CN105367560A - Tetracarboxylic dianhydride containing triazole, polymer, liquid crystal aligning agent, liquid crystal aligning membrane, and display element - Google Patents

Tetracarboxylic dianhydride containing triazole, polymer, liquid crystal aligning agent, liquid crystal aligning membrane, and display element Download PDF

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CN105367560A
CN105367560A CN201510450445.4A CN201510450445A CN105367560A CN 105367560 A CN105367560 A CN 105367560A CN 201510450445 A CN201510450445 A CN 201510450445A CN 105367560 A CN105367560 A CN 105367560A
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formula
liquid crystal
compound
methyl
dicarboximide
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CN105367560B (en
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塚田裕以智
田村典央
藤马大亮
小口雄二郎
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Changsha Dao'anjie New Materials Co ltd
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JNC Corp
Chisso Petrochemical Corp
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D405/00—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom
    • C07D405/14—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing three or more hetero rings
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    • 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
    • C08G73/1085—Polyimides with diamino moieties or tetracarboxylic segments containing heterocyclic moieties
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K19/00—Liquid crystal materials
    • C09K19/52—Liquid crystal materials characterised by components which are not liquid crystals, e.g. additives with special physical aspect: solvents, solid particles
    • C09K19/54—Additives having no specific mesophase characterised by their chemical composition
    • C09K19/56—Aligning agents
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/1337—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers
    • G02F1/133711—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers by organic films, e.g. polymeric films
    • G02F1/133723—Polyimide, polyamide-imide

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Abstract

The invention provides tetracarboxylic dianhydride containing triazole, a polymer, a liquid crystal aligning agent, a liquid crystal aligning membrane, and a display element. The tetracarboxylic dianhydride is represented by the formula (1); wherein in the formula (1), the X represents a divalent organic group containing at least one triazole ring, the R1 and R2 individually represent one of trivalent groups, which are represented in the description; and at least one hydrogen atom of these groups can be replaced by a methyl group, an ethyl group, or a phenyl group. The liquid crystal aligning agent can form a liquid crystal aligning membrane that is hard to peel off or eliminate.

Description

Tetracarboxylic dianhydride containing triazole, polymkeric substance, liquid crystal aligning agent, liquid crystal orientation film and liquid crystal display device
Technical field
The present invention relates to a kind of tetracarboxylic dianhydride of novelty, use itself and the polyamic acid or derivatives thereof of gained, with and uses thereof, particularly relate to a kind of tetracarboxylic dianhydride containing triazole, polymkeric substance, liquid crystal aligning agent, liquid crystal orientation film and liquid crystal display device.In addition, the term " liquid crystal aligning agent " in the present invention is the composition containing polymkeric substance representing to be formed liquid crystal orientation film.
Background technology
At the indicating meter (monitor) of PC (personalcomputer), LCD TV, the view finder (viewfinder) of pick up camera (videocamera), the various display unit such as the projected display (projectiondisplay), optical print head (opticalprinterhead) in addition, optical Fourier transform (opticalFouriertransform) element, in photoelectron (opticalelectronics) related elements such as light valve (lightvalve) etc., obtain commercialization at present and the main flow of liquid crystal display device that usually circulates is the display element using nematic liquid crystal (nematicliquidcrystal).The display mode of nematic liquid crystal display element there will be a known twisted nematic (TwistedNematic, TN) pattern, STN Super TN (SuperTwistedNematic, STN) pattern.In recent years, in order to the visual angle of one of the problem points improving these patterns is narrow, propose the TN type liquid crystal display device that uses optical compensation films and with the vertical orientated multidomain vertical orientation (Multi-domainVerticalAlignment with raised structures thing technology, MVA) the coplanar switching (In-PlaneSwitching of pattern or Transverse electric-field type, IPS) pattern, fringing field conversion (FringeFieldSwitching, FFS) pattern, and be able to practical.
The development of the technology of liquid crystal display device is not only realized by the improvement of these type of drive or component structure, but also is realized by the improvement of member of formation that uses in element.In the member of formation used in liquid crystal display device, particularly liquid crystal orientation film is one of important materials being related to display quality, along with the high-quality of liquid crystal display device, the performance of alignment films is improved and becomes important.
Liquid crystal orientation film is formed by liquid crystal aligning agent.The present liquid crystal aligning agent mainly used makes polyamic acid or soluble polyimide be dissolved in solution (varnish) in organic solvent.After this solution coat is on substrate, the methods such as heating are utilized to carry out film forming and form polyimide system liquid crystal orientation film.
The rubbing manipulation can carrying out big area high speed processing in industrialness is easily used widely by as orientation process method.Rubbing manipulation uses the cloth having transplanted the fibers such as nylon, artificial silk, polyester, in the process that the surface of a direction to liquid crystal orientation film rubs, can obtain the consistent orientation of liquid crystal molecule thus.But, point out in friction treatment, cut down due to liquid crystal orientation film and on the dust that produces or liquid crystal orientation film with wound problem that display quality is reduced, and point out to produce the problem points such as electrostatic, the just active exploitation carrying out the orientation process method of replacement rubbing manipulation.
Instead rubbing manipulation orientation process method and what receive publicity is the light orientation process method of irradiating light and implementation orientation process.Numerous orientation mechanism such as photolysis method, photoisomerization method, photodimerization method, optical cross-linking method (such as with reference to non-patent literature 1, patent documentation 1 and patent documentation 2) is proposed in light orientation process method.Optical alignment method has following advantage: high with the homogeneity of rubbing manipulation Comparatively speaking orientation, and owing to being non-contacting orientation process method, does not therefore make film strips have scar, and can lower dust or electrostatic etc. and produce the bad reason etc. of the display of liquid crystal display device.But anchoring energy (anchoringenergy) is little and orientation is low for rubbing manipulation, the response speed that this phenomenon becomes liquid crystal molecule reduces or produces the reason of burning trace, therefore requires to be improved.
In order to overcome the shortcoming of this kind of light orientation process method, propose following material, described material has the polyimide of liquid crystal liquid crystal property by using, heat-treat this material when masking, can make the anisotropy amplification (such as with reference to patent documentation 3 ~ patent documentation 7) of film.But the optical alignment film applying this kind of technology exists following problem: easily produce film when making panel and peel off or cut down, the foreign matter produced makes the display quality of panel reduce.
[prior art document]
[patent documentation]
[patent documentation 1] Japanese Patent Laid-Open 9-297313 publication
[patent documentation 2] Japanese Patent Laid-Open 10-251646 publication
[patent documentation 3] Japanese Patent Laid-Open 2005-275364 publication
[patent documentation 4] Japanese Patent Laid-Open 2007-248637 publication
[patent documentation 5] Japanese Patent Laid-Open 2009-069493 publication
[patent documentation 6] Japanese Patent Laid-Open 2010-049230 publication
[patent documentation 7] Japanese Patent Laid-Open 2010-197999 publication
[non-patent literature]
[non-patent literature 1] " liquid crystal ", the 3rd volume, No. 4, the 262nd page, 1999 years
Summary of the invention
The invention provides a kind of tetracarboxylic dianhydride containing triazole, polymkeric substance, liquid crystal aligning agent, liquid crystal orientation film and liquid crystal display device.
First problem of the present invention is to provide liquid crystal aligning agent, and it uses the polymkeric substance using specific tetracarboxylic dianhydride in the feed, therefore can form the liquid crystal orientation film being difficult to produce and peeling off or cut down.
Second problem is to provide liquid crystal display device, and it comprises owing to carrying out film to described liquid crystal aligning agent, the liquid crystal orientation film that therefore liquid crystal aligning ability is high, and image retention characteristic is good.
The people such as the present inventor develop the tetracarboxylic dianhydride represented by formula (1).Find, by the liquid crystal aligning agent used containing the polyamic acid or derivatives thereof being raw material with this tetracarboxylic dianhydride, the liquid crystal orientation film that film hardness is high, do not produce described foreign matter can be obtained, thus complete the present invention.
The present invention comprises following formation.
[1] tetracarboxylic dianhydride, wherein: it represents with formula (1);
[changing 1]
In formula (1), X is the divalent organic radical comprising at least one triazole ring;
R 1and R 2independently for being selected from of the group of following 3 valency bases;
[changing 2]
At least one hydrogen of these bases also can be replaced by methyl, ethyl or phenyl.
[2] tetracarboxylic dianhydride according to above-mentioned [1], wherein: it represents with formula (2);
[changing 3]
In formula (2), X is the divalent organic radical comprising at least one triazole ring.
[3] tetracarboxylic dianhydride according to above-mentioned [1], wherein: it represents with formula (3);
[changing 4]
In formula (3), X 1it is triazole ring;
A 1and A 2independently for singly-bound or carbon number are the alkylidene group of 1 ~ 12;
At least one hydrogen in this alkylidene group also can replaced by fluorine; And,
At least one-CH 2-also can be replaced by-O-,-COO-,-OCO-,-CONH-,-NHCO-,-CH=CH-or-C ≡ C-.
[4] tetracarboxylic dianhydride according to above-mentioned [1], wherein: it represents with formula (4);
[changing 5]
In formula (4), X 1with X 2it is triazole ring;
A 1~ A 3independently for singly-bound or carbon number are the alkylidene group of 1 ~ 12;
At least one hydrogen in this alkylidene group also can replaced by fluorine; And,
At least one-CH in this alkylidene group 2-also can be replaced by-O-,-COO-,-OCO-,-CONH-,-NHCO-,-CH=CH-or-C ≡ C-.
[5] a polyamic acid or derivatives thereof, wherein: it makes to comprise the tetracarboxylic dianhydride of the tetracarboxylic dianhydride of at least one according to any one of above-mentioned [1] ~ [4] and diamine reactant and obtains.
[6] liquid crystal aligning agent, wherein: it is containing the polyamic acid or derivatives thereof described in good grounds above-mentioned [5].
[7] liquid crystal aligning agent according to above-mentioned [6], wherein: it is containing the polyamic acid or derivatives thereof described in good grounds above-mentioned [5] and other polymkeric substance.
[8] a light orientation liquid crystal aligning agent, wherein: it is the liquid crystal aligning agent according to above-mentioned [6] or [7].
[9] a kind of friction liquid crystal aligning agent, wherein: it is the liquid crystal aligning agent according to above-mentioned [6] or [7].
[10] liquid crystal aligning agent used for liquid crystal display element for Transverse electric-field type, wherein: it is the liquid crystal aligning agent according to any one of above-mentioned [6] ~ [9].
[11] liquid crystal orientation film, wherein: it is formed by the liquid crystal aligning agent according to any one of above-mentioned [6] ~ [10].
[12] liquid crystal indicator, wherein: it comprises the liquid crystal orientation film according to above-mentioned [11].
[effect of invention]
Film is carried out to the liquid crystal aligning agent containing the polymkeric substance being raw material and gained with tetracarboxylic dianhydride of the present invention and the film hardness of liquid crystal orientation film that formed is high, liquid crystal aligning is also good.And the liquid crystal display device comprising liquid crystal orientation film of the present invention has good display performance, and electrical specification is also good.And, in the liquid crystal aligning agent prepared with other polymer blendings by described polymkeric substance, also show same effect.
Accompanying drawing explanation
Fig. 1 is the sectional view of test panel.
[explanation of symbol]
1: glass substrate
2: column spacer
3:ITO substrate
4: liquid crystal
5: sealing material
6: alignment films
Embodiment
The term used in the present invention is illustrated.Sometimes the compound represented by formula (I-1) is described as compound (I-1).About the compound represented by other formulas, sometimes slightly remember similarly." arbitrarily " that use during definition chemical structural formula represents that not only position is any and number is also any.In chemical structural formula, be the base (ring A) of representative ring structure with the base that circle or hexagon surround word (such as A).
Tetracarboxylic dianhydride of the present invention is illustrated.In addition, sometimes " tetracarboxylic dianhydride " is only recited as " acid anhydrides " or " acid dianhydride " in the description.
Tetracarboxylic dianhydride of the present invention represents with following formula (1).
[changing 6]
In formula (1), X is the divalent organic radical comprising at least one triazole ring, R 1and R 2independently for being selected from of the group of following 3 valency bases,
[changing 7]
At least one hydrogen of these bases also can be replaced by methyl, ethyl or phenyl.
Tetracarboxylic dianhydride of the present invention has 2 acid anhydrides positions, has the tetracarboxylic dianhydride of the spacer comprising triazole ring between acid anhydrides position.Film is carried out to the liquid crystal aligning agent containing polyamic acid or derivatives thereof and the film hardness of the liquid crystal orientation film formed insufficient, there is situation about producing by cutting down the foreign matter caused, described polyamic acid or derivatives thereof makes as 5, the tetracarboxylic dianhydride with the spacer of alkyl chain that 5 '-(octane-1,8-bis-base) two (Tetra hydro Phthalic anhydride) is such and diamine reactant and gained.On the other hand, the tetracarboxylic dianhydride of the application of the invention replaces described tetracarboxylic dianhydride, makes the interaction grow between polymer chain, thus the film hardness of liquid crystal orientation film can be made to improve due to triazole ring interaction each other.
In the tetracarboxylic dianhydride represented by formula (1), the easiness obtained from raw material is considered, is preferably formula (3) or the tetracarboxylic dianhydride represented by formula (4).
[changing 8]
In formula (3), X 1triazole ring, A 1and A 2independently for singly-bound or carbon number are the alkylidene group of 1 ~ 12, any hydrogen in this alkylidene group also can replaced by fluorine, arbitrary-CH 2-also can be replaced by-O-,-COO-,-OCO-,-CONH-,-NHCO-,-CH=CH-or-C ≡ C-.
[changing 9]
In formula (4), X 1with X 2triazole ring, A 1~ A 3independently for singly-bound or carbon number are the alkylidene group of 1 ~ 12, the arbitrary hydrogen in this alkylidene group also can replaced by fluorine, arbitrary-CH 2-also can be replaced by-O-,-COO-,-OCO-,-CONH-,-NHCO-,-CH=CH-or-C ≡ C-.
The tetracarboxylic dianhydride of formula (3) such as synthesizes (synthesis example 1) by following path.
[changing 10]
In described formula, A to be singly-bound or carbon number be 1 ~ 12 alkylidene group, the arbitrary hydrogen in this alkylidene group also can replaced by fluorine, arbitrary-CH 2-also can be replaced by-O-,-COO-,-OCO-,-CONH-,-NHCO-,-CH=CH-or-C ≡ C-.
Azide is carried out to phthalic acid derivatives (a), under the existence of (b), makes copper sulfate pentahydrate and sodium ascorbate play a role, obtain the compound represented by (c) therefrom.Secondly, make sodium hydroxide play a role and be hydrolyzed to ester group, diacetyl oxide is played a role and carries out acid anhydrides, and obtain the tetracarboxylic dianhydride represented by (3) of the present invention.
The tetracarboxylic dianhydride of formula (4) such as synthesizes (synthesis example 2) by following path.
[changing 11]
Azide is carried out to dibrominated alkane (d), under the existence of (c), makes copper sulfate pentahydrate and sodium ascorbate play a role, obtain the compound represented by (e) therefrom.Secondly, make sodium hydroxide play a role and be hydrolyzed to ester group, diacetyl oxide is played a role and carries out acid anhydrides, and obtain the tetracarboxylic dianhydride represented by (4) of the present invention.
Tetracarboxylic dianhydride of the present invention can also use and utilizes the various method of purification such as recrystallize or column chromatography and carried out the tetracarboxylic dianhydride of purifying.In addition, polyamic acid or derivatives thereof of the present invention, except liquid crystal aligning agent purposes, can also be used in various polyimide coating agent, polyimide resin products formed, film, fiber etc.
The example of the tetracarboxylic dianhydride represented by formula (1) can enumerate the compound represented by following formula.
[changing 12]
[changing 13]
[changing 14]
[changing 15]
[changing 16]
[changing 17]
[changing 18]
[changing 19]
[changing 20]
[changing 21]
In described tetracarboxylic dianhydride, high at attention anchoring energy, even if when also the orientation of liquid crystal improves further, be preferably formula (1-1), formula (1-5), formula (1-15) and the tetracarboxylic dianhydride represented by formula (1-26) ~ formula (1-34), when paying attention to making transmissivity improve, the alignment films that can realize desired characteristic is obtained by using the tetracarboxylic dianhydride of the present invention of formula (1-2) ~ formula (1-4) and formula (1-6) ~ formula (1-8), in order to obtain the higher alignment agent of solvability in a solvent, the alignment films that can realize desired characteristic is obtained by using the tetracarboxylic dianhydride of the present invention of formula (1-9) ~ formula (1-11).
From the easiness of synthesis and suppress painted viewpoint to be considered, formula (1-1), formula (1-5) and formula (the 1-22) ~ formula (1-28) of being preferably, is particularly preferably formula (1-1) and formula (1-5).
Be illustrated about polyamic acid of the present invention and derivative thereof.
Polyamic acid of the present invention and derivative thereof are the reaction product of tetracarboxylic dianhydride's compound of diamines and the tetracarboxylic dianhydride's compound represented by contained (1).So-called " derivative of described polyamic acid " is the composition be dissolved in when making the liquid crystal aligning agent described later containing solvent in solvent, when this liquid crystal aligning agent is made liquid crystal orientation film, the composition of the liquid crystal orientation film being principal constituent can be formed with polyimide.The derivative of this kind of polyamic acid include, for example soluble polyimide, poly amic acid ester, and polyamic acid acid amides etc., more specifically can enumerate: 1) all amidos of polyamic acid and carboxyl carry out the polyimide that dehydration closed-loop reacts, 2) the part polyimide of partial dehydration closed-loop reaction is carried out, 3) carboxyl of polyamic acid is converted to the poly amic acid ester of ester, 4) part for acid dianhydride contained in tetracarboxylic dianhydride's compound is replaced into organic dicarboxylic acid, it is made to react and the polyamic acid-polyamide copolymer of gained, and 5) make this polyamic acid-polyamide copolymer part or all carry out the polyamidoimide of dehydration closed-loop reaction.Described polyamic acid and derivative thereof can be a kind of compounds, also can be two or more.And described polyamic acid and derivative thereof, if having the compound of the structure of the reaction product of tetracarboxylic dianhydride and diamines, also can use other raw materials, containing other reaction product of reacting beyond the reaction of tetracarboxylic dianhydride and diamines.
About in order to manufacture polyamic acid of the present invention and derivative thereof and the tetracarboxylic dianhydride used and being illustrated.
Tetracarboxylic dianhydride used in the present invention also unrestrictedly can select in known tetracarboxylic dianhydride.This kind of tetracarboxylic dianhydride belongs to direct bond on aromatic nucleus to have the fragrant family of dicarboxylic anhydride (comprising assorted aromatic ring) and the tetracarboxylic dianhydride of direct any group of the fatty family (comprising heterocycle system) of bond dicarboxylic anhydride on aromatic nucleus.
The aspect of the easiness when easiness, polymer polymerizing that raw material obtains, the electrical specification of film is considered, the suitable example of this kind of tetracarboxylic dianhydride can tetracarboxylic dianhydride represented by enumerative (AN-I) ~ formula (AN-VII).
[changing 22]
In formula (AN-I), formula (AN-IV) and formula (AN-V), X is independently singly-bound or-CH 2-.In formula (AN-II), G is singly-bound, carbon number is alkylidene group ,-CO-,-O-,-the S-,-SO of 1 ~ 20 2-,-C (CH 3) 2-or-C (CF 3) 2-.In formula (AN-II) ~ formula (AN-IV), independent for being selected from the group of following 3 valency bases one of Y, associative key is attached on arbitrary carbon, and at least one hydrogen of this base also can be replaced by methyl, ethyl or phenyl.
[changing 23]
In formula (AN-III) ~ formula (AN-V), ring A 10the base of to be carbon number the be monocyclic hydrocarbon of 3 ~ 10 or carbon number are the base of the condensation polycyclic formula hydrocarbon of 6 ~ 30, at least one hydrogen of this base also can be replaced by methyl, ethyl or phenyl, on ring, connected associative key can link with any carbon forming ring, and 2 associative keys can be attached on same carbon.In formula (AN-VI), X 10to be carbon number be 2 ~ 6 alkylidene group, Me represents methyl, and Ph represents phenyl.In formula (AN-VII), G 10independent is-O-,-COO-or-OCO-, and r is independently 0 or 1.
More specifically, the tetracarboxylic dianhydride represented by following formula (AN-1) ~ formula (AN-16-14) can be enumerated.
[changing 24]
In formula (AN-1), G 11singly-bound, carbon number be 1 ~ 12 alkylidene group, Isosorbide-5-Nitrae-phenylene or Isosorbide-5-Nitrae-cyclohexylidene.X 11independent is singly-bound or-CH 2-.G 12it is independently any base of following 3 valency bases.
[changing 25]
At G 12during for > CH-, the hydrogen of > CH-also can be substituted by-CH 3.At G 12during for > N-, G 11be not singly-bound and-CH 2-, X 11it is not singly-bound.And, R 11for hydrogen or-CH 3.The example of the tetracarboxylic dianhydride represented by formula (AN-1) can enumerate the compound represented by following formula.
[changing 26]
In formula (AN-1-2) and formula (AN-1-14), m is the integer of 1 ~ 12.
[changing 27]
In formula (AN-2), R 12independent is hydrogen ,-CH 3,-CH 2cH 3or phenyl.The example of the tetracarboxylic dianhydride represented by formula (AN-2) can enumerate the compound represented by following formula.
[changing 28]
[changing 29]
In formula (AN-3), ring A 11cyclohexane ring or phenyl ring.The example of the tetracarboxylic dianhydride represented by formula (AN-3) can enumerate the compound represented by following formula.
[changing 30]
[changing 31]
In formula (AN-4), G 13singly-bound ,-(CH 2) m-,-O-,-S-,-C (CH 3) 2-,-SO 2-,-CO-,-C (CF 3) 2-or the following divalent base represented by formula (G13-1), m is the integer of 1 ~ 12.
[changing 32]
In formula (G13-1), G 13aand G 13bdivalent base independently represented by singly-bound ,-O-or-NHCO-.Phenylene is preferably Isosorbide-5-Nitrae-phenylene and 1,3-phenylene.
Ring A 11be independently cyclohexane ring or phenyl ring.G 13can bond at ring A 11optional position.The example of the tetracarboxylic dianhydride represented by formula (AN-4) can enumerate the compound represented by following formula.
[changing 33]
[changing 34]
In formula (AN-4-17), m is the integer of 1 ~ 12.
[changing 35]
[changing 36]
[changing 37]
In formula (AN-5), R 11hydrogen or-CH 3.Binding site unfixed R on the carbon atom forming phenyl ring 11represent that the binding site in phenyl ring is any.The example of the tetracarboxylic dianhydride represented by formula (AN-5) can enumerate the compound represented by following formula.
[changing 38]
[changing 39]
In formula (AN-6), X 11independent is singly-bound or-CH 2-.X 12-CH 2-,-CH 2cH 2-or-CH=CH-.N is 1 or 2.The example of the tetracarboxylic dianhydride represented by formula (AN-6) can enumerate the compound represented by following formula.
[changing 40]
[changing 41]
In formula (AN-7), X 11singly-bound or-CH 2-.The example of the tetracarboxylic dianhydride represented by formula (AN-7) can enumerate the compound represented by following formula.
[changing 42]
[changing 43]
In formula (AN-8), X 11singly-bound or-CH 2-.R 12hydrogen ,-CH 3,-CH 2cH 3or phenyl, ring A 12cyclohexane ring or cyclohexene ring.The example of the tetracarboxylic dianhydride represented by formula (AN-8) can enumerate the compound represented by following formula.
[changing 44]
[changing 45]
In formula (AN-9), r is independently 0 or 1.The example of the tetracarboxylic dianhydride represented by formula (AN-9) can enumerate the compound represented by following formula.
[changing 46]
Formula (AN-10) is following tetracarboxylic dianhydride.
[changing 47]
[changing 48]
In formula (AN-11), ring A 11independent is cyclohexane ring or phenyl ring.The example of the tetracarboxylic dianhydride represented by formula (AN-11) can enumerate the compound represented by following formula.
[changing 49]
[changing 50]
In formula (AN-12), ring A 11be independently cyclohexane ring or phenyl ring.The example of the tetracarboxylic dianhydride represented by formula (AN-12) can enumerate the compound represented by following formula.
[changing 51]
[changing 52]
In formula (AN-13), X 13to be carbon number be 2 ~ 6 alkylidene group, Ph represents phenyl.The example of the tetracarboxylic dianhydride represented by formula (AN-13) can enumerate the compound represented by following formula.
[changing 53]
[changing 54]
In formula (AN-14), G 14independent is-O-,-COO-or-OCO-, and r is independently 0 or 1.The example of the tetracarboxylic dianhydride represented by formula (AN-14) can enumerate the compound represented by following formula.
[changing 55]
[changing 56]
In formula (AN-15), w is the integer of 1 ~ 10.The example of the tetracarboxylic dianhydride represented by formula (AN-15) can enumerate the compound represented by following formula.
[changing 57]
Tetracarboxylic dianhydride beyond described can enumerate following compound.
[changing 58]
In described acid dianhydride, the suitable material improved about making each characteristic and being described.When paying attention to making the orientation of liquid crystal to improve, be preferably formula (AN-1), formula (AN-3) and the compound represented by formula (AN-4), particularly preferably formula (AN-1-2), formula (AN-1-13), formula (AN-3-2), formula (AN-4-17) and the compound represented by formula (AN-4-29), wherein, in formula (AN-1-2), during preferred m=4 or 8, in formula (AN-4-17), preferred m=4 or 8, particularly preferably m=8.
When paying attention to making the transmissivity of liquid crystal display device to improve, formula (AN-1-1), formula (AN-1-2), formula (AN-2-1), formula (AN-3-1), formula (AN-4-17), formula (AN-4-30), formula (AN-5-1), formula (AN-7-2), formula (AN-10), formula (AN-16-3) and the compound represented by formula (AN-16-4) is preferably in described acid dianhydride, wherein, in formula (AN-1-2), during preferred m=4 or 8, in formula (AN-4-17), preferred m=4 or 8, particularly preferably m=8.
When paying attention to making the VHR of liquid crystal display device to improve, formula (AN-1-1), formula (AN-1-2), formula (AN-2-1), formula (AN-3-1), formula (AN-4-17), formula (AN-4-30), formula (AN-7-2), formula (AN-10), formula (AN-16-3) and the compound represented by formula (AN-16-4) is preferably in described acid dianhydride, wherein, in formula (AN-1-2), during preferred m=4 or 8, in formula (AN-4-17), preferred m=4 or 8, particularly preferably m=8.
As preventing one of method of burning trace, effectively by making the volumetric resistivity value of liquid crystal orientation film reduce, the mitigation speed of the residual charge (residual DC) in alignment films is improved.When paying attention to this object, in described acid dianhydride, be preferably formula (AN-1-13), formula (AN-3-2), formula (AN-4-21), formula (AN-4-29) and the compound represented by formula (AN-11-3).
In the present invention, can by the tetracarboxylic dianhydride of formula (1) and photosensitive material and use, unrestrictedly can select in known photosensitivity tetracarboxylic dianhydride.This kind of photosensitivity tetracarboxylic dianhydride can enumerate following formula (PAN-1) ~ formula (PAN-8).
[changing 59]
About in order to manufacture polyamic acid of the present invention and derivative thereof and the diamines used and two hydrazides are illustrated.When manufacturing polyamic acid or derivatives thereof of the present invention, also unrestrictedly can select in known diamines and two hydrazides.
Diamines can be divided into two kinds according to its structure.Also, namely, when skeleton amino for connection 2 is considered as main chain, there is the base of autonomous chain component, the also i.e. diamines of side chain radical and the diamines without side chain radical.This side chain radical has the base making tilt angle become large effect.The side chain radical with this kind of effect must to be carbon number be more than 3 base, concrete example can enumerate carbon number be more than 3 alkyl, carbon number be more than 3 alkoxyl group, carbon number be the alkoxyalkyl of more than 3 and there is the base of steroid skeleton.There is more than one ring, and the ring of its end have carbon number be more than 1 alkyl, carbon number be more than 1 alkoxyl group and carbon number be the effect that the base of any one alternatively base of the alkoxyalkyl of more than 2 also has as side chain radical.In the following description, sometimes the diamines with this kind of side chain radical is called side chain type diamines.And, sometimes the diamines without this kind of side chain radical is called non-side chain type diamines.
By being divided into non-side chain type diamines and side chain type diamines aptly and using, can be corresponding with the tilt angle of necessity respectively.Preferably not undermine the degree of characteristic of the present invention and to use side chain type diamines.And, about side chain type diamines and non-side chain type diamines, preferably to make the vertical orientated property of liquid crystal, voltage retention, burning trace characteristic and orientation are risen to object and accept or reject choice for use.
Be illustrated about non-side chain type diamines.The known diamines without side chain can enumerate the diamines of following formula (DI-1) ~ formula (DI-16).
[changing 60]
In described formula (DI-1), G 20for-CH 2-, at least one-CH 2-also can be substituted by-NH-,-O-, m is the integer of 1 ~ 12, and at least one hydrogen of alkylidene group also can be substituted by-OH.In formula (DI-3) and formula (DI-5) ~ formula (DI-7), G 21independent is singly-bound ,-NH-,-NCH 3-,-O-,-S-,-S-S-,-SO 2-,-CO-,-COO-,-CONCH 3-,-CONH-,-C (CH 3) 2-,-C (CF 3) 2-,-(CH 2) m '-,-O-(CH 2) m '-O-,-N (CH 3)-(CH 2) k-N (CH 3)-,-(O-C 2h 4) m '-O-,-O-CH 2-C (CF 3) 2-CH 2-O-,-O-CO-(CH 2) m '-CO-O-,-CO-O-(CH 2) m '-O-CO-,-(CH 2) m '-NH-(CH 2) m '-,-CO-(CH 2) k-NH-(CH 2) k-,-(NH-(CH 2) m ') k-NH-,-CO-C 3h 6-(NH-C 3h 6) n-CO-or-S-(CH 2) m 'the integer of-S-, m ' be independently 1 ~ 12, k is the integer of 1 ~ 5, and n is 1 or 2.In formula (DI-4), s is independently the integer of 0 ~ 2.In formula (DI-6) and formula (DI-7), G 22independent is singly-bound ,-O-,-S-,-CO-,-C (CH 3) 2-,-C (CF 3) 2-or carbon number be the alkylidene group of 1 ~ 10.Cyclohexane ring in formula (DI-2) ~ formula (DI-7) and at least one hydrogen of phenyl ring can be also the alkylidene group ,-OCH of 1 ~ 3 by-F ,-Cl, carbon number 3,-OH ,-CF 3,-CO 2h ,-CONH 2,-NHC 6h 5, phenyl or benzyl replace, in addition in formula (DI-4), the base that at least one hydrogen of phenyl ring also can be selected from the group of the base represented by following formula (DI-4-a) ~ formula (DI-4-e) replaces.On the carbon atom forming ring, the binding site do not fixed in this ring of basis representation of binding site is any.And ,-NH 2binding site on cyclohexane ring or phenyl ring is except G 21or G 22binding site beyond optional position.
[changing 61]
In formula (DI-4-a) and (DI-4-b), R 20independent is hydrogen or-CH 3.
[changing 62]
In formula (DI-11), r is 0 or 1.In formula (DI-8) ~ formula (DI-11) ,-NH of institute's bond on ring 2binding site be optional position.
[changing 63]
In formula (DI-12), R 21and R 22independently for carbon number is the alkyl or phenyl of 1 ~ 3, G 23independent for carbon number be 1 ~ 6 alkylidene group, phenylene or the phenylene through alkyl replacement, w is the integer of 1 ~ 10.In formula (DI-13), R 23independent for carbon number be 1 ~ 5 alkyl, carbon number be 1 ~ 5 alkoxyl group or-Cl, p be independently 0 ~ 3 integer, q is the integer of 0 ~ 4.In formula (DI-14), ring B is the hetero ring type aromatic series base of monocycle, R 24for alkyl, alkoxyl group, vinyl, alkynyl that hydrogen ,-F ,-Cl, carbon number are 1 ~ 6, q is independently the integer of 0 ~ 4.In formula (DI-15), ring C is hetero ring type aromatic series base or hetero ring type fatty group.In formula (DI-16), G 24for alkylidene group or Isosorbide-5-Nitrae-phenylene that singly-bound, carbon number are 2 ~ 6, r is 0 or 1.And the binding site do not fixed in this ring of basis representation of binding site is any on the carbon atom forming ring.In formula (DI-13) ~ formula (DI-16) ,-NH tied with ring key 2binding site be optional position.
The diamines without side chain of described formula (DI-1) ~ formula (DI-16) can be enumerated with the concrete example of following formula (DI-1-1) ~ formula (DI-16-1).
The example of the diamines represented by following expression (DI-1).
[changing 64]
In formula (DI-1-7) and (DI-1-8), k is independently the integer of 1 ~ 3.
The example of the diamines represented by following expression (DI-2) ~ formula (DI-3) is given.
[changing 65]
The example of the diamines represented by following expression (DI-4).
[changing 66]
[changing 67]
[changing 68]
[changing 69]
The example of the diamines represented by following expression (DI-5).
[changing 70]
In formula (DI-5-1), m is the integer of 1 ~ 12.
[changing 71]
In formula (DI-5-12) and formula (DI-5-13), m is the integer of 1 ~ 12.
[changing 72]
In formula (DI-5-16), v is the integer of 1 ~ 6.
[changing 73]
In formula (DI-5-30), k is the integer of 1 ~ 5.
[changing 74]
In formula (DI-5-35) ~ formula (DI-5-37) and formula (DI-5-39), m is the integer of 1 ~ 12, and in formula (DI-5-38) and formula (DI-5-39), k is the integer of 1 ~ 5, (DI-5-40), in, n is the integer of 1 or 2.
The example of the diamines represented by following expression (DI-6).
[changing 75]
The example of the diamines represented by following expression (DI-7).
[changing 76]
In formula (DI-7-3) and (DI-7-4), m is the integer of 1 ~ 12, and n is independently 1 or 2.
[changing 77]
[changing 78]
The example of the diamines represented by following expression (DI-8).
[changing 79]
The example of the diamines represented by following expression (DI-9).
[changing 80]
The example of the diamines represented by following expression (DI-10).
[changing 81]
The example of the diamines represented by following expression (DI-11).
[changing 82]
The example of the diamines represented by following expression (DI-12).
[changing 83]
The example of the diamines represented by following expression (DI-13).
[changing 84]
[changing 85]
[changing 86]
The example of the diamines represented by following expression (DI-14).
[changing 87]
The example of the diamines represented by following expression (DI-15).
[changing 88]
[changing 89]
The example of the diamines represented by following expression (DI-16).
[changing 90]
Be illustrated about two hydrazides.Known two hydrazides without side chain can enumerate following formula (DIH-1) ~ formula (DIH-3).
[changing 91]
In formula (DIH-1), G 25for singly-bound, carbon number are alkylidene group ,-CO-,-O-,-the S-,-SO of 1 ~ 20 2-,-C (CH 3) 2-or-C (CF 3) 2-.
In formula (DIH-2), ring D is cyclohexane ring, phenyl ring or naphthalene nucleus, and at least one hydrogen of this base also can be replaced by methyl, ethyl or phenyl.In formula (DIH-3), ring E is independently cyclohexane ring or phenyl ring, and at least one hydrogen of this base also can be replaced by methyl, ethyl or phenyl, and Y is singly-bound, carbon number is alkylidene group ,-CO-,-O-,-the S-,-SO of 1 ~ 20 2-,-C (CH 3) 2-or-C (CF 3) 2-.In formula (DIH-2) and formula (DIH-3) ,-CONHNH tied with ring key 2binding site be optional position.
The example of following expression (DIH-1) ~ formula (DIH-3).
[changing 92]
In formula (DIH-1-2), m is the integer of 1 ~ 12.
[changing 93]
[changing 94]
This kind of non-side chain type diamines and two hydrazides have the effect making the ion density reduction etc. of liquid crystal display device improve electrical specification.When using non-side chain type diamines and/or two hydrazides as diamines in order to be manufactured on the polyamic acid or derivatives thereof used in liquid crystal aligning agent of the present invention, preferably its shared ratio in the total amount of diamines and two hydrazides is set to 0mol% (molar percentage) ~ 90mol%, is more preferably set to 0mol% ~ 50mol%.
Be illustrated about side chain type diamines.The side chain radical of side chain type diamines can enumerate following base.
As side chain radical, alkyl, alkoxyl group, alkoxyalkyl, alkyl-carbonyl, alkyl carbonyl oxy, alkoxy carbonyl, alkyl amino-carbonyl, thiazolinyl, alkene oxygen base, alkenyl carbonyl, thiazolinyl carbonyl oxygen base, allyloxycarbonyl, alkenyl amino carbonyl, alkynyl, alkynyloxy group, alkynylcarbonyl groups, alkynyl carbonyl oxygen base, alkynyloxycar bonyl, alkynylaminocarbonyl etc. first can be enumerated.Alkyl in these bases, thiazolinyl and alkynyl to be all carbon numbers be more than 3 base.Wherein, in alkoxyalkyl, the carbon number of base entirety is more than 3.It also can be branch's chain that these bases can be straight-chain.
Secondly, with the ring of end, there is the alkyl that carbon number is more than 1, carbon number be more than 1 alkoxyl group or carbon number be more than 2 alkoxyalkyl alternatively base be condition, phenyl can be enumerated, phenylalkyl, phenyl alkoxyl group, phenoxy group, phenylcarbonyl group, phenyl carbonyl oxygen base, phenyloxycarbonyl, phenyl amino carbonyl, benzyl ring hexyloxy, carbon number is the cycloalkyl of more than 3, cyclohexylalkyl, cyclohexyloxy, cyclohexyloxy carbonyl, cyclohexyl phenyl, cyclohexyl phenyl alkyl, cyclohexyl phenoxy group, two (cyclohexyl) oxygen base, two (cyclohexyl) alkyl, two (cyclohexyl) phenyl, two (cyclohexyl) phenylalkyl, two (cyclohexyl) oxygen base carbonyl, two (cyclohexyl) phenyloxycarbonyl, and the base of the ring structure such as two (phenyl) oxygen base carbonyls of cyclohexyl.
In addition, set cyclic group can be enumerated, described set cyclic group is the base with more than the base of more than 2 phenyl ring, the base with more than 2 cyclohexane rings or 2 rings comprising phenyl ring and cyclohexane ring, and the alkyl replaced through fluorine that in conjunction with base independently for singly-bound ,-O-,-COO-,-OCO-,-CONH-or carbon number are the alkylidene group of 1 ~ 3, the ring of end has alkyl that carbon number is more than I, carbon number is more than 1, carbon number be more than 1 alkoxyl group or carbon number be more than 2 alkoxyalkyl alternatively base.The base with steroid skeleton is also effective as side chain radical.
The diamines with side chain can enumerate the compound represented by following formula (DI-31) ~ formula (DI-35).
[changing 95]
In formula (DI-31), G 26for singly-bound ,-O-,-COO-,-OCO-,-CO-,-CONH-,-CH 2o-,-OCH 2-,-CF 2o-,-OCF 2-or-(CH 2) m '-, m ' is the integer of 1 ~ 12.G 26preferred example be singly-bound ,-O-,-COO-,-OCO-,-CH 2o-and carbon number are the alkylidene group of 1 ~ 3, and more preferred example is singly-bound ,-O-,-COO-,-OCO-,-CH 2o-,-CH 2-and-CH 2cH 2-.R 25the alkyl, phenyl, the base with steroid skeleton or the base represented by following formula (DI-31-a) that be carbon number are 3 ~ 30.In this alkyl, at least one hydrogen also can be replaced by-F, and at least one-CH 2-also can be replaced by-O-,-CH=CH-or-C ≡ C-.The hydrogen of this phenyl also can by-F ,-CH 3,-OCH 3,-OCH 2f ,-OCHF 2,-OCF 3, carbon number be 3 ~ 30 alkyl or carbon number be 3 ~ 30 alkoxyl group replace.-the NH of bond on phenyl ring 2binding site represent for optional position in this ring, but its binding site be preferably between position or contraposition.Also namely, by base " R 25-G 26-" binding site when being set to 1,2 binding site be preferably 3 with 5 or 2 with 5.
[changing 96]
In formula (DI-31-a), G 27, G 28and G 29for in conjunction with base, these bases are independently the alkylidene group of 1 ~ 12 for singly-bound or carbon number, more than one-CH of this alkylidene group 2-also can be replaced by-O-,-COO-,-OCO-,-CONH-,-CH=CH-.Ring B 21, ring B 22, ring B 23and ring B 24independent is Isosorbide-5-Nitrae-phenylene, Isosorbide-5-Nitrae-cyclohexylidene, 1,3-diox-2,5-bis-base, pyrimidine-2,5-bis-base, pyridine-2,5-bis-base, naphthalene-1,5-bis-base, naphthalene-2,7-bis-base or anthracene-9,10-bis-base, at ring B 21, ring B 22, ring B 23and ring B 24in, at least one hydrogen also can by-F or-CH 3replace, s, t and u are independently the integer of 0 ~ 2, they add up to 1 ~ 5, when s, t or u are 2,2 in each bracket in conjunction with base can identical also can be different, and, 2 rings can identical also can be different.R 26the alkyl replaced through fluorine, the carbon number that are 1 ~ 30 for hydrogen ,-F ,-OH, carbon number be 1 ~ 30 alkyl, carbon number are alkoxyl group ,-the CN ,-OCH of 1 ~ 30 2f ,-OCHF 2or-OCF 3, this carbon number is at least one-CH of the alkyl of 1 ~ 30 2-also can replace by the divalent base represented by following formula (DI-31-b).
[changing 97]
In formula (DI-31-b), R 27and R 28independently for carbon number is the alkyl of 1 ~ 3, v is the integer of 1 ~ 6.R 26preferred example to be carbon number be 1 ~ 30 alkyl and carbon number be the alkoxyl group of 1 ~ 30.
[changing 98]
In formula (DI-32) and formula (DI-33), G 30independent is singly-bound ,-CO-or-CH 2-, R 29independent is hydrogen or-CH 3, R 30for hydrogen, carbon number be 1 ~ 20 alkyl or carbon number be the thiazolinyl of 2 ~ 20.The alkyl or phenyl that at least one hydrogen of phenyl ring in formula (DI-33) can be also 1 ~ 20 by carbon number replaces.And the binding site do not fixed in this ring of basis representation of binding site is any on any carbon atom forming ring.2 base "-phenylene-G in preferred formula (DI-32) 30-O-" one of them bond on 3 of steroid core, another bond is on 6 of steroid core.2 base "-phenylene-G in formula (DI-33) 30-O-" binding site on phenyl ring be preferably respectively for the binding site of steroid core between position or contraposition.In formula (DI-32) and formula (DI-33) ,-NH of bond on phenyl ring 2represent that the binding site in this ring is any.
[changing 99]
In formula (DI-34) and formula (DI-35), G 31independently for-O-or carbon number are the alkylidene group of 1 ~ 6, G 32for singly-bound or carbon number are the alkylidene group of 1 ~ 3.R 31for at least one-CH that hydrogen or carbon number are the alkyl of 1 ~ 20, this alkyl 2-also can be replaced by-O-,-CH=CH-or-C ≡ C-.R 32to be carbon number be 6 ~ 22 alkyl, R 33to be hydrogen or carbon number be 1 ~ 22 alkyl.Ring B 25for Isosorbide-5-Nitrae-phenylene or Isosorbide-5-Nitrae-cyclohexylidene, r is 0 or 1.And, with-the NH of phenyl ring bond 2represent that the binding site in this ring is any, preferably relative to G 31binding site be independently between position or contraposition.
The concrete example of following Exemplary sidechain type diamines.The diamines with side chain of described formula (DI-31) ~ formula (DI-35) can enumerate the compound represented by following formula (DI-31-1) ~ formula (DI-35-3).
The example of the compound represented by following expression (DI-31).
[changing 100]
In formula (DI-31-1) ~ formula (DI-31-11), R 34to be carbon number be 1 ~ 30 alkyl or carbon number be the alkoxyl group of 1 ~ 30, be preferably carbon number be 5 ~ 25 alkyl or carbon number be the alkoxyl group of 5 ~ 25.R 35to be carbon number be 1 ~ 30 alkyl or carbon number be the alkoxyl group of 1 ~ 30, be preferably carbon number be 3 ~ 25 alkyl or carbon number be the alkoxyl group of 3 ~ 25.
[changing 101]
In formula (DI-31-12) ~ formula (DI-31-17), R 36to be carbon number be 4 ~ 30 alkyl, being preferably carbon number is the alkyl of 6 ~ 25.R 37to be carbon number be 6 ~ 30 alkyl, being preferably carbon number is the alkyl of 8 ~ 25.
[changing 102]
[changing 103]
[changing 104]
[changing 105]
[changing 106]
In formula (DI-31-18) ~ formula (DI-31-43), R 38to be carbon number be 1 ~ 20 alkyl or carbon number be the alkoxyl group of 1 ~ 20, be preferably carbon number be 3 ~ 20 alkyl or carbon number be the alkoxyl group of 3 ~ 20.R 39the alkyl, the carbon number that are 1 ~ 30 for hydrogen ,-F, carbon number are alkoxyl group ,-the CN ,-OCH of 1 ~ 30 2f ,-OCHF 2or-OCF 3, be preferably carbon number be 3 ~ 25 alkyl or carbon number be the alkoxyl group of 3 ~ 25.And G 33to be carbon number be 1 ~ 20 alkylidene group.
[changing 107]
[changing 108]
[changing 109]
[changing 110]
The example of the compound represented by following expression (DI-32).
[changing 111]
The example of the compound represented by following expression (DI-33).
[changing 112]
[changing 113]
The example of the compound represented by following expression (DI-34).
[changing 114]
[changing 115]
[changing 116]
[changing 117]
In formula (DI-34-1) ~ formula (DI-34-12), R 40to be hydrogen or carbon number be 1 ~ 20 alkyl, be preferably hydrogen or carbon number is the alkyl of 1 ~ 10, and R 41to be hydrogen or carbon number be 1 ~ 12 alkyl.
The example of the compound represented by following expression (DI-35).
[changing 118]
In formula (DI-35-1) ~ formula (DI-35-3), R 37to be carbon number be 6 ~ 30 alkyl, R 41to be hydrogen or carbon number be 1 ~ 12 alkyl.
As the diamines in the present invention, the diamines beyond formula (DI-1-1) ~ formula (DI-16-1), formula (DIH-1-1) ~ formula (DIH-3-6) and the diamines represented by formula (DI-31-1) ~ formula (DI-35-3) can also be used.This kind of diamines include, for example the compound represented by following formula (DI-36-1) ~ formula (DI-36-13).
[changing 119]
In formula (DI-36-1) ~ formula (DI-36-8), R 42separately represent that carbon number is the alkyl of 3 ~ 30.
[changing 120]
In formula (DI-36-9) ~ formula (DI-36-11), e is the integer of 2 ~ 10, in formula (DI-36-12), and R 43be independently hydrogen ,-NHBoc or-N (Boc) 2, R 43at least one be-NHBoc or-N (Boc) 2, in formula (DI-36-13), R 44for-NHBoc or-N (Boc) 2, and m is the integer of 1 ~ 12.Herein, Boc is tert-butoxycarbonyl.
When paying attention to making further the orientation of liquid crystal to improve, in described diamines and two hydrazides, preferred use formula (DI-1-3), formula (DI-5-1), formula (DI-5-5), formula (DI-5-9), formula (DI-5-12), formula (DI-5-13), formula (DI-5-29), formula (DI-6-7), formula (DI-7-3), and the diamines represented by formula (DI-11-2), wherein in formula (DI-5-1), preferred m=2, 4 or 6, particularly preferably m=4, in (DI-5-12), preferred m=2 ~ 6, particularly preferably m=5, in (DI-5-13), preferred m=1 or 2, particularly preferably m=1.
When paying attention to making transmissivity improve, in described diamines and two hydrazides, preferred use formula (DI-1-3), formula (DI-2-1), formula (DI-5-1), formula (DI-5-5), formula (DI-5-24) and the diamines represented by formula (DI-7-3), the diamines particularly preferably represented by (DI-2-1).In formula (DI-5-1), preferred m=2,4 or 6 time, particularly preferably m=4, in formula (DI-7-3), preferred m=2 or 3, n=1 or 2, particularly preferably m=1.
When paying attention to making the VHR of liquid crystal display device to improve, formula (DI-2-1), formula (DI-4-1), formula (DI-4-2), formula (DI-4-10), formula (DI-4-15), formula (DI-5-1), formula (DI-5-28), formula (DI-5-30) and the diamines represented by formula (DI-13-1) is preferably used, particularly preferably formula (DI-2-1), formula (DI-5-1) and the diamines represented by formula (DI-13-1) in described diamines and two hydrazides.Wherein in (DI-5-1), particularly preferably m=1, in (DI-5-30), particularly preferably k=2.
As preventing one of method of burning trace, effectively by making the volumetric resistivity value of liquid crystal orientation film reduce, the mitigation speed of the residual charge (residual DC) in alignment films is improved.When paying attention to this object, formula (DI-4-1), formula (DI-4-2), formula (DI-4-10), formula (DI-4-15), formula (DI-5-1), formula (DI-5-12), formula (DI-5-13), formula (DI-5-28) and the diamines represented by formula (DI-16-1) is preferably used, particularly preferably formula (DI-4-1), formula (DI-5-1), formula (DI-5-12) and the diamines represented by formula (DI-5-13) in described diamines and two hydrazides.Wherein, in formula (DI-5-1), preferred m=2,4 or 6, particularly preferably m=4, in (DI-5-12), preferred m=2 ~ 6, particularly preferably m=5, in (DI-5-13), preferred m=1 or 2, particularly preferably m=1.
In the present invention, also with photosensitive material, and unrestrictedly can select in known photosensitivity diamines.Such as can be selected from azobenzene derivatives, stilbene derivatives, acetylene-derivative, coumarin derivatives, cinnamic acid derivative, benzophenone derivates.This kind of photosensitivity diamine compound can enumerate following formula (PDI-1) ~ formula (PDI-12).
[changing 121]
[changing 122]
[changing 123]
[changing 124]
In formula (PDI-7), R 51independent is-CH 3,-OCH 3,-CF 3or-COOCH 3, s is the integer of 0 ~ 2, and in formula (PDI-12), R 52to be carbon number be 1 ~ 10 alkyl or alkoxyl group, at least one hydrogen can also be substituted by fluorine.
In described photosensitivity diamines, if pay attention to, the orientation of liquid crystal is improved, then preferably (PDI-7).In the form making tetracarboxylic dianhydride of the present invention and photosensitivity diamine reactant, if consider raising and the transmissivity of orientation, then at photosensitivity diamines/do not show in the ratio of photosensitive diamines, be preferably 100/0 (mol%) ~ 50/50 (mol%).And, in order to improve described many characteristics such as electrical specification, image retention characteristic, can also and with other photosensitivity diamines two or more.
In each diamines, can be also in the scope of below 40mol% relative to the ratio of diamines at monoamine, a part for diamines is replaced into monoamine.This kind of displacement can cause the termination (termination) of polyreaction when generating polyamic acid, can suppress the carrying out of further polyreaction.Therefore, by this kind of displacement, easily can control the molecular weight of the polymkeric substance (polyamic acid or derivatives thereof) of gained, such as, improve the coating characteristics of liquid crystal aligning agent with can not undermining effect of the present invention.As for the diamines being replaced into monoamine, if do not undermine effect of the present invention, then it also can be two or more for can be one.Described monoamine include, for example aniline, 4-hydroxyanilines, hexahydroaniline, n-Butyl Amine 99, n-amylamine, normal hexyl Amine, positive heptyl amice, n-octyl amine, positive nonyl amine, n-Decylamine, n-undecane base amine, n-dodecane amine, n-tridecane base amine, n-tetradecane base amine, Pentadecane base amine, n-hexadecyl amine, n-heptadecane base amine, Octadecane base amine and NSC 62789 base amine.
Polyamic acid or derivatives thereof of the present invention can also comprise monoisocyanate compound further in monomer whose.By comprising monoisocyanate compound in monomer, the end of the polyamic acid or derivatives thereof of gained is modified, and molecular weight is adjusted.By using this end modified type polyamic acid or derivatives thereof, such as, improve the coating characteristics of liquid crystal aligning agent with can not undermining effect of the present invention.Consider from described viewpoint, for the total amount of the diamines in monomer and tetracarboxylic dianhydride, the content of the monoisocyanate compound in monomer is preferably 1mol% ~ 10mol%.Described monoisocyanate compound include, for example phenylcarbimide and naphthyl isocyanate.
Polyamic acid of the present invention and derivative thereof obtain by making described tetracarboxylic dianhydride and diamines carry out in a solvent reacting.In this building-up reactions, without the need to special condition except the selection of raw material, the condition of common polyamic acid synthesis directly can be applied.About used solvent as described later.
Liquid crystal aligning agent of the present invention can also further containing other compositions beyond polyamic acid or derivatives thereof.It can also be two or more that other compositions can be one.Other compositions include, for example other polymkeric substance or compounds etc. described later.
Liquid crystal aligning agent of the present invention can also further containing other polymkeric substance beyond polyamic acid or derivatives thereof of the present invention.Other polymkeric substance be make tetracarboxylic dianhydride of the present invention and diamine reactant and gained polyamic acid or derivatives thereof beyond polymkeric substance, can enumerate: make not containing tetracarboxylic dianhydride and the diamine reactant of the tetracarboxylic dianhydride of formula (1) polyamic acid or derivatives thereof (hereinafter referred to as " other polyamic acid or derivatives thereofs "), polyester, polymeric amide, polysiloxane, derivatived cellulose, polyacetal (polyacetal), polystyrene derivative, poly-(vinylbenzene-phenyl maleimide) derivative of gained, gather (methyl) acrylate etc.It also can be two or more for can be one.Preferred other polyamic acid or derivatives thereof and polysiloxane, more preferably other polyamic acid or derivatives thereofs in these compounds.
Have in the alignment agent of polyamic acid or derivatives thereof of the present invention and other polyamic acid or derivatives thereofs blended, control structure or the molecular weight of each polymkeric substance, coat like that as described later on substrate, carry out predrying, polyamic acid or derivatives thereof composition [A] of the present invention can be separated into upper epidermis thus, other polyamic acid or derivatives thereof compositions [B] are separated into layer.It controls by utilizing following phenomenon: in the polymkeric substance that mixing exists, the polymkeric substance that surface energy is little is separated into upper epidermis, and the polymkeric substance that surface energy is large is separated into layer.As for the confirmation that layer is separated, the surface energy by formed alignment films is the value identical or close with the surface energy of the film formed by the liquid crystal aligning agent only containing [A] composition and confirms.
Having in the alignment agent of polyamic acid or derivatives thereof of the present invention and other polyamic acid or derivatives thereofs blended, by controlling structure or the molecular weight of each polymkeric substance, the alignment films being separated into upper epidermis and layer can be formed as described later like that.Such as can be formed and polyamic acid or derivatives thereof composition [A] of the present invention is separated into upper epidermis, other polyamic acid or derivatives thereof compositions [B] are separated into the alignment films of layer.It controls by utilizing following phenomenon: be coated on substrate by described blended alignment agent, when heat drying, the polymkeric substance that surface energy is little is separated into upper epidermis, and the polymkeric substance that surface energy is large is separated into layer.As for the confirmation that layer is separated, the surface energy by formed alignment films is the value identical or close with the surface energy of the film formed by the liquid crystal aligning agent only containing [A] composition and confirms.
As the tetracarboxylic dianhydride in order to synthesize other polyamic acid or derivatives thereofs, unrestrictedly can select in known tetracarboxylic dianhydride from the tetracarboxylic dianhydride of the polyamic acid or derivatives thereof as the required composition in order to synthesize liquid crystal aligning agent of the present invention, the tetracarboxylic dianhydride identical with described illustration can be enumerated.
Wherein, in described acid dianhydride, when paying attention to making layer separation property improve, be preferably formula (AN-3-2), formula (AN-1-13) and formula (AN-4-30).
When paying attention to making the transmissivity of liquid crystal display device to improve, preferred formula (AN-1-1), formula (AN-1-2), formula (AN-2-1), formula (AN-3-1), formula (AN-4-17), formula (AN-4-30), formula (AN-5-1), formula (AN-7-2), formula (AN-10), formula (AN-16-3) and the compound represented by formula (AN-16-4) in described acid dianhydride, wherein in formula (AN-1-2), during preferred m=4 or 8, in formula (AN-4-17), preferred m=4 or 8, particularly preferably m=8.
When paying attention to making the VHR of liquid crystal display device to improve, preferred formula (AN-1-2), formula (AN-2-1), formula (AN-7-2), formula (AN-10), formula (AN-16-3) and the compound represented by formula (AN-16-4) in described acid dianhydride, wherein in formula (AN-1-2), during preferred m=4 or 8.
As preventing one of method of burning trace, effectively by making the volumetric resistivity value of liquid crystal orientation film reduce, the mitigation speed of the residual charge (residual DC) in alignment films is improved.When paying attention to this object, preferred formula (AN-1-13), formula (AN-3-2), formula (AN-4-21), formula (AN-4-29) and the compound represented by formula (AN-11-3) in described acid dianhydride.
As the diamines in order to synthesize other polyamic acid or derivatives thereofs and two hydrazides, can enumerate with as can in order to synthesize the polyamic acid or derivatives thereof of the required composition of liquid crystal aligning agent of the present invention other diamines and in above-mentioned illustrated identical compound.
Wherein, when paying attention to making a layer separation property, also namely the orientation of liquid crystal improving further, formula (DI-4-1), formula (DI-4-2), formula (DI-4-10), formula (DI-5-1), formula (DI-5-9), formula (DI-5-28) and the diamines represented by formula (DIH-2-1) and two hydrazides are preferably used in described diamines and two hydrazides, wherein in formula (DI-5-1), preferred m=1,2 or 4, particularly preferably m=1 or 2.
When paying attention to making transmissivity improve, formula (DI-1-2), formula (DI-2-1), formula (DI-5-1) and the diamines represented by formula (DI-7-3) is preferably used, the diamines particularly preferably represented by (DI-2-1) in described diamines and two hydrazides.In formula (DI-5-1), preferred m=1,2 or 4, particularly preferably m=1 or 2, in formula (DI-7-3), preferred m=2 or 3, n=1 or 2, particularly preferably m=1.
When paying attention to making the VHR of liquid crystal display device to improve, formula (DI-2-1), formula (DI-4-1), formula (DI-4-2), formula (DI-4-15), formula (DI-5-1), formula (DI-5-28), formula (DI-5-30) and the diamines represented by formula (DI-13-1) is preferably used, particularly preferably formula (DI-2-1), formula (DI-5-1) and the diamines represented by formula (DI-13-1) in described diamines and two hydrazides.Wherein in (DI-5-1), particularly preferably m=1 or 2, in (DI-5-30), particularly preferably k=2.
As preventing one of method of burning trace, effectively by making the volumetric resistivity value of liquid crystal orientation film reduce, the mitigation speed of the residual charge (residual DC) in alignment films is improved.When paying attention to this object, formula (DI-4-1) is preferably used in described diamines and two hydrazides, formula (DI-4-2), formula (DI-4-10), formula (DI-4-15), formula (DI-5-1), formula (DI-5-9), formula (DI-5-12), formula (DI-5-13), formula (DI-5-28), formula (DI-5-30), and the diamines represented by formula (DI-16-1), particularly preferably formula (DI-4-1), formula (DI-5-1), formula (DI-5-12), formula (DI-5-13), and the diamines represented by formula (DI-5-30).Wherein in formula (DI-5-1), preferred m=1 or 2, in (DI-5-12), preferred m=2 ~ 6, particularly preferably m=5, in (DI-5-13), preferred m=1 or 2, particularly preferably m=1, in (DI-5-30), particularly preferably k=2.
Other polyamic acid or derivatives thereofs can respectively according to the synthetic method of the polyamic acid or derivatives thereof of the required composition as liquid crystal aligning agent of the present invention in following described and synthesize.
For the total amount of polyamic acid or derivatives thereof of the present invention (described [A] composition) and other polyamic acid or derivatives thereofs (described [B] composition), the ratio of [A] composition is preferably 10 % by weight ~ 100 % by weight, is more preferably 20 % by weight ~ 100 % by weight.
As described polysiloxane, Japanese Patent Laid-Open 2009-036966 publication can be contained further, Japanese Patent Laid-Open 2010-185001 publication, Japanese Patent Laid-Open 2011-102963 publication, Japanese Patent Laid-Open 2011-253175 publication, Japanese Patent Laid-Open 2012-159825 publication, International Publication No. 2008/044644 specification sheets, International Publication No. 2009/148099 specification sheets, International Publication No. 2010/074261 specification sheets, International Publication No. 2010/074264 specification sheets, International Publication No. 2010/126108 specification sheets, International Publication No. 2011/068123 specification sheets, International Publication No. 2011/068127 specification sheets, International Publication No. 2011/068128 specification sheets, International Publication No. 2012/115157 specification sheets, polysiloxane described in International Publication No. 2012/165354 specification sheets etc.
< is through the Na Dike imide compound > of alkenyl substituted
Such as, liquid crystal aligning agent of the present invention can also further containing the Na Dike imide compound through alkenyl substituted for the purpose of the electrical specification long-term stability making liquid crystal display device.Na Dike imide compound through alkenyl substituted can use one, can also and with two or more.As the content of the Na Dike imide compound through alkenyl substituted, consider from described object, for polyamic acid or derivatives thereof, be preferably 1 % by weight ~ 100 % by weight, be more preferably 1 % by weight ~ 70 % by weight, more preferably 1 % by weight ~ 50 % by weight.
Below, illustrated about Na Dike imide compound.
Na Dike imide compound through alkenyl substituted is preferably dissolvable in water the compound in the solvent being dissolved with the polyamic acid or derivatives thereof used in the present invention.This kind can enumerate the compound represented by following formula (NA) through the example of the Na Dike imide compound of alkenyl substituted.
[changing 125]
In formula (NA), L 1and L 2aryl or benzyl that the cycloalkyl that the thiazolinyl that the alkyl that independence is hydrogen, carbon number is 1 ~ 12, carbon number are 3 ~ 6, carbon number are 5 ~ 8, carbon number are 6 ~ 12, n is 1 or 2.
In formula (NA), when n=1, W to be carbon number be 1 ~ 12 alkyl, the carbon number thiazolinyl that is 2 ~ 6, the carbon number cycloalkyl that is 5 ~ 8, carbon number be 6 ~ 12 aryl, benzyl ,-Z 1-(O) r-(Z 2o) k-Z 3-H (herein, Z 1, Z 2and Z 3independent for carbon number be the alkylidene group of 2 ~ 6, r is 0 or 1, and, the integer that k is 1 ~ 30) represented by base ,-(Z 4) r-B-Z 5-H (herein, Z 4and Z 5independent for carbon number be 1 ~ 4 alkylidene group or carbon number be the cycloalkylidene of 5 ~ 8, B is phenylene, and r is 0 or 1) represented by base, (herein, B is phenylene to-B-T-B-H, and T is-CH 2-,-C (CH 3) 2-,-O-,-CO-,-S-or-SO 2-) represented by base or the base that replaced by-OH of 1 ~ 3 hydrogen of these bases.
Now, preferred W to be carbon number be 1 ~ 8 alkyl, carbon number be 3 ~ 4 thiazolinyl, cyclohexyl, phenyl, benzyl, carbon number be the base that one or two hydrogen of poly-(ethyleneoxy group) ethyl, Phenoxyphenyl, phenyl methyl phenyl, phenyl isopropylidene phenyl and these bases of 4 ~ 10 is replaced by-OH.
In formula (NA), when n=2, W to be carbon number be 2 ~ 20 alkylidene group, carbon number be 5 ~ 8 cycloalkylidene, carbon number be the arylidene ,-Z of 6 ~ 12 1-O-(Z 2o) k-Z 3-(herein, Z 1~ Z 3, and the implication of k described above) represented by base ,-Z 4-B-Z 5-(herein, Z 4, Z 5and the implication of B is described above) represented by base ,-B-(O-B) r-T-(B-O) r-B-(herein, B is phenylene, T to be carbon number be 1 ~ 3 alkylidene group ,-O-or-SO 2-, the implication of r is described above) represented by base or the base that replaced by-OH of 1 ~ 3 hydrogen of these bases.
Now, preferred W to be carbon number be 2 ~ 12 alkylidene group, cyclohexylidene, phenylene, tolylene (tolylene), xylylene (xylylene) ,-C 3h 6-O-(Z 2-O) n-O-C 3h 6-(herein, Z 2to be carbon number be 2 ~ 6 alkylidene group, n is 1 or 2) represented by base, (herein, B is phenylene to-B-T-B-, and T is-CH 2-,-O-or-SO 2-) represented by base ,-B-O-B-C 3h 6one or two hydrogen of base represented by-B-O-B-(herein, B is phenylene) and these bases is by the base of-OH replacement.
This kind such as can use through the Na Dike imide compound of alkenyl substituted and make at the temperature of 80 DEG C ~ 220 DEG C, to keep 0.5 hour ~ 20 hours through the Na Dike tetracarboxylic dianhydride derivative of alkenyl substituted and diamines as described in Japanese Patent No. 2729565 publications, carries out thus synthesizing and the compound of gained or commercially available compound.Concrete example through the Na Dike imide compound of alkenyl substituted can enumerate compound shown below.
N-methyl-allyl dicyclo [2.2.1]-5-in heptan alkene-2,3-dicarboximide, N-methyl-allyl methyl bicycle [2.2.1]-5-in heptan alkene-2,3-dicarboximide, N-methyl-methacrylic dicyclo [2.2.1]-5-in heptan alkene-2,3-dicarboximide, N-methyl-methacrylic methyl bicycle [2.2.1]-5-in heptan alkene-2,3-dicarboximide, N-(2-ethylhexyl)-allyl group dicyclo [2.2.1]-5-in heptan alkene-2,3-dicarboximide,
N-(2-ethylhexyl)-allyl group (methyl) dicyclo [2.2.1]-5-in heptan alkene-2, 3-dicarboximide, N-allyl group-allyl group dicyclo [2.2.1]-5-in heptan alkene-2, 3-dicarboximide, N-allyl group-allyl methyl dicyclo [2.2.1]-5-in heptan alkene-2, 3-dicarboximide, N-Allyl-methyl allyl group dicyclo [2.2.1]-5-in heptan alkene-2, 3-dicarboximide, N-pseudoallyl-allyl group dicyclo [2.2.1]-5-in heptan alkene-2, 3-dicarboximide, N-pseudoallyl-allyl group (methyl) dicyclo [2.2.1]-5-in heptan alkene-2, 3-dicarboximide, N-pseudoallyl-methacrylic dicyclo [2.2.1]-5-in heptan alkene-2, 3-dicarboximide, N-cyclohexyl-allyl group dicyclo [2.2.1]-5-in heptan alkene-2, 3-dicarboximide, N-cyclohexyl-allyl group (methyl) dicyclo [2.2.1]-5-in heptan alkene-2, 3-dicarboximide, N-Cyclohexyl-methyl allyl group dicyclo [2.2.1]-5-in heptan alkene-2, 3-dicarboximide, N-Phenyl-allyl dicyclo [2.2.1]-5-in heptan alkene-2, 3-dicarboximide,
N-Phenyl-allyl (methyl) dicyclo [2.2.1]-5-in heptan alkene-2, 3-dicarboximide, N-benzyl-allyl group dicyclo [2.2.1]-5-in heptan alkene-2, 3-dicarboximide, N-benzyl-allyl methyl dicyclo [2.2.1]-5-in heptan alkene-2, 3-dicarboximide, N-benzyl-methyl allyl group dicyclo [2.2.1]-5-in heptan alkene-2, 3-dicarboximide, N-(2-hydroxyethyl)-allyl group dicyclo [2.2.1]-5-in heptan alkene-2, 3-dicarboximide, N-(2-hydroxyethyl)-allyl group (methyl) dicyclo [2.2.1]-5-in heptan alkene-2, 3-dicarboximide, N-(2-hydroxyethyl)-methacrylic dicyclo [2.2.1]-5-in heptan alkene-2, 3-dicarboximide,
N-(2, 2-dimethyl-3-hydroxypropyl)-allyl group dicyclo [2.2.1]-5-in heptan alkene-2, 3-dicarboximide, N-(2, 2-dimethyl-3-hydroxypropyl)-allyl group (methyl) dicyclo [2.2.1]-5-in heptan alkene-2, 3-dicarboximide, N-(2, 3-dihydroxypropyl)-allyl group dicyclo [2.2.1]-5-in heptan alkene-2, 3-dicarboximide, N-(2, 3-dihydroxypropyl)-allyl group (methyl) dicyclo [2.2.1]-5-in heptan alkene-2, 3-dicarboximide, N-(3-hydroxyl-1-propenyl)-allyl group dicyclo [2.2.1]-5-in heptan alkene-2, 3-dicarboximide, N-(4-hydroxy-cyclohexyl)-allyl group (methyl) dicyclo [2.2.1]-5-in heptan alkene-2, 3-dicarboximide,
N-(4-hydroxy phenyl)-allyl group dicyclo [2.2.1]-5-in heptan alkene-2, 3-dicarboximide, N-(4-hydroxy phenyl)-allyl group (methyl) dicyclo [2.2.1]-5-in heptan alkene-2, 3-dicarboximide, N-(4-hydroxy phenyl)-methacrylic dicyclo [2.2.1]-5-in heptan alkene-2, 3-dicarboximide, N-(4-hydroxy phenyl)-methacrylic methyl bicycle [2.2.1]-5-in heptan alkene-2, 3-dicarboximide, N-(3-hydroxy phenyl)-allyl group dicyclo [2.2.1]-5-in heptan alkene-2, 3-dicarboximide, N-(3-hydroxy phenyl)-allyl group (methyl) dicyclo [2.2.1]-5-in heptan alkene-2, 3-dicarboximide, N-(to hydroxybenzyl)-allyl group dicyclo [2.2.1]-5-in heptan alkene-2, 3-dicarboximide, N-{2-(2-hydroxyl-oxethyl) ethyl }-allyl group dicyclo [2.2.1]-5-in heptan alkene-2, 3-dicarboximide,
N-{2-(2-hydroxyl-oxethyl) ethyl }-allyl group (methyl) dicyclo [2.2.1]-5-in heptan alkene-2, 3-dicarboximide, N-{2-(2-hydroxyl-oxethyl) ethyl }-methacrylic dicyclo [2.2.1]-5-in heptan alkene-2, 3-dicarboximide, N-{2-(2-hydroxyl-oxethyl) ethyl }-methacrylic methyl bicycle [2.2.1]-5-in heptan alkene-2, 3-dicarboximide, N-[2-{2-(2-hydroxyl-oxethyl) oxyethyl group } ethyl]-allyl group dicyclo [2.2.1]-5-in heptan alkene-2, 3-dicarboximide, N-[2-{2-(2-hydroxyl-oxethyl) oxyethyl group } ethyl]-allyl group (methyl) dicyclo [2.2.1]-5-in heptan alkene-2, 3-dicarboximide, N-[2-{2-(2-hydroxyl-oxethyl) oxyethyl group } ethyl]-methacrylic dicyclo [2.2.1]-5-in heptan alkene-2, 3-dicarboximide, N-{4-(4-hydroxy phenyl isopropylidene) phenyl }-allyl group dicyclo [2.2.1]-5-in heptan alkene-2, 3-dicarboximide, N-{4-(4-hydroxy phenyl isopropylidene) phenyl }-allyl group (methyl) dicyclo [2.2.1]-5-in heptan alkene-2, 3-dicarboximide, N-{4-(4-hydroxy phenyl isopropylidene) phenyl }-methacrylic dicyclo [2.2.1]-5-in heptan alkene-2, 3-dicarboximide, and their oligomer,
N, N '-ethylidene-bis-(allyl group dicyclo [2.2.1]-5-in heptan alkene-2, 3-dicarboximide), N, N '-ethylidene-bis-(allyl methyl dicyclo [2.2.1]-5-in heptan alkene-2, 3-dicarboximide), N, N '-ethylidene-bis-(methacrylic dicyclo [2.2.1]-5-in heptan alkene-2, 3-dicarboximide), N, N '-trimethylene-bis-(allyl group dicyclo [2.2.1]-5-in heptan alkene-2, 3-dicarboximide), N, N '-hexa-methylene-bis-(allyl group dicyclo [2.2.1]-5-in heptan alkene-2, 3-dicarboximide), N, N '-hexa-methylene-bis-(allyl methyl dicyclo [2.2.1]-5-in heptan alkene-2, 3-dicarboximide), N, N '-ten dimethylene-bis-(allyl group dicyclo [2.2.1]-5-in heptan alkene-2, 3-dicarboximide), N, N '-ten dimethylene-bis-(allyl methyl dicyclo [2.2.1]-5-in heptan alkene-2, 3-dicarboximide), N, N '-cyclohexylidene-bis-(allyl group dicyclo [2.2.1]-5-in heptan alkene-2, 3-dicarboximide), N, N '-cyclohexylidene-bis-(allyl methyl dicyclo [2.2.1]-5-in heptan alkene-2, 3-dicarboximide),
1, two { 3 '-(allyl group dicyclo [2.2.1]-5-in the heptan alkene-2 of 2-, 3-dicarboximide) propoxy-} ethane, 1, two { 3 '-(allyl methyl dicyclo [2.2.1]-5-in the heptan alkene-2 of 2-, 3-dicarboximide) propoxy-} ethane, 1, two { 3 '-(methacrylic dicyclo [2.2.1]-5-in the heptan alkene-2 of 2-, 3-dicarboximide) propoxy-} ethane, two [2 '-{ 3 '-(allyl group dicyclo [2.2.1]-5-in heptan alkene-2, 3-dicarboximide) propoxy-} ethyl] ether, two [2 '-{ 3 '-(allyl methyl dicyclo [2.2.1]-5-in heptan alkene-2, 3-dicarboximide) propoxy-} ethyl] ether, 1, two { 3 '-(allyl group dicyclo [2.2.1]-5-in the heptan alkene-2 of 4-, 3-dicarboximide) propoxy-} butane, 1, two { 3 '-(allyl methyl dicyclo [2.2.1]-5-in the heptan alkene-2 of 4-, 3-dicarboximide) propoxy-} butane,
N, N '-to phenylene-bis-(allyl group dicyclo [2.2.1]-5-in heptan alkene-2, 3-dicarboximide), N, N '-to phenylene-bis-(allyl methyl dicyclo [2.2.1]-5-in heptan alkene-2, 3-dicarboximide), N, N '-metaphenylene-bis-(allyl group dicyclo [2.2.1]-5-in heptan alkene-2, 3-dicarboximide), N, N '-metaphenylene-bis-(allyl methyl dicyclo [2.2.1]-5-in heptan alkene-2, 3-dicarboximide), N, N '-{ (1-methyl)-2, 4-phenylene }-bis-(allyl group dicyclo [2.2.1]-5-in heptan alkene-2, 3-dicarboximide), N, N '-terephthaldehyde's base-bis-(allyl group dicyclo [2.2.1]-5-in heptan alkene-2, 3-dicarboximide), N, N '-terephthaldehyde's base-bis-(allyl methyl dicyclo [2.2.1]-5-in heptan alkene-2, 3-dicarboximide), N, a N '-xylylene-bis-(allyl group dicyclo [2.2.1]-5-in heptan alkene-2, 3-dicarboximide), N, a N '-xylylene-bis-(allyl methyl dicyclo [2.2.1]-5-in heptan alkene-2, 3-dicarboximide),
2, two [4-{4-(allyl group dicyclo [2.2.1]-5-in the heptan alkene-2 of 2-, 3-dicarboximide) phenoxy group } phenyl] propane, 2, two [4-{4-(allyl methyl dicyclo [2.2.1]-5-in the heptan alkene-2 of 2-, 3-dicarboximide) phenoxy group } phenyl] propane, 2, two [4-{4-(methacrylic dicyclo [2.2.1]-5-in the heptan alkene-2 of 2-, 3-dicarboximide) phenoxy group } phenyl] propane, two { 4-(allyl group dicyclo [2.2.1]-5-in heptan alkene-2, 3-dicarboximide) phenyl } methane, two { 4-(allyl methyl dicyclo [2.2.1]-5-in heptan alkene-2, 3-dicarboximide) phenyl } methane,
Two { 4-(methacrylic dicyclo [2.2.1]-5-in heptan alkene-2, 3-dicarboximide) phenyl } methane, two { 4-(methacrylic methyl bicycle [2.2.1]-5-in heptan alkene-2, 3-dicarboximide) phenyl } methane, two { 4-(allyl group dicyclo [2.2.1]-5-in heptan alkene-2, 3-dicarboximide) phenyl } ether, two { 4-(allyl methyl dicyclo [2.2.1]-5-in heptan alkene-2, 3-dicarboximide) phenyl } ether, two { 4-(methacrylic dicyclo [2.2.1]-5-in heptan alkene-2, 3-dicarboximide) phenyl } ether, two { 4-(allyl group dicyclo [2.2.1]-5-in heptan alkene-2, 3-dicarboximide) phenyl } sulfone, two { 4-(allyl methyl dicyclo [2.2.1]-5-in heptan alkene-2, 3-dicarboximide) phenyl } sulfone,
Two { 4-(methacrylic dicyclo [2.2.1]-5-in heptan alkene-2, 3-dicarboximide) phenyl } sulfone, 1, two (allyl group dicyclo [2.2.1]-5-in the heptan alkene-2 of 6-, 3-dicarboximide)-3-hydroxy-hexane, 1, two (methacrylic dicyclo [2.2.1]-5-in the heptan alkene-2 of 12-, 3-dicarboximide)-3, 6-dihydroxyl-dodecane, 1, two (allyl group dicyclo [2.2.1]-5-in the heptan alkene-2 of 3-, 3-dicarboximide)-5-hydroxy-cyclohexan alkane, 1, two { 3 '-(allyl group dicyclo [2.2.1]-5-in the heptan alkene-2 of 5-, 3-dicarboximide) propoxy-}-3-hydroxyl-pentane, 1, two (allyl group dicyclo [2.2.1]-5-in the heptan alkene-2 of 4-, 3-dicarboximide)-2-hydroxyl-benzene,
1, two (allyl methyl dicyclo [2.2.1]-5-in the heptan alkene-2 of 4-, 3-dicarboximide)-2, 5-dihydroxyl-benzene, N, N '-to (2-hydroxyl) xylylene-bis-(allyl group dicyclo [2.2.1]-5-in heptan alkene-2, 3-dicarboximide), N, N '-to (2-hydroxyl) xylylene-bis-(allyl methyl dicyclo [2.2.1]-5-in heptan alkene-2, 3-dicarboximide), N, N '-(2-hydroxyl) xylylene-bis-(allyl group dicyclo [2.2.1]-5-in heptan alkene-2, 3-dicarboximide), N, N '-(2-hydroxyl) xylylene-bis-(methacrylic dicyclo [2.2.1]-5-in heptan alkene-2, 3-dicarboximide), N, N '-to (2, 3-dihydroxyl) xylylene-bis-(allyl group dicyclo [2.2.1]-5-in heptan alkene-2, 3-dicarboximide),
2, two [4-{4-(allyl group dicyclo [2.2.1]-5-in the heptan alkene-2 of 2-, 3-dicarboximide)-2-Hydroxy-phenoxy } phenyl] propane, two { 4-(allyl methyl dicyclo [2.2.1]-5-in heptan alkene-2, 3-dicarboximide)-2-hydroxy-pheny } methane, two { 3-(allyl group dicyclo [2.2.1]-5-in heptan alkene-2, 3-dicarboximide)-4-hydroxy-pheny } ether, two { 3-(methacrylic dicyclo [2.2.1]-5-in heptan alkene-2, 3-dicarboximide)-5-hydroxy-pheny } sulfone, 1, 1, 1-tri-{ 4-(allyl methyl dicyclo [2.2.1]-5-in heptan alkene-2, 3-dicarboximide) } Phenoxymethyl propane, N, N ', N "-three (ethylidene methacrylic dicyclo [2.2.1]-5-in heptan alkene-2, 3-dicarboximide) isocyanuric acid ester, and their oligomer etc.
In addition, the Na Dike imide compound through alkenyl substituted used in the present invention also can be comprise asymmetric alkylidene group, phenylene and compound represented by following formula.
[changing 126]
In the Na Dike imide compound of alkenyl substituted, preferred compound is as follows.
N, N '-ethylidene-bis-(allyl group dicyclo [2.2.1]-5-in heptan alkene-2, 3-dicarboximide), N, N '-ethylidene-bis-(allyl methyl dicyclo [2.2.1]-5-in heptan alkene-2, 3-dicarboximide), N, N '-ethylidene-bis-(methacrylic dicyclo [2.2.1]-5-in heptan alkene-2, 3-dicarboximide), N, N '-trimethylene-bis-(allyl group dicyclo [2.2.1]-5-in heptan alkene-2, 3-dicarboximide), N, N '-hexa-methylene-bis-(allyl group dicyclo [2.2.1]-5-in heptan alkene-2, 3-dicarboximide), N, N '-hexa-methylene-bis-(allyl methyl dicyclo [2.2.1]-5-in heptan alkene-2, 3-dicarboximide), N, N '-ten dimethylene-bis-(allyl group dicyclo [2.2.1]-5-in heptan alkene-2, 3-dicarboximide), N, N '-ten dimethylene-bis-(allyl methyl dicyclo [2.2.1]-5-in heptan alkene-2, 3-dicarboximide), N, N '-cyclohexylidene-bis-(allyl group dicyclo [2.2.1]-5-in heptan alkene-2, 3-dicarboximide), N, N '-cyclohexylidene-bis-(allyl methyl dicyclo [2.2.1]-5-in heptan alkene-2, 3-dicarboximide),
N, N '-to phenylene-bis-(allyl group dicyclo [2.2.1]-5-in heptan alkene-2, 3-dicarboximide), N, N '-to phenylene-bis-(allyl methyl dicyclo [2.2.1]-5-in heptan alkene-2, 3-dicarboximide), N, N '-metaphenylene-bis-(allyl group dicyclo [2.2.1]-5-in heptan alkene-2, 3-dicarboximide), N, N '-metaphenylene-bis-(allyl methyl dicyclo [2.2.1]-5-in heptan alkene-2, 3-dicarboximide), N, N '-{ (1-methyl)-2, 4-phenylene }-bis-(allyl group dicyclo [2.2.1]-5-in heptan alkene-2, 3-dicarboximide), N, N '-terephthaldehyde's base-bis-(allyl group dicyclo [2.2.1]-5-in heptan alkene-2, 3-dicarboximide), N, N '-terephthaldehyde's base-bis-(allyl methyl dicyclo [2.2.1]-5-in heptan alkene-2, 3-dicarboximide), N, a N '-xylylene-bis-(allyl group dicyclo [2.2.1]-5-in heptan alkene-2, 3-dicarboximide), N, a N '-xylylene-bis-(allyl methyl dicyclo [2.2.1]-5-in heptan alkene-2, 3-dicarboximide), 2, two [4-{4-(allyl group dicyclo [2.2.1]-5-in the heptan alkene-2 of 2-, 3-dicarboximide) phenoxy group } phenyl] propane, 2, two [4-{4-(allyl methyl dicyclo [2.2.1]-5-in the heptan alkene-2 of 2-, 3-dicarboximide) phenoxy group } phenyl] propane, 2, two [4-{4-(methacrylic dicyclo [2.2.1]-5-in the heptan alkene-2 of 2-, 3-dicarboximide) phenoxy group } phenyl] propane, two { 4-(allyl group dicyclo [2.2.1]-5-in heptan alkene-2, 3-dicarboximide) phenyl } methane, two { 4-(allyl methyl dicyclo [2.2.1]-5-in heptan alkene-2, 3-dicarboximide) phenyl } methane.
Two { 4-(methacrylic dicyclo [2.2.1]-5-in heptan alkene-2, 3-dicarboximide) phenyl } methane, two { 4-(methacrylic methyl bicycle [2.2.1]-5-in heptan alkene-2, 3-dicarboximide) phenyl } methane, two { 4-(allyl group dicyclo [2.2.1]-5-in heptan alkene-2, 3-dicarboximide) phenyl } ether, two { 4-(allyl methyl dicyclo [2.2.1]-5-in heptan alkene-2, 3-dicarboximide) phenyl } ether, two { 4-(methacrylic dicyclo [2.2.1]-5-in heptan alkene-2, 3-dicarboximide) phenyl } ether, two { 4-(allyl group dicyclo [2.2.1]-5-in heptan alkene-2, 3-dicarboximide) phenyl } sulfone, two { 4-(allyl methyl dicyclo [2.2.1]-5-in heptan alkene-2, 3-dicarboximide) phenyl } sulfone, two { 4-(methacrylic dicyclo [2.2.1]-5-in heptan alkene-2, 3-dicarboximide) phenyl } sulfone.
The preferred Na Dike imide compound through alkenyl substituted is as follows.
N, N '-ethylidene-bis-(allyl group dicyclo [2.2.1]-5-in heptan alkene-2, 3-dicarboximide), N, N '-ethylidene-bis-(allyl methyl dicyclo [2.2.1]-5-in heptan alkene-2, 3-dicarboximide), N, N '-ethylidene-bis-(methacrylic dicyclo [2.2.1]-5-in heptan alkene-2, 3-dicarboximide), N, N '-trimethylene-bis-(allyl group dicyclo [2.2.1]-5-in heptan alkene-2, 3-dicarboximide), N, N '-hexa-methylene-bis-(allyl group dicyclo [2.2.1]-5-in heptan alkene-2, 3-dicarboximide), N, N '-hexa-methylene-bis-(allyl methyl dicyclo [2.2.1]-5-in heptan alkene-2, 3-dicarboximide), N, N '-ten dimethylene-bis-(allyl group dicyclo [2.2.1]-5-in heptan alkene-2, 3-dicarboximide), N, N '-ten dimethylene-bis-(allyl methyl dicyclo [2.2.1]-5-in heptan alkene-2, 3-dicarboximide), N, N '-cyclohexylidene-bis-(allyl group dicyclo [2.2.1]-5-in heptan alkene-2, 3-dicarboximide), N, N '-cyclohexylidene-bis-(allyl methyl dicyclo [2.2.1]-5-in heptan alkene-2, 3-dicarboximide).
N, N '-to phenylene-bis-(allyl group dicyclo [2.2.1]-5-in heptan alkene-2, 3-dicarboximide), N, N '-to phenylene-bis-(allyl methyl dicyclo [2.2.1]-5-in heptan alkene-2, 3-dicarboximide), N, N '-metaphenylene-bis-(allyl group dicyclo [2.2.1]-5-in heptan alkene-2, 3-dicarboximide), N, N '-metaphenylene-bis-(allyl methyl dicyclo [2.2.1]-5-in heptan alkene-2, 3-dicarboximide), N, N '-{ (1-methyl)-2, 4-phenylene }-bis-(allyl group dicyclo [2.2.1]-5-in heptan alkene-2, 3-dicarboximide), N, N '-terephthaldehyde's base-bis-(allyl group dicyclo [2.2.1]-5-in heptan alkene-2, 3-dicarboximide), N, N '-terephthaldehyde's base-bis-(allyl methyl dicyclo [2.2.1]-5-in heptan alkene-2, 3-dicarboximide), N, a N '-xylylene-bis-(allyl group dicyclo [2.2.1]-5-in heptan alkene-2, 3-dicarboximide), N, a N '-xylylene-bis-(allyl methyl dicyclo [2.2.1]-5-in heptan alkene-2, 3-dicarboximide).
2, two [4-{4-(allyl group dicyclo [2.2.1]-5-in the heptan alkene-2 of 2-, 3-dicarboximide) phenoxy group } phenyl] propane, 2, two [4-{4-(allyl methyl dicyclo [2.2.1]-5-in the heptan alkene-2 of 2-, 3-dicarboximide) phenoxy group } phenyl] propane, 2, two [4-(4-(methacrylic dicyclo [2.2.1]-5-in the heptan alkene-2 of 2-, 3-dicarboximide) phenoxy group } phenyl] propane, two { 4-(allyl group dicyclo [2.2.1]-5-in heptan alkene-2, 3-dicarboximide) phenyl } methane, two { 4-(allyl methyl dicyclo [2.2.1]-5-in heptan alkene-2, 3-dicarboximide) phenyl } methane, two { 4-(methacrylic dicyclo [2.2.1]-5-in heptan alkene-2, 3-dicarboximide) phenyl } methane, two { 4-(methacrylic methyl bicycle [2.2.1]-5-in heptan alkene-2, 3-dicarboximide) phenyl } methane.
And, the particularly preferred Na Dike imide compound through alkenyl substituted can enumerate two { 4-(allyl group dicyclo [2.2.1]-5-in the heptan alkene-2 represented by following formula (NA-1), 3-dicarboximide) phenyl methane, N represented by formula (NA-2), a N '-xylylene-bis-(allyl group dicyclo [2.2.1]-5-in heptan alkene-2,3-dicarboximide) and N represented by formula (NA-3), N '-hexa-methylene-bis-(allyl group dicyclo [2.2.1]-5-in heptan alkene-2,3-dicarboximide).
[changing 127]
< has the compound > of free-radical polymerised unsaturated double-bond
Such as consider from the object of the electrical specification long-term stability making liquid crystal display device, liquid crystal aligning agent of the present invention can also further containing the compound with free-radical polymerised unsaturated double-bond.The compound with free-radical polymerised unsaturated double-bond can be a kind of compound, also can be two or more compounds.In addition, in the compound with free-radical polymerised unsaturated double-bond, do not contain the Na Dike imide compound through alkenyl substituted.As the content of compound with free-radical polymerised unsaturated double-bond, consider from described object, for polyamic acid or derivatives thereof, be preferably 1 % by weight ~ 100 % by weight, be more preferably 1 % by weight ~ 70 % by weight, be more preferably 1 % by weight ~ 50 % by weight further.
In addition, as for the ratio of Compound Phase for the Na Dike imide compound through alkenyl substituted with free-radical polymerised unsaturated double-bond, in order to the ion density, the suppression ion density that lower liquid crystal display device are passed through in time and increase, suppress further the generation of image retention, there is the compound of free-radical polymerised unsaturated double-bond/be preferably 0.1 ~ 10 with mass ratio range through the Na Dike imide compound of alkenyl substituted, be more preferably 0.5 ~ 5.
Below, the compound with free-radical polymerised unsaturated double-bond is illustrated.
The compound with free-radical polymerised unsaturated double-bond can enumerate (methyl) acrylic acid derivative and the bismaleimides such as (methyl) acrylate, (methyl) acrylamide.The compound with free-radical polymerised unsaturated double-bond is more preferably (methyl) acrylic acid derivative with the free-radical polymerised unsaturated double-bond of two or more.
As the concrete example of (methyl) acrylate, include, for example (methyl) cyclohexyl acrylate, (methyl) vinylformic acid-2-methyl cyclohexyl, (methyl) vinylformic acid two ring pentyl ester, (methyl) vinylformic acid bicyclopentyl oxygen base ethyl ester, (methyl) isobornyl acrylate, (methyl) phenyl acrylate, (methyl) benzyl acrylate, (methyl) 2-Hydroxy ethyl acrylate and (methyl) 2-hydroxypropyl acrylate.
As the concrete example of 2 officials' energy (methyl) acrylate, include, for example diacrylate second diester (ethylenebisacrylate), sub-Luo Nisi (ARONIX) M-210 of product of East Asia synthetic chemical industry (stock), sub-Luo Nisi (ARONIX) M-240 and sub-Luo Nisi (ARONIX) M-6200, the product OK a karaoke club of Japan's chemical drug (stock) is sub-obtains (KAYARAD) HDDA, OK a karaoke club is sub-obtains (KAYARAD) HX-220, OK a karaoke club sub-(KAYARAD) R-604 and OK a karaoke club sub-(KAYARAD) R-684, the product V260 of Osaka Organic Chemical Industry (stock), V312 and V335HP, and special CALCIUM ACRYLATE (LightAcrylate) BA-4EA in the product of common prosperity society oil chemical industry (stock), interior special CALCIUM ACRYLATE (LightAcrylate) BP-4PA and interior special CALCIUM ACRYLATE (LightAcrylate) BP-2PA.
Can the concrete example of above multifunctional (methyl) acrylate as 3 officials, include, for example 4, 4 '-methylene-bis (N, N-dihydroxyl ethylidene acrylate aniline), sub-Luo Nisi (ARONIX) M-400 of product of East Asia synthetic chemical industry (stock), sub-Luo Nisi (ARONIX) M-405, sub-Luo Nisi (ARONIX) M-450, sub-Luo Nisi (ARONIX) M-7100, sub-Luo Nisi (ARONIX) M-8030, sub-Luo Nisi (ARONIX) M-8060, the product OK a karaoke club of Japan's chemical drug (stock) is sub-obtains (KAYARAD) TMPTA, OK a karaoke club is sub-obtains (KAYARAD) DPCA-20, OK a karaoke club is sub-obtains (KAYARAD) DPCA-30, OK a karaoke club is sub-obtains (KAYARAD) DPCA-60, OK a karaoke club is sub-obtains (KAYARAD) DPCA-120, and the product VGPT of Osaka Organic Chemical Industry (stock).
As the concrete example of (methyl) acrylamide derivative, include, for example NIPA, N-isopropyl acrylamide, N-n-propyl acrylamide, N-n-propyl Methacrylamide, N-cyclopropyl acrylamide, N-Cvclopropvlmethvl acrylamide, N-ethoxyethyl group acrylamide, N-ethoxyethyl group Methacrylamide, N-tetrahydrofuran methyl (tetrahydrofurfuryl) acrylamide, N-tetrahydrofuran methyl Methacrylamide, N-ethyl acrylamide, N-ethyl-N-methyl acrylamide, N, N-acrylamide, N-methyl-N-n-propyl acrylamide, N-methyl-N-isopropyl acrylamide, N-acryloylpiperidine, N-acryl tetramethyleneimine (pyrrolidine), N, N '-methylene bisacrylamide, N, N '-ethylenebisacrylamide, N, N '-dihydroxyl ethylenebisacrylamide, N-(4-hydroxy phenyl) Methacrylamide, N-phenyl methacrylamide, N-butyl methyl acrylamide, N-(isobutyl oxygen methyl) Methacrylamide, N-[2-(N, N-dimethylamino) ethyl] Methacrylamide, N, N-dimethylmethacryl amide, N-[3-(dimethylamino) propyl group] Methacrylamide, N-(methoxymethyl) Methacrylamide, N-(hydroxymethyl)-2-Methacrylamide, N-benzyl-2-Methacrylamide, and N, N '-methylenebismethacrylamide.
In described (methyl) acrylic acid derivative, particularly preferably N, N '-methylene bisacrylamide, N, N '-dihydroxyl ethylidene-bisacrylamide, diacrylate second diester and 4,4 '-methylene-bis (N, N-dihydroxyl ethylidene acrylate aniline).
Bismaleimides include, for example BMl-70 and BMI-80 that KI chemical company (KIChemicalIndustryCo., Ltd.) manufactures and large and change into BMI-1000, BMI-3000, BMI-4000, BMI-5000 and BMI-7000 that industry (stock) manufactures.
< oxazine compounds >
Such as from making the object of the electrical specification long-term stability in liquid crystal display device consider, liquid crystal aligning agent of the present invention can also Jin mono-step Bao Han oxazine compounds.Oxazine compounds can be a kind of compound, also can be two or more compounds.Consider from described object, for polyamic acid or derivatives thereof, the content of ， oxazine compounds is preferably 0.1 % by weight ~ 50 % by weight, is more preferably 1 % by weight ~ 40 % by weight, is more preferably 1 % by weight ~ 20 % by weight further.
Below, Guan Yu oxazine compounds is illustrated.
Oxazine compounds preferably dissolves in the solvent that polyamic acid or derivatives thereof is dissolved, and has ring-opening polymerization oxazine compounds in addition.
Er Qie ， oxazine compounds Zhong oxazine structure number is not particularly limited.
Oxazine structure there will be a known various structure.The structure of ， oxazine is not particularly limited ， oxazine compounds Zhong oxazine structure and can enumerates benzoxazine or Nai Bing oxazine etc. and have the aromatic series Ji oxazine structure comprising fused-ring aromatic base in the present invention.
Oxazine compounds include, for example the compound represented by following formula (OX-1) ~ formula (OX-6).In addition, in following formula, the key represented as turning to Ring current distribution, represents that its bond is at formation ring and can on the substituent any carbon of bond.
[changing 128]
In formula (OX-1) ~ formula (OX-3), L 3and L 4to be carbon number be 1 ~ 30 organic radical, in formula (OX-1) ~ formula (OX-6), L 5~ L 8to be hydrogen or carbon number be 1 ~ 6 alkyl, in formula (OX-3), formula (OX-4) and formula (OX-6), Q 1singly-bound ,-O-,-S-,-S-S-,-SO 2-,-CO-,-CONH-,-NHCO-,-C (CH 3) 2-,-C (CF 3) 2-,-(CH 2) v-,-O-(CH 2) v-O-,-S-(CH 2) v-S-, herein, v is the integer of 1 ~ 6, in formula (OX-5) and formula (OX-6), Q 2independent is singly-bound ,-O-,-S-,-CO-,-C (CH 3) 2-,-C (CF 3) 2-or carbon number be the alkylidene group of 1 ~ 3, Q 2in phenyl ring, the hydrogen of institute's bond also can independently by-F ,-CH on naphthalene nucleus 3,-OH ,-COOH ,-SO 3h ,-PO 3h 2replace.
Er Qie ， oxazine compounds is included in the oligomer of side chain Ju You oxazine structure or polymkeric substance, the oligomer of Ju You oxazine structure or polymkeric substance in main chain.
Oxazine compounds represented by formula (OX-1) include, for example oxazine compounds Xia Yi.
[changing 129]
In formula (OX-1-2), L 3being preferably carbon number is the alkyl of 1 ~ 30, is more preferably the alkyl that carbon number is 1 ~ 20.
Oxazine compounds represented by formula (OX-2) include, for example oxazine compounds Xia Yi.
[changing 130]
[changing 131]
In formula, L 3being preferably carbon number is the alkyl of 1 ~ 30, is more preferably the alkyl that carbon number is 1 ~ 20.
Represented by formula (OX-3), oxazine compounds can enumerate oxazine compounds represented by following formula (OX-3-I).
[changing 132]
In formula (OX-3-I), L 3and L 4to be carbon number be 1 ~ 30 organic radical, L 5to L 8to be hydrogen or carbon number be 1 ~ 6 alkyl, Q 1singly-bound ,-CH 2-,-C (CH 3) 2-,-CO-,-O-,-SO 2-,-C (CH 3) 2-or-C (CF 3) 2-.Oxazine compounds represented by formula (OX-3-I) include, for example oxazine compounds Xia Yi.
[changing 133]
[changing 134]
[changing 135]
[changing 136]
In formula, L 3and L 4being preferably carbon number is the alkyl of 1 ~ 30, is more preferably the alkyl that carbon number is 1 ~ 20.
Oxazine compounds represented by formula (OX-4) include, for example oxazine compounds Xia Yi.
[changing 137]
[changing 138]
Oxazine compounds represented by formula (OX-5) include, for example oxazine compounds Xia Yi.
[changing 139]
Oxazine compounds represented by formula (OX-6) include, for example oxazine compounds Xia Yi.
[changing 140]
[changing 141]
[changing 142]
More preferably oxazine compounds represented by enumerative (OX-2-1), formula (OX-3-1), formula (OX-3-3), formula (OX-3-5), formula (OX-3-7), formula (OX-3-9), formula (OX-4-1) ~ formula (OX-4-6), formula (OX-5-3), formula (OX-5-4) and formula (OX-6-2) ~ formula (OX-6-4) in these compounds.
Oxazine compounds can utilize the method same with method described in International Publication No. 2004/009708 specification sheets, Japanese Patent Laid-Open 11-12258 publication, Japanese Patent Laid-Open 2004-352670 publication and manufacture.
Oxazine compounds represented by formula (OX-1) is by making phenolic compound and primary amine (primaryamine), aldehyde reaction and obtaining (with reference to International Publication No. 2004/009708 specification sheets).
Oxazine compounds represented by formula (OX-2) obtains by such as under type: utilize and primary amine is slowly added to the method in formaldehyde and makes it react, and then adds the compound with naphthols system hydroxyl and makes it react (with reference to International Publication No. 2004/009708 specification sheets).
Oxazine compounds represented by formula (OX-3) obtains by such as under type: in organic solvent, make the phenolic compound of 1 mole under the existence of secondary aliphatic amine (secondaryamine), aliphatic tertiary amine (tertiaryamine) or alkaline nitrogen-containing heterocycle compound, be the primary amine reaction (with reference to International Publication No. 2004/009708 specification sheets and Japanese Patent Laid-Open 11-12258 publication) of the aldehyde of more than at least 2 moles and 1 mole for this phenolic hydroxyl group.
Oxazine compounds represented by formula (OX-4) ~ formula (OX-6) obtains by such as under type: in propyl carbinol, at the temperature of more than 90 DEG C, make 4,4 '-diaminodiphenyl-methane etc. have the aldehyde such as diamines, formalin of the organic radical of multiple phenyl ring and these phenyl ring of bond and phenol carries out dehydration condensation (with reference to Japanese Patent Laid-Open 2004-352670 publication).
< oxazoline compound >
Such as, certainly make the object of the electrical specification long-term stability of liquid crystal display device consider, liquid crystal aligning agent of the present invention can also further Han You oxazoline compound.The compound of oxazoline compound Shi Ju You oxazoline structure.Oxazoline compound can be a kind of compound, also can be two or more compounds.Consider from described object, for polyamic acid or derivatives thereof, the content of ， oxazoline compound is preferably 0.1 % by weight ~ 50 % by weight, is more preferably 1 % by weight ~ 40 % by weight, is more preferably 1 % by weight ~ 20 % by weight further.Or consider from described object, is when oxazoline compound Zhong oxazoline structure Huan Suan Wei oxazoline, and for polyamic acid or derivatives thereof, the content of ， oxazoline compound is preferably 0.1 % by weight ~ 40 % by weight.
Below, Guan Yu oxazoline compound is illustrated.
Oxazoline compound can have only Yi Zhong oxazoline structure in a compound, also can have two or more.Er Qie ， oxazoline compound Ju in a compound has Yi oxazoline structure, but preferably has two or more.Er Qie ， oxazoline compound can be the polymkeric substance at side chain Ju You oxazoline ring structure, also can be multipolymer.At the homopolymer that the polymkeric substance of side chain Ju You oxazoline structure can be the monomer in side chain Ju You oxazoline structure, it also can be the multipolymer at the monomer of side chain Ju You oxazoline structure and the monomer of Bu Ju You oxazoline structure.At the multipolymer that the multipolymer of side chain Ju You oxazoline structure can be the two or more monomers in side chain Ju You oxazoline structure, it can also be the multipolymer at the two or more monomer of side chain Ju You oxazoline structure and the monomer of Bu Ju You oxazoline structure.
Oxazoline structure optimization Weis that one or both of oxygen in Yi oxazoline structure and nitrogen can with the structure in the form Cun Yu oxazoline compound of the carbonyl reaction of polyamic acid.
Oxazoline compound include, for example 2, 2 '-bis-(2-oxazoline), 1, 2, 4-tri--(2-oxazolinyl-2)-benzene, 4-furans-2-methylene-2-phenyl-4H-oxazole-5-ketone, 1, 4-two (4, 5-dihydro-2-oxazolyl) benzene, 1, 3-two (4, 5-dihydro-2-oxazolyl) benzene, 2, two (4-pseudoallyl-2-oxazoline-2-base) butane of 3-, 2, 2 '-bis--4-benzyl-2-oxazoline, 2, two (sec.-propyl-2-oxazoline-2-base) pyridine of 6-, 2, 2 '-isopropylidene two (the 4-tertiary butyl-2-oxazoline), 2, 2 '-isopropylidene two (4-phenyl-2-oxazoline), 2, 2 '-methylene-bis (the 4-tertiary butyl-2-oxazoline), and 2, 2 '-methylene-bis (4-phenyl-2-oxazoline).Except these compounds, the tool can also enumerated as Ai Bokasi (EPOCROS) (trade(brand)name, (stock) Japanese catalyzer manufacture) has polymkeric substance or the oligomer of oxazolyl.More preferably two (4, the 5-dihydro-2-oxazolyl) benzene of 1,3-is enumerated in these compounds.
< epoxy compounds >
Such as consider from the object of the electrical specification long-term stability making liquid crystal display device, liquid crystal aligning agent of the present invention can also contain epoxy compounds further.Epoxy compounds can be a kind of compound, also can be two or more compounds.Consider from described object, for polyamic acid or derivatives thereof, the content of epoxy compounds is preferably 0.1 % by weight ~ 50 % by weight, is more preferably 1 % by weight ~ 40 % by weight, is more preferably 1 % by weight ~ 20 % by weight further.
Below, illustrated about epoxy compounds.
Epoxy compounds can be set forth in molecule the various compounds with one or more oxirane ring.The compound in molecule with an oxirane ring include, for example phenyl glycidyl ether, butylglycidyl ether, 3, 3, 3-trifluoromethyl propylene oxide, Styrene oxide 98min., Propylene oxide hexafluoride, epoxy cyclohexane, 3-glycidoxypropyltrimewasxysilane, 2-(3, 4-epoxycyclohexyl) ethyl trimethoxy silane, N-glycidyl phthalic imidine, (nine fluorine normal-butyls) epoxide, perfluoro-ethyl glycidyl ether, Epicholorohydrin, epibromohydrin, N, N-diglycidylaniline, and 3-[2-(perfluoro hexyl) oxyethyl group]-1, 2-propylene oxide.
The compound in molecule with two oxirane rings include, for example ethylene glycol diglycidylether, polyethyleneglycol diglycidylether, propylene glycol diglycidylether, tripropyleneglycol diglycidyl ether, polypropylene glycol diglycidyl ether, neopentylglycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerin diglycidyl ether, 2,2-dibromoneopentyl glycol diglycidylether, 3,4-epoxy hexane ylmethyl-3 ', 4 '-epoxy hexane carboxylicesters and 3-(N, N-diglycidyl) TSL 8330.
The compound in molecule with 3 oxirane rings include, for example 2-[4-(2,3-glycidoxy) phenyl]-2-[4-[1, two [4-([2,3-glycidoxy] the phenyl)] ethyl of 1-] phenyl] propane (trade(brand)name " Tyke is (Tecmoa) VG3101L not ", (Mitsui Chemicals (stock) manufacture)).
The compound in molecule with 4 oxirane rings include, for example 1, and 3,5,6-four glycidyl group-2,4-hexylene glycol, 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 and 3-(N-allyl group-N-glycidyl) TSL 8330.
Except described, the example in molecule with the compound of oxirane ring can also enumerate the oligomer or polymkeric substance with oxirane ring.The monomer with oxirane ring include, for example (methyl) glycidyl acrylate, (methyl) vinylformic acid-3,4-epoxy cyclohexyl and (methyl) vinylformic acid methylglycidyl esters.
Other monomers carrying out copolymerization with the monomer with oxirane ring include, for example (methyl) vinylformic acid, (methyl) methyl acrylate, (methyl) ethyl propenoate, (methyl) isopropyl acrylate, (methyl) butyl acrylate, (methyl) isobutyl acrylate, (methyl) tert-butyl acrylate, (methyl) cyclohexyl acrylate, (methyl) benzyl acrylate, (methyl) 2-Hydroxy ethyl acrylate, (methyl) 2-hydroxypropyl acrylate, vinylbenzene, vinyl toluene, 1-chloro-4-methyl-benzene, (methyl) vinylformic acid-(3-ethyl-3-oxetanylmethoxy) methyl esters, N-N-cyclohexylmaleimide and N-phenylmaleimide.
The preferred concrete example with the polymkeric substance of the monomer of oxirane ring can enumerate poly (glycidyl methacrylate) etc.And, the preferred concrete example with the monomer of oxirane ring and the multipolymer of other monomers can enumerate N-phenylmaleimide-glycidyl methacrylate copolymer, N-N-cyclohexylmaleimide-glycidyl methacrylate copolymer, benzyl methacrylate-glycidyl methacrylate copolymer, butyl methacrylate glycidyl ester copolymer, methacrylic acid-2-hydroxy methacrylate-glycidyl methacrylate copolymer, methacrylic acid (3-ethyl-3-oxetanylmethoxy) methyl esters-glycidyl methacrylate copolymer and styrene-t glycidyl ester copolymer.
In these examples, particularly preferably N, N, N ', N '-four glycidyl group-m-xylene diamine, 1, two (the N of 3-, N-diglycidyl amino methyl) hexanaphthene, N, N, N ', N '-four glycidyl group-4,4 '-diaminodiphenyl-methane, trade(brand)name " Tyke is (Tecmoa) VG3101L not ", 3,4-epoxy hexane ylmethyl-3 ', 4 '-epoxy hexane carboxylicesters, N-phenylmaleimide-glycidyl methacrylate copolymer and 2-(3,4-epoxycyclohexyl) ethyl trimethoxy silane.
More system, epoxy compounds include, for example glycidyl ether, glycidyl ester, glycidyl amine, acrylic resin, glycidyl amides, glycidyl isocyanuric acid ester, chain fatty race type epoxy compounds and annular aliphatic type epoxy compounds containing epoxy group(ing).In addition, epoxy compounds represents the compound with epoxy group(ing), and epoxy resin represents the resin with epoxy group(ing).
Epoxy compounds include, for example glycidyl ether, glycidyl ester, glycidyl amine, acrylic resin, glycidyl amides, glycidyl isocyanuric acid ester, chain fatty race type epoxy compounds and annular aliphatic type epoxy compounds containing epoxy group(ing).
Glycidyl ether include, for example bisphenol A type epoxy compound, bisphenol F type epoxy compound, bisphenol S type epoxy compound, biphenol type epoxy compound, A Hydrogenated Bisphenol A-A type epoxy compounds, A Hydrogenated Bisphenol A-F type epoxy compounds, A Hydrogenated Bisphenol A-S type epoxy compounds, A Hydrogenated Bisphenol A type epoxy compounds, brominated bisphenol-A type epoxy compounds, brominated bisphenol-F type epoxy compounds, phenol novolak-type epoxy compound, cresol novolak type epoxy compound, brominated phenol novolak type epoxy compounds, bromination cresol novolak type epoxy compound, bisphenol A novolac type epoxy compounds, epoxy compounds containing naphthalene skeleton, aromatic series poly epihydric alcohol ether compound, dicyclopentadiene phenol epoxy compounds, ester ring type 2-glycidyl ether compound, aliphatic polyglycidyl ether compound, polysulfide type 2-glycidyl ether compound, and xenol (biphenol) type epoxy compounds.
Glycidyl ester include, for example 2-glycidyl ester cpds and glycidyl ester epoxy compound.
Glycidyl amine include, for example poly epihydric alcohol amine compound and glycidyl amine type epoxy resin.
Acrylic compounds containing epoxy group(ing) include, for example homopolymer and the multipolymer of the monomer with oxiranyl.
Glycidyl amides include, for example glycidyl amides type epoxy compounds.
Chain fatty race type epoxy compounds include, for example and is oxidized and the compound containing epoxy group(ing) of gained the carbon-to-carbon double bond of alkene (alkene) compound.
Annular aliphatic type epoxy compounds include, for example and is oxidized and the compound containing epoxy group(ing) of gained the carbon-to-carbon double bond of cyclic olefins.
Bisphenol A type epoxy compound include, for example jER828, jER1001, jER1002, jER1003, jER1004, jER1007, jER1010 and (is trade(brand)name; Mitsubishi Chemical's (stock) manufacture), end not great waves (Epotohto) YD-128 (trade(brand)name; Dongdu changes into (stock) manufactures), DER-331, DER-332, DER-324 (be trade(brand)name; Dow Chemical (TheDowChemicalCompany) manufacture), Chinese mugwort than clone (Epiclon) 840, Chinese mugwort than clone (Epiclon) 850, Chinese mugwort than clone (Epiclon) 1050 (be trade(brand)name; Di Aisheng (DIC) (stock) manufactures), Ai Fumaike (EPOMIK) R-140, Ai Fumaike (EPOMIK) R-301 and Ai Fumaike (EPOMlK) R-304 (is trade(brand)name; Mitsui Chemicals (stock) manufactures).
Bisphenol F type epoxy compound include, for example jER806, jER807, jER4004P and (is trade(brand)name; Mitsubishi Chemical's (stock) manufactures), end not great waves (Epotohto) YDF-170, end not great waves (Epotohto) YDF-175S, not great waves (Epotohto) YDF-2001 that ends (be trade(brand)name; Dongdu changes into (stock) manufacture), DER-354 (trade(brand)name; Dow Chemical manufacture), Chinese mugwort than clone (Epiclon) 830 and Chinese mugwort than clone (Epiclon) 835 (be trade(brand)name; Di Aisheng (stock) manufactures).
Biphenol type epoxy compound include, for example the epoxide of 2,2-two (4-hydroxy phenyl)-1,1,1,3,3,3-HFC-236fa.
A Hydrogenated Bisphenol A-A type epoxy compounds include, for example Sa Entao (Santohto) ST-3000 (trade(brand)name; Dongdu changes into (stock) manufacture), physical and chemical resin (RikaResin) HBE-100 (trade(brand)name; New Japan Chemical (stock) manufacture) and Dai En ?(DENACOL) EX-252 (trade(brand)name; Long rapids change into (stock) manufactures).
A Hydrogenated Bisphenol A type epoxy compounds include, for example the epoxide of hydrogenation 2,2-two (4-hydroxy phenyl)-1,1,1,3,3,3-HFC-236fa.
Brominated bisphenol-A type epoxy compounds include, for example jER5050, jER5051 and (is trade(brand)name; Mitsubishi Chemical's (stock) manufactures), end not great waves (Epotohto) YDB-360, not great waves (Epotohto) YDB-400 that ends (be trade(brand)name; Dongdu changes into (stock) manufactures), DER-530, DER-538 (be trade(brand)name; Dow Chemical manufacture), Chinese mugwort than clone (Epiclon) 152 and Chinese mugwort than clone (Epiclon) 153 (be trade(brand)name; Di Aisheng (stock) manufactures).
Phenol novolak-type epoxy compound include, for example jER152, jER154 and (is trade(brand)name; Mitsubishi Chemical's (stock) manufacture), YDPN-638 (trade(brand)name; Dongdu changes into company and manufactures), DEN431, DEN438 (be trade(brand)name: Dow Chemical manufacture), Chinese mugwort is than clone (Epiclon) N-770 (trade(brand)name; Di Aisheng (stock) manufactures), EPPN-20l and EPPN-202 (be trade(brand)name; Japan's chemical drug (stock) manufactures).
Cresol novolak type epoxy compound include, for example jER180S75 (trade(brand)name; Mitsubishi Chemical's (stock) manufactures), YDCN-701, YDCN-702 (be trade(brand)name; Dongdu change into company manufacture), Chinese mugwort than clone (Epiclon) N-665, Chinese mugwort than clone (Epiclon) N-695 (be trade(brand)name; Di Aisheng (stock) manufactures), EOCN-102S, EOCN-103S, EOCN-104S, EOCN-1020, EOCN-1025 and EOCN-1027 (be trade(brand)name; Japan's chemical drug (stock) manufactures).
Bisphenol A novolac type epoxy compounds include, for example jER157S70 (trade(brand)name; Mitsubishi Chemical's (stock) manufactures) and Chinese mugwort ratio clone (Epiclon) N-880 (trade(brand)name; Di Aisheng (stock) manufactures).
Epoxy compounds containing naphthalene skeleton include, for example Chinese mugwort and (is trade(brand)name than clone (Epiclon) HP-4700, Chinese mugwort than clone (Epiclon) HP-4770 than clone (Epiclon) HP-4032, Chinese mugwort; Di Aisheng (stock) manufactures) and NC-7000 (trade(brand)name; Chemical drug Inc. of Japan makes).
Aromatic series poly epihydric alcohol ether compound include, for example Resorcinol diglycidylether (following formula EP-1), diglycidyl ether catechol (following formula EP-2), resorcinol diglycidyl ether (following formula EP-3), 2-[4-(2, 3-glycidoxy) phenyl]-2-[4-[1, two [the 4-([2 of 1-, 3-glycidoxy] phenyl)] ethyl] phenyl] propane (following formula EP-4), three (4-glycidoxypropyl phenyl) methane (following formula EP-5), jER1031S, jER1032H60 (is trade(brand)name, Mitsubishi Chemical's (stock) manufactures), Tyke neat (TACTIX)-742 (trade(brand)name, Dow Chemical manufacture), Dai En ?(DENACOL) EX-201 (trade(brand)name, long rapids changes into (stock) manufactures), De Puen (DPPN)-503, DPPN-502H, DPPN-501H, NC6000 (be trade(brand)name, Japan chemical drug (stock) manufacture), Tyke not (Tecmoa) VG3101L (trade(brand)name, Mitsui Chemicals (stock) manufactures), the compound represented by following formula EP-6 and the compound represented by following formula EP-7.
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Dicyclopentadiene phenol epoxy compounds include, for example Tyke neat (TACTIX)-556 (trade(brand)name; Dow Chemical manufactures) and Chinese mugwort ratio clone (Epiclon) HP-7200 (trade(brand)name; Di Aisheng (stock) manufactures).
Ester ring type 2-glycidyl ether compound include, for example cyclohexanedimethanodiglycidyl diglycidyl ether compound and physical and chemical resin (RikaResin) DME-100 (trade(brand)name; New this physics and chemistry of order (stock) manufactures).
Aliphatic polyglycidyl ether compound include, for example ethylene glycol diglycidylether (following formula EP-8), diethylene glycol diglycidyl glyceryl ether (following formula EP-9), polyethyleneglycol diglycidylether, propylene glycol diglycidylether (following formula EP-10), tripropyleneglycol diglycidyl ether (following formula EP-11), polypropylene glycol diglycidyl ether, neopentylglycol diglycidyl ether (following formula EP-12), BDDE (following formula EP-13), 1,6-hexanediol diglycidyl ether (following formula EP-14), dibromoneopentyl glycol diglycidylether (following formula EP-15), Dai En ?(DENACOL) EX-810, Dai En ?(DENACOL) EX-851, Dai En ?(DENACOL) EX-8301, Dai En ?(DENACOL) EX-911, Dai En ?(DENACOL) EX-920, Dai En ?(DENACOL) EX-931, Dai En ?(DENACOL) EX-211, Dai En ?(DENACOL) EX-212, Dai En ?(DENACOL) EX-313 (be trade(brand)name, long rapids changes into (stock) manufactures), DD-503 (trade(brand)name, (stock) Ai Dike (ADEKA) manufacture), physical and chemical resin (RikaResin) W-100 (trade(brand)name, new Japan Chemical (stock) manufacture), 1,3,5,6-four glycidyl group-2,4-hexylene glycol (following formula EP-16), glycerine polyglycidyl ether, Sorbitol Powder polyglycidyl ether, TriMethylolPropane(TMP) polyglycidyl ether, tetramethylolmethane polyglycidyl ether, Dai En ?(DENACOL) EX-313, Dai En ?(DENACOL) EX-611, Dai En ?(DENACOL) EX-321 and Dai En ?(DENACOL) EX-411 (be trade(brand)name, long rapids change into (stock) manufactures).
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Polysulfide type 2-glycidyl ether compound include, for example FLDP-50 and FLDP-60 and (is trade(brand)name; East beautiful thiorubber (TorayThiokol) (stock) manufactures).
Biphenyl phenolic epoxy compounds include, for example YX-4000, YL-6121H and (is trade(brand)name; Mitsubishi Chemical's (stock) manufactures), NC-3000P and NC-3000S (be trade(brand)name; Japan's chemical drug (stock) manufactures).
2-glycidyl ester cpds include, for example terephthalic acid diglycidyl ester (following formula EP-17), phthalic acid diglycidyl ester (following formula EP-18), two (the 2-methyl oxiranyl methyl) ester (following formula EP-19) of phthalic acid, hexahydrophthalic acid diglycidyl ester (following formula EP-20), compound represented by following formula EP-21, compound represented by following formula EP-22, and the compound represented by following formula EP-23.
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Glycidyl ester epoxy compound include, for example jER871, jER872 and (is trade(brand)name; Mitsubishi Chemical's (stock) manufacture), Chinese mugwort than clone (Epiclon) 200, Chinese mugwort than clone (Epiclon) 400 (be trade(brand)name; Di Aisheng (stock) manufactures), wear grace ?(DENACOL) EX-711 and wear grace ?(DENACOL) EX-721 and (be trade(brand)name; Long rapids change into (stock) manufactures).
Poly epihydric alcohol amine compound include, for example N, N-diglycidylaniline (following formula EP-24), N, N-diglycidyl-Ortho Toluidine (following formula EP-25), N, N-diglycidyl-meta-aminotoluene (following formula EP-26), N, N-diglycidyl-2, 4, 6-bromamide (following formula EP-27), 3-(N, N-diglycidyl) TSL 8330 (following formula EP-28), N, N, O-triglycidyl group-p-aminophenol (following formula EP-29), N, N, O-triglycidyl group-Metha Amino Phenon (following formula EP-30), N, N, N ', N '-four glycidyl group-4, 4 '-diaminodiphenyl-methane (following formula EP-31), N, N, N ', N '-four glycidyl group-m-xylene diamine (Tai Lade (TETRAD)-X (trade(brand)name, Mitsubishi's gas chemistry (stock) manufactures), following formula EP-32), 1,3-two (N, N-diglycidyl amino methyl) hexanaphthene (Tai Lade (TETRAD)-C (trade(brand)name, Mitsubishi's gas chemistry (stock) manufactures), following formula EP-33), Isosorbide-5-Nitrae-bis-(N, N-diglycidyl amino methyl) hexanaphthene (following formula EP-34), 1,3-two (N, N-diglycidyl is amino) hexanaphthene (following formula EP-35), Isosorbide-5-Nitrae-bis-(N, N-diglycidyl is amino) hexanaphthene (following formula EP-36), 1,3-two (N, N-diglycidyl is amino) benzene (following formula EP-37), Isosorbide-5-Nitrae-bis-(N, N-diglycidyl is amino) benzene (following formula EP-38), two (N, N-diglycidyl amino methyl) dicyclo [2.2.1] heptane (following formula EP-39) of 2,6-, N, N, N ', N '-four glycidyl group-4，4′-diaminodicyclohexylmethane (following formula EP-40), 2,2 '-dimethyl-(N, N, N ', N '-four glycidyl group)-4,4 '-benzidine (following formula EP-41), N, N, N ', N '-four glycidyl group-4,4 '-diamino-diphenyl ether (following formula EP-42), 1,3,5-tri-(4-(N, N-diglycidyl) amino-benzene oxygen) benzene (following formula EP-43), 2,4,4 '-three (N, N-diglycidyl is amino) diphenyl ether (following formula EP-44), three (4-(N, N-diglycidyl) aminophenyl) methane (following formula EP-45), 3,4,3 ', 4 '-four (N, N-diglycidyl is amino) biphenyl (following formula EP-46), 3,4,3 ', 4 '-four (N, N-diglycidyl is amino) diphenyl ether (following formula EP-47), compound represented by following formula EP-48, and the compound represented by following formula EP-49.
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The homopolymer with the monomer of oxiranyl include, for example poly (glycidyl methacrylate).The multipolymer with the monomer of oxiranyl include, for example N-phenylmaleimide-glycidyl methacrylate copolymer, N-N-cyclohexylmaleimide-glycidyl methacrylate copolymer, benzyl methacrylate-glycidyl methacrylate copolymer, butyl methacrylate glycidyl ester copolymer, methacrylic acid-2-hydroxy methacrylate-glycidyl methacrylate copolymer, methacrylic acid (3-ethyl-3-oxetanylmethoxy) methyl esters-glycidyl methacrylate copolymer, and styrene-t glycidyl ester copolymer.
The monomer with oxiranyl include, for example (methyl) glycidyl acrylate, (methyl) vinylformic acid-3,4-epoxy cyclohexyl and (methyl) vinylformic acid methylglycidyl esters.
As for have oxiranyl monomer multipolymer in the monomer with oxiranyl beyond other monomers, include, for example (methyl) vinylformic acid, (methyl) methyl acrylate, (methyl) ethyl propenoate, (methyl) isopropyl acrylate, (methyl) butyl acrylate, (methyl) isobutyl acrylate, (methyl) tert-butyl acrylate, (methyl) cyclohexyl acrylate, (methyl) benzyl acrylate, (methyl) 2-Hydroxy ethyl acrylate, (methyl) 2-hydroxypropyl acrylate, vinylbenzene, vinyl toluene, 1-chloro-4-methyl-benzene, (methyl) vinylformic acid (3-ethyl-3-oxetanylmethoxy) methyl esters, N-N-cyclohexylmaleimide, and N-phenylmaleimide.
Glycidyl isocyanuric acid ester include, for example 1,3,5-triglycidyl group-1,3,5-triazine-2,4,6-(1H, 3H, 5H)-triketone (following formula EP-50), 1,3-diglycidyl-5-allyl group-1,3,5-triazines-2,4,6-(1H, 3H, 5H)-triketone (following formula EP-51) and glycidyl isocyanuric acid ester type epoxy resin.
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Chain fatty race type epoxy compounds include, for example epoxidized polybutadiene and Ai Fulide (Epolead) PB3600 (trade(brand)name; (stock) Daicel manufacture).
Annular aliphatic type epoxy compounds include, for example 3,4-epoxy hexane ylmethyl-3 ', 4 '-epoxy hexane carboxylicesters (Sai Luo West Germany (Celloxide) 2021 (trade(brand)name; The manufacture of (stock) Daicel), following formula EP-52), 2-methyl-3,4-epoxycyclohexyl-methyl-2 '-methyl-3 ', 4 '-epoxycyclohexylcarboxylate (following formula EP-53), 2,3-cyclopentane epoxide-2 ', 3 '-cyclopentane epoxide ether (following formula EP-54), 6-caprolactone modification 3,4-epoxycyclohexyl-methyl-3 ', 4 '-epoxycyclohexane carboxylate, 1,2: 8,9-diepoxy limonene (Sai Luo West Germany (Celloxide) 3000 (trade(brand)name; The manufacture of (stock) Daicel), following formula EP-55), the compound represented by following formula EP-56, CY-175, CY-177, CY-179 (be trade(brand)name; Vapour Ba-Jia Ji chemical company (TheCiba-GeigyChemicalCorp.) manufacture (can from Hensel step Japan (stock) (HuntsmanJapanK.K.) obtain)), EHPD-3150 (trade(brand)name; The manufacture of (stock) Daicel) and annular aliphatic type epoxy resin.
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Epoxy compounds is preferably poly epihydric alcohol amine compound, bisphenol A novolac type epoxy compounds, cresol novolak type epoxy compound, and more than one of annular aliphatic type epoxy compounds, be preferably N, N, N ', N '-four glycidyl group-m-xylene diamine, 1, two (the N of 3-, N-diglycidyl amino methyl) hexanaphthene, N, N, N ', N '-four glycidyl group-4, 4 '-diaminodiphenyl-methane, trade(brand)name " Tyke is (Tecmoa) VG3101L not ", 3, 4-epoxy hexane ylmethyl-3 ', 4 '-epoxy hexane carboxylicesters, N-phenylmaleimide-glycidyl methacrylate copolymer, N, N, O-triglycidyl group-p-aminophenol, bisphenol A novolac type epoxy compounds, and more than one of cresol novolak type epoxy compound.
And such as liquid crystal aligning agent of the present invention can also contain various additive further.Various additive include, for example macromolecular compound beyond polyamic acid and derivative thereof and low molecular compound, can according to respective object choice for use.
Such as, described macromolecular compound can be set forth in the macromolecular compound for solubility in organic solvent.The electrical specification of the liquid crystal orientation film that self-acting control is formed or the viewpoint of orientation are considered, are preferably made an addition in liquid crystal aligning agent of the present invention by this kind of macromolecular compound.This macromolecular compound include, for example polymeric amide, urethane, polyureas, polyester, polyepoxide, polyester polyol, silicone-modified polyurethane and silicone modified polyester.
And, as described low molecular compound, such as, 1) when expecting can enumerate tensio-active agent, 2 for realizing this object when improving coating) static inhibitor, 3 can be enumerated when needing to improve antistatic) when expect can to enumerate when improving the adhesion with substrate silane coupling agent or titanium system coupling agent and, 4) can imidization catalyst be enumerated when carrying out imidization at low temperatures.
Silane coupling agent include, for example vinyltrimethoxy silane, vinyltriethoxysilane, N-(2-amino-ethyl)-3-amino propyl methyl dimethoxysilane, N-(2-amino-ethyl)-3-amino propyl methyl Trimethoxy silane, p-aminophenyl Trimethoxy silane, p-aminophenyl triethoxyl silane, m-aminophenyl base Trimethoxy silane, m-aminophenyl ethyl triethoxy silicane alkane, 3-TSL 8330, APTES, 3-glycidoxypropyltrimewasxysilane, 3-glycidoxypropyl dimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-r-chloropropyl trimethoxyl silane, 3-methacryloxypropyl trimethoxy silane, 3-mercaptopropyi Trimethoxy silane, N-(1, 3-dimethylbutylene)-3-(triethoxysilicane alkyl)-1-propyl group amine, and N, N '-bis-[3-(Trimethoxy silane base) propyl group] quadrol.Preferred silane coupling agent is APTES.
Imidization catalyst include, for example the aliphatics amines such as Trimethylamine 99, triethylamine, tripropyl amine, Tributylamine; DMA, N, N-Diethyl Aniline, through methyl substituted aniline, the aromatic amine such as aniline that replaces through hydroxyl; Pyridine, through methyl substituted pyridine, the pyridine replaced through hydroxyl, quinoline, through methyl substituted quinoline, the quinoline replaced through hydroxyl, isoquinoline 99.9, through methyl substituted isoquinoline 99.9, the isoquinoline 99.9 replaced through hydroxyl, imidazoles, through methyl substituted imidazoles, the ring type amine such as imidazoles that replaces through hydroxyl.Described imidization catalyst be preferably selected from DMA, ortho-aminophenol, a hydroxyanilines, para hydroxybenzene amine, adjacent pyridone, a pyridone, to one or more of pyridone and isoquinoline 99.9.
The addition of silane coupling agent is generally 0 % by weight ~ 20 % by weight of the gross weight of polyamic acid or derivatives thereof, is preferably 0.1 % by weight ~ 10 % by weight.
Usually for the carbonyl of polyamic acid or derivatives thereof, the addition of imidization catalyst is 0.01 equivalent ~ 5 equivalent, is preferably 0.05 equivalent ~ 3 equivalent.
The addition of other additives is different because of its purposes, normally polyamic acid or derivatives thereof gross weight 0 % by weight ~ 100 % by weight, be preferably 0.1 % by weight ~ 50 % by weight.
Polyamic acid or derivatives thereof of the present invention can manufacture in the same manner as the known polyamic acid or derivatives thereof used in the formation of polyimide film.Total Intake Quantity of tetracarboxylic dianhydride is preferably set to and roughly waits mole (mol ratio is about 0.9 ~ 1.1) with the total mole number of diamines.
The molecular weight of polyamic acid or derivatives thereof of the present invention is preferably 7,000 ~ 500,000 in the weight average molecular weight of polystyrene conversion (M.W.), is more preferably 10,000 ~ 200,000.The molecular weight of described polyamic acid or derivatives thereof can be obtained according to utilizing the mensuration of gel permeation chromatography (GelPermeationChromatography, GPC) method.
By such as under type, polyamic acid or derivatives thereof of the present invention confirms that it exists: utilize infrared rays (Infrared, IR), nucleus magnetic resonance (NuclearMagneticResonance, NMR) to making it precipitate with a large amount of poor solvents, analyze by the solids component of gained.And, the resolvent of described polyamic acid or derivatives thereof is formed with the aqueous solution of the highly basic such as KOH or NaOH, with gas chromatography (GC), high pressure liquid chromatography (HPLC) (HPLC) or gas chromatography-mass spectrum (GC-MS), the extract utilizing organic solvent to extract from this resolvent is analyzed, used monomer can be determined thus.
And such as consider from the viewpoint of the adjustment of the coating of liquid crystal aligning agent or the concentration of described polyamic acid or derivatives thereof, liquid crystal aligning agent of the present invention can also contain solvent further.Described solvent if having the solvent of the ability of dissolving macromolecule component, then can be applied with no particular limitation.The system that described solvent is extensively included in the macromolecule component such as polyamic acid, soluble polyimide makes step Sudden or the normally used solvent in purposes aspect, can be suitable for selecting according to application target.Described solvent can be a kind of also can be two or more mixed solvents.
Solvent can enumerate described polyamic acid or derivatives thereof mother liquor or to improve other solvents for the purpose of coating.
Can enumerate as the aprotic polar organic solvent for mother liquor for polyamic acid or derivatives thereof: METHYLPYRROLIDONE, dimethyl-imidazolinone (imidazolidinone), N-methyl caprolactam, N-methyl propanamide, N, N-N,N-DIMETHYLACETAMIDE, dimethyl sulfoxide (DMSO), N, the lactones such as dinethylformamide, N, N-diethylformamide, diethyl acetamide, gamma-butyrolactone.
Can enumerate by the example improving other solvents for the purpose of coating etc.: lactic acid alkyl ester, 3-methyl-3-methoxybutanol, tetralin, isophorone, the ethylene glycol monoalkyl ethers such as ethylene glycol monobutyl ether, the Diethylene Glycol monoalky lethers such as diethylene glycol monoethyl ether, glycol monoalkyl or phenylacetic acid ester, triethylene glycol monoalky lether, propylene glycol monomethyl ether, the propylene-glycol monoalky lethers such as propylene glycol monobutyl ether, the dialkyl malonates such as diethyl malonate, the dipropylene glycol monoalkylether such as dipropylene glycol monomethyl ether, the ester cpds such as their acetate esters.
In these compounds, described solvent is METHYLPYRROLIDONE, dimethyl-imidazolinone, gamma-butyrolactone, ethylene glycol monobutyl ether, diethylene glycol monoethyl ether, propylene glycol monobutyl ether, propylene glycol monomethyl ether and dipropylene glycol monomethyl ether particularly preferably.
The concentration of the polyamic acid in alignment agent of the present invention is preferably 0.1 % by weight ~ 40 % by weight.When being coated on substrate by this alignment agent, sometimes need the operation of the polyamic acid used in advance contained by solvent cut to adjust thickness.
Solid component concentration in alignment agent of the present invention is not particularly limited, if select optimal value according to following various coating method.Under normal circumstances, in order to suppress inequality when being coated with or pin hole (pinhole) etc., for varnish weight, being preferably 0.1 % by weight ~ 30 % by weight, being more preferably 1 % by weight ~ 10 % by weight.
The viscosity of liquid crystal aligning agent of the present invention is due to the method for coating, the concentration of polyamic acid or derivatives thereof, the kind of polyamic acid or derivatives thereof used, the kind of solvent and ratio and preferably scope is different.Such as, be 5mPas ~ 100mPas (being more preferably 10mPas ~ 80mPas) when being coated with when utilizing printing press.If be less than 5mPas, then become and be difficult to obtain sufficient thickness; If more than 100mPas, then there is the phenomenon that the uneven change of printing is large.When being coated with when utilizing spin coating, what be applicable to is 5mPas ~ 200mPas (being more preferably 10mPas ~ 100mPas).When being coated with when using ink-jet coating apparatus, what be applicable to is 5mPas ~ 50mPas (being more preferably 5mPas ~ 20mPas).The viscosity of liquid crystal aligning agent measures by rotational viscometry, such as, use rotational viscosimeter (the TVE-20L type that eastern machine industry manufactures) and measure (measuring temperature is 25 DEG C).
Described in detail about liquid crystal orientation film of the present invention.Liquid crystal orientation film of the present invention is the film formed by heating the film of aforesaid liquid crystal aligning agent of the present invention.Liquid crystal orientation film of the present invention obtains by being made the usual method of liquid crystal orientation film by liquid crystal aligning agent.Such as, liquid crystal orientation film of the present invention can be passed through following steps and obtains: the step forming the step of the film of liquid crystal aligning agent of the present invention, carry out the step of heat drying, carry out heating and calcining.About liquid crystal orientation film of the present invention, can also optionally carry out friction treatment to through heat-drying step, heating and calcining step and the film of gained and give anisotropy as described later.Or rayed can also be carried out after film-coating procedures, heat-drying step, or after heating and calcining step, carry out rayed and give anisotropy.And, can also use with liquid crystal orientation film as vertical orientated (VerticalAlignment, the VA) not carrying out friction treatment.
Film is formed by such as under type: on the substrate of liquid crystal display device, be coated with liquid crystal aligning agent of the present invention in the same manner as the making of common liquid crystal orientation film.Substrate can be enumerated and can also be provided with tin indium oxide (IndiumTinOxide, ITO), indium zinc oxide (In 2o 3-ZnO, IZO), Indium sesquioxide gallium zinc (In-Ga-ZnO 4, IGZO) and the glass substrate of electrode or the colored filter etc. such as electrode.
The method coated by liquid crystal aligning agent on substrate there will be a known turner (spinner) method, print process, pickling process, dripping method, ink jet method etc. usually.These methods also can similarly be applied in the present invention.
Described heat-drying step there will be a known the method for carrying out heat treated in baking oven or infra-red furnace, the method etc. of carrying out heat treated on hot plate usually.Implement at the temperature of heat-drying step preferably in the transpirable scope of solvent, implement at more preferably lower for the temperature relative to heating and calcining step temperature.Specifically, heat drying temperature is preferably the scope of 30 DEG C ~ 150 DEG C, is more preferably the scope of 50 DEG C ~ 120 DEG C.
Carry out under the condition that described heating and calcining step can present needed for dehydration, ring-closure reaction at described polyamic acid or derivatives thereof.The calcining of described film there will be a known the method for carrying out heat treated in baking oven or infra-red furnace, the method etc. of carrying out heat treated on hot plate usually.These methods also can similarly be applied in the present invention.Preferably under normal circumstances at the temperature of 100 DEG C ~ about 300 DEG C, carry out 1 minute ~ 3 hours, be more preferably 120 DEG C ~ 280 DEG C, be more preferably 150 DEG C ~ 250 DEG C further.
In the formation method of liquid crystal orientation film of the present invention, in order to make mesomorphic phase orientation in one direction for horizontal and/or vertical, giving anisotropic method to alignment films and can be suitable for using the known formation method such as rubbing manipulation or optical alignment method.Particularly can be suitable for using optical alignment method.
The liquid crystal orientation film of the present invention of rubbing manipulation is used to can be passed through following steps and formed: liquid crystal aligning agent of the present invention to be coated the step on substrate, the substrate being coated with alignment agent carried out to the step of heat drying, this film carried out to the step of heating and calcining, film carried out to the step of friction treatment.
If friction treatment can be carried out in the same manner as the friction treatment of the orientation process in order to carry out common liquid crystal orientation film, in liquid crystal orientation film of the present invention, obtain the condition postponed fully.Preferred condition is mao intrusion is 0.2mm ~ 0.8mm, platform movement speed is 5mm/sec ~ 250mm/sec, roller speed of rotation is 500rpm ~ 2,000rpm.
Described in detail about utilizing the formation method of the liquid crystal orientation film of the present invention of optical alignment method.Use the liquid crystal orientation film of the present invention of optical alignment method to be formed by such as under type: after carrying out heat drying to film, irradiate radioactive rays linear polarization or without polarisation, give film anisotropy therefrom, heating and calcining carried out to this film.Or formed by such as under type: heat drying is carried out to film, after carrying out heating and calcining, irradiate radioactive rays linear polarization or without polarisation.Ask for tropism aspect consider, the irradiating step of radioactive rays is preferably carried out before heating and calcining step.
In addition, in order to improve the liquid crystal aligning ability of liquid crystal orientation film, can also one in the face of film carry out heat one side irradiate radioactive rays linear polarization or without polarisation.The irradiation of radioactive rays can be carried out in the step of film being carried out to heat drying or the step of carrying out heating and calcining, can also carry out between heat-drying step and heating and calcining step.Heat drying temperature in this step is preferably the scope of 30 DEG C ~ 150 DEG C, is more preferably the scope of 50 DEG C ~ 120 DEG C.And the heating and calcining temperature in this step is preferably the scope of 30 DEG C ~ 300 DEG C, be more preferably the scope of 50 DEG C ~ 250 DEG C.
Radioactive rays such as can use ultraviolet or the visible ray of the light comprising 150nm ~ 800nm wavelength, preferably comprise the ultraviolet of the light of 300nm ~ 400nm wavelength.And, linear polarization can be used or without polarisation.If these light can give the light of liquid crystal aligning ability to described film, be then not particularly limited, when for revealing strong orientation restraint to liquid crystal watch, preferred linear polarization.
Even the low-energy rayed of liquid crystal orientation film of the present invention also can demonstrate high liquid crystal aligning ability.The irradiation dose of the linear polarization in described radiation exposure step is preferably 0.05J/cm 2~ 20J/cm 2, be more preferably 0.5J/cm 2~ 10J/cm 2.And the wavelength of linear polarization is preferably 200nm ~ 400nm, is more preferably 300nm ~ 400nm.Linear polarization is not particularly limited relative to the irradiating angle on film surface, when for revealing strong orientation restraint to liquid crystal watch, considers from the viewpoint shortening the orientation process time, preferably vertical as far as possible for film surface.And, liquid crystal orientation film of the present invention by irradiate linear polarization and make liquid crystal aligning in for the polarization direction of linear polarization on vertical direction.
When for showing tilt angle, the light irradiated described film can be linear polarization in the same manner as described, also can be without polarisation.When for showing tilt angle, 0.05J/cm is preferably to the irradiation dose of the light that described film irradiates 2~ 20J/cm 2, be particularly preferably 0.5J/cm 2~ 10J/cm 2, its wavelength is preferably 250nm ~ 400nm, is particularly preferably 300nm ~ 380nm.When for showing tilt angle, the light that described film irradiates being not particularly limited relative to the irradiating angle on described film surface, considering from the viewpoint shortening the orientation process time, being preferably 30 degree ~ 60 degree.
Irradiate radioactive rays linear polarization or without the step of polarisation in the light source that uses can unrestrictedly use: extra-high-pressure mercury vapour lamp, high pressure mercury vapour lamp, Cooper-Hewitt lamp, deep UV (DeepUV) lamp, halogen lamp, metal halide lamp (metalhalidelamp), high-power metal halide lamp, xenon lamp, mercury xenon lamp, Excimer lamp, KrF excimer laser, luminescent lamp, photodiode (LightEmittingDiode, LED) lamp, sodium vapor lamp, microwave-excited electrodeless lamp etc.
Liquid crystal orientation film of the present invention obtains aptly by comprising the method for other steps beyond abovementioned steps further.Such as, although liquid crystal orientation film of the present invention is without the need to the step of cleaning the film after calcining or radiation exposure with scavenging solution, when other steps, can cleaning step be set.
The purging method of scavenging solution is utilized to enumerate: to scrub (brushing), spraying (jetspray), steam flushing or ultrasonic cleaning etc.These methods can be carried out separately, also can be used together.Scavenging solution can use pure water, or the various alcohols such as methyl alcohol, ethanol, Virahol, the halogen series solvents such as benzene,toluene,xylene etc. are aromatic hydrocarbon based, methylene dichloride, the ketone such as acetone, methyl ethyl ketone, but is not limited to these scavenging solutions.Certainly, these scavenging solutions need use through the few scavenging solution of the impurity of abundant purifying.This kind of purging method can also be applied in the described cleaning step in the formation of liquid crystal orientation film of the present invention.
In order to improve the liquid crystal aligning ability of liquid crystal orientation film of the present invention, at the front and back of the front and back of heating and calcining step, rubbing process or polarisation or can use without the front and back of the radiation exposure of polarisation the anneal utilizing heat or light.In this anneal, annealing temperature is 30 DEG C ~ 180 DEG C, is preferably 50 DEG C ~ 150 DEG C, and the time is preferably 1 minute ~ 2 hours.And the annealing light used in anneal can enumerate UV lamp, luminescent lamp, LED etc.The irradiation dose of light is preferably 0.3J/cm 2~ 10J/cm 2.
The thickness of liquid crystal orientation film of the present invention is not particularly limited, and is preferably 10nm ~ 300nm, is more preferably 30nm ~ 150nm.The thickness of liquid crystal orientation film of the present invention can the known determining film thickness device such as the section of use difference meter or ellipsometer (ellipsometer) and measuring.
The feature of liquid crystal orientation film of the present invention is to have king-sized oriented anisotropic.This kind of anisotropic large I utilizes the method for use polarisation IR described in Japanese Patent Laid-Open 2005-275364 publication etc. and evaluates.And, can also utilize like that as illustrated in the examples below and use the method for elliptical polarization and evaluate.Specifically, light splitting ellipsometer can be utilized to measure the length of delay of liquid crystal orientation film.The length of delay of film and the orientation degree of main polymer chain become large pro rata.Also namely, what have large length of delay has large orientation degree, when using when making liquid crystal orientation film, thinks that having larger anisotropic alignment films has large orientation restraint relative to liquid-crystal composition.
The feature of liquid crystal orientation film of the present invention is: painted few, transmissivity is high.Transmissivity can use ultraviolet-visible pectrophotometer and evaluate.In order to show good display characteristic, according to the mean value of the absorbancy of 380nm ~ 780nm and the transmissivity calculated is preferably more than 85%, be more preferably more than 87%.
Liquid crystal orientation film of the present invention can be suitably used in the liquid crystal display device of Transverse electric-field type.In for the liquid crystal display device of Transverse electric-field type, Pt angle is less, and liquid crystal aligning ability is higher, then black display level in the dark state more uprises, and contrast gradient more improves.Pt angle is preferably less than 0.1 °.
Alignment films of the present invention, except the orientation purposes of liquid-crystal display liquid-crystal composition, can also be used in the tropism control of optical compensation material or other all liquid crystal materials.And alignment films of the present invention has large anisotropy, therefore can separately in optical compensation material applications.
Described in detail about liquid crystal display device of the present invention.
The invention provides a kind of liquid crystal display device, its be comprise subtend configuration a pair substrate, be formed in described a pair substrate separately subtend and one of them face or two faces electrode, be formed in described a pair substrate separately the face of subtend liquid crystal orientation film, be formed in the liquid crystal display device of the liquid crystal layer between described a pair substrate, described liquid crystal orientation film is alignment films of the present invention.
If the electrode that described electrode can be formed at a face of substrate is then not particularly limited.This kind of electrode include, for example the vapor-deposited film etc. of ITO or metal.And electrode can be formed on whole of one of them face of substrate, such as, can also be formed as the desired shape of patterning.The described desired shape of electrode include, for example combed or spination (zigzag) structure etc.Electrode can be formed on one of them substrate in a pair substrate, also can be formed on two substrates.The formation form of electrode is different according to the kind of liquid crystal display device, such as, when IPS type liquid crystal display device, described a pair substrate one of them on configure electrode; When other liquid crystal display device, two of described a pair substrate configure electrode.Described substrate or electrode form described liquid crystal orientation film.
Described liquid crystal layer be formed liquid crystal orientation film in the face of towards the form of described a pair substrate clamping liquid-crystal composition formed.In the formation of liquid crystal layer, micropartical or resin sheet etc. can be optionally used to be situated between every the spacer forming appropriate intervals between described a pair substrate.
There is no particular restriction for liquid-crystal composition, can use the various liquid-crystal compositions that dielectric anisotropy (dielectricanisotropy) is plus or minus.Dielectric anisotropy is that positive preferred liquid-crystal composition can enumerate Japanese Patent No. 3086228 publication, Japanese Patent No. 2635435 publication, Japanese Patent JP-A 5-501735 publication, Japanese Patent Laid-Open 8-157826 publication, Japanese Patent Laid-Open 8-231960 publication, Japanese Patent Laid-Open 9-241644 publication (EP885272A1), Japanese Patent Laid-Open 9-302346 publication (EP806466A1), Japanese Patent Laid-Open 8-199168 publication (EP722998A1), Japanese Patent Laid-Open 9-235552 publication, Japanese Patent Laid-Open 9-255956 publication, Japanese Patent Laid-Open 9-241643 publication (EP885271A1), Japanese Patent Laid-Open 10-204016 publication (EP844229A1), Japanese Patent Laid-Open 10-204436 publication, Japanese Patent Laid-Open 10-231482 publication, Japanese Patent Laid-Open 2000-087040 publication, liquid-crystal composition described in Japanese Patent Laid-Open 2001-48822 publication etc.
Can also be that the optically active compound adding more than one in the liquid-crystal composition of plus or minus uses in dielectric anisotropy.
Be that negative liquid-crystal composition is illustrated about described dielectric anisotropy.The liquid-crystal composition of negative dielectric anisotropy include, for example the composition of at least one liquid crystalline cpd as the 1st composition of the group containing the liquid crystalline cpd be selected from represented by following formula (NL-1).
[changing 154]
Herein, R 1aand R 2aindependent for carbon number be 1 ~ 12 alkyl, carbon number be 1 ~ 12 alkoxyl group, carbon number be 2 ~ 12 thiazolinyl or the carbon number that replaced by fluorine of at least one hydrogen be the thiazolinyl of 2 ~ 12; Ring A 2and ring B 2independent is Isosorbide-5-Nitrae-cyclohexylidene, tetrahydropyrans (tetrahydropyran)-2,5-bis-base, 1,3-diox-2, fluoro-Isosorbide-5-Nitrae-the phenylene of 5-bis-base, Isosorbide-5-Nitrae-phenylene, 2-, 2, fluoro-Isosorbide-5-Nitrae-the phenylene of 5-bis-, 2,3-bis-fluoro-1, chloro-Isosorbide-5-Nitrae-the phenylene of the fluoro-3-of 4-phenylene, 2-, 2,3-bis-fluoro-6-methyl isophthalic acids, 4-phenylene, 2,6-naphthalene two bases or 7,8-difluoro chroman (chromane)-2,6-bis-base, herein, ring A 2and ring B 2at least one be the fluoro-Isosorbide-5-Nitrae-phenylene of 2,3-bis-, the chloro-Isosorbide-5-Nitrae-phenylene of the fluoro-3-of 2-, 2,3-bis-fluoro-6-methyl isophthalic acids, 4-phenylene or 7,8-difluoro chroman-2,6-bis-base; Z 1independent is singly-bound ,-(CH 2) 2-,-CH 2o-,-COO-or-CF 2o-; J is 1,2 or 3.
The concrete example of the liquid crystalline cpd of described formula (NL-1) can enumerate the compound represented by following formula (NL-1-1) ~ formula (NL-1-32).
[changing 155]
[changing 156]
[changing 157]
Herein, R 1aand R 2aindependent for carbon number be 1 ~ 12 alkyl, carbon number be 1 ~ 12 alkoxyl group, carbon number be 2 ~ 12 thiazolinyl or the carbon number that replaced by fluorine of at least one hydrogen be the thiazolinyl of 2 ~ 12.In order to make the raising such as stability for ultraviolet or heat, preferred R 1aand R 2ato be carbon number be 1 ~ 12 alkyl, or in order to make the absolute value of dielectric anisotropy improve, preferred R 1aand R 2ato be carbon number be 1 ~ 12 alkoxyl group.
Preferred alkyl is methyl, ethyl, propyl group, butyl, amyl group, hexyl, heptyl or octyl group.In order to make viscosity reduce, preferred alkyl is ethyl, propyl group, butyl, amyl group or heptyl.
Preferred alkoxyl group be methoxyl group, oxyethyl group, propoxy-, butoxy, pentyloxy, hexyloxy or heptan oxygen base.In order to make viscosity reduce, preferred alkoxyl group is methoxy or ethoxy.
Preferred thiazolinyl is vinyl, 1-propenyl, 2-propenyl, 1-butylene base, crotyl, 3-butenyl, 1-pentenyl, pentenyl, 3-pentenyl, 4-pentenyl, 1-hexenyl, 2-hexenyl, 3-hexenyl, 4-hexenyl or 5-hexenyl.In order to make viscosity reduce, preferred thiazolinyl is vinyl, 1-propenyl, 3-butenyl or 3-pentenyl.The preferred steric configuration of-CH=CH-in these thiazolinyls (stericconfiguration) depends on the position of double bond.From in order to make the considerations such as viscosity reduction, preferably trans in the thiazolinyl as 1-propenyl, 1-butylene base, 1-pentenyl, 1-hexenyl, 3-pentenyl, 3-hexenyl.Cis is preferably in the thiazolinyl as crotyl, pentenyl, 2-hexenyl.In these thiazolinyls, be Comparatively speaking preferably the thiazolinyl of straight chain with branch.
The preferred example of the thiazolinyl that at least one hydrogen replaced by fluorine is 2,2-difluoroethylene base, 3,3-bis-fluoro-2-propenyl, 4,4-bis-fluoro-3-butenyls, 5,5-bis-fluoro-4-pentenyls and the fluoro-5-hexenyl of 6,6-bis-.In order to make viscosity reduce, preferred example is the fluoro-3-butenyl of 2,2-difluoroethylene base and 4,4-bis-.
Ring A 2and ring B 2independent is Isosorbide-5-Nitrae-cyclohexylidene, tetrahydropyrans-2,5-bis-base, 1,3-diox-2, fluoro-Isosorbide-5-Nitrae-the phenylene of 5-bis-base, Isosorbide-5-Nitrae-phenylene, 2-, 2, fluoro-Isosorbide-5-Nitrae-the phenylene of 5-bis-, 2,3-bis-fluoro-1, chloro-Isosorbide-5-Nitrae-the phenylene of the fluoro-3-of 4-phenylene, 2-, 2,3-bis-fluoro-6-methyl isophthalic acids, 4-phenylene, 2,6-naphthalene two bases, 7,8-difluoro chromans-2,6-bis-base, herein, ring A 2and ring B 2at least one be the fluoro-Isosorbide-5-Nitrae-phenylene of 2,3-bis-, the chloro-Isosorbide-5-Nitrae-phenylene of the fluoro-3-of 2-, 2,3-bis-fluoro-6-methyl isophthalic acids, 4-phenylene, 7,8-difluoro chroman-2,6-bis-bases, when j is 2 or 3, any two ring A 2can identical also can be different.In order to make dielectric anisotropy improve, preferred ring A 2and ring B 2be respectively the fluoro-Isosorbide-5-Nitrae-phenylene of 2,3-bis-or tetrahydropyrans-2,5-bis-base, in order to make viscosity reduce, preferred ring A 2and ring B 2be respectively Isosorbide-5-Nitrae-cyclohexylidene.
Ring A 21, ring A 22, ring A 23, ring B 21, and ring B 22independent is Isosorbide-5-Nitrae-cyclohexylidene or Isosorbide-5-Nitrae-phenylene.In order to make viscosity reduce, preferred ring A 21, ring A 22, ring A 23, ring B 21, and ring B 22be respectively Isosorbide-5-Nitrae-cyclohexylidene.
Z 1and Z 2independent is singly-bound ,-(CH 2) 2-,-CH 2o-,-COO-,-CF 2o-, when j is 2 or 3, any two Z 1can identical also can be different, when k is 2 or 3, any two Z 2can identical also can be different, in order to make dielectric anisotropy improve, preferred Z 1and Z 2-CH 2o-, in order to make viscosity reduce, preferred Z 1and Z 2it is singly-bound.
Z 11and Z 12independent is singly-bound ,-(CH 2) 2-,-CH 2o-or-COO-.In order to make dielectric anisotropy improve, preferred Z 11and Z 12-CH 2o-, in order to make viscosity reduce, preferred Z 11and Z 12it is singly-bound.
J is 1,2 or 3.In order to make lower limit temperature reduce, preferred j is 1, and in order to make ceiling temperature improve, preferred j is 2.
Described have in the liquid-crystal composition of negative dielectric anisotropy, and as the 1st composition, preferred compound (NL-1) is compound (NL-1-1), compound (NL-1-4), compound (NL-1-7) or compound (NL-1-32).
The described preferred example with the liquid-crystal composition of negative dielectric anisotropy can be set forth in Japanese Patent Laid-Open No. Sho 57-114532 publication, Japanese Patent Laid-Open 2-4725 publication, Japanese Patent Laid-Open 4-224885 publication, Japanese Patent Laid-Open 8-40953 publication, Japanese Patent Laid-Open 8-104869 publication, Japanese Patent Laid-Open 10-168076 publication, Japanese Patent Laid-Open 10-168453 publication, Japanese Patent Laid-Open 10-236989 publication, Japanese Patent Laid-Open 10-236990 publication, Japanese Patent Laid-Open 10-236992 publication, Japanese Patent Laid-Open 10-236993 publication, Japanese Patent Laid-Open 10-236994 publication, Japanese Patent Laid-Open 10-237000 publication, Japanese Patent Laid-Open 10-237004 publication, Japanese Patent Laid-Open 10-237024 publication, Japanese Patent Laid-Open 10-237035 publication, Japanese Patent Laid-Open 10-237075 publication, Japanese Patent Laid-Open 10-237076 publication, Japanese Patent Laid-Open 10-237448 publication (EP967261A1), Japanese Patent Laid-Open 10-287874 publication, Japanese Patent Laid-Open 10-287875 publication, Japanese Patent Laid-Open 10-291945 publication, Japanese Patent Laid-Open 11-029581 publication, Japanese Patent Laid-Open 11-080049 publication, Japanese Patent Laid-Open 2000-256307 publication, Japanese Patent Laid-Open 2001-019965 publication, Japanese Patent Laid-Open 2001-072626 publication, Japanese Patent Laid-Open 2001-192657 publication, Japanese Patent Laid-Open 2010-037428 publication, International Publication No. 2011/024666 specification sheets, International Publication No. 2010/072370 specification sheets, Japanese Patent spy table 2010-537010 specification sheets, Japanese Patent Laid-Open 2012-077201 publication, the liquid-crystal composition disclosed in Japanese Patent Laid-Open 2009-084362 publication etc.
Such as, and such as consider from the viewpoint making orientation improve, the liquid-crystal composition used in element of the present invention can also add additive further.This kind of additive is photopolymerization monomer, optically active compound, antioxidant, UV light absorber, pigment, defoamer, polymerization starter, polymerization retarder etc.
In order to improve the orientation of liquid crystal, the most preferred structure of photopolymerization monomer or oligomer can enumerate the structure of (PM-1-1) ~ (PM-1-6).
[change 1581
In order to show the effect of the vergence direction of the liquid crystal after determining polymerization, photopolymerization monomer or oligomer it is desirable to more than 0.01 % by weight.And in order to make the orientation effect of the polymkeric substance after polymerization be suitable for, or in order to avoid after uv irradiation, unreacted monomer or oligomer stripping, in liquid crystal, it is desirable to less than 30 % by weight.
In order to cause the spirane structure of liquid crystal to give torsion(al)angle, hybrid optical active compound in the composition.The example of this kind of compound is that compound (PAC-1-1) is to compound (PAC-1-4).The preferred proportion of optically active compound is less than 5 % by weight.Preferred ratio is the scope of 0.01 % by weight to 2 % by weight.
[changing 159]
Reduce to prevent the ratio resistance (specificresistance) caused owing to heating in an atmosphere, or in order to after long-time use element, not only at room temperature and at high temperature also can maintain large voltage retention, in liquid-crystal composition, mix antioxidant.
[changing 160]
The compound (AO-1) etc. of the preferred example of antioxidant to be w the be integer of 1 to 10.In compound (AO-1), preferred w is 1,3,5,7 or 9.Preferred w is 1 or 7.W is that the volatility of the compound (AO-1) of 1 is large, therefore effective when the ratio resistance preventing from causing owing to heating in an atmosphere reduces.W is that the volatility of the compound (AO-1) of 7 is little, therefore after long-time use element, not only at room temperature and at high temperature also can effectively maintain large voltage retention.In order to obtain its effect, the preferred ratio of antioxidant is more than 50ppm, and in order to not make ceiling temperature reduce or not make lower limit temperature improve, the preferred ratio of antioxidant is below 600ppm.Preferred ratio is the scope of 100ppm to 300ppm.
The preferred example of UV light absorber is benzophenone derivates, benzoate derivatives, triazole derivative etc.The photostabilizer as amine with sterically hindered (sterichindrance) is also preferred.In order to obtain its effect, the preferred ratio of these absorption agents or stablizer is more than 50ppm, and in order to not make ceiling temperature reduce or not make lower limit temperature improve, the preferred ratio of these absorption agents or stablizer is below 10000ppm.Preferred ratio is the scope of 100ppm to 10000ppm.
In order to the element of applicable host and guest (Guesthost, GH) pattern, the dichroism pigment (dichroicdye) of mixing as azo system pigment, anthraquinone system pigment etc. so in the composition.The preferred ratio of pigment is the scope of 0.01 % by weight to 10 % by weight.
In order to prevent bubbling, mix the defoamer such as dimethyl silicone oil, methyl phenyl silicone oil in the composition.In order to obtain its effect, the preferred ratio of defoamer is more than 1ppm, and in order to prevent display bad, the preferred ratio of defoamer is below 1000ppm.Preferred ratio is the scope of 1ppm to 500ppm.
In order to the element of applicable polymer stabilizing orientation (polymersustainedalignment, PSA) pattern, polymerisable compound can be mixed in the composition.The compound that the preferred example of polymerisable compound is acrylate, methacrylic ester, vinyl compound, ethyleneoxy compounds, propenyl ether, epoxy compounds (oxirane, trimethylene oxide), vinyl ketone etc. have polymerisable base.More preferred example is the derivative of acrylate or methacrylic ester.The example of this kind of compound is that compound (PM-2-1) is to compound (PM-2-9).In order to obtain its effect, the preferred ratio of polymerisable compound is more than about 0.05 % by weight, and in order to prevent display bad, the preferred ratio of polymerisable compound is less than about 10 % by weight.Preferred ratio is the scope of about 0.1 % by weight to about 2 % by weight.
[changing 161]
Herein, R 3a, R 4a, R 5a, and R 6aindependent is acryl or methacryloyl, R 7aand R 8aindependently for hydrogen, halogen or carbon number are the alkyl of 1 to 10, Z 13, Z 14, Z 15, and Z 16independently for singly-bound or carbon number are the alkylidene group of 1 to 12, at least one-CH 2-also can be replaced by-O-or-CH=CH-, s, t and u are independently 0,1 or 2.
As easily producing free radical or ion, cause the material required for chain polymerization reaction, can mixed polymerization initiator.Such as, suitable for radical polymerization as gorgeous good solid (Irgacure) 651 (registered trademark) of Photoepolymerizationinitiater initiater, gorgeous good solid (Irgacure) 184 (registered trademark) or Da Ruoku (Darocure) 1173 (registered trademark) (Japanese Qi Ba limited-liability company (CibaJapanK.K.)).Polymerisable compound preferably comprises Photoepolymerizationinitiater initiater in the scope of 0.1 % by weight to 5 % by weight.Particularly preferably be and comprise Photoepolymerizationinitiater initiater in the scope of 1 % by weight to 3 % by weight.
In radical polymerization assembly system, can object and mixed polymerization inhibitor as follows: promptly react with the free radical produced by polymerization starter or monomer and be changed to stable free radical or the compound of neutrality, its result makes polyreaction stop.Polymerization retarder structurally can be categorized as several.One of them be as three-p-nitrophenyl ylmethyl, two-to himself the stable free radical fluorophenyl amine etc., another kind easily reacts with existing free radical in paradigmatic system and becomes stable free radical, and its representative is nitro, nitroso-group, amino, polyol etc.The representative of the latter can enumerate Resorcinol, dimethoxy benzene etc.In order to obtain its effect, the preferred ratio of polymerization retarder is more than 5ppm, and in order to prevent display bad, the preferred ratio of polymerization retarder is below 1000ppm.Preferred ratio is the scope of 5ppm to 500ppm.
Use in liquid crystal display device of the present invention and there is the liquid-crystal composition of negative dielectric anisotropy, image retention excellent can be provided thus and the good liquid crystal display device of orientation stability.
[embodiment]
Below, by embodiment, the present invention is illustrated.In addition, used in an embodiment evaluation assessment and compound as described below.
< evaluation assessment >
1. viscosity
Use viscometer (manufacture of Dong Ji industry companies, TV-22), measure at 25 DEG C.
2. weight average molecular weight (M.W.)
The weight average molecular weight of polyamic acid utilizes GPC method to measure by using 2695 separation module-2414 differential refractometer (water generation (Waters) manufacture), carries out polystyrene conversion and obtain.Polyamic acid phosphoric acid-DMF the mixing solutions (phosphoric acid/DMF=0.6/100: weight ratio) of gained is diluted to polyamic acid concentration and becomes about 2 % by weight.Tubing string uses HSPgelRTMB-M (water generation (Waters) manufacture), using described mixing solutions as developping agent, tubing string temperature be 50 DEG C, flow velocity measures under being the condition of 0.40mL/min.Polystyrene standard is the TSK polystyrene standard using eastern Cao (stock) to manufacture.
3. pencil hardness
According to JIS standard " JIS-K-5400,8.4, pencil eraser carve test " method.Result is represented by the hardness of pencil-lead.If pencil hardness is low, then easily produces and peel off or cut down, if this value is greater than 2H, then obtain the alignment films being difficult to produce reduction etc.
4. the delay of alignment films and determining film thickness
Use light splitting ellipsometer M-2000U (J.A. Wo Lan limited-liability company (J.A.WoollamCo.Inc.) manufacture) and obtain.When the optical alignment film of the present embodiment, the length of delay of film and the orientation degree of main polymer chain become large pro rata.Also namely, represent there is large length of delay there is large orientation degree, liquid crystal aligning ability is high.If this value is greater than 15, then obtain the good alignment films of display characteristic.
5. resistance to reduction
For liquid crystal cells, after use-testing rod carries out the button of 1 time/second, 1 minute with the load of 1000g, use the presence or absence that microscopic examination film is cut down.
6. tilt angle measures
Measure according to crystal rotation method (Crystalrotationmethod).
7. voltage retention
Utilize method described in " water Wu he, the 14th liquid crystal discussion collection of thesis the 78th page (1988) " and carry out.The square wave of wave height (waveheight) ± 5V is applied to unit (cell) and measures.Measure at 60 DEG C.This value represents that applied voltage keeps the index of which kind of degree afterwards in the frame period (frameperiod), if this value 100% shows keep all electric charges.
8. the ionic weight in liquid crystal measures (ion density)
According to " Applied Physics ", the 65th volume, method described in No. 10,1065 (1996), liquid crystal physical property measurement system 6254 type using Dongyang technology company to manufacture and measuring.Frequency of utilization is the choppy sea of 0.01Hz, carries out measuring that (area of electrode is 1cm under the voltage range, the temperature of 60 DEG C of ± 10V 2).If ion density is large, then easily produce the unfavorable conditions such as the burning trace caused due to ionic impurity.Also namely, ion density becomes the physics value that the index that trace produces is burnt in prediction.
< tetracarboxylic dianhydride >
Acid dianhydride (1-1): by the tetracarboxylic dianhydride of the synthesis path gained of synthesis example 1
Acid dianhydride (1-5): by the tetracarboxylic dianhydride of the synthesis path gained of synthesis example 2
Acid dianhydride (1-6): the tetracarboxylic dianhydride of gained according to the synthesis path of synthesis example 2
Acid dianhydride (1-28): the tetracarboxylic dianhydride of gained according to the synthesis path of synthesis example 2
Acid dianhydride (AN-2-1): 1,2,3,4 ,-tetramethylene tetracarboxylic dianhydride
Acid dianhydride (AN-3-2): pyromellitic acid anhydride
Acid dianhydride (AN-4-1): 3,3 ', 4,4 '-Lian cyclopentanetetracarboxylic dianhydride
Two (3,4-dicarboxyl acidic group phenyl) the octane dianhydride of acid dianhydride (AN-4-17, m=8): 1,8-
Acid dianhydride (AN-4-30): N, N '-(Isosorbide-5-Nitrae-phenylene) two (1,3-dioxo octahydro isobenzofuran-5-carboxylic acid amides)
Acid dianhydride (AN-7-2): 2,3,5-tricarboxylic cyclopentyl acetic acid dianhydride
< diamines >
Diamines (DI-1-3): 1，6-diaminohexane
Diamines (DI-2-1): Isosorbide-5-Nitrae-cyclohexanediamine
Diamines (DI-3-1): 4，4′-diaminodicyclohexylmethane
Diamines (DI-4-1): Isosorbide-5-Nitrae-phenylenediamine
Diamines (DI-5-1, m=4): 4,4 '-diamino-diphenyl butane
Diamines (DI-5-9): 4,4 '-diamino-diphenyl ether
Diamines (DI-5-29): biphenyl-4,4 '-diamines
Diamines (DI-5-30, k=2): N, N '-bis-(4-aminophenyl)-N, N '-dimethyl-ethylenediamine
Diamines (DI-6-7): 4,4 '-to benzene pentanoic
Two (4-((4-aminophenyl) methyl) phenyl) propane of diamines (DI-7-3, m=3, n=1): 1,3-
Diamines (DI-8-1): 2,6-diaminonaphthalene
Two (3-aminopropyl) tetramethyl disiloxane of diamines (DI-12-1): 1,3-
Diamines (DI-13-1): 4,4 '-N, N '-bis-(4-aminophenyl) piperazine
Diamines (DI-16-1): 1-(4-aminophenyl)-1H-indoles-5-amine
Diamines (PDI-7-a): 4,4 '-chrysoidine
Diamines (PDI-8-a): 4,4 '-bis-[(4-aminophenyl) methyl] nitrogen benzide
Diamines (PDI-9): 4-aminophenyl-4-amino-cinnamic acid ester
Diamines (PDI-11): 4,4 '-diamino cinnamophenone
[changing 162]
< solvent >
METHYLPYRROLIDONE: NMP
Ethylene glycol butyl ether (ethylene glycol monobutyl ether): BC
< additive >
Two (4, the 5-dihydro-oxazolyl) benzene of additive (Ad1): 1,3-
Additive (Ad2): N, N, N ', N '-four glycidyl group-4,4 '-diaminodiphenyl-methane
Additive (Ad3): APTES
The synthesis of [embodiment 1] compound (1-1)
[changing 163]
< the 1st stage; Azide >
In the there-necked flask being provided with thermometer, nitrogen ingress pipe, put into 4-(4-brombutyl) diethyl phthalate (12.1g, 34.0mol), add the DMF of 70mL.Add sodiumazide (2.4g, 37.4mmol) wherein.Thereafter, solution is heated to 60 DEG C, at the same temperature, carry out under nitrogen environment stirring for 3 hours.Reaction soln is added in the water of 400mL, carries out 2 extractions with 300mL heptane.After making organic layer drying with magnesium sulfate, solvent underpressure distillation removing is obtained 4-(4-azido-butyl)-diethyl phthalate compound (output be 10.0g, productive rate be 92%).
< the 2nd stage; The formation > of triazole ring
In the there-necked flask being provided with thermometer, nitrogen ingress pipe, put into 4-(4-azido-butyl) diethyl phthalate (10.0g, 31.3mmol), the 4-ethynyl-dimethyl phthalate (7.5g, 34.4mmol) of the 1st stage gained, add the methylene dichloride of 50mL and the water of 50mL.At room temperature carry out stirring and after making compound dissolution, add copper sulfate pentahydrate (0.78g, 3.1mmol) and L-AA sodium (1.2g, 6.3mmol), at room temperature carrying out stirring for 1 hour.Reaction solution is added in 50mL water, carries out 2 extractions with 100mL toluene.After making organic layer drying with magnesium sulfate, solvent underpressure distillation removing is obtained runic.With column chromatography, purifying carried out to runic and obtain following compound (output be 15.7g, productive rate be 93%).
[changing 164]
< the 3rd stage; Hydrolysis >
Take into account in the there-necked flask of return line the compound (15.7g, 29.2mmol) adding gained in the 2nd stage being provided with temperature, add the tetrahydrofuran (THF) of 30mL.In this solution, add 20% aqueous solution of 30mL sodium hydroxide, carry out at reflux stirring for 2 hours.Reaction soln is placed and is cooled to room temperature, with vaporizer by after tetrahydrofuran (THF) distillation removing, add 6NHCl until pH becomes 1.0.Suction strainer takes out the crystallization of separating out, and carries out cleaning and obtain following compound (output be 14.6g, productive rate be 110%) with pure water.
[changing 165]
< the 4th stage; Acid anhydrides >
Take into account in the there-necked flask of return line the compound (13.6g, 30.0mmol), the diacetyl oxide 68mL that add gained in the 3rd stage being provided with temperature, carry out at reflux stirring for 6 hours.Placed by reaction soln after being cooled to room temperature, suction strainer takes out the crystallization of separating out, and carries out cleaning and obtain compound (1-1) (output be 9.6g, productive rate be 77%) with toluene.
1H-NMR(500MHz，CDCl 3)：δ8.99(s，1H)，8.49-8.45(m，2H)，8.17(d，J＝7.5Hz，1H)，8.00(d，J＝7.8Hz，1H)，7.97(s，1H)，7.87-7.84(m，1H)，4.52(t，J＝7Hz，2H)，2.90(t，J＝7.6Hz，2H)，1.97-1.90(m，2H)，1.73-1.65(m，2H)；
Fusing point: 200.2 DEG C ~ 201.9 DEG C.
The synthesis of [embodiment 2] compound (1-5)
[changing 166]
< the 1st stage; Azide >
In the 100mL there-necked flask being provided with thermometer, nitrogen ingress pipe, put into 1,6-dibromo-hexane (5.0g, 20.5mmol), add the DMF of 25mL.Add sodiumazide (2.9g, 45.6mmol) wherein.Thereafter, solution is heated to 60 DEG C, at the same temperature, carry out the stirring of 3 hours under nitrogen environment.Reaction soln is added in 200mL water, carries out 2 extractions with the heptane of 100mL.After making organic layer drying with magnesium sulfate, solvent underpressure distillation removing is obtained 1,6-diazido hexane (output be 3.2g, productive rate be 93%).
< the 2nd stage; The formation > of triazole ring
Put into 1,6-diazido hexane (2.2g, 13.1mmol), the 4-ethynyl-dimethyl phthalate (5.7g, 26.2mmol) of the 1st stage gained, add the methylene dichloride of 5mL and the water of 5mL.At room temperature carry out stirring and after making compound dissolution, add copper sulfate pentahydrate (0.16g, 0.65mmol) and L-AA sodium (0.26g, 13mmol), at room temperature carrying out stirring for 1 hour.Reaction solution is added in 50mL water, carries out 2 extractions with 50mL toluene.After making organic layer drying with magnesium sulfate, solvent underpressure distillation removing is obtained runic.With column chromatography, purifying carried out to runic and obtain following compound (output be 3.2g, productive rate be 93%).
[changing 167]
< the 3rd stage; Hydrolysis >
Take into account in the there-necked flask of return line the compound (6.8g, 11.3mmol) adding gained in the 2nd stage being provided with temperature, add the tetrahydrofuran (THF) of 10mL.In this solution, add 20% aqueous solution of the sodium hydroxide of 10mL, carry out at reflux stirring for 2 hours.Reaction soln is placed and is cooled to room temperature, with vaporizer by after tetrahydrofuran (THF) distillation removing, add 6NHCl until pH becomes 1.0.Suction strainer takes out the crystallization of separating out, and carries out cleaning and obtain following compound (output be 5.8g, productive rate be 94%) with pure water and methyl alcohol.
[changing 168]
< the 4th stage; Acid anhydrides >
Add the compound (5.8g, 10.6mmol) of gained in the 3rd stage, the diacetyl oxide of 29mL being provided with temperature and taking into account in the there-necked flask of return line, carry out at reflux stirring for 6 hours.Placed by reaction soln and be cooled to room temperature, suction strainer takes out the crystallization of separating out, and carries out cleaning and obtain compound (1-5) (output be 4.9g, productive rate be 91%) with toluene.
1H-NMR(500MHz，CDCl 3)：δ9.01(s，2H)，8.50-8.46(m，4H)，8.17(d，J＝8.4Hz，2H)，4.46(t，J＝7Hz，4H)，1.95-1.87(m，4H)，1.39-1.32(m，4H)；
Fusing point: 254.3 DEG C ~ 256.5 DEG C.
The synthesis of [embodiment 3] compound (1-6)
[changing 169]
< the 1st stage; The formation > of triazole ring
Put into 1,6-diazido hexane (2.2g, 13.1mmol), 4-ethynyl-1,2-cyclohexyl dicarboxylic acid dimethyl ester (6.2g, 27.5mmol), add the methylene dichloride of 20ml and the water of 20ml.At room temperature carry out stirring and after making compound dissolution, add copper sulfate pentahydrate (0.16g, 0.65mmol) and L-AA sodium (0.26g, 13mmol), at room temperature carrying out stirring for 1 hour.Reaction solution is added in 50ml water, carries out 2 extractions with 50ml toluene.After making organic layer drying with magnesium sulfate, solvent underpressure distillation removing is obtained runic.With column chromatography, purifying carried out to runic and obtain following compound (output be 7.8g, productive rate be 97%).
[changing 170]
< the 2nd stage; Hydrolysis >
Take into account in the there-necked flask of return line the compound (7.0g, 11.3mmol) adding gained in the 1st stage being provided with temperature, add the tetrahydrofuran (THF) of 10mL.In this solution, add 20% aqueous solution of the sodium hydroxide of 10mL, carry out at reflux stirring for 2 hours.Reaction soln is placed and is cooled to room temperature, with vaporizer by after tetrahydrofuran (THF) distillation removing, add 6NHCl until pH becomes 1.0.Suction strainer takes out the crystallization of separating out, and carries out cleaning and obtain following compound (output be 6.0g, productive rate be 94%) with pure water and methyl alcohol.
[changing 171]
< the 3rd stage; Acid anhydrides >
Take into account in the there-necked flask of return line the compound (5.9g, 10.6mmol) adding gained in the 2nd stage being provided with temperature, add the diacetyl oxide of 30ml, carry out at reflux stirring for 6 hours.Placed by reaction soln and be cooled to room temperature, suction strainer takes out the crystallization of separating out, and carries out cleaning and obtain compound (1-6) (output be 4.7g, productive rate be 84%) with toluene.
The synthesis of [embodiment 4] compound (1-28)
[changing 172]
< the 1st stage; Azide >
In the 100mL there-necked flask being provided with thermometer, nitrogen ingress pipe, put into Isosorbide-5-Nitrae-dibromobutane (6.5g, 30.0mmol), add the DMF of 100ml.Add sodiumazide (4.2g, 65.0mmol) wherein.Thereafter, solution is heated to 60 DEG C, at the same temperature, carry out under nitrogen environment stirring for 3 hours.Reaction soln is added in 500ml water, carries out 2 extractions with 300ml heptane.After making organic layer drying with magnesium sulfate, solvent underpressure distillation removing is obtained Isosorbide-5-Nitrae-diazido butane (output be 4.0g, productive rate be 95%).
< the 2nd stage; The formation > of triazole ring
1 of the 1st stage gained is put in the there-necked flask being provided with thermometer, nitrogen ingress pipe, 4-diazido butane (2.8g, 20.0mmol), 4-(5-hexin base)-dimethyl phthalate (11.1g, 40.4mol), add the methylene dichloride of 40ml and the water of 40ml.At room temperature carry out stirring and after making compound dissolution, add copper sulfate pentahydrate (0.5g, 2.0mol) and L-AA sodium (0.8g, 4.0mol), at room temperature carrying out stirring for 1 hour.Reaction solution is added in 100ml water, carries out 2 extractions with 100ml toluene.After making organic layer drying with magnesium sulfate, solvent underpressure distillation removing is obtained runic.With column chromatography, purifying carried out to runic and obtain following compound (output be 13.2g, productive rate be 96%).
[changing 173]
< the 3rd stage; Hydrolysis >
Take into account in the there-necked flask of return line the compound (11.9g, 17.3mol) adding gained in the 2nd stage being provided with temperature, add the tetrahydrofuran (THF) of 50ml.In this solution, add 20% aqueous solution of the sodium hydroxide of 16ml, carry out at reflux stirring for 2 hours.Reaction soln is placed and is cooled to room temperature, with vaporizer by after tetrahydrofuran (THF) distillation removing, add 6NHCl until pH becomes 1.0.Suction strainer takes out the crystallization of separating out, and carries out cleaning and obtain following compound (output be 10.1g, productive rate be 92%) with pure water.
[changing 174]
< the 4th stage; Acid anhydrides >
Add the compound (9.6g, 15.2mol) of gained in the 3rd stage and the diacetyl oxide of 100ml being provided with temperature and taking into account in the there-necked flask of return line, carry out at reflux stirring for 6 hours.Placed by reaction soln after being cooled to room temperature, suction strainer takes out the crystallization of separating out, and carries out cleaning and obtain compound (1-28) (output be 8.9g, productive rate be 98%) with toluene.
[embodiment 5]
The synthesis > of < polyamic acid
In the there-necked flask being provided with agitating wing, thermometer, take compound (1-1) synthesized in 3.3144g embodiment 1 and 1.6856g compound (PDI-7-a), add the METHYLPYRROLIDONE (NMP) of 65g wherein.At room temperature carry out stirring for 12 hours, add the ethylene glycol monobutyl ether (BC) of 30g wherein, at room temperature continue stirring 24 hours and obtain the solution that polyamic acid concentration is 5 % by weight.Using this solution as varnish A-1.The weight average molecular weight (M.W.) of the polyamic acid in this varnish is 74,000.
[embodiment 6 ~ embodiment 34]
As described in Table 1, obtain according to method described in embodiment 5 varnish that the polyamic acid concentration becoming optical alignment film formation polymkeric substance is 5 % by weight.The total amount of raw material is set to the molar percentage (mol%) when 100mol% by () interior expression.In embodiment 32 ~ embodiment 34, after similarly preparing varnish as aforementioned, respectively being that the ratio of 10 weight parts is added additive (Ad1) ~ additive (Ad3) and is prepared in every 100 parts by weight polymer.Embodiment 5 is also disclosed in Table 1 again.
[table 1-1]
Table 1-1
[table 1-2]
Table 1-2
*) 10 weight parts are added in every 100 parts by weight polymer
[comparative example 1 ~ comparative example 3]
As described in Table 2, obtain according to method described in embodiment 5 varnish that the polyamic acid concentration becoming optical alignment film formation polymkeric substance is 5 % by weight.The total amount of raw material is set to the molar percentage (mol%) when 100mol% by () interior expression.
[table 2]
Table 2
[embodiment 35]
In sample bottle, measure the varnish A-1 of 1.0g, add NMP/BC=1/1 (weight ratio) and become 1.67g.Transparent glass substrate drips this polyamic acid solution of about 3 % by weight, utilizes turner method to carry out being coated with (2,000rpm, 15 seconds).After coating, substrate is carried out at 80 DEG C the heating of 3 minutes, after solvent is evaporated, use multiple light courcess (MultiLight) ML-501C/B that oxtail motor (stock) manufactures, for substrate, from the linear polarization of vertical irradiation ultraviolet radiation across Polarizer.The ultraviolet that exposure energy now uses oxtail motor (stock) to manufacture adds up quantorecorder UIT-150 (optical receiver: UVD-S365) and measures light quantity, to become 1.3J/cm under wavelength 365nm 2± 0.1J/cm 2mode adjust the time shutter.By the substrate after rayed in an oven, carry out the heat treated of 15 minutes at 210 DEG C, obtain the alignment films A-1 that thickness is about 100nm.Measure the delay of this alignment films A-1, result is 19.8nm.And measure the pencil hardness of the alignment films A-1 of gained, result is 3H.
[embodiment 36 ~ embodiment 64] and [comparative example 4 ~ comparative example 6]
As for varnish A-2 ~ varnish A-30 and varnish B-1 ~ varnish B-3, also form alignment films A-2 ~ alignment films A-30 and alignment films B-1 ~ alignment films B-3 by the operation according to embodiment 35, measure delay and pencil hardness according to the method for embodiment 35.These results are shown in table 3 and table 4.About the result of embodiment 35, be also again disclosed in table 3.
[table 3]
Table 3
Embodiment Varnish Alignment films Pencil hardness Postpone
35 A-1 A-1 3H 19.8
36 A-2 A-2 2H 20.1
37 A-3 A-3 3H 18.7
38 A-4 A-4 3H 19.2
39 A-5 A-5 4H 19.4
40 A-6 A-6 2H 18.1
41 A-7 A-7 4H 17.9
42 A-8 A-8 3H 18.5
43 A-9 A-9 2H 19.1
44 A-10 A-10 2H 20.8
45 A-11 A-11 5H 18.7
46 A-12 A-12 4H 19.1
47 A-13 A-13 5H 18.9
48 A-14 A-14 4H 19.8
49 A-15 A-15 3H 20.1
50 A-16 A-16 2H 18.7
51 A-17 A-17 3H 19.2
52 A-18 A-18 3H 19.4
53 A-19 A-19 4H 18.1
54 A-20 A-20 2H 17.9
55 A-21 A-21 4H 18.5
56 A-22 A-22 3H 19.1
57 A-23 A-23 2H 20.8
58 A-24 A-24 2H 18.7
59 A-25 A-25 5H 19.1
60 A-26 A-26 4H 18.9
61 A-27 A-27 5H 19.1
62 A-28 A-28 4H 18.9
63 A-29 A-29 5H 19.1
64 A-30 A-30 4H 18.9
[table 4]
Table 4
Comparative example Varnish Alignment films Pencil hardness Postpone
4 B-1 B-1 4B 19.5
5 B-2 B-2 2H 3.7
6 B-3 B-3 2H 2.9
Known in the alignment films A-1 ~ alignment films A-30 by varnish A-1 ~ varnish A-30 gained, all there is large delay and high pencil hardness in all alignment films.In the alignment films B-1 by varnish B-1 gained, although have large delay, pencil hardness is low.And known in the alignment films by varnish B-2 and varnish B-3 gained, not talkative pencil hardness is enough high, and postpone also little.
[embodiment 65]
Glass substrate is replaced with the transparent glass substrate being provided with ITO electrode at one side, utilize the method according to embodiment 35 in addition and obtain the alignment films A-1 that thickness is about 100nm.Make 2 be formed in ITO electrode the substrate of these alignment films be formed alignment films in the face of to, and arrange in order to the space of injection liquid crystal composite between the alignment films of subtend and fitted.Now, make to become parallel the polarization direction of the linear polarization that each alignment films is irradiated.In this unit, inject following shown positive type liquid crystal composition A, production unit thickness is 3.5 μm liquid crystal cells A-1 (liquid crystal display device) (Fig. 1).
< positive type liquid crystal composition A>
[changing 175]
Physics value: NI is 100.1 DEG C; Δ ε is 5.1; Δ n is 0.093; η is 25.6mPas.
By this liquid crystal cells of visual observation A-1, result is not observed liquid crystal self seeding mouth completely and is arranged as radial so-called flow orientation.Make polarizing microscope become Nicol crossed state, if make liquid crystal cells A-1 rotate, observe clear bright state and dark state.The tilt angle (being sometimes slightly designated as Pt angle below) of this liquid crystal cells A-1 is 0.1 °.And VHR (voltage retention) and ion density are 99.0% (30Hz), 87.0% (0.3Hz) and 80pC.Measure the resistance to reduction of this liquid crystal cells, result, after keystroke handling, is not observed the reduction of alignment films completely or peels off.
[embodiment 66 ~ embodiment 94] and [comparative example 7 ~ comparative example 9]
According to method described in embodiment 65, about varnish A-2 ~ varnish A-30 and varnish B-1 ~ varnish B-3, also make liquid crystal cells A-2 ~ liquid crystal cells A-30 and liquid crystal cells B-1 ~ liquid crystal cells B-3, measure state of orientation, tilt angle, VHR, ion density and resistance to reduction.Measurement result is shown in table 5 and table 6.Embodiment 65 is also disclosed in table 5 again.
Resistance to reduction
Zero: after keystroke handling, do not observe the reduction of alignment films with microscope or peel off
×: after keystroke handling, with microscopic examination to the reduction of alignment films or peel off
[table 5]
Table 5
[table 6]
Table 6
In liquid crystal cells A-1 ~ liquid crystal cells A-30, demonstrate good state of orientation, demonstrate good resistance to reduction.And the electrical specification represented by VHR, ion density is also good result.In liquid crystal cells B-1, show good state of orientation, electrical specification is also good, but produces the reduction of alignment films.In liquid crystal cells B-2 and liquid crystal cells B-3, do not observe the reduction of alignment films, but confirm the flow orientation of liquid crystal, become the liquid crystal cells that display is bad.
[embodiment 95 ~ embodiment 109] and [comparative example 10 ~ comparative example 12]
As shown in following table 7 and table 8, obtain according to method described in embodiment 5 varnish that polyamic acid concentration is 5 % by weight.The total amount of raw material is set to the molar percentage (mol%) when 100mol% by () interior expression.
[table 7]
Table 7
[table 8]
Table 8
[embodiment 110]
In sample bottle, measure the varnish C-1 of 1.0g, add NMP/BC=1/1 (weight ratio) and become 1.67g.Transparent glass substrate drips this polyamic acid solution of about 3 % by weight, utilizes turner method to carry out being coated with (2,000rpm, 15 seconds).After coating, substrate is carried out at 80 DEG C the heating of 3 minutes, after solvent is evaporated, in cleaning oven (manufacture of Ace peck limited-liability company, cleaning oven (PVHC-231)), carry out the heat treated of 15 minutes at 210 DEG C, obtain the alignment films C-1 that thickness is about 100nm.Secondly, the natural pond gauger (Gauge) that makes to have a meal makes the friction treatment device that limited-liability company of institute manufactures, the hair intrusion of friction cloth (staple length 1.8mm: artificial silk) be 0.20mm, platform movement speed is 60mm/sec, roller speed of rotation carries out friction treatment to the liquid crystal orientation film of gained under being the condition of 1,000rpm.Measure the delay of the substrate of gained, result is 0.26nm.And measure the pencil hardness of the alignment films C-1 of gained, result is 5H.
[embodiment 111 ~ embodiment 124] and [comparative example 13 ~ comparative example 15]
As for varnish C-2 ~ varnish C-15 and varnish D-1 ~ varnish D-3, also form alignment films C-2 ~ alignment films C-15 and alignment films D-1 ~ alignment films D-3 by the operation according to embodiment 110, measure delay and pencil hardness according to the method for embodiment 110.These results are shown in table 9 and table 10.About the result of embodiment 110, be also again disclosed in table 9.
[table 9]
Table 9
Embodiment Varnish Alignment films Pencil hardness Postpone
110 C-1 C-1 5H 0.26
111 C-2 C-2 4H 0.27
112 C-3 C-3 3H 0.30
113 C-4 C-4 3H 0.20
114 C-5 C-5 4H 0.35
115 C-6 C-6 5H 0.24
116 C-7 C-7 5H 0.26
117 C-8 C-8 4H 0.27
118 C-9 C-9 3H 0.30
119 C-10 C-10 3H 0.20
120 C-11 C-11 4H 0.35
121 C-12 C-12 5H 0.24
122 C-13 C-13 4H 0.27
123 C-14 C-14 3H 0.30
124 C-15 C-15 3H 0.20
[table 10]
Table 10
Comparative example Varnish Alignment films Pencil hardness Postpone
13 D-1 D-1 HB 0.25
14 D-2 D-2 B 0.22
15 D-3 D-3 F 0.31
More known according to embodiment 110 ~ embodiment 124 and comparative example 13 ~ comparative example 15: alignment films of the present invention can not undermine lingeringly in addition large to pencil hardness improvement.
[embodiment 125]
Glass substrate is replaced with the transparent glass substrate being provided with ITO electrode at one side, utilize the method according to embodiment 110 in addition and obtain the alignment films C-1 that thickness is about 100nm.Make 2 be formed in ITO electrode the substrate of these alignment films be formed alignment films in the face of to, and arrange in order to the space of injection liquid crystal composite between the alignment films of subtend and fitted.Now, make to become parallel the polarization direction of the linear polarization that each alignment films is irradiated.In this unit, inject following shown positive type liquid crystal composition A, production unit thickness is 3.5 μm liquid crystal cells C-1 (liquid crystal display device) (Fig. 1).
< positive type liquid crystal composition A>
[change 1761
Physics value: NI is 100.1 DEG C; Δ ε is 5.1; Δ n is 0.093; η is 25.6mPas.
By this liquid crystal cells of visual observation C-1, result is not observed liquid crystal self seeding mouth completely and is arranged as radial so-called flow orientation.Make polarizing microscope become Nicol crossed state, if make liquid crystal cells C-1 rotate, observe clear bright state and dark state.The tilt angle (being sometimes slightly designated as Pt angle below) of this liquid crystal cells C-1 is 0.1 °.And VHR (voltage retention) and ion density are 99.1% (30Hz), 87.6% (0.3Hz) and 75pC.With this liquid crystal cells of microscopic examination, result is unconfirmed to friction injury or cut slag (cutchips).
[embodiment 126 ~ embodiment 139] and [comparative example 16 ~ comparative example 18]
According to the method recorded in embodiment 125, also make liquid crystal cells C-2 ~ liquid crystal cells C-15 and liquid crystal cells D-1 ~ liquid crystal cells D-3 about varnish C-2 ~ varnish C-15 and varnish D-1 ~ varnish D-3, measure state of orientation, tilt angle, VHR, ion density and resistance to reduction.Measurement result is shown in table 11 and table 12.Embodiment 125 is also disclosed in table 11 again.
Rub resistance
Zero: do not observe friction injury or cut slag
×: observe friction injury or cut slag
[table 11]
Table 11
[table 12]
Table 12
In liquid crystal cells C-1 ~ liquid crystal cells C-15, demonstrate good state of orientation, demonstrate good rub resistance.And the electrical specification represented by VHR, ion density is also good result.In liquid crystal cells D-1 ~ liquid crystal cells D-3, although demonstrate good state of orientation, electrical specification is also good, produces friction injury or cuts slag.
[embodiment 140 ~ embodiment 148]
As shown in following table 13, obtain according to method described in embodiment 5 varnish that the polyamic acid concentration becoming blended polymkeric substance is 5 % by weight.The total amount of raw material is set to the molar percentage (mol%) when 100mol% by () interior expression.
[table 13]
Table 13
[embodiment 149]
Be provided with agitating wing, nitrogen ingress pipe 50mL eggplant type flask in take in 2.0g embodiment 5 varnish E-1 synthesized in synthesized varnish A-1 and 8.0g embodiment 140, add 5.0gN-N-methyl-2-2-pyrrolidone N-and 5.0g ethylene glycol butyl ether wherein and at room temperature carry out stirring for 1 hour, obtaining the alignment agent (varnish A-1/ varnish E-1) that resinous principle concentration is 2.5 % by weight.Use the alignment agent of gained, make alignment films F-1 according to method described in embodiment 35.Measure the delay of this alignment films F-1, result is 19.6nm.And measure the pencil hardness of the alignment films F-1 of gained, result is 4H.
[embodiment 150 ~ embodiment 157 and comparative example 19 ~ comparative example 21]
Change the varnish used, make alignment films F-2 ~ alignment films F-9 and alignment films G-1 ~ alignment films G-3 according to embodiment 149 in addition, measure and postpone and pencil hardness.Used varnish and measurement result and embodiment 149 are shown in table 14, table 15 in the lump.In addition, in table 14, table 15, varnish A is that varnish B is the varnish containing blended polymkeric substance containing using the varnish with the polymkeric substance of the raw material of photoisomerization structure.
[table 14]
Table 14
Embodiment Varnish A Varnish B Alignment films Pencil hardness Postpone
149 A-1 E-1 F-1 4H 19.6
150 A-1 E-2 F-2 5H 18.7
151 A-1 E-3 F-3 3H 18.5
152 A-1 E-4 F-4 4H 19.4
153 A-1 E-5 F-5 5H 19.6
154 A-4 E-6 F-6 4H 18.9
155 A-4 E-7 F-7 4H 19.4
156 A-4 E-8 F-8 5H 18.8
157 A-4 E-9 F-9 3H 19.6
[table 15]
Table 15
Comparative example Varnish A Varnish B Alignment films Pencil hardness Postpone
19 B-1 E-1 G-1 5B 18.6
20 B-2 E-2 G-2 2H 2.4
21 B-3 E-3 G-3 H 2.8
Known in alignment films F-1 ~ alignment films F-9, all there is large delay and high pencil hardness in all alignment films.In alignment films G-1, although have large delay, pencil hardness is low.In alignment films G-2 and alignment films G-3, not talkative pencil hardness is fully high, and postpones also little.
[embodiment 158]
Glass substrate is replaced with the transparent glass substrate being provided with ITO electrode at one side, utilize the method according to embodiment 149 in addition and obtain the alignment films F-1 that thickness is about 100nm.Make 2 be formed in ITO electrode the substrate of these alignment films be formed alignment films in the face of to, and arrange in order to the space of injection liquid crystal composite between the alignment films of subtend and fitted.Now, make to become parallel the polarization direction of the linear polarization that each alignment films is irradiated.In this unit, inject following shown positive type liquid crystal composition A, production unit thickness is the liquid crystal cells F-1 (liquid crystal display device) of 3.5 μm.
By this liquid crystal cells of visual observation F-1, result is not observed liquid crystal self seeding mouth completely and is arranged as radial so-called flow orientation.Make polarizing microscope become Nicol crossed state, if make liquid crystal cells F-1 rotate, observe clear bright state and dark state.The tilt angle of this liquid crystal cells F-1 is 0.1 °.And VHR (voltage retention) and ion density are 99.0% (30Hz), 87.2% (0.3Hz) and 80pC.Measure the resistance to reduction of this liquid crystal cells, result, after keystroke handling, is not observed the reduction of alignment films completely or peels off.
[embodiment 159 ~ embodiment 166 and comparative example 22 ~ comparative example 24]
Change the varnish used, make liquid crystal cells according to embodiment 158 in addition, measure state of orientation, tilt angle, VHR, ion density and resistance to reduction.Used varnish and measurement result and embodiment 158 are shown in table 16, table 17 in the lump.
Resistance to reduction
Zero: after keystroke handling, do not observe the reduction of alignment films with microscope or peel off
×: after keystroke handling, with microscopic examination to the reduction of alignment films or peel off
[table 16]
Table 16
[table 17]
Table 17
In liquid crystal cells F-1 ~ liquid crystal cells F-9, demonstrate good state of orientation, demonstrate good resistance to reduction.And the electrical specification represented by VHR, ion density is also good result.In liquid crystal cells G-1, although demonstrate good state of orientation, electrical specification is also good, produces the reduction of alignment films.In liquid crystal cells G-2 and liquid crystal cells G-3, do not observe the reduction of alignment films, but confirm the flow orientation of liquid crystal, become the liquid crystal cells that display is bad.
[industrial utilizability]
By using alignment agent, in any means of optical alignment method and rubbing manipulation, all can obtain orientation high and do not produce the alignment films of reduction, the polyamic acid or derivatives thereof that it is raw material that described alignment agent uses with the tetracarboxylic dianhydride containing triazole of the present invention.By using this alignment films, the liquid crystal display device of display characteristic and excellent electrical characteristic can be obtained.

Claims (12)

1. a tetracarboxylic dianhydride, is characterized in that: it represents with formula (1);
In formula (1), X is the divalent organic radical comprising at least one triazole ring;
R 1and R 2independently for being selected from of the group of following 3 valency bases;
At least one hydrogen of these bases also can be replaced by methyl, ethyl or phenyl.
2. tetracarboxylic dianhydride according to claim 1, is characterized in that: it represents with formula (2);
In formula (2), X is the divalent organic radical comprising at least one triazole ring.
3. tetracarboxylic dianhydride according to claim 1, is characterized in that: it represents with formula (3);
In formula (3), X 1it is triazole ring;
A 1and A 2independently for singly-bound or carbon number are the alkylidene group of 1 ~ 12;
At least one hydrogen in described alkylidene group also can replaced by fluorine; And,
At least one-CH 2-also can be replaced by-O-,-COO-,-OCO-,-CONH-,-NHCO-,-CH=CH-or-C ≡ C-.
4. tetracarboxylic dianhydride according to claim 1, is characterized in that: it represents with formula (4);
In formula (4), X 1with X 2it is triazole ring;
A 1~ A 3independently for singly-bound or carbon number are the alkylidene group of 1 ~ 12;
At least one hydrogen in described alkylidene group also can replaced by fluorine; And,
At least one-CH in described alkylidene group 2-also can be replaced by-O-,-COO-,-OCO-,-CONH-,-NHCO-,-CH=CH-or-C ≡ C-.
5. a polyamic acid or derivatives thereof, is characterized in that: it makes to comprise the tetracarboxylic dianhydride of at least one tetracarboxylic dianhydride according to any one of claim 1 to 4 and diamine reactant and obtains.
6. a liquid crystal aligning agent, is characterized in that: it is containing polyamic acid or derivatives thereof according to claim 5.
7. liquid crystal aligning agent according to claim 6, is characterized in that: it is containing polyamic acid or derivatives thereof according to claim 5 and other polymkeric substance.
8. a light orientation liquid crystal aligning agent, is characterized in that: it is the liquid crystal aligning agent according to claim 6 or 7.
9. a friction liquid crystal aligning agent, is characterized in that: it is the liquid crystal aligning agent according to claim 6 or 7.
10. a liquid crystal aligning agent used for liquid crystal display element for Transverse electric-field type, is characterized in that: it is the liquid crystal aligning agent according to any one of claim 6 to 9.
11. 1 kinds of liquid crystal orientation films, is characterized in that: it is formed by the liquid crystal aligning agent according to any one of claim 6 to 10.
12. 1 kinds of liquid crystal indicators, is characterized in that: it comprises liquid crystal orientation film according to claim 11.
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