CN105339837A - Method for manufacturing in-plane-switching-type liquid-crystal display element - Google Patents

Method for manufacturing in-plane-switching-type liquid-crystal display element Download PDF

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Publication number
CN105339837A
CN105339837A CN201480029107.7A CN201480029107A CN105339837A CN 105339837 A CN105339837 A CN 105339837A CN 201480029107 A CN201480029107 A CN 201480029107A CN 105339837 A CN105339837 A CN 105339837A
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liquid crystal
side chain
chain type
polymeric membrane
group
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CN105339837B (en
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后藤耕平
芦泽亮一
山之内洋一
万代淳彦
南悟志
名木达哉
川月喜弘
近藤瑞穂
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Nissan Chemical Corp
University of Hyogo
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Nissan Chemical Corp
University of Hyogo
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • 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
    • C08F20/02—Monocarboxylic acids having less than ten carbon atoms, Derivatives thereof
    • C08F20/10—Esters
    • C08F20/26—Esters containing oxygen in addition to the carboxy oxygen
    • C08F20/30—Esters containing oxygen in addition to the carboxy oxygen containing aromatic rings in the alcohol moiety
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/1337—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers
    • G02F1/133711—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers by organic films, e.g. polymeric films
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/1337—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers
    • G02F1/13378—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers by treatment of the surface, e.g. embossing, rubbing or light irradiation
    • G02F1/133788—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers by treatment of the surface, e.g. embossing, rubbing or light irradiation by light irradiation, e.g. linearly polarised light photo-polymerisation
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/1343—Electrodes
    • G02F1/134309—Electrodes characterised by their geometrical arrangement
    • G02F1/134363—Electrodes characterised by their geometrical arrangement for applying an electric field parallel to the substrate, i.e. in-plane switching [IPS]

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  • Physics & Mathematics (AREA)
  • Nonlinear Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Mathematical Physics (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • General Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Liquid Crystal (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Geometry (AREA)
  • Optical Integrated Circuits (AREA)

Abstract

Provided is an in-plane-switching-type liquid-crystal display element having excellent reliability to which an orientation control function is imparted with high efficiency. A method for manufacturing the in-plane-switching-type liquid-crystal display element comprises: [I] a step for forming a light-sensitive side-chain-type polymer film by applying a light-sensitive composition, containing (A) a light-sensitive side-chain-type polymer expressing liquid crystallinity within a prescribed temperature range, and (B) an organic solvent, to a substrate having a conductive film for in-plane switching; [II] a step in which polarized ultraviolet light is radiated on the light-sensitive side-chain-type polymer film to create a side-chain-type polymer film; [III] a step for heating the side-chain-type polymer film; and [IV] a step for then further radiating ultraviolet light.

Description

The driving liquid crystal of transverse electric field represents the manufacture method of element
Technical field
The present invention relates to the manufacture method that the driving liquid crystal of transverse electric field represents element, more specifically, the driving liquid crystal of transverse electric field relating to ghost excellent represents the manufacture method of element.
Background technology
Liquid crystal represents that element is light as quality, volume is thin and the indication equipment that power consumption is low is known, in recent years for large-scale television applications etc., achieves alarming development.Liquid crystal represents that element is such as formed with a pair transparency carrier clamping liquid crystal layer possessing electrode.Further, liquid crystal represents in element, uses the organic film be made up of organic material with the state of orientation making liquid crystal reach expectation between substrate as liquid crystal orientation film.
That is, liquid crystal orientation film is the component parts that liquid crystal represents element, is formed in the face contacted with liquid crystal of the substrate of clamping liquid crystal, bears and make liquid crystal effect along certain orientation orientation between this substrate.Further, for liquid crystal orientation film, except requiring to make liquid crystal except the effect of the certain orientation orientation such as direction being such as parallel to substrate, the effect of the tilt angle controlling liquid crystal is sometimes also required.The ability of the control liquid crystal aligning in this liquid crystal orientation film is (hereinafter referred to as tropism control ability.) by carrying out orientation process to give to the organic film forming liquid crystal orientation film.
As the method for orientation treatment of the liquid crystal orientation film for giving tropism control ability, known brushing method all the time.Brushing method refers to: for the organic film of the polyvinyl alcohol (PVA) on substrate, polyamide, polyimide etc., to cloth such as its surperficial cotton, nylon, polyester along certain orientation friction (brushing), liquid crystal is made to carry out the method for orientation along frictional direction (brushing direction).This brushing method can realize more stable liquid crystal aligning state easily, and the liquid crystal be therefore applied in the past represents in the manufacturing process of element.Further, as the organic film for liquid crystal orientation film, the main polyimide system organic film selecting the reliabilities such as thermotolerance, electrical characteristics excellence.
But sometimes there is the problem of producing dirt, occurring electrostatic in the brushing method on the surface of the liquid crystal orientation film be made up of polyimide etc. that rubs.In addition, due to liquid crystal in recent years represent element high-precision refinement, by the electrode on counterpart substrate or liquid crystal drive switching active element cause concavo-convex, the surface of the liquid crystal orientation film that sometimes cannot rub equably with cloth, cannot realize homogeneous liquid crystal aligning.
Thus, as other method for orientation treatment of liquid crystal orientation film not carrying out brushing, have studied optical alignment method energetically.
There is various method in optical alignment method, is to utilize rectilinearly polarized light or in the organic film forming liquid crystal orientation film, form anisotropy through the light of collimation, makes the method for liquid crystal aligning according to this anisotropy.As main optical alignment method, there will be a known the optical alignment method of breakdown type.Such as known following method: polarized UV rays is irradiated to polyimide film, utilize the polarization direction dependence of the UVA of molecular structure, make it that anisotropic decomposition occur, further, undecomposed and residual polyimide is utilized to make liquid crystal generation orientation (such as with reference to patent documentation 1).
In addition, the optical alignment method of also known photo-crosslinking type, photoisomerization type.Such as, use poly-vinyl cinnamate, irradiate polarized UV rays, in double bond part generation dimerization reaction (cross-linking reaction) of parallel with polarized light 2 side chains.Further, liquid crystal is made orientation to occur (such as with reference to non-patent literature 1 along the direction perpendicular to polarization direction.)。In addition, when using side chain to have the side chain type macromolecule of azobenzene, irradiate polarized UV rays, in the azobenzene portion of the side chain parallel with polarized light, isomerization reaction occurs, make liquid crystal, along the direction perpendicular to polarization direction, orientation (such as with reference to non-patent literature 2) occur.
As above example, in the method for orientation treatment of the liquid crystal orientation film based on optical alignment method, without the need to brushing, do not worry producing dirt, occurring electrostatic.Further, even if the substrate that the irregular liquid crystal of effects on surface tool represents element also can implementation orientation process, the method for orientation treatment of the liquid crystal orientation film being suitable for industrial manufacture process is become.
Prior art document
Patent documentation
Patent documentation 1: Japanese Patent No. 3893659 publication
Non-patent literature
Non-patent literature 1:M.Shadtetal., Jpn.J.Appl.Phys.31,2155 (1992)
Non-patent literature 2:K.Ichimuraetal., Chem.Rev.100,1847 (2000)
Summary of the invention
the problem that invention will solve
As above, with represent the method for orientation treatment of element as liquid crystal and compared with the brushing method all the time industrially implemented, optical alignment method, without the need to brushing operation, therefore possesses obvious advantage.Further, and utilize brushing and tropism control ability reaches compared with constant brushing method substantially, in optical alignment method, the exposure of polarized light can be made to change to control tropism control ability.But, in optical alignment method, when wanting to realize with the tropism control ability utilizing the situation of brushing method to be same degree, sometimes need the exposure of a large amount of polarized light or stable liquid crystal aligning cannot be realized.
Such as, in the breakdown type optical alignment method described in patent documentation 1, need to irradiate to polyimide film the ultraviolet light etc. that high-pressure sodium lamp that 60 minutes is 500W by output power sends, need long-time and a large amount of Ultraviolet radiation.In addition, when the optical alignment method of dimeric form, photoisomerization type, sometimes also need a large amount of ultraviolets irradiating number J (joule) ~ tens of about J.And then, when the optical alignment method of photo-crosslinking type, photoisomerization type, because the thermal stability of liquid crystal aligning, light stability are poor, when making liquid crystal and representing element, exist and the problem that orientation is bad, represent ghost occurs.Especially, represent in element at the driving liquid crystal of transverse electric field, owing to switching liquid crystal molecule in face, therefore the orientating deviation of liquid crystal easily occurs after liquid crystal drive, drives the expression ghost caused to be considered obvious problem by AC.Therefore, in optical alignment method, require to realize the high efficiency of orientation process, stable liquid crystal aligning, requirement can give liquid crystal orientation film, the aligning agent for liquid crystal of high tropism control ability efficiently to liquid crystal orientation film.
The object of the invention is to, provide and represent element with high-level efficiency imparting tropism control ability, the driving liquid crystal of transverse electric field excellent in reliability.
for the scheme of dealing with problems
The present inventor etc. conduct in-depth research to realize above-mentioned problem, found that: on the substrate with transverse electric field driving conducting film, coating is included in specific range of temperatures the high molecular photosensitive composite of photonasty side chain type showing liquid crystal liquid crystal property, the driving liquid crystal of transverse electric field being imparted tropism control ability by ultraviolet irradiation and subsequent heating represents that element can realize above-mentioned problem, thus completes the present invention.The present invention has following purport.
1. the driving liquid crystal of transverse electric field represents a manufacture method for element, it is characterized in that, possesses following operation:
[I] is coated with and in certain temperature range of 100 ~ 250 DEG C, shows the photonasty side chain type macromolecule of liquid crystal liquid crystal property and the photosensitive composite of (B) organic solvent containing (A) on the substrate with transverse electric field driving conducting film, thus forms the operation of photonasty side chain type polymeric membrane;
[II] irradiates the operation of polarized UV rays to photosensitive side chain type polymeric membrane;
[III] heats the operation of aforementioned side chain type polymeric membrane;
[IV] thereafter, the operation of further irradiation ultraviolet radiation.
2. the manufacture method according to above-mentioned 1, wherein, the ultraviolet irradiation amount of operation [II] reaches in the scope of 1% ~ 70% of maximum ultraviolet irradiation amount making Δ A, and described Δ A is aforementioned side chain type polymeric membrane, is parallel to the ultraviolet absorbance in the direction of the polarization direction of aforementioned polarized UV rays and the difference perpendicular to the ultraviolet absorbance in the direction of the polarization direction of aforementioned polarized UV rays.
3. the manufacture method according to above-mentioned 1 or 2, wherein, the ultraviolet irradiation amount of operation [II] reaches in the scope of 1% ~ 50% of maximum ultraviolet irradiation amount making aforementioned Δ A.
4. the manufacture method according to any one of above-mentioned 1 ~ 3, wherein, the heating-up temperature of operation [III] is the temperature of the scope of lower than the upper limit of this temperature range 10 DEG C of the low 10 DEG C ~ temperature of lower limit that temperature shows the temperature range of liquid crystal liquid crystal property than aforementioned side chain type polymeric membrane.
5. the manufacture method of the liquid crystal orientation film according to any one of above-mentioned 1 ~ 4, it is wherein, aforementioned that to show the photonasty group contained in the photonasty side chain type macromolecule of liquid crystal liquid crystal property be azobenzene, Stilbene, cinnamic acid, cinnamate, chalcone, cumarin, tolane, phenol benzoate, or derivatives thereof.
6. the manufacture method according to any one of above-mentioned 1 ~ 5, wherein, the ultraviolet irradiation amount of operation [IV] is more than the 20 moles exposures reacted in average 100 moles of the photonasty group that aforementioned side chain type polymeric membrane is had.
7. the manufacture method according to any one of above-mentioned 1 ~ 6, wherein, operation [IV] is carried out after making liquid crystal represents element.
8. the manufacture method according to any one of above-mentioned 1 ~ 7, is characterized in that, (A) composition has the side chain that photo-crosslinking, photoisomerization or light fries' rearrangement can occur.
9. the manufacture method according to any one of above-mentioned 1 ~ 8, wherein, (A) composition has side chain type macromolecule, and described side chain type macromolecule has at least 1 photonasty side chain in the group being selected from and being made up of aftermentioned formula (1) ~ (13).
10. the manufacture method according to any one of above-mentioned 1 ~ 9, wherein, (A) composition has side chain type macromolecule, and described side chain type macromolecule has at least 1 liquid crystal liquid crystal property side chain in the group being selected from and being made up of aftermentioned formula (5) ~ (8) and (14) ~ (22).
11. 1 kinds of photosensitive composites, it for showing the photonasty side chain type macromolecule of liquid crystal liquid crystal property and the photosensitive composite of (B) organic solvent containing (A) in certain temperature range of 100 ~ 250 DEG C, and the driving liquid crystal of the transverse electric field for possessing following operation successively represents the manufacture method of element:
[I] above-mentioned photosensitive composite is coated on there is transverse electric field driving conducting film substrate on, thus form the operation of photonasty side chain type polymeric membrane; [II] irradiates the operation of polarized UV rays to photosensitive side chain type polymeric membrane; [III] heats the operation of aforementioned side chain type polymeric membrane; [IV] is further to the operation of side chain type polymeric membrane irradiation ultraviolet radiation.
12. photosensitive composites according to above-mentioned 11, it is characterized in that, (A) composition has the side chain that photo-crosslinking, photoisomerization or light fries' rearrangement can occur.
13. photosensitive composites according to above-mentioned 11, wherein, (A) composition is for having the side chain type macromolecule of at least 1 photonasty side chain in the group that is selected from and is made up of aftermentioned formula (1) ~ (13).
14. photosensitive composites according to claim 11, wherein, (A) composition has at least 1 liquid crystal liquid crystal property side chain in the group being selected from and being made up of aftermentioned formula (5) ~ (8) and formula (14) ~ (22).
15. 1 kinds of liquid crystal represent element, and it utilizes the liquid crystal according to any one of above-mentioned 1 ~ 10 to represent the manufacture method manufacture of element.
the effect of invention
The driving liquid crystal of transverse electric field of method manufacture of the present invention is utilized to represent that element is imparted tropism control ability efficiently, even if therefore long-time continuous drives also harmless characterization.
Accompanying drawing explanation
Fig. 1 schematically illustrates that anisotropy in the manufacture method of the liquid crystal orientation film used in the present invention imports the figure of an example of process, be that photonasty side chain uses bridging property organic group and the anisotropy be imported into is less time figure.
Fig. 2 schematically illustrates that anisotropy in the manufacture method of the liquid crystal orientation film used in the present invention imports the figure of an example of process, be that photonasty side chain uses bridging property organic group and the anisotropy be imported into is larger time figure.
Fig. 3 schematically illustrates that anisotropy in the manufacture method of the liquid crystal orientation film used in the present invention imports the figure of an example of process, be that fries' rearrangement or isomerized organic group can occur the use of photonasty side chain and the anisotropy be imported into is less time figure.
Fig. 4 schematically illustrates that anisotropy in the manufacture method of the liquid crystal orientation film used in the present invention imports the figure of an example of process, be that fries' rearrangement or isomerized organic group can occur the use of photonasty side chain and the anisotropy be imported into is larger time figure.
Embodiment
Present inventor has performed further investigation, result obtains following opinion, thus completes the present invention.
The photosensitive composite used in manufacture method of the present invention have can show liquid crystal liquid crystal property photonasty side chain type macromolecule (hereinafter also referred to side chain type macromolecule.), the film using photosensitive composition to obtain is the high molecular film of photonasty side chain type that can show liquid crystal liquid crystal property.This film can carry out orientation process by polarizing light irradiation and make liquid crystal orientation film, and without the need to carrying out brushing process.That is, after carrying out polarizing light irradiation to the high molecular film of side chain type, via the operation heated this side chain type polymeric membrane, thus the film (liquid crystal orientation film) being endowed tropism control ability is become.Now, the small anisotropy shown by polarizing light irradiation becomes driving force, and liquid crystal liquid crystal property side chain type macromolecule self is reorientation effectively by self assembly.Its result, realizes high efficiency orientation process as liquid crystal orientation film, can obtain the liquid crystal orientation film being endowed high tropism control ability.Thereafter, by liquid crystal orientation film irradiation ultraviolet radiation, unreacted photonasty group can be reduced.By such operation, can obtain maintaining high efficiency tropism control ability and liquid crystal excellent in reliability represents element.
< liquid crystal represents the manufacture method > of element
Below, each operation for the operation [I] in manufacture method of the present invention ~ operation [IV] is described.
In operation [I], on the substrate with transverse electric field driving conducting film, the photosensitive composite of coating containing the photonasty side chain type macromolecule and organic solvent that show liquid crystal liquid crystal property in specific range of temperatures is (hereinafter also referred to photosensitive composite.), thus form polymeric membrane.Substrate is not particularly limited, and such as, except glass substrate, can also use the transparency carriers such as plastic base such as acrylic compounds substrate, polycarbonate substrate.Consider the application of gained polymeric membrane, showing the manufacturing process of element from the view point of simplification liquid crystal watch, also can using the substrate of ITO (IndiumTinOxide, the tin indium oxide) electrode be formed with for driving liquid crystal etc.In addition, consider that it represents the application in element at reflective liquid crystal, also can use the opaque substrates such as silicon wafer, as electrode now, also can use the material of the meeting reflected light such as aluminium.
Coating process is not particularly limited, the industrial method normally utilizing serigraphy, hectographic printing, flexible printing or ink-jet method etc. to carry out.As other coating process, there are infusion process, rolling method, slot coated method, spin-coating method (method of spin coating) or spraying process etc., can be used them according to object.
After substrate is coated with photosensitive composite, utilize the heater meanses such as hot plate, thermal cycle type baking oven or IR (infrared ray) type baking oven with 20 ~ 180 DEG C, preferably with 40 ~ 150 DEG C, solvent is evaporated, thus photonasty side chain type polymeric membrane can be obtained.Baking temperature is now preferably lower than side chain type high molecular liquid crystal phase performance temperature.When the thickness of polymeric membrane is blocked up, be disadvantageous at liquid crystal in the power consumption representing element, when crossing thin, liquid crystal represents that the reliability of element reduces sometimes, is therefore preferably 5 ~ 300nm, is more preferably 10 ~ 150nm.
In addition, after operation [I] and before subsequent processing [II], the operation substrate being formed with photonasty side chain type polymeric membrane being cooled to room temperature can also be set.
In operation [II], polarized UV rays is irradiated to the photonasty side chain type polymeric membrane obtained in operation [I].When polarized UV rays is irradiated to the face of photonasty side chain type polymeric membrane, across polarization plates, the ultraviolet of polarization is irradiated to substrate from specific direction.As the ultraviolet that will use, wavelength can be used to be the ultraviolet of 200 ~ 400nm scope.Preferably, according to the kind of the photonasty side chain type polymeric membrane that will use, select best wavelength by wave filter etc.Further, can choice for use wavelength be such as the ultraviolet of 290 ~ 400nm scope, optionally photo-crosslinking can be brought out.As ultraviolet, such as, can use the light sent by high-pressure sodium lamp.
For the exposure of polarized UV rays, be preferably set to realize Δ A maximal value (hereinafter also referred to Δ Amax.) polarized UV rays amount 1% ~ 70% scope in, be more preferably set in the scope of 1 ~ 50%, the ultraviolet absorbance in the direction of polarization direction that described Δ A is the photonasty side chain type polymeric membrane that will use, that be parallel to polarized UV rays and the difference perpendicular to the ultraviolet absorbance in the direction of the polarization direction of polarized UV rays.
In operation [III], heat the side chain type polymeric membrane having irradiated polarized UV rays in operation [II].Heating uses the heater meanses such as hot plate, thermal cycle type baking oven or IR (infrared ray) type baking oven.For heating-up temperature, can consider to make side chain type polymeric membrane used show the temperature of liquid crystal liquid crystal property and determine.In addition, usually on the surface of film, the power that intermolecular force acts on is little, therefore measurable: surperficial Tg (glass transition temperature) is lower than the Tg of entirety, in other words, in the liquid crystal temperature range on liquid crystal orientation film surface, lower than the liquid crystal temperature range of entirety.That is, irradiate the heating-up temperature after polarized UV rays preferably using the temperature of low 10 DEG C of lower limit showing the liquid crystal temperature range of liquid crystal liquid crystal property than side chain type polymeric membrane used as lower limit and using the temperature of the temperature of lower than the upper limit of liquid crystal temperature range 10 DEG C as the scope of the upper limit.
By possessing above operation, in the present invention, realize in photonasty side chain type polymeric membrane, importing anisotropy efficiently.Further, the substrate of the band liquid crystal orientation film used in manufacture method of the present invention can be manufactured efficiently.
In operation [IV], further to the side chain type polymeric membrane irradiation ultraviolet radiation obtained in operation [III].This operation just can terminate rear directly to the aforementioned side chain type polymeric membrane irradiation ultraviolet radiation on substrate at operation [III], thereafter, also irradiation ultraviolet radiation in the operation of element can be represented using the substrate manufacture liquid crystal of the aforementioned side chain type polymeric membrane of band, after making liquid crystal represents element, element irradiation ultraviolet radiation can also be represented to gained liquid crystal.By such operation, when giving tropism control ability with high-level efficiency, unreacted photonasty group generation delustring can be made, therefore, it is possible to manufacture liquid crystal excellent in reliability to represent element.It should be noted that, the liquid crystal temperature range in the present invention refers to and utilizes means of differential scanning calorimetry to measure the value obtained.
< photosensitive composite >
The photosensitive composite used in manufacture method of the present invention comprises the photonasty side chain type macromolecule that can show liquid crystal liquid crystal property, is included in specific range of temperatures the photonasty side chain type macromolecule showing liquid crystal liquid crystal property.Further, main chain is bonded with possesses photosensitive side chain, can induction light and cross-linking reaction, isomerization reaction or light fries' rearrangement occur.The structure with photosensitive side chain is not particularly limited, and is contemplated to be induction light and the structure of cross-linking reaction or light fries' rearrangement occurs, being more contemplated to be the structure that cross-linking reaction occurs.Now, even if be exposed to the external stresses such as heat, the tropism control ability realized can also be kept steadily in the long term.
As long as the structure that can show the photonasty side chain type polymeric membrane of liquid crystal liquid crystal property meets this characteristic and is just not particularly limited, preferential side chain structure has upright and outspoken liquid crystal former (mesogen) composition.Now, when this side chain type polymeric membrane is made liquid crystal orientation film, stable liquid crystal aligning can be obtained.The high molecular structure example of this side chain type is as made following structure: have main chain and be bonded to its side chain, and this side chain has the liquid crystal ultimate constituents such as xenyl, terphenyl, phenylcyclohexyl, phenylamino benzoic acid ester group, azobenzene and is bonded to the induction light of leading section and the photonasty group of cross-linking reaction, isomerization reaction occurs.In addition, can make following structure: have main chain and be bonded to its side chain, this side chain has both for the phenylamino benzoic acid ester group of light Fries rearrangement also can occur liquid crystal ultimate constituent.
As can show liquid crystal liquid crystal property the high molecular structure of photonasty side chain type have more style, preferably there is the structure of main chain and photonasty side chain, described main chain is made up of at least a kind of being selected from group that hydrocarbon, acrylate, methacrylate, maleimide, norborene and siloxane form, and described photonasty side chain comprises at least a kind that is selected from group that following formula (1) ~ (13) form.
Wherein, A, B, D separately represent singly-bound ,-O-,-CH 2-,-COO-,-OCO-,-CONH-,-NH-CO-.A ', B ' separately represent singly-bound ,-O-,-CH 2-,-COO-,-OCO-,-CONH-,-NH-CO-,-CH=CH-CO-O-or-O-CO-CH=CH-.Y 1for being selected from the group in the phenyl ring of 1 valency, naphthalene nucleus, cyclohexyl biphenyl, furan nucleus, pyrrole ring, the cyclic hydrocarbon of carbon number 5 ~ 8 and their combination, the hydrogen atom being bonded to them is optional separately by-NO 2,-CN ,-CH=C (CN) 2,-CH=CH-CN, the alkyl of halogen group or carbon number 1 ~ 4 or alkoxy replace.X represents singly-bound ,-COO-,-OCO-,-N=N-,-CH=CH-,-C ≡ C-, and l represents the integer of 1 ~ 12, and m represents the integer of 0 ~ 2, m1, m2 separately represent the integer of 1 ~ 3, n represents the integer (wherein, during n=0, B is singly-bound) of 0 ~ 12.Y 2for being selected from the group in the phenyl ring of divalent, naphthalene nucleus, cyclohexyl biphenyl, furan nucleus, pyrrole ring, the cyclic hydrocarbon of carbon number 5 ~ 8 and their combination, the hydrogen atom being bonded to them is optional separately by-NO 2,-CN ,-CH=C (CN) 2,-CH=CH-CN, halogen group, alkyl or alkoxy replace.R represents OH, NH 2, the alkoxy of carbon number 1 ~ 6 or the alkyl amino of carbon number 1 ~ 6.R 1represent hydrogen atom ,-NO 2,-CN ,-CH=C (CN) 2,-CH=CH-CN, the alkyl of halogen group or carbon number 1 ~ 12 or alkoxy.One or more phenyl ring in formula (1) ~ (13) are optionally substituted by the identical or different ring be selected from naphthalene nucleus, anthracene nucleus and fluorenes ring.
Side chain shown in above-mentioned formula (1) ~ (13) possesses the structure as liquid crystal ultimate constituent with groups such as xenyl, terphenyl, phenylcyclohexyl, phenol benzoate, azobenzene, naphthalene, anthracene, fluorenes.Further, possess following among at least any one: its leading section has induction light and dimerization reaction occurs, carries out the photonasty group of cross-linking reaction; Or have main chain and be bonded to its side chain, this side chain has both for liquid crystal ultimate constituent also carries out the phenylamino benzoic acid ester group of light Fries rearrangement.
In manufacture method of the present invention, after using photosensitive composite to form photonasty side chain type polymeric membrane on substrate, irradiate polarized UV rays.Then, realize importing efficient anisotropy to side chain type polymeric membrane by carrying out heating, fabricated ribbon possesses the substrate of the liquid crystal orientation film of liquid crystal aligning control ability.In side chain type polymeric membrane, the principle of Molecular reorientation utilizing the light reaction of side chain and bring out based on the self assembly of liquid crystal liquid crystal property, realizes importing efficient anisotropy to side chain type polymeric membrane.In the present invention, when side chain type macromolecule has the structure of photocrosslinking reaction group as photonasty group, after use sense photosensitiveness side chain type macromolecule forms photonasty side chain type polymeric membrane on substrate, irradiate polarized UV rays, then, after heating, make liquid crystal and represent element.
Below, for use have photocrosslinking reaction group as the structure of photonasty group high molecular 1st mode of side chain type, use to there is light fries' rearrangement group or carry out isomerized group and be described as high molecular 2nd mode of side chain type of the structure of photonasty group.
Fig. 1 represents the example schematically illustrating and use in the 1st mode of the present invention and have photocrosslinking reaction group and process as the anisotropy importing in the manufacture method of the high molecular liquid crystal orientation film of side chain type of the structure of photonasty group.Especially when imported anisotropy is less, namely in the 1st mode of the present invention, the schematic diagram that the ultraviolet irradiation amount of operation [II] makes Δ A reach the situation in the scope of 1 ~ 15% of maximum ultraviolet irradiation amount.
(a) of Fig. 1 is the figure of the state of side chain type polymeric membrane 1 before polarizing light irradiation is schematically shown, has the structure of side chain 2 random alignment.Along with the random alignment of this side chain 2, the liquid crystal ultimate constituent of side chain 2 and photonasty group also random orientation, this side chain type polymeric membrane 1 is isotropic.
(b) of Fig. 1 is the figure of the state of side chain type polymeric membrane 1 after polarizing light irradiation is schematically shown, along be parallel to ultraviolet polarization direction direction arrangement side chain 2 among there is the light reactions such as the photonasty group priorities generation dimerization reaction of the side chain 2a of photonasty group.Its result, the density that the side chain 2a of light reaction occurs uprises slightly in the polarization direction of irradiation ultraviolet radiation, and its result, gives very little anisotropy to side chain type polymeric membrane 1.
(c) of Fig. 1 is the figure of the state of side chain type polymeric membrane 1 after heating is schematically shown, in side chain type polymeric membrane 1, be parallel between the direction of polarization direction of irradiation ultraviolet radiation and the direction perpendicular to the polarization direction of irradiation ultraviolet radiation, the amount of the cross-linking reaction produced is different.Now, the cross-linking reaction amount that the direction being parallel to the polarization direction of irradiation ultraviolet radiation produces is very little, and therefore the effect of plastifier is played at this cross-linking reaction position.Therefore, perpendicular to the liquid crystal liquid crystal property in the direction of the polarization direction of irradiation ultraviolet radiation higher than the liquid crystal liquid crystal property of parallel direction, in the direction of the polarization direction being parallel to irradiation ultraviolet radiation, self assembly occurs, the side chain 2 comprising liquid crystal ultimate constituent carries out reorientation.Its result, the very little anisotropy of the side chain type polymeric membrane 1 brought out because of photo-crosslinking is amplified because of heat, gives larger anisotropy to side chain type polymeric membrane 1.
Fig. 2 represents the example schematically illustrating and use in the 1st mode of the present invention and have photocrosslinking reaction group and process as the anisotropy importing in the manufacture method of the high molecular liquid crystal orientation film of side chain type of the structure of photonasty group.Especially when imported anisotropy is larger, namely in the 1st mode of the present invention, the schematic diagram that the ultraviolet irradiation amount of operation [II] makes Δ A reach the situation in the scope of 15 ~ 70% of maximum ultraviolet irradiation amount.
(a) of Fig. 2 is the figure of the state of side chain type polymeric membrane 3 before polarizing light irradiation is schematically shown, has the structure of side chain 4 random alignment.Along with the random alignment of this side chain 4, the liquid crystal ultimate constituent of side chain 4 and photonasty group also random orientation, this side chain type polymeric membrane 3 is isotropic.
(b) of Fig. 2 is the figure of the state of side chain type polymeric membrane 3 after polarizing light irradiation is schematically shown, along be parallel to ultraviolet polarization direction direction arrangement side chain 4 among there is the light reactions such as the photonasty group priorities generation dimerization reaction of the side chain 4a of photonasty group.Its result, the density that the side chain 4a of light reaction occurs uprises in the polarization direction of irradiation ultraviolet radiation, and its result, gives less anisotropy to side chain type polymeric membrane 3.
(c) of Fig. 2 is the figure of the state of side chain type polymeric membrane 3 after heating is schematically shown, in side chain type polymeric membrane 3, be parallel between the direction of polarization direction of irradiation ultraviolet radiation and the direction perpendicular to the polarization direction of irradiation ultraviolet radiation, the amount of the cross-linking reaction produced is different.Therefore, there is self assembly in the direction being parallel to the polarization direction of irradiation ultraviolet radiation, the side chain 4 comprising liquid crystal ultimate constituent carries out reorientation.Its result, the less anisotropy of the side chain type polymeric membrane 3 brought out because of photo-crosslinking is amplified because of heat, gives larger anisotropy to side chain type polymeric membrane 3.
Fig. 3 schematically illustrates the figure using in the 2nd mode of the present invention and have the example that the light fries' rearrangement group shown in above-mentioned formula (5) or (7) processes as the anisotropy importing in the manufacture method of the high molecular liquid crystal orientation film of side chain type of the structure of photonasty group.Especially, when the anisotropy imported is less, namely in the 2nd mode of the present invention, the schematic diagram that the ultraviolet irradiation amount of operation [II] makes Δ A reach the situation in the scope of 1 ~ 15% of maximum ultraviolet irradiation amount.
(a) of Fig. 3 is the figure of the state of side chain type polymeric membrane 5 before polarizing light irradiation is schematically shown, has the structure of side chain 6 random alignment.Along with the random alignment of this side chain 6, the liquid crystal ultimate constituent of side chain 6 and photonasty group also orientation randomly, this side chain type polymeric membrane 5 is isotropic.
(b) of Fig. 3 is the figure of the state of side chain type polymeric membrane 5 after polarizing light irradiation is schematically shown, along be parallel to ultraviolet polarization direction direction arrangement side chain 6 among there is the light reactions such as the photonasty group priorities generation light fries' rearrangement of the side chain 6a of photonasty group.Its result, the density that the side chain 6a of light reaction occurs uprises slightly in the polarization direction of irradiation ultraviolet radiation, and its result, gives very little anisotropy to side chain type polymeric membrane 5.
(c) of Fig. 3 is the figure of the state of side chain type polymeric membrane 5 after heating is schematically shown, in side chain type polymeric membrane 5, be parallel between the direction of polarization direction of irradiation ultraviolet radiation and the direction perpendicular to the polarization direction of irradiation ultraviolet radiation, the amount of the light Fries rearrangement produced is different.Now, the liquid crystal aligning power of the side chain before the liquid crystal aligning force rate reaction of the light fries' rearrangement body produced perpendicular to the direction of the polarization direction of irradiation ultraviolet radiation is strong, there is self assembly in the direction therefore perpendicular to the polarization direction of irradiation ultraviolet radiation, the side chain 6 comprising liquid crystal ultimate constituent carries out reorientation.Its result, the very little anisotropy of the side chain type polymeric membrane 5 brought out because of light Fries rearrangement is amplified because of heat, gives larger anisotropy to side chain type polymeric membrane 5.
Fig. 4 schematically illustrates the figure using in the 2nd mode of the present invention and have the example that the light fries' rearrangement group shown in above-mentioned formula (6) or (8) processes as the anisotropy importing in the manufacture method of the high molecular liquid crystal orientation film of side chain type of the structure of photonasty group.Especially, when the anisotropy imported is larger, namely in the 2nd mode of the present invention, the schematic diagram that the ultraviolet irradiation amount of operation [II] makes Δ A reach the situation in the scope of 15% ~ 70% of maximum ultraviolet irradiation amount.
(a) of Fig. 4 is the figure of the state of side chain type polymeric membrane 7 before polarizing light irradiation is schematically shown, has the structure of side chain 8 random alignment.Along with the random alignment of this side chain 8, the liquid crystal ultimate constituent of side chain 8 and photonasty group also orientation randomly, this side chain type polymeric membrane 7 is isotropic.
(b) of Fig. 4 is the figure of the state of side chain type polymeric membrane 7 after polarizing light irradiation is schematically shown, along be parallel to ultraviolet polarization direction direction arrangement side chain 8 among there is the light reactions such as the photonasty group priorities generation light fries' rearrangement of the side chain 8a of photonasty group.Its result, the density that the side chain 8a of light reaction occurs uprises in the polarization direction of irradiation ultraviolet radiation, and its result, gives less anisotropy to side chain type polymeric membrane 7.
(c) of Fig. 4 is the figure of the state of side chain type polymeric membrane 7 after heating is schematically shown, in side chain type polymeric membrane 7, be parallel between the direction of polarization direction of irradiation ultraviolet radiation and the direction perpendicular to the polarization direction of irradiation ultraviolet radiation, the amount of the light Fries rearrangement produced is different.The anchor force of light fries' rearrangement body 8a is than the side chain Final 8 before rearrangement, and when therefore producing certain a certain amount of above light fries' rearrangement body, self assembly occurs in the direction being parallel to the polarization direction of irradiation ultraviolet radiation, and the side chain 8 comprising liquid crystal ultimate constituent carries out reorientation.Its result, the less anisotropy of the side chain type polymeric membrane 7 brought out because of light Fries rearrangement is amplified because of heat, gives larger anisotropy to side chain type polymeric membrane 7.
Therefore, side chain type polymeric membrane by carrying out successively irradiating polarized UV rays and heating to side chain type polymeric membrane, thus is imported anisotropy efficiently, can make the liquid crystal orientation film of tropism control ability excellence.
Further, for side chain type polymeric membrane, make to side chain type polymeric membrane irradiate the exposure of polarized UV rays and the heating-up temperature of heating carry out optimization.Thereby, it is possible to realize importing anisotropy to side chain type polymeric membrane efficiently.
Present inventor has performed further investigation, found that following opinion.That is, best polarized UV rays exposure is reached for importing the amount of polarized UV rays exposure best for high efficiency anisotropy corresponding to the photonasty group generation photo-crosslinking made in this side chain type polymeric membrane, photoisomerization reaction or light Fries rearrangement in side chain type polymeric membrane.The result of polarized UV rays is irradiated to side chain type polymeric membrane, carry out photo-crosslinking, photoisomerization reaction or light Fries rearrangement the photonasty group of side chain few time, do not reach sufficient light reaction amount.Now, also sufficient self assembly can not be carried out even if carry out heating thereafter.On the other hand, for side chain type polymeric membrane, to the result of structured illumination polarized UV rays with photocrosslinking reaction group, carry out the photonasty group of the side chain of cross-linking reaction excessive time, the cross-linking reaction between side chain can excessively advance.Now, gained side chain type polymeric membrane becomes upright and outspoken, sometimes hinders the propelling of the self assembly by heating thereafter.In addition, for side chain type polymeric membrane, to the result of structured illumination polarized UV rays with light fries' rearrangement group, when the photonasty group carrying out the side chain of light Fries rearrangement becomes excessive, the liquid crystal liquid crystal property of side chain type polymeric membrane can too reduce.Now, the liquid crystal liquid crystal property of gained side chain type polymeric membrane also reduces, and sometimes hinders the propelling of the self assembly by heating thereafter.And then to when having the structured illumination polarized UV rays of light fries' rearrangement group, when ultraviolet irradiation amount is too much, side chain type macromolecule generation light decomposes, sometimes hinder the propelling of the self assembly by heating thereafter.
Therefore, in side chain type polymeric membrane, 0.1 % by mole ~ 40 % by mole that photo-crosslinking occurs because of the irradiation of polarized UV rays for the photonasty group of side chain, the optimised quantity of photoisomerization reaction or light Fries rearrangement is preferably set to the photonasty group that this side chain type polymeric membrane has, be more preferably set to 0.1 % by mole ~ 20 % by mole.By making the photonasty group amount of the side chain carrying out light reaction be this scope, the self assemblyization in heating thereafter can efficiently advance, and can form the high efficiency anisotropy in film.
In side chain type polymeric membrane, by there is the optimization of the ultraviolet irradiation amount of polarization, the amount of the reaction of the photo-crosslinking of the photonasty group in the side chain of side chain type polymeric membrane, photoisomerization or light Fries rearrangement is made to realize optimization.Further, realize in the lump with heating thereafter in side chain type polymeric membrane, importing anisotropy expeditiously.Now, for the polarized UV rays amount be applicable to, can carry out based on the uv absorption evaluation of side chain type polymeric membrane.
That is, for side chain type polymeric membrane, be determined at that polarized UV rays is postradiation respectively, the UVA in direction of polarization direction that is parallel to polarized UV rays and the UVA in the direction perpendicular to the polarization direction of polarized UV rays.Evaluate Δ A by the measurement result of uv absorption, described Δ A is the ultraviolet absorbance being parallel to the direction of the polarization direction of polarized UV rays in this side chain type polymeric membrane and the difference perpendicular to the ultraviolet absorbance in the direction of the polarization direction of polarized UV rays.Further, the exposure of the maximal value (Δ Amax) obtaining the Δ A realized in side chain type polymeric membrane and the polarized UV rays realizing it.In manufacture method of the present invention, the polarized UV rays exposure this being realized Δ Amax, as benchmark, can determine the polarized UV rays amount of the preferred amounts of irradiating in the manufacture of liquid crystal orientation film.
In manufacture method of the present invention, preferably the exposure of the polarized UV rays of irradiating side chain type polymeric membrane is set to and is set in the scope of 1% ~ 50% in the scope of 1% ~ 70% of the amount of the polarized UV rays that can realize Δ Amax, more preferably.In side chain type polymeric membrane, the exposure that can realize the polarized UV rays in the scope of 1% ~ 50% of the polarized UV rays amount of Δ Amax is equivalent to the amount of the polarized UV rays of 0.1 % by mole ~ 20 % by mole generation photo-crosslinkings of the photonasty integrated group that this side chain type polymeric membrane is had.
Then, in manufacture method of the present invention, heat after polarized UV rays is irradiated to side chain type polymeric membrane.This side chain type polymeric membrane is the polymeric membrane that can show liquid crystal liquid crystal property in specific temperature range.The temperature that side chain type polymeric membrane can be shown liquid crystal liquid crystal property by the postradiation heating of polarized UV rays is determined as benchmark.In addition, measurable: the surface exhibits of side chain type polymeric membrane goes out the temperature of liquid crystal liquid crystal property lower than the temperature to show liquid crystal liquid crystal property during whole observation.That is, the postradiation heating-up temperature of polarized UV rays is preferably temperature and shows the temperature range of liquid crystal liquid crystal property (hereinafter also referred to liquid crystal temperature range than side chain type polymeric membrane.) temperature of scope of lower than the upper limit of this liquid crystal temperature range 10 DEG C of low 10 DEG C ~ temperature.
The side chain type polymeric membrane used in the present invention, after irradiation polarized UV rays, being presented mesomorphic state by heating, carrying out self assembly and reorientation occurs along the direction being parallel to polarization direction.Its result, the little anisotropy of the side chain type polymeric membrane brought out by photo-crosslinking, photoisomerization reaction and light Fries rearrangement is amplified because of heat.But, even if when side chain type polymeric membrane presents mesomorphic state because of heating, if heating-up temperature is low, then the viscosity of the side chain type polymeric membrane of mesomorphic state high, be difficult to produce reorientation because of self assembly.Such as, when heating-up temperature is the temperature of lower than the lower limit of the liquid crystal temperature range of side chain type polymeric membrane more than 10 DEG C, in side chain type polymeric membrane to increase anisotropic effect by heat insufficient.
In addition, even if side chain type polymeric membrane presents mesomorphic state because of heating, if heating-up temperature is high, then the state of side chain type polymeric membrane is close to isotropic liquid condition, is difficult to carry out reorientation because of self assembly along single direction.Such as, when heating-up temperature is the temperature of the temperature of low 10 DEG C of the upper limit higher than the liquid crystal temperature range than side chain type polymeric membrane, in side chain type polymeric membrane to increase anisotropic effect by heat insufficient.
Thus, in the present invention, in order to realize importing anisotropy efficiently in side chain type polymeric membrane, the liquid crystal temperature range of this side chain type polymeric membrane is determined the heating-up temperature be applicable to as benchmark.And, as mentioned above, the postradiation heating-up temperature of polarized UV rays is set to: using the temperature of low 10 DEG C of the liquid crystal temperature range lower limit than this side chain type polymeric membrane as lower limit and using the temperature of lower than the liquid crystal temperature range upper limit 10 DEG C as the temperature in the scope of the upper limit.Therefore, such as, when the liquid crystal temperature range of side chain type polymeric membrane is 100 ~ 200 DEG C, expect postradiation for polarized UV rays heating-up temperature to be set to 90 ~ 190 DEG C.By operation like this, give larger anisotropy to side chain type polymeric membrane.By such operation, gained liquid crystal represents that elements relative is in the external stress such as light, heat display high reliability.
The photosensitive composite used in the present invention contains and to react because of the light of the wavelength coverage of 250 ~ 400nm and in certain temperature range of 100 ~ 250 DEG C, to show the side chain type macromolecule of liquid crystal liquid crystal property.The polymkeric substance becoming the composition of photosensitive composite preferably has the photonasty group reacted under the light of the wavelength coverage of 250 ~ 400nm.The polymkeric substance becoming the composition of photosensitive composite preferably has mesogenic group to show liquid crystal liquid crystal property in certain temperature range of 100 ~ 250 DEG C.
The photonasty side chain type macromolecule that can show above-mentioned liquid crystal liquid crystal property can be undertaken being polymerized obtaining by the photonasty side chain monomer and/or liquid crystal liquid crystal property side chain monomer making to have above-mentioned photonasty group.
[photonasty side chain monomer]
There is at high molecular side chain position when photonasty side chain monomer refers to and forms polymkeric substance the monomer of photonasty group.As the photonasty group that side chain has, be preferably following structure or derivatives thereof.
Style is had more as photonasty side chain monomer, preferably there is the structure of main chain and photonasty side chain, described main chain is by least a kind of formation be selected from group that hydrocarbon, (methyl) acrylate, maleimide, norborene and siloxane form, and described photonasty side chain comprises at least a kind that is selected from group that following formula (1) ~ (13) form.
In above-mentioned formula (1) ~ (13), A, B, D separately represent singly-bound ,-O-,-CH 2-,-COO-,-OCO-,-CONH-,-NH-CO-.A ', B ' separately represent singly-bound ,-O-,-CH 2-,-COO-,-OCO-,-CONH-,-NH-CO-,-CH=CH-CO-O-or-O-CO-CH=CH-.Y 1for being selected from the group in the phenyl ring of 1 valency, naphthalene nucleus, cyclohexyl biphenyl, furan nucleus, pyrrole ring, the cyclic hydrocarbon of carbon number 5 ~ 8 and their combination, the hydrogen atom being bonded to them is optional separately by-NO 2,-CN ,-CH=C (CN) 2,-CH=CH-CN, halogen group, alkyl or alkoxy replace.X represents singly-bound ,-COO-,-OCO-,-N=N-,-CH=CH-,-C ≡ C-, and l represents the integer of 1 ~ 12, and m represents the integer of 0 ~ 2, m1, m2 separately represent the integer of 1 ~ 3, n represents the integer (wherein, during n=0, B is singly-bound) of 0 ~ 12.Y 2for being selected from the group in the phenyl ring of divalent, naphthalene nucleus, cyclohexyl biphenyl, furan nucleus, pyrrole ring, the cyclic hydrocarbon of carbon number 5 ~ 8 and their combination, the hydrogen atom being bonded to them is optional separately by-NO 2,-CN ,-CH=C (CN) 2,-CH=CH-CN, halogen group, alkyl or alkoxy replace.R represents-OH ,-NH 2, the alkoxy of carbon number 1 ~ 6 or the alkyl amino of carbon number 1 ~ 6.R 1represent hydrogen atom ,-NO 2,-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 the identical or different ring be selected from naphthalene nucleus, anthracene nucleus and fluorenes ring.
[liquid crystal liquid crystal property side chain monomer]
Liquid crystal liquid crystal property side chain monomer refers to the monomer that polymers exhibit goes out liquid crystal liquid crystal property, high molecular side chain position has mesogenic group.As the mesogenic group that side chain has, can being that biphenyl, phenol benzoate etc. become separately liquid crystal original structure, also as benzoic acid etc., liquid crystal original structure can being become by forming hydrogen bond between side chain.As the mesogenic group that side chain has, be preferably following structure.
And then, style is had more as liquid crystal liquid crystal property side chain monomer, preferably there is the structure of main chain and liquid crystal liquid crystal property side chain, described main chain is by least a kind of formation be selected from group that hydrocarbon, (methyl) acrylate, maleimide, norborene and siloxane form, and described liquid crystal liquid crystal property side chain comprises at least a kind that is selected from group that following formula (5) ~ (8) and (14) ~ (22) form.
(wherein, A, B separately represent singly-bound ,-O-,-CH 2-,-COO-,-OCO-,-CONH-,-NH-CO-.A ', B ' separately represent singly-bound ,-O-,-CH 2-,-COO-,-OCO-,-CONH-,-NH-CO-,-CH=CH-CO-O-or-O-CO-CH=CH-.Y 1for being selected from the group in the phenyl ring of 1 valency, naphthalene nucleus, cyclohexyl biphenyl, furan nucleus, pyrrole ring, the cyclic hydrocarbon of carbon number 5 ~ 8 and their combination, the hydrogen atom being bonded to them is optional separately by-NO 2,-CN ,-CH=C (CN) 2,-CH=CH-CN, halogen group, alkyl or alkoxy replace.R 1represent hydrogen atom ,-NO 2,-CN ,-CH=C (CN) 2,-CH=CH-CN, halogen group, alkyl or alkoxy, Z 1and Z 2separately represent-CO-,-CH 2o-,-CH=N-,-CF 2-.R 2represent hydrogen atom ,-NO 2,-CN ,-CH=C (CN) 2,-CH=CH-CN, halogen group, the alkyl of carbon number 1 ~ 12 or the alkoxy of carbon number 1 ~ 12.L represents the integer of 1 ~ 12, and m represents the integer of 0 ~ 2, and m1, m2 separately represent the integer of 1 ~ 3.One or more phenyl ring in formula (5) ~ (13) are optionally substituted by the identical or different ring be selected from naphthalene nucleus, anthracene nucleus and fluorenes ring.)
[liquid crystal liquid crystal property side chain type macromolecule]
The composition of the photosensitive composite used in the present invention and side chain type macromolecule can be obtained by the above-mentioned polyreaction showing the photonasty side chain monomer of liquid crystal liquid crystal property.In addition, can be obtained by the copolymerization of the photonasty side chain monomer and liquid crystal liquid crystal property side chain monomer that do not show liquid crystal liquid crystal property, the copolymerization of photonasty side chain monomer and liquid crystal liquid crystal property side chain monomer that shows liquid crystal liquid crystal property.In addition, in the scope not damaging the ability expressing liquid crystal liquid crystal property, copolymerization can be carried out with other monomer.
As other monomer, include, for example out and industrially can obtain and the monomer of Raolical polymerizable can occur.As the concrete example of other monomer, unsaturated carboxylic acid, acrylate compounds, methacrylate compound, maleimide compound, vinyl cyanide, maleic anhydride, distyryl compound, vinyl compound etc. can be listed.
As the concrete example of unsaturated carboxylic acid, acrylic acid, methacrylic acid, itaconic acid, maleic acid, fumaric acid etc. can be listed.
As acrylate compounds, include, for example out methyl acrylate, ethyl acrylate, isopropyl acrylate, benzyl acrylate, acrylic acid naphthalene ester, acrylic acid anthracene ester, acrylic acid anthrylmethyl, phenyl acrylate, acrylic acid 2, 2, 2-trifluoro ethyl 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-diamantane ester, acrylic acid 2-propyl group-2-diamantane ester, acrylic acid 8-methyl-8-three ring ester in the last of the ten Heavenly stems, acrylic acid 8-ethyl-8-three ring ester in the last of the ten Heavenly stems etc.
As methacrylate compound, include, for example out methyl methacrylate, β-dimethyl-aminoethylmethacrylate, isopropyl methacrylate, 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, isobornyl methacrylate, methacrylic acid 2-methoxy acrylate, methoxy triethylene methacrylate, methacrylic acid 2-ethoxy ethyl ester, tetrahydrofurfuryl methacrylate, methacrylic acid 3-methoxybutyl, 2-Methacryloyloxy-2-methyladamantane, methacrylic acid 2-propyl group-2-diamantane ester, methacrylic acid 8-methyl-8-three ring ester in the last of the ten Heavenly stems, methacrylic acid 8-ethyl-8-three ring ester in the last of the ten Heavenly stems etc.Also (methyl) glycidyl acrylate, (3-methyl-3-oxetanylmethoxy) methyl (methyl) acrylate, (3-ethyl-3-oxetanylmethoxy) methyl (methyl) acrylate etc. can be used to have (methyl) acrylate compounds of cyclic ether group.
As vinyl compound, include, for example out vinyl ether, methyl vinyl ether, benzyl vinyl ether, 2-hydroxyethyl vinyl ether, Vinyl phenyl ether, propyl vinyl ether etc.
As distyryl compound, include, for example out styrene, methyl styrene, chlorostyrene, bromstyrol etc.
As maleimide compound, include, for example out maleimide, N-methylmaleimido, N-phenylmaleimide, N-N-cyclohexylmaleimide etc.
The high molecular manufacture method of photonasty side chain type in the present invention is not particularly limited, and can utilize the universal method of industrial use.Specifically, can be manufactured by the utilize cationic polymerization of vinyl, free radical polymerization, the anionic polymerisation of liquid crystal liquid crystal property side chain monomer, photonasty side chain monomer.Among these, from the view point of reaction controlling easness etc., be particularly preferably free radical polymerization.
As the polymerization initiator of free radical polymerization, the known compounds such as radical polymerization initiator, reversibility addition-cracking type chain tra nsfer (RAFT) polymerization agent can be used.
Free radical thermal polymerization is the compound producing free radical by being heated to more than decomposition temperature.As this free radical thermal polymerization, include, for example out ketone peroxide class (methyl ethyl ketone peroxide, Cyclohexanone peroxides etc.), diacyl peroxides 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, dilauroyl peroxide 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 persulfate, sodium peroxydisulfate, ammonium persulfate etc.), Azo (azobis isobutyronitrile, 2, 2 '-two (2-hydroxyethyl) azobis isobutyronitrile etc.).This free radical thermal polymerization can be used alone a kind, or, also can combinationally use two or more.
As long as radical photopolymerization initiating agent starts the compound of free radical polymerization because illumination is penetrated, be just not particularly limited.As this radical photopolymerization initiating agent, benzophenone can be listed, Michler's keton, 4,4 '-bis-(lignocaine) benzophenone, xanthone, sulfo-xanthone, isopropyl xanthone, 2,4-diethyl sulfide is for xanthone, 2-EAQ, acetophenone, 2-hydroxy-2-methyl propiophenone, 2-hydroxy-2-methyl-4 '-cumene acetone, 1-hydroxycyclohexylphenylketone, isopropyl benzoin ether, isobutyl benzoin ether, 2,2-diethoxy acetophenone, 2,2-dimethoxy-2-phenyl acetophenone, camphorquinone, benzanthrone, 2-methyl isophthalic acid-[4-(methyl mercapto) phenyl]-2-morpholino third-1-ketone, 2-benzyl-2-dimethylamino-1-(4-morphlinophenyl)-1-butanone, 4-dimethyl ethyl aminobenzoate, 4-dimethylaminobenzoic acid isopentyl ester, 4,4 '-two (t-butylperoxycarbonyl) benzophenone, 3,4,4 '-three (t-butylperoxycarbonyl) benzophenone, TMDPO, two (trichloromethyl) s-triazine of 2-(4 '-methoxyl-styrene)-4,6-, two (trichloromethyl) s-triazine of 2-(3 ', 4 '-dimethoxy-styryl)-4,6-, two (trichloromethyl) s-triazine of 2-(2 ', 4 '-dimethoxy-styryl)-4,6-, two (trichloromethyl) s-triazine of 2-(2 '-methoxyl-styrene)-4,6-, two (trichloromethyl) s-triazine of 2-(4 '-amyl phenyl ether vinyl)-4,6-, 4-[p-N, N-bis-(ethoxy carbonyl methyl)]-2,6-bis-(trichloromethyl) s-triazine, two (trichloromethyl)-5-(2 '-chlorphenyl) s-triazine of 1,3-, two (trichloromethyl)-5-(4 '-methoxyphenyl) s-triazine of 1,3-, 2-is (to dimethylaminostyryl) benzoxazole, 2-(to dimethylaminostyryl) benzothiazole, 2-mercaptobenzothiazole, 3,3 '-carbonyl two (7-lignocaine cumarin), 2-(Chloro-O-Phenyl)-4,4 ', 5,5 '-tetraphenyl-1,2 '-bisglyoxaline, 2,2 '-bis-(2-chlorphenyl)-4,4 ', 5,5 '-four (4-carboethoxyphenyl)-1,2 '-bisglyoxaline, 2,2 '-bis-(2,4-dichlorophenyl)-4,4 ', 5,5 '-tetraphenyl-1,2 '-bisglyoxaline, 2,2 ' two (2,4-dibromo phenyls)-4,4 ', 5,5 '-tetraphenyl-1,2 '-bisglyoxaline, 2,2 '-bis-(2,4,6-trichlorophenyl)-4,4 ', 5,5 '-tetraphenyl-1,2 '-bisglyoxaline, 3-(2-methyl-2-dimethylamino propiono) carbazole, two (2-methyl-2-morpholino the propiono)-9-dodecyl carbazole of 3,6-, 1-hydroxycyclohexylphenylketone, two (5-2,4-cyclopentadiene-1-base)-bis-(the fluoro-3-of 2,6-bis-(1H-pyrroles-1-base)-phenyl) titanium, 3,3 ', 4,4 '-four (t-butylperoxycarbonyl) benzophenone, 3,3 ', 4,4 '-four (tertiary hexyl peroxy carbonyl) benzophenone, 3,3 '-two (methoxycarbonyl)-4,4 '-two (t-butylperoxycarbonyl) benzophenone, 3,4 '-two (methoxycarbonyl)-4,3 '-two (t-butylperoxycarbonyl) 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 isophthalic acid, 3-benzothiazole-2 (3H)-subunit)-1-(2-benzoyl) ethyl ketone etc.These compounds can be used alone, and also can mix two or more use.
Radical polymerization is not particularly limited, and can use emulsion polymerization, suspension polymerization, dispersion copolymerization method, precipitation polymerization method, mass polymerization, solution polymerization process etc.
As the organic solvent used in the high molecular polyreaction of photonasty side chain type of liquid crystal liquid crystal property can be shown, as long as the organic solvent that the macromolecule generated can dissolve just is not particularly limited.Below list its concrete example.
Can list: DMF, DMA, METHYLPYRROLIDONE, N-ethyl-2-pyrrolidone, N-methyl caprolactam, dimethyl sulfoxide (DMSO), tetramethylurea, pyridine, dimethyl sulfone, hexamethyl sulfoxide, gamma-butyrolacton, isopropyl alcohol, methoxy amylalcohol, cinene, ethyl pentyl group ketone, methyl nonyl ketone, MEK, methyl isoamyl ketone, methyl isopropyl Ketone, methyl cellosolve, ethyl cellosolve, methylcellosolve acetate, ethyl cellosolve acetate, butyl carbitol, 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, DPE, 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, 3-methyl-3-methoxybutanol, diisopropyl ether, ethyl isobutyl ether, diisobutylene, pentyl acetate, butyl butyrate, butyl ether, diisobutyl ketone, methylcyclohexene, propyl ether, two hexyl ethers, diox, normal hexane, n-pentane, normal octane, diethyl ether, cyclohexanone, ethylene carbonate, propylene carbonate, methyl lactate, ethyl lactate, methyl acetate, ethyl acetate, n-butyl acetate, acetic acid dihydroxypropane single-ether, methyl pyruvate, ethyl pyruvate, 3-methoxy methyl propionate, 3-ethoxy-propionic acid Methylethyl, 3-methoxypropionate, 3-ethoxy-propionic acid, 3-methoxypropionic acid, 3-methoxy propyl propyl propionate, 3-methoxy propyl acid butyl ester, diethylene glycol dimethyl ether, 4-hydroxy-4-methyl-2-pentanone, 3-methoxyl-N, N-dimethylpropionamide, 3-ethoxy-N, N-dimethylpropionamide, 3-butoxy-N, N-dimethylpropionamide etc.
These organic solvents can be used alone, also can be used in combination.And then, even do not dissolve generated high molecular solvent, as long as in the scope that generated macromolecule can not be separated out, then also can be mixed in above-mentioned organic solvent and use.
In addition, in free radical polymerization, the oxygen in organic solvent can become the reason hindering polyreaction, therefore organic solvent preferably degassed rear use as much as possible.
Polymerization temperature during free radical polymerization can select the arbitrary temp of 30 ~ 150 DEG C, is preferably the scope of 50 ~ 100 DEG C.In addition, reaction can be carried out with any concentration, but is difficult to the polymkeric substance obtaining high molecular when concentration is too low, and during excessive concentration, the viscosity of reactant liquor becomes too high and is difficult to stir equably, and therefore monomer concentration is preferably 1 ~ 50, is 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, the high molecular molecular weight of gained diminishes, during the ratio less of radical polymerization initiator relative to monomer, the high molecular molecule quantitative change of gained is large, and therefore radical initiator is preferably 0.1 ~ 10 % by mole relative to the ratio of polymerization single polymerization monomer.In addition, also various monomer component, solvent, initiating agent etc. can be added during polymerization.
[recovery of polymkeric substance]
From utilize reclaim generated macromolecule above-mentioned that be obtained by reacting, that liquid crystal liquid crystal property can the be shown high molecular reaction solution of photonasty side chain type time, reaction solution is fed into poor solvent, these polymkeric substance is precipitated.As the poor solvent for precipitating, methyl alcohol, acetone, hexane, heptane, butyl cellosolve, heptane, MEK, methyl isobutyl ketone, ethanol, toluene, benzene, diethyl ether, ethyl methyl ether, water etc. can be listed.Be fed into the polymkeric substance that precipitation occurs in poor solvent and after filtered and recycled, air drying or heat drying can be carried out under normal or reduced pressure.In addition, when the polymkeric substance repeating 2 times ~ 10 times precipitation to be reclaimed is dissolved in organic solvent again and precipitates the operation of recovery again, the impurity in polymkeric substance can be reduced.As poor solvent now, include, for example out alcohols, ketone, hydrocarbon etc., when using more than the 3 kinds poor solvents be selected among these, purification efficiency improves further, so preferably.
About the high molecular molecular weight of photonasty side chain type that can show liquid crystal liquid crystal property contained in photosensitive composite used in the present invention, consider gained side chain type macromolecule film strength, workability when forming film and the homogeneity of film time, the weight-average molecular weight utilizing GPC (GelPermeationChromatography, gel permeation chromatography) method to measure is preferably 2000 ~ 1000000, is more preferably 5000 ~ 100000.
[preparation of photosensitive composite]
The photosensitive composite used in the present invention is by forming containing the photonasty side chain type macromolecule that can show liquid crystal liquid crystal property.Further, preferably coating fluid is made in the mode of applicable formation liquid crystal orientation film.That is, prepared by the form that photosensitive composite used in the present invention is preferably dissolved in the solution of organic solvent for the resinous principle forming resin coating.Herein, resinous principle refers to and comprises the above-mentioned high molecular resinous principle of photonasty side chain type that can show liquid crystal liquid crystal property.Now, the content of resinous principle is preferably 1 ~ 20 quality %, is more preferably 3 ~ 15 quality %, is particularly preferably 3 ~ 10 quality % in photosensitive composite.
In above-mentioned photosensitive composite, resinous principle can be all be the photonasty side chain type macromolecule that can show liquid crystal liquid crystal property, in the scope not damaging liquid crystal expressive ability and photonasty ability, also can mix other polymkeric substance in addition.Now, the content of other polymkeric substance in resinous principle is 0.5 ~ 80 quality %, is preferably 1 ~ 50 quality %.
Other polymkeric substance this include, for example out and comprises poly-(methyl) acrylate, polyamic acid, polyimide etc. and be not the high molecular polymkeric substance of photonasty side chain type etc. that can show liquid crystal liquid crystal property.
< organic solvent >
As long as the organic solvent used in photosensitive composite used in the present invention can the organic solvent of dissolving resin composition just be not particularly limited.Below list its concrete example.
Can list: DMF, DMA, METHYLPYRROLIDONE, N-methyl caprolactam, 2-Pyrrolidone, N-ethyl pyrrolidone, NVP, dimethyl sulfoxide (DMSO), tetramethylurea, pyridine, dimethyl sulfone, hexamethyl sulfoxide, gamma-butyrolacton, 3-methoxyl-N, N-dimethylpropionamide, 3-ethoxy-N, N-dimethylpropionamide, 3-butoxy-N, N-dimethylpropionamide, 1,3-dimethyl-2-imidazolidinone, ethyl pentyl group ketone, methyl nonyl ketone, MEK, methyl isoamyl ketone, methyl isopropyl Ketone, cyclohexanone, ethylene carbonate, propylene carbonate, diethylene glycol dimethyl ether, 4-hydroxy-4-methyl-2-pentanone, Propylene glycol monoacetate, propylene glycol monomethyl ether, glycol tertiary butyl ether, dipropylene glycol monomethyl ether, diethylene glycol, diethylene glycol monoacetate, diethylene glycol dimethyl ether, dipropylene glycol monoacetate monomethyl ether, dipropylene glycol monomethyl ether, DPE, 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, also can be used in combination.
The photosensitive composite used in the present invention can containing the composition outside mentioned component.As its example, being solvent or the compound of raising film thickness uniformity, surface smoothness when being coated with photosensitive composite, improving the compound etc. of the adaptation of liquid crystal orientation film and substrate.
As the concrete example of the solvent (poor solvent) of raising film thickness uniformity, surface smoothness, following solvent can be listed.
Include, for example out isopropyl alcohol, methoxy amylalcohol, methyl cellosolve, ethyl cellosolve, butyl cellosolve, methylcellosolve acetate, ethyl cellosolve acetate, butyl carbitol, ethyl carbitol, ethylcarbitol acetate, 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, DPE, 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, 3-methyl-3-methoxybutanol, diisopropyl ether, ethyl isobutyl ether, diisobutylene, pentyl acetate, butyl butyrate, butyl ether, diisobutyl ketone, methylcyclohexene, propyl ether, two hexyl ethers, 1-hexanol, normal hexane, n-pentane, normal octane, diethyl ether, methyl lactate, ethyl lactate, methyl acetate, ethyl acetate, n-butyl acetate, acetic acid dihydroxypropane single-ether, methyl pyruvate, ethyl pyruvate, 3-methoxy methyl propionate, 3-ethoxy-propionic acid Methylethyl, 3-methoxypropionate, 3-ethoxy-propionic acid, 3-methoxypropionic acid, 3-methoxy propyl propyl propionate, 3-methoxy propyl acid butyl ester, 1-methoxy-2-propanol, 1-ethoxy-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-single ether-2-acetic acid esters, dipropylene glycol, 2-(2-ethoxy propoxyl group) propyl alcohol, methyl lactate, ethyl lactate, lactic acid n-propyl ester, n-butyl lactate, isoamyl lactates etc. have the solvent etc. of low surface tension.
These poor solvents can use a kind, also can be used in combination multiple.When using solvent as described above, in order to not make the dissolubility of the solvent entirety comprised in photosensitive composite significantly reduce, being preferably 5 ~ 80 quality % of solvent entirety, being more preferably 20 ~ 60 quality %.
As the compound improving film thickness uniformity, surface smoothness, fluorine system surfactant, silicone based surfactants, nonionic system surfactant etc. can be listed.
More specifically, include, for example out Eftop301, EF303, EF352 (TohkemproductsCorporation system); MegafacF171, F173, R-30 (DICCORPORATION system); FluoradFC430, FC431 (Sumitomo3MLimited system); AsahiGuardAG710 (Asahi Glass Co., Ltd's system); SurflonS-382, SC101, SC102, SC103, SC104, SC105, SC10 (AGCSEIMICHEMICALCO., LTD. system) etc.The usage ratio of these surfactants is preferably 0.01 ~ 2 mass parts relative to resinous principle 100 mass parts contained in photosensitive composite, is more preferably 0.01 ~ 1 mass parts.
As the concrete example of compound of adaptation improving liquid crystal orientation film and substrate, the compound etc. containing functional silanes illustrated as follows can be listed.
Include, for example out 3-TSL 8330, APTES, 2-TSL 8330, 2-aminopropyltriethoxywerene werene, N-(2-amino-ethyl)-3-TSL 8330, N-(2-amino-ethyl)-3-amino propyl methyl dimethoxysilane, 3-urea propyl trimethoxy silicane, 3-urea propyl-triethoxysilicane, N-ethoxy carbonyl-3-TSL 8330, N-ethoxy carbonyl-APTES, N-triethoxysilylpropyltetrasulfide three second triamine, N-trimethoxy-silylpropyl three second triamine, 10-trimethoxysilyl-Isosorbide-5-Nitrae, 7-tri-azepine decane, 10-triethoxysilyl-Isosorbide-5-Nitrae, 7-tri-azepine decane, 9-trimethoxysilyl-3,6-diaza nonyl acetic acid esters, 9-triethoxysilyl-3,6-diaza nonyl acetic acid esters, N-benzyl-3-TSL 8330, N-benzyl-APTES, N-phenyl-3-TSL 8330, N-phenyl-APTES, two (oxygen the ethylidene)-3-TSL 8330 of N-, two (oxygen ethylidene)-APTESs of N-etc.
And then, in order to improve the adaptation of substrate and liquid crystal orientation film and prevent from forming the electrical characteristics reduction etc. caused by backlight when liquid crystal represents element, phenoplast system as following, adjuvant containing the compound of epoxy radicals can be contained in photosensitive composite.Concrete phenoplast system adjuvant is below shown, but is not limited to this structure.
As the concrete compound containing epoxy radicals, can exemplify: ethylene glycol diglycidylether, polyethyleneglycol diglycidylether, propylene glycol diglycidylether, tripropyleneglycol diglycidyl ether, polypropylene glycol diglycidyl ether, neopentylglycol diglycidyl ether, 1, 6-hexanediol diglycidyl ether, glycerin diglycidyl ether, 2, 2-dibromoneopentyl glycol diglycidyl ether, 1, 3, 5, 6-four glycidyl group-2, 4-hexanediol, N, N, N ', N ',-four glycidyl group m-xylene diamine, 1, two (the N of 3-, N-diglycidyl amino methyl) cyclohexane, N, N, N ', N ',-four glycidyl group-4, 4 '-diaminodiphenyl-methane etc.
When using the compound of adaptation for improving liquid crystal orientation film and substrate, its consumption is preferably 0.1 ~ 30 mass parts relative to resinous principle 100 mass parts contained in photosensitive composite, is more preferably 1 ~ 20 mass parts.During by quantity not sufficient 0.1 mass parts, cannot expect the effect improving adaptation, during more than 30 mass parts, the orientation of liquid crystal is deteriorated sometimes.
Photosensitive composite used in the present invention also can add photosensitizer.As photosensitizer, be preferably colourless sensitizer and triplet sensitizer.
As the concrete example of photosensitizer, there is aromatic nitro compound, cumarin (7-lignocaine-4-methylcoumarin, Hymecromone), coumarin ketone, carbonyl bicoumarin, aromatic series 2-hydroxy-ketone, and by aromatic series 2-hydroxy-ketone (2-dihydroxy benaophenonel that amino replaces, single to (dimethylamino)-2-dihydroxy benaophenonel or two to (dimethylamino)-2-dihydroxy benaophenonel), acetophenone, anthraquinone, xanthone, sulfo-xanthone, benzanthrone, thiazoline (2-phenacylidene-3-methyl-β-aphthothiazoles quinoline, 2-(β-naphthoyl methylene)-3-methylbenzothiazole quinoline, 2-(α-naphthoyl methylene)-3-methylbenzothiazole quinoline, 2-(4-xenyl methylene)-3-methylbenzothiazole quinoline, 2-(β-naphthoyl methylene)-3-methyl-β-aphthothiazoles quinoline, 2-(4-xenyl methylene)-3-methyl-β-aphthothiazoles quinoline, 2-(to fluorobenzoyl methylene)-3-methyl-β-aphthothiazoles quinoline), oxazoline (2-phenacylidene-3-methyl-β-Nai Bing oxazoline, 2-(β-naphthoyl methylene)-3-Jia base benzoxazole quinoline, 2-(α-naphthoyl methylene)-3-Jia base benzoxazole quinoline, 2-(4-xenyl methylene)-3-Jia base benzoxazole quinoline, 2-(β-naphthoyl methylene)-3-methyl-β-Nai Bing oxazoline, 2-(4-xenyl methylene)-3-methyl-β-Nai Bing oxazoline, 2-(to fluorobenzoyl methylene)-3-methyl-β-Nai Bing oxazoline), benzothiazole, nitroaniline (meta nitro aniline or paranitroanilinum, 2,4,6-trinitroaniline) or nitro acenaphthene (5-nitro acenaphthene), (2-[(hydroxyl is to methoxyl) styryl] benzothiazole, benzoin alkylether, N-alkylation phthalein ketone, acetophenone ketal (2,2-Dimethoxyphenyl ethyl ketone), naphthalene, anthracene (2-naphthalene methyl alcohol, 2-naphthalene-carboxylic acid, 9-anthryl carbinol, 9-anthracene carboxylic acid), chromene, azo indolizine etc.
Be preferably aromatic series 2-hydroxy-ketone (benzophenone), cumarin, coumarin ketone, carbonyl bicoumarin, acetophenone, anthraquinone, xanthone, sulfo-xanthone or acetophenone ketal.
In photosensitive composite except above-mentioned substance, as long as in the scope not damaging effect of the present invention, for the object of the electrical characteristics such as specific inductive capacity, electric conductivity of change liquid crystal orientation film, dielectric, conductive materials can be added, and then for improving the object of film hardness, density when making liquid crystal orientation film, can cross-linked compound be added.
[liquid crystal orientation film and liquid crystal represent element]
The photosensitive composite used in the present invention is by be coated on substrate and after utilizing illumination to penetrate to implement light orientation process, till being heated to the temperature of liquid crystal orientation film display liquid crystal liquid crystal property, thus give tropism control ability efficiently, and then irradiation ultraviolet radiation thus can by heating the state of orientation immobilization that obtain.Like this, photosensitive composite passes through via light orientation process, is heated to the operation of liquid crystal phase transition temperature and the irradiation without polarized UV rays, thus can form liquid crystal orientation film, and the liquid crystal that can be used in manufacturing transverse electric field driving represents element.
Liquid crystal utilize known method to make liquid crystal cells, thus the liquid crystal making transverse electric field driving represents element after representing that element is obtained being with the substrate of liquid crystal orientation film by the photosensitive composite used in the present invention.
If list a production example of liquid crystal cells, then can exemplify following method: a pair substrate preparing to be formed with liquid crystal orientation film, the liquid crystal orientation film of a substrate scatters sept, the mode becoming inner side with liquid crystal aligning face is pasted on another substrate, and decompression injects liquid crystal and the method for sealing; Or, after the liquid crystal aligning face dropping liquid crystalline substance being scattered with sept, the method etc. that adhesive substrate carrying out seals.Now, substrate preferably uses the substrate of the electrode with transverse electric field driving comb teeth-shaped structure.Sept diameter is now preferably 1 μm ~ 30 μm, is more preferably 2 μm ~ 10 μm.This sept diameter determines the thickness of spacing, the i.e. liquid crystal layer of a pair substrate for clamping liquid crystal layer.
Embodiment
For embodiments of the present invention, enumerate embodiment to illustrate in greater detail.It should be noted that, being not limited to the examples property of the present invention is explained.
The abbreviation used in embodiment is as follows.
(methacrylic monomer)
(organic solvent)
THF: tetrahydrofuran
NMP:N-N-methyl-2-2-pyrrolidone N-
BC: butyl cellosolve
(polymerization initiator)
AIBN:2,2 '-azobis isobutyronitrile
[mensuration of phase transition temperature]
The liquid crystal phase transition temperature of the polymkeric substance obtained by embodiment uses means of differential scanning calorimetry to measure (DSC), DSC3100SR (マ ッ Network サ イ エ Application ス Inc.) and measures.
< synthesis example 1 >
MA1 (2.33g, 7.0mmol) is dissolved in NMP (21.5g), utilize membrane pump carry out degassed after, add AIBN (57.5mg, 0.35mmol) and also again carry out degassed.Thereafter, make it react 20 hours with 65 DEG C, obtain the polymer solution of methacrylate.In this polymer solution, add BC (15.9g) and stir, thus obtaining the aligning agent for liquid crystal (A) as photosensitive composite.The number-average molecular weight of the polymkeric substance in this aligning agent for liquid crystal (A) is 16000, weight-average molecular weight is 28000.The liquid crystal phase transition temperature of this polymkeric substance is 145 ~ 190 DEG C.
< synthesis example 2 >
MA1 (0.47g, 1.4mmol), MA2 (1.72g, 5.6mmol) are dissolved in NMP (20.2g), utilize membrane pump carry out degassed after, add AIBN (57.5mg, 0.35mmol) and also again carry out degassed.Thereafter, make it react 20 hours with 65 DEG C, obtain the polymer solution of methacrylate.In this polymer solution, add BC (14.9g) and stir, thus obtaining the aligning agent for liquid crystal (B) as photosensitive composite.The number-average molecular weight of the polymkeric substance in this aligning agent for liquid crystal is 14000, weight-average molecular weight is 24000.The liquid crystal phase transition temperature of this polymkeric substance is 135 ~ 180 DEG C.
< embodiment 1 >
[making of liquid crystal cells]
Use the aligning agent for liquid crystal (A) obtained in synthesis example 1, carry out the making of liquid crystal cells according to following shown step.Substrate be of a size of 30mm × 40mm, thickness is the glass substrate of 0.7mm, use and be configured with the substrate of the comb teeth-shaped pixel electrode formed by ito film patterning.Pixel electrode has the comb teeth-shaped shape that " < " font electrode key element that middle body bends is formed through multiple arrangement.The width of the Width of each electrode key element is 10 μm, is spaced apart 20 μm between electrode key element.The multiple arrangement of electrode key element of " < " font that the pixel electrode forming each pixel is bent by middle body and forming, therefore the shape of each pixel is not oblong-shaped, and possess in the same manner as electrode key element middle body bend, the shape of " < " word of being similar to runic.Further, each pixel for boundary is split up and down, has the 1st region of the upside of sweep and the 2nd region of downside with the sweep of these central authorities.When contrasting the 1st region and the 2nd region of each pixel, the formation direction forming the electrode key element of their pixel electrode is different.Namely, during using the orientation process direction of aftermentioned liquid crystal orientation film as benchmark, in the 1st region of pixel, the electrode key element of pixel electrode is formed in the mode of the angle (clockwise) presenting+15 °, in the 2nd region of pixel, form the electrode key element of pixel electrode in the mode of the angle (clockwise) presenting-15 °.That is, the 1st region of each pixel and the 2nd region are formed as follows: the liquid crystal brought out by applying voltage between pixel electrode and counter electrode, the direction reverse direction each other of spinning movement (plane switches) in real estate.
The aligning agent for liquid crystal obtained in synthesis example 1 (A) is spin-coated on prepared above-mentioned electroded substrate.Then, with press drying 90 second of 70 DEG C, the photonasty side chain type polymeric membrane that thickness is 100nm is formed.Then, across polarization plates with 5mJ/cm 2this face is irradiated to the ultraviolet of 313nm, heat 10 minutes with the hot plates of 150 DEG C, obtain the substrate being with the liquid crystal orientation film formed by side chain type polymeric membrane.In addition, as subtend substrate, to not forming electrode and the glass substrate of column spacer with height 4 μm forms photonasty side chain type polymeric membrane, implementation orientation process similarly.Printing and sealing agent on the liquid crystal orientation film of a substrate (pull together KCC's system, XN-1500T).Then, with the liquid crystal aligning face of two substrates relatively and after the mode that direction of orientation reaches 0 ° pastes another substrate, make sealant heat curing and make dummy cell.In this dummy cell, liquid crystal MLC-2041 (MERCKCORPORATION system) is injected by decompression injection method, sealing inlet, the liquid crystal obtaining possessing IPS (In-PlanesSwitching, plane switches) pattern represents the liquid crystal cells that element is formed.
(2 irradiation process)
After making liquid crystal cells, utilize the reorientation process that the baking oven of 120 DEG C carries out 60 minutes.Thereafter, under the state making short circuit between the pixel electrode of liquid crystal cells and counter electrode, with 20J/cm 2(2 times irradiate) are irradiated to liquid crystal cells and have passed through the bandpass filter of 365nm and the ultraviolet that obtains.After irradiating for 2 times, measure the voltage retention of liquid crystal cells.In addition, carry out the unit after ghost evaluation, slaking to observe.Liquid crystal cells is carried out in the baking oven of 60 DEG C the slaking of 336 hours.Observe in the liquid crystal cells after slaking whether to produce bright spot, orientation bad etc.
(mensuration of voltage retention)
The mensuration of the voltage retention of liquid crystal cells is by the 5V voltage by applying 60 μ s at the temperature of 70 DEG C, and after 1667ms, which kind of degree voltage is maintained at and calculates as voltage retention.It should be noted that, the mensuration of voltage retention employs the VHR-1 of TOYOCorporation.
(ghost evaluation)
Be arranged on by the IPS pattern liquid crystal cells prepared in embodiment 1 between 2 polarization plates configured in the mode that polarization axle is vertical, light backlight not executing under alive state, the arrangement angles of adjustment liquid crystal cells reaches minimum to make the brightness of transmitted light.Then, will the liquid crystal cells angle the darkest from the 2nd region of pixel be made to rotate to the anglec of rotation during angle that the 1st region is the darkest as initial stage orientation position angle and calculate.Then, in the baking oven of 60 DEG C, the 16V of 336 hours is applied with the frequency of 30Hz pPalternating voltage.Thereafter, make to present short-circuit condition between the pixel electrode of liquid crystal cells and counter electrode, directly at room temperature place 1 hour.After placement, similarly measure orientation position angle, interchange driven the difference at the orientation position angle of front and back as angle delta (degree, deg.) and calculate.
(unit after slaking is observed)
Liquid crystal cells after evaluating for above-mentioned ghost, is observed by polarization microscope polarization plates being made crossed nicols state.Rotating liquid crystal cells and make it present black when representing state, being denoted as there is no the bad state of bright spot, orientation well.
< embodiment 2 >
During 2 irradiation process, with 5J/cm 2irradiate (2 times irradiate) and have passed through the bandpass filter of 313nm and the ultraviolet that obtains, in addition, utilize the step production unit identical with embodiment 1.Evaluation result is shown in table 1.
< embodiment 3 >
Operate similarly to Example 1, the aligning agent for liquid crystal obtained in synthesis example 1 (A) is spun on electroded substrate.Then, with press drying 90 second of 70 DEG C, forming thickness is the liquid crystal orientation film of 100nm.Then, across polarization plates with 5mJ/cm 2its photonasty side chain type macromolecule face is irradiated to the ultraviolet of 313nm, heat 10 minutes with the hot plates of 150 DEG C, substrate is cooled 30 minutes, and then with 1J/cm 2(2 times irradiate) are irradiated to side chain type polymeric membrane face and have passed through the bandpass filter of 365nm and the ultraviolet that obtains, thus obtain the substrate being with liquid crystal orientation film.In addition, operate similarly to Example 1, subtend substrate is carried out combining and the liquid crystal obtaining possessing IPS pattern represents the liquid crystal cells that element is formed.Thereafter, operate similarly to Example 1, carry out reorientation process, the unit carried out after the mensuration of voltage retention and ghost evaluation, slaking is observed.
< embodiment 4 >
When implementing 2 irradiation process to substrate, with 500mJ/cm 2(2 times irradiate) are irradiated to side chain type polymeric membrane face and have passed through the bandpass filter of 313nm and the ultraviolet that obtains, in addition, utilize the step production unit identical with embodiment 3.Evaluation result is shown in table 1.
< embodiment 5 ~ 8 >
Use the aligning agent for liquid crystal (B) obtained in synthesis example 2, use the method identical with embodiment 1 ~ 4 to make liquid crystal cells.Aligning agent for liquid crystal used, ultraviolet irradiation amount (irradiating for 1 time), 2 illumination wavelength, 2 exposures and evaluation results are summed up and are shown in table 1.
< comparative example 1 >
About comparative example 1, after utilizing the step identical with embodiment 1 to make liquid crystal cells, carry out the reorientation process of 60 minutes with the baking ovens of 120 DEG C, but do not carry out 2 irradiation process.For this liquid crystal cells, the unit also carried out after the mensuration of voltage retention and ghost evaluation, slaking is observed.Aligning agent for liquid crystal used, evaluation result are shown in table 1.
< comparative example 2 >
About comparative example 2, after utilizing the step identical with embodiment 5 to make liquid crystal cells, carry out the reorientation process of 60 minutes with the baking ovens of 120 DEG C, but do not carry out 2 irradiation process.For this liquid crystal cells, the unit also carried out after the mensuration of voltage retention and ghost evaluation, slaking is observed.Aligning agent for liquid crystal used, evaluation result are shown in table 1.
[table 1]
According to the above results, compared with the unit not carrying out irradiating for 2 times, the voltage retention having imported the liquid crystal cells of 2 irradiation process shows high numerical value.This is considered because: unreacted photonasty group reduces, made between polymkeric substance crosslinked propelling by photo-crosslinking.
And then observe the result of the unit after slaking, the unit carrying out irradiating for 2 times shows good orientation, but the comparative example 1,2 not carrying out irradiating for 2 times produces small bright spot.This is considered because: residual unreacted photonasty group, monomer move because of thermal maturation or crystallization occurs, thus hinder the orientation of liquid crystal.But can think: by importing 2 irradiation process, residual unreacted group, monomer are consumed, thus suppress the generation of bright spot.
utilizability in industry
According to the present invention, can efficiently be maintained tropism control ability and liquid crystal excellent in reliability represents element, the driving liquid crystal of this transverse electric field represents that element can compatibly for large picture and various expression purposes such as the LCD TV of high-resolution.
It should be noted that, all the elements of the instructions of No. 2013-57047, the Japanese patent application of application on March 19th, 2013, claims, accompanying drawing and summary are quoted so far, introducing as the open of instructions of the present invention.
description of reference numerals
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 (15)

1. the driving liquid crystal of transverse electric field represents a manufacture method for element, it is characterized in that, possesses following operation successively:
Operation [I]: coating shows the photonasty side chain type macromolecule of liquid crystal liquid crystal property and the photosensitive composite of (B) organic solvent containing (A) in certain temperature range of 100 DEG C ~ 250 DEG C on the substrate with transverse electric field driving conducting film, thus forms the operation of photonasty side chain type polymeric membrane;
Operation [II]: polarized UV rays is irradiated to described photonasty side chain type polymeric membrane, thus makes the operation of side chain type polymeric membrane;
Operation [III]: the operation heating described side chain type polymeric membrane;
Operation [IV]: further to the operation of side chain type polymeric membrane irradiation ultraviolet radiation.
2. manufacture method according to claim 1, wherein, the ultraviolet irradiation amount of operation [II] reaches in the scope of 1% ~ 70% of maximum ultraviolet irradiation amount making Δ A, and described Δ A is described side chain type polymeric membrane, is parallel to the ultraviolet absorbance in the direction of the polarization direction of described polarized UV rays and the difference perpendicular to the ultraviolet absorbance in the direction of the polarization direction of described polarized UV rays.
3. manufacture method according to claim 1 and 2, wherein, the ultraviolet irradiation amount of operation [II] reaches in the scope of 1% ~ 50% of maximum ultraviolet irradiation amount making described Δ A.
4. the manufacture method according to any one of claims 1 to 3, wherein, the heating-up temperature of operation [III] is the temperature of the scope of lower than the upper limit of this temperature range 10 DEG C of the low 10 DEG C ~ temperature of lower limit that temperature shows the temperature range of liquid crystal liquid crystal property than described side chain type polymeric membrane.
5. the manufacture method according to any one of Claims 1 to 4, wherein, showing the photonasty group contained in the photonasty side chain type macromolecule of liquid crystal liquid crystal property described in is azobenzene, Stilbene, cinnamic acid, cinnamate, chalcone, cumarin, tolane, phenol benzoate, or derivatives thereof.
6. the manufacture method according to any one of Claims 1 to 5, wherein, the ultraviolet irradiation amount of operation [IV] is more than the 20 moles exposures reacted in average 100 moles of the photonasty group that described side chain type polymeric membrane is had.
7. the manufacture method according to any one of claim 1 ~ 6, wherein, operation [IV] is carried out after making liquid crystal represents element.
8. the manufacture method according to any one of claim 1 ~ 7, is characterized in that, (A) composition has the side chain that photo-crosslinking, photoisomerization or light fries' rearrangement can occur.
9. the manufacture method according to any one of claim 1 ~ 8, wherein, (A) composition has photonasty side chain type macromolecule, described photonasty side chain type macromolecule has at least 1 photonasty side chain in the group being selected from and being made up of following formula (1) ~ (13)
Wherein, A, B, D separately represent singly-bound ,-O-,-CH 2-,-COO-,-OCO-,-CONH-or-NH-CO-; A ', B ' separately represent singly-bound ,-O-,-CH 2-,-COO-,-OCO-,-CONH-,-NH-CO-,-CH=CH-CO-O-or-O-CO-CH=CH-; Y 1for being selected from the group in the phenyl ring of 1 valency, naphthalene nucleus, cyclohexyl biphenyl, furan nucleus, pyrrole ring, the cyclic hydrocarbon of carbon number 5 ~ 8 and their combination, the hydrogen atom being bonded to them is optional separately by-NO 2,-CN ,-CH=C (CN) 2,-CH=CH-CN, the alkyl of halogen group or carbon number 1 ~ 4 or alkoxy replace; X represents singly-bound ,-COO-,-OCO-,-N=N-,-CH=CH-or-C ≡ C-;
X ' represents singly-bound ,-COO-,-OCO-,-N=N-,-CH=CH-,-C ≡ C-,-CH=CH-CO-O-or-O-CO-CH=CH-, X ' number when being 2, X ' is optionally same to each other or different to each other; L represents the integer of 1 ~ 12; M represents the integer of 0 ~ 2; M1, m2, m3 separately represent the integer of 1 ~ 3; N represents the integer of 0 ~ 12, and wherein, during n=0, B is singly-bound; Y 2for being selected from the group in the phenyl ring of divalent, naphthalene nucleus, cyclohexyl biphenyl, furan nucleus, pyrrole ring, the cyclic hydrocarbon of carbon number 5 ~ 8 and their combination, the hydrogen atom being bonded to them is optional separately by-NO 2,-CN ,-CH=C (CN) 2,-CH=CH-CN, the alkyl of halogen group or carbon number 1 ~ 12 or alkoxy replace; R represents-OH ,-NH 2, the alkoxy of carbon number 1 ~ 6 or the alkyl amino of carbon number 1 ~ 6; R 1represent hydrogen atom ,-NO 2,-CN ,-CH=C (CN) 2,-CH=CH-CN, the alkyl of halogen group or carbon number 1 ~ 12 or alkoxy; One or more phenyl ring in formula (1) ~ (8) are optionally substituted by the identical or different ring be selected from naphthalene nucleus, anthracene nucleus and fluorenes ring.
10. the manufacture method according to any one of claim 1 ~ 9, wherein, (A) composition has liquid crystal liquid crystal property side chain type macromolecule, described liquid crystal liquid crystal property side chain type macromolecule has at least 1 liquid crystal liquid crystal property side chain in the group being selected from and being made up of following formula (5) ~ (8) and (14) ~ (22)
Wherein, A, B separately represent singly-bound ,-O-,-CH 2-,-COO-,-OCO-,-CONH-or-NH-CO-; A ', B ' separately represent singly-bound ,-O-,-CH 2-,-COO-,-OCO-,-CONH-,-NH-CO-,-CH=CH-CO-O-or-O-CO-CH=CH-; Y 1for being selected from the group in the phenyl ring of 1 valency, naphthalene nucleus, cyclohexyl biphenyl, furan nucleus, pyrrole ring, the cyclic hydrocarbon of carbon number 5 ~ 8 and their combination, the hydrogen atom being bonded to them is optional separately by-NO 2,-CN ,-CH=C (CN) 2,-CH=CH-CN, halogen group, alkyl or alkoxy replace; R 1represent hydrogen atom ,-NO 2,-CN ,-CH=C (CN) 2,-CH=CH-CN, the alkyl of halogen group or carbon number 1 ~ 12 or alkoxy; Z 1, Z 2separately represent-CO-,-CH 2o-,-CH=N-,-CF 2-; R 2represent hydrogen atom ,-NO 2,-CN ,-CH=C (CN) 2,-CH=CH-CN, the alkyl of halogen group or carbon number 1 ~ 12 or alkoxy; L represents the integer of 1 ~ 12; M represents the integer of 0 ~ 2; M1, m2, m3 separately represent the integer of 1 ~ 3; One or more phenyl ring in formula (5) ~ (8) and (14) ~ (22) are optionally substituted by the identical or different ring be selected from naphthalene nucleus, anthracene nucleus and fluorenes ring.
11. 1 kinds of photosensitive composites, it is for showing the photonasty side chain type macromolecule of liquid crystal liquid crystal property and the photosensitive composite of (B) organic solvent containing (A) certain temperature range of 100 DEG C ~ 250 DEG C, and the driving liquid crystal of the transverse electric field for possessing following operation successively represents the manufacture method of element:
[I] above-mentioned photosensitive composite is coated on there is transverse electric field driving conducting film substrate on, thus form the operation of photonasty side chain type polymeric membrane; [II] irradiates polarized UV rays to described photonasty side chain type polymeric membrane, thus makes the operation of side chain type polymeric membrane; [III] heats the operation of described side chain type polymeric membrane; [IV] is further to the operation of side chain type polymeric membrane irradiation ultraviolet radiation.
12. photosensitive composites according to claim 11, wherein, (A) composition has the side chain that photo-crosslinking, photoisomerization or light fries' rearrangement can occur.
13. photosensitive composites according to claim 11 or 12, wherein, (A) composition has at least 1 photonasty side chain in the group being selected from and being made up of following formula (1) ~ (13),
Wherein, A, B, D separately represent singly-bound ,-O-,-CH 2-,-COO-,-OCO-,-CONH-,-NH-CO-; Y 1for being selected from the group in the phenyl ring of 1 valency, naphthalene nucleus, cyclohexyl biphenyl, furan nucleus, pyrrole ring, the cyclic hydrocarbon of carbon number 5 ~ 8 and their combination, the hydrogen atom being bonded to them is optional separately by-NO 2,-CN ,-CH=C (CN) 2,-CH=CH-CN, halogen group, alkyl or alkoxy replace; X represents singly-bound ,-COO-,-OCO-,-N=N-,-CH=CH-,-C ≡ C-; L represents the integer of 1 ~ 12; M represents the integer of 0 ~ 2; M1, m2 separately represent the integer of 1 ~ 3; N represents the integer of 0 ~ 12, and wherein, during n=0, B is singly-bound; Y 2for being selected from group in the phenyl ring of divalent, naphthalene nucleus, cyclohexyl biphenyl, furan nucleus, pyrrole ring, the cyclic hydrocarbon of carbon number 5 ~ 8 and their combination, the hydrogen atom being bonded to them is optional separately by-NO 2,-CN ,-CH=C (CN) 2,-CH=CH-CN, halogen group, alkyl or alkoxy replace; R represents OH, NH 2, the alkoxy of carbon number 1 ~ 6 or the alkyl amino of carbon number 1 ~ 6; R 1represent hydrogen atom ,-NO 2,-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 the identical or different ring be selected from naphthalene nucleus, anthracene nucleus and fluorenes ring.
14. photosensitive composites according to claim 11 or 12, wherein, (A) composition has at least 1 liquid crystal liquid crystal property side chain in the group being selected from and being made up of following formula (5) ~ (8) and (14) ~ (22)
Wherein, A, B separately represent singly-bound ,-O-,-CH 2-,-COO-,-OCO-,-CONH-,-NH-CO-; A ', B ' separately represent singly-bound ,-O-,-CH 2-,-COO-,-OCO-,-CONH-,-NH-CO-,-CH=CH-CO-O-or-O-CO-CH=CH-; Y 1for being selected from the group in the phenyl ring of 1 valency, naphthalene nucleus, cyclohexyl biphenyl, furan nucleus, pyrrole ring, the cyclic hydrocarbon of carbon number 5 ~ 8 and their combination, the hydrogen atom being bonded to them is optional separately by-NO 2,-CN ,-CH=C (CN) 2,-CH=CH-CN, halogen group, alkyl or alkoxy replace; R 1represent hydrogen atom ,-NO 2,-CN ,-CH=C (CN) 2,-CH=CH-CN, halogen group, alkyl or alkoxy; Z 1and Z 2separately represent-CO-,-CH 2o-,-CH=N-,-CF 2-; R 2represent hydrogen atom ,-NO 2,-CN ,-CH=C (CN) 2,-CH=CH-CN, halogen group, the alkyl of carbon number 1 ~ 12 or the alkoxy of carbon number 1 ~ 12; L represents the integer of 1 ~ 12; M represents the integer of 0 ~ 2; M1, m2 separately represent the integer of 1 ~ 3; One or more phenyl ring in formula (5) ~ (8) and (14) ~ (22) are optionally substituted by the identical or different ring be selected from naphthalene nucleus, anthracene nucleus and fluorenes ring.
15. 1 kinds of liquid crystal represent element, and it utilizes the liquid crystal according to any one of claim 1 ~ 10 to represent what the manufacture method of element manufactured.
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