CN107924090A

CN107924090A - Liquid crystal display element

Info

Publication number: CN107924090A
Application number: CN201680046785.3A
Authority: CN
Inventors: 小川真治; 岩下芳典; 长谷部浩史; 谷口士朗
Original assignee: Dainippon Ink and Chemicals Co Ltd
Current assignee: DIC Corp
Priority date: 2015-08-21
Filing date: 2016-08-18
Publication date: 2018-04-17
Also published as: WO2017033830A1; TW201722996A; KR20180042337A; JPWO2017033830A1

Abstract

Problem to be solved by this invention is to provide a kind of nematic phase stability when will not make dielectric constant anisotropy, viscosity, nematic phase ceiling temperature, low temperature, γ₁The liquid crystal display element being deteriorated Deng each characteristic as liquid crystal display element and the burn-in characteristic of display element.By the present invention in that liquid-crystal composition and optical alignment film with the compound contained represented by general formula (i) and the compound represented by general formula (J), there is provided maintain the high-speed response of the liquid-crystal composition and the liquid crystal display element that low-temperature stability is excellent.

Description

Liquid crystal display element

Technical field

The present invention relates to one kind use as liquid crystal display material is useful and dielectric constant anisotropy (Δ ε) show on the occasion of Nematic liquid-crystal composition liquid crystal display element.

Background technology

At present, the liquid crystal display as smart mobile phone, widely uses the excellent horizontal orientation of high-quality, visual characteristic Liquid crystal display device (the liquid crystal display of fringe field switching mode of mode, the liquid crystal display device of such as IPS patterns, FFS mode Device (Fringe Field Switching mode Liquid CrystalDisplay), FFS mode liquid crystal display device) (with reference to patent document 1, patent document 2).FFS mode is imported to improve the low aperture opening ratio of IPS patterns and transmitance Mode.At present, as liquid-crystal composition used in the liquid crystal display device of horizontal orientation mode, it is easy for the side of lower voltage It is widely used to have used the material that dielectric constant anisotropy is positive p-type liquid-crystal composition for face.Further, since FFS moulds Most of purposes of formula is portable terminal device, therefore is strongly required further electric power saving, and liquid crystal cell manufacturer just persistently accumulates Polar region carries out having used use of the array of IGZO etc. to develop.

In addition, the method for alignment as liquid crystal molecule, use the method for being referred to as rubbing manipulation more.This method is, for applying The aligning film materials such as cloth polyimides and the film for being burnt till and being obtained, while by the roller for being wound with the cloth such as nylon with a level pressure Power press-in on one side make its rotation, thus in a certain direction wipe (friction) alignment layer surface, thus to liquid crystal molecule imparting orientation Restraining force.The tight orientation mechanism of this method is now also indefinite, and due to wiping the surface of alignment films, there are generation striated Display is uneven, a part for aligning film material comes off and is mixed into liquid crystal layer and led because of the electrostatic produced on array base palte The problems such as TFT destructions are caused, thus research does not utilize the orientation adding method of friction.Make especially with the ultraviolet of linear polarization There is alignment films anisotropic optical alignment film can assign orientation in the non-contact case, therefore described above as solving The method of the problem of rubbing manipulation, it, which is developed, is just constantly in progress, even if also gradually groping light in the display element of lateral electric-field type The use of alignment films (with reference to patent document 3).

Prior art literature

Patent document

Patent document 1：Japanese Unexamined Patent Publication 11-202356 publications

Patent document 2：Japanese Unexamined Patent Publication 2003-233083 publications

Patent document 3：Japanese Unexamined Patent Publication 2013-109366 publications

The content of the invention

Problems to be solved by the invention

However, due to the purposes of liquid crystal display element in recent years, the expansion in market, its application method, manufacture method also may be used See big change, not only the type of drive (for example, TN types, STN types, VA types, IPS types, FFS types etc.) of liquid crystal display element, its It is practical that size also has the display element of ultra-large type sizes more than 50 types to be able to, and is accompanied by this, and liquid-crystal composition is to substrate Method for implanting also by conventional vacuum impregnation become by the drop of liquid-crystal composition be added dropwise to a side real estate and with it is another The drip (ODF, One Drop Fill) of the substrate fitting of side becomes the mainstream of method for implanting.Therefore, such as above patent document Described in 1~3, the electrode of the horizontal orientation mode such as IPS, FFS mode is due to possessing the multiple of the substrate surface for being formed at one side The electrode runs parallel arrangement of short strip shape and the entire surface on aforesaid substrate surface are coated with the structure of alignment films, therefore in the one side There are numerous bumps, which causes to be formed on substrate when liquid-crystal composition is added dropwise to substrate surface substrate surface The problem of drop impression, which causes display quality to reduce, becomes to come to the surface.In addition to the problem of such, further with directly connecing Touching the adaptability of the alignment films of liquid-crystal composition also becomes problem.

Further, in the liquid crystal display element manufacturing process carried out by ODF methods, it is necessary to according to liquid crystal display element Optimal liquid crystal injection rate is added dropwise in size.If injection rate becomes larger apart from the deviation of optimum value, the liquid crystal display being pre-designed is first The refractive index of part, the balance of driving electric field are disintegrated, it may occur that the display such as bad of the generation of spot, contrast is bad.It is especially multi-purpose Small-sized liquid crystal display element in nearest popular smart mobile phone, will be apart from optimal since optimal liquid crystal injection rate is few The deviation control of value is inherently difficult in a certain range.Therefore, in order to the yield rate of liquid crystal display element is kept as height, example Such as also require following performance：Relative to produced violent pressure change in Dropping feeder when liquid crystal is added dropwise, impact Influence less, liquid crystal can persistently be added dropwise long-term and stably.

In addition, when improving optical alignment film to the orientation restraining force of liquid crystal molecule, exist must increase irradiation energy, it is long when Between the problem of irradiating.

Thus, in liquid-crystal composition used in the active matrix drive liquid crystal display element by drivings such as TFT elements In, it is desirable to carry out following exploitation：Except maintaining high speed response property etc. as the characteristic required by liquid crystal display element, property While energy, there is the high resistivity value just paid attention in the past or high voltage holding ratio, the characteristic to the outside stimulus such as light, heat stabilization In addition, but also require the manufacture method in view of liquid crystal display element and developed.

Therefore, problem of the invention is to solve the above problems, there is provided a kind of liquid crystal display element, the liquid crystal display element Dielectric constant anisotropy (Δ ε), viscosity (η), the transition temperature (TNI) of nematic phase-isotropic liquid, low temperature when to Each excellent as liquid crystal display element such as row phase stability, rotary viscosity (γ 1), and used by for possessing light The liquid crystal display element of the horizontal alignment mode of alignment films and can realize the p-type liquid-crystal composition of excellent display characteristic.

The present invention another problem be to provide a kind of liquid crystal display element, the liquid crystal display element used by for Possess the liquid crystal display element of the horizontal alignment mode for the alignment films that orientation restraining force improves and can realize excellent display characteristic The liquid crystal display element of the p-type liquid-crystal composition of (contrast etc.).

Solve the technological means of problem

Present inventors etc. concentrate on studies in order to solve the above problems, have studied the liquid crystal display of horizontal alignment mode The composition of element and various liquid-crystal compositions most suitable for which, the composition of alignment films, as a result complete the present application.

Invention effect

Liquid crystal display element of the present invention since resistivity, voltage retention are because of heat, changing very little for being subject to light, Therefore the practicality height of product is, it can be achieved that high-speed response.

Liquid-crystal composition of the present invention can play consistently in the manufacturing process of used liquid crystal display element Performance, thus show bad be suppressed as caused by process and can manufacture to high finished product rate, therefore it is highly useful.

Low-temperature stability and the excellent liquid-crystal composition of high-speed response can be used in liquid crystal display element of the present invention.

The present invention can provide a kind of liquid crystal display element, it possesses the light orientation for the orientation restraining force for improving liquid crystal molecule Film.

Liquid crystal display element of the present invention can realize the excellent high contrast of orientation restraining force.

The liquid crystal display element of the present invention can be realized very due to the use of the liquid-crystal composition containing polymerizable monomer Excellent high contrast.

Brief description of the drawings

Fig. 1 is the figure of an example for the composition for schematically showing the liquid crystal display element of the present invention.

Fig. 2 is by plan obtained by the region surrounded with II lines the amplification for the electrode layer 3 being formed in Fig. 1 on substrate 2.

Fig. 3 be along the III-III lines direction in Fig. 2 by shown in Fig. 1 liquid crystal display element cut-out obtained by sectional view.

Fig. 4 is the variation of Fig. 2, for the region surrounded with II lines of the electrode layer being formed in Fig. 1 on substrate 23 is put Plan obtained by big.

Fig. 5 be along the III-III lines direction in Fig. 4 by shown in Fig. 1 liquid crystal display element cut-out obtained by sectional view.

Fig. 6 is the plan for schematically showing the electrode structure in the liquid crystal display element of the present invention.

Fig. 7 is the plane of the state before and after the polymerization of the liquid crystal layer in the region for the dotted line part VII for schematically showing Fig. 6 Figure.

It is used for the suitable of the liquid crystal display element of the present invention in the region that Fig. 8 is the dotted line part VII for schematically showing Fig. 6 The plan of the driving condition of liquid crystal layer.

Embodiment

The first of the present invention is a kind of liquid crystal display element of horizontally oriented type, it is characterised in that is had：

The first substrate and second substrate configured in opposite directions；

Liquid crystal layer, it contains the liquid-crystal composition being filled between foregoing first substrate and foregoing second substrate；

Electrode layer, it has common electrode, multiple grid with rectangular configuration on foregoing first substrate, in each pixel Pole bus and data/address bus, be arranged at foregoing grid bus and data/address bus cross part thin film transistor (TFT) and by foregoing Thin film transistor (TFT) drives and the pixel electrode relative to the almost parallel electric field of substrate is formed between foregoing common electrode；And

Light redirecting layer, its between liquid crystal display layer and foregoing first substrate and liquid crystal display layer and foregoing second substrate it Between, be formed at least one substrate,

Foregoing liquid crystal composition has positive dielectric constant anisotropy, the transition temperature of nematic phase-isotropic liquid For more than 60 DEG C, and containing the compound selected from least one of the compound group represented by general formula (i) and selected from following It is more than one or both of compound represented by general formula (J).

(in above-mentioned general formula (i), Rⁱ¹And Rⁱ²Separately represent the alkyl of carbon number 1~8, carbon number 2~8 The alkenyloxy group of alkenyl, the alkoxy of carbon number 1~8 or carbon number 2~8, in the alkyl, alkenyl, alkoxy or alkenyloxy group The hydrogen atom of more than 1 can be substituted by fluorine atom, the methylene in the alkyl, alkenyl, alkoxy or alkenyloxy group can be Oxygen atom is substituted by oxygen atom in the case of discontinuously connecting, and can be substituted by the case where carbonyl discontinuously connects Carbonyl,

Aⁱ¹Represent be selected from by

(a) 1,4- cyclohexylidenes (are present in 1-CH in the group₂- or the not adjacent-CH of more than 2₂- can be taken On behalf of-O-)

(b) (the 1-CH=or the not adjacent-CH=of more than 2 being present in the group can be taken 1,4- phenylenes On behalf of-N=) and

(c) (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=in 1,2,3,4- naphthane-2,6- diyls or the not adjacent-CH=of more than 2 can be substituted For-N=)

Group in the group formed, above-mentioned group (a), group (b) and group (c) can separately through cyano group, Fluorine atom, chlorine atom, methyl, trifluoromethyl or trifluoromethoxy substitution,

nⁱ¹1,2,3 or 4 are represented, in nⁱ¹For 2,3 or 4 so as to which there are multiple Aⁱ¹When, they may be the same or different, in nⁱ¹ For 2,3 or 4 so as to which there are multiple Zⁱ¹When, they may be the same or different.)

(in formula, R^J1Represent the alkyl of carbon number 1~8 ,-the CH of more than 2 of 1 or non-adjacent in the alkyl₂- - CH=CH- ,-C ≡ C- ,-O- ,-CO- ,-COO- or-OCO- can be separately substituted by,

n^J1Represent 0,1,2,3 or 4,

A^J1、A^J2And A^J3Separately represent be selected from by

Z^J1And Z^J2Separately represent singly-bound ,-CH₂CH₂-、-(CH₂)₄-、-OCH₂-、-CH₂O-、-OCF₂-、- CF₂O- ,-COO- ,-OCO- or-C ≡ C-,

In n^J1For 2,3 or 4 so as to which there are multiple A^J2When, they may be the same or different, in n^J1For 2,3 or 4 so as to exist Multiple Z^J1When, they may be the same or different,

X^J1Represent hydrogen atom, fluorine atom, chlorine atom, cyano group, trifluoromethyl, fluorine methoxyl group, difluoro-methoxy, trifluoro methoxy Base or 2,2,2- trifluoroethyls.)

Use structures of Fig. 1~Fig. 8 to liquid crystal display element of the present invention and the structure as the liquid crystal display element Substrate and electrode layer into key element illustrate.Next, the inscape on liquid crystal display element, takes liquid crystal layer and light It is described in detail to film layer.

Hereinafter, based on attached drawing, an embodiment of liquid crystal display element of the present invention is illustrated.

Fig. 1 is the figure for the composition for schematically showing liquid crystal display element.In Fig. 1, in order to illustrate, for the sake of convenient and incite somebody to action Each inscape separates record.The composition of liquid crystal display element 10 of the present invention is as described in Fig. 1, it is characterised in that：Its For with the liquid crystal combination being held between configure in opposite directions first (transparent insulation) substrate 2 and second (transparent insulation) substrate 7 The liquid crystal display element of the horizontal alignment pattern of thing (or liquid crystal layer 5), and use foregoing liquid-crystal composition of the invention to be used as and be somebody's turn to do Liquid-crystal composition.First (transparent insulation) substrate 2 is in the face of 5 side of liquid crystal layer formed with electrode layer 3.In addition, in liquid crystal layer 5 and One (transparent insulation) substrate 2 and with second (transparent insulation) substrate 7 it is respective between have with form liquid crystal layer 5 liquid crystal combination Thing directly abuts and causes a pair of of optical alignment film 4 of homogeneous orientation, and the liquid crystal molecule in the liquid-crystal composition is in no applied voltage When be orientated in a manner of almost parallel relative to aforesaid base plate 2,7.As shown in Figures 1 and 3, foregoing second substrate 7 and foregoing First substrate 2 can be as clamped by a pair of of polarizer 1,8.Further, in Fig. 1, between foregoing second substrate 7 and alignment films 4 It is provided with colour filter 6.It should be noted that the form as liquid crystal display element of the present invention, can be so-called integrated Colour filter (COA), also can set colour filter between the electrode layer and liquid crystal layer containing thin film transistor (TFT) or contain film at this Colour filter is set between the electrode layer and second substrate of transistor.

In addition, in Fig. 1~Fig. 8, in explanation, as the suitable embodiment of the liquid crystal display element of the present invention, Describe between liquid crystal layer 5 and first substrate 2 and liquid crystal layer 5 and foregoing second substrate 7 between respectively in first substrate and Example formed with optical alignment film 4 on two substrates, as long as but the present invention liquid crystal display element in first substrate 2 or second substrate At least one on 7 is formed with optical alignment film 4.

For example, before optical alignment film 4 is formed in a manner of being abutted with liquid crystal layer 5 between liquid crystal layer 5 and first substrate 2 When stating on first substrate 2, alignment films are not set between other liquid crystal layer 5 and second substrate 7, and be preferably formed as light orientation Film or friction orientation film, more preferably form optical alignment film.

That is, liquid crystal display element 10 of the present invention is preferably sequentially laminated with the first polarizer 1, first substrate 2, contains There are the electrode layer 3 of thin film transistor (TFT), (first) alignment films 4, the liquid crystal layer 5 containing liquid-crystal composition, (second) alignment films 4, filter The composition that color device 6,7 and second polarizer 8 of second substrate form.

First substrate 2 can be used glass with second substrate 7 or have the transparent material of flexibility as plastics, also may be used One side is the opaque materials such as silicon.Epoxy thermoset composition of two plate bases 2,7 by being configured at neighboring area etc. is close Closure material and closed material and be bonded, in order to keep substrate spacing, such as glass particle, plastic pellet, oxygen can be configured therebetween Change aluminum particulate equigranular sept or the spacer being made of resin formed by photoetching process.Substrate of the present invention is preferred Contain transparent conductive material.

Fig. 2 is by plan obtained by the region surrounded with II lines the amplification for the electrode layer 3 being formed in Fig. 1 on substrate 2. Fig. 3 be along the III-III lines direction in Fig. 2 by shown in Fig. 1 liquid crystal display element cut-out obtained by sectional view.In addition, Fig. 2 and In Fig. 3, the example of FFS mode is described as an example of the liquid crystal display element of horizontal alignment mode of the present invention. On the other hand, in Fig. 4 and Fig. 5 described below, one as the liquid crystal display element of horizontal alignment mode of the present invention Example and describe the example of IPS patterns.As shown in Fig. 2, it is formed at the electrode containing thin film transistor (TFT) on the surface of first substrate 2 In layer 3, to supply multiple grid bus 26 of scanning signal with showing that multiple data/address bus 25 of signal are mutual to supply Intersect and be configured to rectangular.It should be noted that a pair of of grid bus 26 and a pair of of data/address bus 25 are only shown in fig. 2.

The list of liquid crystal display device is formed using the region surrounded by multiple grid bus 26 and multiple data/address bus 25 Position pixel, formed with pixel electrode 21 and common electrode 22 in the unit pixel.In grid bus 26 and 25 phase of data/address bus The cross part mutually intersected is nearby provided with the thin film transistor (TFT) comprising source electrode 27, drain electrode 24 and gate electrode 28.The film is brilliant Body pipe is connected as the switch element that display signal is supplied to pixel electrode 21 with pixel electrode 21.In addition, and grid bus 26 are concurrently provided with bridging line 29.The bridging line 29 connects to supply shared signal to common electrode 22 with common electrode 22 Connect.

A suitable mode for the structure of thin film transistor (TFT) is for example as shown in figure 3, have：It is formed at 2 surface of substrate Gate electrode 11；By the gate insulator 12 set in a manner of covering the substantially entire surface of the gate electrode 11 and covering aforesaid base plate 2； Semiconductor layer 13 by the surface for being formed at foregoing gate insulator 12 in a manner of opposite with foregoing gate electrode 11；It is foregoing to cover The protective layer 14 that the mode of the part on the surface of semiconductor layer 13 is set；To cover foregoing protective layer 14 and aforementioned semiconductor layer The electric leakage that the side end of one and the mode contacted with being formed at the foregoing gate insulator 12 on 2 surface of aforesaid base plate are set in 13 Pole 16；To cover in foregoing protective layer 14 and aforementioned semiconductor layer 13 side end of another one and with being formed at 2 table of aforesaid base plate The source electrode 17 that the mode that the foregoing gate insulator 12 in face contacts is set；And to cover aforementioned electrical leakage pole 16 and foregoing source electrode The insulating protective layer 18 that 17 mode is set., also can be in gate electrode 11 for eliminating the reasons such as the difference of height with gate electrode 11 Surface formed anodic oxidation coating (not shown).

Non-crystalline silicon, polysilicon etc. can be used in aforementioned semiconductor layer 13, if using ZnO, IGZO (In-Ga-Zn-O), ITO etc. Transparent semiconductor film, then the drawbacks of can inhibit the optical carriers as caused by light absorbs, just increase the viewpoint of the aperture opening ratio of element For it is also preferred that.

Further, also can be in semiconductor layer 13 and drain electrode 16 or source electricity in order to reduce the width of Schottky barrier, height Ohmic contact layer 15 is set respectively between pole 17.N-shaped non-crystalline silicon, N-shaped polysilicon etc. can be used to add in high concentration for ohmic contact layer Added with the material of the impurity such as phosphorus.

Grid bus 26, data/address bus 25, bridging line 29 be preferably metal film, more preferably Al, Cu, Au, Ag, Cr, Ta, Ti, Mo, W, Ni or their alloy, particularly preferably using the situation of Al or the distribution of its alloy.In addition, insulating protective layer 18 For the layer with insulation function, formed by silicon nitride, silica, silicon oxynitride film etc..

In the embodiment shown in Fig. 2 and Fig. 3, common electrode 22 is on gate insulator 12 substantially in entire surface The flat electrode formed, on the other hand, pixel electrode 21 are to be formed on the insulating protective layer 18 of covering common electrode 22 Comb shape electrode.That is, common electrode 22 is configured at than pixel electrode 21 closer to the position of first substrate 2, these electrodes every Insulating protective layer 18 to overlap each other and configure.Pixel electrode 21 is with common electrode 22 for example by ITO (tin indium oxide, Indium Tin Oxide), IZO (indium zinc oxide, Indium Zinc Oxide), IZTO (indium oxide zinc-tin, Indium Zinc Tin ) etc. Oxide transparent conductive material is formed.Since pixel electrode 21 and common electrode 22 are formed by transparent conductive material, Therefore the area of unit pixel area split shed becomes larger, aperture opening ratio and transmitance increase.

In addition, pixel electrode 21 and common electrode 22 be between these electrodes in order to form fringe field, with pixel electrode 21 Interelectrode distance (also referred to as minimum separation distances) between common electrode 22：R is less than first substrate 2 and second substrate 7 Distance：The mode of G is formed.Herein, interelectrode distance：R represents interelectrode relative to the distance that substrate is horizontal direction.Fig. 3 In, since flat common electrode 22 and the pixel electrode 21 of comb shape overlap each other, interelectrode distance is shown：R=0's Example, due to foregoing minimum separation distances：R is less than distance (that is, cell gap) G of first substrate 2 and second substrate 7, thus Form fringe field E.Therefore, the liquid crystal display element of FFS types can be utilized along the line relative to the comb shape for forming pixel electrode 21 The electric field of horizontal direction and the electric field of parabolic shape formed for vertical direction.The electrode of the comb section of pixel electrode 21 is wide Degree：L, and the gap of the comb section of pixel electrode 21 width：M is preferably formed as can be by caused electric field driven liquid The width of the degree of whole liquid crystal molecules in crystal layer 5.

Liquid crystal display element of the present invention is preferably the liquid crystal display element for the FFS modes for utilizing fringe field, and It is preferred that interelectrode distance R (common electrode 22 and the adjoining of pixel electrode 21 of the common electrode 22 with being adjacent to the common electrode 22 Component in the direction relative to substrate level of the spacing distance of the pixel electrode 21 of the common electrode 22) it is shorter than oriented layer 4 The most short spacing distance G of (substrate spacing) each other.When the liquid crystal display element of the FFS modes of preferred configuration such as of the invention, If the liquid crystal molecule configured in a manner of to becoming parallel with the differently- oriented directivity of oriented layer by long axis direction applies voltage, in pixel The equipotential line of parabola shaped electric field is formed to pixel electrode 21 and common electrode 22 between electrode 21 and common electrode 22 Top, the major axis of the liquid crystal molecule in liquid crystal layer 5 is along the electric field alignment formed.It is particularly due to liquid crystal group of the present invention Compound uses the liquid crystal molecule with positive dielectric constant anisotropy, therefore the long axis direction of liquid crystal molecule is along caused electricity Field direction arranges.

In liquid crystal display element of the present invention, preferably common electrode and pixel electrode are formed on same substrate. For example, as shown in FIG. 1 to 3, preferably common electrode and pixel electrode is formed on first substrate.

On colour filter 6, for the viewpoint for preventing light leak, preferably corresponding to thin film transistor (TFT) and reservior capacitor 23 Part formed black matrix (not shown).

On electrode layer 3 and colour filter 6, it is equal that the liquid-crystal composition with forming liquid crystal layer 5 is provided with induction with directly abutting A pair of of optical alignment film 4 of matter orientation.

By the way that alignment films are set to optical alignment film, can weaken by the uneven caused orientation restraining force to liquid crystal molecule of friction Reduction, caused by friction the problems such as dust, and the liquid crystal display element of the excellent FFS modes of light transmission rate can be provided.

In addition, polarizer 1 and polarizer 8 can adjust the polarizing axis of each polarizer, so that angle of visibility, contrast become good Good mode is adjusted, and has mutually orthogonal transmission preferably in a manner of their between axlemolecules operate under normally black mode Axis.Particularly preferred any one of polarizer 1 and polarizer 8 are with the between axlemolecules parallel with the differently- oriented directivity of liquid crystal molecule Mode configures.Additionally, it is preferred that the refractive anisotrop Δ n and element thickness of liquid crystal are adjusted in a manner of contrast becomes maximum The product of d.Further, it is possible to use for expanding the phase difference film of angle of visibility.

Further, a mode of liquid crystal display element of the present invention is preferably that common electrode is formed at the first base The substantially entire surface of plate, and be configured at than pixel electrode closer to first substrate side.That is, liquid crystal display element of the present invention Suitable embodiment be with：The first substrate and second substrate configured in opposite directions；Liquid crystal layer, it, which contains, is filled in foregoing Liquid-crystal composition between one substrate and foregoing second substrate；Electrode layer, it has on foregoing first substrate in each pixel Common electrode containing transparent conductive material, with the multiple grid bus and data/address bus of rectangular configuration, be arranged at it is foregoing The thin film transistor (TFT) of the cross part of grid bus and data/address bus and containing transparent conductive material and by aforementioned film crystal Pipe drives and the pixel electrode of fringe field is formed between foregoing common electrode；Light orientation film layer, before it is respectively formed in State liquid crystal layer and foregoing first substrate and between foregoing second substrate and induce homogeneous orientation, the electricity consumption together of foregoing pixel electrode The horizontal component R of interelectrode distance between pole is less than the distance G of foregoing first substrate and second substrate, foregoing common electrode shape Into in the substantially entire surface of foregoing first substrate, and it is configured at than pixel electrode closer to first substrate side.It should be noted that In Fig. 2~Fig. 3 as a kind of mode of the present invention, show that common electrode is formed at the substantially entire surface of first substrate and matches somebody with somebody It is placed in the form closer to first substrate side than pixel electrode.

Liquid crystal display element using Fig. 2~Fig. 3 FFS types illustrated is an example, without departing from the skill of the present invention Art is conceived, then can implement in a manner of other are various.

Fig. 4 and Fig. 5 used below illustrate the other embodiment of liquid crystal display element of the present invention.Fig. 4 And the liquid crystal display element that the liquid crystal display element shown in Fig. 5 is IPS types.For example, Fig. 4 is to be formed in Fig. 1 on substrate 2 The other embodiment of plan obtained by the region surrounded with II lines the amplification of electrode layer 3.As shown in figure 4, pixel electrode 21 Also the composition with slit can be used.Furthermore it is possible to by the pattern of slit according to relative to grid bus 26 or data/address bus 25 Mode with inclination angle is formed.

Pixel electrode 21 shown in the Fig. 4 is with the notch of substantially rectangular frame-shaped by the electrode of generally rectangular platysome The shape that portion is got through.In addition, formed at the back side of the pixel electrode 21 across insulating layer 18 (not shown) in entire surface There is the common electrode 22 of comb teeth-shaped.Also, adjacent common electrode and (most short) the spacing distance R of pixel electrode are longer than oriented layer (or substrate) mutual most short spacing distance G.In addition, the surface of foregoing pixel electrode is preferably by protection dielectric film and orientation film layer It is coated.It should be noted that it can set to preserve and lead in the region surrounded by aforesaid plurality of grid bus 25 and multiple data/address bus 26 Cross the reservior capacitor (not shown) of the display signal of the supply of data wiring 24.It should be noted that the shape of notch part has no spy Do not limit, it is not only substantially rectangular shown in usable Fig. 4, but also ellipse, circle, rectangle, diamond shape, triangle or flat can be used The notch part of shape known to row quadrangle etc..If the configuration of notch part as shown in Figure 4, then due in a manner of symmetrical The direction of notch part is set, therefore can be into the tropism control for multidomain of passing through.

Fig. 5 be the embodiment different from Fig. 3 liquid crystal display element sectional view, be with the III-III lines in Fig. 2 The identical position in direction cuts off the other examples of sectional view obtained by liquid crystal display element shown in Fig. 1.Surface is formed with orientation The first substrate 2 of layer 4 and the electrode layer 3 containing thin film transistor (TFT) is with second substrate 8 of the surface formed with oriented layer 4 according to specific Interval G by oriented layer toward each other in a manner of separate, be filled with the liquid crystal layer 5 containing liquid-crystal composition in the space. The part on one substrate, 2 surface is sequentially laminated with gate insulating film 12, common electrode 22, dielectric film 18, pixel electrode 21 and takes To layer 4.

In addition, in the example as shown in fig. 5, using comb shape or the common electrode 22 with slit, be pixel electrode 21 with The interelectrode distance R of common electrode 22 is not 0 condition.Further, figure 3 illustrates common electrode 22 to be formed at gate insulator Example on film 12, but as shown in figure 5, can also form common electrode 22 on the first substrate 2, and across gate insulating film 12 Pixel electrode 21 is set.The electrode width of pixel electrode 21：L, the electrode width of common electrode 22：N, and interelectrode distance：R is excellent Choosing is suitably adjusted to can be by the width of the degree of whole liquid crystal molecules in caused electric field driven liquid crystal layer 5.In addition, this The preferable a kind of mode for inventing the liquid crystal display element being related to is preferably interelectrode distance：R is longer than mutual most short of substrate Gauge is from G (that is, G<α).In Fig. 5, pixel electrode 21 is to be arranged at than common electrode 22 closer to liquid crystal layer side, but can be by pixel Electrode 21 is arranged to the height of identical thickness direction with common electrode 22, or is alternatively and is arranged to common electrode 22 to compare pixel Structure of the electrode 21 closer to liquid crystal layer side.Identical thickness direction is arranged to as by pixel electrode 21 and common electrode 22 The embodiment of height, can enumerate pixel electrode 21 and common electrode as shown in (A) of Fig. 6 in a manner of being movably fitted together to 22 are arranged at the structure on same substrate.In this specification, if the water of pixel electrode 21 and the interelectrode distance of common electrode 22 Flat components R is longer than substrate spacing G, then the referred to as liquid crystal display element of IPS modes, if foregoing R is shorter than foregoing G, referred to as FFS side The liquid crystal display element of formula.

For example, it is preferable to for as shown in Fig. 1, Fig. 4 and Fig. 5, common electrode and pixel electrode are formed on first substrate.If will Common electrode and pixel electrode are formed on same substrate, then are produced between two electrodes relative to the almost parallel electric field of substrate.

Liquid crystal display element of the present invention is preferably to utilize the liquid relative to substrate for the IPS modes of horizontal electric field Crystalline substance display composition, if common electrode 22 and be adjacent to foregoing common electrode 22 pixel electrode 21 spacing distance relative to base The components R of plate level is longer than the most short spacing distance D of substrate (base distance between plates) each other, then common electrode and pixel electrode it Between form horizontal component of electric field, liquid crystal molecule can be switched to by direction in face by the presence or absence of voltage.As the present invention preferred embodiment that In the case of the liquid crystal display element of the IPS modes of sample, if in a manner of long axis direction is parallel with the differently- oriented directivity of oriented layer The liquid crystal molecule of configuration applies voltage, then the electric field relative to substrate level is formed between pixel electrode 21 and common electrode 22 Equipotential line, the major axis of the liquid crystal molecule in liquid crystal layer 5 is along the electric field alignment formed.It is particularly due to of the present invention Liquid-crystal composition uses the liquid crystal molecule with positive dielectric constant anisotropy, therefore is produced from the long axis direction edge of liquid crystal molecule Raw direction of an electric field arrangement.

Since the liquid crystal display element of IPS patterns of the present invention is taken using specific liquid-crystal composition and specific light To film, therefore high-speed response and the undesirable suppression of display can be taken into account.

In addition, on IPS patterns, FFS mode etc. horizontal alignment mode liquid crystal display element, when first substrate 2 with When liquid crystal layer 5 is injected between second substrate 7, such as carry out the side such as vacuum impregnation or instillation (ODF, One Drop Fill) method Method, in the present application, can inhibit in ODF methods the generation of drop impression when liquid-crystal composition to be added dropwise to substrate.It should be noted It is so-called drop impression, the phenomenon for being defined as being added dropwise the trace whiting of liquid-crystal composition and emerging.

The generation of drop impression is significantly influenced be subject to the liquid crystal material injected, further, the composition based on display element It can not avoid the influence.In the liquid crystal display element of horizontal alignment mode, the thin film transistor (TFT) that is formed in display element and Comb shape has the grade of pixel electrode 21 of slit due to only having thin alignment films 4 or thin alignment films 4 and thin insulating protective layer The component that 18 grades separate liquid-crystal composition, therefore the possibility of ionic substance can not be blocked high completely, it can not avoid forming The generation of drop impression caused by the interaction of the metal material and liquid-crystal composition of electrode, but in the liquid crystal of horizontal alignment mode Show in element, by the way that the liquid-crystal composition of the present application and optical alignment film are applied in combination, the production of drop impression can be effectively inhibited It is raw.

In addition, in the manufacturing process of the liquid crystal display element carried out by ODF methods, it is necessary to according to liquid crystal display element Optimal liquid crystal injection rate is added dropwise in size, since the liquid-crystal composition of the present application is for example relative to caused by dropwise addition liquid crystal Violent pressure change, the influence of impact in Dropping feeder is small, and liquid crystal can persistently be added dropwise long-term and stably, therefore can incite somebody to action The yield rate of liquid crystal display element is kept as height.Especially with respect to the small-sized liquid crystal being chiefly used in the smart mobile phone of nearest prevalence Show element, will be inherently to be stranded in a certain range apart from the deviation control of optimum value since optimal liquid crystal injection rate is few Difficulty, but by using the liquid-crystal composition of the present application, even if can also realize stable liquid in small-sized liquid crystal display element The discharge rate of brilliant material.

Liquid crystal layer to other inscapes as liquid crystal display element of the present invention and light orientation film layer below It is described in detail.

(liquid crystal layer)

Liquid crystal layer of the present invention is the layer containing liquid-crystal composition, is preferably made of liquid-crystal composition.The liquid crystal group Compound is preferably applied to the liquid crystal display element of horizontal alignment mode, such as FFS mode and/or IPS patterns.It can be related in the present invention And liquid-crystal composition in add polymerizable monomer.Therefore, liquid crystal layer of the present invention is preferably contained in liquid-crystal composition Polymerizable monomer polymerization after state.It can hereafter be illustrated to orientation restraining force thus can be improved.

Liquid-crystal composition in the present invention is containing the compound represented by the general formula (i) as first composition and is used as the The compound more than one or both of group being made of the compound represented by general formula (J) and dielectric of binary The anisotropic value of constant is positive liquid-crystal composition, and the compound preferably comprised represented by general formula (i) is one or more kinds of, And containing one or more kinds of as the compound represented by the general formula (J) of second composition.

Relative to the compound represented by the general formula (i) of the total amount of the composition of the present invention and the change represented by general formula (J) The lower limit of the preferred content of compound is 10%, 15%, 20%, 25%, 30%, 35%, 40%, 50%, 55%, 60%, 65%th, 70%, 75%, 80%.The upper limit value of preferred content is 97%, 95%, 85%, 75%, 65%, 55%, 45%, 35%th, 30%, 25%, 20%.

The preferred physics value of liquid-crystal composition of the present invention be preferably Δ ε be 1.5~12, Δ n be 0.08~0.20.

Hereinafter, one by one to contained by liquid-crystal composition of the present invention component (first composition, second composition, other Meaning component) illustrate.

In above-mentioned general formula (i), in nⁱ¹For 2~4 integer when, ring Aⁱ¹It may be the same or different respectively.In addition, on Ring Aⁱ¹, the preferably aromatic series when requiring increase Δ n, is preferably aliphatic to improve response speed, ring Aⁱ¹It is preferred that distinguish Independently represent anti-form-1,4- cyclohexylidenes, 1,3- bis-Alkane -2,5- diyls, oxinane -2,5- diyls, 1,4- phenylenes, The fluoro- 1,4- phenylenes of 2-, the fluoro- 1,4- phenylenes of 3-, the fluoro- 1,4- phenylenes of 3,5- bis-, 1,4- cyclohexadienylidenes, 1,4- are bicyclic [2.2.2] octamethylene, piperidines -1,4- diyls, naphthalene -2,6- diyls, decahydronaphthalene -2,6- diyls or 1,2,3,4- naphthanes -2,6- Diyl, more preferably represents following structures,

Further preferably represent anti-form-1,4- cyclohexylidenes or 1,4- phenylenes.

In above-mentioned general formula (i), Zⁱ¹More preferably singly-bound.In addition, nⁱ¹Preferably 2,3 or 4.In the case of optimum condition, Since there are multiple Z^Mi1, therefore they may be the same or different.

When paying attention to reliability, Rⁱ¹And Rⁱ²Alkyl is preferably all, when paying attention to reducing the volatility of compound, is preferably Alkoxy, when paying attention to the reduction of viscosity, it is alkenyl to be preferably at least one.

On Rⁱ¹And Rⁱ², it is preferably the carbon number of straight-chain when the ring structure that it is connected is phenyl (aromatic series) The alkenyl of 1~5 alkyl, the alkoxy of the carbon number 1~4 of straight-chain or carbon number 4~5, in the ring knot that it is connected Structure for hexamethylene when the ring structure of saturation, be preferably straight-chain carbon number 1~5 alkyl, the carbon number 1 of straight-chain The alkenyl of~4 alkoxy and the carbon number 2~5 of straight-chain.In order to stabilize nematic phase, preferably carbon atom and in the presence of Oxygen atom add up to less than 5, and preferably straight-chain.

Moreover, it relates to alkyl, alkenyl and alkoxy be both preferably straight-chain or branched.Related to as the present invention And preferred alkenyl, be preferably selected from the group represented by formula (R1) to any one of formula (R5).(stain in various represents Carbon atom in ring structure.)

In the liquid-crystal composition of the present invention, the dissolving when content of the compound represented by general formula (i) need to be according to low temperature Property, the institute such as transition temperature, electric reliability, refractive anisotrop, Technological adaptability, drop impression, burn-in, dielectric constant anisotropy It is required that performance suitably adjusted.

If the total amount of the compound represented by the general formula (i) of the first composition in liquid-crystal composition of the present invention is more Ground contains, then due to fully containing polarized is low, i.e. the high component of visbreaking effect is such the reasons why, it can be ensured that high-speed response.Separately Be outside, 1% relative to the lower limit of the preferred content of the compound represented by the formula (i) of the total amount of composition of the invention, 10%th, 15%, 20%, 25%, 30%, 35%, 40%, 50%, 55%, 60%, 65%, 70%, 75%, 80%.It is preferred that contain The upper limit value of amount is 95%, 85%, 75%, 65%, 55%, 45%, 35%, 30%, 25%.

It is preferably foregoing when the viscosity of the composition of the present invention is kept as composition that is low, needing fast response time Lower limit is high, and upper limit value is high.Further, the Tni of the composition of the present invention is being kept as height, is needing temperature stability good Composition when, be preferably that aforementioned minimum value is high, and upper limit value is high.In addition, to increase in order to which driving voltage to be kept as low It is preferably that aforementioned minimum value is low, and upper limit value is low during big dielectric constant anisotropy.

The compound represented by more than one aforementioned formula (i) is preferably comprised, and with relative to the general formula of second composition (M) amount that the compound represented by is 5~20 times contains.By the compound represented by the general formula (i) as first composition and Play high-speed response and other effects.

The liquid-crystal composition of the present invention also compound represented by the general formula (i) containing more than one.It can be combined The species of compound there is no particular restriction, dissolubility, viscosity, transition temperature, electric reliability, the refractive index during according to low temperature are each The desired performance such as anisotropy is appropriately combined and uses.Wherein, the compound represented by the general formula (i) preferably comprises performance visbreaking The compound of effect.In addition, the species of the compound used as the compound represented by first composition, that is, general formula (i) is for example It is one kind as an embodiment of the invention.Or in another embodiment of the present invention be two kinds.In addition, in the present invention Another embodiment in be three kinds.Further, it is in another embodiment of the present invention four kinds.Further, in the present invention Another embodiment in be five kinds.Further, it is in another embodiment of the present invention six kinds.Further, in the present invention Another embodiment in be seven kinds.Further, it is in another embodiment of the present invention eight kinds.Further, in the present invention Another embodiment in be nine kinds.Further, it is in another embodiment of the present invention ten kinds more than.

Compound represented by general formula (i) of the present invention is when requiring the chemical stability of liquid-crystal composition, preferably Its intramolecular does not have chlorine atom.

Compound represented by general formula (i) is preferably selected from the change in the compound group represented by general formula (i-1)~(i-7) Compound.

Compound represented by general formula (i-1) is following compound.

(in formula, Rⁱ¹¹And Rⁱ¹²Separately represent and the R in general formula (i)ⁱ¹And Rⁱ²Identical implication.)

Rⁱ¹¹And Rⁱ¹²Preferably the alkyl of the carbon number 1~5 of straight-chain, straight-chain carbon number 1~4 alkoxy And the alkenyl of the carbon number 2~5 of straight-chain.

Compound represented by general formula (i-1) can be used alone, and also can be combined and uses two or more compounds.It can be combined The species of compound there is no particular restriction, the dissolubility, transition temperature, electric reliability, refractive index during according to low temperature are respectively to different Performance required by property etc. is appropriately combined and uses.The species of used compound is for example as one embodiment of the present invention Formula is one kind, two kinds, three kinds, four kinds, more than five kinds.

The lower limit of preferred content relative to the present invention composition total amount, be 1%, 2%, 3%, 5%, 7%, 10%th, 15%, 20%, 25%, 30%, 35%, 40%, 45%, 50%, 55%.The upper limit value of preferred content is relative to this hair The total amount of bright composition, be 95%, 93%, 90%, 87%, 85%, 82%, 80%, 77%, 75%, 73%, 70%, 67%th, 65%, 63%, 60%, 57%, 55%, 52%, 50%, 47%, 45%, 43%, 40%, 35%, 30%, 25%.

It is preferably foregoing when the viscosity of the composition of the present invention is kept as composition that is low, needing fast response time Lower limit is high, and upper limit value is high.Further, the Tni of the composition of the present invention is being kept as height, is needing temperature stability good Composition when, be preferably that aforementioned minimum value is placed in the middle, and upper limit value is placed in the middle.In addition, in order to by driving voltage be kept as it is low and It is preferably that aforementioned minimum value is low, and upper limit value is low when increasing dielectric constant anisotropy.

Compound represented by general formula (i-1) is preferably selected from the chemical combination in the compound group represented by general formula (i-1-1) Thing.

(R in formulaⁱ¹²Represent the implication identical with the implication in general formula (i-1).)

Compound represented by general formula (i-1-1) is preferably selected from the change represented by formula (i-1-1.1) to formula (i-1-1.3) Compound represented by compound in compound group, preferably formula (i-1-1.2) or formula (i-1-1.3), particularly preferably formula (i- Compound represented by 1-1.3).

Relative to the lower limit of the preferred content of the compound represented by the formula (i-1-1.3) of the total amount of the composition of the present invention It is worth for 1%, 2%, 3%, 5%, 7%, 10%.The upper limit value of preferred content relative to the present invention composition total amount, be 20%th, 15%, 13%, 10%, 8%, 7%, 6%, 5%, 3%.

Compound represented by general formula (i-1) is preferably selected from the chemical combination in the compound group represented by general formula (i-1-2) Thing.

Relative to the lower limit of the preferred content of the compound represented by the formula (i-1-2) of the total amount of the composition of the present invention For 1%, 5%, 10%, 15%, 17%, 20%, 23%, 25%, 27%, 30%, 35%.

The upper limit value of preferred content relative to the present invention composition total amount, be 60%, 55%, 50%, 45%, 42%th, 40%, 38%, 35%, 33%, 30%.

Further, the compound represented by general formula (i-1-2) is preferably selected from formula (i-1-2.1) to formula (i-1-2.4) institute Compound in the compound group of expression, is preferably the compound represented by formula (i-1-2.2) to formula (i-1-2.4).Especially, In order to improve the present invention composition response speed and the compound particularly preferably represented by formula (i-1-2.2).In addition, When high Tni is more required compared to response speed, preferably using the compound represented by formula (i-1-2.3) or formula (i-1-2.4).For Make solubility during low temperature good, preferably do not set the content of the compound represented by formula (i-1-2.3) and formula (i-1-2.4) For more than 30%.

Relative to the lower limit of the preferred content of the compound represented by the formula (i-1-2.2) of the total amount of the composition of the present invention It is worth for 10%, 15%, 18%, 20%, 23%, 25%, 27%, 30%, 33%, 35%, 38%, 40%.Preferred content it is upper Limit value relative to the present invention composition total amount, be 60%, 55%, 50%, 45%, 43%, 40%, 38%, 35%, 32%th, 30%, 27%, 25%, 22%.

Relative to the compound represented by the formula (i-1-1.3) of the total amount of the composition of the present invention and formula (i-1-2.2) institute The lower limit of total preferred content of the compound of expression is 10%, 15%, 20%, 25%, 27%, 30%, 35%, 40%.The upper limit value of preferred content relative to the present invention composition total amount, be 60%, 55%, 50%, 45%, 43%, 40%th, 38%, 35%, 32%, 30%, 27%, 25%, 22%.

Compound represented by general formula (i-1) is preferably selected from the chemical combination in the compound group represented by general formula (i-1-3) Thing.

(R in formulaⁱ¹³And Rⁱ¹⁴Separately represent the alkyl of carbon number 1~8 or the alkoxy of carbon number 1~8.)

Rⁱ¹³And Rⁱ¹⁴Preferably the alkyl of the carbon number 1~5 of straight-chain, straight-chain carbon number 1~4 alkoxy And the alkenyl of the carbon number 2~5 of straight-chain.

Relative to the lower limit of the preferred content of the compound represented by the formula (i-1-3) of the total amount of the composition of the present invention For 1%, 5%, 10%, 13%, 15%, 17%, 20%, 23%, 25%, 30%.The upper limit value of preferred content is relative to this hair The total amount of bright composition, be 60%, 55%, 50%, 45%, 40%, 37%, 35%, 33%, 30%, 27%, 25%, 23%th, 20%, 17%, 15%, 13%, 10%.

Further, the compound represented by general formula (i-1-3) is preferably selected from formula (i-1-3.1) to formula (i-1-3.12) institute Compound in the compound group of expression, is preferably the change represented by formula (i-1-3.1), formula (i-1-3.3) or formula (i-1-3.4) Compound.Especially, in order to improve the present invention composition response speed and the change particularly preferably represented by formula (i-1-3.1) Compound.In addition, when more requiring high Tni compared to response speed, preferably using formula (i-1-3.3), formula (i-1-3.4), formula (i- 1-3.11) and the compound represented by formula (i-1-3.12).Solubility during in order to make low temperature is good, not preferably by formula (i-1- 3.3), total content of the compound represented by formula (i-1-3.4), formula (i-1-3.11) and formula (i-1-3.12) is set to 20% More than.

Relative to the lower limit of the preferred content of the compound represented by the formula (i-1-3.1) of the total amount of the composition of the present invention It is worth for 1%, 2%, 3%, 5%, 7%, 10%, 13%, 15%, 18%, 20%.The upper limit value of preferred content is relative to the present invention Composition total amount, be 20%, 17%, 15%, 13%, 10%, 8%, 7%, 6%.

Compound represented by general formula (i-1) is preferably selected from general formula (i-1-4) and/or the chemical combination represented by (i-1-5) Compound in thing group.

(R in formulaⁱ¹⁵And Rⁱ¹⁶Separately represent the alkyl of carbon number 1~8 or the alkoxy of carbon number 1~8.)

Rⁱ¹⁵And Rⁱ¹⁶Preferably the alkyl of the carbon number 1~5 of straight-chain, straight-chain carbon number 1~4 alkoxy And the alkenyl of the carbon number 2~5 of straight-chain.

Relative to the lower limit of the preferred content of the compound represented by the formula (i-1-4) of the total amount of the composition of the present invention For 1%, 5%, 10%, 13%, 15%, 17%, 20%.The upper limit value of preferred content is total relative to the composition of the present invention Amount, is 25%, 23%, 20%, 17%, 15%, 13%, 10%.

Relative to the lower limit of the preferred content of the compound represented by the formula (i-1-5) of the total amount of the composition of the present invention For 1%, 5%, 10%, 13%, 15%, 17%, 20%.The upper limit value of preferred content is total relative to the composition of the present invention Amount, is 25%, 23%, 20%, 17%, 15%, 13%, 10%.

Further, general formula (i-1-4) and the compound represented by (i-1-5) are preferably selected from formula (i-1-4.1) to formula (i- Chemical combination represented by the compound in compound group represented by 1-5.3), preferably formula (i-1-4.2) or formula (i-1-5.2) Thing.

Relative to the lower limit of the preferred content of the compound represented by the formula (i-1-4.2) of the total amount of the composition of the present invention It is worth for 1%, 2%, 3%, 5%, 7%, 10%, 13%, 15%, 18%, 20%.The upper limit value of preferred content is relative to the present invention Composition total amount, be 20%, 17%, 15%, 13%, 10%, 8%, 7%, 6%.

Preferably combination is selected from formula (i-1-1.3), formula (i-1-2.2), formula (i-1-3.1), formula (i-1-3.3), formula (i-1- 3.4), the two or more compounds in formula (i-1-3.11) and compound represented by formula (i-1-3.12), are preferably combined Selected from formula (i-1-1.3), formula (i-1-2.2), formula (i-1-3.1), formula (i-1-3.3), formula (i-1-3.4) and formula (i-1-4.2) Two or more compounds in represented compound, the lower limit phase of the preferred content of total content of these compounds For the present invention composition total amount, be 1%, 2%, 3%, 5%, 7%, 10%, 13%, 15%, 18%, 20%, 23%, 25%th, 27%, 30%, 33%, 35%, upper limit value relative to the present invention composition total amount, be 80%, 70%, 60%, 50%th, 45%, 40%, 37%, 35%, 33%, 30%, 28%, 25%, 23%, 20%.When the reliability for paying attention to composition When, preferably two kinds in compound of the combination represented by formula (i-1-3.1), formula (i-1-3.3) and the formula (i-1-3.4) with On compound, pay attention to composition response speed when, preferably combination selected from formula (i-1-1.3), formula (i-1-2.2) institute table Two or more compounds in the compound shown.

Compound represented by general formula (i-2) is following compound.

(in formula, Rⁱ²¹And Rⁱ²²Separately represent and the R in general formula (i)ⁱ¹And Rⁱ²Identical implication.)

Rⁱ²¹The preferably alkenyl of the alkyl of carbon number 1~5 or carbon number 2~5, Rⁱ²²Preferably carbon number 1~5 Alkyl, the alkenyl of carbon number 4~5 or the alkoxy of carbon number 1~4.

During dissolubility when paying attention to low temperature, if content is set to more, effect is high, on the contrary, paying attention to ringing When answering speed, if content to be set to few, effect height.Further, when improveing drop impression, burn-in characteristic, preferably will The range set of content is placed in the middle.

The lower limit of preferred content relative to the compound represented by the formula (i-2) of the total amount of the composition of the present invention is 1%th, 2%, 3%, 5%, 7%, 10%.The upper limit value of preferred content relative to the present invention composition total amount, be 20%, 15%th, 13%, 10%, 8%, 7%, 6%, 5%, 3%.

Further, the compound represented by general formula (i-2) is preferably selected from represented by formula (i-2.1) to formula (i-2.6) Compound in compound group, is preferably the chemical combination represented by formula (i-2.1), formula (i-2.3), formula (i-2.4) and formula (i-2.6) Thing.

Compound represented by general formula (i-3) is following compound.

(in formula, Rⁱ³¹And Rⁱ³²Separately represent and the R in general formula (i)ⁱ¹And Rⁱ²Identical implication.)

Rⁱ³¹And Rⁱ³²It is preferred that it is separately alkyl, the alkenyl or carbon atom of carbon number 4~5 of carbon number 1~5 The alkoxy of number 1~4.

Compound represented by general formula (i-3) can be used alone, and also can be combined and uses two or more compounds.It can be combined The species of compound there is no particular restriction, the dissolubility, transition temperature, electric reliability, refractive index during according to low temperature are respectively to different Performance required by property etc. is appropriately combined and uses.The species of used compound is for example as one embodiment of the present invention Formula is one kind, two kinds, three kinds, four kinds, more than five kinds.

The lower limit of preferred content relative to the compound represented by the formula (i-3) of the total amount of the composition of the present invention is 1%th, 2%, 3%, 5%, 7%, 10%.The upper limit value of preferred content relative to the present invention composition total amount, be 20%, 15%th, 13%, 10%, 8%, 7%, 6%, 5%, 3%.

When obtaining high index of refraction anisotropy, if content to be set to more, effect height, on the contrary, paying attention to During high Tni, if content to be set to few, effect height.Further, when improveing drop impression, burn-in characteristic, will preferably contain The range set of amount is placed in the middle.

Further, the compound represented by general formula (i-3) is preferably selected from represented by formula (i-3.1) to formula (i-3.4) Compound in compound group, is preferably the compound represented by formula (i-3.2) to formula (i-3.7).

Compound represented by general formula (i-4) is following compound.

(in formula, Rⁱ⁴¹And Rⁱ⁴²Separately represent and the R in general formula (i)ⁱ¹And Rⁱ²Identical implication.)

Rⁱ⁴¹The preferably alkenyl of the alkyl of carbon number 1~5 or carbon number 2~5, Rⁱ⁴²Preferably carbon number 1~5 Alkyl, the alkenyl of carbon number 4~5 or the alkoxy of carbon number 1~4.

Compound represented by general formula (i-4) can be used alone, and also can be combined and uses two or more compounds.It can be combined The species of compound there is no particular restriction, the dissolubility, transition temperature, electric reliability, refractive index during according to low temperature are respectively to different Performance required by property etc. is appropriately combined and uses.The species of used compound is for example as one embodiment of the present invention Formula is one kind, two kinds, three kinds, four kinds, more than five kinds.

Dissolubility when in the present compositions, the content of the compound represented by general formula (i-4) need to be according to low temperature, Transition temperature, electric reliability, refractive anisotrop, Technological adaptability, drop impression, burn-in, dielectric constant anisotropy etc. are wanted The performance asked suitably is adjusted.

The lower limit of preferred content relative to the compound represented by the formula (i-4) of the total amount of the composition of the present invention is 1%th, 2%, 3%, 5%, 7%, 10%, 14%, 16%, 20%, 23%, 26%, 30%, 35%, 40%.Relative to the present invention Composition total amount formula (i-4) represented by compound preferred content upper limit value for 50%, 40%, 35%, 30%, 20%th, 15%, 10%, 5%.

Compound represented by general formula (i-4) is preferably the compound for example represented by formula (i-4.1) to formula (i-4.3).

Can according to the performance required by dissolubility during low temperature, transition temperature, electric reliability, refractive anisotrop etc., And containing the compound represented by formula (i-4.1), or containing the compound represented by formula (i-4.2), or formula (i- can be contained 4.1) compound and both compounds represented by formula (i-4.2) represented by, or can also contain formula (i-4.1) to formula (i- 4.3) whole compounds represented by.It is represented relative to the formula (i-4.1) or formula (i-4.2) of the total amount of the composition of the present invention The lower limit of preferred content of compound be 3%, 5%, 7%, 9%, 11%, 12%, 13%, 18%, 21%, it is preferable on Limit value is 45%, 40%, 35%, 30%, 25%, 23%, 20%, 18%, 15%, 13%, 10%, 8%.

When containing both compounds represented by the compound represented by formula (i-4.1) and formula (i-4.2), relative to The lower limit of the preferred content of two compounds of the total amount of the composition of the present invention is 15%, 19%, 24%, 30%, preferably Upper limit value is 45,40%, 35%, 30%, 25%, 23%, 20%, 18%, 15%, 13%.

Compound represented by general formula (i-4) is preferably the compound for example represented by formula (i-4.4) to formula (i-4.6), Compound preferably represented by formula (i-4.4).

Can according to the performance required by dissolubility during low temperature, transition temperature, electric reliability, refractive anisotrop etc., And containing the compound represented by formula (i-4.4), or the compound represented by containing formula (i-4.5), or can also contain formula (i- 4.4) compound and both compounds represented by formula (i-4.5) represented by.

Relative to the preferred of the compound represented by the formula (i-4.4) or formula (i-4.5) of the total amount of the composition of the present invention The lower limit of content is 3%, 5%, 7%, 9%, 11%, 12%, 13%, 18%, 21%.Preferable upper limit value is 45,40%, 35%th, 30%, 25%, 23%, 20%, 18%, 15%, 13%, 10%, 8%.

When containing both compounds represented by the compound represented by formula (i-4.4) and formula (i-4.5), relative to The lower limit of the preferred content of two compounds of the total amount of the composition of the present invention is 15%, 19%, 24%, 30%, preferably Upper limit value is 45%, 40%, 35%, 30%, 25%, 23%, 20%, 18%, 15%, 13%.

Compound represented by general formula (i-4) is preferably the compound represented by formula (i-4.7) to formula (i-4.10), especially Compound preferably represented by formula (i-4.9).

Compound represented by general formula (i-5) is following compound.

(in formula, Rⁱ⁵¹And Rⁱ⁵²Separately represent and the R in general formula (i)ⁱ¹And Rⁱ²Identical implication.)

Rⁱ⁵¹The preferably alkenyl of the alkyl of carbon number 1~5 or carbon number 2~5, Rⁱ⁵²Preferably carbon number 1~5 Alkyl, the alkenyl of carbon number 4~5 or the alkoxy of carbon number 1~4.

Compound represented by general formula (i-5) can be used alone, and also can be combined and uses two or more compounds.It can be combined The species of compound there is no particular restriction, the dissolubility, transition temperature, electric reliability, refractive index during according to low temperature are respectively to different Performance required by property etc. is appropriately combined and uses.The species of used compound is for example as one embodiment of the present invention Formula is one kind, two kinds, three kinds, four kinds, more than five kinds.

Dissolubility when in the present compositions, the content of the compound represented by general formula (i-5) need to be according to low temperature, Transition temperature, electric reliability, refractive anisotrop, Technological adaptability, drop impression, burn-in, dielectric constant anisotropy etc. are wanted The performance asked suitably is adjusted.

The lower limit of preferred content relative to the compound represented by the formula (i-5) of the total amount of the composition of the present invention is 1%th, 2%, 3%, 5%, 7%, 10%, 14%, 16%, 20%, 23%, 26%, 30%, 35%, 40%.Relative to the present invention Composition total amount formula (i-5) represented by compound preferred content upper limit value for 50%, 40%, 35%, 30%, 20%th, 15%, 10%, 5%.

Compound represented by general formula (i-5) is preferably formula (i-5.1) or the compound represented by formula (i-5.2), especially Compound preferably represented by formula (i-5.1).

Relative to these compounds of the total amount of the composition of the present invention preferred content lower limit for 1%, 2%, 3%th, 5%, 7%.The upper limit value of the preferred content of these compounds is 20%, 15%, 13%, 10%, 9%.

Compound represented by general formula (i-5) is preferably formula (i-5.3) or the compound represented by formula (i-5.4).

Compound represented by general formula (i-5) is preferably selected from the compound group represented by formula (i-5.5) to formula (i-5.7) In compound, the particularly preferably compound represented by formula (i-5.7).

Compound represented by general formula (i-6) is following compound.

(in formula, Rⁱ⁶¹And Rⁱ⁶²Separately represent and the R in general formula (i)ⁱ¹And Rⁱ²Identical implication, Xⁱ⁶¹And Xⁱ⁶²Point Do not represent hydrogen atom or fluorine atom independently.)

Rⁱ⁶¹And Rⁱ⁶²It is preferred that it is separately the alkyl of carbon number 1~5 or the alkenyl of carbon number 2~5, preferably Xⁱ⁶¹And Xⁱ⁶²Middle one is fluorine atom, another one is hydrogen atom.

Compound represented by general formula (i-6) can be used alone, and also can be combined and uses two or more compounds.It can be combined The species of compound there is no particular restriction, the dissolubility, transition temperature, electric reliability, refractive index during according to low temperature are respectively to different Performance required by property etc. is appropriately combined and uses.The species of used compound is for example as one embodiment of the present invention Formula is one kind, two kinds, three kinds, four kinds, more than five kinds.

The lower limit of preferred content relative to the compound represented by the formula (i-6) of the total amount of the composition of the present invention is 1%th, 2%, 3%, 5%, 7%, 10%, 14%, 16%, 20%, 23%, 26%, 30%, 35%, 40%.Relative to the present invention Composition total amount formula (i-6) represented by compound preferred content upper limit value for 50%, 40%, 35%, 30%, 20%th, 15%, 10%, 5%.When focusing on increasing Δ n, preferably content is set to it is more, when focusing on low temperature It is preferably that content is few during precipitation.

Compound represented by general formula (i-6) is preferably the compound represented by formula (i-6.1) to formula (i-6.9).

There is no particular restriction for the species of combined compound, preferably comprises one kind~tri- in these compounds Kind, it is further preferably a kind of~tetra- kinds.Also have further, since the molecular weight distribution of selected compound is wide to dissolubility Effect, therefore a kind of compound is preferably for example selected from the compound represented by formula (i-6.1) or (i-6.2), from formula (i-6.4) Or a kind of compound is selected in the compound represented by (i-6.5), from the compound represented by formula (i-6.6) or formula (i-6.7) It is middle to select a kind of compound, select a kind of compound from the compound represented by formula (i-6.8) or (i-6.9) and fit them Work as combination.Wherein, it is represented that formula (i-6.1), formula (i-6.3), formula (i-6.4), formula (i-6.6) and formula (i-6.9) are preferably comprised Compound.

Further, the compound represented by general formula (i-6) is preferably that such as formula (i-6.10) is represented to formula (i-6.17) Compound, wherein, be preferably formula (i-6.11) represented by compound.

Compound represented by general formula (i-7) is following compound.

(in formula, Rⁱ⁷¹And Rⁱ⁷²Separately represent and the R in general formula (i)ⁱ¹And Rⁱ²Identical implication, Aⁱ⁷¹And Aⁱ⁷²Point Do not represent independently and the A in general formula (i)ⁱ²And Aⁱ³Identical implication, Aⁱ⁷¹And Aⁱ⁷²On hydrogen atom can separately be taken On behalf of fluorine atom, Zⁱ⁷¹Represent and the Z in general formula (i)ⁱ²Identical implication, Xⁱ⁷¹And Xⁱ⁷²Separately represent fluorine atom or hydrogen Atom.)

In formula, Rⁱ⁷¹And Rⁱ⁷²It is preferred that be separately the alkyl of carbon number 1~5, the alkenyl of carbon number 2~5 or The alkoxy of carbon number 1~4, Aⁱ⁷¹And Aⁱ⁷²It is preferred that be separately Isosorbide-5-Nitrae-cyclohexylidene or Isosorbide-5-Nitrae-phenylene, Aⁱ⁷¹And Aⁱ⁷²On hydrogen atom can separately be substituted by fluorine atom, Qⁱ⁷¹Preferably singly-bound or COO-, preferably singly-bound, Xⁱ⁷¹And Xⁱ⁷²Preferably hydrogen atom.

There is no particular restriction for the species of combined compound, and the dissolubility, transition temperature, electricity during according to low temperature are reliable Performance required by property, refractive anisotrop etc. is combined.The species of used compound is for example as the present invention's One embodiment is one kind, two kinds, three kinds, four kinds.

Dissolubility when in the present compositions, the content of the compound represented by general formula (i-7) need to be according to low temperature, Transition temperature, electric reliability, refractive anisotrop, Technological adaptability, drop impression, burn-in, dielectric constant anisotropy etc. are wanted The performance asked suitably is adjusted.

The lower limit of preferred content relative to the compound represented by the formula (i-7) of the total amount of the composition of the present invention is 1%th, 2%, 3%, 5%, 7%, 10%, 14%, 16%, 20%.Relative to formula (i-7) institute of the total amount of the composition of the present invention The upper limit value of the preferred content of the compound of expression is 30%, 25%, 23%, 20%, 18%, 15%, 10%, 5%.

When it is the embodiment of high Tni to expect the composition of the present invention, preferred compound represented by formula (i-7) Content is more, when expecting the embodiment of low viscosity, preferably makes its content few.

Further, the compound represented by general formula (i-7) is preferably the chemical combination represented by formula (i-7.1) to formula (i-7.4) Thing, is preferably the compound represented by formula (i-7.2).

Further, the compound represented by general formula (i-7) is preferably the change represented by formula (i-7.11) to formula (i-7.13) Compound, is preferably the compound represented by formula (i-7.11).

Further, compound of the compound represented by general formula (i-7) represented by formula (i-7.21) to formula (i-7.23). Compound preferably represented by formula (i-7.21).

Further, the compound represented by general formula (i-7) is preferably the change represented by formula (i-7.31) to formula (i-7.34) Compound represented by compound, preferably formula (i-7.31) and/or formula (i-7.32).

Further, the compound represented by general formula (i-7) is preferably the change represented by formula (i-7.41) to formula (i-7.44) Compound represented by compound, preferably formula (i-7.41) and/or formula (i-7.42).

Compound represented by general formula (i) is preferably selected from the group represented by following general formula (i-8).

(in formula, Rⁱ⁸¹And Rⁱ⁸²Separately represent alkyl, the alkenyl or carbon of carbon number 2~5 of carbon number 1~5 The alkoxy of atomicity 1~4.)

Under preferred content relative to the compound represented by the general formula (i-8) of the total amount of the liquid-crystal composition of the present invention Limit value is 1%, 2%, 4%, 5%, 7%, 9%, 10%, 12%, 15%, 17%.The upper limit value of preferred content for 30%, 28%th, 25%, 23%, 20%, 18%, 15%, 13%, 10%, 8%, 5%.

Liquid-crystal compounds of the end with allyl ether as liquid-crystal composition constituent and with good characteristic, But there are problem for reliability.However, compound represented by general formula (i-8) is by by the certain bits of the phenyl ring with allyl ether Carry out bifluoride is put, and reliability is significantly improved in the case where not damaging the original excellent characteristic of skeleton, is further improved Intermiscibility, reduces viscosity.Further, as dielectric constant anisotropy, existed according to the species of the group of side chain with few Perhaps the situation of positive dielectric constant anisotropy (less than 5), but the structure of the liquid-crystal compounds of neutrality is categorized as in the present specification Into component.

In addition, the R in general formula (i-8)ⁱ⁸²In, when selecting the alkyl through fluorine atom substitution, alkenyl (such as vinyl) etc., Positive dielectric constant anisotropy can be assigned.Such as the compound represented by general formula (i-8) in the form of single component 40~ Show liquid crystalline phase in the range of 110 DEG C, Δ n is 0.26 or so, and kinematic viscosity is low, for 25mPas or so, and dielectric constant is each Anisotropy is+4~5 or so, further in the component as liquid-crystal composition with extremely good intermiscibility.

Further, the compound used in liquid-crystal composition of the invention represented by general formula (i-8) is specifically preferred For the compound represented by formula (i-8.1) to formula (i-8.24), wherein preferably comprising formula (i-8.5), formula (i-8.6), formula (i- And the compound represented by formula (i-8.14) 8.13).

Be 1% relative to the lower limit of the preferred content of these compounds of the total amount of the liquid-crystal composition of the present invention, 2%th, 4%, 5%, 6%, 7%, 8%, 9%, 10%, 13%, 15%, 18%, 20%.The upper limit value of preferred content for 30%, 28%th, 25%, 23%, 20%, 18%, 15%, 13%, 10%, 8%, 5%.

In addition, as the compound represented by the general formula (i-9) of the first composition preferably comprise it is at least one or two with On below general formula (i-9.1) represented by compound.

(in above-mentioned general formula (i-9), R^L72Be each independently selected from the alkyl by carbon number 1~10, carbon number 2~ A kind of group in the group that the alkenyl of 10 and the alkoxy of carbon number 1~10 are formed.)

For the viewpoint of reliability as the light resistance, heat resistance or burn-in that improve liquid-crystal composition, preferably comprise Compound represented by general formula (i-9).

Further, the compound represented by aforementioned formula (i-9) is particularly preferably formula (i-9.1)~formula (i-9.5) institute table The compound shown.

The compound that liquid-crystal composition of the present invention preferably comprises represented by the general formula (J) of one or more is made For second composition (these compounds are positive compound (Δ ε is more than 2) equivalent to dielectricity).General formula as the second composition (J) represented by following chemical constitution.

n^J1Represent 0,1,2,3 or 4,

A^J1、A^J2And A^J3Separately represent be selected from by

In general formula (J), R^J1Preferably the alkyl of carbon number 1~8, the alkoxy of carbon number 1~8, carbon number 2~ 8 alkenyl or the alkenyloxy group of carbon number 2~8, be preferably the alkyl of carbon number 1~5, carbon number 1~5 alkoxy, The alkenyl of carbon number 2~5 or the alkenyloxy group of carbon number 2~5, the more preferably alkyl of carbon number 1~5 or carbon are former The alkenyl of subnumber 2~5, the more preferably alkenyl of the alkyl of carbon number 2~5 or carbon number 2~3, particularly preferably The alkenyl (acrylic) of carbon number 3.

When paying attention to reliability, R^J1Preferably alkyl, is preferably alkenyl when paying attention to the reduction of viscosity.

It is preferably the carbon number 1~5 of straight-chain in addition, when the ring structure that it is connected is phenyl (aromatic series) The alkoxy of carbon number 1~4 and the alkenyl of carbon number 4~5 of alkyl, straight-chain, are ring in the ring structure that it is connected Hexane, pyrans and twoAlkane is preferably alkyl, the carbon of straight-chain of the carbon number 1~5 of straight-chain when the ring structure of saturation The alkenyl of the alkoxy of atomicity 1~4 and the carbon number 2~5 of straight-chain.In order to stabilize nematic phase, preferred carbon atom Oxygen atom in the presence of and adds up to less than 5, and preferably straight-chain.

As alkenyl, the group represented by formula (R1) to any one of formula (R5) is preferably selected from.(stain in various represents Carbon atom in the ring structure that alkenyl is connected.)

When requiring increase Δ n, A^J1、A^J2And A^J3It is preferably aromatic series independently of one another, it is excellent in order to improve response speed Elect aliphatic as, preferably represent anti-form-1,4- cyclohexylidenes, Isosorbide-5-Nitrae-phenylene, Isosorbide-5-Nitrae-cyclohexadienylidene, Isosorbide-5-Nitrae-bicyclic [2.2.2] octamethylene, piperidines -1,4- diyls, naphthalene -2,6- diyls, decahydronaphthalene -2,6- diyls or 1,2,3,4- naphthanes -2,6- Diyl, they can be replaced by fluorine atoms, and more preferably represent following structures,

More preferably represent following structures.

Z^J1And Z^J2Preferred expression-CH independently of one another₂O-、-OCH₂-、-CF₂O-、-CH₂CH₂-、-CF₂CF₂- or singly-bound, into One step is preferably-OCH₂-、-CF₂O-、-CH₂CH₂- or singly-bound, particularly preferably-OCH₂-、-CF₂O- or singly-bound.

X^J1Preferably fluorine atom or trifluoromethoxy, are preferably fluorine atom.

n^J1Preferably 0,1,2 or 3, are preferably 0,1 or 2, when focusing on improving Δ ε, are preferably 0 or 1, are paying attention to It is preferably 1 or 2 during Tni.

There is no particular restriction for the species of combined compound, and the dissolubility, transition temperature, electricity during according to low temperature are reliable The desired combining properties such as property, refractive anisotrop and use.The species of used compound is for example as the present invention's One embodiment is one kind, two kinds, three kinds.In addition further, be in another embodiment of the present invention four kinds, five kinds, Six kinds, more than seven kinds.

In the present compositions, the dissolubility when content of the compound represented by general formula (J) need to be according to low temperature, turn Required by temperature, electric reliability, refractive anisotrop, Technological adaptability, drop impression, burn-in, dielectric constant anisotropy etc. Performance suitably adjusted.

The lower limit of preferred content relative to the compound represented by the general formula (J) of the total amount of the composition of the present invention is 1%th, 10%, 20%, 30%, 40%, 50%, 55%, 60%, 65%, 70%, 75%, 80%.The upper limit value phase of preferred content For the total amount of the composition of the present invention, for example, in one embodiment of the present invention for 95%, 85%, 75%, 65%, 55%, 45%th, 35%, 25%.

, preferably will be above-mentioned when the viscosity of the composition of the present invention is kept as composition that is low, needing fast response time Lower limit is set to lower, and upper limit value is set to lower.Further, kept by the Tni of the composition of the present invention It is high, when needing the good composition of temperature stability, preferably above-mentioned lower limit is set to lower, and upper limit value is set Obtain lower.In addition, in order to by driving voltage be kept as it is low and when increasing dielectric constant anisotropy, preferably will be above-mentioned under Limit value is set to higher, and upper limit value is set to higher.

Compound represented by general formula (J) is preferably selected from represented by compound and general formula (K) represented by general formula (M) One or both of the group that is formed of compound more than.

General formula (M) of the present invention is

(in above-mentioned general formula (M), R^M1Represent the alkyl of carbon number 1~8, the alkenyl of carbon number 2~8, carbon number 1 ~8 alkoxy or the alkenyloxy group of carbon number 2~8, the hydrogen of more than 1 in the alkyl, alkenyl, alkoxy or alkenyloxy group are former Son can be substituted by fluorine atom, 1 in the alkyl, alkenyl, alkoxy or alkenyloxy group or the-CH of more than non-adjacent 2₂- - CH=CH- ,-C ≡ C- ,-O- ,-CO- ,-COO- or-OCO- can be separately substituted by,

PM represents 0,1,2,3 or 4,

C^M1And C^M2Separately represent be selected from by

(d) 1,4- cyclohexylidenes (are present in 1-CH in the group₂- or the not adjacent-CH of more than 2₂- can be taken On behalf of-O- or-S-) and

(e) (the 1-CH=or the not adjacent-CH=of more than 2 being present in the group can be taken 1,4- phenylenes On behalf of-N=.)

Group in the group formed, above-mentioned group (d), group (e) can be separately through cyano group, fluorine atom or chlorine Atom substitutes,

K^M1And K^M2Separately represent singly-bound ,-CH₂CH₂-、-(CH₂)₄-、-OCH₂-、-CH₂O-、-OCF₂-、- CF₂O- ,-COO- ,-OCO- or-C ≡ C-,

In PM for 2,3 or 4 so as to which there are multiple K^M1When, they may be the same or different, in PM for 2,3 or 4 so as to exist Multiple C^M2When, they may be the same or different,

X^M1And X^M3Separately represent hydrogen atom, chlorine atom or fluorine atom,

X^M2Represent hydrogen atom, fluorine atom, chlorine atom, cyano group, trifluoromethyl, fluorine methoxyl group, difluoro-methoxy, trifluoro methoxy Base or 2,2,2- trifluoroethyls.Wherein, except the compound represented by general formula (i).)

In general formula (M), R^M1Preferably the alkyl of carbon number 1~8, the alkoxy of carbon number 1~8, carbon number 2~ 8 alkenyl or the alkenyloxy group of carbon number 2~8, be preferably the alkyl of carbon number 1~5, carbon number 1~5 alkoxy, The alkenyl of carbon number 2~5 or the alkenyloxy group of carbon number 2~5, the more preferably alkyl of carbon number 1~5 or carbon are former The alkenyl of subnumber 2~5, the more preferably alkenyl of the alkyl of carbon number 2~5 or carbon number 2~3, particularly preferably The alkenyl (acrylic) of carbon number 3.

When paying attention to reliability, R^M1Preferably alkyl, is preferably alkenyl when paying attention to the reduction of viscosity.

As alkenyl, the group represented by formula (R1) to any one of formula (R5) is preferably selected from.(stain in various represents Carbon atom in ring structure.)

When requiring increase Δ n, A^M1And A^M2It is preferably independently of one another aromatic series, in order to improve response speed, is preferably Aliphatic, preferably represents anti-form-1,4- cyclohexylidenes, 1,3- bis-Alkane -2,5- diyls, oxinane -2,5- diyls, 1,4- are sub- The fluoro- 1,4- phenylenes of phenyl, 2-, the fluoro- 1,4- phenylenes of 3-, the fluoro- 1,4- phenylenes of 3,5- bis-, the fluoro- 1,4- phenylenes of 2,3- bis-, Bicyclic [2.2.2] octamethylene of 1,4- cyclohexadienylidenes, 1,4-, piperidines -1,4- diyls, naphthalene -2,6- diyls, decahydronaphthalene -2,6- two Base or 1,2,3,4- naphthane -2,6- diyls, more preferably represents following structures,

More preferably represent following structures.

In above-mentioned general formula (M), Z^M1And Z^M2Preferred expression-CH independently of one another₂O-、-CF₂O-、-CH₂CH₂-、- CF₂CF₂- or singly-bound, more preferably-CF₂O-、-CH₂CH₂- or singly-bound, particularly preferably-CF₂O- or singly-bound.X^M1Preferably Fluorine atom.

R^M1It is preferably the alkane of the carbon number 1~5 of straight-chain when the ring structure that it is connected is phenyl (aromatic series) The alkoxy of carbon number 1~4 and the alkenyl of carbon number 4~5 of base, straight-chain, are hexamethylene in the ring structure that it is connected Alkane, pyrans and twoAlkane is preferably alkyl, the carbon original of straight-chain of the carbon number 1~5 of straight-chain when the ring structure of saturation The alkenyl of the alkoxy of subnumber 1~4 and the carbon number 2~5 of straight-chain.When paying attention to reliability, R^M1Preferably alkyl, in weight It is preferably alkenyl during depending on sticky reduction.

Compound represented by general formula (M) of the present invention is when requiring the chemical stability of liquid-crystal composition, preferably Its intramolecular does not have chlorine atom.Further, in liquid-crystal composition, the compound with chlorine atom is preferably less than 5%, excellent Elect less than 3% as, be preferably less than 1%, be preferably less than 0.5%, preferably contain substantially no.It is so-called to contain substantially no, Impurity when meaning only as manufacture compound and compound for generating etc. unintentionally the compound containing chlorine atom be mixed into In liquid-crystal composition.

In the present compositions, the dissolubility when content of the compound represented by general formula (M) need to be according to low temperature, turn Required by temperature, electric reliability, refractive anisotrop, Technological adaptability, drop impression, burn-in, dielectric constant anisotropy etc. Performance suitably adjusted.

The lower limit of preferred content relative to the compound represented by the formula (M) of the total amount of the composition of the present invention is 1%th, 10%, 15%, 20%, 25%, 30%, 35%, 40%, 50%, 55%, 60%, 65%, 70%, 75%, 80%.It is excellent Select the total amount of the upper limit value of content relative to the composition of the present invention, for example, in one embodiment of the present invention be 95%, 85%, 75%th, 65%, 55%, 45%, 35%, 30%, 25%.

Compound represented by general formula (M) of the present invention is preferably the chemical combination being selected from represented by general formula (M-1) Compound in thing group.

(in formula, R^M11Represent alkyl, the alkenyl of carbon number 2~5 or the alkane of carbon number 1~4 of carbon number 1~5 Epoxide, X^M11To X^M15Separately represent hydrogen atom or fluorine atom, Y^M11Represent fluorine atom or OCF₃。)

There is no particular restriction for the species of combined compound, and the dissolubility, transition temperature, electricity during according to low temperature are reliable The desired combining properties such as property, refractive anisotrop and use.The species of used compound is for example as the present invention's One embodiment is one kind, two kinds, more than three kinds.

The lower limit of preferred content relative to the compound represented by the formula (M-1) of the total amount of the composition of the present invention is 1%th, 2%, 5%, 8%, 10%, 13%, 15%, 18%, 20%, 22%, 25%, 30%.The upper limit value of preferred content is 30%th, 28%, 25%, 23%, 20%, 18%, 15%, 13%, 10%, 8%, 5%.

Further, the compound represented by general formula (M-1) is preferably specifically formula (M-1.1) to formula (M-1.4) institute table Compound represented by the compound shown, preferably formula (M-1.1) or formula (M-1.2), more preferably formula (M-1.2) institute table The compound shown.In addition, it is also preferred that at the same time using formula (M-1.1) or the compound represented by formula (M-1.2).

Relative to the lower limit of the preferred content of the compound represented by the formula (M-1.1) of the total amount of the composition of the present invention For 1%, 2%, 5%, 6%.The upper limit value of preferred content is 15%, 13%, 10%, 8%, 5%.

Relative to the lower limit of the preferred content of the compound represented by the formula (M-1.2) of the total amount of the composition of the present invention For 1%, 2%, 5%, 6%.The upper limit value of preferred content is 30%, 25%, 23%, 20%, 18%, 15%, 13%, 10%, 8%.

Relative to the total of the compound represented by the formula (M-1.1) and formula (M-1.2) of the total amount of the composition of the present invention Preferred content lower limit be 1%, 2%, 5%, 6%.The upper limit value of preferred content is 30%, 25%, 23%, 20%, 18%th, 15%, 13%, 10%, 8%.

Further, the compound represented by general formula (M) is preferably and is selected from the compound group represented by general formula (M-2) Compound.

(in formula, R^M21Represent alkyl, the alkenyl of carbon number 2~5 or the alkane of carbon number 1~4 of carbon number 1~5 Epoxide, X^M21And X^M22Separately represent hydrogen atom or fluorine atom, Y^M21Represent fluorine atom, chlorine atom or OCF₃。)

, preferably will be above-mentioned when the viscosity of the composition of the present invention is kept as composition that is low, needing fast response time Lower limit is set to lower, and upper limit value is set to lower.Further, kept by the Tni of the composition of the present invention It is high, when needing to be difficult to happen the composition of burn-in, preferably above-mentioned lower limit is set to lower, and upper limit value is set to It is lower.In addition, in order to by driving voltage be kept as it is low and when increasing dielectric constant anisotropy, preferably by above-mentioned lower limit Value is set to higher, and upper limit value is set to higher.

Further, the compound represented by general formula (M-2) is preferably the chemical combination represented by formula (M-2.1) to formula (M-2.5) Compound represented by thing, preferably formula (M-2.3) and/or formula (M-2.5).

Relative to the lower limit of the preferred content of the compound represented by the formula (M-2.2) of the total amount of the composition of the present invention For 1%, 2%, 5%, 6%.The upper limit value of preferred content is 15%, 13%, 10%, 8%, 5%.

Relative to the lower limit of the preferred content of the compound represented by the formula (M-2.3) of the total amount of the composition of the present invention For 1%, 2%, 5%, 6%.The upper limit value of preferred content is 30%, 25%, 23%, 20%, 18%, 15%, 13%, 10%, 8%.

Relative to the lower limit of the preferred content of the compound represented by the formula (M-2.5) of the total amount of the composition of the present invention For 1%, 2%, 5%, 6%.The upper limit value of preferred content is 30%, 25%, 23%, 20%, 18%, 15%, 13%, 10%, 8%.

Relative to the chemical combination represented by the formula (M-2.2) of the total amount of the composition of the present invention, (M-2.3) and formula (M-2.5) The lower limit of total preferred content of thing is 1%, 2%, 5%, 6%.The upper limit value of preferred content is 30%, 25%, 23%, 20%th, 18%, 15%, 13%, 10%, 8%.

Relative to the total amount of the composition of the present invention, content is preferably more than 1%, and more preferably more than 5%, it is further excellent Elect more than 8% as, more preferably more than 10%, more preferably more than 14%, particularly preferably more than 16%.Separately Outside, it is contemplated that dissolubility, transition temperature, electric reliability during low temperature etc., are preferably limited to less than 30%, into one by maximum rate Step is preferably less than 25%, and more preferably less than 22%, particularly preferably less than 20%.

Compound used in the composition of the present invention represented by general formula (M) is preferably the change represented by general formula (M-3) Compound.

(in formula, R^M31Represent alkyl, the alkenyl of carbon number 2~5 or the alkane of carbon number 1~4 of carbon number 1~5 Epoxide, X^M31To X^M36Separately represent hydrogen atom or fluorine atom, Y^M31Represent fluorine atom, chlorine atom or OCF₃。)

There is no particular restriction for combined compound, and dissolubility, transition temperature when preferably considering low temperature, electricity are reliable Property, refractive anisotrop etc. and combine a kind of to two or more.

Dissolubility, transition temperature during the content consideration low temperature of the compound represented by general formula (M-3), electric reliability, folding Penetrate the characteristics such as rate anisotropy and there are upper limit value and lower limit in each embodiment.

The lower limit of preferred content relative to the compound represented by the formula (M-3) of the total amount of the composition of the present invention is 1%th, 2%, 4%, 5%, 8%, 10%, 13%, 15%, 18%, 20%.The upper limit value of preferred content is 20%, 18%, 15%th, 13%, 10%, 8%, 5%.

Further, the compound used in composition of the invention represented by general formula (M-3) is preferably specifically formula Compound represented by (M-3.1) to formula (M-3.4), wherein preferably comprising represented by formula (M-3.1) and/or formula (M-3.2) Compound.

Relative to the lower limit of the preferred content of the compound represented by the formula (M-3.1) of the total amount of the composition of the present invention For 1%, 2%, 4%, 5%, 8%, 10%, 13%, 15%, 18%, 20%.The upper limit value of preferred content is 20%, 18%, 15%th, 13%, 10%, 8%, 5%.

Relative to the lower limit of the preferred content of the compound represented by the formula (M-3.2) of the total amount of the composition of the present invention For 1%, 2%, 4%, 5%, 8%, 10%, 13%, 15%, 18%, 20%.The upper limit value of preferred content is 20%, 18%, 15%th, 13%, 10%, 8%, 5%.

Relative to the total of the compound represented by the formula (M-3.1) and formula (M-3.2) of the total amount of the composition of the present invention Preferred content lower limit be 1%, 2%, 4%, 5%, 8%, 10%, 13%, 15%, 18%, 20%.Preferred content it is upper Limit value is 20%, 18%, 15%, 13%, 10%, 8%, 5%.

Further, the compound represented by general formula (M) is preferably selected from the compound in the group represented by general formula (M-4).

(in formula, R^M41Represent alkyl, the alkenyl of carbon number 2~5 or the alkane of carbon number 1~4 of carbon number 1~5 Epoxide, X^M41To X^M48Separately represent fluorine atom or hydrogen atom, Y^M41Represent fluorine atom, chlorine atom or OCF₃。)

There is no particular restriction for combined compound, it is considered preferred to dissolubility, transition temperature during low temperature, electric reliability, Refractive anisotrop etc. and combine it is a kind of, more than two or three.

Dissolubility, transition temperature during the content consideration low temperature of the compound represented by general formula (M-4), electric reliability, folding Penetrate the characteristics such as rate anisotropy and there are upper limit value and lower limit in each embodiment.

The lower limit of preferred content relative to the compound represented by the formula (M-4) of the total amount of the composition of the present invention is 1%th, 2%, 4%, 5%, 8%, 10%, 13%, 15%, 18%, 20%.The upper limit value of preferred content is 30%, 28%, 25%th, 23%, 20%, 18%, 15%, 13%, 10%, 8%, 5%.

When the composition of the present invention is used for the small way used for liquid crystal display element of cell gap, suitable for making general formula (M-4) institute The content of the compound of expression is more.When the liquid crystal display element small for driving voltage, suitable for making general formula (M-4) institute table The content for the compound shown is more.In addition, at the way used for liquid crystal display element used under for low temperature environment, suitable for making to lead to The content of compound represented by formula (M-4) is few.When for the composition of the liquid crystal display element for fast response time when, Suitable for making the content of the compound represented by general formula (M-4) few.

Further, the compound used in composition of the invention represented by general formula (M-4) is preferably specifically formula Compound represented by (M-4.1) to formula (M-4.4), wherein preferably comprising the chemical combination represented by formula (M-4.2) to formula (M-4.4) Compound represented by thing, further preferably formula (M-4.2).

Further, the compound represented by general formula (M) is preferably the compound represented by general formula (M-5).

(in formula, R^M51Represent alkyl, the alkenyl of carbon number 2~5 or the alkane of carbon number 1~4 of carbon number 1~5 Epoxide, X^M51And X^M52Separately represent hydrogen atom or fluorine atom, Y^M51Represent fluorine atom, chlorine atom or OCF₃。)

There is no restriction for the species of combined compound, dissolubility, transition temperature when considering low temperature, electric reliability, folding Penetrate rate anisotropy etc. and appropriately combined in various embodiments and use.For example, group in an embodiment of the invention Unification kind, combines two kinds in another embodiment, and three kinds are combined in further another embodiment, in further another reality Apply and four kinds are combined in mode, five kinds are combined in further another embodiment, six are combined in further another embodiment More than kind.

The lower limit of preferred content relative to the compound represented by the formula (M-5) of the total amount of the composition of the present invention is 1%th, 2%, 5%, 8%, 10%, 13%, 15%, 18%, 20%, 22%, 25%, 30%.The upper limit value of preferred content is 50%th, 45%, 40%, 35%, 33%, 30%, 28%, 25%, 23%, 20%, 18%, 15%, 13%, 10%, 8%, 5%.

Further, the compound represented by general formula (M-5) is preferably the chemical combination represented by formula (M-5.1) to formula (M-5.4) Thing, is preferably the compound represented by formula (M-5.1) to formula (M-5.4).

Relative to these compounds of the total amount of the composition of the present invention preferred content lower limit for 1%, 2%, 5%th, 8%, 10%, 13%, 15%.The upper limit value of preferred content is 30%, 28%, 25%, 23%, 20%, 18%, 15%, 13%th, 10%, 8%, 5%.

Further, the compound represented by general formula (M-5) is preferably the change represented by formula (M-5.11) to formula (M-5.17) Compound, is preferably the compound represented by formula (M-5.11), formula (M-5.13) and formula (M-5.17).

Further, the compound represented by general formula (M-5) is preferably the change represented by formula (M-5.21) to formula (M-5.28) Compound, is preferably the compound represented by formula (M-5.21), formula (M-5.22), formula (M-5.23) and formula (M-5.25).

Relative to these compounds of the total amount of the composition of the present invention preferred content lower limit for 1%, 2%, 5%th, 8%, 10%, 13%, 15%, 18%, 20%, 22%, 25%, 30%.The upper limit value of preferred content is 40%, 35%, 33%th, 30%, 28%, 25%, 23%, 20%, 18%, 15%, 13%, 10%, 8%, 5%.

Further, the compound represented by general formula (M) is preferably the compound represented by general formula (M-6).

(in formula, R^M61Represent alkyl, the alkenyl of carbon number 2~5 or the alkane of carbon number 1~4 of carbon number 1~5 Epoxide, X^M61To X^M64Separately represent fluorine atom or hydrogen atom, Y^M61Represent fluorine atom, chlorine atom or OCF₃。)

There is no restriction for the species of combined compound, dissolubility, transition temperature when considering low temperature, electric reliability, folding Penetrate rate anisotropy etc. and appropriately combined in various embodiments.

The lower limit of preferred content relative to the compound represented by the formula (M-6) of the total amount of the composition of the present invention is 1%th, 2%, 4%, 5%, 8%, 10%, 13%, 15%, 18%, 20%.The upper limit value of preferred content is 30%, 28%, 25%th, 23%, 20%, 18%, 15%, 13%, 10%, 8%, 5%.

When the composition of the present invention is used for the small way used for liquid crystal display element of driving voltage, suitable for making general formula (M-6) institute The content of the compound of expression is more.In addition, for the composition of the liquid crystal display element for fast response time when, be suitable for Make the content of the compound represented by general formula (M-6) few.

Further, the compound represented by general formula (M-6) is preferably specifically formula (M-6.1) to formula (M-6.4) institute table The compound shown, wherein preferably comprising formula (M-6.2) and the compound represented by formula (M-6.4).

Relative to these compounds of the total amount of the composition of the present invention preferred content lower limit for 1%, 2%, 4%th, 5%, 8%, 10%, 13%, 15%, 18%, 20%.The upper limit value of preferred content is 30%, 28%, 25%, 23%, 20%th, 18%, 15%, 13%, 10%, 8%, 5%.

Further, the compound represented by general formula (M-6) is preferably specifically formula (M-6.11) to formula (M-6.14) institute The compound of expression, wherein preferably comprising formula (M-6.12) and the compound represented by formula (M-6.14).

Further, the compound represented by general formula (M-6) is preferably specifically formula (M-6.21) to formula (M-6.24) institute The compound of expression, wherein preferably comprising the compound represented by formula (M-6.21), formula (M-6.22) and formula (M-6.24).

Further, the compound represented by general formula (M-6) is preferably specifically formula (M-6.31) to formula (M-6.34) institute The compound of expression.Wherein preferably comprise formula (M-6.31) and the compound represented by formula (M-6.32).

Further, the compound represented by general formula (M-6) is preferably specifically formula (M-6.41) to formula (M-6.44) institute The compound of expression, wherein preferably comprising the compound represented by formula (M-6.42).

Further, the compound represented by general formula (M) is preferably selected from the change in the compound group represented by general formula (M-7) Compound.

(in formula, X^M71To X^M76Separately represent fluorine atom or hydrogen atom, R^M71The alkyl of expression carbon number 1~5, The alkenyl of carbon number 2~5 or the alkoxy of carbon number 1~4, Y^M71Represent fluorine atom or OCF₃。)

There is no particular restriction for the species of combined compound, preferably comprises one kind~two in these compounds Kind, it is further preferably a kind of~tri- kinds, it is further preferably a kind of~tetra- kinds.

Dissolubility, transition temperature during the content consideration low temperature of the compound represented by general formula (M-7), electric reliability, folding Penetrate the characteristics such as rate anisotropy and there are upper limit value and lower limit in each embodiment.

The lower limit of preferred content relative to the compound represented by the formula (M-7) of the total amount of the composition of the present invention is 1%th, 2%, 4%, 5%, 8%, 10%, 13%, 15%, 18%, 20%.The upper limit value of preferred content is 30%, 28%, 25%th, 23%, 20%, 18%, 15%, 13%, 10%, 8%, 5%.

When the composition of the present invention is used for the small way used for liquid crystal display element of cell gap, suitable for making general formula (M-7) institute The content of the compound of expression is more.When the used for liquid crystal display element way small for driving voltage, suitable for making general formula (M-7) The content of represented compound is more.In addition, at the way used for liquid crystal display element used under for low temperature environment, it is suitable for Make the content of the compound represented by general formula (M-7) few.When for the combination of the liquid crystal display element for fast response time During thing, suitable for making the content of the compound represented by general formula (M-7) few.

Further, the compound represented by general formula (M-7) is preferably the chemical combination represented by formula (M-7.1) to formula (M-7.4) Thing, is preferably the compound represented by formula (M-7.2).

Further, the compound represented by general formula (M-7) is preferably the change represented by formula (M-7.11) to formula (M-7.14) Compound represented by compound, preferably formula (M-7.11) and formula (M-7.12).

Further, the compound represented by general formula (M-7) is preferably the change represented by formula (M-7.21) to formula (M-7.24) Compound represented by compound, preferably formula (M-7.21) and formula (M-7.22).

Further, the compound represented by general formula (M) is preferably the compound represented by general formula (M-8).

(in formula, X^M81To X^M84Separately represent fluorine atom or hydrogen atom, Y^M81Represent fluorine atom, chlorine atom or- OCF₃, R^M81Represent alkyl, the alkenyl of carbon number 2~5 or the alkoxy of carbon number 1~4 of carbon number 1~5, A^M81And A^M82Separately represent 1,4- cyclohexylidenes, 1,4- phenylenes or

Hydrogen atom on 1,4- phenylenes can be substituted by fluorine atom.)

Relative to the lower limit of the preferred content of the compound represented by the general formula (M-8) of the total amount of the composition of the present invention For 1%, 2%, 4%, 5%, 8%, 10%, 13%, 15%, 18%, 20%.The upper limit value of preferred content is 30%, 28%, 25%th, 23%, 20%, 18%, 15%, 13%, 10%, 8%, 5%.

, preferably will be above-mentioned when the viscosity of the composition of the present invention is kept as composition that is low, needing fast response time Lower limit is set to lower, and upper limit value is set to lower.Further, needing to be difficult to happen the composition of burn-in When, preferably above-mentioned lower limit is set to lower, and upper limit value is set to lower.In addition, in order to by driving voltage Be kept as it is low and when increasing dielectric constant anisotropy, preferably above-mentioned lower limit is set to higher, and upper limit value is set It is higherly fixed.

Further, the compound used in composition of the invention represented by general formula (M-8) is preferably specifically formula Compound represented by (M-8.1) to formula (M-8.4), wherein preferably comprising formula (M-8.1) and the chemical combination represented by formula (M-8.2) Thing.

Further, the compound used in composition of the invention represented by general formula (M-8) is preferably specifically formula Compound represented by (M-8.11) to formula (M-8.14), wherein preferably comprising the compound represented by formula (M-8.12).

Further, the compound used in composition of the invention represented by general formula (M-8) is preferably specifically formula Compound represented by (M-8.21) to formula (M-8.24), wherein preferably comprising the compound represented by formula (M-8.22).

Further, the compound used in composition of the invention represented by general formula (M-8) is preferably specifically formula Compound represented by (M-8.31) to formula (M-8.34), wherein preferably comprising the compound represented by formula (M-8.32).

Further, the compound used in composition of the invention represented by general formula (M-8) is preferably specifically formula Compound represented by (M-8.41) to formula (M-8.44), wherein preferably comprising the compound represented by formula (M-8.42).

Further, the compound used in composition of the invention represented by general formula (M-8) is preferably specifically formula Compound represented by (M-8.51) to formula (M-8.54), wherein preferably comprising the compound represented by formula (M-8.52).

Further, the compound represented by general formula (M) can have following part-structures in its structure.

(stain in formula represents the carbon atom in the ring structure that preceding sections structure is connected.)

It is preferably the compound represented by general formula (M-10)~(M-18) as the compound with preceding sections structure.

Compound represented by general formula (M-10) is following compound.

(in formula, X^M101And X^M102Separately represent fluorine atom or hydrogen atom, Y^M101Represent fluorine atom, chlorine atom or- OCF₃, R^M101Represent alkyl, the alkenyl of carbon number 2~5 or the alkoxy of carbon number 1~4 of carbon number 1~5, W^M101 And W^M102Separately expression-CH₂- or-O-.)

Relative to the lower limit of the preferred content of the compound represented by the general formula (M-10) of the total amount of the composition of the present invention It is worth for 1%, 2%, 4%, 5%, 8%, 10%, 13%, 15%, 18%, 20%.The upper limit value of preferred content is 30%, 28%, 25%th, 23%, 20%, 18%, 15%, 13%, 10%, 8%, 5%.

Further, the compound used in composition of the invention represented by general formula (M-10) is preferably specifically formula Compound represented by (M-10.1) to formula (M-10.12), wherein it is represented to formula (M-10.12) to preferably comprise formula (M-10.5) Compound.

Compound represented by general formula (M-11) is following compound.

(in formula, X^M111~X^M114Separately represent fluorine atom or hydrogen atom, Y^M111Represent fluorine atom, chlorine atom or- OCF₃, R^M111Represent alkyl, the alkenyl of carbon number 2~5 or the alkoxy of carbon number 1~4 of carbon number 1~5.)

Relative to the lower limit of the preferred content of the compound represented by the general formula (M-11) of the total amount of the composition of the present invention It is worth for 1%, 2%, 4%, 5%, 8%, 10%, 13%, 15%, 18%, 20%.The upper limit value of preferred content is 30%, 28%, 25%th, 23%, 20%, 18%, 15%, 13%, 10%, 8%, 5%.

Further, the compound used in composition of the invention represented by general formula (M-11) is preferably specifically formula Compound represented by (M-11.1) to formula (M-11.8), wherein preferably comprising represented by formula (M-11.1) to formula (M-11.4) Compound.

Compound represented by general formula (M-12) is following compound.

(in formula, X^M121And X^M122Separately represent fluorine atom or hydrogen atom, Y^M121Represent fluorine atom, chlorine atom or- OCF₃, R^M121Represent alkyl, the alkenyl of carbon number 2~5 or the alkoxy of carbon number 1~4 of carbon number 1~5, W^M121 And W^M122Separately expression-CH₂- or-O-.)

Relative to the lower limit of the preferred content of the compound represented by the general formula (M-12) of the total amount of the composition of the present invention It is worth for 1%, 2%, 4%, 5%, 8%, 10%, 13%, 15%, 18%, 20%.The upper limit value of preferred content is 30%, 28%, 25%th, 23%, 20%, 18%, 15%, 13%, 10%, 8%, 5%.

Further, the compound used in composition of the invention represented by general formula (M-12) is preferably specifically formula Compound represented by (M-12.1) to formula (M-12.12), wherein it is represented to formula (M-12.8) to preferably comprise formula (M-12.5) Compound.

Compound represented by general formula (M-13) is following compound.

(in formula, X^M131~X^M134Separately represent fluorine atom or hydrogen atom, Y^M131Represent fluorine atom, chlorine atom or- OCF₃, R^M131Represent alkyl, the alkenyl of carbon number 2~5 or the alkoxy of carbon number 1~4 of carbon number 1~5, W^M131 And W^M132Separately expression-CH₂- or-O-.)

Relative to the lower limit of the preferred content of the compound represented by the general formula (M-13) of the total amount of the composition of the present invention It is worth for 1%, 2%, 4%, 5%, 8%, 10%, 13%, 15%, 18%, 20%.The upper limit value of preferred content is 30%, 28%, 25%th, 23%, 20%, 18%, 15%, 13%, 10%, 8%, 5%.

Further, the compound used in composition of the invention represented by general formula (M-13) is preferably specifically formula Compound represented by (M-13.1) to formula (M-13.28), wherein preferably comprising formula (M-13.1) to (M-13.4), (M- 13.11) to the compound represented by (M-13.14), (M-13.25) to (M-13.28).

Compound represented by general formula (M-14) is following compound.

(in formula, X^M141~X^M144Separately represent fluorine atom or hydrogen atom, Y^M141Represent fluorine atom, chlorine atom or- OCF₃, R^M141Represent alkyl, the alkenyl of carbon number 2~5 or the alkoxy of carbon number 1~4 of carbon number 1~5, W^M141 And W^M142Separately expression-CH₂- or-O-.)

Relative to the lower limit of the preferred content of the compound represented by the general formula (M-14) of the total amount of the composition of the present invention It is worth for 1%, 2%, 4%, 5%, 8%, 10%, 13%, 15%, 18%, 20%.The upper limit value of preferred content is 30%, 28%, 25%th, 23%, 20%, 18%, 15%, 13%, 10%, 8%, 5%.

Further, the compound used in composition of the invention represented by general formula (M-14) is preferably specifically formula Compound represented by (M-14.1) to formula (M-14.8), wherein preferably comprising represented by formula (M-14.5) and formula (M-14.8) Compound.

Compound represented by general formula (M-15) is following compound.

(in formula, X^M151And X^M152Separately represent fluorine atom or hydrogen atom, Y^M151Represent fluorine atom, chlorine atom or- OCF₃, R^M151Represent alkyl, the alkenyl of carbon number 2~5 or the alkoxy of carbon number 1~4 of carbon number 1~5, W^M151 And W^M152Separately expression-CH₂- or-O-.)

Relative to the lower limit of the preferred content of the compound represented by the general formula (M-15) of the total amount of the composition of the present invention It is worth for 1%, 2%, 4%, 5%, 8%, 10%, 13%, 15%, 18%, 20%.The upper limit value of preferred content is 30%, 28%, 25%th, 23%, 20%, 18%, 15%, 13%, 10%, 8%, 5%.

Further, the compound used in composition of the invention represented by general formula (M-15) is preferably specifically formula Compound represented by (M-15.1) to formula (M-15.14), wherein preferably comprising formula (M-15.5) to formula (M-15.8), formula (M- 15.11) to the compound represented by formula (M-15.14).

Compound represented by general formula (M-16) is following compound.

(in formula, X^M161~X^M164Separately represent fluorine atom or hydrogen atom, Y^M161Represent fluorine atom, chlorine atom or- OCF₃, R^M161Represent alkyl, the alkenyl of carbon number 2~5 or the alkoxy of carbon number 1~4 of carbon number 1~5.)

Relative to the lower limit of the preferred content of the compound represented by the general formula (M-16) of the total amount of the composition of the present invention It is worth for 1%, 2%, 4%, 5%, 8%, 10%, 13%, 15%, 18%, 20%.The upper limit value of preferred content is 30%, 28%, 25%th, 23%, 20%, 18%, 15%, 13%, 10%, 8%, 5%.

Further, the compound used in composition of the invention represented by general formula (M-16) is preferably specifically formula Compound represented by (M-16.1) to formula (M-16.8), wherein preferably comprising represented by formula (M-16.1) to formula (M-16.4) Compound.

Compound represented by general formula (M-17) is following compound.

(in formula, X^M171~X^M174Separately represent fluorine atom or hydrogen atom, Y^M171Represent fluorine atom, chlorine atom or- OCF₃, R^M171Represent alkyl, the alkenyl of carbon number 2~5 or the alkoxy of carbon number 1~4 of carbon number 1~5, W^M171 And W^M172Separately expression-CH₂- or-O-.)

Relative to the lower limit of the preferred content of the compound represented by the general formula (M-17) of the total amount of the composition of the present invention It is worth for 1%, 2%, 4%, 5%, 8%, 10%, 13%, 15%, 18%, 20%.The upper limit value of preferred content is 30%, 28%, 25%th, 23%, 20%, 18%, 15%, 13%, 10%, 8%, 5%.

Further, the compound used in composition of the invention represented by general formula (M-17) is preferably specifically formula Compound represented by (M-17.1) to formula (M-17.52), wherein preferably comprising formula (M-17.9) to formula (M-17.12), formula (M- 17.21) to the compound represented by formula (M-17.28), formula (M-17.45) to formula (M-17.48).

Compound represented by general formula (M-18) is following compound.

(in formula, X^M181~X^M186Separately represent fluorine atom or hydrogen atom, Y^M181Represent fluorine atom, chlorine atom or- OCF₃, R^M181Represent alkyl, the alkenyl of carbon number 2~5 or the alkoxy of carbon number 1~4 of carbon number 1~5.)

Relative to the lower limit of the preferred content of the compound represented by the general formula (M-18) of the total amount of the composition of the present invention It is worth for 1%, 2%, 4%, 5%, 8%, 10%, 13%, 15%, 18%, 20%.The upper limit value of preferred content is 30%, 28%, 25%th, 23%, 20%, 18%, 15%, 13%, 10%, 8%, 5%.

Further, the compound used in composition of the invention represented by general formula (M-18) is preferably specifically formula Compound represented by (M-18.1) to formula (M-18.12), wherein it is represented to formula (M-18.8) to preferably comprise formula (M-18.5) Compound.

The composition of the present invention preferably comprises the compound represented by the general formula (K) of one or more.These chemical combination Thing is positive compound equivalent to dielectricity (Δ ε is more than 2).

(in formula, R^K1Represent the alkyl of carbon number 1~8 ,-the CH of more than 2 of 1 or non-adjacent in the alkyl₂- - CH=CH- ,-C ≡ C- ,-O- ,-CO- ,-COO- or-OCO- can be separately substituted by,

n^K1Represent 0,1,2,3 or 4,

A^K1And A^K2Separately represent be selected from by

(a) 1,4- cyclohexylidenes (are present in 1-CH in the group₂- or the not adjacent-CH of more than 2₂- can be taken On behalf of-O- or-S-) and

(b) (the 1-CH=or the not adjacent-CH=of more than 2 being present in the group can be taken 1,4- phenylenes On behalf of-N=.)

Group in the group formed, the hydrogen atom on above-mentioned group (a) and group (b) can be separately substituted For cyano group, fluorine atom or chlorine atom,

Z^K1And Z^K2Separately represent singly-bound ,-CH₂CH₂-、-(CH₂)₄-、-OCH₂-、-CH₂O-、-OCF₂-、- CF₂O- ,-COO- ,-OCO- or-C ≡ C-,

In n^K1For 2,3 or 4 so as to which there are multiple A^K2When, they may be the same or different, in n^K1For 2,3 or 4 so as to exist Multiple Z^K1When, they may be the same or different,

X^K1And X^K3Separately represent hydrogen atom, chlorine atom or fluorine atom,

X^K2Represent hydrogen atom, fluorine atom, chlorine atom, cyano group, trifluoromethyl, fluorine methoxyl group, difluoro-methoxy, trifluoro methoxy Base or 2,2,2- trifluoroethyls.)

In general formula (K), R^K1Preferably the alkyl of carbon number 1~8, the alkoxy of carbon number 1~8, carbon number 2~ 8 alkenyl or the alkenyloxy group of carbon number 2~8, be preferably the alkyl of carbon number 1~5, carbon number 1~5 alkoxy, The alkenyl of carbon number 2~5 or the alkenyloxy group of carbon number 2~5, the more preferably alkyl of carbon number 1~5 or carbon are former The alkenyl of subnumber 2~5, the more preferably alkenyl of the alkyl of carbon number 2~5 or carbon number 2~3, particularly preferably The alkenyl (acrylic) of carbon number 3.

When paying attention to reliability, R^K1Preferably alkyl, is preferably alkenyl when paying attention to the reduction of viscosity.

When requiring increase Δ n, A^K1And A^K2It is preferably independently of one another aromatic series, in order to improve response speed, is preferably Aliphatic, preferably represents anti-form-1, the fluoro- Isosorbide-5-Nitrae-phenylene of 4- cyclohexylidenes, Isosorbide-5-Nitrae-phenylene, 2-, the fluoro- Isosorbide-5-Nitrae-phenylenes of 3-, The fluoro- 1,4- phenylenes of 3,5- bis-, the fluoro- 1,4- phenylenes of 2,3- bis-, 1,4- cyclohexadienylidenes, bicyclic [2.2.2] octamethylenes of 1,4-, Piperidines-Isosorbide-5-Nitrae-diyl, naphthalene -2,6- diyl, decahydronaphthalene -2,6- diyl or 1,2,3,4- naphthane -2,6- diyls, more preferably represent Following structures,

More preferably represent following structures.

Z^K1And Z^K2Preferred expression-CH independently of one another₂O-、-CF₂O-、-CH₂CH₂-、-CF₂CF₂- or singly-bound, it is further excellent Elect-CF as₂O-、-CH₂CH₂- or singly-bound, particularly preferably-CF₂O- or singly-bound.

n^K1Preferably 0,1,2 or 3, are preferably 0,1 or 2, when focusing on improving Δ ε, are preferably 0 or 1, are paying attention to It is preferably 1 or 2 during Tni.

In the present compositions, the dissolubility when content of the compound represented by general formula (K) need to be according to low temperature, turn Required by temperature, electric reliability, refractive anisotrop, Technological adaptability, drop impression, burn-in, dielectric constant anisotropy etc. Performance suitably adjusted.

The lower limit of preferred content relative to the compound represented by the formula (K) of the total amount of the composition of the present invention is 1%th, 10%, 20%, 30%, 40%, 50%, 55%, 60%, 65%, 70%, 75%, 80%.The upper limit value phase of preferred content For the total amount of the composition of the present invention, for example, in one embodiment of the present invention for 95%, 85%, 75%, 65%, 55%, 45%th, 35%, 25%.

Compound represented by general formula (K) is preferably the chemical combination being selected from the compound group represented by general formula (K-1) Thing.

(in formula, R^K11Represent alkyl, the alkenyl of carbon number 2~5 or the alkane of carbon number 1~4 of carbon number 1~5 Epoxide, X^K11~X^K14Separately represent hydrogen atom or fluorine atom, Y^K11Represent fluorine atom or OCF₃。)

The lower limit of preferred content relative to the compound represented by the formula (K-1) of the total amount of the composition of the present invention is 1%th, 2%, 5%, 8%, 10%, 13%, 15%, 18%, 20%, 22%, 25%, 30%.The upper limit value of preferred content is 30%th, 28%, 25%, 23%, 20%, 18%, 15%, 13%, 10%, 8%, 5%.

Further, the compound represented by general formula (K-1) is preferably specifically formula (K-1.1) to formula (K-1.4) institute table Compound represented by the compound shown, preferably formula (K-1.1) or formula (K-1.2), more preferably formula (K-1.2) institute table The compound shown.In addition, it is also preferred that at the same time using formula (K-1.1) or the compound represented by formula (K-1.2).

Compound represented by general formula (K) is preferably the chemical combination being selected from the compound group represented by general formula (K-2) Thing.

(in formula, R^K21Represent alkyl, the alkenyl of carbon number 2~5 or the alkane of carbon number 1~4 of carbon number 1~5 Epoxide, X^K21~X^K24Separately represent hydrogen atom or fluorine atom, Y^K21Represent fluorine atom or OCF₃。)

The lower limit of preferred content relative to the compound represented by the formula (K-2) of the total amount of the composition of the present invention is 1%th, 2%, 5%, 8%, 10%, 13%, 15%, 18%, 20%, 22%, 25%, 30%.The upper limit value of preferred content is 30%th, 28%, 25%, 23%, 20%, 18%, 15%, 13%, 10%, 8%, 5%.

Further, the compound represented by general formula (K-2) is preferably specifically formula (K-2.1) to formula (K-2.6) institute table Compound represented by the compound shown, preferably formula (K-2.5) or formula (K-2.6), more preferably formula (K-2.6) institute table The compound shown.In addition, it is also preferred that at the same time using formula (K-2.5) or the compound represented by formula (K-2.6).

Compound represented by general formula (K) is preferably the chemical combination being selected from the compound group represented by general formula (K-3) Thing.

(in formula, R^K31Represent alkyl, the alkenyl of carbon number 2~5 or the alkane of carbon number 1~4 of carbon number 1~5 Epoxide, X^K31~X^K36Separately represent hydrogen atom or fluorine atom, Y^K31Represent fluorine atom or OCF₃。)

The lower limit of preferred content relative to the compound represented by the formula (K-3) of the total amount of the composition of the present invention is 1%th, 2%, 5%, 8%, 10%, 13%, 15%, 18%, 20%, 22%, 25%, 30%.The upper limit value of preferred content is 30%th, 28%, 25%, 23%, 20%, 18%, 15%, 13%, 10%, 8%, 5%.

Further, the compound represented by general formula (K-3) is preferably specifically formula (K-3.1) to formula (K-3.4) institute table Compound represented by the compound shown, more preferably formula (K-3.1) or formula (K-3.2).In addition, it is also preferred that formula is used at the same time (K-3.1) and the compound represented by formula (K-3.2).

Compound represented by general formula (K) is preferably the chemical combination being selected from the compound group represented by general formula (K-4) Thing.

(in formula, R^K41Represent alkyl, the alkenyl of carbon number 2~5 or the alkane of carbon number 1~4 of carbon number 1~5 Epoxide, X^K41~X^K46Separately represent hydrogen atom or fluorine atom, Y^K41Represent fluorine atom or OCF₃, Z^K41Expression-OCH₂-、- CH₂O-、-OCF₂- or-CF₂O-。)

The lower limit of preferred content relative to the compound represented by the formula (K-4) of the total amount of the composition of the present invention is 1%th, 2%, 5%, 8%, 10%, 13%, 15%, 18%, 20%, 22%, 25%, 30%.The upper limit value of preferred content is 30%th, 28%, 25%, 23%, 20%, 18%, 15%, 13%, 10%, 8%, 5%.

Further, the compound represented by general formula (K-4) is preferably specifically formula (K-4.1) to formula (K-4.18) institute table The compound shown, more preferably formula (K-4.1), formula (K-4.2), formula (K-4.11), the compound represented by (K-4.12).Separately Outside, it is also preferred that at the same time using formula (K-4.1), formula (K-4.2), formula (K-4.11), the compound represented by (K-4.12).

Compound represented by general formula (K) is preferably the chemical combination being selected from the compound group represented by general formula (K-5) Thing.

(in formula, R^K51Represent alkyl, the alkenyl of carbon number 2~5 or the alkane of carbon number 1~4 of carbon number 1~5 Epoxide, X^K51~X^K56Separately represent hydrogen atom or fluorine atom, Y^K51Represent fluorine atom or OCF₃, Z^K51Expression-OCH₂-、- CH₂O-、-OCF₂- or-CF₂O-。)

The lower limit of preferred content relative to the compound represented by the formula (K-5) of the total amount of the composition of the present invention is 1%th, 2%, 5%, 8%, 10%, 13%, 15%, 18%, 20%, 22%, 25%, 30%.The upper limit value of preferred content is 30%th, 28%, 25%, 23%, 20%, 18%, 15%, 13%, 10%, 8%, 5%.

Further, the compound represented by general formula (K-5) is preferably specifically formula (K-5.1) to formula (K-5.18) institute table The compound shown, is preferably the compound represented by formula (K-5.11) to formula (K-5.14), more preferably formula (K-5.12) Represented compound.

Compound represented by general formula (K) is preferably the chemical combination being selected from the compound group represented by general formula (K-6) Thing.

(in formula, R^K61Represent alkyl, the alkenyl of carbon number 2~5 or the alkane of carbon number 1~4 of carbon number 1~5 Epoxide, X^K61~X^K68Separately represent hydrogen atom or fluorine atom, Y^K61Represent fluorine atom or OCF₃, Z^K61Expression-OCH₂-、- CH₂O-、-OCF₂- or-CF₂O-。)

The lower limit of preferred content relative to the compound represented by the formula (K-6) of the total amount of the composition of the present invention is 1%th, 2%, 5%, 8%, 10%, 13%, 15%, 18%, 20%, 22%, 25%, 30%.The upper limit value of preferred content is 30%th, 28%, 25%, 23%, 20%, 18%, 15%, 13%, 10%, 8%, 5%.

Further, the compound represented by general formula (K-6) is preferably specifically formula (K-6.1) to formula (K-6.18) institute table The compound shown, is preferably the compound represented by formula (K-6.15) to formula (K-6.18), more preferably formula (K-6.16) And the compound represented by formula (K-6.17).In addition, it is also preferred that at the same time using represented by formula (K-6.16) and formula (K-6.17) Compound.

In the preferred embodiment of liquid-crystal composition of the present invention, as first composition, preferably lead to from following Formula (I-a) and general formula (I-b)：

(in above-mentioned general formula (I-a) and (I-b), R^1aAnd R^2aRepresent respectively and the R in general formula (i)ⁱ¹Identical implication, R^1bAnd R^2bRepresent respectively and the R in general formula (i)ⁱ²Identical implication, n^1bRepresent 1 or 2, A^1bSeparately represent anti-form-1,4- Asias ring Hexyl, 1,3- bis-Alkane -2,5- diyls, oxinane -2,5- diyls, 1,4- phenylenes, 1,4- cyclohexadienylidenes or naphthalene -2,6- Diyl, 1 hydrogen atom in the group can be substituted by fluorine atom) represented by compound group in select it is at least one or two Kind, more preferably select three kinds.

In addition, the compound of selection at least two is in liquid from the compound group represented by general formula (I-a) and general formula (I-b) Preferably comprise 25~99 mass %, further preferably 30~80 mass % in crystal composite entirety, further preferably 35~ 60 mass %, even more preferably containing 40~55 mass %.

If the combination of the general formula (I-a) and general formula (I-b) accounts for overall 20~70% of liquid-crystal composition, play and ring at a high speed The effect of answering property, if being further used in combination with the combination of second composition described below, with regard in chemical constitution or specific sight Intermiscibility improves for point, and storage stability improves, therefore the problem of can inhibit, prevent the precipitation of liquid-crystal compounds.

The preferred embodiment of liquid-crystal composition of the present invention is preferably from the general formula (II- as second composition A) compound of at least one or two and in the compound represented by general formula (II-b) is selected.

(in above-mentioned general formula (II-a) and (II-b), R^3aAnd R^3bRepresent respectively and the R in general formula (i)ⁱ¹Identical implication, X^1a And X^1bRepresent fluorine atom ,-OCF₃Or-CF₃, A^2aAnd A^2bSeparately represent anti-form-1,4- cyclohexylidenes, 1,3- bis-Alkane- 2,5- diyls, oxinane -2,5- diyl, Isosorbide-5-Nitrae-phenylene, Isosorbide-5-Nitrae-cyclohexadienylidene or naphthalene -2,6- diyl, 1 in the group A hydrogen atom can be substituted by fluorine atom.Z^2aAnd Z^2bSeparately represent singly-bound ,-CF₂O-、OCF₂-、CH₂O- or-OCH₂-, m^2aAnd m^2bRepresent 1 or 2.In addition, in m^2aAnd m^2bFor 2 when, A^2aAnd A^2bIt may be the same or different respectively, Z^2aAnd Z^2bDifference can phase Together also can be different.)

If the combination of the general formula (II-a) and general formula (II-b) accounts for overall 5~35% of liquid-crystal composition, performance ensures The raising of Δ n and the effect of drivable Δ ε, further, if the suitable combination with first composition is used in combination, and compared to second The amount of the component more total amount containing the first composition, then can maintain high-speed response.Further as general formula (II-a) or The combination of general formula (II-b) and general formula (I-a) or general formula (I-b) can specifically improve the compound of the component of liquid-crystal composition Mutual intermiscibility, therefore improved by the storage stability of liquid-crystal composition, it can inhibit, prevent the precipitation of liquid-crystal compounds Problem.

That is, in liquid-crystal composition of the present invention, if from the compound represented by general formula (I-a) and general formula (I-a) The compound more than at least one or two is selected in group as first composition, and it is represented from general formula (IIa) and general formula (IIb) Compound group in selection at least two be used as second composition, then can not only solve liquid-crystal compounds precipitation etc. and low-temperature stability The problem of related, and the whole effects that can be realized and solve the problems, such as drop impression, maintain high-speed response.

Relative to the total excellent of the compound represented by the general formula (i) and general formula (J) of the total amount of the composition of the present invention Select the lower limit of content for 80%, 85%, 88%, 90%, 92%, 93%, 94%, 95%, 96%, 97%, 98%, 99%, 100%.The upper limit value of preferred content is 100%, 99%, 98%, 95%.

Relative to the total of the compound represented by the general formula (i), general formula (M) and (K) of the total amount of the composition of the present invention Preferred content lower limit for 80%, 85%, 88%, 90%, 92%, 93%, 94%, 95%, 96%, 97%, 98%, 99%th, 100%.The upper limit value of preferred content is 100%, 99%, 98%, 95%.

Relative to general formula (i), general formula (M-1) to general formula (M-18) and the general formula (K-1) of the total amount of the composition of the present invention To the compound represented by general formula (K-6) total preferred content lower limit for 80%, 85%, 88%, 90%, 92%, 93%th, 94%, 95%, 96%, 97%, 98%, 99%, 100%.The upper limit value of preferred content is 100%, 99%, 98%, 95%.

The composition of the present application does not preferably contain has the oxygen atoms such as peracid (- CO-OO-) structure each other in the molecule The compound for the structure being formed by connecting.

When paying attention to the reliability and long-time stability of composition, the content of the compound with carbonyl is preferably set to phase Gross mass for foregoing is less than 5%, is more preferably set to less than 3%, is further preferably set to less than 1%, optimal Choosing contains substantially no.

In the stability under paying attention to UV irradiations, preferably the content for substituting the compound for having chlorine atom is set to relative to preceding State composition gross mass be less than 15%, be preferably set to less than 10%, be preferably set to less than 8%, be more preferably set to 5% with Under, less than 3% is preferably set to, is further preferably contained substantially no.

It is preferred that the content of the compound of all 6 yuan of rings of the ring structure of intramolecular is set as it is more, preferably by molecule It is more than 80% that the content of the compound of all 6 yuan of rings of interior ring structure, which is set to relative to the gross mass of foregoing, more More than 90% is preferably set to, is further preferably set to more than 95%, most preferably substantially only by the ring structure of intramolecular all 6 The compound of yuan of rings forms composition.

In order to suppress the deterioration as caused by the oxidation of composition, preferably using the chemical combination with cyclohexadienylidene as ring structure The content of thing is set as that less, preferably the content of the compound with cyclohexadienylidene is set to relative to foregoing Gross mass is less than 10%, is preferably set to less than 8%, is more preferably set to less than 5%, is preferably set to less than 3%, further preferably Contain substantially no.

When paying attention to the improvement of the improvement of viscosity and Tni, preferably there is hydrogen atom can be substituted by halogen intramolecular The content of the compound of 2- methylbenzenes-Isosorbide-5-Nitrae-diyl is set as less, intramolecular preferably being there is foregoing 2- methylbenzenes-Isosorbide-5-Nitrae- It is less than 10% that the content of the compound of diyl, which is set to relative to the gross mass of foregoing, is preferably set to less than 8%, more excellent Choosing is set to less than 5%, is preferably set to less than 3%, further preferably contains substantially no.

In this application, it is so-called to contain substantially no, mean and do not contained in addition to situation about inadvertently containing.

When the compound contained by composition in the first embodiment of the present invention has alkenyl as side chain, in foregoing alkene When base is connected on hexamethylene, the carbon number of the alkenyl is preferably 2~5, when foregoing alkenyl is connected on benzene, the alkenyl Carbon number is preferably 4~5, and the unsaturated bond of preferably foregoing alkenyl is not directly connected with benzene.

Polymerizable monomer and/or the polymerizable monomer can be contained in liquid crystal layer and/or liquid-crystal composition of the present invention Solidfied material (that is, the polymer from the polymerizable monomer), which preferably shows liquid crystal liquid crystal property.That is, it is of the invention The liquid crystal layer being related to is preferably that the polymerizable monomer contained by liquid-crystal composition is carried out polymerization.Contain as of the present invention The concrete content of polymerizable monomer in the liquid-crystal composition of polymerizable monomer, is preferably less than 5%, and more preferably less than 2%, More preferably less than 1.5%, particularly preferably less than 1%, are most preferably less than 0.5%.If less than 5%, then can subtract The generation of few drop impression.In addition, the lower limit of the content of polymerizable monomer in liquid-crystal composition is preferably 1000ppm, it is preferably 3000ppm, more preferably 5000ppm.

If the solidfied material containing polymerizable monomer and/or the polymerizable monomer in liquid-crystal composition, by making the polymerization Property monomer cure, orientation amount of restraint improve.Further, since from polymerizable monomer polymer capture liquid-crystal composition in from Subconstiuent, therefore play the effect that voltage retention does not reduce.

Polymerizable monomer of the present invention is preferably selected from the compound represented by general formula (P-1) and general formula (P-2) It is more than one or both of group formed.

(in above-mentioned general formula (P-1)~general formula (P-2), R^p11、R^p12、R^p21And R^p22Separately represent following formula (R- I) to formula (R-IX)：

Any one of, in previously described formula (R-I)~(R-IX), R²~R⁶Independently of one another hydrogen atom, carbon number 1~5 A alkyl or the halogenated alkyl of carbon number 1~5, W are singly-bound ,-O- or methylene, and T is singly-bound or-COO-, p, t and q Separately represent 0,1 or 2,

A^p11、A^p12And A^p22Separately represent 1,4- phenylenes, 1,4- cyclohexylidenes, anthracene -2,6- diyls, phenanthrene -2,7- Diyl, pyridine -2,5- diyls, pyrimidine -2,5- diyls, naphthalene -2,6- diyls, indane -2,5- diyls, 1,2,3,4- naphthane -2, 6- diyls or 1,3- bis-Alkane -2,5- diyl, is unsubstituted or represents halogen atom, cyano group, nitro, R^p11, carbon number 1~ 12 the alkyl (- CH of more than 2 of 1 or non-adjacent in aforesaid alkyl₂- can separately be substituted by-C ≡ C- ,- O- ,-CO- ,-COO- or-OCO-, the hydrogen atom of more than 2 of 1 or non-adjacent in group can be separately substituted by Fluorine atom),

A^p21And A^p23Separately represent the aromatic series base of divalence~tetravalence or the ester ring type base of divalence~tetravalence,

L^p11、L^p12、L^p21And L^p22Separately represent singly-bound ,-OCH₂-、-CH₂O-、-CO-、-C₂H₄-、-COO-、- OCO-、-COOC₂H₄-、-OCOC₂H₄-、-C₂H₄OCO-、-C₂H₄COO- ,-CH=CH- ,-CF₂-、-CF₂O-、-(CH₂)_z- C (= O)-O-、-(CH₂)_z- O- (C=O)-,-O- (C=O)-(CH₂)_z- ,-(C=O)-O- (CH₂)_z-、-O-(CH₂)_z-O-、- OCF₂- ,-CH=CHCOO- ,-CH=CHOCO- ,-COOCH=CH- ,-OCOCH=CH- or-C ≡ C-, the z in previously described formula represents 1~4 integer,

m^p11、m^p12And m^p22Separately represent 0 to 3 integer, and m^p11+m^p12Represent more than 2 integer,

m^p21And m^p23Separately represent 1 to 4 integer, and represent m^p21+m^p23≤ 3,

In m^p11For more than 2 when, on existing multiple A^p11And L^p11, they may be the same or different respectively, in m^p12 For more than 2 when, on existing multiple A^p12And L^p12, they may be the same or different respectively,

In m^p22For more than 2 when, on existing multiple A^p22And L^p21, they may be the same or different respectively,

In m^p21For more than 2 when, on existing multiple R^p21And Sp^p21, they may be the same or different respectively, in m^p23 For more than 2 when, on existing multiple R^p22And Sp^p22, they may be the same or different respectively.)

In general formula (P-1) and general formula (P-2), preferably Sp^p11、Sp^p12、Sp^p21And Sp^p22It is former to be each independently singly-bound, carbon The alkylidene or-O- (CH of subnumber 1~8₂)_s- (in formula, s represents 2 to 7 integer, and oxygen atom is connected to aromatic rings).

In general formula (P-1) and general formula (P-2), more preferably A^p11、A^p12And A^p22Separately represent 1,4- phenylenes, Anthracene -2,6- diyl, phenanthrene -2,7- diyl or naphthalene -2,6- diyl, which can be unsubstituted or the alkyl through carbon number 1~5, The halogenated alkyl of carbon number 1~5, the alkoxy of carbon number 1~5, the alkyl ester group of carbon number 1~5, carbon number 1 ~5 halogenated alkoxy, fluorine, cyano group substitution.

In general formula (P-1) and general formula (P-2), preferably L^p11、L^p12、L^p21And L^p22It is each independently singly-bound ,-OCH₂-、- CH₂O-、-C₂H₄-、-COO-、-OCO-、-COOC₂H₄-、-OCOC₂H₄-、-C₂H₄OCO-、-C₂H₄COO- ,-CH=CH- ,- CF₂O-、-(CH₂)_z- C (=O)-O- ,-(CH₂)_z- O- (C=O)-,-O- (C=O)-(CH₂)_z- ,-(C=O)-O- (CH₂)_z-、- O-(CH₂)_z-O-、-OCF₂- ,-CH=CHCOO- ,-CH=CHOCO- ,-COOCH=CH- ,-OCOCH=CH- or-C ≡ C-, and Z preferably in previously described formula represents 4.If linking group is above-mentioned group, polymerizable monomer can be linear structure.

In the compound represented by general formula (P-1), more preferably m^p11And m^p12Separately represent 0,1 or 2.In addition, More preferably m^p11+m^p12For 2~5, further preferred m^p11+m^p12For 2~4.

In the compound represented by general formula (P-2), m^p21And m^p23Separately represent 1,2 or 3, preferably m^p22Represent 1 Or 2.In addition, more preferably m^p21+m^p23=3~6.

In general formula (P-2), the aromatic series base of so-called divalence~tetravalence is the organic of divalence~tetravalence containing aromatic rings Base, 2~4 connecting portions are preferably all from aromatic rings, specifically, can enumerate phenyl skeleton, tetrahydrochysene naphthalene skeleton, luxuriant and rich with fragrance skeleton, Anthracene skeleton and naphthalene skeleton etc..

In general formula (P-2), as the ester ring type base of divalence~tetravalence, for divalence~tetravalence containing ester ring type structure Organic group, 2~4 connecting portions are preferably all from ring, can specifically enumerate cyclohexylidene skeleton, cyclohexadienylidene skeleton Deng.

In general formula (P-2), as the aromatic series base of divalence, Isosorbide-5-Nitrae-phenylene, anthracene -2,6- diyl, phenanthrene -2,7- bis- are represented Base, pyridine -2,5- diyls, pyrimidine -2,5- diyls, naphthalene -2,6- diyls, indane -2,5- diyls, 1,2,3,4- naphthanes -2,6- Diyl or 1,3- bis-Alkane -2,5- diyl, is preferably unsubstituted or the alkyl through carbon number 1~12, carbon number 1~12 Halogenated alkyl, the alkoxy of carbon number 1~12, the halogenated alkoxy of carbon number 1~12, halogen atom, cyano group, nitro Or R^p11Substitution.

It it is appointing in following formula (b-i)~(b-ix) as the aromatic series base of divalence~tetravalence in general formula (P-2) One, the aromatic series base are unsubstituted or can the alkyl through carbon number 1~12, the halogenated alkyl of carbon number 1~12, carbon The alkoxy of atomicity 1~12, the halogenated alkoxy of carbon number 1~12, halogen atom, cyano group, nitro or R^p11Substitution.

(in formula, pass through * and Sp^p21Or Sp^p22Connection, passes through * * and L^p21Or L^p22Connection.)

In addition, the tool as the polymerizable monomer represented by above-mentioned general formula (P-1) or (P-2) in liquid-crystal composition entirety Body content, is preferably less than 5%, more preferably less than 3%, more preferably less than 2%, particularly preferably less than 1%, most Preferably less than 0.8%.In addition, the lower limit of the content of the polymerizable monomer in liquid-crystal composition is preferably 1000ppm, it is excellent Elect 3000ppm as, more preferably 5000ppm.

Hereinafter, the preferable structure of the compound represented by general formula of the present invention (P-1)~general formula (P-2) is illustrated.

In the compound represented by above-mentioned general formula (P-1), preferably 4≤m^p11+m^p12≤ 2 and L^p11Or L^p12Expression is selected from By-COO- ,-OCO- ,-COOC₂H₄-、-OCOC₂H₄-、-C₂H₄OCO-、-C₂H₄COO- ,-CH=CHCOO- ,-CH=CHOCO- ,- The polymerizable monomer of one of the group that COOCH=CH- and-OCOCH=CH- is formed.The polymerizable monomer of the structure due to With the linearity same with liquid crystal molecule and with the free degree to a certain degree, thus it is excellent with the intermiscibility of liquid-crystal compounds It is different.

As the preference of the compound represented by general formula of the present invention (P-1), can enumerate following formula (P-a-1)~ Polymerizable compound represented by formula (P-a-33).

In the compound represented by above-mentioned general formula (P-1), preferably m^p11+m^p12=2, A^p11And A^p12For 1,4- phenylenes and L^p11And L^p12For the polymerizable monomer of singly-bound.The polymerizable monomer of the structure possesses biphenyl structural, the polymerization containing these skeletons Orientation restraining force after the polymerization of property compound is most suitable for PSA type liquid crystal display element, can obtain good state of orientation, therefore It is uneven to can inhibit display, or does not produce display inequality completely.

As the preference of the compound represented by general formula of the present invention (P-1), can enumerate following formula (P-b-1)~ Polymerizable compound represented by formula (P-b-34).

In the compound represented by above-mentioned general formula (P-1), preferably m^p11+m^p12=1 and A^p11Or A^p12For phenanthrene -2,7- diyls Polymerizable monomer.For the polymerizable monomer of the structure, it is believed that the photosensitization of composition entirety is big.

As the preference of the compound represented by general formula of the present invention (P-1), can enumerate following formula (P-c-1)~ Polymerizable compound represented by formula (P-c-52).

In general formula (P-2), preferably m^p22Represent more than 1 and less than 3 integer, L^p21Or L^p22At least one be singly-bound And A^p21And A^p23Separately represent to be unsubstituted or (1 or non-neighboring in aforesaid alkyl, the alkyl through carbon number 1~5 - the CH of more than 2 connect₂- it can separately be substituted by-C ≡ C- ,-O- ,-CO- ,-COO- or-OCO-, in aforesaid alkyl The hydrogen atom of more than 2 of 1 or non-adjacent can separately be substituted by fluorine atom), fluorine atom, cyano group, nitro take Following formula (b-i)~(b-ix) in generation.

As the preference of the compound represented by general formula of the present invention (P-2), can enumerate following formula (P-d-1)~ Polymerizable compound represented by formula (P-d-57).

Liquid crystal layer and/or liquid-crystal composition in liquid crystal display element of the present invention be preferably in the liquid crystal layer and/ Or contain polymerizable monomer in liquid-crystal composition, and the polymerizable monomer is subjected to polymerization.Thus, the liquid crystal of optical alignment film The orientation restraining force of molecule improves.More specifically, illustrated using Fig. 6 and Fig. 7.(A) of Fig. 6 is the liquid crystal of IPS patterns The plan of display element, pixel electrode is formed as combed with common electrode, and both are separated in a manner of being movably fitted together to mutually It is formed on same substrate certain distance.It is Fig. 7 (B) in the Fig. 6, obtained from the region for the VII for amplifying dotted portion And (C).In addition, for (B) and (C) and Fig. 8 of Fig. 7, for the sake of convenient, be on the upside of pixel electrode is, under common electrode is The plan of side, but it's not limited to that.(B) of Fig. 7 represents the present invention containing liquid-crystal compounds 1a Yu polymerizable monomer 1b Liquid-crystal composition on optical alignment film along specific direction (along the differently- oriented directivity of optical alignment film) arrange state.(C) of Fig. 7 For liquid-crystal compounds 1a and polymerizable monomer 1b on optical alignment film along specific direction (along the differently- oriented directivity of optical alignment film) Polymerizable monomer is carried out the state of polymerization by (that is, the state of foregoing (B)) in the state of arrangement.Pass through the aggregated materialization Polymer 1c presence, produce towards relative to liquid crystal molecule be specific direction orientation restraining force.That is, if in (B) state Polymerizable monomer is set to carry out polymerization under (no applied voltage), then polymerizable monomer is taken to orientation specific direction each other ((C) state) is connected in the state of.It is therefore contemplated that due to the polymer 1c and liquid crystal that are connected to each other in polymerizable monomer Interact between molecule 1b, therefore the stabilisation of pre-tilt angle, alignment films improve the orientation restraining force of liquid crystal molecule.Separately Outside, in Fig. 7 and Fig. 8, multidomain is set in order to solve the problems such as angle of visibility dependence.

Fig. 8 schematically shows the liquid crystal molecule when state for earlier figures 7 (C), Voltage On state (ON) or disconnection (OFF) Orientation situation.If applying voltage, liquid crystal molecule 1a is orientated along direction of an electric field.If disconnect (OFF) voltage, due to There are the polymer 1c that polymerizable monomer is connected to each other in liquid crystal layer, therefore liquid crystal molecule 1a is easily taken remaining initial Specific differently- oriented directivity is reverted in the state of to direction.

Therefore, in liquid crystal display element, if possess liquid-crystal composition contain polymerizable monomer and liquid-crystal compounds and The polymerizable monomer is carried out to such liquid crystal layer of polymerization, then it is assumed that even if repeating voltage ON-OFF (connects on-off Open) state, due to interacting between the polymer 1c and liquid crystal molecule 1b that polymerizable monomer is connected to each other, because This also can to as it is conventional the problem of time dependent reduce the orientation restraining force to liquid crystal molecule improve.Thus, it is believed that Liquid crystal molecule can maintain the specific differently- oriented directivity applied to optical alignment film, therefore the orientation restraining force of essence improves.Especially When carrying out orientation segmentation, since the differently- oriented directivity in the region that is split to form in pixel is different, can improve to taking The orientation restraining force of differently- oriented directivity into each region being split to form.

When adding polymerizable monomer in liquid-crystal composition of the present invention, even if gathering when polymerization initiator is not present Conjunction can also carry out, but in order to promote to polymerize, can also contain polymerization initiator.As polymerization initiator, can enumerate benzoin ethers, Benzophenone, acetophenones, benzil ketals class, acylphosphine oxide class etc..

Liquid-crystal composition of the present invention is further containing the compound represented by general formula (Q) as antioxidant.

In aforementioned formula (Q), R^QRepresent the alkyl or alkoxy of carbon number 1~22, the CH of more than 1 in the alkyl₂ Base can be substituted by a manner of oxygen atom does not abut directly against-O- ,-CH=CH- ,-CO- ,-OCO- ,-COO- ,-C ≡ C- ,- CF₂O-、-OCF₂-, M^QRepresent anti-form-1,4- cyclohexylidenes, 1,4- phenylenes or singly-bound.

In aforementioned formula (Q), R^QThe preferably alkyl or alkoxy of carbon number 1~22, the alkyl (including foregoing alkane Alkyl in epoxide) can be straight-chain or branched.In addition, foregoing R^QRepresent the straight or branched alkyl of carbon number 1~22 Or straight or branched alkoxyl, the CH of more than 1 in the alkyl (including alkyl in foregoing alkoxy)₂Base can be former with oxygen The mode that son does not abut directly against is substituted by-O- ,-CH=CH- ,-CO- ,-OCO- ,-COO- ,-C ≡ C- ,-CF₂O-、-OCF₂-。 In aforementioned formula (Q), R^QPreferably carbon number 1~20 and for selected from by straight chained alkyl, unbranched alkoxy, 1 CH₂Base quilt It is substituted by straight chained alkyl, branched alkyl, branched alkoxy and 1 CH of-OCO- or-COO-₂Base be substituted by-OCO- or- At least one of group that the branched alkyl of COO- is formed, is more preferably selected from the straight chain alkane by carbon number 1~10 Base, 1 CH₂Base is substituted by straight chained alkyl, branched alkyl, branched alkoxy and 1 CH of-OCO- or-COO-₂Base is substituted At least one of group formed for the branched alkyl of-OCO- or-COO-.

M^QExpression anti-form-1,4- cyclohexylidenes, Isosorbide-5-Nitrae-phenylene or singly-bound, preferably anti-form-1,4- cyclohexylidenes or 1, 4- phenylenes.

Compound represented by aforementioned formula (Q) is preferably selected from represented by following general formula (Q-a)~general formula (Q-d) Compound represented by least one of compound group compound, more preferably general formula (Q-a) and/or (Q-c).

In aforementioned formula (Q-a)~formula (Q-d), R^Q1The preferably straight chained alkyl or branched alkyl of carbon number 1~10, R^Q2The preferably straight chained alkyl or branched alkyl of carbon number 1~20, R^Q3The preferably straight chained alkyl of carbon number 1~8, branch Alkyl group, unbranched alkoxy or branched alkoxy, L^QThe preferably straight-chain alkyl-sub or branched alkylidene of carbon number 1~8.It Among, the compound represented by general formula (Q) is more preferably following formula (Q-a-1) and/or the chemical combination represented by (Q-c-1) Thing.

In the liquid-crystal composition of the present application, the change represented by the aforementioned formula (Q) of one or two is preferably comprised Compound, further preferably a kind of~five kinds, its content is preferably relative to the gross mass of the liquid-crystal composition of the present invention 0.001~1 mass %, is preferably 0.001~0.1 mass %, is preferably 0.001~0.05 mass %.

(oriented layer)

Light redirecting layer of the present invention is arranged at least one of first substrate and second substrate, is preferably disposed on The both sides of one substrate and second substrate.

Oriented layer of the present invention is preferably comprised in response to light and the changed optical Response high score of its chemical constitution The optical alignment film of son.

Thus, in the liquid crystal display element using the horizontal alignment direction mode (IPS or FFS) of p-type material, can reduce Friction inequality, the drop impression of liquid-crystal composition caused by the bumps on the surface that electrode as short strip shape etc. is brought.

In using optical alignment film and the liquid crystal display element of the horizontal alignment direction mode (IPS or FFS) of p-type material, By using the liquid-crystal composition containing polymerizable monomer, the advantage of the high contrast of optical alignment film can be played, and improves orientation Restraining force.

Usual optical alignment film tool there is various ways in which, such as can enumerate：Using with azo group (for example, azobenzene chemical combination Thing), the compound at unsaturated bond position such as schiff bases (Schiff base) and carbon-to-carbon double bond etc. is because of the light that light irradiates and occurs The optical alignment film of isomerization；Utilize the optical alignment film of the photodimerization of cinnamic acid derivative etc.；Using cumarin, chalcone or Optical alignment film of light cracking (photodegradation) (for example, photodegradation polyimides etc.) of the σ keys of polymer in itself etc..

More specifically, which is preferably selected from by optical Response breakdown type macromolecule, optical Response At least one of group that dimerization type macromolecule and optical Response isomerization type macromolecule are formed, particularly preferably photoresponse Property breakdown type macromolecule.

As optical Response breakdown type macromolecule of the present invention, the light of the preferably σ keys using polymer in itself is opened Split the optical Response breakdown type macromolecule of (photodegradation) etc..More specifically, be preferably respectively provided with polysiloxanes, polyimides, And optical Response breakdown type macromolecule of the polyamic acid derivative structure as main chain, more preferably polyimides, polyamic acid spread out Biological structure.As polyamic acid derivative, the Arrcostab of carbon number 1 to 5 or the alkane of carbon number 1 to 18 are preferably set to Base ammonium salt.

Optical Response breakdown type macromolecule of the present invention is preferably comprised selected from by making tetracarboxylic dianhydride and two amine compounds At least one of the group that the polyamic acid and polyimides that thing is reacted and obtained are formed polymer.

As the foregoing tetracarboxylic dianhydride as polyimides, the raw material of polyamic acid derivative, following change can be enumerated Compound.

(in above-mentioned formula, Z¹、Z²、Z³、Z⁴Separately represent hydrogen atom, the alkyl of carbon number 1~5, chlorine atom, fluorine Atom ,-NR₂、-SR、-OH、-CH₂COOR、-CH₂CH₂COOR、-COR、-NO₂,-CN, but Z¹、Z²、Z³、Z⁴At least one of no For hydrogen atom or methyl, R represents the alkyl of carbon number 1~5, and T represents singly-bound ,-CH₂-、-O-、-S-、-C(CH₃)₂-、-C (CF₃)₂-、-CO-、-SO-。)

(T represents singly-bound ,-CH in above-mentioned formula₂-、-O-、-S-、-C(CH₃)₂-、-C(CF₃)₂-、-CO-、-SO-。)

In compound as above, preferred formula (TCA-1), formula (TCA-2), formula (TCA-3), formula (TCA-4), formula (TCA-5), formula (TCA-8) and formula (TCA-10), particularly preferred formula (TCA-1), formula (TCA-8).

As the foregoing diamine compound as polyimides, the raw material of polyamic acid derivative, following change can be enumerated Compound.

In such compound, preferred formula (DA-1), formula (DA-25), formula (DA-31), formula (DA-32), formula (DA-49), Particularly preferred formula (DA-1), formula (DA-25), formula (DA-49).

In addition, when the type using photoisomerization is used in optical alignment film of the present invention, preferably in tetracarboxylic anhydride Or contain at least one of diamine compound and be selected from by following formula (TCA-38) and formula (DA-50)~formula (DA-56) institute group Into at least one of group.

For example, the chemical combination except the exemplary previously described formula (TCA-1) as foregoing tetracarboxylic anhydride~previously described formula (TCA-37) Beyond thing (or replacing), preferably using following formula (TCA-38)：

Represented compound.Or in addition to the compound of formula (DA-1)~formula (DA-49) (or replacing), make For diamine compound, preferably using the compound represented by following formula (DA-50)~formula (DA-56).

In addition, when the type using photodimerization is used in optical alignment film of the present invention, preferably in previously described formula (DA-1) at least one of the hydrogen atom in diamine compound represented by~(DA-49) more preferably contains with following formula (V) By selecting at least one of group that free style (DA-50)~formula (DA-53) formed.

That is, in addition to the compound of previously described formula (DA-1)~(DA-49) (or replacing), as diamine compound, The compound of logical formula (V) is substituted by preferably using the hydrogen atom in the compound of (DA-1)~(DA-49).

(in formula, dotted line represents the connecting key for the atom being connected with the hydrogen atom of (DA-1)~(DA-49), G¹、G²、G³、 G⁴、G⁵Separately represent singly-bound, alkylidene (1-CH of carbon number 2~12₂- base or more than 2 it is non-adjacent- CH₂- base can be substituted by-O- ,-CO- ,-COO- ,-OCO- ,-NR- ,-NRCO- ,-CONR- ,-NRCOO- ,-OCONR- ,- NRCONR- ,-CH=CH- ,-C ≡ C- ,-OCOO-.R represents the alkyl of hydrogen atom or carbon number 1~20) ,-OCH₂-、- CH₂O- ,-COO- ,-OCO- ,-CH=CH- ,-CF=CF- ,-CF₂O-、-OCF₂-、-CF₂CF₂- ,-C ≡ C- ,-CH=CHCOO- ,- OCOCH=CH-.Wherein, G¹、G²、G³、G⁴、G⁵Any one of-CH=CHCOO- indicated above ,-OCOCH=CH-.

n⁵、n⁶、n⁷、n⁸Represent 0 or 1, E¹、E²、E³、E⁴、E⁵Separately represent anti-form-1,4- cyclohexylidenes, trans- 1,4- bis-Alkane -2,5- diyls, 1,4- naphthylenes, 2,6- naphthylenes, pyridine -2,5- diyls, pyrimidine -2,5- diyls, 2,5- are sub- Thiophenyl, 2,5- furylidenes or Isosorbide-5-Nitrae-phenylene, they are unsubstituted or more than one hydrogen atom can be substituted by fluorine Atom, chlorine atom, methyl or methoxy, Z represent hydrogen atom, fluorine atom, alkyl (1-CH of carbon number 1~12₂- base or 2 Non-adjacent-CH more than a₂- base can be substituted by-O- ,-CO- ,-COO- ,-OCO- ,-NR- ,-NRCO- ,-CONR- ,- NRCOO- ,-OCONR- ,-NRCONR- ,-CH=CH- ,-C ≡ C- or-OCOO-.R is the alkane of hydrogen atom or carbon number 1~20 Base), cyano group, nitro, hydroxyl or carboxyl.)

As the concrete example of such diamine compound, such as following formula (DA-57)~(DA-60) can be enumerated.

As the optical alignment film of photodegradation type of the present invention, from the viewpoint that can show good liquid crystal aligning and Speech, tetracarboxylic anhydride are more preferably formula (TCA-1), formula (TCA-2), formula (TCA-3), formula (TCA-4), formula (TCA-5), formula (TCA- 33) (in previously described formula (TCA-33), T is particularly preferably-CO-) and TCA-34 (in previously described formula (TCA-34), T is preferably-CO-), Particularly preferably formula (TCA-1), formula (TCA-2), formula (TCA-3), formula (TCA-4) and formula (TCA-5).In addition, as the present invention The optical alignment film for the photodegradation type being related to, so that it may which for the viewpoint for showing good liquid crystal aligning, diamine compound is special Preferably formula (DA-1), formula (DA-25), formula (DA-49).

Tetracarboxylic anhydride enumerated above, diamine compound can be according to required characteristics individually using a kind of or group Close two or more and use.

In the high molecular preferable polyamic acid of optical Response breakdown type of the present invention, above-mentioned tetracarboxylic dianhydride Mixed proportion with above-mentioned diamine compound is preferably, relative to 1 equivalent of amino of diamines, the anhydride group of tetracarboxylic dianhydride into For the ratio of 0.2~2 equivalent, more preferably the ratio example as 0.3~1.2 equivalent.

In addition, in the optical alignment film of the present invention, pass through the polyamide of the condensation progress of tetracarboxylic anhydride and diamine compound The synthetic reaction of acid preferably carries out in organic solvent.The reaction temperature is preferably -20 DEG C~150 DEG C, and more preferably 0~100 ℃.In addition, when the reaction time is preferably 0.1~24 small, more preferably 0.5~12 it is small when.

As aforementioned organic solvents, such as can enumerate：Alcohol, ketone, ester, ether, aprotic polar solvent, phenol and its derivative Series solvent, halogenation hydrocarbon system solvent, hydrocarbon system solvent etc..

As foregoing alcohol, such as preferably methanol, ethanol, isopropanol, cyclohexanol, ethylene glycol, propane diols, Isosorbide-5-Nitrae-fourth two Alcohol, triethylene glycol, glycol monoethyl ether etc..

As foregoing ketone, such as preferably acetone, methyl ethyl ketone, methyl iso-butyl ketone (MIBK), cyclohexanone etc..

As foregoing ester, such as can enumerate：Ethyl lactate, butyl lactate, methyl acetate, ethyl acetate, butyl acetate, first Ylmethoxy propionic ester, ethyl ethoxy-c acid esters, diethy-aceto oxalate, diethyl malonate etc..

As foregoing ether, such as can enumerate：Diethyl ether, ethylene glycol monomethyl ether, ethylene glycol ethyl ether, ethylene glycol positive propyl ether, second two Alcohol isopropyl ether, ethylene glycol n-butyl ether, glycol dimethyl ether, ethyl cellosolve acetate, diethylene glycol dimethyl ether, diethylene glycol two Ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monomethyl ether acetic acid esters, diethylene glycol monoethyl ether acetic acid esters, Tetrahydrofuran etc..

As the concrete example of foregoing aprotic polar solvent, for example, preferably n-methyl-2-pyrrolidone, N, N- diformazans Yl acetamide, N,N-dimethylformamide, dimethyl sulfoxide (DMSO), gamma-butyrolacton, tetramethylurea and hexamethylphosphoramide etc..

As foregoing phenol and its derivative, such as preferably metacresol, xylenols, halogenation phenol etc..

As foregoing halogenation hydrocarbon system solvent, such as can enumerate：Dichloromethane, 1,2- dichloroethanes, 1,4- dichloroetane, three Chloroethanes, chlorobenzene, o-dichlorohenzene etc..

As foregoing hydrocarbon system solvent, such as can enumerate：Hexane, heptane, octane, benzene,toluene,xylene, isoamyl propionate, Isoamyl isobutyrate, isoamyl ether etc..

Tetracarboxylic dianhydride and diamine compound are preferably relative to the total of reaction solution relative to the total amount of organic solvent Measure and become 0.1~50 weight %.

If under the conditions described above being reacted tetracarboxylic dianhydride and diamine compound, can obtain containing polyamic acid Reaction solution.Can be by the preparation of reaction solution that this is obtained directly for alignment films, or also can be by institute in the reaction solution Preparation after the polyamic acid separation contained for alignment films, for taking after further also the polyamic acid that be isolated can be refined Preparation to film.

In addition, when polyimides is made in the polyamic acid dehydration closed-loop by foregoing acquisition, can be by above-mentioned reaction solution Directly for dehydration closed-loop reaction, also can by after polyamic acid separation contained in reaction solution for dehydration closed-loop reaction, or Also for dehydration closed-loop reaction after the polyamic acid that be isolated can be refined.The separation of polyamic acid and it is refined can be according to known Method carry out.

Imidizate is carried out the method for polyimides is made as the polyamic acid for making to obtain by previous reaction, can be led to Cross polyamic acid dehydration closed-loop and carry out imidizate and obtain.Specifically, method that can be by heating polyamic acid, Or polyamic acid is dissolved in organic solvent, dehydrating agent and dehydration closed-loop catalyst and as needed are added in the solution And the method heated carries out.

As organic solvent used in dehydration closed-loop reaction, can enumerate as organic used in the synthesis of polyamic acid Solvent and the organic solvent illustrated, thus description is omitted herein.

Polyimides as alignment films of the present invention can be by whole acyls possessed by its precursor, that is, polyamic acid Amino acid structure carries out acid imide compound, or be only dehydrated a part for amic acid structure completely obtained by dehydration closed-loop Closed loop and amic acid structure and imide ring structure and the part acid imide compound deposited.On polyimides of the present invention, Its acid imide rate is preferably more than 30%, more preferably 40~99%, more preferably 45~98%.The acid imide rate Ratio for by imide ring structure number relative to the amic acid structure number of polyimides and the total of imide ring structure number shared by Example parameter expressed as a percentage.Herein, a part for imide ring is alternatively different imide ring.

It should be noted that in the present invention, in the assay method of the acid imide rate of polyimides, imidizate will be derived from The proton of front and rear indeclinable structure is determined as reference proton, and the peak aggregate-value using the proton is with coming across 9.5 The proton peak aggregate-value of the NH bases from amic acid near~10.0ppm is calculated.

Temperature when polyamic acid to be carried out to hot-imide in the solution in the present invention is preferably 100 DEG C~400 DEG C, more Preferably 120 DEG C~250 DEG C.In this case, it is preferably while the water generated by imidization reaction is expelled to outside system While the method carried out.

In the present invention when by catalyst by polyamic acid imidizate, the polyamic acid in above-mentioned acquisition can be passed through Basic catalyst is added in solution with acid anhydrides and is stirred and obtains at preferably -20~250 DEG C, more preferably 0~180 DEG C .In addition, in this case, the amount of basic catalyst is 0.5~30 mole times of acid amides acidic group, is preferably 2~20 moles times, The amount of acid anhydrides is 1~50 mole times of acid amides acidic group, is preferably 3~30 moles times.

As aforementioned base catalyst, can enumerate：Pyridine, trimethylpyridine, lutidines, triethylamine, trimethylamine, three Butylamine and trioctylamine etc..In addition, as foregoing acid anhydrides, can enumerate：Acetic anhydride, trimellitic anhydride, pyromellitic acid anhydride etc..

It should be noted that the acid imide rate carried out by catalyst imidizate can be by adjusting catalytic amount and reaction Temperature, reaction time are controlled.

In the present invention, by the polyamic acid generated or polyimides from polyamic acid or the reaction solution of polyimides During middle recycling, reaction solution, which is put into, precipitates it into poor solvent.As poor solvent used in precipitation, can arrange Lift：Methanol, acetone, hexane, butyl cellosolve, heptane, methyl ethyl ketone, methyl iso-butyl ketone (MIBK), ethanol, toluene, benzene, water etc.. The polymer for putting into poor solvent and precipitating can at normal temperatures or heat under normal or reduced pressure after filtering, recycling And it is subject to drying.

When the concentration that polyamic acid and polyimides of the present invention is made is the solution of 10 weight %, more preferably have There are the solution viscosity of 10~800mPas, the more preferably solution viscosity with 15~500mPas.It should be noted that these are poly- The solution viscosity (mPas) of compound is for good solvent (such as gamma-butyrolacton, the N- methyl -2- pyrroles using the polymer Alkanone etc.) prepare 10 weight % of concentration polymer solution, using E types rotation viscometer 25 DEG C measure obtained by value.

It is preferably following general formulas in addition to the foregoing as optical Response dimerization type macromolecule of the present invention The condensation product of optical Response dimerization type macromolecule, its hydrolysate or hydrolysate represented by (1A) or general formula (1B).

(in above-mentioned general formula (1), Sp is selected from by singly-bound ,-(CH₂)_u- (in formula, u represents 1~20) ,-OCH₂-、- CH₂O- ,-COO- ,-OCO- ,-CH=CH- ,-CF=CF- ,-CF₂O-、-OCF₂-、-CF₂CF₂- and the groups that are formed of-C ≡ C- in At least one divalent linker, non-adjacent CH in these substituents₂More than one of base can independently be substituted by- O-、-CO-、-CO-O-、-O-CO-、-Si(CH₃)₂-O-Si(CH₃)₂-、-NR-、-NR-CO-、-CO-NR-、-NR-CO-O-、-O- (in formula, R represents the alkane of hydrogen or carbon number 1 to 5 by CO-NR- ,-NR-CO-NR- ,-CH=CH- ,-C ≡ C- or-O-CO-O- Base),

A¹、A²Separately represent be selected from by

(a) anti-form-1,4- cyclohexylidenes (are present in 1 in the group methylene or the not adjacent methylene of more than 2 Base can be substituted by-O- ,-NH- or-S-),

(b) 1,4- the phenylenes (- CH=of 1 be present in the group or more than 2 can be substituted by-N=) and

(c) bicyclic (2.2.2) octamethylene of 1,4- cyclohexadienylidenes, 2,5- phenylene sulfides base, 2,5- furylidenes, 1,4-, naphthalene- 1,4- diyls, naphthalene -2,6- diyls, decahydronaphthalene -2,6- diyls and 1,2,3,4- naphthane -2,6- diyls

Group in the group formed, above-mentioned group (a), group (b) or group (c) they are respectively to be unsubstituted, or More than one hydrogen atom can be substituted by fluorine atom, chlorine atom, cyano group, methyl or methoxy,

Z¹、Z²And Z³Separately represent singly-bound ,-(CH₂)_u- (in formula, u represents 1~20) ,-OCH₂-、-CH₂O-、- COO- ,-OCO- ,-CH=CH- ,-CF=CF- ,-CF₂O-、-OCF₂-、-CF₂CF₂- or-C ≡ C-, it is non-adjacent in these substituents CH₂More than one of base can independently be substituted by-O- ,-CO- ,-CO-O- ,-O-CO- ,-Si (CH₃)₂-O-Si(CH₃)₂-、- NR- ,-NR-CO- ,-CO-NR- ,-NR-CO-O- ,-O-CO-NR- ,-NR-CO-NR- ,-CH=CH- ,-C ≡ C- or-O-CO-O- (in formula, R independently represents the alkyl of hydrogen or carbon number 1 to 5),

X is-O-, singly-bound ,-NR- or phenylene,

R^bFor the fluorinated alkyl of polymerizable group, alkoxy, cyano group or carbon number 1~12,

M is 0,1 or 2,

M_bAnd M_dIt separately may be the same or different, represent that any of following general formula (U-1)~(U-13) is single Body unit,

(in above-mentioned general formula (U-1)~(U-10), dotted line represents the connecting key with Sp, R^aIndependently represent that hydrogen atom, carbon are former Alkyl, phenyl, the halogen atom of subnumber 1 to 5, any hydrogen atom in each structure can be substituted by fluorine atom, chlorine atom, first Base, phenyl, methoxyl group,

In above-mentioned general formula (U-11)~(U-13), dotted line represents the connecting key with Sp, R¹Represent the ring structure of tetravalence, R²Table Show the organic group of trivalent, R³Represent hydrogen atom, hydroxyl, the alkyl of carbon number 1~15, the alcoxyl of carbon number 1~15 Base.)

The mole fraction of y and w expression copolymers, 0<Y≤1 and 0≤w<1, n represents 4~100,000, M_bAnd M_dMonomer list Member can be independently made of one or more kinds of different units.)

In addition, the high molecular preferred embodiment of optical Response represented by the general formula (1) being related to as the invention described above, preferably Z²For the optical Response dimerization type macromolecule of singly-bound.

Other optical Response dimerization type macromolecules of the present invention are preferably the light represented by following general formulas (2) Response dimerization type macromolecule.

(in above-mentioned general formula (2), M¹And M²Stand alone as mutually respectively selected from by acrylate, methacrylate, 2- chlorine third Olefin(e) acid ester, 2- phenyl acrylates, can carry out the substituted acrylamides of N-, Methacrylamide, 2- chloropropenes through low alkyl group At least one in the group that acid amides, 2- Phenyl Acrylamides, vinethene, vinyl acetate, styrene derivative and type siloxane are formed Kind repetitive unit,

M³For selected from by acrylate, methacrylate, 2- chloropropenes acid esters, 2- phenyl acrylates, can be through rudimentary Alkyl carries out the substituted acrylamides of N-, Methacrylamide, 2- chloroacrylamides, 2- Phenyl Acrylamides, vinethene, ethene Ester, the straight-chain alkyl ester of acrylic or methacrylic acid or branched-chain alkyl ester, acrylic or methacrylic acid allyl ester, Alkyl vinyl ether or alkyl vinyl ester, acrylic acid phenoxyalkyl esters or methacrylic acid phenoxyalkyl ester, dihydroxypropyl Arrcostab or haloalkylacrylates, phenylethyl Arrcostab or methacrylic acid octadecyloxy phenyl base ester, acrylonitrile, first At least one of the group that base acrylonitrile, styrene, 4- methyl styrenes and type siloxane are formed repetitive unit,

A¹、B¹、C¹、A²、B²And C²Respectively independently of each other represent be selected from by

S¹And S²Stand alone as the straight-chain or branched that can substitute through fluorine atom, chlorine atom or cyano group more than at 1 mutually respectively Alkylidene (- (CH₂)_r-) or-(CH₂)_r-L-(CH₂)_s- (in formula, L means singly-bound or-O- ,-COO- ,-OOC- ,-NR¹-、- NR¹-CO-、-CO-NR¹-、-NR¹-COO-、-OCO-NR¹-、-NR¹-CO-NR¹- ,-CH=CH- or-C ≡ C-, R at this time¹Mean Hydrogen atom or low alkyl group, r and s be based on r+s≤24 condition and be 1~20 integer),

D¹、D²Stand alone as-O- ,-NR mutually respectively²- or containing selected from by following formula (d)~(f)：

(d) anti-form-1,4- cyclohexylidenes (are present in 1 in the group methylene or the not adjacent methylene of more than 2 Base can be substituted by-O- ,-NH- or-S-),

(e) 1,4- the phenylenes (- CH=of 1 be present in the group or more than 2 can be substituted by-N=) and

(f) bicyclic (2.2.2) octamethylene of 1,4- cyclohexadienylidenes, 2,5- phenylene sulfides base, 2,5- furylidenes, 1,4-, naphthalene- 1,4- diyls, naphthalene -2,6- diyls, decahydronaphthalene -2,6- diyls and 1,2,3,4- naphthane -2,6- diyls

Group in the group formed, above-mentioned group (d), group (e) or group (f) they are respectively to be unsubstituted, or More than one hydrogen atom can be substituted by fluorine atom, chlorine atom, cyano group, methyl or methoxy, at this time R²For hydrogen atom or low Level alkyl,

X¹、X²、Y¹And Y²Refer to hydrogen atom, fluorine atom independently of each other respectively, chlorine atom, cyano group, optionally taken through fluorine atom Generation and CH₂Base or multiple non-adjacent CH₂The carbon that base can optionally be substituted by-O- ,-COO- ,-OOC- and/or-CH=CH- is former The alkyl of subnumber 1~12,

Z^1a、Z^1b、Z^2aAnd Z^2bSingly-bound ,-(CH are independently of one another respectively₂)t-、-O-、-CO-、-CO-O-、-O-OC-、- NR⁴-、-CO-NR⁴-、-NR⁴-CO-、-(CH₂)_u-O-、-O-(CH₂)_u-、-(CH₂)_u-NR⁴- or-NR⁴-(CH₂)_u-, R at this time⁴The meaning It is hydrogen atom or low alkyl group；T means 1~4 integer；U is 1~3 integer,

p¹、p²、q¹And q²0 or 1 is independently of one another respectively,

R^1aAnd R^2aRefer to independently of each other respectively hydrogen atom, fluorine atom, chlorine atom, cyano group, nitro or carbon number 1~ 20 straight-chain or the alkyl of branched, alkoxy, alkyl-COO-, alkyl-CO-NR³Or alkyl-OCO bases, R at this time³Mean It is former that the hydrogen atom of more than 1 of hydrogen atom or low alkyl group, aforesaid alkyl or foregoing alkoxy can be substituted by fluorine atom, chlorine The CH of son, cyano group or nitro, aforesaid alkyl or foregoing alkoxy₂Base or multiple non-adjacent CH₂Base can be substituted by-O- ,-CH= CH- or-C ≡ C-,

n¹、n²And n³For 0<n¹≦1、0≦n²<1 and 0≤n³The mole fraction of≤0.5 copolymerization monomer.)

Hereinafter, the manufacture method of the liquid crystal display element of the present invention is illustrated.The liquid crystal display element of the present invention is excellent Elect as example, by following process (1)~(3) and manufacture.

The manufacture method of liquid crystal display element of the present invention is preferably that optical alignment film precursor of the present invention is molten After liquid is coated on substrate, by heating the coated face and in formation film (process (1)) on substrate.More specifically, such as Respectively the nesa coating for being provided with patterned interdigitated electrode structure substrate phase of the conducting film forming face with being not provided with conducting film To the optical alignment film precursor solution of the coated on one side present invention of substrate, each coated face is next heated, is consequently formed film.

Optical alignment film precursor solution of the present invention is preferably high molecular molten containing above-mentioned optical Response breakdown type Liquid.In addition, the optical Response breakdown type macromolecule is preferably comprised selected from by making tetracarboxylic dianhydride be reacted with diamine compound At least one of the group that the polyamic acid and polyimides obtained is formed polymer and aforementioned organic solvents.

It is preferred that the optical alignment film of the present invention is respectively coated by flexographic printing process, spin-coating method, rolling method or ink jet printing method Precursor solution.Herein, as substrate, such as can be used：The glass such as float glass, soda-lime glass；By polyethylene terephthalate, The transparent substrate that the plastics such as polybutylene terephthalate, polyether sulfone, makrolon, poly- (ester ring type alkene) are formed.As setting The nesa coating of the one side of (first) substrate is placed in, can be used by tin oxide (SnO₂) form NESA films, by indium oxide-oxygen Change tin (In₂O₃-SnO₂) ito film etc. that forms.Further, in order to obtain the nesa coating being patterned, such as can use Formed pattern-free nesa coating after by photoetch formed pattern method or when forming nesa coating use have Method of the mask of required pattern etc..When being coated with foregoing optical alignment film precursor solution, in order to make substrate surface and electrically conducting transparent The cementability of film and film further becomes good, can be by known to functional silanes compound, functionality titanium compound etc. Method is in advance surface-treated substrate surface.

After being coated with foregoing optical alignment film precursor solution, preliminary drying can be carried out as needed, and preliminary drying temperature in this case is excellent Elect 30~200 DEG C as.In addition, the preliminary drying time is preferably 0.25~10 minute.Then, solvent removed completely and root For the purpose of carrying out hot-imide according to the amic acid structure for needing will be present in polymer, firing process is preferably carried out.At this time Firing temperature be preferably 80~300 DEG C.Firing time is preferably 5~200 minutes.The thickness for the film being consequently formed is preferably 0.001~1 μm.

In addition, when the polymer contained by the optical alignment film precursor solution of the present invention is with polyamic acid or imide ring knot During the imide amination polymer of structure and amic acid structure, can by further heated after film is formed make dehydration closed-loop reaction into OK, the film through further imidizate is made.

The manufacture method of liquid crystal display element of the present invention is preferably to contain polyamides on aforesaid base plate to being formed at The film of amino acid or polyimides carries out light irradiation (process (2)).In addition, the process (3) that the process (2) can be also described below Carry out later.As the light irradiated to the film, the ultraviolet or visible ray of the light of the wavelength containing 150~800nm can be used, The preferably ultraviolet of the light of the wavelength containing 300~400nm.

As the light source of foregoing irradiation light, Cooper-Hewitt lamp, high-pressure mercury-vapor lamp, deuterium lamp, metal halide lamp, argon can be used Gas resonance lamp, xenon lamp, excimer laser etc..It should be noted that the ultraviolet of above-mentioned preferable wavelength region can pass through by Light source with such as wave filter, diffraction grating and means etc. and obtain.It is preferably 1,000J/m as the exposure of light² Above and 100,000J/m²Below.

The manufacture method of the liquid crystal display element of the present invention is preferably by a pair of of substrate formed with optical alignment film or film Configured in opposite directions across gap (cell gap), and fill liquid-crystal composition of the present invention (process (3)) in the gap.

In addition, when mixed polymerization monomer in a liquid crystal composition, also can further have after filling liquid crystal composition The standby process (4) for being polymerize polymerizable monomer by defined method in the state of no applied voltage.

As the method for filling foregoing liquid crystal composition, can enumerate：(1) (this method is vacuum impregnation：For formed with A pair of of substrate of optical alignment film or film, it is (single across gap in a manner of the differently- oriented directivity of the film of two plate bases becomes orthogonal First gap) configured in opposite directions, the periphery of two plate bases is bonded using sealant, by substrate surface and sealant division Cell gap in injection filling liquid crystal, injection hole is sealed and forms liquid crystal cells) or (2) ODF methods.Pass through vacuum impregnation Drop impression will not be produced in the method for the importing liquid-crystal composition of progress, but with the maximization of substrate size, manufacturing time, cost Etc. there are problem.However, in the present application, consider from the combination of optical alignment film and liquid-crystal composition, can more appropriately use In the display element manufactured using ODF methods.

In addition, as described in the present application, in same substrate (for example, being the in Fig. 3 and Fig. 5 in horizontal alignment mode One substrate) surface formed with the electrode layers such as TFT 3 (face that optical alignment film is coated to), therefore exist on the surface it is a large amount of concavo-convex, As the environment for the generation for readily facilitating drop impression, but think the combination by optical alignment film and liquid-crystal composition, which is able to Mitigate.

In addition, polymerizable monomer contained in the liquid-crystal composition containing polymerizable monomer of the present invention pass through it is ultraviolet Line irradiation is polymerize and is endowed liquid crystal aligning ability, is preferred for the birefringence using liquid-crystal composition and is controlled the saturating of light Cross the liquid crystal display element of light quantity.As liquid crystal display element, to VA-IPS-LCD, FFS-LCD, AM-LCD (active-matrix liquid Crystal display element) and IPS-LCD (switched liquid crystal display element in face) it is useful, be particularly useful to AM-LCD, available for infiltration type Or the liquid crystal display element of reflection-type.

Two plate bases of liquid crystal cells used in foregoing liquid crystal display element can be used glass or if plasticlike is with soft Soft transparent material, also can one of which be the opaque material such as silicon.Transparent substrate with transparent electrode layer is for example Can by the transparent substrates such as glass plate sputtered indium-tin-oxide (ITO) and obtain.

Foregoing colour filter such as can by pigment dispersion method, print process, galvanoplastic or decoration method and make.If with logical Cross pigment dispersion method make colour filter method illustrated for an example, then for by the curing colouration composition of colour filter apply It is distributed on the transparent substrate, implements patterned process, its curing is then made by heating or light irradiation.With red, green, blue 3 color point The process is not carried out, thus can make the pixel portion of colour filter.In addition, can also set on the substrate equipped with TFT, thin The pixel electrode of the active components such as film diode.

Make aforesaid base plate opposite in a manner of transparent electrode layer becomes inner side.At this time, also base can be adjusted across sept The interval of plate.At this time, the thickness of the light modulation layer (liquid crystal layer) preferably to be obtained is adjusted in a manner of becoming 1~100 μm.Into One step is preferably 1.5 to 10 μm, and when using polarizer, the refractive index of liquid crystal is preferably adjusted in a manner of contrast becomes maximum The product of anisotropy Δ n and element thickness G.In addition, there are during two panels polarizer, the polarizing axis of each polarizer can also be adjusted And it is adjusted according to making angle of visibility, contrast become good mode.Further, it is possible to use to expand the phase of angle of visibility Potential difference film.As sept, such as can enumerate by structures such as glass particle, plastic pellet, aluminium oxide particles, photo anti-corrosion agent materials Into column spacer etc..Then, by sealants such as epoxy thermoset compositions in the form of being provided with liquid crystal injecting port net Version printing makes the substrate be bonded each other on the substrate, is heated and makes sealant heat cure.

The method of clamping liquid-crystal composition (containing polymerizable monomer as needed) can be used common between two plate bases Vacuum impregnation or ODF methods etc..Although however, vacuum impregnation does not produce drop impression, there is the problem of residual injection trace.This Apply in invention, can more appropriately be used for using the display element manufactured by ODF methods.Manufactured in the liquid crystal display element of ODF methods In process, it is depicted in using dispenser by epoxy photo-thermal and with the sealant of curability etc. with closed loop dike shape in backboard or foreboard Any one substrate on, after the liquid-crystal composition of specified quantitative is added dropwise thereto under degassing phase, foreboard is engaged with backboard, by This can manufacture liquid crystal display element.The liquid-crystal composition of the present invention is due to can stably carry out the liquid-crystal composition in ODF processes Dropwise addition, therefore can suitably use.

As the method for polymerizeing polymerizable monomer, in order to obtain the good orientation characteristic of liquid crystal, it is desired for appropriateness Polymerization speed, therefore preferably by solely or and with or irradiate ultraviolet or electron beam isoreactivity energy line successively and make it The method of polymerization.When using ultraviolet, polarization light source can be used, it is possible to use non-polarized light source.In addition, polymerization will contained by working as Property monomer liquid-crystal composition be held between two plate bases in the state of when being polymerize, at least must be to irradiating the substrate of surface side Assign the appropriate transparency relative to active energy ray.In addition, it is possible to use following means：When light is irradiated using mask only Make it is specific it is partially polymerized after, by varying conditions such as electric field, magnetic field or temperature, become the state of orientation of unpolymerized part Change, further irradiate active energy ray and make its polymerization.Especially when carrying out ultraviolet exposure, preferably not to containing polymerism The liquid-crystal composition of monomer carries out ultraviolet exposure in the state of applying voltage.In the liquid crystal display of lateral electric-field type MVA patterns In element, for the viewpoint of orientation stability and contrast, preferably by pre-tilt angle (major axis of liquid crystal molecule and substrate surface institute Into angle) control be 0 ° or so.

Temperature during irradiation is preferably within the temperature range of the mesomorphic state of the liquid-crystal composition of the present invention is maintained.It is excellent Being selected in for the temperature close to room temperature, i.e. typical case makes its polymerization at a temperature of 15~35 DEG C.As the lamp for producing ultraviolet, can make With metal halide lamp, high-pressure mercury-vapor lamp, extra-high-pressure mercury vapour lamp etc..In addition, the wavelength as the ultraviolet irradiated, preferably according to Penetrate the ultraviolet that wavelength region is not the absorbing wavelength region of liquid-crystal composition, preferably ultraviolet ended as needed and Use.The intensity of the ultraviolet irradiated is preferably 0.1mW/cm²~100W/cm², more preferably 2mW/cm²~50W/cm².Institute The amount of the energy of the ultraviolet of irradiation can be suitably adjusted, and be preferably 10mJ/cm²To 500J/cm², more preferably 100mJ/ cm²To 200J/cm².The time of irradiation ultraviolet can suitably select according to the uitraviolet intensity irradiated, use metal halogen It is preferably 10 seconds to 3600 seconds when compound lamp, high-pressure mercury-vapor lamp or extra-high-pressure mercury vapour lamp, more preferably 10 seconds to 600 seconds, makes It is preferably 60 seconds to 18000 seconds during with fluorescent lamp, is preferably 600 seconds to 10800 seconds.

As long as foregoing 1st substrate or foregoing 2nd substrate are substantially transparent, then material is not particularly limited, usable glass, Ceramics, plastics etc..As plastic base, can be used：The celluloses such as cellulose, triacetyl cellulose, diacetyl cellulose derive Thing；The polyester such as polycyclic alkene derivative, polyethylene terephthalate, polyethylene naphthalate；Polypropylene, polyethylene etc. are poly- Alkene；It is makrolon, polyvinyl alcohol, polyvinyl chloride, polyvinylidene chloride, polyamide, polyimides, polyamidoimide, poly- Styrene, polyacrylate, polymethyl methacrylate, polyether sulfone, polyarylate, further also have fiberglass-epoxy, Inorganic-organic composite materials such as glass fibre-acrylic resin etc..

It should be noted that when using plastic base, barrier film is preferably provided with.The function of barrier film is to reduce plastics base Penetrability possessed by plate, improves the reliability of the electrical characteristics of liquid crystal display element.As barrier film, if for the transparency it is high, The small barrier film of water vapo(u)r transmission, then be not particularly limited, usually using using the inorganic material such as silica and by evaporation, The film that sputtering, chemical vapour deposition technique (CVD method) are formed.

In the present invention, as foregoing 1st substrate or foregoing 2nd substrate, same raw material can be used, it is possible to use different Raw material, are not particularly limited.If using glass substrate, heat resistance, the liquid crystal display member of excellent in dimensional stability can be made Part, thus preferably.In addition, if plastic base, be then suitable for the manufacture method carried out by roll-to-roll method, and be suitable for lightweight or Flexibility, thus preferably.In addition, if purpose is to assign flatness and heat resistance, plastic base and glass substrate are subject to Good result can be obtained if combination.

Embodiment

Hereinafter, enumerate embodiment and the present invention is described in more detail, but the present invention is not limited to these examples of implementation.Separately Outside, " % " in the composition of following embodiment and comparative example means " quality % ".

In embodiment, the characteristic measured is as described below.

Tni：Nematic phase-isotropic liquid phase transition temperature (DEG C)

Δn：Refractive anisotrop (the alias of 295K：Birefringence)

Δε：The dielectric constant anisotropy of 295K

η：The viscosity (mPas) of 295K

γ1：The rotational viscosity (mPas) of 295K

VHR：Voltage retention (%) under conditions of frequency 60Hz, application voltage 5V during 313K

Burn-in：

The burn-in of liquid crystal display element be evaluated as making specific fixed pattern shown in display area 1440 it is small when after, lead to The ghost for crossing fixed pattern when uniformly showing for visually carrying out whole picture according to 4 following Phase Evaluations is horizontal.

◎ is without ghost

Zero has few ghost and is permissible level

△ has ghost, for the level that can not be allowed

× there is ghost, it is excessively poor

Volatility/manufacture device pollution：

The volatility of liquid crystal material is evaluated as utilizing stroboscope to irradiate while observing vacuum stirring defoaming mixer Operating condition, visually observes the foaming of liquid crystal material, is thus evaluated.Specifically, disappear in the vacuum stirring of capacity 2.0L Steep and load liquid-crystal composition 0.8kg in the special container of mixer, with revolution speed 15S under the degassing of 4kPa^-1, rotational velocity 7.5S^-1Operation is stirred under vacuum defoaming mixer, according to the time untill foaming is started, is carried out according to 4 following stages Evaluation.

◎ is more than 3 minutes untill foaming.The possibility that the device caused by volatilization pollutes is low.

Zero until foaming untill for 1 minute less than 3 minutes.There is the load for causing slight device to pollute because of volatilization Sorrow.

△ is untill foaming for 30 seconds less than 1 minute.Device is caused to pollute because of volatilization.

× until foaming untill be 30 seconds within.Have because volatilization causes the worry of serious device pollution.

Technological adaptability：

Technological adaptability is in ODF techniques, is pumped using constant volume measurement and liquid crystal is gradually added dropwise in a manner of each 40pL, will The operation carries out 100000 times, according to 4 following stages to it is following " 0~200 time, 201~400 times, 401~600 It is secondary ... 99801~100000 times " the changes of each 200 amount of liquid crystal being added dropwise evaluated.

◎ is changed very little and (can stably be manufactured liquid crystal display element)

Zero has slight variations and is permissible level

△ is changed, for the level (causing yield rate to be deteriorated because inequality occurs) that can not be allowed

× change, excessively poor (liquid crystal leakage, bubbles of vacuum occurs)

Dissolubility during low temperature：

Dissolubility during low temperature is evaluated as after preparing liquid-crystal composition, weighs the sample that liquid-crystal composition 0.5g is placed in 1mL In bottle, in temperature control formula test flume, by following " -20 DEG C of (when holding 1 is small) → heatings (0.2 DEG C/per minute) → 0 DEG C Cooling (- 0.2 DEG C/per minute) → 0 DEG C (is protected for (when holding 1 is small) → heating (0.2 DEG C/per minute) → 20 DEG C (when holding 1 is small) → Hold 1 it is small when) → cooling (- 0.2 DEG C/per minute) → -20 DEG C " as 1 cycle temperature change is persistently assigned to it, pass through mesh Generation depending on observing the precipitate from liquid-crystal composition, carries out the evaluation in 4 following stages.

Precipitate is not observed more than when ◎ 600 is small.

0 300 it is small when more than do not observe precipitate.

Precipitate is observed within when △ 150 is small.

× 75 it is small when within observe precipitate.

In embodiment, the record of compound used in liquid-crystal composition uses following abbreviation.

(side chain)

(linking group)

(ring structure)

(preparation example 1~16 (liquid-crystal composition 1~16))

The liquid-crystal composition (preparation example 1~16) with composition as shown below is prepared respectively, measures its physics value.Should The results are shown in following table 1 and table 2.[table 1]

[table 2]

[table 3]

In addition, for 99.7 mass parts of nematic liquid crystal composition shown in preparation example 1,2,6 and 13, difference adding type (P.1)：

Represented polymerizable monomer 0.3%, and it is equably dissolved, thus prepare the liquid crystal group containing polymerizable monomer Compound 1, the liquid-crystal composition 2 containing polymerizable monomer, the liquid-crystal composition 6 containing polymerizable monomer and the liquid crystal containing polymerizable monomer Composition 13.

The physical property of the liquid-crystal composition 1,2,6,13 containing polymerizable monomer and each nematic shown in preparation example 1,2,6,13 The physical property of type liquid-crystal composition there's almost no difference.

In addition, the nematic liquid crystal composition 99.7% shown in for preparation example 9,12 and 16, difference adding type (P.2)：

Represented polymerizable monomer 0.3%, and it is equably dissolved, thus prepare the liquid crystal group containing polymerizable monomer Compound 9, the liquid-crystal composition 12 containing polymerizable monomer, the liquid-crystal composition 16 containing polymerizable monomer.This is containing polymerizable monomer The physical property of liquid-crystal composition 9,12,16 also with the physical property of each nematic liquid crystal composition shown in preparation example 9,12,16 hardly Have differences.

Using the liquid-crystal composition of the present invention and the liquid-crystal composition containing polymerizable monomer, the list usually as TV is made The FFS mode of first 3.0 μm of thickness, the liquid crystal display element of IPS patterns, alignment films are made by such as the following method.

" optical alignment film 1 "

After 1.0 moles of % of p-phenylenediamine are dissolved in n-methyl-2-pyrrolidone, cyclobutane tetrabasic carboxylic acid is added wherein 1 mole of % of dianhydride, when making its reaction 12 small for 20 DEG C, it is about 100,000, again to obtain polystyrene standard conversion weight average molecular weight The polyamide acid varnish that average molecular weight/number-average molecular weight (Mv/Mn) is about 1.6.Next, the polyamide acid varnish is diluted to 6% concentration, after the γ aminopropyltriethoxy silane for adding in terms of solid constituent 0.3 weight %, is printed in the 1st film layer In stack and on the 2nd thin-film laminate, heated 30 minutes at 210 DEG C and form the dielectric film (polyimide film) of photodegradation type.

Then, the polyimide film implementation irradiation to the photodegradation type for example has in the wavelength region of 240nm to 400nm The orientation process of the light (ultraviolet) from polarisation UV lamp of bright line.What the orientation process was for example formed using stacking quartz base plate Accumulation type polarizer makes the ultraviolet from high-pressure mercury-vapor lamp become polarisation ratio about 20：1 linear polarization, with about 4J/cm²Photograph Energy is penetrated to be irradiated and carry out.

" optical alignment film 2 "

(synthesis of polyamic acid A)

After 4,4'- diamino-diphenyls ether, 1.0 moles of % are dissolved in n-methyl-2-pyrrolidone, add wherein 1 mole of % of cyclobutane tetracarboxylic dianhydride, when making its reaction 12 small for 20 DEG C, obtains polystyrene standard conversion weight average molecular weight about The polyamic acid solution A for being about 1.6 for 50,000, weight-average molecular weight/number-average molecular weight (Mv/Mn).

(synthesis of polyamic acid B)

After 4,4'- diamino-diphenyls amine, 1.0 moles of % are dissolved in n-methyl-2-pyrrolidone, add wherein 1 mole of % of cyclobutane tetracarboxylic dianhydride, when making its reaction 6 small for 20 DEG C, obtains polystyrene standard conversion weight average molecular weight about The polyamic acid B solution for being about 1.9 for 55,000, weight-average molecular weight/number-average molecular weight (Mv/Mn).

(adjustment of mixture)

It is known as 1 with solid constituent mass ratio：1 mode is mixed polyamic acid solution A, polyamic acid B solution, into The mass ratio of one step n-methyl-2-pyrrolidone and butoxy ethanol is 1：1 mixed solvent is diluted, and is derived from Polyamic acid solution.

It is printed on the 1st thin-film laminate and on the 2nd thin-film laminate, is heated 30 minutes at 230 DEG C, forms light point The dielectric film (polyimide film) of solution type.Then, the light (ultraviolet) from high-pressure UV lamps is made using wire grid polarizer Into extinction ratio about 100：1 linear polarization, with 0.5J/cm²Irradiation energy the polyimide film of the photodegradation type is shone Penetrate and carry out.

" optical alignment film 3 "

(preparation of optical alignment film solution)

N-methyl-2-pyrrolidone 32.40g is added in Isosorbide-5-Nitrae-phenylenediamine 3.24g, is sent into nitrogen while being stirred Mix and make its dissolving.While the diamine solution is stirred, while addition cyclobutane tetracarboxylic dianhydride 7.81g, and further add N- N-methyl-2-2-pyrrolidone N 78.03g, in nitrogen environment, 30 DEG C stirring 18 it is small when and make its reaction.Further, add at normal temperatures It is 1 to add the mass ratio of n-methyl-2-pyrrolidone and butoxy ethanol：1 mixed solvent 62.68g, is diluted stirring, Obtain optical alignment film solution.

(formation of liquid crystal orientation film)

(formation of photolysis resin film)

Foregoing optical alignment film solution is set to form dry thickness on the comb shape transparency electrode of the 1st substrate is formed at by spin-coating method The resin film of 0.1 μm of degree.In the same way also alignment films are formed in the 2nd substrate.By the substrate formed with resin film at 230 DEG C Heat 30 minutes and make its reaction, be consequently formed the resin film (polyimide film) of photodegradation type.

(orientation process)

Ultraviolet using bandpass filter from high-pressure mercury-vapor lamp extraction 256nm, extinction ratio is made using wire grid polarizer About 100：1 linear polarization, with 1.0J/cm²Irradiation energy the resin film of the photodegradation type is irradiated and carries out light and takes To processing.Then, in order to remove the impurity for decomposing and generating, after 30 minutes are burnt till at 230 DEG C, polyimide film is cleaned with pure water And it is subject to drying, it is derived from the glass substrate of the alignment films formed with photodegradation type.

" optical alignment film 4 "

(synthesis example 1)

(synthesis of polymer (PA-1))

The 10 parts of dissolvings of monomer (I-1-1) that will be synthesized in following response path via the intermediate of compound 1~6 In 45 parts of tetrahydrofuran (THF), and add 0.03 part of azodiisobutyronitrile (AIBN), will thus obtained by solution in nitrogen ring Be heated to reflux under border 8 it is small when and make its reaction.

Next, the solution after reaction to be added dropwise in 600 parts of methanol and be stirred, recycle precipitate and be dissolved in After in 50 parts of THF, it is added dropwise in 1200 parts of the hexane through ice bath cooling and is stirred, the solid separated out is recycled.By institute The solid of acquisition is dissolved in 50 parts of THF, is added dropwise in 1200 parts of the methanol through ice bath cooling and is stirred, will be separated out Solid recycling, be dried in vacuo after being dissolved in THF, be derived from polymer (PA-1).Polymer (the PA- obtained 1) weight average molecular weight (Mw) is 383,000, and molecular weight distribution (Mw/Mn) is 2.75.

It should be noted that the molecular weight of polymer be adjusted to by adjust under above-mentioned nitrogen environment when being heated to reflux Between, and measure weight average molecular weight (Mw) and carry out.

(measure of molecular weight)

Mw and Mn is based on following determination condition, passes through GPC (gel permeation chromatography, GelPermeation Chromatography) measure.

The GPC device HLC-8220GPC that measurement device is manufactured using Tosoh companies, analytical column use TSKgel GMHXL × 2, TSKgel G2000XL × 1 piece, TSKgel G1000XL × 1 piece amount to 4 series connection, detector uses differential refractive Rate (RI) detector, to make the polystyrene standard samples that the standard specimen of calibration curve is manufactured using Showa electrician STANDARD SM-105 (molecular weight ranges 1,300~3,800,000).By the polymer obtained with as the dense of 1 μ g/mL The mode of degree is dissolved in THF, mobile phase is set to THF, liquor charging speed is set to 1mL/ minutes, column temperature is set to 40 DEG C, Sample injection rate is set to 300 μ L and is measured.

(measure of glass transformation temperature)

Glass transformation temperature is to be measured by differential scanning calorimeter (DSC).Measurement device uses Seiko The DSC devices DSC6220 of Instruments companies manufacture.Polymer sample about 4mg is enclosed in aluminum pot, with 10 DEG C/minute The ratio of clock from when being warming up to 180 DEG C for -20 DEG C, with the baseline that Glass Transition accompanies move by observation.Read from the intersection point of tangent line Change starting point, be set to glass transformation temperature (Tg).

(formation of liquid crystal orientation film)

(making of photodimerization type resin film)

At room temperature by 47.5 parts of 5 parts of polymer (PA-1), 47.5 parts of 1-methyl-2-pyrrolidinone and butoxy ethanol Mixture stirs 10 minutes, it is equably dissolved.Next, using spin coater by the solution coating on glass substrate, 100 DEG C of dryings 3 minutes, thus form film on above-mentioned glass substrate.Formed film is observed by visual observation, is confirmed and is formd Smooth film.

(light orientation processing)

Next, using possessing the inclined of extra-high-pressure mercury vapour lamp, wavelength cut-off wave filter, bandpass filter and polagizing filter Light irradiation device, irradiates 10 seconds (irradiate light quantity 100mJ/cm to the film formed from vertical direction²) ultraviolet light (wavelength Linear polarization (illumination 313nm)：10mW/cm²), it is derived from optical alignment film.It need not carry out burning till processing and cleaning treatment. The dry thickness of resin film is 0.1 μm.

" optical alignment film 5 "

The synthesis of (synthesis example 1) Dichroic Compounds (a)

The 2% hydrochloric acid 230ml of addition in 2,2'- benzidine-disulfonic acids 8.6g (25mmol), while 0~5 DEG C is remained, one The aqueous solution of sodium nitrite 3.5g (51mmol) is gradually marginally added dropwise in side, and diazonium is prepared when reaction 2 is smallSalt.Next, Salicylic acid 6.9g (50mmol) is dissolved in 5% aqueous sodium carbonate of 300ml, foregoing diazonium is slowly added dropwise wherein Salt mixture.React 1 it is small when after, add 20% saline solution and obtain sediment.Make this heavy by the mixed solvent of ethanol and water Starch is recrystallized, and obtains the azo-compound represented by the formula (a) of 4.8g.

(preparation of embodiment composition composition for optical alignment film (1))

2 parts of compound represented by formula (a) is dissolved in 98 parts of n-methyl-2-pyrrolidone (NMP) (solution A). (Changchun artificial resin manufactures methylated melamine Sumimal M-100C (being below M-100C).With hexamethoxy methylated Melamine monomer meter, molecular weight=390.Average degree of polymerization is 1.3~1.7) 98 parts of butoxy ethanol (BC) is added in 2 parts And homogeneous solution (solution B) is made.100 parts of solution A, 23 parts of solution B and 77 parts of BC are mixed, prepare solid into Divide the solution than 1.0%.The solution obtained by 0.45 μm of membrane filter, obtains composition for optical alignment film (1).

(formation of liquid crystal orientation film)

(making of photoisomerization type resin film)

Composition for optical alignment film (1) is coated on glass substrate by spin coater, it is 1 minute dry at 100 DEG C.

(light orientation processing)

Across wavelength cut-off wave filter and polagizing filter in extra-high-pressure mercury vapour lamp, from vertical relative to glass substrate Direction, to the film coated surface that is obtained with irradiation energy 100mJ/cm²(irradiation is strong for ultraviolet light near illumination wavelength 365nm Degree：10mW/cm²) linear polarization and be parallel light, obtain optical alignment film.It need not carry out burning till processing and cleaning treatment.Tree The dry thickness of adipose membrane is 0.1 μm.

<Friction-type alignment films>

(friction-type alignment films)

(formation of friction-type polyimide liquid crystal direct action membrane)

(preparation of orientation coating solution)

N-methyl-2-pyrrolidone 59.72g is added in 4,4'- diamino-diphenyl amine 5.98g, while being sent into nitrogen While it is stirred and makes its dissolving.While stir the diamine solution, while addition pyromellitic acid anhydride 6.54g, one is gone forward side by side Step addition n-methyl-2-pyrrolidone 65.30g, in nitrogen environment, 30 DEG C stirring 18 it is small when and make its reaction.Further, exist The mass ratio that n-methyl-2-pyrrolidone and butoxy ethanol are added under room temperature is 1：1 mixed solvent 71.06g carries out dilute Stirring is released, obtains polyamic acid solution.

(formation of liquid crystal orientation film)

(making of resin film)

Alignment films solution coating is made in 30 minutes by it in 230 DEG C of heating on the 1st substrate and the 2nd substrate by spin coater Reaction, forms the dielectric film of polyimides.

(orientation process)

The roller for being wound with polishing cloth is rotated along the direction opposite with substrate conveyance direction, wipe be formed in one direction Alignment layer surface on substrate, thus carries out orientation process.The rotating speed of roller is 600rpm, and the conveyance speed of substrate is 5mm/ seconds, Polishing cloth is 0.3mm relative to the compression distance of substrate surface.Then, in order to remove because of friction and ground alignment films Bits, the fibre plate of polishing cloth, clean polyimide film with pure water and are subject to drying.

(evaluation of display quality)

By the way that alignment films are set to optical alignment film, can weaken by the drop of the uneven caused orientation to liquid crystal molecule of friction It is low, and a kind of liquid crystal display element of the FFS modes of excellent light transmission rate can be provided.The liquid crystal of various optical alignment films is taken Tropism is evaluated, its evaluation method is illustrated below.

Thin film transistor (TFT) and transparent electrode layer are formed on the 1st substrate, and is formed on alignment films.If using as connecing The rubbing manipulation for the mode of touching carries out orientation process, then because friction causes to form irregular scratch in alignment layer surface.Especially exist Formed with thin film transistor (TFT), transparency electrode layer pattern the 1st substrate in, since thin film transistor (TFT), transparency electrode layer pattern cause Difference of height and friction roller polishing cloth fiber diameter (tens of μm) and cause easily to form deeper scratch along difference of height. Since formed with the abrasive position, when electric field is closed, liquid crystal molecule can not arrange in a certain direction, therefore in black display When liquid crystal panel can produce light leak.As a result, become difficult to obtain contrast more than certain value.

Further, it is referred to as in recent years practical in the resolution pattern of 4K, in the calculated example of 40 inch faceplate panels, 1 Pixel Dimensions become 0.23mm.In addition, it is referred to as next practical in the resolution pattern of 8K, in 40 inch faceplate panels In calculated example, 1 Pixel Dimensions are even fine to 0.11mm.That is, 1 Pixel Dimensions are straight close to the fiber of the polishing cloth of friction roller Footpath, therefore because of the scratch formed when carrying out orientation process by rubbing manipulation, cause in pixel unit or interrupted pixel list In position, the position that liquid crystal molecule can not arrange in a certain direction is produced when electric field is closed, is had a large amount of when causing by black display The worry for being greatly reduced, largely showing defect of contrast caused by light leak.

Therefore, by carrying out orientation process using optical alignment method in a non-contact manner, will not be produced in alignment layer surface Scratch, therefore can realize the black display of no light leak, high contrast and distinctness.

By spin-coating method, on the comb shape transparency electrode of the 1st substrate is formed at, orientation coating solution is set to form dry thickness 0.1 μm of alignment films.In the same way also alignment films are formed in the 2nd substrate.

(making of liquid crystal cells)

Using the glass substrate for possessing above-mentioned liquid crystal orientation film, liquid crystal cells are made.More specifically, will be respectively formed with According to each liquid crystal orientation film, the opposite and direction of irradiation linear polarization or friction becomes inverse to 1st substrate of alignment films with the 2nd substrate The mode of parallel direction (180 °) configures, and in the state of certain gap (4 μm) is kept between two plate bases, passing through sealant will Periphery is bonded.Next, in by liquid crystal aligning film surface and the cell gap of sealant division, by dripping method, with firm More than the liquid-crystal composition (preparation example 1~12) in the above-mentioned table of the Temperature Fill of clearing point and the liquid crystal combination containing polymerizable monomer Thing 1,2,6,9 and 12, it is then cooled to which room temperature, thus makes liquid crystal cells respectively.

In the case of the liquid-crystal composition 1,2,6,9 and 12 containing polymerizable monomer, make in the same manner as above After liquid crystal cells, the pre-tilt angle (crystal rotation method) of the liquid crystal cells is measured, then, while applying the square of 1.8V with frequency 1kHz Shape ripple, while the wave filter of the ultraviolet across cut-off below 320nm, passes through high-pressure mercury-vapor lamp (Toshiba Lighting＆ The FL15UV34A (NP805) of Technology companies manufacture) ultraviolet is irradiated to liquid crystal cells.It is strong with the irradiation of cell surface Degree becomes 10mW/cm²Mode be adjusted and irradiate 700 seconds, obtain make it is poly- in the liquid-crystal composition containing polymerizable monomer The horizontal alignment liquid crystal display element of conjunction property monomer polymerization.

In following table 3~8, by alignment films used in made liquid crystal cells (liquid crystal display element) with being used Liquid-crystal composition or liquid-crystal composition containing polymerizable monomer combination example (embodiment 1~24 and comparative example 1~2) and institute The result of static contrast (CRS) evaluation result and the VHR measure of the liquid crystal cells of making is recorded in following table 3~8.

[table 4]

[table 5]

[table 6]

[table 7]

[table 8]

[table 9]

[table 10]

The assay method of static state contrast (CRS) described below.

Possessing white light source, optical splitter, polarizer (light incident side polarizer), analyzer (exiting side polarizer), detection Configuration is as measure between polarizer-analyzer of the optical detecting device (manufacture of RETS-100, great Zhong Electronics Co., Ltd) of device The aforementioned optical film of object.Herein, it is 0 degree of (polarization direction of polarizer and analyzer in the anglec of rotation of polarizer and analyzer For parallel position [parallel-nicol]) in the state of, while rotating optical film, while by detector detection through the light of light The light quantity detected, is become rotation position (polarization direction of polarizer and point of polymerizable liquid crystal of maximum optical film by amount Sub- long axis direction is parallel) when the light quantity (light quantity during connection) through light be set to Yon.In addition, will be in fixed polarizer and optics In the state of the position of film, analyzer is set to 90 degree of (polarisation sides of polarizer and analyzer relative to the anglec of rotation of polarizer To for quadrature position [crossed Nicol]) when the light quantity (light quantity during disconnection) through light be set to Yoff.Contrast C RS is under Formula (formula 1) is obtained.

CRS=Yon/Yoff (formula 1)

The numerical value of the static contrast C RS of (formula 1) is bigger, and light quantity Yoff is smaller when representing to disconnect, i.e., light leak is fewer, therefore More excellent black display.

As a result, form display element (embodiment 1~24) and the formation of optical alignment film and the FFSIIPS patterns made The friction orientation film and display element (comparative example 1,2) of FFS mode made is compared, excellent spy is shown in terms of contrast Property.More specifically, if embodiment 1~24 and comparative example 1,2 are compared, if confirming using optical alignment film, contrast Rate and VHR are improved.If in addition, monomer is added in liquid-crystal composition, VHR is not easy to reduce, it is taken as that aforementioned monomer is gathered Close the ion in the polymer capture liquid-crystal composition formed.Especially for friction orientation film, thus it is speculated that due to thinking to be derived from The ion component of friction process, impurity etc. are more than the situation of optical alignment film, therefore the VHR of comparative example 2 rises.

In addition, following orientation restraining force (grappling) measure is carried out to the liquid crystal display element of embodiment 1~24.

Using above-mentioned liquid crystal display element, by the following method for being referred to as torque-balance system, (Japanese liquid crystal association begs for By the methods reported of page 251~252 that can give a lecture collection of thesis (2001)) between measure liquid crystal aligning film surface and liquid crystal layer Interface azimuthal anchoring strength.

As a result, the liquid crystal display element for confirming embodiment 1~24 is generated for being orientated liquid-crystal compounds For be required orientation restraining force, wherein, the liquid crystal display element for confirming 17~embodiment of embodiment 24 passes through polymerism Monomer polymerization, so that optical alignment film is very good relative to the orientation restraining force of liquid-crystal compounds.Confirm horizontal alignment property liquid crystal Display element has excellent optical characteristics and high-speed response.

Symbol description

1a：Liquid crystal molecule；1b：Polymerizable monomer；1c：The polymer that polymerizable monomer is polymerized；100：1st substrate； 102：TFT layer；103：Pixel electrode；104：Passivating film；105：1st alignment films；200：2nd substrate；201：Planarization film (protection Layer)；202：Black matrix；203：Colour filter；204：Transparency electrode；205：2nd alignment films；301：Sealing material；302：Projection (column Shape sept)；303：Liquid crystal layer；304：Projection (column spacer)；401：Mask pattern；402：Resin bed；L：Light；1、8：Partially Tabula rasa；2：First substrate；3：Electrode layer；4：Alignment films；5：Liquid crystal layer；6：Colour filter；6G：Colour filter is green；6R：Colour filter is red； 6B：Colour filter is blue；7：Second substrate；11：Gate electrode；12：Gate insulating film；13：Semiconductor layer；14：Insulating layer；15：Ohm Contact layer；16：Drain electrode；17：Source electrode；18：Insulating protective layer；21：Pixel electrode；22：Common electrode；23：Storage capacitors Device；24：Drain electrode；25：Data wiring；27：Source wiring；29：Bridging line；30：Cushion.

Claims

1. a kind of liquid crystal display element of horizontally oriented type, it is characterised in that have：

The first substrate and second substrate configured in opposite directions；

Liquid crystal layer, contains the liquid-crystal composition being filled between the first substrate and the second substrate；

Electrode layer, on the first substrate, each pixel has common electrode, with multiple grid bus of rectangular configuration and Data/address bus, be arranged at the grid bus and data/address bus cross part thin film transistor (TFT) and by the film crystal Pipe drives and the pixel electrode relative to the almost parallel electric field of substrate is formed between the common electrode；And

Light redirecting layer, between the liquid crystal layer and the first substrate and between the liquid crystal layer and the second substrate, shape Into at least one substrate,

The liquid-crystal composition has positive dielectric constant anisotropy, and the transition temperature of nematic phase-isotropic liquid is 60 More than DEG C, and containing the compound more than one or both of compound represented by general formula (i) and selected from following General formula (J) represented by one or both of compound more than,

In above-mentioned general formula (i), Rⁱ¹And Rⁱ²Separately represent the alkyl of carbon number 1~8, carbon number 2~8 alkenyl, The alkoxy of carbon number 1~8 or the alkenyloxy group of carbon number 2~8,1 in the alkyl, alkenyl, alkoxy or alkenyloxy group Hydrogen atom above can be substituted by fluorine atom, and the methylene in the alkyl, alkenyl, alkoxy or alkenyloxy group can be in oxygen atom Oxygen atom is substituted by the case of discontinuous connection, and carbonyl can be substituted by the case where carbonyl discontinuously connects,

Aⁱ¹Represent the group being selected from the group being made of (a), (b) and (c),

(a) Isosorbide-5-Nitrae-cyclohexylidene, 1-CH being present in the group₂- or the not adjacent-CH of more than 2₂- can be substituted For-O-,

(b) Isosorbide-5-Nitrae-phenylene, 1-CH=being present in the group or the not adjacent-CH=of more than 2 can be substituted by- N=,

(c) (c) naphthalene -2,6- diyl, 1,2,3,4- naphthane -2,6- diyls or decahydronaphthalene -2,6- diyl, are present in naphthalene -2,6- Diyl or 1-CH=in 1,2,3,4- naphthane-2,6- diyls or the not adjacent-CH=of more than 2 can be substituted by-N =,

Above-mentioned group (a), group (b) and group (c) can be separately through cyano group, fluorine atom, chlorine atom, methyl, trifluoro Methyl or trifluoromethoxy substitution,

nⁱ¹1,2,3 or 4 are represented, in nⁱ¹For 2,3 or 4 so as to which there are multiple Aⁱ¹When, they may be the same or different, in nⁱ¹For 2,3 Or 4 so that there are multiple Zⁱ¹When, they may be the same or different,

In formula, R^J1Represent the alkyl of carbon number 1~8 ,-the CH of more than 2 of 1 or non-adjacent in the alkyl₂- can distinguish - CH=CH- ,-C ≡ C- ,-O- ,-CO- ,-COO- or-OCO- are independently substituted by,

n^J1Represent 0,1,2,3 or 4,

A^J1、A^J2And A^J3Separately represent the group being selected from the group being made of (a), (b) and (c),

Z^J1And Z^J2Separately represent singly-bound ,-CH₂CH₂-、-(CH₂)₄-、-OCH₂-、-CH₂O-、-OCF₂-、-CF₂O-、- COO- ,-OCO- or-C ≡ C-,

In n^J1For 2,3 or 4 so as to which there are multiple A^J2When, they may be the same or different, in n^J1For 2,3 or 4 so as to which there are multiple Z^J1When, they may be the same or different,

X^J1Represent hydrogen atom, fluorine atom, chlorine atom, cyano group, trifluoromethyl, fluorine methoxyl group, difluoro-methoxy, trifluoromethoxy or 2,2,2- trifluoroethyls.

2. liquid crystal display element according to claim 1, the pixel electrode is comb shape or has slit.

3. liquid crystal display element according to claim 1 or 2, the electrode spacing between the pixel electrode and common electrode It is less than the first substrate and second substrate distance G from R.

4. liquid crystal display element according to claim 1 or 2, the electrode spacing between the pixel electrode and common electrode It is longer than first substrate and second substrate the distance G from R.

5. liquid crystal display element according to any one of claim 1 to 4, which is photodegradation type.

6. liquid crystal display element according to any one of claim 1 to 5, the liquid crystal layer is in the liquid-crystal composition Solidfied material containing polymerizable monomer.

7. liquid crystal display element according to claim 3, the interelectrode distance R is 0, and the common electrode is described the The substantially entire surface of one substrate is configured at than the pixel electrode closer to the position of first substrate.