CN105393167B - The manufacturing method of the substrate of element liquid crystal orientation film is indicated with the driving liquid crystal of transverse electric field - Google Patents

The manufacturing method of the substrate of element liquid crystal orientation film is indicated with the driving liquid crystal of transverse electric field Download PDF

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CN105393167B
CN105393167B CN201480040018.2A CN201480040018A CN105393167B CN 105393167 B CN105393167 B CN 105393167B CN 201480040018 A CN201480040018 A CN 201480040018A CN 105393167 B CN105393167 B CN 105393167B
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liquid crystal
carbon number
film
group
side chain
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CN105393167A (en
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根木隆之
芦泽亮一
万代淳彦
名木达哉
川月喜弘
近藤瑞穂
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Nissan Chemical Corp
University of Hyogo
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Nissan Chemical Corp
University of Hyogo
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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
    • C08L101/00—Compositions of unspecified macromolecular compounds
    • C08L101/02—Compositions of unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/1337—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers
    • G02F1/133711—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers by organic films, e.g. polymeric films
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/1337—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/1337—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers
    • G02F1/13378—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers by treatment of the surface, e.g. embossing, rubbing or light irradiation
    • G02F1/133788—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers by treatment of the surface, e.g. embossing, rubbing or light irradiation by light irradiation, e.g. linearly polarised light photo-polymerisation
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/1343—Electrodes
    • G02F1/134309—Electrodes characterised by their geometrical arrangement
    • G02F1/134363—Electrodes characterised by their geometrical arrangement for applying an electric field parallel to the substrate, i.e. in-plane switching [IPS]
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/1337—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers
    • G02F1/133711—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers by organic films, e.g. polymeric films
    • G02F1/133726—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers by organic films, e.g. polymeric films made of a mesogenic material

Abstract

Present invention offer, which is endowed the driving liquid crystal of the excellent transverse electric field of tropism control ability, image retention speciality with high efficiency, indicates element.The present invention solves the above subject and indicating element with the manufacturing method of the substrate of liquid crystal orientation film with the driving liquid crystal of transverse electric field, its foregoing liquid crystal alignment films for obtaining having been assigned tropism control ability and having following process: [I] polymer composition is coated on the substrate with transverse electric field driving conductive film and the process that forms film, and the polymer composition contains: (A) shows the photonasty side chain type macromolecule and (B) organic solvent of liquid crystal liquid crystal property within the scope of specific temperature；The process of [II] to the irradiation polarized UV rays of film obtained in [I]；The process that [III] heats film obtained in [II]；And after the film heated in [III] is cooled to the temperature of the glass transition temperature of the insufficient film coated surface by [IV], the process that is again heated to the temperature of the glass transition temperature or more.

Description

The system of the substrate of element liquid crystal orientation film is indicated with the driving liquid crystal of transverse electric field Make method
Technical field
The present invention relates to the manufacturing methods for the substrate that element liquid crystal orientation film is indicated with the driving liquid crystal of transverse electric field. More specifically, it is related to indicating the new method of element for manufacturing the excellent liquid crystal of image retention speciality.
Background technique
Liquid crystal indicate element as light weight, the expression device that section is thin and power consumption is low be it is known, be used in recent years Large-scale tv purposes etc. realizes significant development.Liquid crystal indicates that element is, for example, to utilize a pair of of the transparent substrate for having electrode It clamps liquid crystal layer and constitutes.Also, indicate in element that organic film containing organic material is used as liquid crystal orientation film in liquid crystal Make liquid crystal that desired state of orientation be presented between the substrates.
That is, liquid crystal orientation film be liquid crystal indicate element component parts, be formed in clamping liquid crystal substrate and liquid crystal The surface of contact, undertaking makes liquid crystal be orientated this effect along specific direction between the substrate.Also, for liquid crystal orientation film For, other than making liquid crystal be orientated this effect along specific directions such as the directions for being for example parallel to substrate, also require sometimes Liquid crystal pretilt angle is carried out to control this effect.The ability of the control liquid crystal aligning of this liquid crystal orientation film (is hereinafter referred to as orientated Control ability.) be endowed and carrying out orientation process to the organic film for constituting liquid crystal orientation film.
As the method for orientation treatment of the liquid crystal orientation film for assigning tropism control ability, it has been known that there is brushings all the time Method.Brushing method refers to following method: for the organic film of polyvinyl alcohol, polyamide, polyimides on substrate etc., using cotton The cloth of flower, nylon, polyester etc. is along constant direction friction (brushing) its surface, to make liquid crystal along frictional direction (brushing side To) orientation.The brushing method can easily realize more stable liquid crystal aligning state, therefore be used in previous liquid crystal expression member The manufacturing process of part.Also, it is main to select the reliabilities, electrical characteristics such as heat resistance as organic film used in liquid crystal orientation film Excellent polyimides system organic film.
However, the brushing method to rub to the surface of the liquid crystal orientation film comprising polyimides etc. there are dust, generate The problem of electrostatic.In addition, due to electrode or liquid crystal drive on the high-definition of liquid crystal expression element in recent years, corresponding substrate With switching active element caused by bumps, therefore, it is impossible to the surface for the liquid crystal orientation film that equably rubbed with cloth, cannot achieve Even liquid crystal aligning.
Thus, as other method for orientation treatment of the liquid crystal orientation film without brushing, energetically have studied light orientation Method.
Optical alignment method has various methods, is constituting the organic of liquid crystal orientation film by rectilinearly polarized light or collimated light Anisotropy is formed in film, is orientated liquid crystal according to the anisotropy.
As main optical alignment method, it is known to the optical alignment method of breakdown type.In this method, for example, to polyimide film Polarized UV rays are irradiated, anisotropic decomposition occurs using the polarization direction dependence of the ultraviolet radiation absorption of molecular structure. Also, it is orientated liquid crystal (referring for example to patent document 1) by undecomposed remaining polyimides.
In addition, as other optical alignment methods, it is also known that there is the optical alignment method of photo-crosslinking type, photoisomerization type.In photo-crosslinking In the optical alignment method of type, such as using poly- vinyl cinnamate, polarized UV rays is irradiated, 2 side chains for being parallel to polarised light are made Double bond part occur dimerization reaction (cross-linking reaction).Also, it is orientated liquid crystal along the direction vertical with polarization direction (referring for example to non-patent literature 1).In the optical alignment method of photoisomerization type, the side chain type height in side chain with azobenzene is used When molecule, polarized UV rays are irradiated, makes the azobenzene part for the side chain for being parallel to polarised light that isomerization reaction occur, makes liquid crystal edge The direction vertical with polarization direction be orientated (referring for example to non-patent literature 2).
As above-mentioned example, using optical alignment method to liquid crystal orientation film carry out orientation process method in, without into Row brushing does not have to worry dust, generates electrostatic.Also, the substrate of element is indicated even if having indent and convex liquid crystal for surface It can implement orientation process, to become the method for orientation treatment for being suitable for the liquid crystal orientation film of industrial manufacture process.
Existing technical literature
Patent document
Patent document 1: No. 3893659 bulletins of Japanese Patent Publication No.
Non-patent literature
Non-patent literature 1:M.Shadt et al., Jpn.J.Appl.Phys.31,2155 (1992)
Non-patent literature 2:K.Ichimura et al., Chem.Rev.100,1847 (2000)
Summary of the invention
Problems to be solved by the invention
As described above, with the method for orientation treatment that element is indicated as liquid crystal and carry out the brushing of industrial utilization all the time Method is compared, and optical alignment method is not necessarily to this process of brushing process, therefore has clear advantage.Also, it is taken with caused by brushing The brushing method substantially stationary to control ability is compared, and optical alignment method can change the exposure of polarised light to control tropism control energy Power.However, in the case where optical alignment method wants to realize tropism control ability identical with degree when brushing method is utilized, sometimes It needs a large amount of polarizing light irradiation amount or cannot achieve stable liquid crystal aligning.
For example, needing to irradiate polyimide film 60 minutes in the breakdown type optical alignment method described in above patent document 1 The ultraviolet light etc. that issues of the high-pressure sodium lamp by power 500W, need for a long time and a large amount of ultraviolet light irradiation.In addition, in dimerization In the case where type, photoisomerization type optical alignment method, it is sometimes desirable to a large amount of ultraviolet lights irradiation of number J (joule)~tens of J or so.Into And in the case where photo-crosslinking type, photoisomerization type optical alignment method, the thermal stability of liquid crystal aligning, photostability are poor, therefore make When indicating element at liquid crystal, worry to occur to be orientated bad, expression ghost.Especially, the driving liquid crystal of transverse electric field indicates member In part, liquid crystal molecule is switched in face, therefore is easy to happen the offset of the liquid crystal aligning after liquid crystal drive, is drawn by AC driving The expression ghost risen is considered apparent project.
Therefore, for optical alignment method, it is desirable that realize high efficiency, the stable liquid crystal aligning of orientation process, it is desirable that The liquid crystal orientation film, aligning agent for liquid crystal and alignment method of highly oriented control ability can be efficiently assigned to liquid crystal orientation film.
The object of the present invention is to provide being endowed with high efficiency, tropism control ability, image retention speciality are excellent, have cross The substrate and the driving liquid crystal of transverse electric field with the substrate for indicating element liquid crystal orientation film to electric field drive liquid crystal Indicate element.The present invention also aims to the good liquid crystal aligning that can be realized in liquid crystal orientation film can be expanded by providing The manufacturing method of the substrate with liquid crystal orientation film of the bounds of polarized UV rays exposure.
The solution to the problem
The inventors of the present invention have made intensive studies to realize the above subject, as a result, it has been found that following invention.
<1>a kind of manufacturing method for the substrate that element liquid crystal orientation film is indicated with the driving liquid crystal of transverse electric field, Obtain having been assigned the foregoing liquid crystal alignment films of tropism control ability and having following process:
Polymer composition is coated on the work on the substrate with transverse electric field driving conductive film and forming film by [I] Sequence, the polymer composition contain: (A) shows the photonasty side chain type high score of liquid crystal liquid crystal property within the scope of specific temperature Son and (B) organic solvent；
The process of [II] to the irradiation polarized UV rays of film obtained in [I]；
The process that [III] heats film obtained in [II]；And
After the film heated in [III] is cooled to the temperature of the glass transition temperature of the insufficient film coated surface by [IV], The process for being again heated to the temperature of the glass transition temperature or more.
<2>in above-mentioned<1>, the cooling temperature of the film in [IV] process can be higher than the side chain type as (A) ingredient The temperature of low 10 DEG C of the glass transition point temperature (Tg) of molecule or more.
<3>in above-mentioned<1>or<2>, the heating temperature and relation reheating temperature after cooling of the film after ultraviolet light irradiation can Be film coated surface glass transition temperature more than and insufficient film coated surface homogeneous phase transition temperature temperature.
<4>in any one of above-mentioned<1>~<3>, (A) ingredient, which can have, can occur photo-crosslinking, photoisomerization or light not The photonasty side chain that Li Si is reset.
<5>in any one of above-mentioned<1>~<4>, (A) ingredient be can have selected from the group being made of following formula (1)~(6) In any photonasty side chain.
In formula, A, B, D each independently represent singly-bound ,-O- ,-CH2-、-COO-、-OCO-、-CONH-、-NH-CO-、-CH =CH-CO-O- or-O-CO-CH=CH-；
S is the alkylidene of carbon number 1~12, and the hydrogen atom for being bonded to them is optionally replaced by halogen group；
T is the alkylidene of singly-bound or carbon number 1~12, and the hydrogen atom for being bonded to them is optionally replaced by halogen group；
Y1In the ester ring type hydrocarbon for indicating phenyl ring selected from 1 valence, naphthalene nucleus, cyclohexyl biphenyl, furan nucleus, pyrrole ring and carbon number 5~8 Ring, or identical or different 2~6 ring in these substituent groups is by group made of binding groups B bonding, key Together in their hydrogen atom each independently optionally by-COOR0(in formula, R0Indicate the alkyl of hydrogen atom or carbon number 1~5) ,- NO2,-CN ,-CH=C (CN)2,-CH=CH-CN, halogen group, the alkyl of carbon number 1~5 or carbon number 1~5 alkoxy replace；
Y2For selected from by the phenyl ring of divalent, naphthalene nucleus, cyclohexyl biphenyl, furan nucleus, pyrrole ring, carbon number 5~8 ester ring type hydrocarbon and it The group that is combined into of group in group, be bonded to their hydrogen atom each independently optionally by-NO2,-CN ,-CH=C (CN)2,-CH=CH-CN, halogen group, the alkyl of carbon number 1~5 or carbon number 1~5 alkoxy replace；
R indicates the alkoxy of hydroxyl, carbon number 1~6, or expression and Y1Identical definition；
X indicates singly-bound ,-COO- ,-OCO- ,-N=N- ,-CH=CH- ,-C ≡ C- ,-CH=CH-CO-O- or-O-CO-CH =CH-, when the quantity of X reaches 2, X is optionally same or different to each other；
Cou indicates Coumarin-6-base or coumarin-7-base, be bonded to their hydrogen atom each independently optionally by- NO2,-CN ,-CH=C (CN)2,-CH=CH-CN, halogen group, the alkyl of carbon number 1~5 or carbon number 1~5 alkoxy replace；
One of q1 and q2 are 1, another one 0；
Q3 is 0 or 1；
P and Q is each independently selected from by the phenyl ring of divalent, naphthalene nucleus, cyclohexyl biphenyl, furan nucleus, pyrrole ring, carbon number 5~8 Group in ester ring type hydrocarbon and the group of their combination composition；Wherein, when X is-CH=CH-CO-O- ,-O-CO-CH=CH- ,- The P or Q for the side that CH=CH- is bonded are aromatic rings, and when the quantity of P reaches 2 or more, P is optionally same or different to each other, Q's When quantity reaches 2 or more, Q is optionally same or different to each other；
L1 is 0 or 1；
The integer that l2 is 0~2；
When l1 and l2 are 0, A also illustrates that singly-bound when T is singly-bound；
When l1 is 1, B also illustrates that singly-bound when T is singly-bound；
H and I is each independently in the phenyl ring selected from divalent, naphthalene nucleus, cyclohexyl biphenyl, furan nucleus, pyrrole ring and their combination Group.
<6>in any one of above-mentioned<1>~<4>, (A) ingredient can have to be selected from and be made of following formula (7)~(10) Any photonasty side chain in group.
In formula, A, B, D, Y1、X、Y2There is definition same as described above with R；
L indicates 1~12 integer；
M indicates that 0~2 integer, m1, m2 indicate 1~3 integer；
N indicates 0~12 integer (wherein, when n=0, B is singly-bound).
<7>in any one of above-mentioned<1>~<4>, (A) ingredient can have to be selected from and be made of following formula (11)~(13) Any photonasty side chain in group.
In formula, A, X, l, m, m1 and R have definition same as described above.
<8>in any one of above-mentioned<1>~<4>, (A) ingredient can have photonasty shown in following formula (14) or (15) Side chain.
In formula, A, Y1, l, m1 and m2 have definition same as described above.
<9>in any one of above-mentioned<1>~<4>, (A) ingredient can have photonasty shown in following formula (16) or (17) Side chain.
In formula, A, X, l and m have definition same as described above.
<10>in any one of above-mentioned<1>~<4>, (A) ingredient can have photosensitive shown in following formula (18) or (19) Property side chain.
In formula, A, B, Y1, q1, q2, m1 and m2 have definition same as described above.
R1Indicate hydrogen atom ,-NO2,-CN ,-CH=C (CN)2,-CH=CH-CN, halogen group, carbon number 1~5 alkyl, Or the alkoxy of carbon number 1~5.
<11>in any one of above-mentioned<1>~<4>, (A) ingredient can have photonasty side chain shown in following formula (20).
In formula, A, Y1, X, l and m have definition same as described above.
<12>in any one of above-mentioned<1>~<11>, (A) ingredient can have to be selected from and be made of following formula (21)~(31) Group in any liquid crystal liquid crystal property side chain.
In formula, A, B, q1 and q2 have definition same as described above；
Y3For selected from by the phenyl ring of 1 valence, naphthalene nucleus, cyclohexyl biphenyl, furan nucleus, nitrogen-containing heterocycle and carbon number 5~8 ester ring type hydrocarbon, And the group in the group of their combination composition, their hydrogen atom is bonded to each independently optionally by-NO2,-CN, halogen The alkoxy of plain group, the alkyl of carbon number 1~5 or carbon number 1~5 replaces；
R3Indicate hydrogen atom ,-NO2,-CN ,-CH=C (CN)2,-CH=CH-CN, halogen group, the phenyl ring of 1 valence, naphthalene nucleus, Cyclohexyl biphenyl, furan nucleus, nitrogen-containing heterocycle, the ester ring type hydrocarbon of carbon number 5~8, the alkyl of carbon number 1~12 or carbon number 1~12 alcoxyl Base；
L indicates that 1~12 integer, m indicate 0~2 integer, wherein in formula (23)~(24), the summation of all m is 2 More than, in formula (25)~(26), the summation of all m is 1 or more, and m1, m2 and m3 each independently represent 1~3 integer；
R2Indicate hydrogen atom ,-NO2 ,-CN, halogen group, the phenyl ring of 1 valence, naphthalene nucleus, cyclohexyl biphenyl, furan nucleus, nitrogen-containing heterocycle, And the ester ring type hydrocarbon and alkyl or alkoxy of carbon number 5~8；
Z1、Z2Indicate singly-bound ,-CO- ,-CH2O- ,-CH=N- ,-CF2-。
<13>a kind of substrate that element liquid crystal orientation film is indicated with the driving liquid crystal of transverse electric field, is by above-mentioned <1>manufacture of any one of~<12>.
<14>a kind of driving liquid crystal of transverse electric field indicates element, the substrate with above-mentioned<13>.
<15>a kind of driving liquid crystal of transverse electric field indicates the manufacturing method of element, is obtained and having following process The liquid crystal indicates element:
Prepare the process of the substrate (the 1st substrate) of above-mentioned<13>；
Obtain have following liquid crystal orientation films the 2nd substrate process, by have following processes [I '], [II '] and [III '] and the liquid crystal orientation film for obtaining having been assigned tropism control ability；And
[V] is oppositely disposed aforementioned in such a way that the liquid crystal orientation film of aforementioned 1st substrate and the 2nd substrate is across liquid crystalline phase pair 1st substrate and the 2nd substrate, so that the process that liquid crystal indicates element is obtained,
The process [I '], [II '] and [III '] are as follows:
[I '] coated polymeric composition and the process that forms film, described polymer composition on the 2nd substrate contains: (A) the photonasty side chain type macromolecule and (B) organic solvent of liquid crystal liquid crystal property are shown within the scope of specific temperature；
The process of [II '] to the irradiation polarized UV rays of film obtained in [I ']；And
The process that [III '] heats film obtained in [II '].
<16>in above-mentioned<15>, the process for obtaining aforementioned 2nd substrate can also have [IV '] will [III '] middle painting heated After film is cooled to the temperature of the glass transition temperature of the insufficient film coated surface, it is again heated to the glass transition temperature or more The process of temperature.
<17>a kind of driving liquid crystal of transverse electric field indicates element, is manufactured by above-mentioned<15>or<16>.
In addition, finding to invent as follows as another side.
A kind of<P1>manufacturing method for the substrate that element liquid crystal orientation film is indicated with the driving liquid crystal of transverse electric field, Obtain having been assigned the foregoing liquid crystal alignment films of tropism control ability and having following process
Polymer composition is coated on the work on the substrate with transverse electric field driving conductive film and forming film by [I] Sequence, the polymer composition contain: (A) shows the photonasty side chain type high score of liquid crystal liquid crystal property within the scope of specific temperature Son and (B) organic solvent；
The process of [II] to the irradiation polarized UV rays of film obtained in [I]；
The process that [III] heats film obtained in [II]；And
After the film heated in [III] is cooled to the temperature of the glass transition temperature of the insufficient film coated surface by [IV], The process for being again heated to the temperature of the glass transition temperature or more.
In<P2>above-mentioned<P1>, the cooling temperature of the film in [IV] process be can be than the side chain type as (A) ingredient The temperature of high molecular low 10 DEG C of glass transition point temperature (Tg) or more.
In<P3>above-mentioned<P1>or<P2>, the heating temperature and relation reheating temperature after cooling of the film after ultraviolet light irradiation It can be the temperature of the glass transition temperature of film coated surface or more and the homogeneous phase transition temperature of insufficient film coated surface.
In any one of<P4>above-mentioned<P1>~<P3>, (A) ingredient, which can have, can occur photo-crosslinking, photoisomerization or light The photonasty side chain of fries' rearrangement.
In any one of<P5>above-mentioned<P1>~<P4>, (A) ingredient can have to be selected from and be made of following formula (1)~(6) Group in any photonasty side chain.
In formula, A, B, D each independently represent singly-bound ,-O- ,-CH2-、-COO-、-OCO-、-CONH-、-NH-CO-、-CH =CH-CO-O- or-O-CO-CH=CH-；
S is the alkylidene of carbon number 1~12, and the hydrogen atom for being bonded to them is optionally replaced by halogen group；
T is the alkylidene of singly-bound or carbon number 1~12, and the hydrogen atom for being bonded to them is optionally replaced by halogen group；
Y1In the ester ring type hydrocarbon for indicating phenyl ring selected from 1 valence, naphthalene nucleus, cyclohexyl biphenyl, furan nucleus, pyrrole ring and carbon number 5~8 Ring, or identical or different 2~6 ring in these substituent groups is by group made of binding groups B bonding, key Together in their hydrogen atom each independently optionally by-COOR0(in formula, R0Indicate the alkyl of hydrogen atom or carbon number 1~5) ,- NO2,-CN ,-CH=C (CN)2,-CH=CH-CN, halogen group, the alkyl of carbon number 1~5 or carbon number 1~5 alkoxy replace；
Y2For selected from by the phenyl ring of divalent, naphthalene nucleus, cyclohexyl biphenyl, furan nucleus, pyrrole ring, carbon number 5~8 ester ring type hydrocarbon and it The group that is combined into of group in group, be bonded to their hydrogen atom each independently optionally by-NO2,-CN ,-CH=C (CN)2,-CH=CH-CN, halogen group, the alkyl of carbon number 1~5 or carbon number 1~5 alkoxy replace；
R indicates the alkoxy of hydroxyl, carbon number 1~6, or expression and Y1Identical definition；
X indicates singly-bound ,-COO- ,-OCO- ,-N=N- ,-CH=CH- ,-C ≡ C- ,-CH=CH-CO-O- or-O-CO-CH=CH-；
Cou indicates Coumarin-6-base or coumarin-7-base, be bonded to their hydrogen atom each independently optionally by- NO2,-CN ,-CH=C (CN)2,-CH=CH-CN, halogen group, the alkyl of carbon number 1~5 or carbon number 1~5 alkoxy replace；
One of q1 and q2 are 1, another one 0；
Q3 is 0 or 1；
P and Q is each independently selected from by singly-bound, the phenyl ring of divalent, naphthalene nucleus, cyclohexyl biphenyl, furan nucleus, pyrrole ring, carbon number 5 Group in the group of~8 ester ring type hydrocarbon and their combination composition.Wherein, X is-CH=CH-CO-O- ,-O-CO-CH=CH- When, the P or Q for the side that-CH=CH- is bonded are aromatic rings；
H and I is each independently in the phenyl ring selected from divalent, naphthalene nucleus, cyclohexyl biphenyl, furan nucleus, pyrrole ring and their combination Group.
In any one of<P6>above-mentioned<P1>~<P4>, (A) ingredient can have to be selected from and be made of following formula (7)~(10) Group in any photonasty side chain.
In formula, A, B, D, Y1、X、Y2There is definition same as described above with R；
L indicates 1~12 integer；
M indicates that 0~2 integer, m1, m2 indicate 1~3 integer；
N indicates 0~12 integer (wherein, when n=0, B is singly-bound).
In any one of<P7>above-mentioned<P1>~<P4>, (A) ingredient be can have selected from by following formula (11)~(13) group At group in any photonasty side chain.
In formula, A, X, l, m and R have definition same as described above.
In any one of<P8>above-mentioned<P1>~<P4>, (A) ingredient can have to be felt shown in following formula (14) or (15) Photosensitiveness side chain.
In formula, A, Y1, X, l, m1 and m2 have definition same as described above.
In any one of<P9>above-mentioned<P1>~<P4>, (A) ingredient can have to be felt shown in following formula (16) or (17) Photosensitiveness side chain.
In formula, A, X, l and m have definition same as described above.
In any one of<P10>above-mentioned<P1>~<P4>, (A) ingredient can have to be felt shown in following formula (18) or (19) Photosensitiveness side chain.
In formula, A, B, Y1, q1, q2, m1 and m2 have definition same as described above.
R1Indicate hydrogen atom ,-NO2,-CN ,-CH=C (CN)2,-CH=CH-CN, halogen group, carbon number 1~5 alkyl, Or the alkoxy of carbon number 1~5.
In any one of<P11>above-mentioned<P1>~<P4>, (A) ingredient can have photonasty side chain shown in following formula (20).
In formula, A, Y1, X, l and m have definition same as described above.
In any one of<P12>above-mentioned<P1>~<P11>, (A) ingredient be can have selected from by following formula (21)~(31) Any liquid crystal liquid crystal property side chain in the group of composition.
In formula, A, B, q1 and q2 have definition same as described above；
Y3For selected from by the phenyl ring of 1 valence, naphthalene nucleus, cyclohexyl biphenyl, furan nucleus, nitrogen-containing heterocycle and carbon number 5~8 ester ring type hydrocarbon, And the group in the group of their combination composition, their hydrogen atom is bonded to each independently optionally by-NO2,-CN, halogen The alkoxy of plain group, the alkyl of carbon number 1~5 or carbon number 1~5 replaces；
R3Indicate hydrogen atom ,-NO2,-CN ,-CH=C (CN)2,-CH=CH-CN, halogen group, the phenyl ring of 1 valence, naphthalene nucleus, Cyclohexyl biphenyl, furan nucleus, nitrogen-containing heterocycle, the ester ring type hydrocarbon of carbon number 5~8, the alkyl of carbon number 1~12 or carbon number 1~12 alkoxy；
L indicates that 1~12 integer, m indicate 0~2 integer, wherein in formula (25)~(26), the summation of all m is 2 More than, in formula (27)~(28), the summation of all m is 1 or more, and m1, m2 and m3 each independently represent 1~3 integer；
R2Indicate hydrogen atom ,-NO2,-CN, halogen group, the phenyl ring of 1 valence, naphthalene nucleus, cyclohexyl biphenyl, furan nucleus, nitrogen-containing heterocycle, And the ester ring type hydrocarbon and alkyl or alkoxy of carbon number 5~8；
Z1、Z2Indicate singly-bound ,-CO- ,-CH2O- ,-CH=N- ,-CF2-。
A kind of<P13>substrate that element liquid crystal orientation film is indicated with the driving liquid crystal of transverse electric field, is by upper State any one of<P1>~<P12>manufacture.
A kind of driving liquid crystal of<P14>transverse electric field indicates element, the substrate with above-mentioned<P13>.
A kind of driving liquid crystal of<P15>transverse electric field indicates the manufacturing method of element, is obtained and having following process Element is indicated to the liquid crystal:
Prepare the process of the substrate (the 1st substrate) of above-mentioned<P13>；
Obtain have following liquid crystal orientation films the 2nd substrate process, by have following processes [I '], [II '] and [III '] and the liquid crystal orientation film for obtaining having been assigned tropism control ability；And
[V] is oppositely disposed aforementioned in such a way that the liquid crystal orientation film of aforementioned 1st substrate and the 2nd substrate is across liquid crystalline phase pair 1st substrate and the 2nd substrate, to obtain the process that liquid crystal indicates element；
The process [I '], [II '] and [III '] are as follows:
[I '] coated polymeric composition and the process that forms film, described polymer composition on the 2nd substrate contains: (A) the photonasty side chain type macromolecule and (B) organic solvent of liquid crystal liquid crystal property are shown within the scope of specific temperature；
The process of [II '] to the irradiation polarized UV rays of film obtained in [I ']；And
The process that [III '] heats film obtained in [II '].
In<P16>above-mentioned<P15>,
The process for obtaining aforementioned 2nd substrate can also have [IV '] that the film heated in [III '] is cooled to insufficient be somebody's turn to do After the temperature of the glass transition temperature of film coated surface, the process that is again heated to the temperature of the glass transition temperature or more.
A kind of driving liquid crystal of<P17>transverse electric field indicates element, is manufactured by above-mentioned<P15>or<P16>.
The effect of invention
By means of the invention it is possible to provide with high efficiency be endowed tropism control ability, image retention speciality it is excellent, have laterally Electric field drive liquid crystal indicates the substrate of element liquid crystal orientation film and the driving liquid crystal watch of transverse electric field with the substrate Show element.
The driving liquid crystal of transverse electric field manufactured by means of the present invention indicates that element is efficiently imparted orientation Control ability, therefore characterization will not be damaged long-time Continuous Drive.
In addition, through the invention, the polarised light photograph that can be realized the good liquid crystal aligning in liquid crystal orientation film can be expanded The bounds for the amount of penetrating can play expectation since the bounds of exposure expand in broader range of exposures Effect.
Detailed description of the invention
Fig. 1 is the anisotropy importing processing in the manufacturing method for schematically illustrate liquid crystal orientation film used in the present invention An example figure, being photosensitive side chain uses bridging property organic group and the figure of anisotropy hour that is imported.
Fig. 2 is the anisotropy importing processing in the manufacturing method for schematically illustrate liquid crystal orientation film used in the present invention An example figure, figure when being photosensitive side chain using bridging property organic group and the big anisotropy that is imported.
Fig. 3 is the anisotropy importing processing in the manufacturing method for schematically illustrate liquid crystal orientation film used in the present invention An example figure, be photosensitive side chain using the organic group of fries' rearrangement or isomerization can occur and imported The figure of anisotropy hour.
Fig. 4 is the anisotropy importing processing in the manufacturing method for schematically illustrate liquid crystal orientation film used in the present invention An example figure, be photosensitive side chain using the organic group of fries' rearrangement or isomerization can occur and imported Figure when anisotropy is big.
Specific embodiment
Present inventor has performed further investigations, as a result obtain following opinion, so as to complete the present invention.
Polymer composition used in the manufacturing method of the present invention has the photonasty side chain that can show liquid crystal liquid crystal property Type macromolecule (hereinafter also referred to as side chain type macromolecule), using the film that foregoing polymer compositions obtain be have being capable of table Reveal the high molecular film of photonasty side chain type of liquid crystal liquid crystal property.The film without carrying out brushing processing, by polarizing light irradiation into Row orientation process.Also, after carrying out polarizing light irradiation, via the process for heating the side chain type polymeric membrane, to become quilt Impart the film (hereinafter also referred to liquid crystal orientation film) of tropism control ability.At this point, shown by polarizing light irradiation Small anisotropy becomes driving force, the side chain type macromolecule itself of liquid crystal liquid crystal property effectively reorientation due to self assembly.It is tied Fruit can realize efficient orientation process as liquid crystal orientation film, and the liquid crystal for obtaining having been assigned highly oriented control ability takes To film.
The inventors of the present invention also it has been unexpectedly found that: by after irradiate polarised light, will heat side chain type polymeric membrane and The product obtained is further cooling and reheats, and the film for having been assigned tropism control ability is obtained, so as to obtain wider Has the liquid crystal orientation film of good liquid crystal aligning in wealthy polarizing light irradiation amount bounds.The present invention is based on the opinion And carry out.
Hereinafter, detailed description of embodiments of the present invention for needle.
<manufacturing method of the substrate with liquid crystal orientation film>and<manufacturing method of liquid crystal expression element>
The manufacturing method of substrate with liquid crystal orientation film of the invention has following process:
Polymer composition is coated on the work on the substrate with transverse electric field driving conductive film and forming film by [I] Sequence, the polymer composition contain: (A) shows the photonasty side chain type high score of liquid crystal liquid crystal property within the scope of specific temperature Son and (B) organic solvent；
The process of [II] to the irradiation polarized UV rays of film obtained in [I]；
The process that [III] heats film obtained in [II]；And
After the film heated in [III] is cooled to the temperature of the glass transition temperature of the insufficient film coated surface by [IV], The process for being again heated to the temperature of the glass transition temperature or more.
By above-mentioned operation, the driving liquid crystal of transverse electric field that can obtain having been assigned tropism control ability indicates element With liquid crystal orientation film, the substrate with the liquid crystal orientation film can be obtained.
In addition, by preparing the 2nd substrate, transverse electric field can be obtained other than substrate obtained above (the 1st substrate) Driving liquid crystal indicates element.
2nd substrate is replaced in addition to using the substrate without transverse electric field driving conductive film with transverse electric field driving Except the substrate of conductive film, transverse electric field driving (is not had with leading due to using by using above-mentioned operation [I]~[III] The substrate of electrolemma, therefore for convenience, in this application sometimes referred to simply as process [I ']~[III ']), it can obtain with quilt Impart the 2nd substrate of the liquid crystal orientation film of tropism control ability.
The driving liquid crystal of transverse electric field indicates that the manufacturing method of element has following process:
[V] is by the 1st substrate obtained above and the 2nd substrate with the liquid crystal orientation film of the 1st substrate and the 2nd substrate across liquid crystal Opposite mode carry out it is oppositely disposed, thus obtain liquid crystal indicate element process.It is driving thereby, it is possible to obtain transverse electric field Liquid crystal indicates element.
Hereinafter, being illustrated for each process of [I]~[IV] and [V] that the manufacturing method of the present invention has.
<process [I]>
In process [I], the coated polymeric composition on the substrate with transverse electric field driving conductive film and form painting Film, the polymer composition contain: shown within the scope of specific temperature liquid crystal liquid crystal property photonasty side chain type macromolecule, with And organic solvent.
<substrate>
It is not particularly limited for substrate, the liquid crystal to be manufactured indicates when element is infiltration type, it is preferable to use the transparency is high Substrate.It is not particularly limited at this time, plastic bases such as glass substrate or acrylic compounds substrate, polycarbonate substrate etc. can be used.
Furthermore, it is contemplated that indicating the application in element in reflective liquid crystal, the opaque substrate such as silicon wafer also can be used.
<transverse electric field driving conductive film>
There is substrate transverse electric field driving to use conductive film.
As the conductive film, when liquid crystal indicates that element is infiltration type, ITO (Indium Tin Oxide: oxidation can be enumerated Indium tin), IZO (Indium Zinc Oxide: indium zinc oxide) etc., be not limited to these.
In addition, in the case where reflective liquid crystal indicates element, as conductive film, the material of the meeting reflected light such as aluminium can be enumerated Material etc., is not limited to these.
Conventionally known method can be used in the method that conductive film is formed on substrate.
<polymer composition>
Coated polymeric composition, especially applies on conductive film on the substrate with transverse electric field driving conductive film Cloth polymer composition.
The polymer composition used in the manufacturing method of the present invention contains: (A) is showed within the scope of specific temperature The photonasty side chain type macromolecule of liquid crystal liquid crystal property out；And (B) organic solvent.
<<(A) side chain type macromolecule>>
(A) ingredient is the photonasty side chain type macromolecule that liquid crystal liquid crystal property is shown within the scope of specific temperature.
(A) side chain type macromolecule by react under the light of the wave-length coverage of 250nm~400nm and 100 DEG C~ Liquid crystal liquid crystal property is shown within the temperature range of 300 DEG C.
(A) side chain type macromolecule preferably has the photonasty side to react with the light of the wave-length coverage of 250nm~400nm Chain.
(A) side chain type macromolecule shows liquid crystal liquid crystal property within the temperature range of 100 DEG C~300 DEG C, therefore preferably has liquid crystal Former base group.
(A) the high molecular main chain of side chain type, which has been bonded, has photosensitive side chain, and induction can be crosslinked in light Reaction, isomerization reaction or light fries' rearrangement.It is not particularly limited with photosensitive side-chain structure, is contemplated to be induction in light And crosslink the structure of reaction or light fries' rearrangement, it more desirable to be the structure for crosslinking reaction.At this point, if exposed to The external stresses such as heat can also keep the tropism control ability realized steadily in the long term.It can show the photonasty of liquid crystal liquid crystal property As long as the structure of side chain type polymeric membrane meets this characteristic, there is no particular limitation, preferably have in side-chain structure upright and outspoken Liquid crystal ultimate constituent.At this point, stable liquid crystal aligning can be obtained when liquid crystal orientation film is made in the side chain type macromolecule.
The high molecular structure can for example be made such as flowering structure: with main chain and the side chain for being bonded to it, side chain tool There are the liquid crystal ultimate constituents such as xenyl, terphenyl, phenylcyclohexyl, phenylamino benzoic acid ester group, azobenzene and is bonded to front end The induction light in portion and the photonasty group for crosslinking reaction, isomerization reaction；With main chain and the side chain for being bonded to it, the side It is both liquid crystal ultimate constituent or the phenylamino benzoic acid ester group that light Fries rearrangement can occur that chain, which has,.
The more specific example of structure as the photonasty side chain type polymeric membrane that can show liquid crystal liquid crystal property, it is however preferred to have The structure of following main chain and following side chain, the main chain is by being selected from hydrocarbon, (methyl) acrylate, itaconate, fumarate, horse Come the radically polymerizable groups such as acid esters, alpha-methylene-gamma-butyrolactone, styrene, vinyl, maleimide, norbornene group With at least one kind of composition in group composed by siloxanes, the side chain includes at least one kind of in following formula (1)~(6).
In formula, A, B, D each independently represent singly-bound ,-O- ,-CH2-、-COO-、-OCO-、-CONH-、-NH-CO-、-CH =CH-CO-O- or-O-CO-CH=CH-；
S is the alkylidene of carbon number 1~12, and the hydrogen atom for being bonded to them is optionally replaced by halogen group；
T is the alkylidene of singly-bound or carbon number 1~12, and the hydrogen atom for being bonded to them is optionally replaced by halogen group；
Y1In the ester ring type hydrocarbon for indicating phenyl ring selected from 1 valence, naphthalene nucleus, cyclohexyl biphenyl, furan nucleus, pyrrole ring and carbon number 5~8 Ring, or identical or different 2~6 ring in these substituent groups is by group made of binding groups B bonding, key Together in their hydrogen atom each independently optionally by-COOR0(in formula, R0Indicate the alkyl of hydrogen atom or carbon number 1~5) ,- NO2,-CN ,-CH=C (CN)2,-CH=CH-CN, halogen group, the alkyl of carbon number 1~5 or carbon number 1~5 alkoxy replace；
Y2For selected from by the phenyl ring of divalent, naphthalene nucleus, cyclohexyl biphenyl, furan nucleus, pyrrole ring, carbon number 5~8 ester ring type hydrocarbon and it The group that is combined into of group in group, be bonded to their hydrogen atom each independently optionally by-NO2,-CN ,-CH=C (CN)2,-CH=CH-CN, halogen group, the alkyl of carbon number 1~5 or carbon number 1~5 alkoxy replace；
R indicates the alkoxy of hydroxyl, carbon number 1~6, or expression and Y1Identical definition；
X indicates singly-bound ,-COO- ,-OCO- ,-N=N- ,-CH=CH- ,-C ≡ C- ,-CH=CH-CO-O- or-O-CO-CH =CH-, when the quantity of X reaches 2, X is optionally same or different to each other；
Cou indicates Coumarin-6-base or coumarin-7-base, be bonded to their hydrogen atom each independently optionally by- NO2,-CN ,-CH=C (CN)2,-CH=CH-CN, halogen group, the alkyl of carbon number 1~5 or carbon number 1~5 alkoxy replace；
One of q1 and q2 are 1, another one 0；
Q3 is 0 or 1；
P and Q is each independently selected from by the phenyl ring of divalent, naphthalene nucleus, cyclohexyl biphenyl, furan nucleus, pyrrole ring, carbon number 5~8 Group in ester ring type hydrocarbon and the group of their combination composition；Wherein, when X is-CH=CH-CO-O- ,-O-CO-CH=CH- ,- The P or Q for the side that CH=CH- is bonded are aromatic rings, and when the quantity of P reaches 2 or more, P is optionally same or different to each other, Q's When quantity reaches 2 or more, Q is optionally same or different to each other；
L1 is 0 or 1；
The integer that l2 is 0~2；
When l1 and l2 are 0, A also illustrates that singly-bound when T is singly-bound；
When l1 is 1, B also illustrates that singly-bound when T is singly-bound；
H and I is each independently in the phenyl ring selected from divalent, naphthalene nucleus, cyclohexyl biphenyl, furan nucleus, pyrrole ring and their combination Group.
Side chain can be any photonasty side chain in the group being made of following formula (7)~(10).
In formula, A, B, D, Y1、X、Y2There is definition same as described above with R；
L indicates 1~12 integer；
M indicates that 0~2 integer, m1, m2 indicate 1~3 integer；
N indicates 0~12 integer (wherein, when n=0, B is singly-bound).
Side chain can be any photonasty side chain in the group being made of following formula (11)~(13).
In formula, A, X, l, m, m1 and R have definition same as described above.
Side chain can be photonasty side chain shown in following formula (14) or (15).
In formula, A, Y1, l, m1 and m2 have definition same as described above.
Side chain can be photonasty side chain shown in following formula (16) or (17).
In formula, A, X, l and m have definition same as described above.
In addition, side chain can be photonasty side chain shown in following formula (18) or (19).
In formula, A, B, Y1, q1, q2, m1 and m2 have definition same as described above.
R1Indicate hydrogen atom ,-NO2,-CN ,-CH=C (CN)2,-CH=CH-CN, halogen group, carbon number 1~5 alkyl, Or the alkoxy of carbon number 1~5.
Side chain can be photonasty side chain shown in following formula (20).
In formula, A, Y1, X, l and m have definition same as described above.
In addition, (A) side chain type macromolecule can have selected from any one of the group being made of following formula (21)~(31) Liquid crystal liquid crystal property side chain.
In formula, A, B, q1 and q2 have definition same as described above；
Y3For selected from by the phenyl ring of 1 valence, naphthalene nucleus, cyclohexyl biphenyl, furan nucleus, nitrogen-containing heterocycle and carbon number 5~8 ester ring type hydrocarbon, And the group in the group of their combination composition, their hydrogen atom is bonded to each independently optionally by-NO2,-CN, halogen The alkoxy of plain group, the alkyl of carbon number 1~5 or carbon number 1~5 replaces；
R3Indicate hydrogen atom ,-NO2,-CN ,-CH=C (CN)2,-CH=CH-CN, halogen group, the phenyl ring of 1 valence, naphthalene nucleus, Cyclohexyl biphenyl, furan nucleus, nitrogen-containing heterocycle, the ester ring type hydrocarbon of carbon number 5~8, the alkyl of carbon number 1~12 or carbon number 1~12 alkoxy；
L indicates that 1~12 integer, m indicate 0~2 integer, wherein in formula (23)~(24), the summation of all m is 2 More than, in formula (25)~(26), the summation of all m is 1 or more, and m1, m2 and m3 each independently represent 1~3 integer；
R2Indicate hydrogen atom ,-NO2 ,-CN, halogen group, the phenyl ring of 1 valence, naphthalene nucleus, cyclohexyl biphenyl, furan nucleus, nitrogen-containing heterocycle, And the ester ring type hydrocarbon and alkyl or alkoxy of carbon number 5~8；
Z1、Z2Indicate singly-bound ,-CO- ,-CH2O- ,-CH=N- ,-CF2-。
<<the high molecular preparation method of photonasty side chain type>>
The above-mentioned photonasty side chain type macromolecule that can show liquid crystal liquid crystal property can be by that will have above-mentioned photonasty side chain Photoreactivity side chain monomer and liquid crystal liquid crystal property side chain monomer are polymerize to obtain.
[photoreactivity side chain monomer]
Photoreactivity side chain monomer refers to: when forming macromolecule, can be formed in high molecular side chain position with photosensitive The high molecular monomer of property side chain.
As photoreactive group possessed by side chain, preferably following structures and its derivative.
More specific example as photoreactivity side chain monomer, it is however preferred to have the knot of polymerizable group and photonasty side chain Structure, the polymerizable group is by selected from by hydrocarbon, (methyl) acrylate, itaconate, fumarate, maleate, α-methylene The radically polymerizable groups such as base-gamma-butyrolacton, styrene, vinyl, maleimide, norbornene group and siloxanes composition Group at least one kind of composition, the photonasty side chain is comprising at least one kind of photonasty side in above-mentioned formula (1)~(6) Chain, preferably for example comprising in above-mentioned formula (7)~(10) at least one kind of photonasty side chain, include above-mentioned formula (11)~(13) In at least one kind of photonasty side chain, shown in photonasty side chain, above-mentioned formula (16) shown in above-mentioned formula (14) or (15) or (17) Photonasty side chain, photonasty side chain shown in photonasty side chain, above-mentioned formula (20) shown in above-mentioned formula (18) or (19).
In the application, as photoreactivity and/or liquid crystal liquid crystal property side chain monomer, provide shown in formula below (1)~(11) New compound (1)~(11)；And formula (12) below~(17) compound represented (12)~(17).
In formula, R indicates hydrogen atom or methyl；The alkylidene of S expression carbon number 2~10；R10 indicates Br or CN；S indicates carbon number 2~10 alkylidene；U is expressed as 0 or 1；And Py indicates 2- pyridyl group, 3- pyridyl group or 4- pyridyl group.In addition, v indicates 1 or 2.
[liquid crystal liquid crystal property side chain monomer]
Liquid crystal liquid crystal property side chain monomer refers to: the high molecular form from the monomer reveals liquid crystal liquid crystal property, and the macromolecule is at side chain position It is capable of forming the monomer of mesogenic group.
As mesogenic group possessed by side chain, can be biphenyl, phenol benzoate etc. individually becomes liquid crystal original structure Group, be also possible to the group that such ground such as benzoic acid side chain carries out hydrogen bonding each other and becomes mesogen structure.As side Mesogenic group possessed by chain, preferably following structures.
More specific example as liquid crystal liquid crystal property side chain monomer, it is however preferred to have the knot of following polymerizable group and following side chain Structure, the polymerizable group is by selected from by hydrocarbon, (methyl) acrylate, itaconate, fumarate, maleate, α-methylene The radically polymerizable groups such as base-gamma-butyrolacton, styrene, vinyl, maleimide, norbornene group and siloxanes composition Group at least one kind of composition, the side chain include above-mentioned formula (21)~(31) in it is at least one kind of.
(A) side chain type macromolecule can be obtained by the polymerization reaction of the above-mentioned photoreactivity side chain monomer for showing liquid crystal liquid crystal property ?.Furthermore it is possible to by the copolymerization of the photoreactivity side chain monomer and liquid crystal liquid crystal property side chain monomer that do not show liquid crystal liquid crystal property, show liquid The copolymerization of the photoreactivity side chain monomer of crystalline substance and liquid crystal liquid crystal property side chain monomer obtains.In turn, liquid crystal sex expression energy is not being damaged In the range of power, it can be copolymerized with other monomers.
As other monomers, can enumerate for example can the industrial monomer for being able to carry out Raolical polymerizable obtained.
As the concrete example of other monomers, unsaturated carboxylic acid, acrylate compounds, methacrylated can be enumerated Close object, maleimide compound, acrylonitrile, maleic anhydride, distyryl compound and vinyl compound etc..
As the concrete example of unsaturated carboxylic acid, acrylic acid, methacrylic acid, itaconic acid, maleic acid, fumaric acid can be enumerated Deng.
As acrylate compounds, such as methyl acrylate, ethyl acrylate, isopropyl acrylate, third can be enumerated Olefin(e) acid benzyl ester, acrylic acid naphthalene ester, acrylic acid anthracene ester, acrylic acid anthrylmethyl, phenyl acrylate, acrylic acid 2,2,2- trifluoro second Ester, tert-butyl acrylate, cyclohexyl acrylate, isobornyl acrylate, acrylic acid 2- methoxy acrylate, methoxy triethylene Acrylate, acrylic acid 2- ethoxy ethyl ester, tetrahydrofurfuryl acrylate, acrylic acid 3- methoxybutyl, acrylic acid 2- methyl -2- Adamantane esters, acrylic acid 2- propyl -2- adamantane esters, acrylic acid 8- methyl -8- tricyclodecyl and acrylic acid 8- second Base -8- tricyclodecyl etc..
As methacrylate compound, such as methyl methacrylate, ethyl methacrylate, methyl can be enumerated Isopropyl acrylate, benzyl methacrylate, methacrylic acid naphthalene ester, methacrylic acid anthracene ester, methacrylic acid anthrylmethyl, Phenyl methacrylate, methacrylic acid 2,2,2- trifluoro ethyl ester, Tert-butyl Methacrylate, cyclohexyl methacrylate, first Base isobornyl acrylate, methacrylic acid 2- methoxy acrylate, methoxy triethylene methacrylate, methacrylic acid 2- ethoxy ethyl ester, tetrahydrofurfuryl methacrylate, methacrylic acid 3- methoxybutyl, methacrylic acid 2- methyl -2- gold Rigid Arrcostab, methacrylic acid 2- propyl -2- adamantane esters, methacrylic acid 8- methyl -8- tricyclodecyl and methyl-prop Olefin(e) acid 8- ethyl -8- tricyclodecyl etc..Also (methyl) glycidyl acrylate, (methyl) acrylic acid (3- methyl-can be used 3- oxetanyl) methyl esters and (methyl) acrylic acid (3- ethyl -3- oxetanyl) methyl esters etc. have cyclic ether group (methyl) acrylate compounds.
As vinyl compound, such as vinethene, ethylene methacrylic ether, benzyl ethylene ether, 2- hydroxyethyl can be enumerated Vinethene, phenylvinyl ether and propyl vinyl ether etc..
As distyryl compound, can enumerate such as styrene, methyl styrene, chlorostyrene, bromstyrol.
As maleimide compound, such as maleimide, N- methylmaleimido, N- phenyl horse can be enumerated Come acid imide and N- N-cyclohexylmaleimide etc..
For the high molecular manufacturing method of side chain type of present embodiment, it is not particularly limited, can use and industrially answer Universal method.Specifically, can be by the way that the sun of the vinyl of liquid crystal liquid crystal property side chain monomer, photoreactivity side chain monomer be utilized Ionic polymerization, free radical polymerization, anionic polymerisation manufacture.Among these, from viewpoints such as reaction controlling easness, especially Preferably free radical polymerization.
As the polymerization initiator of free radical polymerization, radical polymerization initiator, invertibity addition-cracking type can be used Compound well known to chain tra nsfer (RAFT) polymerization agent etc..
Free radical thermal polymerization is the compound generated free radicals and being heated to decomposition temperature or more.As this Kind of free radical thermal polymerization, can enumerate such as peroxidating ketone (methyl ethyl ketone peroxide, Cyclohexanone peroxides), Peroxidating two acyl base class (acetyl peroxide, benzoyl peroxide etc.), hydroperoxide kind (hydrogen peroxide, tert-butyl hydroperoxide, Cumene hydroperoxide etc.), dialkyl peroxide class (di-tert-butyl peroxide, dicumyl peroxide, two lauroyl peroxides Compound etc.), ketal peroxide class (dibutyl cyclohexane peroxide etc.), alkyl peroxyesters class (new peroxide tert-butyl caprate, The peroxidating pivalic acid tert-butyl ester, peroxidating 2- cyclohexyl alkanoic acid tert-pentyl ester etc.), persulfuric acid salt (potassium peroxydisulfate, persulfuric acid Sodium, ammonium persulfate etc.), azo compound (azobis isobutyronitrile and 2,2 '-two (2- hydroxyethyl) azobis isobutyronitriles Deng).This free radical thermal polymerization can be used alone, alternatively, two or more can also be applied in combination.
As long as radical photopolymerization initiator starts the compound of free radical polymerization because of light irradiation, just do not limit especially It is fixed.As this radical photopolymerization initiator, benzophenone, Michler's keton, 4,4 '-bis- (lignocaine) hexichol first can be enumerated Ketone, xanthone, thio xanthone, isopropyl xanthone, 2,4- diethyl sulfide are for xanthone, 2- ethyl hydrazine, benzene It is ethyl ketone, 2- hydroxy-2-methyl propiophenone, 2- hydroxy-2-methyl -4 '-cumene acetone, 1- hydroxycyclohexylphenylketone, different Propyl benzoin ether, isobutyl benzoin ether, 2,2- diethoxy acetophenone, 2,2- dimethoxy -2- phenyl acetophenone, camphor Quinone, benzanthrone, 2- methyl-1-[4- (methyl mercapto) phenyl]-2- morpholino propyl- 1- ketone, 2- benzyl-2- dimethylamino-1- (4- Morphlinophenyl) -1- butanone, 4- dimethyl ethyl aminobenzoate, 4- dimethylaminobenzoic acid isopentyl ester, 4,4 '-two (tert-butyls Peroxy carbonyl) benzophenone, 3,4,4 '-three (t-butylperoxycarbonyl) benzophenone, 2,4,6- trimethylbenzoyl Diphenyl phosphine oxide, bis- (trichloromethyl) s-triazine of 2- (4 '-methoxyl-styrene) -4,6-, 2- (3 ', 4 '-dimethoxy benzenes Vinyl) bis- (trichloromethyl) s-triazine of -4,6-, 2- (2 ', 4 '-dimethoxy-styryl) -4,6- bis- (trichloromethyls) be equal Triazine, bis- (trichloromethyl) s-triazine of 2- (2 '-methoxyl-styrene) -4,6-, 2- (4 '-amyl phenyl ether vinyl) -4,6- Bis- (trichloromethyl) s-triazine, 4- [p- N, N- bis- (ethoxy carbonyl methyl)] -2,6- two (trichloromethyl) s-triazine, 1,3- Bis- (trichloromethyl) -5- (2 '-chlorphenyl) s-triazine, bis- (trichloromethyl) -5- (4 '-methoxyphenyl) s-triazine, 2- of 1,3- (to dimethylaminostyryl) benzoxazoles, 2- (to dimethylaminostyryl) benzothiazole, 2-mercaptobenzothiazole, 3, It is 3 '-carbonyls bis- (7- lignocaine cumarins), -4,4 ', 5,5 '-tetraphenyl -1,2 ' of 2- (Chloro-O-Phenyl)-bisglyoxaline, 2,2 '-bis- (2- chlorphenyl) -4,4 ', 5,5 '-four (4- carboethoxyphenyl) -1,2 '-bisglyoxalines, 2,2 '-bis- (2,4 dichloro benzene bases) - 4,4 ', 5,5 '-tetraphenyls -1,2 '-bisglyoxaline, 2,2 ' bis- (2,4- dibromo phenyl) -4,4 ', 5,5 '-tetraphenyl -1,2 '-connection miaows Azoles, 2,2 '-bis- (2,4,6- trichlorophenyl) -4,4 ', 5,5 '-tetraphenyl -1,2 '-bisglyoxalines, 3- (2- methyl -2- dimethylamino Propiono) carbazole, 3,6- bis- (2- methyl -2- morpholino propiono) -9- dodecyl carbazoles, 1- hydroxycyclohexylphenyl Ketone, bis- (5-2,4- cyclopentadiene -1- bases)-bis- (the fluoro- 3- of 2,6- bis- (1H- pyrroles -1- base)-phenyl) titaniums, 3,3 ', 4,4 '-four (t-butylperoxycarbonyl) benzophenone, 3,3 ', 4,4 '-four (tertiary hexyl peroxy carbonyl) benzophenone, 3,3 '-two (first Epoxide carbonyl) -4,4 '-two (t-butylperoxycarbonyl) benzophenone, 3,4 '-two (methoxycarbonyl) -4,3 '-two (tertiary fourths Base peroxy carbonyl) benzophenone, 4,4 '-two (methoxycarbonyl) -3,3 '-two (t-butylperoxycarbonyl) benzophenone, 2- (3- methyl -3H- benzothiazole -2- subunit) -1- naphthalene -2- base-ethyl ketone or 2- (3- methyl-1,3- benzothiazole -2 (3H)-subunit) -1- (2- benzoyl) ethyl ketone etc..These compounds can be used alone, and can also mix two or more make With.
Radical polymerization is not particularly limited, and emulsion polymerization can be used, suspension polymerization, dispersion copolymerization method, sink Shallow lake polymerization, mass polymerization, solution polymerization process etc..
As organic solvent used in the high molecular polymerization reaction of photonasty side chain type of liquid crystal liquid crystal property can be shown, only If the organic solvent that macromolecule generated can dissolve just is not particularly limited.It is exemplified below out its concrete example.
It can enumerate: N,N-dimethylformamide, DMAC N,N' dimethyl acetamide, n-methyl-2-pyrrolidone, N- ethyl- 2-Pyrrolidone, N- methyl caprolactam, dimethyl sulfoxide, tetramethylurea, pyridine, dimethyl sulfone, hexamethyl sulfoxide, γ-fourth Lactone, isopropanol, methoxy amylalcohol, cinene, ethylpentyl ketone, methyl nonyl ketone, methyl ethyl ketone, methyl isoamyl ketone, Methyl isopropyl Ketone, methyl cellosolve, ethyl cellosolve, methylcellosolve acetate, ethyl cellosolve acetate, butyl card must Alcohol, ethyl carbitol, ethylene glycol, ethylene glycol acetate, ethyleneglycol monopropylether, ethylene glycol monobutyl ether, propylene glycol, propylene glycol Monoacetate, propylene glycol monomethyl ether, glycol tertiary butyl ether, dipropylene glycol monomethyl ether, diethylene glycol, diethylene glycol monoacetate, Diethylene glycol dimethyl ether, dipropylene glycol monoacetate monomethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol Monoacetate list ether, dipropylene glycol monopropyl ether, dipropylene glycol monoacetate list propyl ether, 3- methyl -3- methoxybutyl acetic acid Ester, tripropylene glycol methyl ether, 3- methyl -3- methoxybutanol, diisopropyl ether, ethyl isobutyl ether, diisobutylene, pentyl acetate, fourth Acid butyl ester, butyl ether, diisobutyl ketone, methylcyclohexene, propyl ether, two hexyl ethers, dioxanes, n-hexane, pentane, normal octane, diethyl The positive fourth of ether, cyclohexanone, ethylene carbonate, propylene carbonate, methyl lactate, ethyl lactate, methyl acetate, ethyl acetate, acetic acid Ester, acetic acid dihydroxypropane single-ether, methyl pyruvate, ethyl pyruvate, 3- methoxy methyl propionate, 3- ethoxy-c acid methyl second Ester, 3- methoxypropionate, 3- ethoxy-propionic acid, 3- methoxypropionic acid, 3- methoxy propyl propyl propionate, 3- methoxypropionic acid fourth Ester, diethylene glycol dimethyl ether, 4- hydroxy-4-methyl-2-pentanone, 3- methoxyl group-N, N- dimethylpropionamide, 3- ethyoxyl-N, N- Dimethylpropionamide, 3- butoxy-N, N- dimethylpropionamide etc..
These organic solvents can be used alone, and can also be used in mixed way.In turn, even not dissolving high score generated The solvent of son, as long as can also mix into above-mentioned organic solvent makes in the range of macromolecule generated will not be precipitated With.
In addition, the oxygen in organic solvent can become the reason of hindering polymerization reaction, therefore organic molten in free radical polymerization Agent uses after preferably deaerating as much as possible.
Polymerization temperature when free radical polymerization can select 30 DEG C~150 DEG C of arbitrary temp, and preferably 50 DEG C~100 DEG C Range.In addition, reaction can be carried out with any concentration, it is difficult to obtain the polymer of high molecular weight, concentration mistake when concentration is too low Gao Shi, the viscosity of reaction solution becomes excessively high and is difficult to equably stir, therefore monomer concentration is preferably 1 matter of mass %~50 Measure %, more preferably 5 mass of mass %~30 %.Initial reaction stage is carried out with high concentration, can add organic solvent thereafter.
In above-mentioned Raolical polymerizable, when radical polymerization initiator is more relative to the ratio of monomer, gained is high The molecular weight of molecule becomes smaller, when ratio less of the radical polymerization initiator relative to monomer, the high molecular molecule quantitative change of gained Greatly, therefore radical initiator relative to the ratio of polymerized monomer is preferably 0.1 mole of %~10 mole %.In addition, when polymerization Various monomer components, solvent, initiator etc. can also be added.
[recycling of polymer]
From the high molecular reaction solution of photonasty side chain type obtained using above-mentioned reaction, that liquid crystal liquid crystal property can be shown When recycling macromolecule generated, reaction solution is put into poor solvent, precipitates these polymer.As for sinking The poor solvent in shallow lake can enumerate methanol, acetone, hexane, heptane, butyl cellosolve, heptane, methyl ethyl ketone, methylisobutylketone, second Alcohol, toluene, benzene, diethyl ether, ethyl methyl ether, water etc..Putting into the polymer precipitated into poor solvent can filter back After receipts, air drying or heat drying are carried out under normal or reduced pressure.Precipitating is recycled in addition, repeating 2 times~10 times When polymer is re-dissolved in organic solvent and the operation of reprecipitation recycling, the impurity in polymer can be reduced.As at this time Poor solvent can be enumerated such as alcohols, ketone, hydrocarbon, when using 3 kinds or more poor solvents being selected among these, purification Efficiency further increases, so it is preferred that.
About the high molecular molecular weight of (A) side chain type of the invention, it is contemplated that when gained painting film strength, formation film When workability and the uniformity of film, utilize GPC (Gel Permeation Chromatography, gel permeation chromatography) The weight average molecular weight of method measurement is preferably 2000~1000000, more preferably 5000~100000.
[preparation of polymer composition]
Polymer composition used in the present invention is preferably prepared to the form of coating fluid, to suitably form liquid crystal aligning Film.That is, polymer composition used in the present invention preferably be used to form the resin component of resin coating be dissolved in it is organic molten It is prepared by the form of solution made of agent.Herein, which, which refers to, can show liquid crystal liquid crystal property comprising above explained The high molecular resin component of photonasty side chain type.At this point, the content of resin component be preferably 1 mass of mass %~20 %, it is more excellent It is selected as 3 mass of mass %~15 %, particularly preferably 3 mass of mass %~10 %.
In the polymer composition of present embodiment, it is that above-mentioned can show liquid that aforementioned resin ingredient, which can be all, The photonasty side chain type macromolecule of crystalline substance can also be mixed and be removed in the range of not damaging liquid crystal expressive ability and photosensitive property Other polymer except this.At this point, the content of other polymer in resin component is 0.5 mass of mass %~80 %, excellent It is selected as 1 mass of mass %~50 %.
This other polymer can enumerate such as comprising poly- (methyl) acrylate, polyamic acid, polyimides and It is not that can show high molecular polymer of photonasty side chain type of liquid crystal liquid crystal property etc..
<<(B) organic solvent>>
As long as organic solvent used in polymer composition used in the present invention is capable of having for dissolving resin ingredient Solvent is just not particularly limited.It is exemplified below out its concrete example.
Can enumerate: N,N-dimethylformamide, DMAC N,N' dimethyl acetamide, n-methyl-2-pyrrolidone, N- methyl oneself Lactams, 2-Pyrrolidone, N- ethyl pyrrolidone, n-vinyl pyrrolidone, dimethyl sulfoxide, tetramethylurea, pyridine, two Methyl sulfone, hexamethyl sulfoxide, gamma-butyrolacton, 3- methoxyl group-N, N- dimethylpropionamide, 3- ethyoxyl-N, N- dimethyl propionyl Amine, 3- butoxy-N, N- dimethylpropionamide, 1,3- dimethyl-2-imidazolidinone, ethylpentyl ketone, methyl nonyl ketone, first and second Ketone, methyl isoamyl ketone, methyl isopropyl Ketone, cyclohexanone, ethylene carbonate, propylene carbonate, diethylene glycol dimethyl ether, 4- hydroxyl Base -4-methyl-2 pentanone, Propylene glycol monoacetate, propylene glycol monomethyl ether, glycol tertiary butyl ether, dipropylene glycol monomethyl ether, diethyl Glycol, diethylene glycol monoacetate, diethylene glycol dimethyl ether, dipropylene glycol monoacetate monomethyl ether, dipropylene glycol monomethyl ether, two Dihydroxypropane single-ether, dipropylene glycol monoacetate list ether, dipropylene glycol monopropyl ether, dipropylene glycol monoacetate list propyl ether, 3- Methyl -3- methoxybutyl acetic acid esters, tripropylene glycol methyl ether etc..They can be used alone, and can also be used in mixed way.
Polymer composition used in the present invention can contain the ingredient except above-mentioned (A) and (B) ingredient.As its example Son can enumerate the solvent or compound for improving film thickness uniformity, surface smoothness in coated polymeric composition, improve liquid Brilliant alignment films and the compound of the adaptation of substrate etc., but not limited thereto.
As the concrete example for the solvent (poor solvent) for improving film thickness uniformity, surface smoothness, can enumerate following molten Agent.
Such as isopropanol, methoxy amylalcohol, methyl cellosolve, ethyl cellosolve, butyl cellosolve, first can be enumerated Base cellosolve acetate, ethyl cellosolve acetate, butyl carbitol, ethyl carbitol, ethylcarbitol acetate, second two Alcohol, ethylene glycol acetate, ethyleneglycol monopropylether, ethylene glycol monobutyl ether, propylene glycol, Propylene glycol monoacetate, propylene glycol list Methyl ether, propylene glycol mono-n-butyl ether, glycol tertiary butyl ether, dipropylene glycol monomethyl ether, diethylene glycol, diethylene glycol monoacetate, two Glycol dimethyl ether, dipropylene glycol monoacetate monomethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol list Acetic acid esters list ether, dipropylene glycol monopropyl ether, dipropylene glycol monoacetate list propyl ether, 3- methyl -3- methoxybutyl acetic acid esters, Tripropylene glycol methyl ether, 3- methyl -3- methoxybutanol, diisopropyl ether, ethyl isobutyl ether, diisobutylene, pentyl acetate, butyric acid fourth Ester, butyl ether, diisobutyl ketone, methylcyclohexene, propyl ether, two hexyl ethers, 1- hexanol, n-hexane, pentane, normal octane, diethyl ether, cream Sour methyl esters, ethyl lactate, methyl acetate, ethyl acetate, n-butyl acetate, acetic acid dihydroxypropane single-ether, methyl pyruvate, acetone Acetoacetic ester, 3- methoxy methyl propionate, 3- ethoxy-propionic acid Methylethyl, 3- methoxypropionate, 3- ethoxy-propionic acid, 3- Methoxypropionic acid, 3- methoxy propyl propyl propionate, 3- methoxy propyl acid butyl ester, 1- methoxy-2-propanol, 1- ethyoxyl -2- propyl alcohol, 1- butoxy -2- propyl alcohol, 1- phenoxy group -2- propyl alcohol, Propylene glycol monoacetate, propylene-glycol diacetate, propylene glycol -1- list first Ether -2- acetic acid esters, propylene glycol -1- list ether -2- acetic acid esters, dipropylene glycol, 2- (2- ethoxy-c oxygroup) propyl alcohol, lactic acid first Ester, ethyl lactate, lactic acid n-propyl ester, n-butyl lactate, isoamyl lactate etc. have the solvent etc. of low surface tension.
These poor solvents can be used a kind, can also be used in mixed way a variety of.When using solvent as described above, in order to Not making the dissolubility of the solvent for including in polymer composition entirety significantly reduces, preferably 5 mass %~80 of solvent entirety Quality %, more preferably 20 mass of mass %~60 %.
As the compound for improving film thickness uniformity, surface smoothness, fluorine system surfactant, organic silicon-type can be enumerated Surfactant and nonionic surfactants etc..
More specifically, such as Eftop (registered trademark) 301, EF303, EF352 (Tohkem products can be enumerated Corporation system)；Megafac (registered trademark) F171, F173, R-30 (DIC CORPORATION system)；Fluorad FC430, FC431 (Sumitomo 3M Limited system)；AsahiGuard (registered trademark) AG710 (Asahi Glass Co., Ltd System)；Surflon (registered trademark) S-382, SC101, SC102, SC103, SC104, SC105, SC106 (AGC SEIMI CHEMICAL CO., LTD. system) etc..The use ratio of these surfactants is relative to the resin contained in polymer composition 100 mass parts of ingredient are preferably 0.01 mass parts~2 mass parts, more preferably 0.01 mass parts~1 mass parts.
The concrete example of compound as the adaptation for improving liquid crystal orientation film and substrate, can enumerate described below contain The compound etc. of functional silanes.
Such as 3- TSL 8330,3-aminopropyltriethoxysilane, 2- aminopropyl can be enumerated Trimethoxy silane, 2- aminopropyltriethoxywerene werene, N- (2- aminoethyl) -3- TSL 8330, N- (2- Aminoethyl) -3- aminopropylmethyldimethoxysilane, 3- urea propyl trimethoxy silicane, 3- urea propyl-triethoxysilicane, N- ethoxy carbonyl -3- TSL 8330, N- ethoxy carbonyl -3-aminopropyltriethoxysilane, N- tri- Three second triamine of triethoxysilyl propyl, three second triamine of N- trimethoxy-silylpropyl, 10- trimethyoxysilane Three azepine decane of base -1,4,7-, three azepine decane of 10- triethoxysilyl -1,4,7-, 9- trimethoxysilyl - 3,6- diaza nonyl acetic acid esters, 9- triethoxysilyl -3,6- diaza nonyl acetic acid esters, N- benzyl -3- aminopropan Base trimethoxy silane, N- benzyl -3-aminopropyltriethoxysilane, N- phenyl -3- TSL 8330, N- Bis- (oxygen the ethylidene) -3- TSL 8330s of phenyl -3-aminopropyltriethoxysilane, N-, bis- (the oxygen Asia second of N- Base) -3-aminopropyltriethoxysilane etc..
By backlight when in turn, in order to improve the adaptation of substrate and liquid crystal orientation film and prevent from constituting liquid crystal expression element Caused electrical characteristics reduction etc., can contain phenoplasts system as following, the change containing epoxy group in polymer composition Close the additive of object.Specific phenoplasts system additive described below, but it is not limited to the structure.
As specifically containing the compound of epoxy group, ethylene glycol diglycidylether, polyethylene glycol diglycidyl can be exemplified Glycerin ether, propylene glycol diglycidylether, tripropyleneglycol diglycidyl ether, polypropylene glycol diglycidyl ether, neopentyl glycol Diglycidyl ether, 1,6 hexanediol diglycidylether, glycerin diglycidyl ether, 2,2- dibromoneopentyl glycol two shrink sweet Oily ether, 1,3,5,6- four glycidyl group -2,4- hexylene glycol, N, N, N ', N ',-four glycidyl group m-xylene diamine, 1,3- are bis- (N, N- diglycidyl amino methyl) hexamethylene, N, N, N ', N ',-four glycidyl group -4,4 '-diamino-diphenyl first Alkane etc..
Using the adaptation for improving liquid crystal orientation film and substrate compound when, dosage is relative to combination of polymers 100 mass parts of resin component contained in object are preferably 0.1 mass parts~30 mass parts, more preferably 1 mass parts~20 mass Part.When dosage is less than 0.1 mass parts, the effect for improving adaptation can not be expected, when being more than 30 mass parts, the orientation of liquid crystal has When be deteriorated.
As additive, photosensitizer also can be used.Preferably colourless sensitizer and triplet sensitizer.
As photosensitizer, there are aromatic nitro compound, cumarin (7- lignocaine -4- methylcoumarin, 7- hydroxyl 4- Methylcoumarin), coumarin ketone, carbonyl bicoumarin, aromatic series 2- hydroxy-ketone and the aromatic series 2- hydroxyl replaced by amino (2- dihydroxy benaophenonel, single pair (dimethylamino) -2- dihydroxy benaophenonel or two are to (dimethylamino) -2- hydroxy benzophenone for ketone Ketone), acetophenone, anthraquinone, xanthone, thio xanthone, benzanthrone, thiazoline (2- benzoyl methylene -3- first Base-β-aphthothiazoles quinoline, 2- (β-naphthoyl methylene) -3- methylbenzothiazole quinoline, 2- (α-naphthoyl methylene) -3- methyl Benzothiazoline, 2- (4- biphenyl Acylmethylene) -3- methylbenzothiazole quinoline, 2- (β-naphthoyl methylene) -3- methyl-β - Aphthothiazoles quinoline, 2- (4- biphenyl Acylmethylene) -3- methyl-β-aphthothiazoles quinoline, 2- (to fluorobenzoyl methylene) -3- Methyl-β-aphthothiazoles quinoline), ((β-naphthoyl is sub- by 2- benzoyl methylene -3- methyl-β-aphthoxazoles quinoline, 2- for oxazoline Methyl) -3- methylbenzoxazole quinoline, 2- (α-naphthoyl methylene) -3- methylbenzoxazole quinoline, 2- (4- biphenyl acyl group methylene Base) -3- methylbenzoxazole quinoline, 2- (β-naphthoyl methylene) -3- methyl-β-aphthoxazoles quinoline, 2- (4- biphenyl acyl group methylene Base) -3- methyl-β-aphthoxazoles quinoline, 2- (to fluorobenzoyl methylene) -3- methyl-β-aphthoxazoles quinoline), benzothiazole, Nitroaniline (meta nitro aniline or paranitroanilinum, 2,4,6- trinitroaniline) or nitro acenaphthene (5- nitro acenaphthene), (2- [(hydroxyl Base is to methoxyl group) styryl] benzothiazole, benzoin alkylether, N- alkylation phthalein ketone, acetophenone ketal (2,2- dimethoxy Base Phenyl ethyl ketone), naphthalene, anthracene (2- naphthalene methanol, 2- naphthalene-carboxylic acid, 9- anthryl carbinol and 9- anthracene carboxylic acid), chromene, azo indolizine, Plum Lip river cumarin etc..
Preferably aromatic series 2- hydroxy-ketone (benzophenone), cumarin, coumarin ketone, carbonyl bicoumarin, acetophenone, anthracene Quinone, xanthone, thio xanthone and acetophenone ketal.
In polymer composition in addition to the foregoing, if within the scope of the effect of the invention, for changing The purpose for becoming the electrical characteristics such as dielectric constant, electric conductivity of liquid crystal orientation film, can add dielectric substance, conductive materials, and then for Hardness, the purpose of consistency that film is improved when liquid crystal orientation film is made, can add cross-linked compound.
Above-mentioned polymer composition is coated on to the method on the substrate with transverse electric field driving conductive film without spy It does not limit.
About coating method, industrial is usually to be carried out using silk-screen printing, hectographic printing, flexible printing or ink-jet method etc. Method.As other coating methods, there are infusion process, rolling method, slot coated method, spin-coating method (method of spin coating) or spray coating method Deng, can according to purpose use they.
On the substrate with transverse electric field driving conductive film after coated polymeric composition, hot plate, thermal cycle are utilized The heating meanss such as type baking oven or IR (infrared ray) type baking oven evaporate solvent with 50~200 DEG C, preferably with 50~150 DEG C, thus It can obtain film.Drying temperature at this time is preferably shorter than the high molecular liquid crystalline phase performance temperature of side chain type.
When the thickness of film is blocked up, liquid crystal indicate element power consumption in terms of be it is unfavorable, when the thickness of film is excessively thin, liquid Crystalline substance indicates that the reliability of element reduces sometimes, therefore preferably 5nm~300nm, more preferably 10nm~150nm.
In addition, can also be arranged the substrate for being formed with film is cooling after [I] process and before next [II] process To the process of room temperature.
<process [II]>
In process [II], polarized UV rays are irradiated to film obtained in process [I].Polarization is irradiated to the film surface of film When ultraviolet light, from specific direction across polarization plates to the ultraviolet light of substrate irradiation polarization.As ultraviolet light to be used, can make It is the ultraviolet light of 100nm~400nm range with wavelength.Preferably, it according to film type to be used, is selected by filter etc. Select optimal wavelength.Also, such as can choose using wavelength be 290nm~400nm range ultraviolet light, so as to select Induce photo-crosslinking to property.As ultraviolet light, the light for example issued by high-pressure sodium lamp can be used.
For the exposure of polarized UV rays, film to be used is depended on.About exposure, it is preferably set to realize Δ A Maximum value (hereinafter also referred to Δ Amax) polarized UV rays amount 1%~70% in the range of, be more preferably set as 1%~ In the range of 50%, the Δ A be the film, be parallel to polarized UV rays polarization direction direction ultraviolet absorbance And the difference of the ultraviolet absorbance perpendicular to the direction of the polarization direction of polarized UV rays.
<process [III]>
In process [III], the film of polarized UV rays has been irradiated in heating in process [II].It can be to painting by heating Film assigns tropism control ability.
The heating meanss such as hot plate, thermal cycle type baking oven or IR (infrared ray) type baking oven can be used in heating.Heating temperature can It is determined with considering to make film used to show the temperature of liquid crystal liquid crystal property.
Heating temperature is preferably the temperature (hereinafter referred to as liquid crystal performance temperature) that side chain type macromolecule can show liquid crystal liquid crystal property Within the temperature range of.Can be predicted: in the case where the film surface of film etc, the liquid crystal performance temperature of film coated surface is lower than Liquid crystal when whole observation can express the photonasty side chain type macromolecule of liquid crystal liquid crystal property shows temperature.Therefore, heating temperature is more excellent It is selected as within the temperature range of the liquid crystal performance temperature of film coated surface.That is, the temperature model of the heating temperature after irradiation polarized UV rays It encloses preferably using low 10 DEG C of the temperature of lower limit of the temperature range of liquid crystal more high molecular than side chain type used performance temperature as under It limits and using low 10 DEG C of the temperature of the upper limit than the liquid crystal temperature range as the temperature of the range of the upper limit.Heating temperature is lower than upper When stating temperature range, there are the tendencies insufficient by hot bring anisotropy amplification effect in film, in addition, heating temperature When excessively high compared with above-mentioned temperature range, there are film state inclining close to isotropic liquid condition (isotropic phase) To at this point, being difficult to due to self assembly sometimes to a direction reorientation.
It should be noted that liquid crystal performance temperature refers to: side chain type macromolecule or film coated surface are from the opposite liquid crystalline phase of solid The glass transition temperature (Tg) of phase transition or more occurs and phase transition occurs from the opposite homogeneous phase (isotropic phase) of liquid crystal Homogeneous phase transition temperature (Tiso) temperature below.
From with process [I] in record same reasons, the coating thickness formed after heating can be preferably 5nm~ 300nm, more preferably 50nm~150nm.
<process [IV]>
In process [IV], the film heated in process [III] is cooled to the glass transition temperature of the insufficient film coated surface After the temperature of degree, it is again heated to the temperature of the glass transition temperature or more.
That is, film obtained from heating in process [III] to be temporarily cooled to the glass transition temperature of insufficient film coated surface The temperature of degree.In other words, the film as obtained from will heat in process [III] is cooled to the liquid crystal performance temperature than film coated surface The low temperature of the lower limit of degree, to make the liquid crystal liquid crystal property state phase transition (glass transition) of film coated surface to solid-like.Herein, by Liquid crystal when there are the liquid crystal of film coated surface performance temperature than whole observation side chain type macromolecule shows the low tendency of temperature, because The cooling temperature of this film glass transition point temperature (Tg) preferably more high molecular than side chain type as (A) ingredient it is low 10 DEG C with On temperature.As the preference of the cooling temperature, it is room temperature (such as 25 DEG C).
It is energetically cold that cooling chamber, coolant etc. can be used in the cooling of film obtained from heating in process [III] But it to the cooling temperature of target, can also slowly be cooled down by being removed and placed from heating means.
In turn, in process [IV], the film cooled down is again heated to the glass transition temperature of film coated surface or more Temperature.Specifically, the liquid crystal that the film cooled down is again heated to film coated surface is showed temperature.As described above, film table The liquid crystal performance temperature in face refers to: more than the glass transition temperature of film coated surface and the homogeneous phase transition temperature of insufficient film coated surface The temperature of degree.Irradiate polarized UV rays after film heating temperature (heating temperature of process [III]) and it is after cooling again add Heating temperature when hot may be different or the same, after heating temperature when reheating preferably reaches irradiation polarized UV rays The heating temperature of film temperature below.
By with process as above, in the manufacturing method of the present invention, can be realized film is efficiently imported it is each to different Property.Further, it is possible to efficiently manufacture the substrate with liquid crystal orientation film.
<process [V]>
[V] process is the substrate that will have liquid crystal orientation film on the transverse electric field driving conductive film obtained in [IV] (the 1st substrate) band liquid crystal without conductive film obtained in above-mentioned [I ']~[III '] or [I ']~[IV '] in the same manner as The substrate (the 2nd substrate) of alignment films is carried out across liquid crystal in the opposite mode of the liquid crystal orientation film of the two oppositely disposed, utilizes public affairs The method production liquid crystal cells known, to make the process that the driving liquid crystal of transverse electric field indicates element.It should be noted that work Sequence [I ']~[III ']] or process [I ']~[IV '] in, in addition in the process [I] using not having transverse electric field driving with leading It, can be with process [I]~[III] or process except substrate of the substrate of electrolemma to replace having the transverse electric field driving conductive film [I ']~[IV '] is carried out similarly.Process [I]~[IV] only difference is that with process [I ']~[IV '] and lead whether there is or not above-mentioned Electrolemma, therefore omit the explanation of process [I ']~[IV '].
If enumerating liquid crystal cells or liquid crystal indicates a production example of element, following method can be exemplified: in preparation The 1st substrate stated and the 2nd substrate spread spacer on the liquid crystal orientation film of a substrate, become interior with liquid crystal alignment film surface The method that the mode of side is pasted on another substrate, decompression injection liquid crystal and sealing；Alternatively, being taken to the liquid crystal for being scattered with spacer After liquid crystal is added dropwise to film surface, adhesive substrate and the method etc. being sealed.At this point, it is preferable to use have laterally electricity for the substrate of side The substrate of the electrode of field driving comb teeth-shaped structure.Spacer diameter at this time is preferably 1 μm~30 μm, more preferably 2 μm~ 10μm.The spacer diameter is determined for clamping the spacing of a pair of of substrate of liquid crystal layer, the i.e. thickness of liquid crystal layer.
In the manufacturing method of substrate with film of the invention, polymer composition is coated on substrate and forms film Afterwards, polarized UV rays are irradiated.Then, realized and being heated efficiently imported into side chain type polymeric membrane it is each to different Property, so that manufacture has the substrate with liquid crystal orientation film of liquid crystal aligning control ability.
In film used in the present invention, molecule that the light reaction using side chain and the self assembly based on liquid crystal liquid crystal property are induced The principle of reorientation, realization efficiently import anisotropy to film.In the manufacturing method of the present invention, side chain type macromolecule has When structure of the photocrosslinking reaction group as photoreactive group, after forming film on substrate using side chain type macromolecule, irradiation Polarized UV rays, after then being heated, production liquid crystal indicates element.
Hereinafter, will use with photocrosslinking reaction group as the high molecular reality of the side chain type of the structure of photoreactive group The mode of applying is known as the 1st mode, will use with light fries' rearrangement group or has carried out the group of isomerization as photoreactivity The high molecular embodiment of the side chain type of the structure of group is known as the 2nd mode, and is illustrated.
Fig. 1 is schematically to illustrate to have used in the 1st mode of the invention to have photocrosslinking reaction group as light reaction Property group structure side chain type macromolecule made of, the anisotropy in the manufacturing method of liquid crystal orientation film import the one of processing The figure of example.(a) of Fig. 1 is the figure of the state of the side chain type polymeric membrane before schematically illustrating polarizing light irradiation, (b) of Fig. 1 It is the figure of the state of the side chain type polymeric membrane after schematically illustrating polarizing light irradiation, (c) of Fig. 1 is that schematically explanation adds The figure of the state of side chain type polymeric membrane after heat, the anisotropy hour especially imported, i.e., in the 1st mode of the invention In, when the ultraviolet irradiation amount of [II] process is in the range of making Δ A reach the 1%~15% of maximum ultraviolet irradiation amount Schematic diagram.
Fig. 2 is schematically to illustrate to have used in the 1st mode of the invention to have photocrosslinking reaction group as light reaction Property group structure side chain type macromolecule made of, the anisotropy in the manufacturing method of liquid crystal orientation film import the one of processing The figure of example.(a) of Fig. 2 is the figure of the state of the side chain type polymeric membrane before schematically illustrating polarizing light irradiation, (b) of Fig. 2 It is the figure of the state of the side chain type polymeric membrane after schematically illustrating polarizing light irradiation, (c) of Fig. 2 is that schematically explanation adds The figure of the state of side chain type polymeric membrane after heat, when the anisotropy especially imported is big, i.e., in the 1st mode of the invention In, when the ultraviolet irradiation amount of [II] process is in the range of making Δ A reach the 15%~70% of maximum ultraviolet irradiation amount Schematic diagram.
Fig. 3 is schematically to illustrate to have used in the 2nd mode of the invention to have photoisomerization group or above-mentioned formula (18) made of side chain type macromolecule of the light fries' rearrangement group as the structure of photoreactive group shown in, liquid crystal aligning Anisotropy in the manufacturing method of film imports the figure of an example of processing.(a) of Fig. 3 is before schematically illustrating polarizing light irradiation Side chain type polymeric membrane state figure, (b) of Fig. 3 is the side chain type polymeric membrane after schematically illustrating polarizing light irradiation State figure, (c) of Fig. 3 be schematically illustrate heating after side chain type polymeric membrane state figure, especially led The anisotropy hour entered, i.e., in the 2nd mode of the invention, the ultraviolet irradiation amount of [II] process makes Δ A reach maximum Ultraviolet irradiation amount 1%~70% in the range of when schematic diagram.
Fig. 4 is schematically to illustrate to have used in the 2nd mode of the invention to have light shown in above-mentioned formula (19) not sharp This is reset made of side chain type macromolecule of the group as the structure of photoreactive group, in the manufacturing method of liquid crystal orientation film Anisotropy imports the figure of an example of processing.(a) of Fig. 4 is the side chain type polymeric membrane before schematically illustrating polarizing light irradiation State figure, (b) of Fig. 4 is the figure of the state of the side chain type polymeric membrane after schematically illustrating polarizing light irradiation, Fig. 4's It (c) is the figure for schematically illustrating the state of the side chain type polymeric membrane after heating, when the anisotropy especially imported is big, I.e. in the 2nd mode of the invention, the ultraviolet irradiation amount of [II] process makes Δ A reach maximum ultraviolet irradiation amount Schematic diagram when in the range of 1%~70%.
In the 1st mode of the invention, by importing anisotropic processing, the ultraviolet irradiation amount of [II] process to film Be make Δ A reach maximum ultraviolet irradiation amount 1%~15% in the range of when, firstly, on substrate formed film 1.Such as Shown in (a) of Fig. 1 like that, in the film 1 formed on substrate, the structure with 2 random alignment of side chain.According to the side chain 2 of film 1 Random alignment, the liquid crystal ultimate constituent and photonasty group of side chain 2 be also randomly oriented, which is isotropic.
In the 1st mode of the invention, by importing anisotropic processing, the ultraviolet irradiation amount of [II] process to film Be make Δ A reach maximum ultraviolet irradiation amount 15%~70% in the range of when, firstly, on substrate formed film 3.Such as Shown in (a) of Fig. 2 like that, in the film 3 formed on substrate, the structure with 4 random alignment of side chain.According to the side chain 4 of film 3 Random alignment, the liquid crystal ultimate constituent and photonasty group of side chain 4 be also randomly oriented, which is isotropic.
In the 2nd mode of the invention, by importing anisotropic processing to film, using with photoisomerization When the high molecular liquid crystal orientation film of the side chain type of the structure of light fries' rearrangement group shown in property group or above-mentioned formula (18), The ultraviolet irradiation amount of [II] process be make Δ A reach maximum ultraviolet irradiation amount 1%~70% in the range of when, it is first First, film 5 is formed on substrate.As shown in (a) of Fig. 3, in the film 5 that is formed on substrate, there is 6 random alignment of side chain Structure.According to the random alignment of the side chain 6 of film 5, the liquid crystal ultimate constituent and photonasty group of side chain 6 are also randomly oriented, The side chain type polymeric membrane 5 is isotropic.
In the 2nd mode of the invention, by importing anisotropic processing to film, using with above-mentioned formula (19) when the high molecular liquid crystal orientation film of the side chain type of the structure of light fries' rearrangement group shown in, the ultraviolet light of [II] process Exposure be make Δ A reach maximum ultraviolet irradiation amount 1%~70% in the range of when, firstly, on substrate formed apply Film 7.As shown in (a) of Fig. 4, in the film 7 that is formed on substrate, the structure with 8 random alignment of side chain.According to film 7 Side chain 8 random alignment, the liquid crystal ultimate constituent and photonasty group of side chain 8 be also randomly oriented, which is isotropism 's.
In 1st mode of this implementation, the ultraviolet irradiation amount of [II] process is that Δ A is made to reach maximum ultraviolet irradiation amount 1%~15% in the range of when, polarized UV rays are irradiated to the isotropic film 1.As a result, as Fig. 1 (b) shown in that Sample, along side chain 2a's among the side chain 2 of the direction arrangement parallel with the polarization direction of ultraviolet light, with photonasty group The light reactions such as dimerization reaction occur to photonasty group priorities.As a result, the density that the side chain 2a of light reaction has occurred is being irradiated It is slightly got higher on the polarization direction of ultraviolet light, as a result, assigning very small anisotropy to film 1.
In 1st mode of this implementation, the ultraviolet irradiation amount of [II] process is that Δ A is made to reach maximum ultraviolet irradiation amount 15%~70% in the range of when, polarized UV rays are irradiated to the isotropic film 3.As a result, as shown in (b) of Fig. 2 Like that, side chain 4a among the side chain 4 arranged along the direction parallel with the polarization direction of ultraviolet light, with photonasty group Photonasty group priorities the light reactions such as dimerization reaction occur.As a result, the density that the side chain 4a of light reaction has occurred is being shone It penetrates on the polarization direction of ultraviolet light and gets higher, as a result, assigning small anisotropy to film 3.
In the 2nd mode of this implementation, using with light shown in photoisomerization group or above-mentioned formula (18) The high molecular liquid crystal orientation film of the side chain type of the structure of fries' rearrangement group, the ultraviolet irradiation amount of [II] process are to make Δ A When reaching in the range of the 1%~70% of maximum ultraviolet irradiation amount, polarized UV is irradiated to isotropic film 5 Line.As a result, as shown in (b) of Fig. 3, among the side chain 6 that is arranged along the direction parallel with the polarization direction of ultraviolet light, The light reactions such as light fries' rearrangement occur to the photonasty group priorities of side chain 6a with photonasty group.As a result, occurring The density of the side chain 6a of light reaction is slightly got higher on the polarization direction of irradiation ultraviolet light, as a result, assigning very to film 5 Small anisotropy.
In the 2nd mode of this implementation, using with light fries' rearrangement group shown in above-mentioned formula (19) The high molecular film of the side chain type of structure, the ultraviolet irradiation amount of [II] process are that Δ A is made to reach maximum ultraviolet irradiation amount 1%~70% in the range of when, polarized UV rays are irradiated to the isotropic film 7.As a result, as Fig. 4 (b) shown in that Sample, along side chain 8a's among the side chain 8 of the direction arrangement parallel with the polarization direction of ultraviolet light, with photonasty group The light reactions such as light fries' rearrangement occur to photonasty group priorities.As a result, the density that the side chain 8a of light reaction has occurred exists It irradiates on the polarization direction of ultraviolet light and gets higher, as a result, assigning small anisotropy to film 7.
Then, in the 1st mode of this implementation, the ultraviolet irradiation amount of [II] process is that Δ A is made to reach maximum ultraviolet light When in the range of the 1%~15% of exposure, the film 1 after irradiation polarised light is heated and mesomorphic state is made.As a result, as schemed Shown in 1 (c) like that, in film 1, in the direction for being parallel to the polarization direction of irradiation ultraviolet light and perpendicular to irradiation ultraviolet light Between the direction of polarization direction, the amount of the cross-linking reaction of generation is different.At this point, being parallel to the side of the polarization direction of irradiation ultraviolet light Amount to the cross-linking reaction of generation is very small, therefore the cross-linking reaction position is worked as plasticizer.Therefore, perpendicular to photograph The liquid crystal liquid crystal property for penetrating the direction of the polarization direction of ultraviolet light is higher than the liquid crystal liquid crystal property for being parallel to the direction of polarization direction of irradiation ultraviolet light, Self assembly occurs for the direction for being parallel to the polarization direction of irradiation ultraviolet light, and the side chain 2 comprising liquid crystal ultimate constituent carries out reorientation. As a result, the very small anisotropy of the film 1 induced by photo-crosslinking is amplified because of heat, film 1 is assigned bigger Anisotropy.
Similarly, in the 1st mode of this implementation, the ultraviolet irradiation amount of [II] process is that Δ A is made to reach maximum ultraviolet When in the range of the 15%~70% of line exposure, the film 3 after polarizing light irradiation is heated and mesomorphic state is made.As a result, As shown in (c) of Fig. 2, in side chain type polymeric membrane 3, be parallel to irradiation ultraviolet light polarization direction direction with it is vertical Between the direction of the polarization direction of irradiation ultraviolet light, the amount of the cross-linking reaction of generation is different.Therefore, it is parallel to irradiation ultraviolet light The direction of polarization direction self assembly occurs, side chain 4 comprising liquid crystal ultimate constituent carries out reorientation.As a result, because of photo-crosslinking The lesser anisotropy of the film 3 of reaction and induction is amplified because of heat, and bigger anisotropy is assigned to film 3.
Similarly, in the 2nd mode of this implementation, using with shown in photoisomerization group or above-mentioned formula (18) Light fries' rearrangement group structure the high molecular film of side chain type, the ultraviolet irradiation amount of [II] process is to reach Δ A When in the range of to the 1%~70% of maximum ultraviolet irradiation amount, the film 5 after polarizing light irradiation is heated and is made Mesomorphic state.As a result, as shown in (c) of Fig. 3, in film 5, be parallel to irradiation ultraviolet light polarization direction direction with Perpendicular between the direction of the polarization direction of irradiation ultraviolet light, the amount of the light Fries rearrangement of generation is different.At this point, vertical In the light fries' rearrangement body that the direction of the polarization direction of irradiation ultraviolet light generates liquid crystal aligning power than the side chain before reaction Liquid crystal aligning power is strong, therefore self assembly occurs perpendicular to the direction of the polarization direction of irradiation ultraviolet light, includes liquid crystal ultimate constituent Side chain 6 carry out reorientation.As a result, the very small anisotropy of the film 5 induced by light Fries rearrangement because Heat and amplify, to the bigger anisotropy of the imparting of film 5.
Similarly, in the 2nd mode of this implementation, using with light fries' rearrangement base shown in above-mentioned formula (19) The high molecular film of side chain type of the structure of group, the ultraviolet irradiation amount of [II] process are to make Δ A reach maximum ultraviolet light to shine When in the range of the 1%~70% of the amount of penetrating, the film 7 after polarizing light irradiation is heated and mesomorphic state is made.As a result, such as Shown in (c) of Fig. 4 like that, in side chain type polymeric membrane 7, be parallel to irradiation ultraviolet light polarization direction direction with perpendicular to It irradiates between the direction of the polarization direction of ultraviolet light, the amount of the light Fries rearrangement of generation is different.Light fries' rearrangement body 8 (a) anchor force is parallel to photograph than the side chain Final 8 before resetting, therefore when generating certain a certain amount of above light fries' rearrangement body Self assembly occurs for the direction for penetrating the polarization direction of ultraviolet light, and the side chain 8 comprising liquid crystal ultimate constituent carries out reorientation.As a result, The lesser anisotropy of the film 7 induced by light Fries rearrangement is amplified because of heat, and bigger to the imparting of film 7 is each Anisotropy.
Therefore, film used in method of the invention irradiates at polarized UV rays and heating film by successively carrying out Reason, so that the excellent liquid crystal orientation film of tropism control ability can be made by anisotropy is efficiently imported.
Also, for the film used in the method for the invention, optimize the photograph for the polarized UV rays irradiated to film The heating temperature of the amount of penetrating and heat treatment.Thus, it is possible to realize efficiently to import anisotropy to film.
The irradiation of optimal polarized UV rays for efficiently importing anisotropy to film used in the present invention Amount, which corresponds to, makes the photonasty group in the film that photo-crosslinking, photoisomerization reaction or light Fries rearrangement occur Amount reaches optimal polarized UV rays exposure.To the irradiation polarized UV rays of film used in the present invention as a result, carrying out light When the photonasty group of the side chain of cross-linking reaction, photoisomerization reaction or light Fries rearrangement is few, sufficient light is not achieved Reacting dose.At this point, sufficient self assembly will not be carried out being heated behind.On the other hand, in the present invention For the film used, to the structured illumination polarized UV rays with photocrosslinking reaction group as a result, carrying out the side of cross-linking reaction When the photonasty group excess of chain, the cross-linking reaction between side chain can be promoted excessively.At this point, gained film becomes upright and outspoken, interfere sometimes Thereafter the propulsion of the self assembly by heating.In addition, for the film used in the present invention, to light fries Reset the structured illumination polarized UV rays of group as a result, carrying out the photonasty group of side chain of light Fries rearrangement becomes When excessive, the liquid crystal liquid crystal property of film can be reduced excessively.At this point, the liquid crystal liquid crystal property of gained film also reduces, interfere sometimes thereafter by plus The propulsion of the self assembly of heat.When in turn, to the structured illumination polarized UV rays with light fries' rearrangement group, if ultraviolet light Exposure it is excessive, then side chain type macromolecule occur photodegradation, interfere the propulsion of the self assembly by heating thereafter sometimes.
Therefore, in film used in the present invention, the photonasty group of side chain occurs because of the irradiation of polarized UV rays The optimised quantity of photo-crosslinking, photoisomerization reaction or light Fries rearrangement, which is preferably set to the side chain type polymeric membrane, to be had 0.1 mole of %~40 mole % of some photonasty groups, more preferably it is set as 0.1 mole of %~20 mole %.By making to carry out The amount of the photonasty group of the side chain of light reaction is this range, and the self assemblyization in heat treatment thereafter can be promoted efficiently, The efficient anisotropy being capable of forming in film.
In film used in method of the invention, by the optimization of the exposure of polarized UV rays, to optimize side chain The photo-crosslinking of photonasty group in the side chain of type polymeric membrane, photoisomerization reaction or light Fries rearrangement Amount.Also, it is realized together with heat treatment thereafter and efficiently imports anisotropy into film used in the present invention.This When, for suitable polarized UV rays amount, can be carried out based on the evaluation of the UV absorption of film used in the present invention.
That is, for the present invention used in film, measure respectively polarized UV rays irradiation after, be parallel to polarized UV The ultraviolet radiation absorption in the direction of the polarization direction of line and perpendicular to polarized UV rays polarization direction direction ultraviolet radiation absorption. Δ A is evaluated by the measurement result of UV absorption, the Δ A is the side of the polarization direction for being parallel to polarized UV rays in the film To ultraviolet absorbance and perpendicular to polarized UV rays polarization direction direction ultraviolet absorbance difference.Also, it asks The maximum value (Δ Amax) of the Δ A realized in film used in the present invention out and realize its polarized UV rays exposure. In the manufacturing method of the present invention, using the polarized UV rays exposure of realization Δ Amax as benchmark, it can determine and taken in liquid crystal The polarized UV rays amount for the preferred amounts irradiated into the manufacture of film.
In the manufacturing method of the present invention, preferably by the exposure for the polarized UV rays irradiated to film used in the present invention Be set as realizing the amount of the polarized UV rays of Δ Amax 1%~70% in the range of, be more preferably set as 1%~50% range It is interior.In film used in the present invention, it can realize inclined in the range of the 1%~50% of the amount of the polarized UV rays of Δ Amax Vibration ultraviolet irradiation amount is equivalent to 0.1 mole of %~20 for making the entirety of photonasty group possessed by the side chain type polymeric membrane The amount of the polarized UV rays of photo-crosslinking occurs for mole %.
As described above, in the manufacturing method of the present invention, anisotropy is efficiently imported to film to realize, with the side The high molecular liquid crystal temperature range of chain determines suitable heating temperature as described above as benchmark.Thus, for example this hair When the high molecular liquid crystal temperature range of side chain type used in bright is 100 DEG C~200 DEG C, it is expected that after irradiating polarized UV rays Heating temperature is 90 DEG C~190 DEG C.It sets in this way, bigger anisotropy is assigned to film used in the present invention.
It operates in this way, the liquid crystal provided through the invention indicates that element shows that height can to external stresses such as light, heat By property.
Operation as above, the driving liquid crystal of transverse electric field manufactured by the method for the invention indicate component substrate or There is person the driving liquid crystal of the transverse electric field of the substrate to indicate the excellent in reliability of element, can be suitably employed in big picture and high definition Clear LCD TV etc..
Embodiment
It is shown used in embodiment as follows referred to as.
(methacrylic monomer)
MA1 is synthesized by synthetic method described in patent document (WO2011-084546).
MA2 is synthesized by synthetic method described in patent document (Japanese Unexamined Patent Publication 9-118717).
(organic solvent)
THF: tetrahydrofuran
NMP:N- N-methyl-2-2-pyrrolidone N
BC: butyl cellosolve
(polymerization initiator)
AIBN:2,2 '-azobis isobutyronitrile
[measurement of phase transition temperature]
The liquid crystal phase transition temperature of the polymer obtained by embodiment uses differential scanning calorimetry measurement (DSC) DSC3100SR (マ ッ Network サ イ エ Application ス corporation) is measured.
<synthesis example 1>
MA1 (15.29g, 46mmol), MA2 (56.37g, 184mmol) are dissolved in THF (655.1g), diaphragm pump is used After being de-gassed, adds AIBN (1.13g, 6.9mmol) and be de-gassed again.Hereafter, with 60 DEG C are reacted 20 hours and are obtained The polymer solution of methacrylate.The polymer solution is added dropwise to diethyl ether (7000ml), gained sediment is filtered.It will The sediment is cleaned with diethyl ether, is dried under reduced pressure in 40 DEG C of baking oven, to obtain methacrylate polymers powder End.The number-average molecular weight of the polymer is 15000, weight average molecular weight 40500.
The liquid crystal phase transition temperature of gained methacrylate polymers is 120 DEG C~185 DEG C.
NMP (54.0g) is added in gained methacrylate polymer powder (6.0g), to be stirred at room temperature 5 hours It makes it dissolve.BC (40.0g) is added into the solution and is stirred, to obtain aligning agent for liquid crystal (A).
<embodiment 1>
(production of liquid crystal cells)
Using aligning agent for liquid crystal obtained in synthesis example 1 (A), the system of liquid crystal cells is carried out according to following the step of showing Make.
Substrate be having a size of 30mm × 40mm, with a thickness of the glass substrate of 0.7mm, using configured with ito film is patterned And the substrate of the comb teeth-shaped pixel electrode formed." < " font electrode element warp that there is pixel electrode center portion to bend It is multiple arrangement and constitute comb teeth-shaped shape.The width of the width direction of each electrode element is 10 μm, the interval between electrode element It is 20 μm.The electrode element of " < " font that the pixel electrode of each pixel is bent by center portion is formed through multiple arrangements and It constitutes, therefore the shape of each pixel not instead of oblong-shaped, has and bend in the same manner as electrode element in center portion , the shape of " < " word similar to runic.Also, each pixel is divided up and down by boundary of the bending part in the center, has 1st region of the upside of bending part and the 2nd region of downside.When comparing the 1st region and 2 region of each pixel, it is constituted Pixel electrode electrode element formation direction it is different.That is, using the orientation process direction of aftermentioned liquid crystal orientation film as base On time, in the 1st region of pixel, the electrode element of pixel electrode is formed in a manner of+15 ° of angle (clockwise) is presented, In the 2nd region of pixel, the electrode element of pixel electrode is formed in a manner of -15 ° of angle (clockwise) is presented.That is, each 1st region of pixel and the 2nd region are constituted as follows: the liquid induced and applying voltage between pixel electrode and counter electrode The direction of spinning movement (plane switching) brilliant, in real estate opposite direction each other.
Aligning agent for liquid crystal obtained in synthesis example 1 (A) is spin-coated on the above-mentioned electroded substrate prepared.Then, With press drying 90 seconds of 70 DEG C, the liquid crystal orientation film that film thickness is 100nm is formed.Then, across polarization plates with 10mJ/cm2 After the ultraviolet light of coated surface irradiation 313nm, 10 minutes (1 firing) is heated with 150 DEG C of hot plates, by Slow cooling (cooling) Substrate to room temperature uses 150 DEG C of hot plate to heat 10 minutes (2 firings) again, to obtain the substrate with liquid crystal orientation film. Same operation, about ultraviolet irradiation amount, in 10mJ/cm2~100mJ/cm2In with 10mJ/cm2Interval, in 100mJ/ cm2Above with 50mJ/cm2Interval, make different substrates respectively.
In addition, to not formed electrode and the glass substrate with 4 μm of height of column spacer is also same as opposite substrate Film is formed to sample, orientation process is implemented.Printing and sealing agent (assists vertical Chemical Co., Ltd. on the liquid crystal orientation film of a substrate System, XN-1500T).Then, after pasting another substrate in such a way that liquid crystal alignment film surface is opposite and differently- oriented directivity reaches 0 °, make Sealant heat cure and make dummy cell.By injecting liquid crystal MLC-2041 (MERCK in decompression injection normal direction dummy cell CORPORATION system), inlet is sealed, the liquid crystal for having IPS (In-Planes Switching, plane switching) mode is obtained Indicate the liquid crystal cells that element is constituted.
(orientation observation)
Liquid crystal cells are made using the above method.Thereafter, reorientation processing in 60 minutes is carried out in 120 DEG C of baking oven. Thereafter, it is observed by the polarization microscope that crossed nicols state is made in polarization plates.It rotates liquid crystal cells and table is presented When showing the state of black, there is no bright spot, the undesirable states of orientation to be regarded as well.About ultraviolet irradiation amount, as described above, For different substrate observation orientation as a result, the good exposure boundary of orientation as shown in table 1.
<embodiment 2>
Other than the temperature of 2 firing processing is set as 130 DEG C, liquid crystal is made using method same as Example 1 Unit.Liquid crystal cells obtained by use, utilize method same as Example 1, evaluation approach.
The results are shown in Table 1 like that.
<comparative example 1~2>
Other than whether there is or not Slow cooling process and without twice firing processing, method system same as Example 1 is utilized Make liquid crystal cells.Liquid crystal cells obtained by use, utilize method same as Example 1, evaluation approach.
Evaluation result is summarized shown in table 1.
The results are shown in Table 1 like that.
[table 1]
According to as a result, showing good liquid crystal aligning under conditions of via 2 firings of Slow cooling process and progress The boundary of UV exposure expands.
Speculate this is because: being burnt by 1 time and the orientation of main polymer backbone has been determined, but thereafter by Be cooled to insufficient glass transition temperature, be burnt at 1 time at a temperature of for the oligomer more than brocken spectrum or near brocken spectrum at Divide, vitreousness (Comparative Examples 1 and 2) is presented in the case where maintaining mixed and disorderly state of orientation for low molecular weight compositions.Think herein: can Can be again with more than glass transition temperature and when liquid crystal transparent point temperature below is heated again, only oligomer at Point, low molecular weight compositions reset along the form of the orientation by the determining principal polymeric skeleton of 1 firing, thus The orientation of alignment films entirety is improved.(it should be noted that these are theoretical suppositions, not limiting the present invention).
Description of symbols
Fig. 1
1 side chain type polymeric membrane
2,2a side chain
Fig. 2
3 side chain type polymeric membranes
4,4a side chain
Fig. 3
5 side chain type polymeric membranes
6,6a side chain
Fig. 4
7 side chain type polymeric membranes
8,8a side chain

Claims (17)

1. a kind of manufacturing method for the substrate for indicating element liquid crystal orientation film with the driving liquid crystal of transverse electric field, passes through tool Obtain having been assigned the liquid crystal orientation film of tropism control ability for following process:
[I] polymer composition is coated on the substrate with transverse electric field driving conductive film and the process that forms film, The polymer composition contains: (A) shown within the scope of specific temperature liquid crystal liquid crystal property photonasty side chain type macromolecule, with And (B) organic solvent；
The process of [II] to the irradiation polarized UV rays of film obtained in [I]；
The process that [III] heats film obtained in [II]；And
After the film heated in [III] is cooled to the temperature of the glass transition temperature of the insufficient film coated surface by [IV], then plus The process of temperature more than heat to the glass transition temperature.
2. according to the method described in claim 1, wherein, the cooling temperature of the film in [IV] process is than as (A) ingredient High molecular low 10 DEG C of the glass transition point temperature (Tg) of side chain type or more temperature.
3. method according to claim 1 or 2, wherein the heating temperature of film after ultraviolet light irradiation and after cooling Relation reheating temperature is the temperature of the glass transition temperature of film coated surface or more and the homogeneous phase transition temperature of insufficient film coated surface.
4. method according to claim 1 or 2, wherein (A) ingredient have photo-crosslinking, photoisomerization or light can occur not The photonasty side chain that Li Si is reset.
5. method according to claim 1 or 2, wherein (A) ingredient has selected from the group being made of following formula (1)~(6) In any photonasty side chain,
In formula, A, B, D each independently represent singly-bound ,-O- ,-CH2,-COO- ,-OCO- ,-CONH- ,-NH-CO- ,-CH=CH- CO-O- or-O-CO-CH=CH-；
S is the alkylidene of carbon number 1~12, and the hydrogen atom for being bonded to them is optionally replaced by halogen group；
T is the alkylidene of singly-bound or carbon number 1~12, and the hydrogen atom for being bonded to them is optionally replaced by halogen group；
Y1Indicate the ring in the ester ring type hydrocarbon of phenyl ring selected from 1 valence, naphthalene nucleus, cyclohexyl biphenyl, furan nucleus, pyrrole ring and carbon number 5~8, or Person is group made of identical or different 2~6 ring in these substituent groups is bonded by binding groups B, is bonded to Their hydrogen atom is each independently optionally by-COOR0、-NO2,-CN ,-CH=C (CN)2,-CH=CH-CN, halogen group, carbon The alkyl of number 1~5 or the alkoxy of carbon number 1~5 replace, in formula, R0Indicate the alkyl of hydrogen atom or carbon number 1~5；
Y2For selected from the ester ring type hydrocarbon and their group by the phenyl ring of divalent, naphthalene nucleus, cyclohexyl biphenyl, furan nucleus, pyrrole ring, carbon number 5~8 The group in group being combined into is bonded to their hydrogen atom each independently optionally by-NO2,-CN ,-CH=C (CN)2、-CH The alkoxy substitution of=CH-CN, halogen group, the alkyl of carbon number 1~5 or carbon number 1~5；
R indicates the alkoxy of hydroxyl, carbon number 1~6, or expression and Y1Identical definition；
X indicates singly-bound ,-COO- ,-OCO- ,-N=N- ,-CH=CH- ,-C ≡ C- ,-CH=CH-CO-O- or-O-CO-CH= When the quantity of CH-, X reach 2, X is optionally same or different to each other；
Cou indicates Coumarin-6-base or coumarin-7-base, is bonded to their hydrogen atom each independently optionally by-NO2、- CN ,-CH=C (CN)2,-CH=CH-CN, halogen group, the alkyl of carbon number 1~5 or carbon number 1~5 alkoxy replace；
One of q1 and q2 are 1, another one 0；
Q3 is 0 or 1；
P and Q be each independently selected from by the phenyl ring of divalent, naphthalene nucleus, cyclohexyl biphenyl, furan nucleus, pyrrole ring, carbon number 5~8 alicyclic ring Group in the group of formula hydrocarbon and their combination composition；Wherein, when X is-CH=CH-CO-O- ,-O-CO-CH=CH- ,-CH= The P or Q for the side that CH- is bonded are aromatic rings, and when the quantity of P reaches 2 or more, P is optionally same or different to each other, the quantity of Q When reaching 2 or more, Q is optionally same or different to each other；
L1 is 0 or 1；
The integer that l2 is 0~2；
When l1 and l2 are 0, A also illustrates that singly-bound when T is singly-bound；
When l1 is 1, B also illustrates that singly-bound when T is singly-bound；
H and I is each independently the base in the phenyl ring selected from divalent, naphthalene nucleus, cyclohexyl biphenyl, furan nucleus, pyrrole ring and their combination Group.
6. method according to claim 1 or 2, wherein (A) ingredient has to be selected to be made of following formula (7)~(10) Any photonasty side chain in group,
In formula, A, B, D each independently represent singly-bound ,-O- ,-CH2,-COO- ,-OCO- ,-CONH- ,-NH-CO- ,-CH=CH- CO-O- or-O-CO-CH=CH-；
Y1Indicate the ring in the ester ring type hydrocarbon of phenyl ring selected from 1 valence, naphthalene nucleus, cyclohexyl biphenyl, furan nucleus, pyrrole ring and carbon number 5~8, or Person is group made of identical or different 2~6 ring in these substituent groups is bonded by binding groups B, is bonded to Their hydrogen atom is each independently optionally by-COOR0、-NO2,-CN ,-CH=C (CN)2,-CH=CH-CN, halogen group, carbon The alkyl of number 1~5 or the alkoxy of carbon number 1~5 replace, in formula, R0Indicate the alkyl of hydrogen atom or carbon number 1~5；
X indicates singly-bound ,-COO- ,-OCO- ,-N=N- ,-CH=CH- ,-C ≡ C- ,-CH=CH-CO-O- or-O-CO-CH= When the quantity of CH-, X reach 2, X is optionally same or different to each other；
L indicates 1~12 integer；
M indicates that 0~2 integer, m1, m2 indicate 1~3 integer；
N indicates 0~12 integer, wherein when n=0, B is singly-bound；
Y2For selected from the ester ring type hydrocarbon and their group by the phenyl ring of divalent, naphthalene nucleus, cyclohexyl biphenyl, furan nucleus, pyrrole ring, carbon number 5~8 The group in group being combined into is bonded to their hydrogen atom each independently optionally by-NO2,-CN ,-CH=C (CN)2、-CH The alkoxy substitution of=CH-CN, halogen group, the alkyl of carbon number 1~5 or carbon number 1~5；
R indicates the alkoxy of hydroxyl, carbon number 1~6, or expression and Y1Identical definition.
7. method according to claim 1 or 2, wherein (A) ingredient has to be selected to be made of following formula (11)~(13) Any photonasty side chain in group,
In formula, A each independently represents singly-bound ,-O- ,-CH2,-COO- ,-OCO- ,-CONH- ,-NH-CO- ,-CH=CH-CO- O- or-O-CO-CH=CH-；
X indicates singly-bound ,-COO- ,-OCO- ,-N=N- ,-CH=CH- ,-C ≡ C- ,-CH=CH-CO-O- or-O-CO-CH= When the quantity of CH-, X reach 2, X is optionally same or different to each other；
L indicates that 1~12 integer, m indicate that 0~2 integer, m1 indicate 1~3 integer；
R indicates the ring in the ester ring type hydrocarbon of phenyl ring selected from 1 valence, naphthalene nucleus, cyclohexyl biphenyl, furan nucleus, pyrrole ring and carbon number 5~8, or Person is group made of identical or different 2~6 ring in these substituent groups is bonded by binding groups B, is bonded to Their hydrogen atom is each independently optionally by-COOR0、-NO2,-CN ,-CH=C (CN)2,-CH=CH-CN, halogen group, carbon The alkyl of number 1~5 or the alkoxy of carbon number 1~5 replace, in formula, R0Indicate the alkyl or R table of hydrogen atom or carbon number 1~5 Show the alkoxy of hydroxyl or carbon number 1~6.
8. method according to claim 1 or 2, wherein (A) ingredient has photonasty shown in following formula (14) or (15) Side chain,
In formula, A each independently represents singly-bound ,-O- ,-CH2,-COO- ,-OCO- ,-CONH- ,-NH-CO- ,-CH=CH-CO- O- or-O-CO-CH=CH-；
Y1Indicate the ring in the ester ring type hydrocarbon of phenyl ring selected from 1 valence, naphthalene nucleus, cyclohexyl biphenyl, furan nucleus, pyrrole ring and carbon number 5~8, or Person is group made of identical or different 2~6 ring in these substituent groups is bonded by binding groups B, is bonded to Their hydrogen atom is each independently optionally by-COOR0、-NO2,-CN ,-CH=C (CN)2,-CH=CH-CN, halogen group, carbon The alkyl of number 1~5 or the alkoxy of carbon number 1~5 replace, in formula, R0Indicate the alkyl of hydrogen atom or carbon number 1~5；
L indicates that 1~12 integer, m1, m2 indicate 1~3 integer.
9. method according to claim 1 or 2, wherein (A) ingredient has photonasty shown in following formula (16) or (17) Side chain,
In formula, A indicates singly-bound ,-O- ,-CH2,-COO- ,-OCO- ,-CONH- ,-NH-CO- ,-CH=CH-CO-O- or-O-CO- CH=CH-；
X indicates singly-bound ,-COO- ,-OCO- ,-N=N- ,-CH=CH- ,-C ≡ C- ,-CH=CH-CO-O- or-O-CO-CH= When the quantity of CH-, X reach 2, X is optionally same or different to each other；
L indicates that 1~12 integer, m indicate 0~2 integer.
10. method according to claim 1 or 2, wherein (A) ingredient has to be selected to be made of following formula (18) or (19) Group in any photonasty side chain,
In formula, A, B each independently represent singly-bound ,-O- ,-CH2,-COO- ,-OCO- ,-CONH- ,-NH-CO- ,-CH=CH- CO-O- or-O-CO-CH=CH-；
Y1Indicate the ring in the ester ring type hydrocarbon of phenyl ring selected from 1 valence, naphthalene nucleus, cyclohexyl biphenyl, furan nucleus, pyrrole ring and carbon number 5~8, or Person is group made of identical or different 2~6 ring in these substituent groups is bonded by binding groups B, is bonded to Their hydrogen atom is each independently optionally by-COOR0、-NO2,-CN ,-CH=C (CN)2,-CH=CH-CN, halogen group, carbon The alkyl of number 1~5 or the alkoxy of carbon number 1~5 replace, in formula, R0Indicate the alkyl of hydrogen atom or carbon number 1~5；
One of q1 and q2 are 1, another one 0；
L indicates that 1~12 integer, m1, m2 indicate 1~3 integer；
R1Indicate hydrogen atom ,-NO2,-CN ,-CH=C (CN)2,-CH=CH-CN, halogen group, carbon number 1~5 alkyl or carbon The alkoxy of number 1~5.
11. method according to claim 1 or 2, wherein (A) ingredient has photonasty side chain shown in following formula (20),
In formula, A indicates singly-bound ,-O- ,-CH2,-COO- ,-OCO- ,-CONH- ,-NH-CO- ,-CH=CH-CO-O- or-O-CO- CH=CH-；
Y1Indicate the ring in the ester ring type hydrocarbon of phenyl ring selected from 1 valence, naphthalene nucleus, cyclohexyl biphenyl, furan nucleus, pyrrole ring and carbon number 5~8, or Person is group made of identical or different 2~6 ring in these substituent groups is bonded by binding groups B, is bonded to Their hydrogen atom is each independently optionally by-COOR0、-NO2,-CN ,-CH=C (CN)2,-CH=CH-CN, halogen group, carbon The alkyl of number 1~5 or the alkoxy of carbon number 1~5 replace, in formula, R0Indicate the alkyl of hydrogen atom or carbon number 1~5；
X indicates singly-bound ,-COO- ,-OCO- ,-N=N- ,-CH=CH- ,-C ≡ C- ,-CH=CH-CO-O- or-O-CO-CH= When the quantity of CH-, X reach 2, X is optionally same or different to each other；
L indicates that 1~12 integer, m indicate 0~2 integer.
12. method according to claim 1 or 2, wherein (A) ingredient has to be selected to be made of following formula (21)~(31) Group in any liquid crystal liquid crystal property side chain,
In formula, A and B have definition same as described above；
Y3For selected from by the phenyl ring of 1 valence, naphthalene nucleus, cyclohexyl biphenyl, furan nucleus, nitrogen-containing heterocycle and carbon number 5~8 ester ring type hydrocarbon and it The group that is combined into of group in group, be bonded to their hydrogen atom each independently optionally by-NO2,-CN, halogen group, The alkyl of carbon number 1~5 or the alkoxy of carbon number 1~5 replace；
R3Indicate hydrogen atom ,-NO2,-CN ,-CH=C (CN)2,-CH=CH-CN, halogen group, the phenyl ring of 1 valence, naphthalene nucleus, biphenyl Ring, furan nucleus, nitrogen-containing heterocycle, the ester ring type hydrocarbon of carbon number 5~8, the alkyl of carbon number 1~12 or carbon number 1~12 alkoxy；
One of q1 and q2 are 1, another one 0；
L indicates that 1~12 integer, m indicate 0~2 integer, wherein in formula (23)~(24), the summation of all m be 2 with On, in formula (25)~(26), the summation of all m is 1 or more, and m1, m2 and m3 each independently represent 1~3 integer；
R2Indicate hydrogen atom ,-NO2,-CN, halogen group, the phenyl ring of 1 valence, naphthalene nucleus, cyclohexyl biphenyl, furan nucleus, nitrogen-containing heterocycle and The ester ring type hydrocarbon and alkyl or alkoxy of carbon number 5~8；
Z1、Z2Indicate singly-bound ,-CO- ,-CH2O- ,-CH=N- ,-CF2-。
13. a kind of substrate for indicating element liquid crystal orientation film with the driving liquid crystal of transverse electric field, is by claim 1 The manufacture of method described in any one of~12.
14. a kind of driving liquid crystal of transverse electric field indicates element, with the substrate described in claim 13.
15. a kind of driving liquid crystal of transverse electric field indicates the manufacturing method of element, the liquid is obtained and having following process Crystalline substance indicates element:
Prepare the substrate i.e. process of the 1st substrate described in claim 13；
Obtain have following liquid crystal orientation films the 2nd substrate process, by have following processes [I '], [II '] and [III '] and the liquid crystal orientation film for obtaining having been assigned tropism control ability；And
[V] in such a way that the liquid crystal orientation film of the 1st substrate and the 2nd substrate is across liquid crystalline phase pair, oppositely disposed 1st base Plate and the 2nd substrate, so that the process that liquid crystal indicates element is obtained,
The process [I '], [II '] and [III '] are as follows:
[I '] coated polymeric composition and the process that forms film, described polymer composition on the 2nd substrate contains: (A) The photonasty side chain type macromolecule and (B) organic solvent of liquid crystal liquid crystal property are shown within the scope of specific temperature；
The process of [II '] to the irradiation polarized UV rays of film obtained in [I ']；And
The process that [III '] heats film obtained in [II '].
16. according to the method for claim 15, wherein the process for obtaining the 2nd substrate also has [IV '] by [III '] After the film of middle heating is cooled to the temperature of the glass transition temperature of the insufficient film coated surface, it is again heated to the glass transition The process of temperature more than temperature.
It 17. a kind of driving liquid crystal of transverse electric field indicates element, is manufactured by method described in claim 15 or 16.
CN201480040018.2A 2013-05-13 2014-05-13 The manufacturing method of the substrate of element liquid crystal orientation film is indicated with the driving liquid crystal of transverse electric field Active CN105393167B (en)

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