CN107209421A - Liquid crystal display cells and its manufacture method - Google Patents
Liquid crystal display cells and its manufacture method Download PDFInfo
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- CN107209421A CN107209421A CN201580067589.XA CN201580067589A CN107209421A CN 107209421 A CN107209421 A CN 107209421A CN 201580067589 A CN201580067589 A CN 201580067589A CN 107209421 A CN107209421 A CN 107209421A
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Classifications
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K19/00—Liquid crystal materials
- C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
- C09K19/06—Non-steroidal liquid crystal compounds
- C09K19/08—Non-steroidal liquid crystal compounds containing at least two non-condensed rings
- C09K19/10—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing at least two benzene rings
- C09K19/12—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing at least two benzene rings at least two benzene rings directly linked, e.g. biphenyls
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K19/00—Liquid crystal materials
- C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
- C09K19/06—Non-steroidal liquid crystal compounds
- C09K19/08—Non-steroidal liquid crystal compounds containing at least two non-condensed rings
- C09K19/10—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing at least two benzene rings
- C09K19/14—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing at least two benzene rings linked by a carbon chain
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K19/00—Liquid crystal materials
- C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
- C09K19/06—Non-steroidal liquid crystal compounds
- C09K19/08—Non-steroidal liquid crystal compounds containing at least two non-condensed rings
- C09K19/30—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing saturated or unsaturated non-aromatic rings, e.g. cyclohexane rings
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K19/00—Liquid crystal materials
- C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
- C09K19/06—Non-steroidal liquid crystal compounds
- C09K19/32—Non-steroidal liquid crystal compounds containing condensed ring systems, i.e. fused, bridged or spiro ring systems
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K19/00—Liquid crystal materials
- C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
- C09K19/06—Non-steroidal liquid crystal compounds
- C09K19/34—Non-steroidal liquid crystal compounds containing at least one heterocyclic ring
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K19/00—Liquid crystal materials
- C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
- C09K19/38—Polymers
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K19/00—Liquid crystal materials
- C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
- C09K19/42—Mixtures of liquid crystal compounds covered by two or more of the preceding groups C09K19/06 - C09K19/40
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K19/00—Liquid crystal materials
- C09K19/52—Liquid crystal materials characterised by components which are not liquid crystals, e.g. additives with special physical aspect: solvents, solid particles
- C09K19/54—Additives having no specific mesophase characterised by their chemical composition
- C09K19/56—Aligning agents
-
- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells
-
- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells
- G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
- G02F1/1333—Constructional arrangements; Manufacturing methods
- G02F1/1337—Surface-induced orientation of the liquid crystal molecules, e.g. by alignment layers
Landscapes
- Chemical & Material Sciences (AREA)
- Crystallography & Structural Chemistry (AREA)
- Materials Engineering (AREA)
- Engineering & Computer Science (AREA)
- Physics & Mathematics (AREA)
- Organic Chemistry (AREA)
- Nonlinear Science (AREA)
- General Physics & Mathematics (AREA)
- Optics & Photonics (AREA)
- Mathematical Physics (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Liquid Crystal (AREA)
- Liquid Crystal Substances (AREA)
Abstract
The present invention provides a kind of liquid crystal display cells and its manufacture method, and it will not make dielectric anisotropy, viscosity, nematic phase ceiling temperature, rotary viscosity (γ1) etc. be deteriorated as the various characteristics of liquid crystal display cells and the ghost characteristic of liquid crystal display cells, and be not likely to produce the vestige that drips during fabrication.In addition, in accordance with the invention it is possible to manufacture excellent as the high-speed response of liquid crystal display cells, orientation, the pre-tilt angle of liquid crystal molecule are stable, and the ghost of generation is reduced, the few liquid crystal display cells of the generation of the vestige that drips when it is manufactured.Liquid crystal display cells produced by the present invention can act effectively as the display element of LCD TV, monitor etc..
Description
Technical field
Useful liquid crystal display cells and its manufacture method the present invention relates to the component parts as LCD TV etc..
Background technology
Liquid crystal display cells be used for using clock and watch, desk-top electronic calculator as the various sensing equipments of representative, automobile-used panel,
Word processor, electronic notebook, printer, computer, television set, clock and watch, advertising display panel etc..For liquid crystal display side
Formula, as its representational mode, can be enumerated：TN (twisted-nematic) type, STN (super twisted nematic) type, use TFT (films
Transistor) vertical orientating type (vertical orientated, VA), IPS (in-plane switching) type etc..Wish that these liquid crystal display cells are used
Liquid-crystal composition it is stable for external factor such as moisture, empty air and heat, light, in addition, as wide as possible centered on room temperature
Temperature range shows liquid crystalline phase, and viscosity is low, and driving voltage is low.Also, for each liquid crystal display cells, in order that dielectric is each
(Δ n) etc. turns into optimal value, and liquid-crystal composition is by several to tens kinds of chemical combination for anisotropy (Δ ε), refractive anisotrop
Thing is constituted.
In VA escopes, the use of Δ ε is negative liquid-crystal composition, is widely used in LCD TV etc..On the other hand,
In all type of drive, it is desirable to low voltage drive, high-speed response, wide operating temperature range.I.e., it is desirable to which Δ ε's is absolute
Value is big, viscosity (η) is small, nematic phase-isotropic liquid phase transition temperature (Tni) is high.In addition, it is necessary to according to Δ n and cell gap
(d) product is Δ n × d setting, and the Δ n of liquid-crystal composition and cell gap are matchingly adjusted into proper range.In addition,
In the case where liquid crystal display cells are applied into television set etc., due to paying attention to high-speed response, it is therefore desirable to rotary viscosity
(γ 1) small liquid-crystal composition.
On the other hand, in order to improve the viewing angle characteristic of VA escopes, widely use by being provided with projection on substrate
Structure, so that the differently- oriented directivity of the liquid crystal molecule in pixel to be divided into the liquid crystal of multiple MVA (multidomain vertical orientation) types
Display element.Although MVA type liquid crystal display cells viewing angle characteristics are good, the portion near away from the projection structure on substrate
Position, the response speed of liquid crystal molecule is different, due to the influence of the slow liquid crystal molecule of the response speed away from projection structure, exists
The problem of overall response speed is inadequate, there is projection structure caused by transmissivity the problem of decline.To solve the problem, make
For with common MVA types liquid crystal display cells be differently, not in the cells set non-permeable projection structure but
The method that homogeneous pre-tilt angle is assigned in the pixel of segmentation, is developing PSA liquid crystal display cells (polymer sustained
alignment：Polymer maintains orientation, includes PS liquid crystal display cells (polymer stabilised：Polymer stabilising).
PSA liquid crystal display cells are that a small amount of reactive monomer is added into liquid-crystal composition, and are imported into by the liquid-crystal composition
After liquid crystal cells, while applying voltage electrode, the irradiation of lateral dominance active energy beam makes the reactivity in liquid-crystal composition
What monomer polymerize and manufactured.Therefore, it is possible to assign appropriate pre-tilt angle in segmenting pixels, it is based on as a result, can reach
The contrast that transmissivity is improved is improved and based on the high-speed response for assigning homogeneous pre-tilt angle (for example, referring to patent document 1).So
And, reactive monomer is added in PSA liquid crystal display cells, it is necessary in liquid-crystal composition, high voltage retention is being required
Active matrix liquid crystal display device in, problem is more, can also bring the problem of generation display such as ghost is bad.
As the shortcoming of improvement PSA liquid crystal display cells, it will not be mixed into liquid-crystal composition different beyond liquid crystal material
Thing, the method that homogeneous pre-tilt angle is assigned to liquid crystal molecule, develops following manner：Reactive monomer is mixed into alignment films
In material, and after liquid-crystal composition is imported into liquid crystal cells, while applying voltage, lateral dominance active energy beam electrode
Irradiation, the reactive monomer in alignment films is polymerize (for example, referring to patent document 2,3 and 4).
On the other hand, with the large screen of liquid crystal display cells, the manufacture method of liquid crystal display cells also has larger
Change.That is, conventional vacuum type injection method is in the case where manufacturing larger panel, because manufacturing process needs long time,
Therefore, when manufacturing larger panel, the manufacture method of main flow is ODF (one drop fill, be singly instilled into) mode (for example, ginseng
According to patent document 5).Which can shorten injection length compared with vacuum type injection method, therefore, as liquid crystal display cells
Manufacture method main flow.But following new problem can be produced：The vestige that drips after liquid-crystal composition drip even in liquid crystal
After display element manufacture, the phenomenon of liquid crystal display cells can be also remained in the shape dripped.In addition, the vestige that drips is defined as
The phenomenon that the vestige of liquid-crystal composition that dripped in the case of black display floats whitely.Particularly, taken to above-mentioned
Reactive monomer is added into membrane material and liquid crystal molecule is assigned in the mode of pre-tilt angle, due to being dripped liquid crystal group to substrate
It during compound, can be present in as the reactive monomer of foreign matter in alignment films, therefore, easily produce the problem of dripping vestige.In addition,
In general, being due to the selection of liquid crystal material more the generation for the vestige that drips and producing, its reason is failed to understand.
As the suppressing method for the vestige that drips, following method is disclosed：It is mixed into the polymerism chemical combination in liquid-crystal composition
Thing polymerize, and polymeric layer is formed in liquid crystal combination nitride layer, so as to suppress to produce because of the relation with tropism control film
The vestige that drips (for example, referring to patent document 6).However, being only added to liquid with being similarly there are during this method with PSA modes etc.
Caused by reactive monomer in crystal composite the problem of the ghost of display, its effect is inadequate for vestige is dripped in suppression,
Wish that exploitation can be maintained as the fundamental characteristics of liquid crystal display cells and be not likely to produce the liquid crystal display member of ghost, the vestige that drips
Part.Also, therefore, will not be purple because of these because liquid crystal display cells are exposed in ultraviolet light when it is manufactured with the when of use
Outer light irradiation and produce deterioration etc., or even if produce also will not to display bring influence to be important.
Therefore, applicant proposes a kind of liquid crystal in No. 05299595 publication (patent document 12) of Japanese Patent No. etc.
Show element：That is, reactive monomer is contained in vertical alignment layer, after liquid-crystal composition is imported into liquid crystal cells, while to electricity
Interpolar applies voltage, and the irradiation of lateral dominance active energy beam polymerize the reactive monomer in alignment films, also, in the party
Specific liquid-crystal composition is combined in formula.A kind of liquid crystal display cells and its manufacture method can be provided, the liquid crystal display is utilized
Element, will not make dielectric anisotropy, viscosity, nematic phase ceiling temperature, rotary viscosity (γ 1) etc. as liquid crystal display cells
Various characteristics and the ghost characteristic of liquid crystal display cells deteriorate, the vestige that drips when being not likely to produce manufacture.However, due to liquid
The requirement of crystal display element is uprised, and is further improved as the various characteristics of liquid crystal display cells therefore, it is intended that exploitation is a kind of, special
It is not reliability higher liquid-crystal composition and liquid crystal display cells.
Prior art literature
Patent document
Patent document 1：Japanese Unexamined Patent Publication 2002-357830 publications
Patent document 2：Japanese Unexamined Patent Publication 2010-107536 publications
Patent document 3：U.S. Patent Application Publication No. 2011/261295
Patent document 4：Japanese Unexamined Patent Publication 2011-227284 publications
Patent document 5：Japanese Unexamined Patent Publication 6-235925 publications
Patent document 6：Japanese Unexamined Patent Publication 2006-58755 publications
Patent document 7：Japanese Unexamined Patent Publication 2011-95696 publications
Patent document 8：Japanese Unexamined Patent Publication 2011-95697 publications
Patent document 9：Japanese Unexamined Patent Publication 2009-139455 publications
Patent document 10：Japanese Unexamined Patent Publication 2010-32860 publications
Patent document 11：Japanese Unexamined Patent Publication 2010-107537 publications
Patent document 12：No. 05299595 publication of patent
The content of the invention
The problem of present invention is to be solved
The present invention is to complete in view of the foregoing, and its object is to provide a kind of liquid crystal display cells and its manufacturer
Method, it will not make dielectric anisotropy, viscosity, nematic phase ceiling temperature, rotary viscosity (γ 1) etc. as liquid crystal display cells
Various characteristics and the ghost characteristic of liquid crystal display cells deteriorate, and the vestige that drips when being not likely to produce manufacture is used as liquid crystal display
The various characteristics of element are high, and reliability is high.
The solution used to solve the problem
As a result the present inventor etc. are had found by comprising specific to solve the above problems, inquired into various liquid-crystal compositions
Polymerizable compound can solve the problem that above mentioned problem, so far complete the present patent application.
That is, liquid crystal display cells of the invention have：A group substrate with first substrate and second substrate；And pressed from both sides
The liquid crystal combination nitride layer between the substrate is held, also, at least one of the first substrate and the second substrate
With electrode, there are alignment films at least one of the first substrate and the second substrate, the alignment films contain logical
Cross and polymerize the polymerizable group of the compound with polymerizable group to control the liquid crystal molecule in the liquid crystal combination nitride layer
Differently- oriented directivity polymer, the liquid-crystal composition for constituting the liquid crystal combination nitride layer contains from by following formulas (N-1), formula
(N-2) a kind or the compound of more than two kinds and in the compound group of formula (N-3) expression selected,
[chemical formula 1]
(in formula, RN11、RN12、RN21、RN22、RN31And RN32Separately represent the alkyl that carbon number is 1~8, the alkane
1 or the-CH of non-conterminous more than 2 in base2- can separately by-CH=CH- ,-C ≡ C- ,-O- ,-CO- ,-
COO- or-OCO- substitutions,
AN11、AN12、AN21、AN22、AN31And AN32Separately represent from by
(a) 1,4- cyclohexylidenes (are present in 1-CH in the group2- or non-conterminous more than 2-CH2- can be by
It is substituted by-O-)；And
(b) (being present in 1-CH=or non-conterminous more than 2-CH=in the group can be by for 1,4- phenylenes
It is substituted by-N=)；
(c) naphthalene -2,6- diyls, 1,2,3,4- naphthane -2,6- diyls or decahydronaphthalene -2,6- diyls (be present in naphthalene -2,
6- diyls or 1-CH=or non-conterminous more than 2-CH=in 1,2,3,4- naphthane-2,6- diyls can be taken
On behalf of-N=)
The group selected in the group of composition, the group (a), group (b) and group (c) can separately by cyano group,
Fluorine atom or chlorine atom substitution,
ZN11、ZN12、ZN21、ZN22、ZN31And ZN32Separately represent singly-bound ,-CH2CH2-、-(CH2)4-、-OCH2-、-
CH2O-、-COO-、-OCO-、-OCF2-、-CF2O- ,-CH=N-N=CH- ,-CH=CH- ,-CF=CF- or-C ≡ C-,
XN21Hydrogen atom or fluorine atom are represented,
TN31Expression-CH2- or oxygen atom,
nN11、nN12、nN21、nN22、nN31And nN32The separately integer of expression 0~3, but nN11+nN12、nN21+nN22With
nN31+nN32It is separately 1,2 or 3, there are multiple AN11~AN32、ZN11~ZN32In the case of, they can with identical,
Can also be different),
As the compound with polymerizable group, containing a kind or two or more is by leading to the chemical combination that formula (I) is represented
Thing,
[chemical formula 2]
(in formula, X10And X11Separately represent hydrogen atom or methyl, Sp3And Sp4Separately represent singly-bound,
Carbon number is 1~8 alkylidene or-X- (CH2)t- (in formula, t represents 2~7 integer, X represent-O- ,-OCOO- ,-
OCO- or-COO-, X are bonded with phenanthrene ring)).
In addition, a kind of manufacture method of liquid crystal display cells, in the coating of at least one of first substrate and second substrate
Oriented material simultaneously is heated to be formed after aligning film material, and liquid crystal is clamped using the first substrate and the second substrate
Composition, has electrode, and be applied with the state of voltage at least one of the first substrate and the second substrate
Under active energy beam is irradiated to the electrode so that by the chemical combination with polymerizable group included in the aligning film material
The polymerizable group polymerization of thing, the orientation then with the differently- oriented directivity for controlling the liquid crystal molecule in the liquid crystal combination nitride layer
Film, the liquid-crystal composition contains to be selected from the compound group represented by following formulas (N-1), formula (N-2) and formula (N-3)
1 kind or two or more compound gone out,
[chemical formula 3]
(in formula, RN11、RN12、RN21、RN22、RN31And RN32Separately represent the alkyl that carbon number is 1~8, the alkane
1 in base or non-conterminous more than 2-CH2- can be separately by-CH=CH- ,-C ≡ C- ,-O- ,-CO- ,-COO-
Or-OCO- substitutions,
AN11、AN12、AN21、AN22、AN31And AN32Separately represent from by
(a) 1,4- cyclohexylidenes (are present in 1-CH in the group2- or non-conterminous more than 2-CH2- can be by
It is substituted by-O-)；And
(b) (being present in 1-CH=or non-conterminous more than 2-CH=in the group can be by for 1,4- phenylenes
It is substituted by-N=)；
(c) naphthalene -2,6- diyls, 1,2,3,4- naphthane -2,6- diyls or decahydronaphthalene -2,6- diyls (be present in naphthalene -2,
6- diyls or 1-CH=or non-conterminous more than 2-CH=in 1,2,3,4- naphthane-2,6- diyls can be taken
On behalf of-N=)
The group selected in the group of composition, the group (a), group (b) and group (c) can separately by cyano group,
Fluorine atom or chlorine atom substitution,
ZN11、ZN12、ZN21、ZN22、ZN31And ZN32Separately represent singly-bound ,-CH2CH2-、-(CH2)4-、-OCH2-、-
CH2O-、-COO-、-OCO-、-OCF2-、-CF2O- ,-CH=N-N=CH- ,-CH=CH- ,-CF=CF- or-C ≡ C-,
XN21Hydrogen atom or fluorine atom are represented,
TN31Expression-CH2- or oxygen atom,
nN11、nN12、nN21、nN22、nN31And nN32The separately integer of expression 0~3, but nN11+nN12、nN21+nN22With
nN31+nN32It is separately 1,2 or 3, there are multiple AN11~AN32、ZN11~ZN32In the case of, they can with identical,
Can also be different),
As the compound with polymerizable group, containing a kind or two or more is by leading to the chemical combination that formula (I) is represented
Thing,
[chemical formula 4]
(in formula, X10And X11Separately represent hydrogen atom or methyl, Sp3And Sp4Separately represent singly-bound,
Carbon number is 1~8 alkylidene or-X- (CH2)t- (in formula, t represents 2~7 integer, X represent-O- ,-OCOO- ,-
OCO- or-COO-, X are bonded with phenanthrene ring)).
Invention effect
According to the present invention, due to excellent as the high-speed response of liquid crystal display cells, the generation of ghost is few, when it is manufactured
The vestige that drips generation it is few, as the various characteristic goods of liquid crystal display cells, in addition, reliability is high, therefore, it can effectively
As display elements such as LCD TV, monitors.
In addition, in accordance with the invention it is possible to efficiently manufacturing the liquid crystal display cells for being not likely to produce the vestige that drips.
Brief description of the drawings
Fig. 1 is the summary stereogram for an embodiment for showing the liquid crystal display cells of the present invention.
Fig. 2 be show the present invention liquid crystal display cells used in gap electrode (comb poles) an example it is general
Want plan.
Fig. 3 is the figure of the definition for the pre-tilt angle for showing the liquid crystal display cells of the present invention.
The explanation of reference
10 liquid crystal display cells, 11 first substrates, 12 second substrates, 13 liquid crystal combination nitride layer, 14 common electrodes, 15 pixels
Electrode, 16 vertical alignment layers, 17 vertical alignment layers, 18 colored filters, 19 liquid crystal molecules, 20 polymeric layers, 21 polymeric layers
Embodiment
Illustrate the liquid crystal display cells of the present invention and its embodiment of manufacture method.
In addition, present embodiment be in order to more fully understand the content of invention and illustrating for carrying out, as long as no spy
Do not mentionlet alone bright, just do not limit the present invention.
[liquid crystal display cells]
The liquid crystal display cells of the present invention are the liquid crystal displays with the liquid crystal combination nitride layer being clamped between a pair of substrates
Element, based on following principle：Voltage is applied to liquid crystal combination nitride layer, the liquid crystal molecule in liquid crystal combination nitride layer is carried out Fred
Li Kesi changes, so as to be worked as optical switch, at this point, known common technology can be used.
There is the common vertical orientated liquid crystal for the electrode for being used for changing liquid crystal molecule Frankie Fredericks in 2 substrates
It is general by the way of vertical electric charge is applied between 2 substrates in display element.In this case, an electrode is electric to share
Pole, another electrode is pixel electrode.Below, the most typical embodiment of which is shown.
Fig. 1 is the summary stereogram for an embodiment for showing the liquid crystal display cells of the present invention.
The liquid crystal display cells 10 of present embodiment mainly include：First substrate 11；Second substrate 12；It is clamped in the first base
Liquid crystal combination nitride layer 13 between plate 11 and second substrate 12；On the face opposed with liquid crystal combination nitride layer 13 of first substrate 11
The common electrode 14 of setting；The pixel electrode 15 set on the face opposed with liquid crystal combination nitride layer 13 of second substrate 12；
The vertical alignment layer 16 set on the face opposed with liquid crystal combination nitride layer 13 of common electrode 14；Pixel electrode 15 and liquid crystal
The vertical alignment layer 17 set on the opposed face of composition layer 13, as needed, in addition to：It is formed on vertical alignment layer 16
Polymeric layer 20；It is formed at the polymeric layer 21 on vertical alignment layer 17；It is arranged between first substrate 11 and common electrode 14
Colored filter 18.
As first substrate 11, second substrate 12, glass substrate or plastic base are used.
As plastic base, using by acrylic resin, methacrylic resin, polyethylene terephthalate, poly-
The substrate that the resins such as carbonic ester, cyclic olefin resin are constituted.
The material that common electrode 14 generally has the transparency by tin oxide (ITO) of doped indium etc. is constituted.
The material that pixel electrode 15 generally has the transparency by tin oxide (ITO) of doped indium etc. is constituted.
Pixel electrode 15 is disposed in second substrate 12 with rectangular.Pixel electrode 15 is by using TFT switch element as representative
The drain electrode control of active component, has gate line and the conduct as address signal line the TFT switch element matrix shape
The source electrode line of data wire.In addition, herein, the composition of TFT switch element not shown.
Some regions are divided into the toppling direction for entering the liquid crystal molecule being about in pixel to improve viewing angle characteristic
In the case that pixel is split, the pixel electrode with slit (part for not forming electrode) can also be set in each pixel, should
Slit has the pattern of striated, V-arrangement.
Fig. 2 is shown the representative configuration for the gap electrode (comb poles) being divided into pixel in the case of 4 regions
Schematic plan view.The gap electrode from 4 directions of mediad of pixel by having the slit of comb teeth-shaped, so as to not apply
The liquid crystal molecule in each pixel being approximately vertically oriented during voltage with substrate makes the director of liquid crystal molecule with the application of voltage
Towards to 4 different directions, close to horizontal alignment.As a result, due to the orientation of the liquid crystal in pixel can be divided
Be segmented into it is multiple, therefore, with great viewing angle characteristic.
As the method split for pixel, in addition to the method for slit is set in the pixel electrode, it can also make
The method that the structures such as wire projection are set in pixel；Method of electrode beyond setting pixel electrode, common electrode etc..
The differently- oriented directivity of liquid crystal molecule can also be split using these methods, but for transmissivity, the easness of manufacture, be preferably
Use the composition of gap electrode.The pixel electrode of slit is provided with due to not driven to liquid crystal molecule in no applied voltage
Power, it is thus impossible to assign pre-tilt angle to liquid crystal molecule.But, by and with the aligning film material that uses in the present invention, so as to
Enough assign pre-tilt angle, and by splitting with pixel after gap electrode combine, brought so as to reaching pixel segmentation
Wide viewing angle.
In the present invention, refer to pre-tilt angle under no applied voltage state, with real estate (first substrate 11 and second
The face adjacent with liquid crystal combination nitride layer 13 of substrate 12) vertical direction and liquid crystal molecule the slightly different state of director.
(alignment films)
Therefore the liquid crystal display cells of the present invention, are not applying electricity due to being vertically oriented (VA) type liquid crystal display cells
The director of liquid crystal molecule is approximately vertically oriented with real estate during pressure.In order that liquid crystal molecule is vertical orientated, general use (is hung down
Directly) alignment films.
In the present invention using containing by the way that the polymerizable group of the compound with polymerizable group is polymerize, so as to control
Make the alignment films of the polymer of the differently- oriented directivity of liquid crystal molecule in the liquid crystal combination nitride layer.That is, in the present invention using containing
There are the alignment films of the polymer obtained after the polymerizable group polymerization by the compound with polymerizable group, the polymer tool
There is the ability of the differently- oriented directivity of liquid crystal molecule in control composition.
As the material (vertical orientated membrane material) for forming vertical alignment layer, polyimides, polyamide, poly- silica are used
Alkane, solidfied material of polymerizable liquid crystal compound etc..
In the case where using polyimides as the aligning film material for forming vertical alignment layer, preferably using makes tetrabasic carboxylic acid
Mixture, polyamic acid, the polyimides of dianhydride and diisocyanate dissolve or are dispersed in the polyimide solution after solvent,
In this case, the content of the polyimides in polyimide solution is preferably more than 1 mass % and below 10 mass %, more excellent
Elect as more than 3 mass % and below 5 mass %, more preferably below 10 mass %.
In addition, in the case where using polysiloxane-based material as the aligning film material for forming vertical alignment layer, can be with
Using the polysiloxane solution of dissolving polysiloxane, polysiloxanes is by the way that the silicon compound with alkoxy, alcohol are derived
Thing and oxalic acid derivatives are mixed and heated to manufacture with predetermined use level ratio.
In the liquid crystal display cells of the present invention, the vertical alignment layer 16,17 formed by polyimides etc. include by
Polymer etc. formed by the polymerization of polymerizable compound with polymerizable group.The polymerizable compound is assigned liquid crystal point
The function that the pre-tilt angle of son is fixed.That is, gap electrode etc. can be used, the director of the liquid crystal molecule in pixel is being applied electricity
Tilted during pressure to different directions.But, in the composition of gap electrode has been used, in no applied voltage, liquid crystal molecule with
Real estate is almost vertical orientated, will not produce pre-tilt angle, but by applying voltage electrode, and liquid crystal molecule is slightly inclined
Irradiation ultraviolet radiation etc., polymerize the reactive monomer in liquid-crystal composition, so as to assign appropriate pre-tilt angle in the state of tiltedly.
In addition, as needed, the polymeric layer 20,21 is by polymerizable compound contained in liquid-crystal composition
After being clamped between substrate, by solidifying polymerizable compound when applying voltage, polymerizable compound being capable of side progress phase point
Be formed as polymer on the surface of the vertical alignment layer 16,17 from side.
Using the polymer contained in the vertical alignment layer 16,17, as needed formed by the vertical alignment layer
16th, the polymeric layer 20,21 that 17 surface is formed, the orientation of liquid crystal molecule is high, and the generation of ghost is few, when it is manufactured
The vestige that drips generation it is few.
In the present invention, the substantially vertical director for referring to vertical orientated liquid crystal molecule is slightly toppled over simultaneously from vertical direction
Impart the state of pre-tilt angle.If pre-tilt angle completely it is vertical orientated in the case of be 90 °, it is parallel-oriented (with real estate level
Ground be orientated) in the case of be 0 °, it is substantially vertical be preferably 89.5~85 °, more preferably 89.5~87 °.
The vertical alignment layer 16,17 of polymer comprising the polymerizable compound with polymerizable group is to utilize vertically to take
Formed by the effect of the polymerizable compound mixed into membrane material.So, vertical alignment layer and polymerizable compound are complicated
Ground interweaves, although be estimated to be to form a kind of polymer alloy, but can not show that it is accurately constructed.
In addition, the polymeric layer 20,21 polymerism contained in liquid-crystal composition formed by as needed
The surface of the vertical alignment layer 16,17 is formed at when compound polymerize when carrying out phase separation from liquid-crystal composition, it is believed that
It is formed uniformly in the whole surface of vertical alignment layer or is the condition according to manufacture with uneven sea island structure formation
And it is different, it is impossible to show that it is accurately constructed.Situation about being uniformly forming is shown in Fig. 1.
The alignment films used in the present invention need to hang down with real estate with the liquid crystal molecule made in liquid crystal combination nitride layer
The vertical orientated ability of straight direction orientation, and it also requires the tropism control energy of the differently- oriented directivity with control liquid crystal molecule
Power.As the method for obtaining the alignment films with the vertical orientated ability and tropism control ability this 2 functions, have usual
Coordinate the method for the polymerizable compound with polymerizable group in the aligning film material used；Handed over using having in pendant moiety
The polymer of the polymerizable compound of Lian Xing functional groups as aligning film material method；With use polymerizable liquid crystal compound
The method of solidfied material.Below, each method is illustrated.
(method for coordinating the polymerizable compound with polymerizable group in aligning film material)
As the method for coordinating the polymerizable compound with polymerizable group in aligning film material, it can enumerate：To
Described aligning film material coordinates the method for the polymerizable compound with polymerizable group.
The polymerizable compound with polymerizable group contained by aligning film material can be included or not comprising mesomorphism
Position, but be used as the compound with polymerizable group, it is important that containing a kind or two or more is represented by logical formula (I)
Compound,
[chemical formula 5]
(in formula, X10And X11Separately represent hydrogen atom or methyl, Sp3And Sp4Separately represent singly-bound,
Carbon number is 1~8 alkylidene or-X- (CH2)t- (in formula, t represents 2~7 integer, X represent-O- ,-OCOO- ,-
OCO- or-COO-, X are bonded with phenanthrene ring.), any hydrogen atom of the phenanthrene ring in formula can also be replaced by fluorine atoms.).Formula
(I) reaction speed of the compound represented by is fast, therefore, by containing the compound, so as to make to be formed in alignment films
Polymer turn into few energy size, i.e. the exposure of ultraviolet etc. can be reduced.
In the logical formula (I), X10And X11Hydrogen atom or methyl are separately represented, but is paying attention to reaction speed
In the case of be preferably hydrogen atom, pay attention to reduction reaction residual quantity in the case of be preferably methyl.
In the logical formula (I), Sp3And Sp4Separately represent singly-bound, the alkylidene or-X- of carbon number 1~8
(CH2)t- (in formula, t represents 2~7 integer, and X represents-O- ,-OCOO- or-COO-, and X is bonded with phenanthrene ring), but preferably carbochain
Not oversize, preferably singly-bound or carbon number are 1~5 alkylidene, and more preferably singly-bound or carbon number are 1~3
Alkylidene.In addition, in Sp3And Sp4Expression-X- (CH2)t- in the case of, preferably it is also that t is 1~5, more preferably 1~3, more
Preferably Sp3And Sp4At least one party be singly-bound, be particularly preferably all singly-bound.
Compound represented by the logical formula (I) is preferably by following formula (I-1)~(I-52) institute table specifically
The compound shown.
[chemical formula 6]
[chemical formula 7]
[chemical formula 8]
Content of the compound in the high-molecular compound precursor for forming alignment films represented by the logical formula (I) is excellent
Elect 0.1~6 mass %, more preferably more preferably 0.5~5 mass %, 1~4 mass % as.
As the polymerizable compound with polymerizable group contained by aligning film material, except above-mentioned logical formula (I) institute
Beyond the compound of expression, the polymerizable compound represented by following logical formula (V)s can also be included,
[chemical formula 9]
(in formula, X7And X8Separately represent hydrogen atom or methyl, Sp1And Sp2Separately represent singly-bound, carbon
Atomicity is 1~8 alkylidene or-X- (CH2)s- (in formula, s represents 2~7 integer, X represent O, OCOO, OCO or
COO, X are bonded with the aromatic rings being present in U), U represents the straight chain or the polynary alkylidene of side chain, carbon that carbon number is 2~20
The polynary cyclic substituents that the polynary alkenylene of straight chain or side chain or carbon number that atomicity is 3~20 are 5~30, but it is many
The alkenylene in alkylidene or polynary alkenylene in first alkylidene can in the non-conterminous scope of oxygen atom by-O- ,-
CO-、-CF2- substitution, can also for 5~20 alkyl, (alkylidene in base can be non-conterminous in oxygen atom by carbon number
In the range of replaced by oxygen atom) or cyclic substituents replace, k represents 0~5 integer).
In the logical formula (V), X7And X8Hydrogen atom or methyl are separately represented, but is paying attention to reaction speed
In the case of be preferably hydrogen atom, pay attention to reduction reaction residual quantity in the case of be preferably methyl.
In the logical formula (V), Sp1And Sp2Separately represent singly-bound, the alkylidene or-X- of carbon number 1~8
(CH2)s- (in formula, s represents 2~7 integer, and X represents O, OCOO or COO, and X is bonded with the aromatic rings being present in U), but
It is preferred that carbochain is not oversize, preferably singly-bound or carbon number are 1~5 alkylidene, more preferably singly-bound or carbon number
For 1~3 alkylidene.In addition, in Sp1And Sp2Expression-X- (CH2)s- in the case of, preferably also s is 1~5, more preferably 1
~3, more preferably Sp1And Sp2In at least one party be singly-bound, be particularly preferably all singly-bound.
In the logical formula (V), k represents 0~5 integer, the orientation of the liquid crystal molecule in liquid crystal combination nitride layer is paid attention to
In the case of the controlling in direction, preferably k represents 1~5 integer, and more preferably k represents 1~3 integer, further preferred k tables
Show 1.
In the logical formula (V), U represents the straight chain or the polynary alkylidene of side chain, carbon number that carbon number is 2~20
The polynary cyclic substituents that the polynary alkenylene of straight chain or side chain or carbon number for 3~20 are 5~30, but polynary alkylene
Alkylidene in base can be in the non-conterminous scope of oxygen atom by-O- ,-CO- ,-CF2- substitution, can also be by carbon number
5~20 alkyl (alkylidene in base can be replaced in the non-conterminous scope of oxygen atom by oxygen atom) or cyclic substituents takes
In generation, preferably replaced by the cyclic substituents of more than 2.
In the logical formula (V), specifically, U preferably represents following formula (Va-1) to formula (Va-5), more preferably expression
(Va-1), formula (Va-2), particularly preferred expression (Va-1).
[chemical formula 10]
(it is two ends and Sp in formula1Or Sp2It is bonded (above-mentioned k=1 situation), is the situation of 2~5 integer in k
Under, linking group number correspondingly increases.Z1、Z2And Z3Separately expression-OCH2-、-CH2O-、-COO-、-OCO-、-
CF2O-、-OCF2-、-CH2CH2-、-CF2CF2- ,-CH=CH-COO- ,-CH=CH-OCO- ,-COO-CH=CH- ,-OCO-CH=
CH-、-COO-CH2CH2-、-OCO-CH2CH2-、-CH2CH2-COO-、-CH2CH2-OCO-、-COO-CH2-、-OCO-CH2-、-CH2-
COO-、-CH2Any hydrogen atom can be replaced by fluorine atoms in all aromatic rings in-OCO- or singly-bound, formula)
In the U, Z1、Z2And Z3It is preferably separately-OCH2-、-CH2O-、-COO-、-OCO-、-CF2O-、-
OCF2-、-CH2CH2-、-CF2CF2- or singly-bound, it is more preferably-COO- ,-OCO- or singly-bound, particularly preferably singly-bound.
In the case where U has the ring structure, preferably described Sp1And Sp2At least one represent singly-bound, it is also preferred that two
Person is singly-bound.
In the logical formula (V), k represents 0~5 integer, but preferably k be 1 difunctional's compound or k be 2
Trifunctional compound, more preferably k are 1 difunctional's compound.
Compound represented by the logical formula (V) is preferably specifically by below general formula (Va-1-1)~(Va-5-3)
Represented compound.
[chemical formula 11]
[chemical formula 12]
[chemical formula 13]
[chemical formula 14]
[chemical formula 15]
[chemical formula 16]
[chemical formula 17]
[chemical formula 18]
[chemical formula 19]
[chemical formula 20]
[chemical formula 21]
In addition, in the compound represented by above formula (Va-1-1)~formula (Va-5-3), preferred formula (Va-1-1)~formula
(Va-2-11) compound represented by the compound represented by, more preferably formula (Va-1-1)~formula (Va-1-13).
Content of the compound in the aligning film material for forming alignment films represented by the logical formula (V) is preferably 0~6 matter
Measure %, more preferably more preferably 0.5~4 mass %, 1~2 mass %.
Polymerizable compound with the polymerizable group is overall before the high-molecular compound of alignment films is formed
Content in body is preferably 0.1~6 mass %, more preferably 0.5~5 mass %, more preferably 1~4 mass %.
(polymer using the polymerizable compound in pendant moiety with cross-linking functional group is used as aligning film material
Method)
There is the polymerizable compound of cross-linking functional group as in pendant moiety, as long as there is bridging property in pendant moiety
Functional group's (polymerizable group), then backbone portion is not particularly limited, but as backbone portion, preferably uses sub- with the acyl
The compound of amine skeleton, siloxane backbone, more preferably uses the compound for having polyimide backbone in backbone portion.As
Backbone portion has polyimide backbone and with cross-linking functional group as the polymerizable compound of side chain, can enumerate：
The repeat unit (backbone portion) for constituting polyimide structures includes compound of the cross-linking functional group as side chain.Moreover, should
Cross-linking functional group turns into polymerisation starting point, the polymerism chemical combination with polymerizable group coordinated in aligning film material
Radical reaction occurs for thing, forms side chain, so that taking with the differently- oriented directivity for controlling the liquid crystal molecule in liquid crystal combination nitride layer
To control ability.As the cross-linking functional group, if can carry out radical reaction then have any structure can, but
The group preferably represented by (V2-1) described below~(V2-7), the base more preferably represented by (V2-1)~(V2-3)
Group, the group for (V2-1) or (V2-2) expression of further preferably serving as reasons.
[chemical formula 22]
(R1Be represent carbon number be 1~5 alkyl)
, can also be direct with backbone portion as long as the cross-linking functional group is bonded via covalent bond with backbone portion
Bonding, can also be bonded with backbone portion, but as linking group, preferably use-O-C via linker6H4- or-O-
C6H4-(R2O)r-, (R2The alkylidene that carbon number is 1~20 is represented, r represents more than 1 integer).
As with polyimide backbone as main chain and with cross-linking functional group as side chain polymerizable compound,
It can such as enumerate by the compound of formula (V2) expression as shown below.
[chemical formula 23]
(in formula (V2), R3Represent any a kind in the group represented by following (V2-A)~(V2-F), R4And R5Respectively
Independently represent the alkylidene that carbon number is 1~20, R6And R7(V2-1)~(V2-7) described in separately representing is represented
Group in any a kind, n represents more than 1 integer, m1 and m2 represent respectively 0 or 1, m3 and m4 represent 0 or 1 respectively
Integer above, m5 and m6 represent 0 or 1 respectively, but m5 and m6 at least one represents 1.)
[chemical formula 24]
There is polyimide backbone and with polymerism chemical combination of the cross-linking functional group as side chain as with backbone portion
Thing coordinates the polymerizable compound with polymerizable group in aligning film material in the lump, can enumerate and the logical formula (I)
With the compound identical compound represented by the logical formula (V), but certain change containing represented by logical formula (I) is characterized in that
Compound.By containing the compound represented by logical formula (I) this described, so as to few energy formation side chain, i.e. can drop
The exposure of low ultraviolet ray etc..
The use level that compound represented by the logical formula (I) coordinates in aligning film material is preferably 0.1~6 matter
Measure %, more preferably more preferably 0.5~5 mass %, 1~4 mass %.
The use level that polymerizable compound with the polymerizable group integrally coordinates in aligning film material is preferably
0.1~6 mass %, more preferably 0.5~5 mass %, more preferably 1~4 mass %.
In addition, using the polymer for the polymerizable compound that there is cross-linking functional group in pendant moiety as the orientation
In the case of membrane material, simultaneously the known polyimide-type materials can also be used by land used.
(using the solidfied material of polymerizable liquid crystal compound as the method for alignment films)
, can will be sub- comprising the polyamides in the case where using the solidfied material of polymerizable liquid crystal compound as alignment films
Amine material, the alignment films of polysiloxane-based material are used as primary coat alignment films.
In the case where using the solidfied material of polymerizable liquid crystal compound as alignment films, it is characterised in that it is certain contain under
State the compound represented by the polymerizable liquid crystal compound and the logical formula (I) represented by formula (V3).By containing this institute
The compound represented by logical formula (I) is stated, so as to obtain the solidfied material of polymerizable liquid crystal compound with few energy, i.e. energy
Enough reduce the exposure of ultraviolet etc..
In the case where manufacturing alignment films using the solidfied material of polymerizable liquid crystal compound, relative to the logical formula (I)
The total amount of polymerizable liquid crystal compound represented by represented compound and formula (V3), preferably containing 0.1~50 matter
The compound represented by the % logical formula (I) is measured, more preferably containing 0.3~30 mass %, more preferably contains 0.5
~10 mass %.
As the polymerizable liquid crystal compound for forming alignment films, specifically, preferably comprise one kind or two or more by following
The polymerizable compound that formula (V3) is represented,
[chemical formula 25]
(in formula, X1Represent hydrogen atom or methyl, Sp5And Sp6It is 1~8 separately to represent singly-bound, carbon number
Alkylidene or-O- (CH2)s- (in formula, s represents 2~7 integer, and oxygen atom is bonded with aromatic rings), Z4Expression-OCH2-、-
CH2O-、-COO-、-OCO-、-CF2O-、-OCF2-、-CH2CH2-、-CF2CF2- ,-CH=CH-COO- ,-CH=CH-OCO- ,-
COO-CH=CH- ,-OCO-CH=CH- ,-COO-CH2CH2-、-OCO-CH2CH2-、-CH2CH2-COO-、-CH2CH2-OCO-、-
COO-CH2-、-OCO-CH2-、-CH2-COO-、-CH2-OCO-、-CY1=CY2-(Y1And Y2Separately represent hydrogen atom, fluorine
Atom) ,-C ≡ C- or singly-bound, Y represents the alkenyl that the alkyl that carbon number is 1~8, carbon number are 2~8, carbon number
The alkenyloxy group, hydrogen atom, fluorine atom or the cyano group that are 2~8 for 1~8 alkoxy, carbon number or following structure,
[chemical formula 26]
(in formula, X2Represent hydrogen atom or methyl), C rings represent Isosorbide-5-Nitrae-phenylene, anti-form-1,4- cyclohexylidenes or list
Key, in C rings, any hydrogen atom of Isosorbide-5-Nitrae-phenylene can be replaced by fluorine atoms.).
In the formula (V3), X1And X2Hydrogen atom or methyl are separately represented, but is paying attention to reaction speed
In the case of be preferably hydrogen atom, pay attention to reduction reaction residual quantity in the case of be preferably methyl.
In the formula (V3), Sp5And Sp6Separately represent singly-bound, the alkylidene or-O- of carbon number 1~8
(CH2)s- (in formula, s represents 2~7 integer, and oxygen atom is bonded with aromatic rings), but preferably carbochain it is not oversize, preferably singly-bound or
Person's carbon number is 1~5 alkylidene, and more preferably singly-bound or carbon number are 1~3 alkylidene.In addition, in Sp5With
Sp6Expression-O- (CH2)s- in the case of, it is also preferred that s is 1~5, more preferably 1~3, more preferably Sp5And Sp6At least one party be
Singly-bound, is particularly preferably all singly-bound.
In the formula (V3), Z4Expression-OCH2-、-CH2O-、-COO-、-OCO-、-CF2O-、-OCF2-、-
CH2CH2-、-CF2CF2- ,-CH=CH-COO- ,-CH=CH-OCO- ,-COO-CH=CH- ,-OCO-CH=CH- ,-COO-
CH2CH2-、-OCO-CH2CH2-、-CH2CH2-COO-、-CH2CH2-OCO-、-COO-CH2-、-OCO-CH2-、-CH2-COO-、-
CH2-OCO-、-CY1=CY2-(Y1And Y2Separately represent hydrogen atom, fluorine atom.) ,-C ≡ C- or singly-bound, but preferably
For-OCH2-、-CH2O-、-COO-、-OCO-、-CF2O-、-OCF2-、-CH2CH2-、-CF2CF2- or singly-bound, more preferably-
COO- ,-OCO- or singly-bound, particularly preferably singly-bound.
In the formula (V3), C rings represent Isosorbide-5-Nitrae-phenylene that any hydrogen atom can be replaced by fluorine atoms, it is trans-
Isosorbide-5-Nitrae-cyclohexylidene or singly-bound, but preferably Isosorbide-5-Nitrae-phenylene or singly-bound.
In the case of the ring structure that C rings are represented beyond singly-bound, Z4Also the linking group beyond singly-bound is more preferably, in C
In the case that ring is singly-bound, Z4Preferably singly-bound.
The alkane that alkenyl, carbon number that alkyl, carbon number that carbon number is 1~8 are 2~8 are 1~8 is represented for Y
Epoxide, carbon number are the compound of 2~8 alkenyloxy group, hydrogen atom, fluorine atom or cyano group, are the polymerizable liquid crystals of simple function
Compound, Y does not have polymeric matrix.On the other hand, Y represents that the compound of the polymeric matrix is two function polymerism liquid
Crystallization compound.In the present invention, the polymerizable liquid crystal compound or two function polymerizable liquid crystal chemical combination of simple function can be used
Thing it is any, but for the viewpoint of heat resistance, preferably two function polymerizable liquid crystal compounds, can also simultaneously using this two
Person.
As known from the above, as the polymerizable liquid crystal compound with ring structure, preferably by following formula (V3-1) extremely
(V3-6) compound represented, the compound particularly preferably represented by formula (V3-1) to (V3-4), most preferably by formula (V3-
2) compound represented.
[chemical formula 27]
(in above formula, Sp5And Sp6Separately represent and structure identical structure defined above)
In the case where using the solidfied material of polymerizable liquid crystal compound as alignment films, film formation material is orientated in heating
In polymerizable liquid crystal compound and as, it is necessary to make temperature drop, making polymerizable liquid crystal compound after isotropic liquid
Orientation is set as vertical orientated.Afterwards, be applied with from real estate tilt special angle magnetic field in the state of assign pre-tilt angle,
Irradiation ultraviolet radiation, solidifies polymerizable liquid crystal compound in this condition, as alignment films.
In addition, can also have basalis of the horizontal alignment film as alignment films in the alignment films.Specifically, can also
With following horizontal alignment film：Using polyimide horizontal alignment aligning film material etc., using method of spin coating in substrate
Upper Coating levels aligning film material, and after solvent is removed using heating etc., burnt till, be made basalis, carried out at friction
Reason, imparts horizontal alignment.
(for the polymerizable compound contained in alignment layer surface formation polymeric layer in liquid-crystal composition)
In the liquid crystal display cells of the present invention, vertical alignment layer, which is included, passes through the polymerism chemical combination with reactive group
Polymer formed by the polymerization of thing, and appropriate pre-tilt angle can be assigned using the polymer, but it is also possible to further root
According to needs, polymerizable compound is contained in liquid-crystal composition, the liquid-crystal composition is clamped between substrate, then, side applies
Voltage side solidifies the polymerizable compound, so that polymerizable compound side is separated, while in the vertical alignment layer
Surface is formed as polymeric layer, is further able to access the orientation of liquid crystal molecule, the stability height of pre-tilt angle, the generation of ghost
Less, the few liquid crystal display cells of the generation of the vestige that drips during its manufacture.
Forming the polymerizable compound of the polymer layer can enumerate：Mono-functional's with 1 reactive group is poly-
Conjunction property compound, two functions or trifunctional etc. have the multi-functional polymerizable compound of the reactive group of more than 2
Deng, but preferably two functions or trifunctional etc. have the multi-functional polymerizable compound of the reactive group of more than 2.
Used polymerizable compound can be a kind or two or more.
As the polymerizable compound for forming polymeric layer, the compound represented by the logical formula (I) is preferably comprised.Pass through
Using the compound that this is represented by the logical formula (I), so as to form polymeric layer on the surface of alignment films with few energy,
That is, the exposure of ultraviolet etc. can be reduced.
In addition, as the polymerizable compound for forming polymeric layer, preferably in the same manner as the logical formula (V), by formula
(V1) polymerizable compound represented,
[chemical formula 28]
(in formula, X7And X8Separately represent hydrogen atom or methyl, Sp1And Sp2Separately represent singly-bound, carbon
Atomicity is 1~8 alkylidene or-X- (CH2)r- (in formula, r represents 2~7 integer, X represent O, OCOO, OCO or
COO, X are bonded with the aromatic rings being present in U), U represents the straight lock or the polynary alkylidene of side chain, carbon that carbon number is 2~20
Straight lock or the polynary alkenylene of side chain that atomicity is 3~20 or the polynary cyclic substituents that carbon number is 5~30, but it is many
The alkenylene in alkylidene or polynary alkenylene in first alkylidene can in the non-conterminous scope of oxygen atom by-O- ,-
CO-、-CF2- substitution, can also for 5~20 alkyl, (alkylidene in base can be non-conterminous in oxygen atom by carbon number
In the range of replaced by oxygen atom) or cyclic substituents replace, k represents 0~5 integer).
In the formula (V1), X7And X8Hydrogen atom or methyl are separately represented, but is paying attention to reaction speed
In the case of be preferably hydrogen atom, pay attention to reduction reaction residual quantity in the case of be preferably methyl.
In the formula (V1), Sp1And Sp2Separately represent singly-bound, the alkylidene or-X- of carbon number 1~8
(CH2)r- (in formula, r represents 2~7 integer, and X represents O, OCOO or COO, and X is bonded with the aromatic rings being present in U), but
It is that preferred carbochain is not oversize, preferably singly-bound or carbon number are 1~5 alkylidene, more preferably singly-bound or carbon atom
Number is 1~3 alkylidene.In addition, in Sp1And Sp2Expression-X- (CH2)s- in the case of, it is also preferred that r is 1~5, more preferably 1
~3, more preferably Sp1And Sp2At least one party be singly-bound, be particularly preferably all singly-bound.
In the formula (V1), k represents 0~5 integer, but the liquid crystal molecule in liquid crystal combination nitride layer is paid attention to takes
To direction controlling in the case of, preferably k represents 1~5 integer, and more preferably k represents 1~3 integer, further preferred k
Represent 1.
In the formula (V1), U represents the straight chain or the polynary alkylidene of side chain, carbon atom that carbon number is 2~20
The polynary cyclic substituents that the polynary alkenylene of straight chain or side chain or carbon number that number is 3~20 are 5~30, but polynary Asia
Alkylidene in alkyl can be in the non-conterminous scope of oxygen atom by-O- ,-CO- ,-CF2- substitution, can also be by carbon number
For 5~20 alkyl (alkylidene in base can be replaced in the non-conterminous scope of oxygen atom by oxygen atom) or cyclic substituents
Substitution, is preferably to be replaced by the cyclic substituents of more than 2.Specifically, U preferably represents following formula (V1a-1) to formula (V1a-
6), more preferably expression (V1a-1), formula (V1a-2), formula (V1a-6), particularly preferred expression (V1a-1).
[chemical formula 29]
(it is two ends and Sp in formula1Or Sp2It is bonded (above-mentioned is k=1 situation), is the situation of 2~5 integer in k
Under, linking group number correspondingly increases.Z1、Z2And Z3Separately expression-OCH2-、-CH2O-、-COO-、-OCO-、-
CF2O-、-OCF2-、-CH2CH2-、-CF2CF2- ,-CH=CH-COO- ,-CH=CH-OCO- ,-COO-CH=CH- ,-OCO-CH=
CH-、-COO-CH2CH2-、-OCO-CH2CH2-、-CH2CH2-COO-、-CH2CH2-OCO-、-COO-CH2-、-OCO-CH2-、-CH2-
COO-、-CH2Any hydrogen atom can be replaced by fluorine atoms in all aromatic rings in-OCO- or singly-bound, formula.)
In the U, Z1、Z2And Z3Independently, it is preferably-OCH2-、-CH2O-、-COO-、-OCO-、-CF2O-、-
OCF2-、-CH2CH2-、-CF2CF2- or singly-bound, it is more preferably-COO- ,-OCO- or singly-bound, particularly preferably singly-bound.
In the case where U has the ring structure, preferably described Sp1And Sp2At least one represent singly-bound, preferably both
All it is singly-bound.
Compound represented by the formula (V1) is preferably the compound represented by following formula (V1b).
[chemical formula 30]
(in formula, X1And X2Separately represent hydrogen atom or methyl, Sp1bAnd Sp2bSeparately represent singly-bound,
Carbon number is 1~8 alkylidene or-O- (CH2)s- (in formula, s represents 2~7 integer, and oxygen atom is bonded with aromatic rings),
Z4Expression-OCH2-、-CH2O-、-COO-、-OCO-、-CF2O-、-OCF2-、-CH2CH2-、-CF2CF2- ,-CH=CH-COO- ,-CH
=CH-OCO- ,-COO-CH=CH- ,-OCO-CH=CH- ,-COO-CH2CH2-、-OCO-CH2CH2-、-CH2CH2-COO-、-
CH2CH2-OCO-、-COO-CH2-、-OCO-CH2-、-CH2-COO-、-CH2-OCO-、-CY1=CY2-(Y1And Y2Separately
Represent hydrogen atom, fluorine atom) ,-C ≡ C- or singly-bound, C rings represent Isosorbide-5-Nitrae-phenylene, anti-form-1,4- cyclohexylidenes or list
Any hydrogen atom can be replaced by fluorine atoms in all Isosorbide-5-Nitrae-phenylenes in key, formula.)
In the formula (V1b), X1And X2Hydrogen atom or methyl are separately represented, but is preferably all to represent hydrogen
The diacrylate derivative of atom or the dimethyl allene acid derivative all with methyl, it is also preferred that a side represents that hydrogen is former
Son, the opposing party represents the compound of methyl.For the polymerization speed of these compounds, diacrylate derivative is most fast, diformazan
Base acrylic acid derivative is slow, and asymmetric compound is in the middle of it, can to use preferred form according to its purposes.
In the formula (V1b), Sp1bAnd Sp2bSeparately represent the alkylidene that singly-bound, carbon number are 1~8
Or-O- (CH2)s-, but preferably at least a side is singly-bound, preferably all represents that the compound of singly-bound or a side represent that singly-bound is another
One side represents the alkylidene or-O- (CH that carbon number is 1~82)s- form.In such a situation it is preferred that being that carbon number is 1
~4 alkylidene, preferably s are 1~4.
In the formula (V1b), Z4Expression-OCH2-、-CH2O-、-COO-、-OCO-、-CF2O-、-OCF2-、-
CH2CH2-、-CF2CF2- ,-CH=CH-COO- ,-CH=CH-OCO- ,-COO-CH=CH- ,-OCO-CH=CH- ,-COO-
CH2CH2-、-OCO-CH2CH2-、-CH2CH2-COO-、-CH2CH2-OCO-、-COO-CH2-、-OCO-CH2-、-CH2-COO-、-
CH2-OCO-、-CY1=CY2- ,-C ≡ C- or singly-bound, but be preferably-OCH2-、-CH2O-、-COO-、-OCO-、-CF2O-、-
OCF2-、-CH2CH2-、-CF2CF2- or singly-bound, it is more preferably-COO- ,-OCO- or singly-bound, particularly preferably singly-bound.
In the case of the ring structure that C rings are represented beyond singly-bound, Z4It is also preferred that the linking group beyond singly-bound, is in C rings
In the case of singly-bound, Z4Preferably singly-bound.
As described above, in the formula (V1b), it is preferred that C rings represent singly-bound and ring structure is by 2 annulars
Into as the polymerizable compound with ring structure, specifically, preferably by following formula (V1b-1) to (V1b-6) expression
Compound, the compound particularly preferably represented by formula (V1b-1) to (V1b-4), most preferably by formula (V1b-2) represent
Compound.
[chemical formula 31]
(Sp1bAnd Sp2bRepresent respectively and the Sp described in formula (V1b)1And Sp2Identical is looked like.)
Compound represented by the formula (V1) is specifically it is also preferred that the chemical combination represented by following formula (V1c)
Thing.
[chemical formula 32]
(in formula, X1、X2And X3Separately represent hydrogen atom or methyl, Sp1c、Sp2cAnd Sp3cIndependently earth's surface
Show alkylidene or-O- (CH that singly-bound, carbon number are 1~82)s- (in formula, s represents 2~7 integer, oxygen atom and fragrance
Ring is bonded), Z11Expression-OCH2-、-CH2O-、-COO-、-OCO-、-CF2O-、-OCF2-、-CH2CH2-、-CF2CF2- ,-CH=
CH-COO- ,-CH=CH-OCO- ,-COO-CH=CH- ,-OCO-CH=CH- ,-COO-CH2CH2-、-OCO-CH2CH2-、-
CH2CH2-COO-、-CH2CH2-OCO-、-COO-CH2-、-OCO-CH2-、-CH2-COO-、-CH2-OCO-、-CY1=CY2-、-C≡
C- or singly-bound, J rings represent in all Isosorbide-5-Nitrae-phenylenes in Isosorbide-5-Nitrae-phenylene or singly-bound, formula that any hydrogen atom can be by
Fluorine atom replaces.)
For the liquid crystal group by leading to the compound that formula (I) is represented for forming polymeric layer on vertical alignment layer surface and using
Total content in compound is preferably 0~1 mass %, preferably 0.03~0.8 mass %, more preferably 0.05~0.6 matter
Measure %.
In addition, for the polymerism represented by formula (V1) for forming polymeric layer on vertical alignment layer surface and using
Total content in the liquid-crystal composition of compound is preferably 0~1 mass %, preferably 0.03~0.8 mass %, more preferably
0.05~0.6 mass %.
Polymerizable compound for forming polymeric layer on vertical alignment layer surface and using is overall in liquid-crystal composition
In total content be preferably 0~1 mass %, preferably 0.03~0.8 mass %, more preferably 0.05~0.6 mass %.
(liquid-crystal composition)
The liquid-crystal composition of the present invention contains a kind or of more than two kinds by formula (N-1), formula (N-2) and formula (N-
3) compound represented.
[chemical formula 33]
In formula, RN11、RN12、RN21、RN22、RN31And RN32Separately represent the alkyl that carbon number is 1~8, the alkane
1 or the-CH of non-conterminous more than 2 in base2- can separately by-CH=CH- ,-C ≡ C- ,-O- ,-CO- ,-
COO- or-OCO- substitutions,
AN11、AN12、AN21、AN22、AN31And AN32Separately represent from by
(a) 1,4- cyclohexylidenes (are present in 1-CH in the group2- or non-conterminous more than 2-CH2- can also
It is substituted by-O-)；
(b) (the 1-CH=or non-conterminous more than 2-CH=being present in the group can also for 1,4- phenylenes
It is substituted by-N=)；And
(c) naphthalene -2,6- diyls, 1,2,3,4- naphthane -2,6- diyls or decahydronaphthalene -2,6- diyls (be present in naphthalene -2,
6- diyls or 1-CH=or non-conterminous more than 2-CH=in 1,2,3,4- naphthane-2,6- diyls can be taken
On behalf of-N=)
The group selected in the group of composition, the base (a), base (b) and base (c) can be separately former by cyano group, fluorine
Son or chlorine atom substitution,
ZN11、ZN12、ZN21、ZN22、ZN31And ZN32Separately represent singly-bound ,-CH2CH2-、-(CH2)4-、-OCH2-、-
CH2O-、-COO-、-OCO-、-OCF2-、-CF2O- ,-CH=N-N=CH- ,-CH=CH- ,-CF=CF- or-C ≡ C-,
XN21Hydrogen atom or fluorine atom are represented,
TN31Expression-CH2- or oxygen atom,
nN11、nN12、nN21、nN22、nN31And nN32The separately integer of expression 0~3, but nN11+nN12、nN21+nN22With
nN31+nN32It is independently 1,2 or 3, in AN11~AN32、ZN11~ZN32Exist it is multiple in the case of, these can be with identical
Can be different.
The compound represented by formula (N-1), (N-2) and (N-3) is preferably the change that Δ ε is more than 3 for negative and its absolute value
Compound.
In formula (N-1), (N-2) and (N-3), RN11、RN12、RN21、RN22、RN31And RN32Independently, preferably carbon
The alkenyl or carbon number that alkoxy that alkyl that atomicity is 1~8, carbon number are 1~8, carbon number are 2~8 are 2
Alkoxy that alkyl that~8 alkenyloxy group, preferably carbon number are 1~5, carbon number are 1~5, carbon number are 2~5
Alkenyl or alkenyloxy group that carbon number is 2~5, the alkyl or carbon number that further preferred carbon number is 1~5 be
2~5 alkenyl, the alkenyl that the alkyl or carbon number that further preferred carbon number is 2~5 are 2~3, particularly preferred carbon
Atomicity is 3 alkenyl (acrylic).
In addition, in the case where its ring structure being bonded is phenyl (aromatic series), preferably the carbon number of straight-chain is 1
The alkenyl that the alkoxy and carbon number that~5 alkyl, the carbon number of straight-chain are 1~4 are 4~5, the ring being bonded at it
Structure is hexamethylene, pyrans and dioxanes etc. in the case of the ring structure of saturation, preferably the carbon number of straight-chain be 1~
The alkenyl that the carbon number of 5 alkyl, the alkoxy that the carbon number of straight-chain is 1~4 and straight-chain is 2~5.In order that to
Row are mutually stabilized, and preferably carbon atom and oxygen atom when there is oxygen atom adds up to less than 5, preferably straight-chain.
As alkenyl, preferably from by formula (R1) to formula (R5) in select in the group that represents of any formula.(the stain in various
Represent the carbon atom in ring structure.)
[chemical formula 34]
AN11、AN12、AN21、AN22、AN31And AN32Independently, it is desirable that in the case of increase Δ n, preferably aromatic series,
If in order to improve response speed, preferably aliphatic, and preferably representing anti-form-1,4- cyclohexylidenes, Isosorbide-5-Nitrae-phenylene, 2-
The fluoro- 1,4- phenylenes of fluoro- 1,4- phenylenes, 3-, the fluoro- 1,4- phenylenes of 3,5- bis-, the fluoro- 1,4- phenylenes of 2,3- bis-, 1,4- are sub-
Bicyclic [2.2.2] octamethylene of cyclohexenyl group, 1,4-, piperidines -1,4- diyls, naphthalene -2,6- diyls, decahydronaphthalene -2,6- diyls or
1,2,3,4- naphthane -2,6- diyl, more preferably represents following constructions,
[chemical formula 35]
More preferably represent anti-form-1,4- cyclohexylidenes or 1,4- phenylenes.
ZN11、ZN12、ZN21、ZN22、ZN31And ZN32It is preferred that separately expression-CH2O-、-CF2O-、-CH2CH2-、-
CF2CF2- or singly-bound, more preferably-CH2O-、-CH2CH2- or singly-bound, particularly preferably-CH2O- or singly-bound.
XN21Preferably fluorine atom.
TN31Preferably oxygen atom.
nN11+nN12、nN21+nN22And nN31+nN32Preferably 1 or 2, and preferably nN11For 1 and nN12For 0 combination, nN11For
2 and nN12For 0 combination, nN11For 1 and nN12For 1 combination, nN11For 2 and nN12For 1 combination, nN21For 1 and nN22For 0 group
Conjunction, nN21For 2 and nN22For 0 combination, nN31For 1 and nN32For 0 combination, nN31For 2 and nN32For 0 combination.
Total amount (liquid-crystal composition included in of the compound phase represented by formula (N-1) for the composition of the present invention
Liquid-crystal compounds total amount.The lower limit of preferred content similarly hereinafter) is 1 mass % (following, quality % is referred to as into %), is
10%, it is 20%, is 30%, be 40%, be 50%, be 55%, be 60%, be 65%, be 70%, be 75%, is 80%.It is excellent
The higher limit for selecting content is 95%, is 85%, is 75%, is 65%, is 55%, is 45%, is 35%, is 25%, is 20%.
It is for the lower limit of the preferred content of the total amount of the composition of the present invention by the compound phase of formula (N-2) expression
1 mass % (following, quality % is referred to as into %), is 10%, is 20%, be 30%, be 40%, be 50%, be 55%, be
60%, it is 65%, is 70%, be 75%, is 80%.The higher limit of preferred content is 95%, is 85%, is 75%, is 65%,
It is 55%, is 45%, be 35%, be 25%, is 20%.
It is for the lower limit of the preferred content of the total amount of the composition of the present invention by the compound phase of formula (N-3) expression
1 mass % (following, quality % is referred to as into %), is 10%, is 20%, be 30%, be 40%, be 50%, be 55%, be
60%, it is 65%, is 70%, be 75%, is 80%.The higher limit of preferred content is 95%, is 85%, is 75%, is 65%,
It is 55%, is 45%, be 35%, be 25%, is 20%.
It is excellent in the case where needing the viscosity of the composition of the present invention remaining relatively low and fast response time composition
Select that the lower limit is low and higher limit is low.Also, remain higher and temperature stabilization needing the Tni by the composition of the present invention
In the case of the good composition of property, preferably described lower limit is low and higher limit is low.In addition, in order to driving voltage is remained
When relatively low and hope increases dielectric anisotropy, preferably the lower limit is improved and higher limit is high.
Compound represented by formula (N-1) is preferably from the compound group represented by formula (N-1-1)~(N-1-21)
In the compound selected.
Compound represented by formula (N-1-1) is following compounds.
[chemical formula 36]
(in formula, RN111And RN112Separately represent and the R in formula (N-1)N11And RN12Identical is looked like.)
RN111The alkenyl that the alkyl or carbon number that preferably carbon number is 1~5 are 2~5, and preferably propyl group or
Person's amyl group.RN112The alkenyl or carbon number that alkyl that preferably carbon number is 1~5, carbon number are 4~5 are 1~4
Alkoxy, and preferably ethyoxyl or butoxy.
Compound represented by formula (N-1-1) can be used alone, but it is also possible to combine two or more compound to make
With.The species for the compound that can be combined is not particularly limited, but will according to the dissolubility of low temperature, transition temperature, electric reliability,
Performance desired by birefringence etc. carrys out appropriately combined use.For the species of the compound used, such as the one of the present invention
Individual embodiment is a kind, is 2 kinds, is 3 kinds, is 4 kinds, is more than 5 kinds.
In the case where paying attention to Δ ε improvement, content is preferably set as to higher, the deliquescent feelings in the case where paying attention to low temperature
Under condition, if content is set as more, effect is good, in the case where paying attention to TNI, if content is set as it is less,
Effect is good.Also, in the case where being improved to the vestige that drips, ghost characteristic, preferably by the range set of content in centre.
It is for the lower limit of the preferred content of the total amount of the composition of the present invention by the compound phase of formula (N-1-1) expression
5 mass % (following, quality % is referred to as into %), are 10%, are 13%, be 15%, be 17%, be 20%, be 23%, be
25%, it is 27%, is 30%, be 33%, is 35%.Relative to the total amount of the composition of the present invention, the higher limit of preferred content
It is 50%, is 40%, be 38%, be 35%, be 33%, be 30%, be 28%, be 25%, be 23%, be 20%, is 18%,
It is 15%, is 13%, be 10%, be 8%, be 7%, be 6%, be 5%, is 3%.
Also, the compound represented by formula (N-1-1) is preferably represented from formula (N-1-1.1) to formula (N-1-1.14)
Compound group in the compound selected, the preferably compound represented by formula (N-1-1.1)~(N-1-1.4), preferably formula
And the compound represented by formula (N-1-1.3) (N-1-1.1).
[chemical formula 37]
Compound represented by formula (N-1-1.1)~(N-1-1.4) may be used alone, can also be used in combination, but single
Only or these compound phases are that 5 mass % (below, will for the lower limit of the preferred content of the total amount of the composition of the present invention
Quality % is referred to as %), it is 10%, is 13%, be 15%, be 17%, be 20%, be 23%, be 25%, is 27%, is
30%, it is 33%, is 35%.Relative to the total amount of the composition of the present invention, the higher limit of preferred content is 50%, is 40%,
It is 38%, is 35%, be 33%, be 30%, be 28%, be 25%, be 23%, be 20%, be 18%, be 15%, is 13%,
It is 10%, is 8%, be 7%, be 6%, be 5%, is 3%.
Compound represented by formula (N-1-2) is following compounds.
[chemical formula 38]
(in formula, RN121And RN122Separately represent and the R in formula (N-1)N11And RN12Identical is looked like.)
RN121The alkenyl that the alkyl or carbon number that preferably carbon number is 1~5 are 2~5, and preferably ethyl,
Propyl group, butyl or amyl group.RN122The alkenyl or carbon that alkyl that preferably carbon number is 1~5, carbon number are 4~5 are former
Subnumber is 1~4 alkoxy, and preferably methyl, propyl group, methoxyl group, ethyoxyl or propoxyl group.
Compound represented by formula (N-1-2) can be used alone, but it is also possible to combine two or more compound to make
With.The species for the compound that can be combined is not particularly limited, but will according to the dissolubility of low temperature, transition temperature, electric reliability,
Performance desired by birefringence etc. carrys out appropriately combined use.For the species of used compound, such as the present invention's
One embodiment is a kind, is 2 kinds, is 3 kinds, is 4 kinds, is more than 5 kinds.
Pay attention to Δ ε improvement in the case of, be preferably content is set as it is higher, pay attention to low temperature under it is deliquescent
In the case of, if content is set as less, effect is good, is paying attention to TNIIn the case of, if content is set as it is more,
Effect is good.Also, in the case where being improved to the vestige that drips, ghost characteristic, preferably by the range set of content in centre.
It is for the lower limit of the preferred content of the total amount of the composition of the present invention by the compound phase of formula (N-1-2) expression
5 mass % (following, quality % is referred to as into %), are 7%, are 10%, be 13%, be 15%, be 17%, be 20%, be
23%, it is 25%, is 27%, be 30%, be 33%, be 35%, be 37%, be 40%, is 42%.Relative to the group of the present invention
The total amount of compound, the higher limit of preferred content is 50%, is 48%, is 45%, is 43%, is 40%, is 38%, is 35%,
It is 33%, is 30%, be 28%, be 25%, be 23%, be 20%, be 18%, be 15%, be 13%, be 10%, is 8%,
It is 7%, is 6%, is 5%.
Also, the compound represented by formula (N-1-2) is preferably represented from formula (N-1-2.1) to formula (N-1-2.13)
Compound group in the compound selected, preferably formula (N-1-2.3) to formula (N-1-2.7), formula (N-1-2.10), formula (N-1-
2.11) and the compound represented by formula (N-1-2.13), in the case where paying attention to Δ ε improvement, preferably formula (N-1-2.3) is extremely
Compound represented by formula (N-1-2.7), is paying attention to TNIImprovement in the case of, preferably formula (N-1-2.10), formula (N-1-
2.11) with the compound represented by formula (N-1-2.13).
[chemical formula 39]
Compound represented by formula (N-1-2.1) to formula (N-1-2.13) may be used alone, can also be used in combination, but
Individually or these compound phases for the lower limit of the preferred content of the total amount of the composition of the present invention be 5 mass % (it is following,
Quality % is referred to as %), it is 10%, is 13%, be 15%, be 17%, be 20%, be 23%, be 25%, is 27%, is
30%, it is 33%, is 35%.Relative to the total amount of the composition of the present invention, the higher limit of preferred content is 50%, is 40%,
It is 38%, is 35%, be 33%, be 30%, be 28%, be 25%, be 23%, be 20%, be 18%, be 15%, is 13%,
It is 10%, is 8%, be 7%, be 6%, be 5%, is 3%.
Compound represented by formula (N-1-3) is following compounds.
[chemical formula 40]
(in formula, RN131And RN132Separately represent and the R in formula (N-1)N11And RN12Identical is looked like.)
RN131The alkenyl that the alkyl or carbon number that preferably carbon number is 1~5 are 2~5, and preferably ethyl,
Propyl group or butyl.RN132Alkenyl or carbon number that alkyl that preferably carbon number is 1~5, carbon number are 4~5
For 1~4 alkoxy, and preferably ethyoxyl, propoxyl group or butoxy.
Compound represented by formula (N-1-3) can be used alone, but it is also possible to combine two or more compound to make
With.The species for the compound that can be combined is not particularly limited, but will according to the dissolubility of low temperature, transition temperature, electric reliability,
Performance desired by birefringence etc. carrys out appropriately combined use.For the species of used compound, such as the present invention's
One embodiment is a kind, is 2 kinds, is 3 kinds, is 4 kinds, is more than 5 kinds.
In the case where paying attention to Δ ε improvement, content is preferably set as to higher, the deliquescent feelings in the case where paying attention to low temperature
Under condition, if content is set as more, effect is good, is paying attention to TNIIn the case of, if content is set as more, imitate
It is really good.Also, in the case where being improved to the vestige that drips, ghost characteristic, preferably by the range set of content in centre.
It is for the lower limit of the preferred content of the total amount of the composition of the present invention by the compound phase of formula (N-1-3) expression
5 mass % (following, quality % is referred to as into %), are 10%, are 13%, be 15%, be 17%, be 20%.Relative to this hair
The total amount of bright composition, the higher limit of preferred content is 35%, is 30%, is 28%, is 25%, is 23%, is 20%, is
18%, it is 15%, is 13%.
Also, the compound represented by formula (N-1-3) is preferably represented from formula (N-1-3.1) to formula (N-1-3.11)
Compound group in the compound selected, the preferably compound represented by formula (N-1-3.1)~(N-1-3.7), preferably formula
(N-1-3.1), the compound represented by formula (N-1-3.2), formula (N-1-3.3), formula (N-1-3.4) and formula (N-1-3.6).
[chemical formula 41]
Compound represented by formula (N-1-3.1)~formula (N-1-3.4) and formula (N-1-3.6) can be used alone, and also may be used
With using combination, but it is preferably from the combination of formula (N-1-3.1) and formula (N-1-3.2), from formula (N-1-3.3), formula (N-1-3.4)
With 2 kinds or 3 kinds of the combination selected in formula (N-1-3.6).Composition of independent or these compound phases for the present invention
Total amount preferred content lower limit be 5 mass % (it is following, quality % is referred to as %.), it is 10%, is 13%, is
15%, it is 17%, is 20%.Relative to the total amount of the composition of the present invention, the higher limit of preferred content is 35%, is 30%,
It is 28%, is 25%, be 23%, be 20%, be 18%, be 15%, is 13%.
Compound represented by formula (N-1-4) is following compounds.
[chemical formula 42]
(in formula, RN141And RN142Separately represent and the R in formula (N-1)N11And RN12Identical is looked like.)
RN141And RN142Independently, alkenyl that preferably carbon number is 1~5 alkyl, carbon number are 4~5 or
Carbon number is 1~4 alkoxy, and preferably methyl, propyl group, ethyoxyl or butoxy.
Compound represented by formula (N-1-4) can be used alone, but it is also possible to combine two or more compound to make
With.The species for the compound that can be combined is not particularly limited, but will according to the dissolubility of low temperature, transition temperature, electric reliability,
Performance desired by birefringence etc. carrys out appropriately combined use.For the species of used compound, such as the present invention's
One embodiment is a kind, is 2 kinds, is 3 kinds, is 4 kinds, is more than 5 kinds.
In the case where paying attention to Δ ε improvement, content is preferably set as to higher, the deliquescent feelings in the case where paying attention to low temperature
Under condition, if content is set as more, effect is good, is paying attention to TNIIn the case of, if content is set as less, imitate
It is really good.Also, in the case where being improved to the vestige that drips, ghost characteristic, preferably by the range set of content in centre.
It is for the lower limit of the preferred content of the total amount of the composition of the present invention by the compound phase of formula (N-1-4) expression
3 mass % (following, quality % is referred to as into %), are 5%, are 7%, be 10%, be 13%, be 15%, be 17%, be
20%.For the total amount of the composition of the present invention, the higher limit of preferred content is mutually 35%, is 30%, is 28%, is 25%,
It is 23%, is 20%, be 18%, be 15%, be 13%, be 11%, be 10%, is 8%.
Also, the compound represented by formula (N-1-4) is preferably represented from formula (N-1-4.1) to formula (N-1-4.14)
Compound group in the compound selected, the preferably compound represented by formula (N-1-4.1)~(N-1-4.4), preferably formula
And the compound represented by formula (N-1-4.2) (N-1-4.1).
[chemical formula 43]
Compound represented by formula (N-1-4.1)~(N-1-4.4) may be used alone, can also be used in combination, but single
Only or these compound phases are that 3 mass % (below, will for the lower limit of the preferred content of the total amount of the composition of the present invention
Quality % is referred to as %), it is 5%, is 7%, be 10%, be 13%, be 15%, be 17%, is 20%.Relative to the present invention's
The total amount of composition, the higher limit of preferred content is 35%, is 30%, is 28%, is 25%, is 23%, is 20%, is
18%, it is 15%, is 13%, be 11%, be 10%, is 8%.
Compound represented by formula (N-1-5) is following compounds.
[chemical formula 44]
(in formula, RN151And RN152Separately represent and the R in formula (N-1)N11And RN12Identical is looked like.)
RN151And RN152Independently, alkenyl that preferably carbon number is 1~5 alkyl, carbon number are 4~5 or
Carbon number is 1~4 alkoxy, and preferably ethyl, propyl group or butyl.
Compound represented by formula (N-1-5) can be used alone, but it is also possible to combine two or more compound to make
With.The species for the compound that can be combined is not particularly limited, but will according to the dissolubility of low temperature, transition temperature, electric reliability,
Performance desired by birefringence etc. carrys out appropriately combined use.For the species of used compound, such as the present invention's
One embodiment is a kind, is 2 kinds, is 3 kinds, is 4 kinds, is more than 5 kinds.
In the case where paying attention to Δ ε improvement, content is preferably set as to higher, the deliquescent feelings in the case where paying attention to low temperature
Under condition, if content is set as less, effect is good, is paying attention to TNIIn the case of, if content is set as more, imitate
It is really good.Also, in the case where being improved to the vestige that drips, ghost characteristic, preferably by the range set of content in centre.
It is for the lower limit of the preferred content of the total amount of the composition of the present invention by the compound phase of formula (N-1-5) expression
5 mass % (following, quality % is referred to as into %), are 8%, are 10%, be 13%, be 15%, be 17%, be 20%.Relatively
In the total amount of the composition of the present invention, the higher limit of preferred content is 35%, is 33%, is 30%, is 28%, is 25%, is
23%, it is 20%, is 18%, be 15%, is 13%.
Also, the compound represented by formula (N-1-5) is preferably represented from formula (N-1-5.1) to formula (N-1-5.6)
Compound group in the compound selected, the preferably compound represented by formula (N-1-3.2) and formula (N-1-3.4).
[chemical formula 45]
(N-1-3.2 and the compound represented by formula (N-1-3.4) may be used alone, can also be used in combination formula, but single
Only or these compound phases are that 5 mass % (below, will for the lower limit of the preferred content of the total amount of the composition of the present invention
Quality % is referred to as %), it is 8%, is 10%, be 13%, be 15%, be 17%, is 20%.Relative to the composition of the present invention
Total amount, the higher limit of preferred content is 35%, is 33%, is 30%, is 28%, is 25%, is 23%, is 20%, is
18%, it is 15%, is 13%.
Compound represented by formula (N-1-10) is following compounds.
[chemical formula 46]
(in formula, RN1101And RN1102Separately represent and the R in formula (N-1)N11And RN12Identical is looked like.)
RN1101The alkenyl that the alkyl or carbon number that preferably carbon number is 1~5 are 2~5, and preferably ethyl,
Propyl group or butyl.RN1102Alkenyl or carbon number that alkyl that preferably carbon number is 1~5, carbon number are 4~5
For 1~4 alkoxy, and preferably ethyoxyl, propoxyl group or butoxy.
Compound represented by formula (N-1-10) can be used alone, but it is also possible to combine two or more compound to make
With.The species for the compound that can be combined is not particularly limited, but will according to the dissolubility of low temperature, transition temperature, electric reliability,
Performance desired by birefringence etc. carrys out appropriately combined use.For the species of used compound, such as the present invention's
One embodiment is a kind, is 2 kinds, is 3 kinds, is 4 kinds, is more than 5 kinds.
In the case where paying attention to Δ ε improvement, content is preferably set as to higher, the deliquescent feelings in the case where paying attention to low temperature
Under condition, if content is set as more, effect is good, is paying attention to TNIIn the case of, if content is set as more, imitate
It is really good.Also, in the case where being improved to the vestige that drips, ghost characteristic, preferably by the range set of content in centre.
By formula (N-1-10) represent compound phase for the present invention composition total amount preferred content lower limit
It is 5 mass % (following, quality % is referred to as %), is 10%, is 13%, be 15%, be 17%, be 20%.Relative to this
The total amount of the composition of invention, the higher limit of preferred content is 35%, is 30%, is 28%, is 25%, is 23%, is 20%,
It is 18%, is 15%, is 13%.
Also, the compound represented by formula (N-1-10) is preferably from formula (N-1-10.1) to formula (N-1-10.11) institute
Compound represented by the compound selected in the compound group of expression, preferably formula (N-1-10.1)~(N-1-10.5), it is excellent
Elect formula (N-1-10.1) and the compound represented by formula (N-1-10.2) as.
[chemical formula 47]
Compound represented by formula (N-1-10.1) and formula (N-1-10.2) may be used alone, can also be used in combination,
But individually or these compound phases for the present invention composition total amount preferred content lower limit be 5 mass % (with
Under, quality % is referred to as %), it is 10%, is 13%, be 15%, be 17%, is 20%.Relative to the composition of the present invention
Total amount, the higher limit of preferred content is 35%, is 30%, is 28%, is 25%, is 23%, is 20%, is 18%, is
15%, it is 13%.
Compound represented by formula (N-1-11) is following compounds.
[chemical formula 48]
(in formula, RN1111And RN1112Separately represent and the R in formula (N-1)N11And RN12Identical is looked like.)
RN1111The alkenyl that the alkyl or carbon number that preferably carbon number is 1~5 are 2~5, and preferably ethyl,
Propyl group or butyl.RN1112Alkenyl or carbon number that alkyl that preferably carbon number is 1~5, carbon number are 4~5
For 1~4 alkoxy, and preferably ethyoxyl, propoxyl group or butoxy.
Compound represented by formula (N-1-11) can be used alone, but it is also possible to combine two or more compound to make
With.The species for the compound that can be combined is not particularly limited, but will according to the dissolubility of low temperature, transition temperature, electric reliability,
Performance desired by birefringence etc. carrys out appropriately combined use.For the species of used compound, such as the present invention's
One embodiment is a kind, is 2 kinds, is 3 kinds, is 4 kinds, is more than 5 kinds.
In the case where paying attention to Δ ε improvement, content is preferably set as to higher, the deliquescent feelings in the case where paying attention to low temperature
Under condition, if content is set as more, effect is good, is paying attention to TNIIn the case of, if content is set as more, imitate
It is really good.Also, in the case where being improved to the vestige that drips, ghost characteristic, preferably by the range set of content in centre.
By formula (N-1-11) represent compound phase for the present invention composition total amount preferred content lower limit
It is 5 mass % (following, quality % is referred to as %), is 10%, is 13%, be 15%, be 17%, be 20%.Relative to this
The total amount of the composition of invention, the higher limit of preferred content is 35%, is 30%, is 28%, is 25%, is 23%, is 20%,
It is 18%, is 15%, is 13%.
Also, the compound represented by formula (N-1-11) is preferably from formula (N-1-11.1) to formula (N-1-11.15) institute
Compound represented by the compound selected in the compound group of expression, preferably formula (N-1-11.1)~(N-1-11.15), it is excellent
Elect formula (N-1-11.2) and the compound represented by formula (N-1-11.4) as.
[chemical formula 49]
Formula (N-1-11.2 and the compound represented by formula (N-1-11.4) may be used alone, can also be used in combination, but
Individually or these compound phases for the lower limit of the preferred content of the total amount of the composition of the present invention be 5 mass % (it is following,
Quality % is referred to as %), it is 10%, is 13%, be 15%, be 17%, is 20%.It is total relative to composition of the invention
Amount, the higher limit of preferred content is 35%, is 30%, is 28%, is 25%, is 23%, is 20%, is 18%, is 15%, is
13%.
Compound represented by formula (N-1-12) is following compounds.
[chemical formula 50]
(in formula, RN1121And RN1122Separately represent and the R in formula (N-1)N11And RN12Identical is looked like.)
RN1121The alkenyl that the alkyl or carbon number that preferably carbon number is 1~5 are 2~5, and preferably ethyl,
Propyl group or butyl.RN1122Alkenyl or carbon number that alkyl that preferably carbon number is 1~5, carbon number are 4~5
For 1~4 alkoxy, and preferably ethyoxyl, propoxyl group or butoxy.
Compound represented by formula (N-1-12) can be used alone, but it is also possible to combine two or more compound to make
With.The species for the compound that can be combined is not particularly limited, but will according to the dissolubility of low temperature, transition temperature, electric reliability,
Performance desired by birefringence etc. carrys out appropriately combined use.For the species of used compound, such as the present invention's
One embodiment is a kind, is 2 kinds, is 3 kinds, is 4 kinds, is more than 5 kinds.
In the case where paying attention to Δ ε improvement, content is preferably set as to higher, the deliquescent feelings in the case where paying attention to low temperature
Under condition, if content is set as more, effect is good, is paying attention to TNIIn the case of, if content is set as more, imitate
It is really good.Also, in the case where being improved to the vestige that drips, ghost characteristic, preferably by the range set of content in centre.
By formula (N-1-12) represent compound phase for the present invention composition total amount preferred content lower limit
It is 5 mass % (following, quality % is referred to as %), is 10%, is 13%, be 15%, be 17%, be 20%.Relative to this
The total amount of the composition of invention, the higher limit of preferred content is 35%, is 30%, is 28%, is 25%, is 23%, is 20%,
It is 18%, is 15%, is 13%.
Compound represented by formula (N-1-13) is following compounds.
[chemical formula 51]
(in formula, RN1131And RN1132Separately represent and the R in formula (N-1)N11And RN12Identical is looked like.)
RN1131The alkenyl that the alkyl or carbon number that preferably carbon number is 1~5 are 2~5, and preferably ethyl,
Propyl group or butyl.RN1132Alkenyl or carbon number that alkyl that preferably carbon number is 1~5, carbon number are 4~5
For 1~4 alkoxy, and preferably ethyoxyl, propoxyl group or butoxy.
Compound represented by formula (N-1-13) can be used alone, but it is also possible to combine two or more compound to make
With.The species for the compound that can be combined is not particularly limited, but will according to the dissolubility of low temperature, transition temperature, electric reliability,
Performance desired by birefringence etc. carrys out appropriately combined use.For the species of used compound, such as the present invention's
One embodiment is a kind, is 2 kinds, is 3 kinds, is 4 kinds, is more than 5 kinds.
In the case where paying attention to Δ ε improvement, content is preferably set as to higher, the deliquescent feelings in the case where paying attention to low temperature
Under condition, if content is set as more, effect is good, is paying attention to TNIIn the case of, if content is set as more, imitate
It is really good.Also, in the case where being improved to the vestige that drips, ghost characteristic, preferably by the range set of content in centre.
By formula (N-1-13) represent compound phase for the present invention composition total amount preferred content lower limit
It is 5 mass % (following, quality % is referred to as %), is 10%, is 13%, be 15%, be 17%, be 20%.Relative to this
The total amount of the composition of invention, the higher limit of preferred content is 35%, is 30%, is 28%, is 25%, is 23%, is 20%,
It is 18%, is 15%, is 13%.
Compound represented by formula (N-1-14) is following compounds.
[chemical formula 52]
(in formula, RN1141And RN1142Separately represent and the R in formula (N-1)N11And RN12Identical is looked like.)
RN1141The alkenyl that the alkyl or carbon number that preferably carbon number is 1~5 are 2~5, and preferably ethyl,
Propyl group or butyl.RN1142Alkenyl or carbon number that alkyl that preferably carbon number is 1~5, carbon number are 4~5
For 1~4 alkoxy, and preferably ethyoxyl, propoxyl group or butoxy.
Compound represented by formula (N-1-14) can be used alone, but it is also possible to combine two or more compound to make
With.The species for the compound that can be combined is not particularly limited, but will according to the dissolubility of low temperature, transition temperature, electric reliability,
Performance desired by birefringence etc. carrys out appropriately combined use.For the species of used compound, such as the present invention's
One embodiment is a kind, is 2 kinds, is 3 kinds, is 4 kinds, is more than 5 kinds.
In the case where paying attention to Δ ε improvement, content is preferably set as to higher, the deliquescent feelings in the case where paying attention to low temperature
Under condition, if content is set as more, effect is good, is paying attention to TNIIn the case of, if content is set as more, imitate
It is really good.Also, in the case where being improved to the vestige that drips, ghost characteristic, preferably by the range set of content in centre.
By formula (N-1-14) represent compound phase for the present invention composition total amount preferred content lower limit
It is 5 mass % (following, quality % is referred to as %), is 10%, is 13%, be 15%, be 17%, be 20%.Relative to this
The total amount of the composition of invention, the higher limit of preferred content is 35%, is 30%, is 28%, is 25%, is 23%, is 20%,
It is 18%, is 15%, is 13%.
Compound represented by formula (N-1-15) is following compounds.
[chemical formula 53]
(in formula, RN1151And RN1152Separately represent and the R in formula (N-1)N11And RN12Identical is looked like.)
RN1151The alkenyl that the alkyl or carbon number that preferably carbon number is 1~5 are 2~5, and preferably ethyl,
Propyl group or butyl.RN1152Alkenyl or carbon number that alkyl that preferably carbon number is 1~5, carbon number are 4~5
For 1~4 alkoxy, and preferably ethyoxyl, propoxyl group or butoxy.
Compound represented by formula (N-1-15) can be used alone, but it is also possible to combine two or more compound to make
With.The species for the compound that can be combined is not particularly limited, but will according to the dissolubility of low temperature, transition temperature, electric reliability,
Performance desired by birefringence etc. carrys out appropriately combined use.For the species of used compound, such as the present invention's
One embodiment is a kind, is 2 kinds, is 3 kinds, is 4 kinds, is more than 5 kinds.
In the case where paying attention to Δ ε improvement, content is preferably set as to higher, the deliquescent feelings in the case where paying attention to low temperature
Under condition, if content is set as more, effect is good, is paying attention to TNIIn the case of, if content is set as more, imitate
It is really good.Also, in the case where being improved to the vestige that drips, ghost characteristic, preferably by the range set of content in centre.
By formula (N-1-15) represent compound phase for the present invention composition total amount preferred content lower limit
It is 5 mass % (following, quality % is referred to as %), is 10%, is 13%, be 15%, be 17%, be 20%.Relative to this
The total amount of the composition of invention, the higher limit of preferred content is 35%, is 30%, is 28%, is 25%, is 23%, is 20%,
It is 18%, is 15%, is 13%.
Compound represented by formula (N-1-16) is following compounds.
[chemical formula 54]
(in formula, RN1161And RN1162Separately represent and the R in formula (N-1)N11And RN12Identical is looked like.)
RN1161The alkenyl that the alkyl or carbon number that preferably carbon number is 1~5 are 2~5, and preferably ethyl,
Propyl group or butyl.RN1162Alkenyl or carbon number that alkyl that preferably carbon number is 1~5, carbon number are 4~5
For 1~4 alkoxy, and preferably ethyoxyl, propoxyl group or butoxy.
Compound represented by formula (N-1-16) can be used alone, but it is also possible to combine two or more compound to make
With.The species for the compound that can be combined is not particularly limited, but will according to the dissolubility of low temperature, transition temperature, electric reliability,
Performance desired by birefringence etc. carrys out appropriately combined use.For the species of used compound, such as the present invention's
One embodiment is a kind, is 2 kinds, is 3 kinds, is 4 kinds, is more than 5 kinds.
In the case where paying attention to Δ ε improvement, content is preferably set as to higher, the deliquescent feelings in the case where paying attention to low temperature
Under condition, if content is set as more, effect is good, is paying attention to TNIIn the case of, if content is set as more, imitate
It is really good.Also, in the case where being improved to the vestige that drips, ghost characteristic, preferably by the range set of content in centre.
By formula (N-1-16) represent compound phase for the present invention composition total amount preferred content lower limit
It is 5 mass % (following, quality % is referred to as %), is 10%, is 13%, be 15%, be 17%, be 20%.Relative to this
The total amount of the composition of invention, the higher limit of preferred content is 35%, is 30%, is 28%, is 25%, is 23%, is 20%,
It is 18%, is 15%, is 13%.
Compound represented by formula (N-1-17) is following compounds.
[chemical formula 55]
(in formula, RN1171And RN1172Separately represent and the R in formula (N-1)N11And RN12Identical is looked like.)
RN1171The alkenyl that the alkyl or carbon number that preferably carbon number is 1~5 are 2~5, and preferably ethyl,
Propyl group or butyl.RN1172Alkenyl or carbon number that alkyl that preferably carbon number is 1~5, carbon number are 4~5
For 1~4 alkoxy, and preferably ethyoxyl, propoxyl group or butoxy.
Compound represented by formula (N-1-17) can be used alone, but it is also possible to combine two or more compound to make
With.The species for the compound that can be combined is not particularly limited, but will according to the dissolubility of low temperature, transition temperature, electric reliability,
Performance desired by birefringence etc. carrys out appropriately combined use.For the species of used compound, such as the present invention's
One embodiment is a kind, is 2 kinds, is 3 kinds, is 4 kinds, is more than 5 kinds.
In the case where paying attention to Δ ε improvement, content is preferably set as to higher, the deliquescent feelings in the case where paying attention to low temperature
Under condition, if content is set as more, effect is good, is paying attention to TNIIn the case of, if content is set as more, imitate
It is really good.Also, in the case where being improved to the vestige that drips, ghost characteristic, preferably by the range set of content in centre.
By formula (N-1-17) represent compound phase for the present invention composition total amount preferred content lower limit
It is 5 mass % (following, quality % is referred to as %), is 10%, is 13%, be 15%, be 17%, be 20%.Relative to this
The total amount of the composition of invention, the higher limit of preferred content is 35%, is 30%, is 28%, is 25%, is 23%, is 20%,
It is 18%, is 15%, is 13%.
Compound represented by formula (N-1-18) is following compounds.
[chemical formula 56]
(in formula, RN1181And RN1182Separately represent and the R in formula (N)N11And RN12Identical is looked like.)
RN1181The alkenyl that the alkyl or carbon number that preferably carbon number is 1~5 are 2~5, and preferably ethyl,
Propyl group or butyl.RN1182Alkenyl or carbon number that alkyl that preferably carbon number is 1~5, carbon number are 4~5
For 1~4 alkoxy, preferably ethyoxyl, propoxyl group or butoxy.
Compound represented by formula (N-1-18) can be used alone, but it is also possible to combine two or more compound to make
With.The species for the compound that can be combined is not particularly limited, but will according to the dissolubility of low temperature, transition temperature, electric reliability,
Performance desired by birefringence etc. carrys out appropriately combined use.For the species of used compound, such as the present invention's
One embodiment is a kind, is 2 kinds, is 3 kinds, is 4 kinds, is more than 5 kinds.
In the case where paying attention to Δ ε improvement, content is preferably set as to higher, the deliquescent feelings in the case where paying attention to low temperature
Under condition, if content is set as more, effect is good, is paying attention to TNIIn the case of, if content is set as more, imitate
It is really good.Also, in the case where being improved to the vestige that drips, ghost characteristic, preferably by the range set of content in centre.
By formula (N-1-18) represent compound phase for the present invention composition total amount preferred content lower limit
It is 5 mass % (following, quality % is referred to as %), is 10%, is 13%, be 15%, be 17%, be 20%.Relative to this
The total amount of the composition of invention, the higher limit of preferred content is 35%, is 30%, is 28%, is 25%, is 23%, is 20%,
It is 18%, is 15%, is 13%.
Compound represented by formula (N-1-20) is following compounds.
[chemical formula 57]
(in formula, RN1201And RN1202Separately represent and the R in formula (N)N11And RN12Identical is looked like.)
Compound represented by formula (N-1-21) is following compounds.
[chemical formula 58]
(in formula, RN1211And RN1212Separately represent and the R in formula (N-1)N11And RN12Identical is looked like.)
Compound represented by formula (N-2) is preferably from the compound group represented by formula (N-2-1)~(N-2-3)
The compound selected.
Compound represented by formula (N-2-1) is following compounds.
[chemical formula 59]
(in formula, RN211And RN212Separately represent and the R in formula (N-2)N21And RN22Identical is looked like.)
Compound represented by formula (N-2-2) is following compounds.
[chemical formula 60]
(in formula, RN221And RN222Separately represent and the R in formula (N-2)N21And RN22Identical is looked like.)
Compound represented by formula (N-2-3) is following compounds.
[chemical formula 61]
(in formula, RN231And RN232Separately represent and the R in formula (N-3)N31And RN32Identical is looked like.)
Compound represented by formula (N-3) is preferably from the compound group represented by formula (N-3-1)~(N-3-2)
The compound selected.
Compound represented by formula (N-3-1) is following compounds.
[chemical formula 62]
(in formula, RN311And RN312Separately represent and the R in formula (N-1)N11And RN12Identical is looked like.)
Compound represented by formula (N-3-2) is following compounds.
[chemical formula 63]
(in formula, RN321And RN322Separately represent and the R in formula (N-1)N11And RN12Identical is looked like.)
The compound phase represented by formula (N-1), formula (N-2) and formula (N-3) is for the total of the composition of the present invention
The total content for measuring (total amount of the liquid-crystal compounds included in liquid-crystal composition) is preferably 10~90 mass percentages, further excellent
Elect 20~80 mass %, more preferably more preferably 20~70 mass %, 20~60 mass % as, further preferably
For 20~55 mass %, particularly preferably more preferably 25~55 mass %, 30~55 mass %.
Contain more particularly, for the total of compound represented by formula (N-1), formula (N-2) and formula (N-3)
Amount, as lower limit in the composition, preferably comprises more than 1 mass % (following, quality % is referred to as into %), preferably comprises
More than 5%, more than 10% is preferably comprised, more than 13% is preferably comprised, more than 15% is preferably comprised, more than 18% is preferably comprised,
More than 20% is preferably comprised, more than 23% is preferably comprised, more than 25% is preferably comprised, more than 28% is preferably comprised, preferably comprised
More than 30%, more than 33% is preferably comprised, more than 35% is preferably comprised, more than 38% is preferably comprised, more than 40% is preferably comprised.
In addition, as higher limit, preferably comprising less than 95%, less than 90% is preferably comprised, less than 88% is preferably comprised, preferably comprised
Less than 85%, less than 83% is preferably comprised, less than 80% is preferably comprised, less than 78% is preferably comprised, less than 75% is preferably comprised,
Less than 73% is preferably comprised, less than 70% is preferably comprised, less than 68% is preferably comprised, less than 65% is preferably comprised, preferably comprised
Less than 63%, less than 60% is preferably comprised, less than 55% is preferably comprised, less than 50% is preferably comprised, less than 40% is preferably comprised.
The liquid-crystal composition of the present invention is preferably the compound that containing a kind or two or more is represented by formula (L).Formula
(L) compound of the compound equivalent to medium substantially neutrality represented by (Δ ε value is -2~2).
[chemical formula 64]
(in formula, RL1And RL2The alkyl that carbon number is 1~8 is separately represented, 1 in the alkyl or not phase
Adjacent-the CH of more than 22- separately can be taken by-CH=CH- ,-C ≡ C- ,-O- ,-CO- ,-COO- or-OCO-
Generation,
nL10,1,2 or 3 are represented,
AL1、AL2And AL3Separately represent from
(a) 1,4- cyclohexylidenes (1-CH present in the group2- or-the CH of non-conterminous more than 22- can also
It is substituted by-O-)；
(b) (the 1-CH=or-CH=of non-conterminous more than 2 present in the base can also be by for 1,4- phenylenes
It is substituted by-N=)；And
(c) naphthalene -2,6- diyls, 1,2,3,4- naphthane -2,6- diyls or decahydronaphthalene -2,6- diyls (naphthalene -2,6- diyls
Or the 1-CH=or-CH=of non-conterminous more than 2 present in 1,2,3,4- naphthane-2,6- diyls can be taken
On behalf of-N=)
The group selected in the group of composition, the group (a), group (b) and group (c) can be separately by cyanogen
Base, fluorine atom or chlorine atom substitution,
ZL1And ZL2Separately represent singly-bound ,-CH2CH2-、-(CH2)4-、-OCH2-、-CH2O-、-COO-、-OCO-、-
OCF2-、-CF2O- ,-CH=N-N=CH- ,-CH=CH- ,-CF=CF- or-C ≡ C-,
In nL1It is 2 or 3 and AL2Exist it is multiple in the case of, these can be with identical, can also be different, in nL1Be 2 or
3 and ZL3Exist it is multiple in the case of, these can be with identical, can also be different, but do not include by formula (N-1), formula (N-2) and
The compound that formula (N-3) is represented.)
Compound represented by formula (L) can be used alone, but it is also possible to be applied in combination.The compound that can be combined
Species is not particularly limited, but will according to desired by the dissolubility of low temperature, transition temperature, electric reliability, birefringence etc. performance
Carry out appropriately combined use.For the species of used compound, such as it is a kind as an embodiment of the invention.Or
Person is 2 kinds, is 3 kinds, be 4 kinds, be 5 kinds, be 6 kinds, be 7 kinds, be 8 kinds, be 9 kinds, be in the other embodiment of the present invention
More than 10 kinds.
In the present compositions, the compound represented by formula (L) content need according to the dissolubility under low temperature,
Performance desired by transition temperature, electric reliability, birefringence, processing compatibility, the vestige that drips, ghost, dielectric anisotropy etc.
Suitably adjust.
It is for the lower limit of the preferred content of the total amount of the liquid-crystal composition of the present invention by the compound phase of formula (L) expression
1 mass % (following, quality % is referred to as into %), is 10%, is 20%, be 30%, be 40%, be 50%, be 55%, be
60%, it is 65%, is 70%, be 75%, is 80%.The higher limit of preferred content is 95%, is 85%, is 75%, is 65%,
It is 55%, is 45%, be 35%, is 25%.
By the present invention composition viscosity remain it is relatively low, it is necessary to fast response time composition in the case of, it is excellent
Select the lower limit high and higher limit is high.Also, it is higher, it is necessary to temperature stabilization the Tni of the composition of the present invention is remained
Property good composition in the case of, preferably described lower limit is high and higher limit is high.In addition, in order to driving voltage is remained
When relatively low and hope increases dielectric anisotropy, preferably the lower limit is reduced and higher limit is low.
In the case where paying attention to reliability, preferably RL1And RL2All it is alkyl, is paying attention to volatile feelings of reduction compound
Under condition, preferably alkoxy is being paid attention in the case that viscosity declines, preferably at least a side is alkenyl.
In RL1And RL2In the case that the ring structure being bonded is phenyl (aromatic series), RL1And RL2The preferably carbon of straight-chain
The alkenyl of alkyl, the alkoxy that the carbon number of straight-chain is 1~4 and carbon number 4~5 that atomicity is 1~5, in RL1With
RL2The ring structure being bonded is hexamethylene, pyrans and dioxanes etc. in the case of the ring structure of saturation, RL1And RL2It is preferably straight
The carbon number of alkyl, the alkoxy that the carbon number of straight-chain is 1~4 and straight-chain that the carbon number of chain is 1~5 is
2~5 alkenyl.In order that nematic phase is stabilized, preferably carbon atom and the oxygen atom in the case where there is oxygen atom is total
For less than 5, preferably straight-chain.
As alkenyl, preferably selected from the group represented by any formula of the formula (R1) into formula (R5).It is (black in various
Point represents the carbon atom in ring structure.)
[chemical formula 65]
nL1Be preferably 0 in the case where paying attention to response speed, in order to improve nematic ceiling temperature and it is preferred that 2 or 3,
In order to obtain their balance and it is preferred that 1.In addition, in order to meet the desired characteristic as composition, preferably by different value
Compound is combined.
AL1、AL2And AL3It is desirable that be preferably aromatic series in the case of increase Δ n, it is preferably to improve response speed
Aliphatic, is preferably separately to represent anti-form-1, the fluoro- Isosorbide-5-Nitrae-phenylene of 4- cyclohexylidenes, Isosorbide-5-Nitrae-phenylene, 2-, 3- are fluoro-
Bicyclic [2.2.2] octamethylene of the fluoro- 1,4- phenylenes of 1,4- phenylenes, 3,5- bis-, 1,4- cyclohexadienylidenes, 1,4-, piperidines -1,4-
Diyl, naphthalene -2,6- diyl, decahydronaphthalene -2,6- diyl or 1,2,3,4- naphthane -2,6- diyls, are more preferably represented following
Construction,
[chemical formula 66]
More preferably represent anti-form-1,4- cyclohexylidenes or 1,4- phenylenes.
ZL1And ZL2It is preferably singly-bound in the case where paying attention to response speed.
Compound represented by formula (L) is preferably what is selected from the compound group represented by formula (L-1)~(L-7)
Compound.
Compound represented by formula (L-1) is following compounds.
[chemical formula 67]
(in formula, RL11And RL12Separately represent and the R in formula (L)L1And RL2Identical is looked like.)
RL11And RL12The alkane that alkyl that the carbon number of preferably straight-chain is 1~5, the carbon number of straight-chain are 1~4
The carbon number of epoxide and straight-chain is 2~5 alkenyl.
Compound represented by formula (L-1) can be used alone, but it is also possible to combine two or more compound to use.
The species for the compound that can be combined is not particularly limited, but will be according to the dissolubility of low temperature, transition temperature, electric reliability, double
Performance desired by refractive index etc. carrys out appropriately combined use.For the species of used compound, such as of the invention one
Embodiment is a kind, is 2 kinds, is 3 kinds, is 4 kinds, is more than 5 kinds.
Relative to the total amount of the liquid-crystal composition of the present invention, the lower limit of preferred content be 1 mass % (it is following, by matter
Amount % is referred to as %) it is 2%, it is 3%, is 5%, be 7%, be 10%, be 15%, be 20%, be 25%, is 30%, is
35%, it is 40%, is 45%, be 50%, is 55%.Relative to the total amount of the composition of the present invention, the higher limit of preferred content
It is 95%, is 90%, be 85%, be 80%, be 75%, be 70%, be 65%, be 60%, be 55%, be 50%, is 45%,
It is 40%, is 35%, be 30%, is 25%.
By the present invention composition viscosity remain it is relatively low, it is necessary to fast response time composition in the case of, it is excellent
Select the lower limit high and higher limit is high.Also, it is higher, it is necessary to temperature stabilization the Tni of the composition of the present invention is remained
In the case of the good composition of property, preferably described lower limit is moderate and higher limit is moderate.In addition, in order to driving voltage is protected
Hold for it is relatively low wish increase dielectric anisotropy when, preferably described lower limit is low and higher limit is low.
Compound represented by formula (L-1) is preferably the change selected from the compound group represented by formula (L-1-1)
Compound.
[chemical formula 68]
(R in formulaL12Represent and the meaning equivalent in meaning in formula (L-1).)
Compound represented by formula (L-1-1) is preferably from the chemical combination represented by formula (L-1-1.1) to formula (L-1-1.3)
Compound represented by the compound selected in thing group, preferably formula (L-1-1.2) or formula (L-1-1.3), particularly preferably
Compound represented by formula (L-1-1.3).
[chemical formula 69]
Compound phase represented by formula (L-1-1.3) is for the preferred content of the total amount of the liquid-crystal composition of the present invention
Lower limit is that 1 mass % (following, quality % is referred to as into %) is 2%, is 3%, is 5%, be 7%, is 10%.Relative to this
The total amount of the composition of invention, the higher limit of preferred content is 20%, is 15%, is 13%, is 10%, is 8%, is 7%, is
6%, it is 5%, is 3%.
Compound represented by formula (L-1) is preferably the change selected from the compound group represented by formula (L-1-2)
Compound.
[chemical formula 70]
(R in formulaL12Represent and the meaning equivalent in meaning in formula (L-1).)
By formula (L-1-2) represent compound phase for the present invention liquid-crystal composition total amount preferred content lower limit
Value is 1 mass % (following, quality % is referred to as into %), is 5%, is 10%, be 15%, be 17%, be 20%, is 23%,
It is 25%, is 27%, be 30%, is 35%.Relative to the total amount of the composition of the present invention, the higher limit of preferred content is
60%, it is 55%, is 50%, be 45%, be 42%, be 40%, be 38%, be 35%, be 33%, is 30%.
Also, the compound represented by formula (L-1-2) is preferably represented from formula (L-1-2.1) to formula (L-1-2.4)
Compound group in the compound selected, the preferably compound represented by formula (L-1-2.2) to formula (L-1-2.4).Particularly,
Compound represented by formula (L-1-2.2) is obviously improved the response speed of the composition of the present invention, therefore preferably.In addition, wanting
When seeking the Tni higher than response speed, formula (L-1-2.3) or the compound represented by formula (L-1-2.4) are preferably used.In order to
Make the solubility under low temperature good, the content of the compound represented by formula (L-1-2.3) and formula (L-1-2.4) is set as 30 matter
% is measured above is undesirable.
[chemical formula 71]
The compound phase represented by formula (L-1-2.2) is under the preferred content of the total amount of the liquid-crystal composition of the present invention
Limit value is 10 mass % (following, quality % is referred to as into %), is 15%, is 18%, be 20%, be 23%, is 25%, is
27%, it is 30%, is 33%, be 35%, be 38%, is 40%.Relative to the total amount of the composition of the present invention, preferred content
Higher limit is 60%, is 55%, is 50%, is 45%, is 43%, is 40%, is 38%, is 35%, is 32%, is 30%,
It is 27%, is 25%, is 22%.
The compound phase represented by the compound of formula (L-1-1.3) expression and by formula (L-1-2.2) is for liquid of the invention
The lower limit of total preferred content of the total amount of crystal composite is 10 mass % (following, quality % is referred to as into %), is
15%, it is 20%, is 25%, be 27%, be 30%, be 35%, is 40%.It is excellent relative to the total amount of the composition of the present invention
The higher limit for selecting content is 60%, is 55%, is 50%, is 45%, is 43%, is 40%, is 38%, is 35%, is 32%,
It is 30%, is 27%, be 25%, is 22%.
Compound represented by formula (L-1) is preferably the change selected from the compound group represented by formula (L-1-3)
Compound.
[chemical formula 72]
(R in formulaL13And RL14Separately represent the alkane that alkyl or carbon number that carbon number is 1~8 are 1~8
Epoxide.)
RL13And RL14The alkane that alkyl that the carbon number of preferably straight-chain is 1~5, the carbon number of straight-chain are 1~4
The carbon number of epoxide and straight-chain is 2~5 alkenyl.
By formula (L-1-3) represent compound phase for the present invention liquid-crystal composition total amount preferred content lower limit
Value is 1 mass % (following, quality % is referred to as into %), is 5%, is 10%, be 13%, be 15%, be 17%, is 20%,
It is 23%, is 25%, is 30%.Relative to the total amount of the composition of the present invention, the higher limit of preferred content is 60%, is
55%, it is 50%, is 45%, be 40%, be 37%, be 35%, be 33%, be 30%, be 27%, be 25%, is 23%, is
20%, it is 17%, is 15%, be 13%, is 10%.
Also, the compound represented by formula (L-1-3) is preferably represented from formula (L-1-3.1) to formula (L-1-3.12)
Compound group in the compound selected, preferably represented by formula (L-1-3.1), formula (L-1-3.3) or formula (L-1-3.4)
Compound.Particularly, the compound represented by formula (L-1-3.1) significantly improves the response speed of the composition of the present invention, therefore
It is preferred that.In addition, when requiring the Tni higher than response speed, preferably using formula (L-1-3.3), formula (L-1-3.4), formula (L-1-
3.11) with the compound represented by formula (L-1-3.12).In order that the solubility under low temperature is good, by formula (L-1-3.3), formula
(L-1-3.4), total content of formula (L-1-3.11) and the compound represented by formula (L-1-3.12) be set as 20 mass % with
On be undesirable.
[chemical formula 73]
The compound phase represented by formula (L-1-3.1) is under the preferred content of the total amount of the liquid-crystal composition of the present invention
Limit value is 1 mass % (following, quality % is referred to as into %), is 2%, is 3%, be 5%, be 7%, be 10%, is 13%, is
15%, it is 18%, is 20%.Relative to the total amount of the composition of the present invention, the higher limit of preferred content is 20%, is 17%,
It is 15%, is 13%, be 10%, be 8%, be 7%, is 6%.
Compound represented by formula (L-1) is preferably from the compound represented by formula (L-1-4) and/or (L-1-5)
The compound selected in group.
[chemical formula 74]
(R in formulaL15And RL16Separately represent the alkane that alkyl or carbon number that carbon number is 1~8 are 1~8
Epoxide.)
RL15And RL16The alkane that alkyl that the carbon number of preferably straight-chain is 1~5, the carbon number of straight-chain are 1~4
The carbon number of epoxide and straight-chain is 2~5 alkenyl.
By formula (L-1-4) represent compound phase for the present invention liquid-crystal composition total amount preferred content lower limit
Value is 1 mass % (following, quality % is referred to as into %), is 5%, is 10%, be 13%, be 15%, be 17%, is 20%.
Relative to the total amount of the composition of the present invention, the higher limit of preferred content is 25%, is 23%, is 20%, is 17%, is
15%, it is 13%, is 10%.
By formula (L-1-5) represent compound phase for the present invention liquid-crystal composition total amount preferred content lower limit
Value is 1 mass % (following, quality % is referred to as into %), is 5%, is 10%, be 13%, be 15%, be 17%, is 20%.
Relative to the total amount of the composition of the present invention, the higher limit of preferred content is 25%, is 23%, is 20%, is 17%, is
15%, it is 13%, is 10%.
Also, formula (L-1-4) and the compound represented by (L-1-5) are preferably from formula (L-1-4.1) to formula (L-1-
5.3) change represented by the compound selected in the compound group represented by, preferably formula (L-1-4.2) or formula (L-1-5.2)
Compound.
[chemical formula 75]
The compound phase represented by formula (L-1-4.2) is under the preferred content of the total amount of the liquid-crystal composition of the present invention
Limit value is 1 mass % (following, quality % is referred to as into %), is 2%, is 3%, be 5%, be 7%, be 10%, is 13%, is
15%, it is 18%, is 20%.Relative to the total amount of the composition of the present invention, the higher limit of preferred content is 20%, is 17%,
It is 15%, is 13%, be 10%, be 8%, be 7%, is 6%.
It is preferred that will from formula (L-1-1.3), formula (L-1-2.2), formula (L-1-3.1), formula (L-1-3.3), formula (L-1-3.4),
Two or more compound combination selected in compound represented by formula (L-1-3.11) and formula (L-1-3.12), preferably will be from formula
(L-1-1.3), formula (L-1-2.2), formula (L-1-3.1), formula (L-1-3.3), formula (L-1-3.4) and formula (L-1-4.2) are represented
Compound in select two or more compound combination, relative to the present invention liquid-crystal composition total amount, these compounds
The lower limit of the preferred content of total content is 1 mass % (following, quality % is referred to as into %), is 2%, is 3%, is 5%,
It is 7%, is 10%, be 13%, be 15%, be 18%, be 20%, be 23%, be 25%, be 27%, be 30%, is 33%,
It is 35%, relative to the total amount of the composition of the present invention, higher limit is 80%, is 70%, is 60%, is 50%, is 45%, is
40%, it is 37%, is 35%, be 33%, be 30%, be 28%, be 25%, be 23%, is 20%.Pay attention to composition can
In the case of by property, preferably by from formula (L-1-3.1), formula (L-1-3.3) and formula (L-1-3.4)) represented by compound select
Two or more compound combination, pay attention to composition response speed in the case of, preferably will be from formula (L-1-1.3), formula (L-
Two or more compound combination that compound represented by 1-2.2) is selected.
Compound represented by formula (L-2) is following compounds.
[chemical formula 76]
(in formula, RL21And RL22Separately represent and the R in formula (L)L1And RL2Identical is looked like.)
RL21The alkenyl that the alkyl or carbon number that preferably carbon number is 1~5 are 2~5, RL22Preferably carbon atom
The alkoxy that the alkenyl or carbon number that alkyl that number is 1~5, carbon number are 4~5 are 1~4.
Compound represented by formula (L-1) can be used alone, but it is also possible to combine two or more compound to use.
The species for the compound that can be combined is not particularly limited, but will be according to the dissolubility of low temperature, transition temperature, electric reliability, double
Performance desired by refractive index etc. carrys out appropriately combined use.For the species of used compound, such as of the invention one
Embodiment is a kind, is 2 kinds, is 3 kinds, is 4 kinds, is more than 5 kinds.
In the case of deliquescent under paying attention to low temperature, if content is set as more, effect is good, on the contrary, in weight
In the case of depending on response speed, if content is set as less, effect is good.Also, dripped vestige, ghost characteristic in improvement
In the case of, preferably by the range set of content in centre.
By formula (L-2) represent compound phase for the present invention liquid-crystal composition total amount preferred content lower limit
It is that 1 mass % (following, quality % is referred to as into %) is 2%, is 3%, is 5%, be 7%, be 10%.Relative to the present invention's
The total amount of composition, the higher limit of preferred content is 20%, is 15%, is 13%, is 10%, is 8%, is 7%, is 6%, is
5%, it is 3%.
Also, the compound represented by formula (L-2) is preferably from the chemical combination represented by formula (L-2.1) to formula (L-2.6)
The compound selected in thing group, preferably formula (L-2.1), formula (L-2.3), formula (L-2.4) and the chemical combination represented by formula (L-2.6)
Thing.
[chemical formula 77]
Compound represented by formula (L-3) is following compounds.
[chemical formula 78]
(in formula, RL31And RL32Separately represent and the R in formula (L)L1And RL2Identical is looked like.)
RL31And RL32Independently, alkenyl that preferably carbon number is 1~5 alkyl, carbon number are 4~5 or
Carbon number is 1~4 alkoxy.
Compound represented by formula (L-3) can be used alone, but it is also possible to combine two or more compound to use.
The species for the compound that can be combined is not particularly limited, but will be according to the dissolubility of low temperature, transition temperature, electric reliability, double
Performance desired by refractive index etc. carrys out appropriately combined use.For the species of used compound, such as of the invention one
Embodiment is a kind, is 2 kinds, is 3 kinds, is 4 kinds, is more than 5 kinds.
By formula (L-3) represent compound phase for the present invention liquid-crystal composition total amount preferred content lower limit
It is 1 mass %, is 2%, be 3%, be 5%, be 7%, is 10%.Relative to the total amount of the composition of the present invention, preferred content
Higher limit be 20%, be 15%, be 13%, be 10%, be 8%, be 7%, be 6%, be 5%, be 3%.
In the case where obtaining high birefringence, if content is set as more, effect is good, on the contrary, paying attention to
In the case of high Tni, if content is set as less, effect is good.Also, change to the vestige that drips, ghost characteristic
In the case of good, preferably by the range set of content in centre.
Also, the compound represented by formula (L-3) is preferably from the chemical combination represented by formula (L-3.1) to formula (L-3.4)
Compound represented by the compound selected in thing group, preferably formula (L-3.2) to formula (L-3.7).
[chemical formula 79]
Compound represented by formula (L-4) is following compounds.
[chemical formula 80]
(in formula, RL41And RL42Separately represent and the R in formula (L)L1And RL2Identical is looked like.)
RL41The alkenyl that the alkyl or carbon number that preferably carbon number is 1~5 are 2~5, RL42Preferably carbon atom
The alkoxy that the alkenyl or carbon number that alkyl that number is 1~5, carbon number are 4~5 are 1~4.
Compound represented by formula (L-4) can be used alone, but it is also possible to combine two or more compound to use.
The species for the compound that can be combined is not particularly limited, but will be according to the dissolubility of low temperature, transition temperature, electric reliability, double
Performance desired by refractive index etc. carrys out appropriately combined use.For the species of used compound, such as of the invention one
Embodiment is a kind, is 2 kinds, is 3 kinds, is 4 kinds, is more than 5 kinds.
In the present compositions, the content of the compound represented by formula (L-4) is needed according to the dissolving under low temperature
Property, property desired by transition temperature, electric reliability, birefringence, processing compatibility, the vestige that drips, ghost, dielectric anisotropy etc.
Can suitably it adjust.
By formula (L-4) represent compound phase for the present invention liquid-crystal composition total amount preferred content lower limit
It is 1 mass % (following, quality % is referred to as %), is 2%, is 3%, be 5%, be 7%, be 10%, be 14%, be
16%, it is 20%, is 23%, be 26%, be 30%, be 35%, is 40%.Relative to the total amount of the composition of the present invention, formula
(L-4) higher limit of the preferred content of the compound represented by is 50%, is 40%, is 35%, is 30%, is 20%, is
15%, it is 10%, is 5%.
Compound represented by formula (L-4) is preferably the compound for example represented by formula (L-4.1) to formula (L-4.3).
[chemical formula 81]
The performance according to desired by the dissolubility under low temperature, transition temperature, electric reliability, birefringence etc., can contain formula
(L-4.1) compound represented by, can also contain formula (L-4.1) institute table containing the compound represented by formula (L-4.2)
Both compounds represented by compound and formula (L-4.2) shown, can also include whole formula (L-4.1) to formula (L-
4.3) compound represented by.Relative to the total amount of the composition of the present invention, represented by formula (L-4.1) or formula (L-4.2)
The lower limit of the preferred content of compound is 3%, is 5%, is 7%, is 9%, is 11%, is 12%, is 13%, is 18%,
It is 21%, higher limit preferably is 45, is 40%, is 35%, is 30%, is 25%, is 23%, is 20%, is 18%, is
15%, it is 13%, is 10%, is 8%.
In the case of containing both compounds represented by the compound represented by formula (L-4.1) and formula (L-4.2),
Relative to the total amount of the liquid-crystal composition of the present invention, the lower limit of the preferred content of two compounds be 15 mass % (it is following, by matter
Amount % is referred to as %), it is 19%, is 24%, be 30%, higher limit preferably is 45, is 40%, is 35%, is 30%, is
25%, it is 23%, is 20%, be 18%, be 15%, is 13%.
Compound represented by formula (L-4) is preferably the compound for example represented by formula (L-4.4) to formula (L-4.6),
Compound preferably represented by formula (L-4.4).
[chemical formula 82]
The performance according to desired by the dissolubility under low temperature, transition temperature, electric reliability, birefringence etc., can contain formula
(L-4.4) compound represented by, can also can also contain formula (L-4.4) institute containing the compound represented by formula (L-4.5)
Both compounds represented by the compound and formula (L-4.5) of expression.
The compound phase represented by formula (L-4.4) or formula (L-4.5) is for the total amount of the liquid-crystal composition of the present invention
The lower limit of preferred content is 3 mass % (following, quality % is referred to as into %), is 5%, is 7%, be 9%, is 11%, is
12%, it is 13%, is 18%, is 21%.It is preferred that higher limit be 45, be 40%, be 35%, be 30%, be 25%, be
23%, it is 20%, is 18%, be 15%, be 13%, be 10%, is 8%.
In the case of containing both compounds represented by the compound represented by formula (L-4.4) and formula (L-4.5),
Relative to the total amount of the liquid-crystal composition of the present invention, the lower limit of the preferred content of two compounds be 15 mass % (it is following, by matter
Amount % is referred to as %), it is 19%, is 24%, be 30%, higher limit preferably is 45, is 40%, is 35%, is 30%, is
25%, it is 23%, is 20%, be 18%, be 15%, is 13%.
Compound represented by formula (L-4) is preferably the compound represented by formula (L-4.7) to formula (L-4.10), especially
Compound preferably represented by formula (L-4.9).
[chemical formula 83]
Compound represented by formula (L-5) is following compounds.
[chemical formula 84]
(in formula, RL51And RL52Separately represent and the R in formula (L)L1And RL2Identical is looked like.)
RL51The alkenyl that the alkyl or carbon number that preferably carbon number is 1~5 are 2~5, RL52Preferably carbon atom
The alkoxy that the alkenyl or carbon number that alkyl that number is 1~5, carbon number are 4~5 are 1~4.
Compound represented by formula (L-5) can be used alone, but it is also possible to combine two or more compound to use.
The species for the compound that can be combined is not particularly limited, but will be according to the dissolubility of low temperature, transition temperature, electric reliability, double
Performance desired by refractive index etc. carrys out appropriately combined use.For the species of used compound, such as of the invention one
Embodiment is a kind, is 2 kinds, is 3 kinds, is 4 kinds, is more than 5 kinds.
In the present compositions, the content of the compound represented by formula (L-5) is needed according to the dissolving under low temperature
Property, property desired by transition temperature, electric reliability, birefringence, processing compatibility, the vestige that drips, ghost, dielectric anisotropy etc.
Can suitably it adjust.
Relative to the total amount of the liquid-crystal composition of the present invention, the lower limit of the preferred content of the compound represented by formula (L-5)
Value is 1 mass % (following, quality % is referred to as into %), is 2%, is 3%, be 5%, be 7%, be 10%, is 14%, is
16%, it is 20%, is 23%, be 26%, be 30%, be 35%, is 40%.Relative to the total amount of the composition of the present invention, formula
(L-5) higher limit of the preferred content of the compound represented by is 50%, is 40%, is 35%, is 30%, is 20%, is
15%, it is 10%, is 5%.
Compound represented by formula (L-5) is preferably formula (L-5.1) or the compound represented by formula (L-5.2), special
Compound that You Xuanwei be represented by formula (L-5.1).
Relative to the total amount of the liquid-crystal composition of the present invention, the lower limit of the preferred content of these compounds is 1 mass %
(following, quality % is referred to as into %), is 2%, is 3%, be 5%, be 7%.The higher limit of the preferred content of these compounds
It is 20%, is 15%, be 13%, be 10%, is 9%.
[chemical formula 85]
Compound represented by formula (L-5) is preferably formula (L-5.3) or the compound represented by formula (L-5.4).
Relative to the total amount of the liquid-crystal composition of the present invention, the lower limit of the preferred content of these compounds is 1 mass %
(following, quality % is referred to as into %), is 2%, is 3%, be 5%, be 7%.The higher limit of the preferred content of these compounds
It is 20%, is 15%, be 13%, be 10%, is 9%.
[chemical formula 86]
Compound represented by formula (L-5) is preferably from the compound group represented by formula (L-5.5) to formula (L-5.7)
Compound represented by the compound selected, particularly preferably formula (L-5.7).
Relative to the total amount of the liquid-crystal composition of the present invention, the lower limit of the preferred content of these compounds is 1 mass %
(following, quality % is referred to as into %), is 2%, is 3%, be 5%, be 7%.The higher limit of the preferred content of these compounds
It is 20%, is 15%, be 13%, be 10%, is 9%.
[chemical formula 87]
Compound represented by formula (L-6) is following compounds.
[chemical formula 88]
(in formula, RL61And RL62Separately represent and the R in formula (L)L1And RL2Identical is looked like, XL61And XL62Point
Do not represent hydrogen atom or fluorine atom independently.)
RL61And RL62Independently, the alkenyl that the alkyl or carbon number that preferably carbon number is 1~5 are 2~5,
It is preferred that XL61And XL62In a side be fluorine atom and the opposing party is hydrogen atom.
Compound represented by formula (L-6) can be used alone, but it is also possible to combine two or more compound to use.
The species for the compound that can be combined is not particularly limited, but will be according to the dissolubility of low temperature, transition temperature, electric reliability, double
Performance desired by refractive index etc. carrys out appropriately combined use.For the species of used compound, such as of the invention one
Embodiment is a kind, is 2 kinds, is 3 kinds, is 4 kinds, is more than 5 kinds.
Relative to the total amount of the liquid-crystal composition of the present invention, the lower limit of the preferred content of the compound represented by formula (L-6)
Value is 1 mass % (following, quality % is referred to as into %), is 2%, is 3%, be 5%, be 7%, be 10%, is 14%, is
16%, it is 20%, is 23%, be 26%, be 30%, be 35%, is 40%.Relative to the total amount of the composition of the present invention, formula
(L-6) higher limit of the preferred content of the compound represented by is 50%, is 40%, is 35%, is 30%, is 20%, is
15%, it is 10%, is 5%.In the case where focusing on increase Δ n, preferably increase content, in the case where focusing on low temperature
In the case of precipitation, preferably reduce content.
Compound represented by formula (L-6) is preferably the compound represented by formula (L-6.1) to formula (L-6.9).
[chemical formula 89]
The species of compound to that can combine is not particularly limited, but preferably comprise in these compounds a kind~3
Kind, further preferably a kind~4 kinds.Also have for dissolubility further, since the molecular weight distribution of the compound of selection is wide
Effect, therefore preferably for example select a kind, from formula (L-6.4) or (L- from the compound represented by formula (L-6.1) or (L-6.2)
6.5) compound represented by selects a kind, a kind selected from the compound represented by formula (L-6.6) or formula (L-6.7), from formula
(L-6.8) it is or the compound represented by (L-6.9) selects a kind of compound, and they are appropriately combined.Among these, preferably
Include the compound represented by formula (L-6.1), formula (L-6.3), formula (L-6.4), formula (L-6.6) and formula (L-6.9).
Also, the compound represented by formula (L-6) is preferably represented by such as formula (L-6.10) to formula (L-6.17)
Compound, the among these compound preferably represented by formula (L-6.11).
[chemical formula 90]
Relative to the total amount of the liquid-crystal composition of the present invention, the lower limit of the preferred content of these compounds is 1 mass %
(following, quality % is referred to as into %), is 2%, is 3%, be 5%, be 7%.The higher limit of the preferred content of these compounds
It is 20%, is 15%, be 13%, be 10%, is 9%.
Compound represented by formula (L-7) is following compounds.
[chemical formula 91]
(in formula, RL71And RL72Separately represent and the R in formula (L)L1And RL2Identical is looked like, AL71And AL72Point
Do not represent independently and the A in formula (L)L2And AL3Identical is looked like, but AL71And AL72In hydrogen atom can also be independently
Ground is replaced by fluorine atoms, ZL71Represent the Z with formula (L)L2Identical is looked like, XL71And XL72Separately represent fluorine atom or
Person's hydrogen atom.)
In formula, RL71And RL72Independently, the alkenyl that preferably carbon number is 1~5 alkyl, carbon number are 2~5
Or the alkoxy that carbon number is 1~4, AL71And AL72Independently, preferably Isosorbide-5-Nitrae-cyclohexylidene or Isosorbide-5-Nitrae-phenylene,
AL71And AL72In hydrogen atom can separately be replaced by fluorine atoms, QL71Preferably singly-bound or COO-, are preferably single
Key, XL71And XL72Preferably hydrogen atom.
The species for the compound that can be combined is not particularly limited, but will can according to the dissolubility of low temperature, transition temperature, electricity
Combined by performance desired by property, birefringence etc..For the species of used compound, such as a reality of the invention
The mode of applying is a kind, is 2 kinds, is 3 kinds, is 4 kinds.
In the liquid-crystal composition of the present invention, the content of the compound represented by formula (L-7) is needed according under low temperature
Dissolubility, transition temperature, electric reliability, birefringence, processing compatibility, the vestige that drips, ghost, dielectric anisotropy etc. are wished
Performance come suitably adjust.
Relative to the total amount of the composition of the present invention, the lower limit of the preferred content of the compound represented by formula (L-7) is 1
Quality % (following, quality % is referred to as into %), is 2%, is 3%, be 5%, be 7%, be 10%, be 14%, be 16%, be
20%.Relative to the total amount of the composition of the present invention, the higher limit of the preferred content of the compound represented by formula (L-7) is
30%, it is 25%, is 23%, be 20%, be 18%, be 15%, be 10%, is 5%.
In the case where expecting embodiment of the composition of the present invention for high Tni, preferably make the change represented by formula (L-7)
The content of compound is more, in the case where expecting the embodiment of low viscosity, and it is less preferably to make content.
Also, the compound represented by formula (L-7) is preferably the compound represented by formula (L-7.1) to formula (L-7.4),
Compound preferably represented by formula (L-7.2).
[chemical formula 92]
Also, the compound represented by formula (L-7) is preferably the chemical combination represented by formula (L-7.11) to formula (L-7.13)
Compound represented by thing, preferably formula (L-7.11).
[chemical formula 93]
Also, the compound represented by formula (L-7) is the compound represented by formula (L-7.21) to formula (L-7.23).It is excellent
Elect the compound represented by formula (L-7.21) as.
[chemical formula 94]
Also, the compound represented by formula (L-7) is preferably the chemical combination represented by formula (L-7.31) to formula (L-7.34)
Compound represented by thing, preferably formula (L-7.31) or/and formula (L-7.32).
[chemical formula 95]
Also, the compound represented by formula (L-7) is preferably the chemical combination represented by formula (L-7.41) to formula (L-7.44)
Compound represented by thing, preferably formula (L-7.41) or/and formula (L-7.42).
[chemical formula 96]
Additive (antioxidant, UV absorbers etc.) in liquid-crystal composition involved in the present invention is preferably
The mass % of 100ppm~1.
Although the liquid-crystal composition of the present invention is that nematic phase-isotropic liquid phase transformation can be used in wider scope
Temperature (Tni), but nematic phase-isotropic liquid phase transition temperature (Tni) is preferably 60~120 DEG C, more preferably 70~100
DEG C, particularly preferably 70~85 DEG C.
The dielectric anisotropy Δ ε of the liquid-crystal composition of the present invention is preferably -2.0~-6.0 at 25 DEG C, more preferably -
2.5~-5.0, particularly preferably -2.5~-3.5.
The refractive anisotrop Δ n of the liquid-crystal composition of the present invention is preferably 0.08~0.13 at 25 DEG C, but more excellent
Elect 0.09~0.12 as.More it is described in detail, in the case of corresponding to thin cell gap, liquid-crystal composition of the invention
Refractive anisotrop is preferably 0.10~0.12 at 25 DEG C, is further described, corresponding to thin cell gap (unit
Gap is less than 3.4 μm) in the case of, preferably from about 0.9 to about 0.12 or so, corresponding to thick cell gap (cell gap
For more than 3.5 μm) in the case of, preferably from about 0.08 to about 0.1 or so.
The higher limit of the rotary viscosity (γ 1) of liquid-crystal composition involved in the present invention be preferably 150 (mPas) below,
Below, particularly preferably 120 (mPas) are below by more preferably 130 (mPas).On the other hand, the rotary viscosity (γ 1)
Lower limit is preferably more than 20 (mPas) more than more preferably 30 (mPas), more than more preferably 40 (mPas),
It is still more preferably more than 50 (mPas), much further preferably from more than 60 (mPas), particularly preferably 70 (mPa
S) more than.
In liquid-crystal composition involved in the present invention, the function of preferably rotary viscosity and refractive anisotrop is Z tables
Show specific value.
[mathematical expression 1]
(the Δ n) of Z=γ 1/2
(in the mathematical expression, γ1Rotary viscosity is represented, Δ n represents refractive anisotrop.)
Z is preferably less than 13000, more preferably less than 12000, particularly preferably less than 11000.
In the case where liquid-crystal composition involved in the present invention is used in active matrix display element, it is necessary to have 1011
Ratio resistance more than (Ω m), preferably 1012(Ω m), more preferably 1013More than (Ω m).
Although liquid-crystal composition involved in the present invention can use nematic phase-isotropic liquid phase in wide scope
Temperature (TNI), but the phase transition temperature (TNI) it is preferably 60~120 DEG C, more preferably 70~110 DEG C, particularly preferably 75~
100℃。
[manufacture methods of liquid crystal display cells]
Next, reference picture 1, illustrates the manufacture method of the liquid crystal display cells of the present invention.
There are the face of common electrode 14 and the formation of second substrate 12 to have pixel electrode 15 in the formation of first substrate 11
Face, aligning film material or polymerizable liquid crystal compound of the coating containing the polymerizable compound with polymerizable group, and lead to
Heating is crossed to form vertical alignment layer 16,17.In addition, in the case where using polymerizable liquid crystal compound as alignment films,
There can be common alignment films to be used as substrate alignment films.
Herein, first, prepare comprising the high-molecular compound precursor as the 1st high-molecular compound and/or by described logical
Compound and the compound represented by the logical formula (I) and the change represented by logical formula (V) as needed that formula (V2) is represented
The aligning film material of compound of the polymerizable compounds such as compound either with optical polymerism and photocrosslinking reaction or preparation are included
The compound and the aligning film material of polymerizable liquid crystal compound represented by logical formula (I).
, for example can example as high-molecular compound precursor in the case where the 1st high-molecular compound is polyimides
Lift：The mixture of tetracarboxylic dianhydride and diisocyanate, polyamic acid, polyimides is set to dissolve or be distributed in solvent and obtain
Polyimide solution etc..The content of polyimides in the polyimide solution is preferably more than 1 mass % and 10 mass %
Hereinafter, more preferably more than 3 mass % and below 5 mass %.
In addition, in the case where the 1st high-molecular compound is polysiloxanes, as high-molecular compound precursor, such as may be used
To enumerate：By the silicon compound with alkoxy, the silicon compound with halogenated alkoxy, alcohol and oxalic acid with predetermined use level
Than being mixed and heated, so as to synthesize polysiloxanes, and polysiloxane solution obtained from solvent etc. is dissolved it in.
In addition it is also possible to which as needed, compound of the addition with photocrosslinking reaction, photopolymerization trigger in aligning film material
Agent, solvent etc..
After direction of adjustment membrane material, by the aligning film material to cover common electrode 14, pixel electrode 15 and its slit
The mode in portion (not shown) is respectively coated or is printed on after first substrate 11 and second substrate 12, and progress such as heats at the processing.By
This, be applied or the aligning film material that prints in the high-molecular compound precursor that includes and/or the formula (V2) it is represented
Compound or polymerizable liquid crystal compound occur polymerization and solidify, as high-molecular compound, form high-molecular compound
With by leading to the compound that represents of formula (I) and the compound represented by logical formula (V) as needed is mixed or by formula
(I) vertical alignment layer 16,17 after the compound and polymerizable liquid crystal compound semi-solid preparation that represent.
Herein, in the case where being heated, its temperature is preferably more than 80 DEG C, more preferably 150~200 DEG C.
In addition, in the stage, being formed makes the liquid crystal molecule in liquid crystal combination nitride layer be orientated in the direction vertical with real estate
Vertical orientated ability.Afterwards, the processing such as friction can also be implemented as needed.
Next, first substrate 11 is overlapped with second substrate 12, and liquid of the sealed bundle containing liquid crystal molecule between them
Crystal composite layer 13.
Specifically, the formation to either one in first substrate 11 and second substrate 12 has the face of vertical alignment layer 16,17,
Spread for ensuring the sept thrust of cell gap, such as plastic microbead, also, for example using silk screen print method, make
With the printing and sealing such as epoxy adhesive portion.
Afterwards, via sept thrust and sealing by first substrate 11 and second substrate 12 with vertical alignment layer
16th, 17 opposed modes are fitted, and inject the liquid-crystal composition comprising liquid crystal molecule and polymerizable compound as needed.
Afterwards, heat etc., solidify sealing, so that liquid-crystal composition is sealed in into the base of first substrate 11 and second
Between plate 12.
Next, using application voltage cell to applying voltage between common electrode 14 and pixel electrode 15.For example, with 5
~30 (V) size applies voltage.There is also generally perpendicularly apply electric charge with first substrate and second substrate for the application
Situation.Thus, produce (opposed with liquid crystal combination nitride layer 13 relative to the face adjacent with liquid crystal combination nitride layer 13 of first substrate 11
Face) and second substrate 12 the face (with liquid crystal combination nitride layer 13 opposed face) adjacent with liquid crystal combination nitride layer 13 constitute it is pre-
Determine the electric field in the direction of angle, the normal direction of liquid crystal molecule 19 from first substrate 11 and second substrate 12 is tilted to predetermined direction
Ground is orientated.Now, the inclination angle of liquid crystal molecule 19 and the pretilt theta that liquid crystal molecule 19 is assigned in aftermentioned process are roughly equal.
So, the size of appropriate regulation voltage, so as to the size (reference picture 3) for the pretilt theta for controlling liquid crystal molecule 19.
Also, in the state of voltage is applied with, by by ultraviolet light UV for example from the outer lateral liquid crystal of first substrate 11
Composition layer 13 irradiates so that in vertical alignment layer 16,17 by leading to the compound that represents of formula (I) and as needed by leading to
Polymerizable compound polymerization in compound or polymerizable liquid crystal compound and liquid-crystal composition that formula (V) is represented, generation
High molecular polymer.
In this case, the ultraviolet light UV of irradiation intensity can be certain, can also not necessarily, when changing exposure intensity
The irradiation time of each intensity is also arbitrary, but in the case of using 2 the irradiation process more than stage, preferably the 2nd stage
The exposure intensity of later irradiation process selects the intensity weaker than the exposure intensity in the 1st stage, total photograph after preferably the 2nd stage
Penetrate the time it is longer than the irradiation time in the 1st stage and irradiation gross energy it is big.In addition, in the situation for making exposure intensity discontinuously change
Under, the average shot intensity of the average shot light strength ratio latter half of the first half of preferably all irradiation process times is more
By force, the intensity more preferably just started after irradiation is most strong, and further preferably with the process of irradiation time, exposure intensity is held always
It is continuous to reduce, until some definite value.Ultraviolet (UV) intensity in this case is preferably 2mW/cm-2~100mW/cm-2, but it is more excellent
Be selected in the multistage irradiation in the case of the 1st stage or discontinuously exposure intensity change in the case of all irradiation works
Highest exposure intensity in sequence is 10mW/cm-2~100mW/cm-2, and after the 2nd stage in the case of multistage irradiation
Or the minimum exposure intensity in the case where making exposure intensity discontinuously change is 2mW/cm-2~50mW/cm-2.In addition,
It is preferably 10J~300J to irradiate gross energy, but more preferably 50J~250J, more preferably 100J~250J.
In this case, the voltage of application can be exchange or direct current.
As a result, including vertical orientated membrane material with what the tropism control portion with vertical alignment layer 16,17 was fixedly secured
The tropism control ability (not shown) of material, then, forms polymeric layer 20,21 on its surface as needed.The tropism control portion
Under non-driven state, with the boundary being located at polymeric layer 20,21 (vertical alignment layer 16,17) to liquid crystal combination nitride layer 13
Liquid crystal molecule 19 near face assigns the function (tropism control ability) of pretilt theta.In addition, although herein from first substrate 11
Outside irradiating ultraviolet light UV, but it is also possible to irradiated from the outside of second substrate 12, can also be from first substrate 11 and second substrate
The outside irradiation of substrate both 12.
So, in the liquid crystal display cells of the present invention, in liquid crystal combination nitride layer 13, liquid crystal molecule 19 has predetermined
Pretilt theta.Thus, with the liquid crystal display cells of pre-tilt angle processing are not carried out completely and possess the liquid crystal display device phase of the element
Than the response speed for driving voltage can be greatly improved.
It is excellent as the high-molecular compound precursor for constituting vertical alignment layer 16,17 in the liquid crystal display cells of the present invention
Select the polyimide precursor of non-photosensitive.
Embodiment
Below, the present invention is further elaborated with using embodiment and comparative example, but the invention is not restricted to following reality
Apply example.In addition, following embodiment and " % " of the composition of comparative example refer to " quality % ".
In following embodiment and comparative example, Tni, Δ n, Δ ε, η, γ 1 are defined as follows respectively.
Tni：Nematic phase-isotropic liquid phase transition temperature (DEG C)
Tcn：Solid phase-nematic phase transition temperature (DEG C)
Δn：Refractive anisotrop at 25 DEG C
Δε：Dielectric anisotropy at 25 DEG C
γ1：Rotary viscosity (mPas) at 25 DEG C
K33：The elastic constant (pN) of bending at 20 DEG C
Voltage retention (initial VHR) before ultraviolet light：In the 343K under conditions of frequency 60Hz, application voltage 1V
Voltage retention (%)
VHR after ultraviolet light：To after following embodiment, the liquid crystal display cells irradiating ultraviolet light of comparative example, with
Above-mentioned VHR assay methods identical condition is measured.
In following embodiment and comparative example, the ghost of liquid crystal display cells is evaluated using following methods, is dripped
Vestige and pre-tilt angle.
(ghost)
The ghost evaluation of liquid crystal display cells is that predetermined fixed pattern is shown in viewing area after 1000 hours, range estimation
The image retention level of fixed pattern when having carried out the uniform display of whole picture is evaluated, and is evaluated using following 4 grades.
◎：Without image retention
○：Slightly image retention but the level that can be allowed
△：There are image retention and unacceptable level
×：There is image retention and excessively poor
(drip vestige)
The evaluation of the vestige that drips of liquid crystal display device is visual observations in the case where whole surface is shown as black
The vestige that drips emerged whitely, and evaluated using following 4 grade.
◎：Without image retention
○：Slightly image retention but the level that can be allowed
△：There are image retention and unacceptable level
×：There is image retention and excessively poor
(pre-tilt angle)
In face at random to liquid crystal display cells 5 at measure, regard average value as pre-tilt angle.In addition, commenting
In the case of the stability of valency pre-tilt angle, compare the change of the pre-tilt angle before and after stress.Stress is via by liquid crystal display device
Put into the stove for remaining 70 DEG C, and apply 168 hours 1kHz, 30V square wave and be endowed.
Pre-tilt angle changes angle (°)：The pre-tilt angle before pre-tilt angle-stress after stress
In addition, the record to compound in embodiment has used following abbreviation.In addition, n represents natural number.
(side chain)
(linking group)
(ring structure)
[chemical formula 97]
(embodiment 1)
Manufacture possesses the transparent electrode layer being made up of transparent common electrode and the first substrate of color filter layers (is shared
Electrode base board)；And possess the second substrate (pixel of the pixel electrode layer with the transparent pixel electrode driven by active component
Electrode base board).
In pixel electrode substrate, as each pixel electrode, using in order to the orientation of liquid crystal molecule is split and with picture
The mode that there is the slit without electrode in plain electrode etched ITO electrode.
Using method of spin coating, by the vertical of the polymerizable compound comprising polyimide precursor and with polymerizable group
Aligning film material is respectively coated in common electrode substrate and pixel electrode substrate, and the coated film is heated with 200 DEG C, so that vertically
Polyimide precursor solidification in aligning film material, 100nm ± 20nm vertical alignment layer is formed with the surface of each substrate.
In the stage, the polymerizable compound with polymerizable group in the vertical alignment layer is simultaneously uncured.
As vertical orientated film formation material, using in the polyimide solution (commodity containing 3% polyimide precursor
Name：JALS2131-R6, JSR company manufacture) in containing 3.0% by following formula (I-1) represent compound solution.
[chemical formula 98]
By containing be clamped in as the liquid-crystal composition (LC-A) of compound that the chemical formula shown in following table is represented be formed with it is vertical
After the common electrode substrate and pixel electrode substrate of straight alignment films, solidify the encapsulant, form liquid crystal combination nitride layer.This
When, using the sept that thickness is 3.0 μm, the thickness of liquid crystal combination nitride layer is set to 3.0 μm.
[table 1]
In the state of the AC field of rectangle is applied, to obtained liquid crystal display cells irradiation ultraviolet radiation, make the formula
(I-1) compound cures represented by.The UIS-S2511RZ manufactured using oxtail Motor Corporation is made as irradiation unit
The USH-250BY manufactured with oxtail Motor Corporation is as ultraviolet lamp, with 20mW to liquid crystal display cells irradiation ultraviolet radiation 300
Second, obtain the liquid crystal display cells of embodiment 1.Using the process, hanging down comprising the compound represented by the formula (I-1) is formed
Straight alignment films, and assign pre-tilt angle to the liquid crystal molecule in liquid crystal combination nitride layer.
Herein, pre-tilt angle is defined as illustrated in fig. 3.In the case where progress is completely vertical orientated, pre-tilt angle (θ) is 90 °,
In the case where imparting pre-tilt angle, pre-tilt angle (θ) is less than 90 °.
The slit of pixel electrode shown in the liquid crystal display cells along Fig. 2 of embodiment 1 is in 4 blocks towards not Tongfang
To with pre-tilt angle, after polymerizable compound solidification, in the state of cut-out AC field, pre-dumping is also maintained
Angle.
Before and after each physical property of liquid-crystal composition used in the liquid crystal display cells of embodiment 1, ultraviolet light
VHR and vestige evaluation of dripping, the ghost evaluation of obtained liquid crystal display cells be shown in following table 2.As a result, implementing
Declining to a great extent for VHR is not observed in liquid-crystal composition before and after ultraviolet light used in the liquid crystal display cells of example 1.Grind
Trace it to its cause and be：Containing the polymerizable compound represented by logical formula (I) in aligning film material, therefore, it is possible to which orientation will be made
Ultraviolet light gross energy during the polymerization of the polymerizable compound with polymerizable group in film be suppressed to it is relatively low, so can
Suppress the decomposition of the liquid-crystal compounds of composition liquid-crystal composition.
[table 2]
| Embodiment 1 | |
| Ultraviolet pre-irradiation VHR (%) | 99.1 |
| VHR (%) after ultraviolet irradiation | 99.0 |
| Drip vestige evaluation | ○ |
| Ghost is evaluated | ◎ |
(comparative example 1)
As vertical orientated film formation material, using in the polyimide solution (commodity containing 3% polyimide precursor
Name：JALS2131-R6, JSR company manufacture) in containing 3.0% by following formula (Va-1-1) represent compound solution, except this with
Outside, similarly to Example 1, the liquid crystal display cells of comparative example 1 are obtained.
[chemical formula 99]
In the state of the AC field of rectangle is applied, to obtained liquid crystal display cells irradiation ultraviolet radiation, make described take
The solidification of the polymerizable compound with reactive group into film.The UIS-S2511RZ manufactured using oxtail Motor Corporation is made
For irradiation unit, also, the USH-250BY manufactured using oxtail Motor Corporation is as ultraviolet lamp, with 20mW to liquid crystal display
Element irradiation ultraviolet radiation 600 seconds, obtains the liquid crystal display cells of comparative example 1.In addition, with the identical conditions of embodiment 1 (20mW,
300 seconds) under to liquid crystal display cells irradiation ultraviolet radiation, assign pre-tilt angle, but due to the reactive group that has in alignment films
The solidification of polymerizable compound is insufficient, and pre-tilt angle is not assigned stably, therefore, in order to maintain pre-tilt angle to need to shine with 20mW
Penetrate 600 seconds.
Before and after each physical property of liquid-crystal composition used in the liquid crystal display cells of comparative example 1, ultraviolet light
VHR and vestige evaluation of dripping, the ghost evaluation of obtained liquid crystal display cells be shown in following table 3.As a result, due to
The polymerizable compound represented by logical formula (I) is not contained in the aligning film material of comparative example 1, therefore, for by alignment films
The solidification of the polymerizable compound with polymerism ultraviolet light total energy quantitative change it is big, as a result observe that VHR declines, it is thus identified that
Physical property caused by the decomposition of liquid-crystal compounds in liquid-crystal composition declines.
[table 3]
| Comparative example 1 | |
| Ultraviolet pre-irradiation VHR (%) | 99.1 |
| VHR (%) after ultraviolet irradiation | 97.5 |
| Drip vestige evaluation | × |
| Ghost is evaluated | △ |
(embodiment 2)
The liquid-crystal composition (LC-A2) containing the compound shown in following table is prepared, the liquid-crystal composition is used.In addition
Condition it is same as Example 1, obtain the liquid crystal display cells of embodiment 2.
[table 4]
In the state of the AC field of rectangle is applied with, to obtained liquid crystal display cells irradiation ultraviolet radiation, make described
Compound cures represented by formula (I-1).The UIS-S2511RZ manufactured using oxtail Motor Corporation is used as irradiation unit
The USH-250BY of oxtail Motor Corporation manufacture is as ultraviolet lamp, with 20mW to liquid crystal display cells irradiation ultraviolet radiation 300 seconds,
Obtain the liquid crystal display cells of embodiment 2.The liquid crystal display cells of embodiment 2 have pre-tilt angle similarly to Example 1, in institute
State after polymerizable compound solidification, in the state of cut-out AC field, also maintain pre-tilt angle.
Before and after each physical property of liquid-crystal composition used in the liquid crystal display cells of embodiment 2, ultraviolet light
VHR and vestige evaluation of dripping, the ghost evaluation of obtained liquid crystal display cells be shown in following table 5.As a result, implementing
VHR decline is not observed in liquid-crystal composition before and after ultraviolet light used in the liquid crystal display cells of example 2.Study it
Reason is：Containing the polymerizable compound represented by logical formula (I) in aligning film material, therefore, it is possible to make in alignment films
With polymerizable group polymerizable compound polymerization when ultraviolet light gross energy be suppressed to it is relatively low, so, can press down
System constitutes the decomposition of the liquid-crystal compounds of liquid-crystal composition.
[table 5]
| Embodiment 2 | |
| Ultraviolet pre-irradiation VHR (%) | 99.5 |
| VHR (%) after ultraviolet irradiation | 99.5 |
| Drip vestige evaluation | ◎ |
| Ghost is evaluated | ◎ |
(embodiment 3)
The liquid-crystal composition (LC-A3) containing the compound shown in following table is prepared, the liquid-crystal composition is used.In addition
Condition it is same as Example 1, obtain the liquid crystal display cells of embodiment 3.
[table 6]
In the state of the AC field of rectangle is applied with, to obtained liquid crystal display cells irradiation ultraviolet radiation, make described
Compound cures represented by formula (I-1).The UIS-S2511RZ manufactured using oxtail Motor Corporation is used as irradiation unit
The USH-250BY of oxtail Motor Corporation manufacture is as ultraviolet lamp, with 20mW to liquid crystal display cells irradiation ultraviolet radiation 300 seconds,
Obtain the liquid crystal display cells of embodiment 3.The liquid crystal display cells of embodiment 3 have pre-tilt angle similarly to Example 1, in institute
State after polymerizable compound solidification, in the state of cut-out AC field, also maintain pre-tilt angle.
Before and after each physical property of liquid-crystal composition used in the liquid crystal display cells of embodiment 3, ultraviolet light
VHR and vestige evaluation of dripping, the ghost evaluation of obtained liquid crystal display cells be shown in following table 7.As a result, implementing
Declining to a great extent for VHR is not observed in liquid-crystal composition before and after ultraviolet light used in the liquid crystal display cells of example 3.Study carefully
Its reason is：Containing the polymerizable compound represented by logical formula (I) in aligning film material, therefore, it is possible to which alignment films will be made
In with polymerizable group polymerizable compound polymerization when ultraviolet light gross energy be suppressed to it is relatively low, so, can
Suppress the decomposition of the liquid-crystal compounds of composition liquid-crystal composition.
[table 7]
| Embodiment 3 | |
| Ultraviolet pre-irradiation VHR (%) | 99.3 |
| VHR (%) after ultraviolet irradiation | 99.2 |
| Drip vestige evaluation | ◎ |
| Ghost is evaluated | ◎ |
(embodiment 4)
The liquid-crystal composition (LC-A4) containing the compound shown in following table is prepared, the liquid-crystal composition is used.In addition, making
For vertical orientated film formation material, using in the polyimide solution (trade name containing 3% polyimide precursor：
JALS2131-R6, JSR company manufacture) in containing 1.5% compound represented by following formula (I-1) and 1.5% by formula
(Va-1-1) solution of the compound represented.In addition condition is same as Example 1, obtains the liquid crystal display of embodiment 4
Element.
[chemical formula 100]
[table 8]
In the state of the AC field of rectangle is applied with, to obtained liquid crystal display cells irradiation ultraviolet radiation, make described
The compound cures represented by compound and formula (Va-1-1) represented by formula (I-1).Manufactured using oxtail Motor Corporation
The USH-250BY that UIS-S2511RZ is manufactured as irradiation unit, using oxtail Motor Corporation as ultraviolet lamp, with 20mW to
Liquid crystal display cells irradiation ultraviolet radiation 300 seconds, obtains the liquid crystal display cells of embodiment 4.The liquid crystal display cells tool of embodiment 4
There is pre-tilt angle similarly to Example 1, after polymerizable compound solidification, in the state of cut-out AC field,
Also pre-tilt angle is maintained.
Before and after each physical property of liquid-crystal composition used in the liquid crystal display cells of embodiment 4, ultraviolet light
VHR and vestige evaluation of dripping, the ghost evaluation of obtained liquid crystal display cells be shown in following table 9.As a result, implementing
Declining to a great extent for VHR is not observed in liquid-crystal composition before and after ultraviolet light used in the liquid crystal display cells of example 4.Study carefully
Its reason is：Containing the polymerizable compound represented by logical formula (I) in aligning film material, therefore, it is possible to which alignment films will be made
In with polymerizable group polymerizable compound polymerization when ultraviolet light gross energy be suppressed to it is relatively low, so, can
Suppress the decomposition of the liquid-crystal compounds of composition liquid-crystal composition.
[table 9]
| Embodiment 4 | |
| Ultraviolet pre-irradiation VHR (%) | 99.4 |
| VHR (%) after ultraviolet irradiation | 98.9 |
| Drip vestige evaluation | ○ |
| Ghost is evaluated | ◎ |
(embodiment 5)
The liquid-crystal composition (LC-A5) containing the compound shown in following table is prepared, the liquid-crystal composition is used.In addition, making
For vertical orientated film formation material, using in the polyimide solution (trade name containing 3% polyimide precursor：
JALS2131-R6, JSR company manufacture) in containing 3.0% by following formula (I-21) represent compound solution.In addition
Condition is same as Example 1, obtains the liquid crystal display cells of embodiment 5.
[chemical formula 101]
[table 10]
In the state of the AC field of rectangle is applied with, to obtained liquid crystal display cells irradiation ultraviolet radiation, make described
Compound cures represented by formula (I-21).The UIS-S2511RZ manufactured using oxtail Motor Corporation is used as irradiation unit
The USH-250BY of oxtail Motor Corporation manufacture is as ultraviolet lamp, with 20mW to liquid crystal display cells irradiation ultraviolet radiation 300 seconds,
Obtain the liquid crystal display cells of embodiment 5.The liquid crystal display cells of embodiment 5 have pre-tilt angle similarly to Example 1, in institute
State after polymerizable compound solidification, in the state of cut-out AC field, also maintain pre-tilt angle.
Before and after each physical property of liquid-crystal composition used in the liquid crystal display cells of embodiment 5, ultraviolet light
VHR and vestige evaluation of dripping, the ghost evaluation of obtained liquid crystal display cells be shown in following table 11.As a result, real
Apply liquid-crystal composition used in the liquid crystal display cells of example 5 and declining to a great extent for VHR is not observed before and after ultraviolet light.
Trace it to its cause and be：Containing the polymerizable compound represented by logical formula (I) in aligning film material, therefore, it is possible to which orientation will be made
In film with polymerizable group polymerizable compound polymerization when ultraviolet light gross energy be suppressed to it is relatively low, so, energy
Enough decomposition for suppressing to constitute the liquid-crystal compounds of liquid-crystal composition.
[table 11]
| Embodiment 5 | |
| Ultraviolet pre-irradiation VHR (%) | 99.4 |
| VHR (%) after ultraviolet irradiation | 99.3 |
| Drip vestige evaluation | ◎ |
| Ghost is evaluated | ◎ |
(embodiment 6)
The liquid-crystal composition (LC-A6) containing the compound shown in following table is prepared, the liquid-crystal composition is used.In addition
Condition it is same as Example 5, obtain the liquid crystal display cells of embodiment 6.
[table 12]
In the state of the AC field of rectangle is applied with, to obtained liquid crystal display cells irradiation ultraviolet radiation, make described
Compound cures represented by formula (I-21).The UIS-S2511RZ manufactured using oxtail Motor Corporation is used as irradiation unit
The USH-250BY of oxtail Motor Corporation manufacture is as ultraviolet lamp, with 20mW to liquid crystal display cells irradiation ultraviolet radiation 300 seconds,
Obtain the liquid crystal display cells of embodiment 6.The liquid crystal display cells of embodiment 6 have pre-tilt angle similarly to Example 5, in institute
State after polymerizable compound solidification, in the state of cut-out AC field, also maintain pre-tilt angle.
Before and after each physical property of liquid-crystal composition used in the liquid crystal display cells of embodiment 6, ultraviolet light
VHR and vestige evaluation of dripping, the ghost evaluation of obtained liquid crystal display cells be shown in following table 13.As a result, real
Apply liquid-crystal composition used in the liquid crystal display cells of example 6 and declining to a great extent for VHR is not observed before and after ultraviolet light.
Trace it to its cause and be：Containing the polymerizable compound represented by logical formula (I) in aligning film material, therefore, it is possible to which orientation will be made
In film with polymerizable group polymerizable compound polymerization when ultraviolet light gross energy be suppressed to it is relatively low, so, energy
Enough decomposition for suppressing to constitute the liquid-crystal compounds of liquid-crystal composition.
[table 13]
| Embodiment 6 | |
| Ultraviolet pre-irradiation VHR (%) | 99.2 |
| VHR (%) after ultraviolet irradiation | 99.0 |
| Drip vestige evaluation | ◎ |
| Ghost is evaluated | ◎ |
(embodiment 7)
The liquid-crystal composition (LC-B) containing the compound shown in following table is prepared, the liquid-crystal composition is used.In addition, conduct
Vertical orientated film formation material, using in the polyimide solution (trade name containing 3% polyimide precursor：JALS2131-
R6, JSR company manufacture) in containing 3.0% by following formula (I-33) represent compound solution.In addition condition and implementation
Example 1 is identical, obtains the liquid crystal display cells of embodiment 7.
[chemical formula 102]
[table 14]
In the state of the AC field of rectangle is applied with, to obtained liquid crystal display cells irradiation ultraviolet radiation, make described
Compound cures represented by formula (I-33).The UIS-S2511RZ manufactured using oxtail Motor Corporation is used as irradiation unit
The USH-250BY of oxtail Motor Corporation manufacture is as ultraviolet lamp, with 20mW to liquid crystal display cells irradiation ultraviolet radiation 300 seconds,
Obtain the liquid crystal display cells of embodiment 7.The liquid crystal display cells of embodiment 7 have pre-tilt angle similarly to Example 1, in institute
State after polymerizable compound solidification, in the state of cut-out AC field, also maintain pre-tilt angle.
Before and after each physical property of liquid-crystal composition used in the liquid crystal display cells of embodiment 7, ultraviolet light
VHR and vestige evaluation of dripping, the ghost evaluation of obtained liquid crystal display cells be shown in following table 15.As a result, real
Apply liquid-crystal composition used in the liquid crystal display cells of example 7 and declining to a great extent for VHR is not observed before and after ultraviolet light.
Trace it to its cause and be：Containing the polymerizable compound represented by logical formula (I) in aligning film material, therefore, it is possible to which orientation will be made
In film with polymerizable group polymerizable compound polymerization when ultraviolet light gross energy be suppressed to it is relatively low, so, energy
Enough decomposition for suppressing to constitute the liquid-crystal compounds of liquid-crystal composition.
[table 15]
| Embodiment 7 | |
| Ultraviolet pre-irradiation VHR (%) | 99.3 |
| VHR (%) after ultraviolet irradiation | 99.1 |
| Drip vestige evaluation | ○ |
| Ghost is evaluated | ◎ |
(comparative example 2)
As vertical orientated film formation material, using in the polyimide solution (commodity containing 3% polyimide precursor
Name：JALS2131-R6, JSR company manufacture) in containing 3.0% by following formula (Va-1-1) represent compound solution, except this with
Outside similarly to Example 7, the liquid crystal display cells of comparative example 2 are obtained.
[chemical formula 103]
In the state of the AC field of rectangle is applied with, to obtained liquid crystal display cells irradiation ultraviolet radiation, make described
The solidification of the polymerizable compound with reactive group in alignment films.The UIS-S2511RZ manufactured using oxtail Motor Corporation
As irradiation unit, the USH-250BY manufactured using oxtail Motor Corporation is as ultraviolet lamp, with 20mW to liquid crystal display cells
Irradiation ultraviolet radiation 600 seconds, obtains the liquid crystal display cells of comparative example 2.In addition, with the identical conditions of embodiment 7 (20mW, 300
Second) under to liquid crystal display cells irradiation ultraviolet radiation, assign pre-tilt angle, but due to the polymerization with reactive group in alignment films
Property compound solidification it is insufficient, pre-tilt angle is not assigned stably, therefore, in order to maintain pre-tilt angle need irradiated with 20mW
600 seconds.
Before and after each physical property of liquid-crystal composition used in the liquid crystal display cells of comparative example 2, ultraviolet light
VHR and vestige evaluation of dripping, the ghost evaluation of obtained liquid crystal display cells be shown in following table 16.As a result, by
The polymerizable compound represented by logical formula (I) is not contained in the aligning film material in comparative example 2, therefore, for by alignment films
In the solidification of the polymerizable compound with polymerism ultraviolet light total energy quantitative change it is big, as a result observe that VHR declines, and confirms
Physical property caused by the decomposition of liquid-crystal compounds in liquid-crystal composition declines.
[table 16]
| Comparative example 2 | |
| Ultraviolet pre-irradiation VHR (%) | 99.3 |
| VHR (%) after ultraviolet irradiation | 98.0 |
| Drip vestige evaluation | △ |
| Ghost is evaluated | × |
(embodiment 8)
The liquid-crystal composition (LC-B2) containing the compound shown in following table is prepared, the liquid-crystal composition is used.In addition
Condition it is same as Example 1, obtain the liquid crystal display cells of embodiment 8.
[table 17]
In the state of the AC field of rectangle is applied with, to obtained liquid crystal display cells irradiation ultraviolet radiation, make described
Compound cures represented by formula (I-1).The UIS-S2511RZ manufactured using oxtail Motor Corporation is used as irradiation unit
The USH-250BY of oxtail Motor Corporation manufacture is as ultraviolet lamp, with 20mW to liquid crystal display cells irradiation ultraviolet radiation 300 seconds,
Obtain the liquid crystal display cells of embodiment 8.The liquid crystal display cells of embodiment 8 have pre-tilt angle similarly to Example 1, in institute
State after polymerizable compound solidification, in the state of cut-out AC field, also maintain pre-tilt angle.
Before and after each physical property of liquid-crystal composition used in the liquid crystal display cells of embodiment 8, ultraviolet light
VHR and vestige evaluation of dripping, the ghost evaluation of obtained liquid crystal display cells be shown in following table 18.As a result, real
Apply the decline that VHR is not observed in liquid-crystal composition used in the liquid crystal display cells of example 8 before and after ultraviolet light.Study carefully it
Reason is：Containing the polymerizable compound represented by logical formula (I) in aligning film material, therefore, it is possible to make in alignment films
With polymerizable group polymerizable compound polymerization when ultraviolet light gross energy be suppressed to it is relatively low, so, can press down
System constitutes the decomposition of the liquid-crystal compounds of liquid-crystal composition.
[table 18]
| Embodiment 8 | |
| Ultraviolet pre-irradiation VHR (%) | 99.6 |
| VHR (%) after ultraviolet irradiation | 99.5 |
| Drip vestige evaluation | ◎ |
| Ghost is evaluated | ◎ |
(embodiment 9)
Manufacture possesses the transparent electrode layer being made up of transparent common electrode and the first substrate of color filter layers (is shared
Electrode base board)；And possess the second substrate (pixel of the pixel electrode layer with the transparent pixel electrode driven by active component
Electrode base board).
In pixel electrode substrate, as each pixel electrode, using in order to the orientation of liquid crystal molecule is split and with picture
The mode that there is the slit without electrode in plain electrode etched ITO electrode.
Using method of spin coating by the vertical of the polymerizable compound comprising polyimide precursor and with polymerizable group
Aligning film material is respectively coated in common electrode substrate and pixel electrode substrate, and the coated film is heated with 200 DEG C, so that vertically
Polyimide precursor solidification in aligning film material, 100nm vertical alignment layer is formed on the surface of each substrate.In the stage
In, the polymerizable compound with polymerizable group in the vertical alignment layer is simultaneously uncured.
As vertical orientated film formation material, using containing 3% polyimide derivatives being expressed from the next, 3.0%
By formula (I-1) represent polymerizable compound METHYLPYRROLIDONE solution.
[chemical formula 104]
Liquid-crystal composition (LC-A) containing the compound represented by chemical formula as shown below is clamped in be formed with it is vertical
After the common electrode substrate and pixel electrode substrate of straight alignment films, solidify the encapsulant, form liquid crystal combination nitride layer.This
When, using the sept that thickness is 3.0 μm, the thickness of liquid crystal combination nitride layer is set to 3.0 μm.
[table 19]
In the state of the AC field of rectangle is applied with, to obtained liquid crystal display cells irradiation ultraviolet radiation, make described
Polymerizable compound solidification with reactive group.Filled using the UIS-S2511RZ that oxtail Motor Corporation manufactures as irradiation
Put, the USH-250BY manufactured using oxtail Motor Corporation is as ultraviolet lamp, with 20mW to liquid crystal display cells irradiation ultraviolet radiation
300 seconds, obtain embodiment △ liquid crystal display cells.Using the process, being formed to include, there is polyimide backbone to be used as main chain
And with vertical alignment layer of the polymerizable group as the polymer of the polymerizable compound of side chain, and in liquid crystal combination nitride layer
Liquid crystal molecule assign pre-tilt angle.
The slit of pixel electrode shown in the liquid crystal display cells along Fig. 2 of embodiment 9 is in 4 blocks towards not Tongfang
To with pre-tilt angle, after polymerizable compound solidification, in the state of cut-out AC field, pre-dumping is also maintained
Angle.
Before and after each physical property of liquid-crystal composition used in the liquid crystal display cells of embodiment 9, ultraviolet light
VHR and vestige evaluation of dripping, the ghost evaluation of obtained liquid crystal display cells be shown in following table 20.As a result, real
Declining to a great extent for VHR is not observed in the liquid-crystal composition used in the liquid crystal display cells for applying example 9 before and after ultraviolet light.
Trace it to its cause and be：Containing the polymerizable compound represented by logical formula (I) in aligning film material, therefore, it is possible to which orientation will be made
In film with polymerizable group polymerizable compound polymerization when ultraviolet light gross energy be suppressed to it is relatively low, so, energy
Enough decomposition for suppressing to constitute the liquid-crystal compounds of liquid-crystal composition.
[table 20]
| Embodiment 9 | |
| Ultraviolet pre-irradiation VHR (%) | 99.1 |
| VHR (%) after ultraviolet irradiation | 99.0 |
| Drip vestige evaluation | ○ |
| Ghost is evaluated | ◎ |
(comparative example 3)
As vertical orientated film formation material, the polyimide derivatives represented by the following formula containing 3% and 3% are used
Formula (Va-1-1) represented by polymerizable compound METHYLPYRROLIDONE solution, it is in addition same with embodiment 9
Sample, obtains the liquid crystal display cells of comparative example 3.
[chemical formula 105]
In the state of the AC field of rectangle is applied with, to obtained liquid crystal display cells irradiation ultraviolet radiation, make described
The solidification of the polymerizable compound with reactive group in alignment films.The UIS-S2511RZ manufactured using oxtail Motor Corporation
As irradiation unit, the USH-250BY manufactured using oxtail Motor Corporation is as ultraviolet lamp, with 20mW to liquid crystal display cells
Irradiation ultraviolet radiation 600 seconds, obtains the liquid crystal display cells of comparative example 3.In addition, with the identical conditions of embodiment 9 (20mW, 300
Second) under to liquid crystal display cells irradiation ultraviolet radiation, assign pre-tilt angle, but due to the polymerization with reactive group in alignment films
The solidification of property compound is insufficient, pre-tilt angle is not assigned stably, therefore, in order to maintain pre-tilt angle, it is necessary to be irradiated with 20mW
600 seconds.
Before and after each physical property of liquid-crystal composition used in the liquid crystal display cells of comparative example 3, ultraviolet light
VHR and vestige evaluation of dripping, the ghost evaluation of obtained liquid crystal display cells be shown in following table 21.As a result, by
The polymerizable compound represented by logical formula (I) is not contained in the aligning film material in comparative example 3, therefore, for by alignment films
In the solidification of the polymerizable compound with polymerism ultraviolet light total energy quantitative change it is big, as a result observe that VHR declines, and confirms
Physical property caused by the decomposition of liquid-crystal compounds in liquid-crystal composition declines.
[table 21]
| Comparative example 3 | |
| Ultraviolet pre-irradiation VHR (%) | 99.1 |
| VHR (%) after ultraviolet irradiation | 97.0 |
| Drip vestige evaluation | × |
| Ghost is evaluated | △ |
(embodiment 10)
The liquid-crystal composition (LC-A3) containing the compound shown in following table is prepared, the liquid-crystal composition is used.In addition
Condition it is same as Example 9, obtain the liquid crystal display cells of embodiment 10.
[table 22]
In the state of the AC field of rectangle is applied with, to obtained liquid crystal display cells irradiation ultraviolet radiation, make described
Polymerizable compound solidification with reactive group.Filled using the UIS-S2511RZ that oxtail Motor Corporation manufactures as irradiation
Put, the USH-250BY manufactured using oxtail Motor Corporation is as ultraviolet lamp, with 20mW to liquid crystal display cells irradiation ultraviolet radiation
600 seconds, obtain the liquid crystal display cells of embodiment 10.The liquid crystal display cells of embodiment 10 have similarly to Example 9 pre-
Inclination angle, after polymerizable compound solidification, in the state of cut-out AC field, also maintains pre-tilt angle.
Before and after each physical property of liquid-crystal composition used in the liquid crystal display cells of embodiment 10, ultraviolet light
VHR and vestige evaluation of dripping, the ghost evaluation of obtained liquid crystal display cells be shown in following table 23.As a result, real
Apply liquid-crystal composition used in the liquid crystal display cells of example 10 be not observed before and after ultraviolet light VHR significantly under
Drop.Trace it to its cause and be：Containing the polymerizable compound represented by logical formula (I) in aligning film material, therefore, it is possible to make to take
Into film with polymerizable group polymerizable compound polymerization when ultraviolet light gross energy be suppressed to it is relatively low, so,
The decomposition of the liquid-crystal compounds of composition liquid-crystal composition can be suppressed.
[table 23]
| Embodiment 10 | |
| Ultraviolet pre-irradiation VHR (%) | 99.3 |
| VHR (%) after ultraviolet irradiation | 99.2 |
| Drip vestige evaluation | ◎ |
| Ghost is evaluated | ◎ |
(embodiment 11)
The liquid-crystal composition (LC-A6) containing the compound shown in following table is prepared, the liquid-crystal composition is used.In addition, making
For vertical orientated film formation material, using the polyimide derivatives represented by the following formula containing 3%, 3% by following formula (I-
21) the METHYLPYRROLIDONE solution of the polymerizable compound represented.In addition condition is same as Example 9, obtains
The liquid crystal display cells of embodiment 11.
[table 24]
[chemical formula 106]
In the state of the AC field of rectangle is applied with, to obtained liquid crystal display cells irradiation ultraviolet radiation, make described
Polymerizable compound solidification with reactive group.Filled using the UIS-S2511RZ that oxtail Motor Corporation manufactures as irradiation
Put, the USH-250BY manufactured using oxtail Motor Corporation is as ultraviolet lamp, with 20mW to liquid crystal display cells irradiation ultraviolet radiation
600 seconds, obtain the liquid crystal display cells of embodiment 11.The liquid crystal display cells of embodiment 11 have similarly to Example 9 pre-
Inclination angle, after polymerizable compound solidification, in the state of cut-out AC field, also maintains pre-tilt angle.
Before and after each physical property of liquid-crystal composition used in the liquid crystal display cells of embodiment 11, ultraviolet light
VHR and vestige evaluation of dripping, the ghost evaluation of obtained liquid crystal display cells be shown in following table 25.As a result, real
Apply liquid-crystal composition used in the liquid crystal display cells of example 11 be not observed before and after ultraviolet light VHR significantly under
Drop.Trace it to its cause and be：Containing the polymerizable compound represented by logical formula (I) in aligning film material, therefore, it is possible to make to take
Into film with polymerizable group polymerizable compound polymerization when ultraviolet light gross energy be suppressed to it is relatively low, so,
The decomposition of the liquid-crystal compounds of composition liquid-crystal composition can be suppressed.
[table 25]
| Embodiment 11 | |
| Ultraviolet pre-irradiation VHR (%) | 99.2 |
| VHR (%) after ultraviolet irradiation | 99.0 |
| Drip vestige evaluation | ◎ |
| Ghost is evaluated | ○ |
(embodiment 12)
The liquid-crystal composition (LC-B) containing the compound shown in following table is prepared, the liquid-crystal composition is used.In addition, conduct
Vertical orientated film formation material, using the polyimide derivatives represented by the following formula containing 3%, 3% by following formula (I-33)
The METHYLPYRROLIDONE solution of the polymerizable compound of expression.In addition condition is same as Example 9, obtains reality
Apply the liquid crystal display cells of example 12.
[table 26]
[chemical formula 107]
In the state of the AC field of rectangle is applied with, to obtained liquid crystal display cells irradiation ultraviolet radiation, make described
Polymerizable compound solidification with reactive group.Filled using the UIS-S2511RZ that oxtail Motor Corporation manufactures as irradiation
Put, the USH-250BY manufactured using oxtail Motor Corporation is as ultraviolet lamp, with 20mW to liquid crystal display cells irradiation ultraviolet radiation
600 seconds, obtain the liquid crystal display cells of embodiment 12.The liquid crystal display cells of embodiment 12 have similarly to Example 9 pre-
Inclination angle, after polymerizable compound solidification, in the state of cut-out AC field, also maintains pre-tilt angle.
Before and after each physical property of liquid-crystal composition used in the liquid crystal display cells of embodiment 12, ultraviolet light
VHR and vestige evaluation of dripping, the ghost evaluation of obtained liquid crystal display cells be shown in following table 27.As a result, real
Apply liquid-crystal composition used in the liquid crystal display cells of example 12 be not observed before and after ultraviolet light VHR significantly under
Drop.Trace it to its cause and be：Containing the polymerizable compound represented by logical formula (I) in aligning film material, therefore, it is possible to make to take
Into film with polymerizable group polymerizable compound polymerization when ultraviolet light gross energy be suppressed to it is relatively low, so,
The decomposition of the liquid-crystal compounds of composition liquid-crystal composition can be suppressed.
[table 27]
| Embodiment 12 | |
| Ultraviolet pre-irradiation VHR (%) | 99.3 |
| VHR (%) after ultraviolet irradiation | 99.1 |
| Drip vestige evaluation | ◎ |
| Ghost is evaluated | ◎ |
(comparative example 4)
As vertical orientated film formation material, the polyimide derivatives represented by the following formula containing 3% and 3% are used
The METHYLPYRROLIDONE solution of polymerizable compound represented by formula (Va-1-1), in addition similarly to Example 12, is obtained
The liquid crystal display cells of comparative example 4.
[chemical formula 108]
In the state of the AC field of rectangle is applied with, to obtained liquid crystal display cells irradiation ultraviolet radiation, make described
The solidification of the polymerizable compound with reactive group in alignment films.The UIS-S2511RZ manufactured using oxtail Motor Corporation
As irradiation unit, the USH-250BY manufactured using oxtail Motor Corporation is as ultraviolet lamp, with 20mW to liquid crystal display cells
Irradiation ultraviolet radiation 600 seconds, obtains the liquid crystal display cells of comparative example 4.In addition, with the identical conditions of embodiment 12 (20mW, 300
Second) under to liquid crystal display cells irradiation ultraviolet radiation, assign pre-tilt angle, but due to the polymerization with reactive group in alignment films
The solidification of property compound is insufficient, pre-tilt angle is not assigned stably, therefore, in order to maintain pre-tilt angle, it is necessary to be irradiated with 20mW
600 seconds.
Before and after each physical property of liquid-crystal composition used in the liquid crystal display cells of comparative example 4, ultraviolet light
VHR and vestige evaluation of dripping, the ghost evaluation of obtained liquid crystal display cells be shown in following table 28.As a result, by
The polymerizable compound represented by logical formula (I) is not contained in the aligning film material in comparative example 4, therefore, for by alignment films
In the solidification of the polymerizable compound with polymerism ultraviolet light total energy quantitative change it is big, as a result observe that VHR declines, and confirms
Physical property caused by the decomposition of liquid-crystal compounds in liquid-crystal composition declines.
[table 28]
| Comparative example 4 | |
| Ultraviolet pre-irradiation VHR (%) | 99.3 |
| VHR (%) after ultraviolet irradiation | 97.5 |
| Drip vestige evaluation | △ |
| Ghost is evaluated | × |
(embodiment 13)
Manufacture possesses the transparent electrode layer being made up of transparent common electrode and the first substrate of color filter layers (is shared
Electrode base board)；And possess the second substrate (pixel of the pixel electrode layer with the transparent pixel electrode driven by active component
Electrode base board).
Using method of spin coating, the vertical orientated membrane material comprising polymerizable liquid crystal compound and polymerization initiator is distinguished
Common electrode substrate and pixel electrode substrate are coated on, the precursor layer of thickness 200nm vertical alignment layer is formed.As vertically taking
To film formation material, 3.0% polymerizable compound and 97.0% UCL-011-K1 (DIC that are represented by following formula (I-1) is used
Co. Ltd. system) polymerizable compound.
[chemical formula 109]
Each substrate for being coated with vertical orientated film formation material is heated 15 minutes in 70 DEG C of thermostat, so that
Polymerizable liquid crystal compound in the vertical orientated film formation material having been coated with turns into isotropic liquid.
Afterwards, temperature is made to drop to room temperature with 10 DEG C/minute of speed, by the polymerism liquid in vertical orientated film formation material
The orientation of crystallization compound is set to vertical orientated.
Pixel electrode substrate and common electrode substrate are applied respectively 70 ° of magnetic field has been tilted from substrate surface, to polymerization
Property liquid-crystal compounds assign pre-tilt angle.In this condition, irradiation ultraviolet radiation, solidifies polymerizable liquid crystal compound, forms vertical
Alignment films.
Liquid-crystal composition (LC-A) containing the compound represented by chemical formula as shown below is clamped in be formed with it is vertical
After the common electrode substrate and pixel electrode substrate of straight alignment films, solidify the encapsulant, form liquid crystal combination nitride layer.This
When, using the sept that thickness is 3.0 μm, the thickness of liquid crystal combination nitride layer is set to 3.0 μm.
[table 29]
In the state of the AC field of rectangle is applied with, to obtained liquid crystal display cells irradiation ultraviolet radiation, make described
Polymerizable compound solidifies.The UIS-S2511RZ manufactured using oxtail Motor Corporation uses oxtail motor public as irradiation unit
The USH-250BY of manufacture is taken charge of as ultraviolet lamp, with 20mW to liquid crystal display cells irradiation ultraviolet radiation 300 seconds, embodiment is obtained
13 liquid crystal display cells.Using the process, the vertical alignment layer of the polymer comprising polymerizable liquid crystal compound is formed, and it is right
Liquid crystal molecule in liquid crystal combination nitride layer assigns pre-tilt angle.
The slit of pixel electrode shown in the liquid crystal display cells along Fig. 2 of embodiment 13 is in 4 blocks towards different
Direction has pre-tilt angle, after the polymerizable liquid crystal compound solidification, in the state of cut-out AC field, also maintains pre-
Inclination angle.
Before and after each physical property of liquid-crystal composition used in the liquid crystal display cells of embodiment 13, ultraviolet light
VHR and vestige evaluation of dripping, the ghost evaluation of obtained liquid crystal display cells be shown in following table.As a result, implementing
Declining to a great extent for VHR is not observed in liquid-crystal composition before and after ultraviolet light used in the liquid crystal display cells of example 13.
Trace it to its cause and be：Containing the polymerizable compound represented by logical formula (I) in aligning film material, therefore, it is possible to which orientation will be made
In film polymerizable liquid crystal compound polymerization when ultraviolet light gross energy be suppressed to it is relatively low, so, can suppress constitute liquid
The decomposition of the liquid-crystal compounds of crystal composite.
[table 30]
| Embodiment 13 | |
| Ultraviolet pre-irradiation VHR (%) | 99.1 |
| VHR (%) after ultraviolet irradiation | 99.0 |
| Drip vestige evaluation | ○ |
| Ghost is evaluated | ◎ |
(comparative example 5)
As vertical orientated film formation material, UCL-011-K1 (Dainippon Ink Chemicals's system) using 100% is as vertically taking
To film formation material, in addition similarly to Example 13, the liquid crystal display cells of comparative example 5 are obtained.
In the state of the AC field of rectangle is applied with, to obtained liquid crystal display cells irradiation ultraviolet radiation, make described
Polymerizable compound solidifies.The UIS-S2511RZ manufactured using oxtail Motor Corporation uses oxtail motor public as irradiation unit
The USH-250BY of manufacture is taken charge of as ultraviolet lamp, with 20mW to liquid crystal display cells irradiation ultraviolet radiation 600 seconds, comparative example 5 is obtained
Liquid crystal display cells.In addition, with irradiating ultraviolet to liquid crystal display cells under the identical conditions of embodiment 13 (20mW, 300 seconds)
Line, assigns pre-tilt angle, but because the solidification of the polymerizable liquid crystal compound in alignment films is insufficient, pre-dumping is not assigned stably
Angle, therefore, in order to maintain pre-tilt angle, it is necessary to be irradiated 600 seconds with 20mW.
Before and after each physical property of liquid-crystal composition used in the liquid crystal display cells of comparative example 5, ultraviolet light
VHR and vestige evaluation of dripping, the ghost evaluation of obtained liquid crystal display cells be shown in following table 31.As a result, by
The polymerizable compound represented by logical formula (I) is not contained in the aligning film material in comparative example 5, therefore, for by alignment films
In polymerizable liquid crystal compound solidification ultraviolet light total energy quantitative change it is big, as a result observe that VHR declines, it is thus identified that liquid crystal group
Physical property caused by the decomposition of liquid-crystal compounds in compound declines.
[table 31]
| Comparative example 5 | |
| Ultraviolet pre-irradiation VHR (%) | 99.1 |
| VHR (%) after ultraviolet irradiation | 97.7 |
| Drip vestige evaluation | × |
| Ghost is evaluated | × |
(embodiment 14)
The liquid-crystal composition (LC-A3) containing the compound shown in following table is prepared, using the liquid-crystal composition, in addition
With the identical condition of embodiment 13, the liquid crystal display cells of embodiment 14 are obtained.
[table 32]
In the state of the AC field of rectangle is applied with, to obtained liquid crystal display cells irradiation ultraviolet radiation, make described
Polymerizable compound solidifies.The UIS-S2511RZ manufactured using oxtail Motor Corporation uses oxtail motor public as irradiation unit
The USH-250BY of manufacture is taken charge of as ultraviolet lamp, with 20mW to liquid crystal display cells irradiation ultraviolet radiation 300 seconds, embodiment is obtained
14 liquid crystal display cells.The liquid crystal display cells of embodiment 14 have pre-tilt angle similarly to Example 13, in the polymerization
Property compound cures after, even in cut-out AC field in the state of, also maintain pre-tilt angle.
Before and after each physical property of liquid-crystal composition used in the liquid crystal display cells of embodiment 14, ultraviolet light
VHR and vestige evaluation of dripping, the ghost evaluation of obtained liquid crystal display cells be shown in following table 33.As a result, real
Apply liquid-crystal composition used in the liquid crystal display cells of example 14 be not observed before and after ultraviolet light VHR significantly under
Drop.Trace it to its cause and be：Containing the polymerizable compound represented by logical formula (I) in aligning film material, therefore, it is possible to make to take
Into film polymerizable liquid crystal compound polymerization when ultraviolet light gross energy be suppressed to it is relatively low, so, can suppress constitute
The decomposition of the liquid-crystal compounds of liquid-crystal composition.
[table 33]
| Embodiment 14 | |
| Ultraviolet pre-irradiation VHR (%) | 99.3 |
| VHR (%) after ultraviolet irradiation | 99.2 |
| Drip vestige evaluation | ◎ |
| Ghost is evaluated | ◎ |
(embodiment 15)
The liquid-crystal composition (LC-A6) containing the compound shown in following table is prepared, the liquid-crystal composition is used.As vertical
Film formation material is orientated, 3.0% polymerizable compound and 97.0% UCL-011-K1 that are represented by following formula (I-21) is used
(Dainippon Ink Chemicals's system) polymerizable compound.In addition, with the identical condition of embodiment 13, obtain the liquid of embodiment 15
Crystal display element.
[table 34]
[chemical formula 110]
In the state of the AC field of rectangle is applied with, to obtained liquid crystal display cells irradiation ultraviolet radiation, make described
Polymerizable compound solidifies.The UIS-S2511RZ manufactured using oxtail Motor Corporation uses oxtail motor public as irradiation unit
The USH-250BY of manufacture is taken charge of as ultraviolet lamp, with 20mW to liquid crystal display cells irradiation ultraviolet radiation 300 seconds, embodiment is obtained
15 liquid crystal display cells.The liquid crystal display cells of embodiment 15 have pre-tilt angle similarly to Example 13, in the polymerization
Property compound cures after, even in cut-out AC field in the state of, also maintain pre-tilt angle.
Before and after each physical property of liquid-crystal composition used in the liquid crystal display cells of embodiment 15, ultraviolet light
VHR and vestige evaluation of dripping, the ghost evaluation of obtained liquid crystal display cells be shown in following table 35.As a result, real
Apply liquid-crystal composition used in the liquid crystal display cells of example 15 be not observed before and after ultraviolet light VHR significantly under
Drop.Trace it to its cause and be：Containing the polymerizable compound represented by logical formula (I) in aligning film material, therefore, it is possible to make to take
Into film polymerizable liquid crystal compound polymerization when ultraviolet light gross energy be suppressed to it is relatively low, so, can suppress constitute
The decomposition of the liquid-crystal compounds of liquid-crystal composition.
[table 35]
| Embodiment 15 | |
| Ultraviolet pre-irradiation VHR (%) | 99.2 |
| VHR (%) after ultraviolet irradiation | 99.0 |
| Drip vestige evaluation | ○ |
| Ghost is evaluated | ◎ |
(embodiment 16)
The liquid-crystal composition (LC-B) containing the compound shown in following table is prepared, the liquid-crystal composition is used.As vertical
Film formation material is orientated, 3.0% polymerizable compound and 97.0% UCL-011-K1 that are represented by following formula (I-33) is used
(Dainippon Ink Chemicals's system) polymerizable compound.In addition, with the identical condition of embodiment 13, obtain the liquid of embodiment 16
Crystal display element.
[table 36]
[chemical formula 111]
In the state of the AC field of rectangle is applied with, to obtained liquid crystal display cells irradiation ultraviolet radiation, make described
Polymerizable compound solidifies.The UIS-S2511RZ manufactured using oxtail Motor Corporation uses oxtail motor public as irradiation unit
The USH-250BY of manufacture is taken charge of as ultraviolet lamp, with 20mW to liquid crystal display cells irradiation ultraviolet radiation 300 seconds, embodiment is obtained
16 liquid crystal display cells.The liquid crystal display cells of embodiment 16 have pre-tilt angle similarly to Example 13, in the polymerization
Property compound cures after, even in cut-out AC field in the state of, also maintain pre-tilt angle.
Before and after each physical property of liquid-crystal composition used in the liquid crystal display cells of embodiment 16, ultraviolet light
VHR and vestige evaluation of dripping, the ghost evaluation of obtained liquid crystal display cells be shown in following table 37.As a result, real
Apply liquid-crystal composition used in the liquid crystal display cells of example 16 be not observed before and after ultraviolet light VHR significantly under
Drop.Trace it to its cause and be：Containing the polymerizable compound represented by logical formula (I) in aligning film material, therefore, it is possible to make to take
Into film polymerizable liquid crystal compound polymerization when ultraviolet light gross energy be suppressed to it is relatively low, so, can suppress constitute
The decomposition of the liquid-crystal compounds of liquid-crystal composition.
[table 37]
| Embodiment 16 | |
| Ultraviolet pre-irradiation VHR (%) | 99.3 |
| VHR (%) after ultraviolet irradiation | 99.1 |
| Drip vestige evaluation | ◎ |
| Ghost is evaluated | ○ |
(comparative example 6)
As vertical orientated film formation material, UCL-011-K1 (Dainippon Ink Chemicals's system) using 100% is as vertically taking
To film formation material, in addition similarly to Example 16, the liquid crystal display cells of comparative example 6 are obtained.
In the state of the AC field of rectangle is applied with, to obtained liquid crystal display cells irradiation ultraviolet radiation, make described
Polymerizable compound solidifies.The UIS-S2511RZ manufactured using oxtail Motor Corporation uses oxtail motor public as irradiation unit
The USH-250BY of manufacture is taken charge of as ultraviolet lamp, with 20mW to liquid crystal display cells irradiation ultraviolet radiation 600 seconds, comparative example 6 is obtained
Liquid crystal display cells.In addition, with irradiating ultraviolet to liquid crystal display cells under the identical conditions of embodiment 16 (20mW, 300 seconds)
Line, assigns pre-tilt angle, but because the solidification of the polymerizable liquid crystal compound in alignment films is insufficient, pre-dumping is not assigned stably
Angle, therefore, in order to maintain pre-tilt angle, it is necessary to be irradiated 600 seconds with 20mW.
Before and after each physical property of liquid-crystal composition used in the liquid crystal display cells of comparative example 6, ultraviolet light
VHR and vestige evaluation of dripping, the ghost evaluation of obtained liquid crystal display cells be shown in following table 38.As a result, by
The polymerizable compound represented by logical formula (I) is not contained in the aligning film material in comparative example 6, therefore, for by alignment films
In polymerizable liquid crystal compound solidification ultraviolet light total energy quantitative change it is big, as a result observe that VHR declines, it is thus identified that liquid crystal group
Physical property caused by the decomposition of liquid-crystal compounds in compound declines.
[table 38]
| Comparative example 6 | |
| Ultraviolet pre-irradiation VHR (%) | 99.3 |
| VHR (%) after ultraviolet irradiation | 98.0 |
| Drip vestige evaluation | × |
| Ghost is evaluated | × |
Claims (12)
1. a kind of liquid crystal display cells, wherein,
The liquid crystal display cells have：A group substrate with first substrate and second substrate；And it is clamped in the base
Liquid crystal combination nitride layer between plate, also, there is electrode at least one of the first substrate and the second substrate,
At least one of the first substrate and the second substrate have alignment films, and the alignment films contain by that will have polymerization
Property group the polymerizable group of compound polymerize to control the differently- oriented directivity of liquid crystal molecule in the liquid crystal combination nitride layer
Polymer, the liquid-crystal composition for constituting the liquid crystal combination nitride layer contains from by following formulas (N-1), formula (N-2) and formula
(N-3) a kind or the compound of more than two kinds selected in the compound group represented,
[chemical formula 1]
(in formula, RN11、RN12、RN21、RN22、RN31And RN32Separately represent in the alkyl that carbon number is 1~8, the alkyl
1 or non-conterminous more than 2-CH2- can separately by-CH=CH- ,-C ≡ C- ,-O- ,-CO- ,-COO- or
Person-OCO- replaces,
AN11、AN12、AN21、AN22、AN31And AN32Separately represent from by
(a) 1,4- cyclohexylidenes (are present in 1-CH in the group2- or non-conterminous more than 2-CH2- can be substituted
For-O-)；And
(b) (being present in 1 in the group-CH=or non-conterminous more than 2-CH=can be substituted 1,4- phenylenes
For-N=)；
(c) naphthalene -2,6- diyls, 1,2,3,4- naphthane -2,6- diyls or decahydronaphthalene -2,6- diyls (are present in naphthalene -2,6- two
Base or 1-CH=or non-conterminous more than 2-CH=in 1,2,3,4- naphthane-2,6- diyls can be substituted
For-N=)
The group selected in the group of composition, the group (a), group (b) and group (c) can be separately former by cyano group, fluorine
Son or chlorine atom substitution,
ZN11、ZN12、ZN21、ZN22、ZN31And ZN32Separately represent singly-bound ,-CH2CH2-、-(CH2)4-、-OCH2-、-
CH2O-、-COO-、-OCO-、-OCF2-、-CF2O- ,-CH=N-N=CH- ,-CH=CH- ,-CF=CF- or-C ≡ C-,
XN21Hydrogen atom or fluorine atom are represented,
TN31Expression-CH2- or oxygen atom,
nN11、nN12、nN21、nN22、nN31And nN32The separately integer of expression 0~3, but nN11+nN12、nN21+nN22And nN31+
nN32It is separately 1,2 or 3, there are multiple AN11~AN32、ZN11~ZN32In the case of, they can also may be used with identical
With difference),
As the compound with polymerizable group, containing a kind or two or more is by leading to the compound that formula (I) is represented,
[chemical formula 2]
(in formula, X10And X11Separately represent hydrogen atom or methyl, Sp3And Sp4Separately represent that singly-bound, carbon are former
Subnumber is 1~8 alkylidene or-X- (CH2)t- (in formula, t represents 2~7 integer, X represent-O- ,-OCOO- ,-OCO- or
Person-COO-, X are bonded with phenanthrene ring), any hydrogen atom in phenanthrene ring in formula can be replaced by fluorine atoms).
2. liquid crystal display cells as claimed in claim 1, wherein,
The liquid crystal display cells have multiple pixels, have 2 different area above of pre-tilt angle in the pixel.
3. liquid crystal display cells as claimed in claim 1 or 2, wherein,
The first substrate has common electrode, and second substrate has pixel electrode.
4. liquid crystal display cells as claimed in claim 3, wherein,
There are the alignment films between the common electrode and the pixel electrode, the alignment films pass through to first base
Plate and the second substrate generally perpendicularly apply electric charge, so as to control the liquid crystal molecule in the liquid crystal combination nitride layer.
5. the liquid crystal display cells as described in any one of Claims 1-4, wherein,
The alignment films include the polymer for the differently- oriented directivity for controlling the liquid crystal molecule in the liquid crystal combination nitride layer or by gathering
The solidfied material of conjunction property liquid-crystal compounds is formed.
6. liquid crystal display cells as claimed in claim 5, wherein,
As the polymer for the differently- oriented directivity for controlling the liquid crystal molecule in the liquid crystal combination nitride layer, comprising with polymerizable group
Compound polymer or comprising as main chain and being used as side chain with cross-linking functional group with polyimide backbone
The polymer of polymerizable compound.
7. the liquid crystal display cells as any one of claim 1 to 6, wherein,
1 kind or two or more polymerism that also there is the orientation of control liquid crystal molecule and stabilize it in the alignment layer surface
The polymer of compound.
8. a kind of manufacture method of liquid crystal display cells, wherein,
Oriented material is coated with least one of first substrate and second substrate and is heated so as to be formed after aligning film material,
Liquid-crystal composition is clamped using the first substrate and the second substrate, in the first substrate and the second substrate
At least one there is electrode, and active energy beam is irradiated to the electrode in the state of voltage is applied with, so that by institute
The polymerizable group polymerization of the compound with polymerizable group included in aligning film material is stated, then with the control liquid
Crystal composite layer in liquid crystal molecule differently- oriented directivity alignment films, the liquid-crystal composition contain from by following formulas (N-1),
1 kind or two or more compound selected in the compound group that formula (N-2) and formula (N-3) are represented,
[chemical formula 3]
(in formula, RN11、RN12、RN21、RN22、RN31And RN32Separately represent in the alkyl that carbon number is 1~8, the alkyl
1 or non-conterminous more than 2-CH2- can separately by-CH=CH- ,-C ≡ C- ,-O- ,-CO- ,-COO- or
Person-OCO- replaces,
AN11、AN12、AN21、AN22、AN31And AN32Separately represent from by
(a) 1,4- cyclohexylidenes (are present in 1-CH in the group2- or non-conterminous more than 2-CH2- can be substituted
For-O-)；And
(b) (being present in 1 in the group-CH=or non-conterminous more than 2-CH=can be substituted 1,4- phenylenes
For-N=)；
(c) naphthalene -2,6- diyls, 1,2,3,4- naphthane -2,6- diyls or decahydronaphthalene -2,6- diyls (are present in naphthalene -2,6- two
Base or 1-CH=or non-conterminous more than 2-CH=in 1,2,3,4- naphthane-2,6- diyls can be substituted
For-N=)
The group selected in the group of composition, the group (a), group (b) and group (c) can be separately former by cyano group, fluorine
Son or chlorine atom substitution,
ZN11、ZN12、ZN21、ZN22、ZN31And ZN32Separately represent singly-bound ,-CH2CH2-、-(CH2)4-、-OCH2-、-
CH2O-、-COO-、-OCO-、-OCF2-、-CF2O- ,-CH=N-N=CH- ,-CH=CH- ,-CF=CF- or-C ≡ C-,
XN21Hydrogen atom or fluorine atom are represented,
TN31Expression-CH2- or oxygen atom,
nN11、nN12、nN21、nN22、nN31And nN32The separately integer of expression 0~3, but nN11+nN12、nN21+nN22And nN31+
nN32It is separately 1,2 or 3, there are multiple AN11~AN32、ZN11~ZN32In the case of, they can also may be used with identical
With difference),
As the compound with polymerizable group, containing a kind or two or more is by leading to the compound that formula (I) is represented,
[chemical formula 4]
(in formula, X10And X11Separately represent hydrogen atom or methyl, Sp3And Sp4Separately represent that singly-bound, carbon are former
Subnumber is 1~8 alkylidene or-X- (CH2)t- (in formula, t represents 2~7 integer, X represent-O- ,-OCOO- ,-OCO- or
Person-COO-, X are bonded with phenanthrene ring), any hydrogen atom in phenanthrene ring in formula can be replaced by fluorine atoms).
9. the manufacture method of liquid crystal display cells as claimed in claim 8, wherein,
Polymer of the aligning film material comprising the differently- oriented directivity for controlling the liquid crystal molecule in the liquid crystal combination nitride layer or
Formed by the solidfied material of polymerizable liquid crystal compound.
10. the manufacture method of liquid crystal display cells as claimed in claim 9, wherein,
As the polymer for the differently- oriented directivity for controlling the liquid crystal molecule in the liquid crystal combination nitride layer, comprising with polymerism
The polymer of the compound of group or comprising as main chain and being used as side with cross-linking functional group with polyimide backbone
The polymer of the polymerizable compound of chain.
11. the manufacture method of the liquid crystal display cells as described in claim 9 or 10, wherein,
1 kind or two or more polymerism that also there is the orientation of control liquid crystal molecule and stabilize it in the alignment layer surface
The polymer of compound.
12. the manufacture method of the liquid crystal display cells as any one of claim 9~11, wherein,
The active energy beam is ultraviolet, and its intensity is 2mW/cm-2~100mW/cm-2, irradiation gross energy be 10J~
300J。
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| WO2017217311A1 (en) * | 2016-06-17 | 2017-12-21 | Dic株式会社 | Liquid crystal composition and liquid crystal display element |
| JP2018054761A (en) * | 2016-09-27 | 2018-04-05 | Jsr株式会社 | Liquid crystal element and method for manufacturing the same |
| WO2018079528A1 (en) * | 2016-10-27 | 2018-05-03 | Dic株式会社 | Liquid crystal display element |
| TWI794515B (en) * | 2018-07-03 | 2023-03-01 | 日商Ｄｉｃ股份有限公司 | Liquid crystal display element and method for manufacturing liquid crystal display element |
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| CN112437802A (en) * | 2018-10-11 | 2021-03-02 | Dic株式会社 | Liquid crystal composition and liquid crystal display element |
Also Published As
| Publication number | Publication date |
|---|---|
| JPWO2016093142A1 (en) | 2017-04-27 |
| JP6011904B1 (en) | 2016-10-25 |
| KR102450332B1 (en) | 2022-10-04 |
| KR20170094331A (en) | 2017-08-17 |
| TW201632608A (en) | 2016-09-16 |
| WO2016093142A1 (en) | 2016-06-16 |
| CN107209421B (en) | 2020-11-13 |
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