CN102193250B - Manufacturing method of liquid crystal display element, polymer composition and liquid crystal display element - Google Patents

Manufacturing method of liquid crystal display element, polymer composition and liquid crystal display element Download PDF

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CN102193250B
CN102193250B CN201110052217.3A CN201110052217A CN102193250B CN 102193250 B CN102193250 B CN 102193250B CN 201110052217 A CN201110052217 A CN 201110052217A CN 102193250 B CN102193250 B CN 102193250B
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liquid crystal
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CN102193250A (en
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吉泽纯司
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JSR Corp
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    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/1337—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers
    • G02F1/133711—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers by organic films, e.g. polymeric films
    • G02F1/133723—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
    • 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
    • C08G73/1067—Wholly aromatic polyimides, i.e. having both tetracarboxylic and diamino moieties aromatically bound
    • 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
    • C08L79/085—Unsaturated polyimide precursors
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K19/00—Liquid crystal materials
    • C09K19/52—Liquid crystal materials characterised by components which are not liquid crystals, e.g. additives with special physical aspect: solvents, solid particles
    • C09K19/54—Additives having no specific mesophase characterised by their chemical composition
    • C09K19/56—Aligning agents
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/1337—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers
    • G02F1/13378—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers by treatment of the surface, e.g. embossing, rubbing or light irradiation
    • G02F1/133788—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers by treatment of the surface, e.g. embossing, rubbing or light irradiation by light irradiation, e.g. linearly polarised light photo-polymerisation

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  • Nonlinear Science (AREA)
  • Organic Chemistry (AREA)
  • Crystallography & Structural Chemistry (AREA)
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  • Optics & Photonics (AREA)
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  • Spectroscopy & Molecular Physics (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Engineering & Computer Science (AREA)
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  • Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
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Abstract

The present invention relates to a manufacturing method of a liquid crystal display element, a polymer composition and a liquid crystal display element. The invention provides the manufacturing method for the liquid crystal display element which has the following advantages: wide visual angle, high response speed of liquid crystal element, excellent display characteristic and excellent long-term reliability. The manufacturing method of the liquid crystal display element is characterized by comprising the following steps: respectively coating a polymer composition which comprises (A) polyamic acid and/or polyimide with a group that is represented by a formula (A-I) and (B) an organic agent on conductive films of a pair of substrates with the conductive films for forming coating films; oppositely equipping the pair of substrates with the coating films through the liquid crystal module layers so the coating films are opposite from each other thereby forming a liquid crystal box; and performing light irradiation for the liquid crystal box at a state that a voltage is performed between the conductive films of the pair of substrates (wherein in the formula (A-I), R is a hydrogen atom or methyl, Y1 and Y2 respectively represent an oxygen atom or sulphur atom).

Description

The manufacture method of liquid crystal display cells, polymer composition and liquid crystal display cells
Technical field
The present invention relates to the manufacture method of liquid crystal display cells, polymer composition and liquid crystal display cells.In more detail, relate to for the manufacture of visual angle wide, the new method of the liquid crystal display cells of fast response time.
Background technology
In liquid crystal display cells, as vertical orientation mode, MVA (multi-domain vertical alignment) profile plate known at present, forms thrust, limits the vergence direction of liquid crystal molecule thus, thus can expand visual angle in liquid crystal panel.But, according to which, the deficiency of transmittance because thrust causes and contrast cannot be avoided, in addition, there is the problem that the response speed of liquid crystal molecule is slowly such.
In recent years, in order to solve the problem as above-mentioned MVA profile plate, PSA (polymer stabilizing orientation) mode is proposed.PSA mode, there is following technology: by having the substrate of pattern-like conducting film and there is the gap of a pair substrate that patternless conductive film substrate is formed, or by the liquid-crystal composition of seizing on both sides by the arms in the gap of a pair substrate formed with two pattern-like conducting films containing polymerizable compound, irradiation ultraviolet radiation under alive state is executed between conducting film, polymerizable compound is polymerized, embody tilt angle characteristic thus, control liquid crystal aligning direction.According to this technology, by making conducting film be ad hoc structure, thus can visual angle be expanded, realizing the high speed of liquid crystal molecule response, also can solve the problem of inevitable transmittance and contrast deficiency in MVA profile plate.But, find in PSA mode, in order to be polymerized by above-mentioned polymerizable compound, such as, must 100,000J/m be irradiated 2ultraviolets a large amount of like this, therefore, liquid crystal molecule can be produced and decompose such trouble, in addition, the unreacted compound be not also polymerized by Ultraviolet radiation remains in liquid crystal layer, and these 2 combine, display can be produced uneven, bad impact is produced on voltage retention performance, or has problems on the long-term reliability of panel, not yet realize practicality.
On the contrary, non-patent literature 1, proposes the method using the liquid crystal orientation film formed by the polyimide aligning agent for liquid crystal of reactive mesogen.According to non-patent literature 1, the response speed with the liquid crystal molecule of the liquid crystal aligning element of the liquid crystal orientation film formed by the method is higher.But, in non-patent literature 1, for needing the policy using this reactive mesogen with what amount, completely without any record, in addition, still need ultraviolet irradiation amount required in a large number, for display characteristic, especially the mystery of voltage retention performance is not also opened.
Prior art document
Patent documentation
Patent documentation 1: Japanese Unexamined Patent Publication 5-107544 publication
Non-patent literature
Non-patent literature 1:Y.-J.Lee et.al.SID 09DIGEST, p.666 (2009)
Non-patent literature 2:T.J.Scheffer et.al.J.Appl.Phys.vo.19, p.2013 (1980)
Summary of the invention
The present invention makes in view of above-mentioned thing, and its object is to provides a kind of visual angle wide, the fast response time of liquid crystal molecule, the manufacture method of the liquid crystal display cells of display characteristic and long-term reliability excellence.
According to the present invention, above-mentioned problem of the present invention is realized by the manufacture method of following liquid crystal display cells:
It is through following operation:
On this conducting film of a pair substrate with conducting film, coating contains respectively: (A) is by having the polyamic acid of the represented group of following formula (A-I) and having above formula (A-I) and represent at least one polymkeric substance selected in the group that the polyimide of group is formed, and the polymer composition of (B) organic solvent, form film, a pair substrate forming above-mentioned film is arranged by layer of liquid crystal molecule subtend, make above-mentioned film relative, thus formation liquid crystal cell, execute alive state between the conducting film with above-mentioned a pair substrate under, light-struck operation is carried out to above-mentioned liquid crystal cell,
In formula (A-I), R is hydrogen atom or methyl, Y 1and Y 2be oxygen atom or sulphur atom independently of one another.
By liquid crystal display cells prepared by the inventive method, visual angle is wide, the fast response time of liquid crystal molecule, can demonstrate enough transmittances and contrast, and display characteristic is excellent, based on this, even if long-time continuous drives, also can not damage display characteristic.
In addition, according to method of the present invention, the amount of the light needed in irradiating can be reduced, so there is no the problem that liquid crystal molecule decomposes, the manufacturing cost of liquid crystal display cells can also be reduced.
Therefore, the liquid crystal display cells manufactured by method of the present invention both in aspect of performance and cost in, all excellent than liquid crystal display cells known at present, can preferably use in a variety of applications where.
Accompanying drawing explanation
Fig. 1 be represent prepared by embodiment and comparative example have in the liquid crystal cell forming transparent pattern conducting film, the key diagram of the pattern of nesa coating.
Fig. 2 be represent prepared by embodiment have in the liquid crystal cell forming transparent pattern conducting film, the key diagram of the pattern of nesa coating.
Fig. 3 be represent prepared by embodiment have in the liquid crystal cell forming transparent pattern conducting film, the key diagram of the pattern of nesa coating.
Embodiment
< polymer composition >
The polymer composition used in the method for the invention comprises:
Represent the polyamic acid of group by having above formula (A-I) and there is above formula (A-I) represent at least one polymkeric substance (hereinafter referred to as " polymkeric substance (A) ") and (B) organic solvent selected in the group that the polyimide of group is formed.
[polymkeric substance (A)]
The polymkeric substance (A) used in the present invention, has the group that above formula (A-I) represents.Y in above formula (A-I) 1and Y 2be preferably oxygen atom separately.
Polymkeric substance (A), preferably in the scope of 0.4 ~ 3.0mmol/g, more preferably contains the group that above formula (A-I) represents in the scope of 1.0 ~ 2.5mmol/g.
Polymkeric substance (A), except the group that above formula (A-I) represents, preferably also contains the group represented by following formula (P),
In formula (P), R ito be carbon number be 4 ~ 40 alkyl or carbon number be the fluoro-alkyl of 4 ~ 40, or the carbon number with steroid skeleton is the alkyl of 17 ~ 51; Z ifor singly-bound, *-O-, *-COO-, *-OCO-(wherein, with the connecting key of " * " at R iside,
R iIfor cyclohexylidene or phenylene,
Z iIfor singly-bound or *-(CH 2) n5-(wherein, with the connecting key of " * " at R iside, n5 is the integer of 1 ~ 5),
N1 is the integer of 1 ~ 5,
Wherein, when n1 is more than 2, multiple R of existence iIand Z iIcan be mutually the same or not identical respectively,
N2 is 0 or 1;
Z iIIfor *-O-, *-COO-or *-OCO-(wherein, with the connecting key of " * " at R iside),
N3 is the integer of 0 ~ 2,
N4 is 0 or 1.
As R in above formula (P) icarbon number be the alkyl of 4 ~ 40, being preferably carbon number is the straight chained alkyl of 6 ~ 40, specifically, can enumerate such as n-hexyl, n-octyl, positive decyl, dodecyl, n-hexadecyl, n-octadecane base etc.;
Be the fluoro-alkyl of 4 ~ 40 as carbon number, preferred carbon number is the linear fluoroalkyl of 4 ~ 20, specifically, such as 3-(trifluoromethyl) propyl group, 4-(trifluoromethyl) butyl, 6-(trifluoromethyl) hexyl, 10-(trifluoromethyl) decyl, 3-(pentafluoroethyl group) propyl group, 4-(pentafluoroethyl group) butyl, 8-(pentafluoroethyl group) octyl group etc. can be enumerated;
Be the alkyl of 17 ~ 51 as the carbon number with steroid skeleton, such as cholestane base, cholesteryl, lanostane base etc. can be enumerated respectively.
R in above formula (P) iIcyclohexylidene and phenylene, be separately preferably Isosorbide-5-Nitrae-cyclohexylidene and Isosorbide-5-Nitrae-phenylene.
N 1 in above formula (P) is preferably the integer of 1 ~ 4.
As in above formula (P)-(R iI-Z iI) n1the divalent group of-expression, when n1 is 1, as preferred group, can enumerate such as Isosorbide-5-Nitrae-phenylene, 1,2-cyclohexylidene etc.;
When n1 is 2, as preferred group, such as 4 can be enumerated, 4 '-biphenylene, 4, the group etc. that 4 '-two cyclohexylidene, following formula represent separately,
(in above formula, with the connecting key of " * " at R iside);
When n1 is 3, as preferred group, the group etc. that following formula represents can be enumerated,
(in above formula, with the connecting key of " * " at R iside);
When n1 is 4, as preferred group, the group etc. that following formula represents can be enumerated,
(in above formula, with the connecting key of " * " at R iside).
N3 in above formula (P) is preferably 2.As Z iIfor *-(CH 2) n5n5 in-situation, is preferably 1 or 2.
Polymkeric substance (A), preferably in the scope of below 0.7mmol/g, more preferably contains the group that above formula (P) represents in the scope of 0.1 ~ 0.5mmol/g.
As long as meet above-mentioned condition, to polymkeric substance (A), just there is no particular limitation, can be by such as:
(A-1) tetracarboxylic dianhydride with comprise polyamic acid (hereinafter referred to as " polymkeric substance (A-1) ") that the diamine reactant with group that above formula (A-I) represents and two amino compounds obtains,
The polyimide (hereinafter referred to as " polymkeric substance (A-2) ") (A-2) above-mentioned polyamic acid dehydration closed-loop obtained,
(A-3) by tetracarboxylic dianhydride and the polyamic acid comprising the diamine reactant with carboxyl and two amino compounds and obtain, the polymkeric substance (hereinafter referred to as " polymkeric substance (A-3) ") be obtained by reacting with the compound with group that above formula (A-I) represents and epoxy radicals,
(A-4) by tetracarboxylic dianhydride and the polyamic acid comprising the diamine reactant with carboxyl and two amino compounds and obtain, the polyimide that dehydration closed-loop obtains with there is above formula (A-I) represent at least one selected in the group that the polymkeric substance (hereinafter referred to as " polymkeric substance (A-4) ") that the compound of group and epoxy radicals is obtained by reacting is formed.
{ polymkeric substance (A-1) }
Above-mentioned polymkeric substance (A-1) can by synthesizing tetracarboxylic dianhydride with comprising the diamine reactant with group that above formula (A-I) represents and two amino compounds (hereinafter referred to as " diamines (A-I) ").Here, as diamines, by using except above-mentioned diamines (A-I), also comprise and there is group that above formula (P) represents and two amino compounds are (following, be called " diamines (P) ") diamines, thus the polymkeric substance (A-1) simultaneously with group that above formula (A-I) represents and the group that above formula (P) represents can be obtained.
As the tetracarboxylic dianhydride for the synthesis of polymkeric substance (A-1), such as aliphatics tetracarboxylic dianhydride, ester ring type tetracarboxylic dianhydride, aromatic tetracarboxylic acid's dianhydride etc. can be enumerated.As their concrete example, as aliphatics tetracarboxylic dianhydride, such as butane tetracarboxylic acid dianhydride etc. can be enumerated, as ester ring type tetracarboxylic dianhydride, such as 1 can be enumerated, 2, 3, 4-cyclo-butane tetracarboxylic dianhydride, 2, 3, 5-tricarboxylic cyclopentyl acetic acid dianhydride, 1, 3, 3a, 4, 5, 9b-six hydrogen-5-(tetrahydrochysene-2, 5-dioxy-3-furyl)-naphthalene [1, 2-c] furans-1, 3-diketone, 1, 3, 3a, 4, 5, 9b-six hydrogen-8-methyl-5-(tetrahydrochysene-2, 5-dioxy-3-furyl)-naphthalene [1, 2-c] furans-1, 3-diketone, 3-oxabicyclo [3.2.1] pungent-2, 4-diketone-6-spiral shell-3 '-(tetrahydrofuran-2 ', 5 '-diketone), 5-(2, 5-dioxotetrahydrol-3-furyl)-3-methyl-3-cyclohexene-1, 2-dicarboxylic anhydride, 3, 5, 6-tri-carboxyl-2-carboxymethyl group norborneol alkyl-2:3, 5:6-dianhydride, 4, 9-dioxa three ring [5.3.1.0 2,6] 11 carbon-3,5,8,10-tetraketones etc.,
As aromatic tetracarboxylic acid's dianhydride, such as pyromellitic acid dianhydride etc. can be enumerated, in addition, the tetracarboxylic dianhydride recorded during No. 2009-157556, Japanese Patent Application can also be used to apply for.
As the tetracarboxylic dianhydride for the synthesis of above-mentioned polymkeric substance (A-1), wherein, preferably only use ester ring type tetracarboxylic dianhydride, or use the potpourri of ester ring type tetracarboxylic dianhydride and aromatic tetracarboxylic acid's dianhydride.When using the latter, the ratio that ester ring type tetracarboxylic dianhydride accounts in whole tetracarboxylic dianhydride is preferably more than 20mol%, is more preferably more than 40mol%.
For the synthesis of the diamines of polymkeric substance (A-1), comprise above-mentioned diamines (A-I), preferably also containing diamines (P).
As diamines (A-I), preferably there are structure represented by following formula (A-I-1) and two amino compounds,
(in (A-I-1), R defines identical with above formula (A-I), X be singly-bound, oxygen atom or *-COO-, wherein, connecting key and phenyl ring bonding with " * ")
As its concrete example, such as benzoic acid 3 can be enumerated, 5-diamido (2 '-acryloyl group oxygen base) ethyl ester, benzoic acid 3, 5-diamido (2 '-methacryl oxygen base) ethyl ester, 4, 4 '-two (2-(2 '-acryloyl group oxygen base) ethyl-4-Amino-phenoxv)-biphenyl, 4, 4 '-two (2-(2 '-methacryl oxygen base) ethyl-4-Amino-phenoxv)-biphenyl, 2, 4-diamido (2 '-acryloyl group oxygen base) ethoxybenzene, 2, 4-diamido (2 '-methacryl oxygen base) ethoxybenzene etc., the at least one be selected from wherein can be used.As diamines (A-I), preferably use benzoic acid 3,5-diamido (2 '-methacryl oxygen base) ethyl ester.
As above-mentioned diamines (P), preferably there is the aromatic diamine that above formula (P) represents group, as its concrete example, such as dodecyloxy-2 can be enumerated, 4-diaminobenzene, pentadecane oxygen base-2, 4-diaminobenzene, hexadecane oxygen base-2, 4-diaminobenzene, octadecane oxygen base-2, 4-diaminobenzene, dodecyloxy-2, 5-diaminobenzene, pentadecane oxygen base-2, 5-diaminobenzene, hexadecane oxygen base-2, 5-diaminobenzene, octadecane oxygen base-2, 5-diaminobenzene, cholestane oxygen base-3, 5-diaminobenzene, cholesterol oxygen base-3, 5-diaminobenzene, 3, 5-diaminobenzoic acid cholestane, 3, 5-diaminobenzoic acid cholesterol, 3, 5-diaminobenzoic acid lanostane etc., can use wherein one or more.As the specific diamines in the present invention, particularly preferably use at least one being selected from hexadecane oxygen base-2,5-diaminobenzene, octadecane oxygen base-2,5-diaminobenzene, cholestane oxygen base-3,5-diaminobenzene and cholesterol oxygen base-3,5-diaminobenzene.
As the diamines for the synthesis of polymkeric substance (A-1), only can use diamines described above (A-I) or be only diamines (A-I) and diamines (P) or except diamines (A-I) or diamines (A-I) and diamines (P), also other diamines of coupling.
As other diamines that can use wherein, represent that for there is no above formula (A-I) simultaneously group and above formula (P) represent that the diamines of group is (following, be called " other diamines (1) "), can be aliphatic diamine, ester ring type diamines, aromatic diamine, diamido organosiloxane etc., but with above-mentioned diamines (A-I) or diamines (P) uncorrelated.As these concrete examples, as aliphatic diamine, such as m-xylene diamine, 1,3-propane diamine, tetra-methylenedimine, five methylene diamine, hexamethylene diamine etc. can be enumerated;
As ester ring type diamines, such as Isosorbide-5-Nitrae-diamino-cyclohexane, 4 can be enumerated, 4 '-methylene two (cyclo-hexylamine), 1,3-bis-(amino methyl) cyclohexane etc.;
As aromatic diamine, such as p-phenylenediamine (PPD) can be enumerated, 4,4 '-diaminodiphenyl-methane, 4,4 '-diamino diphenyl sulfide, 1,5-diaminonaphthalene, 2,2 '-dimethyl-4,4 '-benzidine, 4,4 '-diamido-2,2 '-two (trifluoromethyl) biphenyl, 2,7-diamino-fluorene, 4,4 '-diamino-diphenyl ether, 2,2-bis-[4-(4-amino-benzene oxygen) phenyl] propane, 9,9-bis-(4-aminophenyl) fluorenes, 2,2-bis-[4-(4-amino-benzene oxygen) phenyl] HFC-236fa, 2,2-bis-(4-aminophenyl) HFC-236fa, 4,4 '-(to benzene diisopropylidene) two (aniline), 4,4 '-(isophthalic diisopropylidene) two (aniline), Isosorbide-5-Nitrae-two (4-amino-benzene oxygen) benzene, 4,4 '-two (4-amino-benzene oxygen) biphenyl, DAP, 3,4-diamino-pyridine, 2,4-di-amino-pyrimidine, 3,6-proflavin, 3,6-diaminocarbazole, N-methyl-3,6-diaminocarbazole, N-ethyl-3,6-diaminocarbazole, N-phenyl-3,6-diaminocarbazole, N, N '-two (4-aminophenyl)-biphenylamine, N, N '-two (4-aminophenyl)-N, N '-dimethyl biphenylamine etc.,
As diamido organosiloxane, such as 1,3-bis-(3-aminopropyl)-tetramethyl disiloxane etc. can be enumerated respectively, in addition, diamines described later (C) can also be used, the diamines recorded during No. 2009-157556, Japanese Patent Application can also be used further to apply for.
As other diamines (1), can use wherein more than one.
As the diamines for the synthesis of polymkeric substance (A-1), preferably relative to whole diamines, containing more than 20mol%, more preferably containing 30 ~ 80mol%, particularly preferably containing 40 ~ 70mol% diamines described above (A-I).
As the diamines for the synthesis of polymkeric substance (A-1), preferably relative to whole diamines, containing below 70mol%, more preferably containing 10 ~ 60mol%, particularly preferably containing 20 ~ 50mol% diamines described above (P).
For the diamines for the synthesis of polymkeric substance (A-1), preferably relative to whole diamines, containing below 70mol%, more preferably containing 10 ~ 60mol%, particularly preferably containing 10 ~ 50mol% other diamines (1) described above.
The tetracarboxylic dianhydride supplied to the synthetic reaction of polymkeric substance (A-1) and the usage ratio of diamines, preferably relative to the amino of 1 equivalent diamines, the anhydride group of tetracarboxylic dianhydride is 0.2 ~ 2 equivalent, is more preferably 0.3 ~ 1.2 equivalent.
Wherein, when synthetic polymer (A-1), tetracarboxylic dianhydride described above and diamines can also be used, and suitable molecular weight regulator, thus synthesize the polymkeric substance of end modified type.By forming the polymkeric substance of this end modified type, thus can not damage under effect of the present invention, improving the coating (printing) of polymer composition further.
As above-mentioned molecular weight regulator, such as sour single acid anhydride, monoamine compound, monoisocyanate compound etc. can be enumerated.As the concrete example of these materials,
As acid list acid anhydride, such as maleic anhydride, phthalic anhydride, itaconic anhydride, positive decyl succinic anhydride, dodecyl succinic anhydride, n-tetradecane base succinic anhydride, n-hexadecyl succinic anhydride etc. can be enumerated;
As monoamine compound, such as aniline, cyclohexylamine, n-butylamine, n-amylamine, n-hexylamine, positive heptyl amice, n-octyl amine etc. can be enumerated;
As monoisocyanate compound, such as phenyl isocyanate, naphthyl isocyanate etc. can be enumerated.
The tetracarboxylic dianhydride that the usage ratio of molecular weight regulator uses relative to total 100 weight portion and diamines, be preferably below 10 weight portions.
The synthetic reaction of polymkeric substance (A-1) preferably in organic solvent, preferably at-20 DEG C ~ 150 DEG C, more preferably carries out preferably 0.1 ~ 24 hour, more preferably 0.5 ~ 12 hour at 0 ~ 100 DEG C.
Wherein, as organic solvent, the aprotic polar solvent such as such as METHYLPYRROLIDONE, DMA, DMF, dimethyl sulfone, gamma-butyrolacton, 4-methyl urea, HMPA can be enumerated; The phenol solvents such as metacresol, xylenol, phenol, halogenated phenol.The use amount (a) of organic solvent is preferred, and the total amount (b) of tetracarboxylic dianhydride and diamines, relative to the total amount (a+b) of reaction solution, is the amount of 0.1 ~ 30 % by weight.
As above the reaction solution having dissolved polymkeric substance (A-1) is obtained.
This reaction solution directly can be supplied in the preparation of polymer composition, also can after polymkeric substance (A-1) contained in reaction solution be separated, be supplied in the preparation of polymer composition, or after the polymkeric substance (A-1) that will be separated is refining, be supplied in the preparation of polymer composition.By polymkeric substance (A-1) dehydration closed-loop, when formation polymkeric substance (A-2) (aftermentioned), above-mentioned reaction solution directly can be supplied in dehydration closed-loop reaction, can after polymkeric substance (A-1) contained in reaction solution be separated, be supplied in dehydration closed-loop reaction, or also after the polymkeric substance (A-1) that will be separated is refining, can be supplied in dehydration closed-loop reaction.The separation of polymkeric substance (A-1) and refiningly can to carry out according to known method.
{ polymkeric substance (A-2) }
Above-mentioned polymkeric substance (A-2) can by using the polyamic acid dehydration closed-loop as polymkeric substance (A-1) of such as above-mentioned synthesis, imidizate and obtaining.Wherein, as the polymkeric substance (A-1) of precursor, by using except above-mentioned diamines (A-1), also there is the polymkeric substance that above formula (P) represents group, thus can obtain and there is above formula (A-1) simultaneously represent that group and above formula (P) represent the polymkeric substance (A-2) of group.
Polymkeric substance (A-2) in the present invention can be the complete acid imide compound of the whole amic acid structure dehydration closed-loops had by polymkeric substance (A-1), also can be only by a part of dehydration closed-loop of amic acid structure, amic acid structure and imide ring structure the acid imide compound of depositing.Polymkeric substance (A-2) in the present invention preferably its acid imide rate is more than 40%.This acid imide rate represents with number percent, relative to the summation of the quantity of the amic acid structure of the imide amination polymer as polymkeric substance (A-2) and the quantity of imide ring structure, and the ratio shared by the quantity of imide ring structure.
The dehydration closed-loop of polymkeric substance (A-1), preferably by the method for heated polymerizable thing (A-1), or pass through dissolve polymer (A-1) in organic solvent, in this solution, add dewatering agent and dehydration closed-loop catalyzer, the method carrying out as required heating is carried out.Wherein, the method for preferred the latter.
Add in the method for dewatering agent and dehydration closed-loop catalyzer in the solution dissolving above-mentioned polymkeric substance (A-1), as dewatering agent, the acid anhydrides such as such as acetic anhydride, propionic andydride, trifluoroacetic anhydride can be used.The use amount of dewatering agent, relative to the amic acid structure of 1mol polyamic acid, is preferably 0.01 ~ 20mol.As dehydration closed-loop catalyzer, the tertiary amines such as such as pyridine, trimethylpyridine, lutidines, triethylamine can be used.The use amount of dehydration closed-loop catalyzer, relative to the 1mol dewatering agent used, is preferably 0.01 ~ 10mol.As the organic solvent used in dehydration closed-loop reaction, can enumerate as the organic solvent illustrated in the solvent used in the synthesis of polymkeric substance (A-1).The temperature of reaction of dehydration closed-loop reaction is preferably 0 ~ 180 DEG C, is more preferably 10 ~ 150 DEG C.Reaction time is preferably 1.0 ~ 120 hours, is more preferably 2.0 ~ 30 hours.
Obtain the reaction solution containing polymkeric substance (A-2) thus.This reaction solution can be directly supplied in the preparation of polymer composition, also can after removing dewatering agent and dehydration closed-loop catalyzer by reaction solution, be supplied to polymer composition, can also be supplied in the preparation of polymer composition after isolating polymer (A-2), or after the polymkeric substance (A-2) that will be separated is refining, be supplied in the preparation of polymer composition.These purification operations can be undertaken by known method.
{ polymkeric substance (A-3) }
Above-mentioned polymkeric substance (A-3), with to comprise the diamines with carboxyl and two amino compounds (following by tetracarboxylic dianhydride, being called " diamines (C) ") polyamic acid that is obtained by reacting is (following, be called " polymkeric substance (A-3a) "), with there is above formula (A-I) represent that the compound (hereinafter referred to as " compound (E) ") of group and epoxy radicals reacts and synthesizes.Wherein, as diamines, by using except above-mentioned diamines (C), also containing, for example the diamines of above-mentioned diamines (P), thus can obtain and there is above formula (A-I) simultaneously represent that the above formula (P) of group represents the polymkeric substance (A-2) of group.
As the tetracarboxylic dianhydride for the synthesis of polymkeric substance (A-3a), can be used as the synthesis of the tetracarboxylic dianhydride of polymkeric substance (A-1) at above-mentioned illustrative material.The kind of preferred tetracarboxylic dianhydride is identical with the situation of polymkeric substance (A-1) with the ratio preferably used.
As the diamines (C) for the synthesis of polymkeric substance (A-3a), such as 3 can be enumerated, 5-diaminobenzoic acid, 1-(2,4-diamino-phenyl)-piperazine-4-carboxylic acid, 4,4 '-benzidine base-2,2 '-carboxylic acid, 3,5-bis-(4-amino-benzene oxygen) benzoic acid etc., can use at least one be selected from wherein.
As the diamines (P) being preferred for synthetic polymer (A-3a), can be used as the synthesis of the diamines (P) of polymkeric substance (A-1) at above-mentioned illustrative material.
As the diamines for the synthesis of polymkeric substance (A-3a), only can use diamines described above (C), or only use diamines (C) and diamines (P), or except diamines (C) or diamines (C) and diamines (P), also other diamines of coupling.
Other diamines that can use wherein, the diamines being the group that the group that do not have above formula (C) to represent and above formula (P) represent is (following, be called " other diamines (2) "), can be aliphatic diamine, ester ring type diamines, aromatic diamine, diamido organosiloxane etc., but uncorrelated with diamines (P) with above-mentioned diamines (C).As its example, can enumerate the concrete example as other diamines (1), in above-mentioned illustrative compound, removing meets the compound of diamines (C), in addition, can also use diamines (A-I).As other diamines (2), can use wherein more than one.Other diamines (2) preferably do not comprise diamines (A-I).
For the synthesis of the diamines of polymkeric substance (A-3a) preferably relative to whole diamines, containing more than 30mol%, more preferably containing 40 ~ 90mol%, particularly preferably containing 50 ~ 80mol% diamines described above (C).
For the synthesis of the diamines of polymkeric substance (A-3a) preferably relative to whole diamines, containing below 70mol%, more preferably containing 10 ~ 60mol%, particularly preferably containing 15 ~ 50mol% diamines described above (P).
For the synthesis of the diamines of polymkeric substance (A-3a) preferably relative to whole diamines, containing below 60mol%, more preferably containing 10 ~ 50mol%, particularly preferably containing 10 ~ 40mol% other diamines (2) described above.
The synthesis of polymkeric substance (A-3a), except using tetracarboxylic dianhydride described above and diamines, to carry out equally with the synthesis of polymkeric substance (A-1).The solution containing polymkeric substance (A-3a) obtained thus can be direct by it, or be separated by contained polymkeric substance (A-3a), or in separation with after refining, be supplied in the reaction of compound (E).
Then, by making polymkeric substance (A-3a) and compound (E) react, thus polymkeric substance (A-3) can be obtained.
As the compound wherein used (E), can epoxy radicals be used as, there is the compound of oxirane base (1,2-epoxy radicals) and the compound of oxetanyl (1,3-epoxy radicals).As the compound (E) with oxirane base, such as glycidyl acrylate can be enumerated, glycidyl methacrylate, methylglycidyl acrylate, methylglycidyl methacrylate, acrylic acid 4-hydroxybutyl glycidyl ether, methacrylic acid 4-hydroxybutyl glycidyl ether, acrylic acid 2-hydroxy methacrylate glycidyl ether, 2-hydroxyethyl methacrylate glycidyl ether, acrylic acid 3-hydroxy propyl ester glycidyl ether, methacrylic acid 3-hydroxy propyl ester glycidyl ether, 2-(4-vinyl-benzyloxymethyl) oxirane, acrylic acid 3, 4-expoxycyclohexyl methyl esters, methacrylic acid 3, 4-expoxycyclohexyl methyl esters, 3-vinyl-7-oxa--dicyclo [4.1.0] heptane etc., as the compound (E) with oxetanyl, such as acrylic acid (3-methyl-3-oxetanyl) methyl esters, methacrylic acid (3-methyl-3-oxetanyl) methyl esters, 3-acryloyloxymethyl-3-ethyl-oxetane etc. can be enumerated, at least one be selected from wherein can be used.As the compound (E) in the present invention, preferred use is selected from glycidyl acrylate, glycidyl methacrylate, methylglycidyl acrylate, methylglycidyl methacrylate, 2-(4-vinyl benzyloxymethyl) oxirane, acrylic acid 3, at least one in 4-expoxycyclohexyl methyl esters and methacrylic acid 3,4-expoxycyclohexyl methyl esters.
As the usage ratio of compound (E), relative to the carboxyl from the diamines (C) in 1mol polymkeric substance (A-3a), be preferably 0.1 ~ 1.0mol, be more preferably 0.4 ~ 0.8mol.
Polymkeric substance (A-3a) is preferred in organic solvent with the reaction of compound (E), as required, carries out in the presence of a catalyst.
As the organic solvent wherein used, can to use with the organic solvent used in the synthesis as polymkeric substance (A-1) and at the identical solvent of above-mentioned illustration.The solid component concentration (in reaction solution, beyond organic solvent, the general assembly (TW) of composition accounts for the ratio of reaction solution total weight) of the usage ratio preferred reaction solution of organic solvent is 5 ~ 30 % by weight.
As above-mentioned catalyzer, be the catalyzer that can promote that epoxy ring-opening reacts, such as tertiary amine, quaternary ammonium salt, alkyl urea, imidazolium compounds etc. can be enumerated.As its concrete example,
As tertiary amine, such as dimethyl benzyl amine etc. can be enumerated;
As above-mentioned quaternary ammonium salt, such as tetrabutyl ammonium bromide, 4-butyl phosphonium chloride, 4-phenyl phosphonium bromide, HMPA etc. can be enumerated;
As abovementioned alkyl urea, such as 3-(3 ', 4 '-dichlorophenyl)-1,1-dimethyl urea etc. can be enumerated;
As above-mentioned imidazolium compounds, such as glyoxal ethyline, 2-ethyl-4-methylimidazole, 2-undecyl imidazole, 2-phenylimidazole etc. can be enumerated.
The polymkeric substance (A-3a) that the usage ratio of catalyzer uses relative to 100 weight portions, be preferably below 10 weight portions, be more preferably 0.001 ~ 2 weight portion, wherein, after the synthesis of polymkeric substance (A-3a), in the solution containing polymkeric substance (A-3a), add compound (E), directly carry out the reaction of next stage, this, the simple viewpoint of sequence of operation, is preferred.
Polymkeric substance (A-3a) is preferably 70 ~ 110 DEG C with the temperature of reaction of compound (E), is more preferably 75 ~ 90 DEG C.Reaction time is preferably 2 ~ 15 hours, is more preferably 5 ~ 10 hours.
In addition, in the reaction of polymkeric substance (A-3a) with compound (E), even if the carboxylic acid reaction of the amic acid structure of a part for compound (E) and polymkeric substance (A-3a), also effect of the present invention can not be damaged.
Obtain the reaction solution containing polymkeric substance (A-3) thus.It can directly be supplied in the preparation of polymer composition by this reaction solution, also after can removing dewatering agent and dehydration closed-loop catalyzer from reaction solution, be supplied in the preparation of polymer composition, also can after isolating polymer (A-3), be supplied in the preparation of polymer composition, or after the polymkeric substance (A-3) that will be separated is refining, be supplied in the preparation of polymer composition.These purification operations methods can be carried out according to known method.
{ polymkeric substance (A-4) }
Polymkeric substance (A-4), be by tetracarboxylic dianhydride with comprise polyimide (hereinafter referred to as " polymkeric substance (A-4a) ") that polyamic acid dehydration closed-loop that the diamine reactant with carboxyl and two amino compounds obtains obtains and there is above formula (A-I) represent that the compound (E) of group and epoxy radicals reacts and synthesizes.
Above-mentioned polymkeric substance (A-4a) by by above-mentioned polymkeric substance (A-3a) dehydration closed-loop, can carry out imidizate and obtains.Make the reaction of polymkeric substance (A-3a) dehydration closed-loop, can with conduct described above by polymkeric substance (A-1) dehydration closed-loop, the situation obtaining polymkeric substance (A-2) is identical.The preferred acid imide rate of polymkeric substance (A-4a) is also identical with the situation of polymkeric substance (A-2).
Thus obtained polymkeric substance (A-4a) and the reaction of compound (E), can carry out with the reacting phase of compound (E) is same as polymkeric substance (A-3a) with described above.
In addition, in the reaction of polymkeric substance (A-4a) with compound (E), even if the carboxylic acid reaction of the amic acid structure retained in a part for compound (E) and polymkeric substance (A-3a), also can not damage effect of the present invention.
Obtain the reaction solution containing polymkeric substance (A-4) thus.It can directly be supplied in the preparation of polymer composition by this reaction solution, also after can removing dewatering agent and dehydration closed-loop catalyzer from reaction solution, be supplied in the preparation of polymer composition, also can after isolating polymer (A-4), be supplied in the preparation of polymer composition, or after the polymkeric substance (A-4) that will be separated is refining, be supplied in the preparation of polymer composition.These purification operations methods can be carried out according to known method.
[other compositions]
The polymer composition used in the present invention contains polymkeric substance described above (A) and (B) described later organic solvent, but only otherwise damage effect of the present invention, just can also containing other compositions in addition.
As other compositions, the polymkeric substance (hereinafter referred to as " other polymkeric substance ") etc. beyond such as above-mentioned polymkeric substance (A) can be enumerated.
Other polymkeric substance above-mentioned are the polymkeric substance not having above formula (A-I) to represent group, can enumerate the polyamic acid, polyimide etc. that such as do not have above formula (A-I) to represent group.
As the usage ratio of other polymkeric substance, (be the summation of polymkeric substance (A) and other polymkeric substance relative to the summation of polymkeric substance.Identical below), be preferably below 95 weight portions, be more preferably below 85 weight portions.
[(B) organic solvent]
As (B) organic solvent in the present invention, such as METHYLPYRROLIDONE can be enumerated, gamma-butyrolacton, N, dinethylformamide, N, N-dimethyl acetamide, 4-hydroxy-4-methyl-2-pentanone, ethylene glycol monomethyl ether, butyl lactate, butyl acetate, methyl methoxypropionate, ethyl ethoxy-c acid esters, Ethylene Glycol Methyl ether, glycol ethyl ether, ethylene glycol n-propyl ether, ethylene glycol isopropyl ether, ethylene glycol n-butyl ether (butyl cellosolve), 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 acid esters, diethylene glycol monoethyl ether acetic acid esters, diisobutyl ketone, isopentyl propionic ester, isopentyl isobutyrate, diisoamyl ether etc.
[polymer composition]
The polymer composition used in the present invention, preferably by polymkeric substance described above (A) or by the composition of polymkeric substance (A) with other compositions optionally used, be dissolved in (B) organic solvent described above, form solution and prepare.
As the usage ratio of (B) organic solvent, preferably make the solid component concentration of polymer composition (general assembly (TW) of the composition in polymer composition beyond (B) organic solvent accounts for the ratio of polymer composition total weight) be 1 ~ 15 % by weight, be more preferably 1.5 ~ 8 % by weight.
The manufacture method > of < liquid crystal display cells
The feature of the manufacture method of liquid crystal display cells of the present invention is, it is through following operation:
On this conducting film of a pair substrate with conducting film, be coated with polymer composition described above respectively, thus form film,
The layer subtend of a pair substrate of above-mentioned formation film by liquid crystal molecule is arranged, makes above-mentioned film relative, thus form liquid crystal cell,
Between the above-mentioned conducting film with a pair substrate, apply voltage, carry out illumination to above-mentioned liquid crystal cell in this condition and penetrate.
Here, as substrate, can use by such as float glass, soda-lime glass etc.; The transparency carrier etc. that plastics etc. as polyethylene terephthalate, polybutylene terephthalate, polyethersulfone, polycarbonate are formed.
As above-mentioned conducting film, preferably use nesa coating, can use such as by SnO 2form NESA (registered trademark) film, by In 2o 3-SnO 2the ito film etc. formed.This conducting film is preferably divided into the pattern-like conducting film in multiple region respectively.As long as be this conductive film structure, then, when applying voltage between conducting film (aftermentioned), by applying different voltage in regional, thus the direction of liquid crystal molecule tilt angle can be changed in each region, viewing angle characteristic can be improved further thus.
In order to coated polymeric composition on the conducting film of this substrate, can be undertaken by suitable coating processes such as such as rolling method, spin-coating method, print process, ink-jet methods.After coating, this coated face heated in advance (prebake), then calcine (curing afterwards), thus form film.The condition of prebake such as carries out 0.1 ~ 5 minute at 40 ~ 120 DEG C, after the condition of curing preferably at 120 ~ 300 DEG C, more preferably at 150 ~ 250 DEG C, preferably carry out 5 ~ 200 minutes, more preferably carry out 10 ~ 100 minutes.After cure rear film thickness be preferably 0.001 ~ 1 μm, be more preferably 0.005 ~ 0.5 μm.
The film formed thus can directly be supplied in the manufacture of the liquid crystal cell of following operation, or in the manufacture of liquid crystal cell, as required, first carries out grinding process to coated surface.This grinding process to coated surface, can rub with the roller including the cloth that the fibers such as such as nylon, rayon, cotton are formed and carries out in a certain direction.Wherein, as recorded in patent documentation 1 (Japanese Unexamined Patent Publication 5-107544 publication), once after grinding process, part coated surface forms resist film, grinding process is carried out further on the direction different from grinding process before, then carry out the process removing resist film, form different grinding directions in each area, thus the viewing angle characteristic of gained liquid crystal display cells can be improved further.
Then, a pair substrate of above-mentioned formation film is arranged by layer of liquid crystal molecule subtend, make above-mentioned film relative, thus form liquid crystal cell.
As liquid crystal molecule used herein, preferably there is the nematic crystal of negative dielectric anisotropy, such as dicyanobenzenes class liquid crystal, pyridazine class liquid crystal, Schiff bases liquid crystal, azoxy class liquid crystal, biphenyls liquid crystal, cyclohexylbenzene class liquid crystal etc. can be used.The thickness of the layer of liquid crystal molecule is preferably 1 ~ 5 μm.
In order to use this liquid crystal to manufacture liquid crystal cell, such as following two kinds of methods can be enumerated.
As first method, gap (box gap) can be passed through by the subtend setting respectively of two substrates, make each liquid crystal orientation film subtend, sealant is used to be fitted by the peripheral part of two substrates, inject filling liquid crystal in the unit interstices divided by substrate surface and sealant after, by sealing filling orifice, thus liquid crystal cell can be manufactured.Or as the second method, in predetermined portion on a substrate in two substrates forming liquid crystal orientation film, such as by the sealant of coated UV curable, on liquid crystal orientation film, instill liquid crystal again, other substrates of then fitting, make liquid crystal orientation film subtend, and open on whole real estate, then irradiating ultraviolet light on whole of substrate, makes sealant cures, thus manufactures liquid crystal cell.
Then, between the above-mentioned conducting film with a pair substrate, apply voltage, in this condition illumination is carried out to above-mentioned liquid crystal cell and penetrate.
The voltage wherein applied can be direct current or the interchange of such as 5 ~ 50V.
As the light irradiated, the ultraviolet and luminous ray that comprise such as 150 ~ 800nm wavelength light can be used, preferably comprise the ultraviolet of 300 ~ 400nm wavelength light.As the light source irradiating light, such as Cooper-Hewitt lamp, high-pressure mercury-vapor lamp, deuterium lamp, metal halide lamp, argon gas resonance lamp, xenon lamp, excimer lasers etc. can be used.The ultraviolet in above-mentioned optimal wavelength region can by acquisitions such as the methods by above-mentioned light source and the such as coupling such as light filter, diffraction lattice.As the exposure of light, be preferably 1,000J/m 2above, less than 100,000J/m 2, be more preferably 1,000 ~ 50,000J/m 2.In the manufacture of the liquid crystal display cells of PSA pattern known at present, 100,000J/m must be irradiated 2the light of left and right, but in the method for the invention, even if be 50,000J/m in light exposure 2below, even at 10,000J/m 2when following, also can obtain the liquid crystal display cells of expectation, except reducing the manufacturing cost of liquid crystal display cells, the reduction of electrical characteristics because strong illumination causes, the reduction of long-term reliability can also be avoided.
In addition, by attaching Polarizer on the outer surface having carried out the liquid crystal cell after as above-mentioned process, thus liquid crystal display cells can be obtained.As Polarizer used herein, can enumerate the Polarizer of seizing on both sides by the arms with cellulose acetate diaphragm, this Polarizer is by polyvinyl alcohol (PVA) diffraction orientation and absorbs the light polarizing film being called as " H film " of iodine, or the Polarizer etc. self be made up of H film.
Embodiment
The synthesis example > of < polymkeric substance (A)
Synthesis example 1
The 110g (0.50mol) 2 as tetracarboxylic dianhydride is dissolved in 800g METHYLPYRROLIDONE (NMP); 3; 5-tricarboxylic cyclopentyl acetic acid dianhydride and 49g (0.15mol) p-phenylenediamine (PPD), 49g (0.30mol) 3 as diamines; 5-diaminobenzoic acid and 26g (0.05mol) 3 (3; 5-diaminobenzene formoxyl oxygen base) cholestane; react 6 hours at 60 DEG C, obtain the solution containing polyamic acid.A small amount of taking-up gained polyamic acid solution, adds NMP, and form the solution of polyamic acid concentration 10 % by weight, the solution viscosity of mensuration is 60mPas.
In polyamic acid solution obtained above, add 1,800g NMP again, add 80g pyridine and 100g acetic anhydride, at 110 DEG C, carry out dehydration closed-loop react 4 hours.After dehydration closed-loop reaction, the new NMP of solvent in system is carried out solvent displacement (by this operation, can by outside the pyridine that uses in imidization reaction and acetic anhydride eliminating system, identical below), thus obtain the solution being about the polyimide of 50% containing acid imide rate.
Then, in polyimide solution obtained above, add 36g (0.25mol) glycidyl methacrylate, react 8 hours at 80 DEG C, thus obtain the solution containing 15 % by weight polymkeric substance (A-4-1) of having an appointment.
Synthesis example 2
The 110g (0.50mol) 2 as tetracarboxylic dianhydride is dissolved in 800g NMP; 3; 5-tricarboxylic cyclopentyl acetic acid dianhydride and 49g (0.15mol) p-phenylenediamine (PPD), 49g (0.30mol) 3 as diamines; 5-diaminobenzoic acid and 26g (0.05mol) 3 (3; 5-diaminobenzene formoxyl oxygen base) cholestane; react 6 hours at 60 DEG C, obtain the solution containing polyamic acid.A small amount of taking-up gained polyamic acid solution, adds NMP, and form the solution of polyamic acid concentration 10 % by weight, the solution viscosity of mensuration is 60mPas.
In polyamic acid solution obtained above, add 1,800g NMP again, add 80g pyridine and 100g acetic anhydride, at 110 DEG C, carry out dehydration closed-loop react 4 hours.After dehydration closed-loop reaction, the new NMP of the solvent in system is carried out solvent displacement, thus obtain the solution being about the polyimide of 50% containing acid imide rate.
Then, in polyimide solution obtained above, add 49g (0.25mol) methacrylic acid 3,4-expoxycyclohexyl methyl esters, react 8 hours at 80 DEG C, thus obtain the solution containing 15 % by weight polymkeric substance (A-4-2) of having an appointment.
Synthesis example 3
The 110g (0.50mol) 2 as tetracarboxylic dianhydride is dissolved in 750g NMP; 3; 5-tricarboxylic cyclopentyl acetic acid dianhydride and 16g (0.15mol) p-phenylenediamine (PPD), 79g (0.30mol) benzoic acid 3 as diamines; 5-diamido (2 '-methacryl oxygen base) ethyl ester and 26g (0.05mol) 3 (3; 5-diaminobenzene formoxyl oxygen base) cholestane; react 6 hours at 60 DEG C, obtain the solution containing polyamic acid.A small amount of taking-up gained polyamic acid solution, adds NMP, and form the solution of polyamic acid concentration 10 % by weight, the solution viscosity of mensuration is 59mPas.
In polyamic acid solution obtained above, add 1,800g NMP again, add 40g pyridine and 51g acetic anhydride, at 110 DEG C, carry out dehydration closed-loop react 4 hours.After dehydration closed-loop reaction, the new NMP of the solvent in system is carried out solvent displacement, thus acquisition is about the solution of the polymkeric substance (A-2-1) of 50% containing 15 % by weight acid imide rates of having an appointment.
A small amount of taking-up gained polymeric form solution, adds NMP, and form the solution of polymer concentration 10 % by weight, the solution viscosity of mensuration is 67mPas.
< compares synthesis example >
Relatively synthesis example 1
The 110g (0.50mol) 2 as tetracarboxylic dianhydride is dissolved in 750g NMP; 3; 5-tricarboxylic cyclopentyl acetic acid dianhydride and as 49g (0.45mol) p-phenylenediamine (PPD) of diamines and 26g (0.05mol) 3 (3; 5-diaminobenzene formoxyl oxygen base) cholestane; react 6 hours at 60 DEG C, obtain the solution containing polyamic acid.A small amount of taking-up gained polyamic acid solution, adds NMP, and form the solution of polyamic acid concentration 10 % by weight, the solution viscosity of mensuration is 58mPas.
In polyamic acid solution obtained above, add 1,800g NMP again, add 40g pyridine and 51g acetic anhydride, at 110 DEG C, carry out dehydration closed-loop react 4 hours.After dehydration closed-loop reaction, the new NMP of the solvent in system is carried out solvent displacement, thus acquisition is about the solution of the polymkeric substance (a-1) of 50% containing 15 % by weight acid imide rates of having an appointment.
A small amount of taking-up resulting polymers solution, adds NMP, and form the solution of polymer concentration 10 % by weight, the solution viscosity of mensuration is 69mPas.
The synthesis > of other polymkeric substance of <
Synthesis example 4
By 370g NMP and 3, the 200g (1.0mol) 1 as tetracarboxylic dianhydride is dissolved in the mixed solvent that 300g gamma-butyrolacton is formed, 2,3,4-cyclo-butane tetracarboxylic dianhydride and the 210g (1.0mol) 2 as diamines, 2 '-dimethyl-4,4 '-benzidine, react 3 hours at 40 DEG C, thus obtain the solution of the polyamic acid (a-2) containing 10 % by weight.The solution viscosity of this polyamic acid solution is 160mPas.
Embodiment 1
The preparation > of < polymer composition
In the solution of the polymkeric substance (A-4-1) obtained containing the above-mentioned synthesis example 1 as polymkeric substance (A), add the METHYLPYRROLIDONE (NMP) as organic solution and butyl cellosolve (BC), forming BC relative concentration is 20 % by weight in whole organic solvent, and frozen composition concentration is the solution of 6.0 % by weight.Use this solution of metre filter in 1 μm, aperture, thus prepare polymer composition.
The manufacture > of < liquid crystal cell
Use the polymer composition of above-mentioned preparation, change pattern (two kinds) and the ultraviolet irradiation amount (three levels) of transparency electrode, prepare 6 liquid crystal display cells altogether, evaluate as follows.
[there is the manufacture of the liquid crystal cell of patternless transparency electrode]
Use liquid crystal orientation film printing machine (Japan's description printing (strain) manufactures), the polymer composition of above-mentioned preparation is coated on the transparent electrical pole-face of the glass substrate with the transparency electrode be made up of ito film, the hot plate of 80 DEG C heats 1 minute (prebake), except desolventizing, then on the hot plate of 150 DEG C, heat 10 minutes (curing afterwards), form average film thickness film.
For this film, by having the mill of the roller being wound with rayon cloth, at roller rotation number 400rpm, platform movement speed 3cm/ second, under hair foot extruding total length 0.1mm, carry out grinding process.Then, in ultrapure water, carry out ultrasonic cleansing 1 minute, then in 100 DEG C of clean baking ovens dry 10 minutes, thus obtain the substrate with liquid crystal orientation film.Repeat this operation, obtain the substrate that a pair (two) have liquid crystal orientation film.
In addition, above-mentioned grinding process is to control swinging to of liquid crystal, carries out orientation distribution and the weak grinding process of carrying out by simple method.
Then, to one in above-mentioned a pair substrate, on the outward flange in face with alignment films, coating adds the epoxy adhesive of the alumina balls of diameter 5.5 μm, then by attached for a pair substrates while stacking pressure, makes liquid crystal orientation film relative, is solidified by bonding agent.Then, between a pair substrate, fill nematic crystal (メ ルク society manufactures, MLC-6608) by liquid crystal injecting port, then use acrylic compounds Photocurable adhesive encapsulated liquid crystals inlet, thus manufacture liquid crystal cell.
Repeat aforesaid operations, prepare 3 and there is the liquid crystal cell not having figuratum transparency electrode.One of them is directly used in the evaluation of tilt angle described later.For two remaining liquid crystal cells, respectively by following method, carry out illumination execute alive state between conducting film under and penetrate, then in the evaluation of tilt angle and voltage retention.
For two in the liquid crystal cell of above-mentioned acquisition, between electrode, apply the interchange 10V of frequency number 60Hz respectively, under the driven state of liquid crystal, in light source, adopt the ultraviolet lamp using metal halide lamp, by 10,000J/m 2or 100,000J/m 2exposure irradiation ultraviolet radiation.In addition, this exposure uses the value measured with the quantometer of wavelength 365nm reference measurement.
[evaluation of tilt angle]
For each liquid crystal cell of above-mentioned manufacture, basis is at non-patent literature 2 (T.J.Scheffer et.al.J.Appl.Phys.Vol.19 respectively, p.2013 the method (1980)) recorded, using by use the crystal diffraction method of He-Ne laser to measure by the value at liquid crystal molecule real estate angle of inclination as tilt angle.
Illustrate that liquid crystal cell, the exposure of not irradiating light are 10,000J/m in Table 1 2liquid crystal cell and exposure be 100,000J/m 2liquid crystal cell tilt angle separately.
[evaluation of voltage retention]
For each liquid crystal cell of above-mentioned manufacture, at 23 DEG C, with the application time of 60 microseconds, the interval of 167 milliseconds applies the voltage of 5V, then measures the voltage retention from stopping after applying 167 milliseconds.As determinator, use (strain) Dongyang テ Network ニ カ system, VHR-1.
Exposure 10,000J/m is shown in Table 1 2liquid crystal cell and exposure 100,000J/m 2liquid crystal cell voltage retention separately.
[there is the manufacture of the liquid crystal cell of the transparency electrode forming pattern]
The polymer composition of above-mentioned preparation is formed the pattern of strip shown in Fig. 1, use liquid crystal orientation film printing machine (Japan's description printing (strain) manufactures), each electrode surface of glass substrate two respectively with the ITO electrode being divided into multiple region is coated with, the hot plate of 80 DEG C heats (prebake) 1 minute, except desolventizing, then on the hot plate of 150 DEG C, heat (curing afterwards) 10 minutes, form average film thickness film.For this film, in ultrapure water, carry out ultrasonic cleansing 1 minute, then in the clean baking oven of 100 DEG C dry 10 minutes, thus obtain the substrate with liquid crystal orientation film.Repeat this operation, obtain the substrate that a pair (two) have liquid crystal orientation film.
Then, for a substrate in above-mentioned a pair substrate, on the outward flange in face with liquid crystal orientation film, coating adds the epoxy adhesive of the alumina balls of diameter 5.5 μm, then by attached for a pair substrates while stacking pressure, make liquid crystal aligning face relative, bonding agent is solidified.Then, between a pair substrate, fill nematic crystal (メ ルク society manufactures, MLC-6608) by liquid crystal injecting port, then use acrylic compounds Photocurable adhesive encapsulated liquid crystals inlet, thus manufacture liquid crystal cell.
Repeat aforesaid operations, prepare 3 and there is the liquid crystal cell forming transparent pattern electrode.One of them is directly used in the evaluation of response speed described later.For two remaining liquid crystal cells, by the method identical with the above-mentioned manufacture with the liquid crystal cell of patternless transparency electrode, carrying out exposure execute alive state between conducting film under is 10,000J/m 2or exposure is 100,000J/m 2illumination penetrate, then in the evaluation of response speed.
In addition, the pattern of electrode used herein is the pattern identical with the electrode pattern in PSA pattern.
[evaluation of response speed]
For each liquid crystal cell of above-mentioned manufacture, first not applying voltage just irradiates visible lamp, measures the brightness through liquid crystal cell light, with this value for relative light transmission 0% by optical universal meter.Then, transmittance when exchanging 60V for 5 seconds is applied between the electrode being determined at liquid crystal cell as described above, using this value as relative light transmission 100%.
When applying to exchange 60V to each liquid crystal cell now, measuring the time of relative light transmission from 10% to 90% change, is that response speed is evaluated by this timing definition.
Not light-struck liquid crystal cell, exposure 10,000J/m are shown in Table 1 2liquid crystal cell and exposure 100,000J/m 2liquid crystal cell response speed separately.
Embodiment 2 ~ 4 and comparative example 1
In above-described embodiment 1, except the use amount of each composition is distinguished as described in table 1, prepare polymer composition similarly to Example 1, use it to prepare various liquid crystal cell and evaluate.In addition, in embodiment 3, by polymkeric substance (A) and other polymkeric substance couplings, in comparative example 2, as polymkeric substance, other polymkeric substance are only used.
Evaluation result illustrates in Table 1.
Table 1
Found that by table 1, in the method for the invention, if ultraviolet irradiation amount is 100,000J/m 2(in PSA pattern, the value adopted at present), then the degree of gained tilt angle is excessive, at 10,000J/m 2or in exposure under it, form suitable tilt angle.In addition, even if when exposure is less, also can obtain enough fast response speed, in addition, voltage retention is also excellent.
Therefore, according to method of the present invention, the advantage of PSA pattern just can be realized with less light exposure, therefore can manufacture the generation uneven less than the display caused due to high light exposure, do not have the worry of the reduction of voltage retention performance and long-term reliability deficiency, visual angle is wide, the fast response time of liquid crystal molecule, transmittance is high, in addition, and the liquid crystal display cells that contrast is higher.
In addition, use each polymer composition used in above-described embodiment 1 ~ 4, except changing the pattern of the ITO electrode that glass substrate has, manufacture various liquid crystal cell similarly to Example 1 and evaluate.Even if when use any polymer composition, in fig. 2 shown in pattern and the pattern shown in Fig. 3 in, also all can obtain the effect identical with embodiment 1 ~ 4.
Symbol description
1:ITO electrode
2: slit section
3: photomask.

Claims (8)

1. a manufacture method for liquid crystal display cells, it is through following operation:
On this conducting film of a pair substrate with conducting film, coating contains respectively: at least one polymkeric substance selected in the group that (A) is made up of the polyamic acid with the represented group of following formula (A-I) and the polyimide with the represented group of following formula (A-I), and the polymer composition of (B) organic solvent, form film, a pair substrate forming above-mentioned film is arranged by the layer subtend of liquid crystal molecule, make above-mentioned film relative, thus formation liquid crystal cell, execute alive state between the conducting film with above-mentioned a pair substrate under, light-struck operation is carried out to above-mentioned liquid crystal cell,
In formula (A-I), R is hydrogen atom or methyl, Y 1and Y 2be oxygen atom or sulphur atom independently of one another,
Above-mentioned (A) polymkeric substance is at least one selected in the group be made up of following material:
(A-1) tetracarboxylic dianhydride with comprise there is group that above formula (A-I) represents and two amino compound 20 ~ 80mol%, polyamic acid that the diamine reactant with group that following formula (P) represents and two amino compound 10 ~ 70mol% and other diamines 10 ~ 70mol% obtains,
The polyimide (A-2) above-mentioned (A-1) polyamic acid dehydration closed-loop obtained,
(A-3) by tetracarboxylic dianhydride and the polyamic acid comprising the diamine reactant with carboxyl and two amino compounds and obtain, with have polymkeric substance that above formula (A-I) represents that the compound of group and epoxy radicals is obtained by reacting,
(A-4) by tetracarboxylic dianhydride and the polyimide comprising polyamic acid dehydration closed-loop that the diamine reactant with carboxyl and two amino compounds obtains and obtain, with there is above formula (A-I) represent the polymkeric substance that the compound of group and epoxy radicals is obtained by reacting
In formula (P), R ito be carbon number be 4 ~ 40 alkyl or carbon number be the fluoro-alkyl of 4 ~ 40, or the carbon number with steroid skeleton is the alkyl of 17 ~ 51; Z ifor singly-bound, *-O-, *-COO-, *-OCO-, wherein, with the connecting key of " * " at R iside,
R iIfor cyclohexylidene or phenylene,
Z iIfor singly-bound or *-(CH 2) n5-, wherein, with the connecting key of " * " at R iside, n5 is the integer of 1 ~ 5,
N1 is the integer of 1 ~ 5,
Wherein, when n1 is more than 2, multiple R of existence iIand Z iIcan be mutually the same or not identical respectively,
N2 is 0 or 1;
Z iIIfor *-O-, *-COO-, *-OCO-, wherein, with the connecting key of " * " at R iside,
N3 is the integer of 0 ~ 2,
N4 is 0 or 1.
2. the manufacture method of liquid crystal display cells as claimed in claim 1, wherein, above-mentioned (A) polymkeric substance is at least one selected in the group be made up of above-mentioned (A-2) polyimide, (A-3) polymkeric substance and (A-4) polymkeric substance.
3. the manufacture method of liquid crystal display cells as claimed in claim 2, wherein, above-mentioned (A) polymkeric substance is at least one selected in the group be made up of above-mentioned (A-3) polymkeric substance and (A-4) polymkeric substance.
4. the manufacture method of the liquid crystal display cells as described in claims 1 to 3 any one, wherein, above-mentioned conducting film is the pattern-like conducting film being divided into multiple region respectively.
5. a polymer composition, contain: (A) represents the polyamic acid of group by having following formula (A-I) and have following formula (A-I) and represent at least one polymkeric substance selected in the group that the polyimide of group is formed, and (B) organic solvent, it is characterized in that: this polymer composition is in the manufacture method of the liquid crystal display cells through following operation, for the formation of above-mentioned film: form film respectively on this conducting film of a pair substrate with conducting film, a pair substrate forming above-mentioned film is arranged by the layer subtend of liquid crystal molecule, make above-mentioned film relative, thus formation liquid crystal cell, execute alive state between the conducting film with above-mentioned a pair substrate under, light-struck operation is carried out to above-mentioned liquid crystal cell,
In formula (A-I), R is hydrogen atom or methyl, Y 1and Y 2be oxygen atom or sulphur atom independently of one another,
Above-mentioned (A) polymkeric substance is at least one selected in the group be made up of following material:
(A-1) tetracarboxylic dianhydride with comprise there is group that above formula (A-I) represents and two amino compound 20 ~ 80mol%, polyamic acid that the diamine reactant with group that following formula (P) represents and two amino compound 10 ~ 70mol% and other diamines 10 ~ 70mol% obtains,
The polyimide (A-2) above-mentioned (A-1) polyamic acid dehydration closed-loop obtained,
(A-3) by tetracarboxylic dianhydride and the polyamic acid comprising the diamine reactant with carboxyl and two amino compounds and obtain, with have polymkeric substance that above formula (A-I) represents that the compound of group and epoxy radicals is obtained by reacting,
(A-4) by tetracarboxylic dianhydride and the polyimide comprising polyamic acid dehydration closed-loop that the diamine reactant with carboxyl and two amino compounds obtains and obtain, with there is above formula (A-I) represent the polymkeric substance that the compound of group and epoxy radicals is obtained by reacting
In formula (P), R ito be carbon number be 4 ~ 40 alkyl or carbon number be the fluoro-alkyl of 4 ~ 40, or the carbon number with steroid skeleton is the alkyl of 17 ~ 51; Z ifor singly-bound, *-O-, *-COO-, *-OCO-, wherein, with the connecting key of " * " at R iside,
R iIfor cyclohexylidene or phenylene,
Z iIfor singly-bound or *-(CH 2) n5-, wherein, with the connecting key of " * " at R iside, n5 is the integer of 1 ~ 5,
N1 is the integer of 1 ~ 5,
Wherein, when n1 is more than 2, multiple R of existence iIand Z iIcan be mutually the same or not identical respectively,
N2 is 0 or 1;
Z iIIfor *-O-, *-COO-, *-OCO-, wherein, with the connecting key of " * " at R iside,
N3 is the integer of 0 ~ 2,
N4 is 0 or 1.
6. polymer composition as claimed in claim 5, wherein, above-mentioned (A) polymkeric substance is at least one selected in the group be made up of above-mentioned (A-2) polyimide, (A-3) polymkeric substance and (A-4) polymkeric substance.
7. polymer composition as claimed in claim 6, wherein, above-mentioned (A) polymkeric substance is at least one selected in the group be made up of above-mentioned (A-3) polymkeric substance and (A-4) polymkeric substance.
8. a liquid crystal display cells, is characterized in that the manufacture method manufacture by liquid crystal display cells as described in Claims 1 to 4 any one.
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