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CN102337140A - Liquid crystal aligning agent for retardation film, liquid crystal alignment film for retardation film, and retardation film and process for production thereof - Google Patents

Liquid crystal aligning agent for retardation film, liquid crystal alignment film for retardation film, and retardation film and process for production thereof Download PDF

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Publication number
CN102337140A
CN102337140A CN2011102046487A CN201110204648A CN102337140A CN 102337140 A CN102337140 A CN 102337140A CN 2011102046487 A CN2011102046487 A CN 2011102046487A CN 201110204648 A CN201110204648 A CN 201110204648A CN 102337140 A CN102337140 A CN 102337140A
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liquid crystal
group
crystal aligning
phase
aligning agent
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CN102337140B (en
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永尾隆
安田博幸
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JSR Corp
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
    • C08L83/04—Polysiloxanes
    • C08L83/06—Polysiloxanes containing silicon bound to oxygen-containing groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
    • C08L83/04—Polysiloxanes
    • C08L83/08—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/30—Polarising elements

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  • Polymers & Plastics (AREA)
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  • General Physics & Mathematics (AREA)
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  • Silicon Polymers (AREA)
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Abstract

The invention relates to a liquid crystal aligning agent for a retardation film, a liquid crystal alignment film for a retardation film, and a retardation film and a process for production thereof. The invention aims at providing a liquid crystal aligning agent capable of forming a liquid crystal alignment film for a retardation film, a retardation film provided with a liquid crystal alignment film for the retardation film and excellent liquid crystal alignment performance and thermal stability, and a manufacture method for the retardation film, the liquid crystal aligning agent can be in light alignment even few radioactive rays illuminate, and no heating procedure is needed during and after illumination. The invention is a liquid crystal aligning agent for a retardation film comprising [A] polysiloxane provided with a light alignment group. The light alignment group is preferably a group provided with a cinnamic acid structure.

Description

Phase-contrast film with liquid crystal aligning agent, phase-contrast film with liquid crystal orientation film, phase-contrast film and method of manufacture thereof
Technical field
The present invention relates to phase-contrast film with liquid crystal aligning agent, phase-contrast film with liquid crystal orientation film, phase-contrast film and method of manufacture thereof.
Background technology
Liquid-crystal display (LCD) is in widespread uses such as TV and various watch-dogs.As (with reference to patent documentations 1 and 2) such as the known for example STN of display element of LCD (supertwist is to row) type, TN (twisted-nematic) type, IPS (face intra) type, VA (vertical orientated) type, PSA (polymkeric substance continues to aim at) types.Various optical materials have been used in this liquid crystal display device; In them based on eliminate to show painted purpose and eliminate the purpose that changes the such view angle dependency of Show Color and contrast gradient according to the angle of seeing, use phase-contrast film (with reference to patent documentation 3 and 4).
At present, phase-contrast film utilizes the extension operation manufacturing of plastics film, is polymerizable liquid crystal is solidified and to make for the phase-contrast film with more complicated optical property.In the method, in order to make the relative real estate of polymerizable liquid crystal molecule,, generally be the method that liquid crystal orientation film is set at substrate surface in the prescribed direction orientation.This liquid crystal orientation film forms in the certain orientation rubbed substrate surperficial rubbing manipulation of the surperficial organic membrane that forms usually through cloth materials such as nylon.Yet, if carry out friction treatment, in operation, be easy to generate dust or static, thus at the surface adhesion dust of liquid crystal orientation film, possibly produce show bad.In addition, in friction treatment,, be difficult on direction arbitrarily and critically control the liquid crystal aligning direction because the restriction of manufacturing process is big.
Therefore; As with the friction treatment diverse ways; Known have through to photosensitive films such as the polyvinyl cinnamate irradiation polarized light of substrate surface formation or the radioactive rays of non-polarized light, gives the optical alignment method (with reference to patent documentation 5～15) of liquid crystal aligning ability.According to this optical alignment method, can not produce dust or static, can realize uniform liquid crystal aligning.And, compare with friction treatment, can go up and critically control the liquid crystal aligning direction in any direction.In addition,, use photomask etc., can on a substrate, form the different a plurality of zones of liquid crystal aligning direction arbitrarily through when the radiation exposure.Yet, in existing technology, have the such problem (with reference to patent documentation 16) of cumulative exposure amount that must heat when shining radioactive rays and must be very big.
On the other hand, the technology of popular in recent years demonstration 3D rendering also can watch the indicating meter of 3D rendering to popularize gradually in the family.For example in patent documentation 17, introduced the method for the polaroid glasses that use polaroid with following configuration as the display mode of 3D rendering: right eye with image and left eye with image in; Form the polarized condition pictures different, right eye and left eye can only be seen the image (with reference to patent documentation 17) of polarized condition separately.The stereo-picture that this mode obtains is flicker not, and through putting on light weight and cheap polaroid glasses, the viewer can observe stereo-picture.
As forming the prior art of polarized condition pictures different in image with image and left eye at above-mentioned right eye, for Projection Display, be to use two polarisation projector, on screen,, form stereo-picture with both picture registrations; Perhaps be image for direct-view shows, perhaps form through the polarisation that is configured in the polarizing film on the real estate is disposed each pixel through axle differently through half-mirror or synthetic two display unit of polarizer.Yet, in order to make two different images of polarizing axis projection simultaneously usually, necessarily require two display unit or projecting device, be unfavorable for using in the family.As in a display unit; Form right eye with image and left eye prior art with the polarized condition pictures different of image; Known have a following manner: will be between pixel adjacent, and the polarizing layer of the mosaic shape that polarizing axis is mutually orthogonal, the front of driving fit to a display unit; The viewer can observe stereo-picture through putting on polaroid glasses.
Must form the formation pattern phase-contrast film of micrometre-grade pattern as this polarizing layer.As the method for manufacture of this formation pattern phase-contrast film, for example in patent documentation 18, disclose the method for photosensitive polymer layer irradiation polarized light etc.Yet polarisation irradiation must very big irradiation dose, and the thermostability of photosensitive polymer layer can't fully meet the demands.
Based on this problem, hope that developing the high phase-contrast film of a kind of productivity uses liquid crystal aligning agent, this liquid crystal aligning agent can be made liquid crystal aligning property and excellent heat stability effectively, and the formation pattern phase-contrast film that can critically control.
[prior art document]
[patent documentation]
[patent documentation 1] japanese kokai publication sho 56-91277 communique
[patent documentation 2] japanese kokai publication hei 1-120528 communique
[patent documentation 3] japanese kokai publication hei 4-229828 communique
[patent documentation 4] japanese kokai publication hei 4-258923 communique
[patent documentation 5] japanese kokai publication hei 6-287453 communique
[patent documentation 6] japanese kokai publication hei 10-251646 communique
[patent documentation 7] japanese kokai publication hei 11-2815 communique
[patent documentation 8] japanese kokai publication hei 11-152475 communique
[patent documentation 9] TOHKEMY 2000-144136 communique
[patent documentation 10] TOHKEMY 2000-319510 communique
[patent documentation 11] TOHKEMY 2000-281724 communique
[patent documentation 12] japanese kokai publication hei 9-297313 communique
[patent documentation 13] TOHKEMY 2003-307736 communique
[patent documentation 14] TOHKEMY 2004-163646 communique
[patent documentation 15] TOHKEMY 2002-250924 communique
[patent documentation 16] japanese kokai publication hei 10-278123 communique
No. 3461680 communique of [patent documentation 17] japanese
[patent documentation 18] TOHKEMY 2005-49865 communique
Summary of the invention
The present invention is based on the problems referred to above proposition; Its purpose be to provide a kind of can form phase-contrast film with the liquid crystal aligning agent of liquid crystal orientation film, have phase-contrast film and the method for manufacture thereof of this phase-contrast film with liquid crystal orientation film and liquid crystal aligning property and excellent heat stability; Even above-mentioned liquid crystal aligning agent shines a spot of radioactive rays; Also can be orientated by light, and when irradiation with after the irradiation, do not need heating process.
The present invention who proposes in order to address the above problem is that a kind of phase-contrast film is used liquid crystal aligning agent, and it comprises the organopolysiloxane that [A] have light orientation group (below, be also referred to as " [A] light orientation organopolysiloxane ").
Because this liquid crystal aligning agent contains [A] light orientation organopolysiloxane, thus through highly sensitive smooth orientation, can reduce be orientated the rayed amount of palpus.In addition, because this liquid crystal aligning agent does not need heating process when radiation exposure with after the irradiation, so can make phase-contrast film effectively.In addition, owing to adopt organopolysiloxane as main chain, the phase-contrast film that is formed by this liquid crystal aligning agent has excellent chemicalstability, thermostability.
In this liquid crystal aligning agent, the group that above-mentioned smooth orientation group preferably has the styracin structure.As light orientation group, use to have the group of styracin or derivatives thereof as the styracin structure of basic framework, thus, introduce easily and have higher light orientation characteristic by the phase-contrast film that this liquid crystal aligning agent forms.
In this liquid crystal aligning agent; Group with above-mentioned styracin structure be preferably by select in the group that constitutes from the group of the compound shown in the following formula (1) with from the group of the compound shown in the formula (2) at least a (below; Also the compound shown in compound shown in the following formula (1) and the formula (2) is called " specific cinnamic acid derivative ")
(in the formula (1), R 1Be phenylene, biphenylene, inferior terphenyl or cyclohexylidene.The part of the Wasserstoffatoms of this phenylene, biphenylene, inferior terphenyl or cyclohexylidene or can be that 1～10 alkyl, the carbonatoms that can have fluorine atom are that 1～10 alkoxyl group, fluorine atom or cyanic acid replace all by carbonatoms.R 2Be singly-bound, carbonatoms be 1～3 alkane 2 basis, Sauerstoffatom, sulphur atom ,-CH=CH-,-NH-,-COO-or-OCO-.A is 0～3 integer.Wherein, be 2 when above at a, R 1And R 2Separately can be identical, also can be different.R 3Be fluorine atom or cyanic acid.B is 0～4 integer;
In the formula (2), R 4Be phenylene or cyclohexylidene.The part of the Wasserstoffatoms of this phenylene or cyclohexylidene or can be that 1～10 chain or cyclic alkyl, carbonatoms are that 1～10 chain or cyclic naphthenic base, fluorine atom or cyanic acid replace all by carbonatoms.R 5Be singly-bound, carbonatoms be 1～3 alkane 2 basis, Sauerstoffatom, sulphur atom or-NH-.C is 1～3 integer.Wherein, c is 2 when above, R 4And R 5Separately can be identical, also can be different.R 6Be fluorine atom or cyanic acid.D is 0～4 integer.R 7Be Sauerstoffatom ,-COO-* or-OCO-*.Wherein, the connecting key and the R of band " * " 8Connect.R 8Be the aromatic group of divalent, the ester ring type group of divalent, the heterocyclic radical of divalent or the condensed ring radical of divalent.R 9Be singly-bound ,-OCO-(CH 2) f-* or-O (CH 2) g-*.Wherein, the connecting key of band " * " is connected with carboxyl.F and g are respectively 1～10 integers.E is 0～3 integer.Wherein, be 2 when above at e, R 7And R 8Separately can be identical, also can be different).
As group,, can further improve the light orientation characteristic through using group from above-mentioned specific cinnamic acid derivative with above-mentioned styracin structure.
In this liquid crystal aligning agent; That selects in the group that [A] light orientation organopolysiloxane preferably is made up of the condenses of the organopolysiloxane with epoxy group(ing), its hydrolyzate and hydrolyzate thereof is at least a, with at least a reaction product of selecting in the group that is made up of the compound shown in compound shown in the above-mentioned formula (1) and the above-mentioned formula (2).In this liquid crystal aligning agent; Have the organopolysiloxane of epoxy group(ing) and the reactivity between the specific cinnamic acid derivative through utilization, in as the organopolysiloxane of main chain, can easily import side-chain radical from specific cinnamic acid derivative with light orientation.
This liquid crystal aligning agent preferably further contains [B] by at least a polymkeric substance of selecting in polyamic acid, polyimide, vinyl unsaturated polymerizable compound thing and the group that do not have the organopolysiloxane of light orientation group to constitute (below, be also referred to as " [B] other polymkeric substance ").When containing these [B] other polymkeric substance, the phase-contrast film that forms by this liquid crystal aligning agent with liquid crystal orientation film in, obviously near its top layer, have organopolysiloxane unevenly.Therefore, through increasing the content of other polymkeric substance, even reduce the content of the organopolysiloxane in this liquid crystal aligning agent, organopolysiloxane is existed unevenly at alignment layer surface, so can obtain enough liquid crystal aligning property.Therefore, in the present invention, can reduce the content of the high organopolysiloxane of manufacturing cost in this liquid crystal aligning agent, consequently can reduce the manufacturing cost of this liquid crystal aligning agent.
This liquid crystal aligning agent preferably further contains the compound that [C] have more than two at least a structure of selecting in the group that the tert-butyl ester structure by the 1-alkyl-cycloalkyl ester structure of the ketal ester structure of the acetal ester structure of carboxylic acid, carboxylic acid, carboxylic acid and carboxylic acid constitutes (below, be also referred to as " compound that [C] contains ester structure " sometimes).Contain the compound that [C] contains ester structure through this liquid crystal aligning agent, in ablating work procedure (afterwards curing), produce acid,, thereby can improve the thermotolerance of the phase-contrast film that obtains because of the acid that produces promotes the crosslinked of [A] light orientation organopolysiloxane.
This liquid crystal aligning agent preferably further contains the solvent shown in [D] following formula (6) (below, be also referred to as " [D] solvent " sometimes),
R d1-COO-R d2 (6)
(in the formula (6), R D1Be that carbonatoms is that 1～6 alkyl, carbonatoms are 3～6 naphthenic base, phenyl or benzyl.Wherein, abovementioned alkyl can have between C-C-O-.R D2Be that carbonatoms is 1～8 1 valency organic group).
Comprise [D] solvent of the ad hoc structure with ester group through this liquid crystal aligning agent, thereby can improve this liquid crystal aligning agent and phase-contrast film adaptation with substrate.
This liquid crystal aligning agent preferably further contains [E] phase-contrast film is had rodent solvent (below, be also referred to as " [E] solvent " sometimes) with substrate.Comprise through this liquid crystal aligning agent phase-contrast film is had rodent [E] solvent with substrate, can further improve this liquid crystal aligning agent and phase-contrast film adaptation with substrate.
This liquid crystal aligning agent preferably further contains the compound that [F] contain the group with polymerizability carbon-to-carbon double bond (below, be also referred to as " [F] compound ").Contain [F] compound through this liquid crystal aligning agent, can further improve and the adaptation of phase-contrast film with substrate or liquid crystal layer.
This liquid crystal aligning agent is suitable for forming liquid crystal orientation film through optical alignment method, particularly forms phase-contrast film and makes employed liquid crystal orientation film.In addition, in the present invention, also be fit to comprise: the phase-contrast film that contains the different zone of two or more liquid crystal aligning directions with liquid crystal orientation film, have the phase-contrast film of this phase-contrast film with liquid crystal orientation film.
The method of manufacture of the phase-contrast film that comprises among the present invention comprises following operation:
(1) on substrate, is coated with the operation of this phase-contrast film with liquid crystal aligning agent;
(2) to the irradiation radioactive rays of filming, give the liquid crystal aligning ability, form the operation of phase-contrast film with liquid crystal orientation film;
(3) to the operation of phase-contrast film with at least a portion coating polymerizable liquid crystal of liquid crystal orientation film, and
(4) make the operation of the curing of coating that has been coated with polymerizable liquid crystal.
In method of manufacture of the present invention, even shine a spot of radioactive rays, also can be orientated by light, and when irradiation with after the irradiation, do not need heating process.Therefore, can make phase-contrast film effectively, productivity is high, and helps to cut down manufacturing cost.
In addition, also be fit to comprise the method for manufacture that contains the phase-contrast film in the 3D video purposes in the present invention with out of phase difference zone.Comprise following operation in the above-mentioned operation (2) of this method of manufacture:
(2-1) to the radioactive rays of the irradiation first direction of filming, give the operation of the liquid crystal aligning ability of first direction; And
(2-2) to the radioactive rays of the part irradiation of the filming second direction different, further give the operation of the liquid crystal aligning ability of second direction with first direction.
In addition, as other method of manufacture, comprise following operation in the above-mentioned operation (2):
(2-1 ') to the radioactive rays of the irradiation first direction of filming, give the operation of the liquid crystal aligning ability of first direction; And
(2-2 ') in the above-mentioned part of not shining radioactive rays at least of filming, shine the radioactive rays of the second direction different with first direction, give the operation of the liquid crystal aligning ability of second direction.
Use liquid crystal aligning agent through phase-contrast film of the present invention, even shine a spot of radioactive rays, also can be orientated by light, and when irradiation with after the irradiation, do not need heating process.Therefore, use this phase-contrast film to have excellent liquid crystal aligning property and thermostability with liquid crystal orientation film and phase-contrast film with the phase-contrast film of liquid crystal aligning agent.In addition, through the method for manufacture of phase-contrast film of the present invention, can make the phase-contrast film of liquid crystal aligning property and excellent heat stability simple and reliablely.
Embodiment
< phase-contrast film is used liquid crystal aligning agent >
Phase-contrast film of the present invention contains [A] light orientation organopolysiloxane with liquid crystal aligning agent.Owing to contain [A] light orientation organopolysiloxane, thus through highly sensitive smooth orientation, can reduce be orientated the rayed amount of palpus.In addition, because this liquid crystal aligning agent does not need heating process when radiation exposure with after the irradiation, so can make phase-contrast film effectively.In addition, the liquid crystal aligning property and the excellent heat stability of the resulting phase-contrast film of this liquid crystal aligning agent.In addition, this liquid crystal aligning agent preferably contains compound, [D] solvent, [E] solvent, [F] compound that [B] other polymkeric substance, [C] contain ester structure, only otherwise damage effect of the present invention, and then can contain other optional member.Below, the compound, [D] solvent, [E] solvent, [F] compound and the optional member that [A] light orientation organopolysiloxane, [B] other polymkeric substance, [C] are contained ester structure are described in detail.
< [A] light orientation organopolysiloxane >
[A] light orientation organopolysiloxane is at least a part of in the group that the condenses that comes free organopolysiloxane, its hydrolyzate and hydrolyzate thereof constitutes, selecting as main chain, introduces light orientation group.Through light orientation group, the sensitivity of light orientation is good, can realize low rayed amount, and the liquid crystal aligning property of phase-contrast film is excellent.In addition, owing to adopt organopolysiloxane as main chain, the phase-contrast film that is formed by this liquid crystal aligning agent has excellent chemicalstability, thermostability.
As light orientation group; Can adopt group from all cpds that shows the bright dipping orientation, can enumerate out for example contain the nitrogen benzide or derivatives thereof as basic framework contain azobenzene group, contain the styracin or derivatives thereof as the group with styracin structure of basic framework, contain cinnamophenone or derivatives thereof containing the cinnamophenone group, contain UVNUL MS-40 or derivatives thereof containing the UVNUL MS-40 group, contain tonka bean camphor or derivatives thereof containing the tonka bean camphor group, contain the polyimide or derivatives thereof and contain polyimide structures etc. as basic framework as basic framework as basic framework as basic framework.In these light orientation groups,, preferably contain the group with styracin structure of styracin or derivatives thereof as basic framework if consider the easy property that high orientation can and import.
The structure of group with styracin structure does not just have special qualification so long as contain the styracin or derivatives thereof as basic framework, preferably from the group of above-mentioned specific cinnamic acid derivative.In addition, R 1Be phenylene, biphenylene, inferior terphenyl or cyclohexylidene.The part of the Wasserstoffatoms of this phenylene, biphenylene, inferior terphenyl or cyclohexylidene or can be that 1～10 alkyl, the carbonatoms with fluorine atom are that 1～10 alkoxyl group, fluorine atom or cyanic acid replace all by carbonatoms.R 2Be singly-bound, carbonatoms be 1～3 alkane 2 basis, Sauerstoffatom, sulphur atom ,-CH=CH-,-NH-,-COO-or-OCO-.A is 0～3 integer.Wherein, be 2 when above at a, R 1And R 2Separately can be identical, also can be different.R 3Be fluorine atom or cyanic acid.B is 0～4 integer.
As the compound shown in the above-mentioned formula (1), can enumerate out the compound shown in the for example following formula.
Among them, as R 1Be preferably unsubstituted phenylene or be 1～3 the substituted phenylene of alkyl by fluorine atom or carbonatoms.R 2Preferred singly-bound, Sauerstoffatom or-CH 2=CH 2-.B preferred 0～1.A is 1～3 o'clock, and b is preferably 0 especially.
In the above-mentioned formula (2), R 4Be phenylene or cyclohexylidene.The part of the Wasserstoffatoms of this phenylene or cyclohexylidene or can be that 1～10 chain or cyclic alkyl, carbonatoms are that 1～10 chain or cyclic alkoxyl group, fluorine atom or cyanic acid replace all by carbonatoms.R 5Be singly-bound, carbonatoms be 1～3 alkane 2 basis, Sauerstoffatom, sulphur atom or-NH-.C is 1～3 integer.Wherein, be 2 when above at c, R 4And R 5Separately can be identical, also can be different.R 6Be fluorine atom or cyanic acid.D is 0～4 integer.R 7Be Sauerstoffatom ,-COO-* or-OCO-*.Wherein, the connecting key and the R of band " * " 8Connect.R 8Be the aromatic group of divalent, the ester ring type group of divalent, the heterocyclic radical of divalent or the condensed ring radical of divalent.R 9Be singly-bound ,-OCO-(CH 2) f-* or-O (CH 2) g-*.Wherein, the connecting key of band " * " is connected with carboxyl.F and g are respectively 1～10 integers.E is 0～3 integer.Wherein, be 2 when above at e, R 7And R 8Separately can be identical, also can be different.
As the compound shown in the above-mentioned formula (2), can enumerate out the compound shown in the for example following formula (2-1)～(2-2)
Figure BSA00000541896400121
(in the formula, Q is that carbonatoms is that 1～10 chain or cyclic alkyl, carbonatoms are 1～10 chain or cyclic alkoxyl group, fluorine atom or cyanic acid.F is identical with the definition of formula (2)).
Synthesis step to specific cinnamic acid derivative does not have special qualification, can make up existing known method and carry out.As representational synthesis step, for example can enumerate out (i) under alkaline condition, make compound and vinylformic acid with the substituted phenyl ring skeleton of halogen atom, in the presence of transition-metal catalyst, react, obtain the method for specific cinnamic acid derivative; (ii) under alkaline condition, the Wasserstoffatoms that makes phenyl ring is by substituted styracin of halogen atom and the compound with the substituted phenyl ring skeleton of halogen atom, and reaction forms the method for specific cinnamic acid derivative etc. in the presence of transition-metal catalyst.
At least a part of selecting in the group that the condenses of next free organopolysiloxane, its hydrolyzate and the hydrolyzate thereof that in [A] light orientation organopolysiloxane, contains as main chain constitutes; So long as have from can just not having special qualification in the part of the structure of himself introducing above-mentioned smooth orientation group.[A] light orientation organopolysiloxane comprises at least a part of selecting in the group that this condenses that comes free organopolysiloxane, its hydrolyzate, its hydrolyzate constitutes, with the group from the compound that demonstrates above-mentioned smooth orientation.
As the structure that can introduce above-mentioned smooth orientation group, can enumerate out for example hydroxyl, epoxy group(ing), amino, carboxyl, sulfydryl, ester group, carboxamido-group etc.Among them, if consider the easy property of importing and preparation, then preferred epoxy group(ing).
[A] light orientation organopolysiloxane; Be preferably select in the group that the condenses by the organopolysiloxane with epoxy group(ing), its hydrolysate and hydrolyzate thereof constitutes at least a (below; Sometimes be also referred to as " organopolysiloxane " with epoxy group(ing)), with the reaction product of the compound shown in above-mentioned formula (1) and/or (2).In this liquid crystal aligning agent; Have the organopolysiloxane of epoxy group(ing) and the reactivity between the specific cinnamic acid derivative through utilization, in as the organopolysiloxane of main chain, can import group easily from specific cinnamic acid derivative with light orientation.
Above-mentioned have the organopolysiloxane of epoxy group(ing) so long as on organopolysiloxane, import epoxy group(ing) as side chain, just do not have special qualification.Be preferably select in the group that constitutes by the condenses of the organopolysiloxane with the structural unit shown in the following formula (3), its hydrolyzate and hydrolyzate thereof at least a as above-mentioned organopolysiloxane with epoxy group(ing),
Figure BSA00000541896400141
(in the formula (3), X 1It is 1 valency organic group with epoxy group(ing).Y 1Be that hydroxyl, carbonatoms are that 1～10 alkoxyl group, carbonatoms are that 1～20 alkyl or carbonatoms are 6～20 aryl).
In addition; Hydrolytic condensate with organopolysiloxane of the structural unit shown in the above-mentioned formula (3) is not only the hydrolytic condensate between this organopolysiloxane; Generate in the process of organopolysiloxane but also be included in, produce the notion of the hydrolytic condensate of the branch of main chain or the situation that the organopolysiloxane that obtains such as crosslinked has the structural unit shown in the above-mentioned formula (3) by the hydrolytic condensation of the structural unit shown in the above-mentioned formula (3).
X in the above-mentioned formula (3) 1So long as have 1 valency organic group of epoxy group(ing), just there is not special qualification, can enumerate out group that for example comprises glycidyl, glycidoxypropyl, epoxycyclohexyl etc.As X 1Preferred following formula (X 1-1) or (X 1It is-2) represented,
Figure BSA00000541896400142
(formula (X 1-1) in, A is Sauerstoffatom or singly-bound.H is 1～3 integer.I is 0～6 integer.Wherein, be 0 o'clock at i, A is a singly-bound.
Formula (X 1-2) in, j is 1～6 integer.
Formula (X 1-1) and (X 1-2) in, " * " representes connecting key respectively).
In addition, above-mentioned formula (X 1-1) and (X 1-2) in the epoxy group(ing) shown in, preferred following formula (X 1-1-1) or formula (X 1-the group shown in 2-1),
Figure BSA00000541896400151
(formula (X 1-1-1) or formula (X 1-2-1) in, " * " representes connecting key).
Y in the above-mentioned formula (3) 1In, be 1～10 alkoxyl group as carbonatoms, can enumerate out for example methoxyl group, oxyethyl group etc.;
As carbonatoms is 1～20 alkyl, can enumerate out for example methyl, ethyl, n-propyl, normal-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, positive decyl, dodecyl, n-tridecane base, n-tetradecane base, Pentadecane base, n-hexadecyl, NSC 172782 base, Octadecane base, NSC 77136 base, NSC 62789 base etc.;
As carbonatoms is 6～20 aryl, can enumerate out for example phenyl etc.
Organopolysiloxane with epoxy group(ing) is preferably 500～100,000 through the weight-average molecular weight (Mw) of the polystyrene conversion that GPC (GPC) is measured, and more preferably 1,000～10,000, be preferably 1,000～5,000 especially.
In addition, the Mw in this specification sheets is the value of the polystyrene conversion measured of the GPC through following manner.
Post: eastern ソ one manufactured, TSKgelGRCXLII
Solvent: THF
Temperature: 40 ℃
Pressure: 6.8MPa
This organopolysiloxane with epoxy group(ing) preferably will have epoxy group(ing) silane compound, or have the silane compound of epoxy group(ing) and a mixture of other silane compound; Preferably can be in the presence of suitable organic solvent, water and catalyzer, synthetic through hydrolysis or hydrolysis, condensation.
As above-mentioned silane compound with epoxy group(ing); Can enumerate out for example 3-glycidyl ether oxygen base propyl trimethoxy silicane, 3-glycidyl ether oxygen base propyl-triethoxysilicane, 3-glycidyl ether oxygen base propyl group methyl dimethoxysilane, 3-glycidyl ether oxygen base propyl group methyldiethoxysilane, 3-glycidyl ether oxygen base propyl-dimethyl methoxy silane, 3-glycidyl ether oxygen base propyl-dimethyl Ethoxysilane, 2-(3; The 4-epoxycyclohexyl) ethyl trimethoxy silane, 2-(3, the 4-epoxycyclohexyl) ethyl triethoxysilane etc.
Examples of the other silane compounds, can include, for example tetrachloro-silane, tetramethoxysilane, tetraethoxysilane, tetra-n-propoxy silane, tetraisopropoxy silane, tetra-n-butoxy silane, tetra-sec butoxy, trichlorosilane, trimethoxysilane, triethoxysilane, tri-n-propoxysilane, triisopropoxysilane, tri-n-butoxy silane, tri-sec-butoxy silane, fluoro trichloro-silane, fluoro trimethoxysilane, triethoxysilane fluoro, fluoroalkyl silane tri-n-propoxy group, a fluoroalkyl triisopropoxysilane, tri-n-butoxy silane fluoro, fluoro three butoxy silane, methyltrichlorosilane, methyltrimethoxysilane, methyltriethoxysilane, methyl tri-propoxysilane, methyl triisopropoxysilane, methyl tri- butoxy silane, methyl tri-sec-butoxy silane, 2 - (trifluoromethyl) ethyl trichloro silane, 2 - (trifluoromethyl) ethyl trimethoxysilane, 2 - ( fluoromethyl) ethyl triethoxysilane, 2 - (trifluoromethyl) ethyl tri-n-propoxy silane, 2 - (trifluoromethyl) ethyl triisopropoxysilane, 2 - (trifluoromethyl) ethyl tri-n-butoxy silane, 2 - (trifluoromethyl) ethyl tri-sec-butoxy silane, 2 - (perfluoro-n-hexyl) chlorosilane ethyltriphenylphosphonium 2 - (perfluoro-n-hexyl) ethyl trimethoxysilane, 2 - (perfluoro-n-hexyl) ethyl triethoxysilane, 2 - (perfluoro-n-hexyl)? ethyl tri-n-propoxy silane, 2 - (perfluoro-n-hexyl) ethyl triisopropoxysilane, 2 - (perfluoro-n-hexyl) ethyl tri-n-butoxy silane, 2 - (perfluoro-n-hexyl)-ethyl tri-sec-butoxy silane, 2 - (perfluoro-n-octyl) ethyl trichloro silane, 2 - (perfluoro-n-octyl) ethyl trimethoxysilane, 2 - (perfluoro-n-octyl ) ethyl triethoxysilane, 2 - (perfluoro-n-octyl) ethyl tri-n-propoxy silane, 2 - (perfluoro-n-octyl) ethyl triisopropoxysilane, 2 - ( perfluoro-n-octyl) ethyl tri-n-butoxy silane, 2 - (perfluoro-n-octyl) ethyl tri-sec-butoxy silane, methyltrichlorosilane hydroxy, hydroxymethyl trimethoxysilane , hydroxyethyl trimethoxysilane, hydroxymethyl tri-n-propoxy silane, hydroxy methyl triisopropoxysilane, tri-n-butoxy silane hydroxymethyl, hydroxymethyl tri-sec-butoxy silane, 3 - (meth) acryloxy propyl triethoxy chlorosilane, 3 - (meth) acryloxy propyl trimethoxy silane, 3 - (meth) acryloxy propyl triethoxysilane 3 - (meth) acryloxypropyl tri-n-propoxy silane, 3 - (meth) acryloxypropyl triisopropoxysilane, 3 - (meth) acryloyloxy C -n-butoxy silane, 3 - (meth) acryloxypropyl tri-sec-butoxy silane, 3 - mercaptopropyl trichlorophenyl silane, 3 - mercaptopropyl trimethoxy silane, 3 - mercapto- propyl triethoxy silane, 3 - mercapto-propyl-tri-propoxy silane, 3 - mercaptopropyl triisopropoxysilane 3 - mercapto-propyl-tri-n-butoxy silane, 3 - mercapto-propyl triethoxy butoxy silane, mercaptomethyl trimethoxysilane, mercaptomethyl triethoxysilane, vinyl triethoxy chlorosilane, vinyl trimethoxysilane, vinyl triethoxysilane, vinyl tri-C silane, vinyl triisopropoxysilane, vinyl tri-n-butoxy silane, vinyl tri-sec-butoxy silane, allyl chloride, allyl trimethoxysilane, allyl triethoxysilane, allyl tri-n-propoxy group, allyl triisopropoxysilane, allyl tri-n-butoxy group, allyl tri-sec-butoxy silane, phenyl trichloro generation of silane, phenyl trimethoxysilane, phenyl triethoxysilane, phenyl tri-n-propoxysilane, phenyl triisopropoxysilane, phenyl tri-n-butoxy silane, phenyl-tri-sec-butyl silane, dimethyl dichloro silane, methyl dimethoxy silane, methyl diethoxy silicon? dioxane, methyl-di-n-propoxy silane, dimethyl diisopropoxy silane, dimethyl n-butoxy silane, methyl di-sec-butoxy silane, dimethyl chlorosilane, dimethyl dimethoxy silane, dimethyl diethoxy silane, dimethyl-n-propyl silane , dimethyl diisopropoxy silane, dimethyl di-n-butoxy silane, dimethyl di-sec-butoxy silane, (methyl) [2 - (perfluoro-n-octyl) ethyl] chloro silane, (meth) [2 - (perfluoro-n-octyl) ethyl] dimethoxysilane, (meth) [2 - (perfluoro-n-octyl) ethyl] diethoxy- silane, (meth) [2 - (perfluoro-n-octyl) ethyl] di-n-propoxy silane, (meth) [2 - (perfluoro-n-octyl) ethyl]-propoxy silane, (meth) [2 - (perfluoro-n-octyl) ethyl] di-n-butoxy silane, (meth) [2 - (perfluoro-n-octyl) ethyl] di-sec-butoxy silane, (methyl) (3 - mercaptopropyl) dichloro silane, (methyl) (3 - mercaptopropyl) dimethoxysilane, (methyl) (3 - mercapto-propyl) diethoxy silane, (methyl) (3 - mercaptopropyl) di-n-propoxy silane, (methyl) (3 - mercaptopropyl) diisopropyl silane, (meth) (3 - mercaptopropyl) At n-butoxy silane, (methyl) (3 - mercaptopropyl) di-sec-butoxy silane, (methyl) (vinyl) dichloro silane, (methyl) (vinyl) dimethoxysilane , (methyl) (vinyl) diethoxysilane, (methyl) (vinyl) di-n-propoxy silane, (methyl) (vinyl) diisopropyl silane, (meth) ( vinyl) di-n-butoxy silane, (methyl) (vinyl) di-sec-butoxy silane, divinyl chlorosilane, divinyl dimethoxysilane, divinyl diethoxysilane , divinyl di-n-propoxy silane, divinyl silane isopropoxy, n-butoxy group, divinyl silane, divinyl di-sec-butoxy silane, diphenyl chlorosilane, di phenyl dimethoxy silane, diphenyl diethoxy silane, diphenyl di-n-propoxy silane, diphenyl silane isopropoxy, n-butyl diphenyl silane, diphenyl di-sec-butoxy silane, chloromethyl dimethyl silane, dimethyl methoxy silane, ethoxy dimethyl silane, trimethylsilyl chloride, trimethylsilyl bromide, trimethylsilyl iodide , trimethyl methoxy silane, trimethyl ethoxy silane, n-propyl trimethyl silane, trimethyl silane isopropoxy, n-butoxy trimethylsilane, sec-butyl trimethoxy silane, tert-butoxy trimethylsilyl? alkyl, (chloro) (vinyl) dimethylsilane, (methoxy) (vinyl) dimethylsilane, (ethoxy) (vinyl) dimethylsilane, (chloro) (methyl) diphenylsilane, (methoxy) (methyl) diphenylsilane, (ethoxy) (methyl)-diphenyl silane having a silicon- atom silane compound.
Represent with trade(brand)name, for example can enumerate out:
KC-89, KC-89S, X-21-3153, X-21-5841, X-21-5842, X-21-5843, X-21-5844, X-21-5845, X-21-5846, X-21-5847, X-21-5848, X-22-160AS, X-22-170B, X-22-170BX, X-22-170D, X-22-170DX, X-22-176B, X-22-176D, X-22-176DX, X-22-176F, X-40-2308, X-40-2651, X-40-2655A, X-40-2671, X-40-2672, X-40-9220, X-40-9225, X-40-9227, X-40-9246, X-40-9247, X-40-9250, X-40-9323, X-41-1053, X-41-1056, X-41-1805, X-41-1810, KF6001, KF6002, KF6003, KR212, KR-213, KR-217, KR220L, KR242A, KR271, KR282, KR300, KR311, KR401N, KR500, KR510, KR5206, KR5230, KR5235, KR9218, KR9706 (more than, chemical industrial company of SHIN-ETSU HANTOTAI);
グ ラ ス レ ジ Application (clear and electrician company);
SH804, SH805, SH806A, SH840, SR2400, SR2402, SR2405, SR2406, SR2410, SR2411, SR2416, more than the SR2420(, eastern レ ダ ウ コ one ニ Application グ company);
FZ3711, FZ3722 (more than, Japanese ユ ニ カ one company);
DMS-S12, DMS-S15, DMS-S21, DMS-S27, DMS-S31, DMS-S32, DMS-S33, DMS-S35, DMS-S38, DMS-S42, DMS-S45, DMS-S51, DMS-227, PSD-0332, PDS-1615, PDS-9931, XMS-5025 (more than, チ Star ソ company);
メ チ Le シ リ ケ one ト MS51, メ チ Le シ リ ケ one ト MS56 (more than, Mitsubishi Chemical Ind);
エ チ Le シ リ ケ one ト 28, エ チ Le シ リ ケ one ト 40, エ チ Le シ リ ケ one ト 48 (more than, コ Le コ one ト company);
GR100, GR650, GR908, more than the GR950(, clear and electrician company) etc. partial condensate.
In these other silane compounds; From the orientation of the liquid crystal orientation film of gained and the viewpoint of chemicalstability, preferred tetramethoxy-silicane, tetraethoxysilane, methyltrimethoxy silane, Union carbide A-162,3-(methyl) acryloxy propyl trimethoxy silicane, 3-(methyl) acryloxy propyl-triethoxysilicane, vinyltrimethoxy silane, vinyltriethoxysilane, allyltrimethoxysilanis, allyltriethoxysilane, phenyltrimethoxysila,e, phenyl triethoxysilane, 3-sulfydryl propyl trimethoxy silicane, 3-sulfydryl propyl-triethoxysilicane, mercapto methyl Trimethoxy silane, mercapto methyl triethoxyl silane, dimethyldimethoxysil,ne or dimethyldiethoxysilane.
The organopolysiloxane with epoxy group(ing) that uses among the present invention is in order to import the side chain with light orientation of q.s; And for the import volume that makes epoxy group(ing) can be inexcessive; Suppress side reaction etc., be preferably 100g/mol～10 as its epoxy equivalent (weight), 000g/mol; 150g/mol～1 more preferably, 000g/mol.Therefore, when having the organopolysiloxane of epoxy group(ing), preferably setting the usage ratio of silane compound He other silane compound with epoxy group(ing) synthetic, is above-mentioned scope thereby make the epoxy equivalent (weight) of the organopolysiloxane of gained.
Particularly, this other silane compound preferably uses 0 quality %～50 quality % with respect to the total amount of the organopolysiloxane with epoxy group(ing) and other silane compound, more preferably uses 5 quality %～30 quality %.
As the organic solvent that can when synthesizing organopolysiloxane, use, can enumerate out for example hydrocarbon compound, ketone compound, ester cpds, ether compound, alkylol cpd etc. with epoxy group(ing).
As above-mentioned hydrocarbon compound, can enumerate out for example toluene, YLENE etc.; As above-mentioned ketone, can enumerate out for example methyl ethyl ketone, MIBK, methyl-n-amyl ketone, metacetone, pimelinketone etc.; As above-mentioned ester, can enumerate out for example ETHYLE ACETATE, n-butyl acetate, Isoamyl Acetate FCC, propylene glycol monomethyl ether, 3-methoxyl group butylacetic acid ester, ethyl lactate etc.; As above-mentioned ether, can enumerate out for example ethylene glycol dimethyl ether, ethylene glycol bisthioglycolate ethyl ether, THF 、 diox etc.; As above-mentioned alcohol, can enumerate out for example 1-hexanol, 4-methyl-2-amylalcohol, glycol monomethyl methyl ether, ethylene glycol monomethyl ether, glycol monomethyl n-propyl ether, glycol monomethyl n-butyl ether, propylene glycol monomethyl ether, Ucar 35 list ethyl ether, Ucar 35 list n-propyl ether etc.Among them, preferred non-water-soluble those.These solvents can separately or mix two or more uses.
With respect to the whole silane compound of 100 mass parts, the consumption of organic solvent is preferably 10 mass parts～10,000 mass parts, more preferably 50 mass parts～1,000 mass parts.The consumption of water during the organopolysiloxane that in addition, has epoxy group(ing) as manufacturing.With respect to whole silane compounds, be preferably 0.5 times of mole～100 times mole, more preferably 1 times of mole～30 times mole.
As above-mentioned catalyzer, can use for example alkali metal cpd, organic bases, titanium compound, zirconium compounds etc.
As above-mentioned alkali metal cpd, can enumerate out for example sodium hydroxide, Pottasium Hydroxide, sodium methoxide, methoxyl group potassium, Sodium Ethoxide, oxyethyl group potassium etc.
As above-mentioned organic bases, for example can enumerate out:
Organic primary, secondary amine such as ethamine, diethylamine, piperazine, piperidines, tetramethyleneimine, pyrroles;
Trimethylamines such as triethylamine, three n-propyl amine, tri-n-butyl amine, pyridine, 4-dimethylaminopyridine, diazabicylo hendecene;
Organic quaternary ammonium salts such as tetramethyl ammonium hydroxide etc.In these organic basess, consider stable viewpoint of reacting, trimethylamines such as preferred triethylamine, three n-propyl amine, tri-n-butyl amine, pyridine, 4-dimethylaminopyridine; Organic quaternary ammonium salts such as tetramethyl ammonium hydroxide.
Catalyzer during the organopolysiloxane that has epoxy group(ing) as manufacturing, preferred as alkali compound or organic bases.Through using basic metal or organic bases as catalyzer, can not produce the side reactions such as open loop of epoxy group(ing), with high hydrolysis, condensation rates, obtain the organopolysiloxane of target, so production stability is excellent, the preferred use.In addition; The organic semiconductor orientation of the present invention of reactant that contains the organopolysiloxane and the specific cinnamic acid derivative that use alkali metal cpd or organic bases to have epoxy group(ing) as the catalyzer synthetic with compsn because storage stability excellence very, so suitable.
Its reason such as Chemical Reviews; The 95th volume; 1409 pages of (nineteen ninety-five) pointed that kind; Supposition is if in hydrolysis, condensation reaction, use alkali metal cpd or organic bases as catalyzer, then forms random structure, trapezoidal-structure or cagelike structure, can't obtain containing of silanol group of proportional few organopolysiloxane.Supposition is because containing of silanol group is proportional few; Then suppress the condensation reaction between the silanol group; And then during other polymkeric substance of after organic semiconductor of the present invention orientation contains with compsn, stating, suppress the condensation reaction of silanol group and other polymkeric substance, thereby cause excellent storage stability.
As the preferred especially organic bases of catalyzer.The consumption of organic bases can suitably be set according to reaction conditionss such as the kind of organic bases, temperature etc. and different.As the concrete consumption of organic bases, for example with respect to whole silane compounds, be preferably 0.01 times of mole～3 times mole, more preferably 0.05 times of mole～1 times mole.
Hydrolysis during organopolysiloxane that manufacturing has epoxy group(ing) or hydrolysis, condensation reaction preferably are dissolved in the organic solvent through the silane compound that will have epoxy group(ing) and other silane compound that uses as required; This solution is mixed with organic bases and water, implement through heating such as for example oil baths.
When hydrolysis, condensation reaction, hope that the Heating temperature of oil bath is preferably below 130 ℃, more preferably 40 ℃～100 ℃, preferably heated 0.5 hour～12 hours, more preferably heated 1 hour～8 hours.During heating, promptly can mix liquid, also can place and reflux down.
After reaction finishes, the organic solvent layer that preferably uses water washing to obtain from reaction solution.This when washing, carrying out easily aspect the washing operation, preferably through containing the water of small amounts of salts, the for example washings such as aqueous ammonium nitrate solution about 0.2 quality %.Washing proceeds to water layer after the washing for neutral, use siccative such as anhydrous calciumsulphate, molecular sieve with the organic solvent layer drying afterwards as required after, remove and desolvate, can obtain organopolysiloxane with epoxy group(ing) as target.
In the present invention, can use commercially available commodity as organopolysiloxane with epoxy group(ing).As this commodity, for example can enumerate out DMS-E01, DMS-E12, DMS-E21, EMS-32 (more than, チ Star ソ company) etc.
[A] light orientation polyorganosiloxane compounds can comprise the part of the hydrolyzate that hydrolysis own generates from the organopolysiloxane with epoxy group(ing), and forms the part of hydrolytic condensate from hydrolytic condensation between the organopolysiloxane with epoxy group(ing).These hydrolyzates and hydrolytic condensate as the constituent material of above-mentioned part also can likewise prepare with hydrolysis, the condensation condition of the organopolysiloxane with epoxy group(ing).
< synthesizing of [A] light orientation organopolysiloxane >
[A] polyorganosiloxane compounds that uses among the present invention for example can preferably react synthetic in the presence of catalyzer through with above-mentioned organopolysiloxane and specific cinnamic acid derivative with epoxy group(ing).
Here, as the consumption of specific cinnamic acid derivative, the epoxy group(ing) with respect to the 1mol organopolysiloxane is had is preferably 0.001mol～10mol, more preferably 0.01mol～5mol, especially preferably 0.05mol～2mol.
As above-mentioned catalyzer, can use as the so-called curing catalyst of the reaction that promotes organic bases or epoxy compounds and acid anhydrides and known compound.As above-mentioned organic bases, can enumerate out the organic bases same with above-mentioned organic bases.
As above-mentioned curing catalyst, for example can enumerate out:
Benzyl dimethyl amine, 2,4, tertiary amines such as 6-three (dimethylaminomethyl) phenol, cyclohexyl dimethyl amine, trolamine;
Glyoxal ethyline, 2-n-heptyl imidazoles, 2-n-undecane base imidazoles, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 1 benzyl 2 methyl imidazole, 1-benzyl-2-phenylimidazole, 1; 2-methylimidazole, 2-ethyl-4-methylimidazole, 1-(2-cyano ethyl)-glyoxal ethyline, 1-(2-cyano ethyl)-2-n-undecane base imidazoles, 1-(2-cyano ethyl)-2-phenylimidazole, 1-(2-cyano ethyl)-2-ethyl-4-methylimidazole, 2 phenyl 4 methyl 5 hydroxy methylimidazole, 2-phenyl-4; 5-two (methylol) imidazoles, 1-(2-cyano ethyl)-2-phenyl-4; 5-two [(2 '-cyanic acid oxyethyl group) methyl] imidazoles, 1-(2-cyano ethyl)-2-n-undecane base imidazoles trihemellitic acid salt, 1-(2-cyano ethyl)-2-phenylimidazole trihemellitic acid salt, 1-(2-cyano ethyl)-2-ethyl-4-methylimidazole trihemellitic acid salt, 2; 4-diamino--6-[2 '-methylimidazolyl-(1 ')] ethyl-s-triazine, 2; 4-diamino--6-(2 '-n-undecane base imidazolyl) ethyl-s-triazine, 2; 4-diamino--6-[2 '-ethyl-4 '-methylimidazolyl-(1 ')] ethyl-s-triazine, the tricarbimide affixture of glyoxal ethyline, the tricarbimide affixture and 2 of 2-phenylimidazole, the imidazolium compoundss such as tricarbimide affixture of 4-diamino--6-[2 '-methylimidazolyl-(1 ')] ethyl-s-triazine;
Organo phosphorous compoundss such as diphenylphosphine, triphenylphosphine, tricresyl phosphite phenylester;
Zephiran chloride triphenyl phosphonium, bromination Si Zheng Ding Ji Phosphonium, Diethylaminoethyl triphenyl phosphonium, bromination Yi base triphenyl phosphonium, bromination normal-butyl triphenyl phosphonium, Xiuization tetraphenylphosphoniphenolate, iodate Yi base triphenyl phosphonium, Yi base triphenyl phosphonium acetate, Si Zheng Ding Ji Phosphonium O, quaternary alkylphosphonium salts such as O-diethylammonium idol phosphorus dithio vitriol, Si Zheng Ding Ji Phosphonium benzotriazole salt, tetraphenylphosphoniphenolate tetraphenyl borate salts, Si Zheng Ding Ji Phosphonium a tetrafluoro borate, Si Zheng Ding Ji Phosphonium tetraphenyl borate salts;
1, two azos, two cycloolefins such as 8-diazabicylo [5.4.0] hendecene-7 and organic acid salt thereof;
Organometallic compounds such as zinc octoate, stannous octoate, methyl ethyl diketone aluminium complex;
Quaternary ammonium salts such as tetraethylammonium bromide, bromination tetra-n-butyl ammonium, etamon chloride, chlorination tetra-n-butyl ammonium;
Boron cpds such as boron trifluoride, boric acid triphenyl ester;
Metal halide such as zinc chloride, tin chloride;
HMP decentralized potentiality curing catalysts such as amine add-on type promotor such as the affixture of dicyano diamide and amine and epoxy resin;
The surface of curing catalysts such as above-mentioned imidazolium compounds, organo phosphorous compounds and quaternary alkylphosphonium salt covers the microcapsule-type potentiality curing catalyst that forms with polymkeric substance;
Amine salt type potentiality curing catalyst;
Potentiality curing catalysts such as the hot cationic polymerization type potentiality of pyrolytic decomposition type curing catalyst such as lewis acid, Brnsted acid (Bronsted acid) salt etc.
In these catalyzer, quaternary ammonium salts such as preferred tetraethylammonium bromide, bromination tetra-n-butyl ammonium, etamon chloride, chlorination tetra-n-butyl ammonium.
As catalyst consumption, with respect to the organopolysiloxane that 100 mass parts have epoxy group(ing), below preferred 100 mass parts, more preferably 0.01 mass parts～100 mass parts, preferred especially 0.1 mass parts～20 mass parts.
Be preferably 0 ℃～200 ℃ as temperature of reaction, more preferably 50 ℃～150 ℃.As the reaction times be preferably 0.1 hour～50 hours, more preferably 0.5 hour～20 hours.
[A] light orientation organopolysiloxane can synthesize in the presence of organic solvent as required.As this organic solvent, can enumerate out for example hydrocarbon compound, ether compound, ester cpds, ketone compound, amide compound, alkylol cpd etc.Among them, ether compound, ester cpds, ketone compound are preferred from the viewpoint of the refining easy property of the solvability of raw material and product and product.Solvent is preferably more than the 0.1 quality %, below the 70 quality % with solid component concentration (quality of the composition beyond the solvent in the reaction soln occupies the ratio of solution all-mass), above, the use of the amount below the 50 quality % of 5 quality % more preferably.
Mw as [A] light orientation organopolysiloxane that obtains does not like this have special qualification, and is preferred 1,000～20,000, and more preferably 3,000～15,000.Through being this molecular weight ranges, can guarantee that liquid crystal orientation film has good orientation and stability.
[A] light orientation organopolysiloxane be carboxylic acid group through specific cinnamic acid derivative to the open loop addition of epoxy group(ing), and in having the organopolysiloxane of epoxy group(ing), import structure from specific cinnamic acid derivative.This method of manufacture is simple, and is very suitable method improving aspect the importing rate of the structure of specific cinnamic acid derivative.
In the present invention, in the scope of not damaging effect of the present invention, can use the compound shown in the following formula (4) to replace the part of above-mentioned specific cinnamic acid derivative and use.At this moment, synthetic organopolysiloxane and the mixture reaction of the compound shown in specific cinnamic acid derivative and the following formula (4) that can be through will having epoxy group(ing) of [A] light orientation polyorganosiloxane compounds carries out.
R 10-R 11-R 12 (4)
As the R in the above-mentioned formula (4) 10, be preferably carbonatoms and be 8～20 alkyl or alkoxyl group, perhaps carbonatoms is 4～21 fluoro-alkyl or fluoroalkyl.As R 11Be preferably singly-bound, 1,4-cyclohexylidene or 1,4-phenylene.As R 12Be preferably carboxyl.
As the compound shown in the above-mentioned formula (4), can enumerate out the compound shown in the for example following formula (4-1)～(4-3).
Figure BSA00000541896400261
Compound shown in the above-mentioned formula (4) can make the reactive site inactivation of [A] light orientation organopolysiloxane, helps to improve the stability of this liquid crystal aligning agent.In the present invention; When the compound shown in specific cinnamic acid derivative and the above-mentioned formula (4) is used together; The epoxy group(ing) that total usage ratio of the compound shown in specific cinnamic acid derivative and the above-mentioned formula (4) is had with respect to the 1mol organopolysiloxane; Be preferably 0.001mol～1.5mol, more preferably 0.01mol～1mol further is preferably 0.05mol～0.9mol.In this case, as the consumption of the compound shown in the above-mentioned formula (4), with respect to the total amount of specific cinnamic acid derivative, below the preferred 50mol%, more preferably below the 25mol%.If the usage ratio of the compound shown in the above-mentioned formula (4) surpasses 50mol%, then may produce the problem that the orientation in the liquid crystal orientation film reduces.
< [B] other polymkeric substance >
This liquid crystal aligning agent can contain [B] other polymkeric substance as being fit to composition.As [B] other polymkeric substance, can enumerate out by polyamic acid, polyimide, vinyl unsaturated polymerizable compound thing, do not have the organopolysiloxane of light orientation group to constitute group at least a polymkeric substance selected.When containing these [B] other polymkeric substance, be illustrated in the phase-contrast film that forms by this liquid crystal aligning agent with in the liquid crystal orientation film, near its top layer, there is organopolysiloxane unevenly.Therefore,,, organopolysiloxane is existed unevenly at alignment layer surface, can obtain enough liquid crystal aligning property even reduce the content of the organopolysiloxane in this liquid crystal aligning agent through increasing the content of other polymkeric substance.Therefore, in the present invention, can reduce the content in this liquid crystal aligning agent of the high organopolysiloxane of manufacturing cost, thereby can reduce the manufacturing cost of this liquid crystal aligning agent.
[polyamic acid]
Polyamic acid can obtain through making the reaction of tetracarboxylic dianhydride and diamine compound.
As the tetracarboxylic dianhydride, can enumerate out for example aliphatics tetracarboxylic dianhydride, ester ring type tetracarboxylic dianhydride, aromatic tetracarboxylic acid's dianhydride etc.These tetracarboxylic dianhydrides can be two or more alone or in combination.
As the aliphatics tetracarboxylic dianhydride, can enumerate out for example butanetetra-carboxylic acid dianhydride etc.
As the ester ring type tetracarboxylic dianhydride, for example can enumerate out 1,2,3,4-tetramethylene tetracarboxylic dianhydride, 2,3; 5-tricarboxylic basic ring amyl group acetate dianhydride, 1,3,3a, 4,5,9b-six hydrogen-5-(tetrahydrochysene-2; 5-dioxo-3-furyl)-and naphtho-[1,2-c] furans-1,3-diketone, 1,3,3a, 4; 5,9b-six hydrogen-8-methyl-5-(tetrahydrochysene-2,5-dioxo-3-furyl)-naphtho-[1,2-c] furans-1,3-diketone, 3-oxabicyclo [3.2.1] suffering-2,4-diketone-6-spiral shell-3 '-(THF-2 '; 5 '-diketone), 5-(2,5-dioxo tetrahydrochysene-3-furyl)-3-methyl-3-tetrahydrobenzene-1,2-dicarboxylic anhydride, 3,5,6-three carboxyls-2-ethyloic norbornane-2:3,5:6-dianhydride, 2; 4,6,8-tetracarboxylic two ring [3.3.0] octane-2:4,6:8-dianhydride, 4,9-dioxa three ring [5.3.1.0 2,6] 11 carbon-3,5,8,10-tetraketone etc.
As aromatic tetracarboxylic acid's dianhydride, can enumerate out for example pyromellitic acid dianhydride, and the special tetracarboxylic dianhydride who is willing to record in 2010-97188 number of Japan.
Among these tetracarboxylic dianhydrides, preferred ester ring type tetracarboxylic dianhydride, more preferably 2,3,5-tricarboxylic basic ring amyl group acetate dianhydride or 1,2,3,4-tetramethylene tetracarboxylic dianhydride, preferred especially 2,3,5-tricarboxylic basic ring amyl group acetate dianhydride.
As 2,3,5-tricarboxylic basic ring amyl group acetate dianhydride or 1,2; 3,4-tetramethylene tetracarboxylic dianhydride's consumption, relatively all the tetracarboxylic dianhydride is preferably more than the 10mol%; More preferably more than the 20mol%, preferred especially only by 2,3,5-tricarboxylic basic ring amyl group acetate dianhydride or 1; 2,3,4-tetramethylene tetracarboxylic dianhydride constitutes.
As diamine compound, can enumerate out for example aliphatie diamine, ester ring type diamines, diamino-organo-siloxane, aromatic diamine etc.These diamine compounds can be two or more alone or in combination.
As aliphatie diamine, can enumerate out for example m-xylene diamine, 1,3-tn, 1,4-tetramethylenediamine, 1,5-pentamethylene diamine, 1,6-hexanediamine etc.
As the ester ring type diamines, for example can enumerate out 1,4-DACH, 4,4 '-methylene radical two (cyclo-hexylamine), 1,3-two (amino methyl) hexanaphthene etc.
As the diamino-organo-siloxane, for example can enumerate out 1,3-two (3-aminopropyl)-tetramethyl disiloxane etc., and Japan is special is willing to the diamines put down in writing among the 2009-97188.
As aromatic diamine, can enumerate out for example Ursol D, 4,4 '-diaminodiphenyl-methane, 4,4 '-diamino-diphenyl thioether, 1; 5-diaminonaphthalene, 2,2 '-dimethyl--4,4 '-benzidine, 4,4 '-diamino--2; 2 '-two (trifluoromethyl) biphenyl, 2,7 diamin of luorene, 4,4 '-diamino-diphenyl ether, 2,2-two [4-(4-amino-benzene oxygen) phenyl] propane, 9; 9-two (4-aminophenyl) fluorenes, 2,2-two [4-(4-amino-benzene oxygen) phenyl] HFC-236fa, 2,2-two (4-aminophenyl) HFC-236fa, 4,4 '-(to benzene two isopropylidenes) two (aniline), 4; 4 '-(benzene two isopropylidenes) two (aniline), 1,4-two (4-amino-benzene oxygen) benzene, 4,4 '-two (4-amino-benzene oxygen) biphenyl, 2,6-diamino-pyridine, 3; 4-diamino-pyridine, 2,4-di-amino-pyrimidine, 3,6-proflavin, 3,6-diamino-carbazole, N-methyl-3; 6-diamino-carbazole, N-ethyl-3,6-diamino-carbazole, N-phenyl-3,6-diamino-carbazole, N, N '-two (4-aminophenyl)-p-diaminodiphenyl, N; N '-two (4-aminophenyl)-N, N '-tolidine, 1,4-two (4-aminophenyl) piperazine, 3,5-diaminobenzoic acid, dodecyloxy-2; 4-diaminobenzene, tetradecyloxyaniline-2,4-diaminobenzene, pentadecane oxygen base-2,4-diaminobenzene, n-Hexadecane oxygen base-2,4-diaminobenzene, octadecane oxygen base-2; 4-diaminobenzene, dodecyloxy-2,5-diaminobenzene, tetradecyloxyaniline-2,5-diaminobenzene, pentadecane oxygen base-2; 5-diaminobenzene, n-Hexadecane oxygen base-2,5-diaminobenzene, octadecane oxygen base-2,5-diaminobenzene, cholestane oxygen base-3; 5-diaminobenzene, cholestene oxygen base-3,5-diaminobenzene, cholestane oxygen base-2,4-diaminobenzene, cholestene oxygen base-2; 4-diaminobenzene, 3,5-diaminobenzoic acid cholestane base ester, 3,5-diaminobenzoic acid cholesteryl ester, 3; 5-diaminobenzoic acid lanostane base ester, 3,6-two (4-aminobenzoic acyl-oxygen base) cholestane, 3,6-two (4-amino-benzene oxygen) cholestane, 4-(4 '-trifluoromethoxy benzoyloxy) cyclohexyl-3; 5-diaminobenzoic acid ester, 4-(4 '-trifluoromethyl benzoyloxy) cyclohexyl-3,5-diaminobenzoic acid ester, 1,1-two (4-((aminophenyl) methyl) phenyl)-4-butyl cyclohexane, 1; 1-two (4-((aminophenyl) methyl) phenyl)-4-heptyl hexanaphthene, 1,1-two (4-((amino-benzene oxygen) methyl) phenyl)-4-heptyl hexanaphthene, 1,1-two (4-((aminophenyl) methyl) phenyl)-4-(4-heptyl cyclohexyl) hexanaphthene, 2; The 4-diamino-N, the compound shown in N-diallyl aniline, 4-aminobenzyl amine, 3-aminobenzyl amine and the following formula (A-1) etc.
Figure BSA00000541896400301
(in the formula (A-1), X 1Be that carbonatoms is 1～3 alkane 2 basis, *-O-, *-COO-or *-OCO-.Wherein, the connecting key of band " * " is connected with diamino-phenyl.R is 0 or 1.S is 0～2 integer.T is 1～20 integer).
The tetracarboxylic dianhydride who uses in the building-up reactions as polyamic acid and the usage ratio of diamine compound, with respect to the amino that contains in the 1 equivalent diamine compound, preferred 0.2 equivalent of tetracarboxylic dianhydride's anhydride group～2 equivalents, more preferably 0.3 equivalent～1.2 equivalents.
Building-up reactions is preferably carried out in organic solvent.Be preferably-20 ℃～150 ℃ as temperature of reaction, more preferably 0 ℃～100 ℃.As the reaction times be preferably 0.5 hour～24 hours, more preferably 2 hours～12 hours.
As organic solvent; As long as what can dissolve the synthetic polyamic acid does not just have a special qualification; Can enumerate out for example N-N-methyl-2-2-pyrrolidone N-(NMP), N; N-N,N-DIMETHYLACETAMIDE, N, dinethylformamide, N, aprotic polar solvents such as N-methylimidazole alkane ketone, DMSO 99.8MIN., gamma-butyrolactone, tetramethyl-urea, HMPA; Phenol property solvents such as meta-cresol, xylenol, phenol, halogenated phenol.
With respect to the total amount (b) of tetracarboxylic dianhydride and diamine compound and the total amount (a+b) of the consumption (a) of organic solvent, be preferably 0.1 quality %～50 quality %, more preferably 5 quality %～30 quality % as the consumption (a) of organic solvent.
The polyamic acid solution that obtains after the reaction can directly be used to prepare liquid crystal aligning agent, behind the polyamic acid that also can in separating reaction solution, contain, is used to prepare liquid crystal aligning agent, after can also isolating polyamic acid being made with extra care, is used to prepare liquid crystal aligning agent.As the separation method of polyamic acid, for example can enumerate out reaction soln is injected a large amount of poor solvents, the method for the precipitate that drying obtains under the decompression; Distillate the method for reaction soln etc. through the vaporizer decompression.As the process for purification of polyamic acid, can enumerate out that isolated polyamic acid is dissolved in the organic solvent once more, the method for in poor solvent, separating out; Repeat 1 time or repeatedly distillate the method for the step of organic solvent etc. through vaporizer decompression.
[polyimide]
Polyimide can be through with the amido acid structure dehydration closed-loop that above-mentioned polyamic acid had, and carries out imidization and makes.Polyimide can be the complete imidization thing as the amido acid structure fully dehydrating closed loop that polyamic acid had of its precursor; Also can be a part of dehydration closed-loop of amido acid structure, amido acid structure and imide ring structure and the part imidization thing of depositing.
Compound method as polyimide; Can enumerate out for example (i) heating polyamic acid method (below; Sometimes be also referred to as " method (i) "), (ii) polyamic acid is dissolved in the organic solvent, in this solution, add dewatering agent and dehydration closed-loop catalyzer; The method that the dehydration closed-loop reaction of passing through polyamic acid of the method that heats as required (below, be also referred to as " method (ii) " sometimes) etc. is carried out.
Be preferably 50 ℃～200 ℃ as the temperature of reaction in the method (i), more preferably 60 ℃～170 ℃.During 50 ℃ of temperature of reaction less thaies, can't fully carry out the dehydration closed-loop reaction; If temperature of reaction surpasses 200 ℃, then the molecular weight of the polyimide of gained possibly reduce.As the reaction times be preferably 0.5 hour～48 hours, more preferably 2 hours～20 hours.
The polyimide that obtains in the method (i) can directly be used to prepare liquid crystal aligning agent; Also can after separating polyimide, be used to prepare liquid crystal aligning agent, after perhaps can also isolating polyimide being made with extra care; After maybe the polyimide that obtains being made with extra care, be used to prepare liquid crystal aligning agent.
As the dewatering agent of method in (ii), can enumerate out for example acid anhydrides such as diacetyl oxide, propionic anhydride, trifluoroacetic anhydride.
As the consumption of dewatering agent, suitably to select according to desirable imidization rate, the amido acid structure with respect to the 1mol polyamic acid is preferably 0.01mol～20mol.
As the dehydration closed-loop catalyzer of method in (ii), can enumerate out for example pyridine, trimethylpyridine, lutidine, triethylamine etc.
As the dehydration closed-loop catalyst consumption, the dewatering agent with respect to 1mol contains is preferably 0.01mol～10mol.In addition, the imide rate can be that the consumption of above-mentioned dewatering agent and dehydration closed-loop agent is many more, and is high more.
As the organic solvent that method is used in (ii), for example can enumerate out the identical organic solvent of the illustrative organic solvent of solvent that uses with acid etc. as synthesizing polyamides.
Be preferably 0 ℃～180 ℃, more preferably 10 ℃～150 ℃ as the temperature of reaction of method in (ii).As the reaction times be preferably 0.5 hour～20 hours, more preferably 1 hour～8 hours.Through making reaction conditions is above-mentioned scope, and the dehydration closed-loop sufficient reacting carries out, and can make the molecular weight of the polyimide that obtains suitable.
Method (ii) in, can obtain containing the reaction soln of polyimide.This reaction soln can directly be used to prepare liquid crystal aligning agent; After also can removing dewatering agent and dehydration closed-loop catalyzer from reaction soln; Be used to prepare liquid crystal aligning agent, can also separate polyimide after, be used to prepare liquid crystal aligning agent; After perhaps isolating polyimide being made with extra care, be used to prepare liquid crystal aligning agent.As the method for removing dewatering agent and dehydration closed-loop catalyzer from reaction soln, can enumerate out method of solvent exchange for example etc.As the separation method and the process for purification of polyimide, for example can enumerate out and separation method and process for purification and illustrative same method etc. as polyamic acid.
[vinyl unsaturated polymerizable compound thing]
As the vinyl unsaturated polymerizable compound thing of [B] other polymkeric substance, can known vinyl unsaturated polymerizable compound be obtained through using known method.For example, can enumerate out following scheme.Vinyl unsaturated polymerizable compound thing as [B] other polymkeric substance can use two or more polymkeric substance together.
As the vinyl unsaturated polymerizable compound thing of [B] other polymkeric substance, for example can by
(a) contain epoxy group(ing) vinyl unsaturated compound (below, be also referred to as " (a) " unsaturated compound sometimes),
(b) contain carboxyl or hydroxyl vinyl unsaturated compound (below, be also referred to as " (b) " unsaturated compound sometimes) and
(c) (a) unsaturated compound and polymerizable unsaturated compound beyond (b) unsaturated compound (below, be also referred to as " (c) " unsaturated compound sometimes)
The multipolymer of at least two kinds of unsaturated compounds selecting in the group that constitutes (below, be also referred to as " (A) multipolymer " sometimes) obtain.In addition, here, epoxy group(ing) comprises Oxyranyle and propylene oxide base.In addition, as the vinyl unsaturated polymerizable compound thing of [B] other polymkeric substance, can respectively each two or more unsaturated compounds be used together.
As (a) unsaturated compound, for example can enumerate out:
As contain the unsaturated compound of Oxyranyle as epoxy group(ing) (below; Sometimes be also referred to as " (a-1) unsaturated compound "); Can enumerate out (methyl) glycidyl acrylate, α-Yi Jibingxisuan glycidyl ester, α-n-propyl glycidyl acrylate, α-normal-butyl glycidyl acrylate, (methyl) vinylformic acid 3; 4-epoxy butyl ester, α-Yi Jibingxisuan 3; 4-epoxy butyl ester, (methyl) vinylformic acid 6,7-epoxy heptyl ester, α-Yi Jibingxisuan 6,7-epoxy heptyl ester etc.;
As contain the unsaturated compound of propylene oxide base as epoxy group(ing) (below; Sometimes be also referred to as " (a-2) unsaturated compound "); Can enumerate out 3-((methyl) acryloyl-oxy ylmethyl) propylene oxide, 3-((methyl) acryloyl-oxy ylmethyl)-3-ethyl propylene oxide, 3-((methyl) acryloyl-oxy ylmethyl)-2-methyl propylene oxide, 3-((methyl) acryloyl-oxy ylmethyl)-2-trifluoromethyl propylene oxide, 3-((methyl) acryloyl-oxy ylmethyl)-2-pentafluoroethyl group propylene oxide, 3-((methyl) acryloyl-oxy ylmethyl)-2-benzyl ring Ethylene Oxide, 3-((methyl) acryloyl-oxy ylmethyl)-2; 2-two fluoro propylene oxide, 3-((methyl) acryloyl-oxy ylmethyl)-2; 2; 4-three fluoro propylene oxide, 3-((methyl) acryloyl-oxy ylmethyl)-2; 2,4, the 4-tetrafluoro is for propylene oxide, 3-((methyl) acryloxy ethyl) propylene oxide, 3-((methyl) acryloxy ethyl)-3-ethyl propylene oxide, 2-ethyl-3-((methyl) acryloxy ethyl) propylene oxide, 3-((methyl) acryloxy ethyl)-2-trifluoromethyl propylene oxide, 3-((methyl) acryloxy ethyl)-2-pentafluoroethyl group propylene oxide, 3-((methyl) acryloxy ethyl)-2-benzyl ring Ethylene Oxide, 2; 2-two fluoro-3-((methyl) acryloxy ethyl) propylene oxide, 3-((methyl) acryloxy ethyl)-2; 2,4-three fluoro propylene oxide, 3-((methyl) acryloxy ethyl)-2,2; 4, the 4-tetrafluoro is for propylene oxide etc.
As (b) unsaturated compound, for example can enumerate out:
Unsaturated carboxylic acid classes such as (methyl) vinylformic acid, Ba Dousuan, α-Yi Jibingxisuan, α-n-propyl vinylformic acid, α-normal-butyl vinylformic acid, toxilic acid, fumaric acid, citraconic acid, methylfumaric acid, methylene-succinic acid;
Maleic anhydride, itaconic anhydride, citraconic anhydride, suitable-1,2,3, unsaturated polybasic acid anhydride classes such as 4-Tetra Hydro Phthalic Anhydride;
(methyl) vinylformic acid 2-hydroxy methacrylate, (methyl) vinylformic acid 2-hydroxy propyl ester, (methyl) vinylformic acid 3-hydroxy propyl ester, (methyl) vinylformic acid 4-hydroxyl butyl ester, Diethylene Glycol list (methyl) propenoate, polyethyleneglycol (methyl) propenoate, W 166 list (methyl) propenoate, 2,3-dihydroxypropyl (methyl) propenoate, 2-(methyl) acryloxy ethyl glycosides etc. has (methyl) propenoate of hydroxyl etc.
As (c) unsaturated compound, for example can enumerate out:
(methyl) alkyl-acrylates such as (methyl) methyl acrylate, (methyl) ethyl propenoate, (methyl) vinylformic acid n-propyl, (methyl) isopropyl acrylate, (methyl) n-butyl acrylate, (methyl) NSC 20949, (methyl) sec-butyl acrylate, (methyl) tert-butyl acrylate;
(methyl) vinylformic acid ring pentyl ester, (methyl) cyclohexyl acrylate, (methyl) vinylformic acid 2-methyl cyclohexane ester, (methyl) vinylformic acid three ring [5.2.1.02; 6] last of the ten Heavenly stems-8-base ester (below; With three rings [5.2.1.02,6] last of the ten Heavenly stems-the 8-base is called " two cyclopentyl "), (methyl) CALCIUM ACRYLATE ring type ester classes such as (methyl) vinylformic acid 2-two cyclopentyloxy ethyl esters, (methyl) vinylformic acid isophorone base ester;
(methyl) acrylic acid aryl ester classes such as (methyl) phenyl acrylate, (methyl) vinylformic acid tolyl ester;
(methyl) acrylic acid aralkyl ester classes such as (methyl) benzyl acrylate, (methyl) vinylformic acid styroyl ester;
Heterocyclic esters such as (methyl) vinylformic acid tetrahydro furfuryl ester, (methyl) vinylformic acid tetrahydropyrans ester;
Unsaturated dicarboxylic acid diester classes such as ethyl maleate, DEF, diethyl itaconate;
Unsaturated dicarbapentaborane imide derivatives such as N-phenylmaleimide, N-benzyl maleimide, N-cyclohexyl maleimide, N-succinimido-3-maleimide benzoic ether, N-succinimido-4-maleimide butyric ester, N-succinimido-6-maleimide capronate, N-succinimido-3-maleimide propionic ester, N-(9-acridyl) maleimide;
Cyanic acid vinyl compounds such as (methyl) propenyl, α-Lv Daibingxijing, the inferior ethene of cyanic acidization;
(methyl) acrylic amide, N, unsaturated acyl amine compound such as N-dimethyl-(methyl) acrylic amide, N-(methyl) acryloyl morpholine;
Vinylbenzene, alpha-methyl styrene ,-vinyl toluene, p-methylstyrene, neighbour-vinyl toluene, to aromatic ethenyl compounds such as methoxy styrenes;
Indene derivative classes such as indenes, 1-methyl indenes;
1,3-butadiene, isoprene, 2,3-dimethyl--1,3-butadiene equiconjugate dienes compound; And vinylchlorid, vinylidene chloride, vinyl acetate etc.
In (A) multipolymer, with respect to the entire infrastructure unit, be preferably 10 quality %～100 quality % from the containing ratio of the structural unit of (a) unsaturated compound, more preferably 20 quality %～100 quality % further are preferably 30 quality %～80 quality %.Containing ratio as from the structural unit of (a-1) unsaturated compound with respect to the entire infrastructure unit, is preferably 5 quality %～60 quality %, more preferably 10 quality %～70 quality %.Containing ratio as from the structural unit of (a-2) unsaturated compound with respect to the entire infrastructure unit, is preferably 5 quality %～40 quality %, more preferably 10 quality %～30 quality %.In addition; With respect to entire infrastructure unit from (a) unsaturated compound; Containing ratio from the structural unit of (a-2) unsaturated compound is preferably 0 quality %～80 quality %, and more preferably 10 quality %～70 quality % further are preferably 20 quality %～60 quality %.
In (A) multipolymer, with respect to the entire infrastructure unit, be preferably 0 quality %～40 quality % from the containing ratio of the structural unit of (b) unsaturated compound, more preferably 5 quality %～40 quality % further are preferably 10 quality %～30 quality %.
In (A) multipolymer, with respect to the entire infrastructure unit, be preferably 0 quality %～80 quality % from the containing ratio of the structural unit of (c) unsaturated compound, more preferably 0 quality %～70 quality % further are preferably 20 quality %～60 quality %.
(A) multipolymer can be in the presence of appropriate solvent and polymerization starter, for example through making radical polymerization incompatible synthetic.As organic solvent, for example can enumerate out the identical organic solvent of the illustrative organic solvent of solvent that uses with acid etc. as synthesizing polyamides.
As polymerization starter, for example can enumerate out:
2,2 '-Diisopropyl azodicarboxylate, 2,2 '-azo two-(2, the 4-methyl pentane nitrile), 2,2 '-azo two-azo cpds such as (4-methoxyl group-2,4-methyl pentane nitriles);
Organo-peroxides such as Lucidol, lauroyl peroxide, the peroxo-PIVALIC ACID CRUDE (25) tert-butyl ester, 1,1 '-two (tert-butyl hydroperoxide) hexanaphthene;
Hydrogen peroxide;
Oxidation-reduction type initiator that forms by these superoxide and reductive agent etc.These polymerization starters can separately or mix two or more uses.
[organopolysiloxane that does not have light orientation group]
This liquid crystal aligning agent can also further contain the organopolysiloxane that does not have light orientation group as [B] other polymkeric substance except [A] light orientation organopolysiloxane.As the organopolysiloxane that does not have light orientation group, be preferably select in the group that constitutes by the condenses of the organopolysiloxane with the structural unit shown in the following formula (5), its hydrolyzate and hydrolyzate thereof at least a.In addition; When this liquid crystal aligning agent comprises the organopolysiloxane that does not have light orientation group; The major part of organopolysiloxane that does not have light orientation group is so long as have an independent existence with described [A] light orientation organopolysiloxane, and the form that another part can be used as the condenses of [A] light orientation organopolysiloxane exists.
Figure BSA00000541896400371
In the above-mentioned formula (5), X 2Be that hydroxyl, halogen atom, carbonatoms are that 1～20 alkyl, carbonatoms are that 1～6 alkoxyl group or carbonatoms are 6～20 aryl.Y 2Be that hydroxyl or carbonatoms are 1～10 alkoxyl group.
As carbonatoms is 1～20 alkyl, can enumerate out methyl, ethyl, propyl group, butyl, amyl group, hexyl, heptyl, octyl group, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl of straight chain shape for example or branched etc.
As carbonatoms is 1～6 alkoxyl group, can enumerate out for example methoxyl group, oxyethyl group, positive propoxy, isopropoxy, n-butoxy, isobutoxy.
As carbonatoms is 6～20 aryl, can enumerate out for example phenyl, naphthyl etc.
Do not have at least a silane compound that the organopolysiloxane of light orientation group can be through selecting in the group that for example will be made up of alkoxysilane compound containing trialkylsilyl group in molecular structure and halogenated silane compound (below; Be also referred to as " raw silicon hydride compounds "); Preferably in suitable organic solvent; In the presence of water and catalyzer, hydrolysis or hydrolysis, condensation and synthesize.
As the raw silicon hydride compounds, for example can enumerate out:
Tetramethoxy-silicane, tetraethoxysilane, four positive propoxy silane, tetraisopropoxysilan, four n-butoxy silane, four sec.-butoxy silane, four tert.-butoxy silane, tetrachloro are for silane etc.;
Methyltrimethoxy silane; Union carbide A-162; Methyl three positive propoxy silane; Methyl three isopropoxy silane; Methyl three n-butoxy silane; Methyl three sec.-butoxy silane; Methyl three tert.-butoxy silane; Methyl triple phenoxyl silane; Methyl three chloro silane; Ethyl trimethoxy silane; Ethyl triethoxysilane; Ethyl three positive propoxy silane; Ethyl three isopropoxy silane; Ethyl three n-butoxy silane; Ethyl three sec.-butoxy silane; Ethyl three tert.-butoxy silane; Ethyl three chloro silane; Phenyltrimethoxysila,e; Phenyl triethoxysilane; Phenyl three chloro silane etc.;
Dimethyldimethoxysil,ne, dimethyldiethoxysilane, dimethyl-dichloro-silane etc.;
Trimethylammonium methoxy silane, trimethylethoxysilane, trimethylammonium chlorosilane etc.
Among them, preferred tetramethoxy-silicane, tetraethoxysilane, methyltrimethoxy silane, Union carbide A-162, phenyltrimethoxysila,e, phenyl triethoxysilane, dimethyldimethoxysil,ne, dimethyldiethoxysilane, trimethylammonium methoxy silane or trimethylethoxysilane.
Synthetic when not having the organopolysiloxane of light orientation group,, for example can enumerate out perhaps other aprotic compound of alkylol cpd, ketone compound, amide compound, ester cpds as the organic solvent that can choose use.They can separately or mix two or more uses.
The amount of the water that uses during as the synthetic organopolysiloxane that does not have a light orientation group; The alkoxyl group and the halogen atom that are had with respect to the raw silicon hydride compounds amount to 1mol; Be preferably 0.01mol～100mol, more preferably 0.1mol～30mol is preferably 1mol～1.5mol especially.
As employable catalyzer when synthesizing the organopolysiloxane that does not have light orientation group, can enumerate out for example metallo-chelate, organic acid, mineral acid, organic bases, alkali metal cpd, alkali earth metallic compound, amine etc.They can two or more alone or in combination uses.
With respect to 100 mass parts raw silicon hydride compounds, as catalyst consumption, be preferably 0.001 mass parts～10 mass parts, more preferably 0.001 mass parts～1 mass parts.
The water that is added during the synthetic organopolysiloxane that does not have a light orientation group can be discontinuously or add to continuously in as the silane compound of raw material or silane compound is dissolved in the solution that organic solvent forms.Catalyzer can add in advance as in the silane compound of raw material or silane compound be dissolved in the solution that organic solvent forms, also can dissolve or be distributed in the water that is added.
Temperature of reaction during as the synthetic organopolysiloxane that does not have a light orientation group is preferably 0 ℃～100 ℃, more preferably 15 ℃～80 ℃.As the reaction times be preferably 0.5 hour～24 hours, more preferably 1 hour～8 hours.
This liquid crystal aligning agent is when containing [B] other polymkeric substance, though as the kind that contains other polymkeric substance of proportional basis [B] of [B] other polymkeric substance and different, with respect to 100 mass parts [A] light orientation organopolysiloxane, be preferably below 10,000 mass parts.
< [C] contains the compound of ester structure >
This liquid crystal aligning agent is through containing the compound that [C] contains ester structure, and the phase-contrast film that can form excellences such as thermotolerance is used liquid crystal orientation film.
The compound that [C] contains ester structure is the compound that has more than two at least a structure of selecting in the group that the tert-butyl ester structure by the 1-alkyl-cycloalkyl ester structure of the ketal ester structure of the acetal ester structure of carboxylic acid, carboxylic acid, carboxylic acid and carboxylic acid constitutes at intramolecularly.The compound that [C] contains ester structure can be to have more than two the compound of the structure of identical type in these structures, also can be the compound with combination different types of structure in these structures more than two.As the above-mentioned group that contains the acetal ester structure of carboxylic acid, can enumerate out the group shown in following formula (C-1) and the formula (C-2),
Figure BSA00000541896400401
(in the formula (C-1), R 13And R 14Alkyl, the carbonatoms that is carbonatoms 1～20 independently of one another is that 3～10 alicyclic group, carbonatoms are that 6～10 aryl or carbonatoms are 7～10 aralkyl.
In the formula (C-2), n1 is 2～10 integer).
R in the above-mentioned formula (C-1) 13In, be 1～20 alkyl as carbonatoms, preferable methyl; As carbonatoms is 3～10 alicyclic group, preferred cyclohexyl; As carbonatoms is 6～10 aryl, preferred phenyl; As carbonatoms is 7～10 aralkyl, preferred benzyl.As R 14Carbonatoms be 1～20 alkyl, preferred carbonatoms is 1～6 alkyl; As carbonatoms is 3～10 alicyclic group, and preferred carbonatoms is 6～10 alicyclic group; As carbonatoms is 6～10 aryl, preferred phenyl; As carbonatoms is 7～10 aralkyl, preferred benzyl or 2-phenylethyl.As the n1 in the formula (C-2) preferred 3 or 4.
As the group shown in the above-mentioned formula (C-1), can enumerate out for example 1-methoxy ethoxy carbonyl, 1-ethoxy ethoxy carbonyl, 1-positive propoxy ethoxy carbonyl, 1-n-butoxy ethoxy carbonyl, 1-isobutoxy ethoxy carbonyl, 1-sec.-butoxy ethoxy carbonyl, 1-tert.-butoxy ethoxy carbonyl, 1-cyclohexyloxy ethoxy carbonyl, 1-norborneol alkyl oxygen base oxethyl carbonyl, 1-phenoxy ethoxy carbonyl, (cyclohexyl) (methoxyl group) methoxycarbonyl, (cyclohexyl) (cyclohexyl oxygen base) methoxycarbonyl, (cyclohexyl) (phenoxy) methoxycarbonyl, (cyclohexyl) (benzyl oxygen base) methoxycarbonyl, (phenyl) (methoxyl group) methoxycarbonyl, (phenyl) (cyclohexyl oxygen base) methoxycarbonyl, (phenyl) (phenoxy) methoxycarbonyl, (phenyl) (benzyl oxygen base) methoxycarbonyl, (benzyl) (methoxyl group) methoxycarbonyl, (benzyl) (cyclohexyl oxygen base) methoxycarbonyl, (benzyl) (phenoxy) methoxycarbonyl, (benzyl) (benzyl oxygen base) methoxycarbonyl etc.
As the group shown in the above-mentioned formula (C-2), can enumerate out for example 2-tetrahydrofuran oxygen base carbonyl, 2-tetrahydro-pyran oxy carbonyl etc.
Among them, preferred 1-ethoxy ethoxy carbonyl, 1-positive propoxy ethoxy carbonyl, 1-cyclohexyl oxygen base oxethyl carbonyl, 2-tetrahydrofuran oxygen base carbonyl, 2-tetrahydro-pyran oxy carbonyl.
As the above-mentioned group that contains the ketal ester structure of carboxylic acid, can enumerate out the group shown in the for example following formula (C-3)～(C-5),
Figure BSA00000541896400411
(in the formula (C-3), R 15Be that carbonatoms is 1～12 alkyl.R 16And R 17Alkyl, the carbonatoms that is carbonatoms 1～12 independently of one another is that 3～20 alicyclic group, carbonatoms are that 6～20 aryl or carbonatoms are 7～20 aralkyl.
In the formula (C-4), R 18Be that carbonatoms is 1～12 alkyl.N2 is 2～8 integer,
In the formula (C-5), R 19Be that carbonatoms is 1～12 alkyl.N3 is 2～8 integer).
As the R in the above-mentioned formula (C-3) 15Carbonatoms be 1～12 alkyl, preferable methyl; As R 16In carbonatoms be 1～12 alkyl, preferable methyl; As carbonatoms is 3～20 alicyclic group, preferred cyclohexyl; As carbonatoms is 6～20 aryl, preferred phenyl; As carbonatoms is 7～20 aralkyl, preferred benzyl.As R 17Carbonatoms be that to be preferably carbonatoms be 1～6 alkyl for 7～20 alkyl.As carbonatoms is 3～20 alicyclic group, and preferred carbonatoms is 6～10 alicyclic group.As carbonatoms is 6～20 aryl, preferred phenyl.As carbonatoms is 7～20 aralkyl, preferred benzyl or 2-phenylethyl.As the R in the formula (C-4) 18Carbonatoms be 1～12 alkyl, preferable methyl.As n2 preferred 3 or 4.As the R in the formula (C-5) 19Carbonatoms be 1～12 alkyl, preferable methyl.As n3 preferred 3 or 4.
As the group shown in the above-mentioned formula (C-3), can enumerate out for example 1-methyl isophthalic acid-methoxy ethoxy carbonyl, 1-methyl isophthalic acid-positive propoxy ethoxy carbonyl, 1-methyl isophthalic acid-n-butoxy ethoxy carbonyl, 1-methyl isophthalic acid-isobutoxy ethoxy carbonyl, 1-methyl isophthalic acid-sec.-butoxy ethoxy carbonyl, 1-methyl isophthalic acid-tert.-butoxy ethoxy carbonyl, 1-methyl isophthalic acid-cyclohexyl oxygen base oxethyl carbonyl, 1-methyl isophthalic acid-norborneol alkyl oxygen base oxethyl carbonyl, 1-methyl isophthalic acid-phenoxy ethoxy carbonyl, 1-methyl isophthalic acid-benzyloxy ethoxy carbonyl, 1-methyl isophthalic acid-benzene ethoxy ethoxy carbonyl, 1-cyclohexyl-1-methoxy ethoxy carbonyl, 1-cyclohexyl-1-cyclohexyloxy ethoxy carbonyl, 1-cyclohexyl-1-phenoxy ethoxy carbonyl, 1-phenyl-1-methoxy ethoxy carbonyl, 1-phenyl-1-ethoxy ethoxy carbonyl, 1-phenyl-1-phenoxy ethoxy carbonyl, 1-phenyl-1-benzyloxy ethoxy carbonyl, 1-benzyl-1-methoxy ethoxy carbonyl, 1-benzyl-1-cyclohexyloxy ethoxy carbonyl, 1-benzyl-1-phenoxy ethoxy carbonyl, 1-benzyl-1-benzyloxy ethoxy carbonyl etc.
As the group shown in the above-mentioned formula (C-4), can enumerate out for example 2-(2-methyltetrahydrofuran base) oxygen base carbonyl, 2-(2-methyl THP trtrahydropyranyl) oxygen base carbonyl etc.
As the group shown in the above-mentioned formula (C-5), can enumerate out for example 1-methoxyl group cyclopentyloxy carbonyl, 1-methoxyl group cyclohexyl oxygen base carbonyl etc.
Among them, preferred 1-methyl isophthalic acid-methoxy ethoxy carbonyl, 1-methyl isophthalic acid-cyclohexyl oxygen base oxethyl carbonyl.
As the above-mentioned group that contains the 1-alkyl-cycloalkyl ester structure of carboxylic acid, can enumerate out the group shown in the following formula (C-6),
Figure BSA00000541896400431
(in the formula (C-6), R 20Be that carbonatoms is 1～12 alkyl.N4 is 1～8 integer).
As the R in the above-mentioned formula (C-6) 20Carbonatoms be that to be preferably carbonatoms be 1～10 alkyl for 1～12 alkyl.
As the group shown in the above-mentioned formula (C-6), can enumerate out for example 1-methyl ring propoxycarbonyl, 1-methyl cyclobutoxy group carbonyl, 1-methyl cyclopentyloxy carbonyl, 1-methyl cyclohexane oxygen base carbonyl, 1-methyl ring oxygen in last of the ten Heavenly stems base carbonyl, 1-ethyl cyclobutoxy group carbonyl, 1-ethyl cyclopentyloxy carbonyl, 1-ethyl cyclohexyloxy carbonyl, 1-ethyl ring oxygen in last of the ten Heavenly stems base carbonyl, 1-(different) propyl group ring propoxycarbonyl, 1-(different) propyl group cyclobutoxy group carbonyl, 1-(different) propyl group ring oxygen in last of the ten Heavenly stems base carbonyl, 1-(different) butyl cyclobutoxy group carbonyl, 1-(different) butyl cyclopentyloxy carbonyl, 1-(different) butyl cyclohexyloxy carbonyl, 1-(different) butyl ring oxygen in heptan base carbonyl, 1-(different) butyl ring oxygen in last of the ten Heavenly stems base carbonyl, 1-(different) amyl group ring oxygen in heptan base carbonyl, 1-(different) amyl group ring carbonyl octyloxy, 1-(different) hexyl ring propoxycarbonyl, 1-(different) hexyl cyclobutoxy group carbonyl, 1-(different) hexyl cyclopentyloxy carbonyl, 1-(different) hexyl cyclohexyloxy carbonyl, 1-(different) hexyl ring oxygen in ninth of the ten Heavenly Stems base carbonyl, 1-(different) hexyl ring oxygen in last of the ten Heavenly stems base carbonyl, 1-(different) octyl group ring propoxycarbonyl, 1-(different) octyl group cyclobutoxy group carbonyl, 1-(different) octyl group cyclopentyloxy carbonyl, 1-(different) octyl group cyclohexyloxy carbonyl, 1-(different) octyl group ring oxygen in heptan base carbonyl, 1-(different) octyl group ring carbonyl octyloxy, 1-(different) octyl group ring oxygen in last of the ten Heavenly stems base carbonyl etc.
The described above-mentioned group that contains the tert-butyl ester structure of carboxylic acid is a tert-butoxycarbonyl.
Contain the compound of ester structure, the compound shown in the preferred following formula (C) as [C] among the present invention.
T nR (C)
(in the formula (C); T is group or the tert-butoxycarbonyl shown in each in the above-mentioned formula (C-1)～(C-6); N be 2 and R be singly-bound, perhaps n is that 2～10 integer and R are to be that to remove n valency group that dehydrogenation obtains or carbonatoms be 1～18 n valency alkyl for 3～10 heterogeneous ring compound from carbonatoms).
N preferred 2 or 3.
As the R in the above-mentioned formula (C), be 2 o'clock at n, can enumerate out singly-bound, carbonatoms and be 1～12 alkane 2 basis, 1; 2-phenylene, 1,3-phenylene, 1,4-phenylene, 2; 6-naphthylidene, 5-sodium sulfo group-1,3-phenylene, 5-4-butyl-phosphonium sulfo group-1,3-phenylene etc.
At n is 3 o'clock, as above-mentioned R, can enumerate out the group shown in the following formula, benzene-1,3,5-three bases etc.
Figure BSA00000541896400441
As the preferred straight chain shape of above-mentioned alkane 2 basis.
The compound that [C] shown in the above-mentioned formula (C) contains ester structure can synthesize through the vitochemical ordinary method of appropriate combination.
For example, the T in the above-mentioned formula (C) is that the compound of the group shown in the above-mentioned formula (C-1) (wherein, removes R 13Be the situation of phenyl) preferably in the presence of phosphoric acid catalyst, through making compound R-(COOH) n(wherein, R is identical with the definition of above-mentioned formula (C) respectively with n), and compound R 14-O-CH=R 13' (wherein, R 14Identical with the definition of above-mentioned formula (C-1).R 13' be the R from above-mentioned formula (C-1) 13A carbon remove the group that Wasserstoffatoms obtains) addition is synthetic.
T in the above-mentioned formula (C) is the compound of the group shown in the above-mentioned formula (C-2), preferably in the presence of the Catalyzed by p-Toluenesulfonic Acid agent, through making compound R-(COOH) nCompound addition shown in (wherein, R is identical with the definition of above-mentioned formula (C) respectively with n) and the following formula is synthetic,
Figure BSA00000541896400451
(in the formula, n1 is identical with the definition of above-mentioned formula (C-2)).
The content that contains the compound of ester structure as [C] in this liquid crystal aligning agent; As long as consider the decisions such as thermotolerance of requirement; Just do not have special qualification, with respect to 100 mass parts [A] light orientation organopolysiloxane, [C] contains preferred 0.1 mass parts of compound～50 mass parts of ester structure; More preferably 1 mass parts～20 mass parts, preferred especially 2 mass parts～10 mass parts.
< [D] solvent >
This liquid crystal aligning agent can contain [D] solvent as being fit to composition.[D] solvent is shown in above-mentioned formula (6).This liquid crystal aligning agent can improve this liquid crystal aligning agent and the phase-contrast film adaptation with base material through containing [D] solvent.
In the above-mentioned formula (6), R D1Be that carbonatoms is that 1～6 alkyl, carbonatoms are 3～6 naphthenic base, phenyl or benzyl.Wherein, abovementioned alkyl can have between C-C-O-.R D2Be that carbonatoms is 1～8 1 valency organic group.
As above-mentioned R D1Shown carbonatoms is 1～6 alkyl, can enumerate out for example methyl, ethyl, propyl group, butyl etc.Among them, preferable methyl, ethyl and propyl group, more preferably methyl.
As above-mentioned R D1Shown carbonatoms is 3～6 naphthenic base, can enumerate out for example cyclopropyl, cyclobutyl etc.
As above-mentioned R D2Shown in carbonatoms be 1～8 1 valency organic group, can enumerate out carbonatoms for example and be 1～8 straight chain shape or alkyl of branched etc.; Can also be included between the C-C of these alkyl and have-group of O-etc.
As [D] solvent, can enumerate out for example methyl acetate, ETHYLE ACETATE, propyl acetate, isopropyl acetate, butylacetate, sec-butyl acetate, isobutyl acetate, pentyl acetate, sec-amyl acetate, Isoamyl Acetate FCC, methylcellosolve acetate, propylene glycol monomethyl ether, methyl amyl acetate, methyl propionate, ethyl propionate, propyl propionate, butyl propionate, isobutyl propionate, methyl-butyrate, ethyl n-butyrate, cellosolve acetic ester, Ucar 35 list ethyl ether acetic ester, sec-hexyl acetate, acetate 2-ethyl butyl ester, 3-ethoxyl ethyl propionate, hexalin acetate, methylcyclohexyl acetate, butyl cellosolve acetate, acetate phenylester, acetate 2-ethylhexyl, acetate benzyl ester, the complete alcohol acetic ester of methyl card, the complete alcohol acetic ester of card, the complete alcohol acetic ester of butyl card, methoxyl group butylacetic acid ester, methoxyl group triglycol acetic ester, methyl-3-methoxy propyl acid esters, amyl propionate, propylene glycol monomethyl ether, butyl butyrate, isoamyl butyrate, oil of Niobe, ethyl benzoate, phenylformic acid benzyl ester, methoxy butyl acetate, 3-methyl-3-methoxyl group butylacetic acid ester, 3-methoxyl group-3-methylbutyl acetic ester, ethyl-3-ethoxy-c acid esters, butyl cellosolve acetate etc.
Among them, when forming liquid crystal orientation film by this liquid crystal aligning agent, preferably the viewpoint of evaporable solvent is set out at low temperatures, is the solvent below 150 ℃ as the preferred boiling point of [D] solvent.As this solvent, can enumerate out methyl acetate, ETHYLE ACETATE, propyl acetate, isopropyl acetate, butylacetate, sec-butyl acetate, isobutyl acetate, pentyl acetate, sec-amyl acetate, Isoamyl Acetate FCC, methylcellosolve acetate, propylene glycol monomethyl ether, methyl amyl acetate, methyl propionate, ethyl propionate, propyl propionate, butyl propionate, isobutyl propionate, methyl-butyrate and ethyl n-butyrate.
In addition, preferably can not produce the solvent of influences such as distortion, dissolving with substrate as [D] solvent to the phase-contrast film of coating of liquid crystalline alignment agent.For example, when using tri acetyl cellulose (TAC) use substrate as above-mentioned phase-contrast film, in the above-mentioned preferred solvent, more preferably acetate esters solvent and propionic acid ester solvent, further preferably acetate esters solvent.Wherein, preferred especially propyl acetate, isopropyl acetate, butylacetate, sec-butyl acetate and isobutyl acetate.
This liquid crystal aligning agent is when containing [D] solvent, and is proportional as containing of [D] solvent, with respect to whole solvents, more than preferred 50 weight parts, more preferably more than 75 weight parts.In addition, [D] solvent can mix two or more uses.
< [E] solvent >
This liquid crystal aligning agent can contain [E] solvent as being fit to composition.[E] solvent is that phase-contrast film is had rodent organic solvent with substrate.This liquid crystal aligning agent can further improve this liquid crystal aligning agent and the phase-contrast film adaptation with base material through containing [E] solvent.
Use substrate as above-mentioned phase-contrast film, can enumerate out glass baseplates such as for example comprising float glass, soda glass; The transparency carrier of plastic basis materials such as tri acetyl cellulose (TAC), polyethyleneterephthalate, polybutylene terephthalate, polyethersulfone, polymeric amide, polyimide, polymethylmethacrylate, polycarbonate etc.Among them, preferably comprise the transparency carrier of plastic basis material, wherein more preferably TAC.
Here, described have rodent organic solvent to phase-contrast film with substrate, is meant to be applied to above-mentioned phase-contrast film with on the substrate time, has the part that makes aforesaid substrate or whole organic solvents of distortion and/or dissolved character.
As this [E] solvent, for example when using the TAC film, can enumerate out methylethylketone (MEK), acetone, pimelinketone, ketopentamethylene, methyl acetate, ETHYLE ACETATE, ethyl lactate, methyl-3-methoxy propyl acid esters etc. as base material.Among them, from improving the viewpoint of adaptation, preferred MEK and ETHYLE ACETATE.
This liquid crystal aligning agent is when containing [E] solvent, and is proportional as containing of [E] solvent, with respect to the whole solvents of 100 mass parts, and preferred 0.5～50 mass parts, preferred especially 2～30 mass parts.In addition, [E] solvent can mix two or more uses.
This liquid crystal aligning agent can contain [E] solvent separately as solvent, also can use together with other solvent.From improving the viewpoint of adaptation, preferably use together with [D] solvent.When [D] solvent and [E] solvent are used together; With respect to 100 mass parts [D] solvent; [E] solvent is preferably above, less than 50 mass parts of 0.5 mass parts, and above, less than 40 mass parts of 1 mass parts more preferably are preferably further that 2 mass parts are above, less than 30 mass parts.In addition, satisfy [D] solvent and the solvent that [E] solvent requires simultaneously, also can reach and the above-mentioned identical effect of using simultaneously of situation even use separately.
When using the TAC film as the base material of coating of liquid crystalline alignment agent; Form as this liquid crystal aligning agent; For example preferably comprise propyl acetate, isopropyl acetate, n-butyl acetate, sec-butyl acetate, tert.-butyl acetate or isobutyl acetate, with MEK or ETHYLE ACETATE as [E] solvent as [D] solvent.
< [F] compound >
This liquid crystal aligning agent can contain [F] compound as being fit to composition, should comprise the group with polymerizability carbon-to-carbon double bond by [F] compound.This liquid crystal aligning agent can further improve and the adaptation of phase-contrast film with substrate or liquid crystal layer through containing [F] compound.
Here, described group with polymerizability carbon-to-carbon double bond is to form the carbon atom of above-mentioned pair of key through addition polymerization, can produce the group of new C-C.As above-mentioned group, can enumerate out for example vinyl, allyl group, styryl, acryl, methacryloyl, acrylamido, crotonyl, isocrotonoyl, cinnamoyl etc. with polymerizability carbon-to-carbon double bond.
For example can enumerate out polymkeric substance such as the monomeric compound with (methyl) Acrylic Acid Monomer etc., acrylic acid or the like, type siloxane etc. as [F] compound with (methyl) acryl.Among them; Preferably has polymkeric substance such as acrylic acid or the like, type siloxane of (methyl) acryl etc. etc.; More preferably have polymkeric substance such as acrylic acid or the like, type siloxane of (methyl) acryl etc., further preferably have the type siloxane polymkeric substance of (methyl) acryl.
Content as [F] compound in this liquid crystal aligning agent; Amount to 100 mass parts with respect to [A] light orientation organopolysiloxane and [B] other polymkeric substance; Preferred 0.1 mass parts of [F] compound～30 mass parts; More preferably 0.5 mass parts～20 mass parts, preferred especially 1 mass parts～10 mass parts.
< other optional member >
This liquid crystal aligning agent is in the scope of not damaging effect of the present invention; Except above-mentioned radiation-sensitive polymer; Can also contain solidifying agent, curing catalysts, curing catalyst, intramolecularly have at least one epoxy group(ing) compound (below; Sometimes be also referred to as " epoxy compounds "), functional silanes compound, tensio-active agent, photosensitizing agent, [D] solvent and other solvent beyond [E] solvent (below, be also referred to as " other solvent " sometimes) etc.Below, these other optional members are described in detail.
[solidifying agent, curing catalysts and curing catalyst]
Based on the more firm purpose of crosslinking reaction that makes [A] light orientation organopolysiloxane, can in this liquid crystal aligning agent, contain solidifying agent and curing catalysts.In addition, the purpose based on the corresponding curing reaction that promotes solidifying agent can contain above-mentioned curing catalyst in this liquid crystal aligning agent.
As solidifying agent, in the time of using the curing of the solidification compound that comprises solidified nature compound with epoxy group(ing) or compound with epoxy group(ing), solidifying agent commonly used; Can enumerate out for example multivalence amine, polybasic acid anhydride, polycarboxylic acid etc.
As polybasic acid anhydride, can enumerate out acid anhydrides and other polyprotonic acid acid anhydrides of for example hexanaphthene three acid.As the object lesson of hexanaphthene three acid anhydrides, can enumerate out for example hexanaphthene-1,2,4-three acid, hexanaphthene-1,3,5-three acid, hexanaphthene-1; 2,3-three acid, hexanaphthene-1,3,4-three acid-3,4-acid anhydride, hexanaphthene-1,3; 5-three acid-3,5-acid anhydride, hexanaphthene-1,2,3-three acid-2,3-acid anhydride etc.
As other polyprotonic acid acid anhydrides; Can enumerate out compound shown in 4-methyl tetrahydrophthalic anhydride, methyl carbic anhydride, dodecenylsuccinic anhydride, succinyl oxide, maleic anhydride, Tetra hydro Phthalic anhydride, trihemellitic acid acid anhydride, the following formula (7) for example and polyamic acid tetracarboxylic dianhydride commonly used when synthetic; And α-terpenes, alloocimene etc. have alicyclic compound and the Diels-Alder reaction product of maleic anhydride and their hydrogenate etc. of conjugated double bond
Figure BSA00000541896400501
(in the formula (7), p is 1～20 integer).
As the usage ratio of solidifying agent with respect to 100 mass parts [A] light orientation organopolysiloxane, below preferred 100 mass parts, more preferably below 50 mass parts.This liquid crystal aligning agent contains proportional [B] other polymkeric substance with respect to above-mentioned [A] light orientation organopolysiloxane and optional use as it and amounts to 100 mass parts, below preferred 100 mass parts, more preferably below 50 mass parts when containing curing catalysts.
As curing catalysts, can enumerate out for example two diazo salts, salt compounded of iodine, sulfonium salt, aluminum alcoholate, aluminum chelate etc.As commodity, can list AMERICURE(BF 4) (two diazo salts of ACC company), ULTRASET(BF 4, PF 6) (two diazo salts of Asahi Electro-Chemical Co. Ltd), UVE シ リ one ズ (salt compounded of iodine of GE company), Photoinitiator2074((C 6F 6) 4B) (salt compounded of iodine of ロ one ヌ プ one ラ Application company); CYRACURE UVI-6974; More than the CYRACURE UVI-6990(; The sulfonium salt of UCC company); UVI-508; More than the UVI-509(; The sulfonium salt of GE company); OPTOMER SP-150; The sulfonium salt of OPTOMER SP-170(Asahi Electro-Chemical Co. Ltd); サ Application エ イ De SI-60L; サ Application エ イ De SI-80L; サ Application エ イ De SI-100L; More than the サ Application エ イ De SI-110L(, the sulfonium salt of three new chemical industrial companies); The Metallocenic compound of IRUGACURE 261(チ バ ガ イ ギ one company); ア Le ミ キ レ one ト A(W) (Off ア イ Application ケ ミ カ Le society is ground in the river) etc.These curing catalysts can use separately, also can be two or more mixtures.
As the usage ratio of curing catalysts with respect to 100 mass parts [A] light orientation organopolysiloxane, below preferred 20 mass parts, more preferably below 10 mass parts.This liquid crystal aligning agent contains proportional [B] other polymkeric substance with respect to above-mentioned [A] light orientation organopolysiloxane and optional use as it and amounts to 100 mass parts, below preferred 30 mass parts, more preferably below 20 mass parts when containing curing catalysts.
In these curing catalysts, preferred sulfonium salt, aluminum chelate in the sulfonium salt, more preferably comprise the compound as the negatively charged ion kind such as antimony hexafluoride, phosphorus hexafluoride.As these sulfonium salts, can enumerate out the antimony hexafluoride salt of aminomethyl phenyl dimethyl sulfonium for example, the antimony hexafluoride salt of ethylphenyl dimethyl sulfonium, hexafluorophosphate of aminomethyl phenyl dimethyl sulfonium etc.These sulfonium salts can use separately, also can be two or more mixtures.Commodity as these sulfonium salts; Can enumerate out サ Application エ イ De SI-60L, サ Application エ イ De SI-80L, サ Application エ イ De SI-100L (more than; Three new chemical industrial companies), UVI-6990, UVI-6992, UVI-6974 (more than; ユ ニ オ Application カ one バ イ De company), ア デ カ オ プ ト マ one SP-150, ア デ カ オ プ ト マ one SP-170, ア デ カ オ プ ト Application CP-66, ア デ カ オ プ ト Application CP-77 (more than, Asahi Electro-Chemical Co. Ltd), IRGACURE 261 (チ バ ガ イ ギ one company) etc.
As curing catalyst, for example can enumerate out:
Imidazolium compounds;
Quaternary phosphonium compound;
Quaternary ammonium compound;
Picture 1, the diazabicylo alkene that 8-diazabicylo [5.4.0] hendecene-7 and organic acid salt thereof are such;
Organometallic compound as zinc octoate, stannous octoate, methyl ethyl diketone aluminium complex;
Boron cpd as boron trifluoride, boric acid triphenyl ester; Metal halide as zinc chloride, tin chloride;
HMP decentralized potentiality curing catalysts such as the amine add-on type promotor as the affixture of dicyano diamide, amine and epoxy resin;
The surface of Shang quaternary alkylphosphonium salt etc. covers the microcapsule-type potentiality curing catalyst that forms with polymkeric substance;
Amine salt type potentiality curing catalyst;
The hot cationic polymerization type potentiality of pyrolytic decomposition type curing catalyst as lewis acid, Brnsted acid salt etc.
As the usage ratio of curing catalyst with respect to 100 mass parts [A] light orientation organopolysiloxane, below preferred 20 mass parts.This liquid crystal aligning agent contains proportional [B] other polymkeric substance with respect to above-mentioned [A] light orientation organopolysiloxane and optional use as it and amounts to 100 mass parts, below preferred 30 mass parts when containing curing catalyst.
[epoxy compounds]
Based on the fusible purpose of the liquid crystal orientation film that forms from further raising, can in this liquid crystal aligning agent, contain epoxy compounds to substrate surface.
As epoxy compounds, can enumerate out 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-dibrominated neopentylglycol diglycidyl ether, 1; 3,5,6-four glycidyl group-2; 4-pinakon, N, N, N '; N '-four glycidyl group-m-xylene diamine, 1,3-two (N, N-diglycidyl amino methyl) hexanaphthene, N; N, N ', N '-four glycidyl group-4; 4 '-diaminodiphenyl-methane, N, N-diglycidyl-benzyl amine, N, N-diglycidyl-amino methyl hexanaphthene etc.
As proportionally amounting to 100 mass parts containing of epoxidation catalyst with respect to [A] light orientation organopolysiloxane and optional [B] other polymkeric substance that contains, below preferred 40 mass parts, 0.1 mass parts～30 mass parts more preferably.In addition, this liquid crystal aligning agent based on the purpose that produces crosslinking reaction effectively, can use with alkaline catalystss such as 1 benzyl 2 methyl imidazoles when containing epoxy compounds together.
[functional silanes compound]
Based on the fusible purpose of the liquid crystal orientation film that improves formation, can use above-mentioned functional silanes compound to substrate surface.
As the functional silanes compound; Can enumerate out for example 3-TSL 8330,3-aminopropyltriethoxywerene werene, 2-TSL 8330,2-aminopropyltriethoxywerene werene, N-(2-amino-ethyl)-3-TSL 8330, N-(2-amino-ethyl)-3-aminopropyl methyl dimethoxysilane, 3-uride propyl trimethoxy silicane, 3-uride propyl-triethoxysilicane, N-ethoxy carbonyl-3-TSL 8330, N-ethoxy carbonyl-3-aminopropyltriethoxywerene werene, N-triethoxysilylpropyltetrasulfide diethylenetriamine, N-trimethoxy-silylpropyl diethylenetriamine, 10-trimethoxysilyl-1; 4; 7-three azepine decane, 10-triethoxysilyl-1; 4; 7-three azepine decane, 9-trimethoxysilyl-3; 6-diaza nonyl acetic ester, 9-triethoxysilyl-3; 6-diaza nonyl acetic ester, N-benzyl-3-TSL 8330, N-benzyl-3-aminopropyltriethoxywerene werene, N-phenyl-3-TSL 8330, N-phenyl-3-aminopropyltriethoxywerene werene, N-two (oxidation ethylidene)-3-TSL 8330, N-two (oxidation ethylidene)-3-aminopropyltriethoxywerene werene, 3-glycidoxypropyltrimewasxysilane, 2-(3; The 4-epoxycyclohexyl) ethyl trimethoxy silane, tetracarboxylic dianhydride and have the reactant etc. of amino silane compound, the tetracarboxylic dianhydride that can also enumerate out the record of japanese kokai publication sho 63-291922 communique in addition and reactant etc. with amino silane compound.
As proportionally amounting to 100 mass parts containing of functional silanes compound, below preferred 50 mass parts, more preferably below 20 mass parts with respect to [A] light orientation organopolysiloxane and optional [B] other polymkeric substance that contains.
[tensio-active agent]
As tensio-active agent, can enumerate out for example nonionic surfactant, anionic surfactant, cationic surfactant, amphoterics, organic silicon surfactant, polyalkylene oxide tensio-active agent, fluorochemical surfactant etc.
As the usage ratio of tensio-active agent, with respect to integral body 100 mass parts of this liquid crystal aligning agent, below preferred 10 mass parts, more preferably below 1 mass parts.
[photosensitizing agent]
The photosensitizing agent that can in this liquid crystal aligning agent, contain, be have by carboxyl, hydroxyl ,-SH ,-NCO ,-NHR (wherein, R is that Wasserstoffatoms or carbonatoms are 1～6 alkyl) ,-CH=CH 2And SO 2At least a group of selecting in the group that Cl constitutes and the compound of light enhanced sensitivity property structure.Through making above-mentioned the have organopolysiloxane of epoxy group(ing) and the mixture reaction of specific cinnamic acid derivative and photosensitizing agent, [A] light orientation organopolysiloxane that contains in this liquid crystal aligning agent have concurrently from specific cinnamic acid derivative photosensitive structure (styracin structure) and from the light enhanced sensitivity property structure of photosensitizing agent.This light enhanced sensitivity property structure has through rayed and excites, and the function near the photosensitive structure of this excitation energy is provided in polymer.This excited state can be a substance, also can be treble, but be based on the long lifetime and effectively energy move, preferably treble.The light that above-mentioned smooth enhanced sensitivity property structure absorbs is preferably ultraviolet ray or the visible rays of wavelength in the scope of 150nm～600nm.The shorter light of the above-mentioned lower limit of wavelength ratio is owing to can't operate in common optical system, so be not suitable in optical alignment method, using.On the other hand, the light that the above-mentioned upper limit of wavelength ratio is longer, energy is little, is difficult to bring out the excited state of above-mentioned smooth enhanced sensitivity property structure.
As this light enhanced sensitivity property structure; For example can enumerate out phenyl methyl ketone structure, benzophenone structural, anthraquinone ring, biphenyl structural, carbazole structure, nitro aryl structure, fluorene structured, naphthalene structure, anthracene structure, acridine structure, indole structure etc., can be with they two or more alone or in combination uses.These light enhanced sensitivity property structures are meant by removing the group that 1～4 Wasserstoffatoms obtains and the structure that forms from phenyl methyl ketone, UVNUL MS-40, anthraquinone, biphenyl, carbazole, oil of mirbane or dinitrobenzene, naphthalene, fluorenes, anthracene, acridine or indoles respectively.Here, the various structure optimizations of phenyl methyl ketone structure, carbazole structure and indole structure are by from the Wasserstoffatoms that phenyl ring had of phenyl methyl ketone, carbazole or indoles, removing the structure that 1～4 group that obtains forms.In these light enhanced sensitivity property structures; Be preferably select in the group that constitutes by phenyl methyl ketone structure, benzophenone structural, anthraquinone ring, biphenyl structural, carbazole structure, nitro aryl structure and naphthalene structure at least a, be preferably select in the group that constitutes by phenyl methyl ketone structure, benzophenone structural and nitro aryl structure at least a especially.
As the compound that photosensitizing agent preferably has carboxyl and light enhanced sensitivity property structure, as preferred compound, can enumerate out the compound shown in the for example following formula (H-1)～(H-10) etc.,
Figure BSA00000541896400551
(in the formula, q is 1～6 integer).
The light orientation polyorganosiloxane compounds that uses among the present invention; Has the organopolysiloxane of epoxy group(ing) and the specific cinnamic acid derivative except above-mentioned; Can also pass through the combined light sensitizer, preferably in the presence of catalyzer, preferably reaction is synthetic in organic solvent.
In this case, as the consumption of specific cinnamic acid derivative, the Siliciumatom with respect to 1mol has the organopolysiloxane of epoxy group(ing) is preferably 0.001mol～10mol, more preferably 0.01mol～5mol, especially preferably 0.05mol～2mol.As the consumption of photosensitizing agent, has the Siliciumatom of the organopolysiloxane of epoxy group(ing) with respect to 1mol, preferred 0.0001mol～0.5mol, more preferably 0.0005mol～0.2mol, preferred especially 0.001mol～0.1mol.
[other solvent]
Except that [D] solvent and [E] the solvent, this liquid crystal aligning agent can contain other solvent.As other solvent preferred dissolution [A] light orientation organopolysiloxane and optional other composition that uses, and not can with the solvent of their reactions.As the organic solvent that can in this liquid crystal aligning agent, preferably use, according to the kind of optional other polymkeric substance that contains etc. and different.
When this liquid crystal aligning agent contains [A] light orientation organopolysiloxane with [B] other polymkeric substance; As preferred organic; The illustrative organic solvent, can also enumerate out ethylene glycol monobutyl ether (EGMB) and diethylene glycol methyl ethyl ether (DEGME) etc. except that the solvent that uses as synthesizing polyamides when acid.Among them, preferred NMP, EGMB and DEGME.These organic solvents can two or more alone or in combination uses.
< phase-contrast film is with the preparation of liquid crystal aligning agent >
Phase-contrast film of the present invention with liquid crystal aligning agent as stated; Contain [A] light orientation organopolysiloxane and be necessary composition; Can contain suitable composition, other optional member as required; Preferably each composition is dissolved into as in [D] solvent and/or [E] solvent that are fit to composition, is allocated as the compsn of solution shape.The solvent that uses during as the preparation of this liquid crystal aligning agent can also suitably use above-mentioned other solvent.
The solvent that uses during the preparation of this liquid crystal aligning agent can not separated out each composition that contains in the liquid crystal aligning agent under following preferred solid component concentration, and the surface tension of liquid crystal aligning agent is the scope of 25mN/m～40mN/m.
The solid component concentration of liquid crystal aligning agent of the present invention, just the quality of the whole compositions beyond the solvent in this liquid crystal aligning agent ratio that occupies the all-mass of liquid crystal aligning agent is considered selections such as viscosity, volatility, is preferably 1 quality %～10 quality %.When solid component concentration less than 1 quality %, the thickness of the liquid crystal orientation film that is formed by this liquid crystal aligning agent is too small, possibly can't obtain good liquid crystal orientation film.On the other hand, if solid component concentration surpasses 10 quality %, the thickness of then filming is excessive, possibly can't obtain good liquid crystal orientation film, and in addition, the viscosity of liquid crystal aligning agent increases, and coating character has insufficient situation.The method that adopts when preferably the scope of solid component concentration is according to coated with liquid crystal alignment agent on substrate is different and different.For example, when using spin-coating method to carry out, the scope of solid component concentration is preferably 1.5 quality %～4.5 quality %.When using print process to carry out, preferred solid component concentration is the scope of 3 quality %～9 quality %, and thus, soltion viscosity is the scope of 12mPas～50mPas.When using ink jet method to carry out, preferred solid component concentration is the scope of 1 quality %～5 quality %, and thus, soltion viscosity is the scope of 3mPas～15mPas.
Temperature during as preparation liquid crystal aligning agent of the present invention is preferably 0 ℃～200 ℃, more preferably 0 ℃～40 ℃.
< phase-contrast film is with liquid crystal orientation film and forming method thereof >
This liquid crystal aligning agent is suitable for forming liquid crystal orientation film through optical alignment method, particularly can be formed for making phase-contrast film and the liquid crystal orientation film that uses.
As forming the method for phase-contrast film with liquid crystal orientation film, can enumerate out for example on substrate, forming filming of liquid crystal orientation film, follow, through optical alignment method this is filmed and give the method for liquid crystal aligning ability.
Use the phase-contrast film of this liquid crystal aligning agent to use liquid crystal orientation film, for example can be through following method manufacturing.For example, on substrate, be coated with this liquid crystal aligning agent through suitable coating processes such as rolling method, spin-coating method, print process, ink jet methods.Then, through this coated face is preheated (prebake), cure after then to form and film.As the prebake condition for example is under 40 ℃～120 ℃, carries out 0.1 minute～5 minutes.As after 100 ℃～300 ℃ of the condition optimizations that cure, more preferably 110 ℃～250 ℃, preferred 1 minute～200 minutes, more preferably 5 minutes～100 minutes.After the thickness of filming after curing be preferably 0.001 μ m～1 μ m, 0.005 μ m～0.5 μ m more preferably.
As aforesaid substrate, can enumerate out glass baseplates such as for example comprising float glass, soda glass; The transparency carrier of plastic basis materials such as tri acetyl cellulose (TAC), polyethyleneterephthalate, polybutylene terephthalate, polyethersulfone, polymeric amide, polyimide, polymethylmethacrylate, polycarbonate etc.Particularly, TAC generally is the resist use as the light polarizing film that plays critical function in LCD.Phase-contrast film in most of the cases and light polarizing film combination use.The polarizing axis that phase-contrast film necessarily requires critically to control relative light polarizing film can have been given play to the angle of desirable optical property and fit.Therefore, on the TAC film, through optical alignment method; Forming the liquid crystal orientation film that can make liquid crystal aligning on the direction arbitrarily; In order to have given play to the optical property of hope, be coated with and the curing polymerizable liquid crystal, form phase retardation film; The phase retardation film of making can be saved the bonding process of existing light polarizing film and phase-contrast film, helps to improve productivity.In addition, also help small-sized, the lighting of LCD material, can also be applicable to flexible display etc.Yet the TAC film has the characteristic of poor solvent resistance, and employable solvent was limited when alignment films formed, and the solvent that the such solvability of NMP is high can't use.In addition, it is low that the TAC film has thermotolerance, in order to form the characteristic that alignment films can not at high temperature be handled.
In addition, this liquid crystal aligning agent is applied on the such LCD component parts of filter for example and comprises on the optical thin film of polaroid, phase-contrast film, through the radiation exposure operation of stating later, can use as liquid crystal orientation film.In addition, on the phase-contrast film that uses this liquid crystal aligning agent to make, repeat to be coated with this liquid crystal aligning agent,, also can use as liquid crystal orientation film through same operation.
When applying this liquid crystal aligning agent, better in order to make substrate with the cohesiveness of filming, can on substrate, apply functional silanes compound, titanate etc. in advance.
Then, to above-mentioned radioactive rays that shine rectilinearly polarized light or partial poolarized light or the radioactive rays that do not have polarized light of filming, give the liquid crystal aligning ability.As radioactive rays, can use the ultraviolet ray and the visible rays of the light of the wavelength that for example comprises 150nm～800nm, preferably comprise the ultraviolet ray of light of the wavelength of 300nm～400nm.The radioactive rays that use are during as linear polarization or part polarisation, and irradiation can be carried out from the direction of vertical substrate face, in order to give tilt angle, also can carry out from vergence direction, perhaps can also make up these modes and carry out.When the radioactive rays of irradiation non-polarized light, direction of illumination must be a vergence direction.In addition, " tilt angle " described in this specification sheets is meant the angle that liquid crystal molecule tilts from the direction parallel with real estate.
Light source as using can use for example Cooper-Hewitt lamp, high pressure mercury vapour lamp, deuterium lamp, metal halide lamp, argon resonance lamp, xenon lamp, PRK, mercury-xenon lamp (Hg-Xe lamp) etc.The ultraviolet ray in above-mentioned optimal wavelength zone can obtain through mechanism that above-mentioned light source and for example spectral filter, diffraction grating etc. are used together etc.
Irradiation dose as radioactive rays is preferably 1J/m 2More than, less than 10,000J/m 2, 10J/m more preferably 2～3,000J/m 2In addition, when giving the liquid crystal aligning ability to filming of forming by existing known liquid crystal aligning agent, necessarily require 10,000J/m through optical alignment method 2Above radiation exposure amount, if but use this liquid crystal aligning agent, even the radiation exposure amount 3 of optical alignment method then, 000J/m 2Below, and then be 1,000J/m 2Below, also can give good liquid crystal aligning ability, the manufacturing cost that helps to cut down liquid crystal display device.
< phase-contrast film and method of manufacture thereof >
The present invention also is fit to comprise and has the phase-contrast film of phase-contrast film with liquid crystal orientation film.The phase-contrast film that uses this liquid crystal aligning agent to form for example can be made as follows.The formation method of the phase-contrast film that contains among the present invention comprises:
(1) on substrate, is coated with the operation of this phase-contrast film with liquid crystal aligning agent;
(2) to the irradiation radioactive rays of filming, give the liquid crystal aligning ability, form the operation of phase-contrast film with liquid crystal orientation film;
(3) to the operation of phase-contrast film with at least a portion coating polymerizable liquid crystal of liquid crystal orientation film, and
(4) make the operation of the curing of coating that has been coated with polymerizable liquid crystal.
In operation (1) and (2) and above-mentioned phase-contrast film likewise operate with the formation method of liquid crystal orientation film, on substrate, form phase-contrast film and use liquid crystal orientation film.In operation (3), on phase-contrast film at least a portion that forms, be coated with polymerizable liquid crystal with liquid crystal orientation film.As the method for coating polymerizable liquid crystal, can enumerate out for example suitable coating processes such as rolling method, spin-coating method, print process, ink jet method.Then, in operation (4),, make the solvent seasoning that contains in the polymerizable liquid crystal, and polymerizable liquid crystal is solidified through heating and/or shining unpolarized radioactive rays etc.In addition, this polymerization process can also can carry out under inert atmospheres such as nitrogen under air, can select the condition that is fit to according to the polymerizable group and the initiator of the polymerizable liquid crystal that uses.The film that obtains like this can make polymerizable liquid crystal solidify under the state of orientation of regulation, can use as phase-contrast film.
As above-mentioned polymerizable liquid crystal, so long as, just do not have special qualification through heating or irradiation radioactive rays ability polymeric compounds.For example, this nematic liquid crystal compound that can be UV キ ユ ア ラ Block Le liquid crystal と そ ying put down in writing with (with reference to liquid crystal, the 3rd volume, the 1st phase, 1999, the 34th page～the 42nd page) also can be the mixture with a plurality of compounds.In addition, can comprise known Photoepolymerizationinitiater initiater or thermal polymerization.These polymerizable liquid crystal compounds or its mixture can be dissolved in the appropriate solvent and use.In addition, through adding chiral reagent etc., can use on substrate, the liquid crystal of the twisted nematic orientation of distortion also can use cholesterol liquid crystal in vertical direction, can also use dish-shaped liquid crystal.
The thickness of polymerizable liquid crystal selects to obtain the thickness of desirable optical property.For example, when 1/2 wavelength plate of the visible light of making wavelength 540nm, selecting the phase differential of the phase-contrast film of formation is the thickness of 240nm～300nm, if 1/4 wavelength plate, then selecting phase differential is the thickness of 120nm～150nm.The thickness that obtains target phase difference is according to the optical property of the polymerizable liquid crystal that uses and different.For example, when using the polymerizable liquid crystal (RMS03-013C) of メ Le Network company, in the scope of 0.6 μ m～1.5 μ m, select as the thickness that is used to make 1/4 wavelength plate.
Temperature during as heated polymerizable property liquid crystal, selection obtains the temperature of good orientation.For example, when using the polymerizable liquid crystal RMS03-013C of メ Le Network manufactured, in 40 ℃～80 ℃ scope, select.
As the radioactive rays of irradiation during radioactive rays, can enumerate out the ultraviolet ray of non-polarisation for example etc.Irradiation dose as radioactive rays is preferably 1,000J/m 2～less than 100,000J/m 2, more preferably 10,000J/m 2～50,000J/m 2
< method of manufacture that comprises the phase-contrast film in the different zone of two or more liquid crystal aligning directions >
In addition, also be fit to comprise the method for manufacture of the phase-contrast film in 3D video purposes etc. in the present invention with the different zone of two or more liquid crystal aligning directions.Use the phase-contrast film in the 3D video purposes that this liquid crystal aligning agent forms for example can make as follows with the different zone of liquid crystal aligning direction.The method of manufacture of this phase-contrast film is to comprise following operation in the above-mentioned operation (2):
(2-1) to the radioactive rays of the irradiation first direction of filming, give the operation of the liquid crystal aligning ability of first direction; And
(2-2) to the radioactive rays of the part irradiation of the filming second direction different, further give the operation of the liquid crystal aligning ability of second direction with first direction.
In addition, be to comprise following operation in the above-mentioned operation (2) as other method of manufacture:
(2-1 ') to the radioactive rays of the irradiation first direction of filming, give the operation of the liquid crystal aligning ability of first direction; And
(2-2 ') in the above-mentioned part of not shining radioactive rays at least of filming, shine the radioactive rays of the second direction different with first direction, give the operation of the liquid crystal aligning ability of second direction.
" direction " described here is meant incidence of radiation direction or polarization direction.As the second direction among operation (2-2) and (2-2 ') so long as and in operation (2-1) or (2-1 '); It is different that the irradiation radioactive rays are given the first direction of liquid crystal aligning ability; Just there is not special qualification; The polarization direction of rotation is preferably 70 °～110 °, and more preferably 85 °～95 °, most preferably 90 °.As the mechanism of shining on the different directions, can enumerate out method through mask irradiation radioactive rays.In addition, preferably form the mask of strip pattern according to transmittance section and the mutual mode arranged side by side of light shielding part as mask.
[embodiment]
Below, through embodiment, the present invention is more specifically explained, but the present invention does not receive the qualification of these embodiment.In addition, as required through repeating the synthetic route shown in the following synthetic example, synthesis material compound and polymkeric substance, thereby the starting compound of guaranteeing to use in following examples and the necessary amount of polymkeric substance.
< organopolysiloxane synthetic>with epoxy group(ing)
[synthetic example 1]
In the reaction vessel that has whisking appliance, TM, tap funnel and reflux condensing tube, add 2-(3, the 4-epoxycyclohexyl) ethyl trimethoxy silane (ECETS), 500g MIBK and the 10.0g triethylamine of 100.0g, at room temperature mix.Then, from tap funnel, dripped the 100g deionized water with 30 minutes after, refluxing following the mixing, the limit is 80 ℃ of reactions 6 hours down.After reaction finishes, take out organic layer, be neutrality through the water after the aqueous ammonium nitrate solution washing of 0.2 quality % after, decompression distillates solvent and water down, obtains having the organopolysiloxane of epoxy group(ing), is the heavy-gravity transparent liquid.
This organopolysiloxane with epoxy group(ing) is carried out 1H-NMR analyzes, and near chemical shift (δ)=3.2ppm, obtains the peak based on epoxy group(ing) of theoretical strength, confirms that epoxy group(ing) does not produce side reaction in reaction.The Mw of the organopolysiloxane with epoxy group(ing) that obtains is 2,200, and epoxy equivalent (weight) makes 186g/mol.
< synthesizing of specific cinnamic acid derivative >
The building-up reactions of specific cinnamic acid derivative is all carried out in inert atmosphere.
[synthetic example 2]
In having the 500mL there-necked flask of prolong, mix 4-bromo diphenyl ether, 0.18g palladium, 0.98g three (2-tolyl) phosphine, 32.4g triethylamine, the 135mL N,N-DIMETHYLACETAMIDE of 20g.Then, through syringe 7g vinylformic acid is joined in the mixing solutions and stir.This mixing solutions is further 120 ℃ of following heated and stirred 3 hours.After TLC (thin-layer chromatography) affirmation reaction end, with the reaction soln cool to room temperature.Behind the filtering precipitate, filtrating is injected in the 1N aqueous hydrochloric acid of 300mL, reclaims throw out.These throw outs obtain the compound shown in the following formula of 8.4g (K-1) (specific cinnamic acid derivative (K-1)) through 1: 1 (mass ratio) solution weight crystallization of ETHYLE ACETATE and hexane.
Figure BSA00000541896400631
[synthetic example 3]
In having the 300mL there-necked flask of prolong, mix 4-fluorobenzene ylboronic acid, the 4-bromo styracin of 10g, 2.7g tetrakis triphenylphosphine palladium, 4g yellow soda ash, 80mL THF, the 39mL pure water of 6.5g.Then, reaction soln 80 ℃ of following heated and stirred 8 hours, is confirmed that through TLC reaction finishes.Behind the reaction soln cool to room temperature, be injected in the 1N-aqueous hydrochloric acid of 200mL, filter the solid of separating out.The solid that obtains is dissolved in the ETHYLE ACETATE, with the order separatory washing of the 1N-aqueous hydrochloric acid of 100mL, 100mL pure water, 100mL saturated aqueous common salt.Then, organic layer is used anhydrous magnesium sulfate drying, distillates solvent.With the solid vacuum-drying that obtains, obtain the compound shown in the following formula of 9g (K-2) (specific cinnamic acid derivative (K-2)).
Figure BSA00000541896400641
[synthetic example 4]
In having the 200mL there-necked flask of prolong, mix 4-fluorostyrene, the 4-bromo styracin of 6g, 0.059g palladium, 0.32g three (2-tolyl) phosphine, 11g triethylamine, the 50mL N,N-DIMETHYLACETAMIDE of 3.6g.This solution is 120 ℃ of following heated and stirred 3 hours, confirm that through TLC reaction finishes after, with the reaction soln cool to room temperature.Behind the filtering precipitate, filtrating is injected in the 1N aqueous hydrochloric acid of 300mL, reclaims throw out.These throw outs obtain the compound shown in the following formula of 4.1g (K-3) (specific cinnamic acid derivative (K-3)) through re-crystallizing in ethyl acetate.
Figure BSA00000541896400642
[synthetic example 5]
In having the 200mL there-necked flask of prolong, mix 4-vinyl biphenyl, the 4-bromo styracin of 10g, 0.099g palladium, 0.54g three (2-tolyl) phosphine, 18g triethylamine, the 80mL N,N-DIMETHYLACETAMIDE of 9.5g.This solution is 120 ℃ of following heated and stirred 3 hours, confirm that through TLC reaction finishes after, with the reaction soln cool to room temperature.Behind the filtering precipitate, filtrating is injected in the 1N aqueous hydrochloric acid of 500mL, reclaims throw out.These throw outs obtain the compound shown in the following formula of 11g (K-4) (specific cinnamic acid derivative (K-4)) through N,N-DIMETHYLACETAMIDE, ethanol solution weight crystallization in 1: 1.
Figure BSA00000541896400651
< synthesizing of [A] light orientation organopolysiloxane >
[synthetic example 6]
In the there-necked flask of 100mL; Specific cinnamic acid derivative (K-1) and 0.10g quaternary ammonium salt (サ Application ア プ ロ company that the synthetic example 2 of the organopolysiloxane with epoxy group(ing), 26g MIBK, 3g that the synthetic example 1 of adding 9.3g obtains obtains; UCAT18X), stirred 12 hours down at 80 ℃.Reaction precipitates with methyl alcohol after finishing once more, and throw out is dissolved in the ETHYLE ACETATE, obtains solution, and this solution distillates solvent after washing 3 times, obtains [A] light orientation organopolysiloxane (S-1) of 6.3g, is white powder.The weight-average molecular weight Mw of light orientation polyorganosiloxane compounds (S-1) is 3,500.
[synthetic example 7]
Except using the specific cinnamic acid derivative (K-2) that the synthetic example 3 of 3g obtains and the operation likewise of synthetic example 7, obtain the white powder of 7.0g [A] light orientation organopolysiloxane (S-2).The weight-average molecular weight Mw of light orientation polyorganosiloxane compounds (S-2) is 4,900.
[synthetic example 8]
Except using the specific cinnamic acid derivative (K-3) that the synthetic example 4 of 4g obtains and the operation likewise of synthetic example 7, obtain the white powder of 10g [A] light orientation organopolysiloxane (S-3).The weight-average molecular weight Mw of light orientation polyorganosiloxane compounds (S-3) is 5,000.
[synthetic example 9]
Except using the specific cinnamic acid derivative (K-4) that the synthetic example 5 of 4.1g obtains and the operation likewise of synthetic example 7, obtain the white powder of 10g light orientation organopolysiloxane (S-4).The weight-average molecular weight Mw of light orientation polyorganosiloxane compounds (S-4) is 4,200.
< synthesizing of [B] other polymkeric substance >
[synthetic example 10]
With tetramethylene tetracarboxylic dianhydride and the 21.23g (0.1mol) 4 of 19.61g (0.1mol), 4 '-diamino--2,2 '-dimethyl diphenyl are dissolved among the NMP of 367.6g, at room temperature react 6 hours.Then, reaction mixture is injected a large amount of excessive methyl alcohol, make the reaction product deposition.Throw out is used methanol wash, and decompression, 40 ℃ dry 15 hours down obtain 35g polyamic acid (PA-1).
[synthetic example 11]
With 2,3 of 22.4g (0.1mol), 5-tricarboxylic basic ring amyl group acetate dianhydride and 14.23g (0.1mol) hexanaphthene two (methylamine) are dissolved among the NMP of 329.3g, react 6 hours down at 60 ℃.Then, reaction mixture is injected a large amount of excessive methyl alcohol, make the reaction product deposition.Throw out is used methanol wash, and decompression, 40 ℃ dry 15 hours down obtain 32g polyamic acid (PA-2).
[synthetic example 12]
Take out (PA-2) that the synthetic example 11 of 17.5g obtains, add NMP, 3.8g pyridine and the 4.9g diacetyl oxide of 232.5g therein, reacted 4 hours imidization at 120 ℃ down.Then, reaction mixture is injected a large amount of excessive methyl alcohol, make the reaction product deposition.Throw out is used methanol wash, and decompression dry 15 hours down obtains 15g polyimide (PI-1).
[synthetic example 13]
In flask, add 5 mass parts 2,2 '-azo two (2, the 4-methyl pentane nitrile), 200 mass parts diethylene glycol methyl ethyl ethers (DEGME) with prolong and whisking appliance.Then, add 40 mass parts SY-Monomer Gs, 10 mass parts vinylbenzene, 30 mass parts methylacrylic acids and 20 mass parts cyclohexyl maleimides, behind the nitrogen replacement, beginning is slowly stirred.The temperature of solution is risen to 70 ℃, this temperature was kept 5 hours, obtain containing the polymers soln of the multipolymer (MA-1) that gathers (methyl) propenoate.The solid component concentration of the polymers soln that obtains is 33.1 quality %.The number-average molecular weight of the multipolymer that obtains is 7,000.
< [C] contains compound synthetic of ester structure >
According to following synthetic route, synthesized the compound (C-1-1) that contains ester structure.
Figure BSA00000541896400671
[synthetic example 14]
In the there-necked flask of the 500mL that has return line, TM and nitrogen ingress pipe, add n-butyl vinyl ether and the 0.09g phosphoric acid of 21g trimesic acid, 60g, stir down at 50 ℃ and reacted in 30 hours.After reacting end, in reaction mixture, add the 500mL hexane, the organic layer that obtains is washed 3 times with 1M aqueous sodium hydroxide solution separatory washing 2 times and water separatory successively.Afterwards, distillate solvent, obtain the compound (C-1-1) that 50g contains ester structure, be colourless transparent liquid from organic layer.
< phase-contrast film is with the preparation of liquid crystal aligning agent >
[embodiment 1]
Choose the solution that comprises polyamic acid (PA-1) that obtains as synthetic routine 11 of [B] other polymkeric substance; Be scaled the polyamic acid (PA-1) that wherein contains and be equivalent to 1; The amount of 000 mass parts; Add [A] light orientation organopolysiloxane (S-1) that the synthetic example 7 of 100 mass parts obtains therein, mix NMP and ethylene glycol monobutyl ether (EGMB) then, forming solvent composition is NMP: EGMB=50: 50 (mass ratioes), solid component concentration are the solution of 4.0 quality %.This solution uses the strainer of aperture 1 μ m to filter, and the preparation phase-contrast film is with liquid crystal aligning agent (A-1).
[embodiment 2～6]
[A] light orientation organopolysiloxane, [B] other polymkeric substance, [C] that add kind shown in the below table 1 and amount contain the compound and the solvent of ester structure; Likewise operate with embodiment 1, the preparation phase-contrast film is with liquid crystal aligning agent (A-2)～(A-6) (solid component concentration separately is 4.0 quality %).
[embodiment 7]
Choose the solution that comprises the multipolymer (MA-1) that gathers (methyl) propenoate that obtains as synthetic routine 14 of [B] other polymkeric substance; Be scaled the multipolymer that gathers (methyl) propenoate (MA-1) that wherein contains and be equivalent to 1; The amount of 000 mass parts; Add [A] light orientation organopolysiloxane (S-2) that the synthetic example 8 of 100 mass parts obtains therein; Add the sulfonium salt (サ Application エ イ De SI-60L, three new chemical industrial companies) of 50 mass parts as curing catalysts then, mix butylacetate and diethylene glycol methyl ethyl ether (DEGME), forming solvent composition is butylacetate: DEGME=90: 10 (mass ratioes), solid component concentration are the solution of 4.0 quality %.This solution uses the strainer of aperture 1 μ m to filter, and the preparation phase-contrast film is with liquid crystal aligning agent (A-7).
[embodiment 8～10]
Except adding the kind shown in the below table 1 and [A] light orientation organopolysiloxane and the solvent of amount; Add 50 mass parts therein in addition as the aluminium three (acetyl pyruvate) (Off ア イ Application ケ ミ カ Le company is ground in ア Le ミ キ レ one ト A (W), river) of curing catalysts; Likewise operate with embodiment 7, the preparation phase-contrast film is with liquid crystal aligning agent (A-8)～(A-10) (solid component concentration separately is 4.0 quality %).
[embodiment 11]
The silsesquioxane (ACSQ that adds 1,000 mass parts [A] light orientation organopolysiloxane (S-2), 50 mass parts conduct [F] compound with acryl; AC-SQ TA-100; East Asia Synesis Company makes); And 50 mass parts as the sulfonium salt (three new chemical industrial companies, サ Application エ イ De SI-60L) of curing catalysts, the formation solvent composition is EGMB: DEGME=90: the solution of 10 (mass ratioes), solid component concentration 4.0 quality %.This solution uses the strainer of aperture 1 μ m to filter, and the preparation phase-contrast film is with liquid crystal aligning agent (A-11).
[table 1]
Figure BSA00000541896400691
[reference example 1]
13.1g is gathered (methylacrylic acid 2-hydroxyl ethyl ester) heating for dissolving in the NMP of 50mL, behind the cool to room temperature, add the 10mL pyridine.Add the 17.0g cinnamyl chloride therein, stirred 8 hours.Reaction mixture adds methyl alcohol after diluting with NMP, abundant water washing and precipitating, and drying obtains the 25g polymkeric substance.Add NMP and ethylene glycol monobutyl ether therein, forming solvent composition is NMP: EGMB=50: 50 (mass ratioes), solid component concentration are the solution of 4.0 quality %.This solution uses the strainer of aperture 1 μ m to filter, preparation compsn (CA-1).
[reference example 2]
With 2,2 of 4-(the 2-methacryloxy oxyethyl group) nitrogen benzide of 1.00g, 0.01g '-azo two (isopropyl cyanide) and 2.00g dry benzene join in the ampoule, tube sealing after the degasification is injected in the methyl alcohol, obtains the throw out of macromolecular compound.After it is filtered, once more throw out is dissolved in the benzene, precipitates once more, filter, after repeating to operate for twice, make its drying with methyl alcohol.Add NMP and EGMB therein, forming solvent composition is NMP: EGMB=50: 50 (mass ratioes), solid component concentration are the solution of 4.0 quality %.This solution uses the strainer of aperture 1 μ m to filter, preparation compsn (CA-2).
< phase-contrast film is with the manufacturing of liquid crystal orientation film >
[embodiment 12]
On the one side of transparent glass substrate, use spinner, the phase-contrast film of coating embodiment 1 preparation is with liquid crystal aligning agent (A-1); On 80 ℃ hot plate, prebake is after 1 minute, in case in the baking oven of nitrogen replacement; Under 200 ℃, after cured 1 hour, form filming of thickness 0.1 μ m.Then,, use Hg-Xe lamp and Glan-Taylor prism, vertically shine the polarisation ultraviolet ray 300J/m of the bright line that contains 313nm from substrate normal on this surface of filming 2, make phase-contrast film and use liquid crystal orientation film.
[embodiment 13～22, reference example 3～5]
Except using the phase-contrast film shown in the table 2 use liquid crystal aligning agent, use beyond the above-mentioned ultraviolet ray of regulation irradiation dose and embodiment 12 likewise operates, the manufacturing phase-contrast film is used liquid crystal orientation film.
[table 2]
Figure BSA00000541896400711
[to the coating of TAC film and the evaluation of liquid crystal aligning property]
Phase-contrast film to (A-2) is used liquid crystal aligning agent, adds the sulfonium salt (three new chemical industrial companies, サ Application エ イ De SI-60L) as curing catalysts, and making catalyst concn is the preparations of 5 quality % ground with respect to solids component weight.In addition, except using aluminium three (acetyl pyruvate) (Off ア イ Application ケ ミ カ Le company, ア Le ミ キ レ one ト A (W) are ground in the river) as beyond the curing catalysts, operation likewise prepares to (A-3).In addition, except using sulfonium salt (three new chemical industrial companies, サ Application エ イ De SI-60L) as beyond the curing catalysts, operation likewise prepares to (A-7)～(A-11).On the one side of TAC film, use spinner coating phase-contrast film to use liquid crystal aligning agent, on 80 ℃ hot plate, prebake in the baking oven of nitrogen replacement, under 120 ℃, was cured after the heating 10 minutes in case after 1 minute, formed filming of thickness 0.1 μ m.At this moment, under the situation of not finding the TAC Film Fractionation, with the TAC coating as good.Good for the TAC coating, in this film coated surface, use Hg-Xe lamp and Glan-Taylor prism, vertically shine the polarisation ultraviolet ray 300J/m of the bright line that contains 313nm from substrate normal 2, form phase-contrast film and use liquid crystal orientation film, the liquid crystal aligning property of stating after carrying out and the evaluation of adaptation.The result representes in table 1.
[evaluation of adaptation]
Use uniformly-spaced partition at the phase-contrast film that forms on the TAC film on liquid crystal orientation film, add otch at interval with 1mm, form 10 * 10 tartan design through cutting knife with lead-in wire.Then, scotch tape is set on tartan design, after pasting securely, opens scotch tape.Observation open behind the scotch tape film remove part.The number that produces the grid of peeling off along the line that removes or in the point that intersects of filming is during with respect to the whole number less than 10% of tartan design; Judge that adaptation is good (" A "); More than 10%, the situation of less than 40%; Be judged as adaptation good (" B "), the situation more than 40% is judged as adaptation bad (" C ").
< manufacturing of phase-contrast film >
[embodiment 23～33, comparative example 1～3]
With polymerizable liquid crystal (メ Le Network company; RMS03-013C), after the strainer filtration through aperture 0.2 μ m, use spinner to be applied to and form on the face of phase-contrast film with liquid crystal orientation film of embodiment 12～22 and reference example 3～5 manufacturings; After curing 1 minute on 60 ℃ the hot plate; Use the Hg-Xe lamp then, to polymerizable liquid crystal coated face irradiation 30,000J/m 2Comprise the ultraviolet ray of non-polarisation of the bright line of wavelength 365nm, make phase-contrast film, carry out following evaluation.The result representes in table 3.
[evaluation of liquid crystal aligning property]
Phase-contrast film to embodiment 23～33, comparative example 1～3 manufacturing; Have or not abnormal area through polarized light microscope observing; In the situation of not observing abnormal area, estimating the liquid crystal orientation is " A ", and the situation evaluation liquid crystal orientation of observing abnormal area is " B ".
[evaluation of heat-resistant stability]
Except being under the illuminate condition of " A " in liquid crystal aligning property, make phase-contrast film with liquid crystal orientation film after, before the coating polymerizable liquid crystal; Heat beyond 1 hour down at 150 ℃; With above-mentioned operation likewise, make phase-contrast film and above-mentioned and likewise carry out the evaluation of liquid crystal aligning property; The situation that to not observe abnormal area is as thermostability " A ", and the situation of observing abnormal area is as thermostability " B ".
[table 3]
Figure BSA00000541896400731
Shown in the result of table 3; In the time of can knowing that using this liquid crystal aligning agent to make phase-contrast film uses liquid crystal orientation film; Light orientation institute must the rayed amount extremely low, and have this phase-contrast film with the phase-contrast film of liquid crystal orientation film have excellence liquid crystal aligning property, thermotolerance and with the adaptation of base material.
< comprising the manufacturing of the phase-contrast film in the different zone of liquid crystal aligning direction >
[embodiment 34]
With embodiment 12 likewise; After formation phase-contrast film on the substrate is with liquid crystal orientation film; At polarization direction from initial polarisation ultraviolet ray half-twist; To see through the mask that the mutual mode arranged side by side of portion and light shielding part forms the strip pattern, shine second polarisation ultraviolet ray (polarisation ultraviolet ray 300J/m of the bright line that comprises 313nm that use Hg-Xe lamp and Glan-Taylor prism obtain 2).Then, with polymerizable liquid crystal (メ Le Network company, RMS03-013C); After the strainer filtration through aperture 0.2 μ m; Use spinner to be applied to and form on the face of phase-contrast film with liquid crystal orientation film, after curing 1 minute on 60 ℃ the hot plate, use the Hg-Xe lamp then; To polymerizable liquid crystal coated face irradiation 30,000J/m 2Comprise the ultraviolet ray of non-polarisation of the bright line of wavelength 365nm, make the phase-contrast film that comprises the different zone of liquid crystal aligning direction.
[embodiment 35]
With embodiment 12 likewise; After coating phase-contrast film on the substrate is with liquid crystal aligning agent; Under the state of the half the light that covers substrate, shine initial polarisation ultraviolet ray (the polarisation ultraviolet ray 300J/m of the bright line that comprises 313nm that use Hg-Xe lamp and Glan-Taylor prism obtain 2).Then; At polarization direction from initial polarisation ultraviolet ray half-twist; Cover the light of the exposure portion of initial exposure; For to the ultraviolet ray of unexposed irradiation polarisation, shine second polarisation ultraviolet ray (polarisation ultraviolet ray 300J/m of the bright line that comprises 313nm that use Hg-Xe lamp and Glan-Taylor prism obtain 2).Then, with polymerizable liquid crystal (メ Le Network company, RMS03-013C); After the strainer filtration through aperture 0.2 μ m; Use spinner to be applied to and form on the face of phase-contrast film with liquid crystal orientation film, after curing 1 minute on 60 ℃ the hot plate, use the Hg-Xe lamp then; To polymerizable liquid crystal coated face irradiation 30,000J/m 2Comprise the ultraviolet ray of non-polarisation of the bright line of wavelength 365nm, make the phase-contrast film that comprises the different zone of liquid crystal aligning direction.
[comprising the evaluation of the phase-contrast film in the different zone of liquid crystal aligning direction]
The phase-contrast film that embodiment 34 is obtained is configured crossing between the polaroid that disposes under the Nicol condition; Use is from when observing the rightabout viewed in transmitted light of side; Under situation parallel with the ultraviolet polarization direction of polarisation of irradiation or configuration vertically, it all is dark forming pattern.On the other hand, if phase-contrast film is rotated 45 ° on this plane, then the formation pattern of phase-contrast film all brightens, and expression has double refraction.
With above-mentioned when likewise observing the phase-contrast film that embodiment 35 obtains, parallel with the ultraviolet polarization direction of polarisation of irradiation or vertically under the configuring condition, no matter the ultraviolet polarization direction of polarisation of irradiation how, whole face all is dark.On the other hand, if phase-contrast film is rotated 45 ° on this plane, then phase-contrast film is no matter the ultraviolet polarization direction of polarisation of irradiation how, all brightens, and expression has double refraction.
In addition; Can confirm to use with embodiment 23 and likewise operate the phase-contrast film of making; At the ultraviolet polarization direction of the polarisation that will shine, the irradiation of the phase-contrast film that comprises the different zone of two kinds of liquid crystal aligning directions that obtains with the foregoing description 34 and 35 the ultraviolet polarization direction of polarisation, be configured with parallel or vertical mode; When under crossing the Nicol condition, observing, the pattern that brightens and the pattern of deepening are told profile ground through clear and definite frontier district and are existed.
Industrial applicibility
Through the present invention provide a kind of can form phase-contrast film with the liquid crystal aligning agent of liquid crystal orientation film, have this phase-contrast film with liquid crystal orientation film and liquid crystal aligning property, thermostability and to the adaptation of base material excellent phase-contrast film and method of manufacture thereof; Even above-mentioned liquid crystal aligning agent shines a spot of radioactive rays; Also can be orientated by light, and when irradiation with after the irradiation, do not need heating process.

Claims (15)

1. a phase-contrast film is used liquid crystal aligning agent, and this liquid crystal aligning agent comprises the organopolysiloxane that [A] has light orientation group.
2. the phase-contrast film of putting down in writing according to claim 1 is used liquid crystal aligning agent, and wherein above-mentioned smooth orientation group is the group with styracin structure.
3. the phase-contrast film of putting down in writing according to claim 2 is used liquid crystal aligning agent, and the group that wherein has above-mentioned styracin structure is at least a by what select in the group that constitutes from the group of the compound shown in the following formula (1) with from the group of the compound shown in the formula (2);
Figure FSA00000541896300011
In the formula (1), R 1Be phenylene, biphenylene, inferior terphenyl or cyclohexylidene; The part of the Wasserstoffatoms of this phenylene, biphenylene, inferior terphenyl or cyclohexylidene or can be that 1～10 alkyl, the carbonatoms that can have fluorine atom are that 1～10 alkoxyl group, fluorine atom or cyanic acid replace R all by carbonatoms 2Be singly-bound, carbonatoms be 1～3 alkane 2 basis, Sauerstoffatom, sulphur atom ,-CH=CH-,-NH-,-COO-or-OCO-, a is 0～3 integer, wherein, is 2 when above at a, R 1And R 2Separately can be identical, also can be different, R 3Be fluorine atom or cyanic acid, b is 0～4 integer;
In the formula (2), R 4Be phenylene or cyclohexylidene, the part of the Wasserstoffatoms of this phenylene or cyclohexylidene or can be that 1～10 chain or cyclic alkyl, carbonatoms are that 1～10 chain or cyclic alkoxyl group, fluorine atom or cyanic acid replace R all by carbonatoms 5Be singly-bound, carbonatoms be 1～3 alkane 2 basis, Sauerstoffatom, sulphur atom or-NH-, c is 1～3 integer, wherein, is 2 when above at c, R 4And R 5Separately can be identical, also can be different, R 6Be fluorine atom or cyanic acid, d is 0～4 integer, R 7Be Sauerstoffatom ,-COO-* or-OCO-*, wherein, the band " * " connecting key and R 8Connect R 8Be the aromatic group of divalent, the ester ring type group of divalent, the heterocyclic radical of divalent or the condensed ring radical of divalent, R 9Be singly-bound ,-OCO-(CH 2) f-* or-O (CH 2) g-*, wherein, the connecting key of band " * " is connected with carboxyl, and f and g are respectively 1～10 integers, and e is 0～3 integer, wherein, is 2 when above at e, R 7And R 8Separately can be identical, also can be different.
4. the phase-contrast film of putting down in writing according to claim 3 is used liquid crystal aligning agent, and wherein [A] has the reaction product that the organopolysiloxane of light orientation group is at least a compound selected at least a compound of selecting and the group that is made up of the compound shown in compound shown in the above-mentioned formula (1) and the above-mentioned formula (2) in the group that constitutes of the condenses by the organopolysiloxane with epoxy group(ing), its hydrolyzate and hydrolyzate thereof.
5. use liquid crystal aligning agent according to each phase-contrast film of being put down in writing of claim 1～4, this liquid crystal aligning agent further contains [B] by at least a polymkeric substance of selecting in polyamic acid, polyimide, vinyl unsaturated polymerizable compound thing and the group that do not have the organopolysiloxane of light orientation group to constitute.
6. use liquid crystal aligning agent according to each phase-contrast film of being put down in writing of claim 1～4, this liquid crystal aligning agent further contains the compound that [C] has more than two at least a structure of selecting in the group that the tert-butyl ester structure by the 1-alkyl-cycloalkyl ester structure of the ketal ester structure of the acetal ester structure of carboxylic acid, carboxylic acid, carboxylic acid and carboxylic acid constitutes.
7. use liquid crystal aligning agent according to each phase-contrast film of being put down in writing of claim 1～4, this liquid crystal aligning agent further contains the solvent shown in [D] following formula (6),
R d1-COO-R d2 (6)
In the formula (6), R D1Be that carbonatoms is that 1～6 alkyl, carbonatoms are 3～6 naphthenic base, phenyl or benzyl, wherein, abovementioned alkyl can have between C-C-O-, R D2Be that carbonatoms is 1～8 1 valency organic group.
8. use liquid crystal aligning agent according to each phase-contrast film of being put down in writing of claim 1～4, this liquid crystal aligning agent further contains [E] phase-contrast film is had rodent solvent with substrate.
9. use liquid crystal aligning agent according to each phase-contrast film of being put down in writing of claim 1～4, this liquid crystal aligning agent further contains the compound that [F] contains the group with polymerizability carbon-to-carbon double bond.
10. use liquid crystal orientation film by each phase-contrast film of being put down in writing of claim 1～9 with the phase-contrast film that liquid crystal aligning agent forms.
11. the phase-contrast film according to claim 10 is put down in writing is used liquid crystal orientation film, this liquid crystal orientation film comprises the different zone of two or more liquid crystal aligning directions.
12. having the phase-contrast film that claim 10 or claim 11 put down in writing, a phase-contrast film, this phase-contrast film use liquid crystal orientation film.
13. the method for manufacture of a phase-contrast film, this method comprises following operation:
(1) coating is used liquid crystal aligning agent by each phase-contrast film of being put down in writing of claim 1～9 on substrate, forms the operation of filming;
(2) to the irradiation radioactive rays of filming, give the liquid crystal aligning ability, form the operation of phase-contrast film with liquid crystal orientation film;
(3) to the operation of phase-contrast film with at least a portion coating polymerizable liquid crystal of liquid crystal orientation film, and
(4) make the operation of the curing of coating that has been coated with polymerizable liquid crystal.
14. the method for manufacture of the phase-contrast film of putting down in writing according to claim 13 comprises following operation in the wherein above-mentioned operation (2):
(2-1) to the radioactive rays of the irradiation first direction of filming, give the operation of the liquid crystal aligning ability of first direction; And
(2-2) to the radioactive rays of the part irradiation of the filming second direction different, further give the operation of the liquid crystal aligning ability of second direction with first direction.
15. the method for manufacture of the phase-contrast film of putting down in writing according to claim 13 comprises following operation in the wherein above-mentioned operation (2):
(2-1 ') to the radioactive rays of the irradiation first direction of filming, give the operation of the liquid crystal aligning ability of first direction; And
(2-2 ') in the above-mentioned part of not shining radioactive rays at least of filming, shine the radioactive rays of the second direction different with first direction, give the operation of the liquid crystal aligning ability of second direction.
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