CN102127459A - Liquid crystal aligning agent, liquid crystal alignment film and liquid crystal display element - Google Patents

Liquid crystal aligning agent, liquid crystal alignment film and liquid crystal display element Download PDF

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Publication number
CN102127459A
CN102127459A CN2011100042053A CN201110004205A CN102127459A CN 102127459 A CN102127459 A CN 102127459A CN 2011100042053 A CN2011100042053 A CN 2011100042053A CN 201110004205 A CN201110004205 A CN 201110004205A CN 102127459 A CN102127459 A CN 102127459A
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liquid crystal
solution
tetracarboxylic dianhydride
aligning agent
polyamic acid
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CN102127459B (en
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犬饲裕子
泉谦一
内山克博
加藤孝人
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JSR Corp
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JSR Corp
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    • 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
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C08G73/1003—Preparatory processes
    • 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
    • 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
    • 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
    • C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G2261/50—Physical properties
    • C08G2261/53—Physical properties liquid-crystalline

Abstract

The present invention relates to a liquid crystal aligning agent, a liquid crystal alignment film and a liquid crystal display element. The liquid crystal aligning agent provided by the invention has excellent storing stability and can form the liquid crystal alignment film which can keep high-quality displaying when the liquid crystal display element is used for long time. The liquid crystal aligning agent comprises at least one polymer which is selected from a group that is composed of: polyamic acid, and polyimide which is formed through performing dewatering ring-closing to the polyamic acid. The polyamic acid is obtained through the reaction between tetracarboxylic dianhydride and diamine, wherein the tetracarboxylic dianhydride comprises 5-80mol% of at least one member selected from a group which is composed of 1S,2S,4R,5R-cyclohexane tetracarboxylic dianhydride and 1R,2S,4S-5R-cyclohexane tetracarboxylic dianhydride relatively to the total tetracarboxylic dianhydride.

Description

Liquid crystal aligning agent, liquid crystal orientation film and liquid crystal display device
Technical field
The present invention relates to liquid crystal aligning agent and liquid crystal display device.In more detail, the liquid crystal aligning agent, the liquid crystal orientation film that relate to excellent storage stability, particularly excellent heat resistance; And can show, suppress the demonstration variation that thermal stresses causes, can long playing liquid crystal display device. high-qualityly
Background technology
The material of the liquid crystal orientation film that uses in the liquid crystal display device, known have resin materials such as polyimide, polymeric amide, polyamic acid, polyester.Especially, by the liquid crystal orientation film that polyamic acid or polyimide form, the excellences such as affinity of its thermotolerance, physical strength and liquid crystal are used in most liquid crystal display device by (patent documentation 1～6).
Wherein, polyamic acid is because to the solvability height of organic solvent commonly used, so the printing process that has in the manufacturing process of liquid crystal display device can easily obtain liquid crystal aligning agent, and the cheap such advantage of resin price.Yet the liquid crystal display device of the liquid crystal orientation film that is formed by polyamic acid is fragile under thermal stresses, when the long-play liquid crystal display device, has the liquid crystal orientation film variation and causes the low problem of voltage retention.In recent years, be representative with the LCD TV, the design premises in the life-span of liquid crystal display device is above 10 years.Therefore,, also can keep high-quality demonstration, importantly demonstrate long-time stable voltage retention, need to improve the heat-resisting reliability of alignment films in a hurry for when the long-play liquid crystal display device.As the method for the heat-resisting reliability (thermal stresses tolerance) of present known raising alignment films, having proposed increases the method (patent documentation 7) of the chemical stability of liquid crystal orientation film by hybrid epoxidized compound in liquid crystal aligning agent; Imported monomeric polyamic acid by use, when the firing of liquid crystal orientation film, formed intermolecular crosslinkedly, increased the method (patent documentation 8) of the stability of film etc. thus with carboxylic acid.Yet, according to these technology, in order to have given play to desirable performance, must use epoxy compounds or carboxylic acid in a large number, can be detrimental to the doing over again property (liquid crystal aligning agent prints when bad, the easiness of filming and peeling off), wear resistance of liquid crystal orientation film etc., need further improvement.
On the other hand, though the thermal stresses tolerance that contains the liquid crystal orientation film that the liquid crystal orientation film of polyimide obtains is than higher, but because present known polyimide is to the solvability deficiency of organic solvent commonly used, so the storage stability of liquid crystal aligning agent has situation about having problems.
Based on this problem, the organic solvent that needs can form commonly used has enough solvabilities, and the polyamic acid/polyimide of the liquid crystal orientation film of thermal stresses tolerance excellence is a liquid crystal aligning agent.
Yet, in recent years, developed Stereoselective and made hexanaphthene tetracarboxylic dianhydride's method, can distinguish and optionally make 1S, 2S, 4R, 5R-hexanaphthene tetracarboxylic dianhydride and 1R, 2S, 4S, 5R-hexanaphthene tetracarboxylic dianhydride (patent documentation 9, patent documentation 10 and non-patent literature 1).In patent documentation 9 and 10, put down in writing and used 100% above-mentioned diastereomer respectively, and illustrated that they are the polymkeric substance with sufficiently high molecular weight as tetracarboxylic dianhydride's synthetic polyamic acid.And, having put down in writing above-mentioned polyamic acid can use in the liquid crystal orientation film purposes of liquid crystal display device, but all the character of liquid crystal orientation film is not carried out any mensuration in these documents, do not study related as the thermal stresses tolerance of the liquid crystal orientation film of the storage stability of the tetracarboxylic dianhydride's of raw material structure and the liquid crystal aligning agent that obtains and formation fully.
[prior art document]
[patent documentation]
[patent documentation 1] Japanese kokai publication hei 4-153622 communique
[patent documentation 2] TOHKEMY 60-107020 communique
[patent documentation 3] Japanese kokai publication hei 11-258605 communique
[patent documentation 4] Japanese kokai publication sho 56-91277 communique
The 5th, 928, No. 733 specification sheetss of [patent documentation 5] United States Patent (USP)
[patent documentation 6] Japanese kokai publication sho 62-165628 communique
[patent documentation 7] TOHKEMY 2008-299318 communique
[patent documentation 8] TOHKEMY 2009-157351 communique
[patent documentation 9] TOHKEMY 2009-191253 communique
[patent documentation 10] TOHKEMY 2009-286706 communique
[patent documentation 11] Japanese kokai publication hei 6-222366 communique
[patent documentation 12] Japanese kokai publication hei 6-281937 communique
[patent documentation 13] Japanese kokai publication hei 5-107544 communique
[patent documentation 14] TOHKEMY 2010-97188 communique
[non-patent literature]
[non-patent literature 1] polymer association gives the original text collection, the 57th volume, the 2nd phase (2002)
Summary of the invention
The present invention proposes according to the problems referred to above, and its purpose is to provide a kind of liquid crystal aligning agent, this liquid crystal aligning agent excellent storage stability, even can form when using liquid crystal display device for a long time, and the also liquid crystal orientation film that can continue to show high-qualityly.
Even another object of the present invention provides when using for a long time, also the liquid crystal display device that can continue to show high-qualityly.
Other purposes of the present invention and advantage are expressed by following explanation.
According to the present invention, above-mentioned purpose of the present invention and advantage, the firstth, realize by a kind of liquid crystal aligning agent,
This liquid crystal aligning agent contains at least a polymkeric substance of selecting in the group that is made of polyamic acid and polyimide that this polyamic acid dehydration closed-loop is formed, and this polyamic acid obtains tetracarboxylic dianhydride and diamine reactant,
Wherein, above-mentioned tetracarboxylic dianhydride is with respect to whole tetracarboxylic dianhydrides, contain 5～80mol% by 1S, 2S, 4R, 5R-hexanaphthene tetracarboxylic dianhydride and 1R, 2S, 4S, that selects in the group that 5R-hexanaphthene tetracarboxylic dianhydride constitutes is at least a.
Above-mentioned purpose of the present invention and advantage, the secondth, realize by liquid crystal display device with the liquid crystal orientation film that forms by above-mentioned liquid crystal aligning agent.
Liquid crystal aligning agent excellent storage stability of the present invention can be provided in when using in the liquid crystal display device simultaneously, even with its long-play, and the also liquid crystal orientation film that can continue to show high-qualityly.Therefore, have the liquid crystal display device of the present invention of the liquid crystal orientation film that forms by this liquid crystal aligning agent,, also can keep high-quality demonstration even when using for a long time.
Liquid crystal display device of the present invention can be applicable to various devices effectively, for example can use in display unit such as clock and watch, pocket game machine, WP, notebook computer, navigationsystem, pick up camera, portable information terminal, digital camera, mobile telephone, various watch-dog, LCD TV.
Embodiment
Liquid crystal aligning agent of the present invention is the liquid crystal aligning agent that contains at least a polymkeric substance of selecting in the group that is made of polyamic acid and polyimide that this polyamic acid dehydration closed-loop is formed, and this polyamic acid obtains tetracarboxylic dianhydride and diamine reactant,
Wherein, above-mentioned tetracarboxylic dianhydride is with respect to whole tetracarboxylic dianhydrides, contain 5～80mol% by 1S, 2S, 4R, 5R-hexanaphthene tetracarboxylic dianhydride and 1R, 2S, 4S, that selects in the group that 5R-hexanaphthene tetracarboxylic dianhydride constitutes is at least a.
At least a polymkeric substance of selecting in the group that this polyamic acid that is obtained by specific tetracarboxylic dianhydride and diamine reactant and the polyimide that this polyamic acid dehydration closed-loop is formed constitute in this manual, below is called " particular polymers ".
＜tetracarboxylic dianhydride 〉
As the tetracarboxylic dianhydride of the polyamic acid that is used for synthetic the present invention, will be by 1S, 2S, 4R, 5R-hexanaphthene tetracarboxylic dianhydride and 1R, 2S, 4S, at least a and other tetracarboxylic dianhydride who selects in the group that 5R-hexanaphthene tetracarboxylic dianhydride constitutes uses together.
Here, with respect to whole tetracarboxylic dianhydrides, by 1S, 2S, 4R, 5R-hexanaphthene tetracarboxylic dianhydride and 1R, 2S, 4S, at least a usage ratio of selecting in the group that 5R-hexanaphthene tetracarboxylic dianhydride constitutes is 5～80mol%, preferred its contains 10～60mol%, more preferably contains 15～50mol%.This ratio is during less than 5mol%, and the heat-resisting reliability of the liquid crystal orientation film of formation may be poor; On the other hand, when surpassing 80mol%, the storage stability of the liquid crystal orientation film that obtains may be poor, so improper.
Above-mentioned tetracarboxylic dianhydride more preferably contains 1S in above-mentioned scope, 2S, 4R, 5R-hexanaphthene tetracarboxylic dianhydride.
As above-mentioned other tetracarboxylic dianhydride, can list for example aliphatics tetracarboxylic dianhydride, ester ring type tetracarboxylic dianhydride, aromatic tetracarboxylic acid's dianhydride etc.As their example particularly,, can list for example butane tetracarboxylic acid dianhydride etc. wherein as the aliphatics tetracarboxylic dianhydride;
As the ester ring type tetracarboxylic dianhydride, for example can list 1,2,3,4-tetramethylene tetracarboxylic dianhydride, 2,3,5-tricarboxylic basic ring amyl group acetate dianhydride, 1,3,3a, 4,5,9b-six hydrogen-5-(tetrahydrochysene-2,5-dioxo-3-furyl)-and naphtho-[1,2-c] furans-1, the 3-diketone, 1,3,3a, 4,5,9b-six hydrogen-8-methyl-5-(tetrahydrochysene-2,5-dioxo-3-furyl)-naphtho-[1,2-c] furans-1, the 3-diketone, 3-oxabicyclo [3.2.1] suffering-2,4-diketone-6-spiral shell-3 '-(tetrahydrofuran (THF)-2 ', 5 '-diketone), 5-(2,5-dioxo tetrahydrochysene-3-furyl)-3-methyl-3-tetrahydrobenzene-1, the 2-dicarboxylic acid anhydride, 3,5,6-three carboxyls-2-carboxymethyl norbornane-2:3,5:6-dianhydride, 2,4,6,8-tetracarboxylic two ring [3.3.0] octane-2:4, the 6:8-dianhydride, 4,9-two oxatricyclo [5.3.1.0 2,6] 11 carbon-3,5,8,10-tetraketone etc.;
As aromatic tetracarboxylic acid's dianhydride, can list for example pyromellitic acid dianhydride etc.;
And the tetracarboxylic dianhydride who uses record in the patent documentation 14 (TOHKEMY 2010-97188 communique).
As above-mentioned other tetracarboxylic dianhydride, preferably comprise by 1,2,3,4-tetramethylene tetracarboxylic dianhydride, 2,3,5-tricarboxylic basic ring amyl group acetate dianhydride, 1,3,3a, 4,5,9b-six hydrogen-5-(tetrahydrochysene-2,5-dioxo-3-furyl)-and naphtho-[1,2-c] furans-1, the 3-diketone, 1,3,3a, 4,5,9b-six hydrogen-8-methyl-5-(tetrahydrochysene-2,5-dioxo-3-furyl)-naphtho-[1,2-c] furans-1, the 3-diketone, 3-oxabicyclo [3.2.1] suffering-2,4-diketone-6-spiral shell-3 '-(tetrahydrofuran (THF)-2 ', 5 '-diketone), 5-(2,5-dioxo tetrahydrochysene-3-furyl)-3-methyl-3-tetrahydrobenzene-1, the 2-dicarboxylic acid anhydride, 3,5,6-three carboxyls-2-carboxymethyl norbornane-2:3,5:6-dianhydride, 2,4,6,8-tetracarboxylic two ring [3.3.0] octane-2:4,6:8-dianhydride and 4,9-two oxatricyclo [5.3.1.0 2,6] 11 carbon-3,5,8, at least a (below, be called " specific tetracarboxylic dianhydride ") who selects in the group that the 10-tetraketone constitutes.
Above-mentioned specific tetracarboxylic dianhydride's usage ratio is preferably more than the 50mol% with respect to above-mentioned other tetracarboxylic dianhydride's integral body, more preferably more than the 80mol%, is preferably 100mol% especially.
＜diamines 〉
Diamines as the polyamic acid that is used for synthetic the present invention can list for example aliphatie diamine, ester ring type diamines, aromatic diamine, diamino organo-siloxane etc.As their object lesson, be respectively as aliphatie diamine, can list for example m-xylene diamine, 1,3-propylene diamine, 1,4-butanediamine, 1,5-pentamethylene diamine, 1,6-hexanediamine etc.;
As the ester ring type diamines, for example can list 1,4-diamino-cyclohexane, 4,4 '-methylene radical two (cyclo-hexylamine), 1,3-two (amino methyl) hexanaphthene etc.;
As aromatic diamine, can list for example Ursol D, 4,4 '-diaminodiphenyl-methane, 4,4 '-diamino-diphenyl thioether, 4,4 '-diamino-diphenyl amine, 1, the 5-diaminonaphthalene, 2,2 '-dimethyl-4,4 '-benzidine, 4,4 '-diamino-2,2 '-two (trifluoromethyl) biphenyl, 2, the 7-diamino-fluorene, 4,4 '-diamino-diphenyl ether, 2,2-two [4-(4-amino-benzene oxygen) phenyl] propane, 9,9-two (4-aminophenyl) fluorenes, 2,2-two [4-(4-amino-benzene oxygen) phenyl] HFC-236fa, 2,2-two (4-aminophenyl) HFC-236fa, 4,4 '-(to benzene two isopropylidenes) two (aniline), 4,4 '-(benzene two isopropylidenes) two (aniline), 1,4-two (4-amino-benzene oxygen) benzene, 4,4 '-two (4-amino-benzene oxygen) biphenyl, 2, the 6-diamino-pyridine, 3, the 4-diamino-pyridine, 2, the 4-di-amino-pyrimidine, 3, the 6-proflavin, 3,6-diamino carbazole, N-methyl-3,6-diamino carbazole, N-ethyl-3,6-diamino carbazole, N-phenyl-3,6-diamino carbazole, N, N '-two (4-aminophenyl)-p-diaminodiphenyl, N, N '-two (4-aminophenyl)-N, N '-tolidine, 1,4-two-(4-aminophenyl)-piperazine, 3, the 5-diaminobenzoic acid, cholestane oxygen base-3, the 5-diaminobenzene, cholestene oxygen base-3, the 5-diaminobenzene, cholestane oxygen base-2, the 4-diaminobenzene, cholestene oxygen base-2, the 4-diaminobenzene, 3,5-diaminobenzoic acid cholestane base ester, 3,5-diaminobenzoic acid cholesteryl ester, 3,5-diaminobenzoic acid lanostane base ester, 3,6-two (4-aminobenzoic acyl-oxygen base) cholestane, 3,6-two (4-amino-benzene oxygen) cholestane, 4-(4 '-trifluoromethoxy benzoyloxy) cyclohexyl-3,5-diaminobenzoic acid ester, 4-(4 '-trifluoromethyl benzoyloxy) cyclohexyl-3,5-diaminobenzoic acid ester, 1,1-two (4-((aminophenyl) methyl) phenyl)-4-butyl cyclohexane, 1,1-two (4-((aminophenyl) methyl) phenyl)-4-heptyl hexanaphthene, 1,1-two (4-((amino-benzene oxygen) methyl) phenyl)-4-heptyl hexanaphthene, 1, the compound shown in 1-two (4-((aminophenyl) methyl) phenyl)-4-(4-heptyl cyclohexyl) hexanaphthene and the following formula (A-1) etc.;
Figure BSA00000416150900071
In the formula (A-1), X IBe that carbonatoms is 1～3 alkylidene group, *-O-, *-COO-or *-OCO-(wherein, the connecting key of band " * " is connected with diamino-phenyl), a is 0 or 1, and b is 0～2 integer, and c is 1～20 integer;
As the diamino organo-siloxane, for example can list 1,3-two (3-aminopropyl)-tetramethyl disiloxane etc., and the diamines that uses record in the patent documentation 14 (TOHKEMY 2010-97188 communique).
As the X in the following formula (A-1) IBe preferably carbonatoms and be 1～3 alkylidene group, *-O-or *-COO-(wherein, the connecting key of band " * " is connected with diamino-phenyl).As group C cH 2c+1-object lesson, for example can list methyl, ethyl, n-propyl, normal-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, positive decyl, dodecyl, n-tridecane base, n-tetradecane base, Pentadecane base, n-hexadecyl, n-heptadecane base, Octadecane base, NSC 77136 base, NSC 62789 base etc.2 amino of diamino-phenyl are preferably 2 with respect to other group, 4-position or 3,5-position.
Object lesson as the compound of above-mentioned formula (A-1) expression, can list dodecyloxy-2 for example, the 4-diaminobenzene, tetradecyloxyaniline-2, the 4-diaminobenzene, pentadecane oxygen base-2, the 4-diaminobenzene, n-Hexadecane oxygen base-2, the 4-diaminobenzene, octadecane oxygen base-2, the 4-diaminobenzene, dodecyloxy-2, the 5-diaminobenzene, tetradecyloxyaniline-2, the 5-diaminobenzene, pentadecane oxygen base-2, the 5-diaminobenzene, n-Hexadecane oxygen base-2, the 5-diaminobenzene, octadecane oxygen base-2, the compound that 5-diaminobenzene and following formula (A-1-1)～(A-1-3) are represented respectively etc.
Figure BSA00000416150900081
In the above-mentioned formula (A-1), a and b preferably are not 0 simultaneously.
Above-mentioned diamines preferably comprises by Ursol D, 3,5-diaminobenzoic acid, 4,4 '-diamino-diphenyl ether, 4,4 '-diaminodiphenyl-methane, 2,2 '-dimethyl-4,4 '-benzidine, 4,4 '-diamino-2,2 '-two (trifluoromethyl) biphenyl, 4,4 '-diamino-diphenyl amine and 4,4 '-at least a (below, be called " specific diamines 1 ") that select in the group that (benzene two isopropylidenes) two (aniline) constitute.
In addition, during the liquid crystal orientation film of liquid crystal aligning agent of the present invention in being used to form vertical orientating type (VA type) liquid crystal display device, except above-mentioned specific diamines, preferably further contain by cholestane oxygen base-3, the 5-diaminobenzene, cholestene oxygen base-3, the 5-diaminobenzene, cholestane oxygen base-2, the 4-diaminobenzene, cholestene oxygen base-2, the 4-diaminobenzene, 3,5-diaminobenzoic acid cholestane base ester, 3,5-diaminobenzoic acid cholesteryl ester, 3,5-diaminobenzoic acid lanostane base ester, 3,6-two (4-aminobenzoic acyl-oxygen base) cholestane, 3, at least a (below, be called " specific diamines 2 ") who selects in the group that compound shown in 6-two (4-amino-benzene oxygen) cholestane and the above-mentioned formula (A-1) constitutes.
Liquid crystal aligning agent of the present invention is when being used to form the liquid crystal orientation film of VA type vertical alignment-type liquid crystal display device, and above-mentioned specific diamines 1 and specific diamines 2 are as follows with respect to the preferred usage ratio of whole diamines.
Specific diamines 1: be preferably 20～97mol%, more preferably 50～95mol% is preferably 60～90mol% especially;
Specific diamines 2: be preferably 3～80mol%, more preferably 5～50mol% is preferably 10～40mol% especially.
In this case, total usage ratio of above-mentioned specific diamines 1 and specific diamines 2 is preferably 100mol% with respect to whole diamines.
On the other hand, liquid crystal aligning agent of the present invention is being used to form liquid crystal display device beyond the VA type (TN (Twisted Nematic for example, twisted-nematic) type, STN (SuperTwisted Nematic, supertwist is to row) type, lateral electric field type (IPS (In-PlaneSwitching for example, switching in the face), FFS (Fringe Field Switching, fringing field switches) etc.) etc.) and in liquid crystal orientation film the time, above-mentioned specific diamines 1 and specific diamines 2 are with respect to the following record of preferred usage ratio of whole diamines.
Specific diamines 1: be preferably more than the 50mol%, more preferably more than the 80mol%, be preferably 100mol% especially.
Specific diamines 2: be preferably below the 30mol%, more preferably below the 10mol%, be preferably 0mol% especially.
In this case, preferably make above-mentioned specific diamines 1 and specific diamines 2 add up to 100mol%, more preferably only use specific diamines 1 as diamines.
＜molecular weight regulator 〉
When synthetic above-mentioned polyamic acid, can use suitable molecular weight regulator and tetracarboxylic dianhydride as implied above with diamines, synthetic end modified type polymkeric substance.By making polyamic acid is this end modified type polymkeric substance, contain the harmless effect of the present invention of liquid crystal aligning agent of at least a polymkeric substance of selecting in the group that constitutes by this polyamic acid and polyimide that its dehydration closed-loop is formed, can further improve its screening characteristics (printing).
As above-mentioned molecular weight regulator, can list for example sour single acid anhydride, monoamine compound, monoisocyanates compound etc.As their object lesson, be respectively as sour single acid anhydride, can list for example maleic anhydride, Tetra hydro Phthalic anhydride, itaconic anhydride, positive decyl bigcatkin willow acid anhydrides, dodecyl bigcatkin willow acid anhydrides, n-tetradecane base bigcatkin willow acid anhydrides, n-hexadecyl bigcatkin willow acid anhydrides etc.;
As monoamine compound, can list for example aniline, cyclo-hexylamine, n-Butyl Amine 99, n-amylamine, normal hexyl Amine, positive heptyl amice, n-octylamine etc.;
As the monoisocyanates compound, can list for example isocyanic acid phenylester, isocyanic acid naphthyl ester etc.
The usage ratio of molecular weight regulator with respect to the tetracarboxylic dianhydride who uses and total 100 weight parts of diamines, is preferably below 20 weight parts, more preferably below 10 weight parts.
Synthesizing of＜polyamic acid 〉
The tetracarboxylic dianhydride who uses in the building-up reactions as polyamic acid and the usage ratio of diamines, with respect to the amino of 1 equivalent diamines, tetracarboxylic dianhydride's anhydride group preferred 0.2～2 normal ratio, more preferably 0.3～1.2 normal ratio.
The building-up reactions of polyamic acid preferably in organic solvent, preferably at-20 ℃～150 ℃, more preferably under 0 ℃～100 ℃, was preferably carried out 0.1～24 hour, more preferably carried out 0.5～12 hour.
As organic solvent, can list for example non-proton property polar solvent, phenol derivmives blend biology, alcohol, ketone, ester, ether, halohydrocarbon, hydrocarbon etc. herein.
Object lesson as these organic solvents is respectively, as above-mentioned non-proton property polar solvent, can list for example N-N-methyl-2-2-pyrrolidone N-, N,N-dimethylacetamide, N, dinethylformamide, dimethyl sulfoxide (DMSO), gamma-butyrolactone, tetramethyl-urea, HMPA etc.;
As above-mentioned phenol derivatives, can list for example meta-cresol, xylenol, halogenated phenol etc.;
As above-mentioned alcohol, can list for example methyl alcohol, ethanol, Virahol, hexalin, ethylene glycol, propylene glycol, 1,4-butyleneglycol, triglycol, glycol monomethyl methyl ether etc.;
As above-mentioned ketone, can list for example acetone, methylethylketone, methyl iso-butyl ketone (MIBK), pimelinketone etc.;
As above-mentioned ester, can list for example ethyl lactate, n-Butyl lactate, methyl acetate, ethyl acetate, butylacetate, methoxypropionic acid methyl esters, ethoxyl ethyl propionate, oxalic acid diethyl ester, diethyl malonate etc.;
As above-mentioned ether, can list for example Anaesthetie Ether, Ethylene Glycol Methyl ether, glycol ethyl ether, ethylene glycol n-propyl ether, ethylene glycol isopropyl ether, ethylene glycol n-butyl ether, ethylene glycol dimethyl ether, ethylene glycol monoethyl ether acetate, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol monomethyl ether, TC, diethylene glycol monomethyl ether acetic ester, TC acetic ester, tetrahydrofuran (THF) etc.;
As above-mentioned halohydrocarbon, can list for example methylene dichloride, 1,2-ethylene dichloride, 1,4-dichlorobutane, trichloroethane, chlorobenzene, orthodichlorobenzene etc.;
As above-mentioned hydrocarbon, can list for example hexane, heptane, octane, benzene,toluene,xylene, isoamyl propionate, isoamyl isobutyrate, diisoamyl ether etc.
In these organic solvents, preferred more than one that select in the group's (organic solvent of the 1st group) that is made of non-proton property polar solvent and phenol derivmives blend biology that use perhaps are selected from more than one the mixture of selecting in more than one and the group's (organic solvent of the 2nd group) that is made of alcohol, ketone, ester, ether, halohydrocarbon and hydrocarbon of organic solvent of above-mentioned first group.Under latter event, the usage ratio of the organic solvent of the 2nd group, the total amount with respect to the organic solvent of the organic solvent of the 1st group and the 2nd group is preferably below the 50 weight %, more preferably below the 40 weight %, more preferably below the 30 weight %.
The total amount (b) that the consumption of organic solvent (a) is preferably tetracarboxylic dianhydride and diamines is the amount of 0.1～50 weight % with respect to whole amounts (a+b) of reaction soln.
As above, can obtain dissolving the reaction soln that polyamic acid forms.
This reaction soln can be directly used in the preparation liquid crystal aligning agent, also behind the polyamic acid that can contain, is used to prepare liquid crystal aligning agent in separating reaction solution, after perhaps isolating polyamic acid being made with extra care, is used to prepare liquid crystal aligning agent.When the polyamic acid dehydration closed-loop is formed polyimide, above-mentioned reaction soln can be directly used in the dehydration closed-loop reaction; Behind the polyamic acid that contains in also can separating reaction solution, be used for the dehydration closed-loop reaction; After perhaps isolating polyamic acid being made with extra care, be used for the dehydration closed-loop reaction.The separation of polyamic acid and refining can being undertaken by known method.
Synthesizing of＜polyimide 〉
Above-mentioned polyimide can pass through as above synthetic polyamic acid dehydration closed-loop, and imidization obtains.
Polyimide among the present invention can be the complete imidization thing as the amido acid structure fully dehydrating closed loop that polyamic acid had of its precursor; Also can be a part of dehydration closed-loop of amido acid structure, amido acid structure and imide ring structure and the part imidization thing of depositing.The imidization rate of the polyimide among the present invention is preferably more than 30%, more preferably more than 50%, is preferably more than 55% especially.This imidization rate is to represent the quantity of imide ring structure with percentage, occupies the ratio of total amount of the quantity of the quantity of amido acid structure of polyimide and imide ring structure.Here, the part of imide ring can be different imide ring.
The dehydration closed-loop of polyamic acid preferably by the method for heating polyamic acid, perhaps is dissolved in polyamic acid in the organic solvent, adds dewatering agent and dehydration closed-loop catalyzer in this solution, and Jia Re method is carried out as required.Wherein, a kind of method in preferred back is carried out.
In above-mentioned polyamic acid solution, add in the method for dewatering agent and dehydration closed-loop catalyzer,, can list for example acid anhydrides such as diacetyl oxide, propionic anhydride, trifluoroacetic anhydride as dewatering agent.The consumption of dewatering agent, the amido acid structure with respect to the 1mol polyamic acid is preferably 0.01～20mol.As the dehydration closed-loop catalyzer, can list for example tertiary amines such as pyridine, trimethylpyridine, lutidine, triethylamine.As the dehydration closed-loop catalyst consumption, the dewatering agent with respect to 1mol uses is preferably 0.01～10mol.As the organic solvent that uses in the dehydration closed-loop reaction, can list the illustrative organic solvent of solvent that acid is used as synthesizing polyamides.Temperature of reaction as the dehydration closed-loop reaction is preferably 0～180 ℃, more preferably 10～150 ℃.Reaction times is preferably 1.0～120 hours, more preferably 2.0～30 hours.
Can obtain containing the reaction soln of polyimide like this.This reaction soln can be directly used in it preparation liquid crystal aligning agent, also can remove dewatering agent and dehydration closed-loop catalyzer from reaction soln after, be used to prepare liquid crystal aligning agent; After polyimide can also be separated, be used to prepare liquid crystal aligning agent; After perhaps isolating polyimide being made with extra care, be used to prepare liquid crystal aligning agent.These purification operations can be carried out according to known method.
The soltion viscosity of＜polymkeric substance 〉
The particular polymers that as above obtains preferably has the soltion viscosity of 20～800mPas when it is formed the solution of concentration 10 weight %, more preferably have the soltion viscosity of 30～500mPas.
The soltion viscosity of above-mentioned polymkeric substance (mPas) is to use the polymers soln of good solvent (for example, gamma-butyrolactone, N-N-methyl-2-2-pyrrolidone N-etc.) the preparation concentration 10 weight % of this polymkeric substance, uses E type rotational viscosimeter, under 25 ℃ to the value of its mensuration.
＜other additive 〉
Liquid crystal orientation film of the present invention contains the necessary composition of particular polymers conduct as above, also can contain other composition as required.As this other composition, can list other polymkeric substance for example, have compound (below, be called " epoxy compounds "), functional silanes compound of at least 1 epoxy group(ing) etc. at intramolecularly.
[other polymkeric substance]
Above-mentioned other polymkeric substance can be used to improve SOLUTION PROPERTIES and electrical property.As this other polymkeric substance, it is the polymkeric substance beyond the particular polymers, can list the polyamic acid that for example tetracarboxylic dianhydride and diamine reactant obtain, and with respect to whole tetracarboxylic dianhydrides, by 1S, 2S, 4R, 5R-hexanaphthene tetracarboxylic dianhydride and 1R, 2S, 4S, select in the group that 5R-hexanaphthene tetracarboxylic dianhydride constitutes at least a contain proportional less than 5mol%, the above-mentioned polyamic acid (below, be called " other polyamic acid ") that perhaps surpasses 80mol%, the polyimide that this polyamic acid dehydration closed-loop is formed (below, be called " other polyimide "), poly amic acid ester, polyester, polymeric amide, polysiloxane, derivatived cellulose, polyacetal, polystyrene derivative, poly-(vinylbenzene-phenyl maleimide) derivative, poly-(methyl) acrylate etc.Among them, preferably other polyamic acid and other polyimide, more preferably other polyamic acid.
As the tetracarboxylic dianhydride who is used for synthetic above-mentioned other polyamic acid or other polyimide, can list preferred other tetracarboxylic dianhydride's who uses above-mentioned same tetracarboxylic dianhydride as being used for synthetic particular polymers, preferably use by 1,2,3,4-tetramethylene tetracarboxylic dianhydride, pyromellitic acid dianhydride, 2,3,5-tricarboxylic basic ring amyl group acetate dianhydride and 1,3,3a, 4,5,9b-six hydrogen-5-(tetrahydrochysene-2,5-dioxo-3-furyl)-and naphtho-[1,2-c] furans-1, that selects in the group that the 3-diketone constitutes is at least a.
As the diamines that is used for synthetic above-mentioned other polyamic acid or other polyimide, the preferred use is selected from as the diamines that uses when the synthetic particular polymers and at least a at illustrative diamines above.As the diamines that is used for synthetic other polyamic acid or other polyimide, preferably use by 4,4 '-diaminodiphenyl-methane, 2,2 '-dimethyl-4,4 '-benzidine, cholestane base-2,4-diaminobenzene, 3,5-diaminobenzoic acid and 1, that selects in the group that 4-two-(4-aminophenyl) piperazine constitutes is at least a.
As the usage ratio of other polymkeric substance, (be meant the total amount of above-mentioned particular polymers and other polymkeric substance with respect to the total amount of polymkeric substance.Below identical), be preferably below the 50 weight %, more preferably below the 40 weight %, more preferably below the 30 weight %.When using other polymkeric substance, its usage ratio is with respect to the total amount of polymkeric substance, so long as more than the 0.1 weight %, just can find the effect of its interpolation wittingly.
[epoxy compounds]
The liquid crystal orientation film that epoxy compounds obtains based on further raising can contain in liquid crystal aligning agent of the present invention purposes such as the binding property of substrate and thermotolerances.
As above-mentioned epoxy compounds, be preferably the compound that has the epoxy group(ing) more than 2 at intramolecularly, can list for example ethylene glycol diglycidylether, polyethyleneglycol diglycidylether, propylene glycol diglycidylether, tripropyleneglycol diglycidyl ether, polypropylene glycol diglycidyl ether, neopentylglycol diglycidyl ether, 1, the 6-hexanediol diglycidyl ether, glycerin diglycidyl ether, trihydroxymethylpropanyltri diglycidyl ether, 2,2-two bromo neopentylglycol diglycidyl ethers, N, N, N ', N '-four glycidyl group-m-xylene diamine, 1,3-two (N, N-diglycidyl amino methyl) hexanaphthene, N, N, N ', N '-four glycidyl group-4,4 '-diaminodiphenyl-methane, N, N-diglycidyl-benzyl amine, N, N-diglycidyl-amino methyl hexanaphthene, N, N-diglycidyl-cyclo-hexylamine etc.
If its usage ratio of epoxy compounds is too small, then can't fully show above-mentioned the sort of desired effects; On the other hand, if usage ratio is excessive, then can damage the doing over again property and the wear resistance of liquid crystal orientation film.Based on this viewpoint, amount to 100 weight parts with respect to polymkeric substance, the blending ratio of epoxy compounds is preferably below 30 weight parts, 0.1～15 weight part more preferably, more preferably 0.5～8 weight part is preferably 1～3 weight part especially.
[functional silanes compound]
As above-mentioned functional silanes compound, can list for example 3-TSL 8330, the 3-aminopropyltriethoxywerene werene, the 2-TSL 8330, the 2-aminopropyltriethoxywerene werene, N-(2-amino-ethyl)-3-TSL 8330, N-(2-amino-ethyl)-3-aminopropyl methyl dimethoxysilane, 3-uride propyl trimethoxy silicane, 3-uride propyl-triethoxysilicane, N-ethoxy carbonyl-3-TSL 8330, N-ethoxy carbonyl-3-aminopropyltriethoxywerene werene, N-triethoxysilylpropyltetrasulfide diethylenetriamine, N-trimethoxy-silylpropyl diethylenetriamine, 10-trimethoxysilyl-1,4,7-three azepine decane, 10-triethoxysilyl-1,4,7-three azepine decane, 9-trimethoxysilyl-3,6-diaza nonyl acetic ester, 9-triethoxysilyl-3,6-diaza nonyl acetic ester, 9-trimethoxysilyl-3,6-diaza methyl pelargonate, 9-triethoxysilyl-3,6-diaza methyl pelargonate, N-benzyl-3-TSL 8330, N-benzyl-3-aminopropyltriethoxywerene werene, N-phenyl-3-TSL 8330, N-phenyl-3-aminopropyltriethoxywerene werene, the glycidoxypropyl methyltrimethoxy silane, the glycidoxypropyl Union carbide A-162,2-glycidoxypropyl ethyl trimethoxy silane, 2-glycidoxypropyl ethyl triethoxysilane, the 3-glycidoxypropyltrimewasxysilane, 3-glycidoxypropyl triethoxyl silane etc.
Amount to 100 weight parts with respect to polymkeric substance, the blending ratio of these functional silanes compounds is preferably below 2 weight parts, more preferably 0.02～0.2 weight part.
＜liquid crystal aligning agent 〉
Liquid crystal aligning agent of the present invention as above particular polymers and any as required other additive of blended dissolves in preferred organic and contains and constitute.
As the organic solvent that in liquid crystal aligning agent of the present invention, uses, can list the N-N-methyl-2-2-pyrrolidone N-, gamma-butyrolactone, butyrolactam, N, dinethylformamide, N,N-dimethylacetamide, 4-hydroxy-4-methyl-2 pentanone, the glycol monomethyl methyl ether, n-Butyl lactate, butylacetate, the methoxypropionic acid methyl esters, ethoxyl ethyl propionate, Ethylene Glycol Methyl ether, glycol ethyl ether, the ethylene glycol n-propyl ether, the ethylene glycol isopropyl ether, ethylene glycol n-butyl ether (ethylene glycol butyl ether), ethylene glycol dimethyl ether, ethylene glycol monoethyl ether acetate, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol monomethyl ether, TC, the diethylene glycol monomethyl ether acetic ester, the TC acetic ester, diisobutyl ketone, propionic acid isopentyl ester, isopropylformic acid isopentyl ester, diisoamyl ether, NSC 11801, propylene carbonate etc.They can use separately, perhaps also can mix two or more uses.
Solid component concentration in the liquid crystal aligning agent of the present invention (gross weight of the composition beyond the solvent of liquid crystal aligning agent occupies the ratio of the gross weight of liquid crystal aligning agent) is considered suitably selection such as viscosity, volatility, is preferably the scope of 1～10 weight %.Just, liquid crystal aligning agent of the present invention as described later, be coated to substrate surface, preferably by heating, form liquid crystal orientation film film or liquid crystal aligning is film formed films, but when solid component concentration less than 1 weight %, this thickness of filming is too small, may be difficult to obtain good liquid crystal orientation film; On the other hand, when solid component concentration surpassed 10 weight %, the thickness of filming was excessive, be difficult to obtain good liquid crystal orientation film, and the viscosity of liquid crystal aligning agent increased coating character deficiency.
The method that the scope of particularly preferred solid component concentration adopts during according to coated with liquid crystal alignment agent on substrate and different.For example, when using spin-coating method to carry out, solid component concentration is preferably the scope of 1.5～4.5 weight % especially.When using print process to carry out, solid component concentration is the scope of 3～9 weight %, and thus, soltion viscosity is preferably the scope of 12～50mPas especially.When using ink jet method to carry out, solid component concentration is the scope of 1～5 weight %, and thus, soltion viscosity is preferably the scope of 3～15mPas especially.
Temperature when preparing liquid crystal aligning agent of the present invention is preferably 10～50 ℃, more preferably 20～30 ℃.
＜liquid crystal display device 〉
Liquid crystal display device of the present invention has the liquid crystal orientation film that is formed by as above liquid crystal aligning agent of the present invention.In more detail, liquid crystal display device of the present invention is to dispose polaroids in two outsides of liquid crystal cell to form, it is characterized in that: this liquid crystal cell has the substrate subtend configuration that has liquid crystal orientation film with two, so that each liquid crystal aligning face is relative, in the gap, clamp the structure of liquid crystal layer, and above-mentioned liquid crystal orientation film is formed by liquid crystal aligning agent of the present invention.
This liquid crystal display device of the present invention for example can be by the operation manufacturing of following (1) to (3).Operation (1) is according to desirable operational mode, the substrate difference of use.Operation (2) is identical with (3) under various operational modes.
(1) at first, coating liquid crystal aligning agent of the present invention on substrate then, by the heating applicator surface, forms on substrate and films.
(1-1) when making TN type, STN type or VA type liquid crystal display device, two substrates that will be provided with the nesa coating that forms pattern on one side form a pair of, on their each transparent conducting film formation face, preferably by adherography, spin-coating method or ink jet printing method, apply liquid crystal aligning agent of the present invention respectively, then, by heating each applicator surface, formation is filmed.At this moment, as substrate, can use for example by glass such as float glass, soda glass; The transparency carrier that polyethylene terephthalate, polybutylene terephthalate, polyethersulfone, polycarbonate, poly-plastics such as (ester ring type alkene) form.As the nesa coating that on the one side of substrate, is provided with, can use by stannic oxide (SnO 2) form NESA film (registered trademark of U.S. PPG company), by Indium sesquioxide-stannic oxide (In 2O 3-SnO 2) the ITO film that forms etc., in order to obtain forming the nesa coating of pattern, can form method of patterning by photoetch by after for example forming the pattern-free nesa coating; When forming nesa coating, use the method etc. of mask to obtain with desirable pattern.During the coated with liquid crystal alignment agent, better for the cohesiveness that makes substrate surface and nesa coating and film, can in substrate surface, should form on the face of filming, apply functional silanes compound, functionality titanium compound etc. in advance and carry out pre-treatment.
Behind the coated with liquid crystal alignment agent, the purposes such as alignment agent stream of liquid droplets based on preventing to apply preferably preheat (prebake).The temperature of prebake is preferably 30～200 ℃, more preferably 40～150 ℃, is preferably 40～100 ℃ especially.The time of prebake is preferably 0.25～10 minute, more preferably 0.5～5 minute.Afterwards, desolvate,, fire (afterwards curing) operation as required with the purpose of polyamic acid hot-imide based on removing fully.This is fired (afterwards curing) temperature and is preferably 80～300 ℃, more preferably 120～250 ℃.After the time of curing be preferably 5～200 minutes, more preferably 10～100 minutes.So, the thickness of the film of formation is preferably 0.001～1 μ m, more preferably 0.005～0.5 μ m.
(1-2) on the other hand, when making the liquid crystal display device of lateral electric field type, the conducting film that one side is provided with the substrate of the nesa coating that forms the interdigitated electrode structure pattern forms face and is not provided with on the one side of subtend substrate of conducting film, apply liquid crystal aligning agent of the present invention respectively, then, by heating each applicator surface, formation is filmed.
The thickness of filming of coating method, the heating means behind the coated with liquid crystal alignment agent and the formation of the formation pattern method of the substrate that use this moment and the material of nesa coating, nesa coating, the pre-treatment of substrate, liquid crystal aligning agent is identical with above-mentioned (1-1).
(2) liquid crystal display device of making by method of the present invention is when be VA type liquid crystal display device, filming directly as the liquid crystal orientation film use of as above forming also can be able to be carried out using after the grinding process as described below as required.
On the other hand, during liquid crystal display device beyond making the VA type,, form liquid crystal orientation film by filming of as above forming carried out grinding process.
Grinding process is the coated surface that forms as above, by reeling for example by the roller of fibroplastic cloth such as nylon, artificial silk, cotton, carries out in the certain orientation friction.Thus, the orientation of liquid crystal molecule can be given and being filmed, and forms liquid crystal orientation film.
Then, the liquid crystal orientation film that as above forms is handled, this processing is for example to a part of irradiation ultraviolet radiation of liquid crystal orientation film, changes the processing (with reference to patent documentation 11 (Japanese kokai publication hei 6-222366 communique) and patent documentation 12 (Japanese kokai publication hei 6-281937 communique)) of tilt angle in the part zone of liquid crystal orientation film; After the part on liquid crystal orientation film surface formed etchant resist, on the direction different with before grinding process, carry out grinding process after, the processing of removing etchant resist; Have different liquid crystal aligning energy by each zone that makes liquid crystal orientation film, the perspective nature that can improve the liquid crystal display device of gained is (with reference to patent documentation 13 (Japanese kokai publication hei 5-107544 communique).
(3) prepare two substrates that as above form liquid crystal orientation film,, make liquid crystal cell by between two substrates of subtend configuration, disposing liquid crystal.Here, when carrying out grinding process to filming, the configuration of two substrate subtends is so that the polishing direction of respectively filming predetermined angular each other mutually for example is quadrature or antiparallel.
When making liquid crystal cell, can list for example following two kinds of methods.
First method is present known method.At first, make each liquid crystal orientation film subtend, two substrate subtends are disposed by gap (gap of box), use sealing agent, fitted in the peripheral position of two substrates, in the box gap of cutting apart by substrate surface and sealing agent, inject filling liquid crystal after, the sealing filling orifice can be made liquid crystal cell.
The twoth kind of method is the method that is called ODF (One Drop Fill instils) mode.Prescribed position on the substrate in two substrates that form liquid crystal orientation film, apply for example sealing material of ultraviolet light curable, then after the several position of the regulation on the liquid crystal aligning face drips liquid crystal, fit another substrate and make the liquid crystal orientation film subtend, simultaneously liquid crystal is spread out at the whole face of substrate, then, in whole irradiating ultraviolet light of substrate, make sealant cures, can make liquid crystal cell.
Under the situation of any one method, the liquid crystal cell of hope to as above making, after reheat arrives the temperature of the liquid crystal isotropic phase that uses, slow cool to room temperature, the flow orientation when removing the liquid crystal injection.
Then, the outer surface applying polaroid by at liquid crystal cell can obtain liquid crystal display device of the present invention.
At this moment, as sealing agent, can use and for example contain solidifying agent and as Resins, epoxy of the alumina balls of partition etc.
As above-mentioned liquid crystal, can use nematic liquid crystal, dish-like liquid crystal etc.; Among them, preferred nematic liquid crystal, for example can using, schiff alkali class liquid crystal, azoxy are liquid crystal, biphenyls liquid crystal, Santosol 360 class liquid crystal, ester liquid crystal, Terphenyls liquid crystal, xenyl cyclohexanes liquid crystal, miazines liquid crystal, dioxane liquid crystal, double-octane class liquid crystal, cube alkanes liquid crystal etc.In addition, in these liquid crystal, can further add and use for example cholesterol liquid crystals such as chlorination beta-cholestanol, Cholesteryl pelargonate, cholesterol carbonic ether; Chiral reagent with trade(brand)name C-15, CB-15 (manufacturing of メ Le Network company) sale; To oxygen base benzylidene-to strong dielectricity liquid crystal such as amino-2-methyl butyl laurate etc. in the last of the ten Heavenly stems.
As the polaroid that fits to the liquid crystal cell outside surface, can list the orientation that on one side polyvinyl alcohol extended, will absorb polaroid that light polarizing film that iodine be called " H film " with cellulose acetate protective membrane clamp or the polaroid that by H film itself form on one side.
[embodiment]
Below, by embodiment, the present invention is described more specifically, but the present invention is not subjected to the qualification of these embodiment.The imidization rate of the soltion viscosity of each polymers soln in the polymerization example and polyimide is measured by following method.
[soltion viscosity of polymers soln]
The soltion viscosity of polymkeric substance (mPas) is under the solvent of putting down in writing in each synthesis example and concentration, uses E type rotational viscosimeter, measures down at 25 ℃.
[the imidization rate of polyimide]
A small amount of solution of getting polyimide that divides drops in the pure water, behind the at room temperature abundant drying under reduced pressure of precipitation with gained, is dissolved in the heavy-hydrogenated dimethyl sulfoxide (DMSO),, at room temperature measures as primary standard with tetramethylsilane 1H-NMR.From gained 1H-NMR spectrum is tried to achieve the imidization rate from the formula shown in the following mathematical expression (1).
Imidization rate (%)=(1-A 1/ A 2* α) * 100 (1)
In the mathematical expression (1), A 1Be peak area near the proton of the NH base that shows the chemical shift 10ppm,
A 2Be peak area from other proton,
α is the ratio of the number of other proton with respect to the proton of the NH base in the precursor (polyamic acid) of 1 polymkeric substance.
＜TN type liquid crystal aligning agent synthesizes and estimation of stability with polymkeric substance 〉
[as the synthesis example of the polyamic acid of particular polymers]
Synthesis example A-TN1
Will be as tetracarboxylic dianhydride's 112g (0.50mol) 1S, 2S, 4R, 5R-hexanaphthene tetracarboxylic dianhydride and 109g (0.50mol) pyromellitic acid dianhydride and as the 198g (1.0mol) 4 of diamines, 4 '-diaminodiphenyl-methane, be dissolved into N-N-methyl-2-2-pyrrolidone N-and 2, in the mixed solvent that the gamma-butyrolactone of 213g forms by 246g, reacted 3 hours down at 40 ℃, obtain containing the solution of 15 weight % polyamic acids (A-TN1).The soltion viscosity of this solution is 179mPas.
This polymers soln left standstill under 20 ℃ 3 days, did not have gelation, and storage stability is good.
Synthesis example A-TN2
Will be as tetracarboxylic dianhydride's 67g (0.30mol) 1R, 2S, 4S, 5R-hexanaphthene tetracarboxylic dianhydride and 153g (0.70mol) pyromellitic acid dianhydride and as the 198g (1.0mol) 4 of diamines, 4 '-diaminodiphenyl-methane, be dissolved into N-N-methyl-2-2-pyrrolidone N-and 2, in the mixed solvent that the gamma-butyrolactone of 213g forms by 246g, reacted 3 hours down at 40 ℃, obtain containing the solution of 15 weight % polyamic acids (A-TN2).The soltion viscosity of this solution is 153mPas.
This polymers soln left standstill under 20 ℃ 3 days, did not have gelation, and storage stability is good.
[synthesis example of other polyamic acid]
Synthesis example a-TN3
Will be as tetracarboxylic dianhydride's 109g (0.50mol) pyromellitic acid dianhydride and 98g (0.50mol) 1,2,3,4-tetramethylene tetracarboxylic dianhydride and as the 198g (1.0mol) 4 of diamines, 4 '-diaminodiphenyl-methane, be dissolved into N-N-methyl-2-2-pyrrolidone N-and 2, in the mixed solvent that the gamma-butyrolactone of 068g forms by 230g, reacted 3 hours down at 40 ℃, obtain containing the solution of 15 weight % polyamic acids (a-TN3).The soltion viscosity of this solution is 193mPas.
This polymers soln left standstill under 20 ℃ 3 days, did not have gelation, and storage stability is good.
[as the synthesis example of the polyimide of particular polymers]
Synthesis example B-TN1
Will be as tetracarboxylic dianhydride's 112g (0.50mol) 1S, 2S, 4R, 5R-hexanaphthene tetracarboxylic dianhydride and 112g (0.50mol) 2,3,5-tricarboxylic basic ring amyl group acetate dianhydride and as 106g (0.985mol) Ursol D and 7.8g (0.015mol) 3-(3 of diamines, 5-diaminobenzene methanoyl) cholestane is dissolved into 3, in the N-N-methyl-2-2-pyrrolidone N-of 042g, reacted 6 hours down at 60 ℃, obtain containing the solution of polyamic acid.The soltion viscosity of the polyamic acid solution that obtains here is 160mPas.
Append 3 in the polyamic acid solution of gained, the N-N-methyl-2-2-pyrrolidone N-of 380g adds 395g pyridine and 306g diacetyl oxide, carries out dehydration closed-loop reaction in 4 hours under 110 ℃.After the dehydration closed-loop reaction, intrasystem solvent carries out solvent exchange (by this operation with new gamma-butyrolactone, with the pyridine that uses in the imidization reaction and diacetyl oxide except that going to system, below identical), and then concentrate, thereby obtain containing the solution of the polyimide (B-TN 1) of 10 weight % imidization rates about 94%.
Get this solution a small amount of the branch, adds gamma-butyrolactone, forms the solution of concentration 6 weight %, and the soltion viscosity of mensuration is 28mPas.
This polymers soln left standstill under 20 ℃ 3 days, did not have gelation, and storage stability is good.
[synthesis example of other polyimide]
Synthesis example b-TN2
Will be as tetracarboxylic dianhydride's 110g (0.50mol) 2,3,5-tricarboxylic basic ring amyl group acetate dianhydride and 155g (0.50mol) 1,3,3a, 4,5,9b-six hydrogen-8-methyl-5-(tetrahydrochysene-2,5-dioxo-3-furyl) naphtho-[1,2-c] furans-1, the 3-diketone, 92g (0.87mol) Ursol D as diamines, 25g (0.10mol) two (aminopropyl) tetramethyl disiloxanes and 13g (0.02mol) 3,6-two (4-aminobenzoic acyl-oxygen base) cholestane and as 2.7g (0.030mol) aniline of monoamine is dissolved in the N-N-methyl-2-2-pyrrolidone N-of 960g, reacted 6 hours down at 60 ℃, obtain containing the solution of polyamic acid.A small amount of polyamic acid solution of getting gained that divides adds the N-N-methyl-2-2-pyrrolidone N-, forms the solution of polyamic acid concentration 10 weight %, and the soltion viscosity of mensuration is 59mPas.
Then, append 2 in the polyamic acid solution of gained, the N-N-methyl-2-2-pyrrolidone N-of 700g adds 396g pyridine and 409g diacetyl oxide, carries out 4 hours dehydration closed-loops under 110 ℃.After the dehydration closed-loop reaction, intrasystem solvent is with new gamma-butyrolactone solvent exchange, and then concentrated, obtains approximately 2, and 520g contains the solution of the polyimide (b-TN2) of 15 weight % imidization rates about 95%.Get this polyimide solution a small amount of the branch, adds gamma-butyrolactone, forms the solution of polyimide concentration 6.0 weight %, and the soltion viscosity of mensuration is 18mPas.
This polymers soln left standstill under 20 ℃ 3 days, did not have gelation, and storage stability is good.
Synthesis example b-TN3
Will be as tetracarboxylic dianhydride's 224g (1.0mol) 2,3,5-tricarboxylic basic ring amyl group acetate dianhydride and as 106g (0.985mol) Ursol D and 7.8g (0.015mol) 3-(3 of diamines, 5-diaminobenzene methanoyl) cholestane, be dissolved into 3, in the N-N-methyl-2-2-pyrrolidone N-of 042g, reacted 6 hours down, obtain containing the solution of polyamic acid at 60 ℃.The soltion viscosity of the polyamic acid solution that obtains here is 181mPas.
Append 3 in the polyamic acid solution of gained, the N-N-methyl-2-2-pyrrolidone N-of 380g adds 395g pyridine and 306g diacetyl oxide, carries out dehydration closed-loop reaction in 4 hours under 110 ℃.After the dehydration closed-loop reaction, intrasystem solvent is with new gamma-butyrolactone solvent exchange, and then concentrated, obtains containing the solution of the polyimide (b-TN3) of 10 weight % imidization rates about 95%.
Get this solution a small amount of the branch, adds gamma-butyrolactone, forms the solution of concentration 6 weight %, and the soltion viscosity of mensuration is 35mPas.
This polymers soln left standstill under 20 ℃ 3 days, did not have gelation, and storage stability is good.
＜VA type liquid crystal aligning agent synthesizes and estimation of stability with polymkeric substance 〉
[as the synthesis example of the polyimide of particular polymers]
Synthesis example B-VA1
Will be as tetracarboxylic dianhydride's 112g (0.50mol) 1S, 2S, 4R, 5R-hexanaphthene tetracarboxylic dianhydride and 112g (0.50mol) 2,3,5-tricarboxylic basic ring amyl group acetate dianhydride and as the 52g (0.1mol) 3 of diamines, 5-diaminobenzoic acid cholestane base ester, 49g (0.1mol) cholestane oxygen base-2,4-diaminobenzene and 87g (0.80mol) Ursol D, be dissolved into 1, in the N-N-methyl-2-2-pyrrolidone N-of 652g, reacted 6 hours down, obtain the solution of polyamic acid at 60 ℃.A small amount of polyamic acid solution of getting gained that divides adds the N-N-methyl-2-2-pyrrolidone N-, forms the solution of polymer concentration 10 weight %, and the soltion viscosity of mensuration is 79mPas.
Then, append 3 in the polyamic acid solution of gained, the N-N-methyl-2-2-pyrrolidone N-of 835g adds 79g pyridine and 102g diacetyl oxide, carries out 4 hours dehydration closed-loops under 110 ℃.After the dehydration closed-loop reaction, intrasystem solvent is with new N-N-methyl-2-2-pyrrolidone N-solvent exchange, obtains containing the solution of polyimide (B-VA1) of imidization rate about 51% of 15 weight % of having an appointment respectively.A small amount of polyimide solution of getting gained that divides adds the N-N-methyl-2-2-pyrrolidone N-, forms the solution of polyimide concentration 10 weight %, and the soltion viscosity of mensuration is 102mPas.
This polymers soln left standstill under 20 ℃ 3 days, did not have gelation, and storage stability is good.
Synthesis example B-VA2
Will be as tetracarboxylic dianhydride's 112g (0.50mol) 1R, 2S, 4S, 5R--hexanaphthene tetracarboxylic dianhydride and 112g (0.50mol) 2,3,5-tricarboxylic basic ring amyl group acetate dianhydride and as the 52g (0.1mol) 3 of diamines, 5-diaminobenzoic acid cholestane base ester, 49g (0.1mol) cholestane oxygen base-2,4-diaminobenzene and 87g (0.80mol) Ursol D, be dissolved into 1, in the N-N-methyl-2-2-pyrrolidone N-of 652g, reacted 6 hours down, obtain the solution of polyamic acid at 60 ℃.A small amount of polyamic acid solution of getting gained that divides adds the N-N-methyl-2-2-pyrrolidone N-, forms the solution of polymer concentration 10 weight %, and the soltion viscosity of mensuration is 71mPas.
Then, append 3 in the polyamic acid solution of gained, the N-N-methyl-2-2-pyrrolidone N-of 835g adds 79g pyridine and 102g diacetyl oxide, carries out 4 hours dehydration closed-loops under 110 ℃.After the dehydration closed-loop reaction, intrasystem solvent is with new N-N-methyl-2-2-pyrrolidone N-solvent exchange, obtains containing the solution of polyimide (B-VA2) of imidization rate about 48% of 15 weight % of having an appointment.A small amount of polyimide solution of getting gained that divides adds the N-N-methyl-2-2-pyrrolidone N-, forms the solution of polyimide concentration 10 weight %, and the soltion viscosity of mensuration is 99mPas.
This polymers soln left standstill under 20 ℃ 3 days, did not have gelation, and storage stability is good.
Synthesis example B-VA3
Will be as tetracarboxylic dianhydride's 45g (0.20mol) 1S, 2S, 4R, 5R-hexanaphthene tetracarboxylic dianhydride and 180g (0.80mol) 2,3,5-tricarboxylic basic ring amyl group acetate dianhydride and as the 105g (0.20mol) 3 of diamines, 5-diaminobenzoic acid cholestane base ester and 87g (0.80mol) Ursol D are dissolved into 1, in the N-N-methyl-2-2-pyrrolidone N-of 663g, reacted 6 hours down at 60 ℃, obtain the solution of polyamic acid.A small amount of polyamic acid solution of getting gained that divides adds the N-N-methyl-2-2-pyrrolidone N-, forms the solution of polymer concentration 10 weight %, and the soltion viscosity of mensuration is 59mPas.
Then, append 3 in the polyamic acid solution of gained, the N-N-methyl-2-2-pyrrolidone N-of 861g adds 79g pyridine and 102g diacetyl oxide, carries out 4 hours dehydration closed-loops under 110 ℃.After the dehydration closed-loop reaction, intrasystem solvent is with new N-N-methyl-2-2-pyrrolidone N-solvent exchange, obtains containing the solution of polyimide (B-VA3) of imidization rate about 47% of 15 weight % of having an appointment.A small amount of polyimide solution of getting gained that divides adds the N-N-methyl-2-2-pyrrolidone N-, forms the solution of polyimide concentration 10 weight %, and the soltion viscosity of mensuration is 80mPas.
This polymers soln left standstill under 20 ℃ 3 days, did not have gelation, and storage stability is good.
Synthesis example B-VA4
Will be as tetracarboxylic dianhydride's 45g (0.20mol) 1R, 2S, 4S, 5R-hexanaphthene tetracarboxylic dianhydride and 180g (0.80mol) 2,3,5-tricarboxylic basic ring amyl group acetate dianhydride and as the 105g (0.2mol) 3 of diamines, 5-diaminobenzoic acid cholestane base ester and 87g (0.80mol) Ursol D are dissolved into 1, in the N-N-methyl-2-2-pyrrolidone N-of 663g, reacted 6 hours down at 60 ℃, obtain the solution of polyamic acid.A small amount of polyamic acid solution of getting gained that divides adds the N-N-methyl-2-2-pyrrolidone N-, forms the solution of polymer concentration 10 weight %, and the soltion viscosity of mensuration is 66mPas.
Then, append 3 in the polyamic acid solution of gained, the N-N-methyl-2-2-pyrrolidone N-of 861g adds 79g pyridine and 102g diacetyl oxide, carries out 4 hours dehydration closed-loops under 110 ℃.After the dehydration closed-loop reaction, intrasystem solvent is with new N-N-methyl-2-2-pyrrolidone N-solvent exchange, obtains containing the solution of polyimide (B-VA4) of imidization rate about 50% of 15 weight % of having an appointment respectively.A small amount of polyimide solution of getting gained that divides adds the N-N-methyl-2-2-pyrrolidone N-, forms the solution of polyimide concentration 10 weight %, and the soltion viscosity of mensuration is 89mPas.
This polymers soln left standstill under 20 ℃ 3 days, did not have gelation, and storage stability is good.
Synthesis example B-VA5
Will be as tetracarboxylic dianhydride's 135g (0.60mol) 1S, 2S, 4R, 5R-hexanaphthene tetracarboxylic dianhydride and 90g (0.40mol) 2,3,5-tricarboxylic basic ring amyl group acetate dianhydride and as the 105g (0.20mol) 3 of diamines, 5-diaminobenzoic acid cholestane base ester, 65g (0.60mol) Ursol D and 30g (0.20mol) 3,5-diaminobenzoic acid, be dissolved into 1, in the N-N-methyl-2-2-pyrrolidone N-of 697g, reacted 6 hours down, obtain polyamic acid solution at 60 ℃.A small amount of polyamic acid solution of getting gained that divides adds the N-N-methyl-2-2-pyrrolidone N-, forms the solution of polymer concentration 10 weight %, and the soltion viscosity of mensuration is 50mPas.
Then, append 3 in the polyamic acid solution of gained, the N-N-methyl-2-2-pyrrolidone N-of 939g adds 119g pyridine and 153g diacetyl oxide, carries out 4 hours dehydration closed-loops under 110 ℃.After the dehydration closed-loop reaction, intrasystem solvent is with new N-N-methyl-2-2-pyrrolidone N-solvent exchange, obtains containing the solution of polyimide (B-VA5) of imidization rate about 66% of 15 weight % of having an appointment respectively.A small amount of polyimide solution of getting gained that divides adds the N-N-methyl-2-2-pyrrolidone N-, forms the solution of polyimide concentration 10 weight %, and the soltion viscosity of mensuration is 79mPas.
This polymers soln left standstill under 20 ℃ 3 days, did not have gelation, and storage stability is good.
Synthesis example B-VA6
Will be as tetracarboxylic dianhydride's 45g (0.20mol) 1R, 2S, 4S, 5R-hexanaphthene tetracarboxylic dianhydride and 179g (0.80mol) 2,3,5-tricarboxylic basic ring amyl group acetate dianhydride and as the 131g (0.25mol) 3 of diamines, 5-diaminobenzoic acid cholestane base ester, 53g (0.50mol) Ursol D and 38g (0.25mol) 3,5-diaminobenzoic acid, be dissolved into 1, in the N-N-methyl-2-2-pyrrolidone N-of 697g, reacted 6 hours down, obtain polyamic acid solution at 60 ℃.A small amount of polyamic acid solution of getting gained that divides adds the N-N-methyl-2-2-pyrrolidone N-, forms the solution of polymer concentration 10 weight %, and the soltion viscosity of mensuration is 58mPas.
Then, append 3 in the polyamic acid solution of gained, the N-N-methyl-2-2-pyrrolidone N-of 939g adds 119g pyridine and 153g diacetyl oxide, carries out 4 hours dehydration closed-loops under 110 ℃.After the dehydration closed-loop reaction, intrasystem solvent is with new N-N-methyl-2-2-pyrrolidone N-solvent exchange, obtains containing the solution of polyimide (B-VA6) of imidization rate about 69% of 15 weight % of having an appointment.A small amount of polyimide solution of getting gained that divides adds the N-N-methyl-2-2-pyrrolidone N-, forms the solution of polyimide concentration 10 weight %, and the soltion viscosity of mensuration is 81mPas.
This polymers soln left standstill under 20 ℃ 3 days, did not have gelation, storage stability
Well.
[synthesis example of other polyimide]
Synthesis example b-VA7
Will be as tetracarboxylic dianhydride's 224g (1.0mol) 2,3,5-tricarboxylic basic ring amyl group acetate dianhydride and as the 52g (0.10mol) 3 of diamines, 5-diaminobenzoic acid cholestane base ester, 49g (0.10mol) cholestane oxygen base-2,4-diaminobenzene and 87g (0.80mol) Ursol D is dissolved into 1, in the N-N-methyl-2-2-pyrrolidone N-of 652g, reacted 6 hours down at 60 ℃, obtain polyamic acid solution.A small amount of polyamic acid solution of getting gained that divides adds the N-N-methyl-2-2-pyrrolidone N-, forms the solution of polymer concentration 10 weight %, and the soltion viscosity of mensuration is 70mPas.
Then, append 3 in the polyamic acid solution of gained, the N-N-methyl-2-2-pyrrolidone N-of 835g adds 79g pyridine and 102g diacetyl oxide, carries out 4 hours dehydration closed-loops under 110 ℃.After the dehydration closed-loop reaction, intrasystem solvent is with new N-N-methyl-2-2-pyrrolidone N-solvent exchange, obtains containing the solution of polyimide (b-VA7) of imidization rate about 49% of 15 weight % of having an appointment.A small amount of polyimide solution of getting gained that divides adds the N-N-methyl-2-2-pyrrolidone N-, forms the solution of polyimide concentration 10 weight %, and the soltion viscosity of mensuration is 80mPas.
This polymers soln left standstill under 20 ℃ 3 days, did not have gelation, and storage stability is good.
Synthesis example b-VA8
Will be as tetracarboxylic dianhydride's 224g (1.0mol) 2,3,5-tricarboxylic basic ring amyl group acetate dianhydride and as the 105g (0.20mol) 3 of diamines, 5-diaminobenzoic acid cholestane base ester, 65g (0.60mol) Ursol D and 30g (0.20mol) 3, the 5-diaminobenzoic acid is dissolved into 1, in the N-N-methyl-2-2-pyrrolidone N-of 697g, reacted 6 hours down at 60 ℃, obtain polyamic acid solution.A small amount of polyamic acid solution of getting gained that divides adds the N-N-methyl-2-2-pyrrolidone N-, forms the solution of polymer concentration 10 weight %, and the soltion viscosity of mensuration is 50mPas.
Then, append 3 in the polyamic acid solution of gained, the N-N-methyl-2-2-pyrrolidone N-of 939g adds 119g pyridine and 153g diacetyl oxide, carries out 4 hours dehydration closed-loops under 110 ℃.After the dehydration closed-loop reaction, intrasystem solvent is with new N-N-methyl-2-2-pyrrolidone N-solvent exchange, obtains containing the solution of polyimide (b-VA8) of imidization rate about 67% of 15 weight % of having an appointment.A small amount of polyimide solution of getting gained that divides adds the N-N-methyl-2-2-pyrrolidone N-, forms the solution of polyimide concentration 10 weight %, and the soltion viscosity of mensuration is 73mPas.
This polymers soln left standstill under 20 ℃ 3 days, did not have gelation, and storage stability is good.
＜IPS type liquid crystal aligning agent synthesizes and estimation of stability with polymkeric substance 〉
[as the synthesis example of the polyamic acid of particular polymers]
Synthesis example A-IPS1
Will be as tetracarboxylic dianhydride's 45g (0.20mol) 1S, 2S, 4R, 5R-hexanaphthene tetracarboxylic dianhydride and 174g (0.80mol) pyromellitic acid dianhydride and as 108g (1.0mol) Ursol D of diamines, be dissolved into 1, in the N-N-methyl-2-2-pyrrolidone N-of 900g, reacted 3 hours down, obtain containing the solution of 15 weight % polyamic acids (A-IPS 1) at 40 ℃.
Get this solution a small amount of the branch, adds the N-N-methyl-2-2-pyrrolidone N-, forms the solution of polyamic acid concentration 10 weight %, the soltion viscosity 75mPas of mensuration.
This polymers soln left standstill under 20 ℃ 3 days, did not have gelation, and storage stability is good.
[synthesis example of other polyamic acid]
Synthesis example a-IPS2
Except using 190g (0.85mol) 1R, 2S, 4S, 5R-hexanaphthene tetracarboxylic dianhydride and 33g (0.15mol) pyromellitic acid dianhydride as beyond the tetracarboxylic dianhydride and synthesis example A-IPS1 similarly obtain containing the solution of 15 weight % polyamic acids (a-IPS2).
Get this solution a small amount of the branch, adds the N-N-methyl-2-2-pyrrolidone N-, forms the solution of polyamic acid concentration 10 weight %, and the soltion viscosity of mensuration is 63mPas.
When this polymers soln leaves standstill 3 days under 20 ℃, find gelation, storage stability is bad.
This polyamic acid (a-IPS2) is not carried out other evaluation.
[as the synthesis example of the polyamic acid of particular polymers]
Synthesis example A-IPS3
Will be as tetracarboxylic dianhydride's 180g (0.80mol) 1S, 2S, 4R, 5R-hexanaphthene tetracarboxylic dianhydride and 44g (0.20mol) pyromellitic acid dianhydride and as the 160g (0.80mol) 4 of diamines, 4 '-diamino-diphenyl ether and 110g (0.20mol) Ursol D, be dissolved into 2, in the N-N-methyl-2-2-pyrrolidone N-of 300g, reacted 3 hours down at 40 ℃, obtain containing the solution of 15 weight % polyamic acids (A-IPS3).
Get this solution a small amount of the branch, adds the N-N-methyl-2-2-pyrrolidone N-, forms the solution of polyamic acid concentration 10 weight %, and the soltion viscosity of mensuration is 74mPas.
When this polymers soln leaves standstill 3 days under 20 ℃, do not have gelation, storage stability is good.
Synthesis example A-IP S4
Except using 180g (0.80mol) 1R, 2S, 4S, 5R-hexanaphthene tetracarboxylic dianhydride and 44g (0.20mol) pyromellitic acid dianhydride as beyond the tetracarboxylic dianhydride and synthesis example A-IPS3 similarly, obtain containing the solution of 15 weight % polyamic acids (A-IP S4).
Get this solution a small amount of the branch, adds the N-N-methyl-2-2-pyrrolidone N-, forms the solution of polyamic acid concentration 10 weight %, and the soltion viscosity of mensuration is 60mPas.
When this polymers soln leaves standstill 3 days under 20 ℃, do not have gelation, storage stability is good.
Synthesis example A-IPS5
Will be as tetracarboxylic dianhydride's 180g (0.80mol) 1S, 2S, 4R, 5R-hexanaphthene tetracarboxylic dianhydride and 44g (0.20mol) pyromellitic acid dianhydride and as the 200g (1.0mol) 4 of diamines, 4 '-diamino-diphenyl amine, be dissolved into 2, in the N-N-methyl-2-2-pyrrolidone N-of 400g, reacted 3 hours down at 40 ℃, obtain containing the solution of 15 weight % polyamic acids (A-IPS 5).
Get this solution a small amount of the branch, adds the N-N-methyl-2-2-pyrrolidone N-, forms the solution of polyamic acid concentration 10 weight %, and the soltion viscosity of mensuration is 65mPas.
When this polymers soln leaves standstill 3 days under 20 ℃, do not have gelation, storage stability is good.
Synthesis example A-IPS6
Except using 180g (0.80mol) 1R respectively, 2S, 4S, 5R-hexanaphthene tetracarboxylic dianhydride and 44g (0.20mol) pyromellitic acid dianhydride is as the tetracarboxylic dianhydride and use 100g (0.50mol) 4,4 '-diamino-diphenyl ether and 100g (0.50mol) 4,4 '-diamino-diphenyl amine as beyond the tetracarboxylic dianhydride and synthesis example A-IPS 5 similarly obtain containing the solution of 15 weight % polyamic acids (A-IPS6).
Get this solution a small amount of the branch, adds the N-N-methyl-2-2-pyrrolidone N-, forms the solution of polyamic acid concentration 10 weight %, and the soltion viscosity of mensuration is 70mPas.
When this polymers soln leaves standstill 3 days under 20 ℃, do not have gelation, storage stability is good.
[synthesis example of other polyamic acid]
Synthesis example a-IPS7
Will be as tetracarboxylic dianhydride's 224g (1.0mol) 1S, 2S, 4R, 5R-hexanaphthene tetracarboxylic dianhydride and as 108g (1.0mol) Ursol D of diamines, be dissolved into 1, in the N-N-methyl-2-2-pyrrolidone N-of 900g, reacted 3 hours down, obtain containing the solution of 15 weight % polyamic acids (a-IPS7) at 40 ℃.
Get this solution a small amount of the branch, adds the N-N-methyl-2-2-pyrrolidone N-, forms the solution of polyamic acid concentration 10 weight %, and the soltion viscosity of mensuration is 99mPas.
When this polymers soln leaves standstill 3 days under 20 ℃, observe gelation, storage stability is bad.
This polyamic acid (a-IPS7) is not carried out other evaluation.
Synthesis example a-IPS8
Except using 224g (1.0mol) 1R, 2S, 4S, 5R-hexanaphthene tetracarboxylic dianhydride as beyond the tetracarboxylic dianhydride and synthesis example A-IPS5 similarly, obtain containing the solution of 15 weight % polyamic acids (a-IPS8).
This solution is the solution shape under temperature of reaction (40 ℃), produces gelation in the process with its cool to room temperature, so can't measure viscosity.
This polyamic acid (a-IPS8) is not carried out other evaluation.
Synthesis example a-IPS9
Will be as tetracarboxylic dianhydride's 220g (1.0mol) pyromellitic acid dianhydride and as 110g (1.0mol) Ursol D of diamines, be dissolved into 1, in the N-N-methyl-2-2-pyrrolidone N-of 800g, reacted 3 hours down, obtain containing the solution of 15 weight % polyamic acids (a-IPS9) at 40 ℃.
The soltion viscosity of this solution is 180mPas.
When this polymers soln leaves standstill 3 days under 20 ℃, do not have gelation, storage stability is good.
Synthesis example a-IPS10
Will be as tetracarboxylic dianhydride's 220g (1.0mol) pyromellitic acid dianhydride and as the 160g (0.80mol) 4 of diamines, 4 '-diamino-diphenyl ether and 22g (0.20mol) Ursol D, be dissolved into 2, in the N-N-methyl-2-2-pyrrolidone N-of 300g, reacted 3 hours down at 40 ℃, obtain containing the solution of 15 weight % polyamic acids (a-IPS 10).
Get this solution a small amount of the branch, adds the N-N-methyl-2-2-pyrrolidone N-, forms the solution of polyamic acid concentration 10 weight %, and the soltion viscosity of mensuration is 71mPa.s.
When this polymers soln leaves standstill 3 days under 20 ℃, do not have gelation, storage stability is good.
Synthesis example a-IPS11
Will be as tetracarboxylic dianhydride's 200g (0.90mol) pyromellitic acid dianhydride and 20g (0.10mol) 1,2,3,4-tetramethylene tetracarboxylic dianhydride and as the 160g (0.80mol) 4 of diamines, 4 '-diamino-diphenyl ether and 22g (0.20mol) Ursol D, be dissolved into 2, in the N-N-methyl-2-2-pyrrolidone N-of 300g, reacted 3 hours down at 40 ℃, obtain containing the solution of 15 weight % polyamic acids (a-IPS11).
Get this solution a small amount of the branch, adds the N-N-methyl-2-2-pyrrolidone N-, forms the solution of polyamic acid concentration 10 weight %, and the soltion viscosity of mensuration is 77mPas.
When this polymers soln leaves standstill 3 days under 20 ℃, do not have gelation, storage stability is good.
[as the synthesis example of the polyimide of particular polymers]
Synthesis example B-IPS1
Will be as tetracarboxylic dianhydride's 112g (0.50mol) 1S, 2S, 4R, 5R-hexanaphthene tetracarboxylic dianhydride and 112g (0.50mol) 2,3,5-tricarboxylic basic ring amyl group acetate dianhydride and as 86g (0.80mol) Ursol D, 23g (0.10mol) 4,4 '-diaminodiphenyl-methane and the 32g (0.10mol) 4 of diamines, 4 '-diamino-2,2 '-two (trifluoromethyl) biphenyl is dissolved into 2, in the N-N-methyl-2-2-pyrrolidone N-of 100g, reacted 3 hours down at 40 ℃, obtain polyamic acid solution.A small amount of polyamic acid solution of getting gained that divides adds the N-N-methyl-2-2-pyrrolidone N-, forms the solution of polymer concentration 10 weight %, and the soltion viscosity of mensuration is 40mPas.
Then, append 2 in the polyamic acid solution of gained, the N-N-methyl-2-2-pyrrolidone N-of 800g adds 400g pyridine and 310g diacetyl oxide, carries out dehydration closed-loop reaction in 4 hours under 110 ℃.After the dehydration closed-loop reaction, intrasystem solvent then, by concentrating, obtains 2 with new gamma-butyrolactone solvent exchange, and 300g contains the solution of the polyimide (B-IPSl) of 15 weight % imidization rates about 92%.Get this solution a small amount of the branch, adds gamma-butyrolactone, forms the solution of polyimide concentration 10 weight %, and the soltion viscosity of mensuration is 36mPas.
When this polymers soln leaves standstill 3 days under 20 ℃, do not have gelation, storage stability is good.
Synthesis example B-IPS2
Except using 112g (0.50mol) 1R, 2S, 4S, 5R-hexanaphthene tetracarboxylic dianhydride and 112g (0.50mol) 2,3,5-tricarboxylic basic ring amyl group acetate dianhydride as beyond the tetracarboxylic dianhydride and synthesis example B-IPS1 similarly, obtain polyamic acid solution.Get this solution a small amount of the branch, adds the N-N-methyl-2-2-pyrrolidone N-, forms the solution of polymer concentration 10 weight %, and the soltion viscosity of mensuration is 35mPas.
Then and after synthesis example B-IPS1 similarly carries out dehydration closed-loop reaction, intrasystem solvent gamma-butyrolactone solvent exchange then, by concentrated, obtains 2, and 300g contains the solution of the polyimide (B-IPS2) of 15 weight % imidization rates about 94%.Get this solution a small amount of the branch, adds gamma-butyrolactone, forms the solution of polyimide concentration 10 weight %, and the viscosity of mensuration is 34mPas.
When this polymers soln leaves standstill 3 days under 20 ℃, do not have gelation, storage stability is good.
Synthesis example B-IPS3
Will be as tetracarboxylic dianhydride's 112g (0.50mol) 1S, 2S, 4R, 5R-hexanaphthene tetracarboxylic dianhydride and 112g (0.50mol) 2,3,5-tricarboxylic basic ring amyl group acetate dianhydride and as 97g (0.90mol) Ursol D and 32g (0.10mol) 4,4 '-diamino-2,2 '-two (trifluoromethyl) biphenyl of diamines, be dissolved into 2, in the N-N-methyl-2-2-pyrrolidone N-of 000g, reacted 3 hours down, obtain polyamic acid solution at 40 ℃.A small amount of polyamic acid solution of getting gained that divides adds the N-N-methyl-2-2-pyrrolidone N-, forms the solution of polymer concentration 10 weight %, and the soltion viscosity of mensuration is 46mPas.
Then, append 2 in the polyamic acid solution of gained, the N-N-methyl-2-2-pyrrolidone N-of 700g adds 400g pyridine and 310g diacetyl oxide, carries out dehydration closed-loop reaction in 4 hours under 110 ℃.After the dehydration closed-loop reaction, intrasystem solvent gamma-butyrolactone solvent exchange then, by concentrating, obtains 2, and 300g contains the solution of the polyimide (B-IPS3) of 15 weight % imidization rates about 93%.Get this solution a small amount of the branch, adds gamma-butyrolactone, forms the solution of polyimide concentration 10 weight %, and the soltion viscosity of mensuration is 42mPas.
When this polymers soln leaves standstill 3 days under 20 ℃, do not have gelation, storage stability is good.
Synthesis example B-IPS4
Except using 112g (0.50mol) 1R, 2S, 4S, 5R-hexanaphthene tetracarboxylic dianhydride and 112g (0.50mol) 2,3,5-tricarboxylic basic ring amyl group acetate dianhydride as beyond the tetracarboxylic dianhydride and synthesis example B-IPS3 similarly obtain polyamic acid solution.Get this solution a small amount of the branch, adds the N-N-methyl-2-2-pyrrolidone N-, forms the solution of polymer concentration 10 weight %, and the soltion viscosity of mensuration is 35mPas.
Then and after synthesis example B-IP S3 similarly carries out dehydration closed-loop reaction, intrasystem solvent gamma-butyrolactone solvent exchange then, by concentrated, obtains 2, and 300g contains the solution of the polyimide (B-IPS4) of 15 weight % imidization rates about 91%.Get this solution a small amount of the branch, adds gamma-butyrolactone, forms the solution of polyimide concentration 10 weight %, and the soltion viscosity of mensuration is 33mPas.
When this polymers soln leaves standstill 3 days under 20 ℃, do not have gelation, storage stability is good.
[synthesis example of other polyimide]
Synthesis example b-IPS5
Except using 220g (1.0mol) 2,3,5-tricarboxylic basic ring amyl group acetate dianhydride as beyond the tetracarboxylic dianhydride and synthesis example B-IPS 1 similarly, obtain polyamic acid solution.Get this solution a small amount of the branch, adds the N-N-methyl-2-2-pyrrolidone N-, forms the solution of polymer concentration 10 weight %, and the soltion viscosity of mensuration is 48mPas.
Then and after synthesis example B-IPS 1 similarly carries out dehydration closed-loop reaction, intrasystem solvent gamma-butyrolactone solvent exchange then, by concentrated, obtains 2, and 300g contains the solution of the polyimide (b-IPS5) of 15 weight % imidization rates about 93%.Get this solution a small amount of the branch, adds gamma-butyrolactone, forms the solution of polyimide concentration 10 weight %, and the viscosity of mensuration is 45mPas.
When this polymers soln leaves standstill 3 days under 20 ℃, do not have gelation, storage stability is good.
Synthesis example b-IPS6
Except using 220g (1.0mol) 2,3,5-tricarboxylic basic ring amyl group acetate dianhydride as beyond the tetracarboxylic dianhydride and synthesis example B-IPS4 similarly obtain polyamic acid solution.Get this solution a small amount of the branch, adds the N-N-methyl-2-2-pyrrolidone N-, forms the solution of polymer concentration 10 weight %, and the soltion viscosity of mensuration is 45mPas.
Then and after synthesis example B-IP S4 similarly carries out dehydration closed-loop reaction, intrasystem solvent gamma-butyrolactone solvent exchange then, by concentrated, obtains 2, and 300g contains the solution of the polyimide (b-IP S6) of 15 weight % imidization rates about 93%.Get this solution a small amount of the branch, adds gamma-butyrolactone, forms the solution of polyimide concentration 10 weight %, and the viscosity of mensuration is 41mPas.
When this polymers soln leaves standstill 3 days under 20 ℃, do not have gelation, storage stability is good.
The preparation and the evaluation of＜TN type liquid crystal aligning agent 〉
Embodiment TN-1
(I) preparation of liquid crystal aligning agent
The solution that contains polyamic acid (A-TN 1) that combination obtains as the above-mentioned synthesis example A-TN 1 of particular polymers, being scaled polyamic acid (A-TN 1) is the amount of 80 weight parts, the solution that contains polyimide (b-TN2) that obtains with above-mentioned synthesis example b-TN2 as other polymkeric substance, be scaled the amount that polyimide (b-TN2) is equivalent to 20 weight parts, add N-N-methyl-2-2-pyrrolidone N-(NMP) therein, gamma-butyrolactone (BL) and ethylene glycol butyl ether (BC), and to make final solvent composition be NMP: BL: BC=17: 71: 12 (weight ratio), add the N of 2 weight parts then as epoxy compounds, N, N ', N '-four glycidyl group-4,4 '-diaminodiphenyl-methane, the solution of preparation solid component concentration 3.5 weight %.After this solution fully stirs, use the strainer of aperture 1 μ m to filter, the preparation liquid crystal aligning agent.
(II) evaluation of liquid crystal aligning agent
(1) manufacturing of TN type liquid crystal cell
Use liquid crystal orientation film printing press (Japan's description printing (strain) is made), on the transparency electrode face that has by the glass substrate of the film formed transparency electrode of ITO, apply the liquid crystal aligning agent of above-mentioned preparation, on 80 ℃ hot plate, heat 1 minute (prebake), except that after desolvating, on 200 ℃ hot plate, heat 10 minutes (afterwards curing), form average film thickness
Figure BSA00000416150900391
Film.
This is filmed, use the sander of the roller with the artificial silk of having reeled, at roller revolution 500rpm, platen translational speed 3cm/s, fine hair is pressed into and carries out grinding process under the length 0.4mm, gives the liquid crystal aligning energy.Afterwards, carry out 1 minute ultrasonic washing in ultrapure water, then, drying is 10 minutes in 100 ℃ cleaning oven, thereby obtains having the substrate of liquid crystal orientation film.Repeat this operation, obtain the substrate that a pair of (two) have liquid crystal orientation film.
Then, the external margin of 1 face in above-mentioned a pair of substrate with liquid crystal orientation film, coating has added the epoxy resin binder of alumina balls of diameter 5.5 μ m, so that the relative mode of liquid crystal aligning face is solidified tackiness agent in the face of behind a pair of substrate of crimping.Then, from liquid crystal injecting port, between a pair of substrate, fill nematic liquid crystal (メ Le Network company makes, MLC-6221) after, with acrylic acid or the like Photocurable adhesive encapsulated liquid crystals inlet, make liquid crystal cell.
(2) evaluation of heat-resistant stability
With the voltage retention is index, estimates the weather resistance to thermal stresses.Determinator as voltage retention uses the (device of the model " VHR-1 " that the) East Yang テ of Co., Ltd. Network two power are made.
To the liquid crystal cell of above-mentioned manufacturing, under 60 ℃, with the application time of 60 microseconds, 167 milliseconds interval liquid crystal display device is applied the voltage of 5V after, measure from releasing and apply voltage retention (initial stage voltage retention VHR0) behind the voltage to 167 millisecond.
Then, to before applying thermal stresses, measure the liquid crystal display device after the voltage retention, in 100 ℃ baking oven, left standstill 1,000 hour, apply after the thermal stresses and the above-mentioned voltage retention (apply thermal stresses after voltage retention VHR1) of similarly measuring once more.
Use the VHR0 of said determination and the value of VHR1,, try to achieve the poor Δ VHR of the voltage retention that applies the thermal stresses front and back by following mathematical expression (1).
ΔVHR＝VHR0-VHR?1(1)
This value is in 5% the time, and heat-resistant stability is evaluated as well.
Evaluation result is as shown in table 1.
Embodiment TN-2 and TN-3 and comparative example tn-1 and tn-2
Except in the foregoing description TN-1, use the solution of the polymkeric substance of the kind that contains record in the table 1 and amount respectively as particular polymers and other polymkeric substance, and add each solvent so that final solvent composition such as table 1 beyond the record, similarly prepare liquid crystal aligning agent with embodiment TN-1, estimate.
Evaluation result is as shown in table 1.
The polymkeric substance that meets this hurdle is not used in "-" expression in the table 1.Among the comparative example tn-1, mix and use two kinds of polymkeric substance as other polymkeric substance.
The abbreviation of the solvent in the table 1 is respectively following implication.
The NMP:N-N-methyl-2-2-pyrrolidone N-
BL: gamma-butyrolactone
BC: ethylene glycol butyl ether
The preparation and the evaluation of＜VA type liquid crystal aligning agent 〉
EXAMPLE V A-1
(I) preparation of liquid crystal aligning agent
In the solution that contains polyimide (B-VA1) that the above-mentioned synthesis example B-VA1 as polymkeric substance obtains, add N-N-methyl-2-2-pyrrolidone N-and ethylene glycol butyl ether, the polyimide that relative then 100 weight parts use adds the N of 5 weight parts as epoxy compounds, N, N ', N '-four glycidyl group-m-xylene diamine, fully stir, forming solvent composition is the N-N-methyl-2-2-pyrrolidone N-: the solution of ethylene glycol butyl ether=50: 50 (weight ratio), solid component concentration 3.5 weight %.This solution uses the strainer of aperture 1 μ m to filter, the preparation liquid crystal aligning agent.
(II) evaluation of liquid crystal aligning agent
(1) manufacturing of VA type liquid crystal cell
Use spinner, on the nesa coating that constitutes by the ITO film that is provided with on the one side of the glass substrate of thickness 1mm, apply the liquid crystal aligning agent of above-mentioned preparation, on hot plate, under 80 ℃, prebake 1 minute is then by on hot plate, after under 210 ℃, cured 30 minutes, form film (liquid crystal orientation film) of thickness 80nm.Repeat this operation, obtain the substrate that two (1 pairs) have liquid crystal orientation film.
Then, the external margin of 1 face in above-mentioned a pair of substrate with liquid crystal orientation film, coating has added the epoxy resin binder of alumina balls of diameter 3.5 μ m, so that the relative mode of liquid crystal orientation film is solidified tackiness agent in the face of behind a pair of substrate of crimping.Then, from liquid crystal injecting port, between substrate, fill negative type liquid crystal (メ Le Network company makes, MLC-6608) after, use the acrylic acid or the like Photocurable adhesive, encapsulated liquid crystals inlet, manufacturing liquid crystal cell.
(2) evaluation of heat-resistant stability
Use liquid crystal cell and the foregoing description TN-1 of above-mentioned manufacturing similarly to estimate heat-resistant stability.But, when being VA type liquid crystal cell, be in 2% the time in the poor Δ VHR value that applies the voltage retention before and after the thermal stresses, heat-resistant stability can be evaluated as well.
Evaluation result is as shown in table 2.
EXAMPLE V A-2～VA-6 and comparative example va-1 and va-2
Except in the foregoing description VA-1, use beyond the solution of the polymkeric substance that contains in the table 2 record respectively as polymkeric substance and EXAMPLE V A-1 similarly prepares liquid crystal aligning agent, estimate.
Evaluation result is as shown in table 2.
The polymkeric substance that meets this hurdle is not used in "-" expression in the table 2.
The abbreviation of the solvent in the table 2 is identical with the situation of table 1.
Figure BSA00000416150900441
The preparation and the evaluation of＜IPS type liquid crystal aligning agent 〉
Example I PS-1
(I) preparation of liquid crystal aligning agent
In the solution that contains polyamic acid (A-IPS1) that the above-mentioned synthesis example A-IPS1 as polymkeric substance obtains, adding is as the N-N-methyl-2-2-pyrrolidone N-and the ethylene glycol butyl ether of solvent, the polyamic acid that relative then 100 weight parts use adds the N of 5 weight parts as epoxy compounds, N, N ', N '-four glycidyl group-m-xylene diamine, fully stir, forming solvent composition is the N-N-methyl-2-2-pyrrolidone N-: the solution of ethylene glycol butyl ether=80: 20 (weight ratio), solid component concentration 3.5 weight %.This solution uses the strainer of aperture 1 μ m to filter, the preparation liquid crystal aligning agent.
(II) evaluation of liquid crystal aligning agent
(1) manufacturing of liquid crystal cell
Except the liquid crystal aligning agent that uses above-mentioned preparation and the situation among the embodiment TN-1 similarly prepare liquid crystal cell, estimate heat-resistant stability.
Evaluation result is as shown in table 3.
In addition, the liquid crystal cell of Zhi Zaoing is a TN type liquid crystal cell here, and present inventors confirm to use TN type liquid crystal cell to substitute the sample of IPS type liquid crystal cell as heat-resistant stability evaluation usefulness by experience.
Example I PS-2～IPS-5 and comparative example ips-1～ips-3
Except in the foregoing description IPS-1, use beyond the solution of the polymkeric substance that contains in the table 3 record respectively as polymkeric substance and example I PS-1 similarly prepares liquid crystal aligning agent, estimate.
Evaluation result is as shown in table 3.
Example I PS-6～9 and comparative example ips-4 and comparative example ips-5
Except in the foregoing description IPS-1, use the solution that contains the polymkeric substance of record in the table 3 respectively as polymkeric substance, use N-N-methyl-2-2-pyrrolidone N-(NMP), gamma-butyrolactone (BL) and ethylene glycol butyl ether (BC) respectively as solvent, adding these all kinds of SOLVENTS and making final solvent composition is NMP: BL: BC=10: 70: 20 (weight ratio) in addition, similarly prepare liquid crystal aligning agent with example I PS-1, estimate.
Evaluation result is as shown in table 3.
The polymkeric substance that meets this hurdle is not used in "-" expression in the table 3.
The abbreviation of the solvent in the table 3 is identical with the situation of table 1.
Figure BSA00000416150900471

Claims (6)

1. liquid crystal aligning agent, this liquid crystal aligning agent contain at least a polymkeric substance of selecting in the group that is made of polyamic acid and polyimide that this polyamic acid dehydration closed-loop is formed, and this polyamic acid obtains tetracarboxylic dianhydride and diamine reactant,
It is characterized in that: above-mentioned tetracarboxylic dianhydride is with respect to whole tetracarboxylic dianhydrides, contain 5～80mol% by 1S, 2S, 4R, 5R-hexanaphthene tetracarboxylic dianhydride and 1R, 2S, 4S, that selects in the group that 5R-hexanaphthene tetracarboxylic dianhydride constitutes is at least a.
2. the liquid crystal aligning agent of putting down in writing according to claim 1, wherein above-mentioned tetracarboxylic dianhydride further comprises by 1,2,3,4-tetramethylene tetracarboxylic dianhydride, 2,3,5-tricarboxylic basic ring amyl group acetate dianhydride, 1,3,3a, 4,5,9b-six hydrogen-5-(tetrahydrochysene-2,5-dioxo-3-furyl)-and naphtho-[1,2-c] furans-1, the 3-diketone, 1,3,3a, 4,5,9b-six hydrogen-8-methyl-5-(tetrahydrochysene-2,5-dioxo-3-furyl)-naphtho-[1,2-c] furans-1, the 3-diketone, 3-oxabicyclo [3.2.1] suffering-2,4-diketone-6-spiral shell-3 '-(tetrahydrofuran (THF)-2 ', 5 '-diketone), 5-(2,5-dioxo tetrahydrochysene-3-furyl)-3-methyl-3-tetrahydrobenzene-1, the 2-dicarboxylic acid anhydride, 3,5,6-three carboxyls-2-carboxymethyl norbornane-2:3, the 5:6-dianhydride, 2,4,6,8-tetracarboxylic two ring [3.3.0] octane-2:4,6:8-dianhydride and 4,9-two oxatricyclo [5.3.1.0 2,6] 11 carbon-3,5,8, that selects in the group that the 10-tetraketone constitutes is at least a.
3. the liquid crystal aligning agent of putting down in writing according to claim 1, wherein above-mentioned diamines comprises by Ursol D, 3,5-diaminobenzoic acid, 4,4 '-diamino-diphenyl ether, 4,4 '-diaminodiphenyl-methane, 2,2 '-dimethyl-4,4 '-benzidine, 4,4 '-diamino-2,2 '-two (trifluoromethyl) biphenyl, 4,4 '-diamino-diphenyl amine and 4,4 '-select in the group that (benzene two isopropylidenes) two (aniline) constitute at least a.
4. according to each liquid crystal aligning agent of being put down in writing of claim 1～3, this liquid crystal aligning agent further contains the compound that has at least one epoxy group(ing) at intramolecularly.
5. a liquid crystal orientation film is characterized in that: formed by each liquid crystal aligning agent of being put down in writing of claim 1～4.
6. a liquid crystal display device is characterized in that: possess the liquid crystal orientation film that claim 5 is put down in writing.
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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103059876A (en) * 2011-10-21 2013-04-24 Jsr株式会社 Liquid crystal aligning agent, liquid crystal aligning film and liquid crystal display element
CN104756002A (en) * 2012-11-21 2015-07-01 Jsr株式会社 Liquid crystal orientation agent, liquid crystal orientation membrane and method for manufacturing same, and liquid crystal display element
CN105385455A (en) * 2014-08-29 2016-03-09 Jsr株式会社 Liquid crystal orientation agent, liquid crystal orientation film and liquid crystal display element
CN106795372A (en) * 2014-10-17 2017-05-31 三菱瓦斯化学株式会社 Polyimide resin composition, Kapton and layered product
CN111647412A (en) * 2020-06-12 2020-09-11 江苏三月科技股份有限公司 Liquid crystal aligning agent, liquid crystal alignment film, and liquid crystal display element

Families Citing this family (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20140045556A (en) * 2011-07-12 2014-04-16 닛산 가가쿠 고교 가부시키 가이샤 Composition liquid crystal alignment treatment agent, liquid crystal alignment film, and liquid crystal display element
JP5845918B2 (en) * 2012-01-20 2016-01-20 宇部興産株式会社 Polyimide precursor and polyimide
JP5884979B2 (en) * 2012-03-09 2016-03-15 Jsr株式会社 (1R, 2S, 4S, 5R) Method for producing cyclohexanetetracarboxylic dianhydride
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US20160297995A1 (en) * 2013-10-11 2016-10-13 Ube Industries, Ltd. Polyimide precursor, polyimide, polyimide film, varnish, and substrate
JP6557963B2 (en) * 2014-02-25 2019-08-14 Jsr株式会社 Liquid crystal alignment agent, liquid crystal alignment film, and liquid crystal display element

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1306222A (en) * 1999-12-09 2001-08-01 捷时雅株式会社 Liquid crystal directional membrane and liquid crystal displaying componnet
CN1339554A (en) * 2000-08-21 2002-03-13 捷时雅株式会社 Liquid crystal orientational agent and super torsional nematic liquid crystal display element
CN1576293A (en) * 2003-06-26 2005-02-09 三菱瓦斯化学株式会社 Process for producing solvent-soluble polyimide
CN101299119A (en) * 2007-05-02 2008-11-05 Jsr株式会社 Vertical alignment type liquid crystal aligning agent and vertical alignment type liquid crystal display
CN101299120A (en) * 2007-05-02 2008-11-05 Jsr株式会社 Vertical alignment type liquid crystal aligning agent and vertical alignment type liquid crystal display

Family Cites Families (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS61238809A (en) * 1985-04-16 1986-10-24 Ube Ind Ltd Liquid photosensitive polyimide resin composition
JP2002155139A (en) * 2000-11-22 2002-05-28 Hitachi Cable Ltd Solvent-soluble block polyimide composition for liquid crystal orientated film and its manufacturing method
JP2008297360A (en) * 2007-05-29 2008-12-11 New Japan Chem Co Ltd Solvent-soluble polyimide resin
JP5315496B2 (en) * 2008-01-18 2013-10-16 和光純薬工業株式会社 Novel (1S, 2S, 4R, 5R) -cyclohexanetetracarboxylic dianhydride and use thereof
JP5325460B2 (en) * 2008-05-27 2013-10-23 和光純薬工業株式会社 Novel (1R, 2S, 4S, 5R) -cyclohexanetetracarboxylic dianhydride and use thereof
JP2009294281A (en) * 2008-06-03 2009-12-17 Jsr Corp Liquid crystal aligning agent, liquid crystal alignment film and liquid crystal display element
JP5325491B2 (en) * 2008-08-01 2013-10-23 株式会社カネカ Novel coating type optical compensation film and method for producing the same
JP2010070721A (en) * 2008-09-22 2010-04-02 Sekisui Chem Co Ltd Polyimide and method of producing the same
JP5630139B2 (en) * 2009-08-18 2014-11-26 Jnc株式会社 Liquid crystal alignment agent, liquid crystal alignment film, and liquid crystal display element

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1306222A (en) * 1999-12-09 2001-08-01 捷时雅株式会社 Liquid crystal directional membrane and liquid crystal displaying componnet
CN1339554A (en) * 2000-08-21 2002-03-13 捷时雅株式会社 Liquid crystal orientational agent and super torsional nematic liquid crystal display element
CN1576293A (en) * 2003-06-26 2005-02-09 三菱瓦斯化学株式会社 Process for producing solvent-soluble polyimide
CN101299119A (en) * 2007-05-02 2008-11-05 Jsr株式会社 Vertical alignment type liquid crystal aligning agent and vertical alignment type liquid crystal display
CN101299120A (en) * 2007-05-02 2008-11-05 Jsr株式会社 Vertical alignment type liquid crystal aligning agent and vertical alignment type liquid crystal display

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103059876A (en) * 2011-10-21 2013-04-24 Jsr株式会社 Liquid crystal aligning agent, liquid crystal aligning film and liquid crystal display element
CN103059876B (en) * 2011-10-21 2015-07-29 Jsr株式会社 Crystal aligning agent, liquid crystal orienting film and liquid crystal display device
CN104756002A (en) * 2012-11-21 2015-07-01 Jsr株式会社 Liquid crystal orientation agent, liquid crystal orientation membrane and method for manufacturing same, and liquid crystal display element
CN104756002B (en) * 2012-11-21 2018-06-08 Jsr株式会社 Aligning agent for liquid crystal, liquid crystal orientation film and its manufacturing method and liquid crystal display element
CN105385455A (en) * 2014-08-29 2016-03-09 Jsr株式会社 Liquid crystal orientation agent, liquid crystal orientation film and liquid crystal display element
CN106795372A (en) * 2014-10-17 2017-05-31 三菱瓦斯化学株式会社 Polyimide resin composition, Kapton and layered product
CN106795372B (en) * 2014-10-17 2019-06-18 三菱瓦斯化学株式会社 Polyimide resin composition, Kapton and laminated body
CN111647412A (en) * 2020-06-12 2020-09-11 江苏三月科技股份有限公司 Liquid crystal aligning agent, liquid crystal alignment film, and liquid crystal display element

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