.66g,17.5mmol)をNMP(19.4g)中で混合し、80℃で5時間反応させた後、TCA(2.24g,9.99mmol)とNMP(15.9g)を加え、40℃で6時間反応させ、樹脂固形分濃度が25.2質量%のポリアミド酸溶液を得た。
BODA(4.38g,17.5mmol)、PBCH5DAB(3.24g,7.49mmol)、p-PDA(1.89g,17.5mmol)をNMP(18.2g)中で混合し、80℃で5時間反応させた後、TCA(1.68g,7.49mmol)とNMP(14.9g)を加え、40℃で6時間反応させ、樹脂固形分濃度が25.3質量%のポリアミド酸溶液を得た。
TDA(1.80g,5.99mmol)、PCH7DAB(2.28g,5.99mmol)、DBA(2.13g,14.0mmol)をNMP(14.8g)中で混合し、80℃で6時間反応させた後、CBDA(2.75g,14.0mmol)とNMP(12.1g)を加え、40℃で6時間反応させ、樹脂固形分濃度が25.0質量%のポリアミド酸溶液を得た。
TDA(1.80g,5.99mmol)、PBCH5DAB(2.60g,6.01mmol)、p-PDA(1.51g,14.0mmol)をNMP(14.3g)中で混合し、80℃で6時間反応させた後、CBDA(2.75g,14.0mmol)とNMP(11.7g)を加え、40℃で6時間反応させ、樹脂固形分濃度が25.0質量%のポリアミド酸溶液を得た。
TDA(1.80g,5.99mmol)、m-PBCH5DABz(2.68g,6.00mmol)、DBA(2.13g,14.0mmol)をNMP(15.6g)中で混合し、80℃で6時間反応させた後、CBDA(2.75g,14.0mmol)とNMP(12.8g)を加え、40℃で6時間反応させ、樹脂固形分濃度が24.8質量%のポリアミド酸溶液を得た。
TDA(1.80g,5.99mmol)、ColDAB-1(1.57g,3.00mmol)、DBA(2.59g,17.0mmol)をNMP(14.3g)中で混合し、80℃で6時間反応させた後、CBDA(2.75g,14.0mmol)とNMP(11.7g)を加え、40℃で6時間反応させ、樹脂固形分濃度が25.1質量%のポリアミド酸溶液を得た。
CBDA(4.90g,25.0mmol)、AP18(4.71g,12.5mmol)、p-PDA(1.35g,12.5mmol)をNMP(32.9g)中で混合し、40℃で6時間反応させ、樹脂固形分濃度が25.0質量%のポリアミド酸溶液(22)を得た。このポリアミド酸の数平均分子量は28,100、重量平均分子量は78,100であった。
BODA(4.38g,17.5mmol)、AP18(4.71g,12.5mmol)、DBA(1.90g,12.5mmol)をNMP(20.5g)中で混合し、80℃で5時間反応させた後、CBDA(1.47g,7.50mmol)とNMP(16.7g)を加え、40℃で6時間反応させ、樹脂固形分濃度が25.1質量%のポリアミド酸溶液(23)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61,100であった。
BODA(4.38g,17.5mmol)、AP18(4.71g,12.5mmol)、DBA(1.90g,12.5mmol)をNMP(20.5g)中で混合し、80℃で5時間反応させた後、CBDA(1.47g,7.50mmol)とNMP(16.7g)を加え、40℃で6時間反応させ、樹脂固形分濃度が25.1質量%のポリアミド酸溶液を得た。
BODA(4.38g,17.5mmol)、AP18(3.77g,10.0mmol)、DBA(2.28g,15.0mmol)をNMP(19.5g)中で混合し、80℃で5時間反応させた後、CBDA(1.47g,7.50mmol)とNMP(15.9g)を加え、40℃で6時間反応させ、樹脂固形分濃度が25.2質量%のポリアミド酸溶液を得た。
TCA(5.60g,25.0mmol)、AP18(4.71g,12.5mmol)、DBA(1.90g,12.5mmol)をNMP(36.2g)中で混合し、40℃で8時間反応させ、樹脂固形分濃度が25.2質量%のポリアミド酸溶液を得た。
BODA(4.38g,17.5mmol)、AP18(4.71g,12.5mmol)、DBA(1.90g,12.5mmol)をNMP(20.9g)中で混合し、80℃で5時間反応させた後、TCA(1.68g,7.49mmol)とNMP(17.1g)を加え、40℃で6時間反応させ、樹脂固形分濃度が25.0質量%のポリアミド酸溶液を得た。
TDA(2.25g,7.49mmol)、AP18(2.82g,7.49mmol)、p-PDA(1.89g,17.5mmol)をNMP(17.3g)中で混合し、80℃で6時間反応させた後、CBDA(3.43g,17.5mmol)とNMP(14.2g)を加え、40℃で6時間反応させ、樹脂固形分濃度が24.8質量%のポリアミド酸溶液を得た。
下記する実施例1~実施例31、及び比較例1~比較例7では、液晶配向処理剤の製造例を記載するが、各液晶配向処理剤の評価のために使用される本発明の液晶配向処理剤を表45~表47に示す。
液晶配向処理剤を、中心に10×10mmのパターン間隔20μmのITO電極付き基板と中心に10×40mmのITO電極付き基板のITO面にスピンコートし、ホットプレート上にて、80℃で5分間、熱循環型クリーンオーブン中にて、210℃で30分間加熱処理をして、膜厚100nmのポリイミド塗膜を得た。塗膜面を純水にて洗浄し、その後、熱循環型クリーンオーブン中にて、100℃で15分加熱処理をして、液晶配向膜付き基板を得た。
上記の「液晶セルの作製」で得られた紫外線照射前の液晶セルと紫外線照射後の液晶セルの液晶の応答速度を測定した。透過率が90%から10%まで変化するのにかかった時間(表中「T90→T10」と記載する。)を応答速度とした。液晶の配向方向が制御されたことは、紫外線照射前(表中「処理前」と記載する。)の液晶セルに比べて、紫外線照射後(表中「処理後」と記載する。)の液晶セルの応答速度が早くなったことで確認した。
上記の「液晶セルの作製」で得られた紫外線照射前の液晶セルと紫外線照射後の液晶セルに、80℃の温度下で4Vの電圧を60μm印加し、16.67ms後及び1667ms後の電圧を測定し、電圧がどのくらい保持できているかを電圧保持率として計算した。
合成例1で得られた樹脂固形分濃度25.5質量%のポリアミド酸溶液(1)(10.5g)、NMP(11.8g)、及びBCS(22.3g)を、25℃にて8時間混合して、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で得られた樹脂固形分濃度25.2質量%のポリアミド酸溶液(2)(10.0g)、NMP(11.0g)、及びBCS(21.0g)を、25℃にて8時間混合して、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で得られた樹脂固形分濃度25.1質量%のポリアミド酸溶液(3)(11.0g)、NMP(12.0g)、及びBCS(23.0g)を、25℃にて8時間混合して、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で得られたポリイミド粉末(4)(2.50g)、NMP(18.3g)、及びBCS(20.8g)を、25℃にて12時間混合し、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5で得られたポリイミド粉末(5)(2.51g)、NMP(22.6g)、及びBCS(16.7g)を、25℃にて12時間混合し、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6で得られたポリイミド粉末(6)(2.48g)、NMP(18.2g)、及びBCS(20.7g)を、25℃にて12時間混合し、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7で得られたポリイミド粉末(7)(2.50g)、NMP(22.5g)、及びBCS(16.7g)を、25℃にて12時間混合し、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8で得られたポリイミド粉末(8)(2.50g)、NMP(18.3g)、及びBCS(20.8g)を、25℃にて12時間混合し、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9で得られたポリイミド粉末(9)(2.51g)、NMP(24.7g)、及びBCS(14.6g)を、25℃にて12時間混合し、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10で得られたポリイミド粉末(10)(2.50g)、NMP(24.6g)、及びBCS(14.6g)を、25℃にて12時間混合し、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11で得られた樹脂固形分濃度25.1質量%のポリアミド酸溶液(11)(10.5g)、NMP(11.5g)、及びBCS(22.0g)を、25℃にて8時間混合して、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12で得られたポリイミド粉末(12)(2.51g)、NMP(22.6g)、及びBCS(16.7g)を、25℃にて12時間混合し、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13で得られたポリイミド粉末(13)(2.50g)、NMP(18.3g)、及びBCS(20.8g)を、25℃にて12時間混合し、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14で得られたポリイミド粉末(14)(2.50g)、NMP(18.3g)、及びBCS(20.8g)を、25℃にて12時間混合し、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15で得られたポリイミド粉末(15)(2.41g)、NMP(21.7g)、及びBCS(16.1g)を、25℃にて12時間混合し、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16で得られたポリイミド粉末(16)(2.50g)、NMP(16.3g)、及びBCS(22.9g)を、25℃にて12時間混合し、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17で得られたポリイミド粉末(17)(2.47g)、NMP(18.1g)、及びBCS(20.6g)を、25℃にて12時間混合し、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18で得られたポリイミド粉末(18)(2.50g)、NMP(18.3g)、及びBCS(20.8g)を、25℃にて12時間混合し、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19で得られたポリイミド粉末(19)(2.50g)、NMP(18.3g)、及びBCS(20.8g)を、25℃にて12時間混合し、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20で得られたポリイミド粉末(20)(2.46g)、NMP(22.1g)、及びBCS(16.4g)を、25℃にて12時間混合し、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21で得られたポリイミド粉末(21)(2.50g)、NMP(18.3g)、及びBCS(20.8g)を、25℃にて12時間混合し、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で得られた樹脂固形分濃度25.2質量%のポリアミド酸溶液(2)(10.5g)、NMP(11.6g)、BCS(22.1g)、及び架橋性化合物(1)(0.27g)を、25℃にて12時間混合して、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で得られた樹脂固形分濃度25.2質量%のポリアミド酸溶液(2)(10.0g)、NMP(11.0g)、BCS(21.0g)、及び架橋性化合物(4)(0.25g)を、25℃にて12時間混合して、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4で得られたポリイミド粉末(4)(2.50g)、NMP(18.3g)、BCS(20.8g)、及び架橋性化合物(2)(0.50g)を、25℃にて15時間混合し、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4で得られたポリイミド粉末(4)(2.51g)、NMP(18.4g)、BCS(20.9g)、及び架橋性化合物(4)(0.50g)を、25℃にて15時間混合し、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7で得られたポリイミド粉末(7)(2.50g)、NMP(18.3g)、BCS(20.8g)、及び架橋性化合物(2)(0.25g)を、25℃にて15時間混合し、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7で得られたポリイミド粉末(7)(2.50g)、NMP(18.3g)、BCS(20.8g)、及び架橋性化合物(4)(0.25g)を、25℃にて15時間混合し、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9で得られたポリイミド粉末(9)(2.50g)、NMP(18.3g)、BCS(20.8g)、及び架橋性化合物(1)(0.25g)を、25℃にて15時間混合し、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9で得られたポリイミド粉末(9)(2.47g)、NMP(18.1g)、BCS(20.6g)、及び架橋性化合物(4)(0.47g)を、25℃にて15時間混合し、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15で得られたポリイミド粉末(15)(2.50g)、NMP(18.3g)、BCS(20.8g)、及び架橋性化合物(3)(0.08g)を、25℃にて15時間混合し、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17で得られたポリイミド粉末(17)(2.49g)、NMP(18.3g)、BCS(20.8g)、及び架橋性化合物(5)(0.08g)を、25℃にて15時間混合し、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22で得られた樹脂固形分濃度25.0質量%のポリアミド酸溶液(22)(10.5g)、NMP(11.4g)、及びBCS(21.9g)を、25℃にて8時間混合して、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。
合成例23で得られた樹脂固形分濃度25.1質量%のポリアミド酸溶液(23)(10.0g)、NMP(10.9g)、及びBCS(20.9g)を、25℃にて8時間混合して、液晶配向処理剤(33)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24で得られたポリイミド粉末(24)(2.50g)、NMP(26.7g)、及びBCS(12.5g)を、25℃にて12時間混合し、液晶配向処理剤(34)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25で得られたポリイミド粉末(25)(2.52g)、NMP(22.7g)、及びBCS(16.8g)を、25℃にて12時間混合し、液晶配向処理剤(35)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26で得られたポリイミド粉末(26)(2.50g)、NMP(24.6g)、及びBCS(14.6g)を、25℃にて12時間混合し、液晶配向処理剤(36)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27で得られたポリイミド粉末(27)(2.45g)、NMP(24.1g)、及びBCS(14.3g)を、25℃にて12時間混合し、液晶配向処理剤(37)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28で得られたポリイミド粉末(28)(2.48g)、NMP(20.3g)、及びBCS(18.6g)を、25℃にて12時間混合し、液晶配向処理剤(38)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。
Claims (11)
- 液晶に熱や紫外線照射により重合する重合性化合物を混合した液晶材料を用いて、液晶層に電圧を印加しながら前記重合性化合物を重合させて得られるポリマーで、駆動時の液晶の配向方向を制御する方法により得られる液晶表示素子に用い、且つ、下記の式[1]で示される側鎖を有するポリイミド前駆体及びポリイミドの内の少なくとも1種の重合体を含有する液晶配向処理剤。
(式[1]中、X1は-O-、-CH2O-、-COO-、-(CH2)a-(aは1~10の整数である)、-NH-、-N(CH3)-、-CONH-、-NHCO-、-OCO-、-CON(CH3)-、-N(CH3)CO-、又は単結合より選ばれる2価の有機基であり、X2は単結合、又は-(CH2)b-(bは1~10の整数である)より選ばれる2価の有機基であり、X3は単結合、-(CH2)c-(cは1~10の整数である)、-O-、-NH-、-N(CH3)-、-CONH-、-NHCO-、-CH2O-、-COO-、-OCO-、-CON(CH3)-、又は-N(CH3)CO-より選ばれる2価の有機基であり、X4はベンゼン環、シクロへキシル環、又は複素環から選ばれる2価の環状基、又は、ステロイド骨格を有する炭素数12~25の2価の有機基を示し、前記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、又は炭素数1~3のフッ素含有アルコキシル基、フッ素原子から選ばれるもので置換されていても良く、X5はシクロへキシル環、ベンゼン環、又は複素環から選ばれる2価の環状基を示し、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、又は炭素数1~3のフッ素含有アルコキシル基、フッ素原子から選ばれるもので置換されていても良く、nは0~4の整数であり、X6は、炭素数1~18のアルキル基、炭素数1~18のフッ素含有アルキル基、炭素数1~18のアルコキシル基、炭素数1~18のフッ素含有アルコキシル基又は水素原子である)。 - 前記重合体が、式[1]の側鎖を有するジアミン化合物を原料の一部に用いた重合体である請求項1に記載の液晶配向処理剤。
- 式[1]の側鎖を有するジアミン化合物が、下記の式[1a]で示される構造である請求項2に記載の液晶配向処理剤。
(式[1a]中、X1は-O-、-CH2O-、-COO-、-(CH2)a-(aは1~10の整数である)、-NH-、-N(CH3)-、-CONH-、-NHCO-、-OCO-、-CON(CH3)-、-N(CH3)CO-、又は単結合より選ばれる2価の有機基であり、X2は単結合、又は-(CH2)b-(bは1~10の整数である)より選ばれる2価の有機基であり、X3は単結合、-(CH2)c-(cは1~10の整数である)、-O-、-NH-、-N(CH3)-、-CONH-、-NHCO-、-CH2O-、-COO-、-OCO-、-CON(CH3)-、又は-N(CH3)CO-より選ばれる2価の有機基であり、X4はベンゼン環、シクロへキシル環、又は複素環から選ばれる2価の環状基、又は、ステロイド骨格を有する炭素数12~25の2価の有機基を示し、前記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、又は炭素数1~3のフッ素含有アルコキシル基、フッ素原子から選ばれるもので置換されていても良く、X5はシクロへキシル環、ベンゼン環、又は複素環から選ばれる2価の環状基を示し、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、又は炭素数1~3のフッ素含有アルコキシル基、フッ素原子から選ばれるもので置換されていても良く、nは0~4の整数であり、X6は炭素数1~18のアルキル基、炭素数1~18のフッ素含有アルキル基、炭素数1~18のアルコキシル基、炭素数1~18のフッ素含有アルコキシル基又は水素原子であり、mは1~4の整数である)。 - 式[1a]で示される構造のジアミン化合物が、ジアミン成分中の5~80モル%である請求項3に記載の液晶配向処理剤。
- 液晶配向処理剤中に、エポキシ基、オキセタン基、イソシアネート基及びシクロカーボネート基からなる群より選ばれる少なくとも1種の置換基を有する架橋性化合物、ヒドロキシル基、ヒドロキシアルキル基、アルコキシル基及び低級アルコキシアルキル基からなる群より選ばれる少なくとも1種の置換基を有する架橋性化合物、又は重合性不飽和結合を有する架橋性化合物を有する請求項1~請求項6のいずれか一項に記載液晶配向処理剤。
- 液晶配向処理剤中の重合体がポリアミド酸を脱水閉環させて得られるポリイミドである請求項1~請求項7のいずれか一項に記載の液晶配向処理剤。
- 液晶配向処理剤中に5~60質量%の貧溶媒を含有する請求項1~請求項8のいずれか一項に記載の液晶配向処理剤。
- 請求項1~請求項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10に記載の液晶配向膜を有する液晶表示素子。
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CN102947752A (zh) | 2013-02-27 |
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