CN105339837B - The driving liquid crystal of transverse electric field indicates the manufacturing method of element - Google Patents
The driving liquid crystal of transverse electric field indicates the manufacturing method of element Download PDFInfo
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F20/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
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- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells
- G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
- G02F1/1333—Constructional arrangements; Manufacturing methods
- G02F1/1337—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers
- G02F1/133711—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers by organic films, e.g. polymeric films
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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
- G02F1/13378—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers by treatment of the surface, e.g. embossing, rubbing or light irradiation
- G02F1/133788—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers by treatment of the surface, e.g. embossing, rubbing or light irradiation by light irradiation, e.g. linearly polarised light photo-polymerisation
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- G—PHYSICS
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- 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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Abstract
It provides and assigns tropism control ability with high efficiency, the driving liquid crystal of transverse electric field excellent in reliability indicates element.A kind of driving liquid crystal of transverse electric field indicates the manufacturing method of element, it has following process: the photosensitive composite of liquid crystal liquid crystal property is shown in specific range of temperatures containing (A) photonasty side chain type macromolecule and (B) organic solvent is coated on the substrate with transverse electric field driving conductive film by [I], thus the process for forming photonasty side chain type polymeric membrane；[II] irradiates polarized UV rays to photosensitive side chain type polymeric membrane, thus the process that side chain type polymeric membrane is made；The process that [III] heats aforementioned side chain type polymeric membrane；[IV] thereafter, further irradiates the process of ultraviolet light.
Description
Technical field
The present invention relates to the manufacturing methods that the driving liquid crystal of transverse electric field indicates element, more specifically, are related to ghost spy
Property the excellent driving liquid crystal of transverse electric field indicate the manufacturing method of element.
Background technique
Liquid crystal indicate element as light weight, the expression equipment that volume is thin and power consumption is low be it is known, in recent years for greatly
The television applications etc. of type, realize alarming development.Liquid crystal indicates that element is, for example, with a pair of of transparent substrate folder for having electrode
It holds liquid crystal layer and constitutes.Also, liquid crystal indicates to use the organic film made of organic material as liquid crystal orientation film in element
So that liquid crystal reaches desired state of orientation between substrate.
That is, liquid crystal orientation film is the component parts that liquid crystal indicates element, it is formed in connecing with liquid crystal for the substrate of clamping liquid crystal
The face of touching undertakes the effect for being orientated liquid crystal between the substrate along certain orientation.Also, it is directed to liquid crystal orientation film, in addition to wanting
It asks except the effect for being orientated liquid crystal along certain orientations such as the directions for being for example parallel to substrate, also requires control liquid crystal sometimes
The effect of pre-tilt angle.Ability (the hereinafter referred to as tropism control ability of control liquid crystal aligning in this liquid crystal orientation film.) can lead to
It crosses and orientation process is carried out to the organic film for constituting liquid crystal orientation film to assign.
As the method for orientation treatment of the liquid crystal orientation film for assigning tropism control ability, known brushing all the time
Method.Brushing method refers to: for the organic film of polyvinyl alcohol, polyamide, polyimides on substrate etc., to its surface with cotton, Buddhist nun
The cloth such as dragon, polyester are along certain orientation friction (brushing), the method for being orientated liquid crystal along frictional direction (brushing direction).
The brushing method can easily realize more stable liquid crystal aligning state, therefore apply the system in previous liquid crystal expression element
It makes in technique.Also, it is main to select reliabilities, the electrical characteristics such as heat resistance excellent as the organic film for liquid crystal orientation film
Polyimides system organic film.
However, occasionally there are dusts, appearance for the brushing method on the surface of friction liquid crystal orientation film made of polyimides etc.
The problem of electrostatic.In addition, since liquid crystal in recent years indicates the High precision of element, by the electrode or liquid crystal drive on counterpart substrate
The bumps caused by switching active element, the surface for the liquid crystal orientation film that can not equably be rubbed with cloth sometimes cannot achieve uniform
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 is to constitute having for liquid crystal orientation film using rectilinearly polarized light or collimated light there are various methods
Anisotropy is formed in machine film, and the method for liquid crystal aligning is made according to the anisotropy.As main optical alignment method, it is known to point
The optical alignment method of solution type.Such as known following method: polarized UV rays are irradiated to polyimide film, utilize the ultraviolet of molecular structure
The polarization direction dependence of line absorption brings it about anisotropic decomposition, also, utilizes undecomposed and remaining polyimides
Make liquid crystal that orientation occur (referring for example to patent document 1).
In addition, it is also known that the optical alignment method of photo-crosslinking type, photoisomerization type.For example, using poly- vinyl cinnamate, irradiation
In the double bond part of 2 side chains parallel with polarised light dimerization reaction (cross-linking reaction) occurs for polarized UV rays.Also, make liquid
Crystalline substance occurs to be orientated (referring for example to non-patent literature 1 along the direction perpendicular to polarization direction.).In addition, being had using side chain even
When the side chain type macromolecule of pyridine, polarized UV rays are irradiated, isomerization occurs in the azobenzene portion of the side chain parallel with polarised light
Reaction makes liquid crystal occur to be orientated (referring for example to non-patent literature 2) along the direction perpendicular to polarization direction.
As example above, in the method for orientation treatment of the liquid crystal orientation film based on optical alignment method, it is not necessarily to brushing, no
With worry dust, there is electrostatic.Also, it can implement to be orientated having the substrate of indent and convex liquid crystal expression element even if to surface
Processing, becomes 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 above, the brushing industrially implemented all the time with the method for orientation treatment that indicates element as liquid crystal
Method is compared, and optical alignment method is not necessarily to brushing process, therefore has clear advantage.Also, with the tropism control ability using brushing
It basically reaches constant brushing method to compare, in optical alignment method, the exposure of polarised light can be made to change to control orientation control
Ability processed.However, in optical alignment method, it is desirable to the case where realizing with using brushing method for same degree tropism control ability when,
Exposure sometimes for a large amount of polarised lights cannot achieve stable liquid crystal aligning.
For example, needing to irradiate polyimide film 60 minutes by defeated in the breakdown type optical alignment method described in patent document 1
The ultraviolet light etc. that the high-pressure sodium lamp that power is 500W out issues needs for a long time and a large amount of ultraviolet light irradiates.In addition, in dimerization
Type, photoisomerization type optical alignment method in the case where, be also required to a large amount of ultraviolet of irradiation number J (joule)~tens of J or so sometimes
Line.In turn, photo-crosslinking type, photoisomerization type optical alignment method in the case where, due to the thermal stability of liquid crystal aligning, light stablize
Property it is poor, be made liquid crystal indicate element when, there are problems that occur orientation it is bad, indicate ghost.Especially, it is driven in transverse electric field
Ejector half liquid crystal indicates in element, since the orientation for being easy to happen liquid crystal after in-plane switching liquid crystal molecule, liquid crystal drive is inclined
Difference is considered apparent project by the expression ghost that AC driving causes.Therefore, in optical alignment method, it is desirable that realize orientation process
High efficiency, stable liquid crystal aligning, it is desirable that the liquid crystal of highly oriented control ability can be efficiently assigned to liquid crystal orientation film
Alignment films, aligning agent for liquid crystal.
The object of the present invention is to provide assign tropism control ability, transverse electric field drive excellent in reliability with high efficiency
Ejector half liquid crystal indicates 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: it is driven with transverse electric field
Employ on the substrate of conductive film coating include shown in specific range of temperatures liquid crystal liquid crystal property photonasty side chain type it is high molecular
Photosensitive composite, the transverse electric field for imparting tropism control ability by ultraviolet irradiation and subsequent heating are driving
Liquid crystal indicates that element can be realized the above subject, so as to complete the present invention.The present invention has following purport.
1. the manufacturing method that a kind of driving liquid crystal of transverse electric field indicates element, which is characterized in that have following process:
[I] coating on the substrate with transverse electric field driving conductive film contains certain temperature of (A) at 100~250 DEG C
The photonasty side chain type macromolecule of liquid crystal liquid crystal property and the photosensitive composite of (B) organic solvent are shown in range, to form sense
The process of photosensitiveness side chain type polymeric membrane；
The process of [II] to photosensitive side chain type polymeric membrane irradiation polarized UV rays；
The process that [III] heats aforementioned side chain type polymeric membrane；
[IV] thereafter, further irradiates the process of ultraviolet light.
2. the manufacturing method according to above-mentioned 1, wherein the ultraviolet irradiation amount of process [II] reaches maximum making Δ A
Ultraviolet irradiation amount 1%~70% in the range of, the Δ A be aforementioned side chain type polymeric membrane, be parallel to it is aforementioned partially
The ultraviolet absorbance in the direction of the polarization direction of vibration ultraviolet light and the direction of the polarization direction perpendicular to aforementioned polarized UV rays
Ultraviolet absorbance difference.
3. the manufacturing method according to above-mentioned 1 or 2, wherein the ultraviolet irradiation amount of process [II] is reached making aforementioned Δ A
To in the range of the 1%~50% of maximum ultraviolet irradiation amount.
4. the manufacturing method according to above-mentioned any one of 1~3, wherein the heating temperature of process [III] is temperature ratio
The upper limit of the low 10 DEG C~temperature of the lower limit for the temperature range that aforementioned side chain type polymeric membrane shows liquid crystal liquid crystal property than the temperature range
The temperature of low 10 DEG C of range.
5. the manufacturing method of the liquid crystal orientation film according to above-mentioned any one of 1~4, wherein aforementioned to show liquid crystal
Property photonasty side chain type macromolecule in the photonasty group that contains be azobenzene, Stilbene, cinnamic acid, cinnamate, chalcone, perfume (or spice)
Legumin, tolans, phenol benzoate, or derivatives thereof.
6. the manufacturing method according to above-mentioned any one of 1~5, wherein the ultraviolet irradiation amount of process [IV] is to make
20 moles or more the exposures to react during photonasty group possessed by aforementioned side chain type polymeric membrane is 100 moles average.
7. the manufacturing method according to above-mentioned any one of 1~6, wherein process [IV] indicates element in production liquid crystal
After carry out.
8. the manufacturing method according to above-mentioned any one of 1~7, which is characterized in that (A) ingredient is handed over light can occur
The side chain of connection, photoisomerization or light fries' rearrangement.
9. the manufacturing method according to above-mentioned any one of 1~8, wherein (A) ingredient has side chain type macromolecule, institute
Stating side chain type macromolecule has at least one photonasty side chain in the group being made of aftermentioned formula (1)~(13).
10. the manufacturing method according to above-mentioned any one of 1~9, wherein (A) ingredient has side chain type macromolecule, institute
Stating side chain type macromolecule has at least one liquid crystal liquid crystal property side in the group being made of aftermentioned formula (5)~(8) and (14)~(22)
Chain.
11. a kind of photosensitive composite, to show liquid crystal liquid crystal property in 100~250 DEG C certain temperature range containing (A)
Photonasty side chain type macromolecule and (B) organic solvent photosensitive composite, for successively have following process laterally electricity
The driving liquid crystal in field indicates the manufacturing method of element:
Above-mentioned photosensitive composite is coated on the substrate with transverse electric field driving conductive film by [I], to be formed
The process of photonasty side chain type polymeric membrane；The work of [II] to photosensitive side chain type polymeric membrane irradiation polarized UV rays
Sequence；The process that [III] heats aforementioned side chain type polymeric membrane；[IV] is further to the work of side chain type polymeric membrane irradiation ultraviolet light
Sequence.
12. the photosensitive composite according to above-mentioned 11, which is characterized in that (A) ingredient have photo-crosslinking, light can occur
The side chain of isomerization or light fries' rearrangement.
13. the photosensitive composite according to above-mentioned 11, wherein (A) ingredient be with selected from by aftermentioned formula (1)~
(13) the side chain type macromolecule of at least one photonasty side chain in the group formed.
14. photosensitive composite according to claim 11, wherein (A) ingredient have selected from by aftermentioned formula (5)~
(8) and formula (14)~(22) composition group at least one liquid crystal liquid crystal property side chain.
It is the manufacture that element is indicated using liquid crystal described in above-mentioned any one of 1~10 15. a kind of liquid crystal indicates element
Method manufacture.
The effect of invention
The driving liquid crystal of the transverse electric field manufactured using method of the invention indicates that element is efficiently imparted orientation control
Ability processed, therefore lossless characterization long-time Continuous Drive.
Detailed description of the invention
Fig. 1 is the anisotropy importing processing in the manufacturing method for illustrate schematically that liquid crystal orientation film used in the present invention
An example figure, figure when being photonasty side chain using bridging property organic group and smaller imported anisotropy.
Fig. 2 is the anisotropy importing processing in the manufacturing method for illustrate schematically that liquid crystal orientation film used in the present invention
An example figure, figure when being photonasty side chain using bridging property organic group and larger imported anisotropy.
Fig. 3 is the anisotropy importing processing in the manufacturing method for illustrate schematically that liquid crystal orientation film used in the present invention
An example figure, being photonasty side chain uses organic group that fries' rearrangement or isomerization can occur and imported each
Figure when anisotropy is smaller.
Fig. 4 is the anisotropy importing processing in the manufacturing method for illustrate schematically that liquid crystal orientation film used in the present invention
An example figure, being photonasty side chain uses organic group that fries' rearrangement or isomerization can occur and imported each
Figure when anisotropy is larger.
Specific embodiment
Present inventor has performed further investigations, as a result obtain following opinion, so as to complete the present invention.
Photosensitive composite 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 side chain type macromolecule.), it the use of the film that photosensitive composition obtains is that can show liquid
The high molecular film of photonasty side chain type of crystalline substance.The film can carry out orientation process by polarizing light irradiation and liquid crystal aligning is made
Film, without carrying out brushing processing.That is, after carrying out polarizing light irradiation to the high molecular film of side chain type, via to side chain type height
The process that molecular film is heated, to become the film (liquid crystal orientation film) for having been assigned tropism control ability.At this point, by inclined
The irradiation of vibration light and the small anisotropy that shows become driving force, liquid crystal liquid crystal property side chain type macromolecule self by self assembly and
Effectively reorientation.As a result, realize efficient orientation process as liquid crystal orientation film, it can obtain having been assigned height and take
To the liquid crystal orientation film of control ability.Thereafter, by irradiating ultraviolet light to liquid crystal orientation film, unreacted photonasty can be reduced
Group.It operates in this way, can obtain maintaining efficient tropism control ability and liquid crystal excellent in reliability indicates element.
The manufacturing method > of < liquid crystal expression element
Hereinafter, being illustrated for process [I]~process [IV] each process in the manufacturing method of the present invention.
In process [I], coating is containing in specific range of temperatures on the substrate with transverse electric field driving conductive film
Show the photonasty side chain type macromolecule of liquid crystal liquid crystal property and photosensitive composite (the hereinafter also referred to photosensitive composition of organic solvent
Object.), to form polymeric membrane.Substrate is not particularly limited, such as other than glass substrate, can also use acrylic acid
The transparent substrates such as the plastic bases such as class substrate, polycarbonate substrate.In view of the application of gained polymeric membrane, from simplified liquid crystal watch
From the perspective of showing the manufacturing process of element, ITO (the Indium Tin being formed with for driving liquid crystal also can be used
Oxide, tin indium oxide) electrode etc. substrate.Additionally, it is contemplated that it indicates the application in element in reflective liquid crystal, can also make
The material of the meeting reflected light such as aluminium also can be used as electrode at this time with the opaque substrate such as silicon wafer.
Coating method is not particularly limited, and industrial is usually to utilize silk-screen printing, hectographic printing, flexible printing or ink-jet
The method of the progress such as 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 etc., them can be used according to purpose.
After being coated with photosensitive composite on substrate, hot plate, thermal cycle type baking oven or IR (infrared ray) type baking oven etc. are utilized
Heating means evaporates solvent with 20~180 DEG C, preferably with 40~150 DEG C, so as to obtain photonasty side chain type macromolecule
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 polymeric membrane is blocked up,
Liquid crystal indicate element power consumption in terms of be it is unfavorable, when excessively thin, liquid crystal indicate element reliability reduce sometimes, therefore preferably
For 5~300nm, more preferably 10~150nm.
In addition, can also be arranged will be formed with photonasty side chain type height after process [I] and before subsequent processing [II]
The process that the substrate of molecular film is cooled to room temperature.
In process [II], polarized UV rays are irradiated to photonasty side chain type polymeric membrane obtained in process [I].To sense
When the film surface of photosensitiveness side chain type polymeric membrane irradiates polarized UV rays, from specific direction across polarization plates to substrate irradiation polarization
Ultraviolet light.As ultraviolet light to be used, the ultraviolet light that wavelength is 200~400nm range can be used.Preferably, according to
The type of photonasty side chain type polymeric membrane to be used selects optimal wavelength by filter etc..Also, it such as can select
The ultraviolet light using wavelength for 290~400nm range is selected, so as to selectively induce photo-crosslinking.As ultraviolet light,
The light issued by high-pressure sodium lamp can be used for example.
For the exposure of polarized UV rays, it is preferably set to realize maximum value (the hereinafter also referred to Δ Amax of Δ A.) it is inclined
In the range of the 1%~70% of the amount of vibration ultraviolet light, more preferably it is set as in the range of 1~50%, the sense that the Δ A is used to
The ultraviolet absorbance in photosensitiveness side chain type polymeric membrane, the polarization direction that is parallel to polarized UV rays direction with perpendicular to inclined
The difference of the ultraviolet absorbance in the direction of the polarization direction of vibration ultraviolet light.
In process [III], the side chain type polymeric membrane of polarized UV rays has been irradiated in heating in process [II].Heating uses
The heating meanss such as hot plate, thermal cycle type baking oven or IR (infrared ray) type baking oven.For heating temperature, it may be considered that make side chain used
Type polymeric membrane shows the temperature of liquid crystal liquid crystal property and determination.In addition, the power that molecular separating force is acted on is small usually on the surface of film,
Therefore predictable: the Tg (glass transition temperature) on surface is lower than whole Tg, in other words, in the liquid crystal of liquid crystal aligning film surface
In temperature range, lower than whole liquid crystal temperature range.That is, the heating temperature after irradiation polarized UV rays preferably will be than used
Side chain type polymeric membrane shows low 10 DEG C of the temperature of lower limit of the liquid crystal temperature range of liquid crystal liquid crystal property as lower limit and will compare liquid crystal
The temperature of range of low 10 DEG C of the temperature of the upper limit of temperature range as the upper limit.
By having an above process, in the present invention, realization efficiently imported into photonasty side chain type polymeric membrane it is each to
It is anisotropic.Further, it is possible to efficiently manufacture the substrate with liquid crystal orientation film used in the manufacturing method of the present invention.
In process [IV], ultraviolet light further is irradiated to side chain type polymeric membrane obtained in process [III].The process can
With process [III] just after ultraviolet light directly is irradiated to the aforementioned side chain type polymeric membrane on substrate, thereafter, can also be
It indicates to irradiate ultraviolet light in the process of element using the substrate manufacture liquid crystal with aforementioned side chain type polymeric membrane, can also make
After liquid crystal indicates element, element, which irradiates ultraviolet light, to be indicated to gained liquid crystal.It operates, can be taken with high efficiency imparting in this way
In the case where control ability, make unreacted photonasty group that delustring occur, therefore liquid crystal excellent in reliability can be manufactured
Indicate element.It should be noted that the liquid crystal temperature range in the present invention, which refers to, measures the value found out using differential scanning calorimetry.
< photosensitive composite >
Photosensitive composite used in the manufacturing method of the present invention includes the photonasty side chain that can show liquid crystal liquid crystal property
Type macromolecule includes the photonasty side chain type macromolecule that liquid crystal liquid crystal property is shown in specific range of temperatures.Also, main chain is bonded with
Have photosensitive side chain, light can be incuded and crosslink reaction, isomerization reaction or light fries' rearrangement.With photonasty
The structure of side chain be not particularly limited, be contemplated to be induction light and crosslink the structure of reaction or light fries' rearrangement, the more phase
Prestige is to crosslink the structure of reaction.At this point, can also keep having realized steadily in the long term if exposed to external stresses such as heat
Tropism control ability.
The structure that can show the photonasty side chain type polymeric membrane of liquid crystal liquid crystal property is no special as long as meeting this characteristic
It does not limit, preferably side-chain structure has upright and outspoken mesogen (mesogen) ingredient.At this point, the side chain type polymeric membrane is made
When liquid crystal orientation film, stable liquid crystal aligning can be obtained.The high molecular structure of the side chain type can for example be made such as flowering structure:
With main chain and the side chain for being bonded to it, which has xenyl, terphenyl, phenylcyclohexyl, phenylamino benzoic acid ester group, idol
It the liquid crystal such as pyridyl ultimate constituent and is bonded to the induction light of front end and crosslinks the photonasty base of reaction, isomerization reaction
Group.Furthermore it is possible to be made such as flowering structure: with main chain and be bonded to its side chain, the side chain have both for liquid crystal ultimate constituent or
The phenylamino benzoic acid ester group of light Fries rearrangement can occur.
More specific example as the high molecular structure of photonasty side chain type that can show liquid crystal liquid crystal property, it is however preferred to have main
The structure of chain and photonasty side chain, the main chain is by being selected from hydrocarbon, acrylate, methacrylate, maleimide, norborneol
At least one kind of composition in the group of alkene and siloxanes composition, the photonasty side chain include selected from following formula (1)~(13) composition
It is at least one kind of in group.
Wherein, A, B, D separately indicate singly-bound ,-O- ,-CH2-、-COO-、-OCO-、-CONH-、-NH-CO-。A’、
B ' separately indicates singly-bound ,-O- ,-CH2,-COO- ,-OCO- ,-CONH- ,-NH-CO- ,-CH=CH-CO-O- or-O-
CO-CH=CH-.Y1For selected from 1 valence phenyl ring, naphthalene nucleus, cyclohexyl biphenyl, furan nucleus, pyrrole ring, carbon number 5~8 cyclic hydrocarbon and they
Combination in group, be bonded to their hydrogen atom optionally separately by-NO2,-CN ,-CH=C (CN)2,-CH=CH-
CN, the alkyl of halogen group or carbon number 1~4 or alkoxy replace.X indicates singly-bound ,-COO- ,-OCO- ,-N=N- ,-CH=
CH- ,-C ≡ C-, l indicate that 1~12 integer, m indicate 0~2 integer, and m1, m2 separately indicate 1~3 integer, n table
Show 0~12 integer (wherein, when n=0, B is singly-bound).Y2For the phenyl ring selected from divalent, naphthalene nucleus, cyclohexyl biphenyl, furan nucleus, pyrroles
Ring, carbon number 5~8 cyclic hydrocarbon and their combination in group, be bonded to their hydrogen atom optionally separately by-
NO2,-CN ,-CH=C (CN)2,-CH=CH-CN, halogen group, alkyl or alkoxy replace.R indicates OH, NH2, carbon number 1~6
Alkoxy or carbon number 1~6 alkyl amino.R1Indicate hydrogen atom ,-NO2,-CN ,-CH=C (CN)2,-CH=CH-CN, halogen
The alkyl or alkoxy of group or carbon number 1~12.One or more phenyl ring in formula (1)~(13), which are optionally substituted by, to be selected from
Identical or different ring in naphthalene nucleus, anthracene nucleus and fluorenes ring.
Side chain shown in above-mentioned formula (1)~(13) has as liquid crystal ultimate constituent and has xenyl, terphenyl, phenyl
The structure of the groups such as cyclohexyl, phenol benzoate, azobenzene, naphthalene, anthracene, fluorenes.Also, have at least either among following:
Its front end has induction light and the photonasty group of dimerization reaction, progress cross-linking reaction occurs；Alternatively, having main chain and bonding
In its side chain, it is both liquid crystal ultimate constituent or the phenylamino benzoic acid ester group for carrying out light Fries rearrangement which, which has,.
In the manufacturing method of the present invention, photonasty side chain type polymeric membrane is formed on substrate using photosensitive composite
Afterwards, polarized UV rays are irradiated.Then, it is realized and being heated and efficient anisotropy is imported to side chain type polymeric membrane,
Manufacture band has the substrate of the liquid crystal orientation film of liquid crystal aligning control ability.It is anti-using the light of side chain in side chain type polymeric membrane
The principle for the Molecular reorientation that should be induced with the self assembly based on liquid crystal liquid crystal property is realized and is imported efficiently to side chain type polymeric membrane
Anisotropy.In the present invention, when side chain type macromolecule has structure of the photocrosslinking reaction group as photonasty group, use feeling
After photosensitiveness side chain type macromolecule forms photonasty side chain type polymeric membrane on substrate, polarized UV rays are irradiated, are then added
After heat, production liquid crystal indicates element.
Hereinafter, having photocrosslinking reaction group as the side chain type of the structure of photonasty group the high molecular 1st for using
Mode uses the group with light fries' rearrangement group or progress isomerization high as the side chain type of the structure of photonasty group
2nd mode of molecule is illustrated.
Fig. 1 shows illustrate schematically that use with photocrosslinking reaction group in the 1st mode of the invention as photonasty base
Anisotropy in the manufacturing method of the high molecular liquid crystal orientation film of side chain type of the structure of group imports an example of processing.Especially
When the anisotropy imported is smaller, i.e., in the 1st mode of the invention, the ultraviolet irradiation amount of process [II] reaches Δ A
The schematic diagram of the case where in the range of to the 1~15% of maximum ultraviolet irradiation amount.
(a) of Fig. 1 is the figure of the state of the side chain type polymeric membrane 1 before schematically illustrating polarizing light irradiation, has side chain 2
The structure of random alignment.With the random alignment of the side chain 2, the liquid crystal ultimate constituent and photonasty group of side chain 2 also random orientation,
The side chain type polymeric membrane 1 is isotropic.
(b) of Fig. 1 is the figure of the state of the side chain type polymeric membrane 1 after schematically illustrating polarizing light irradiation, along parallel
The photonasty group priorities of the side chain 2a with photonasty group among the side chain 2 that the direction of ultraviolet linear polarization arranges
The light reactions such as dimerization reaction occur.As a result, the density that the side chain 2a of light reaction occurs is omited in the polarization direction of irradiation ultraviolet light
It is slightly variable height, as a result, assigning very small anisotropy to side chain type polymeric membrane 1.
(c) of Fig. 1 is the figure for schematically illustrating the state of the side chain type polymeric membrane 1 after heating, side chain type polymeric membrane 1
In, be parallel to irradiation ultraviolet light polarization direction direction and perpendicular to irradiation ultraviolet light polarization direction direction between,
The amount of generated cross-linking reaction is different.At this point, the cross-linking reaction that the direction for being parallel to the polarization direction of irradiation ultraviolet light generates
Amount is very small, therefore plasticizer is played the role of at the cross-linking reaction position.Therefore, perpendicular to the polarization direction of irradiation ultraviolet light
The liquid crystal liquid crystal property in direction is higher than the liquid crystal liquid crystal property of parallel direction, and self assembly occurs in the direction for the polarization direction for being parallel to irradiation ultraviolet light
Change, the side chain 2 comprising liquid crystal ultimate constituent carries out reorientation.As a result, the side chain type polymeric membrane 1 induced by photo-crosslinking
Very small anisotropy amplify because of heat, assign bigger anisotropy to side chain type polymeric membrane 1.
Fig. 2, which is illustrated schematically that, to be used with photocrosslinking reaction group in the 1st mode of the invention as photonasty base
Anisotropy in the manufacturing method of the high molecular liquid crystal orientation film of side chain type of the structure of group imports an example of processing.Especially
When the anisotropy imported is larger, i.e., in the 1st mode of the invention, the ultraviolet irradiation amount of process [II] reaches Δ A
The schematic diagram of the case where in the range of to the 15~70% of maximum ultraviolet irradiation amount.
(a) of Fig. 2 is the figure of the state of the side chain type polymeric membrane 3 before schematically illustrating polarizing light irradiation, has side chain 4
The structure of random alignment.With the random alignment of the side chain 4, the liquid crystal ultimate constituent and photonasty group of side chain 4 also random orientation,
The side chain type polymeric membrane 3 is isotropic.
(b) of Fig. 2 is the figure of the state of the side chain type polymeric membrane 3 after schematically illustrating polarizing light irradiation, along parallel
The photonasty group priorities of the side chain 4a with photonasty group among the side chain 4 that the direction of ultraviolet linear polarization arranges
The light reactions such as dimerization reaction occur.As a result, the density that the side chain 4a of light reaction occurs becomes in the polarization direction of irradiation ultraviolet light
Height, as a result, assigning lesser anisotropy to side chain type polymeric membrane 3.
(c) of Fig. 2 is the figure for schematically illustrating the state of the side chain type polymeric membrane 3 after heating, side chain type polymeric membrane 3
In, be parallel to irradiation ultraviolet light polarization direction direction and perpendicular to irradiation ultraviolet light polarization direction direction between,
The amount of generated cross-linking reaction is different.Therefore, self assembly, packet occur for the direction for being parallel to the polarization direction of irradiation ultraviolet light
The side chain 4 of the ultimate constituent containing liquid crystal carries out reorientation.As a result, the side chain type polymeric membrane 3 induced by photo-crosslinking compared with
Small anisotropy is amplified because of heat, and bigger anisotropy is assigned to side chain type polymeric membrane 3.
Fig. 3 is illustrated schematically that in the 2nd mode of the invention using not sharp with light shown in above-mentioned formula (5) or (7)
This resets group as each to different in the manufacturing method of the high molecular liquid crystal orientation film of side chain type of the structure of photonasty group
Property import processing an example figure.Especially, when the anisotropy imported is smaller, i.e., in the 2nd mode of the invention,
The case where ultraviolet irradiation amount of process [II] is in the range of making Δ A reach the 1~15% of maximum ultraviolet irradiation amount
Schematic diagram.
(a) of Fig. 3 is the figure of the state of the side chain type polymeric membrane 5 before schematically illustrating polarizing light irradiation, has side chain 6
The structure of random alignment.With the random alignment of the side chain 6, the liquid crystal ultimate constituent and photonasty group of side chain 6 are also randomly taken
To the side chain type polymeric membrane 5 is isotropic.
(b) of Fig. 3 is the figure of the state of the side chain type polymeric membrane 5 after schematically illustrating polarizing light irradiation, along parallel
The photonasty group priorities of the side chain 6a with photonasty group among the side chain 6 that the direction of ultraviolet linear polarization arranges
The light reactions such as light fries' rearrangement occur.As a result, the density of the side chain 6a of light reaction occurs in the polarization side of irradiation ultraviolet light
To slightly getting higher, as a result, assigning very small anisotropy to side chain type polymeric membrane 5.
(c) of Fig. 3 is the figure for schematically illustrating the state of the side chain type polymeric membrane 5 after heating, side chain type polymeric membrane 5
In, be parallel to irradiation ultraviolet light polarization direction direction and perpendicular to irradiation ultraviolet light polarization direction direction between,
The amount of generated light Fries rearrangement is different.At this point, generated perpendicular to the direction of the polarization direction of irradiation ultraviolet light
The liquid crystal aligning power of light fries' rearrangement body is stronger than the liquid crystal aligning power of the side chain before reaction, therefore perpendicular to irradiation ultraviolet light
Self assembly occurs for the direction of polarization direction, and the side chain 6 comprising liquid crystal ultimate constituent carries out reorientation.As a result, because of light fries
Rearrangement reaction and the very small anisotropy of side chain type polymeric membrane 5 induced are amplified because of heat, to side chain type polymeric membrane 5
Assign bigger anisotropy.
Fig. 4 is illustrated schematically that in the 2nd mode of the invention using not sharp with light shown in above-mentioned formula (6) or (8)
This resets group as each to different in the manufacturing method of the high molecular liquid crystal orientation film of side chain type of the structure of photonasty group
Property import processing an example figure.Especially, when the anisotropy imported is larger, i.e., in the 2nd mode of the invention,
The case where ultraviolet irradiation amount of process [II] is in the range of making Δ A reach the 15%~70% of maximum ultraviolet irradiation amount
Schematic diagram.
(a) of Fig. 4 is the figure of the state of the side chain type polymeric membrane 7 before schematically illustrating polarizing light irradiation, has side chain 8
The structure of random alignment.With the random alignment of the side chain 8, the liquid crystal ultimate constituent and photonasty group of side chain 8 are also randomly taken
To the side chain type polymeric membrane 7 is isotropic.
(b) of Fig. 4 is the figure of the state of the side chain type polymeric membrane 7 after schematically illustrating polarizing light irradiation, along parallel
The photonasty group priorities of the side chain 8a with photonasty group among the side chain 8 that the direction of ultraviolet linear polarization arranges
The light reactions such as light fries' rearrangement occur.As a result, the density of the side chain 8a of light reaction occurs in the polarization side of irradiation ultraviolet light
To getting higher, as a result, assigning lesser anisotropy to side chain type polymeric membrane 7.
(c) of Fig. 4 is the figure for schematically illustrating the state of the side chain type polymeric membrane 7 after heating, side chain type polymeric membrane 7
In, be parallel to irradiation ultraviolet light polarization direction direction and perpendicular to irradiation ultraviolet light polarization direction direction between,
The amount of generated light Fries rearrangement is different.The anchor force of light fries' rearrangement body 8a than reset before the side chain Final 8, because
When this generates certain a certain amount of above light fries' rearrangement body, the direction for being parallel to the polarization direction of irradiation ultraviolet light occurs from group
Dressization, the side chain 8 comprising liquid crystal ultimate constituent carry out reorientation.As a result, the side chain type induced by light Fries rearrangement
The lesser anisotropy of polymeric membrane 7 is amplified because of heat, and bigger anisotropy is assigned to side chain type polymeric membrane 7.
Therefore, side chain type polymeric membrane irradiates at polarized UV rays and heating side chain type polymeric membrane 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 side chain type polymeric membrane, make the irradiation for the polarized UV rays irradiated to side chain type polymeric membrane
Amount and the heating temperature of heat treatment are optimized.Thereby, it is possible to realize efficiently to side chain type polymeric membrane import it is each to
It is anisotropic.
Present inventor has performed further investigations, as a result, it has been found that following opinion.That is, for being imported into side chain type polymeric membrane
Optimal polarized UV rays exposure corresponds to the photonasty made in the side chain type polymeric membrane for efficient anisotropy
The amount that photo-crosslinking, photoisomerization reaction or light Fries rearrangement occur for group reaches optimal polarized UV rays irradiation
Amount.To side chain type polymeric membrane irradiation polarized UV rays as a result, carrying out photo-crosslinking, photoisomerization reaction or light fries
When the photonasty group of the side chain of rearrangement reaction is few, sufficient light reaction amount is not achieved.At this point, even if being heated behind
Sufficient self assembly is not will do it.On the other hand, for side chain type polymeric membrane, to the knot with photocrosslinking reaction group
Structure irradiate polarized UV rays as a result, cross-linking reaction when carrying out the photonasty group excess of the side chain of cross-linking reaction, between side chain
It can excessively promote.At this point, gained side chain type polymeric membrane becomes upright and outspoken, the self assembly by heating thereafter is interfered sometimes
It promotes.In addition, for side chain type polymeric membrane, to the structured illumination polarized UV rays with light fries' rearrangement group
As a result, when the photonasty group of the side chain of progress light Fries rearrangement becomes excessive, the liquid crystal liquid crystal property of side chain type polymeric membrane
It can excessively reduce.At this point, the liquid crystal liquid crystal property of gained side chain type polymeric membrane also reduces, interfere sometimes thereafter by heating from group
The propulsion of dressization.When in turn, to the structured illumination polarized UV rays with light fries' rearrangement group, ultraviolet irradiation amount mistake
When more, photodegradation occurs for side chain type macromolecule, interferes the propulsion of the self assembly by heating thereafter sometimes.
Therefore, in side chain type polymeric membrane, light friendship occurs because of the irradiation of polarized UV rays for the photonasty group of side chain
The optimised quantity of connection reaction, photoisomerization reaction or light Fries rearrangement is preferably set to possessed by the side chain type polymeric membrane
0.1 mole of %~40 mole % of photonasty group, more preferably it is set as 0.1 mole of %~20 mole %.By keeping progress light anti-
The photonasty group amount for the side chain answered is this range, and the self assemblyization in heat treatment thereafter can be promoted efficiently, being capable of shape
Efficient anisotropy in film forming.
In side chain type polymeric membrane, by the optimization of the ultraviolet irradiation amount polarized, make side chain type high score
Photo-crosslinking, photoisomerization reaction or the amount realization of light Fries rearrangement of photonasty group in the side chain of sub- film are most
Goodization.Also, it is realized together with heat treatment thereafter and expeditiously imports anisotropy into side chain type polymeric membrane.This
When, for suitable polarized UV rays amount, can be evaluated based on the UV absorption of side chain type polymeric membrane to carry out.
That is, be directed to side chain type polymeric membrane, respectively measure it is after polarized UV rays irradiation, be parallel to polarized UV rays
The ultraviolet radiation absorption in the direction of polarization direction and perpendicular to polarized UV rays polarization direction direction ultraviolet radiation absorption.By purple
The measurement result of outer absorption evaluates Δ A, and the Δ A is the polarization side for being parallel to polarized UV rays in the side chain type polymeric membrane
To direction ultraviolet absorbance and perpendicular to polarized UV rays polarization direction direction ultraviolet absorbance difference.And
And it finds out the maximum value (Δ Amax) of the Δ A realized in side chain type polymeric membrane and realizes the exposure of its polarized UV rays.
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 the exposure for the polarized UV rays irradiated to side chain type polymeric membrane is set as
In the range of realizing the 1%~70% of the amount of the polarized UV rays of Δ Amax, more preferably it is set as in the range of 1%~50%.
In side chain type polymeric membrane, the polarized UV rays in the range of the 1%~50% of the polarized UV rays amount of Δ Amax can be realized
Exposure be equivalent to and send out 0.1 mole of %~20 mole % of the entirety of photonasty group possessed by the side chain type polymeric membrane
The amount of the polarized UV rays of third contact of a total solar or lunar eclipse cross-linking reaction.
Then, in the manufacturing method of the present invention, heated after irradiating polarized UV rays to side chain type polymeric membrane.It should
Side chain type polymeric membrane is the polymeric membrane that liquid crystal liquid crystal property can be shown within the scope of specific temperature.After polarized UV rays irradiation
Heat treatment side chain type polymeric membrane can be shown to the temperature of liquid crystal liquid crystal property determined as benchmark.In addition, predictable: side
The surface exhibits of chain polymeric membrane go out the temperature of liquid crystal liquid crystal property lower than the temperature to show liquid crystal liquid crystal property when whole observation.That is, partially
Heating temperature after vibration ultraviolet light irradiation is preferably that temperature is (following than the temperature range that side chain type polymeric membrane shows liquid crystal liquid crystal property
Also referred to as liquid crystal temperature range.) low 10 DEG C~temperature 10 DEG C of range lower than the upper limit of the liquid crystal temperature range temperature.
Side chain type polymeric membrane used in the present invention is heated after irradiating polarized UV rays and mesomorphic state is presented,
Self assembly is carried out along the direction for being parallel to polarization direction and reorientation occurs.As a result, by photo-crosslinking, photoisomerization
The small anisotropy for the side chain type polymeric membrane that reaction and light Fries rearrangement induce is amplified because of heat.But even if
In the case that mesomorphic state is presented because of heating in side chain type polymeric membrane, if heating temperature is low, the side chain type of mesomorphic state is high
The viscosity of molecular film is high, is difficult to generate reorientation because of self assembly.For example, heating temperature is the liquid than side chain type polymeric membrane
When low 10 DEG C of the lower limit of brilliant temperature range or more of temperature, anisotropic effect is increased not by heat in side chain type polymeric membrane
Sufficiently.
In addition, even if mesomorphic state is presented because of heating for side chain type polymeric membrane, if heating temperature is high, side chain type high score
The state of sub- film is close to isotropic liquid condition, it is difficult to carry out reorientation along single direction due to self assembly.For example,
When heating temperature is above the temperature of 10 DEG C of temperature lower than the upper limit of the liquid crystal temperature range of side chain type polymeric membrane, side chain type
It is insufficient by the anisotropic effect of heat increase in polymeric membrane.
As a result, in the present invention, anisotropy is efficiently imported into side chain type polymeric membrane in order to realize, by the side chain type
The liquid crystal temperature range of polymeric membrane determines suitable heating temperature as benchmark.Also, as described above, polarized UV rays are shone
Heating temperature after penetrating is set as: using low 10 DEG C of the temperature of the liquid crystal temperature range lower limit than the side chain type polymeric membrane as under
It limits and using 10 DEG C of temperature lower than the liquid crystal temperature range upper limit as the temperature in the range of the upper limit.Thus, for example side chain type is high
When the liquid crystal temperature range of molecular film is 100~200 DEG C, it is expected that the heating temperature after polarized UV rays are irradiated be set as 90~
190℃.By so operating, bigger anisotropy is assigned to side chain type polymeric membrane.It operates in this way, gained liquid crystal watch
Show that element shows high reliability relative to external stresses such as light, heat.
Photosensitive composite used in the present invention contain react because of the light of the wave-length coverage of 250~400nm and
The side chain type macromolecule of liquid crystal liquid crystal property is shown in 100~250 DEG C certain temperature range.Ingredient as photosensitive composite it is poly-
Closing object preferably has the photonasty group to react under the light of the wave-length coverage of 250~400nm.As photosensitive composite
Ingredient polymer in order to show liquid crystal liquid crystal property in 100~250 DEG C certain temperature range and it is preferred that having mesogenic group.
The photonasty side chain type macromolecule that can show above-mentioned liquid crystal liquid crystal property can be by making have above-mentioned photonasty group
Photonasty side chain monomer and/or liquid crystal liquid crystal property side chain monomer polymerize to obtain.
[photonasty side chain monomer]
There is when photonasty side chain monomer refers to form polymer at high molecular side chain position the monomer of photonasty group.
As photonasty group possessed by side chain, preferably following structures or derivatives thereof.
More specific example as photonasty side chain monomer, it is however preferred to have the structure of main chain and photonasty side chain, the master
Chain by least one kind of composition in the group that forms selected from hydrocarbon, (methyl) acrylate, maleimide, norbornene and siloxanes,
The photonasty side chain includes at least one kind of in the group selected from following formula (1)~(13) composition.
In above-mentioned formula (1)~(13), A, B, D separately indicate singly-bound ,-O- ,-CH2-、-COO-、-OCO-、-
CONH-,-NH-CO-.A ', B ' separately indicate singly-bound ,-O- ,-CH2-、-COO-、-OCO-、-CONH-、-NH-CO-、-
CH=CH-CO-O- or-O-CO-CH=CH-.Y1For phenyl ring, naphthalene nucleus, cyclohexyl biphenyl, furan nucleus, pyrrole ring, carbon number 5 selected from 1 valence
Group in~8 cyclic hydrocarbon and their combination is bonded to their hydrogen atom optionally separately by-NO2、-CN、-
CH=C (CN)2,-CH=CH-CN, halogen group, alkyl or alkoxy replace.X indicates singly-bound ,-COO- ,-OCO- ,-N=
N- ,-CH=CH- ,-C ≡ C-, l indicate that 1~12 integer, m indicate 0~2 integer, and m1, m2 separately indicate 1~3
Integer, n indicate 0~12 integer (wherein, when n=0, B is singly-bound).Y2For phenyl ring, naphthalene nucleus, cyclohexyl biphenyl, furans selected from divalent
Ring, pyrrole ring, carbon number 5~8 cyclic hydrocarbon and their combination in group, be bonded to their hydrogen atom optionally independently
Ground is by-NO2,-CN ,-CH=C (CN)2,-CH=CH-CN, halogen group, alkyl or alkoxy replace.R expression-OH ,-NH2, carbon
The alkoxy of number 1~6 or the alkyl amino of carbon number 1~6.R1Indicate hydrogen atom ,-NO2,-CN ,-CH=C (CN)2,-CH=CH-
CN, halogen group, alkyl or alkoxy.One or more phenyl ring in formula (1)~(8) are optionally substituted by selected from naphthalene nucleus, anthracene nucleus
With the identical or different ring in fluorenes ring.
[liquid crystal liquid crystal property side chain monomer]
Liquid crystal liquid crystal property side chain monomer refers to that polymer shows liquid crystal liquid crystal property, high molecular side chain position has mesogenic group
Monomer.As mesogenic group possessed by side chain, can be biphenyl, phenol benzoate etc. individually becomes liquid crystal original structure,
Mesogen structure can be become by forming hydrogen bond between side chain as benzoic acid etc..As liquid crystal possessed by side chain
Former base group, preferably following structures.
In turn, as the more specific example of liquid crystal liquid crystal property side chain monomer, it is however preferred to have the structure of main chain and liquid crystal liquid crystal property side chain, institute
Main chain is stated by least one kind of in the group that hydrocarbon, (methyl) acrylate, maleimide, norbornene and siloxanes form
It constitutes, the liquid crystal liquid crystal property side chain includes at least one kind of in the group that following formula (5)~(8) and (14)~(22) form.
(wherein, A, B separately indicate singly-bound ,-O- ,-CH2-、-COO-、-OCO-、-CONH-、-NH-CO-。A’、
B ' separately indicates singly-bound ,-O- ,-CH2,-COO- ,-OCO- ,-CONH- ,-NH-CO- ,-CH=CH-CO-O- or-O-
CO-CH=CH-.Y1For selected from 1 valence phenyl ring, naphthalene nucleus, cyclohexyl biphenyl, furan nucleus, pyrrole ring, carbon number 5~8 cyclic hydrocarbon and they
Combination in group, be bonded to their hydrogen atom optionally separately by-NO2,-CN ,-CH=C (CN)2,-CH=CH-
CN, halogen group, alkyl or alkoxy replace.R1Indicate hydrogen atom ,-NO2,-CN ,-CH=C (CN)2,-CH=CH-CN, halogen
Group, alkyl or alkoxy, Z1And Z2Separately expression-CO- ,-CH2O- ,-CH=N- ,-CF2-。R2Expression hydrogen atom ,-
NO2,-CN ,-CH=C (CN)2,-CH=CH-CN, halogen group, the alkyl of carbon number 1~12 or carbon number 1~12 alkoxy.L table
Show that 1~12 integer, m indicate 0~2 integer, m1, m2 separately indicate 1~3 integer.1 in formula (5)~(13)
A or multiple phenyl ring are optionally substituted by the identical or different ring in naphthalene nucleus, anthracene nucleus and fluorenes ring.)
[liquid crystal liquid crystal property side chain type macromolecule]
The ingredient of photosensitive composite used in the present invention, that is, side chain type macromolecule can show liquid crystal by above-mentioned
The polymerization reaction of the photonasty side chain monomer of property obtains.Furthermore it is possible to pass through the photonasty side chain monomer for not showing liquid crystal liquid crystal property
Copolymerization with liquid crystal liquid crystal property side chain monomer, the copolymerization of the photonasty side chain monomer for showing liquid crystal liquid crystal property and liquid crystal liquid crystal property side chain monomer obtain
?.In addition, can be copolymerized with other monomers in the range of not damaging the ability of expression liquid crystal liquid crystal property.
As other monomers, such as the list that can industrially obtain and can occur Raolical polymerizable can be enumerated
Body.As the concrete example of other monomers, can enumerate unsaturated carboxylic acid, acrylate compounds, methacrylate compound,
Maleimide compound, acrylonitrile, maleic anhydride, distyryl compound, 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-
Buddha's warrior attendant alkyl ester, acrylic acid 2- propyl -2- Buddha's warrior attendant alkyl ester, acrylic acid 8- methyl -8- tricyclodecyl, acrylic acid 8- ethyl -8- tricyclic
Last of the ten Heavenly stems ester 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 alkyl ester, methacrylic acid 2- propyl -2- Buddha's warrior attendant alkyl ester, methacrylic acid 8- methyl -8- tricyclodecyl, methacrylic acid 8- second
Base -8- tricyclodecyl etc..Also (methyl) glycidyl acrylate, (3- methyl -3- oxetanylmethoxy) methyl (first can be used
Base) (methyl) propylene with cyclic ether group such as acrylate, (3- ethyl -3- oxetanylmethoxy) methyl (methyl) acrylate
Ester compound.
As vinyl compound, such as vinyl ethers, methyl vinyl ether, benzyl vinyl ether, 2- hydroxyl can be enumerated
Base ethyl vinyl ether, Vinyl phenyl ether, propyl vinyl ether etc..
As distyryl compound, such as styrene, methyl styrene, chlorostyrene, bromstyrol can be enumerated etc..
As maleimide compound, such as maleimide, N- methylmaleimido, N- phenyl horse can be enumerated
Come acid imide, N- N-cyclohexylmaleimide etc..
The high molecular manufacturing method of photonasty side chain type in the present invention is not particularly limited, and can use industrial use
Universal method.Specifically, liquid crystal liquid crystal property side chain monomer, the cation using vinyl of photonasty side chain monomer can be passed through
Polymerization, free radical polymerization, anionic polymerisation manufacture.It is especially excellent from the viewpoint of reaction controlling easness etc. among these
It is selected as 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, for example, can enumerate peroxidating ketone (methyl ethyl ketone peroxide, Cyclohexanone peroxides etc.),
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, 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 starts the compound of free radical polymerization because of light irradiation, just do not limit especially
It is fixed.As this radical photopolymerization initiator, benzophenone, Michler's keton, 4,4 '-bis- (lignocaine) hexichol first can be enumerated
Ketone, xanthone, thio xanthone, isopropyl xanthone, 2,4- diethyl sulfide are for xanthone, 2- ethyl hydrazine, benzene
It is ethyl ketone, 2- hydroxy-2-methyl propiophenone, 2- hydroxy-2-methyl -4 '-cumene acetone, 1- hydroxycyclohexylphenylketone, different
Propyl benzoin ether, isobutyl benzoin ether, 2,2- diethoxy acetophenone, 2,2- dimethoxy -2- phenyl acetophenone, camphor
Quinone, benzanthrone, 2- methyl-1-[4- (methyl mercapto) phenyl]-2- morpholino propyl- 1- ketone, 2- benzyl-2- dimethylamino-1- (4-
Morphlinophenyl) -1- butanone, 4- dimethyl ethyl aminobenzoate, 4- dimethylaminobenzoic acid isopentyl ester, 4,4 '-two (tert-butyls
Peroxy carbonyl) benzophenone, 3,4,4 '-three (t-butylperoxycarbonyl) benzophenone, 2,4,6- trimethylbenzoyl
Diphenyl phosphine oxide, bis- (trichloromethyl) s-triazine of 2- (4 '-methoxyl-styrene) -4,6-, 2- (3 ', 4 '-dimethoxy benzenes
Vinyl) bis- (trichloromethyl) s-triazine of -4,6-, 2- (2 ', 4 '-dimethoxy-styryl) -4,6- bis- (trichloromethyls) be equal
Triazine, bis- (trichloromethyl) s-triazine of 2- (2 '-methoxyl-styrene) -4,6-, 2- (4 '-amyl phenyl ether vinyl) -4,6-
Bis- (trichloromethyl) s-triazine, 4- [p- N, N- bis- (ethoxy carbonyl methyl)] -2,6- two (trichloromethyl) s-triazine, 1,3-
Bis- (trichloromethyl) -5- (2 '-chlorphenyl) s-triazine, bis- (trichloromethyl) -5- (4 '-methoxyphenyl) s-triazine, 2- of 1,3-
(to dimethylaminostyryl) benzoxazoles, 2- (to dimethylaminostyryl) benzothiazole, 2-mercaptobenzothiazole, 3,
It is 3 '-carbonyls bis- (7- lignocaine cumarins), -4,4 ', 5,5 '-tetraphenyl -1,2 ' of 2- (Chloro-O-Phenyl)-bisglyoxaline, 2,2 '-bis-
(2- chlorphenyl) -4,4 ', 5,5 '-four (4- carboethoxyphenyl) -1,2 '-bisglyoxalines, 2,2 '-bis- (2,4 dichloro benzene bases) -
4,4 ', 5,5 '-tetraphenyls -1,2 '-bisglyoxaline, 2,2 ' bis- (2,4- dibromo phenyl) -4,4 ', 5,5 '-tetraphenyl -1,2 '-connection miaows
Azoles, 2,2 '-bis- (2,4,6- trichlorophenyl) -4,4 ', 5,5 '-tetraphenyl -1,2 '-bisglyoxalines, 3- (2- methyl -2- dimethylamino
Propiono) carbazole, 3,6- bis- (2- methyl -2- morpholino propiono) -9- dodecyl carbazoles, 1- hydroxycyclohexylphenyl
Ketone, bis- (5-2,4- cyclopentadiene -1- bases)-bis- (the fluoro- 3- of 2,6- bis- (1H- pyrroles -1- base)-phenyl) titaniums, 3,3 ', 4,4 '-four
(t-butylperoxycarbonyl) benzophenone, 3,3 ', 4,4 '-four (tertiary hexyl peroxy carbonyl) benzophenone, 3,3 '-two (first
Epoxide carbonyl) -4,4 '-two (t-butylperoxycarbonyl) benzophenone, 3,4 '-two (methoxycarbonyl) -4,3 '-two (tertiary fourths
Base peroxy carbonyl) benzophenone, 4,4 '-two (methoxycarbonyl) -3,3 '-two (t-butylperoxycarbonyl) benzophenone,
2- (3- methyl -3H- benzothiazole -2- subunit) -1- naphthalene -2- base-ethyl ketone or 2- (3- methyl-1,3- benzothiazole -2
(3H)-subunit) -1- (2- benzoyl) ethyl ketone etc..These compounds can be used alone, and can also mix two or more make
With.
Radical polymerization is not particularly limited, and emulsion polymerization can be used, suspension polymerization, dispersion copolymerization method, sink
Shallow lake polymerization, mass polymerization, solution polymerization process etc..
As organic solvent used in the high molecular polymerization reaction of photonasty side chain type of liquid crystal liquid crystal property can be shown, only
If the organic solvent that macromolecule generated can dissolve just is not particularly limited.It is exemplified below out its concrete example.
It can enumerate: N,N-dimethylformamide, DMAC N,N' dimethyl acetamide, n-methyl-2-pyrrolidone, N- ethyl-
2-Pyrrolidone, N- methyl caprolactam, dimethyl sulfoxide, tetramethylurea, pyridine, dimethyl sulfone, hexamethyl sulfoxide, γ-fourth
Lactone, isopropanol, methoxy amylalcohol, cinene, ethylpentyl ketone, methyl nonyl ketone, methyl ethyl ketone, methyl isoamyl ketone,
Methyl isopropyl Ketone, methyl cellosolve, ethyl cellosolve, methylcellosolve acetate, ethyl cellosolve acetate, butyl card must
Alcohol, ethyl carbitol, ethylene glycol, ethylene glycol acetate, ethyleneglycol monopropylether, ethylene glycol monobutyl ether, propylene glycol, propylene glycol
Monoacetate, propylene glycol monomethyl ether, glycol tertiary butyl ether, dipropylene glycol monomethyl ether, diethylene glycol, diethylene glycol monoacetate,
Diethylene glycol dimethyl ether, dipropylene glycol monoacetate monomethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol
Monoacetate list ether, dipropylene glycol monopropyl ether, dipropylene glycol monoacetate list propyl ether, 3- methyl -3- methoxybutyl acetic acid
Ester, tripropylene glycol methyl ether, 3- methyl -3- methoxybutanol, diisopropyl ether, ethyl isobutyl ether, diisobutylene, pentyl acetate, fourth
Acid butyl ester, butyl ether, diisobutyl ketone, methylcyclohexene, propyl ether, two hexyl ethers, dioxanes, n-hexane, pentane, normal octane, diethyl
The positive fourth of ether, cyclohexanone, ethylene carbonate, propylene carbonate, methyl lactate, ethyl lactate, methyl acetate, ethyl acetate, acetic acid
Ester, acetic acid dihydroxypropane single-ether, methyl pyruvate, ethyl pyruvate, 3- methoxy methyl propionate, 3- ethoxy-c acid methyl second
Ester, 3- methoxypropionate, 3- ethoxy-propionic acid, 3- methoxypropionic acid, 3- methoxy propyl propyl propionate, 3- methoxypropionic acid fourth
Ester, diethylene glycol dimethyl ether, 4- hydroxy-4-methyl-2-pentanone, 3- methoxyl group-N, N- dimethylpropionamide, 3- ethyoxyl-N, N-
Dimethylpropionamide, 3- butoxy-N, N- dimethylpropionamide etc..
These organic solvents can be used alone, and can also be used in mixed way.In turn, even not dissolving high score generated
The solvent of son, as long as can also mix into above-mentioned organic solvent makes in the range of macromolecule generated will not be precipitated
With.
In addition, the oxygen in organic solvent can become the reason of hindering polymerization reaction, therefore organic molten in free radical polymerization
Agent uses after preferably deaerating as much as possible.
Polymerization temperature when free radical polymerization can select 30~150 DEG C of arbitrary temp, preferably 50~100 DEG C of model
It encloses.In addition, reaction can be carried out with any concentration, but when concentration is too low, is difficult to obtain the polymer of high molecular weight, excessive concentration
When, the viscosity of reaction solution becomes excessively high and is difficult to equably stir, therefore monomer concentration is preferably 1~50, more preferably 5~
30.Initial reaction stage is carried out with high concentration, can add organic solvent thereafter.
In above-mentioned Raolical polymerizable, when radical polymerization initiator is more relative to the ratio of monomer, gained is high
The molecular weight of molecule becomes smaller, when ratio less of the radical polymerization initiator relative to monomer, the high molecular molecule quantitative change of gained
Greatly, therefore radical initiator relative to the ratio of polymerized monomer is preferably 0.1~10 mole of %.In addition, can also be with when polymerization
Additional various monomer components, solvent, initiator etc..
[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, methyl iso-butyl ketone (MIBK),
Ethyl alcohol, toluene, benzene, diethyl ether, ethyl methyl ether, water etc..Putting into the polymer precipitated into poor solvent can filter
After recycling, air drying or heat drying are carried out under normal or reduced pressure.Precipitating is recycled in addition, repeating 2 times~10 times
Polymer be re-dissolved in organic solvent and reprecipitation recycling operation when, the impurity in polymer can be reduced.As at this time
Poor solvent, such as alcohols, ketone, hydrocarbon can be enumerated etc., when using 3 kinds or more poor solvents among these, essence
Efficiency processed further increases, so it is preferred that.
About the photonasty side chain type that can show liquid crystal liquid crystal property contained in photosensitive composite used in the present invention
High molecular molecular weight, it is contemplated that the uniformity of workability and film when gained side chain type macromolecule film strength, formation film
When, the weight average molecular weight measured using GPC (Gel Permeation Chromatography, gel permeation chromatography) method is preferred
It is 2000~1000000, more preferably 5000~100000.
[preparation of photosensitive composite]
Photosensitive composite used in the present invention passes through containing the photonasty side chain type high score that can show liquid crystal liquid crystal property
Son and constitute.Also, it is preferred that coating fluid is made in a manner of suitably forming liquid crystal orientation film.That is, used in the present invention photosensitive
Property composition is prepared preferably in the form of the resin component for being used to form resin coating is dissolved in solution made of organic solvent.
Herein, resin component refers to comprising the above-mentioned high molecular resin component of photonasty side chain type that can show liquid crystal liquid crystal property.At this point,
The content of resin component is preferably 1~20 mass % in photosensitive composite, is more preferably 3~15 mass %, is particularly preferred
For 3~10 mass %.
In above-mentioned photosensitive composite, it is the photonasty side chain that can show liquid crystal liquid crystal property that resin component, which can be all,
Type macromolecule can also mix in addition to this other poly- in the range of not damaging liquid crystal expressive ability and photonasty ability
Close object.At this point, the content of other polymer in resin component is 0.5~80 mass %, preferably 1~50 mass %.
This other polymer can for example enumerate comprising poly- (methyl) acrylate, polyamic acid, polyimides etc. and
It is not that can show high molecular polymer of photonasty side chain type of liquid crystal liquid crystal property etc..
< organic solvent >
As long as organic solvent used in photosensitive composite used in the present invention is capable of having for dissolving resin ingredient
Solvent is just not particularly limited.It is exemplified below out its concrete example.
Can enumerate: N,N-dimethylformamide, DMAC N,N' dimethyl acetamide, n-methyl-2-pyrrolidone, N- methyl oneself
Lactams, 2-Pyrrolidone, N- ethyl pyrrolidone, n-vinyl pyrrolidone, dimethyl sulfoxide, tetramethylurea, pyridine, two
Methyl sulfone, hexamethyl sulfoxide, gamma-butyrolacton, 3- methoxyl group-N, N- dimethylpropionamide, 3- ethyoxyl-N, N- dimethyl propionyl
Amine, 3- butoxy-N, N- dimethylpropionamide, 1,3- dimethyl-2-imidazolidinone, ethylpentyl ketone, methyl nonyl ketone, first and second
Ketone, methyl isoamyl ketone, methyl isopropyl Ketone, cyclohexanone, ethylene carbonate, propylene carbonate, diethylene glycol dimethyl ether, 4- hydroxyl
Base -4-methyl-2 pentanone, Propylene glycol monoacetate, propylene glycol monomethyl ether, glycol tertiary butyl ether, dipropylene glycol monomethyl ether, diethyl
Glycol, diethylene glycol monoacetate, diethylene glycol dimethyl ether, dipropylene glycol monoacetate monomethyl ether, dipropylene glycol monomethyl ether, two
Dihydroxypropane single-ether, dipropylene glycol monoacetate list ether, dipropylene glycol monopropyl ether, dipropylene glycol monoacetate list propyl ether, 3-
Methyl -3- methoxybutyl acetic acid esters, tripropylene glycol methyl ether etc..They can be used alone, and can also be used in mixed way.
Photosensitive composite used in the present invention can contain the ingredient except mentioned component.As its example, be
The solvent or compound that film thickness uniformity, surface smoothness are improved when being coated with photosensitive composite, improve liquid crystal orientation film and base
The compound etc. of the adaptation of plate.
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
Base ketone, methylcyclohexene, propyl ether, two hexyl ethers, 1- hexanol, n-hexane, pentane, normal octane, diethyl ether, methyl lactate, lactic acid
Ethyl ester, methyl acetate, ethyl acetate, n-butyl acetate, acetic acid dihydroxypropane single-ether, methyl pyruvate, ethyl pyruvate, 3- first
Oxygroup methyl propionate, 3- ethoxy-propionic acid Methylethyl, 3- methoxypropionate, 3- ethoxy-propionic acid, 3- methoxypropionic acid,
3- methoxy propyl propyl propionate, 3- methoxy propyl acid butyl ester, 1- methoxy-2-propanol, 1- ethyoxyl -2- propyl alcohol, 1- butoxy -2-
Propyl alcohol, 1- phenoxy group -2- propyl alcohol, Propylene glycol monoacetate, propylene-glycol diacetate, propylene glycol -1- monomethyl ether -2- acetic acid esters,
Propylene glycol -1- list ether -2- acetic acid esters, dipropylene glycol, 2- (2- ethoxy-c oxygroup) propyl alcohol, methyl lactate, ethyl lactate, cream
Sour 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 photosensitive composite entirety significantly reduces, preferably 5~80 mass % of solvent entirety,
More preferably 20~60 mass %.
As the compound for improving film thickness uniformity, surface smoothness, fluorine system surfactant, organic silicon-type can be enumerated
Surfactant, nonionic surfactants etc..
More specifically, such as Eftop 301, EF303, EF352 (Tohkem products can be enumerated
Corporation system)；Megafac F171, F173, R-30 (DIC CORPORATION system)；Fluorad FC430,FC431
(Sumitomo 3M Limited system)；AsahiGuard AG710 (Asahi Glass Co., Ltd's system)；Surflon S-382,
SC101, SC102, SC103, SC104, SC105, SC10 (AGC SEIMI CHEMICAL CO., LTD. system) etc..These surfaces
The use ratio of activating agent is preferably 0.01~2 mass relative to 100 mass parts of resin component contained in photosensitive composite
Part, more preferably 0.01~1 mass parts.
The concrete example of compound as the adaptation for improving liquid crystal orientation film and substrate can enumerate containing of showing as follows
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 photosensitive composite
Close the additive of object.Specific phenoplasts system additive described below, but it is not limited to the structure.
As containing the compound of epoxy group, can specifically exemplifying: ethylene glycol diglycidylether, polyethylene glycol diglycidyl
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 photosensitive composition
100 mass parts of resin component contained in object are preferably 0.1~30 mass parts, more preferably 1~20 mass parts.Dosage is insufficient
When 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 is deteriorated sometimes.
Photosensitive composite used in the present invention can also add photosensitizer.As photosensitizer, preferably colourless enhanced sensitivity
Agent and triplet sensitizer.
As the concrete example of photosensitizer, have aromatic nitro compound, cumarin (7- lignocaine -4- methylcoumarin,
Hymecromone), coumarin ketone, carbonyl bicoumarin, aromatic series 2- hydroxy-ketone and the virtue replaced by amino
(2- dihydroxy benaophenonel, single pair (dimethylamino) -2- dihydroxy benaophenonel or two are to (dimethylamino) -2- for fragrant race 2- hydroxy-ketone
Dihydroxy benaophenonel), acetophenone, anthraquinone, xanthone, thio xanthone, benzanthrone, thiazoline (2- benzoyl methylene
Base -3- methyl-β-aphthothiazoles quinoline, 2- (β-naphthoyl methylene) -3- methylbenzothiazole quinoline, 2- (α-naphthoyl methylene
Base) -3- methylbenzothiazole quinoline, 2- (4- biphenyl methylene) -3- methylbenzothiazole quinoline, 2- (β-naphthoyl methylene) -
3- methyl-β-aphthothiazoles quinoline, 2- (4- biphenyl methylene) -3- methyl-β-aphthothiazoles quinoline, 2- are (to fluorobenzoyl methylene
Base) -3- methyl-β-aphthothiazoles quinoline), oxazoline (2- phenacylidene -3- methyl-β-aphthoxazoles quinoline, 2- (β-naphthoyl
Methylene) -3- methylbenzoxazole quinoline, 2- (α-naphthoyl methylene) -3- methylbenzoxazole quinoline, (the 4- xenyl Asia 2-
Methyl) -3- methylbenzoxazole quinoline, 2- (β-naphthoyl methylene) -3- methyl-β-aphthoxazoles quinoline, 2- (4- xenyl methylene
Base) -3- methyl-β-aphthoxazoles quinoline, 2- (to fluorobenzoyl methylene) -3- methyl-β-aphthoxazoles quinoline), benzothiazole, nitre
Base aniline (meta nitro aniline or paranitroanilinum, 2,4,6- trinitroaniline) or nitro acenaphthene (5- nitro acenaphthene), (2- [(hydroxyl
To methoxyl group) styryl] benzothiazole, benzoin alkylether, N- alkylation phthalein ketone, acetophenone ketal (2,2- dimethoxy
Phenyl ethyl ketone), naphthalene, anthracene (2- naphthalene methanol, 2- naphthalene-carboxylic acid, 9- anthryl carbinol, 9- anthracene carboxylic acid), chromene, azo indolizine etc..
Preferably aromatic series 2- hydroxy-ketone (benzophenone), cumarin, coumarin ketone, carbonyl bicoumarin, acetophenone, anthracene
Quinone, xanthone, thio xanthone or acetophenone ketal.
In photosensitive composite 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
The purpose that film hardness, consistency are improved when liquid crystal orientation film is made, can add cross-linked compound.
[liquid crystal orientation film and liquid crystal indicate element]
Photosensitive composite used in the present invention is by being coated on substrate and being implemented at light orientation using light irradiation
After reason, until being heated to the temperature that liquid crystal orientation film shows liquid crystal liquid crystal property, to efficiently assign tropism control ability, and then irradiate
Ultraviolet light is so as to the state of orientation immobilization that will be obtained by heating.Like this, photosensitive composite passes through via light orientation
The process and no polarization ultraviolet irradiation of liquid crystal phase transition temperature are handled, are heated to, so as to form liquid crystal orientation film, energy
Being enough in the driving liquid crystal of manufacture transverse electric field indicates element.
After liquid crystal indicates that element photosensitive composite as used in the present invention obtains the substrate with liquid crystal orientation film, utilize
Known method makes liquid crystal cells, so that the driving liquid crystal of transverse electric field, which is made, indicates element.
If enumerating a production example of liquid crystal cells, can exemplify following method: preparation is formed with liquid crystal orientation film
A pair of of substrate, spread spacer on the liquid crystal orientation film of a substrate, by liquid crystal alignment film surface become inside in a manner of glue
The method for being affixed on another substrate, decompression injection liquid crystal and sealing；Alternatively, being added dropwise to the liquid crystal alignment film surface for being scattered with spacer
After liquid crystal, adhesive substrate and the method etc. being sealed.At this point, it is preferable to use with transverse electric field driving comb teeth for a substrate
The substrate of the electrode of shape structure.Spacer diameter at this time is preferably 1 μm~30 μm, more preferably 2 μm~10 μm.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.
Embodiment
For embodiments of the present invention, embodiment is enumerated to be described in more detail.It should be noted that the present invention not by
The limited explanation of these embodiments.
It is referred to as follows used in embodiment.
(methacrylic monomer)
(organic solvent)
THF: tetrahydrofuran
NMP:N- N-methyl-2-2-pyrrolidone N
BC: butyl cellosolve
(polymerization initiator)
AIBN:2,2 '-azobis isobutyronitrile
[measurement of phase transition temperature]
The liquid crystal phase transition temperature of the polymer obtained by embodiment using differential scanning calorimetry measurement (DSC),
DSC3100SR (マ ッ Network サ イ エ Application ス corporation) is measured.
1 > of < synthesis example
MA1 (2.33g, 7.0mmol) is dissolved in NMP (21.5g), after being de-gassed using diaphragm pump, adds AIBN
It (57.5mg, 0.35mmol) and is de-gassed again.Thereafter, it is reacted 20 hours with 65 DEG C, obtain methacrylate
Polymer solution.BC (15.9g) is added into the polymer solution and is stirred, to obtain the liquid crystal as photosensitive composite
Alignment agent (A).The number-average molecular weight of polymer in the aligning agent for liquid crystal (A) is 16000, weight average molecular weight 28000.This is poly-
The liquid crystal phase transition temperature for closing object is 145~190 DEG C.
2 > of < synthesis example
MA1 (0.47g, 1.4mmol), MA2 (1.72g, 5.6mmol) are dissolved in NMP (20.2g), diaphragm pump is utilized
After being de-gassed, adds AIBN (57.5mg, 0.35mmol) and be de-gassed again.Thereafter, react it 20 hours with 65 DEG C,
Obtain the polymer solution of methacrylate.BC (14.9g) is added into the polymer solution and is stirred, to obtain conduct
The aligning agent for liquid crystal (B) of photosensitive composite.The number-average molecular weight of polymer in the aligning agent for liquid crystal is 14000, divides equally again
Son amount is 24000.The liquid crystal phase transition temperature of the polymer is 135~180 DEG C.
1 > of < embodiment
[production of liquid crystal cells]
Using aligning agent for liquid crystal obtained in synthesis example 1 (A), the system of liquid crystal cells is carried out according to following shown steps
Make.Substrate be having a size of 30mm × 40mm, with a thickness of the glass substrate of 0.7mm, formed using configured with ito film is patterned
Comb teeth-shaped pixel electrode substrate." < " font electrode element that there is pixel electrode center portion to bend is through multiple rows
The comb teeth-shaped shape of column and composition.The width of the width direction of each electrode element is 10 μm, between electrode element between be divided into 20 μm.
It forms the multiple arrangements of electrode element of " < " font that the pixel electrode of each pixel is bent by center portion and constitutes, therefore
The shape of each pixel is not oblong-shaped, and have it is bending in the same manner as electrode element in center portion, be similar to it is thick
The shape of " < " word of body.Also, each pixel is divided up and down by boundary of the bending part in the center, upper with bending part
1st region of side and the 2nd region of downside.When comparing the 1st region and 2 region of each pixel, their pixel electrode is constituted
Electrode element formation direction it is different.That is, using the orientation process direction of aftermentioned liquid crystal orientation film as when benchmark, in pixel
In 1st region, the electrode element of pixel electrode is formed in a manner of+15 ° of angle (clockwise) is presented, in the 2nd area of pixel
In domain, the electrode element of pixel electrode is formed in a manner of -15 ° of angle (clockwise) is presented.That is, the 1st region of each pixel
Constituted as follows with the 2nd region: by between pixel electrode and counter electrode apply voltage and induce liquid crystal, in real estate
Spinning movement (plane switching) direction opposite direction each other.
Aligning agent for liquid crystal obtained in synthesis example 1 (A) is spin-coated on the above-mentioned electroded substrate prepared.Then,
With press drying 90 seconds of 70 DEG C, the photonasty side chain type polymeric membrane that film thickness is 100nm is formed.Then, across polarization plates
With 5mJ/cm2To the ultraviolet light of film surface irradiation 313nm, is heated 10 minutes with 150 DEG C of hot plates, obtain band by side chain type high score
The substrate for the liquid crystal orientation film that sub- film is formed.In addition, as opposite substrate, to not formed electrode and with 4 μm of height of column
The glass substrate of spacer similarly forms photonasty side chain type polymeric membrane, implements orientation process.In the liquid of a substrate
Printing and sealing agent (Chemical Co., Ltd. system of pulling together, XN-1500T) in brilliant alignment films.Then, with the liquid crystal alignment film surface of two substrates
After the mode that opposite and differently- oriented directivity reaches 0 ° pastes another substrate, makes sealant heat cure and make dummy cell.By subtracting
Pressure injection enters injection liquid crystal MLC-2041 (MERCK CORPORATION system) in the normal direction dummy cell, seals inlet, is had
The liquid crystal of IPS (In-Planes Switching, plane switching) mode indicates the liquid crystal cells that element is constituted.
(2 irradiation process)
After making liquid crystal cells, handled using the reorientation that 120 DEG C of baking ovens carry out 60 minutes.Thereafter, make liquid crystal list
Between the pixel electrode and counter electrode of member in the state of short circuit, with 20J/cm2Liquid crystal cells irradiation (2 irradiations) is had passed through
Ultraviolet light obtained from the bandpass filter of 365nm.After 2 irradiations, the voltage retention of liquid crystal cells is measured.In addition, carrying out
Unit observation after ghost evaluation, curing.Liquid crystal cells are carried out to curing in 336 hours in 60 DEG C of baking oven.Observation curing
It is bad etc. whether bright spot, orientation are generated in liquid crystal cells afterwards.
(measurement of voltage retention)
The measurement of the voltage retention of liquid crystal cells by by 70 DEG C at a temperature of apply the 5V voltage of 60 μ s,
Which kind of degree voltage is maintained at as voltage retention to be calculated after 1667ms.It should be noted that voltage retention
Measurement has used the VHR-1 of TOYO Corporation.
(ghost evaluation)
The IPS mode prepared in embodiment 1 is arranged in 2 configured in the vertical mode of polarization axle with liquid crystal cells partially
Between vibration plate, light backlight in the state of no applied voltage, adjust the arrangement angles of liquid crystal cells so that transmitted light brightness
Reach minimum.Then, when rotating liquid crystal cells to the most dark angle in the 1st region from the most dark angle in the 2nd region of pixel
Rotation angle as initial stage orientation angle and calculate.Then, applied 336 hours in 60 DEG C of baking oven with the frequency of 30Hz
16VPPAlternating voltage.Thereafter, make that short-circuit condition is presented between the pixel electrode of liquid crystal cells and counter electrode, directly in room
Temperature is lower to place 1 hour.After placement, similarly measure orientation angle, will exchange driving front and back orientation angle difference as
Angle delta (degree, deg.) simultaneously calculates.
(the unit observation after curing)
It is micro- by the polarised light that crossed nicols state is made in polarization plates for the liquid crystal cells after the evaluation of above-mentioned ghost
Mirror is observed.When rotating liquid crystal cells and making it that black expression state be presented, it will remember without bright spot, the undesirable state of orientation
Make good.
2 > of < embodiment
When 2 irradiation process, with 5J/cm2Irradiation (2 irradiations) has passed through purple obtained from the bandpass filter of 313nm
In addition to this outside line utilizes step production unit same as Example 1.Show the results of the evaluation table 1.
3 > of < embodiment
It operates similarly to Example 1, aligning agent for liquid crystal obtained in synthesis example 1 (A) is spun on electroded substrate.It connects
, with press drying 90 seconds of 70 DEG C, form the liquid crystal orientation film that film thickness is 100nm.Then, across polarization plates with 5mJ/
cm2To the ultraviolet light of its photonasty side chain type macromolecule film surface irradiation 313nm, heated 10 minutes with 150 DEG C of hot plates, by substrate
It is 30 minutes cooling, and then with 1J/cm2The bandpass filter of 365nm is had passed through to side chain type polymeric membrane face irradiation (2 irradiations)
Obtained from ultraviolet light, to obtain the substrate with liquid crystal orientation film.In addition, operate similarly to Example 1, by opposite substrate into
The liquid crystal that row combination obtains having IPS mode indicates the liquid crystal cells that element is constituted.Thereafter, it operates similarly to Example 1, into
The processing of row reorientation, the measurement and the unit observation after ghost evaluation, curing for carrying out voltage retention.
4 > of < embodiment
When implementing 2 irradiation process to substrate, with 500mJ/cm2Side chain type polymeric membrane face irradiation (2 irradiations) is worn
Ultraviolet light obtained from the bandpass filter of 313nm has been crossed, in addition to this, has utilized step production unit same as Example 3.
Show the results of the evaluation table 1.
5~8 > of < embodiment
Using aligning agent for liquid crystal obtained in synthesis example 2 (B), liquid crystal list is made using method identical with Examples 1 to 4
Member.Aligning agent for liquid crystal used, ultraviolet irradiation amount (1 irradiation), 2 illumination wavelengths, 2 exposures and evaluation result is total
It ties shown in table 1.
1 > of < comparative example
60 are carried out with 120 DEG C of baking ovens after making liquid crystal cells using step same as Example 1 about comparative example 1
The reorientation processing of minute, but 2 irradiation process are not carried out.For the liquid crystal cells, the measurement of voltage retention has also been carried out
With the unit observation after ghost evaluation, curing.By aligning agent for liquid crystal used, evaluation result is shown in table 1.
2 > of < comparative example
60 are carried out with 120 DEG C of baking ovens after making liquid crystal cells using step same as Example 5 about comparative example 2
The reorientation processing of minute, but 2 irradiation process are not carried out.For the liquid crystal cells, the measurement of voltage retention has also been carried out
With the unit observation after ghost evaluation, curing.By aligning agent for liquid crystal used, evaluation result is shown in table 1.
[table 1]
The liquid crystal cells of 2 irradiation process have been imported compared with the unit for not carrying out 2 irradiations according to the above results
Voltage retention shows high numerical value.This is considered because: unreacted photonasty group reduces, makes to gather by photo-crosslinking
The crosslinking closed between object promotes.
In turn, observation curing after unit as a result, carry out 2 times irradiation units show good orientation, but not into
The Comparative Examples 1 and 2 of row 2 times irradiations generates small bright spot.This is considered because: remaining unreacted photonasty group, monomer because
Thermal maturation and it is mobile or crystallize, to hinder the orientation of liquid crystal.But it can consider: residual by importing 2 irradiation process
Unreacted group, the monomer stayed is consumed, to inhibit the generation of bright spot.
Industrial availability
In accordance with the invention it is possible to obtain efficiently maintaining tropism control ability and liquid crystal expression element excellent in reliability, it should
The driving liquid crystal of transverse electric field indicates that element can be suitably employed in the various expressions such as LCD TV of big picture and high-resolution and use
On the way.
It should be noted that by Japanese patent application 2013-57047 specification, power filed on March 19th, 2013
Sharp claim, drawings and abstract all the elements quote so far, as description of the invention disclosure and introduce.
Description of symbols
1: side chain type polymeric membrane, 2,2a: side chain
3: side chain type polymeric membrane, 4,4a: side chain
5: side chain type polymeric membrane, 6,6a: side chain
7: side chain type polymeric membrane, 8,8a: side chain
Claims (11)
1. the manufacturing method that a kind of driving liquid crystal of transverse electric field indicates element, which is characterized in that successively have following preparation solution
The process of brilliant alignment films:
Process [I]: certain temperature of coating containing (A) at 100 DEG C~250 DEG C on the substrate with transverse electric field driving conductive film
The photonasty side chain type macromolecule of liquid crystal liquid crystal property and the photosensitive composite of (B) organic solvent are shown in degree range, to be formed
The process of photonasty side chain type polymeric membrane；
Process [II]: polarized UV rays are irradiated to the photonasty side chain type polymeric membrane, so that side chain type polymeric membrane be made
Process, the side chain type polymeric membrane is used to form liquid crystal orientation film；
Process [III]: the process for heating the side chain type polymeric membrane；
Process [IV]: further to the process of side chain type polymeric membrane irradiation ultraviolet light.
2. the manufacturing method according to claim 1, wherein the ultraviolet irradiation amount of process [II] reaches maximum making Δ A
Ultraviolet irradiation amount 1%~70% in the range of, the Δ A be the side chain type polymeric membrane, be parallel to it is described partially
The ultraviolet absorbance in the direction of the polarization direction of vibration ultraviolet light is purple perpendicular to the polarization with the side chain type polymeric membrane
The difference of the ultraviolet absorbance in the direction of the polarization direction of outside line.
3. manufacturing method according to claim 2, wherein the ultraviolet irradiation amount of process [II] reaches making the Δ A
In the range of the 1%~50% of maximum ultraviolet irradiation amount.
4. manufacturing method described in any one of claim 1 to 3, wherein the heating temperature of process [III] is temperature ratio
The upper limit of the low 10 DEG C~temperature of the lower limit for the temperature range that the side chain type polymeric membrane shows liquid crystal liquid crystal property than the temperature range
The temperature of low 10 DEG C of range.
5. manufacturing method described in any one of claim 1 to 3, wherein the photonasty side for showing liquid crystal liquid crystal property
The photonasty group contained in chain macromolecule is azobenzene, Stilbene, cinnamic acid, cinnamate, chalcone, cumarin, hexichol second
Alkynes, phenol benzoate, or derivatives thereof.
6. manufacturing method described in any one of claim 1 to 3, wherein the ultraviolet irradiation amount of process [IV] is to make
20 moles or more the irradiations to react in averagely 100 moles of photonasty group possessed by the side chain type polymeric membrane
Amount.
7. manufacturing method described in any one of claim 1 to 3, wherein process [IV] indicates element in production liquid crystal
After carry out.
8. manufacturing method described in any one of claim 1 to 3, which is characterized in that (A) ingredient is handed over light can occur
The side chain of connection, photoisomerization or light fries' rearrangement.
9. manufacturing method described in any one of claim 1 to 3, wherein (A) ingredient has photonasty side chain type high score
Son, the photonasty side chain type macromolecule have at least one photonasty side in the group being made of following formula (1)~(13)
Chain,
Wherein, A, B, D separately indicate singly-bound ,-O- ,-CH2,-COO- ,-OCO- ,-CONH- or-NH-CO-；A ' is indicated
Singly-bound ,-O- ,-CH2,-COO- ,-OCO- ,-CONH- ,-NH-CO- ,-CH=CH-CO-O- or-O-CO-CH=CH-；Y1For choosing
From the phenyl ring of 1 valence, naphthalene nucleus, cyclohexyl biphenyl, furan nucleus, pyrrole ring, carbon number 5~8 cyclic hydrocarbon and their combination in group, key
Together in their hydrogen atom optionally separately by-NO2,-CN ,-CH=C (CN)2,-CH=CH-CN, halogen group or
The alkyl or alkoxy of carbon number 1~4 replace；X indicates singly-bound ,-COO- ,-OCO- ,-N=N- ,-CH=CH- or-C ≡ C-；
X ' indicates singly-bound ,-COO- ,-OCO- ,-N=N- ,-CH=CH- ,-C ≡ C- ,-CH=CH-CO-O- or-O-CO-CH=
CH-, X ' number be 2 when, X ' is optionally same or different to each other；L indicates 1~12 integer；M indicates 0~2 integer；m1,m2
Separately indicate 1~3 integer；N indicates 0~12 integer, wherein when n=0, B is singly-bound；Y2For the benzene selected from divalent
Ring, naphthalene nucleus, cyclohexyl biphenyl, furan nucleus, pyrrole ring, carbon number 5~8 cyclic hydrocarbon and their combination in group, be bonded to them
Hydrogen atom optionally separately by-NO2,-CN ,-CH=C (CN)2,-CH=CH-CN, halogen group or carbon number 1~12
Alkyl or alkoxy replace；R expression-OH ,-NH2, the alkoxy of carbon number 1~6 or the alkyl amino of carbon number 1~6；R1Indicate hydrogen
Atom ,-NO2,-CN ,-CH=C (CN)2,-CH=CH-CN, halogen group or carbon number 1~12 alkyl or alkoxy；Formula
(1) one or more phenyl ring in~(8) are optionally substituted by the identical or different ring in naphthalene nucleus, anthracene nucleus and fluorenes ring.
10. manufacturing method described in any one of claim 1 to 3, wherein (A) ingredient has liquid crystal liquid crystal property side chain type high
Molecule, the liquid crystal liquid crystal property side chain type macromolecule have in the group being made of following formula (5)~(8) and (14)~(22) extremely
Few 1 liquid crystal liquid crystal property side chain,
Wherein, A, B separately indicate singly-bound ,-O- ,-CH2,-COO- ,-OCO- ,-CONH- or-NH-CO-；A ', B ' are respectively
Independently indicate singly-bound ,-O- ,-CH2,-COO- ,-OCO- ,-CONH- ,-NH-CO- ,-CH=CH-CO-O- or-O-CO-CH=
CH-；Y1For phenyl ring, naphthalene nucleus, cyclohexyl biphenyl, furan nucleus, pyrrole ring, the cyclic hydrocarbon of carbon number 5~8 and their combination selected from 1 valence
In group, be bonded to their hydrogen atom optionally separately by-NO2,-CN ,-CH=C (CN)2,-CH=CH-CN, halogen
Plain group, alkyl or alkoxy replace；R1Indicate hydrogen atom ,-NO2,-CN ,-CH=C (CN)2,-CH=CH-CN, halogen group,
Or the alkyl or alkoxy of carbon number 1~12；Z1、Z2Separately expression-CO- ,-CH2O- ,-CH=N- ,-CF2-；R2It indicates
Hydrogen atom ,-NO2,-CN ,-CH=C (CN)2,-CH=CH-CN, halogen group or carbon number 1~12 alkyl or alkoxy；l
Indicate 1~12 integer；M indicates 0~2 integer；M1, m2, m3 separately indicate 1~3 integer；Formula (5)~(8) and
(14) one or more phenyl ring in~(22) are optionally substituted by the identical or different ring in naphthalene nucleus, anthracene nucleus and fluorenes ring.
It is the system that element is indicated using liquid crystal described in any one of claim 1~10 11. a kind of liquid crystal indicates element
Make method manufacture.
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| JP2013-057047 | 2013-03-19 | ||
| JP2013057047 | 2013-03-19 | ||
| PCT/JP2014/057587 WO2014148569A1 (en) | 2013-03-19 | 2014-03-19 | Method for manufacturing in-plane-switching-type liquid-crystal display element |
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| JP6676932B2 (en) * | 2014-11-12 | 2020-04-08 | 日産化学株式会社 | Liquid crystal alignment agent, liquid crystal alignment film and liquid crystal display device |
| TWI685525B (en) * | 2014-11-12 | 2020-02-21 | 日商日產化學工業股份有限公司 | Liquid crystal alignment agent, liquid crystal alignment film and liquid crystal display element |
| KR102435082B1 (en) * | 2015-01-15 | 2022-08-22 | 닛산 가가쿠 가부시키가이샤 | Liquid crystal alignment agent using photoreactive hydrogen-bonding polymer liquid crystal, and liquid crystal alignment film |
| WO2016113931A1 (en) * | 2015-01-15 | 2016-07-21 | 日産化学工業株式会社 | Liquid crystal alignment agent using non-photoreactive hydrogen-bonding polymer liquid crystal, and liquid crystal alignment film |
| JP6925584B2 (en) * | 2015-10-07 | 2021-08-25 | 日産化学株式会社 | A composition for producing a liquid crystal alignment film, a liquid crystal alignment film using the composition and a method for producing the same, and a liquid crystal display element having the liquid crystal alignment film and a method for producing the same. |
| WO2017069133A1 (en) * | 2015-10-20 | 2017-04-27 | 日産化学工業株式会社 | Liquid crystal aligning agent, liquid crystal alignment film, and liquid crystal display element |
| CN105500857B (en) * | 2015-12-18 | 2017-12-29 | 北京大学 | A kind of optical drive composite with double membrane structure and preparation method thereof |
| KR20180094100A (en) * | 2015-12-25 | 2018-08-22 | 닛산 가가쿠 가부시키가이샤 | Liquid crystal display element, liquid crystal optical element and composition for stabilizing liquid crystal structure |
| JP6956948B2 (en) * | 2016-10-14 | 2021-11-02 | 日産化学株式会社 | Liquid crystal alignment agent, liquid crystal alignment film and liquid crystal display element |
| WO2021024581A1 (en) * | 2019-08-08 | 2021-02-11 | 株式会社ジャパンディスプレイ | Liquid crystal display device manufacturing method and liquid crystal display device |
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| JP2007304215A (en) * | 2006-05-09 | 2007-11-22 | Hayashi Telempu Co Ltd | Photo-alignment material and method for manufacturing optical element and liquid crystal alignment film |
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| JP5578079B2 (en) * | 2008-10-14 | 2014-08-27 | 日産化学工業株式会社 | Polymerizable liquid crystal compound, polymerizable liquid crystal composition and alignment film |
| KR101777880B1 (en) * | 2010-09-22 | 2017-09-12 | 제이엔씨 주식회사 | Photosensitive compound and its photosensitive polymer |
| CN107473969B (en) * | 2012-10-05 | 2020-10-16 | 日产化学工业株式会社 | Method for manufacturing substrate having liquid crystal alignment film for horizontal electric field drive type liquid crystal display element |
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| JP2007304215A (en) * | 2006-05-09 | 2007-11-22 | Hayashi Telempu Co Ltd | Photo-alignment material and method for manufacturing optical element and liquid crystal alignment film |
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| KR102258545B1 (en) | 2021-05-28 |
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