CN102372808A - Photoreactive polymer and preparation method thereof - Google Patents
Photoreactive polymer and preparation method thereof Download PDFInfo
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- CN102372808A CN102372808A CN2011101973372A CN201110197337A CN102372808A CN 102372808 A CN102372808 A CN 102372808A CN 2011101973372 A CN2011101973372 A CN 2011101973372A CN 201110197337 A CN201110197337 A CN 201110197337A CN 102372808 A CN102372808 A CN 102372808A
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F32/00—Homopolymers and copolymers of cyclic compounds having no unsaturated aliphatic radicals in a side chain, and having one or more carbon-to-carbon double bonds in a carbocyclic ring system
- C08F32/08—Homopolymers and copolymers of cyclic compounds having no unsaturated aliphatic radicals in a side chain, and having one or more carbon-to-carbon double bonds in a carbocyclic ring system having two condensed rings
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G61/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G61/02—Macromolecular compounds containing only carbon atoms in the main chain of the macromolecule, e.g. polyxylylenes
- C08G61/04—Macromolecular compounds containing only carbon atoms in the main chain of the macromolecule, e.g. polyxylylenes only aliphatic carbon atoms
- C08G61/06—Macromolecular compounds containing only carbon atoms in the main chain of the macromolecule, e.g. polyxylylenes only aliphatic carbon atoms prepared by ring-opening of carbocyclic compounds
- C08G61/08—Macromolecular compounds containing only carbon atoms in the main chain of the macromolecule, e.g. polyxylylenes only aliphatic carbon atoms prepared by ring-opening of carbocyclic compounds of carbocyclic compounds containing one or more carbon-to-carbon double bonds in the ring
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L45/00—Compositions of homopolymers or copolymers of compounds having no unsaturated aliphatic radicals in side chain, and having one or more carbon-to-carbon double bonds in a carbocyclic or in a heterocyclic ring system; Compositions of derivatives of such polymers
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- C09K19/00—Liquid crystal materials
- C09K19/52—Liquid crystal materials characterised by components which are not liquid crystals, e.g. additives with special physical aspect: solvents, solid particles
- C09K19/54—Additives having no specific mesophase characterised by their chemical composition
- C09K19/56—Aligning agents
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- G—PHYSICS
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- G02B5/00—Optical elements other than lenses
- G02B5/30—Polarising elements
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- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells
- G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
- G02F1/1333—Constructional arrangements; Manufacturing methods
- G02F1/1337—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers
Abstract
This disclosure relates to photoreactive polymer exhibiting more rapid photoreaction speed and excellent alignment, a preparation method thereof, and an alignment layer comprising the same. The photoreactive polymer comprises a specific repeat unit including an azo type functional group in the content of 50 mole % or more of the total polymer.
Description
Technical field
The present invention relates to a kind of photoreactive polymer that shows photoresponse speed faster and excellent orientation and preparation method thereof and the oriented layer that comprises this photoreactive polymer.
Background technology
In recent years, because liquid-crystal display has in light weight, advantage of low energy consumption, be regarded as the most competitive indicating meter that can replace Braun tube.Especially; Through the Thin Film Transistor-LCD (TFT-LCD) that thin film transistor drives, owing to each pixel of driven independently, so liquid crystal response speed is very fast; Can realize the dynamic image of high resolution, its range of application expands to notebook computer, wall-hanging TV machine etc.
In these TFT-LCD,, liquid crystal is gone up at the formed layer of the innermost thin film transistor of display unit (cell) pressed the certain orientation initial orientation, adopt liquid crystal aligning layer for this reason for liquid crystal is used as photoswitch.
In order to obtain this liquid crystal aligning, once adopted friction process (rubbingprocess).That is, thermotolerance polymer such as coating polyimide etc. on transparent glass, with stratification (stratification) macromolecular orientation layer, and high speed rotating is wound with the rotation roller of friction cloth such as nylon, regenerated fiber, makes its orientation with the wiping oriented layer.
Yet, when friction process rubs, can on the liquid crystal aligning agent surface, produce mechanical mark, or cause strong static, therefore may destroy thin film transistor.In addition, because substandard products take place friction micro fiber that cloth produced etc., the raising of casting yield has been formed obstacle.。
In order to overcome the problem that exists in the above-mentioned friction process, and to bringing innovation and the liquid crystal aligning mode that proposes is the liquid crystal aligning (to call " light orientation " in the following text) that adopts ultraviolet ray light such as (UV) in the production efficiency aspect.
The light orientation is meant the photosensitivity functional group on the photoreactivity polymer that is combined in regulation; Under the effect of linear polarising UV, cause photoresponse; High molecular main chain is pressed the certain orientation arrangement in this process, and the result forms the mechanism of the photo-polymerization type liquid crystal aligning layer that makes liquid crystal aligning.
The representative instance of this light orientation is people (Jpn.J.Appl.Phys. such as M.Schadt; Vol31., 1992,2155), people's (USP the 5th such as DaeS.Kang; 464; No. 669), YuriyReznikov (Jpn.J.Appl.Phys.Vol.34,1995, L1000) deliver based on photopolymerisable light orientation.The light orientated polymer that uses in these patents and the paper mainly is that PVCN (poly (vinylcinnamate)) or PVMC (poly (vinylmethoxycinnamate)) etc. gather the laurate base polymer.When making its light orientation; Pass through the ultraviolet ray (UV) of being shone; Two keys of laurate can produce [2+2] cycloaddition ([2+2] cycloaddition) reaction, and generate tetramethylene (cyclobutane), and form anisotropy thus; Liquid crystal molecule is arranged, to cause liquid crystal aligning to a direction.
But above-mentioned smooth orientated polymer in the past because of the thermostability of its high polymer main chain is low, exists the orientation stability or the thermostability that reduce oriented layer, perhaps the sufficient inadequately shortcoming of liquid crystal aligning property.For example; There is following shortcoming in polymkeric substance with acrylic backbone, promptly reduces oriented layer stability greatly because of thermostability is low, and when photosensitivity functional group is fettered by main chain; Can not react rapidly shining, thereby reduce liquid crystal aligning property or speed of orientation in the polarized light of oriented layer.As stated, when liquid crystal aligning property or speed of orientation descended, the liquid crystal aligning of processing procedure decrease in efficiency or liquid crystal display device was abundant inadequately, caused dichroic ratio's contrast gradient deterioration that diminishes.
On the other hand, Bull.KoreanChem.Soc.2002, Vol.23 in 957, has proposed to comprise the photoreactive polymer that is combined with the repeating unit of azo-group as the part of repeating unit.But this photoreactive polymer still exists orientation abundant inadequately, and owing to photoresponse speed reduces processing procedure efficient slowly, or the problems such as contrast gradient deterioration of liquid crystal display device.
Summary of the invention
The object of the present invention is to provide a kind of photoreactive polymer that shows photoresponse speed faster and excellent orientation and preparation method thereof.
Another purpose of the present invention is to provide a kind of oriented layer, and it comprises said photoreactive polymer, can be used for liquid crystal display device etc.
The present invention provides a kind of photoreactive polymer, and it comprises more than the 50mol% that content is total polymer, by the repeating unit of following chemical formula 3 or 4 expressions.
[chemical formula 3] [chemical formula 4]
In said chemical formula 3 and 4, n is 50～5000, and p is 0～4 integer, R
1, R
2, R
3And R
4In at least one is the group that is selected from the group of being made up of following Chemical formula 1 a, 1b and 1c, remaining is independently selected from respectively by hydrogen; Halogen; Replace or unsubstituted C1～C20 alkyl; Replace or unsubstituted C2～C20 thiazolinyl; Replace or unsubstituted C2～C20 alkynyl; Replace or unsubstituted C3～C12 cyclic hydrocarbon radical; Replace or unsubstituted C6～C40 aryl; And comprise and be selected from the group that the polar functional group of at least one is formed in oxygen, nitrogen, phosphorus, sulphur, silicon and the boron, as said R
1～R
4When not being hydrogen, halogen or polar functional group, R
1And R
2, or R
3And R
4Interconnect and form the alkylidene (alkylidene group) of C1～C10, perhaps R
1Or R
2With R
3And R
4In one connect and form the saturated or undersaturated ring of C4～C12 or the aromatic ring of C6～C24,
[Chemical formula 1 a]
[Chemical formula 1 b]
[Chemical formula 1 c]
In said Chemical formula 1 a, 1b and 1c; N1, p1, r1 and m1 are 0～4 integer; N2, p2, r2 and m2 are 0～5 integer; A is for replacing or unsubstituted C1～C20 alkylidene group, carbonyl, carboxyl, replacement or unsubstituted C6～C40 arylidene or singly-bound, B be oxygen, sulphur ,-NH-or singly-bound, R
9Be the inferior cyclic hydrocarbon radical of singly-bound, replacement or unsubstituted C1～C20 alkylidene group, replacement or unsubstituted C2～C20 alkenylene, replacement or unsubstituted C2～C20 alkynylene, replacement or unsubstituted C3～C12, replacement or unsubstituted C6～C40 arylidene or replacement or the inferior aralkyl of unsubstituted C7～C15, R
10And R
11For hydrogen, halogen, replacement or unsubstituted C1～C20 alkyl, replacement or unsubstituted C1～C20 alkoxyl group, replacement or unsubstituted C6～C30 aryloxy, or replace or unsubstituted C6～C40 aryl.
In addition; The present invention also provides a kind of preparation method of said photoreactive polymer; It comprises: in the presence of the catalyst composition that comprises pre-catalyst with the 10th family's transition metal and promotor, and the monomer that addition polymerization is represented by Chemical formula 1 and form step by the repeating unit of chemical formula 3 expressions.
[Chemical formula 1]
In the said Chemical formula 1, p, R
1, R
2, R
3And R
4Like 3 definition of said chemical formula.
The present invention also provides a kind of preparation method of said photoreactive polymer; It comprises: comprise have the 4th family, the catalyst composition of the pre-catalyst of the 6th family or the 8th family's transition metal and promotor in the presence of, the monomer that addition polymerization is represented by Chemical formula 1 and form step by the repeating unit of chemical formula 4 expressions.
In addition, the present invention provides a kind of oriented layer that comprises said photoreactive polymer.
The present invention also provides a kind of liquid crystal retardation film that comprises the liquid crystal layer on said oriented layer and this oriented layer.
The present invention also provides a kind of display device that comprises said oriented layer.
Through comprising norbornylene repeating unit, can demonstrate excellent thermostability according to photoreactive polymer of the present invention with high-vitrification invert point as main repeating unit.And through comprising the high-load relatively norbornylene repeating unit that contains specific azo-type photoreactive group, said photoreactive polymer can demonstrate photoresponse speed and excellent orientation and the light utilization efficiency that is greatly improved.
Therefore, the oriented layer of using said photoreactive polymer to provide to have excellent properties, liquid crystal retardation film etc., and can improve production efficiency greatly.
Description of drawings
The 1H NMR data of the polymkeric substance that Fig. 1 representes to make among the embodiment 1.
The 1H NMR data of the polymkeric substance that Fig. 2 representes to make in the comparative example 1.
Fig. 3 is the anisotropy measured in the Test Example 3 of expression and the figure of ultraviolet ray (UV) photoreactivity detected result.
Embodiment
Below, specify photoreactive polymer of the embodiment of the invention and preparation method thereof, and the oriented layer that comprises this photoreactive polymer.
According to embodiments of the invention a kind of photoreactive polymer is provided, it comprises more than the 50mol% that content is total polymer, by the repeating unit of following chemical formula 3 or 4 expressions.
[chemical formula 3] [chemical formula 4]
In the said chemical formula 3 and 4, n is 50～5000, and p is 0～4 integer, R
1, R
2, R
3And R
4In at least one is the group that is selected from the group of being made up of following Chemical formula 1 a, 1b and 1c; Remaining is independently selected from hydrogen, halogen, replacement or unsubstituted C1～C20 alkyl, replacement or unsubstituted C2～C20 thiazolinyl, replacement or unsubstituted C2～C20 alkynyl, replacement or unsubstituted C3～C12 cyclic hydrocarbon radical, replacement or unsubstituted C6～C40 aryl respectively; And comprise and be selected from the group that the polar functional group of at least one is formed in oxygen, nitrogen, phosphorus, sulphur, silicon and the boron; When said R1～R4 all is not hydrogen, halogen or polar functional group, R
1And R
2, or R
3And R
4Interconnect and form C1～C10 alkylidene group, perhaps R1 or R2 are connected with one of R3 and R4 and form the saturated or undersaturated ring of C4～C12 or the aromatic ring of C6～C24,
[Chemical formula 1 a]
[Chemical formula 1 b]
[Chemical formula 1 c]
In said Chemical formula 1 a, 1b and 1c; N1, p1, r1 and m1 are 0～4 integer; N2, p2, r2 and m2 are 0～5 integer; A is for replacing or unsubstituted C1～C20 alkylidene group, carbonyl, carboxyl, replacement or unsubstituted C6～C40 arylidene or singly-bound, B be oxygen, sulphur ,-NH-or singly-bound, R
9Be the inferior cyclic hydrocarbon radical of singly-bound, replacement or unsubstituted C1～C20 alkylidene group, replacement or unsubstituted C2～C20 alkenylene, replacement or unsubstituted C2～C20 alkynylene, replacement or unsubstituted C3～C12, replacement or unsubstituted C6～C40 arylidene; Or replacement or the inferior aralkyl of unsubstituted C7～C15, R
10And R
11Be hydrogen, halogen, replacement or unsubstituted C1～C20 alkyl, replacement or unsubstituted C1～C20 alkoxyl group, replacement or unsubstituted C6～C30 aryloxy independently, perhaps replace or unsubstituted C6～C40 aryl.
This photoreactive polymer comprises the norbornylene class repeating unit by chemical formula 3 or 4 expressions of the specific azo class photoreactivity functional group that is combined with Chemical formula 1 a～1c as main repeating unit.This norbornylene class repeat unit structure is firm; Its second-order transition temperature of photoreactive polymer (Tg) that comprises this repeating unit is higher, is about more than 300 ℃ preferred about 300～350 ℃; Therefore compare with photoreactive polymer in the past, can show excellent thermostability.And, since said photoreactive polymer combine the structural performance of photoreactivity functional group at said norbornylene class repeating unit, photoreactivity functional group can migration relatively freely in high polymer main chain, therefore can show excellent orientation.
And, as by after the further confirmation that obtains such as the Test Example stated, the inventor's experimental result shows, said photoreactive polymer has been owing to combined specific azo class photoreactivity functional group, shows than photoresponse speed faster and speed of orientation in the past.Said azo class photoreactivity functional group, (N=N-) absorbing polarization light and carry out cis-trans isomerization reaction (trans-cisisomerization) to a direction plays the effect that causes liquid crystal aligning to its azo-group thus.This photoresponse and epitaxy mechanism estimate to be exactly the factor that can realize photoresponse speed faster and speed of orientation with respect to other photoreactivity functional groups.
Particularly; Photoreactive polymer according to a said embodiment; Can comprise more than high-load about 50mol%; Concrete about 50～100mol%, the repeating unit that is combined with said azo class photoreactivity functional group of about more specifically 60～100mol% or 70～100mol% by chemical formula 3 or 4 expressions.Thus, can characterize the photoresponse speed of the azo-based class photoreactivity functional group that is greatly improved.In contrast to this; As through after state the further confirmation that comparative example obtains; Comprise below about 50mol% of low levels, below about 40mol%; In fact the polymkeric substance of the repeating unit that is combined with said azo class photoreactivity functional group of about 20mol% for example can't realize the fast photoresponse speed based on said azo class photoreactivity functional group.This possibly be because content is low; Though the photoresponse mechanism that the said azo class of part photoreactivity functional group occurs is like cis-trans isomerization reaction (trans-cisisomerization); But owing to be included in the low levels of the azo class photoreactivity functional group in the oriented layer; Can not normally characterize liquid crystal aligning, perhaps receive at random the influence of other repeating units of (randomly) dispersive, can not realize the orientation of pre-determined direction.
In contrast; The photoreactive polymer of one embodiment; Show very fast photoresponse speed and speed of orientation, show excellent orientation and thermostability simultaneously, therefore applicable to the oriented layer of liquid crystal display device etc.; And, can significantly improve processing procedure efficient through photoresponse speed fast.
Below, the said photoreactive polymer of further explain.
Said photoreactive polymer can be the polymkeric substance by the repeating unit in the repeating unit of said chemical formula 3 and 4 expressions that is selected from that only comprises 100mol%; But in not influencing, can also comprise other repeating units based on the scope of photoreactive polymer effect by the repeating unit of said chemical formula 3 and 4 expressions.For example; Said photoreactive polymer can be the multipolymer that further comprises the repeating unit of being represented by following Chemical formula 2 a or 2b; Owing to further comprise the repeating unit of representing by said Chemical formula 2 a or 2b that belongs to the norbornylene class, can show excellent thermostability.
[Chemical formula 2 a] [Chemical formula 2 b]
In said Chemical formula 2 a and 2b, m is 50～5000, and q ' is 0～4 integer, R ', R
2', R
3' and R
4' be independently selected from the group of representing by Chemical formula 2 c respectively; Hydrogen; Halogen; Replace or unsubstituted C1～C20 alkyl; Replace or unsubstituted C2～C20 thiazolinyl; Replace or unsubstituted C2～C20 alkynyl; Replace or unsubstituted C3～C12 cyclic hydrocarbon radical; Replace or unsubstituted C6～C40 aryl; And comprise and be selected from the group that the polar functional group of at least one is formed in oxygen, nitrogen, phosphorus, sulphur, silicon and the boron said R1 '～R
4' when all not being hydrogen, halogen or polar functional group, R
1' and R
2', or R
3' and R
4' interconnect and form C1～C10 alkylidene group, perhaps R
1' or R
2' with R
3' and R
4' one of connect and form the saturated or undersaturated ring of C4～C12, or C6～C24 aromatic ring,
[Chemical formula 2 c]
Among the said Chemical formula 2 c; 1 is 0 or 1; D and D ' be independently selected from respectively the inferior cyclic hydrocarbon radical of straight or branched type alkylidene group, replacement or the unsubstituted C3 of singly-bound, nitrogen, oxygen, sulphur, replacement or unsubstituted C1～C20～C12, replacement or unsubstituted C1～C20 straight or branched type epoxy alkyl (alkylene oxide), and replace or group that the inferior cyclic hydrocarbon radical oxygen base of unsubstituted C3～C12 (cycloalkylene oxide) is formed in; X and Y be independently selected from respectively hydrogen, halogen, cyanogen, and replace or group that the straight or branched type alkyl of unsubstituted C1～C20 is formed in, R
10'～R
14' be independently selected from hydrogen respectively; Halogen; Cyanogen; Replace or unsubstituted C1～C20 alkyl; Replace or unsubstituted C1～C20 alkoxyl group; Replace or unsubstituted C6～C30 aryloxy; Replace or unsubstituted C6～C40 aryl; Comprise the heteroatomic C6 of the 14th family, the 15th family or the 16th family～C40 heteroaryl; And in replacement or the group that unsubstituted C6～the C40 alkoxy aryl is formed.
This repeating unit of being represented by Chemical formula 2 a or 2b can be conventional norbornylene class repeating unit, also can be the photoreactivity repeating unit that is combined with the cinnamate derivative photoreactivity functional group that is represented by said Chemical formula 2 c.Preferably, said R
1', R
2', R
3' and R
4' at least one group for representing by Chemical formula 2 c, the repeating unit of being represented by said Chemical formula 2 a or 2b is the photoreactivity repeating unit.
Said photoreactive polymer further comprises this cinnamate derivative photoreactivity repeating unit, can show more excellent photoreactivity and orientation thus.Particularly, azo class photoreactivity functional group is to showing photoreactivity near the light of long wavelength's scope of visible light, and cinnamate derivative photoreactivity functional group relatively shows excellent photoreactivity to the light in short wavelength ultraviolet (UV) zone.Therefore; When said photoreactive polymer comprises the repeating unit of chemical formula 3 or 4 expressions; Further comprise under the situation of the cinnamate derivative repeating unit that Chemical formula 2 a or 2b represent; Light utilization efficiency be can further improve when using conventional light source, and more excellent photoreactivity and orientation shown.
Said photoreactive polymer is except the repeating unit content by said chemical formula 3 or 4 expressions; For example; Can comprise greater than 0mol% and below the 50mol%; Particularly greater than 0mol% and below the 40mol%, or greater than 0mol% and the repeating unit of representing by said Chemical formula 2 a or 2b below the 20mol%.In addition; At least a portion in the repeating unit of being represented by said Chemical formula 2 a or 2b comprises when representing photoreactivity functional group by Chemical formula 2 c; Its content is 10～50mol%, and 20～50mol% more specifically is to embody the photoreactivity based on this repeating unit.
On the other hand, constitute said photoreactive polymer by in chemical formula 3 or 4 expression repeating units and the repeating unit represented by Chemical formula 2 a or 2b, the group that the following functional group of the optional freedom of said polar functional group forms.In addition, also can be to comprise at least one various polar functional groups that are selected from oxygen, nitrogen, phosphorus, sulphur, silicon or the boron:
-R
5OR
6、-OR
6、-OC(O)OR
6、-R
5OC(O)OR
6、-C(O)OR
6、-R
5C(O)OR
6、-C(O)R
6、-R
5C(O)R
6、-OC(O)R
6、-R
5OC(O)R
6、-(R
5O)
r-OR
6、-(OR
5)
r-OR
6、-C(O)-O-C(O)R
6、-R
5C(O)-O-C(O)R
6、-SR
6、-R
5SR
6、-SSR
6、-R
5SSR
6、-S(＝O)R
6、-R
5S(＝O)R
6、-R
5C(＝S)R
6-、-R
5C(＝S)SR
6、-R
5SO
3R
6、-SO
3R
6、-R
5N＝C＝S、-N＝C＝S、-NCO、-R
5-NCO、-CN、-R
5CN、-NNC(＝S)R
6、-R
5NNC(＝S)R
6、-NO
2、-R
5NO
2；
In above-mentioned each functional group, r is 1～10 integer, R
5For replacing or the inferior cyclic hydrocarbon radical of unsubstituted C1～C20 alkylidene group, replacement or unsubstituted C2～C20 alkenylene, replacement or unsubstituted C2～C20 alkynylene, replacement or unsubstituted C3～C12, replacement or the inferior carbonyl oxygen of unsubstituted C6～C40 arylidene, replacement or unsubstituted C1～C20 base; Or replacement or unsubstituted C1～C20 alkylene oxide group
R
6, R
7And R
8Be selected from by hydrogen, halogen, replacement or unsubstituted C1～C20 alkyl, replacement or unsubstituted C2～C20 thiazolinyl, replacement or unsubstituted C2～C20 alkynyl, replacement or unsubstituted C3～C12 cyclic hydrocarbon radical, replacement or unsubstituted C6～C40 aryl, replacement or unsubstituted C1～C20 alkoxyl group, and replace or group that unsubstituted C1～C20 carbonyl oxygen base is formed in.
Constitute said photoreactive polymer by the repeating unit of chemical formula 3 or 4 expressions and represent repeating unit by Chemical formula 2 a or 2b, its polymerization degree is 50～5000, is preferably 100～4000, more preferably 1000～3000.Because these repeating units have the polymerization degree in the above-mentioned scope, said photoreactive polymer can be suitable comprises the alignment agent compsn that is used to form oriented layer, so can show excellent coating.
Below, specify each substituent definition in the said photoreactive polymer structure.
At first, " alkyl " expression carbonatoms is 1～20, preferred 1～10, and more preferably 1～6 the saturated monovalence hydrocarbon of straight or branched type position.Said alkyl is not only represented unsubstituted group, can also represent the substituted group of the specified substituent that is described below.But alkyl exemplified by methyl, ethyl, propyl group, 2-propyl group, normal-butyl, isobutyl-, the tertiary butyl, amyl group, hexyl, dodecyl, methyl fluoride, difluoromethyl, trifluoromethyl, chloromethyl, dichloromethyl, trichloromethyl, iodomethyl, brooethyl etc.
" thiazolinyl " expression has one or more carbon-to-carbon double bonds and carbonatoms is 2～20, is preferably 2～10, more preferably 2～6 straight or branched type monovalence hydrocarbon position.Thiazolinyl can be through having carbon-to-carbon double bond carbon atom or saturated carbon atom combined.Thiazolinyl is not only represented unsubstituted group, also representes the substituted group of the specified substituent that is described below.But thiazolinyl exemplified by vinyl, 1-propenyl, 2-propenyl, crotyl, 3-crotonyl, pentenyl, 5-hexenyl, laurylene base etc.
" cyclic hydrocarbon radical " expression has the monocyclic, bicyclic or tricyclic hydrocarbon of the saturated or undersaturated non-aromatics monovalence position of 3～12 ring carbon atoms, the substituted group of specified substituent of also representing to be described below.Cyclopropyl, cyclobutyl, cyclopentyl, cyclopentenyl, cyclohexyl, cyclohexenyl, suberyl, ring octyl group, decahydro naphthyl, adamantyl, norbornene of can giving an example (that is, dicyclo [2,2,1] heptan-5-thiazolinyl) etc.
" aryl " expression has 6～40, preferably has the monocyclic, bicyclic or tricyclic aromatic hydrocarbons of the monovalence position of 6～12 annular atomses, also representes the substituted group of the specified substituent that is described below.But aryl exemplified by phenyl, naphthyl and fluorenyl etc.
The substituted base of one or more Wasserstoffatoms alkoxies in the said aryl of " alkoxy aryl " expression.Alkoxy aryl can give an example p-methoxy-phenyl, ethoxyl phenenyl, propoxy-phenyl, butoxy phenyl, pentyloxy phenyl, hexyloxy phenyl, heptan oxygen base, octyloxy, ninth of the ten Heavenly Stems oxygen base, methoxyl group phenylbenzene, methoxyl group naphthyl, methoxyl group fluorenyl or methoxyl group anthryl (anthracenyl) etc.
One or more Wasserstoffatomss can also be represented the substituted group of the specified substituent that is described below by the substituted base of aryl in the said alkyl that is defined of " aralkyl " expression.But exemplified by benzyl, diphenyl-methyl and trityl etc.
" alkynyl " expression has one or more carbon-to-carbon triple bonds and carbonatoms is 2～20, is preferably 2～10, more preferably 2～6 straight or branched type monovalence hydrocarbon position.Said alkynyl can be combined through carbon atom or the saturated carbon atom with carbon-to-carbon triple bond.The alkynyl substituted group of specified substituent of can also representing to be described below.Can give an example ethynyl and proyl etc.
" alkylidene group " expression carbonatoms is 1～20, is preferably 1～10, more preferably 1～6 the saturated divalent hydrocarbon of straight or branched type position.Said alkylidene group can also represent by after the substituted group of certain substituting group stated.Alkylidene group can give an example methylene radical, ethylidene, propylidene, butylidene, hexylidene etc.
" alkenylene " expression has one or more carbon-to-carbon double bonds and carbonatoms is 2～20, is preferably 2～10, more preferably 2～6 straight or branched type divalent hydrocarbon position.Said alkenylene can be combined through having carbon-to-carbon double bond carbon atom and/or saturated carbon atom.Alkenylene can also be represented the substituted group of the specified substituent that is described below.
" inferior cyclic hydrocarbon radical " representative ring carbon atom is 3～12 the monocyclic, bicyclic or tricyclic hydrocarbon of saturated or unsaturated non-aromatic divalent position, can also represent the substituted group of the specified substituent that is described below.Can give an example cyclopropylene, cyclobutene etc.
" arylidene " expression has 6～20, preferably has the monocyclic, bicyclic or tricyclic aromatic hydrocarbon of the divalent position of 6～12 annular atomses, can also represent the substituted group of the specified substituent that is described below.The aromatics part only comprises carbon atom.The arylidene phenylene etc. of can giving an example.
One or more Wasserstoffatomss can also be represented the substituted group of the specified substituent that is described below by the substituted divalent of aryl position in the said alkyl of " inferior aralkyl " expression.The tolylene etc. of can giving an example.
" alkynylene " expression has one or more carbon-to-carbon triple bonds and carbonatoms is 2～20, is preferably 2～10, more preferably 2～6 straight or branched type divalent hydrocarbon position.Said alkynylene can be combined through carbon atom or the saturated carbon atom with carbon-to-carbon triple bond.Alkynylene can also be represented the substituted group of the specified substituent that is described below.Ethynylene or the propine support (propynylene) etc. of can giving an example.
In the above-mentioned explanation, substituting group " replaces or not replacement " and not only refers to each substituting group itself, also refers to further by the substituted group of certain substituting group.In this specification sheets, can halogen, alkyl, thiazolinyl, alkynyl, alkylhalide group, haloalkenyl, alkynyl halide, aryl, halogen aryl, aralkyl, halogen aralkyl, alkoxyl group, halogen alkoxyl group, carbonyl oxygen base, halogen carbonyl oxygen base, aryloxy, halogen aryloxy, siloyl group or siloxy etc. for example be arranged further substituted substituting group.
Said photoreactive polymer can show its photoreactivity under the polarisation with about 150～450nm wavelength exposes.For example, can have about 200～400nm wavelength, the polarisation of more specifically about 250～370nm wavelength exposes down, shows its photoreactivity.Different with the photoreactivity functional group of general reactive other kinds of display light under the polarisation condition of short wavelength range ultraviolet ray (UV); The photoreactivity functional group that is comprised in the repeating unit by said chemical formula 3 or 4 expressions; The azo class functional group that is promptly represented by Chemical formula 1 a～1c is to belonging to visible-range or also showing excellent photoreactivity and photoresponse speed fast near long wavelength's polarisation of its scope.In view of the above, use conventional i-line light source, said photoreactive polymer and the oriented layer that comprises this polymkeric substance also can show excellent light utilization efficiency.This is because conventional light sources such as said i-line also can send the light near visible wavelength that accounts for considerable part though belong to visible light.That is, when using said photoreactive polymer, the light that the visible light that is sent by this light source capable of using reaches near visible wavelength carries out photoresponse and orientation, therefore can further improve light utilization efficiency.And then; When said photoreactive polymer further comprises the repeating unit of being represented by Chemical formula 2 a or 2b with cinnamate derivative photoreactivity functional group; The light of the broader area that is sent by light source capable of using carries out photoresponse and orientation, thereby can further improve light utilization efficiency.
In sum, said photoreactive polymer can show excellent photoreactivity and photoresponse speed fast under the polarisation in the wavelength region of about 150～450nm exposes.More specifically, with the light in about 150～450nm wavelength region with 50～900mJ/cm
2Energy, preferably with 50～500mJ/cm
2The said photoreactive polymer of energy exposure the time, the flexible mode intensity of the C=C key that comprises among said Chemical formula 1 a～1c reaches the time (t of initial value till half the
1/2) be about below 1.5 minutes, be 1～1.5 minute more specifically, show fast photoresponse speed.
A kind of preparation method of said photoreactive polymer is provided on the other hand, according to another embodiment of the present invention.Said preparing method's a embodiment comprises, in the presence of the catalyst composition that comprises pre-catalyst with the 10th family's transition metal and promotor, and the monomer that addition polymerization is represented by Chemical formula 1 and form step by the repeating unit of chemical formula 3 expressions.
[Chemical formula 1]
In the said Chemical formula 1, p, R
1, R
2, R
3And R
4Like 3 definition of chemical formula.
At this moment, said polyreaction can be carried out under 10 ℃～200 ℃ temperature.If said temperature of reaction is lower than 10 ℃, can reduce polymerization activity, if be higher than 200 ℃, then can make catalyst decomposes, therefore inadvisable.
And, said promotor can comprise be selected from by be used to provide can with first promotor of complex bound Lewis base a little less than the metal of said pre-catalyst; And the group formed of second promotor that is used for providing the compound that contains the 15th family's electron donor ligand is at least a.Preferably, said promotor can use the catalyst mixture that comprises first promotor that said Lewis base is provided and second promotor of the compound that selectively contains neutral the 15th family's electron donor ligand is provided.
At this moment, said catalyst mixture can comprise said first promotor of 1～1000mol with respect to the said pre-catalyst of 1mol, and said second promotor of 1～1000mol.If the content of first promotor or second promotor is low excessively, might normally bring into play catalyst activity, if content is excessive, activity of such catalysts is descended.
In addition; The said pre-catalyst that comprises the 10th transition metal can use to have and be easy to participate in Lewis acid-alkali reaction; Thereby, thereby make this pre-catalyst make the center transition metal be converted into the catalyst activity kind through the first promotor separate easily that Lewis base is provided by the compound with lewis base functional group of central metal disengaging.[(Allyl) Pd (Cl)] for example arranged
2(Allylpalladiumchloridedimer), (CH
3CO
2)
2Pd [Palladium (II) acetate], [CH
3COCH=C (O-) CH
3]
2Pd [Palladium (II) acetylacetonate], NiBr (NP (CH
3)
3)
4, [PdCl (NB) O (CH
3)]
2Deng.
In addition; Provide first promotor of complex bound Lewis base a little less than can carrying out with the metal of said pre-catalyst to use to be easy to and the Lewis base reaction to form the room of transition metal; And for the stable transition metal that so forms and excessive metallic compound carry out a little less than complex bound compound or the compound of this transition metal is provided.B (C is for example arranged
6F
5)
3Deng borine, xylidine four (pentafluorophenyl group) boric acid ester boric acid ester, MAO (MAO) or Al (C such as (dimethylaniliniumtetrakis (pentafluorophenyl) borate)
2H
5)
3Deng aluminum alkyls, perhaps AgSbF
6Etc. transition metal halogenide etc.
In addition, provide said second promotor of the compound that contains neutral the 15th family's electron donor ligand can use alkylphosphines, cyclic hydrocarbon radical phosphorus or phosphniline etc.
In addition, can use said first promotor and second promotor separately, also can two kinds of promotors be processed a kind of salt after, use as the compound that is used for deactivated catalyst.For example, use ionic bond alkylphosphines and borine or boric acid ester compound and the compound that generates.
Can prepare repeating unit of representing by chemical formula 3 and the photoreactive polymer that comprises an embodiment of this repeating unit through aforesaid method.And, also can prepare the repeating unit of representing by Chemical formula 2 a through this preparation method, also can form the photoreactive polymer of the multipolymer form that comprises the repeating unit of representing by chemical formula 3 and/or 2a thus.
On the other hand, photoreactive polymer comprises the repeating unit by chemical formula 4 expression, or when comprising the repeating unit of representing by Chemical formula 2 b selectively, can be according to said preparing method's preparation of another embodiment.The preparation method of this another embodiment comprises: comprise have the 4th family, in the presence of the catalyst composition of the pre-catalyst of the 6th family or the 8th family's transition metal and promotor, the monomer that ring-opening polymerization is represented by said Chemical formula 1 and form step by the repeating unit of chemical formula 4 expressions.
In the said ring-opening polymerization step, hydrogenation in the two keys in the norbornylene basic ring of representing by said Chemical formula 1 that monomer comprised and carry out open loop and polymerization, preparation is by the repeating unit of said chemical formula 4 expressions and comprise the photoreactive polymer of this repeating unit.In addition, this preparation method is also applicable to the repeating unit of being represented by Chemical formula 2 b and comprise the preparation of the photoreactive polymer of this repeating unit.
Said ring-opening polymerization can be at the pre-catalyst that contains the 4th family (for example Ti, Zr, Hf), the 6th family (for example Mo, W) or the 8th family (for example Ru, Os) transition metal; The promotor of complex bound Lewis base a little less than can carrying out with the metal of said pre-catalyst is provided; And can strengthen selectively containing of said procatalyst metal active neutral the 15th family and the catalyst mixture existence of acvator (activator) composition of etc.ing of the 16th family's element under carry out.And; In the presence of said catalyst mixture; Based on normal olefines (linearalkene) such as the big or small 1-alkene of the adjustable whole molecule amount of monomer content interpolation 1～100mol%, 2-alkene; In 10 ℃～200 ℃ TRs, carry out polymerization; And the catalyzer that contains the 4th family (for example Ti, Zr) or the 8th family～the 10th family (for example Ru, Ni, Pd) transition metal based on monomer content interpolation 1～30 weight % carries out the hydrogenation reaction on the two keys in the norbornylene basic ring in 10 ℃～250 ℃ TRs.
If it is low that said reaction temperature is spent, can reduce polymerization activity, if too high then can make catalyst decomposes, therefore inadvisable.And, if said hydrogenation reaction temperature is low excessively, can reduce the activity of hydrogenation reaction, if too high then can make catalyst decomposes, therefore inadvisable.
Said catalyst mixture is with respect to the pre-catalyst that contains the 4th family (for example Ti, Zr, Hf), the 6th family (for example Mo, W) or the 8th family (for example Ru, Os) transition metal of 1mol; Comprise 1～100, the promotor of complex bound Lewis base a little less than the providing of 000mol can be carried out with the metal of said pre-catalyst; And the acvator (activator) that contains neutrality the 15th family and the 16th family's element that can strengthen the pre-catalyst metal active selectively of 1～100mol.
When the content of said promotor was lower than 1mol, catalyzer lost activity, and content during 000mol, can reduce activity of such catalysts more than 100, and is therefore inadvisable.According to the kind of pre-catalyst, or need not to use said acvator.When the content of acvator was lower than 1mol, catalyzer lost activity, and during more than 100mol, can reduce molecular weight, and is therefore inadvisable.
Hydrogenation reaction is employed (for example to contain the 4th family; Ti, Zr) or the 8th family～the 10th family is (for example; Ru, Ni, Pd) content of catalyzer of transition metal is when being lower than 1 weight % in monomer content; Hydrogenation reaction is insufficient, and polymkeric substance variable color when its content surpasses 30 weight % is therefore inadvisable.
The pre-catalyst that contains said the 4th family (for example, Ti, Zr, Hf), the 6th family (for example, Mo, W) or the 8th family (for example, Ru, Os) transition metal, can use have the functional group that is easy to participate in Lewis acid-alkali reaction and breaks away from central metal like TiCl
4, WCl
6, MoCl
5Or excessive metallic compounds such as RuCl3 and ZrCl4, make through providing lewis acidic promotor to break away from easily, thereby the center transition metal of making is converted into the catalyst activity kind.
In addition, the promotor of complex bound Lewis base a little less than can carrying out with the metal of said pre-catalyst is provided, can uses (C like B
6F
5)
3Deng borine or boric acid ester, MAO (MAO) or Al (C
2H
5)
3Or Al (CH
3) Cl
2In aluminum alkyls, halogenated aluminum, haloalkyl aluminium.Perhaps replace aluminium can use replacement such as lithium (lithium), magnesium (magnesium), germanium (germanium), lead, zinc, tin, silicon.This promotor can comprise, and is easy to form with Lewis base reaction the room of transition metal, and for the stable transition metal that generates thus with excessive metallic compound a little less than complex bound compound or the compound of this transition metal is provided.
Can add acvator in the polymerization, but according to the kind of procatalyst or need not to use acvator.The acvator (activator) that contains neutrality the 15th family and the 16th family's element that can strengthen said procatalyst metal active has water, methyl alcohol, ethanol, Virahol, phenylcarbinol, phenol, sulfur alcohol (ethylmercaptan), ethylene chlorhydrin, Trimethylamine 99, triethylamine, pyridine (pyridine), oxyethane (ethyleneoxide), Lucidol (benzoylperoxide), tert-butyl peroxide (t-butylperoxide) etc.
Employedly in the hydrogenation reaction (for example contain the 4th family; Ti, Zr) or the 8th family～the 10th family is (for example; Ru, Ni, Pd) catalyzer of transition metal is for can be dissolved in homogeneous (homogeneous) shape of solvent at once, and perhaps said metal catalyst coordination compound is carried on the catalyzer on the particle carrier.Said particle carrier, preferred silicon-dioxide, titanium oxide, silicon-dioxide/chromic oxide, silicon-dioxide/chromic oxide/titanium oxide, silica/alumina, phosphaljel, silylanizing silica, silica-alumina hydrogel, illiteracy are taken off clay or zeolite.
Can prepare repeating unit of representing by chemical formula 4 and the photoreactive polymer that comprises another embodiment of this repeating unit through aforesaid method.And, can prepare the repeating unit of representing by Chemical formula 2 b through this preparation method, also can form the photoreactive polymer of the polymer form that comprises the repeating unit of representing by chemical formula 4 and/or 2b thus.
On the other hand, a kind of oriented layer that comprises said photoreactive polymer is provided according to still another embodiment of the invention.Said oriented layer also can comprise the oriented layer of film forms except comprising form of film.A kind of liquid crystal retardation film that comprises the liquid crystal layer on said oriented layer and the oriented layer is provided according to still another embodiment of the invention.
Except comprising photoreactive polymer, can use material as known in the art and preparation method to prepare said oriented layer and liquid crystal retardation film as the light orientated polymer.
For example, mix said photoreactive polymer, adhesive resin and light trigger, and in organic solvent, dissolve, obtain coating composition after, its coating composition is coated on the substrate, solidify to form said oriented layer through UV.
At this moment, said adhesive resin can use the acrylate resinoid, can use pentaerythritol triacrylate, double pentaerythritol methacrylate, Viscoat 295, triol (2-acrylyl oxy-ethyl) chlorinated isocyanurates etc. particularly.Said light trigger can use the known conventional light trigger that can be used in oriented layer and not receive special restriction.For example, can use known commodity to be called Irgacure907,819 light trigger.
In addition, said organic solvent can use toluene, methyl-phenoxide, chlorobenzene, ethylene dichloride, hexanaphthene, pentamethylene, 1-Methoxy-2-propyl acetate etc.Because of said photoreactivity norbornylene analog copolymer shows excellent solubleness to most of organic solvents,, can use various organic solvents so this is not done special restriction.
In the said coating composition; The concentration that comprises the solid shape powder of said photoreactive polymer, adhesive resin and light trigger is 1～15 weight %, and for the said oriented layer of casting with film forms, is preferably 10～15 weight %; And, be preferably 1～5 weight % in order to form with form of film.
The oriented layer that so forms can be formed on the substrate, and is formed on below the liquid crystal to play the effect of orientation.At this moment; Said substrate can use the substrate that comprises cyclic polymer, comprise the substrate of XPA or comprise substrate of cellulose polymer compound etc.; And use methods such as scraper coating, rotary coating, scraper plate coating; Behind the said coating composition of coating on the said substrate, be solidified to form oriented layer through UV.
Light orientation possibly take place in the said UV solidification process, but the illumination wavelength scope is that the polarization UV of about 150～450nm carries out orientation process in this step.At this moment, exposure energy is about 50mJ/cm
2～10J/cm
2, preferably about 500mJ/cm
2～5J/cm
2
Said UV is applicable to be selected from through UV being seen through or reflecting in the polarising means that 1. utilizes the substrate of coating dielectric anisotropy material on the transparency carrier surfaces such as silica glass, soda-lime glass, no soda-lime glass; The polarization plates of 2. accurate deposition of aluminum or metal wire; Or 3. carry out the polarization UV among the UV of polarization manipulation based on the method for Brewster (Brewster) polarising means of silica glass reflection etc.
Substrate temperature when shining said UV is preferably normal temperature.But in case of necessity, can under substrate being heated to 100 ℃ of states in the following TR, shine UV.The thickness of the coating that forms through said a series of processes is preferably 30～1000nm.
Form oriented layer through aforesaid method, form liquid crystal layer in the above, thereby prepare liquid crystal retardation film with ordinary method.
Above-mentioned oriented layer or liquid crystal retardation film are also applicable to optical film that represents stereopsis or optical filter.
A kind of display device that comprises said oriented layer is provided according to still another embodiment of the invention.This display device can be applicable to, and comprises the liquid-crystal display of said oriented layer for liquid crystal aligning, perhaps is used for representing the optical film of stereopsis or dimensional image display that wave filter comprises said oriented layer etc.The structure of these display devices is except that comprising said photoreactive polymer and oriented layer this point, and its structure is as the criterion with the structure of conventional device, therefore omits its detailed description.
In order to help to understand the present invention, preferred embodiment is proposed below.Yet following examples just are used for schematically representing the present invention, can not only limit the present invention with it.
In following examples, all operations that relates to the compound of air or water sensitive all uses standard Shu Lunke technology (standardSchlenktechnique) or dry box method (dry box method) to implement.Nucleus magnetic resonance (NMR) spectrum obtains through using Brooker 300 spectrometers (Bruker 300spectrometer), at this moment
1H NMR under 300MHz, and
13C NMR detects respectively under 75MHz.The molecular weight of open loop hydrogenation polymkeric substance and MWD detect through using GPC (gel permeation chromato graphy), this moment with PS (poly styrene) sample as standard.Toluene is by potassium/benzophenone (potassium/benzo phenone) distillatory refining, and methylene dichloride is by CaH
2Distillatory refining.
< embodiment 1 >: the polymerization of
In 250mL Shu Lunke (Schlenk) flask, add as monomeric 1.26g (3mmol)
with the 3mL toluene of solvent refined.In this flask, add the 6.73mg Pd (OAc) that is dissolved in the 1mL methylene dichloride as catalyzer then
2With the 7.76mg tricyclohexyl phosphine, add 6.53mg dimethyl-puratized agricultural spray four (pentafluorophenyl group) borate (dimethylaniliniumtetrakiss (pentafluorophenyl) borate) as promotor, stirring reaction is 18 hours under 90 ℃ of temperature.
React after 18 hours, said reactant is put into excess ethanol obtain the white polymer throw out.Use glass funnel to filter this throw out,, the polymkeric substance of collecting drying in 60 ℃ of vacuum drying ovens was got 1.19g polymkeric substance (Mw=31,000 in 24 hours with collected polymer; PDI=1.7; Productive rate=94%).With the 1HNMR data representation of the polymkeric substance that makes among the embodiment 1 in Fig. 1.
< embodiment 2 >: the polymerization of
In 250mL schlenk flask, add as monomeric 3.0g (6.69m mol)
with the 4mL toluene of solvent refined.In this flask, add the 0.75mg Pd (OAc) 2 and 0.86mg tricyclohexyl phosphine that is dissolved in the 1mL methylene dichloride as catalyzer then, add 0.72mg dimethyl-puratized agricultural spray four (pentafluorophenyl group) borate as promotor, stirring reaction is 18 hours under 90 ℃ of temperature.
React after 18 hours, said reactant is put into excess ethanol obtained the white polymer throw out.Use glass funnel to filter this throw out, with collected polymer, and this polymkeric substance that will collect drying in 60 ℃ of vacuum drying ovens got 2.55g polymkeric substance (Mw=56,000 in 24 hours; PDI=1.9; Productive rate=85%).
< embodiment 3 >: the copolymerization of
In 250mL schlenk flask, add as monomeric 0.628g (1.5mmol)
0.249g (1.5mmol)
with the 3mL toluene of solvent refined.In this flask, add the 6.73mg Pd (OAc) 2 and 7.76mg tricyclohexyl phosphine that is dissolved in the 1mL methylene dichloride as catalyzer then, add 6.53mg dimethyl-puratized agricultural spray four (pentafluorophenyl group) borate as promotor, stirring reaction is 18 hours under 90 ℃ of temperature.
React after 18 hours, said reactant is put into excess ethanol obtain the white polymer throw out.Use glass funnel to filter this throw out,, and the polymkeric substance of collecting obtained 0.75g multipolymer (Mw=29,000 in dry 24 hours in 60 ℃ of vacuum drying ovens with collected polymer; PDI=2.1; Productive rate=86%).
< embodiment 4 >: the polymerization of
In 250mL schlenk flask, add as monomeric 1.46g (3mmol)
with the 3mL toluene of solvent refined.In this flask, add the 6.73mg Pd (OAc) 2 and 7.76mg tricyclohexyl phosphine that is dissolved in the 1mL methylene dichloride as catalyzer then, add 6.53mg dimethyl-puratized agricultural spray four (pentafluorophenyl group) borate as promotor, stirring reaction is 18 hours under 90 ℃ of temperature.
React after 18 hours, said reactant is put into excess ethanol obtain the yellow polymer throw out.Use glass funnel to filter this throw out,, and the polymkeric substance of collecting obtained 0.88g multipolymer (Mw=61,000 in dry 24 hours in 60 ℃ of vacuum drying ovens with collected polymer; PDI=2.6; Productive rate=64%).
< embodiment 5 >: the polymerization of
In 250mL Schlenk flask, add as monomeric 1.2g (3mmol)
with the 3mL toluene of solvent refined.In this flask, add the 6.73mg Pd (OAc) 2 and 7.76mg tricyclohexyl phosphine that is dissolved in the 1mL methylene dichloride as catalyzer then, add 6.53mg dimethyl-puratized agricultural spray four (pentafluorophenyl group) borate as promotor, stirring reaction is 18 hours under 90 ℃ of temperature.
React after 18 hours, said reactant is put into excess ethanol obtain the yellow polymer throw out.Use glass funnel to filter this throw out,, and the polymkeric substance of collecting obtained 1.06g multipolymer (Mw=47,000 in dry 24 hours in 60 ℃ of vacuum drying ovens with collected polymer; PDI=3.5; Productive rate=51%).
< embodiment 6 >: ring-opening polymerization of 5-norbornylene-2-methyl alcohol (ring opening methathesis polymerization) and hydrogenation reaction (hydrogenation)
Under the Ar atmosphere, in the 250ml Schlenk flask, behind adding 6.20g (50mmol) 5-norbornylene-2-methyl alcohol, add 34g toluene again with solvent refined.This flask is remained under the state of 80 ℃ of polymerization temperatures, add 11.4mg (1.0mmol) triethyl aluminum (triethylaluminum) earlier as promotor.The mixed of then adding with 1: 3 has tungsten hexachloride (WCl8) and alcoholic acid 0.01M (mol/L) toluene solution 1ml (0.01mmol WCl8,0.03mmol ethanol).After adding 0.84g (7.5mmol) the 1-octene as molecular weight adjustment agent at last, stirring reaction is 18 hours under 80 ℃ of temperature.After reaction finishes, in polymer fluid, splash into a small amount of polymerization terminator ethyl vinyl ether (ethyl vinyl ether) and stirred 5 minutes.
Said polymer fluid is transferred in the 300mL high-pressure reactor, added 0.06mL triethyl aluminum (TEA).After then adding 0.50g Gray Si Raney's nickel (grace raney Nickel) (the slurry phase in the water), hydrogen pressure is remained on 80atm, and under 150 ℃ of temperature stirring reaction 2 hours.After reaction finishes, polymer fluid splashed into carry out post precipitation in the acetone and filter, and in 70 ℃ of vacuum drying ovens dry 15 hours.Make open loop hydrogenation polymkeric substance (ring-opened hydrogenated polymer) (productive rate=90.6% of 5.62g 5-norbornylene-2-methyl alcohol; Mw=69,900; PDI=4.92).
< embodiment 7 >: the open loop hydrogenation polymkeric substance of
synthetic
In 250mL2-wide neck flask (neckflask), add the 5-norbornylene-2-methyl alcohol that makes among the embodiment 6 the hydrogenation polymkeric substance (15g, 0.121mol), triethylamine (Aldrich, 61.2g, 0.605mol), behind the 50mlTHF, ice-stirred in water bath of 0 ℃.Make (32.5g; 0.133mol) after 60ml
is dissolved among the THF, slowly put into another flask.After 10 minutes temperature of charge was brought up to behind the normal temperature restir 18 hours.Use the ETHYLE ACETATE diluting soln, use separating funnel to shift and water and NaHC0
3Cleaning many times splashes in the acetone deposition with reaction solution then and filters, and in 70 ℃ of vacuum drying ovens dry 15 hours (productive rates: 93%).
<Example 8>:
and
copolymerization of
In 250mL Schlenk flask, add as monomeric 0.674g (1.5mmol)
and 0.43g (1.5mmol)
and with the 3mL toluene of solvent refined.In this flask, add 26.73mg Pd (OAc) and the 7.76mg tricyclohexyl phosphine that is dissolved in the 1mL methylene dichloride as catalyzer then, add 6.53mg dimethyl-puratized agricultural spray four (pentafluorophenyl group) borate as promotor, stirring reaction is 18 hours under 90 ℃ of temperature.
React after 18 hours, said reactant is put into excess ethanol obtain light yellow polymer precipitation thing.Use glass funnel to filter this throw out,, and the polymkeric substance of collecting obtained 0.91g multipolymer (Mw=92,000 in dry 24 hours in 60 ℃ of vacuum drying ovens with collected polymer; PDI=2.96; Productive rate=82%).
< comparative example 1 >: the copolymerization of
In 250mL Schlenk flask, add as monomeric 0.251g (0.6mmol)
and 0.398g (2.4m mol)
and with the 3mL toluene of solvent refined.In this flask, add the 6.73mg Pd (OAc) that is dissolved in the 1mL methylene dichloride as catalyzer then
2With the 7.76mg tricyclohexyl phosphine, add 6.53mg dimethyl-puratized agricultural spray four (pentafluorophenyl group) borate as promotor, stirring reaction is 18 hours under 90 ℃ of temperature.
React after 18 hours, said reactant is put into obtained the white polymer throw out in the excess ethanol.Use glass funnel to filter this throw out,, and the polymkeric substance of collecting obtained 0.53g multipolymer (Mw=26,000 in dry 24 hours in 60 ℃ of vacuum drying ovens with collected polymer; PDI=1.88; Productive rate=82%).With the 1HNMR data representation of the polymkeric substance of comparative example 1 in Fig. 2.
< preparation example 1 >: use the polymkeric substance of embodiment 1 to prepare oriented layer
To use the monomeric photoreactive polymer of synthetic among the said embodiment 1
; Concentration with 2 weight % is dissolved in c-pentanone (c-pentanone) solvent; With rolling method it being coated on thickness is 80 microns polyethyleneterephthalate (trade(brand)name: SH71; The production of Korea S SKC company) on the substrate; Dried thickness reaches
then; Heating is 3 minutes in 80 ℃ of baking ovens; Removing the coated film internal solvent, thereby form coated film.
It is 200mW/cm that exposure light source adopts intensity
2High voltage mercury lamp, and use wiregrating (Wire-grid) polarizer of Moxtek manufactured, obtain the UV with film orientation vertical polarization, obtain liquid crystal arrangement 5 seconds with this light source irradiation coated film, with the formation oriented layer.
Then; To be mixed with the solid shape powder of 5.0 weight % gorgeous good solid 907 (productions of Switzerland Ciba-Geigy company) with the UV polymerizability cyanobiphenyl base propenoate of 95.0 weight % with as light trigger; Be dissolved in the toluene solvant; So that reach 25 weight parts, thereby make polymerisable reactive liquid crystalline solution with respect to the liquid crystal content of the liquid crystal solution of 100 weight.
With the roller coating method liquid crystal solution that makes is coated on the said established smooth oriented layer, reaches 1 μ m until dried thickness, drying made liquid crystal molecule be able to orientation in 2 minutes under 80 ℃ of temperature afterwards.Use intensity to be 200mW/cm
2High voltage mercury lamp as the unpolarized UV of light source, the liquid crystal film that irradiation has been arranged with fixing liquid crystal state of orientation, thereby makes phase shift films.
For the orientation of the above-mentioned phase shift films that makes, compare with light leak between printing opacity appearance (transmittance) the measurement polarization plates, and use Axoscan (Axomatrix manufactured) to detect quantitative property phase difference.
< comparative preparation example 1 >
Except replace employed pure 100%
among the embodiment 1photoreactive polymer of monomer-polymer; Use outside the multipolymer of monomer ratio
and
=2: 8 (adding monomeric mol ratio), prepared oriented layer with routine 1 same procedure of preparation.
< Test Example 1 >
Photoreactivity evaluation-FT-IR spectrum
For the photoreactive evaluation of oriented layer, observe the FT-IR spectrum of the liquid crystal aligning layer that makes in preparation example 1～comparative preparation example 1, so that (use has 20mW/cm in exposure
2The mercury lamp of intensity) down in the polymkeric substance of said Chemical formula 1 a～1c the intensity of the flexible pattern of C=C key reach time (t1/2) and the Energy Conversion value (E of initial value till half the
1/2=20mW/cm
2Xt
1/2) estimate as benchmark.Its result is illustrated in the following table 1.
Compare t
1/2Can know, with the t of comparative preparation example 1
1/2Compare the t of preparation example 1
1/2Shortened approximately more than 1/2, can confirm to use the polymkeric substance of embodiment thus, the speed of orientation of liquid crystal aligning layer is faster.
[table 1]
< Test Example 2 >
Orientation is estimated (light leak degree evaluation)
For the evaluation of oriented layer orientation, use polarizing microscope between two polarizers of arranged perpendicular, observed the liquid crystal retardation film that makes in preparation example 1 and the comparative preparation example 1.Promptly; Polyethyleneterephthalate (trade(brand)name: SH71 with 80 microns of thickness; Korea S SKC company produces) as benchmark, between the polarizer of arranged perpendicular, put into the liquid crystal retardation film that preparation example 1 and comparative preparation example 1 make after; Observe the degree that irradiates light sees through polarization plates and phase shift films with polarizing microscope, measure the light leak degree with this.Its liquid crystal aligning of phase shift films of preparation example 1 does not receive the influence of lambda1-wavelength, and differently-oriented directivity is even, and when using the oriented layer of comparative preparation example 1, alignment capability descends, and causes the liquid crystal aligning direction inhomogeneous.
< Test Example 3 >
The synthetic photoreactive polymer has been tested anisotropy and UV reactivity among the use embodiment 1.With the 2wt% pentamethylene solution of the said polymkeric substance of dissolving, be spin-coated on the silicon chip with 1000rpm speed after, in the baking oven of 80 degree dry 1 minute.Working strength be 15mW/cm2 pass through UV lamp (level 82%) polarising UV, shine about 60 seconds (with the 365nm standard, the 0.9J/cm2 energy exposure), observe its variation.Its result is illustrated among Fig. 3.With reference to Fig. 3, confirm that polarization UV irradiation back forms anisotropy.When the placement direction of sample is vertical with polarization UV direction of illumination, compares demonstration when parallel and more beat big light absorption ratio (absorbance) value, hence one can see that forms anisotropy along the vertical direction of polarization UV.In addition, can know through these tests, the photoreactive polymer of embodiment, the polarized light to its photoreactive 365nm long wavelength of the difficult demonstration of photoreactive polymer in the past also shows excellent photoreactivity.
Photoreactive polymer according to the present invention comprises the high norbornylene class repeating unit of second-order transition temperature as main repeating unit, therefore can show excellent thermostability.And said photoreactive polymer comprises the more relatively norbornylene class repeating unit that contains specific azo class photoreactivity functional group of content, has therefore not only significantly improved photoresponse speed, and shows excellent orientation and light utilization efficiency.
Therefore, use said photoreactive polymer, oriented layer with excellent specific property and liquid crystal retardation film etc. can be provided, can also significantly improve processing procedure efficient.
Claims (14)
1. a photoreactive polymer is characterized in that, comprising content is the above repeating unit by following chemical formula 3 or 4 expressions of 50mol% of total polymer:
[chemical formula 3] [chemical formula 4]
In chemical formula 3 or 4, n is 50～5000, and p is 0～4 integer,
R
1, R
2, R
3And R
4In at least one be the group that is selected from the group of being formed by following Chemical formula 1 a, 1b and 1c,
Remaining R
1, R
2, R
3And R
4Be independently selected from respectively by hydrogen; Halogen; Replace or unsubstituted C1～C20 alkyl; Replace or unsubstituted C2～20 thiazolinyls; Replace or unsubstituted C2～20 alkynyls, replacement or unsubstituted C3～12 cyclic hydrocarbon radical; The aryl of replacement or unsubstituted C6～40; And comprise and be selected from the group that at least a polar functional group in oxygen, nitrogen, phosphorus, sulphur, silicon and the boron forms,
Wherein, as said R
1～R
4When all not being hydrogen, halogen or polar functional group, R
1And R
2Perhaps R
3And R
4Interconnect and form the alkylidene of C1～C10, perhaps R
1Or R
2With R
3And R
4In one connect and form the saturated or undersaturated ring of C4～C12 or form the aromatic ring of C6～C24,
[Chemical formula 1 a]
[Chemical formula 1 b]
Perhaps
[Chemical formula 1 c]
Among said Chemical formula 1 a, 1b or the 1c, n1, p1, r1 and m1 are 0～4 integer, and n2, p2, r2 and m2 are 0～5 integer,
A is replacement or unsubstituted C1～C20 alkylidene group, carbonyl, carboxyl, replacement or unsubstituted C6～C40 arylidene or singly-bound,
B be oxygen, sulphur ,-NH-or singly-bound,
R
9For the arylidene of inferior cyclic hydrocarbon radical, replacement or the unsubstituted C6～C40 of alkynylene, replacement or the unsubstituted C3～C12 of alkenylene, replacement or the unsubstituted C2～C20 of alkylidene group, replacement or the unsubstituted C2～C20 of singly-bound, replacement or unsubstituted C1～C20, or replace or the inferior aralkyl of unsubstituted C7～C15
R
10And R
11Be independently hydrogen, halogen, replacement or unsubstituted C1～C20 alkyl, replacement or unsubstituted C1～C20 alkoxyl group, replacement or unsubstituted C6～C30 aryloxy, or replace or unsubstituted C6～C40 aryl.
2. photoreactive polymer according to claim 1 is characterized in that, further comprises the repeating unit of being represented by following Chemical formula 2 a or 2b:
[Chemical formula 2 a] [Chemical formula 2 b]
Among said Chemical formula 2 a or the 2b, m is 50～5000, and q ' is 0～4 integer,
R
1', R
2', R
3' and R
4' be independently selected from the group of representing by Chemical formula 2 c respectively; Hydrogen; Halogen; Replace or unsubstituted C1～C20 alkyl; Replace or unsubstituted C2～C20 thiazolinyl; Replace or unsubstituted C2～C20 alkynyl; Replace or unsubstituted C3～C12 cyclic hydrocarbon radical; Replace or unsubstituted C6～C40 aryl; And comprise and be selected from the group that at least a polar functional group in oxygen, nitrogen, phosphorus, sulphur, silicon and the boron forms,
Wherein, as said R
1'～R
4' when all not being hydrogen, halogen or polar functional group, R
1' and R
2' or R
3' and R
4' interconnect and form the alkylidene of C1～C10, perhaps R
1' or R
2' with R
3' and R
4' in one connect and form the saturated or unsaturated ring of C4～C12 or form the aromatic ring of C6～C24,
[Chemical formula 2 c]
In said Chemical formula 2 c, L is 0 or 1,
D and D ' are independently selected from respectively in the group of being made up of the straight chain of the inferior cyclic hydrocarbon radical of the straight chain of singly-bound, nitrogen, oxygen, sulphur, replacement or unsubstituted C1～C20 or branched chain type alkylidene group, replacement or unsubstituted C3～C12, replacement or unsubstituted C1～C20 or branched chain type epoxy alkyl and replacement or the inferior cyclic hydrocarbon radical oxygen of unsubstituted C3～C12 base
X and Y be independently selected from respectively by hydrogen, halogen, cyanogen, and replace or the straight chain of unsubstituted C1～C20 or group that branch chain type alkyl is formed in,
R
10'～R
14' be independently selected from respectively by hydrogen; Halogen; Cyanogen; Replace or unsubstituted C1～C20 alkyl; Replace or unsubstituted C1～C20 alkoxyl group; Replace or unsubstituted C6～C30 aryloxy; Replace or unsubstituted C6～C40 aryl; The heteroaryl that comprises the 14th family, the 15th family, the heteroatomic C6～C40 of the 16th family; And in the group formed of the alkoxy aryl of replacement or unsubstituted C6～C40.
3. photoreactive polymer according to claim 2 is characterized in that:
R
1', R
2', R
3' and R
4' at least one be the group of representing by Chemical formula 2 c.
4. photoreactive polymer according to claim 1 and 2 is characterized in that, said polar functional group is selected from the group of being made up of following functional group:
-R
5OR
6、-OR
6、-OC(O)OR
6、-R
5OC(O)OR
6、-C(O)OR
6、-R
5C(O)OR
6、-C(O)R
6、-R
5C(O)R
6、-OC(O)R
6、-R
5OC(O)R
6、-(R
5O)
r-OR
6、-(OR
5)
r-OR
6、-C(O)-O-C(O)R
6、-R
5C(O)-O-C(O)R
6、-SR
6、-R
5SR
6、-SSR
6、-R
5SSR
6、-S(＝O)R
6、-R
5S(＝O)R
6、-R
5C(＝S)R
6-、-R
5C(＝S)SR
6、-R5SO
3R
6、-SO
3R
6、-R
5N＝C＝S、-N＝C＝S、-NCO、-R
5-NCO、-CN、-R
5CN、-NNC(＝S)R
6、-R
5NNC(＝S)R
6、-NO
2、-R
5NO
2；
In above-mentioned each functional group, r is 1～10 integer, R
5For replacing or the inferior cyclic hydrocarbon radical of unsubstituted C1～C20 alkylidene group, replacement or unsubstituted C2～C20 alkenylene, replacement or unsubstituted C2～C20 alkynylene, replacement or unsubstituted C3～C12, replacement or the inferior carbonyl oxygen of unsubstituted C6～40 arylidene, replacement or unsubstituted C1～C20 base, or replacing or unsubstituted C1～C20 alkylene oxide group
R
6, R
7And R
8Be selected from by hydrogen; Halogen, replacement or unsubstituted C1～C20 alkyl, replacement or unsubstituted C2～C20 thiazolinyl, replacement or unsubstituted C2～C20 alkynyl, replacement or unsubstituted C3～C12 cyclic hydrocarbon radical, replacement or unsubstituted C6～C40 aryl, replacement or unsubstituted C1～C20 alkoxyl group, and replace or group that the carbonyl oxygen base of unsubstituted C1～C20 is formed in.
5. photoreactive polymer according to claim 1 is characterized in that:
At least a repeating unit in the group of forming by the repeating unit of chemical formula 3 and 4 expressions that is selected from that comprises 100mol%.
6. according to claim 2 or 3 described photoreactive polymers, it is characterized in that:
Comprise the multipolymer that is selected from least a repeating unit in the group of forming by at least a repeating unit in the group formed of repeating unit of chemical formula 3 and 4 expressions with greater than the repeating unit that 0mol% and being selected from below the 50mol% are represented by Chemical formula 2 a and 2b that is less than 100mol% more than the 50mol%.
7. photoreactive polymer according to claim 1 is characterized in that:
Under polarizing light irradiation, show photoreactivity with 150～450nm wavelength.
8. photoreactive polymer according to claim 7 is characterized in that:
When having the polarized light of 150～450nm wavelength with 50～900mJ/cm2 energy exposure, the intensity of the flexible pattern of the C=C key that comprises among said Chemical formula 1 a～1c reaches the time (t of initial value till half the
1/2) smaller or equal to 1.5 minutes.
9. the preparation method of the described photoreactive polymer of claim 1; It is characterized in that comprising; In the presence of the catalyst composition that comprises pre-catalyst with the 10th family's transition metal and promotor, the monomer that addition polymerization is represented by Chemical formula 1 and form step by the repeating unit of chemical formula 3 expressions:
[Chemical formula 1]
In the said Chemical formula 1, p, R
1, R
2, R
3And R
4Like 3 definition of chemical formula.
10. the preparation method of the described photoreactive polymer of claim 1; It is characterized in that comprising; Comprise have the 4th family, in the presence of the catalyst composition of the pre-catalyst of the 6th family or the 8th family's transition metal and promotor, the monomer that ring-opening polymerization is represented by Chemical formula 1 and form step by the repeating unit of chemical formula 4 expressions:
[Chemical formula 1]
In the said Chemical formula 1, p, R
1, R
2, R
3And R
4Like 4 definition of chemical formula.
11. method according to claim 10 is characterized in that:
In the said ring-opening polymerization step, hydrogenation in two keys of the norbornylene basic ring of representing by Chemical formula 1 that monomer comprised and carry out open loop and polymerization.
12. an oriented layer is characterized in that, comprises each described photoreactive polymer in the claim 1～8.
13. a liquid crystal retardation film is characterized in that, comprises the liquid crystal layer on described oriented layer of claim 12 and the oriented layer.
14. a display device is characterized in that, comprises the described oriented layer of claim 12.
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| CN107109231A (en) * | 2014-12-18 | 2017-08-29 | 株式会社Lg化学 | Include the vertical orientated layer of cycloolefin (common) polymers |
| CN107111192A (en) * | 2014-11-18 | 2017-08-29 | 夏普株式会社 | Liquid crystal display device |
| CN108885375A (en) * | 2016-11-28 | 2018-11-23 | 株式会社Lg化学 | Liquid crystal orientation film, methods for making them and the liquid crystal display device using it |
| CN110235055A (en) * | 2017-10-17 | 2019-09-13 | 株式会社Lg化学 | Liquid crystal orientation film and the liquid crystal display device for using it |
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| WO2013115628A1 (en) | 2012-02-02 | 2013-08-08 | 주식회사 엘지화학 | Liquid crystal composition |
| KR101515527B1 (en) | 2012-08-21 | 2015-04-27 | 주식회사 엘지화학 | Optical anistropic film |
| KR101976864B1 (en) * | 2013-08-22 | 2019-05-09 | 전북대학교산학협력단 | Method for manufacturing liquid crystal display device and liquid crystal display device manufactured by using the same |
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| CN108885375A (en) * | 2016-11-28 | 2018-11-23 | 株式会社Lg化学 | Liquid crystal orientation film, methods for making them and the liquid crystal display device using it |
| CN108885375B (en) * | 2016-11-28 | 2021-05-18 | 株式会社Lg化学 | Liquid crystal alignment film, method for preparing the same, and liquid crystal display device using the same |
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| CN110235055A (en) * | 2017-10-17 | 2019-09-13 | 株式会社Lg化学 | Liquid crystal orientation film and the liquid crystal display device for using it |
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| JP2012022317A (en) | 2012-02-02 |
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