WO2015053394A1 - 組成物、液晶配向処理剤、液晶配向膜および液晶表示素子 - Google Patents

組成物、液晶配向処理剤、液晶配向膜および液晶表示素子 Download PDF

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Publication number: WO2015053394A1
Authority: WO; WIPO (PCT)
Prior art keywords: liquid crystal; group; composition; formula; carbon atoms
Prior art date: 2013-10-10

Application number

PCT/JP2014/077219

Other languages

English (en)

French (fr)

Japanese (ja)

Inventor

徳俊三木

橋本　淳

暁子若林

保坂　和義

Original Assignee

日産化学工業株式会社

Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)

2013-10-10

Filing date

2014-10-10

Publication date

2015-04-16

2014-10-10 Application filed by 日産化学工業株式会社 filed Critical 日産化学工業株式会社

2014-10-10 Priority to CN201480067004.XA priority Critical patent/CN105814141B/zh

2014-10-10 Priority to JP2015541652A priority patent/JP6668754B2/ja

2014-10-10 Priority to KR1020167011818A priority patent/KR102259997B1/ko

2015-04-16 Publication of WO2015053394A1 publication Critical patent/WO2015053394A1/ja

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JHBTWRUZFVKEIJ-UHFFFAOYSA-N CC(C)CCCC(C)C(CC1)C(C)(CC2)C1C(CC1)C2C(C)(CC2)C1CC2Oc(ccc(N)c1)c1N Chemical compound CC(C)CCCC(C)C(CC1)C(C)(CC2)C1C(CC1)C2C(C)(CC2)C1CC2Oc(ccc(N)c1)c1N JHBTWRUZFVKEIJ-UHFFFAOYSA-N 0.000 description 1
XAJTUWXWXLEOLN-UHFFFAOYSA-N CC(C)CCCC(C)C(CC1)C2(C)C1C1C=CC(CC(CC3)Oc(ccc(N)c4)c4N)C3(C3)C1C3C2 Chemical compound CC(C)CCCC(C)C(CC1)C2(C)C1C1C=CC(CC(CC3)Oc(ccc(N)c4)c4N)C3(C3)C1C3C2 XAJTUWXWXLEOLN-UHFFFAOYSA-N 0.000 description 1
LRZYNMOMAYJERG-UHFFFAOYSA-N CC(CCC=C(C)C)C(CC1)C(C)(CC2)C1C(CC1)C2C(C)(CC2)C1CC2Oc(ccc(N)c1)c1N Chemical compound CC(CCC=C(C)C)C(CC1)C(C)(CC2)C1C(CC1)C2C(C)(CC2)C1CC2Oc(ccc(N)c1)c1N LRZYNMOMAYJERG-UHFFFAOYSA-N 0.000 description 1
SNJIQSMDGPZZKS-UHFFFAOYSA-N CC(CCC=C(C)C)C(CC1)C2(C)C1C1C=CC(CC(CC3)Oc(ccc(N)c4)c4N)C3(C3)C1C3C2 Chemical compound CC(CCC=C(C)C)C(CC1)C2(C)C1C1C=CC(CC(CC3)Oc(ccc(N)c4)c4N)C3(C3)C1C3C2 SNJIQSMDGPZZKS-UHFFFAOYSA-N 0.000 description 1
XYOCJDXOOLVMSM-UHFFFAOYSA-M C[O](N[In](OO)=N)=C Chemical compound C[O](N[In](OO)=N)=C XYOCJDXOOLVMSM-UHFFFAOYSA-M 0.000 description 1
NVMHHXLEDGFQPF-UHFFFAOYSA-N O=C([N]1(C(O2)=O)C2=O)OC1=O Chemical compound O=C([N]1(C(O2)=O)C2=O)OC1=O NVMHHXLEDGFQPF-UHFFFAOYSA-N 0.000 description 1

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Classifications

- 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
- C08G73/1003—Preparatory processes
- C08G73/1007—Preparatory processes from tetracarboxylic acids or derivatives and diamines
- C08G73/1028—Preparatory processes from tetracarboxylic acids or derivatives and diamines characterised by the process itself, e.g. steps, continuous
- C08G73/1032—Preparatory processes from tetracarboxylic acids or derivatives and diamines characterised by the process itself, e.g. steps, continuous characterised by the solvent(s) used
- 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
- 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
- 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
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D179/00—Coating compositions based on 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 C09D161/00 - C09D177/00
- C09D179/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
- C09D179/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K19/00—Liquid crystal materials
- C09K19/52—Liquid crystal materials characterised by components which are not liquid crystals, e.g. additives with special physical aspect: solvents, solid particles
- C09K19/54—Additives having no specific mesophase characterised by their chemical composition
- C09K19/56—Aligning agents
- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells
- G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
- G02F1/1333—Constructional arrangements; Manufacturing methods
- G02F1/1337—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers
- G02F1/133711—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers by organic films, e.g. polymeric films
- G02F1/133723—Polyimide, polyamide-imide

Definitions

the present invention relates to a composition used for forming a polyimide film, a liquid crystal alignment treatment agent used in the production of a liquid crystal display element, a liquid crystal alignment film obtained from the liquid crystal alignment treatment agent, and a liquid crystal display element using the liquid crystal alignment film. Is.
a film made of an organic material such as a polymer material is widely used as an interlayer insulating film, a protective film, and the like in electronic devices because of its ease of formation and insulation performance.
an organic film made of an organic material is used as a liquid crystal alignment film.
liquid crystal display devices have been widely put into practical use for large-screen liquid crystal televisions and high-definition mobile applications (display portions of digital cameras and mobile phones).
the size of the substrate to be used is increased compared to the conventional one, and the unevenness of the step of the substrate has become larger. Even in such a situation, it has been demanded that the liquid crystal alignment film is uniformly coated on a large substrate or a step from the viewpoint of display characteristics.
liquid crystal alignment film when a liquid crystal alignment treatment agent using a polyimide polymer (also referred to as resin) such as polyamic acid or solvent-soluble polyimide (also referred to as polyimide) is applied to a substrate, industrially In general, the flexographic printing method or the ink jet coating method is used. At that time, as a solvent for the liquid crystal alignment treatment agent, N-methyl-2-pyrrolidone (also referred to as NMP) or ⁇ -butyrolactone (also referred to as ⁇ -BL), which is a solvent having excellent resin solubility (also referred to as a good solvent), is used.
NMP N-methyl-2-pyrrolidone
⁇ -BL ⁇ -butyrolactone
ethylene glycol monobutyl ether which is a solvent having low resin solubility (also referred to as a poor solvent), or the like is mixed (for example, see Patent Document 1).
Polyimide-based organic films are widely used as interlayer insulating films and protective films in electronic devices in addition to liquid crystal alignment films.
the liquid crystal alignment film it can be formed from a composition (also referred to as a coating solution) containing a polyamic acid or polyimide solution that is a polyimide precursor.
a coating solution containing a polyamic acid or polyimide solution that is a polyimide precursor.
the liquid crystal aligning agent using the polyamic acid and polyimide obtained by using the diamine compound which has a side chain has the tendency for the coating property of a liquid crystal aligning film to fall because the hydrophobicity of a side chain site
uniform coating properties cannot be obtained, that is, when pinholes accompanying repelling occur, when the liquid crystal display element is formed, that portion becomes a display defect. Therefore, in order to obtain uniform coating properties, it is necessary to increase the mixing amount of a poor solvent having high wettability of the coating solution to the substrate.
a poor solvent is inferior in the ability to dissolve a polyamic acid or a polyimide, there exists a problem that resin precipitation will occur when it mixes in large quantities.
liquid crystal display elements have been used for mobile applications such as smartphones and mobile phones.
the substrates of the liquid crystal display elements are bonded together.
the sealant used in is present at a position close to the end of the liquid crystal alignment film. Therefore, when the coating property of the end portion of the liquid crystal alignment film is lowered, that is, when the end portion of the liquid crystal alignment film is not a straight line, or when the end portion is raised, the liquid crystal alignment film and the sealing agent Adhesive (also referred to as adhesion) effect is reduced, and the display characteristics and reliability of the liquid crystal display element are lowered.
the composition or the liquid crystal alignment treatment agent using polyimide since the boiling point of NMP and ⁇ -BL which are the solvents used for them is high, a polyimide film such as an interlayer insulating film and a protective film and a liquid crystal alignment film are produced. In this case, firing at a high temperature is required. Therefore, from the viewpoint of reducing energy costs, baking at a low temperature is required when producing these polyimide films and liquid crystal alignment films.
an object of the present invention is to provide a composition having the above characteristics. That is, an object of the present invention is to provide a composition that can suppress the occurrence of pinholes accompanying repelling when forming a polyimide film and is excellent in the coating properties at the end. In that case, it aims also at becoming the composition which can produce a polyimide film also by baking at low temperature.
an object of the present invention is to provide a liquid crystal aligning agent excellent in these characteristics even when it is a liquid crystal aligning agent using a polyamic acid or polyimide obtained by using a diamine compound having a side chain. It is another object of the present invention to provide a liquid crystal alignment treatment agent which is excellent in electrical characteristics, particularly voltage holding ratio (also referred to as VHR) in a liquid crystal display element even when firing at the time of producing a liquid crystal alignment film is at a low temperature.
VHR voltage holding ratio
another object is to provide a polyimide film obtained from the composition, a liquid crystal alignment film obtained from the liquid crystal alignment treatment agent, and a liquid crystal display device having the liquid crystal alignment film.
the present invention has the following gist.
Component (A) Formula [A] below: (Wherein, X 1 and X 2 each independently represent an alkyl group having 1 to 3 carbon atoms, and X 3 and X 4 each independently represent an alkyl group having 1 to 3 carbon atoms) And (B) component: a composition containing at least one polymer selected from polyimide precursors and polyimides.
the solvent of the component (A) is represented by the following formula [A-1]: The composition as described in said (1) which is a solvent shown by these.
the component (B) is represented by the following formula [1-1] and formula [1-2]: Wherein Y 1 is a single bond, — (CH 2 ) a — (a is an integer of 1 to 15), —O—, —CH 2 O—, —CONH—, —NHCO—, —CON At least one linking group selected from (CH 3 ) —, —N (CH 3 ) CO—, —COO— and —OCO—, wherein Y 2 represents a single bond or — (CH 2 ) b — (b Is an integer of 1 to 15, and Y 3 is a single bond, — (CH 2 ) c — (c is an integer of 1 to 15), —O—, —CH 2 O—, —COO Y represents at least one linking group selected from — and —OCO—, and Y 4 represents a carbon having a divalent cyclic group of at least one ring selected from a benzene ring, a cycl
Y 7 is a single bond, —O—, —CH 2 O—, —CONH—, —NHCO—, —CON (CH 3 ) —, —N (CH 3 ) CO—, —COO— and At least one linking group selected from —OCO—
Y 8 represents an alkyl group having 8 to 22 carbon atoms or a fluorine-containing alkyl group having 6 to 18 carbon atoms) (1) or (2) above, which is at least one polymer selected from polyimide precursors and polyimides using a diamine compound having at least one structure selected from the structure represented by A composition according to 1.
a diamine compound having a structure represented by the formula [1-1] and the formula [1-2] is represented by the following formula [1a]: (Wherein Y represents at least one structure selected from the structures represented by the formulas [1-1] and [1-2], and m represents an integer of 1 to 4)
the composition as described in said (3) which is a diamine compound shown by these.
the diamine compound having a carboxyl group and a hydroxyl group is represented by the following formula [2a]: ⁇ In the formula, A represents the following formula [2-1] and formula [2-2]: (In the formula [2-1], a represents an integer of 0 to 4, and in the formula [2-2], b represents an integer of 0 to 4). M represents an integer of 1 to 4 ⁇
the polymer of the component (B) is represented by the following formula [3a]: Wherein B 1 is —O—, —NH—, —N (CH 3 ) —, —CONH—, —NHCO—, —CH 2 O—, —OCO—, —CON (CH 3 ) — and Represents at least one linking group selected from —N (CH 3 ) CO—, wherein B 2 is a single bond, a divalent group of an aliphatic hydrocarbon having 1 to 20 carbon atoms, a non-aromatic cyclic hydrocarbon; And B 3 is a single bond, —O—, —NH—, —N (CH 3 ) —, —CONH—.
At least one selected linking group B 4 represents a nitrogen-containing heterocyclic group, and n represents an integer of 1 to 4.
B 1 represents —CONH—
B 2 represents an alkylene group having 1 to 5 carbon atoms
B 3 represents a single bond
B 4 represents an imidazolyl group or a pyridyl group.
the polymer of the component (B) is represented by the following formula [4]: ⁇ In the formula, Z represents the following formula [4a] to formula [4k]: (In formula [4a], Z 1 to Z 4 each independently represent a hydrogen atom, a methyl group, a chlorine atom or a phenyl group, and in formula [4g], Z 5 and Z 6 are each independently Represents a hydrogen atom or a methyl group) and represents a group having at least one structure selected from The composition according to any one of the above (1) to (8), which is at least one polymer selected from a polyimide precursor and a polyimide using a tetracarboxylic acid compound represented by the formula:
composition according to any one of (1) to (9) above, wherein the polymer of the component (B) is at least one polymer selected from polyamic acid alkyl ester and polyimide.
composition at least one substituent selected from the group consisting of 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.
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.
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 display device comprising the liquid crystal alignment film according to (23).
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.
a liquid crystal display element comprising the liquid crystal alignment film according to (25).
composition containing a solvent having a specific structure of the present invention and at least one polymer selected from polyimide precursors or polyimides can suppress the generation of pinholes accompanying repelling when forming a polyimide film.
the polyimide film which is excellent also in the coating property of the edge part can be produced. At that time, the polyimide film can be formed by baking at a low temperature.
an object of the present invention is to provide a liquid crystal aligning agent excellent in these characteristics even when it is a liquid crystal aligning agent using a polyamic acid or polyimide obtained by using a diamine compound having a side chain. It is another object of the present invention to provide a liquid crystal alignment treatment agent that is excellent in electrical characteristics, particularly voltage holding ratio (VHR) in a liquid crystal display element even when firing at the time of producing a liquid crystal alignment film is at a low temperature.
VHR voltage holding ratio
the composition of the present invention as a liquid crystal alignment treatment agent, it is possible to suppress the occurrence of pinholes due to repellency, and to provide a liquid crystal alignment film having excellent coating properties at the end portions Can do.
the liquid crystal aligning film which is excellent in these characteristics can be provided.
the liquid crystal aligning film which is excellent in the electrical property in a liquid crystal display element, especially a voltage holding ratio (VHR) can be provided.
the 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 is used for a large-screen high-definition liquid crystal television, a small-sized car navigation system, a smartphone, and the like. It can be suitably used.
the present invention provides a composition containing the following components (A) and (B), a liquid crystal alignment treatment agent, a liquid crystal alignment film obtained using the liquid crystal alignment treatment agent, and a liquid crystal having the liquid crystal alignment film It is a display element.
Component (B) at least one polymer selected from a polyimide precursor and polyimide (also referred to as a specific polymer).
the specific solvent of the present invention can be used as a solvent capable of dissolving a polyimide polymer such as a polyimide precursor and polyimide (also referred to as a good solvent), and further, coating properties of a polyimide film and a liquid crystal alignment film There is also an effect to increase. That is, the specific solvent of the present invention usually has a lower surface tension as a solvent than NMP that is used as a good solvent, so that a coating solution using the specific solvent is compared with a coating solution that does not use it. As a result, the spreadability of the coating solution on the substrate is increased. As a result, the linearity of the end portions of these films becomes high when the polyimide film and the liquid crystal alignment film are formed. Furthermore, since the wettability of the coating solution on the substrate is increased, the occurrence of pinholes accompanying repelling can be suppressed.
the specific solvent of the present invention has a lower boiling point than NMP or ⁇ -BL, which is usually used as a good solvent. Therefore, baking at the time of producing a polyimide film and a liquid crystal alignment film can be performed at a low temperature. Therefore, a liquid crystal alignment film excellent in VHR in a liquid crystal display element can be obtained even when firing at the time of producing the liquid crystal alignment film is at a low temperature.
the component (B) of the present invention is at least one polymer selected from a polyimide precursor or a polyimide.
a liquid crystal alignment film is produced using the composition of the present invention as a liquid crystal alignment treatment agent, at least selected from structures represented by the following formulas [1-1] and [1-2]: It is preferable to use at least one polymer (also referred to as a specific polymer) selected from polyimide precursors or polyimides having one type of side chain (also referred to as a specific side chain structure).
Y 1 is a single bond, — (CH 2 ) a — (a is an integer of 1 to 15), —O—, —CH 2 O—, —CONH—, — At least one linking group selected from NHCO-, -CON (CH 3 )-, -N (CH 3 ) CO-, -COO- and -OCO-, and Y 2 represents 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 Represents at least one linking group selected from O—, —COO— and —OCO—, and Y 4 represents a divalent cyclic group of at least one ring selected from a benzene ring, a cyclohexane ring and a heterocyclic ring, or A divalent organic group having 17 to
Y 5 represents a divalent cyclic group of at least one ring selected from a benzene ring, a cyclohexane ring and a heterocyclic ring, and an arbitrary hydrogen atom on these cyclic groups has 1 to 3 carbon atoms.
Y 6 represents an alkyl group having 1 to 22 carbon atoms, an alkenyl group having 2 to 22 carbon atoms, a fluorine-containing alkyl group having 1 to 22 carbon atoms, an alkoxyl group having 1 to 22 carbon atoms, and 1 carbon atom.
⁇ 22 At least one selected from fluorine-containing alkoxyl groups).
Y 7 represents a single bond, —O—, —CH 2 O—, —CONH—, —NHCO—, —CON (CH 3 ) —, —N (CH 3 ) CO— , -COO- and -OCO-, Y 8 represents an alkyl group having 8 to 22 carbon atoms or a fluorine-containing alkyl group having 6 to 18 carbon atoms).
the specific side chain structure represented by the formula [1-1] has a carbon number of 17 to 51 having a benzene ring, a cyclohexyl ring or a heterocyclic divalent cyclic group, or a steroid skeleton in the side chain portion. Having a valent organic group.
divalent cyclic groups such as a benzene ring, a cyclohexyl ring or a heterocyclic ring, or a divalent organic group having 17 to 51 carbon atoms and having a steroid skeleton have a rigid structure.
the composition containing the specific solvent of the present invention and at least one polymer selected from polyimide precursors or polyimides is excellent in coating properties and forms a polyimide film even at low temperature firing. It becomes the composition which can be obtained.
the liquid crystal aligning agent obtained from the composition of the present invention can provide a liquid crystal alignment film having excellent coating properties. Furthermore, a liquid crystal alignment film having excellent VHR in a liquid crystal display element can be obtained even when the baking for producing the liquid crystal alignment film is performed at a low temperature. Therefore, by using this liquid crystal alignment film, a highly reliable liquid crystal display element having excellent display characteristics can be provided.
the liquid crystal alignment treatment obtained from the composition containing the specific solvent of the present invention and the polyimide precursor having the specific side chain structure represented by the formula [1-1] or at least one polymer selected from polyimides can obtain a liquid crystal alignment film having excellent VHR in the liquid crystal display element even when the above-described effects, that is, baking during the production of the liquid crystal alignment film is at a low temperature. Therefore, by using this liquid crystal alignment film, a highly reliable liquid crystal display element having more excellent display characteristics can be provided.
the specific solvent of the present invention is a solvent represented by the following formula [A].
X 1 and X 2 each independently represent an alkyl group having 1 to 3 carbon atoms (eg, a methyl group, an ethyl group, a propyl group or an isopropyl group), preferably a methyl group or ethyl Group, particularly preferably a methyl group.
X 3 and X 4 each independently represent an alkyl group having 1 to 3 carbon atoms (eg, a methyl group, an ethyl group, a propyl group, or an isopropyl group), preferably a methyl group or an ethyl group Group, particularly preferably a methyl group.
the amount of the specific solvent of the present invention is preferably 5 to 80% by mass of the total solvent contained in the composition and the liquid crystal aligning agent in order to further improve the wettability of the coating solution to the substrate described above. Among these, 5 to 75% by mass is preferable. A more preferred range is 5 to 70% by mass, and a further more preferred range is 10 to 60% by mass.
the specific polymer which is the component (B) of the present invention is at least one polymer selected from a polyimide precursor and a polyimide (also collectively referred to as a polyimide polymer).
the polyimide-type polymer of this invention is a polyimide precursor or a polyimide obtained by making a diamine component and a tetracarboxylic acid component react.
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 are each independently a hydrogen atom or a carbon number of 1 to 5 represents an alkyl group
a 3 and A 4 each independently represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms or an acetyl group
n represents a positive integer
diamine component examples include diamine compounds having two primary or secondary amino groups in the molecule.
examples of the tetracarboxylic acid component include a tetracarboxylic acid compound, a tetracarboxylic dianhydride, a tetracarboxylic acid dihalide compound, a tetracarboxylic acid dialkyl ester compound, and a tetracarboxylic acid dialkyl ester dihalide compound.
a diamine compound having two primary or secondary amino groups in the molecule a tetracarboxylic acid compound or tetra It can be obtained by reacting with a carboxylic anhydride.
the diamine compound, a tetracarboxylic acid dihalide compound, a tetracarboxylic acid dialkyl ester compound, or It can be obtained by reacting with a tetracarboxylic acid dialkyl ester dihalide compound.
an alkyl group having 1 to 5 carbon atoms can be introduced into A 1 and A 2 represented by the formula [a] in the polyamic acid obtained by the above method.
the polyimide polymer of the present invention uses a diamine compound having at least one specific side chain structure selected from the structures represented by the following formulas [1-1] and [1-2] as a part of the raw material. It is preferably at least one polymer selected from polyimide precursors and polyimides.
Y 1 is a bond, — (CH 2 ) a — (a is an integer of 1 to 15), —O—, —CH 2 O—, —CONH—, —NHCO—. , —CON (CH 3 ) —, —N (CH 3 ) CO—, —COO— and —OCO—.
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 is a single bond, — (CH 2 ) c — (c is an integer of 1 to 15), —O—, —CH 2 O—, —COO— and —OCO.
Y 4 is a divalent cyclic group of at least one ring selected from a benzene ring, a cyclohexane ring and a heterocyclic ring, and an arbitrary hydrogen atom on these cyclic groups is a carbon It may be substituted with 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, a fluorine-containing alkoxyl group having 1 to 3 carbon atoms, or a fluorine atom.
Y 4 may be a divalent organic group selected from organic groups having 17 to 51 carbon atoms and having a steroid skeleton.
a divalent cyclic group of a benzene ring or a cyclohexane ring, or a divalent organic group having 17 to 51 carbon atoms and having a steroid skeleton is preferable.
Y 5 represents a divalent cyclic group of at least one ring selected from a benzene ring, a cyclohexane ring, and a heterocyclic ring, and any hydrogen atom on these cyclic groups is carbon It may be substituted with 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, a fluorine-containing alkoxyl group having 1 to 3 carbon atoms, or a fluorine atom.
a benzene ring or a cyclohexane ring is preferable.
n represents an integer of 0 to 4.
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 22 carbon atoms, an alkenyl group having 2 to 22 carbon atoms, a fluorine-containing alkyl group having 1 to 22 carbon atoms, an alkoxyl group having 1 to 22 carbon atoms, and At least one selected from fluorine-containing alkoxyl groups having 1 to 22 carbon atoms is shown.
Groups are preferred. More preferably, it is an alkyl group having 1 to 12 carbon atoms, an alkenyl group having 2 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 1 to Y 6 and n in the formula [1-1] are listed in Tables 6 to 47 on pages 13 to 34 of International Publication No. 2011/132751 (published 2011.10.27). (2-1) to (2-629) are the same combinations.
Y 1 to Y 6 in the present invention are shown as Y 1 to Y 6 , but Y 1 to Y 6 are read as Y 1 to Y 6 .
the organic group having 17 to 51 carbon atoms having a steroid skeleton in the present invention has 12 to 20 carbon atoms having a steroid skeleton.
An organic group having 12 to 25 carbon atoms having a steroid skeleton is to be read as an organic group having 17 to 51 carbon atoms having a steroid skeleton.
Y 7 represents a single bond, —O—, —CH 2 O—, —CONH—, —NHCO—, —CON (CH 3 ) —, —N (CH 3 ) CO—, — It represents at least one linking group selected from COO— and —OCO—.
a single bond, —O—, —CH 2 O—, —CONH—, —CON (CH 3 ) — or —COO— is preferable. More preferably, they are a single bond, —O—, —CONH— or —COO—.
Y 8 represents an alkyl group having 8 to 22 carbon atoms or a fluorine-containing alkyl group having 6 to 18 carbon atoms. Of these, an alkyl group having 8 to 18 carbon atoms is preferable.
the method for introducing the specific side chain structure of the present invention into the specific polymer is not particularly limited, but a diamine compound having a specific side chain structure is preferably used for the diamine component.
a diamine compound also referred to as a specific side chain diamine compound
the diamine compound whose amino group in following formula [1a] is a secondary amino group can also be used.
Y represents at least one structure selected from the structures represented by Formula [1-1] and Formula [1-2].
a preferable combination of Y 1 to Y 6 and n when Y in the formula [1a] represents the formula [1-1] is as described above.
m represents an integer of 1 to 4. Of these, 1 is preferable.
Specific examples of the specific side chain type diamine compound of the present invention include, for example, diamine compounds represented by the following formulas [1a-1] to [1a-34], and these amino groups are secondary amino groups. A certain diamine compound is mentioned.
R 1 , R 3 and R 5 are each independently —O—, —OCH 2 —, —CH 2 O—, —COOCH 2 — Or —CH 2 OCO—, wherein R 2 , R 4 and R 6 are each independently linear or branched having 1 to 22 carbon atoms in the formulas [1a-1] to [1a-3] And a linear or branched alkoxyl group having 1 to 22 carbon atoms, a linear or branched fluorine-containing alkyl group having 1 to 22 carbon atoms, or a fluorine-containing alkoxyl group having 1 to 22 carbon atoms).
R 1 , R 3 and R 5 are each independently —COO—, —OCO—, —CONH—, —NHCO—, —COOCH 2 —, —CH 2 OCO—, —CH 2 O—, —OCH 2 — or —CH 2 —, in which R 2 , R 4 and R 6 are represented by the formulas [1a-4] to [1a-6] Each independently containing a linear or branched alkyl group having 1 to 22 carbon atoms, a linear or branched alkoxyl group having 1 to 22 carbon atoms, or a linear or branched fluorine group having 1 to 22 carbon atoms An alkyl group or a fluorine-containing alkoxyl group having 1 to 22 carbon atoms).
R 1 and R 3 are each independently —COO—, —OCO—, —CONH—, —NHCO—, —COOCH 2 —, — CH 2 OCO—, —CH 2 O—, —OCH 2 —, —CH 2 —, —O— or —NH—, wherein R 2 and R 4 are each independently fluorine, cyano, trifluoro A methyl group, a nitro group, an azo group, a formyl group, an acetyl group, an acetoxy group or a hydroxyl group).
R 1 and R 2 each independently represents a linear or branched alkyl group having 3 to 12 carbon atoms, and 1,4-cyclohexene
the cis-trans isomerism of silene is the trans isomer, respectively).
R 1 and R 2 each independently represents a linear or branched alkyl group having 3 to 12 carbon atoms, and represents 1,4-cyclohexene.
the cis-trans isomerism of silene is the trans isomer, respectively).
a 4 is a linear or branched alkyl group having 3 to 20 carbon atoms which may be substituted with a fluorine atom, and A 3 is a 1,4-cyclohexylene group or A 2 -phenylene group, A 2 is an oxygen atom or —COO— * (where a bond marked with “*” is bonded to A 3 ), and 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.
a 1 to A 4 each independently represents an alkyl group having 1 to 22 carbon atoms or a fluorine-containing alkyl group).
the particularly preferred side chain type diamine compounds having the particularly preferred structures are those represented by the formulas [1a-1] to [1a- 6], formula [1a-9] to formula [1a-13] or formula [1a-24] to formula [1a-31].
the specific side chain diamine compound in the specific polymer of the present invention is preferably 10 mol% or more and 80 mol% or less of the entire diamine component. Particularly preferred is 10 mol% or more and 70 mol% or less.
the specific side chain type diamine compound of the present invention includes the solubility of the specific polymer of the present invention in a solvent, the coating properties of the composition and the liquid crystal alignment agent, the alignment property of liquid crystal when used as a liquid crystal alignment film, and the voltage holding ratio. Depending on the characteristics such as accumulated charge, one kind or a mixture of two or more kinds may be used.
the specific polymer of the present invention is preferably a polymer using, as a diamine component, a diamine compound having at least one substituent selected from a carboxyl group (COOH group) and a hydroxyl group (OH group).
diamine compound represented by the following formula [2a] it is preferable to use a diamine compound represented by the following formula [2a].
the diamine compound whose amino group in following formula [2a] is a secondary amino group can also be used.
A represents a substituent having at least one structure selected from the following formulas [2-1] and [2-2].
a represents an integer of 0 to 4.
b represents an integer of 0 to 4.
m represents an integer of 1 to 4.
2,4-diaminophenol 3,5-diaminophenol, 3,5-diaminobenzyl alcohol, 2,4-diaminobenzyl alcohol, 4,6-diaminoresorcinol, 2,4-diaminobenzoic acid 2,5-diaminobenzoic acid or 3,5-diaminobenzoic acid.
2,4-diaminobenzoic acid 2,5-diaminobenzoic acid or 3,5-diaminobenzoic acid is preferable.
diamine compounds represented by the following formulas [2a-1] to [2a-4] and diamine compounds in which these amino groups are secondary amino groups can also be used.
a 1 represents 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 And represents at least one linking group selected from (CH 3 ) — and —N (CH 3 ) CO—, each of m 1 and m 2 independently represents an integer of 0 to 4, and m 1 + m 2 represents an integer of 1 to 4, and in formula [2a-2], m 3 and m 4 each independently represent an integer of
the diamine compound having at least one substituent selected from a carboxyl group (COOH group) and a hydroxyl group (OH group) in the specific polymer of the present invention is 10 mol% or more and 80 mol% or less of the entire diamine component. Is preferred. Particularly preferred is 10 mol% or more and 70 mol% or less.
the diamine compound having at least one substituent selected from the carboxyl group (COOH group) and hydroxyl group (OH group) of the present invention is soluble in the solvent of the specific polymer of the present invention, composition and liquid crystal alignment treatment.
One type or a mixture of two or more types can be used depending on the properties such as the coating property of the agent, the orientation of the liquid crystal in the case of the liquid crystal alignment film, the voltage holding ratio, and the accumulated charge.
B 1 represents —O—, —NH—, —N (CH 3 ) —, —CONH—, —NHCO—, —CH 2 O—, —OCO—, —CON (CH 3 ).
at least one linking group selected from — and —N (CH 3 ) CO— represents a diamine compound. It is preferable because it is easy to synthesize.
Particularly preferred is —O—, —CONH— or —CH 2 O—.
B 2 is a single bond, a divalent group of an aliphatic hydrocarbon having 1 to 20 carbon atoms, a divalent group of a non-aromatic cyclic hydrocarbon, or a divalent group of an aromatic hydrocarbon. At least one selected from the group is shown.
the divalent group of the aliphatic hydrocarbon having 1 to 20 carbon atoms may be linear or branched. Moreover, you may have an unsaturated bond. Of these, an alkylene group having 1 to 10 carbon atoms is preferable.
non-aromatic hydrocarbon examples include a cyclopropane ring, a cyclobutane ring, a cyclopentane ring, a cyclohexane ring, a cycloheptane ring, a cyclooctane ring, a cyclononane ring, a cyclodecane ring, a cycloundecane ring, a cyclododecane ring, a cyclo Tridecane ring, cyclotetradecane ring, cyclopentadecane ring, cyclohexadecane ring, cycloheptadecane ring, cyclooctadecane ring, cyclononadecane ring, cycloicosane ring, tricycloeicosane ring, tricyclodecosan ring, bicycloheptane ring, decahydr
a cyclopropane ring, cyclobutane ring, cyclopentane ring, cyclohexane ring, cycloheptane ring, norbornene ring or adamantane ring is preferred.
the aromatic hydrocarbon group include a benzene ring, naphthalene ring, tetrahydronaphthalene ring, azulene ring, indene ring, fluorene ring, anthracene ring, phenanthrene ring or phenalene ring.
a benzene ring, naphthalene ring, tetrahydronaphthalene ring, fluorene ring or anthracene ring is preferred.
Preferred B 2 in the formula [3a] is a single bond, an alkylene group having 1 to 10 carbon atoms, or a cyclopropane ring, a cyclobutane ring, a cyclopentane ring, a cyclohexane ring, a cycloheptane ring, a norbornene ring, an adamantane ring, or a benzene ring.
a single bond, an alkylene group having 1 to 5 carbon atoms, or a divalent group of a cyclohexane ring or a benzene ring is preferable.
B 3 represents a single bond, —O—, —NH—, —N (CH 3 ) —, —CONH—, —NHCO—, —COO—, —OCO—, —CON (CH 3 ) —, —N (CH 3 ) CO— and —O (CH 2 ) m — (m is an integer of 1 to 5).
a single bond, —O—, —COO—, —OCO— or —O (CH 2 ) m — (m is an integer of 1 to 5) is preferable. More preferred is a single bond, —O—, —OCO— or —O (CH 2 ) m — (m is an integer of 1 to 5).
B 4 is a nitrogen-containing heterocyclic group, and contains at least one structure selected from the following formulas [3a-1], [3a-2] and [3a-3] Heterocyclic group.
Z 11 represents an alkyl group having 1 to 5 carbon atoms).
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, cinnoline ring, phenanthroline ring, indole ring, quinoxaline ring, benzothiazole ring, phenothiazine ring, oxadiazole ring or acridine ring.
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, or a benzimidazole ring is preferable. More preferred are a pyrrole ring, an imidazole ring, a pyrazole ring, a pyridine ring or a pyrimidine ring. Also, B 3 in the formula [3a] are expressions included in the B 4 [3a-1], that is bonded to the structure and not adjacent ring atoms of the formula [3a-2] and the formula [3a-3] Is preferred.
n is an integer of 1 to 4, preferably 1 or 2 from the viewpoint of reactivity with the tetracarboxylic acid component.
B 1 represents —CONH—
B 2 represents an alkylene group having 1 to 5 carbon atoms
B 3 represents a single bond
4 is a diamine compound in which 4 represents an imidazole ring or a pyridine ring and n represents 1.
the bonding position of the two amino groups (—NH 2 ) in the formula [3a] is not limited. Specifically, with respect to the side chain linking group (—B 1 —), 2, 3 position, 2, 4 position, 2, 5 position, 2, 6 position on the benzene ring, 3, 6 4 positions or 3, 5 positions. Among these, from the viewpoint of reactivity when synthesizing the polyamic acid, the 2,4 position, the 2,5 position, or the 3,5 position is preferable. Considering the ease in synthesizing the diamine compound, the positions 2, 4 or 2, 5 are more preferable.
the diamine compound having a nitrogen-containing heterocycle represented by the formula [3a] in the specific polymer of the present invention is preferably 10 mol% or more and 80 mol% or less of the entire diamine component. Particularly preferred is 10 mol% or more and 70 mol% or less.
the diamine compound having a nitrogen-containing heterocyclic ring represented by the above formula [3a] of the present invention is soluble in the solvent of the specific polymer of the present invention, the coating property of the composition and the liquid crystal aligning agent, and the liquid crystal alignment film.
the liquid crystal orientation voltage holding ratio, accumulated charge, etc., one kind or a mixture of two or more kinds can be used.
the specific polymer of the present invention includes diamine compounds represented by the following formulas [a-1] to [a-13] and amino groups thereof as other diamine compounds.
a diamine compound which is a secondary amino group can also be used.
a 1 and A 3 each independently represent —COO—, —OCO—, —CONH—, —NHCO—, —CH 2 —, —O—, —CO— and Represents at least one linking group selected from —NH—
a 2 represents a linear or branched alkyl group having 1 to 22 carbon atoms, or a linear or branched fluorine group having 1 to 22 carbon atoms.
a 4 and A 6 are each independently —COO—, —OCO—, —CONH—, —NHCO—, —CH 2 —, —O—. , —CO— and —NH—, wherein A 5 represents a linear or branched alkyl group having 1 to 22 carbon atoms, or a linear group having 1 to 22 carbon atoms. Or a branched fluorine-containing alkyl group).
a 1 and A 3 each independently represent —COO—, —OCO—, —CONH—, —NHCO—, —CH 2 —, —O—, —CO— and Represents at least one linking group selected from —NH—, and A 2 represents a linear or branched alkyl group having 1 to 22 carbon atoms, or a linear or branched fluorine group having 1 to 22 carbon atoms.
a 4 and A 6 are each independently —COO—, —OCO—, —CONH—, —NHCO—, —CH 2 —, —O—.
a 5 represents a linear or branched alkyl group having 1 to 22 carbon atoms, or a linear group having 1 to 22 carbon atoms. Or a branched fluorine-containing alkyl group).
a 1 and A 3 each independently represent —COO—, —OCO—, —CONH—, —NHCO—, —CH 2 —, —O—, —CO— and Represents at least one linking group selected from —NH—
a 2 represents a linear or branched alkyl group having 1 to 22 carbon atoms, or a linear or branched fluorine group having 1 to 22 carbon atoms.
a 4 and A 6 each independently represent —COO—, —OCO—, —CONH—, —NHCO—, —CH 2 —, —O—. , —CO— and —NH—, wherein A 5 represents a linear or branched alkyl group having 1 to 22 carbon atoms, or a linear group having 1 to 22 carbon atoms. Or a branched fluorine-containing alkyl group).
p represents an integer of 1 to 10
R 1 represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms
n represents an integer of 1 to 10).
diamine compounds the following diamine compounds and diamine compounds in which these amino groups are secondary amino groups can also be used.
p-phenylenediamine 2,3,5,6-tetramethyl-p-phenylenediamine, 2,5-dimethyl-p-phenylenediamine, m-phenylenediamine, 2,4-dimethyl-m- Phenylenediamine, 2,5-diaminotoluene, 2,6-diaminotoluene, 4,4'-diaminobiphenyl, 3,3'-dimethyl-4,4'-diaminobiphenyl, 3,3'-dimethoxy-4,4 '-Diaminobiphenyl, 3,3'-dihydroxy-4,4'-diaminobiphenyl, 3,3'-dicarboxy-4,4'-diaminobiphenyl, 3,3'-difluoro-4,4'-diaminobiphenyl 3,3′-trifluoromethyl-4,4′-diaminobiphenyl, 3,4′-diaminobipheny
the other diamine compound of the present invention includes the solubility of the specific polymer of the present invention in a solvent, the coating property of the composition and the liquid crystal alignment treatment agent, the alignment property of the liquid crystal when used as a liquid crystal alignment film, the voltage holding ratio, and the accumulated charge. Depending on the characteristics, one kind or a mixture of two or more kinds can be used.
tetracarboxylic acid component for producing these polyimide polymers
a tetracarboxylic dianhydride represented by the following formula [4] not only the tetracarboxylic dianhydride represented by the formula [4] but also the tetracarboxylic acid derivative tetracarboxylic acid, tetracarboxylic acid dihalide compound, tetracarboxylic acid dialkyl ester compound or tetracarboxylic acid dialkyl ester di Halide compounds can also be used (the tetracarboxylic dianhydride represented by the formula [4] and its derivatives are collectively referred to as a specific tetracarboxylic acid component). (In Formula [4], Z represents at least one structure selected from structures represented by Formula [4a] to Formula [4k] below).
Z 1 to Z 4 each independently represent a hydrogen atom, a methyl group, an ethyl group, a propyl group, a chlorine atom or a phenyl group.
Z 5 and Z 6 each independently represent a hydrogen atom or a methyl group.
formula [4a], formula [4c] to formula [4g] or formula [4k] The tetracarboxylic dianhydride of the structure shown by these and its tetracarboxylic acid derivative are preferable. More preferable is the structure represented by the formula [4a] or the formula [4e] to the formula [4g]. Particularly preferred are tetracarboxylic dianhydrides and their tetracarboxylic acid derivatives having the structure represented by [4a], formula [4e] or formula [4f].
the specific tetracarboxylic acid component in the specific polymer of the present invention is preferably 1 mol% to 100 mol% in 100 mol% of all tetracarboxylic acid components. Of these, 5 mol% to 95 mol% is preferable. More preferred is 20 mol% to 80 mol%.
the specific tetracarboxylic acid component of the present invention includes the solubility of the specific polymer of the present invention in a solvent, the coating properties of the composition and the liquid crystal alignment treatment agent, the alignment of liquid crystals when used as a liquid crystal alignment film, the voltage holding ratio, One type or a mixture of two or more types can be used depending on characteristics such as accumulated charge.
tetracarboxylic acid components other than the specific tetracarboxylic acid component can be used as long as the effects of the present invention are not impaired.
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 1,2,5,6-naphthalenetetracarboxylic acid, 1,4,5,8-naphthalenetetracarboxylic 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 ′ -Benzophenone tetracarboxylic 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-2,2-bis (3,4-dicarboxyphenyl) propane, bis (3,4-dicarboxyphenyl) dimethylsilane
the other tetracarboxylic acid components of the present invention are the solubility of the specific polymer of the present invention in a solvent, the coating properties of the composition and the liquid crystal aligning agent, the orientation of the liquid crystal when used as a liquid crystal alignment film, and the voltage holding ratio. Depending on the characteristics such as accumulated charge, one kind or a mixture of two or more kinds may be used.
the specific polymer that is, the method for producing these polyimide polymers is not particularly limited. Usually, it is obtained by reacting a diamine component and a tetracarboxylic acid component. In general, at least one tetracarboxylic acid component selected from the group consisting of tetracarboxylic dianhydrides and their derivatives is reacted with a diamine component consisting of one or more diamine compounds. And a method of obtaining a polyamic acid.
a method of obtaining polyamic acid by polycondensation of tetracarboxylic dianhydride and primary or secondary diamine compound, dehydration polycondensation reaction of tetracarboxylic acid and primary or secondary diamine compound A method of obtaining polyamic acid by polycondensation of a tetracarboxylic acid dihalide and a primary or secondary diamine compound is used.
polyimide In order to obtain 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 carried out in a solvent with the diamine component and the tetracarboxylic acid component.
the solvent used in that case may be the specific solvent of the present invention, but is not particularly limited as long as the produced polyimide precursor is dissolved. Although the specific example of the solvent used for reaction below is given, it is not limited to these examples.
Examples include N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone or ⁇ -butyrolactone, N, N-dimethylformamide, N, N-dimethylacetamide, dimethyl sulfoxide or 1,3-dimethyl-imidazolidinone. It is done.
the solvent solubility of the polyimide precursor is high, methyl ethyl ketone, cyclohexanone, cyclopentanone, 4-hydroxy-4-methyl-2-pentanone, or the following formulas [D-1] to [D-3]
the indicated solvents can be used.
D 1 represents an alkyl group having 1 to 3 carbon atoms
D 2 represents an alkyl group having 1 to 3 carbon atoms
D-3 represents an alkyl group having 1 to 4 carbon atoms
solvents may be used alone or in combination. Furthermore, even if it is a solvent which does not melt
the polymerization temperature 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 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 reaction can be carried out at a high concentration, and then a 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.
Examples of the method for imidizing the polyimide precursor include thermal imidization in which the polyimide precursor solution is heated as it is or catalytic imidization in which a catalyst is added to the polyimide precursor solution.
the 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 catalytic 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 ° C to 250 ° C, preferably 0 ° C to 180 ° C. it can.
the amount of the basic catalyst is 0.5 mol times to 30 mol times, preferably 2 mol times to 20 mol times of the amic acid groups, and the amount of the acid anhydride is 1 mol times to 50 mol times of the amic acid groups, The amount is preferably 3 mole times to 30 mole times.
the basic catalyst include pyridine, triethylamine, trimethylamine, tributylamine, and trioctylamine.
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.
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 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 precipitated in the solvent can be collected by filtration, and then dried by normal temperature or reduced pressure at room temperature or by heating.
the polymer collected by precipitation is redissolved in a solvent and then re-precipitation and collection is repeated 2 to 10 times, impurities in the polymer can be reduced.
the solvent at this time include alcohols, ketones, and hydrocarbons, and it is preferable to use three or more kinds of solvents selected from these because purification efficiency is further increased.
composition of the present invention and the liquid crystal alignment treatment agent using the composition are coating solutions for forming a polyimide film and a liquid crystal alignment film (also collectively referred to as a resin film), and contain a specific solvent and a specific polymer.
a coating solution for forming a resin film is a coating solution for forming a resin film.
the specific polymer of the present invention may be any polyimide polymer such as polyamic acid, polyamic acid alkyl ester and polyimide. Of these, polyamic acid alkyl ester or polyimide is preferable. More preferably, it is a polyimide.
All the polymer components in the composition and the liquid crystal aligning agent of the present invention may all be the specific polymer of the present invention. In that case, you may use 2 or more types of specific polymers of this invention in mixture.
other polymers may be mixed with the specific polymer. Examples of other polymers include cellulosic polymers, acrylic polymers, methacrylic polymers, polystyrene, polyamides, and polysiloxanes.
the content of the other polymer is 0.5 to 30 parts by mass with respect to 100 parts by mass of the specific polymer of the present invention. Of these, 1 to 20 parts by mass is preferable.
the specific polymer has a specific side chain structure represented by the formula [1-1] of the present invention. Is preferably used. Among these, it is preferable to use a specific polymer using the specific side chain diamine compound represented by the formula [1a] having the specific side chain structure represented by the formula [1-1].
a liquid crystal alignment film for a mode that requires a pretilt angle of liquid crystal such as a TN (twisted nematic) mode or a VA (vertical alignment) mode, may be a specific polymer using a specific side chain type diamine compound. good.
a specific polymer using a specific side chain diamine compound and a specific polymer not using a specific side chain diamine compound may be mixed and used.
the content of the specific polymer not using the specific side chain diamine compound is 10 to 300 parts by mass with respect to 100 parts by mass of the specific polymer using the specific side chain diamine compound. preferable. Of these, 20 to 200 parts by mass is preferable.
the solvent in the composition of the present invention and the liquid crystal aligning agent is preferably 70 to 99.9% by mass from the viewpoint of forming a uniform resin film by coating. This content can be appropriately changed depending on the film thickness of the target polyimide film and liquid crystal alignment film.
the solvent at that time all may be the specific solvent of the present invention, but a solvent for dissolving the specific polymer of the present invention, that is, a good solvent may be used at the same time.
a good solvent is given to the following, it is not limited to these examples.
N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone or ⁇ -butyllactone (also referred to as component (C) above) is preferably used.
components (C) are preferably 1 to 70% by mass of the entire solvent contained in the composition and the liquid crystal aligning agent. Among these, 5 to 65% by mass is preferable. A more preferred range is 5 to 60% by mass, and a further more preferred range is 10 to 60% by mass.
the good solvent may be used alone or in combination of two or more depending on the solubility of the specific polymer of the present invention in the solvent and the applicability of the composition and the liquid crystal alignment treatment agent.
the composition of the present invention and the liquid crystal aligning agent are organic solvents that improve the coating properties and surface smoothness of the resin film when the composition and the liquid crystal aligning agent are applied, That is, it is also preferable to use a poor solvent.
a poor solvent is given to the following, it 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, 1,2- Ethane All, 1,2-propanediol, 1,3-propan
1-hexanol, cyclohexanol, 1,2-ethanediol, 1,2-propanediol, propylene glycol monobutyl ether, ethylene glycol monobutyl ether, dipropylene glycol dimethyl ether or the above formulas [D-1] to [D -3] (also referred to as component (D) above) is preferably used.
components (D) are preferably 10 to 80% by mass of the total solvent contained in the composition and the liquid crystal aligning agent.
10 to 70% by mass is preferable.
a more preferred range is 20 to 70% by mass, and a further more preferred range is 20 to 60% by mass.
the poor solvent may be used alone or in combination of two or more depending on the solubility of the specific polymer of the present invention in the solvent and the applicability of the composition and the liquid crystal alignment treatment agent.
composition and the liquid crystal aligning agent of the present invention include at least one substitution selected from 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. It is preferable to introduce a crosslinkable compound having a group or a crosslinkable compound having a polymerizable unsaturated bond. It is necessary to have two or more of these substituents and polymerizable unsaturated bonds 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-
the crosslinkable compound having an oxetane group is a crosslinkable compound having at least two oxetane groups represented by the following formula [4A].
crosslinkable compounds represented by the formulas [4a] to [4k] described in the 58th to 59th items of International Publication No. 2011/132751 (published 2011.10.27) can be mentioned.
the crosslinkable compound having a cyclocarbonate group is a crosslinkable compound having at least two cyclocarbonate groups represented by the following formula [5A].
crosslinkable compounds represented by the formulas [5-1] to [5-42] described in the paragraphs 76 to 82 of International Publication No. 2012/014898 (published in 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, a urea resin, a guanamine resin, and a glycoluril.
a melamine resin, a urea resin, a guanamine resin, and a glycoluril such as a melamine resin, a urea resin, a guanamine resin, and a glycoluril.
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 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
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.
Examples of the benzene or phenolic compound 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 or 2,6-dihydroxymethyl-p-tert-butylphenol.
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 or glycerin polyglycidyl ether poly (meth) acrylate, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, tetraethylene glycol di (Meth) acrylate, polyethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, butylene Cold di (meth) 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 diglycidyl ether
E 1 represents at least one selected from a cyclohexane ring, a bicyclohexane ring, a benzene ring, a biphenyl ring, a terphenyl ring, a naphthalene ring, a fluorene ring, an anthracene ring, and a phenanthrene ring
E 2 represents And represents a group selected from the following formula [7a] or [7b], and n represents an integer of 1 to 4.
crosslinkable compound used for the composition of this invention and a liquid-crystal aligning agent may be one type, and may combine two or more types.
the content of the crosslinkable compound in the composition and 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 the polymer components.
the amount is preferably 0.1 parts by mass to 100 parts by mass with respect to 100 parts by mass of all the polymer components. More preferred is 1 to 50 parts by mass.
composition and liquid crystal alignment treatment agent of the present invention improve the uniformity of the film thickness and surface smoothness of the resin film when the composition and the liquid crystal alignment treatment agent are applied. Can be used.
Examples of the compound that improves the uniformity of the film thickness and the surface smoothness of the resin coating include fluorine-based surfactants, silicone-based surfactants, and nonionic surfactants.
F-top EF301, EF303, EF352 (above, manufactured by Tochem Products), MegaFuck F171, F173, R-30 (above, manufactured by Dainippon Ink), Florard FC430, FC431 (or more) And Asahi Guard AG710, Surflon S-382, SC101, SC102, SC103, SC104, SC105, SC106 (above, manufactured by Asahi Glass Co., Ltd.).
the ratio of these surfactants to be used is preferably 0.01 parts by mass to 2 parts by mass, and more preferably 0.00 parts by mass with respect to 100 parts by mass of all the polymer components contained in the composition and the liquid crystal aligning agent. 01 parts by mass to 1 part by mass.
the composition and liquid crystal alignment treatment agent of the present invention include As long as the effects of the invention are not impaired, a dielectric material or a conductive material for the purpose of changing electrical characteristics such as dielectric constant and conductivity of the resin coating may be added.
the composition of the present invention can be used as a polyimide film after coating and baking on a substrate.
a plastic substrate such as a glass substrate, a silicon wafer, an acrylic substrate, a polycarbonate substrate, or a PET (polyethylene terephthalate) substrate can be used depending on a target device.
a polyimide film can also be used as a film substrate as it is.
the coating method of the composition is not particularly limited, but industrially, there are methods such as a dipping method, a roll coater method, a slit coater method, a spinner method, a spray method, screen printing, offset printing, flexographic printing, or an inkjet method. It is common. You may use these according to the objective.
the solvent is evaporated at 50 to 300 ° C., preferably 80 to 250 ° C. by a heating means such as a hot plate, a heat circulation oven or an IR (infrared) oven, and the polyimide film and can do.
a heating means such as a hot plate, a heat circulation oven or an IR (infrared) oven
the polyimide film can be produced even at a temperature of 200 ° C. or lower.
the thickness of the polyimide film after firing can be adjusted to 0.01 to 100 ⁇ m depending on the purpose.
the liquid crystal alignment treatment agent using the composition of the present invention can be used as a liquid crystal alignment film by applying alignment treatment by rubbing treatment or light irradiation after coating and baking on a substrate.
alignment treatment by rubbing treatment or light irradiation after coating and baking on a substrate.
VA mode it can be used as a liquid crystal alignment film without alignment treatment.
the substrate used in this case is not particularly limited as long as it is a highly transparent substrate.
a plastic substrate such as an acrylic substrate, a polycarbonate substrate, or a PET (polyethylene terephthalate) substrate can also be used.
a substrate on which an ITO (indium tin oxide) electrode or the like 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, a method of screen printing, offset printing, flexographic printing, an inkjet method, or the like is generally used.
Other coating methods include a dipping method, a roll coater method, a slit coater method, a spinner method, and a spray method, and these may be used depending on the purpose.
the liquid crystal aligning agent 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.
a liquid crystal aligning film can be produced also at the temperature of 200 degrees C or less. 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 150 nm. When the liquid crystal is horizontally aligned or tilted, the fired liquid crystal alignment film is treated by rubbing or irradiation with polarized ultraviolet rays.
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 aligning 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 of one substrate, and place the other side of the liquid crystal alignment film on the other side. And a method of sealing the substrate by injecting liquid crystal under reduced pressure, or 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 also preferably used for a liquid crystal display device produced 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.
ultraviolet rays are suitable as the active energy ray.
the wavelength of ultraviolet rays is 300 to 400 nm, preferably 310 to 360 nm. In the case of polymerization by heating, 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 liquid crystal display element controls a 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.
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 method, a liquid crystal cell is prepared, and a polymerizable compound is applied by at least one of ultraviolet irradiation and heating. Polymerization can control the orientation of liquid crystal molecules.
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 and the liquid crystal is injected under reduced pressure, or 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 substrate is bonded and sealed.
a polymerizable compound that is polymerized by heat or ultraviolet irradiation is mixed.
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 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 After producing the liquid crystal cell, the polymerizable compound is polymerized by irradiating heat or ultraviolet rays while applying an AC or DC voltage to the liquid crystal cell. Thereby, the alignment of the liquid crystal molecules can be controlled.
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 preferable to use it for a liquid crystal display element manufactured through a step of arranging a liquid crystal alignment film containing a group and applying a voltage between electrodes, that is, an SC-PVA mode.
ultraviolet rays are suitable as the active energy ray.
the wavelength of ultraviolet rays is 300 to 400 nm, preferably 310 to 360 nm. In the case of polymerization by heating, the heating temperature is 40 to 120 ° C, preferably 60 to 80 ° C.
a pair of substrates on which the liquid crystal alignment film of the present invention is formed is prepared, spacers are dispersed on the liquid crystal alignment film of one substrate, and the liquid crystal alignment film surface is prepared.
the other substrate is bonded so that the inner side is on the inside and the liquid crystal is injected under reduced pressure to seal, or the liquid crystal is dropped on the liquid crystal alignment film surface on which spacers are dispersed and then the substrate is bonded and sealed.
the orientation of the liquid crystal molecules can be controlled 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 becomes a liquid crystal alignment film having excellent coating properties, and furthermore, even when firing at the time of producing the liquid crystal alignment film is at a low temperature, It becomes a liquid crystal alignment film excellent in VHR which is a characteristic. Therefore, the 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 is used for a large-screen high-definition liquid crystal television, a small-sized car navigation system, a smartphone, and the like. It can be suitably used.
⁇ Monomer for producing the polyimide polymer of the present invention (Specific side chain diamine compound of the present invention) A1: 1,3-diamino-4- [4- (trans-4-n-heptylcyclohexyl) phenoxy] benzene (specific side chain having a specific side chain structure represented by the formula [1-1] of the present invention) Type diamine compound) A2: 1,3-diamino-4- [4- (trans-4-n-heptylcyclohexyl) phenoxymethyl] benzene (specific side having a specific side chain structure represented by the formula [1-1] of the present invention) Chain-type diamine compounds) A3: 1,3-diamino-4- ⁇ 4- [trans-4- (trans-4-n-pentylcyclohexyl) cyclohexyl] phenoxy ⁇ benzene (shown by the formula [1-1] of the present invention) Specific side chain type diamine compound having specific side chain structure)
C1 A diamine compound represented by the following formula [C1] (a diamine compound having a nitrogen-containing heterocycle represented by the formula [3a] of the present invention)
C2 a diamine compound represented by the following formula [C2] (a diamine compound having a nitrogen-containing heterocycle represented by the formula [3a] of the present invention)
E1 1,2,3,4-cyclobutanetetracarboxylic dianhydride
E2 bicyclo [3,3,0] octane-2,4,6,8-tetracarboxylic dianhydride
E3 the following formula [E3
E4 tetracarboxylic dianhydride represented by the following formula [E4]
E5 tetracarboxylic dianhydride represented by the following formula [E5]
NMP N-methyl-2-pyrrolidone
NEP N-ethyl-2-pyrrolidone
⁇ -BL ⁇ -butyrolactone
BCS ethylene glycol monobutyl ether
PB propylene glycol monobutyl ether
EC diethylene glycol monoethyl ether
DME dipropylene glycol dimethyl ether
the imidation ratio of polyimide of the present invention was measured as follows. 20 mg of polyimide powder was put into an NMR (nuclear magnetic resonance) sample tube (NMR sampling tube standard, ⁇ 5 (manufactured by Kusano Kagaku)), and deuterated dimethyl sulfoxide (DMSO-d 6 , 0.05 mass% TMS (tetramethylsilane). ) Mixture) (0.53 ml) was added and completely dissolved by sonication. This solution was measured for proton NMR at 500 MHz with an NMR measuring instrument (JNW-ECA500) (manufactured by JEOL Datum).
NMR nuclear magnetic resonance
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.
NEP was added to the obtained polyamic acid solution (30.0 g), diluted to 6% by mass, acetic anhydride (4.40 g) and pyridine (3.30 g) were added as an imidization catalyst, and 3.80 ° C. was added. The reaction was allowed for 5 hours. This reaction solution was put into methanol (460 ml), and the resulting precipitate was separated by filtration. This deposit was wash
Tables 1 and 2 show the polyimide polymers of the present invention.
Tables 3 to 5 show the compositions and liquid crystal aligning agents of the present invention.
the printing area was in the range of 80 ⁇ 80 mm with respect to the center of the substrate, the printing pressure was 0.2 mm, the number of discarded substrates was 5, and printing was temporarily performed.
the time until drying was 90 seconds, temporary drying was performed on a hot plate at 70 ° C. for 5 minutes, and main firing was performed in a heat-circulating clean oven at 160 ° C. for 15 minutes.
the number of pinholes in the obtained substrate with the polyimide film was confirmed. Specifically, this polyimide film-coated substrate was visually observed under a sodium lamp, and the number of pinholes on the polyimide film was counted. The smaller the number of pinholes, the fewer the precipitates in the composition, and the better the evaluation.
Tables 6 to 8 show the number of pinholes obtained in the examples and comparative examples.
compositions obtained in the examples and comparative examples of the present invention can be used for liquid crystal alignment treatment agents. Therefore, the evaluation of pinholes in the polyimide film of the compositions obtained in the examples and comparative examples of the present invention was also evaluated as pinholes in the liquid crystal alignment film.
evaluation of printability of composition and liquid crystal aligning agent evaluation of coating film edge
evaluation of the coating film end of the polyimide film that is, polyimide film end Evaluation of linearity (also referred to as evaluation of linearity) and swell of the polyimide film end (also referred to as evaluation of swell) were performed.
Evaluation of the linearity of the end of the polyimide film was performed by observing the polyimide film at the right end with respect to the printing direction using an optical microscope. More specifically, the difference between (1) and (2) in FIG. 1 of the polyimide film image obtained by observing at an optical microscope magnification of 25 times, that is, the length of A in FIG. did. At that time, images of all polyimide films were obtained at the same magnification. The shorter the length of A, the better the linearity of the end of the polyimide film.
the evaluation of the bulge at the end of the polyimide film was performed by observing the polyimide film at the right end with respect to the printing direction with an optical microscope. Specifically, the length of B in FIG. 2 of the polyimide film image obtained by observing at an optical microscope magnification of 25 was measured. At that time, all polyimide film images were obtained at the same magnification. The shorter the length of B, the better the rise of the end of the polyimide film.
Tables 6 to 8 show the lengths A and B obtained in the examples and comparative examples.
compositions obtained in the examples and comparative examples of the present invention can be used for liquid crystal alignment treatment agents. Therefore, evaluation of the coating film edge part of the polyimide film obtained by the present Example and the comparative example was also made evaluation of the coating film edge part of a liquid crystal aligning film.
VHR voltage holding ratio
these liquid crystal alignment treatment agents were pressure filtered through a membrane filter having a pore size of 1 ⁇ m and washed with pure water and IPA (isopropyl alcohol) (40 mm long ⁇ 30 mm wide, thickness) 0.7mm)) is spin-coated on the ITO surface and heat-treated on a hot plate at 80 ° C. for 3 minutes and in a heat-circulating clean oven at 160 ° C. for 15 minutes with a liquid crystal alignment film with a thickness of 100 nm
An ITO substrate was obtained.
a rubbing apparatus having a roll diameter of 120 mm is used to rub the coated surface of this ITO substrate under the conditions of roll rotation speed: 300 rpm, roll progression speed: 20 mm / sec, push-in amount: 0.4 mm. It was.
the liquid crystal aligning agent (19) obtained by 19 methods, the liquid crystal aligning agent (21) obtained by the method of Comparative Example 1 and the liquid crystal aligning agent (22) obtained by the method of Comparative Example 2 were used.
the liquid crystal cell used was MLC-2003 (manufactured by Merck Japan) as the liquid crystal.
MLC-6608 manufactured by Merck Japan was used for the liquid crystal in the liquid crystal cell using the liquid crystal aligning agent obtained in the examples and comparative examples other than the above.
VHR voltage holding ratio
liquid crystal cell in which the measurement of VHR was completed was stored in a high-temperature bath at a temperature of 80 ° C. for 720 hours, and VHR was measured again (also referred to after storage in a high-temperature bath) under the same conditions as described above.
the evaluation was made better as the decrease in the VHR value after storage in the high-temperature bath was smaller than the VHR value immediately after production of the liquid crystal cell.
Tables 9 to 11 show the voltage holding ratio (VHR) values obtained in the examples and comparative examples.
Liquid crystal aligning agent (4) obtained by the method of Example 4 of the present invention Liquid crystal aligning agent (7) obtained by the method of Example 7 and Liquid crystal aligning agent obtained by the method of Example 15 (15) was used to evaluate ink jet coatability.
these liquid crystal alignment treatment agents are pressure filtered through a membrane filter having a pore size of 1 ⁇ m, and washed with pure water and IPA using an HIS-200 (manufactured by Hitachi Plant Technology) as an inkjet coating machine.
the coating area is 70 ⁇ 70 mm
the nozzle pitch is 0.423 mm
the scan pitch is 0.5 mm
the coating speed is 40 mm / second
the time from coating to temporary drying is 60 Second, preliminary drying was performed on a hot plate at 70 ° C. for 5 minutes, and main baking was performed in a heat circulation type clean oven at 160 ° C. for 15 minutes.
the obtained substrate with a liquid crystal alignment film was visually observed under a sodium lamp and the number of pinholes on the liquid crystal alignment film was counted. It was less than 5. Moreover, the liquid crystal aligning film excellent in the coating-film uniformity was obtained in any Example.
VHR voltage holding ratio
Liquid crystal aligning agent (6) obtained by the method of Example 6 of the present invention
Liquid crystal aligning agent (9) obtained by the method of Example 9
Liquid crystal aligning agent obtained by the method of Example 14 Using (14), production of a liquid crystal cell and evaluation of liquid crystal orientation (PSA cell) were performed. Specifically, these liquid crystal aligning agents were pressure filtered through a membrane filter having a pore size of 1 ⁇ m, washed with pure water and IPA, and a substrate with ITO electrodes (length: 40 mm ⁇ width) of 10 ⁇ 10 mm and a pattern spacing of 20 ⁇ m.
the response speed of the liquid crystal before and after UV irradiation of this liquid crystal cell was measured.
T90 ⁇ T10 from 90% transmittance to 10% transmittance was measured.
the PSA cell obtained in any of the examples confirmed that the alignment direction of the liquid crystal was controlled because the response speed of the liquid crystal cell after ultraviolet irradiation was higher than that of the liquid crystal cell before ultraviolet irradiation. . Further, in any liquid crystal cell, it was confirmed by observation with a polarizing microscope (ECLIPSE E600WPOL) (manufactured by Nikon Corporation) that the liquid crystal was uniformly aligned.
ECLIPSE E600WPOL polarizing microscope
Liquid crystal aligning agent (6) obtained by the method of Example 6 of the present invention Liquid crystal aligning agent (9) obtained by the method of Example 9 and Liquid crystal aligning agent obtained by the method of Example 14 Using (14), production of a liquid crystal cell and evaluation of liquid crystal orientation (SC-PVA cell) were performed.
the polymerizable compound (1) shown above is added to these liquid crystal aligning agents in an amount of 2% by mass with respect to 100% by mass of the total polymer components in the liquid crystal aligning agent, and at 25 ° C. for 4 hours. Stir.
the obtained liquid crystal aligning agent was pressure filtered through a membrane filter having a pore size of 1 ⁇ m, washed with pure water and IPA, and a 10 ⁇ 10 mm substrate with an ITO electrode having a pattern spacing of 20 ⁇ m (length 40 mm ⁇ width 30 mm).
Thickness 0.7mm and the center of the 10x40mm ITO electrode substrate (length 40mm x width 30mm, thickness 0.7mm) on the ITO surface is spin-coated on a hot plate at 80 ° C for 3 minutes, A heat treatment was performed at 160 ° C. for 15 minutes in a heat circulation type clean oven to obtain a substrate with a liquid crystal alignment film having a film thickness of 100 nm.
the response speed of the liquid crystal before and after UV irradiation of this liquid crystal cell was measured.
T90 ⁇ T10 from 90% transmittance to 10% transmittance was measured.
the response speed of the liquid crystal cell after ultraviolet irradiation was higher than that of the liquid crystal cell before ultraviolet irradiation. confirmed. Further, in any liquid crystal cell, it was confirmed by observation with a polarizing microscope (ECLIPSE E600WPOL) (manufactured by Nikon Corporation) that the liquid crystal was uniformly aligned.
ECLIPSE E600WPOL polarizing microscope
Example 1 To the polyamic acid solution (1) (10.0 g) having a resin solid concentration of 25% by mass obtained by the synthesis method of Synthesis Example 1, S1 (8.17 g), K1 (0.18 g), NEP (3.92 g) ) And PB (19.6 g) were added, and the mixture was stirred at 25 ° C. for 8 hours to obtain a composition (1). In this composition, no abnormality such as turbidity and generation of precipitates was observed, and it was confirmed that the composition was a uniform solution. In addition, this composition (1) was used for evaluation also as a liquid-crystal aligning agent (1).
composition (1) and liquid crystal aligning agent (1) “evaluation of printability of composition and liquid crystal aligning agent (evaluation of pinhole)”, “composition and liquid crystal aligning agent Evaluation of printability (evaluation of coating film edge) ”and“ evaluation of voltage holding ratio (VHR) (normal cell) ”were performed.
VHR voltage holding ratio
Example 2 S1 (16.8 g) and BCS (16.4 g) were added to the polyamic acid solution (2) (10.5 g) having a resin solid content concentration of 25% by mass obtained by the synthesis method of Synthesis Example 2, and at 25 ° C. The mixture was stirred for 4 hours to obtain a composition (2). In this composition, no abnormality such as turbidity and generation of precipitates was observed, and it was confirmed that the composition was a uniform solution. In addition, this composition (2) was used for evaluation also as a liquid-crystal aligning agent (2).
composition (2) and liquid crystal aligning agent (2) evaluation of printability of composition and liquid crystal aligning agent (evaluation of pinhole)
evaluation of printability evaluation of coating film edge
VHR voltage holding ratio
Example 3 S1 (13.8 g) was added to the polyimide powder (3) (1.60 g) obtained by the synthesis method of Synthesis Example 3, and dissolved by stirring at 70 ° C. for 24 hours. BCS (11.3 g) was added to this solution and stirred at 40 ° C. for 3 hours to obtain a composition (3). In this composition, no abnormality such as turbidity and generation of precipitates was observed, and it was confirmed that the composition was a uniform solution. In addition, this composition (3) was used for evaluation also as a liquid-crystal aligning agent (3).
composition (3) and liquid crystal aligning agent (3) evaluation of printability of composition and liquid crystal aligning agent (evaluation of pinhole)
evaluation of printability evaluation of coating film edge
VHR voltage holding ratio
Example 4 S1 (14.1 g) and NEP (9.37 g) were added to the polyimide powder (4) (1.70 g) obtained by the synthesis method of Synthesis Example 4, and dissolved by stirring at 70 ° C. for 24 hours. BCS (9.37 g) and PB (14.1 g) were added to this solution, and the mixture was stirred at 40 ° C. for 3 hours to obtain a composition (4). In this composition, no abnormality such as turbidity and generation of precipitates was observed, and it was confirmed that the composition was a uniform solution. In addition, this composition (4) was used for evaluation as a liquid-crystal aligning agent (4).
composition (4) and liquid crystal aligning agent (4) evaluation of printability of composition and liquid crystal aligning agent (pinhole evaluation)", evaluation of voltage holding ratio (VHR)” (Normal cell) "and” Evaluation of ink-jet coating property of liquid crystal aligning agent ".
Example 5 S1 (14.0 g) and BCS (17.7 g) were added to a polyamic acid solution (5) (10.0 g) having a resin solid content concentration of 25 mass% obtained by the synthesis method of Synthesis Example 5, and the mixture was added at 25 ° C. The mixture was stirred for 4 hours to obtain a composition (5). In this composition, no abnormality such as turbidity and generation of precipitates was observed, and it was confirmed that the composition was a uniform solution. In addition, this composition (5) was used for evaluation also as a liquid-crystal aligning agent (5).
composition and liquid crystal aligning agent (5) evaluation of printability of composition and liquid crystal aligning agent (evaluation of pinhole)
composition and liquid crystal aligning agent Evaluation of printability evaluation of coating film edge
VHR voltage holding ratio
Example 6 S1 (14.7 g) was added to the polyimide powder (6) (1.70 g) obtained by the synthesis method of Synthesis Example 6, and dissolved by stirring at 70 ° C. for 24 hours. To this solution, BCS (12.0 g) was added and stirred at 40 ° C. for 3 hours to obtain a composition (6). In this composition, no abnormality such as turbidity and generation of precipitates was observed, and it was confirmed that the composition was a uniform solution. In addition, this composition (6) was used for evaluation also as a liquid-crystal aligning agent (6).
composition and liquid crystal aligning agent (6) evaluation of printability of composition and liquid crystal aligning agent (evaluation of pinhole)
composition and liquid crystal aligning agent evaluation of printability (evaluation of coating film edge)
VHR voltage holding ratio
PSA cell Preparation of liquid crystal cell and evaluation of liquid crystal orientation
SC-PVA Cell Liquid crystal cell Preparation and Evaluation of Liquid Crystal Orientation
Example 7 S1 (9.10 g) and NEP (13.7 g) were added to the polyimide powder (6) (1.65 g) obtained by the synthesis method of Synthesis Example 6, and dissolved by stirring at 70 ° C. for 24 hours. To this solution, PB (22.8 g) was added and stirred at 40 ° C. for 3 hours to obtain a composition (7). In this composition, no abnormality such as turbidity and generation of precipitates was observed, and it was confirmed that the composition was a uniform solution. In addition, this composition (7) was used for evaluation as a liquid-crystal aligning agent (7).
composition (7) and liquid crystal aligning agent (7) evaluation of printability of composition and liquid crystal aligning agent (pinhole evaluation)” and “evaluation of voltage holding ratio (VHR)” (Normal cell) "and” Evaluation of ink-jet coating property of liquid crystal aligning agent ".
Example 8 S1 (6.27 g) and NEP (7.52 g) were added to the polyimide powder (7) (1.60 g) obtained by the synthesis method of Synthesis Example 7, and dissolved by stirring at 70 ° C. for 24 hours. BCS (2.51 g) and PB (8.77 g) were added to this solution, and the mixture was stirred at 40 ° C. for 3 hours to obtain a composition (8). In this composition, no abnormality such as turbidity and generation of precipitates was observed, and it was confirmed that the composition was a uniform solution. In addition, this composition (8) was used for evaluation also as a liquid-crystal aligning agent (8).
composition and liquid crystal aligning agent (8) evaluation of printability of composition and liquid crystal aligning agent (evaluation of pinhole)
composition and liquid crystal aligning agent Evaluation of printability evaluation of coating film edge
VHR voltage holding ratio
Example 9 S1 (7.52 g) and NMP (5.01 g) were added to the polyimide powder (8) (1.60 g) obtained by the synthesis method of Synthesis Example 8, and dissolved by stirring at 70 ° C. for 24 hours. PB (10.0 g) and DME (2.51 g) were added to this solution, and the mixture was stirred at 40 ° C. for 5 hours to obtain a composition (9). In this composition, no abnormality such as turbidity and generation of precipitates was observed, and it was confirmed that the composition was a uniform solution. In addition, this composition (9) was used for evaluation also as a liquid-crystal aligning agent (9).
composition (9) and liquid crystal aligning agent (9) evaluation of printability of composition and liquid crystal aligning agent (evaluation of pinhole)
composition and liquid crystal aligning agent evaluation of printability (evaluation of coating film edge)
VHR voltage holding ratio
PSA cell Preparation of liquid crystal cell and evaluation of liquid crystal orientation
SC-PVA Cell Liquid crystal cell Preparation and Evaluation of Liquid Crystal Orientation
Example 10 S1 (10.3 g) and NEP (7.76 g) were added to the polyimide powder (9) (1.65 g) obtained by the synthesis method of Synthesis Example 9, and the mixture was dissolved by stirring at 70 ° C. for 24 hours. To this solution, PB (6.46 g) and EC (1.29 g) were added, and the mixture was stirred at 40 ° C. for 3 hours to obtain a composition (10). In this composition, no abnormality such as turbidity and generation of precipitates was observed, and it was confirmed that the composition was a uniform solution. In addition, this composition (10) was used for evaluation also as a liquid-crystal aligning agent (10).
composition (10) and liquid crystal alignment treatment agent (10) evaluation of printability of composition and liquid crystal alignment treatment agent (evaluation of pinhole)
composition and liquid crystal alignment treatment agent Evaluation of printability evaluation of coating film edge
VHR voltage holding ratio
Example 11 S1 (3.76 g) and NEP (10.0 g) were added to the polyimide powder (10) (1.60 g) obtained by the synthesis method of Synthesis Example 10, and dissolved by stirring at 70 ° C. for 24 hours. BCS (11.3 g) was added to this solution, and the mixture was stirred at 40 ° C. for 3 hours to obtain a composition (11). In this composition, no abnormality such as turbidity and generation of precipitates was observed, and it was confirmed that the composition was a uniform solution. In addition, this composition (11) was used for evaluation also as a liquid-crystal aligning agent (11).
Example 12 S1 (5.33 g) and ⁇ -BL (13.3 g) were added to the polyimide powder (11) (1.70 g) obtained by the synthesis method of Synthesis Example 11, and dissolved by stirring at 70 ° C. for 24 hours. It was. To this solution, BCS (7.9 g) was added and stirred at 40 ° C. for 3 hours to obtain a composition (12). In this composition, no abnormality such as turbidity and generation of precipitates was observed, and it was confirmed that the composition was a uniform solution. In addition, this composition (12) was used for evaluation also as a liquid-crystal aligning agent (12).
composition (12) and liquid crystal aligning agent (12) evaluation of printability of composition and liquid crystal aligning agent (evaluation of pinhole)
composition and liquid crystal aligning agent Evaluation of printability evaluation of coating film edge
VHR voltage holding ratio
Example 13 S1 (7.76 g) and NMP (5.17 g) were added to the polyimide powder (12) (1.65 g) obtained by the synthesis method of Synthesis Example 12, and dissolved by stirring at 70 ° C. for 24 hours. To this solution, BCS (5.17 g) and PB (7.76 g) were added and stirred at 40 ° C. for 3 hours to obtain a composition (13). In this composition, no abnormality such as turbidity and generation of precipitates was observed, and it was confirmed that the composition was a uniform solution. In addition, this composition (13) was used for evaluation also as a liquid-crystal aligning agent (13).
composition (13) and liquid crystal alignment treatment agent (13) evaluation of printability of composition and liquid crystal alignment treatment agent (evaluation of pinhole)
composition and liquid crystal alignment treatment agent Evaluation of printability evaluation of coating film edge
VHR voltage holding ratio
Example 14 S1 (5.01 g) and NEP (7.52 g) were added to the polyimide powder (13) (1.60 g) obtained by the synthesis method of Synthesis Example 13, and dissolved by stirring at 70 ° C. for 24 hours. To this solution, PB (12.5 g) was added and stirred at 40 ° C. for 3 hours to obtain a composition (14). In this composition, no abnormality such as turbidity and generation of precipitates was observed, and it was confirmed that the composition was a uniform solution. In addition, this composition (14) was used for evaluation also as a liquid-crystal aligning agent (14).
composition (14) and liquid crystal aligning agent (14) “evaluation of printability of composition and liquid crystal aligning agent (evaluation of pinhole)”, “composition and liquid crystal aligning agent “Evaluation of printability (evaluation of coating film edge)”, “Evaluation of voltage holding ratio (VHR) (normal cell)”, “Preparation of liquid crystal cell and evaluation of liquid crystal orientation (PSA cell)” and “Liquid crystal cell Preparation and Evaluation of Liquid Crystal Orientation (SC-PVA Cell) ”were performed.
VHR voltage holding ratio
PSA cell Preparation of liquid crystal cell and evaluation of liquid crystal orientation
SC-PVA Cell Liquid Crystal Cell Preparation and Evaluation of Liquid Crystal Orientation
Example 15 S1 (4.69 g) and ⁇ -BL (18.8 g) were added to the polyimide powder (13) (1.70 g) obtained by the synthesis method of Synthesis Example 13, and dissolved by stirring at 70 ° C. for 24 hours. It was. To this solution, BCS (9.37 g) and PB (14.1 g) were added and stirred at 40 ° C. for 3 hours to obtain a composition (15). In this composition, no abnormality such as turbidity and generation of precipitates was observed, and it was confirmed that the composition was a uniform solution. In addition, this composition (15) was used for evaluation as a liquid-crystal aligning agent (15).
Example 16 S1 (12.5 g) and NEP (2.51 g) were added to the polyimide powder (14) (1.60 g) obtained by the synthesis method of Synthesis Example 14, and dissolved by stirring at 70 ° C. for 24 hours. To this solution, K1 (0.08 g) and BCS (10.0 g) were added and stirred at 40 ° C. for 5 hours to obtain a composition (16). In this composition, no abnormality such as turbidity and generation of precipitates was observed, and it was confirmed that the composition was a uniform solution. In addition, this composition (16) was used for evaluation also as a liquid-crystal aligning agent (16).
composition (16) and liquid crystal alignment treatment agent (16) evaluation of printability of composition and liquid crystal alignment treatment agent (pinhole evaluation)
composition and liquid crystal alignment treatment agent Evaluation of printability evaluation of coating film edge
VHR voltage holding ratio
Example 17 S1 (15.0 g) and ⁇ -BL (2.51 g) were added to the polyimide powder (15) (1.60 g) obtained by the synthesis method of Synthesis Example 15, and dissolved by stirring at 70 ° C. for 24 hours. It was. To this solution, K1 (0.08 g), BCS (2.51 g) and PB (5.01 g) were added and stirred at 40 ° C. for 5 hours to obtain a composition (17). In this composition, no abnormality such as turbidity and generation of precipitates was observed, and it was confirmed that the composition was a uniform solution. In addition, this composition (17) was used for evaluation also as a liquid-crystal aligning agent (17).
composition (17) and liquid crystal aligning agent (17) evaluation of printability of composition and liquid crystal aligning agent (evaluation of pinhole)
composition and liquid crystal aligning agent Evaluation of printability evaluation of coating film edge
VHR voltage holding ratio
Example 18 S1 (2.66 g) and NEP (10.7 g) were added to the polyimide powder (16) (1.70 g) obtained by the synthesis method of Synthesis Example 16, and dissolved by stirring at 70 ° C. for 24 hours. To this solution were added BCS (5.33 g) and PB (7.99 g), and the mixture was stirred at 40 ° C. for 3 hours to obtain a composition (18). In this composition, no abnormality such as turbidity and generation of precipitates was observed, and it was confirmed that the composition was a uniform solution. In addition, this composition (18) was used for evaluation also as a liquid-crystal aligning agent (18).
composition (18) and liquid crystal aligning agent (18) evaluation of printability of composition and liquid crystal aligning agent (evaluation of pinhole)
composition and liquid crystal aligning agent Evaluation of printability evaluation of coating film edge
VHR voltage holding ratio
Example 19 S1 (8.77 g) and NMP (5.01 g) were added to the polyimide powder (17) (1.60 g) obtained by the synthesis method of Synthesis Example 17, and dissolved by stirring at 70 ° C. for 24 hours. To this solution, BCS (8.77 g) and EC (2.51 g) were added, and the mixture was stirred at 40 ° C. for 3 hours to obtain a composition (19). In this composition, no abnormality such as turbidity and generation of precipitates was observed, and it was confirmed that the composition was a uniform solution. In addition, this composition (19) was used for evaluation also as a liquid-crystal aligning agent (19).
composition (19) and liquid crystal aligning agent (19) evaluation of printability of composition and liquid crystal aligning agent (evaluation of pinhole)
composition and liquid crystal aligning agent Evaluation of printability evaluation of coating film edge
VHR voltage holding ratio
Example 20 S1 (10.0 g) and NEP (3.76 g) were added to the polyimide powder (18) (1.60 g) obtained by the synthesis method of Synthesis Example 18, and dissolved by stirring at 70 ° C. for 24 hours. BCS (3.76 g) and PB (7.52 g) were added to this solution, and the mixture was stirred at 40 ° C. for 3 hours to obtain a composition (20). In this composition, no abnormality such as turbidity and generation of precipitates was observed, and it was confirmed that the composition was a uniform solution. In addition, this composition (20) was used for evaluation also as a liquid-crystal aligning agent (20).
composition (20) and liquid crystal aligning agent (20) evaluation of printability of composition and liquid crystal aligning agent (evaluation of pinhole)
composition and liquid crystal aligning agent Evaluation of printability evaluation of coating film edge
VHR voltage holding ratio
composition (21) and liquid crystal aligning agent (21) evaluation of printability of composition and liquid crystal aligning agent (evaluation of pinhole)
composition and liquid crystal aligning agent Evaluation of printability evaluation of coating film edge
VHR voltage holding ratio
NMP (14.7 g) was added to the polyimide powder (3) (1.70 g) obtained by the synthesis method of Synthesis Example 3, and dissolved by stirring at 70 ° C. for 24 hours.
BCS (12.0 g) was added and stirred at 40 ° C. for 3 hours to obtain a composition (22).
this composition no abnormality such as turbidity and generation of precipitates was observed, and it was confirmed that the composition was a uniform solution.
this composition (22) was used for evaluation also as a liquid-crystal aligning agent (22).
composition and liquid crystal aligning agent evaluation of printability of composition and liquid crystal aligning agent (evaluation of pinhole)
evaluation of printability evaluation of coating film edge
VHR voltage holding ratio
composition and liquid crystal aligning agent evaluation of printability of composition and liquid crystal aligning agent evaluation of pinhole
composition and liquid crystal aligning agent Evaluation of printability evaluation of coating film edge
VHR voltage holding ratio
NMP (14.2 g) was added to the polyimide powder (6) (1.65 g) obtained by the synthesis method of Synthesis Example 6 and dissolved by stirring at 70 ° C. for 24 hours.
BCS (11.6g) was added to this solution, and it stirred at 40 degreeC for 3 hours, and obtained the composition (24).
this composition no abnormality such as turbidity and generation of precipitates was observed, and it was confirmed that the composition was a uniform solution.
this composition (24) was used for evaluation also as a liquid-crystal aligning agent (24).
composition and liquid crystal aligning agent evaluation of printability of composition and liquid crystal aligning agent (evaluation of pinhole)
composition and liquid crystal aligning agent Evaluation of printability evaluation of coating film edge
VHR voltage holding ratio
the polyimide film obtained from the composition of the example of the present invention has a uniform coating property that does not generate pinholes compared to the polyimide film obtained from the composition of the comparative example. Furthermore, the linearity of the end portion of the polyimide film was high, and the rise of the end portion was small.
a comparison between the composition using the specific solvent which is the component (A) of the present invention and a composition not using it that is, comparison between Example 2 and Comparative Example 1, Example 3
Example 6 and Comparative Example 2 The comparison between Example 6 and Comparative Example 2
Example 5 and Comparative Example 3 the comparison between Example 6 and Comparative Example 4.
the number of pinholes on the polyimide film was large as compared with the corresponding examples, and furthermore, the coating property at the coating film end portion of the polyimide film was also poor.
the composition of these Examples was used also for evaluation as a liquid-crystal aligning agent, the result of the Example using these compositions was also made into the result of a liquid-crystal aligning agent.
the liquid crystal aligning film obtained from the liquid crystal aligning agent using the composition of the present invention is fired when producing a liquid crystal aligning film as compared with the liquid crystal aligning film obtained from the liquid crystal aligning agent of the comparative example. Even when the temperature was low, a result of excellent voltage holding ratio (also referred to as VHR) in the liquid crystal display element was obtained.
VHR voltage holding ratio
a comparison between a liquid crystal aligning agent using a specific solvent which is the component (A) of the present invention and a liquid crystal aligning agent not using the same that is, a comparison between Example 2 and Comparative Example 1.
the comparison between Example 3 and Comparative Example 2 the comparison between Example 5 and Comparative Example 3
the value of VHR was lower than in the corresponding examples.
the VHR was greatly reduced with high temperature.
the composition of the present invention can suppress the generation of pinholes accompanying repelling when forming a polyimide film, and can provide a polyimide film having excellent coating properties at the edges. At that time, a polyimide film can be produced even by baking at a low temperature.
the composition of the present invention when used for a liquid crystal alignment treatment agent, the generation of pinholes accompanying repelling can be suppressed, and a liquid crystal alignment film having excellent coating properties at the end can be obtained. Furthermore, even when the firing for producing the liquid crystal alignment film is performed at a low temperature, the liquid crystal alignment film has excellent electrical characteristics, particularly voltage holding ratio (also referred to as VHR). Therefore, the 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 is used for a large-screen high-definition liquid crystal television, a small-sized car navigation system, a smartphone, and the like. It can be suitably used, and is useful for a TN element, STN element, TFT liquid crystal element, particularly a vertical alignment type liquid crystal display element such as VA mode, PSA mode and SC-PVA mode.

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PCT/JP2014/077219 2013-10-10 2014-10-10 組成物、液晶配向処理剤、液晶配向膜および液晶表示素子 WO2015053394A1 (ja)

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