CN103922932A - Polymerizable Compounds And Use Thereof In Liquid Crystal Displays - Google Patents
Polymerizable Compounds And Use Thereof In Liquid Crystal Displays Download PDFInfo
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- 0 CCC(C=C(*)C(C1=C(*C)C=C(**)*(C)C)=C2NC1=CC)=C*2IC=C Chemical compound CCC(C=C(*)C(C1=C(*C)C=C(**)*(C)C)=C2NC1=CC)=C*2IC=C 0.000 description 24
- JPJFBLIUWXXTTA-UHFFFAOYSA-N CC(C)(c1c-2c(CC3)cc(Br)c1)c1c-2c3cc(Br)c1 Chemical compound CC(C)(c1c-2c(CC3)cc(Br)c1)c1c-2c3cc(Br)c1 JPJFBLIUWXXTTA-UHFFFAOYSA-N 0.000 description 2
- ZZLCFHIKESPLTH-UHFFFAOYSA-N Cc(cc1)ccc1-c1ccccc1 Chemical compound Cc(cc1)ccc1-c1ccccc1 ZZLCFHIKESPLTH-UHFFFAOYSA-N 0.000 description 1
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Abstract
The present invention relates to polymerisable compounds, to processes and intermediates for the preparation thereof, and to the use thereof for optical, electro-optical and electronic purposes, in particular in liquid-crystal (LC) media and LC displays, especially in LC displays of the PS (''polymer sustained'') or PSA (''polymer sustained alignment'') type.
Description
The application is that application number is the divisional application of 201180030386.5 Chinese patent application.
The method that the present invention relates to polymerizable compound, prepare for it and intermediate, with its purposes for optics, electrooptics and electronics object, particularly in liquid crystal (FK) medium and liquid-crystal display, the especially purposes in the liquid-crystal display of PS (" polymer stabilizing ") and PSA (" polymer-stabilized alignment ") type.
Normally those of TN (" twisted-nematic ") type of the liquid-crystal display (FK-indicating meter) using at present.But these have the defect of striking contrast degree view angle dependency.In addition, known so-called VA (" the vertical orientation ") indicating meter with wider visual angle.The liquid crystal cell of VA indicating meter is included in two liquid crystal media layers between transparency electrode, and wherein this liquid crystal media has negative dielectric (DK-) anisotropy value conventionally.Under off-position, the molecule of liquid crystal layer perpendicular to electrode surface (vertical plane ground) orientation or inclination vertical plane ground (" inclinations ") be orientated.In the time voltage being applied on two electrodes, there is the reorientation that liquid crystal molecule is parallel to electrode surface.
In addition, known OCB (" optical compensation curved ") indicating meter, it is based on birefringence effect and have and have so-called " bending " orientation and common positive (DK-) anisotropic liquid crystal layer.In the time applying voltage, there is the reorientation of liquid crystal molecule perpendicular to electrode surface.In addition, OCB indicating meter contains one or more double refraction optics phase shift films conventionally, to prevent the less desirable light transmission of " bending " box under dark state.OCB indicating meter has wider visual angle and shorter time of response compared with TN indicating meter.
Also known have so-called IPS (" face in switch ") indicating meter, and it contains the liquid crystal layer between two substrates, and it is upper that wherein two electrodes are only arranged in of two substrates, and preferably have comb shaped structure interlaced with each other.When to electrode application voltage, between them, produce the electric field with the remarkable component that is parallel to liquid crystal layer thus.This causes liquid crystal molecule reorientation in aspect.
In addition, so-called FFS (" fringing field switching ") indicating meter is proposed (especially referring to S.H.Jung etc., Jpn.J.Appl.Phys., the 43rd volume, No.3,2004,1028), it contains two electrodes equally in same substrate, but contrary with IPS indicating meter, a wherein electrode that is configured to comb shaped structure only, and another electrode is non-structured.Produce thus strong so-called " fringing field ", i.e. the highfield of adjacent electrode edge, and produce electric field in whole box, this electric field has strong vertical component and has strong horizontal component.IPS indicating meter and FFS indicating meter have low contrast gradient view angle dependency.
In the VA indicating meter compared with novel type, the homogeneous of liquid crystal molecule orientation be limited to multiple less farmland within liquid crystal cell (
) on.These farmlands, are also known as between tilt domain (English: tilt domains) and can have disclination.Compared with traditional VA indicating meter, the VA indicating meter with tilt domain has the not dependency of visual angle of larger contrast gradient and gray scale.In addition, such indicating meter is more easily prepared, because no longer need the additional electrode surface treatment of for example passing through friction for make molecule homogeneous orientation under on-state.On the contrary, control the preferential sensing of inclination angle or tilt angle (English: pretilt) by the particular configuration of electrode.
In so-called MVA (" multi-zone vertical alignment nematic ") indicating meter, this causes the projection of local pre-tilt or projection to realize by electrode is had conventionally.Therefore, in the time applying voltage, in different, specific box region, make in different directions liquid crystal molecule be parallel to electrode surface orientation.Realize thus " controlled " and switch, and prevent the formation of interfering disclination line.Although this layout has been improved the visual angle of indicating meter, but cause the reduction of its light transmission.
Further developing of MVA used the only projection in an electrode side, and opposed electrode has otch (English: slits) on the contrary, and this has improved light transmission.In the time that the electrode of otch is applying voltage, in liquid crystal cell, produce inhomogeneous electric field, make to have realized in addition controlled switching.For further improving light transmission, can expand the spacing between otch and projection, but this causes again the prolongation of time of response.
In so-called PVA (patterning VA), need not projection also feasible, because two electrodes carry out structurizing by otch on opposite side, this causes the contrast gradient and the improved light transmission that increase, but this be technically difficulty and make indicating meter more responsive to mechanical influence (" beating " etc.).But for many application, for example watch-dog and especially TV screen, contrast gradient and the brightness (transmissivity) expecting to shorten the time of response and improve indicating meter.
Another kind of development is so-called PS (polymer stabilizing) or PSA (polymer-stabilized alignment) indicating meter, also uses once in a while the term " polymer " stable for it ".In these indicating meters, (for example 0.3 % by weight on a small quantity, typically <1 % by weight) one or more polymerizable compounds add liquid crystal media, and after introducing liquid crystal cell, be to apply or do not apply under voltage condition between electrode conventionally make its in-situ polymerization or be cross-linked by UV photopolymerization.By polymerisable mesomorphic or liquid crystalline cpd, also referred to as reactive mesogen or " RM ", it is suitable especially adding liquid crystal compound to confirm.
Unless otherwise indicated, below, use typically term " PSA " for PS indicating meter and PSA indicating meter.
Meanwhile, PS (A) principle is for various traditional liquid-crystal displays.Therefore, for example known PSA-VA, PSA-OCB, PSA-IPS, PSA-FFS and PSA-TN indicating meter.Preferably under the voltage applying, applying or do not execute under alive situation, carry out the polymerization of polymerizable compound for PSA-IPS indicating meter for PSA-VA and PSA-OCB indicating meter.As can be verified in testing cassete, PS (A) method causes the pre-tilt in box.For example the in the situation that of PSA-OCB indicating meter, can realize warp architecture stabilization, thereby offset voltage is not needed or can reduce.The in the situation that of PSA-VA indicating meter, this pre-tilt has active influence to the time of response.For PSA-VA indicating meter, can use MVA or PVA pixel and the electrode lay-out of standard.But in addition, for example, only adopt a structurized electrode side and do not adopt the projection also can be enough, this has significantly simplified and produces and produced fabulous contrast gradient simultaneously, has fabulous light transmission simultaneously.
In addition, so-called positivity-VA indicating meter (" Positiv-VA ") has proved particularly advantageous embodiment.Here, the initial orientation of liquid crystal under no-voltage initial state, as in the situation of traditional VA indicating meter, is vertical plane, is basically perpendicular to substrate.But contrary with traditional VA indicating meter, in positivity-VA indicating meter, use dielectric positivity liquid crystal media.By voltage being applied to (this generation is basically parallel to the electric field of liquid crystal media layer) on interdigitated electrodes, liquid crystal molecule changes into the orientation that is basically parallel to substrate.This class interdigitated electrodes is also generally used in IPS indicating meter.Even for positivity VA indicating meter, corresponding polymer stabilising (PSA) has also been proved to be favourable, can realize thus the remarkable minimizing of time of response.
PSA-VA indicating meter is described in for example JP10-036847A, EP1170626A2, US6, and 861,107, US7,169,449, in US2004/0191428A1, US2006/0066793A1 and US2006/0103804A1.PSA-OCB indicating meter is described in the people such as such as T.-J-Chen, Jpn.J.Appl.Phys.45, and 2006,2702-2704 and S.H.Kim, L.-C-Chien, Jpn.J.Appl.Phys.43, in 2004,7643-7647.PSA-IPS indicating meter is described in for example US6, in 177,972 and Appl.Phys.Lett.1999,75 (21), 3264.PSA-TN indicating meter is described in for example Optics Express2004, in 12 (7), 1221.
As conventional liquid-crystal display as above, PSA indicating meter can be used as active matrix or passive matrix display operates.In the situation of Active Matrix Display, single pixel conventionally for example, is carried out addressing by integrated, for example transistor of non-linear active component (thin film transistor (" TFT ")), and conventionally carry out addressing according to multiple transmission method in the situation of passive matrix display, wherein these two kinds of methods are that prior art is known.
Particularly, for monitor and particularly TV application, still require the contrast gradient of time of response and liquid-crystal display and the optimization of brightness (being also therefore light transmission).PSA method can provide important advantage at this.Particularly, in the situation of PSA-VA, PSA-IPS, PSA-FFS and PSA-positivity-VA indicating meter, can in the situation that not having significant adverse to affect on other parameter, realize the shortening to the time of response that measurable pre-tilt is relevant in testing cassete.
In the prior art, for example use the polymerizable compound of following formula:
Wherein P represents polymerisable group, normally acrylate or methacrylate based group, and for example US7, described in 169,449.
But produce problem, be that the not every combination being made up of liquid crystal compound (being also below called " liquid crystal main body mixture ")+polymerizable components (usually RM) is all suitable for PSA indicating meter, obtain inclination fully or do not tilt because for example do not regulate, or because for example so-called " voltage keeps ratio " (VHR or HR) is not enough to the display application for TFT.In addition, have been found that when for PSA indicating meter, still there are some defects from liquid crystal compound well known in the prior art and RM.Therefore not, that each known RM dissolving in liquid crystal compound is applicable to PSA indicating meter.In addition,, except the pre-tilt of direct measurement in PSA indicating meter, be usually difficult to find the suitable choice criteria for RM.If expect not add light trigger to carry out polymerization (this may be favourable to some application) by means of UV light, the selection of suitable RM becomes even less.
In addition, the combination of selected liquid crystal main body mixture/RM should have alap rotary viscosity and electrical property as well as possible.Particularly, it should have high as far as possible VHR.In PSA indicating meter, need to, at the high VHR with after UV photoirradiation, because UV exposure is requisite part in indicating meter production process, but also occur as normal burden (Belastung) at the indicating meter run duration of making especially.
Particularly, the available type material for PSA indicating meter that has an especially little pre-tilt angle of generation will be desirable.Preferred material is between polymerization period, under the identical time shutter, to produce the pre-tilt angle lower than hitherto known material herein, and/or by using it can realize after the shorter time shutter with those of known material obtainable (higher) pre-tilt angle.Thus, the production time of indicating meter (" pitch time (tact time) ") can be shortened and the cost of production technique.
Another problem of producing in PSA indicating meter is existence or the removal of the unpolymerized RM of residual volume, particularly for after producing the polymerization procedure of pre-tilt angle at indicating meter.For example, the unreacted RM of this class may be by for example affecting negatively during operation the performance of indicating meter after indicating meter is made with uncontrollable mode polymerization.
Therefore, the known PSA indicating meter of prior art often demonstrates undesirable effect of what is called " image retention (image sticking) " or " image burns ", and the image being produced by the temporary transient addressing of single pixel in liquid-crystal display is after even the electric field in these pixels has been turned off or remain visible after other address pixels.
If use on the one hand the liquid crystal main component with low VHR, this " image retention " may occur.Wherein the UV-composition of daylight or background illumination may cause in liquid crystal molecule decomposition reaction undesirably and cause thus ion or the generation of free radical impurity.These may be accumulated, and particularly in electrode or oriented layer, and they may reduce the voltage effectively applying there.This effect can also be observed in the conventional liquid-crystal display that there is no polymeric constituent.
In addition, owing to existing extra " image retention " effect that unpolymerized RM causes to observe in the PSA indicating meter of being everlasting.Remaining RM not controlled is aggregated in here by the UV light from environment or caused by background illumination.In the display area of connecting, after multiple addressing periods, change pitch angle thus.As a result, in the region of connecting, may occur that transmission changes, and it remains unchanged in the region of access failure.
Therefore, be worth expecting, carry out as far as possible completely and get rid of as far as possible in indicating meter the not existence of polymerization RM or be reduced to minimum value in the polymerization of PSA indicating meter production period RM.For this reason, needing can be as far as possible effectively and the material of polymerization completely.In addition be that these residual volume controlled reactions fall by what expect.If than hitherto known material sooner and more effectively polymerization, this will be simpler to RM.
Therefore still exist to PSA indicating meter always, particularly VA and OCB type, and for the very big demand of liquid crystal media and the polymerizable compound of such indicating meter, and they do not demonstrate above-mentioned shortcoming or only demonstrate these shortcomings with little degree and have the performance of improvement.In addition, there is very big demand for PSA indicating meter and for the material of PSA indicating meter, these have favourable performance, even particularly can realize in large operating temperature range, have short response time at low temperatures of high specific resistance and low threshold voltage, low pre-tilt angle, a large amount of gray scale, high-contrast and wide visual angle, and " voltage keep than " after UV exposure with high numerical value (VHR) with the low-temperature stability of high numerical value, also be known as " LTS ", liquid crystal compound is for single component spontaneous crystallization stability out.
The present invention is based on such object: the novel applicable material that is provided for PSA indicating meter, particularly RM and the liquid crystal media that comprises it, described material does not have above-mentioned defect or has these defects with less degree, as far as possible soon with fully polymerization, can realize as quickly as possible and regulate and obtain low pre-tilt angle, reduce or prevent from indicating meter occurring " image retention " and preferably realizing very high ratio resistance, low threshold voltage and short response time simultaneously.In addition, liquid crystal media should have favourable mesomorphic phase performance and high VHR and LTS value.
Further task of the present invention is to provide novel RM, especially for optics, electrooptics and electronic application and be provided for preparing its proper method and intermediate.
Particularly, the present invention is based on such object: the polymerizable compound of the maximum pre-tilt that generation is larger after photopolymerization is provided, and this causes the production of liquid crystal displays time of realizing quickly desired pre-tilt and therefore significantly shortening.
This object according to the present invention by providing material as described in the present application, method and liquid-crystal display to realize.Especially, be surprised to find by provide comprise one or more according to the PSA indicating meter of the compound of polymerization of the present invention or by use comprise one or more according to the liquid crystal media of polymerizable compound of the present invention for the production of this class PSA indicating meter, can partly or entirely realize above-mentioned object.
In liquid crystal media according to the present invention and PSA indicating meter, use this class polymerizable compound to cause desired pre-tilt realize especially soon and cause the time in the remarkable indicating meter production of shortening.This can measure by means of the pre-tilt angle that relies on the time shutter in VA inclining test box, verifies relatively with liquid crystal media.Particularly, in the situation that not adding light trigger, can realize pre-tilt.
Because polymerizable compound according to the present invention demonstrates significantly higher rate of polymerization in PSA indicating meter, therefore less unreacted residual volume is retained in liquid crystal cell, has improved thus its electrooptics performance and made controlled reaction fall these residual volumes to become simpler.
JP2000-281629A has described clavate polymerizable compound and the cholesteric polymeric film as the reflective polarizer prepared therefrom of following formula.
WO2008/121585A1 has described the 1-vinylpyrene as the following formula of the monomer for compensate film.
But this compound was not both described for the purposes that produces pre-tilt angle at PSA indicating meter in JP2000-281629A and WO2008121585, neither be apparent.
Polymerizable compound according to the present invention for by the purposes that obtains pitch angle in electric field situ polymerization quick adjustment, was not equally both described in the prior art in PSA indicating meter, neither be apparent.
In addition, be surprised to find completely, polymerizable compound according to the present invention in the time being used for PSA indicating meter, show than from the known polymerizable compound of prior art obviously faster pitch angle produce and faster and polymerization more completely.This confirms by direct comparative experiments.This result was not both described in the prior art, neither be apparent.
The purposes of the compound (below also referred to as " according to polymerizable compound of the present invention ") that therefore the present invention relates to formula I in liquid crystal (FK) medium and the liquid-crystal display of PS or PSA (polymer-stabilized alignment) type,
Wherein each group has following implication:
W
1, W
2expression-CY independently of one another separately
2cY
2-,-CY=CY-,-CY
2-O-,-O-CY
2-,-C (O)-O-,-O-C (O)-,-C (R
cr
d)-,-O-,-S-,-NR
e-,
When occurring at every turn, Y represents H or F identical or differently,
R
a, R
brepresent independently of one another separately P-Sp-, H, F, Cl, Br, I ,-CN ,-NO
2,-NCO ,-NCS ,-OCN ,-SCN, SF
5, there is the straight or branched alkyl of 1-25 C atom, wherein one or more non-conterminous CH
2group also can be separately independently of one another by arylidene ,-C (R
0)=C (R
00)-,-C ≡ C-,-N (R
0)-,-O-,-S-,-CO-,-CO-O-,-O-CO-,-O-CO-O-with make O and/or S atom not each other directly the mode of keyed jointing replace, and wherein one or more H atoms also can be replaced by F, Cl, Br, I, CN or P-Sp-, or preferably there is aryl or the heteroaryl of 2-25 C atom, it also can comprise two or more fused rings and optionally mono-or polysubstituted by L, wherein radicals R
aand R
bat least one expression or comprise group P-Sp-,
R
c, R
d, R
erepresent independently of one another separately H or there is the straight or branched alkyl of 1-12 C atom,
When occurring at every turn, P represents polymerizable groups identical or differently,
When occurring at every turn, Sp represents spacer groups or singly-bound identical or differently,
A
1, A
2the aromatics, heteroaromatic, the alicyclic or heterocyclic group that represent preferably to have independently of one another separately 4-25 C atom, it also can comprise fused rings and optionally mono-or polysubstituted by L,
When occurring at every turn, L represents P-Sp-, OH, CH identical or differently
2oH, halogen ,-CN ,-NO
2,-NCO ,-NCS ,-OCN ,-SCN ,-C (=O) N (R
x)
2,-C (=O) Y
1,-C (=O) R
x,-N (R
x)
2, the optional silyl replacing or optional carbon back or the alkyl replacing,
R
xrepresent P-Sp-, H, halogen, has 1-25, preferably straight chain, side chain or the cyclic alkyl of 1-12 C atom, wherein one or more non-conterminous CH
2group can also by-O-,-S-,-CO-,-CO-O-,-O-CO-,-O-CO-O-with make O and/or S atom not each other directly the mode of keyed jointing replace, and wherein one or more H atoms also can replace by F, Cl or P-Sp-,
Y
1represent halogen,
Z
1, Z
2expression-O-,-S-,-CO-,-CO-O-,-OCO-,-O-CO-O-,-OCH independently of one another separately
2-,-CH
2o-,-SCH
2-,-CH
2s-,-CF
2o-,-OCF
2-,-CF
2s-,-SCF
2-,-(CH
2)
n-,-CF
2cH
2-,-CH
2cF
2-,-(CF
2)
n-,-CH=CH-,-CF=CF-,-CH=CF-,-CF=CH-,-C ≡ C-,-CH=CH-COO-,-OCO-CH=CH-,-CH
2-CH
2-COO-,-OCO-CH
2-CH
2-,-C (R
0r
00)-,-C (R
yr
z)-or singly-bound,
R
0, R
00while appearance independently of one another and at every turn separately, represent H identical or differently or there is the alkyl of 1-12 C atom,
R
y, R
zrepresent independently of one another separately H, F, CH
3or CF
3,
When occurring at every turn, n represents 1,2,3 or 4 identical or differently,
P, q represents 0,1 or 2 separately independently of one another,
When occurring at every turn, r represents 0,1 or 2 identical or differently.
The invention further relates to the compound that comprises one or more formulas I and one or more and can be also the liquid crystal media of mesomorphic, liquid crystal and/or polymerisable extra compound.
The invention further relates to the liquid crystal media that comprises the polymkeric substance that can obtain by the compound of one or more formulas of polymerization I and one or more extra compounds, wherein said extra compound can be also mesomorphic, liquid crystal and/or polymerisable.
The invention further relates to liquid crystal media, it comprises:
-polymerizable components A), the compound that it comprises one or more formulas I, and
-liquid crystal components B), hereinafter also referred to as " liquid crystal main body mixture ", its comprise one or more, preferred two or more as above lower molecular weight (monomer and not polymerisable) compounds hereinafter described.
The invention further relates to for the preparation of the as above method of liquid crystal media hereinafter described, wherein by as above one or more combinations of low molecular weight liquid crystals compounds hereinafter described or the compound of liquid crystal main body mixture and one or more formulas I, and optional and further liquid crystalline cpd and/or additive mix.
The invention further relates to the purposes in PS and PSA indicating meter according to the compound of formula I of the present invention and liquid crystal media, the particularly purposes in the PS that comprises liquid crystal media and PSA indicating meter, for preferably in the situation that applying electric field or magnetic field the compound of through type I produce pitch angle in the situ polymerization of PSA indicating meter at liquid crystal media.
The invention further relates to and comprise one or more according to the liquid-crystal display of the compound of formula I of the present invention or liquid crystal media, particularly PS or PSA indicating meter, particularly preferably PSA-VA, PSA-OCB, PSA-IPS, PSA-FFS, PSA-VA or PSA-positivity-VA indicating meter.
The invention further relates to PS or the PSA type liquid-crystal display of the liquid crystal cell of the layer that comprises the liquid crystal media with two substrates and two electrodes and the component that comprises polymerization between substrate and lower-molecular-weight component, wherein at least one substrate be printing opacity there is one or two electrode with at least one substrate, the component of wherein said polymerization can be by being preferably aggregated in one or more polymerizable compounds in liquid crystal media between the substrate of liquid crystal cell and obtaining in the situation that voltage imposing on electrode, at least one of wherein said polymerizable compound is the compound of formula I.
The invention further relates to for the production of the as above method of liquid-crystal display hereinafter described, wherein the liquid crystal media of compound of one or more combinations of low molecular weight liquid crystals compounds hereinafter described or liquid crystal main body mixture and one or more formulas I will be comprised as above, introduce as above in the liquid crystal cell with two substrates and two electrodes hereinafter described, and preferably in the situation that voltage is imposed on to electrode, make polymerizable compound polymerization.
Have preferably two electrodes with the form of transparent layer according to PS of the present invention and PSA indicating meter, described electrode is applied on one or two substrate that forms liquid crystal cell.Under each situation or by an electrode, put in each of two substrates, for example, in PSA-VA according to the present invention, PSA-OCB or PSA-TN indicating meter, or two electrodes are only put on in two substrates, for example, and another substrate does not have electrode, in PSA-positivity-VA according to the present invention, PSA-IPS or PSA-FFS indicating meter.
The invention further relates to new formula I compound, for its preparation method and for these methods or thus obtained new intermediate.
In context, be suitable for following implication:
Term " inclination " and " pitch angle " refer to the liquid crystal molecule of liquid crystal media with respect to the surperficial inclination of box or oblique orientation in liquid-crystal display (preferred PS or PSA indicating meter herein).Pitch angle is illustrated in the average angle (<90 °) between the molecule longitudinal axis (liquid crystal director) of liquid crystal molecule and the parallel plane supporting plate surface of formation liquid crystal cell here.Here the pitch angle of low numerical value (deviating from greatly 90 ° of angles) is corresponding to large inclination.Suitable incline measurement method provides in an embodiment.Except as otherwise noted, in context, disclosed pitch angle numerical value relates to this measuring method.
Term " mesomorphic group " is well known by persons skilled in the art and has in the literature description, and represent such group, it contributes to cause liquid crystal (FK) phase in low molecular weight substance or polymeric material substantially due to the interactional anisotropy of its attraction and repulsion.The compound (mesomorphic compound) that contains mesomorphic group also not necessarily itself has mesomorphic phase.Mesomorphic compound only with other compound after and/or polymerization after show that Mesomorphic behavior is also possible.Typical mesomorphic group is clavate or the disc-shaped units of for example rigidity.Pure Appl.Chem.73 (5), 888 (2001) and C.Tschierske, G.Pelzl, S.Diele, Angew.Chem.2004, has provided in 116,6340-6368 about the summary mesomorphic or term and definition that liquid crystalline cpd uses.
Term " spacer groups " (English " spacer " or " spacer group "), in context also referred to as " Sp ", be well known by persons skilled in the art and have in the literature description, for example, referring to Pure Appl.Chem.73 (5), 888 (2001) and C.Tschierske, G.Pelzl, S.Diele, Angew.Chem.2004,116,6340-6368.Unless the contrary indicated otherwise, term " spacer groups " or " spacer " are illustrated in polymerizable mesomorphic compound mesomorphic group and polymerizable groups flexible group connected with each other in context.
Term " reactive mesogen " or " RM " represent the compound that contains a mesomorphic group and one or more functional groups (also referred to as polymerizable groups or group P) that are suitable for polymerization.
Term " low-molecular weight compound " and " not polymerisable compound " represent not contain be suitable under condition well known by persons skilled in the art, the particularly functional group of polymerization and the compound of monomer normally under the condition for RM polymerization.
Term " organic group " represents carbon back or alkyl.
Term " carbon back " represents to contain at least one carbon atom, preferably unit price or the multivalence organic group of 1-40 C atom, itself or do not contain other atom (for example-C ≡ C-) or optionally contain one or more other atoms such as N, O, S, P, Si, Se, As, Te or Ge (such as carbonyl etc.).Term " alkyl " represents to contain in addition one or more H atoms and the carbon back of one or more heteroatomss (such as N, O, S, P, Si, Se, As, Te or Ge) optionally.
" halogen " represents F, Cl, Br or I.
Carbon back or alkyl can be saturated or unsaturated groups.Unsaturated group is for example aryl, alkenyl or alkynyl.Having more than carbon back or the alkyl of 3 C atoms can be straight chain, side chain and/or ring-type, and also can have spiral shell connection or condensed ring.
Term " alkyl ", " aryl ", " heteroaryl " etc. also comprise multivalence group, such as alkylidene group, arylidene, inferior heteroaryl etc.
Term " aryl " represents aromatics carbon back or derivative group thus.Term " heteroaryl " represents that foundation is defined above, contains one or more heteroatomic " aryl ".
Preferred carbon back and alkyl are alkyl, thiazolinyl, alkynyl, alkoxyl group, alkyl-carbonyl, alkoxy carbonyl, alkyl-carbonyl oxygen base and the alkoxy-carbonyl oxies with 1-40, preferably 1-25, the particularly preferably optional replacement of 1-18 C atom, there is aryl or the aryloxy of 6-40, the preferably optional replacement of 6-25 C atom, or there is alkylaryl, arylalkyl, alkyl-aryloxy, alkoxy aryl, aryl carbonyl, aryloxycarbonyl, aryl carbonyl oxygen base and the aryloxycarbonyl oxygen base of 6-40, the preferably optional replacement of 6-25 C atom.
Preferred carbon back and alkyl are C in addition
1-C
40alkyl, C
2-C
40thiazolinyl, C
2-C
40alkynyl, C
3-C
40allyl group, C
4-C
40alkane dialkylene, C
4-C
40polyene-based, C
6-C
40aryl, C
6-C
40alkylaryl, C
6-C
40arylalkyl, C
6-C
40alkyl-aryloxy, C
6-C
40alkoxy aryl, C
2-C
40heteroaryl, C
4-C
40cycloalkyl, C
4-C
40cycloalkenyl group etc.Particularly preferably be C
1-C
22alkyl, C
2-C
22thiazolinyl, C
2-C
22alkynyl, C
3-C
22allyl group, C
4-C
22alkane dialkylene, C
6-C
12aryl, C
6-C
20arylalkyl and C
2-C
20heteroaryl.
Preferred carbon back and alkyl are the alkyl with straight chain, side chain or the ring-type of 1-40, preferred 1-25 C atom in addition, and it is unsubstituted or mono-or polysubstituted by F, Cl, Br, I or CN, and wherein one or more non-conterminous CH
2group can be separately independently of one another by-C (R
x)=C (R
x)-,-C ≡ C-,-N (R
x)-,-O-,-S-,-CO-,-CO-O-,-O-CO-,-O-CO-O-are replace O and/or S atom mode not directly connected to each other.
R
xpreferably represent H, halogen, there is the alkyl chain of straight chain, side chain or the ring-type of 1-25 C atom, wherein one or more non-conterminous C atoms also can by-O-,-S-,-CO-,-CO-O-,-O-CO-,-O-CO-O-replace, wherein one or more H atoms also can be replaced by fluoro, or represent aryl or the aryloxy of the optional replacement with 6-40 C atom, or there is heteroaryl or the heteroaryloxy of the optional replacement of 2-40 C atom.
Preferred alkoxyl group is, for example, methoxyl group, oxyethyl group, 2-methoxy ethoxy, positive propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy, tert.-butoxy, 2-methyl butoxy, n-pentyloxy, positive hexyloxy, positive heptan oxygen base, n-octyloxy, positive ninth of the ten Heavenly Stems oxygen base, n-decyloxy, n-undecane oxygen base, n-dodecane oxygen base etc.
Preferred alkyl is, for example, methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, isobutyl-, sec-butyl, the tertiary butyl, 2-methyl butyl, n-pentyl, sec.-amyl sec-pentyl secondary amyl, cyclopentyl, n-hexyl, cyclohexyl, 2-ethylhexyl, n-heptyl, suberyl, n-octyl, ring octyl group, n-nonyl, positive decyl, n-undecane base, dodecyl, dodecyl, trifluoromethyl, perfluor normal-butyl, 2,2,2-trifluoroethyl, perfluoro capryl, perfluoro hexyl etc.
Preferably thiazolinyl is, for example, and vinyl, propenyl, butenyl, pentenyl, cyclopentenyl, hexenyl, cyclohexenyl, heptenyl, cycloheptenyl, octenyl, cyclooctene base etc.
Preferably alkynyl is, for example, and ethynyl, proyl, butynyl, pentynyl, hexin base, octyne base etc.
Preferred alkoxyl group is, for example, methoxyl group, oxyethyl group, 2-methoxy ethoxy, positive propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy, tert.-butoxy, 2-methyl butoxy, n-pentyloxy, positive hexyloxy, positive heptan oxygen base, n-octyloxy, positive ninth of the ten Heavenly Stems oxygen base, n-decyloxy, n-undecane oxygen base, n-dodecane oxygen base etc.
Preferably amino is, for example, and dimethylamino, methylamino, aminomethyl phenyl amino, phenyl amino etc.
Aryl and heteroaryl can be monocycle or many rings, be that they can contain a ring (such as phenyl) or two or more rings, it can be also (such as naphthyl) or (such as the xenyl) of covalency keyed jointing condensing, or contains the combination condensing with the ring of keyed jointing.Heteroaryl contains one or more heteroatomss, is preferably selected from O, N, S and Se.
Particularly preferably have the list of 6-25 C atom-, two-or three cyclophane bases, and have the list of 2-25 C atom-, two-or tricyclic heteroaryl, it optionally contains fused rings and is optional replacement.Preferably aryl and the heteroaryl of 5-, 6-or 7-unit in addition, wherein one or more CH groups also can by N, S or O with make O atom and/or S atom not each other directly the mode of keyed jointing replace.
Preferred aryl is for example phenyl, xenyl, terphenyl, [1,1 ': 3 ', 1 "] terphenyl-2 '-Ji, naphthyl, anthryl, binaphthylyl, phenanthryl, pyrene, dihydropyrene, 5, perylene, tetracene, pentacene, benzopyrene, fluorenes, indenes, indenofluorene, spiral shell two fluorenes etc.
Preferred heteroaryl is that for example 5-ring, such as pyrroles, pyrazoles, imidazoles, 1,2,3-triazoles, 1,2,4-triazole, tetrazolium, furans, thiophene, selenophen, oxazole, isoxazole, 1,2-thiazole, 1,3-thiazoles, 1,2,3-oxadiazole, 1,2,4-oxadiazole, 1,2,5-oxadiazole, 1,3,4-oxadiazole, 1,2,3-thiadiazoles, 1,2,4-thiadiazoles, 1,2,5-thiadiazoles, 1,3,4-thiadiazoles, 6-ring, such as pyridine, pyridazine, pyrimidine, pyrazine, 1,3,5-triazines, 1,2,4-triazine, 1,2,3-triazine, 1,2,4,5-tetrazine, 1,2,3,4-tetrazine, 1,2,3,5-tetrazine, or condense group as indoles, isoindole, indolizine, indazole, benzoglyoxaline, benzotriazole, purine, naphtho-imidazoles, phenanthro-imidazoles, pyridine-imidazole, pyrazine imidazoles, quinoxaline imidazoles, benzoxazole, Nai Bing oxazole, En Bing oxazole, Fei Bing oxazole, isoxazole, benzothiazole, cumarone, isobenzofuran, diphenylene-oxide, quinoline, isoquinoline 99.9, pteridine, benzo-5,6-quinoline, benzo-6,7-quinoline, benzo-7,8-quinoline, benzisoquinoline, acridine, thiodiphenylamine, phenoxazine, benzo pyridazine, benzo pyrimidine, quinoxaline, azophenlyene, naphthyridines, azepine carbazole, benzo carboline, phenanthridines, phenanthroline, thieno-[2,3b] thiophene, thieno-[3,2b] thiophene, two thienothiophenes, different thionaphthene, dibenzothiophene, diazosulfide thiophene, or the combination of these groups.These heteroaryls also can be replaced by alkyl, alkoxyl group, alkylthio, fluorine, fluoroalkyl or other aryl or heteroaryl.
(non-aromatic) is alicyclic comprises saturated rings with heterocyclic group, only contains those of singly-bound, and the undersaturated ring of part, also can contain those of multiple bond.Heterocycle contains one or more heteroatomss, is preferably selected from Si, O, N, S and Se.
(non-aromatic) alicyclic and heterocyclic group can be monocycle, only containing a ring (such as hexanaphthene), or encircle, contain multiple rings (such as perhydronaphthalene or double-octane). moreParticularly preferably saturated group.Preferably have in addition the list of 3-25 C atom-, two-or three cyclic groups, it optionally contains fused rings and is optionally substituted.Further preferably 5-, 6-, 7-or 8-unit carbon ring group, wherein one or more C atoms also can be replaced and/or one or more CH group can be replaced and/or one or more non-conterminous CH by N by Si
2group can by-O-and/or-S-replaces.
Preferred alicyclic and heterocyclic group is, for example, 5 yuan of group such as pentamethylene, tetrahydrofuran (THF), tetramethylene sulfide, tetramethyleneimine, 6 yuan of group such as hexanaphthenes, Silinane (Silinan), tetrahydrobenzene, tetrahydropyrans, tetrahydric thiapyran, 1,3-diox, 1,3-dithiane, piperidines, 7 yuan of groups are such as suberane, with condense group such as naphthane, perhydronaphthalene, indane, dicyclo [1.1.1] pentane-1,3-bis-bases, dicyclo [2.2.2] octane-Isosorbide-5-Nitrae-bis-base, spiroheptane-2,6-bis-bases, octahydro-4,7-endo-methylene group indane-2,5-bis-bases.
Preferred substituting group is, for example, dissolve promotion property group as alkyl or alkoxyl group, electron-withdrawing group is as fluorine, nitro or nitrile, or for improving the substituting group of polymkeric substance second-order transition temperature (Tg), particularly bulky group such as the tertiary butyl or the optional aryl replacing.
Preferred substituting group, also referred to as " L ", is for example F, Cl, Br, I, OH ,-CN ,-NO in context
2,-NCO ,-NCS ,-OCN ,-SCN ,-C (=O) N (R
x)
2,-C (=O) Y
1,-C (=O) R
x,-C (=O) OR
x,-N (R
x)
2, wherein R
xthere is above-mentioned implication and Y
1represent halogen, the optional silyl replacing, there is aryl or the heteroaryl of 4-40, the preferably optional replacement of 4-20 C atom, and thering is alkyl, thiazolinyl, alkynyl, alkoxyl group, alkyl-carbonyl, alkoxy carbonyl, alkyl-carbonyl oxygen base or the alkoxy-carbonyl oxy of the straight or branched of 1-25 C atom, wherein one or more H atoms can optionally be replaced by F or Cl.
" silyl of replacement or aryl " preferably represents by halogen ,-CN, R
0,-OR
0,-CO-R
0,-CO-O-R
0,-O-CO-R
0or-O-CO-O-R
0replace wherein R
0there is above-mentioned implication.
Particularly preferred substituting group L is for example F, Cl, CN, NO
2, CH
3, C
2h
5, OCH
3, OC
2h
5, COCH
3, COC
2h
5, COOCH
3, COOC
2h
5, CF
3, OCF
3, OCHF
2, OC
2f
5, also have in addition phenyl.
be preferably
Wherein L has the one of above-mentioned implication.
Polymerizable groups P is such group: it is suitable for polyreaction, for example free radical or ion chain polymerization, addition polymerization or polycondensation, or be suitable for polymer phase like transformation reaction, for example addition or be condensed on main polymer chain.Particularly preferably be the group that is suitable for chain polymerization, particularly contain the two keys of C=C or-those of C ≡ C-triple bond, and the group that is suitable for ring-opening polymerization is such as oxetane groups or epoxide group.
Preferred group P is selected from CH
2=CW
1-CO-O-, CH
2=CW
1-CO-,
cH
2=CW
2-(O)
k3-, CW
1=CH-CO-(O)
k3-, CW
1=CH-CO-NH-, CH
2=CW
1-CO-NH-, CH
3-CH=CH-O-, (CH
2=CH)
2cH-OCO-, (CH
2=CH-CH
2)
2cH-OCO-, (CH
2=CH)
2cH-O-, (CH
2=CH-CH
2)
2n-, (CH
2=CH-CH
2)
2n-CO-, HO-CW
2w
3-, HS-CW
2w
3-, HW
2n-, HO-CW
2w
3-NH-, CH
2=CW
1-CO-NH-, CH
2=CH-(COO)
k1-Phe-(O)
k2-, CH
2=CH-(CO)
k1-Phe-(O)
k2-, Phe-CH=CH-, HOOC-, OCN-and W
4w
5w
6si-, wherein W
1represent H, F, Cl, CN, CF
3, phenyl or there is alkyl, particularly H, F, Cl or the CH of 1-5 C atom
3, W
2and W
3represent independently of one another separately H or there is alkyl, particularly H, methyl, ethyl or the n-propyl of 1-5 C atom, W
4, W
5and W
6represent independently of one another separately Cl, the oxa alkyl with 1-5 C atom or oxa-carbonylic alkyl, W
7and W
8represent independently of one another separately H, Cl or have the alkyl of 1-5 C atom, Phe represents Isosorbide-5-Nitrae-phenylene, and it is optionally replaced by one or more group L that is different from P-Sp-as defined above, k
1, k
2and k
3represent independently of one another separately 0 or 1, k
3preferably represent 1, and k
4represent the integer of 1-10.
Particularly preferred group P is selected from CH
2=CW
1-CO-O-, CH
2=CW
1-CO-,
cH
2=CW
2-O-, CW
1=CH-CO-(O)
k3-, CW
1=CH-CO-NH-, CH
2=CW
1-CO-NH-, (CH
2=CH)
2cH-OCO-, (CH
2=CH-CH
2)
2cH-OCO-, (CH
2=CH)
2cH-O-, (CH
2=CH-CH
2)
2n-, (CH
2=CH-CH
2)
2n-CO-, CH
2=CW
1-CO-NH-, CH
2=CH-(COO)
k1-Phe-(O)
k2-, CH
2=CH-(CO)
k1-Phe-(O)
k2-, Phe-CH=CH-and W
4w
5w
6si-, wherein W
1represent H, F, Cl, CN, CF
3, phenyl or there is alkyl, particularly H, F, Cl or the CH of 1-5 C atom
3, W
2and W
3represent independently of one another separately H or there is alkyl, particularly H, methyl, ethyl or the n-propyl of 1,2,3,4 or 5 C atom, W
4, W
5and W
6represent independently of one another separately Cl, the oxa alkyl with 1-5 C atom or oxa-carbonylic alkyl, W
7and W
8represent independently of one another separately H, Cl or have the alkyl of 1-5 C atom, Phe represents Isosorbide-5-Nitrae-phenylene, k
1, k
2and k
3represent independently of one another separately 0 or 1, k
3preferably represent 1, and k
4represent the integer of 1-10.
Group P is very particularly preferably selected from CH
2=CW
1-CO-O-, particularly CH
2=CH-CO-O-, CH
2=C (CH
3)-CO-O-and CH
2=CF-CO-O-, also has CH
2=CH-O-, (CH
2=CH)
2cH-O-CO-, (CH
2=CH)
2cH-O-,
Further group P very particularly preferably
a,bbe selected from vinyl oxygen base, acrylate-based, methacrylate based, fluoro acrylic ester base, chloropropene perester radical, oxetanyl, 3-Ethyloxetane base and epoxide group, and particularly preferably represent acrylate-based or methacrylate based.
Preferred spacer groups Sp is selected from formula Sp " X ", makes group " P-Sp-" meet formula " P-Sp " X "-", wherein
" expression has the alkylidene group of 1-20, preferred 1-12 C atom to Sp, and it is optionally mono-or polysubstituted by F, Cl, Br, I or CN, and wherein one or more non-conterminous CH
2group also can be separately independently of one another by-O-,-S-,-NH-,-N (R
0)-,-Si (R
00r
000)-,-CO-,-CO-O-,-O-CO-,-O-CO-O-,-S-CO-,-CO-S-,-N (R
00)-CO-O-,-O-CO-N (R
00)-,-N (R
00)-CO-N (R
00)-,-CH=CH-or-C ≡ C-with make O and/or S atom not each other directly the mode of keyed jointing replace,
X " expression-O-,-S-,-CO-,-CO-O-,-O-CO-,-O-CO-O-,-CO-N (R
00)-,-N (R
00)-CO-,-N (R
00)-CO-N (R
00)-,-OCH
2-,-CH
2o-,-SCH
2-,-CH
2s-,-CF
2o-,-OCF
2-,-CF
2s-,-SCF
2-,-CF
2cH
2-,-CH
2cF
2-,-CF
2cF
2-,-CH=N-,-N=CH-,-N=N-,-CH=CR
0-,-CY
2=CY
3-,-C ≡ C-,-CH=CH-CO-O-,-O-CO-CH=CH-or singly-bound,
R
00and R
000represent independently of one another separately H or there is the alkyl of 1-12 C atom, and
Y
2and Y
3represent independently of one another separately H, F, Cl or CN.
Be preferably-O-of X ' ,-S-,-CO-,-COO-,-OCO-,-O-COO-,-CO-NR
0-,-NR
0-CO-,-NR
0-CO-NR
0-or singly-bound.
Typical spacer groups Sp " is for example-(CH
2)
p1-,-(CH
2cH
2o)
q1-CH
2cH
2-,-CH
2cH
2-S-CH
2cH
2-,-CH
2cH
2-NH-CH
2cH
2-or-(SiR
00r
000-O)
p1-, wherein p1 is the integer of 1-12, q1 is the integer of 1-3, and R
00and R
000there is above-mentioned implication.
Particularly preferred group-Sp " X "-be-(CH
2)
p1-,-(CH
2)
p1-O-,-(CH
2)
p1-O-CO-,-(CH
2)
p1-O-CO-O-, wherein p1 and q1 have above-mentioned implication.
Particularly preferred group Sp " is for example ethylidene, propylidene, butylidene, pentylidene, hexylidene, sub-heptyl, octylene, nonamethylene, sub-decyl, sub-undecyl, sub-dodecyl, sub-octadecyl, ethyleneoxy group ethylidene, methylene radical oxygen base butylidene, ethylidene sulfo-ethylidene, ethylidene-N-methyl-imino ethylidene, 1-methyl alkylidene group, vinylidene, propenylidene and the crotonylidene of straight chain under each situation.
In the embodiment of present invention further optimization, the P in formula I represents the group (multifunctional polymerizable groups) that comprises two or more polymerizable groups.Such proper group, and the polymerizable compound that contains them and preparation thereof be described in for example US7, in 060,200B1 or US2006/0172090A1.Particularly preferably be the multifunctional polymerizable groups that is selected from following formula:
-X-alkyl-CHP
1-CH
2-CH
2P
2 I*a
-X-alkyl-C(CH
2P
1)(CH
2P
2)-CH
2P
3 I*b
-X-alkyl-CHP
1CHP
2-CH
2P
3 I*c
-X-alkyl-C(CH
2P
1)(CH
2P
2)-C
aaH
2aa+1 I*d
-X-alkyl-CHP
1-CH
2P
2 I*e
-X-alkyl-CHP
1P
2 I*f
-X-alkyl-CP
1P
2-C
aaH
2aa+1 I*g
-X-alkyl-C(CH
2P
1)(CH
2P
2)-CH
2OCH
2-C(CH
2P
3)(CH
2P
4)CH
2P
5 I*h
-X-alkyl-CH((CH
2)
aaP
1)((CH
2)
bbP
2) I*i
-X-alkyl-CHP
1CHP
2-C
aaH
2aa+1 I*k
-X′-alkyl-C(CH
3)(CH
2P
1)(CH
2P
2) I*m
Wherein
Alkyl represents singly-bound or has the straight chain of 1-12 C atom or the alkylidene group of branching, wherein one or more non-conterminous CH
2group can be separately independently of one another by-C (R
00)=C (R
000)-,-C ≡ C-,-N (R
00)-,-O-,-S-,-CO-,-CO-O-,-O-CO-,-O-CO-O-with make O and/or S atom not each other directly the mode of keyed jointing replace, and wherein one or more H atoms also can replace by F, Cl or CN, wherein R
00and R
000there is above-mentioned implication,
Aa and bb represent 0,1,2,3,4,5 or 6 separately independently of one another,
X has for a kind of implication shown in X ', and
P
1-5have independently of one another for P separately
ashown a kind of implication.
The compound of particularly preferred formula I is those of formula IA
Wherein R
a, R
b, W
1, W
2, A
1, A
2, Z
1, Z
2, L, p, q and r have in one of the implication described in formula I or the implication described in context.
The particularly preferably compound of such formula I and IA, wherein:
A
1and A
2represent independently of one another separately Isosorbide-5-Nitrae-phenylene, naphthalene-Isosorbide-5-Nitrae-bis-base or naphthalene-2,6-bis-bases, wherein in these groups, one or more CH groups also can be replaced by N, hexanaphthene-Isosorbide-5-Nitrae-bis-base, wherein one or more non-conterminous CH
2group also can be replaced by O and/or S, 1, 4-phenylidene, dicyclo [1.1.1] pentane-1, 3-bis-bases, dicyclo [2.2.2] octane-1, 4-bis-bases, volution [3.3] heptane-2, 6-bis-bases, piperidines-1, 4-bis-bases, perhydronaphthalene-2, 6-bis-bases, 1, 2, 3, 4-tetraline-2, 6-bis-bases, indane-2, 5-bis-bases, octahydro-4, 7-endo-methylene group indane-2, 5-bis-bases, luxuriant and rich with fragrance-2, 7-bis-bases, anthracene-2, 7-bis-bases, luxuriant and rich with fragrance-2, 7-bis-bases, 9, 10-dihydro phenanthrene-2, 7-bis-bases, 6H-benzo [c]-chromene-3, 8-bis-bases, 9H-fluorenes-2, 7-bis-bases, 9, 9-dimethyl-9H-fluorenes-2, 7-bis-bases, diphenylene-oxide-3, 7-bis-bases, 2-oxygen base-2H-chromene-7-base, 4-phenyl-2-oxygen base-2H-chromene-7-base, 4-oxygen base-4H-chromene-6-base, 4-phenyl-4-oxygen base-4H-chromene-6-base, wherein all these groups can be not replace or mono-or polysubstituted by L, and wherein in all these groups, hexanaphthene and aromatic group are very particularly preferred,
L represents P-Sp-, OH, CH
2oH, F, Cl, Br, I ,-CN ,-NO
2,-NCO ,-NCS ,-OCN ,-SCN ,-C (=O) N (R
x)
2,-C (=O) Y
1,-C (=O) R
x,-N (R
x)
2the optional silyl replacing, there is the aryl of the optional replacement of 6-20 C atom, there is 1-25 alkyl or alkoxyl group individual, the preferably straight or branched of 1-12 C atom, or there is 2-25 thiazolinyl, alkynyl, alkyl-carbonyl, alkoxy carbonyl, alkyl-carbonyl oxygen base or alkoxy-carbonyl oxy individual, the preferably straight or branched of 2-12 C atom, wherein in all these groups, one or more H atoms also can be replaced by F, Cl, P or P-Sp-
Y
1represent halogen, and
R
xrepresent P-Sp-, H, halogen, has 1-25, preferably straight chain, side chain or the cyclic alkyl of 1-12 C atom, wherein one or more non-conterminous CH
2group also can by-O-,-S-,-CO-,-CO-O-,-O-CO-,-O-CO-O-with make O and/or S atom not each other directly the mode of keyed jointing replace, and wherein one or more H atoms also can be replaced by F, Cl or P-Sp-.
Further the formula I shown in preferred context and IA with and the compound of minor be selected from the one or more of following preferred embodiment, these are combination with one another as required, wherein
-W
1, W
2expression-CH independently of one another separately
2cH
2-,-CH=CH-,-CH
2-O-,-O-CH
2--,-C (R
cr
d)-or-O-,
-W
1and W
2all represent-CH=CH-when different, all represent-CY=CY-when preferred difference, wherein Y is H or F,
-R
cand R
drepresent independently of one another separately H or there is the alkyl of 1-6 C atom, preferably H, methyl or ethyl,
-group W
1and W
2only one or two expression-N (R
e), and R
erepresent H or there is the alkyl of 1-6 C atom, preferred H, methyl or ethyl,
-group W
1and W
2in an expression-CH
2cH
2-or-CH=CH-and another expression-CH
2cH
2-,-CH
2o-,-OCH
2-or-C (CR
cr
d)
2-, wherein R
cand R
dpreferably represent methyl,
-group W
1and W
2in an expression-CH
2cH
2-and another expression-CH
2o-or-OCH
2-,
-group W
1and W
2in an expression-CH=CH-and another expression-CH
2o-or-OCH
2-,
-group W
1and W
2in an expression-CH
2cH
2-and another expression-C (CH
3)
2-,
-group W
1and W
2in an expression-CH=CH-and another expression-C (CH
3)
2-,
-W
1expression-CH
2cH
2-and W
2expression-CH
2o-,
-W
1expression-CH=CH-and W
2expression-CH
2o-,
-W
1and W
2expression-CH
2cH
2-,
-W
1and W
2expression-CH=CH-,
-Y represents H,
-radicals R
aand R
bin one represent that P-Sp-and another are different from P-Sp-,
-R
aand R
brepresent identical or different group P-Sp-,
-R
aand R
brepresent P-Sp-, wherein in radicals R
aand R
ba middle Sp represent singly-bound, and in radicals R
aand R
banother in Sp be different from singly-bound and preferably expression Sp " X "-group, make this group P-Sp-meet formula P-Sp " X "-,
-R
aand R
brepresent identical or different group P-Sp-, wherein two group Sp represent singly-bound,
-radicals R
aand R
bone represent or comprise group P-Sp-, and another represent not polymerisable group, be preferably selected from and there is the straight chain of 1-25 C atom or the alkyl of branching, wherein one or more non-conterminous CH
2group also can be separately independently of one another by-C (R
00)=C (R
000)-,-C ≡ C-,-N (R
00)-,-O-,-S-,-CO-,-CO-O-,-O-CO-,-O-CO-O-with make O and/or S atom not each other directly the mode of keyed jointing replace, and wherein one or more H atoms also can replace by F, Cl, Br, I or CN,
-R
aand R
bbe different from H,
-radicals R
aand R
bone represent that P-Sp-and another are different from H,
-be different from the radicals R of P-Sp-
aor R
brepresent to there is 1-12, the preferred alkyl of 5-12 C atom, there is the alkoxyl group of 1-12 C atom or there is the thiazolinyl of 2-11 C atom, wherein the one or more H atoms in all these groups also can be replaced by F,
-R
aand/or R
bexpression has the straight or branched alkyl of 1-25, preferred 1-12 C atom, wherein one or more non-conterminous CH
2group also can be separately independently of one another by-C (R
00)=C (R
000)-,-C ≡ C-,-N (R
00)-,-O-,-S-,-CO-,-CO-O-,-O-CO-,-O-CO-O-with make O and/or S atom not each other directly the mode of keyed jointing replace, and wherein one or more H atoms also can replace by F, Cl, Br, I or CN,
-Sp represents singly-bound,
Represent-(CH of-Sp
2)
p1-,-(CH
2)
p1-O-,-(CH
2)
p1-O-CO-,-(CH
2)
p1-O-CO-O-, preferably-(CH
2)
p1-or-(CH
2)
p1-O-, wherein p1 represents 1-12, preferably 1-5, the integer of 1-3 particularly preferably,
-Sp and/or Sp " expression has the alkylidene group of 1-5, preferred 1-3 C atom,
-A
1and A
2separately independently of one another and in the time occurring, represent to be selected from phenylene-1 at every turn identical or differently, 4-bis-bases, naphthalene-2,6-bis-bases, 1,2,3,4-naphthane-2,6-bis-bases, perhydronaphthalene-2,6-bis-bases, trans-cyclohexylidene-Isosorbide-5-Nitrae-bis-base, diphenylene-oxide-3, the group of 7-bis-bases, wherein in the above-mentioned group that comprises unsaturated ring or aromatic ring, one or two CH group in these rings also can be replaced by N, and wherein the single ring in all above-mentioned groups also can be as above hereinafter described mono-or polysubstituted by L
-A
1and A
2represent phenylene-Isosorbide-5-Nitrae-bis-base, it also can be as above hereinafter described mono-or polysubstituted by L,
-L neither represents also not comprise polymerizable groups,
-L represents not polymerisable group, is preferably selected from F, Cl ,-CN and have 1-25, the particularly preferably straight chain of 1-10 C atom or the alkyl of branching, wherein one or more non-conterminous CH
2group also can be separately independently of one another by-C (R
00)=C (R
000)-,-C ≡ C-,-N (R
00)-,-O-,-S-,-CO-,-CO-O-,-O-CO-,-O-CO-O-with make O and/or S atom not each other directly the mode of keyed jointing replace, and wherein one or more H atoms also can replace by F, Cl, Br, I or CN,
-L represents F, Cl, Br, I ,-CN ,-NO
2,-NCO ,-NCS ,-OCN or-SCN, preferably F,
-at one or two group (L)
rmiddle r represents 1,
-at one or two group (L)
rmiddle r represent 1 and L represent F,
-L represents alkyl or the alkoxyl group of the straight or branched with 1-12 C atom, or there is thiazolinyl, alkynyl, alkyl-carbonyl, alkoxy carbonyl, alkyl-carbonyl oxygen base or the alkoxy-carbonyl oxy of the straight or branched of 2-12 C atom, wherein in all these groups, one or more H atoms also can be replaced by F, Cl or P-Sp-
-L represents P-Sp-,
-Z
1and Z
2be selected from independently of one another and in the time occurring separately-O-at every turn identical or differently ,-CO-O-,-OCO-,-OCH
2-,-CH
2o-,-CF
2o-,-OCF
2-,-CH
2cH
2-,-CH=CH-,-CF=CF-,-CH=CF-,-CF=CH-,-C ≡ C-, singly-bound,
-Z
1and Z
2represent singly-bound,
-Z
1and Z
2be different from-C ≡ C-,
-p=0 and q=0,
-p=1 and q=1,
-p=0 and q=1, or p=1 and q=0,
If-W
1and W
2expression-CH=CH-, Z
1do not represent-C ≡ C-and/or A
1do not represent Isosorbide-5-Nitrae-phenylene, and particularly preferably do not represent aryl,
If-W
1and W
2expression-CH=CH-, Z
2do not represent-C ≡ C-and/or A
2do not represent Isosorbide-5-Nitrae-phenylene, and particularly preferably do not represent aryl,
-R
a-(A
1-Z
1)
p-and-(Z
2-A
2)
q-R
bdo not represent hydrogen.
The compound of particularly preferred formula I and IA is selected from following formula:
Wherein Sp, L and r have one of implication described in context, P
aand P
bthere is independently of one another separately for one of implication described in P R ' and R and " represent independently of one another separately H or there is the alkyl of 1-12 C atom, and s1 is 0 or 1.R ' and R " preferably represent methyl or ethyl.
In the compound of formula I and IA and minor I1-I28, P, P
aand P
bpreferably represent acrylate or methacrylic ester, also have in addition fluoro acrylic ester.
In the compound of formula I and IA and minor I1-I28, preferably represent-(CH of Sp
2)
p1-,-(CH
2)
p1-O-,-(CH
2)
p1-O-CO-or-(CH
2)
p1-O-CO-O-or its mirror image, wherein p1 represents 1-12, preferably 1-6,1,2,3 or 4 integer particularly preferably, and is wherein undertaken and the keyed jointing of adjacent phenyl rings by O atom.
The invention further relates to as the formula I of contextual definition and IA with and the novel cpd of minor, if W wherein
1and W
2expression-CH=CH-,
Z
1do not represent-C ≡ C-and/or A
1do not represent Isosorbide-5-Nitrae-phenylene, and particularly preferably do not represent aryl, and
Z
2do not represent-C ≡ C-and/or A
2do not represent Isosorbide-5-Nitrae-phenylene, and particularly preferably do not represent aryl, and get rid of 1-vinylpyrene.
The invention further relates to the new intermediate for the preparation of formula I compound, it is selected from formula II
And be preferably selected from formula IIA
Wherein W
1, W
2, Sp, L, A
1, A
2, Z
1, Z
2, p, q and r have the implication in formula I or described in context, and G and G ' represent H atom or blocking group separately independently of one another.
Suitable blocking group G is well known by persons skilled in the art.Preferred blocking group is alkyl, acyl group and alkyl silyl or aryl silyl, 2-THP trtrahydropyranyl or methoxymethyl.
The intermediate of particularly preferred formula II and IIA is selected from above-mentioned minor I1-I28, wherein P
ain each situation, represent G-O-and P
bexpression-O-G ' in each situation, wherein G and G ' preferably represent H.
The suitable especially and preferred method of the compound of preparation formula I and II and minor thereof and intermediate is for example described in following signal formula and preferably includes one or more steps as described below.
It is known and be described in organic chemistry classic that the compound of formula I and II and minor thereof and intermediate can be similar to those skilled in the art, for example Houben-Weyl, Methoden der organischen Chemie, Thieme-Verlag, the method preparation in Stuttgart.
For example, the intermediate that corresponding acid, acid derivative or the halogenated compound that the compound of formula I comprises group P by employing comes esterification or etherificate formula II synthesizes.As for example as shown in signal formula 1, wherein R
aand R
brepresent that P-Sp-and P are for example for the formula I compound of acrylate group or methacrylate based group can use acid derivative, for example (methyl) acrylate chloride or (methyl) acrylic anhydride, alkali and optionally under the existence of 4-(N, N-dimethylamino) pyridine (DMAP) by esterification wherein the corresponding alcohol of the formula II of G=G '=H obtain.In addition, also can use (methyl) vinylformic acid under the existence of dewatering agent, for example, according to adopting the Steglich method of dicyclohexylcarbodiimide (DCC) by alcohol esterification.
Therefore the present invention further relates to the method for preparation I compound, wherein use comprise group P corresponding acid, acid derivative or halogenated compound under the existence of dewatering agent by compound esterification or the etherificate of formula II.
signal formula 1
(R=H or CH
3; W
1, W
2, Sp, L, A
1, A
2, Z
1, Z
2, p, q and r be suc as formula defining in II)
Obtain agent structure 4,5,9, and 10-tetrahydrochysene pyrene (1, W=W '=CH
2cH
2) approach provide (P.Soustek etc., Dyes and Pigments78 (2008) 139-147) by the hydrogenation of pyrene, and can be by halogenation by selectivity functionalized (signal formula 2).According to A.D.Abell etc., J.Chem.Soc., Perkin Trans.1,1997,1663-1668, by 4,5,9,10-tetrahydrochysene pyrene (4) obtains 2, and 7-bis-is bromo-4,5,9,10-tetrahydrochysene pyrene (5, Hal=Br).According to H.Suzuki, Organic Syntheses, Coll. the 6th volume, it is corresponding 2 that the iodate of the 700th page (1988) obtains, 7-bis-iodo-4,5,9,10-tetrahydrochysene pyrene (5, Hal=I).
signal formula 2
Can be for example by using the metallization of butyllithium and preparing boric acid with reacting by dihalide compound 5 of boric acid ester, and its oxidation can be obtained to phenol 6 (schematic diagram 3).A kind of replacement scheme is according to S.L.Buchwald etc., J.Am.Chem.Soc.2006, and 128,10694-10695 processes with KOH under palladium catalyst exists.Use acrylic acid esterification to obtain (methyl) acrylate 7.
signal formula 3
(R=H or CH
3)
Single metallization under tri-isopropylborate exists obtains boric acid diisopropyl ester, and its hydrolysis and oxidation obtain monohydroxy compound (8, signal formula 4), and this compound can further transform in second step.Therefore, obtain alkynes 9 with the Sonogashira coupling of end alkynol, can obtain the compound 10 with spacer groups by hydrogenation and esterification by it.
signal formula 4
(R=H or CH
3, p1=is 1-12 such as)
Correspondingly, as by S.Song etc., Tetrahedron Letters2008,49, described in 3582-3587, derivative 12 can obtain (signal formula 5) by the 4H-ring penta [def] of commercially available acquisition luxuriant and rich with fragrance 11, and is set out and can be obtained compound 13 and 14 by it according to signal formula 3 and 4.
signal formula 5
(R=H or CH
3, p1=is 1-12 such as)
By suitable intermediate, for example the aromizing of compound 5,8 or 12 obtains corresponding unsaturated compound 15-18.For example to process (V.V.Filichev etc. in DDQ for inert solvent (DDQ) for the suitable reaction conditions of aromizing, Chemistry-AEuropean Journal2008,14 (32), 9968-9980), or at the halogenation (P.Soustek etc., Dyes and Pigments78 (2008) 139-147 that eliminate in hydrogen halide situation; S.Song etc., Tetrahedron Letters49 (2008) 3582-3587).
(R=H or CH
3, p1=is 1-12 such as)
Flavidin (19) is natural product and from orchid, separates (referring to such as G.K.Jayaprakasha etc., Bioorganic & Medicinal Chemistry2004,12,5141-5146).
(R=H or CH
3)
Derivative 20 according to the present invention is by 19 acquisitions as mentioned above; Aromizing as above obtains 21.
Midbody compound shown in schematic diagram can further change into according to compound of the present invention (schematic diagram 6) by multiple standard reactions.For example, aryl derivatives 23 can be by transition metal-catalyzed linked reaction, for example Suzuki coupling (22, M=-B (OH)
2) obtained by arylide, and can be similar to above-mentioned signal formula and change into target compound 25.
signal formula 6
(R=H or CH
3; M=B (OH)
2, ZnHal, MgHal; Hal=halogen; G, W
1, W
2, A
1, Z
1, p, Sp be suc as formula described in II)
The invention further relates to the compound for the preparation of formula I and II described in context, especially for the method for the compound preparation I compound by formula II.
In order to prepare PSA indicating meter, by polymerizable compound in the liquid crystal media applying between the substrate that is liquid-crystal display under voltage condition by in-situ polymerization polymerization or crosslinked (if a kind of compound comprises two or more polymerizable groups).Polymerization can be carried out in a step.Also can be first in first step, carry out polymerization to produce pre-tilt angle applying under voltage condition, then in the second polymerization procedure, do not applying under voltage condition polymerization or be cross-linked compound not reacted in first step (" finally solidifying ").
Suitable and preferred polymerization process is, for example, and heat or photopolymerization, preferred light polymerization, particularly UV photopolymerization.Also can optionally add one or more initiators at this.Suitable polymerizing condition and suitable initiator type and consumption are well known by persons skilled in the art and have in the literature description.Be suitable for radical polymerization, for example, the light trigger of commercially available acquisition
or
if use initiator, its ratio is preferably 0.001-5 % by weight, particularly preferably 0.001-1 % by weight.
Also be suitable for not having the polymerization of initiator according to polymerizable compound of the present invention, this is accompanied by significant advantage, and the liquid crystal media that for example lower material cost and the initiator by possible residual content especially still less or its degradation production cause pollutes.Therefore polymerization also can not add initiator to carry out.Therefore in preferred embodiments, liquid crystal media does not comprise polymerization starter.
Polymerizable components A) or liquid crystal media also can comprise one or more stablizers, to prevent less desirable RM spontaneous polymerization, for example store or In transit.The suitable type of stablizer and consumption are well known by persons skilled in the art and have in the literature description.Suitable especially, for example, commercially available acquisition
the stablizer of series (Ciba AG) for example
if use stablizer, the total amount meter of their ratio (based on RM or polymerizable components A)) be preferably 10-10,000ppm, is particularly preferably 50-500ppm.
What be used for PSA indicating meter preferably comprises <5 % by weight according to liquid crystal media of the present invention, particularly preferably <1 % by weight, the polymerizable compound of the very particularly preferably polymerizable compound of <0.5 % by weight, particularly above-mentioned formula I and its minor.
Particularly preferably comprise a kind of, two or three according to the liquid crystal media of polymerizable compound of the present invention.
In addition preferred such liquid crystal media: wherein polymerizable components (component A) only comprises according to polymerizable compound of the present invention.
In addition preferred such liquid crystal media: wherein B component) be liquid crystalline cpd or the liquid crystal compound with Nematic liquid crystalline phase.
Also preferably according to achirality polymerizable compound of the present invention and component A wherein) and/or compound B) be only selected from the liquid crystal media of non-chiral compound.
In addition preferred such liquid crystal media: wherein polymerizable components or component A) comprise one or more contain a polymerizable groups (single reaction) according to polymerizable compound of the present invention and one or more contain two or more, preferably two polymerizable groups (two or multiple reactionness) according to polymerizable compound of the present invention.
In addition preferred such PSA indicating meter and liquid crystal media: wherein polymerizable components or component A) only comprise contain two polymerizable groups (two reactivities) according to polymerizable compound of the present invention.
Polymerizable components or component A) the preferred <5% of ratio in liquid crystal media according to the present invention, particularly preferably <1%, very particularly preferably <0.5%.
Liquid crystal components or B component) the preferred >95% of ratio in liquid crystal media according to the present invention, particularly preferably >99%.
According to polymerizable compound of the present invention polymerization separately, but also can aggregate packet containing two or more according to the mixture of polymerizable compound of the present invention, or comprise one or more according to preferably mixture of other polymerizable compounds (comonomer) of mesomorphic or liquid crystal of polymerizable compound of the present invention and one or more.Under the such mixture situation of polymerization, form multipolymer.The invention still further relates to as above polymerizable mixture hereinafter described.This polymerizable compound and comonomer are mesomorphic or non-mesomorphic, preferably mesomorphic or liquid crystal.
Suitable and preferred, the mesomorphic comonomer that is used in particular for PSA indicating meter is selected from for example following formula:
Wherein, each group has following implication:
P
1and P
2represent independently of one another separately polymerizable groups, preferably have if context is for one of implication as shown in P, particularly preferably acrylate group, methacrylate based group, fluorate acrylic acid ester group, oxetane groups, ethylene oxy group or epoxide group
Sp
1and Sp
2represent independently of one another separately singly-bound or spacer groups, preferably have if context is for one of implication as shown in Sp, and expression-(CH particularly preferably
2)
p1-,-(CH
2)
p1-O-,-(CH
2)
p1-CO-O-or-(CH
2)
p1-O-CO-O-, wherein p1 is that the keyed jointing of adjacent ring in the integer of 1-12 and the group wherein in the end mentioned is undertaken by O atom,
Wherein one or more group P
1-Sp
1-and P
2-Sp
2-also can represent R
aa, condition is the group P existing
1-Sp
1-and P
2-Sp
2-at least one do not represent R
aa,
R
aarepresent H, F, Cl, CN or there is the straight or branched alkyl of 1-25 carbon atom, wherein one or more non-conterminous CH
2group also can be separately independently of one another by C (R
0)=C (R
00)-,-C ≡ C-,-N (R
0)-,-O-,-S-,-CO-,-CO-O-,-O-CO-,-O-CO-O-are so that the not direct mode of keyed jointing each other of O and/or S atom is replaced, and wherein one or more H atoms also can be by F, Cl, CN or P
1-Sp
1-replace, particularly preferably there is the straight chain of 1-12 C atom or branching, optional single or polyfluorizated alkyl, alkoxyl group, thiazolinyl, alkynyl, alkyl-carbonyl, alkoxy carbonyl, alkyl-carbonyl oxygen base or alkoxy-carbonyl oxy (wherein thiazolinyl and alkynyl there are at least two C atoms and branching group has at least three C atoms)
R
0, R
00while appearance independently of one another and at every turn separately, represent H identical or differently or there is the alkyl of 1-12 C atom,
R
yand R
zrepresent independently of one another separately H, F, CH
3or CF
3,
Z
1expression-O-,-CO-,-C (R
yr
z)-or-CF
2cF
2-,
Z
2and Z
3expression-CO-O-,-O-CO-,-CH independently of one another separately
2o-,-OCH
2-,-CF
2o-,-OCF
2-or-(CH
2)
n-, wherein n is 2,3 or 4,
When occurring at every turn, L represents F, Cl, CN identical or differently, or there is the straight chain of 1-12 C atom or branching, optional single or polyfluorizated alkyl, alkoxyl group, thiazolinyl, alkynyl, alkyl-carbonyl, alkoxy carbonyl, alkyl-carbonyl oxygen base or alkoxy-carbonyl oxy, preferably F
L ' and L " represent independently of one another separately H, F or Cl,
R represents 0,1,2,3 or 4,
S represents 0,1,2 or 3,
T represents 0,1 or 2,
X represents 0 or 1.
Except above-mentioned polymerizable compound, for also comprising liquid crystal compound (" main body mixture ") according to the liquid crystal media of liquid-crystal display of the present invention, its contain one or more, preferred two or more lower molecular weights (being monomer or unpolymerized) compound.The latter is stable or nonreactive for polyreaction under the condition for polymerizable compound polymerization.In principle, the arbitrary liquid crystal compound that is suitable for traditional VA and OCB indicating meter is all suitable as main body mixture.Suitable liquid crystal compound is well known by persons skilled in the art and has in the literature description, for example mixture in the VA indicating meter in EP1378557A1, and the mixture for OCB indicating meter in EP1306418A1 and DE10224046A1.
In the first preferred embodiment of the present invention, liquid crystal media comprises the liquid crystal main body mixture of compound based on having negative dielectric anisotropic.This liquid crystal media is specially adapted to PSA-VA indicating meter.In the particularly preferred embodiment of this class liquid crystal media paragraph a-x below, describe:
A) liquid crystal media that comprises the one or more of compounds that are selected from following formula CY and PY:
Wherein each group has following implication:
A represents 1 or 2,
B represents 0 or 1,
represent
R
1and R
2represent to have independently of one another separately the alkyl of 1-12 C atom, wherein one or two non-conterminous CH
2group also can by-O-,-CH=CH-,-CO-,-OCO-or-COO-with make O atom directly each other the mode of keyed jointing replace, preferably there is alkyl or the alkoxyl group of 1-6 C atom,
Z
xand Z
yexpression-CH independently of one another separately
2cH
2-,-CH=CH-,-CF
2o-,-OCF
2-,-CH
2o-,-OCH
2-,-CO-O-,-O-CO-,-C
2f
4-,-CF=CF-,-CH=CH-CH
2o-or singly-bound, preferably singly-bound,
L
1-4represent independently of one another separately F, Cl, OCF
3, CF
3, CH
3, CH
2f, CHF
2.
Preferably, group L
1and L
2all represent F or group L
1and L
2in one represent that F and another represent Cl, or group L
3and L
4all represent F or group L
3and L
4in one represent that F and another represent Cl.
The compound of formula CY is preferably selected from following minor:
Wherein a represent 1 or 2, Alkyl and Alkyl* represent to have independently of one another separately the straight chained alkyl of 1-6 C atom, and Alkenyl represents to have the straight-chain alkenyl of 2-6 C atom, and (O) expression Sauerstoffatom or singly-bound.Alkenyl preferably represents CH
2=CH-, CH
2=CHCH
2cH
2-, CH
3-CH=CH-, CH
3-CH
2-CH=CH-, CH
3-(CH
2)
2-CH=CH-, CH
3-(CH
2)
3-CH=CH-or CH
3-CH=CH-(CH
2)
2-.
The compound of formula PY is preferably selected from following minor:
Wherein Alkyl and Alkyl* represent to have the straight chained alkyl of 1-6 C atom separately independently of one another, and Alkenyl represents to have the straight-chain alkenyl of 2-6 C atom, and (O) expression Sauerstoffatom or singly-bound.Alkenyl preferably represents CH
2=CH-, CH
2=CHCH
2cH
2-, CH
3-CH=CH-, CH
3-CH
2-CH=CH-, CH
3-(CH
2)
2-CH=CH-, CH
3-(CH
2)
3-CH=CH-or CH
3-CH=CH-(CH
2)
2-.
B) comprise in addition the liquid crystal media of the compound of one or more of following formulas:
Wherein each group has following implication:
represent
represent
R
3and R
4represent to have independently of one another separately the alkyl of 1-12 C atom, wherein one or two non-conterminous CH
2group also can by-O-,-CH=CH-,-CO-,-O-CO-or-CO-O-with make O atom directly each other the mode of keyed jointing replace,
Z
yexpression-CH
2cH
2-,-CH=CH-,-CF
2o-,-OCF
2-,-CH
2o-,-OCH
2-,-CO-O-,-O-CO-,-C
2f
4-,-CF=CF-,-CH=CH-CH
2o-or singly-bound, preferably singly-bound.
The compound of formula ZK is preferably selected from following minor:
Wherein Alkyl and Alkyl* represent to have the straight chained alkyl of 1-6 C atom separately independently of one another, and Alkenyl represents to have the straight-chain alkenyl of 2-6 C atom.Alkenyl preferably represents CH
2=CH-, CH
2=CHCH
2cH
2-, CH
3-CH=CH-, CH
3-CH
2-CH=CH-, CH
3-(CH
2)
2-CH=CH-, CH
3-(CH
2)
3-CH=CH-or CH
3-CH=CH-(CH
2)
2-.
C) comprise in addition the liquid crystal media of the compound of one or more of following formulas:
Wherein each group has following implication at every turn in the time occurring identical or differently:
R
5and R
6on having independently of one another separately, regard to R
1one of described implication,
represent
represent
with
E represents 1 or 2.
The compound of formula DK is preferably selected from following minor:
Wherein Alkyl and Alkyl* represent to have the straight chained alkyl of 1-6 C atom separately independently of one another, and Alkenyl and Alkenyl* separately independently of one another expression there is the straight-chain alkenyl of 2-6 C atom.Alkenyl and Alkenyl* preferably represent CH
2=CH-, CH
2=CHCH
2cH
2-, CH
3-CH=CH-, CH
3-CH
2-CH=CH-, CH
3-(CH
2)
2-CH=CH-, CH
3-(CH
2)
3-CH=CH-or CH
3-CH=CH-(CH
2)
2-.
D) comprise in addition the liquid crystal media of the compound of one or more of following formulas:
Wherein each group has following implication:
represent
F represents 0 or 1,
R
1and R
2represent to have independently of one another separately the alkyl of 1-12 C atom, wherein one or two non-conterminous CH
2group also can by-O-,-CH=CH-,-CO-,-OCO-or-COO-with make O atom directly each other the mode of keyed jointing replace,
Z
xand Z
yexpression-CH independently of one another separately
2cH
2-,-CH=CH-,-CF
2o-,-OCF
2-,-CH
2o-,-OCH
2-,-CO-O-,-O-CO-,-C
2f
4-,-CF=CF-,-CH=CH-CH
2o-or singly-bound, preferably singly-bound.
L
1and L
2represent independently of one another separately F, Cl, OCF
3, CF
3, CH
3, CH
2f, CHF
2.
Preferably, group L
1and L
2all represent F or group L
1and L
2in one represent that F and another represent Cl.
The compound of formula LY is preferably selected from following minor:
Wherein R
1have above-mentioned implication, alkyl represents to have the straight chained alkyl of 1-6 C atom, (O) represent Sauerstoffatom or singly-bound, and v represents the integer of 1-6.R
1preferably represent the straight-chain alkenyl, particularly CH that there is the straight chained alkyl of 1-6 C atom or there is 2-6 C atom
3, C
2h
5, n-C
3h
7, n-C
4h
9, n-C
5h
11, CH
2=CH-, CH
2=CHCH
2cH
2-, CH
3-CH=CH-, CH
3-CH
2-CH=CH-, CH
3-(CH
2)
2-CH=CH-, CH
3-(CH
2)
3-CH=CH-or CH
3-CH=CH-(CH
2)
2-.
E) comprise in addition the liquid crystal media of the one or more of compounds that are selected from following formula:
Wherein alkyl represents C
1-6-alkyl, L
xrepresent H or F, and X represents F, Cl, OCF
3, OCHF
2or OCH=CF
2.Particularly preferably wherein X represents the compound of the formula G1 of F.
F) comprise in addition the liquid crystal media of the one or more of compounds that are selected from following formula:
Wherein R
5on having, regard to R
1one of described implication, alkyl represents C
1-6-alkyl, d represents 0 or 1, and z and m represent the integer of 1-6 separately independently of one another.R in these compounds
5be particularly preferably C
1-6-alkyl or alkoxyl group or C
2-6-thiazolinyl, d is preferably 1.Preferably comprise the compound of the one or more of above-mentioned formulas of quantity >=5 % by weight according to liquid crystal media of the present invention.
G) comprise in addition the liquid crystal media of the one or more of biphenol compounds that are selected from following formula:
Wherein Alkyl and Alkyl* represent to have the straight chained alkyl of 1-6 C atom separately independently of one another, and Alkenyl and Alkenyl* separately independently of one another expression there is the straight-chain alkenyl of 2-6 C atom.Alkenyl and Alkenyl* preferably represent CH
2=CH-, CH
2=CHCH
2cH
2-, CH
3-CH=CH-, CH
3-CH
2-CH=CH-, CH
3-(CH
2)
2-CH=CH-, CH
3-(CH
2)
3-CH=CH-or CH
3-CH=CH-(CH
2)
2-.
The ratio of the biphenyl of liquid crystal compound Chinese style B1-B3 is preferably at least 3 % by weight, especially >=5 % by weight.
The particularly preferably compound of formula B2.
The compound of formula B1-B3 is preferably selected from following minor:
Wherein Alkyl* represents to have the alkyl of 1-6 C atom.Particularly preferably comprise the compound of one or more of formula B1a and/or B2c according to medium of the present invention.
H) comprise in addition the liquid crystal media of the terphenyl compounds of one or more of following formulas:
Wherein R
5and R
6on having independently of one another separately, regard to R
1one of described implication, and
Represent independently of one another separately
Wherein L
5represent F or Cl, preferably F, and L
6represent F, Cl, OCF
3, CF
3, CH
3, CH
2f or CHF
2, preferably F.
The compound of formula T is preferably selected from following minor:
Wherein R represents to have straight chained alkyl or the alkoxyl group of 1-7 C atom, and R* represents to have the straight-chain alkenyl of 2-7 C atom, (O) represent Sauerstoffatom or singly-bound, and m represents the integer of 1-6.R* preferably represents CH
2=CH-, CH
2=CHCH
2cH
2-, CH
3-CH=CH-, CH
3-CH
2-CH=CH-, CH
3-(CH
2)
2-CH=CH-, CH
3-(CH
2)
3-CH=CH-or CH
3-CH=CH-(CH
2)
2-.
R preferably represents methyl, ethyl, propyl group, butyl, amyl group, hexyl, methoxyl group, oxyethyl group, propoxy-, butoxy or pentyloxy.
The preferred contained T of liquid crystal media according to the present invention and the preferably terphenyl of minor, its amount is preferably 0.5-30 % by weight, particularly 1-20 % by weight.
The compound of formula T1, T2, T3 and T21 is particularly preferred.In these compounds, R preferably represents alkyl, also has alkoxyl group, has separately 1-5 C atom.
If the Δ n value of mixture, by >=0.1, is preferably used terphenyl in mixture according to the present invention.The terphenyl compounds of one or more formulas T that preferred mixture comprises 2-20 % by weight, is preferably selected from compound T1-T22.
I) comprise in addition one or more and be selected from the liquid crystal media of the compound of following formula:
Wherein R
1and R
2there is above-mentioned implication and preferably represent independently of one another separately and there is the straight chained alkyl of 1-6 C atom, or there is the straight-chain alkenyl of 2-6 C atom.
Preferred medium comprises one or more and is selected from the compound of formula O1, O3 and O4.
K) comprise in addition the liquid crystal media of the compound of one or more following formulas:
Wherein
represent
R
9represent H, CH
3, C
2h
5or n-C
3h
7, (F) represent optional fluoro substituents, and q represents 1,2 or 3, and R
7have for R
1one of described implication, described compound preferred amount is >3 % by weight, especially>=5 % by weight and very particularly preferably 5-30 % by weight.
The compound of particularly preferred formula IF is selected from following minor:
Wherein R
7preferably represent straight chained alkyl, and R
9represent CH
3, C
2h
5or n-C
3h
7.The particularly preferably compound of formula FI1, FI2 and FI3.
M) comprise in addition one or more and be selected from the liquid crystal media of the compound of following formula:
Wherein R
8have for R
1described implication, and Alkyl represents to have the straight chained alkyl of 1-6 C atom.
N) comprise in addition the one or more of compounds with tetralyl or naphthyl unit, for example, be selected from the liquid crystal media of the compound of following formula:
Wherein R
10and R
11have independently of one another for R separately
1one of described implication, preferably represents to have straight chained alkyl or the alkoxyl group of 1-6 C atom or have the straight-chain alkenyl of 2-6 C atom, and Z
1and Z
2expression-C independently of one another separately
2h
4-,-CH=CH-,-(CH
2)
4-,-(CH
2)
3o-,-O (CH
2)
3-,-CH=CH-CH
2cH
2-,-CH
2cH
2cH=CH-,-CH
2o-,-OCH
2-,-CO-O-,-O-CO-,-C
2f
4-,-CF=CF-,-CF=CH-,-CH=CF-,-CH
2-or singly-bound.
O) comprising in addition one or more of preferred amounts is 3-20 % by weight, and quantity is the two fluoro dibenzo chromans of following formula of 3-15 % by weight and/or the liquid crystal media of chroman especially:
Wherein R
11and R
12have independently of one another separately above-mentioned implication, ring M represents anti-form-1,4-cyclohexylidene or Isosorbide-5-Nitrae-phenylene, Z
mexpression-C
2h
4-,-CH
2o-,-OCH
2-,-CO-O-or-O-CO-, and c represents 0 or 1.
The compound of particularly preferred formula BC and CR is selected from following minor:
Wherein Alkyl and Alkyl* represent to have the straight chained alkyl of 1-6 C atom separately independently of one another, (O) represent Sauerstoffatom or singly-bound, and Alkenyl and Alkenyl* separately independently of one another expression there is the straight-chain alkenyl of 2-6 C atom.Alkenyl and Alkenyl* preferably represent CH
2=CH-, CH
2=CHCH
2cH
2-, CH
3-CH=CH-, CH
3-CH
2-CH=CH-, CH
3-(CH
2)
2-CH=CH-, CH
3-(CH
2)
3-CH=CH-or CH
3-CH=CH-(CH
2)
2-.
Very particularly preferably comprise the mixture of the compound of a kind of, two or three formula BC-2.
P) comprise in addition the liquid crystal media of fluoridizing phenanthrene and/or diphenylene-oxide of one or more of following formulas:
Wherein R
11and R
12there is independently of one another separately above-mentioned implication, b represent 0 or 1, L represent F, and r represents 1,2 or 3.
The compound of particularly preferred formula PH and BF is selected from following minor:
Wherein R and R ' have straight chained alkyl or the alkoxyl group of 1-7 C atom separately independently of one another.
Q), outside the polymerizable compound and comonomer except polymerizable compound according to the present invention, particularly formula I or its minor, do not comprise and there is terminal ethylenyl groups oxygen base (O-CH=CH
2) the liquid crystal media of compound.
R) comprise 1-5, preferably 1,2 or 3 kind of polymerizable compound, be preferably selected from according to polymerizable compound of the present invention, particularly the liquid crystal media of the polymerizable compound of formula I or its minor.
S) wherein polymerizable compound, the particularly ratio of the polymerizable compound of formula I or its minor are 0.05-5%, the preferred liquid crystal media of 0.1-1% in whole mixture.
The liquid crystal media of the compound that t) comprises 1-8, preferred 1-5 kind formula CY1, CY2, PY1 and/or PY2.The ratio of these compounds in whole mixture is preferably 5-60%, is particularly preferably 10-35%.These single content of planting compound are preferably 2-20% under each situation.
The liquid crystal media of the compound that u) comprises 1-8, preferred 1-5 kind formula CY9, CY10, PY9 and/or PY10.The ratio of these compounds in whole mixture is preferably 5-60%, is particularly preferably 10-35%.These single content of planting compound are preferably 2-20% under each situation.
V) comprise 1-10, preferably the compound, the particularly liquid crystal media of the compound of formula ZK1, ZK2 and/or ZK6 of 1-8 kind formula ZK.The ratio of these compounds in whole mixture is preferably 3-25%, is particularly preferably 5-45%.These single content of planting compound are preferably 2-20% under each situation.
W) ratio of the compound of its Chinese style CY, PY and ZK in whole mixture is greater than 70%, is preferably more than 80% liquid crystal media.
X) wherein pre-tilt angle preferably≤85 °, the PSA-VA indicating meter of particularly preferably≤80 °.
In the second preferred embodiment of the present invention, liquid crystal media comprises the liquid crystal main body mixture of compound based on having positive dielectric anisotropy.This class liquid crystal media is particularly suitable in PSA-OCB, PSA-TN, PSA-positivity-VA, PSA-IPS and PSA-FFS indicating meter.The particularly preferred embodiment of this class display provides below:
The liquid crystal media of the compound that comprises the one or more of compounds that are selected from following formula:
Except the compound of formula AA and/or BB, also comprise the liquid crystal media of the compound of one or more of following formulas:
In formula AA, BB and CC, each group has following implication:
Represent separately independently of one another, and in the time occurring at every turn identical or differently
Represent separately independently of one another, and in the time occurring at every turn identical or differently
R
21, R
31, R
41, R
42represent independently of one another separately to there is alkyl, alkoxyl group, oxa alkyl or the fluoroalkyl of 1-9 C atom, or there is the thiazolinyl of 2-9 C atom,
X
0represent F, Cl, the haloalkyl with 1-6 C atom or alkoxyl group or there is haloalkenyl group or the alkene oxygen base of 2-6 C atom,
Z
31expression-CH
2cH
2-,-CF
2cF
2-,-COO-, trans-CH=CH-, trans-CF=CF-,-CH
2o-or singly-bound, preferably-CH
2cH
2-,-COO-, trans-CH=CH-or singly-bound, particularly preferably-COO-, trans-CH=CH-or singly-bound,
Z
41, Z
42expression-CH
2cH
2-,-COO-, trans-CH=CH-, trans-CF=CF-,-CH
2o-,-CF
2o-,-C ≡ C-or singly-bound, preferably singly-bound,
L
21, L
22, L
31, L
32represent H or F,
G represents 1,2 or 3,
H represents 0,1,2 or 3.
X
0preferably represent F, Cl, CF
3, CHF
2, OCF
3, OCHF
2, OCFHCF
3, OCFHCHF
2, OCFHCHF
2, OCF
2cH
3, OCF
2cHF
2, OCF
2cHF
2, OCF
2cF
2cHF
2, OCF
2cF
2cHF
2, OCFHCF
2cF
3, OCFHCF
2cHF
2, OCF
2cF
2cF
3, OCF
2cF
2cClF
2, OCClFCF
2cF
3or CH=CF
2, particularly preferably F or OCF
3.
The compound of formula AA is preferably selected from following formula:
Wherein A
21, R
21, X
0, L
21and L
22have at the implication described in formula AA, L
23and L
24represent independently of one another separately H or F, and X
0preferably represent F.The particularly preferably compound of formula AA1 and AA2.
The compound of particularly preferred formula AA1 is selected from following minor:
Wherein R
0have in formula AA1 for R
21one of described implication, X
0, L
21and L
22have at the implication described in formula AA1, L
23, L
24, L
25and L
26represent independently of one another separately H or F, and X
0preferably represent F.
The compound of formula AA1 is very particularly preferably selected from following minor:
Wherein R
0have in formula AA1 for R
21described implication.
The compound of particularly preferred formula AA2 is selected from following minor:
Wherein R
0have in formula AA1 for R
21described implication, X
0, L
21and L
22have at the implication described in formula AA, L
23, L
24, L
25and L
26represent independently of one another separately H or F, and X
0preferably represent F.
The compound of formula AA2 is very particularly preferably selected from following minor:
Wherein R
0have in formula AA1 for R
21described implication.
The compound of particularly preferred formula AA3 is selected from following minor:
Wherein R
0have in formula AA1 for R
21described implication, X
0, L
21and L
22have in the implication described in formula AA3, and X
0preferably represent F.
The compound of particularly preferred formula AA4 is selected from following minor:
Wherein R
0have in formula AA1 for R
21described implication.
The compound of formula BB is preferably selected from following minor:
Wherein A
31, A
32, R
31, X
0, L
31and L
32have in the implication described in formula BB, and X
0preferably represent F.The particularly preferably compound of formula BB1 and BB2.
The compound of particularly preferred formula BB1 is selected from following minor:
Wherein R
3have in formula BB1 for R
31described implication, X
0, L
31and L
32have in the implication described in formula BB1, and X
0preferably represent F.
The compound of formula BB1a is very particularly preferably selected from following minor:
Wherein R
3have in formula BB1 for R
31described implication.
The compound of formula BB1b is very particularly preferably selected from following minor:
Wherein R
3have in formula BB1 for R
31described implication.
The compound of particularly preferred formula BB2 is selected from following minor:
Wherein R
0have in formula BB2 for R
21one of described implication, X
0, L
31and L
32have at the implication described in formula BB2, L
33, L
34, L
35and L
36represent independently of one another separately H or F, and X
0preferably represent F.
The compound of formula BB2a is very particularly preferably selected from following minor:
Wherein R
3have in formula BB2 for R
31described implication.
The compound of formula BB2b is very particularly preferably selected from following minor:
Wherein R
3have in formula BB2 for R
31described implication.
The compound of formula BB2c is very particularly preferably selected from following minor:
Wherein R
3have in formula BB2 for R
31described implication.
Formula BB2d very particularly preferably and the compound of BB2e are selected from following minor:
Wherein R
3have in formula BB2 for R
31described implication.
The compound of formula BB2f is very particularly preferably selected from following minor:
Wherein R
3have in formula BB2 for R
31described implication.
The compound of formula BB2g is very particularly preferably selected from following minor:
Wherein R
3have in formula BB2 for R
31described implication.
The compound of formula BB2h is very particularly preferably selected from following minor:
Wherein R
3have in formula BB2 for R
31described implication.
The compound of formula BB2i is very particularly preferably selected from following minor:
Wherein R
3have in formula BB2 for R
31described implication.
The compound of formula BB2k is very particularly preferably selected from following minor:
Wherein R
3have in formula BB2 for R
31described implication.
Alternatively or except the compound of formula BB1 and/or BB2, liquid crystal media can also comprise the compound of the one or more of BB3 of formula as defined above.
The compound of particularly preferred formula BB3 is selected from following minor:
Wherein R
3have in formula BB3 for R
31described implication.
Except the compound of formula AA and/or BB, preferably comprise the dielectric neutral compound of the one or more of dielectric anisotropies with-1.5 to+3 according to liquid crystal media described in this second preferred embodiment, it is selected from the compound of formula CC as defined above.
The compound of particularly preferred formula CC is selected from following minor:
Wherein R
41and R
42have in the implication described in formula CC, and preferably represent independently of one another separately there is alkyl, alkoxyl group, the fluorinated alkyl of 1-7 C atom or fluoridize alkoxyl group, or there is thiazolinyl, alkene oxygen base, the alkoxyalkyl of 2-7 C atom or fluoridize thiazolinyl, and L
4represent H or F.
Except the dielectric neutral compound of formula CC or the dielectric neutral compound of replacement formula CC, preferably comprise the dielectric neutral compound of the one or more of dielectric anisotropies with-1.5 to+3 according to liquid crystal media described in this second preferred embodiment, it is selected from the compound of formula DD
Wherein A
41, A
42, Z
41, Z
42, R
41, R
42have in the implication described in formula CC with h.
The compound of particularly preferred formula DD is selected from following minor:
Wherein R
41and R
42have in the implication described in formula DD, and R
41preferably represent alkyl, and in formula DD1 R
42preferably represent thiazolinyl, particularly preferably-(CH
2)
2-CH=CH-CH
3, and in formula DD2 R
42preferably represent alkyl ,-(CH
2)
2-CH=CH
2or-(CH
2)
2-CH=CH-CH
3.
In liquid crystal media according to the present invention, the concentration of the compound of formula AA and BB is preferably the 2%-60% of whole mixture, particularly preferably 3%-35%, very particularly preferably 4%-30%.
In liquid crystal media according to the present invention, the concentration of the compound of formula CC and DD is preferably the 2%-70% of whole mixture, is in particular 5%-65%, 10%-60% particularly preferably, and very particularly preferably from 10%, preferably 15% to 55%.
As according to the low-molecular weight compound of component of liquid crystal main body mixture of above-mentioned preferred embodiment and the combination of the compound of above-mentioned polymerization, low threshold voltage, low rotary viscosity and extraordinary low-temperature stability in liquid crystal media according to the present invention, are realized, keep high clearing point and high HR value simultaneously, and allow in PSA indicating meter to regulate rapidly and obtain low especially pre-tilt angle.Especially, this liquid crystal media demonstrates the time of response of remarkable shortening in PSA indicating meter with respect to the medium of prior art, particularly also has the gray-tone response time.
This liquid crystal compound preferably has at least 80K, the nematic phase range of 100K at least particularly preferably, and at 20 DEG C, is not more than 250mPas, is preferably not more than the rotary viscosity of 200mPas.
In VA types of display according to the present invention, the molecule in the layer of liquid crystal media is orientated perpendicular to electrode surface (vertical plane ground) orientation or inclination vertical plane ground (English " tilted ") under off-position.In the time applying voltage to electrode, there is the reorientation of liquid crystal molecule, its molecule longitudinal axis is parallel to electrode surface.
According to the liquid crystal media of the first preferred embodiment of the present invention, especially for those in the indicating meter of PSA-VA type, under 20 DEG C and 1kHz, there is negative dielectric anisotropy, preferably approximately-0.5 to-10, especially approximately-2.5 to-7.5.
According to the liquid crystal media of the first preferred embodiment of the present invention, be preferably less than 0.16 especially for the degree of birefringence Δ n in those in the indicating meter of PSA-VA type, particularly preferably 0.06-0.14, is in particular 0.07-0.12.
In OCB-types of display according to the present invention, the molecule in liquid crystal media layer has " bending " orientation.While applying voltage, the reorientation of liquid crystal molecule occurs, its molecule longitudinal axis is perpendicular to electrode surface.
Be preferably and have according to those of the positive dielectric anisotropy Δ ε of the second preferred embodiment for the liquid crystal media according to the present invention of PSA-OCB types of display, and preferably under 20 DEG C and 1kHz, there is approximately+4 to+17 dielectric anisotropy Δ ε.
According to the liquid crystal media for OCB types of display of the second preferred embodiment of the present invention, degree of birefringence Δ n is preferably 0.14-0.22, is in particular 0.16-0.22.
According to the liquid crystal media of the second preferred embodiment of the present invention, under 20 DEG C and 1kHz, there is the positive dielectric anisotropy Δ ε of preferably+2 to+30, particularly preferably+2 to+17, very particularly preferably+3 to+15 especially for those of PSA-TN, PSA-positivity-VA, PSA-IPS and PSA-FFS types of display.
According to the liquid crystal media of the second preferred embodiment of the present invention, in those liquid crystal medias especially for PSA-TN, PSA-IPS and PSA-FFS types of display, degree of birefringence Δ n is preferably 0.07-0.15, is in particular 0.08-0.13.
Can also comprise further and description additive and auxiliary agent in the literature known to those skilled in the art, for example polymerization starter, inhibitor, stablizer, surfactant or chiral dopant according to liquid crystal media of the present invention.These can be polymerisable or not polymerisable.Therefore polymerisable additive is sorted out into polymerizable components or component A).Therefore not polymerisable additive is sorted out into not polymerizable components or B component).
Liquid crystal media can for example comprise one or more chiral dopants, is preferably selected from those of compound of following table B.
In addition the pleochroism dyestuff of for example 0-15 % by weight can be added to liquid crystal media, and also have nano particle, for improve electroconductibility the preferred 4-hexyloxybenzoate of conducting salt ethyl dimethyl dodecyl ammonium, tetraphenyl boric acid TBuA or crown ether complexing salt (referring to such as Haller etc., Mol.Cryst.Liq.Cryst.
24, 249-258 (1973)), or for changing the material of dielectric anisotropy, viscosity and/or nematic phase orientation.This class substance description is in DE-A2209127,2240864,2321632,2338281,2450088,2637430 and 2853728 for example.
According to the preferred implementation of liquid crystal media of the present invention a)-each component z) or known, or various equivalent modifications can easily derive their preparation method from prior art, because they are standard methods based on describing in document.Corresponding formula CY compound is for example described in EP-A-0364538.Corresponding formula ZK compound is described in for example DE-A-2636684 and DE-A-3321373.
Liquid crystal media that can be used according to the invention is prepared in conventional mode itself, for example, by by one or more above-claimed cpds and one or more polymerizable compound as defined above, and optionally mixes with other liquid crystalline cpd and/or additive.Conventionally, advantageously at elevated temperatures by components dissolved desired amt, that use with lesser amt forming in the component of main component.Also can blending ingredients in organic solvent, for example solution in acetone, chloroform or methyl alcohol, and for example remove again desolventizing by distillation after fully mixing.The invention still further relates to preparation according to the method for liquid crystal media of the present invention.
Without it should be noted that, also can comprise wherein according to liquid crystal media of the present invention the compound that for example H, N, O, Cl, F have been replaced by corresponding isotropic substance to those skilled in the art.
According to the structure of liquid-crystal display of the present invention corresponding to the geometrical shape conventional for PSA indicating meter, described in the prior art quoted in the time starting.Preferably without protruding geometrical shape, particularly wherein in addition the electrode in colour filter side be not structured and only the electrode in TFT side there are those of otch.The electrode structure of suitable especially and preferred PSA-VA indicating meter is for example described in US2006/0066793A1.
Following embodiment has set forth the present invention, but not it is limited.But, they to those skilled in the art shown have the compound of preferred use and its separately concentration with and the preferred mixture design of combination each other.In addition, these embodiment have set forth and can obtain which kind of performance and performance combination.
Use following abbreviation:
(n, m, z: under each situation, represent independently of one another 1,2,3,4,5 or 6)
table A
In a preferred embodiment of the invention, liquid crystal media according to the present invention comprises one or more and is selected from the compound of Table A compound.
table B
Table B has shown the possible chiral dopant that can be added to according in liquid crystal media of the present invention.
This liquid crystal media preferably comprises 0-10 % by weight, 0.01-5 % by weight especially, the particularly preferably doping agent of 0.1-3 % by weight.This liquid crystal media preferably comprises one or more and is selected from the doping agent of compound of table B.
table C
Table C has shown the possible stablizer that can be added to according in liquid crystal media of the present invention.
(represent integer 1-12 at this n, preferably 1,2,3,4,5,6,7 or 8, terminal methyl group does not show).
This liquid crystal media preferably comprises 0-10 % by weight, 1ppm-5 % by weight, the stablizer of 1ppm-1 % by weight particularly preferably especially.This liquid crystal media preferably comprises one or more and is selected from the stablizer of compound of table C.
table D
Table D has been enumerated and can be used for according to the preferred exemplary compounds as reactive mesogen compound in liquid crystal media of the present invention.
In preferred embodiment of the present invention, mesomorphic medium comprises one or more and is selected from the compound of showing D compound.
In addition, adopt following abbreviation and symbol:
V
0threshold voltage, capacitive character [V], at 20 DEG C,
N
eextraordinary refractive index under 20 DEG C and 589nm,
N
othe ordinary index of refraction under 20 DEG C and 589nm,
The optical anisotropy of Δ n under 20 DEG C and 589nm,
ε
⊥under 20 DEG C and 1kHz perpendicular to pointing to the dielectric susceptibility of vowing,
ε
||under 20 DEG C and 1kHz, be parallel to and point to the dielectric susceptibility of vowing,
Dielectric anisotropy under 20 DEG C of Δ ε and 1kHz,
Kp., T (N, I) clearing point [DEG C],
γ
1rotary viscosity [mPa s] at 20 DEG C,
K
1elastic constant, " tiltedly exhibition " distortion [pN] at 20 DEG C,
K
2elastic constant, " distortion " distortion [pN] at 20 DEG C,
K
3elastic constant, " bending " distortion [pN] at 20 DEG C.
Unless explicitly pointed out on the contrary, all concentration in the application provide with weight percent, and relate to corresponding whole mixture, comprise all solids or liquid crystal components and there is no the liquid crystal media of solvent.
Unless expressly stated otherwise,, the all temperature values that indicate in this application, as fusing point T (C, N), from smectic (S) mutually to row (N) phase transformation T (S, N) and clearing point T (N, I), all with degree Celsius (DEG C) represent.Fp. represent fusing point, Kp.=clearing point.In addition K=crystal form, N=nematic phase, S=smectic phase and I=isotropic phase.Data representation transition temperature between these symbols.
All physicalies are according to " Merck Liquid Crystals; Physical Properties of Liquid Crystals ", Status Nov.1997, that Merck KGaA (Germany) measures and 20 DEG C of Applicable temperatures, and Δ n determines under 1kHz with Δ ε under 589nm, unless explicitly pointed out on the contrary under every kind of situation.
For the present invention, term " threshold voltage " refers to capacitive character threshold value (V0), is also known as Freedericks threshold value, unless explicitly pointed out on the contrary.In embodiment, as conventionally, the optical threshold (V for 10% relative contrast also can be described
10).
Formed by two that are spaced apart 20 μ m parallel plane glass support plates for the indicating meter of measuring capacitive character threshold voltage, described supporting plate have in side therein separately electrode layer and be located thereon, without the polyimide alignment layers of friction, it causes the edge orientation of the vertical plane of liquid crystal molecule.
Formed by two that are spaced apart 4 μ m parallel plane glass support plates for indicating meter or the testing cassete of measuring pitch angle, the polyimide alignment layers that described supporting plate has electrode layer and is located thereon in side therein separately, wherein two polyimide layers antiparallel friction and cause the edge orientation of the vertical plane of liquid crystal molecule each other.
Make polymerizable compound polymerization in indicating meter or testing cassete by the UVA light with some strength (conventionally 365nm) the irradiation scheduled time, apply voltage (being generally 10V-30V alternating-current, 1kHz) to indicating meter simultaneously.In embodiment, unless explanation on the contrary adopts 50mW/cm
2mercury vapor lamp, adopt and be equipped with standard UV gauge (the Fabrikat Ushio UNI gauge) measured intensity of 365nm bandpass filter.
Test (Autronic-Melchers TBA-105) by Crystal Rotation and determine pitch angle.At this, little value large the departing from of 90 ° of angles (with respect to) is corresponding to large inclination.
VHR value is measured as follows: 0.3% polymerisable monomer compound is added to liquid crystal main body mixture, and the mixture that obtains is thus introduced in TN-VHR testing cassete to (90 ° of frictions, TN polyimide alignment layers, layer thickness d ≈ 6 μ m).At 100 DEG C after 5min at 1V, 60Hz, under 64 μ s pulses in UV expose 2h (sun test) measure before and afterwards HR value (surveying instrument: Autronic-Melchers VHRM-105).
In order to study low-temperature stability, also referred to as " LTS ", liquid crystal compound is for each component stability of spontaneous crystallization at low temperatures, and the bottle that contains 1g FK/RM mixture is placed at-10 DEG C and is stored, and the whether crystallization of periodical survey mixture.
embodiment 1
2-methacrylic acid-7-(2-methacryloxy)-4,5,9,10-tetrahydrochysene pyrene-2-base ester
1.1
2,7-, bis-iodo-4,5,9,10-tetrahydrochysene pyrene
By 4 of 7.70g (36.2mmol), 5,9,10-tetrahydrochysene pyrene, 3.30g (14.5mmol) periodic acid and 9.00g (35.5mmol) iodine in the solution of 70ml Glacial acetic acid, heat 1h at the 2.2ml vitriol oil and 15ml water at 70 DEG C.Subsequently solution added to frozen water and be extracted with ethyl acetate three times.Sodium sulfite solution and saturated sodium bicarbonate solution washing by the organic phase merging with dilution, and dry on sodium sulfate.Solvent is removed in a vacuum and resistates is used toluene/heptane (2:1) stratographic analysis on silica gel.Obtained as 2 of colorless solid 7-bis-iodo-4,5,9,10-tetrahydrochysene pyrene by heptane/toluene (1:1) crystallization crude product.
1H-NMR(CDCl
3)
δ=2.80ppm(s,8H,CH
2),7.43(s,4H,Ar-H)。
1.2
4,5,9,10-tetrahydrochysene pyrene-2,7-glycol
At first by 2 of 3.20g (6.80mmol), 7-bis-iodo-4,5,9,10-tetrahydrochysene pyrene is introduced in 40ml diox, add solution, 300mg (0.522mmol) two (dibenzalacetone) palladiums and the 450mg of 1.50g (26.7mmol) Potassium peroxide in 20ml water (2-di-t-butyl phosphino--2 ', 4 ', 6 '-tri isopropyl biphenyl), and batch of material is heated to 3h at 80 DEG C.Subsequently by 100ml dilution with toluene and water extraction for solution.Use the hydrochloric acid of dilution by the aqueous phase as acidified merging, and be extracted with ethyl acetate three times.The organic phase of merging is washed with water and be dried on sodium sulfate.Solvent is removed in a vacuum, and resistates is used toluene/ethyl acetate (7:3) stratographic analysis on silica gel, and by toluene/heptane (1:1) recrystallization crude product.Obtain as 4,5,9 of clear crystal 10-tetrahydrochysene pyrene-2,7-glycol.
1H-NMR(CDCl
3)
δ=2.80ppm(s,8H,CH
2),4.73(s,2H,OH),6.54(s,4H,Ar-H)。
1.3 2-methacrylic acid-7-(2-methacryloxy)-4,5,9,10-tetrahydrochysene pyrene
-2-base ester
By 4,5,9 of 900mg (3.55mmol), 10-tetrahydrochysene pyrene-2,7-glycol is suspended in 15ml methylene dichloride, adds 1.3ml pyridine and 50mg DMAP, and is accompanied by subsequently the solution of ice-cooled dropping 1.5g (9mmol) acrylic anhydride in 25ml methylene dichloride.After 30min, remove coolingly, and batch of material is stayed at room temperature to stir and spend the night.Subsequently by solution by filtered through silica gel, concentrate eluant and by heptane/toluene recrystallization crude product.Obtain the 2-methacrylic acid-7-as clear crystal (2-methacryloxy)-4,5,9 of 146 DEG C of fusing points, 10-tetrahydrochysene pyrene-2-base ester.
embodiment 2
2-methacrylic acid-7-[4-(2-methacryloxy)-uncle-1-alkynyl]-4,5,9,10
-tetrahydrochysene pyrene-2-base ester
2.1 2,7-bis-is bromo-4,5,9,10-tetrahydrochysene pyrene
At first by 20.6g (94.6mmol) 4,5,9,10-tetrahydrochysene pyrene is introduced in 160ml trimethyl phosphite 99, and is accompanied by and slight coolingly adds the solution of 17ml (332mmol) bromine in 40ml trimethyl phosphite 99 temperature is no more than under the mode of 25 DEG C.Batch of material is stirred to 3h in addition and add in 800ml frozen water, by adding sodium sulfite solution that excessive bromine is decomposed.After 15min, suction strainer goes out the product of precipitation, it is dissolved in toluene under heating state, by filtered through silica gel and by toluene/heptane (1:1) recrystallization.Obtain as 2 of clear crystal, 7-bis-is bromo-4,5,9,10-tetrahydrochysene pyrene.
2.2 7-are bromo-4,5,9,10-tetrahydrochysene pyrene-2-alcohol
At first by 2 of 6.40g (16.9mmol), 7-bis-bromo-4,5,9,10-tetrahydrochysene pyrene and 7ml (30mmol) triisopropyl borate ester is introduced in 200ml THF and at-70 DEG C, is added 15% solution of 15ml (24mmol) n-Butyl Lithium in hexane.When adding while finishing, then stir 1h, use 2M hydrochloric acid hydrolysis, material is melted and by MTB ether extracting twice.The concentrated organic phase merging, is accompanied by vigorous stirring resistates is suspended in the mixture being made up of 100ml toluene, 20ml2M sodium hydroxide solution and 20ml water, and at 40 DEG C, slowly add the hydrogen peroxide of 10ml30%.In the time adding end, then batch of material is stirred to 1h, add in 100ml water and use 2M hcl acidifying.By aqueous phase separation and be extracted with ethyl acetate three times.By ammonium sulfate iron (II) solution and saturated nacl aqueous solution washing for the organic phase merging, and dry on sodium sulfate.Solvent is removed in a vacuum, and resistates is used methylene dichloride stratographic analysis on silica gel, and by toluene recrystallization crude product.Obtain as the 7-of clear crystal bromo-4,5,9,10-tetrahydrochysene pyrene-2-alcohol.
2.3 7-(4-hydroxyl fourth-1-alkynyl)-4,5,9,10-tetrahydrochysene pyrene-2-alcohol
At first by the 7-of 8.80g (28.3mmol) bromo-4,5,9,10-tetrahydrochysene pyrene-2-alcohol is introduced 100ml THF, add 1.7g (2.42mmol) two (triphenylphosphine) Palladous chloride (II), 0.4g (2.10mmol) cupric iodide (I) and 11ml diisopropylamine, and at 65 DEG C, in 1h, drip subsequently the solution of 5.0g (78.3mmol) ethyl acetylene in 20ml THF.In the time of reinforced end, then batch of material is stirred to 2h, be added to the water and use 2N hcl acidifying.Aqueous phase separation and being extracted with ethyl acetate three times.The organic phase of merging is washed with water, dry and in solvent removed in vacuo on sodium sulfate.Crude product filters by silica gel dichloromethane/ethyl acetate (4:1), and by toluene recrystallization.Obtain 7-iodo-9 as colorless solid, 10-dihydro phenanthrene-2-alcohol.
2.4 2-methacrylic acid-7-[4-(2-methacryloxy)-Ding-1-alkynes
base]-4,5,9,10-tetrahydrochysene pyrene-2-base ester
Be similar to embodiment 1, by 7-(4-hydroxyl fourth-1-alkynyl)-4,5,9,10-tetrahydrochysene pyrene-2-alcohol obtains the 2-methacrylic acid-7-[4-as clear crystal (2-methacryloxy)-Ding-1-alkynyl of 121 DEG C of fusing points]-4,5,9,10-tetrahydrochysene pyrene-2-base ester.
embodiment 3
2-methacrylic acid-4-[7-(2-methacryloxy)-4,5,9,10-tetrahydrochysene pyrene-2-
base] butyl ester
3.1 7-(4-hydroxybutyl)-4,5,9,10-tetrahydrochysene pyrene-2-alcohol
In THF, on palladium/activated-carbon catalyst, carry out 7-(4-hydroxyl fourth-1-alkynyl)-4,5,9, the hydrogenation of 10-tetrahydrochysene pyrene-2-alcohol is until stop.Leach catalyzer, in a vacuum except desolventizing and by toluene recrystallization resistates.Obtain the 7-(4-hydroxybutyl)-4,5,9 as colorless solid, 10-tetrahydrochysene pyrene-2-alcohol.
3.2 2-methacrylic acid-4-[7-(2-methacryloxy)-4,5,9,10-tetrahydrochysene
pyrene-2-yl] butyl ester
Be similar to embodiment 1, by 7-(4-hydroxybutyl)-4,5,9,10-tetrahydrochysene pyrene-2-alcohol obtains the 2-methacrylic acid-4-[7-as clear crystal (2-methacryloxy)-4,5 of 110 DEG C of fusing points, 9,10-tetrahydrochysene pyrene-2-yl] butyl ester.
embodiment 4
2-methacrylic acid-4,4-dimethyl-6-(2-methacryloxy)-8,9-dihydro
-4H-ring penta [def] phenanthrene-2-base ester
4.1 2,6-bis-is bromo-4,4-dimethyl-8, and 9-dihydro-4H-encircles penta [def] phenanthrene
At first by 4 of 3.50g (19.9mmol), 4-dimethyl-8,9-dihydro-4H-ring penta [def] luxuriant and rich with fragrance (CAS 1035304-31-4) is introduced trimethyl phosphite 99 and at 25 DEG C, is accompanied by the solution of slight cooling dropping 3.5ml (68mmol) bromine in 10ml trimethyl phosphite 99.Batch of material is at room temperature stirred to 4h, add in 150ml frozen water and 100ml toluene and use sodium sulfite solution to destroy excessive bromine.Water phase separated and extracting once with toluene.The organic phase of merging is washed with water to dry and solvent removed in vacuo on sodium sulfate.Crude product is filtered by silica gel toluene/heptane (1:1), and by toluene/heptane (1:1) recrystallization.Obtain as 2 of clear crystal, 6-bis-is bromo-4,4-dimethyl-8, and 9-dihydro-4H-encircles penta [def] phenanthrene.
1H-NMR(500MHz,CDCl
3)
δ=1.48ppm(s,6H,CH
3),3.08(s,4H,CH
2),7.24(s,2H,Ar-H),7.33(s,2H,Ar-H)。
4.2 4,4-dimethyl-8,9-dihydro-4H-ring penta [def] phenanthrene-2,6-glycol
Be similar to synthetic described in embodiment 1.2, bromo-4 by 2,6-bis-, 4-dimethyl-8,9-dihydro-4H-ring penta [def] phenanthrene obtains as 4 of clear crystal, 4-dimethyl-8,9-dihydro-4H-ring penta [def] is luxuriant and rich with fragrance-2,6-glycol.
1H-NMR(400MHz,CDCl
3)
δ=1.46ppm(s,6H,CH
3),3.04(s,4H,CH
2),4.59(s,br.2H,OH),6.55(d,J=1.7Hz,2H,Ar-H),6.67(d,J=1.7Hz,2H,Ar-H)。
4.3 2-methacrylic acid-4,4-dimethyl-6-(2-methacryloxy)-8,9-bis-
hydrogen-4H-ring penta [def] phenanthrene-2-base ester
Be similar to embodiment 1, by 4,4-dimethyl-8,9-dihydro-4H-ring penta [def] luxuriant and rich with fragrance-2,6-glycol obtains 2-methacrylic acid-4 as clear crystal of 77 DEG C of fusing points, 4-dimethyl-6-(2-methacryloxy)-8,9-dihydro-4H-ring penta [def] phenanthrene-2-base ester.
embodiment 5
2-methacrylic acid-4,4-dimethyl-6-(2-methacryloxy)-4H-encircles penta [def]
phenanthrene-2-base ester
5.1 2,6-bis-is bromo-4, and 4-dimethyl-4H-encircles penta [def] phenanthrene
At first by 2 of 2.20g (5.82mmol), 6-bis-bromo-4,4-dimethyl-8,9-dihydro-4H-ring penta [def] phenanthrene, 1.10g (6.18mmol) N-bromosuccinimide and 50mg azo two (isopropyl cyanide) are introduced in 30ml tetracol phenixin and are slowly heated to boiling.After 3h, batch of material is cooled to 60 DEG C, adds the solution of 1.5g sodium acetate in 20ml Glacial acetic acid and at 70 DEG C, stir 4h subsequently.Subsequently solution is added in methylene dichloride, wash twice with water, dry and vacuum concentration on sodium sulfate.Resistates by silica gel with toluene filter and by heptane recrystallization.Obtain as 2 of clear crystal, 6-bis-is bromo-4, and 4-dimethyl-4H-encircles penta [def] phenanthrene.
1H-NMR(400MHz,CDCl
3)
δ=1.66ppm(s,6H,CH
3),7.67(d,J=1.2Hz,2H,Ar-H),7.77(s,2H,Ar-H),7.97(d,J=1.2Hz,2H,Ar-H)。
5.2 4,4-dimethyl-4H-ring penta [def] phenanthrene-2,6-glycol
Be similar to synthetic described in embodiment 1.2, bromo-4 by 2,6-bis-, 4-dimethyl-8,9-dihydro-4H-ring penta [def] phenanthrene obtains as 4 of clear crystal, and 4-dimethyl-4H-ring penta [def] is luxuriant and rich with fragrance-2,6-glycol.
5.3 2-methacrylic acid-4,4-dimethyl-6-(2-methacryloxy)-4H-ring
penta [def] phenanthrene-2-base ester
Be similar to embodiment 1, by 4,4-dimethyl-4H-ring penta [def] phenanthrene-2,6-glycol obtains 2-methacrylic acid-4 as clear crystal of 170 DEG C of fusing points, 4-dimethyl-6-(2-methacryloxy)-4H-ring penta [def] phenanthrene-2-base ester.
application examples 1
Following preparation nematic liquid crystal mixture N1:
Deriving from the polymerisable monomer compound of example as mentioned below by 0.3% adds in liquid crystal compound N1, and the mixture forming is thus introduced in VA-e/o testing cassete (through antiparallel friction, VA-polyimide alignment layers, layer thickness d ≈ 4 μ m).Under the voltage condition that applies 24V (alternating-current) by this box 50mW/cm
2the UV rayed specific time of intensity, makes monomeric compound polymerization thus.UV irradiate before and afterwards, by rotation crystallization trial (Autronic-Melchers TBA-105) measure pitch angle.
In order to measure rate of polymerization, after the different time shutter, measure the residual content (in % by weight) of unpolymerized RM in testing cassete by HPLC method.For this reason, by each mixture shown in polymerization in testing cassete under condition.Then adopt methylethylketone mixture is washed out from testing cassete and measure.
For comparison purposes, adopt and carry out experiment as above from the known polymerizable compound V1-V3 of prior art.
Pitch angle result is summarized in table 1.RM concentration after the different time shutter is summarized in table 2.
table 1 (t=time shutter)
table 2 (t=time shutter)
As can be seen from Table 1, and use from compared with the monomer V1-V3 of prior art, use from embodiment 1-5 according to monomer of the present invention, can after polymerization, realize quickly little pitch angle.In addition as can be seen from Table 2, compared with using monomer V1-V3, use and also realized rate of polymerization significantly faster according to the monomer from embodiment 1-3 of the present invention.
Claims (14)
1. the compound of formula IA,
Wherein each group has following implication:
W
1, W
2expression-CY=CY-independently of one another separately,
When occurring at every turn, Y represents H or F identical or differently,
R
a, R
brepresent independently of one another separately P-Sp-, H, F, Cl, Br, I ,-CN ,-NO
2,-NCO ,-NCS ,-OCN ,-SCN, SF
5, there is the straight or branched alkyl of 1-25 C atom, wherein one or more non-conterminous CH
2group also can be separately independently of one another by arylidene ,-C (R
0)=C (R
00)-,-C ≡ C-,-N (R
0)-,-O-,-S-,-CO-,-CO-O-,-O-CO-,-O-CO-O-with make O and/or S atom not each other directly the mode of keyed jointing replace, and wherein one or more H atoms also can be replaced by F, Cl, Br, I, CN or P-Sp-, or preferably there is aryl or the heteroaryl of 2-25 C atom, it also can comprise two or more fused rings and optionally mono-or polysubstituted by L, wherein radicals R
aand R
bat least one expression or comprise group P-Sp-,
When occurring at every turn, P represents polymerizable groups identical or differently,
When occurring at every turn, Sp represents spacer groups or singly-bound identical or differently,
A
1and A
2represent independently of one another separately Isosorbide-5-Nitrae-phenylene, naphthalene-Isosorbide-5-Nitrae-bis-base or naphthalene-2,6-bis-bases, wherein in these groups, one or more CH groups also can be replaced by N, hexanaphthene-Isosorbide-5-Nitrae-bis-base, wherein one or more non-conterminous CH
2group also can be replaced by O and/or S, 1, 4-phenylidene, dicyclo [1.1.1] pentane-1, 3-bis-bases, dicyclo [2.2.2] octane-1, 4-bis-bases, spiroheptane-2, 6-bis-bases, piperidines-1, 4-bis-bases, perhydronaphthalene-2, 6-bis-bases, 1, 2, 3, 4-tetraline-2, 6-bis-bases, indane-2, 5-bis-bases, octahydro-4, 7-endo-methylene group indane-2, 5-bis-bases, luxuriant and rich with fragrance-2, 7-bis-bases, anthracene-2, 7-bis-bases, luxuriant and rich with fragrance-2, 7-bis-bases, 9, 10-dihydro phenanthrene-2, 7-bis-bases, 6H-benzo [c]-chromene-3, 8-bis-bases, 9H-fluorenes-2, 7-bis-bases, 9, 9-dimethyl-9H-fluorenes-2, 7-bis-bases, diphenylene-oxide-3, 7-bis-bases, 2-oxygen base-2H-chromene-7-base, 4-phenyl-2-oxygen base-2H-chromene-7-base, 4-oxygen base-4H-chromene-6-base, 4-phenyl-4-oxygen base-4H-chromene-6-base, all these groups can be unsubstituted or mono-or polysubstituted by L, and wherein in all these groups, hexanaphthene and aromatic group are particularly preferred, with
L represents P-Sp-, OH, CH
2oH, F, Cl, Br, I ,-CN ,-NO
2,-NCO ,-NCS ,-OCN ,-SCN ,-C (=O) N (R
x)
2,-C (=O) Y
1,-C (=O) R
x,-N (R
x)
2the optional silyl replacing, there is the aryl of the optional replacement of 6-20 C atom, there is 1-25 alkyl or alkoxyl group individual, the preferably straight or branched of 1-12 C atom, or there is 2-25 thiazolinyl, alkynyl, alkyl-carbonyl, alkoxy carbonyl, alkyl-carbonyl oxygen base or alkoxy-carbonyl oxy individual, the preferably straight or branched of 2-12 C atom, wherein in all these groups, one or more H atoms also can be replaced by F, Cl, P or P-Sp-
R
xrepresent P-Sp-, H, halogen, has 1-25, preferably straight chain, side chain or the cyclic alkyl of 1-12 C atom, wherein one or more non-conterminous CH
2group also can by-O-,-S-,-CO-,-CO-O-,-O-CO-,-O-CO-O-with make O and/or S atom not each other directly the mode of keyed jointing replace, and wherein one or more H atoms also can replace by F, Cl or P-Sp-,
Y
1represent halogen,
Z
1, Z
2expression-O-,-S-,-CO-,-CO-O-,-OCO-,-O-CO-O-,-OCH independently of one another separately
2-,-CH
2o-,-SCH
2-,-CH
2s-,-CF
2o-,-OCF
2-,-CF
2s-,-SCF
2-,-(CH
2)
n-,-CF
2cH
2-,-CH
2cF
2-,-(CF
2)
n-,-CH=CH-,-CF=CF-,-CH=CF-,-CF=CH-,-C ≡ C-,-CH=CH-COO-,-OCO-CH=CH-,-CH
2-CH
2-COO-,-OCO-CH
2-CH
2-,-C (R
0r
00)-,-C (R
yr
z)-or singly-bound,
R
0, R
00while appearance independently of one another and at every turn separately, represent H identical or differently or there is the alkyl of 1-12 C atom,
R
y, R
zrepresent independently of one another separately H, F, CH
3or CF
3,
When occurring at every turn, n represents 1,2,3 or 4 identical or differently,
P, q represents 0,1 or 2 separately independently of one another,
When occurring at every turn, r represents 0,1 or 2 identical or differently.
2. the compound of formula IA as claimed in claim 1, if W wherein
1and W
2represent CH=CH,
Z
1do not represent-C ≡ C-and/or A
1do not represent Isosorbide-5-Nitrae-phenylene, and
Z
2do not represent-C ≡ C-and/or A
2do not represent Isosorbide-5-Nitrae-phenylene, and
Get rid of 1-vinylpyrene.
3. the purposes in liquid crystal media and the liquid-crystal display of PS or PSA type according to the compound of the formula IA of claim 1 or 2.
4. the purposes in the liquid-crystal display of PS or PSA type according to claim 3, the liquid crystal cell that wherein said indicating meter comprises the layer with two substrates and two electrodes and the liquid crystal media that comprises polymeric component and lower-molecular-weight component between substrate, wherein at least one substrate be printing opacity and at least one substrate there is one or two electrode, wherein said polymeric component can be by preferably in the situation that imposing on electrode by voltage, between the substrate of liquid crystal cell, in liquid crystal media, make one or more polymerizable compound polymerizations and obtain, wherein at least one of polymerizable compound is the one or more polymerizable compound according to claim 1-2.
5. according to the one or more purposes of claim 3-4, be characterised in that the compound that liquid crystal media comprises one or more formulas CY and/or PY:
Wherein each group has following implication:
A represents 1 or 2,
B represents 0 or 1,
represent
R
1and R
2represent to have independently of one another separately the alkyl of 1-12 C atom, wherein one or two non-conterminous CH
2group also can by-O-,-CH=CH-,-CO-,-O-CO-or-CO-O-with make O atom not each other directly the mode of keyed jointing replace,
Z
xexpression-CH=CH-,-CH
2o-,-OCH
2-,-CF
2o-,-OCF
2-,-O-,-CH
2-,-CH
2cH
2-or singly-bound, preferably singly-bound,
L
1-4represent independently of one another separately F, Cl, OCF
3, CF
3, CH
3, CH
2f, CHF
2.
6. according to the one or more purposes of claim 3-5, be characterised in that the compound that described liquid crystal media comprises one or more following formulas:
Wherein each group has following implication:
represent
represent
R
3and R
4represent to have independently of one another separately the alkyl of 1-12 C atom, wherein one or two non-conterminous CH
2group also can by-O-,-CH=CH-,-CO-,-O-CO-or-CO-O-to be so that O atom mode not directly connected to each other is replaced,
Z
yexpression-CH
2cH
2-,-CH=CH-,-CF
2o-,-OCF
2-,-CH
2o-,-OCH
2-,-COO-,-OCO-,-C
2f
4-,-CF=CF-or singly-bound.
7. according to the one or more liquid-crystal display of claim 3-6.
8. according to the liquid-crystal display of claim 7, it is characterized in that it is PSA-VA, PSA-OCB, PSA-IPS, PSA-FFS, PSA-positivity-VA or PSA-TN indicating meter.
9. comprise one or more according to the liquid crystal media of the polymerizable compound of claim 1 or 2.
10. according to the liquid crystal media of claim 9, comprise:
-polymerisable component A), it comprises one or more polymerizable compounds, and
-liquid crystal components B), it comprises one or more low-molecular weight compounds,
Be characterised in that component A) comprise one or more according to the polymerizable compound of claim 1 or 2.
11. according to the liquid crystal media of claim 10, wherein B component) comprise one or more be selected from as in claim 5 or 6 definition formula CY, PY and the compound of ZK.
The compound of 12. formula IIA
Wherein W
1, W
2, Sp, A
1, A
2, Z
1, Z
2, L, p, q and r have the implication shown in claim 1-2 one or more, and G and G ' represent H atom or blocking group separately independently of one another.
13. preparations, according to the method for the compound of any one of claim 1-2, wherein will come esterification or etherificate with the corresponding acid, acid derivative or the halogenated compound that comprise group P according to the compound of claim 12 under dewatering agent exists.
14. manufacture the method for the liquid-crystal display of PS or PSA type, wherein will introduce and have in the liquid crystal cell of two substrates and two electrodes according to the one or more liquid crystal media of claim 9-11, wherein at least one substrate be printing opacity and at least one substrate there is one or two electrode, and preferably in the situation that voltage is imposed on to electrode, make polymerizable compound polymerization.
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| DE102010025101.1 | 2010-06-25 |
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| CN201180030386.5A Division CN102959048B (en) | 2010-06-25 | 2011-06-01 | Polymerizable compounds and use thereof in liquid crystal displays |
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| JP (2) | JP5694525B2 (en) |
| KR (2) | KR101803118B1 (en) |
| CN (2) | CN103922932A (en) |
| DE (1) | DE102011103182A1 (en) |
| TW (1) | TWI532714B (en) |
| WO (1) | WO2011160764A1 (en) |
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| CN112279768A (en) * | 2014-07-30 | 2021-01-29 | 默克专利股份有限公司 | Polymerizable compounds and their use in liquid crystal displays |
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| CN112585243A (en) * | 2018-08-22 | 2021-03-30 | 默克专利股份有限公司 | Liquid crystal mixture and liquid crystal display |
| EP3894513A2 (en) * | 2018-12-12 | 2021-10-20 | Merck Patent GmbH | Liquid crystal mixture and liquid crystal display |
| CN109825308B (en) * | 2019-03-19 | 2021-02-02 | 石家庄晶奥量新材料有限公司 | Negative liquid crystal compound, negative liquid crystal composition and application |
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Also Published As
| Publication number | Publication date |
|---|---|
| KR20170117225A (en) | 2017-10-20 |
| TW201204701A (en) | 2012-02-01 |
| CN102959048A (en) | 2013-03-06 |
| JP5694525B2 (en) | 2015-04-01 |
| WO2011160764A1 (en) | 2011-12-29 |
| JP6125470B2 (en) | 2017-05-10 |
| CN102959048B (en) | 2015-05-20 |
| KR101902726B1 (en) | 2018-09-28 |
| KR101803118B1 (en) | 2017-11-29 |
| DE102011103182A1 (en) | 2011-12-29 |
| JP2013535033A (en) | 2013-09-09 |
| KR20130132736A (en) | 2013-12-05 |
| TWI532714B (en) | 2016-05-11 |
| JP2015025130A (en) | 2015-02-05 |
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