CN105593751B - Polymer, polymer composition and the driving liquid crystal of transverse electric field indicate element liquid crystal orientation film - Google Patents
Polymer, polymer composition and the driving liquid crystal of transverse electric field indicate element liquid crystal orientation film Download PDFInfo
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- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells
- G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
- G02F1/1333—Constructional arrangements; Manufacturing methods
- G02F1/1343—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]
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D4/00—Coating compositions, e.g. paints, varnishes or lacquers, based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; Coating compositions, based on monomers of macromolecular compounds of groups C09D183/00 - C09D183/16
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- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells
- G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
- G02F1/1333—Constructional arrangements; Manufacturing methods
- G02F1/1337—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers
- G02F1/133703—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers by introducing organic surfactant additives into the liquid crystal material
Abstract
Present invention offer, which has been assigned 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 by following side chain type macromolecule, the side chain type macromolecule is the photonasty side chain type macromolecule that liquid crystal liquid crystal property is shown within the scope of specific temperature, it also has following formula (0) [in formula, G is that (in formula, dotted line indicates connecting key selected from following formula (G-1), (G-2), (G-3) and (G-4);R50Indicate the group in hydrogen atom, halogen atom, the alkyl of carbon number 1~3, phenyl, there are multiple R50When, optionally it is same or different to each other;J indicates O, S, NH or NR51, R51Indicate alkyl and phenyl selected from carbon number 1~3 in group) in group] shown in side chain.
Description
Technical field
The present invention relates to new polymers, the composition comprising the polymer and the driving liquid of transverse electric field for having used it
Crystalline substance indicates the manufacturing method of element liquid crystal orientation film and the substrate with the alignment films.In turn, the present invention relates to for making
Making the excellent liquid crystal of image retention speciality indicates the new method of element.
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 expectation 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 can be used in previous liquid crystal expression
The manufacturing process of element.It is main to select the reliabilities such as heat resistance, electricity special also, as organic film used in liquid crystal orientation film
The excellent polyimides system organic film of property.
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.For example, it is purple to irradiate polarization to polyimide film
Outside line brings it about anisotropic decomposition using the polarization direction dependence of the ultraviolet radiation absorption of molecular structure.Also, it is logical
Crossing undecomposed and remaining polyimides is orientated liquid crystal (referring for example to patent document 1.).
In addition, it is also known that have the optical alignment method of photo-crosslinking type, photoisomerization type.Such as it using poly- vinyl cinnamate, shines
Polarized UV rays are penetrated, make the double bond part for 2 side chains for being parallel to polarised light that dimerization reaction (cross-linking reaction) occur.Also, make
Liquid crystal is orientated along the direction vertical with polarization direction (referring for example to non-patent literature 1.).In addition, having using in side chain
When having the side chain type macromolecule of azobenzene, polarized UV rays are irradiated, the azobenzene part for the side chain for being parallel to polarised light occurs
Isomerization reaction is orientated liquid crystal (referring for example to non-patent literature 2 along the direction vertical with polarization direction.).
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 the orientation of liquid crystal, photostability are poor, therefore
When liquid crystal, which is made, indicates element, there are problems that occurring to be orientated bad, expression ghost.Especially, the driving liquid of transverse electric field
Crystalline substance indicates to switch over liquid crystal molecule in face in element, therefore is easy to happen the offset of the liquid crystal aligning after liquid crystal drive, by
Indicate that ghost is considered apparent project caused by AC driving.
Therefore, for optical alignment method, it is desirable that realize high efficiency, the stable liquid crystal aligning of orientation process, it is desirable that
Liquid crystal orientation film, the aligning agent for liquid crystal 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.
In addition, it is an object of the present invention to providing on the basis of above-mentioned purpose and having the cross that voltage retention improves
To electric field drive liquid crystal cell and for the liquid crystal orientation film of the element.
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 side chain type macromolecule is the photonasty side chain type that liquid crystal liquid crystal property is shown within the scope of specific temperature
Macromolecule also has side chain shown in following formula (0).
[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-;
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;
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 are 2, X is optionally same or different to each other;
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 is 2 or more, P is optionally same or different to each other, the number of Q
When amount is 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;
G is the group in following formula (G-1), (G-2), (G-3) and (G-4),
(in formula, dotted line indicates connecting key;R50It indicates in hydrogen atom, halogen atom, the alkyl of carbon number 1~3, phenyl
Group, there are multiple R50When, optionally it is same or different to each other;The integer that t is 1~7;J indicates O, S, NH or NR51, R51It indicates
Group in alkyl and phenyl selected from carbon number 1~3)]
<2>in above-mentioned<1>, side chain type macromolecule, which can have, can occur photo-crosslinking, photoisomerization or light fries' rearrangement
Photonasty side chain.
<3>in above-mentioned<1>or<2>, side chain type macromolecule be can have in the group being made of following formula (1)~(6)
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
When the quantity of=CH-, X are 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 is 2 or more, P is optionally same or different to each other, the number of Q
When amount is 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.
<4>in above-mentioned<1>or<2>, side chain type macromolecule be can have in the group being made of following formula (7)~(10)
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).
<5>in above-mentioned<1>or<2>, side chain type macromolecule be can have selected from the group being made of following formula (11)~(13)
In any photonasty side chain.
In formula, A, X, l, m, m1 and R have definition same as described above.
<6>in above-mentioned<1>or<2>, side chain type macromolecule can have photonasty side shown in following formula (14) or (15)
Chain.
In formula, A, Y1, l, m1 and m2 have definition same as described above.
<7>in above-mentioned<1>or<2>, side chain type macromolecule can have photonasty side shown in following formula (16) or (17)
Chain.
In formula, A, X, l and m have definition same as described above.
<8>in above-mentioned<1>or<2>, side chain type macromolecule can have photonasty side shown in following formula (18) or (19)
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.
<9>in above-mentioned<1>or<2>, side chain type macromolecule can have photonasty side chain shown in following formula (20).
In formula, A, Y1, X, l and m have definition same as described above.
<10>in any one of above-mentioned<1>~<9>, side chain type macromolecule 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 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 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 the alkoxy of carbon number 1~12;
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 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-。
<11>a kind of polymer composition, which is characterized in that it contains described in any one of above-mentioned<1>~<10>(A)
Side chain type macromolecule and (B) organic solvent.
<12>in above-mentioned<11>, polymer composition can also contain (C) amine compounds, and the amine compounds are in the molecule
With 1 primary amino group and nitrogenous heteroaromatic, and aforementioned primary amino group is bonded to aliphatic alkyl or non-aromatic ring type hydrocarbon
Base.
<13>in above-mentioned<12>, (C) ingredient can for following formula A- [1] (in formula, Y11For with aliphatic alkyl or non-aromatic
The divalent organic group of fragrant race's ring type alkyl, Y12For nitrogenous heteroaromatic) shown in amine compounds.
<14>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:
Any combination object in above-mentioned<11>~<13>is coated on the substrate with transverse electric field driving conductive film by [I]
And the process for forming film;
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].
<15>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
<14>method and manufacture.
<16>a kind of driving liquid crystal of transverse electric field indicates element, the substrate with above-mentioned<15>.
<17>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<15>;
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
[IV] 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 substrate
With the 2nd substrate, thus obtain liquid crystal indicate element process,
The process [I '], [II '] and [III '] are as follows:
Any polymer composition that [I '] is coated in above-mentioned<11>~<13>on the 2nd substrate and the work for forming film
Sequence;
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 '].
<18>a kind of driving liquid crystal of transverse electric field indicates element, is manufactured by above-mentioned<17>.
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, on the basis of the above effect, being capable of providing the Interfacial Adsorption liquid crystal in liquid crystal orientation film
In ionic impurity, have the driving liquid crystal cell of transverse electric field for the voltage retention being improved and for the element
Liquid crystal orientation film.
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 film obtained from foregoing polymer compositions be have can
Show the high molecular film of photonasty side chain type of liquid crystal liquid crystal property.The film passes through polarizing light irradiation without carrying out brushing processing
Carry out orientation process.Also, after carrying out polarizing light irradiation, via the process for heating the side chain type polymeric membrane, to become
Have been assigned the film (hereinafter also referred to liquid crystal orientation film) of tropism control ability.At this point, being shown by polarizing light irradiation
Small anisotropy become driving force, the side chain type macromolecule itself of liquid crystal liquid crystal property effectively reorientation due to self assembly.Its
As a result, it is possible to realize efficient orientation process as liquid crystal orientation film, the liquid crystal for having been assigned highly oriented control ability is obtained
Alignment films.
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 containing (A) side chain type macromolecule and (B) organic solvent is coated on transverse electric field by [I]
The process for forming film on the substrate of driving conductive film, (A) the side chain type macromolecule is within the scope of specific temperature
The photonasty side chain type macromolecule of liquid crystal liquid crystal property is shown, also there is side chain shown in above-mentioned formula (0);
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].
By above-mentioned operation, the driving liquid crystal expression element of transverse electric field for having been assigned tropism control ability can be obtained
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.
For the 2nd substrate, replace that there is laterally electricity in addition to using the substrate without transverse electric field driving conductive film
Except the substrate of field driving conductive film, transverse electric field drive (is not had due to using by using above-mentioned operation [I]~[III]
The substrate of conductive film is employed, therefore for convenience, in this application sometimes referred to simply as process [I ']~[III ']), it can obtain
The 2nd substrate with the liquid crystal orientation film for having been assigned tropism control ability.
The driving liquid crystal of transverse electric field indicates that the manufacturing method of element has following process:
[IV] 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
The mode of crystal phase pair carry out it is oppositely disposed, thus obtain liquid crystal indicate element process.Thereby, it is possible to obtain transverse electric field driving
Type liquid crystal indicates element.
Hereinafter, being illustrated for each process of [I]~[III] and [IV] 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 side chain type macromolecule, organic solvent and amine compounds as needed, the side chain type
Macromolecule is the photonasty side chain type macromolecule that liquid crystal liquid crystal property is shown within the scope of specific temperature, also has above-mentioned formula (0) institute
The side chain shown, the amine compounds have 1 primary amino group and nitrogenous heteroaromatic, and aforementioned primary amino group key in the molecule
Together in aliphatic alkyl or non-aromatic ring type alkyl.
<substrate>
It is not particularly limited for substrate, the liquid crystal to be manufactured indicates when element is transmission-type, it is preferable to use the transparency is high
Substrate.It is not particularly limited at this time, the plastic bases such as glass substrate or acrylic compounds substrate, polycarbonate substrate can be used
Deng.
Furthermore, it is contemplated that being suitable for reflective liquid crystal indicates element, 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 transmission-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., but it is not limited to these.
Conventionally known gimmick 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;(B) organic solvent;And 1 primaquine is had according to desired (C) intramolecular
Base and nitrogenous heteroaromatic and aforementioned primary amino group are bonded to the amine compounds of aliphatic alkyl or non-aromatic ring type alkyl
Object.
<<(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, is also had upper
State side chain shown in formula (0).
(A) side chain type macromolecule reacts under the light of the wave-length coverage of 250nm~400nm and 100 DEG C~300
Liquid crystal liquid crystal property is shown within the temperature range of DEG C.
(A) side chain type macromolecule preferably has the photonasty to react by the light of the wave-length coverage of 250nm~400nm
Side chain.
(A) side chain type macromolecule is in order to show liquid crystal liquid crystal property within the temperature range of 100 DEG C~300 DEG C and it is preferred that have 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, have in preferred 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.
(A) it is reliable to assign voltage retention (VHR) etc. and with group shown in above-mentioned formula (0) for side chain type macromolecule
The high liquid crystal orientation film of property.This is considered because: when liquid crystal orientation film is made, group such as crosslinking agent shown in above-mentioned formula (0) that
It plays a role to sample, so that film density improves, dissolution of the ionic impurity into liquid crystal is minimized.
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 that reaction, isomerization reaction can be crosslinked;It, should with main chain and the side chain for being bonded to it
It is both liquid crystal ultimate constituent or the phenylamino benzoic acid ester group that light Fries rearrangement can occur that side 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 by selected from by hydrocarbon, (methyl) acrylate, itaconate, fumarate,
The radically polymerizable groups such as maleate, alpha-methylene-gamma-butyrolactone, styrene, vinyl, maleimide, norbornene
At least one kind of composition in the group of group and siloxanes composition, the side chain include group and following formula shown in above-mentioned formula (0)
(1) at least one kind of in~(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
When the quantity of=CH-, X are 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 is 2 or more, P is optionally same or different to each other, the number of Q
When amount is 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 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 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 the alkoxy of carbon number 1~12;
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 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 with above-mentioned photonasty side chain
Photoreactivity side chain monomer and liquid crystal liquid crystal property side chain monomer, which are polymerize, to be obtained.
[monomer with side chain shown in formula (0)]
More specific example as the monomer with side chain shown in previously described formula (0), it is however preferred to have following polymerizable group and
The structure of following side chain, the polymerizable group is by selected from by hydrocarbon, (methyl) acrylate, itaconate, fumarate, Malaysia
The radically polymerizable groups such as acid esters, alpha-methylene-gamma-butyrolactone, styrene, vinyl, maleimide, norbornene group and
At least one kind of composition in the group of siloxanes composition, the side chain are indicated with above-mentioned formula (0).
Among that monomer, as the monomer with epoxy group, specifically, such as (methyl) acrylic acid contracting can be enumerated
The compounds such as water glyceride, (methyl) acrylic acid (3,4- epoxycyclohexyl) methyl esters, allyl glycidyl ether, wherein can arrange
It is double to enumerate (methyl) glycidyl acrylate, (methyl) acrylic acid (3,4- epoxycyclohexyl) methyl esters, 3- vinyl -7- oxa-
Ring [4.1.0] heptane, 1,2- epoxy group -5- hexene, 1,7- octadiene monoepoxide etc..
As the monomer with thiirane, specifically, can enumerate in for example above-mentioned monomer with epoxy group
Epoxy based structures are replaced as monomer made of thiirane etc..
As the monomer with aziridine, specifically, the ring in for example above-mentioned monomer with epoxy group can be enumerated
Oxygroup structure is replaced as monomer made of aziridine or 1- methylaziridine etc..
As the monomer with oxetanyl, such as (methyl) acrylic acid with oxetanyl can be enumerated
Ester etc..Among this monomer, preferably 3- (methacryloxymethyl) oxetanes, 3- (acryloyloxymethyl) oxygen
Azetidine, 3- (methacryloxymethyl) -3- Ethyloxetane, 3- (acryloyloxymethyl) -3- ethyl oxygen
Azetidine, 3- (methacryloxymethyl) -2- trifluoromethyl oxetanes, 3- (acryloyloxymethyl) -2- three
Methyl fluoride oxetanes, 3- (methacryloxymethyl) -2- phenyl oxetanes, 3- (acryloyloxymethyl) -
2- phenyl oxetanes, 2- (methacryloxymethyl) oxetanes, 2- (acryloyloxymethyl) oxa- ring fourth
Alkane, 2- (methacryloxymethyl) -4- trifluoromethyl oxetanes, 2- (acryloyloxymethyl) -4- trifluoromethyl
Oxetanes can enumerate 3- (methacryloxymethyl) -3- Ethyloxetane, 3- (acryloxy first
Base) -3- Ethyloxetane etc..
As the monomer with Thietane base, preferably for example by the oxa- in the monomer with oxetanyl
Cyclobutane base is replaced into monomer made of Thietane base.
As the monomer with Azetane base (ア ゼ タ Application base, azetidinyl), preferably will for example have oxa-
Oxetanyl in the monomer of cyclobutane base is replaced into monomer made of Azetane base.
Among above-mentioned, from the viewpoint of availability etc., it is however preferred to have the monomer of epoxy group and have oxetanes
The monomer of base, more preferably with the monomer of epoxy group.Wherein, from the viewpoint of availability, preferably (methyl) acrylic acid
Ethylene oxidic ester.
[photoreactivity side chain monomer]
Photoreactivity side chain monomer refers to following monomer: when forming macromolecule, can be formed in high molecular side chain portion
Position has the macromolecule of photonasty 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 following polymerizable group and following photonasty side
The structure of chain: the polymerizable group by selected from by hydrocarbon, (methyl) acrylate, itaconate, fumarate, maleate,
The radically polymerizable groups such as alpha-methylene-gamma-butyrolactone, styrene, vinyl, maleimide, norbornene group and silicon oxygen
At least one kind of composition in the group of alkane composition;And the photonasty side chain is comprising at least one kind of in above-mentioned formula (1)~(6), it is excellent
Be selected as example comprising in above-mentioned formula (7)~(10) at least one kind of photonasty side chain, comprising in above-mentioned formula (11)~(13) extremely
It is photonasty side chain shown in few a kind of photonasty side chain, above-mentioned formula (14) or (15), photosensitive shown in above-mentioned formula (16) or (17)
Photonasty side chain shown in property side chain, above-mentioned formula (18) or (19), photonasty side chain shown in above-mentioned formula (20).
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;R10Indicate Br or CN;S indicates carbon number 2
~10 alkylidene;U indicates 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 following monomer: the high molecular form from the monomer reveals liquid crystal liquid crystal property, the macromolecule
Mesogenic group is capable of forming at side chain position.
As the had mesogenic group of side chain, being also possible to 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..
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..
Formula from raising reliability, the influence this point to liquid crystal aligning, side chain type macromolecule of the invention
(0) content of side chain shown in is preferably 0.1 mole of %~20 mole %, is more preferably 0.5 mole of %~10 mole %, is further
Preferably 1 mole of %~5 mole %.
From liquid crystal aligning this point, the content of the photoreactivity side chain in side chain type macromolecule of the invention is preferred
It rubs for 20 moles of %~99.9 mole %, more preferably 30 moles of %~95 mole %, further preferably 40 moles of %~90
You are %.
From liquid crystal aligning this point, the content of the liquid crystal liquid crystal property side chain in side chain type macromolecule of the invention is preferably
80 moles of % or less, more preferably 10 moles of %~70 mole %, further preferably 20 moles of %~60 mole %.
Side chain type macromolecule of the invention can be containing except side chain, photoreactivity side chain and liquid crystal shown in above-mentioned formula (0)
Other side chains except property side chain.Its content side chain shown in above-mentioned formula (0), photoreactivity side chain and liquid crystal liquid crystal property side chain it is total
Content is unsatisfactory for being its remainder when 100%.
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 etc.).
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 causes 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 the ratio of radical initiator relative to 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 5000~200000.
[preparation of polymer composition]
Polymer composition used in the present invention is preferably prepared to the form of coating fluid, for suitably forming 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..
<amine compounds>
Polymer composition used in the present invention preferably has specific amine compounds, specifically, being in the molecule
With 1 primary amino group and nitrogenous heteroaromatic, and aforementioned primary amino group is bonded to aliphatic alkyl or non-aromatic ring type hydrocarbon
The amine compounds of base.It is perhaps because reducing ionic impurity when liquid crystal orientation film is made by containing the amine compounds
Dissolution and promote previously described formula (0) shown in group cross-linking reaction, it is thus possible to obtain the higher liquid crystal orientation film of durability.
As long as specific amine compounds can be played when polymer composition used in the present invention forms liquid crystal orientation film
Following effect i) and/or ii), just it is not particularly limited.It plays i) ionic in the Interfacial Adsorption liquid crystal of liquid crystal orientation film
Impurity, and/or ii) voltage retention improves.
The amount of specific amine compounds is not particularly limited as long as playing said effect, in polymerization used in the present invention
It is 0.01~10 mass parts, preferably 0.1~5 mass parts in 100 mass parts of compositions.
As the concrete example of aliphatic alkyl, straight-chain alkylidene can be enumerated, the alkylidene with apparatus derivatorius, had
The divalent alkyl etc. of unsaturated bond.The carbon number of aliphatic alkyl is preferably 1~20, more preferably 1~15, further preferably 1~
10。
The concrete example of non-aromatic ring type alkyl as divalent, can enumerate cyclopropane ring, cyclobutane ring, pentamethylene ring,
Cyclohexane ring, cycloheptane ring, cyclooctane ring, cyclononane ring, cyclodecane ring, ring hendecane ring, cyclododecane ring, ring tridecane
Ring, ring tetradecane ring, cyclopentadecane ring, ring hexadecane ring, ring heptadecane ring, ring octadecane ring, ring nonadecane ring, 20 carbon of ring
Alkane ring, tricyclic icosane ring, tricyclic docosane ring, norbornane ring, decahydro naphthalene nucleus, norbornene ring, adamantane ring etc..
Preferably include the ring of 3~20 carbon, be more preferably the ring comprising 3~15 carbon, further preferably comprising 3~10 carbon
The non-aromatic ring type alkyl of ring.
The nitrogenous heteroaromatic for including in amine compounds can be containing at least one, preferably comprise 1~4 and be selected from
By following formula [20a], formula [20b] and formula [20c] (in formula, Z2For the straight chain or branch alkyl of carbon number 1~5) composition group in
The aromatic series ring type hydrocarbon of structure.
Specifically, pyrrole ring, imidazole ring, oxazole ring, thiazole ring, pyrazole ring, pyridine ring, pyrimidine ring, quinoline can be enumerated
Quinoline ring, pyrazoline ring, isoquinolin ring, carbazole ring, purine ring, Thiadiazole, pyridazine ring, pyrazoline ring, triazine ring, pyrazolidine
Ring, triazole ring, pyridine ring, benzimidazole ring, benzimidazole ring, quinoline ring, phenanthroline ring, indole ring, quinoxaline ring, benzo thiophene
Azoles ring, phenthazine ring, oxadiazoles ring, acridine ring etc..In turn, the carbon atom of these nitrogenous heteroaromatics optionally has comprising miscellaneous
The substituent group of atom.
Preferred amine compounds can be following formula A- [1] (in formula, Y11For with aliphatic alkyl or non-aromatic ring
The divalent organic group of formula alkyl, Y12For nitrogenous heteroaromatic) shown in amine compounds.In formula A- [1], Y12As long as having
The divalent organic group of aliphatic alkyl or non-aromatic ring type alkyl, is just not particularly limited.
Preferred Y in formula A- [1]11It can be with the non-aromatic of the aliphatic alkyl and carbon number 3~20 for being selected from carbon number 1~20
1 kind of divalent organic group in fragrant race's ring type alkyl.As non-aromatic ring type alkyl, above structure can be enumerated.Y11It can be more
Preferably enumerate aliphatic alkyl, cyclopropane ring, cyclobutane ring, pentamethylene ring, the cyclohexane ring, cycloheptane of carbon number 1~15
Ring, cyclooctane ring, cyclononane ring, cyclodecane ring, ring hendecane ring, cyclododecane ring, ring tridecane ring, ring tetradecane ring, drop
Bornylene ring, adamantane ring etc..Y11The straight chain or branch alkylidene of carbon number 1~10 can be particularly preferably.
In addition, Y11In any aliphatic alkyl not adjacent with amino or non-aromatic ring type alkyl for being included-
CH2Optionally by-O- ,-NH- ,-CO-O- ,-O-CO- ,-CO-NH- ,-NH-CO- ,-CO- ,-S- ,-S (O)2-、-CF2-、-C
(CF3)2-、-C(CH3)2-、-Si(CH3)2-、-O-Si(CH3)2-、-Si(CH3)2-O-、-O-Si(CH3)2The cyclic hydrocarbon of-O-, divalent
Base or heterocycle displacement.In addition, be bonded to the hydrogen atom of any carbon atom optionally by the straight chain of carbon number 1~20 or branch alkylidene,
Cyclic hydrocarbon group, carbon number 1~10 containing fluoroalkyl, heterocycle, fluorine atom, hydroxyl replace.
As the concrete example of divalent cyclic hydrocarbon group, can enumerate phenyl ring, naphthalene nucleus, tetrahydric naphthalene ring, azulenes, indenes ring, fluorenes ring,
Anthracene nucleus, phenanthrene ring, that non-alkene ring, cyclopropane ring, cyclobutane ring, pentamethylene ring, cyclohexane ring, cycloheptane ring, cyclooctane ring, ring nonyl
Alkane ring, cyclodecane ring, ring hendecane ring, cyclododecane ring, ring tridecane ring, ring tetradecane ring, cyclopentadecane ring, ring hexadecane
Ring, ring heptadecane ring, ring octadecane ring, ring nonadecane ring, ring icosane ring, tricyclic icosane ring, tricyclic docosane
Ring, norbornane ring, decahydro naphthalene nucleus, norbornene ring, adamantane ring etc..
In addition, the concrete example as divalent heterocycle, can enumerate pyrrole ring, imidazole ring, oxazole ring, thiazole ring, pyrazole ring,
Pyridine ring, pyrimidine ring, quinoline ring, pyrazoline ring, isoquinolin ring, carbazole ring, purine ring, Thiadiazole, pyridazine ring, pyrazoline
Ring, triazine ring, pyrazolidine ring, triazole ring, pyridine ring, benzimidazole ring, benzimidazole ring, quinoline ring, phenanthroline ring, indoles
Ring, quinoxaline ring, benzothiazole ring, phenthazine ring, oxadiazoles ring, acridine ring etc..
Y in formula A- [1]12It is nitrogenous heteroaromatic, is can be as described above containing selecting free style [20a], formula
The aromatic series ring type hydrocarbon of at least one structure in the group of [20b] and formula [20c] composition.As its concrete example, it can enumerate above-mentioned
Structure.Among these, preferably pyrrole ring, imidazole ring, pyrazole ring, pyridine ring, pyrimidine ring, pyridazine ring, triazine ring, triazole ring,
Pyridine ring, benzimidazole ring, benzimidazole ring, quinoxaline ring, azepines ring, two azepines rings, naphthyridines ring, azophenlyene ring, phthalazines
Ring.
In addition, from the electrostatic phase of nitrogenous heteroaromatic and carboxyl forming salt, referred to as hydrogen bond in specific polyimides
From the perspective of interaction easness, Y11It is preferred that being bonded to Y12In include not with formula [20a], formula [20b] and formula [20c] phase
Adjacent substituent group.
In turn, the conduct Y of formula A- [1]12The carbon atom of nitrogenous heteroaromatic optionally there is halogen atom and/or organic
The substituent group of base, the organic group optionally contain the hetero atoms such as oxygen atom, sulphur atom, nitrogen-atoms.
Y in formula A- [1]11With Y12Preferred combination be: Y11For with selected from by carbon number 1~20 aliphatic alkyl and
1 kind of divalent organic group in the group of the non-aromatic ring type alkyl composition of carbon number 3~20, Y12For pyrrole ring, imidazole ring, pyrazoles
Ring, pyridine ring, pyrimidine ring, pyridazine ring, triazine ring, triazole ring, pyridine ring, benzimidazole ring, benzimidazole ring, quinoxaline ring,
Azepines ring, two azepines rings, naphthyridines ring, azophenlyene ring or phthalazines ring.It should be noted that Y12Nitrogenous heteroaromatic carbon
Atom optionally has the substituent group of halogen atom and/or organic group, which can contain oxygen atom, sulphur atom, nitrogen
The hetero atoms such as atom.
As further preferred amine compounds, be following formula A- [2] (in formula, Y13For the fat of the divalent of carbon number 1~10
Race's alkyl or non-aromatic ring type alkyl, Y14For singly-bound or-O- ,-NH- ,-S- ,-SO2Or the divalent organic group of carbon number 1~19
Group.In addition, Y13And Y14Possessed entire carbon atom is 1~20.Y15For nitrogenous heteroaromatic.) shown in amine compounds.
Y in formula A- [2]13For the aliphatic alkyl or non-aromatic ring type alkyl of the divalent of carbon number 1~10.If enumerating
Its concrete example is then the straight chain of carbon number 1~10 or branch alkylidene, the unsaturated alkylene of carbon number 1~10, cyclopropane ring, ring
Butane ring, pentamethylene ring, cyclohexane ring, cycloheptane ring, cyclooctane ring, cyclononane ring, cyclodecane ring, ring hendecane ring, ring ten
Dioxane ring, ring tridecane ring, ring tetradecane ring, cyclopentadecane ring, ring hexadecane ring, ring heptadecane ring, ring octadecane ring, ring ten
Nine alkane rings, ring icosane ring, tricyclic icosane ring, tricyclic docosane ring, norbornane ring, decahydro naphthalene nucleus, norborneol
Alkene ring, adamantane ring etc..The straight chain or branch alkylidene, cyclopropane ring, cyclobutane of carbon number 1~10 can more preferably be enumerated
Ring, pentamethylene ring, cyclohexane ring, cycloheptane ring, cyclooctane ring, cyclononane ring, cyclodecane ring, ring hendecane ring, cyclododecane
Ring, ring tridecane ring, ring tetradecane ring, norbornene ring, adamantane ring.The particularly preferably straight chain or branch of carbon number 1~10
Alkylidene.
Y13In include ,-CH in not adjacent with amino any aliphatic alkyl or non-aromatic ring type alkyl2Appoint
Choosing is by-O- ,-NH- ,-CO-O- ,-O-CO- ,-CO-NH- ,-NH-CO- ,-CO- ,-S- ,-S (O)2-、-CF2-、-C(CF3)2-、-C
(CH3)2-、-Si(CH3)2-、-O-Si(CH3)2-、-Si(CH3)2-O-、-O-Si(CH3)2- O-, the cyclic hydrocarbon group of divalent or heterocycle
Displacement.In addition, being bonded to the hydrogen atom of any carbon atom optionally by the straight chain of carbon number 1~20 or branch alkyl, cyclic hydrocarbon group, carbon
Number 1~10 replaces containing fluoroalkyl, heterocycle, fluorine atom, hydroxyl.In cyclic hydrocarbon group and heterocycle and formula A- [1] mentioned herein
Y11The meaning of the definition is identical.
Y in formula A- [2]14For singly-bound or-O- ,-NH- ,-S- ,-SO2Or the divalent organic group of carbon number 1~19.The carbon
The divalent organic group of number 1~19 is the divalent organic group with 1~19 carbon atom, optionally includes oxygen atom, nitrogen-atoms, sulphur
Atom, silicon atom etc..It is exemplified below out this Y14Concrete example.
It can enumerate for example, singly-bound ,-O- ,-NH- ,-S- ,-SO2, the alkyl of carbon number 1~19 ,-CO-O- ,-O-CO- ,-
CO-NH-、-NH-CO-、-CO-、-CF2-、-C(CF3)2-、-CH(OH)-、-C(CH3)2-、-Si(CH3)2-、-O-Si(CH3)2-、-
Si(CH3)2-O-、-O-Si(CH3)2- O-, cyclopropane ring, cyclobutane ring, pentamethylene ring, cyclohexane ring, cycloheptane ring, cyclooctane
Ring, cyclononane ring, cyclodecane ring, ring hendecane ring, cyclododecane ring, ring tridecane ring, ring tetradecane ring, cyclopentadecane ring,
Ring hexadecane ring, ring heptadecane ring, ring octadecane ring, ring nonadecane ring, ring icosane ring, tricyclic icosane ring, tricyclic
Docosane ring, norbornane ring, decahydro naphthalene nucleus, norbornene ring, adamantane ring, phenyl ring, naphthalene nucleus, tetrahydric naphthalene ring, azulenes,
Indenes ring, fluorenes ring, anthracene nucleus, phenanthrene ring, that non-alkene ring, pyrrole ring, imidazole ring, oxazole ring, thiazole ring, pyrazole ring, pyridine ring, pyrimidine
Ring, quinoline ring, pyrazoline ring, isoquinolin ring, carbazole ring, purine ring, Thiadiazole, pyridazine ring, triazine ring, pyrazolidine ring, three
Azoles ring, pyridine ring, benzimidazole ring, benzimidazole ring, quinoline ring, phenanthroline ring, indole ring, quinoxaline ring, benzothiazole ring,
Phenthazine ring, oxadiazoles ring, acridine ring, oxazole ring, piperazine ring, piperidine ring, dioxanes ring, morpholine ring etc..As Y14, optionally wrap
Containing two or more in these.
As described comprising concrete example of more than two kinds ,-NH-CH can be enumerated2-、-NH-C2H4-、-NH-C3H6-、-NH-
C4H8-、-S-CH2-、-S-C2H4-、-S-C3H6-、-S-C4H8-、-O-CH2-、-O-C2H4-、-O-C3H6-、-O-C4H8-、-NH-
CO-CH2-、-NH-CO-C2H4-、-NH-CO-C3H6-、-NH-CO-C4H8-、-CO-CH2-、-CO-C2H4-、-CO-C3H6-、-CO-
C4H8-、-CO-NH-CH2-、-CO-NH-C2H4-、-CO-NH-C3H6-、-CO-NH-C4H8-、-NH-CH2-CH(CH3)-、-NH-
C2H4-CH(CH3)-、-NH-C3H6-CH(CH3)-、-NH-C4H8-CH(CH3)-、-S-CH2-CH(CH3)-、-S-C2H4-CH
(CH3)-、-S-C3H6-CH(CH3)-、-S-C4H8-CH(CH3)-、-O-CH3-CH(CH3)-、-O-C2H4-CH(CH3)-、-O-C3H6-
CH(CH3)-、-O-C4H8-CH(CH3)-、-NH-CO-CH2-CH(CH3)-、-NH-CO-C2H4-CH(CH3)-、-NH-CO-C3H6-CH
(CH3)-、-NH-CO-C4H8-CH(CH3)-、-CH(OH)-CH2-、-CH(OH)-C2H4-、-CH(OH)-C3H6-、-CH(OH)-
C4H8-、-CH(CH2OH)-CH2-、-CH(CH2OH)-C2H4-、-CH(CH2OH)-C3H6-、-CH(CH2OH)-C4H8-、-NH-CH
(CH2OH)-CH2-、-CO-NH-CH(CH2OH)-CH2-、-NH-CO-CH(CH2OH)-CH2-、-CO-CH(CH2OH)-CH2-、-S-
CH(CH2OH)-CH2-、-O-CH(CH2OH)-CH2-、-CH(N(CH3)2)-、-C6H4-O-、-C6H4-NH-、-C6H4-CO-NH-、-
C6H4-NH-CO-、-C6H4-CO-、-C6H4-CH2-、-C6H4- S- etc..
Y in formula A- [2]15For the Y in nitrogenous heteroaromatic, with formula A- [1]12Definition it is identical.It is specific as it
Example, can enumerate and above-mentioned Y12Identical structure.Among these, preferably pyrrole ring, imidazole ring, pyrazole ring, pyridine ring, pyrimidine
Ring, pyridazine ring, triazine ring, triazole ring, pyridine ring, benzimidazole ring, benzimidazole ring, quinoxaline ring, azepines ring, two a word used for translation heptan
Because of ring, naphthyridines ring, azophenlyene ring or phthalazines ring.
In addition, from the electrostatic phase of nitrogenous heteroaromatic and carboxyl forming salt, referred to as hydrogen bond in specific polyimides
From the perspective of interaction easness, Y14It is preferred that being bonded to Y15In include not with formula [20a], formula [20b] or formula [20c] phase
Adjacent carbon atom.
In turn, the conduct Y of formula A- [2]15The carbon atom of nitrogenous heteroaromatic optionally there is halogen atom and/or organic
The substituent group of group, the organic group optionally contain the hetero atoms such as oxygen atom, sulphur atom, nitrogen-atoms.
Y in formula A- [2]13、Y14With Y15Preferred combination be: Y13For the straight chain or branch alkylidene, ring of carbon number 1~10
Propane ring, cyclobutane ring, pentamethylene ring, cyclohexane ring, cycloheptane ring, cyclooctane ring, cyclononane ring, cyclodecane ring, ring 11
Alkane ring, cyclododecane ring, ring tridecane ring, ring tetradecane ring, norbornene ring or adamantane ring, Y14For singly-bound, carbon number 1~10
Straight chain or branch alkylidene ,-O- ,-NH- ,-CO-O- ,-O-CO- ,-CO-NH- ,-NH-CO- ,-CO- ,-S- ,-SO2-、-
CF2-、-C(CF3)2-、-Si(CH3)2-、-O-Si(CH3)2-、-Si(CH3)2-O-、-O-Si(CH3)2-O-、-CH(OH)-、-NH-
CH2-、-NH-C2H4-、-NH-C3H6-、-NH-C4H8-、-S-CH2-、-S-C2H4-、-S-C3H6-、-S-C4H8-、-O-CH2-、-O-
C2H4-、-O-C3H6-、-O-C4H8-、-NH-CO-CH2-、-NH-CO-C2H4-、-NH-CO-C3H6-、-NH-CO-C4H8-、-CO-
CH2-、-CO-C2H4-、-CO-C3H6-、-CO-C4H8-、-CO-NH-CH2-、-CO-NH-C2H4-、-CO-NH-C3H6-、-CO-NH-
C4H8-、-NH-CH2-CH(CH3)-、-NH-C2H4-CH(CH3)-、-NH-C3H6-CH(CH3)-、-NH-C4H8-CH(CH3)-、-S-
CH2-CH(CH3)-、-S-C2H4-CH(CH3)-、-S-C3H6-CH(CH3)-、-S-C4H8-CH(CH3)-、-O-CH3-CH(CH3)-、-
O-C2H4-CH(CH3)-、-O-C3H6-CH(CH3)-、-O-C4H8-CH(CH3)-、-NH-CO-CH2-CH(CH3)-、-NH-CO-
C2H4-CH(CH3)-、-NH-CO-C3H6-CH(CH3)-、-NH-CO-C4H8-CH(CH3)-、-CH(OH)-CH2-、-CH(OH)-
C2H4-、-CH(OH)-C3H6-、-CH(OH)-C4H8-、-CH(CH2OH)-CH2-、-CH(CH2OH)-C2H4-、-CH(CH2OH)-
C3H6-、-CH(CH2OH)-C4H8-、-NH-CH(CH2OH)-CH2-、-CO-NH-CH(CH2OH)-CH2-、-NH-CO-CH
(CH2OH)-CH2-、-CO-CH(CH2OH)-CH2-、-S-CH(CH2OH)-CH2-、-O-CH(CH2OH)-CH2-、-CH(N
(CH3)2)-、-C6H4-O-、-C6H4-NH-、-C6H4-CO-NH-、-C6H4-NH-CO-、-C6H4-CO-、-C6H4-CH2-、-C6H4-
S-, cyclopropane ring, cyclobutane ring, pentamethylene ring, cyclohexane ring, cycloheptane ring, cyclooctane ring, cyclononane ring, cyclodecane ring, ring
Hendecane ring, cyclododecane ring, norbornene ring, adamantane ring, phenyl ring, naphthalene nucleus, tetrahydric naphthalene ring, azulenes, indenes ring, fluorenes ring,
Anthracene nucleus, phenanthrene ring, that non-alkene ring, Y15For pyrrole ring, imidazole ring, pyrazole ring, pyridine ring, pyrimidine ring, pyridazine ring, triazine ring, triazole
Ring, pyridine ring, benzimidazole ring, benzimidazole ring, quinoxaline ring, azepines ring, two azepines rings, naphthyridines ring, azophenlyene ring or
Phthalazines ring.It should be noted that Y15The carbon atom of nitrogenous heteroaromatic optionally there is halogen atom and/or organic group
Substituent group, the organic group optionally contain the hetero atoms such as oxygen atom, sulphur atom, nitrogen-atoms.
Y in formula A- [2]13、Y14With Y15It is more preferable combination be: Y13For the straight chain or branch alkylidene, ring of carbon number 1~5
Propane ring, cyclobutane ring, pentamethylene ring, cyclohexane ring, cycloheptane ring, norbornene ring or adamantane ring, Y14For singly-bound, carbon number
1~5 straight chain or branch alkylidene ,-O- ,-NH- ,-CO-O- ,-O-CO- ,-CO-NH- ,-NH-CO- ,-CO- ,-S- ,-S
(O)2-、-CH(OH)-、-NH-CH2-、-S-CH2-、-O-CH2-、-O-C2H4-、-NH-CO-CH2-、-CO-CH2-、-CO-NH-
CH2-、-NH-CH2-CH(CH3)-、-S-CH2-CH(CH3)-、-O-CH3-CH(CH3)-、-NH-CO-CH2-CH(CH3)-、-CH
(OH)-CH2-、-CH(OH)-C2H4-、-CH(CH2OH)-CH2-、-NH-CH(CH2OH)-CH2-、-CO-NH-CH(CH2OH)-
CH2-、-NH-CO-CH(CH2OH)-CH2-、-CO-CH(CH2OH)-CH2-、-S-CH(CH2OH)-CH2-、-O-CH(CH2OH)-
CH2-、-CH(N(CH3)2)-、-C6H4-O-、-C6H4-NH-、-C6H4-CO-NH-、-C6H4-NH-CO-、-C6H4-CO-、-C6H4-
CH2-、-C6H4- S-, cyclopropane ring, cyclobutane ring, pentamethylene ring, cyclohexane ring, cycloheptane ring, norbornene ring, adamantane
Ring, phenyl ring, naphthalene nucleus, tetrahydric naphthalene ring, azulenes, indenes ring, fluorenes ring, anthracene nucleus, phenanthrene ring or that non-alkene ring, Y15For pyrrole ring, imidazoles
Ring, pyrazole ring, pyridine ring, pyrimidine ring, pyridazine ring, triazine ring, triazole ring, pyridine ring, benzimidazole ring, benzimidazole ring, quinoline
Quinoline ring, azepines ring, two azepines rings, naphthyridines ring, azophenlyene ring or phthalazines ring.It should be noted that Y15Nitrogenous aromatic series
The carbon atom of heterocycle optionally has the substituent group of halogen atom and/or organic group, which optionally contains oxygen atom, sulphur
The hetero atoms such as atom, nitrogen-atoms.
Y in formula A- [2]13、Y14With Y15Further preferred combination be: Y13It is sub- for the straight chain or branch of carbon number 1~5
Alkyl, cyclopropane ring, cyclobutane ring, pentamethylene ring or cyclohexane ring, Y14For singly-bound, the straight chain of carbon number 1~5 or branch alkylene
Base ,-O- ,-NH- ,-CO-O- ,-O-CO- ,-CO-NH- ,-NH-CO- ,-CO- ,-CH (OH)-,-NH-CH2-、-S-CH2-、-O-
CH2-、-NH-CO-CH2-、-CO-CH2-、-CO-NH-CH2-、-NH-CH2-CH(CH3)-、-S-CH2-CH(CH3)-、-O-CH3-CH
(CH3)-、-NH-CO-CH2-CH(CH3)-、-CH(OH)-CH2-、-CH(OH)-C2H4-、-CH(CH2OH)-CH2-、-NH-CH
(CH2OH)-CH2-、-CO-NH-CH(CH2OH)-CH2-、-NH-CO-CH(CH2OH)-CH2-、-CO-CH(CH2OH)-CH2-、-S-
CH(CH2OH)-CH2-、-O-CH(CH2OH)-CH2-、-CH(N(CH3)2)-、-C6H4-O-、-C6H4-NH-、-C6H4-CO-NH-、-
C6H4-NH-CO-、-C6H4-CO-、-C6H4-CH2-、-C6H4- S-, cyclopropane ring, cyclobutane ring, pentamethylene ring, cyclohexane ring, ring
Heptane ring, norbornene ring, adamantane ring, phenyl ring, naphthalene nucleus, tetrahydric naphthalene ring, fluorenes ring or anthracene nucleus, Y15For pyrrole ring, imidazole ring, pyrrole
Azoles ring, pyridine ring, pyrimidine ring, pyridazine ring, triazine ring, triazole ring, pyridine ring, benzimidazole ring or benzimidazole ring.It needs
It is bright, Y15The carbon atom of nitrogenous heteroaromatic optionally there is the substituent group of halogen atom and/or organic group, this is organic
Group optionally contains the hetero atoms such as oxygen atom, sulphur atom, nitrogen-atoms.
Y in formula A- [2]13、Y14With Y15Particularly preferred combination be: Y13For the straight chain or branch alkylene of carbon number 1~5
Base, cyclobutane ring or cyclohexane ring, Y14For singly-bound ,-O- ,-CO-O- ,-O-CO- ,-CO-NH- ,-NH-CO- ,-CH (OH)-, benzene
Ring, naphthalene nucleus, fluorenes ring or anthracene nucleus, Y15For pyrrole ring, imidazole ring, pyrazole ring, pyridine ring or pyrimidine ring.It should be noted that Y15's
The carbon atom of nitrogenous heteroaromatic optionally has the substituent group of halogen atom and/or organic group, which optionally contains
There are the hetero atoms such as oxygen atom, sulphur atom, nitrogen-atoms.
The concrete example of specific amine compounds as (B) ingredient of the invention, can enumerate the compound of M1~M156.
Compound more preferably can enumerate M6~M8, M10, M16~M21, M31~M36, M40~M45, M47
~M57, M59~M63, M68, M69, M72~M82, M95~M98, M100~M103, M108~M125, M128~M137,
M139~M143, M149~M156.Further preferably M6~M8, M16~M20, M32~M36, M40, M41, M44, M49~
M54, M59~M62, M68, M69, M75~M82, M100~M103, M108~M112, M114~M116, M118~M121,
M125, M134~M136, M139, M140, M143, M150, M152~M156.
<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-imidazolinone, ethylpentyl ketone, methyl nonyl ketone, methyl ethyl ketone,
Methyl isoamyl ketone, methyl isopropyl Ketone, cyclohexanone, ethylene carbonate, propylene carbonate, diethylene glycol dimethyl ether, 4- hydroxyl -4-
Methyl -2 pentanone, 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, dipropyl two
Alcohol list 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), (B) and (C) ingredient.As
Its example can enumerate the solvent or compound for improving film thickness uniformity, surface smoothness in coated polymeric composition, mention
The compound etc. of the adaptation of high liquid crystal orientation film and substrate, 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, glycol tertiary butyl ether, dipropylene glycol monomethyl ether, diethylene glycol, diethylene glycol monoacetate, diethylene glycol dimethyl ether, two
Propylene glycol monoacetate monomethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monoacetate list ether, two
Propylene 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, butyl butyrate, butyl ether, two isobutyls
Ketone, methylcyclohexene, propyl ether, two hexyl ethers, 1- hexanol, n-hexane, pentane, normal octane, diethyl ether, methyl lactate, lactic acid second
Ester, methyl acetate, ethyl acetate, n-butyl acetate, acetic acid dihydroxypropane single-ether, methyl pyruvate, ethyl pyruvate, 3- methoxy
Base 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- third
Alcohol, 1- phenoxy group -2- propyl alcohol, Propylene glycol monoacetate, propylene-glycol diacetate, propylene glycol -1- monomethyl ether -2- acetic acid esters, third
Glycol -1- list ether -2- acetic acid esters, dipropylene glycol, 2- (2- ethoxy-c oxygroup) propyl alcohol, methyl lactate, ethyl lactate, lactic acid
N-propyl, 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- amino-ethyl) -3- TSL 8330, N-
(2- amino-ethyl) -3- aminopropylmethyldimethoxysilane, 3- urea propyl trimethoxy silicane, 3- urea propyl triethoxy
Silane, N- ethoxy carbonyl -3- TSL 8330, N- ethoxy carbonyl -3-aminopropyltriethoxysilane,
Three second triamine of N- triethoxysilylpropyltetrasulfide, three second triamine of N- trimethoxy-silylpropyl, 10- trimethoxy first silicon
Three azepine decane of alkyl -1,4,7-, three azepine decane of 10- triethoxysilyl -1,4,7-, 9- trimethyoxysilane
Base -3,6- diaza nonyl acetic acid esters, 9- triethoxysilyl -3,6- diaza nonyl acetic acid esters, N- benzyl -3- amino
Propyl trimethoxy silicane, N- benzyl -3-aminopropyltriethoxysilane, N- phenyl -3- TSL 8330,
Bis- (oxygen the ethylidene) -3- TSL 8330s of N- phenyl -3-aminopropyltriethoxysilane, N-, N- are bis-, and (oxygen is sub-
Ethyl) -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- hydroxyl hexichol for base 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, polarized UV rays are irradiated to substrate from particular aspects across polarization plates.As ultraviolet light to be used, can be used
Wavelength is the ultraviolet light of 100nm~400nm range.Preferably, it according to film type to be used, is selected by filter etc.
Optimal wavelength.Also, such as can choose using wavelength be 290nm~400nm range ultraviolet light, so as to selectivity
Ground induces photo-crosslinking.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 that film used is made 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 not being inclined to very in film by hot bring anisotropy amplification effect, 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.
For the reason identical as the reasons why record in process [I], the thickness of the film formed after heating can be preferably
5nm~300nm, more preferably 50nm~150nm.
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 [IV]>
[IV] process is the substrate that will have liquid crystal orientation film on the transverse electric field driving conductive film obtained in [III]
(the 1st substrate) substrate with liquid crystal orientation film without conductive film obtained in above-mentioned [I ']~[III '] in the same manner as
(the 2nd substrate) carried out across liquid crystal in the opposite mode of the liquid crystal orientation film of the two it is oppositely disposed, utilize well known method production
Liquid crystal cells, to make the process that the driving liquid crystal of transverse electric field indicates element.It should be noted that process [I ']~
In [III '], in addition to replacing that there is the transverse direction using the substrate without transverse electric field driving conductive film in process [I]
Except the substrate of electric field driven conductive film, it can be carried out similarly with process [I]~[III].Process [I]~[III] and process
[I ']~[III's '] only difference is that whether there is or not above-mentioned conductive films, therefore omit the explanation of process [I ']~[III '].
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 side chain type polymeric membrane state before schematically showing polarizing light irradiation, and (b) of Fig. 1 is
The figure of side chain type polymeric membrane state after schematically showing polarizing light irradiation, (c) of Fig. 1 are after schematically showing heating
Side chain type polymeric membrane state figure, the anisotropy hour especially imported, i.e., in the 1st mode of the invention,
The showing when ultraviolet irradiation amount of [II] process is in the range of making Δ A reach the 1%~15% of maximum ultraviolet irradiation amount
It is intended to.
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 side chain type polymeric membrane state before schematically showing polarizing light irradiation, and (b) of Fig. 2 is
The figure of side chain type polymeric membrane state after schematically showing polarizing light irradiation, (c) of Fig. 2 are after schematically showing heating
Side chain type polymeric membrane state figure, when the anisotropy especially imported is big, i.e., in the 1st mode of the invention,
The showing when ultraviolet irradiation amount of [II] process is in the range of making Δ A reach the 15%~70% of maximum ultraviolet irradiation amount
It is intended to.
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 showing polarizing light irradiation
Side chain type polymeric membrane state figure, (b) of Fig. 3 is that the side chain type macromolecule after schematically showing polarizing light irradiation is membranaceous
The figure of state, (c) of Fig. 3 are the figures for schematically showing the side chain type polymeric membrane state after heating, and what is especially imported is each
Anisotropy hour, i.e., in the 2nd mode of the invention, the ultraviolet irradiation amount of [II] process makes Δ A reach maximum ultraviolet
Schematic diagram when in the range of the 1%~70% of line exposure.
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 showing polarizing light irradiation
The figure of state, (b) of Fig. 4 are the figure of the side chain type polymeric membrane state after schematically showing polarizing light irradiation, (c) of Fig. 4
It is the figure of side chain type polymeric membrane state after schematically showing heating exists when the anisotropy especially imported is big
In the 2nd mode of the invention, the ultraviolet irradiation amount of [II] process make Δ A reach maximum ultraviolet irradiation amount 1%~
Schematic diagram when in the range of 70%.
In the 1st mode of the invention, by importing anisotropic processing, the ultraviolet irradiation amount of [II] process to film
When in the range of making Δ A reach the 1%~15% of maximum ultraviolet irradiation amount, firstly, forming film 1 on substrate.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
When in the range of making Δ A reach the 15%~70% of maximum ultraviolet irradiation amount, firstly, forming film 3 on substrate.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),
It is first when the ultraviolet irradiation amount of [II] process is in the range of making Δ A reach the 1%~70% of maximum ultraviolet irradiation amount
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
When exposure is in the range of making Δ A reach the 1%~70% of maximum ultraviolet irradiation amount, applied firstly, being formed on substrate
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 makes Δ A 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 makes Δ A 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 ultraviolet irradiation amount of the high molecular liquid crystal orientation film of the side chain type of the structure of fries' rearrangement group, [II] process makes Δ A
When reaching in the range of the 1%~15% 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 preferentially occur for the photonasty base of the side chain 6a with photonasty group.As a result, having occurred
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 to film 5 very small
Anisotropy.
In the 2nd mode of this implementation, using with light fries' rearrangement group shown in above-mentioned formula (19)
The ultraviolet irradiation amount of the high molecular film of the side chain type of structure, [II] process makes Δ A 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 makes Δ A 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 makes Δ A 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 reaches 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 ultraviolet irradiation amount of the high molecular film of side chain type of the structure of group, [II] process makes Δ A reach maximum ultraviolet light photograph
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..
Hereinafter, illustrating the present invention using embodiment, but the present invention is not limited to the embodiments.
Embodiment
Methacrylic monomer MA1, MA2 used in embodiment described below;As the list with epoxy base side chain
GMA, HBAGE, G1 and additive T1 of body.
It should be noted that MA1 and MA2 following synthesis respectively.That is, MA1 is by patent document (WO2011-084546)
The synthetic method and synthesize.MA2 is by synthetic method described in patent document (Japanese Unexamined Patent Publication 9-118717)
Synthesis.
G1 is synthesized by synthetic method described in following synthesis examples 1.
GMA (glycidyl methacrylate), HBAGE (hydroxy butyl acrylate glycidol ether), additive T1 (3-
Aminomethyl pyridine) use the substance of commercially available purchase.
<synthesis example 1>
The synthesis of specific glycidyl compound (G1)
(COCl) is added into THF (tetrahydrofuran) solution (184g) of carboxylic acid derivates (MA2) (18.4g, 60mmol)2
(oxalyl chloride) (11.4g, 90mmol) and DMF (dimethylformamide) 2 drop, react it at room temperature 2 hours.The solution is dense
Solid obtained from contracting is dissolved with THF (350g).It expends 1 hour and the solution is added dropwise to glycidol (8.89g, 120mmol)
With the THF solution (88g) of triethylamine (13.4g, 132mmol), react it 18 hours.Thereafter, ethyl acetate (500g) is added,
Organic phase is cleaned 3 times with water (300g), is made it dry with magnesium sulfate.After removing magnesium sulfate by filtering, be concentrated and
Obtain crude product.Silica gel column chromatography is carried out to gained crude product using ethyl acetate and hexane, obtains the G1 of white solid forms.
(receipts amount: 14.9g, yield: 69%).
Glycidyl derivatives (G1):
1H-NMR(CDCl3, δ ppm): 8.01 (d, 2H), 7.01 (d, 2H), 6.01 (s, 1H), 5.56 (s, 1H), 4.65-
4.61(m,1H),4.18-4.12(m,3H),4.02(t,2H),3.36-3.32(m,1H),2.91-2.89(m,1H),2.74-
2.72(m,1H),1.95-1.94(m,3H),1.86-1.79(m,2H),1.76-1.69(m,2H),1.57-1.44(m,4H).
<synthesis example 2>
The synthesis of specific oxetane compound (G2)
To carboxylic acid derivates (MA2) (21.4g, 70mmol), dimethylamino naphthyridine (0.85g, 7mmol), 1- ethyl -3-
3- is added in THF (tetrahydrofuran) solution (107g) of (3- dimethylamino-propyl) carbodiimide hydrochloride (14.8g, 77mmol)
Ethyl -3- oxetane methanol (8.58g, 73.5mmol), reacts it at room temperature 18 hours.Thereafter, pass through filtering
Insoluble matter be precipitated is removed to be cleaned 3 times with water (200g), made it dry with magnesium sulfate after addition ethyl acetate (500g).It is logical
Filtering and after removing magnesium sulfate, be concentrated and obtain G2 (the receipts amount: 27.3g, yield: 96%) of colorless liquid.
Oxetane compound (G2):
1H-NMR(CDCl3, δ ppm): 7.97 (d, 2H), 6.91 (d, 2H), 6.10 (s, 1H), 5.55 (s, 1H), 4.60 (d,
2H),4.48(d,2H),4.43(s,2H),4.16(t,2H),4,02(t,2H),1.94(s,3H),1.88-1.79(m,4H),
1.76-1.69(m,2H),1.57-1.43(m,4H),0.97(t,3H).
<synthesis example 3>
The synthesis of specific oxetane compound (G3)
It is same as above-mentioned synthesis example to operate, synthesize oxetane compound below (G3).
Oxetane compound (G3):
1H-NMR(CDCl3, δ ppm): 7.98 (d, 2H), 6.90 (d, 2H), 6.10 (s, 1H), 5.55 (s, 1H), 4.45 (d,
2H),4.39(d,2H),4.31(t,2H),4.16(t,2H),4,01(t,2H),4.01(t,2H),3.54-3.50(m,4H),
1.87-1.66(m,10H)1.56-1.44(m,4H),0.89(t,3H).
In addition, reagent used in the present embodiment described below is referred to as.
(organic solvent)
THF: tetrahydrofuran.
NMP:N- N-methyl-2-2-pyrrolidone N.
BC: butyl cellosolve.
(polymerization initiator)
AIBN:2,2 '-azobis isobutyronitrile.
<Macroscopic single crystal example 1>
MA1 (9.67g, 29.1mmol), GMA (0.13g, 0.9mmol) are dissolved in THF (56.3g), with diaphragm pump into
After row degassing, adds AIBN (0.15g, 3mmol) and be de-gassed again.Thereafter it is reacted 12 hours with 60 DEG C, obtains methyl-prop
The polymer solution of olefin(e) acid ester.The polymer solution is added dropwise to diethyl ether (1000ml), gained sediment is filtered.By the precipitating
Object is cleaned with diethyl ether, is dried under reduced pressure in 40 DEG C of baking oven, and methacrylate polymer powder P1 is obtained.
<Macroscopic single crystal example 2~6>
It forms according to shown in table 1, is synthesized using method identical with Macroscopic single crystal example 1.
[table 1]
<embodiment 1>
To addition NMP in the methacrylate polymer powder P1 (6.0g) obtained using Macroscopic single crystal example 1
(54.0g) is stirred at room temperature 5 hours and makes it dissolve.By adding BC (40.0g) into the solution and stirring, gathered
Polymer solution A1.The polymer solution is directly as the aligning agent for liquid crystal for being used to form liquid crystal orientation film.
<embodiment 2~12>
It is formed according to shown in table 2, is prepared using method same as Example 1, obtain the liquid of embodiment 2~12
Brilliant alignment agent A2~A12.
[table 2]
<comparison polymer synthesis example 1>
MA1 (9.97g, 30mmol) is dissolved in THF (57.5g), after being de-gassed with diaphragm pump, adds AIBN
It (0.15g, 3mmol) and is de-gassed again.Thereafter it is reacted 12 hours with 60 DEG C, the polymer for obtaining methacrylate is molten
Liquid.The polymer solution is added dropwise to diethyl ether (1000ml), gained sediment is filtered.The sediment is cleaned with diethyl ether,
It is dried under reduced pressure in 40 DEG C of baking oven, obtains methacrylate polymer powder CP1.
<comparison polymer synthesis example 2>
Utilize MA1 (5.9g, 18mmol), MA2 (3.7g, 12mmol), THF (55.5g), AIBN (0.15g, 3mmol)
Composition, using with compare 1 identical method, obtain methacrylate polymer powder CP2.
<control 1 and 2>
The aligning agent for liquid crystal B1 of control 1 is obtained using method same as Example 1 using CP1.Similarly, it uses
CP2 obtains the aligning agent for liquid crystal B2 of control 2.
<<preparations of liquid crystal cells>>
Using aligning agent for liquid crystal A1 obtained in embodiment 1, the production of liquid crystal cells is carried out according to following the step of showing.
Substrate is to be formed having a size of 30mm × 40mm and with a thickness of the glass substrate of 0.7mm using configured with ito film is patterned
Comb teeth-shaped pixel electrode substrate.
The comb teeth that " < " font electrode element that there is pixel electrode center portion to bend is constituted through multiple arrangements
Shape shape.The width of the width direction of each electrode element is 10 μm, between electrode element between be divided into 20 μm.Form the picture of each pixel
The electrode element of " < " font that plain electrode is bent by center portion is constituted through multiple arrangements, therefore the shape of each pixel
Not instead of oblong-shaped has " < " word bending in the same manner as electrode element in center portion, similar to runic
Shape.
Each pixel using its center bending part divided up and down as boundary, with bending part upside the 1st region with
2nd region of downside.When comparing the 1st region and 2 region of each pixel, the shape of the electrode element of their pixel electrode is constituted
At direction difference.That is, using the orientation process direction of aftermentioned liquid crystal orientation film as when benchmark, in the 1st region of pixel, to be in
The mode of existing+15 ° of angle (clockwise) forms the electrode element of pixel electrode, in the 2nd region of pixel, to be presented -15 °
The mode of angle (clockwise) form the electrode element of pixel electrode.That is, the 1st region of each pixel and the 2nd following structure in region
At: the liquid crystal induced and applying voltage between pixel electrode and counter electrode, spinning movement (plane in real estate
Switching) direction opposite direction each other.
Aligning agent for liquid crystal A1 obtained in embodiment 1 is spin-coated on the above-mentioned electroded substrate prepared.Then, it uses
70 DEG C of press drying 90 seconds forms the liquid crystal orientation film that film thickness is 100nm.Then, across polarization plates with 20mJ/cm2It is right
After coated surface irradiates the ultraviolet light of 313nm, is heated 10 minutes with 150 DEG C of hot plates, obtain the substrate with liquid crystal orientation film.Separately
Outside, to the not formed electrode as opposite substrate and also the same landform of glass substrate with the column spacer for being highly 4 μm
At film, implement orientation process.Printing and sealing agent (assists vertical Chemical Co., Ltd. system, XN- on the liquid crystal orientation film of a substrate
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.
Using aligning agent for liquid crystal A2~A12 obtained in embodiment 2~12, aligning agent for liquid crystal B1 obtained in control 1,2,
B2 similarly makes liquid crystal cells.
<<voltage retention (VHR) evaluation>>
Using the liquid crystal cells of above-mentioned production, 70 DEG C at a temperature of apply the 5V voltage of 60 μ s, after measuring 16.67ms
Voltage is able to maintain and calculates for which kind of degree as voltage retention (VHR1) by voltage.In turn by unit after measured
With the 16Vpp alternating voltage of the frequency application 168 hours of 30Hz under 70 DEG C of isoperibol.Thereafter, make the picture of liquid crystal cells
Short-circuit condition is presented between plain electrode and counter electrode, directly places 1 hour at room temperature.It is being surveyed under the same conditions with VHR1
The fixed gained unit, voltage is able to maintain and is calculated for which kind of degree as voltage retention (VHR2).It needs to illustrate
It is that the measurement of voltage retention has used the voltage retention measurement device VHR-1 of TOYO Corporation.
The result of the composition and VHR of embodiment and the aligning agent for liquid crystal of control is shown in table 3 together.
[table 3]
Aligning agent for liquid crystal | VHR1 | VHR2 | |
Embodiment 1 | A1 | 97.1 | 95.8 |
Embodiment 2 | A2 | 96.5 | 94.9 |
Embodiment 3 | A3 | 96.2 | 95.2 |
Embodiment 4 | A4 | 96.9 | 95.4 |
Embodiment 5 | A5 | 96.4 | 96.4 |
Embodiment 6 | A6 | 96.5 | 96.6 |
Embodiment 7 | A7 | 96.3 | 96.3 |
Embodiment 8 | A8 | 97 | 97.1 |
Embodiment 9 | A9 | 96.6 | 95 |
Embodiment 10 | A10 | 96.5 | 94.8 |
Embodiment 11 | A11 | 96.6 | 96.5 |
Embodiment 12 | A12 | 96.4 | 96.5 |
Control 1 | B1 | 94.5 | 93.2 |
Control 2 | B2 | 94 | 92.8 |
As shown in Table 3: compared with the control 1,2 not being copolymerized, by that will have the list of epoxy group in embodiment 1~12
Body is copolymerized, so that VHR1 is improved.In addition we know: by the way that additive T1 is further added in embodiment 5~8,11 and 12, from
And the result of VHR2 is good.
<afterimage evaluation>
The IPS mode prepared in Examples 1 to 8 is arranged in liquid crystal cells and is configured in the vertical mode of polarizing axis
Between 2 polarization plates, backlight is lighted in the state of no applied voltage, adjusts the arrangement angles of liquid crystal cells so that transmitted light
Brightness reaches minimum.Also, liquid crystal cells will be made from the 2nd region of pixel to reach most dark angle and rotate to the 1st region to reach
Rotation angle when until most dark angle is calculated as initial stage orientation angle.
Then, apply 168 hours 16V with the frequency of 30Hz in 60 DEG C of baking ovenPPAlternating voltage.Thereafter, make liquid crystal
Short-circuit condition is presented between the pixel electrode and counter electrode of unit, directly places 1 hour at room temperature.It is same to grasp after placement
Make and measure orientation angle, the difference at the orientation angle of exchange driving front and back is calculated as angle delta (deg.).
It similarly measures in other embodiments.
As a result, angle delta is 0.1 or less in all embodiments.
After irradiating ultraviolet light to the side chain type polymeric membrane for showing liquid crystal liquid crystal property, in the range of liquid crystal shows temperature
It is heated, is perhaps that macromolecule is integrally efficiently assigned liquid crystal aligning ability because of self assembly, therefore long-term AC drives
The offset of orientation is not almost observed after dynamic yet.
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 (11)
1. a kind of side chain type macromolecule is the photonasty side chain type high score for showing liquid crystal liquid crystal property within the scope of specific temperature
Son also has side chain shown in side chain shown in following formula (0) and following formula (2),
In formula (0), A, B 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;
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 are 2, X is optionally same or different to each other;
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 is 2 or more, P is optionally same or different to each other, and the quantity of Q is 2
When above, 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;
G is the group in following formula (G-1), (G-2), (G-3) and (G-4),
In formula (G-1), (G-2), (G-3) and (G-4), dotted line indicates connecting key;R50It indicates to be selected from hydrogen atom, halogen atom, carbon
Group in the alkyl of number 1~3, phenyl, there are multiple R50When, optionally it is same or different to each other;The integer that t is 1~7;J is indicated
O, S, NH or NR51, R51Indicate the group in alkyl and phenyl selected from carbon number 1~3,
In formula (2), 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;
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 indicates the phenyl ring, naphthalene nucleus, cyclohexyl biphenyl, the furan nucleus, pyrroles that are selected from 1 valence
Ring in the ester ring type hydrocarbon of ring and carbon number 5~8, or identical or different 2~6 ring in these substituent groups by
Group made of binding groups B bonding, is bonded to their hydrogen atom each independently optionally by-COOR0、-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, in formula, R0It indicates
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 are 2, X is optionally same or different to each other;
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 is 2 or more, P is optionally same or different to each other, and the quantity of Q is 2
When above, 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.
2. side chain type macromolecule according to claim 1, the photonasty side chain with following formula (9),
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 are 2, X is optionally same or different to each other;
L indicates 1~12 integer;
M indicates 0~2 integer;
R indicates the alkoxy of hydroxyl, carbon number 1~6, or indicates the phenyl ring, naphthalene nucleus, cyclohexyl biphenyl, the furan nucleus, pyrroles that are selected from 1 valence
Ring in the ester ring type hydrocarbon of ring and carbon number 5~8, or identical or different 2~6 ring in these substituent groups by
Group made of binding groups B bonding, is bonded to their hydrogen atom each independently optionally by-COOR0、-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, in formula, R0It indicates
The alkyl of hydrogen atom or carbon number 1~5.
3. side chain type macromolecule according to claim 1 has in the group being made of following formula (21)~(31)
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, phenyl ring, naphthalene nucleus, the biphenyl of 1 valence
Ring, furan nucleus, nitrogen-containing heterocycle, the ester ring type hydrocarbon of carbon number 5~8, the alkyl of carbon number 1~12 or the alkoxy of carbon number 1~12;
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, phenyl ring, naphthalene nucleus, cyclohexyl biphenyl, furan nucleus, nitrogen-containing heterocycle and the carbon number of 1 valence
5~8 ester ring type hydrocarbon and alkyl or alkoxy;
Z1、Z2Indicate singly-bound ,-CO- ,-CH2O- ,-CH=N- ,-CF2-。
4. a kind of polymer composition, containing (A) side chain type macromolecule according to any one of claims 1 to 3 and (B) has
Solvent.
5. polymer composition according to claim 4, wherein polymer composition also contains (C) amine compounds, described
Amine compounds have 1 primary amino group and nitrogenous heteroaromatic in the molecule, and the primary amino group is bonded to aliphatic alkyl
Or non-aromatic ring type alkyl.
6. polymer composition according to claim 5, wherein (C) ingredient is amination shown in following formula A- [1]
Object is closed,
In formula, Y11For the divalent organic group with aliphatic alkyl or non-aromatic ring type alkyl, Y12It is miscellaneous for nitrogenous aromatic series
Ring.
7. 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:
Polymer composition described in any one of claim 4~6 is coated on transverse electric field driving conductive film by [I]
Substrate on and the process that forms film;
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].
8. a kind of substrate for indicating element liquid crystal orientation film with the driving liquid crystal of transverse electric field, is by claim 7
The method and manufacture.
9. a kind of driving liquid crystal of transverse electric field indicates element, with substrate according to any one of claims 8.
10. 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 according to any one of claims 8 i.e. process of the 1st substrate;
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
[IV] in such a way that the liquid crystal orientation film of the 1st substrate and the 2nd substrate is across liquid crystalline phase pair, the oppositely disposed described 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 '] is coated with polymer composition described in any one of claim 4~6 on the 2nd substrate and forms the work of film
Sequence;
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 '].
It 11. a kind of driving liquid crystal of transverse electric field indicates element, is manufactured by method described in any one of claim 10.
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PCT/JP2014/069529 WO2015012341A1 (en) | 2013-07-24 | 2014-07-24 | Polymer, polymer composition, and liquid crystal alignment film for horizontal-electric-field drive-type liquid crystal display element |
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JP6794257B2 (en) * | 2014-08-05 | 2020-12-02 | 日産化学株式会社 | Liquid crystal alignment agent, liquid crystal alignment film and liquid crystal display element |
CN107849365A (en) * | 2015-07-30 | 2018-03-27 | 日产化学工业株式会社 | Aligning agent for liquid crystal, liquid crystal orientation film and liquid crystal represent element |
JP6738036B2 (en) * | 2015-10-14 | 2020-08-12 | 日産化学株式会社 | Liquid crystal aligning agent, liquid crystal aligning film and liquid crystal display device |
JP6864251B2 (en) * | 2015-10-29 | 2021-04-28 | 日産化学株式会社 | Liquid crystal alignment agent, liquid crystal alignment film and liquid crystal display element |
KR102573453B1 (en) * | 2017-02-27 | 2023-08-31 | 닛산 가가쿠 가부시키가이샤 | Liquid crystal aligning agent, liquid crystal aligning film, and liquid crystal display element |
JP6987883B2 (en) * | 2017-12-15 | 2022-01-05 | 富士フイルム株式会社 | Photo-aligned copolymer, photo-aligned film and optical laminate |
JP7389567B2 (en) * | 2018-06-07 | 2023-11-30 | 住友化学株式会社 | Compound, resin, resist composition, and method for producing resist pattern |
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