CN108780246A

CN108780246A - Liquid crystal display element and its manufacturing method

Info

Publication number: CN108780246A
Application number: CN201780019311.4A
Authority: CN
Inventors: 藤泽宣; 小寺史晃
Original assignee: Dainippon Ink and Chemicals Co Ltd
Current assignee: DIC Corp
Priority date: 2016-04-05
Filing date: 2017-04-03
Publication date: 2018-11-09
Also published as: JPWO2017175704A1; TWI736604B; WO2017175704A1; TW201803973A; KR20180123688A; JP6403037B2

Abstract

In the parallel-oriented liquid crystal displays such as the vertically aligned liquid crystal displays such as PVA, MVA, IPS patterns, FFS mode, TN patterns, driving voltage is inhibited to rise, birefringence is inhibited to reduce, improve transmissivity, and improve the fall time of liquid crystal simultaneously, to provide high-transmission rate and the excellent liquid crystal display element of high-speed response.Further it is provided that the manufacturing method of the liquid crystal display element.A kind of liquid crystal display element is provided, it contains polymer or copolymer in the liquid-crystal composition between being held at least one 2 transparent substrate with electrode, the content of the polymer or copolymer is 0.5 mass % of total quality of the liquid-crystal composition and the polymer or copolymer less than 40 mass %, the polymer or copolymer form polymer network, the polymer network has the refractive anisotrop of uniaxiality or easy axis of orientation, and has different state of orientation of more than two kinds.

Description

Liquid crystal display element and its manufacturing method

Technical field

The present invention is about a kind of liquid crystal display element and its manufacturing method.

Background technology

Though LCD TV is widely available, with the higher image quality that enlargement is brought, the display object being displaced on screen Movement speed it is faster than small liquid crystal television, it is therefore desirable to accelerate the response speed of liquid crystal, promote video image quality.

The full-color display mode of field sequence for not needing colour filter is characterized in that using the sequence point according to " red → green → blue " Bright backlight.In common CRT, liquid crystal display, the frame time (frame time) is 16.7ms, and sequence on the scene is full-color In display mode, then the frame time is 5.6ms, it is desirable that high-speed response.

As the index for indicating high-speed response, the sum of τ d and τ r can be enumerated.τ d are the decline response time of liquid crystal, and τ r are The rising response time of liquid crystal.In order to meet the high-speed response in the full-color display mode of a sequence, it is expected that the sum of τ d and τ r are less than 1.5ms。

It is referred to as the liquid crystal material of nematic liquid crystal on the market at present, is generally used in TV, monitor, mobile electricity The flat-panel monitors such as words, smart mobile phone, tablet terminal.However, the response speed due to nematic liquid crystal is slow, about more than ten milliseconds extremely Several milliseconds, so it is expected to improve.Response speed due to can by liquid crystal the prodigious influence of rotational viscosity γ 1 and elastic constant, Therefore have studied the exploitation by compounds, the optimization of composition improves, but what is improved makes slow progress.In contrast, making The high-speed response of hundreds of microseconds can be achieved with the ferroelectric liquid crystal (FLC) of smectic liquid crystal.However, due to being only bright and dark two kinds of shapes State uses the methods of region gradual change so being not easy to realize that the intervening fade needed for full-color display is shown.

In FLC, stabilizing polymer V-arrangement ferroelectric liquid crystals (PSV-FLC) element being made of the mixture of FLC and monomer is in iron It is formed with fine polymer network in electrical liquid crystal, other than as the high-speed response of FLC specialities, can also realize centre Gradual change is shown, in addition, impact resistance is also promoted (patent document 1) than previous FLC.

In addition, in nematic liquid crystal and high molecular composite material, if the polymerizable compound of 70 mass % or more is added It is added on nematic liquid crystal medium, although the high-speed response that the response time is tens of microseconds then can be obtained, driving voltage can be more than About 80V, and it is impracticable, and the birefringence of actual effect can reduce by 1 digit or more than the liquid crystal birefringence rate used, therefore so that The transmissivity of element declines.On the other hand, propose there are following PS (polymer-stabilised：It is polymer-stabilized) or PSA(polymer-sustained alignment：Macromolecule maintains to be orientated) display：By 0.3 mass % less than 1 1 kind or more of the polymerizable compound of quality % makes an addition to liquid crystal media, applies or do not apply voltage, by UV photopolymerization, Raised structures object fine obtained from polymerization or crosslinking is formed on glass substrate interface, mainly induces pre-tilt (pretilt) (patent document 2~6).The displays such as PS or PSA are mainly configured under vertical alignment mode using interaction fine The fish bone well pattern electrode of the linear slit of width and the wire electrode of fine width, formation are divided into 4 multiple domain (multi- Domain), high visual field angling is realized.If at this point, applying voltage, liquid crystal can be towards linear slit direction tilted alignment.If herein Polymerizable compound is set to polymerize under state of orientation, then macromolecule membrane can be formed in substrate interface, the liquid crystal near substrate interface Orientation can stabilize.At this point, tilted alignment orientation can be induced as pre-tilt, divide by using the orientation that pattern electrode is formed It cuts, without the orientation process process (non-patent literature 1) of complicated vertical alignment layer.In addition, it was recently reported that the response time can Improve from 10 milliseconds to several milliseconds.About other macromolecular orientation stabilization technologies, using there is the polymerism made in liquid crystal The method for closing object reaction.State of orientation when application voltage is set to stabilize to obtain required electro-optic properties by macromolecule, And it can show the characteristic (patent document 7~14) being only unable to get with liquid crystal simple substance.

However, even if in these elements, under the viewpoint of high-speed response, also there is the space of improvement.Especially with respect to liquid The high-speed response of the rate of climb of crystal device, actual use be liquid-crystal composition low viscosity, high-k Change, assigns pre-tilt angle or the various methods such as the improvement of driving methods such as (overdrive) method of overdriving at low spring constant, But about decrease speed, present situation be other than the low viscosity of liquid-crystal composition, it is not yet found that effect method, and it is expected change It is kind.

Existing technical literature

Patent document

Patent document 1：Japanese Unexamined Patent Publication 2002-31821 bulletins

Patent document 2：Japanese Unexamined Patent Application Publication 2013-536271 bulletins

Patent document 3：Japanese Unexamined Patent Application Publication 2013-538249 bulletins

Patent document 4：Japanese Unexamined Patent Application Publication 2012-527495 bulletins

Patent document 5：Japanese Unexamined Patent Application Publication 2012-513482 bulletins

Patent document 6：Japanese Unexamined Patent Publication 2012-219270 bulletins

Patent document 7：Japanese Patent 4175826

Patent document 8：Japanese Unexamined Patent Publication 2009-192600 bulletins

Patent document 9：Japanese Patent 5020203

Patent document 10：Japanese Unexamined Patent Publication 1999-0258758 bulletins

Patent document 11：Japanese Patent 5383994

Patent document 12：US8940375

Patent document 13：WO2011/055571

Patent document 14：WO2015/122457

Non-patent literature

Non-patent literature 1：Journal of the SID17/7,553-559 (2009)

Invention content

The subject that the invention solves

Project to be solved by this invention is that (Patterned vertical alignment, patterning are vertical in PVA Be orientated), vertical orientation (VA) liquid crystal display of MVA (Multi-domain Vertical Alignment, multidomain vertical orientation) Device, IPS (In-plane switching, in-plane switching) pattern, FFS (cut by Fringe Field switching, fringing field Change) in the parallel-oriented liquid crystal display of pattern, TN (Twisted Nematic, twisted-nematic) pattern etc., inhibit driving voltage Rising, inhibit the reduction of birefringence, improve transmissivity, and improve the fall time of liquid crystal simultaneously, thus provide highly transmissive Rate and the excellent liquid crystal display element of high-speed response, additionally, it is provided the manufacturing method of the liquid crystal display element.

Means for solving the problems

In order in the polymerizable liquid crystal compound containing liquid-crystal composition and polymerizable compound, in liquid crystal cells entirety It is formed with refraction ansiotropy and with the polymer network for being orientated function, seeks high-speed response, and it is steady to carry out macromolecule For fixedization to make the tilted alignment orientation of liquid crystal molecule unanimously towards the direction of electrode pattern defined, the present inventor is conceived to polymerization Property compound containing ratio and polymer network formation condition, and complete the present invention.

[1] a kind of manufacturing method of liquid crystal display element, contains：For being held at least one 2 with electrode thoroughly Polymerizable liquid crystal compound between bright substrate applies the voltage of the threshold voltage of the polymerizable liquid crystal compound or more, and simultaneously The process that irradiation ultraviolet light carries out polymerization phase separation；And voltage is then made in the state of irradiating ultraviolet light to be less than threshold value electricity Pressure, and further irradiate the process of ultraviolet light.

[2] manufacturing method for the liquid crystal display element recorded such as aforementioned [1], in the threshold value for applying polymerizable liquid crystal compound It more than voltage voltage and irradiates simultaneously in the process that ultraviolet light carries out polymerization phase separation, the liquid crystal in polymerizable liquid crystal compound Molecule is orientated relative to transparent substrate plane with 0 degree to 30 degree of range inclination, and before making in the state of irradiating ultraviolet light Voltage is stated less than threshold voltage and is further irradiated in the process of ultraviolet light, foregoing liquid crystal molecule inclines relative to transparent substrate plane Oblique 80 degree to 90 degree and be orientated.

[3] manufacturing method for the liquid crystal display element recorded such as aforementioned [1] or [2] is applying polymerizable liquid crystal compound Threshold voltage more than voltage and irradiate simultaneously ultraviolet light carry out polymerization phase separation process in, in polymerizable liquid crystal compound Liquid crystal molecule relative to transparent substrate plane with 0 degree to 90 degree of range tilts and is orientated, and in the state for irradiating ultraviolet light Under make aforesaid voltage be less than threshold voltage and further irradiate ultraviolet light process in, foregoing liquid crystal molecule is relative to transparent substrate Plane tilts 0 degree to 30 degree and is orientated.

[4] manufacturing method for the liquid crystal display element recorded such as any one of aforementioned [1]~[3], the voltage of application are to hand over Waveform is flowed, the frequency of the range of dielectric anisotropy is shown with polymerizable liquid crystal compound.

[5] manufacturing method for the liquid crystal display element recorded such as any one of aforementioned [1]~[4], more than threshold voltage Voltage is voltage V10 or more, and wherein voltage V10 is relative in the voltage-transmission rate characteristic voltage of polymerizable liquid crystal compound Transmissivity total variation is 10% or more.

[6] manufacturing method for the liquid crystal display element recorded such as any one of aforementioned [1]~[5] is less than threshold voltage Voltage is 90% voltages of the 0V less than threshold voltage.

[7] manufacturing method for the liquid crystal display element recorded such as any one of aforementioned [1]~[6], as polymerizable liquid crystal Polymerizable compound in composition uses a kind or 2 kinds in the compound selected from the following general formula (V) and the expression of logical formula (VI) Above compound,

(in formula, X¹And X²Each independently represent hydrogen atom or methyl, Sp¹And Sp²It is former to each independently represent singly-bound, carbon The alkylidene (alkylene group) or-O- (CH of subnumber 1~12₂)_s(in formula, s indicates 1~11 integer, oxygen atom connection In aromatic rings.), U indicates the straight chain of carbon atom number 2~20 or the multivalence ring of branch's polyvalent alkylene or carbon atom number 5~30 Shape substituent group, the alkylidene in polyvalent alkylene can be replaced in the range that oxygen atom does not abut by oxygen atom, can also be by carbon (alkylidene in base can be replaced in the range that oxygen atom does not abut by oxygen atom the alkyl of atomicity 5~20.) or ring-type take Replace for base, k indicates 1~5 integer.Arbitrary hydrogen atom can be substituted by-CH in all 1,4- phenylenes in formula₃、- OCH₃, fluorine atom or cyano.)

(in formula, X³Indicate hydrogen atom or methyl, Sp³The alkylidene or-O- (CH of expression singly-bound, carbon atom number 1~12₂)_t- (in formula, t indicates that 2~11 integer, oxygen atom are connected to aromatic rings.), V indicates straight chain or the branch of carbon atom number 2~20 The multivalence cyclic substituents of polyvalent alkylene or carbon atom number 5~30, the alkylidene in polyvalent alkylene can be not adjacent in oxygen atom Replaced by oxygen atom in the range of connecing, or can (alkylidene in base can not be abutted in oxygen atom by the alkyl of carbon atom number 5~20 In the range of replaced by oxygen atom.) or cyclic substituents substitution, W indicate hydrogen atom, halogen atom or carbon atom number 1~15 alkane Base.Arbitrary hydrogen atom can be substituted into-CH in all 1,4- phenylenes in formula₃、-OCH₃, fluorine atom or cyano.).

[8] manufacturing method for the liquid crystal display element recorded such as aforementioned [7], as aforementioned polymeric compound, using logical The Sp that formula (V) indicates¹With Sp²Identical one kind or two or more compound.

[9] as the manufacturing method for the liquid crystal display element that aforementioned [7] or [8] are recorded makes as aforementioned polymeric compound The Sp indicated with logical formula (V)¹With Sp²Identical compound of more than two kinds, the wherein mutual Sp of compound of more than two kinds¹And Sp²It is different.

[10] manufacturing method for the liquid crystal display element recorded such as any one of aforementioned [1] to [9], as polymerizable liquid crystal Liquid-crystal compounds in composition, the liquid-crystal compounds indicated using the following general formula (LC),

(in general formula (LC), R^LCIndicate the alkyl of carbon atom number 1~15.1 or 2 or more CH in the alkyl₂Base can Replaced by-O- ,-CH=CH- ,-CO- ,-OCO- ,-COO- or-C ≡ C- in such a way that oxygen atom does not abut directly against, in the alkyl 1 or 2 or more hydrogen atom can arbitrarily be substituted into halogen atom.A^LC1And A^LC2It each independently represents selected from by following Group (a), group (b) and group (c) composition group in group.

(a) anti-form-1,4- cyclohexylidenes (are present in 1 CH in the group₂Base or 2 or more not adjacent CH₂Base It can be replaced by oxygen atom or sulphur atom.),

(b) 1,4- phenylenes (are present in 1 CH base in the group or 2 or more CH bases of adjoining can be by nitrogen originals Son substitution.),

(c) bicyclic (2.2.2) octamethylenes of 1,4-, naphthalene -2,6- diyls, decahydronaphthalene -2,6- diyls, 1,2,3,4- naphthanes - 2,6- diyls or chroman -2,6- diyl,

1 or 2 or more hydrogen atom contained by group (a) above-mentioned, group (b) or group (c) respectively can be by fluorine original Son, chlorine atom ,-CF₃Or-OCF₃Substitution.

Z^LCIndicate singly-bound ,-CH=CH- ,-CF=CF- ,-C ≡ C- ,-CH₂CH₂-、-(CH₂)₄-、-OCH₂-、-CH₂O-、- OCF₂-、-CF₂O- ,-COO- or-OCO-.

Y^LCIndicate the alkyl of hydrogen atom, fluorine atom, chlorine atom, cyano and carbon atom number 1~15.1 or 2 in the alkyl A above CH₂Base can be in such a way that oxygen atom abut directly against by-O- ,-CH=CH- ,-CO- ,-OCO- ,-COO- ,-C ≡ C-、-CF₂O-、-OCF₂Replace, 1 or 2 or more hydrogen atom in the alkyl can arbitrarily be replaced by halogen atom.

A indicates 1~4 integer.When a expressions 2,3 or 4, there are multiple A in general formula (LC)^LC1When, it is multiple A^LC1It may be the same or different, when there are multiple Z^LCWhen, multiple Z^LCIt may be the same or different.)

[11] manufacturing method for the liquid crystal display element recorded such as any one of aforementioned [1] to [10], liquid crystal display element Cellular construction be VA patterns, IPS patterns, FFS mode, VA-TN patterns, TN patterns or ecb mode.

[12] a kind of liquid crystal display element, the liquid crystal group between being held at least one 2 transparent substrate with electrode It closes and contains polymer or copolymer in object, the content of the polymer or copolymer is the liquid-crystal composition and the polymer or copolymerization 0.5 mass % of total quality of object forms polymer network less than 40 mass %, the polymer or copolymer, this is poly- Polymeric network has the refractive anisotrop of uniaxiality or easy axis of orientation, and has different state of orientation of more than two kinds.

[13] such as the liquid crystal display element that aforementioned [12] are recorded, the different orientations of more than two kinds as polymer network State has：Relative to transparent substrate plane 0 degree to 30 degree of range tilted alignment, and it is flat relative to transparent substrate Tilted alignment of the face in 80 degree to 90 degree of range.

[14] such as the liquid crystal display element that aforementioned [12] or [13] are recorded, having can be by the display pixel of liquid crystal display element It is inside divided into the electrode of the shape in multiple domains, in a domain being divided out according to electrode shape, as polymer network Different state of orientation of more than two kinds, have：Relative to transparent substrate plane 0 degree to 30 degree of range tilted alignment, And the tilted alignment azimuth direction of the tilted alignment is fixed；And relative to transparent substrate plane in 80 degree to 90 degree of range Tilted alignment,

The liquid crystal molecular orientation in liquid-crystal composition when without application voltage has vertical orientation or parallel-oriented.

[15] liquid crystal display element that any one of such as aforementioned [12]~[14] are recorded, according to the optical axis side of polymer network To or be easily orientated the axis direction mode consistent with the liquid crystal molecular orientation in liquid-crystal composition and be orientated, as two or more different State of orientation, have：Relative to transparent substrate plane 0 degree to 30 degree of range tilted alignment, and relative to transparent Tilted alignment of the base plan at 80 degree to 90 degree,

When without voltage is applied, the liquid crystal molecule in liquid-crystal composition has 0 degree~90 degree relative to transparent substrate plane Pre-tilt angle.

[16] liquid crystal display element that any one of such as aforementioned [12]~[15] are recorded, relative to unit section direction, shape At the polymeric web network layers for having at least 0.5% or more thickness of element thickness.

[17] liquid crystal display element that any one of such as aforementioned [12]~[16] are recorded, as in polymerizable liquid crystal compound Polymerizable compound, using selected from by the following general formula (V) and logical formula (VI) expression compound in it is one kind or two or more Compound,

(in formula, X¹And X²Each independently represent hydrogen atom or methyl, Sp¹And Sp²It is former to each independently represent singly-bound, carbon The alkylidene or-O- (CH of subnumber 1~12₂)_s(in formula, s indicates that 1~11 integer, oxygen atom are connected to aromatic rings.), U is indicated The straight chain or branch's polyvalent alkylene of carbon atom number 2~20 or the multivalence cyclic substituents of carbon atom number 5~30, multivalence alkylene Alkylidene in base can be replaced in the range that oxygen atom does not abut by oxygen atom, or can be by the alkyl (base of carbon atom number 5~20 In alkylidene can be replaced by oxygen atom in the range that oxygen atom does not abut.) or cyclic substituents substitution, k expressions 1~5 Integer.Arbitrary hydrogen atom can be substituted by-CH in all 1,4- phenylenes in formula₃、-OCH₃, fluorine atom or cyano.)

(in formula, X³Indicate hydrogen atom or methyl, Sp³The alkylidene or-O- (CH of expression singly-bound, carbon atom number 1~12₂)_t- (in formula, t indicates that 2~11 integer, oxygen atom are connected to aromatic rings.), V indicates straight chain or the branch of carbon atom number 2~20 The multivalence cyclic substituents of polyvalent alkylene or carbon atom number 5~30, the alkylidene in polyvalent alkylene can be not adjacent in oxygen atom Replaced by oxygen atom in the range of connecing, or can (alkylidene in base can not be abutted in oxygen atom by the alkyl of carbon atom number 5~20 In the range of replaced by oxygen atom.) or cyclic substituents substitution, W indicate hydrogen atom, halogen atom or carbon atom number 1~15 alkane Base.Arbitrary hydrogen atom can be substituted by-CH in all 1,4- phenylenes in formula₃、-OCH₃, fluorine atom or cyano.).

[18] liquid crystal display element as aforementioned [17] are recorded is indicated as aforementioned polymeric compound using logical formula (V) Sp¹With Sp²Identical one kind or two or more compound.

[19] liquid crystal display element as aforementioned [17] or [18] are recorded uses general formula as aforementioned polymeric compound (V) Sp indicated¹With Sp²Identical compound of more than two kinds, the wherein mutual Sp of compound of more than two kinds¹And Sp²No Together.

[20] liquid crystal display element that any one of such as aforementioned [11]~[19] are recorded, as in polymerizable liquid crystal compound Liquid-crystal compounds, use the following general formula (LC) indicate liquid-crystal compounds.

(c) bicyclic (2.2.2) octamethylenes of 1,4-, naphthalene -2,6- diyls, decahydronaphthalene -2,6- diyls, 1,2,3,4- naphthanes - 2,6- diyls or chroman -2,6- diyls.

[21] such as the liquid crystal display element that any one of aforementioned [12]~[20] are recorded, cellular construction is VA patterns, IPS moulds Formula, FFS mode, VA-TN patterns, TN patterns or ecb mode.

The effect of invention

Inhibit the reduction of birefringence by inhibiting the rising of driving voltage according to the present invention, improve transmissivity, and same The fall time of Shi Gaishan liquid crystal, to provide a kind of high-transmission rate and the excellent liquid crystal display element of high-speed response.

Description of the drawings

Fig. 1 is the schematic diagram of the liquid crystal display element of the present invention.

Fig. 2 is the magnified partial view of Fig. 1.

Fig. 3 is the sectional view of the liquid crystal display element of the present invention.

Fig. 4 is the magnified partial view of Fig. 1.

Fig. 5 is the sectional view of the liquid crystal display element of the present invention.

Fig. 6 is the schematic diagram of the liquid crystal display element of the present invention.

Fig. 7 is the magnified partial view of Fig. 6.

Fig. 8 is the sectional view of the liquid crystal display element of the present invention.

Fig. 9 is the petrographic microscope photo of embodiment 1.

Figure 10 is the petrographic microscope photo of comparative example 2.

Figure 11 is the electrode structure and Liquid Crystal Molecules Alignment for indicating the oblique electric field mode liquid crystal display device of the present invention Schematic diagram.

Figure 12 is the electrode structure for indicating the oblique electric field mode liquid crystal display device for being divided into 8 parts of the present invention Schematic diagram.

Figure 13 is the schematic diagram of the electrode structure of the fish bone well VA liquid crystal cells of embodiment.

Specific implementation mode

<Liquid-crystal composition>

[liquid-crystal compounds]

Liquid-crystal composition used in the present invention preferably comprises the liquid-crystal compounds of general formula (LC) expression.

In general formula (LC), R^LCIndicate the alkyl of carbon atom number 1~15.1 or 2 or more CH in the alkyl₂Base can Replaced by-O- ,-CH=CH- ,-CO- ,-OCO- ,-COO- or-C ≡ C- in such a way that oxygen atom does not abut directly against, in the alkyl 1 or 2 or more hydrogen atom can arbitrarily be substituted into halogen atom.R^LCAlkyl respectively can be branched base, or Straight-chain base, preferably straight-chain base.

In general formula (LC), A^LC1And A^LC2It each independently represents selected from by following groups (a), group (b) and group (c) Group in the group of composition.

In general formula (LC), Z^LCIndicate singly-bound ,-CH=CH- ,-CF=CF- ,-C ≡ C- ,-CH₂CH₂-、-(CH₂)₄-、- OCH₂-、-CH₂O-、-OCF₂-、-CF₂O- ,-COO- or-OCO-.

In general formula (LC), Y^LCIndicate the alkyl of hydrogen atom, fluorine atom, chlorine atom, cyano and carbon atom number 1~15.The alkane 1 or 2 or more CH in base₂Base can in such a way that oxygen atom does not abut directly against by-O- ,-CH=CH- ,-CO- ,- OCO-、-COO-、-C≡C-、-CF₂O-、-OCF₂Replace, 1 or 2 or more hydrogen atom in the alkyl can be arbitrarily by halogen Atom replaces.

In general formula (LC), a indicates 1~4 integer.When a expressions 2,3 or 4, there are multiple A in general formula (LC)^LC1When, Multiple A^LC1It may be the same or different, when there are multiple Z^LCWhen, multiple Z^LCIt may be the same or different.

The chemical combination that the compound that aforementioned formula (LC) indicates is preferably selected from the following general formula (LC1) and general formula (LC2) indicates One kind or two or more compound in object group.

In general formula (LC1) or (LC2), R^LC11And R^LC21The alkyl of carbon atom number 1~15 is each independently represented, the alkyl In 1 or 2 or more CH₂Base can in such a way that oxygen atom does not abut directly against by-O- ,-CH=CH- ,-CO- ,-OCO- ,- COO- or-C ≡ C- replace, and 1 or 2 or more hydrogen atom in the alkyl can arbitrarily be replaced by halogen atom.As general formula (LC1) or (LC2) indicate compound, R^LC11And R^LC21It is preferred that being each independently the alkyl of carbon atom number 1~7, carbon atom number The alcoxyl of 1~7 alkoxy, the alkenyl of carbon atom number 2~7, the more preferably alkyl of carbon atom number 1~5, carbon atom number 1~5 The alkenyl of base, carbon atom number 2~5, further preferably straight-chain most preferably indicate following structures as alkenyl.

(in formula, right end is connected to ring structure.)

In general formula (LC1) or (LC2), A^LC11And A^LC21Each independently represent following any structures.In the structure, sub- ring 1 or 2 or more CH in hexyl₂Base can be replaced by oxygen atom, and the CH bases of 1 in Isosorbide-5-Nitrae-phenylene or 2 or more can Replaced by nitrogen-atoms, in addition, the hydrogen atom of 1 in the structure or 2 or more can be by fluorine atom, chlorine atom ,-CF₃Or-OCF₃ Substitution.

As the compound that general formula (LC1) or (LC2) are indicated, A^LC11And A^LC21It is preferred that being each independently following any Structure.

In general formula (LC1) or (LC2), X^LC11、X^LC12、X^LC21~X^LC23Each independently represent hydrogen atom, chlorine atom, fluorine Atom ,-CF₃Or-OCF₃, Y^LC11And Y^LC21Each independently represent hydrogen atom, chlorine atom, fluorine atom, cyano ,-CF₃、- OCH₂F、-OCHF₂Or-OCF₃.As the compound that general formula (LC1) or (LC2) are indicated, Y^LC11And Y^LC21It is preferred that being each independently Fluorine atom, cyano ,-CF₃Or-OCF₃, more preferably fluorine atom or-OCF₃, particularly preferably fluorine atom.

In general formula (LC1) or (LC2), Z^LC11And Z^LC21Each independently represent singly-bound ,-CH=CH- ,-CF=CF- ,-C ≡ C-、-CH₂CH₂-、-(CH₂)₄-、-OCH₂-、-CH₂O-、-OCF₂-、-CF₂O- ,-COO- or-OCO-.As general formula (LC1) or (LC2) compound indicated, Z^LC11And Z^LC21It is preferred that being each independently singly-bound ,-CH₂CH₂-、-COO-、-OCO-、-OCH₂-、- CH₂O-、-OCF₂Or-CF₂O-, more preferably singly-bound ,-CH₂CH₂-、-OCH₂-、-OCF₂Or-CF₂O-, further preferably singly Key ,-OCH₂Or-CF₂O-。

In general formula (LC1) or (LC2), m^LC11And m^LC21Each independently represent 1~4 integer.As general formula (LC1) or (LC2) compound indicated, m^LC11And m^LC21It is preferred that 1,2 or 3 are each independently, storage stability, sound when paying attention to low temperature When answering speed, more preferably 1 or 2, when improving the upper limit value of nematic phase ceiling temperature, further preferably 2 or 3.When logical There are multiple A by formula (LC1) or (LC2)^LC11、A^LC21、Z^LC11And Z^LC21When, these may be the same or different.

As the compound that general formula (LC1) indicates, it is preferably selected from by the following general formula (LC1-a) to general formula (LC1-c) table One kind or two or more compound in the group of the compound composition shown.

In general formula (LC1-a)~(LC1-c), R^LC11、Y^LC11、X^LC11And X^LC12It each independently represents and aforementioned formula (LC1) R in^LC11、Y^LC11、X^LC11And X^LC12Identical meaning.The chemical combination indicated to general formula (LC1-c) as general formula (LC1-a) Object, R^LC11It is preferred that being each independently the alkyl of carbon atom number 1~7, the alkoxy of carbon atom number 1~7, carbon atom number 2~7 The alkenyl of alkenyl, the more preferably alkyl of carbon atom number 1~5, the alkoxy of carbon atom number 1~5, carbon atom number 2~5.In addition, X^LC11And X^LC12It is preferred that being each independently hydrogen atom or fluorine atom, Y^LC11It is preferred that being each independently fluorine atom ,-CF₃Or- OCF₃。

In general formula (LC1-a)~(LC1-c), A^LC1a1、A^LC1a2And A^LC1b1Indicate anti-form-1,4- cyclohexylidenes, tetrahydrochysene pyrrole Mutter -2,5- diyls, 1,3- bis-Alkane -2,5- diyls.In addition, in general formula (LC1-a)~(LC1-c), X^LC1b1、X^LC1b2、X^LC1c1 ~X^LC1c4Each independently represent hydrogen atom, chlorine atom, fluorine atom ,-CF₃Or-OCF₃.As general formula (LC1-a) to general formula (LC1-c) compound indicated, X^LC1b1、X^LC1b2、X^LC1c1~X^LC1c4It is preferred that being each independently hydrogen atom or fluorine atom.

In addition, general formula (LC1) is preferably also selected from the compound indicated to general formula (LC1-p) by the following general formula (LC1-d) One kind or two or more compound in the group of composition.

In general formula (LC1-d)~(LC1-p), R^LC11、Y^LC11、X^LC11And X^LC12It each independently represents and aforementioned formula (LC1) R in^LC11、Y^LC11、X^LC11And X^LC12Identical meaning.As general formula (LC1-d)~(LC1-p) indicate compound, R^LC11It is preferred that being each independently the alkene of the alkyl of carbon atom number 1~7, the alkoxy of carbon atom number 1~7, carbon atom number 2~7 The alkenyl of base, the more preferably alkyl of carbon atom number 1~5, the alkoxy of carbon atom number 1~5, carbon atom number 2~5.In addition, X^LC11And X^LC12It is preferred that being each independently hydrogen atom or fluorine atom.Y^LC11It is preferred that being each independently fluorine atom ,-CF₃Or- OCF₃。

In general formula (LC1-d)~(LC1-p), A^LC1d1、A^LC1f1、A^LC1g1、A^LC1j1、A^LC1k1、A^LC1k2、A^LC1m1~A^LC1m3Respectively From independently expression 1,4- phenylenes, anti-form-1,4- cyclohexylidenes, oxinane -2,5- diyls or 1,3- bis-Alkane -2,5- Diyl.

In general formula (LC1-d)~(LC1-p), X^LC1d1、X^LC1d2、X^LC1f1、X^LC1f2、X^LC1g1、X^LC1g2、X^LC1h1、X^LC1h2、 X^LC1i1、X^LC1i2、X^LC1j1~X^LC1j4、X^LC1k1、X^LC1k2、X^LC1m1And X^LC1m2It is former to each independently represent hydrogen atom, chlorine atom, fluorine Son ,-CF₃Or-OCF₃.As the compound that general formula (LC1-d)~(LC1-m) is indicated, X^LC1d1~X^LC1m2It is preferred that each independently For hydrogen atom or fluorine atom.

In general formula (LC1-d)~(LC1-p), Z^LC1d1、Z^LC1e1、Z^LC1j1、Z^LC1k1、Z^LC1m1Each independently represent singly-bound ,- CH=CH- ,-CF=CF- ,-C ≡ C- ,-CH₂CH₂-、-(CH₂)₄-、-OCH₂-、-CH₂O-、-OCF₂-、-CF₂O- ,-COO- or- OCO-.As the compound that general formula (LC1-d)~(LC1-p) is indicated, Z^LC1d1~Z^LC1m1It is preferred that be each independently singly-bound ,- CH₂CH₂-、-(CH₂)₄-、-CF₂O- or-OCH₂-。

As the compound that general formula (LC1-d)~(LC1-p) is indicated, it is preferably selected from extremely logical by the following general formula (LC1-1) One kind or two or more compound in the group for the compound composition that formula (LC1-45) indicates.General formula (LC1-1) is to general formula (LC1- 45) in, R^LC11Each independently represent the alkyl of carbon atom number 1~7.

General formula (LC2) is preferably selected from the group that the compound indicated to general formula (LC2-g) by the following general formula (LC2-a) forms In one kind or two or more compound.

In general formula (LC2-a)~(LC2-g), R^LC21、Y^LC21、X^LC21~X^LC23It each independently represents and aforementioned formula (LC2) R in^LC21、Y^LC21、X^LC21~X^LC23Identical meaning.As general formula (LC2-a)~(LC2-g) indicate compound, R^LC21It is preferred that being each independently the alkene of the alkyl of carbon atom number 1~7, the alkoxy of carbon atom number 1~7, carbon atom number 2~7 The alkenyl of base, the more preferably alkyl of carbon atom number 1~5, the alkoxy of carbon atom number 1~5, carbon atom number 2~5.In addition, X^LC21~X^LC23It is preferred that being each independently hydrogen atom or fluorine atom, Y^LC21It is preferred that being each independently fluorine atom ,-CF₃Or- OCF₃。

In general formula (LC2-a)~(LC2-g), X^LC2d1~X^LC2d4、X^LC2e1~X^LC2e4、X^LC2f1~X^LC2f4And X^LC2g1~ X^LC2g4Each independently represent hydrogen atom, chlorine atom, fluorine atom ,-CF₃Or-OCF₃.As general formula (LC2-a)~(LC2-g) table The compound shown, X^LC2d1~X^LC2g4It is preferred that being each independently hydrogen atom or fluorine atom.

In general formula (LC2-a)~(LC2-g), Z^LC2a1、Z^LC2b1、Z^LC2c1、Z^LC2d1、Z^LC2e1、Z^LC2f1And Z^LC2g1It is respectively independent Ground indicates singly-bound ,-CH=CH- ,-CF=CF- ,-C ≡ C- ,-CH₂CH₂-、-(CH₂)₄-、-OCH₂-、-CH₂O-、-OCF₂-、- CF₂O- ,-COO- or-OCO-.As the compound that general formula (LC2-a)~(LC2-g) is indicated, Z^LC2a1~Z^LC2g4It is preferred that respectively solely It is on the spot-CF₂O- or-OCH₂-。

The compound that aforementioned formula (LC) indicates is preferably also the change indicated selected from the following general formula (LC3)~general formula (LC5) Close the one kind or two or more compound in object group.

(in formula, R^LC31、R^LC32、R^LC41、R^LC42、R^LC51And R^LC52The alkyl of carbon atom number 1~15 is each independently represented, 1 or 2 or more-CH in the alkyl₂Can in such a way that oxygen atom does not abut directly against by-O- ,-CH=CH- ,-CO- ,- OCO- ,-COO- or-C ≡ C- replace, and 1 or 2 or more hydrogen atom in the alkyl can arbitrarily be replaced by halogen atom, A^LC31、A^LC32、A^LC41、A^LC42、A^LC51And A^LC52Following any structures is each independently represented,

(in the structure, 1 or 2 or more-CH in cyclohexylidene₂It can be replaced by oxygen atom, in Isosorbide-5-Nitrae-phenylene 1 or 2 or more-CH- can be replaced by nitrogen-atoms, in addition, the hydrogen atom of 1 in the structure or 2 or more can be by fluorine Atom, chlorine atom ,-CF₃Or-OCF₃Substitution.), Z^LC31、Z^LC32、Z^LC41、Z^LC42、Z^LC51And Z^LC51Each independently represent singly-bound ,- CH=CH- ,-C ≡ C- ,-CH₂CH₂-、-(CH₂)₄-、-COO-、-OCH₂-、-CH₂O-、-OCF₂Or-CF₂O-, Z⁵Expression-CH₂- Or oxygen atom, X^LC41Indicate hydrogen atom or fluorine atom, m^LC31、m^LC32、m^LC41、m^LC42、m^LC51And m^LC52Each independently represent 0~ 3, m^LC31+m^LC32、m^LC41+m^LC42And m^LC51+m^LC52It is 1,2 or 3, when there are multiple A^LC31~A^LC52、Z^LC31~Z^LC52When, they It may be the same or different.)

R^LC31~R^LC52It is preferred that it is former to be each independently the alkyl of carbon atom number 1~7, the alkoxy of carbon atom number 1~7, carbon The alkenyl of subnumber 2~7 most preferably indicates following structures as alkenyl,

(in formula, right end is connected to ring structure.)

A^LC31~A^LC52It is preferred that it is each independently following structures,

Z^LC31~Z^LC51It is preferred that being each independently singly-bound ,-CH₂O-、-COO-、-OCO-、-CH₂CH₂-、-CF₂O-、- OCF₂Or-OCH₂-。

As the compound that general formula (LC3), general formula (LC4) and general formula (LC5) indicate, preferably comprise at least one kind of selected from logical Compound in the compound group that formula (LC3-1), general formula (LC4-1) and general formula (LC5-1) indicate.

(in formula, R³¹~R³³Indicate the alkyl of carbon atom number 1~8, the alkenyl of carbon atom number 2~8, carbon atom number 1~8 The alkenyloxy group of alkoxy or carbon atom number 2~8, R⁴¹~R⁴³Indicate the alkyl of carbon atom number 1~8, the alkene of carbon atom number 2~8 The alkenyloxy group of base, the alkoxy of carbon atom number 1~8 or carbon atom number 2~8, Z³¹~Z³³Indicate singly-bound ,-CH=CH- ,-C ≡ C-、-CH₂CH₂-、-(CH₂)₄-、-COO-、-OCO-、-OCH₂-、-CH₂O-、-OCF₂Or-CF₂O-, X⁴¹Indicate hydrogen atom or fluorine Atom, Z³⁴Expression-CH₂Or oxygen atom.)

In general formula (LC3-1)~general formula (LC5-1), R³¹~R³³Indicate alkyl, the carbon atom number 2 of carbon atom number 1~8 The alkenyloxy group of~8 alkenyl, the alkoxy of carbon atom number 1~8 or carbon atom number 2~8 preferably indicates the alkane of carbon atom number 1~5 The alkenyl of base or carbon atom number 2~5 more preferably indicates the alkyl of carbon atom number 2~5 or the alkenyl of carbon atom number 2~4, into one The alkenyl of the preferred alkyl or carbon atom number 2 for indicating carbon atom number 3~5 of step, particularly preferably indicates the alkyl of carbon atom number 3.

R⁴¹~R⁴³Indicate the alkoxy of the alkyl of carbon atom number 1~8, the alkenyl of carbon atom number 2~8, carbon atom number 1~8 Or the alkenyloxy group of carbon atom number 2~8, preferably indicate the alkyl of carbon atom number 1~5 or the alkoxy of carbon atom number 1~5, or The alkenyl of carbon atom number 4~8 or the alkenyloxy group of carbon atom number 3~8 more preferably indicate that the alkyl of carbon atom number 1~3 or carbon are former The alkoxy of subnumber 1~3 further preferably indicates the alkyl of carbon atom number 3 or the alkoxy of carbon atom number 2, particularly preferred table Show the alkoxy of carbon atom number 2.

Z³¹~Z³³Indicate singly-bound ,-CH=CH- ,-C ≡ C- ,-CH₂CH₂-、-(CH₂)₄-、-COO-、-OCO-、-OCH₂-、- CH₂O-、-OCF₂Or-CF₂O- preferably indicates singly-bound ,-CH₂CH₂-、-COO-、-OCH₂-、-CH₂O-、-OCF₂Or-CF₂O-, more It is preferred that indicating singly-bound or-CH₂O-。

In a liquid crystal composition, it preferably comprises and indicates selected from general formula (LC3-1), general formula (LC4-1) and general formula (LC5-1) The 5 mass % of mass %~50 of compound in compound group, preferably comprise the 5 mass % of mass %~40, further preferably 5 matter Measure the mass % of %~30, the further preferably 8 mass % of mass %~27, further preferably 10 mass of mass %~25 %.

The compound that general formula (LC3-1) indicates is preferably specifically following general formula (the LC3-11)~general formula recorded (LC3-15) compound indicated.

(in formula, R³¹Indicate the alkyl of carbon atom number 1~5 or the alkenyl of carbon atom number 2~5, R^41aExpression carbon atom number 1~ 5 alkyl.)

The compound that general formula (LC4-1) indicates is preferably specifically following general formula (the LC4-11)~general formula recorded (LC4-14) compound indicated.

(in formula, R³²Indicate the alkyl of carbon atom number 1~5 or the alkenyl of carbon atom number 2~5, R^42aExpression carbon atom number 1~ 5 alkyl, X⁴¹Indicate hydrogen atom or fluorine atom.)

The compound that general formula (LC5-1) indicates is preferably specifically following general formula (the LC5-11)~general formula recorded (LC5-14) compound indicated.

(in formula, R³³Indicate the alkyl of carbon atom number 1~5 or the alkenyl of carbon atom number 2~5, R^43aExpression carbon atom number 1~ 5 alkyl, Z³⁴Expression-CH₂Or oxygen atom.)

General formula (LC3-11), general formula (LC3-13), general formula (LC4-11), general formula (LC4-13), general formula (LC5-11) and In general formula (LC5-13), R³¹~R³³Same embodiment preferably in general formula (LC3-1)~general formula (LC5-1).R^41a~ R^41cThe preferably alkyl of carbon atom number 1~3, the more preferably alkyl of carbon atom number 1 or 2, particularly preferably carbon atom number 2 Alkyl.

General formula (LC3-12), general formula (LC3-14), general formula (LC4-12), general formula (LC4-14), general formula (LC5-12) and In general formula (LC5-14), R³¹~R³³Same embodiment preferably in general formula (LC3-1)~general formula (LC5-1).R^41a~ R^41cThe preferably alkyl of carbon atom number 1~3, the more preferably alkyl of carbon atom number 1 or 3, particularly preferably carbon atom number 3 Alkyl.

In general formula (LC3-11)~general formula (LC5-14), in order to increase the absolute value of dielectric constant anisotropy, preferably General formula (LC3-11), general formula (LC4-11), general formula (LC5-11), general formula (LC3-13), general formula (LC4-13) and general formula (LC5- 13), more preferably general formula (LC3-11), general formula (LC4-11), general formula (LC5-11).

In liquid crystal layer in the liquid crystal display element of the present invention, the general formulas (LC3-11) of preferably contain one or more kinds~ The compound that general formula (LC5-14) indicates, further preferably a kind or 2 kinds, particularly preferably containing a kind or 2 kinds of general formula (LC3-1) The compound of expression.

In addition, as the compound that general formula (LC3), general formula (LC4) and general formula (LC5) indicate, at least one kind of choosing is preferably comprised Compound in the compound group that self-drifting (LC3-2), general formula (LC4-2) and general formula (LC5-2) indicate.

(in formula, R⁵¹~R⁵³Indicate the alkyl of carbon atom number 1~8, the alkenyl of carbon atom number 2~8, carbon atom number 1~8 The alkenyloxy group of alkoxy or carbon atom number 2~8, R⁶¹~R⁶³Indicate the alkyl of carbon atom number 1~8, the alkene of carbon atom number 2~8 The alkenyloxy group of base, the alkoxy of carbon atom number 1~8 or carbon atom number 2~8, B¹~B³Indicate 1,4- phenylenes that can be fluorine-substituted Or anti-form-1,4- cyclohexylidenes, Z⁴¹~Z⁴³Indicate singly-bound ,-CH=CH- ,-C ≡ C- ,-CH₂CH₂-、-(CH₂)₄-、-COO-、- OCO-、-OCH₂-、-CH₂O-、-OCF₂Or-CF₂O-, X⁴²Indicate hydrogen atom or fluorine atom, Z⁴⁴Expression-CH₂Or oxygen atom.)

In general formula (LC3-2), general formula (LC4-2) and general formula (LC5-2), R⁵¹~R⁵³Indicate the alkane of carbon atom number 1~8 The alkenyloxy group of base, the alkenyl of carbon atom number 2~8, the alkoxy of carbon atom number 1~8 or carbon atom number 2~8 preferably indicates that carbon is former The alkyl of subnumber 1~5 or the alkenyl of carbon atom number 2~5 more preferably indicate the alkyl or carbon atom number 2~4 of carbon atom number 2~5 Alkenyl, further preferably indicate carbon atom number 3~5 alkyl or carbon atom number 2 alkenyl, particularly preferably indicate carbon atom number 3 alkyl.

R⁶¹~R⁶³Indicate the alkoxy of the alkyl of carbon atom number 1~8, the alkenyl of carbon atom number 2~8, carbon atom number 1~8 Or the alkenyloxy group of carbon atom number 2~8, preferably indicate carbon atom number 1~5 alkyl or carbon atom number 1~5 alkoxy or The alkenyl of carbon atom number 4~8 or the alkenyloxy group of carbon atom number 3~8 more preferably indicate that the alkyl of carbon atom number 1~3 or carbon are former The alkoxy of subnumber 1~3 further preferably indicates the alkyl of carbon atom number 3 or the alkoxy of carbon atom number 2, particularly preferred table Show the alkoxy of carbon atom number 2.

B³¹~B³³Indicate that Isosorbide-5-Nitrae-phenylene or anti-form-1 that can be fluorine-substituted, 4- cyclohexylidenes are preferably unsubstituted Isosorbide-5-Nitrae-phenylene or anti-form-1,4- cyclohexylidenes, more preferably anti-form-1,4- cyclohexylidenes.

Z⁴¹~Z⁴³Indicate singly-bound ,-CH=CH- ,-C ≡ C- ,-CH₂CH₂-、-(CH₂)₄-、-COO-、-OCO-、-OCH₂-、- CH₂O-、-OCF₂Or-CF₂O- preferably indicates singly-bound ,-CH₂CH₂-、-COO-、-OCH₂-、-CH₂O-、-OCF₂Or-CF₂O-, more It is preferred that indicating singly-bound or-CH₂O-。

The compound that general formula (LC3-2), general formula (LC3-3), general formula (LC4-2) and general formula (LC5-2) indicate, preferably in liquid Contain 10~60 mass %, further preferably 20~50 mass %, further preferably 25~45 mass % in crystal composite, it is more excellent Choosing contains 28~42 mass %, further preferably 30~40 mass %.

The compound that general formula (LC3-2) indicates is preferably specifically following general formula (the LC3-21)~general formula recorded (LC3-29) compound indicated.

In addition, as the compound that general formula (LC3-3) indicates, preferably also following general formula (the LC3-31)~general formula recorded (LC3-33) compound indicated.

(in formula, R⁵¹Indicate the alkyl of carbon atom number 1~5 or the alkenyl of carbon atom number 2~5, R^61aExpression carbon atom number 1~ 5 alkyl, preferably with the R in general formula (LC3-2)⁵¹And R⁶¹Same embodiment.)

The compound that general formula (LC4-2) indicates is preferably specifically following general formula (the LC4-21)~general formula recorded (LC4-26) compound indicated.

(in formula, R⁵²Indicate the alkyl of carbon atom number 1~5 or the alkenyl of carbon atom number 2~5, R^62aExpression carbon atom number 1~ 5 alkyl, X⁴²Indicate hydrogen atom or fluorine atom, preferably with the R in general formula (LC4-2)⁵²And R⁶²Same embodiment.)

The compound that general formula (LC5-2) indicates is preferably specifically following general formula (the LC5-21)~general formula recorded (LC5-26) compound indicated.

(in formula, R⁵³Indicate the alkyl of carbon atom number 1~5 or the alkenyl of carbon atom number 2~5, R^63aExpression carbon atom number 1~ 5 alkyl, W²Expression-CH₂Or oxygen atom, preferably with the R in general formula (LC5-2)⁵³And R⁶³Same embodiment.)

In general formula (LC3-21), general formula (LC3-22), general formula (LC3-25), general formula (LC4-21), general formula (LC4-22), lead to In formula (LC4-25), general formula (LC5-21), general formula (LC5-22) and general formula (LC5-25), R⁵¹~R⁵³Preferably general formula (LC3- 2), the same embodiment in general formula (LC4-2) and general formula (LC5-2).R^61a~R^63aThe preferably alkane of carbon atom number 1~3 Base, the more preferably alkyl of carbon atom number 1 or 2, the particularly preferably alkyl of carbon atom number 2.

General formula (LC3-23), general formula (LC3-24) and general formula (LC3-26), general formula (LC4-23), general formula (LC4-24) and In general formula (LC4-26), general formula (LC5-23), general formula (LC5-24) and general formula (LC5-26), R⁵¹~R⁵³Preferably general formula (LC3- 2), the same embodiment in general formula (LC4-2) and general formula (LC5-2).R^61a~R^63aThe preferably alkane of carbon atom number 1~3 Base, the more preferably alkyl of carbon atom number 1 or 3, the particularly preferably alkyl of carbon atom number 3.

In general formula (LC3-21)~general formula (LC5-26), in order to increase the absolute value of dielectric constant anisotropy, preferably General formula (LC3-21), general formula (Lc3-22) and general formula (LC3-25), general formula (LC4-21), general formula (LC4-22) and general formula (LC4- 25), general formula (LC5-21), general formula (LC5-22) and general formula (LC5-25).

The compound that general formula (LC3-2), general formula (LC4-2) and general formula (LC5-2) indicate can contain it is one kind or two or more, it is excellent Choosing contains B¹~B³Indicate the compound and B of 1,4- phenylenes¹~B³Indicate anti-form-1, the compound of 4- cyclohexylidenes respectively at least 1 Kind or more.

In addition it is also preferably to be selected from the following general formula (LC3-a) and general formula in addition, as the compound that general formula (LC3) indicates (LC3-b) the one kind or two or more compound in the compound group indicated.

(in formula, R^LC31、R^LC32、A^LC31And Z^LC31It each independently represents and the R in aforementioned formula (LC3)^LC31、R^LC32、 A^LC31And Z^LC31Identical meaning, X^LC3b1~X^LC3b6Indicate hydrogen atom or fluorine atom, X^LC3b1And X^LC3b2Or X^LC3b3And X^LC3b4In At least one combination in indicate fluorine atom, m^LC3a1It is 1,2 or 3, m^LC3b10 or 1 is indicated, when there are multiple A^LC31And Z^LC31 When, they may be the same or different.)

R^LC31And R^LC32It is preferred that each independently representing the alkyl of carbon atom number 1~7, the alkoxy of carbon atom number 1~7, carbon The alkenyl of atomicity 2~7 or the alkenyloxy group of carbon atom number 2~7.

A^LC31It is preferred that indicating 1,4- phenylenes, anti-form-1,4- cyclohexylidenes, oxinane -2,5- diyls, 1,3- bis- Alkane -2,5- diyl more preferably indicates Isosorbide-5-Nitrae-phenylene, anti-form-1,4- cyclohexylidenes.

Z^LC31It is preferred that indicating singly-bound ,-CH₂O-、-COO-、-OCO-、-CH₂CH₂, more preferably indicate singly-bound.

As general formula (LC3-a), the following general formula (LC3-a1) is preferably indicated.

(in formula, R^LC31And R^LC32It each independently represents and the R in aforementioned formula (LC3)^LC31And R^LC32It is identical to contain Justice.)

R^LC31And R^LC32It is preferred that it is former to be each independently the alkyl of carbon atom number 1~7, the alkoxy of carbon atom number 1~7, carbon The alkenyl of subnumber 2~7, more preferable R^LC31Indicate the alkyl and R of carbon atom number 1~7^LC32Indicate the alkoxy of carbon atom number 1~7.

As general formula (LC3-b), preferably indicates the following general formula (LC3-b1)~general formula (LC3-b12), more preferably indicate logical Formula (LC3-b1), general formula (LC3-b6), general formula (LC3-b8), general formula (LC3-b11) further preferably indicate general formula (LC3-b1) And general formula (LC3-b6), most preferably indicate general formula (LC3-b1).

R^LC31And R^LC32It is preferred that it is former to be each independently the alkyl of carbon atom number 1~7, the alkoxy of carbon atom number 1~7, carbon The alkenyl of subnumber 2~7, more preferable R^LC31Indicate the alkyl and R of carbon atom number 2 or 3^LC32Indicate the alkyl of carbon atom number 2.

In addition, the compound that general formula (LC4) indicates is preferably the change that the following general formula (LC4-a) is indicated to general formula (LC4-c) Object is closed, the compound that general formula (LC5) indicates is preferably the compound that the following general formula (LC5-a) is indicated to general formula (LC5-c).

(in formula, R^LC41、R^LC42And X^LC41It each independently represents and the R in aforementioned formula (LC4)^LC41、R^LC42And X^LC41Phase Same meaning, R^LC51And R^LC52It each independently represents and the R in aforementioned formula (LC5)^LC51And R^LC52Identical meaning, Z^LC4a1、 Z^LC4b1、Z^LC4c1、Z^LC5a1、Z^LC5b1And Z^LC5c1Each independently represent singly-bound ,-CH=CH- ,-C ≡ C- ,-CH₂CH₂-、- (CH₂)₄-、-COO-、-OCH₂-、-CH₂O-、-OCF₂Or-CF₂O-。)

R^LC41、R^LC42、R^LC51And R^LC52It is preferred that each independently representing the alkyl of carbon atom number 1~7, carbon atom number 1~7 Alkoxy, the alkenyl of carbon atom number 2~7 or the alkenyloxy group of carbon atom number 2~7.

Z^LC4a1~Z^LC5c1It is preferred that each independently representing singly-bound ,-CH₂O-、-COO-、-OCO-、-CH₂CH₂, more preferable table Show singly-bound.

(wherein, no the compound that aforementioned formula (LC) indicates is preferably also the compound selected from the following general formula (LC6) expression The compound indicated including general formula (LC1)~general formula (LC5).) in one kind or two or more compound.

In general formula (LC6), R^LC61And R^LC62Each independently represent the alkyl of carbon atom number 1~15.1 in the alkyl Or 2 or more CH₂Base can be in such a way that oxygen atom abut directly against by-O- ,-CH=CH- ,-CO- ,-OCO- ,-COO- or-C ≡ C- replace, and 1 or 2 or more hydrogen atom in the alkyl can be arbitrarily optionally substituted by halogen.It is indicated as general formula (LC6) Compound, R^LC61And R^LC62It is preferred that it is former to be each independently the alkyl of carbon atom number 1~7, the alkoxy of carbon atom number 1~7, carbon The alkenyl of subnumber 2~7 most preferably indicates following any structures as alkenyl.

(in formula, right end is connected to ring structure.)

In general formula (LC6), A^LC61~A^LC63Each independently represent following any structures.In the structure, in cyclohexylidene 1 or 2 or more CH₂CH₂Base can be by-CH=CH- ,-CF₂O-、-OCF₂Substitution, 1 or 2 in Isosorbide-5-Nitrae-phenylene with On CH bases can be replaced by nitrogen-atoms.

As the compound that general formula (LC6) indicates, A^LC61~A^LC63It is preferred that being each independently following any structures.

In general formula (LC6), Z^LC61And Z^LC62Each independently represent singly-bound ,-CH=CH- ,-C ≡ C- ,-CH₂CH₂-、- (CH₂)₄-、-COO-、-OCH₂-、-CH₂O-、-OCF₂Or-CF₂O-, mLC61 indicate 0~3.The change indicated as general formula (LC6) Close object, Z^LC61And Z^LC62It is preferred that being each independently singly-bound ,-CH₂CH₂-、-COO-、-OCH₂-、-CH₂O-、-OCF₂Or-CF₂O-。

As the compound that general formula (LC6) indicates, it is preferably selected from by the following general formula (LC6-a) to general formula (LC6-v) table One kind or two or more compound in the group of the compound composition shown.In the formula of general formula (LC6-a1)~general formula (LC6-p1), R^LC61And R^LC62Each independently represent the alkyl of carbon atom number 1~7, the alkoxy of carbon atom number 1~7, carbon atom number 2~7 The alkenyloxy group of alkenyl or carbon atom number 2~7.

[polymerizable compound]

As the polymerizable compound of the present invention, can enumerating tool, there are one mono-functional's polymerism chemical combination of reactive base Object and difunctionality or trifunctional etc. have the multi-functional polymerizable compound of more than two reactive bases.With reactivity The polymerizable compound of base, which can contain or can be free of, mesogen (mesogen) property position.

In the polymerizable compound with reactive base, reactive base is preferably the substituent group with optical polymerism.Especially It by thermal polymerization when generating vertical alignment layer, when vertical orientation membrane material thermal polymerization, has reactivity due to can inhibit The reaction of the polymerizable compound of base, therefore, reactive base are particularly preferably the substituent group with optical polymerism.

As the polymerizable compound of the present invention, the compound of general formula (P) expression preferably below.

(in above-mentioned general formula (P), Z^p1Indicate that fluorine atom, cyano, hydrogen atom, hydrogen atom can be substituted by the carbon original of halogen atom Alkyl, the hydrogen atom of subnumber 1~15 can be substituted by the alkoxy of halogen atom carbon atom number 1~15, hydrogen atom and can be substituted by Alkenyl, the hydrogen atom of the carbon atom number 1~15 of halogen atom can be substituted by the carbon atom number 1~15 of halogen atom alkenyloxy group or- Sp^p2-R^p2,

R^p1And R^p2Formula below (R-I) is each independently represented any one of to formula (R-IX),

In previously described formula (R-I)~(R-IX), R²~R⁶Independently of each other be hydrogen atom, carbon atom number 1~5 alkyl or The halogenated alkyl that carbon atom number is 1~5, W are singly-bound ,-O- or methylene (methylene), and T is singly-bound or-COO-, p, t and q 0,1 or 2 are each independently represented,

Sp^p1And Sp^p2Indicate spacer group (spacer group), Sp^p1And Sp^p2Each independently represent singly-bound, carbon atom The alkylidene or-O- (CH of number 1~12₂)_s(in formula, s indicates that 1~11 integer, oxygen atom are connected to aromatic rings.),

L^p1And L^p2Each independently represent singly-bound ,-O- ,-S- ,-CH₂-、-OCH₂-、-CH₂O-、-CO-、-C₂H₄-、- COO-、-OCO-、-OCOOCH₂-、-CH₂OCOO-、-OCH₂CH₂O-、-CO-NR^a-、-NR^a-CO-、-SCH₂-、-CH₂S- ,-CH= CR^a- COO- ,-CH=CR^a-OCO-、-COO-CR^a=CH- ,-OCO-CR^a=CH- ,-COO-CR^a=CH-COO- ,-COO-CR^a= CH-OCO-、-OCO-CR^a=CH-COO- ,-OCO-CR^a=CH-OCO- ,-(CH₂)_z- C (=O)-O- ,-(CH₂) z-O- (C= O)-,-O- (C=O)-(CH₂) z- ,-(C=O)-O- (CH₂) z- ,-CH=CH- ,-CF=CF- ,-CF=CH- ,-CH=CF- ,- CF₂-、-CF₂O-、-OCF₂-、-CF₂CH₂-、-CH₂CF₂-、-CF₂CF₂Or-C ≡ C- (in formula, R^aEach independently represent hydrogen original The alkyl of son or carbon atom number 1~4, in previously described formula, z indicates 1~4 integer.),

M^p2Indicate 1,4- phenylenes, 1,4- cyclohexylidenes, anthracene -2,6- diyls, phenanthrene -2,7- diyls, 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- diyls, M^p2It is unsubstituted or can be by the alkyl of carbon atom number 1~12, the halogenated alkyl of carbon atom number 1~12, carbon atom number 1~12 alkoxy, halogenated alkoxy, halogen atom, cyano, nitro or the-R of carbon atom number 1~12^p1Substitution,

M^p1Indicate any one of formula below (i-11)~(ix-11),

(in formula, in ★ and Sp^p1Connection, in ★ ★ and L^p1Or L^p2Connection.),

M^p3Indicate any one of formula below (i-13)~(ix-13).

(in formula, in ★ and Z^p1Connection, in ★ ★ and L^p2Connection.),

m^p2~m^p4Each independently represent 0,1,2 or 3, m^p1And m^p51,2 or 3 are each independently represented, when there are multiple Z^p1When, they may be the same or different, when there are multiple R^p1When, they may be the same or different, when there are multiple R^p2When, they can It is identical or different, when there are multiple Sp^p1When, they may be the same or different, when there are multiple Sp^p2When, they can be identical or not Together, when there are multiple L^p1When, they may be the same or different, when there are multiple M^p2When, they may be the same or different.) in addition, should Polymerizable compound preferably contain one or more kinds.

In the general formula (P) of the present invention, Z^p1Preferably-Sp^p2-R^p2, R¹¹And R¹²It is preferred that being each independently formula (R-1) extremely Any one of formula (R-3).

In addition, in aforementioned formula (P), preferably m^p1+m^p5It is 2 or more.

In addition, in aforementioned formula (P), L^p1For 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- ,-CH=CH-COO- ,-COO-CH=CH- ,-OCOCH=CH- ,-(C= O)-O-(CH₂)z-、-OCF₂Or-C ≡ C-, L^p2For-OCH₂CH₂O-、-COOC₂H₄-、-OCOC₂H₄-、-(CH₂)_z- C (=O)- O-、-(CH₂) z-O- (C=O)-,-O- (C=O)-(CH₂) z- ,-(C=O)-O- (CH₂) z- ,-CH=CH-COO- ,-COO-CH =CH- ,-OCOCH=CH- ,-C₂H₄OCO- or-C₂H₄COO-, the z in previously described formula are preferably 1~4 integer.

Furthermore it is preferred that being the L of aforementioned formula (P)^p1And L^p2At least either be selected from by-(CH₂)_z- C (=O)- O-、-(CH₂) z-O- (C=O)-and-O- (C=O)-(CH₂) z- ,-(C=O)-O- (CH₂) z- composition group in it is at least one kind of.

In addition, in aforementioned formula (P), R^p1And R^p2It is more preferably each independently formula below (R-1) to formula (R-15) Any one of.

In addition, the m of aforementioned formula (P)^p3It indicates 0,1,2 or 3, works as m^p2When being 1, L^p1For singly-bound, work as m^p2It is more when being 2 or 3 A existing L^p1At least one be preferably singly-bound.

In addition, the m of aforementioned formula (P)^p3It indicates 0,1,2 or 3, works as m^p3When being 1, M^p2For Isosorbide-5-Nitrae-phenylene, work as m^p3It is 2 or 3 When, multiple M^p2In preferably at least across L^p1And and M^p1Adjacent M^p2For 1,4- phenylenes.

Further, the m of aforementioned formula (P)^p3Indicate 0,1,2 or 3, M^p2In at least one preferably through 1 or 2 or more Fluorine-substituted 1,4- phenylenes.

Further, the m of aforementioned formula (P)^p4Indicate 0,1,2 or 3, M^p3In at least one preferably through 1 or 2 or more Fluorine-substituted 1,4- phenylenes.

In addition, as the spacer group (Sp in aforementioned formula (P)^p1, Sp^p2, Sp^p4), preferably singly-bound ,-OCH₂-、- (CH₂)_zO-、-CO-、-C₂H₄-、-COO-、-OCO-、-COOC₂H₄-、-OCOC₂H₄-、-(CH₂)_z-、-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=CH-COO- ,-COO-CH=CH- ,-OCOCH =CH- or-C ≡ C-, the Z are preferably 1 or more 10 integer below.

The polymerizable compound of the general formula (P) of the present invention, is preferably selected from by general formula (P-a), general formula (P-b), general formula (P- C) and general formula (P-d) indicate compound composition group at least one kind of compound.

In above-mentioned general formula (P-a)~general formula (P-d), R^p1And R^p2Formula below (R-I) is each independently represented to formula (R- Any one of IX),

In previously described formula (R-I)~(R-IX), R²~R⁶Independently of each other be hydrogen atom, carbon atom number 1~5 alkyl or The halogenated alkyl that carbon atom number is 1~5, W are singly-bound ,-O- or methylene, and T is singly-bound or-COO-, and p, t and q are each independently Indicate 0,1 or 2,

Ring A and ring B each independently represents 1,4- phenylenes, 1,4- cyclohexylidenes, anthracene -2,6- diyls, phenanthrene -2,7- two 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, be preferably unsubstituted or the alkyl through carbon atom number 1~12, carbon atom number 1~ 12 halogenated alkyl, the alkoxy of carbon atom number 1~12, the halogenated alkoxy of carbon atom number 1~12, halogen atom, cyano, nitro Or-R^p1Substitution,

Ring C indicates any one of formula (c-i)~(c-ix) below,

(in formula, in ★ and Sp^p1Connection, in ★ ★ and L^p5Or L^p6Connection.)

Sp^p1And Sp^p4Indicate spacer group, X^p1~X^p4It is preferred that hydrogen atom or halogen atom are each independently represented,

L^p4、L^p5And L^p6It is preferred that being each independently 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- ,-COOCH=CH- ,-OCOCH=CH- or-C ≡ C-, the z in previously described formula are preferably 1~4 integer.

L^p3Preferably-CH=CHCOO- ,-COOCH=CH- or-OCOCH=CH-.

In the compound that above-mentioned general formula (P-a) indicates, m^p6And m^p7It is preferred that each independently representing 0,1,2 or 3.In addition, More preferably m^p6+m^p7=2~5.

In the compound that above-mentioned general formula (P-d) indicates, m^p12And m^p15Each independently represent 1,2 or 3, m^p13It is preferred that table Show 0,1,2 or 3, m^p14It is preferred that indicating 0 or 1.In addition, more preferably m^p12+m^p15=2~5.When there are multiple R^p1When, they can phase It is same or different, when there are multiple R^p1When, they may be the same or different, when there are multiple R^p2When, they may be the same or different, when There are multiple Sp^p1When, they may be the same or different, when there are multiple Sp^p4When, they may be the same or different, when there are multiple L^p4 And L^p5When, they may be the same or different, and when there are multiple ring A~ring C, they may be the same or different.

The preferred structure for the compound that the general formula (P-a) of the present invention illustrated below~general formula (P-d) indicates.

The preference for the compound that general formula (P-a) as the present invention indicates, can enumerate following formula (P-a-1)~formula (P- A-31) the polymerizable compound indicated.

The preference for the compound that general formula (P-b) as the present invention indicates, can enumerate following formula (P-b-1)~formula (P- B-34) the polymerizable compound indicated.

The preference for the compound that general formula (P-c) as the present invention indicates, can enumerate following formula (P-c-1)~formula (P- C-52) the polymerizable compound indicated.

The compound that the general formula (P-d) of the present invention indicates, the compound that general formula (P-d ') preferably below indicates.

(in the compound that above-mentioned general formula (P-d ') indicates, m^p10More preferably indicate 2 or 3.Other marks lead to above-mentioned Formula (p-d) is identical, thus omits.)

The preference for the compound that general formula (P-d) as the present invention indicates, can enumerate following formula (P-d-1)~formula (P- D-31) the polymerizable compound indicated.

" alkyl that carbon atom number is 1~15 " of the present invention is preferably straight-chain or branch-like alkyl, more preferably straight chain Shape alkyl.In addition, in above-mentioned general formula (1), R¹And R²It is each independently the alkyl of carbon atom number 1~15, R¹And R²It is preferred that each From the alkyl for independently being carbon atom number 1~8, the more preferably alkyl of carbon atom number 1~6.

The example of " alkyl that carbon atom number is 1~15 " as the present invention, can enumerate：Methyl, ethyl, propyl, butyl, Isopropyl, isobutyl group, tertiary butyl, 3- amyls, isopentyl, neopentyl, amyl, hexyl, heptyl, octyl, nonyl, decyl, 12 Base, pentadecyl etc..It should be noted that in the present specification, the example of alkyl be it is common, can be according to the carbon atom number of each alkyl Number, suitably selected from above-mentioned illustration.

The example of " alkoxy that carbon atom number is 1~15 " of the present invention, at least one oxygen preferably in the substituent group are former Son is present in the position being directly connected to ring structure, more preferably methoxyl group, ethyoxyl, propoxyl group (positive propoxy (n- Propoxy), isopropoxy (i-propoxy)), butoxy, amoxy, octyloxy, decyloxy.It should be noted that in this explanation In book, the example of alkoxy is common, can be suitably subject to from above-mentioned illustration according to the number of the carbon atom number of each alkoxy Selection.

The example of " alkenyls that carbon atom number is 2~15 " of the present invention, can enumerate：Vinyl, allyl, 1- acrylic, Isopropenyl, 2- cyclobutenyls, 3- cyclobutenyls, 1,3- butadienyls, 2- pentenyls, 3- pentenyls, 2- hexenyls etc..In addition, making For the preferred alkenyl of the present invention, with the formula (i) (vinyl) of following records, formula (ii) (1- acrylic), formula (iii) (3- fourths Alkenyl) and formula (iv) (3- pentenyls) expression,

(in above-mentioned formula (i)~(iv), * indicates the position for being connected to ring structure.), but when the liquid crystal group of the present application When conjunction object contains polymerizable monomer, the structure of the structure that preferably formula (ii) and formula (iv) indicate, more preferably formula (ii) expression. It should be noted that in the present specification, the example of alkenyl be it is common, can be according to the number of the carbon atom number of each alkenyl, suitably It is selected from above-mentioned illustration.

In addition, in the polymerizable compound of the present invention, crystallized with the dissolubility of low molecular weight liquid crystal, inhibition as improving The polymerism that the polymerizable compound with reactive group of preferred mono-functional for change, preferably the following general formula (VI) indicate Compound.

(in formula, X³Indicate hydrogen atom or methyl, Sp³The alkylidene or-O- (CH of expression singly-bound, carbon atom number 1~12₂)_t- (in formula, t indicates that 2~11 integer, oxygen atom are connected to aromatic rings.), V indicates straight chain or the branch of carbon atom number 2~20 The multivalence cyclic substituents of polyvalent alkylene or carbon atom number 5~30, the alkylidene in polyvalent alkylene can be not adjacent in oxygen atom Replaced by oxygen atom in the range of connecing, or can (alkylidene in base can not be abutted in oxygen atom by the alkyl of carbon atom number 5~20 In the range of replaced by oxygen atom.) or cyclic substituents substitution, W indicate hydrogen atom, halogen atom or carbon atom number 1~15 alkane Base.Arbitrary hydrogen atom can be substituted by-CH in all 1,4- phenylenes in formula₃、-OCH₃, fluorine atom or cyano.)

In above-mentioned logical formula (VI), X³Indicate hydrogen atom or methyl, but when paying attention to reaction speed, preferably hydrogen atom, When paying attention to reducing reaction residual quantity, then preferably methyl.

In above-mentioned logical formula (VI), Sp³The alkylidene or-O- (CH of expression singly-bound, carbon atom number 1~12₂)_t(in formula, t Indicate that 2~11 integer, oxygen atom are connected to aromatic rings.), since the length of carbochain can impact Tg, work as polymerization Property compounds content when being less than 10 weight %, preferably not too long, preferably singly-bound or the alkylidene of carbon atom number 1~5, when poly- When conjunction property compounds content is less than 6 weight %, more preferably singly-bound or the alkylidene of carbon atom number 1~3.Work as polymerizable compound When content is more than 10 weight %, the preferably alkylidene of carbon number 5~10.In addition, working as Sp³Expression-O- (CH₂)_tWhen it is also the same, T is preferably 1~5, and more preferably 1~3.Further, in the substrate surface containing alignment films, since carbon atom number can be to pre-tilt angle It impacts, therefore, as needed, preferably mixes Sp³Carbon atom number different plural polymerizable compound use, with To desired pre-tilt angle.

In above-mentioned logical formula (VI), the straight chain or branch's polyvalent alkylene or carbon atom number of V expression carbon atom numbers 2~20 5~30 multivalence cyclic substituents, the alkylidene in polyvalent alkylene can be taken in the range that oxygen atom does not abut by oxygen atom Generation, or can (alkylidene in base can be taken in the range that oxygen atom does not abut by oxygen atom by the alkyl of carbon atom number 5~20 Generation.) or cyclic substituents substitution, preferably replaced by 2 or more cyclic substituents.

More specifically the polymerizable compound that logical formula (VI) indicates can enumerate the compound of general formula (X1a) expression.

(in formula, A¹Indicate hydrogen atom or methyl,

A²Indicating the alkylidene of singly-bound or carbon atom number 1~8, (1 or 2 or more methylene in the alkylidene can be with The mode that oxygen atom is not connected directly to one another is replaced by oxygen atom ,-CO- ,-COO- or-OCO- each independently, in the alkylidene 1 or 2 or more hydrogen atom can be replaced each independently by fluorine atom, methyl or ethyl.),

A³And A⁶Each independently represent hydrogen atom, halogen atom or carbon atom number 1~10 alkyl (1 in the alkyl or 2 or more methylene can in such a way that oxygen atom is not connected directly to one another each independently by oxygen atom ,-CO- ,-COO- or- OCO- replaces, and 1 or 2 or more hydrogen atom in the alkyl can be each independently by halogen atom or carbon atom number 1~17 Alkyl replaces.),

A⁴And A⁷Each independently represent hydrogen atom, halogen atom or carbon atom number 1~10 alkyl (1 in the alkyl or 2 or more methylene can in such a way that oxygen atom is not connected directly to one another each independently by oxygen atom ,-CO- ,-COO- or- OCO- replaces, and 1 or 2 or more hydrogen atom in the alkyl can halogen atom or the alkyl of carbon atom number 1~9 each independently Substitution.),

P indicates 0~10,

B¹、B²And B³Each independently represent hydrogen atom, the straight-chain of carbon atom number 1~10 or branched-chain alkyl (alkane 1 or 2 or more methylene in base can in such a way that oxygen atom is not connected directly to one another each independently by oxygen atom ,- CO- ,-COO- or-OCO- replace, and 1 or 2 or more hydrogen atom in the alkyl can be former by halogen atom or carbon each independently The tri-alkoxy silicon substrate (trialkoxysilyl) of subnumber 3~6 replaces.)

Above-mentioned general formula (X1a) is preferably the compound that the following general formula (II-b) indicates.

General formula (II-b)

General formula (II-b) indicate compound specifically be preferably following formula (II-q)~(II-z), (II-aa)~ (II-al) compound indicated.

The compound that above-mentioned logical formula (VI), general formula (XaI) and general formula (II-b) indicate can be only a kind, or be alternatively 2 kinds with On.

In addition, as the polymerizable compound that logical formula (VI) indicates, the compound of general formula (X1b) expression can be also enumerated.

(in formula, A⁸Indicate hydrogen atom or methyl, 6 membered ring T¹、T²And T³Any one following is each independently represented,

(wherein q indicates 1 to 4 integer.)

Q indicates 0 or 1,

Y¹And Y²Each independently represent singly-bound ,-CH₂CH₂-、-CH₂O-、-OCH₂-、-COO-、-OCO-、-C≡C-、-CH =CH- ,-CF=CF- ,-(CH₂)₄-、-CH₂CH₂CH₂O-、-OCH₂CH₂CH₂,-CH=CHCH₂CH₂Or-CH₂CH₂CH=CH-,

Y³And Y⁴Each independently represent singly-bound, carbon atom number 1~12 alkylidene (1 or 2 in the alkylidene with On methylene can be in such a way that oxygen atom be connected directly to one another each independently by oxygen atom ,-CO- ,-COO- or-OCO- Replace, 1 or 2 or more hydrogen atom in the alkylidene can be replaced by fluorine atom, methyl or ethyl each independently.),

B⁸The alkyl or end for indicating hydrogen atom, cyano, halogen atom or carbon atom number 1~8 have acryloyl group or methyl The alkylidene of acryloyl group.)

As exemplary compounds, as follows, but it is not limited to these.

Further, lead to the chemical combination that the polymerizable compound that formula (VI) indicates specifically can also enumerate general formula (X1c) expression Object.

(in formula, R⁷⁰Indicate hydrogen atom or methyl, R⁷¹Indicate the alkyl with condensed ring.)

As exemplary compounds, as follows, but it is not limited to these.

In addition, in the polymerizable compound of the present invention, crystallized with the dissolubility of low molecular weight liquid crystal, inhibition as improving The polymerism that the preferred multi-functional polymerizable compound with reactive group for change, preferably the following general formula (V) indicate Close object.

(in formula, X¹And X²Each independently represent hydrogen atom or methyl, Sp¹And Sp²It is former to each independently represent singly-bound, carbon The alkylidene or-O- (CH of subnumber 1~12₂)_s(in formula, s indicates that 1~11 integer, oxygen atom are connected to aromatic rings.), U is indicated The straight chain or branch's polyvalent alkylene of carbon atom number 2~20 or the multivalence cyclic substituents of carbon atom number 5~30, multivalence alkylene Alkylidene in base can be replaced in the range that oxygen atom does not abut by oxygen atom, or can be by the alkyl (base of carbon atom number 5~20 In alkylidene can be replaced by oxygen atom in the range that oxygen atom does not abut.) or cyclic substituents substitution, k expressions 1~5 Integer.Arbitrary hydrogen atom can be substituted into-CH in all 1,4- phenylenes in formula₃、-OCH₃, fluorine atom or cyano.)

In above-mentioned logical formula (V), X¹And X²Hydrogen atom or methyl are each independently represented, but when paying attention to reaction speed, it is excellent It is selected as hydrogen atom, when paying attention to reducing reaction residual quantity, then preferably methyl.

In above-mentioned logical formula (V), Sp¹And Sp²Each independently represent singly-bound, carbon atom number 1~12 alkylidene or-O- (CH₂)_s(in formula, s indicates that 2~11 integer, oxygen atom are connected to aromatic rings.), the pre-dumping of liquid crystal display element of the invention Angle can by the carbon atom number, with liquid crystalline phase than content and type, the orientation process condition of used alignment films influenced. It is preferable to use the compounds that can spontaneously induce pre-tilt angle depending on the molecular structure of polymerizable compound in alignment layer surface. Therefore, be not necessarily to be limited, for example, make pre-tilt angle be 5 degree or so when, preferably carbochain is not too long, more preferably singly-bound Or the alkylidene of carbon atom number 1~5, more preferably singly-bound or the alkylidene of carbon atom number 1~3.Further, in order to make pre-tilt angle , it is preferable to use the polymerizable compound that carbon atom number is 6~12, more preferable carbon atom number are 8~10 within 2 degree or so.This Outside, work as Sp¹And Sp²Expression-O- (CH₂)_sWhen, due to that can be impacted to pre-tilt angle, it is therefore preferable that suitably right as needed Sp¹And Sp²Length could be adjusted to use, in order to increase pre-tilt angle, s is preferably 1~5, more preferably 1~3.In order to reduce Pre-tilt angle, s are preferably 6~10.Further, since Sp¹And Sp²At least one can show the asymmetry of molecule when being singly-bound, Pre-tilt is thus induced, thus preferably.

In addition, in above-mentioned logical formula (V), it is also preferred that Sp¹With Sp²Identical compound is, it is preferable to use Sp¹With Sp²It is identical Two or more compound.At this point, more preferably using mutual Sp¹And Sp²Different compounds of more than two kinds.

In above-mentioned logical formula (V), the straight chain or branch's polyvalent alkylene or carbon atom number 5 of U expression carbon atom numbers 2~20 ~30 multivalence cyclic substituents, the alkylidene in polyvalent alkylene can be taken in the range that oxygen atom does not abut by oxygen atom Generation, or can (alkylidene in base can be taken in the range that oxygen atom does not abut by oxygen atom by the alkyl of carbon atom number 5~20 Generation.), cyclic substituents substitution, preferably replaced by 2 or more cyclic substituents.

In above-mentioned logical formula (V), U specifically preferably indicates formula below (Va-1) to formula (Va-13).In order to improve anchor Fixed (anchoring) power, the preferably high biphenyl etc. of linearity, preferably expression (Va-1) to formula (Va-6).In addition, expression (Va-6) to formula (Va-11) structure in terms of high with the dissolubility of liquid crystal on it is preferred, preferably with formula (Va-1) to formula (Va- 6) it is applied in combination.

(in formula, both ends are connected to Sp¹Or Sp²。Z^p1And Z^p2Each independently represent-OCH₂-、-CH₂O-、-COO-、- OCO-、-CF₂O-、-OCF₂-、-CH₂CH₂-、-CF₂CF₂,-CH=CH-COO- ,-CH=CH-OCO- ,-COO-CH=CH- ,- OCO-CH=CH- ,-COO-CH₂CH₂-、-OCO-CH₂CH₂-、-CH₂CH₂-COO-、-CH₂CH₂-OCO-、-COO-CH₂-、-OCO- CH₂-、-CH₂-COO-、-CH₂-OCO-、-CY¹=CY²,-C ≡ C- or singly-bound.Arbitrary hydrogen in all 1,4- phenylenes in formula Atom can be substituted by-CH₃、-OCH₃, fluorine atom or cyano.In addition, 1 or 2 or more CH in cyclohexylidene₂CH₂Base It can be by-CH=CH- ,-CF₂O-、-OCF₂Substitution.)

When U has ring structure, aforementioned Sp¹And Sp²Preferably at least one expression-O- (CH₂)_s(in formula, s indicates 1~7 Integer, oxygen atom is connected to aromatic rings.), it is also preferred that the two is all-O- (CH₂)_s-。

In above-mentioned logical formula (V), k indicates 1~5 integer, three officials that the difunctional compound or k that preferably k is 1 are 2 It can compound, more preferably difunctional compound.

The compound that above-mentioned logical formula (V) indicates is preferably specifically the compound that general formula (Vb) below indicates.

(in formula, X¹And X²Each independently represent hydrogen atom or methyl, Sp¹And Sp²It is former to each independently represent singly-bound, carbon The alkylidene or-O- (CH of subnumber 1~12₂)_s(in formula, s indicates that 1~7 integer, oxygen atom are connected to aromatic rings.), Z¹Table Show-OCH₂-、-CH₂O-、-COO-、-OCO-、-CF₂O-、-OCF₂-、-CH₂CH₂-、-CF₂CF₂,-CH=CH-COO- ,-CH= CH-OCO- ,-COO-CH=CH- ,-OCO-CH=CH- ,-COO-CH₂CH₂-、-OCO-CH₂CH₂-、-CH₂CH₂-COO-、- CH₂CH₂-OCO-、-COO-CH₂-、-OCO-CH₂-、-CH₂-COO-、-CH₂-OCO-、-CY¹=CY²-(Y¹And Y²Each independently Indicate hydrogen atom or fluorine atom.) ,-C ≡ C- or singly-bound, C indicates Isosorbide-5-Nitrae-phenylene, anti-form-1,4- cyclohexylidenes or singly-bound, formula In in all 1,4- phenylenes arbitrary hydrogen atom can be replaced by fluorine atoms.)

In above-mentioned general formula (Vb), X¹And X²Hydrogen atom or methyl are each independently represented, preferably all indicates hydrogen atom Diacrylate derivative, or all dimethylacrylate derivatives with methyl, preferably also one indicate hydrogen atom, separately One indicates the compound of methyl.The polymerization speed of these compounds is that diacrylate derivative is most fast, dimethacrylate Ester derivant is slow, and asymmetric compound is centre, can use preferred mode according to its purposes.

In above-mentioned general formula (Vb), Sp¹And Sp²Each independently represent singly-bound, carbon atom number 1~12 alkylidene or-O- (CH₂) s-, preferably at least one is-O- (CH₂) s-, more preferably the two expression-O- (CH₂) s- mode.In this case, s Preferably 1~6.

In above-mentioned general formula (Vb), Z¹Expression-OCH₂-、-CH₂O-、-COO-、-OCO-、-CF₂O-、-OCF₂-、- CH₂CH₂-、-CF₂CF₂,-CH=CH-COO- ,-CH=CH-OCO- ,-COO-CH=CH- ,-OCO-CH=CH- ,-COO- CH₂CH₂-、-OCO-CH₂CH₂-、-CH₂CH₂-COO-、-CH₂CH₂-OCO-、-COO-CH₂-、-OCO-CH₂-、-CH₂-COO-、- CH₂-OCO-、-CY¹=CY²-(Y¹And Y²Each independently represent hydrogen atom or fluorine atom.) ,-C ≡ C- or singly-bound, preferably- OCH₂-、-CH₂O-、-COO-、-OCO-、-CF₂O-、-OCF₂-、-CH₂CH₂-、-CF₂CF₂Or singly-bound, more preferably-COO- ,- OCO- or singly-bound, particularly preferably singly-bound.In above-mentioned general formula (Vb), C indicates 1 that arbitrary hydrogen atom can be replaced by fluorine atoms, 4- phenylenes, anti-form-1,4- cyclohexylidenes or singly-bound, preferably Isosorbide-5-Nitrae-phenylene or singly-bound.When C indicates the ring knot other than singly-bound When structure, Z¹Linking group preferably also other than singly-bound, when C is singly-bound, Z¹Preferably singly-bound.

According to above-mentioned, in above-mentioned general formula (Vb), the case where C indicates singly-bound, and ring structure is formed by two rings be it is preferred, As the polymerizable compound with ring structure, chemical combination that specifically general formula (V-1) to (V-6) preferably below indicates The compound that the compound that object, particularly preferably general formula (V-1) to (V-4) indicate, most preferably general formula (V-2) indicate.

In addition, in above-mentioned general formula (Vb), the compound that general formula (V1-1) to (V1-5) below indicates is in improve and liquid The deliquescent aspect of crystal composite is preferred, the compound that particularly preferably general formula (V1-1) indicates.

In addition, above-mentioned general formula (Vb) is also preferably used when being formed by three ring structures, general formula (V1-6) to (V1-13) The compound of expression is preferred with the deliquescent aspect of liquid-crystal composition in raising.Further, with strong logical of the anchorage force of liquid crystal In the compound that formula (V-1) to (V-6) indicates, it is also preferred that the good general formula of weak with anchorage force but with liquid-crystal composition intermiscibility The compound that (V1-1) to (V1-5) indicates mixes to use.

(in formula, q1 and q2 each independently represent 1~12 integer, R³Indicate hydrogen atom or methyl.)

As the compound that above-mentioned logical formula (V) indicates, specifically, the compound that general formula below (Vc) indicates is improving The aspect of reaction speed is preferred, further, since pre-tilt angle thermostabilization can be made, therefore preferably.Further, it can also adjust as needed Whole Sp¹、Sp²And Sp³Carbon atom number and obtain desired pre-tilt angle.About the relationship of pre-tilt and the carbon atom number, show Identical tendency when with functional group being 2.

(in formula, X¹、X²And X³Each independently represent hydrogen atom or methyl, Sp¹、Sp²And Sp³Each independently represent list Key, the alkylidene of carbon atom number 1~12 or-O- (CH₂)_s(in formula, s indicates that 2~7 integer, oxygen atom are connected to fragrance Ring.), Z¹¹Expression-OCH₂-、-CH₂O-、-COO-、-OCO-、-CF₂O-、-OCF₂-、-CH₂CH₂-、-CF₂CF₂,-CH=CH- COO- ,-CH=CH-OCO- ,-COO-CH=CH- ,-OCO-CH=CH- ,-COO-CH₂CH₂-、-OCO-CH₂CH₂-、-CH₂CH₂- COO-、-CH₂CH₂-OCO-、-COO-CH₂-、-OCO-CH₂-、-CH₂-COO-、-CH₂-OCO-、-CY¹=CY²,-C ≡ C- or list Key, J indicate Isosorbide-5-Nitrae-phenylene, anti-form-1,4- cyclohexylidenes or singly-bound, arbitrary hydrogen atom in all Isosorbide-5-Nitrae-phenylenes in formula It can be replaced by fluorine atoms.)

As polymerizable compound, further preferably using the compound with light orientation function.Wherein, it is preferable to use showing The compound of photoisomerization.

As the polymerizable compound with light orientation function, specifically preferably following compound：In general formula (Vb) in, X¹And X²Each independently represent hydrogen atom or methyl, Sp¹And Sp²Each independently represent singly-bound, carbon atom number 1~ 8 alkylidene or-O- (CH₂)_s(in formula, s indicates that 1~7 integer, oxygen atom are connected to aromatic rings.), Z¹Expression-N=N-, C Indicate 1,4- phenylenes, anti-form-1, (arbitrary hydrogen atom can be replaced by fluorine atoms 4- cyclohexylidenes.) or singly-bound.

Wherein, the compound that general formula (Vn) preferably below indicates.

(in formula, Rn₁And Rn₂Each independently representing hydrogen atom or methyl, in formula, pn and qn each independently represent 1~ 12 integer.)

[polymerization initiator]

As the polymerization of the polymerizable compound used in the present invention, it can be used free radical polymerization, anion poly- Conjunction, cationic polymerization etc. are preferably polymerize by free radical polymerization, more preferably by light Fries rearrangement carry out from By base polymerization, pass through the free radical polymerization of Photoepolymerizationinitiater initiater progress.

As radical polymerization initiator, thermal polymerization, Photoepolymerizationinitiater initiater, preferably photopolymerization can be used to cause Agent.Specifically preferred compound below.

It is preferred that：Diethoxy acetophenone, 2- hydroxy-2-methyl -1- phenyl-propane -1- ketone, benzyl dimethyl ketal, 1- (4- isopropyl phenyls) -2- hydroxy-2-methyl propane -1- ketone, 4- (2- hydroxyl-oxethyls) phenyl-(2- hydroxyl -2- propyl) ketone, 1- hydroxycyclohexyl-phenylketones, 2- methyl -2-N- morpholinyl (4- thiomethylphenyls) propane -1- ketone, 2- benzyl -2- diformazans The acetophenones systems such as base amino -1- (4- morpholino phenyls)-butanone, 4'- metaphenoxy acetophenones, 4'- acetophenones；

The styraxes such as styrax, benzoin isopropyl ether, benzoin isobutyl ether, benzoin methyl ether, benzoin ethyl ether system；

The acylphosphine oxides systems such as 2,4,6- trimethylbenzoyldiphenyl oxides；

Benzyl, aminomethyl phenyl acetaldehyde base ester；

Benzophenone, o-benzoyl yl benzoic acid methyl esters, 4- phenyl benzophenones, 4,4'- dichloro benzophenones, hydroxyl two Benzophenone, 4- benzoyls -4'- methyl-diphenyl sulfide, acrylated benzophenone, 3,3', tetra- (tert-butyl hydroperoxides of 4,4'- Carbonyl) benzophenone, 3,3'- dimethyl -4- methoxy benzophenones, 2,5- dimethyl benzophenones, 3,4- dimethyl hexichol The benzophenone series such as ketone；

The thioxanthenes such as 2-isopropylthioxanthone, 2,4- dimethyl thioxanthones, 2,4- diethyl thioxanthones, bis- clopenthixal ketones of 2,4- Ketone system；

The aminobenzophenones systems such as michaelis ketone, 4,4'- diethylamino benzophenone；

10- butyl -2- chloro-acridines ketone, 2- ethyl hydrazine, 9,10- phenanthrenequione, camphorquinone etc..Wherein, most preferably benzyl two Methyl ketal.

In addition, it is contemplated that the service life of free radical, reactivity, it is also preferred that using a variety of polymerization initiators.

Further, as without using above-mentioned polymerization initiator, but as the freedom carried out using light Fries rearrangement Base polymerize, and so that it is contained the polymerizable liquid crystal compound with the conjugated structure for absorbing ultraviolet light and makes its polymerization.For example, passing through Polymerization is replaced to cause using the polymerizable liquid crystal compound with conjugated system structure that general formula (X1c-1) to (X1c-4) indicates Agent will not be such that the voltage retention of liquid crystal cell declines, thus preferably.In addition, in order to promote to polymerize, it is also preferred that by them and gathering It closes initiator and merges use.

[polymerizable liquid crystal compound]

The polymerizable liquid crystal compound used in the present invention, preferably comprise it is above-mentioned illustrated by liquid-crystal composition and above-mentioned institute For the 0.5 mass % illustrated less than the polymerizable compound of 10 mass %, the lower limiting value of the content of polymerizable compound is excellent It is selected as 1 mass % or more, preferably 2 mass % or more, upper limit value is preferably smaller than 9 mass %, more preferably less than 7 mass %.This Outside, the polymerizable liquid crystal compound that uses in the present invention, it is also preferred that containing liquid-crystal composition and above-mentioned institute's example illustrated by above-mentioned The 10 mass % shown are less than the polymerizable compound of 40 mass %, the lower limiting value of the content of polymerizable compound at this time Preferably 15 mass % or more, preferably 20 mass % or more, upper limit value are preferably smaller than 30 mass %, more preferably less than 25 matter Measure %.Further, in the present invention polymerizable liquid crystal compound that uses preferably comprise it is above-mentioned illustrated by liquid-crystal composition with it is upper Polymerizable compounds of the 5 mass % less than 15 mass % illustrated by stating.

About the polymerizable liquid crystal compound used in the present invention, preferably by containing 0.5 mass % less than 40 The polymerizable compound of quality %, to be formed with uniaxiality optical anisotropy or uniaxiality refractive anisotrop or easily be taken Polymer network axially, more preferably according to the easy of the optic axis of the polymer network or easy axis of orientation and low molecular weight liquid crystal Roughly the same mode of axis of orientation is formed.It should be noted that the polymer network is also formed including multiple polymer network set Polymer adhesive made of macromolecule membrane.Polymer adhesive is characterized in that：With the folding for showing uniaxial orientation Rate anisotropy is penetrated, low molecular weight liquid crystal is scattered in the film, the uniaxiality optic axis of the film and the optic axis of low molecular weight liquid crystal Substantially all towards same direction.Thus, thus, characterized in that be different from the high-molecular dispersed liquid as light scattering type liquid crystal Brilliant or polymer network type liquid crystal, will not occur light scattering, in the liquid crystal cell using polarisation, can get the aobvious of high contrast Show, and shorten fall time, improves the response of liquid crystal cell.Further, about the polymerizable liquid crystal group used in the present invention Object is closed, polymeric web network layers are formed in liquid crystal cell entirety, is different from forming the film of polymer on liquid crystal cell substrate Layer and PSA (Polymer Sustained Alignment, macromolecule maintain be orientated) the type liquid-crystal composition for inducing pre-tilt.

No matter in which kind of concentration, it is preferably to for containing polymerizable compounds different at least two or more Tg and according to need Adjust Tg.The precursor of polymer as Tg high, polymerizable compound are preferably the molecular structure got higher with crosslink density Polymerizable compound and function radix be 2 or more.In addition, the precursor of polymer low Tg is preferably function radix 1 or 2 The structure that there is alkylidene as interval base etc. above and between functional group and keep molecular length elongated.In order to cope with polymer The thermal stability of network, the promotion of impact resistance and when adjusting the Tg of polymer network, preferably suitably adjustment polyfunctional monomer with The ratio of monofunctional monomer.In addition, Tg is also related to the warm-up movement of the main chain and the molecular level in side chain of polymer network, Also electro-optic properties can be impacted.If such as improve crosslink density, the transport properties of molecules of main chain can decline, with low molecule The anchorage force of liquid crystal improves, and driving voltage is got higher, and fall time shortens.On the other hand, if reducing crosslink density so that Tg Decline, then shows to reduce with the anchorage force of low molecular weight liquid crystal because the warm-up movement of main polymer chain is promoted, under driving voltage Drop, fall time elongated tendency.The anchorage force of polymer network interface, also can be by other than being influenced by above-mentioned Tg The influence of the transport properties of molecules of polymer lateral chain, by using the polymerism chemical combination with multivalence branched alkylidene and multivalence alkyl The anchorage force of object, polymer interface can reduce.In addition, the polymerizable compound with multivalence branched alkylidene and multivalence alkyl can Pre-tilt angle effectively is induced in substrate interface, the direction for the anchorage force for reducing polar angle direction can be acted on.

In the state that polymerizable liquid crystal compound shows liquid crystalline phase, make the polymerism in polymerizable liquid crystal compound It closes object to be polymerize, thus increases the molecular weight of polymerizable compound, make liquid-crystal composition that phase occur with polymerizable compound Separation.Be separated into the form of two-phase largely can according to containing the type of liquid-crystal compounds, polymerizable compound Type and it is different.Phase separation structure can be formed by bimodal decomposition (binodal decomposition), can also pass through rotation Section decomposes (spinodal decomposition) and forms phase separation structure, which is the polymerism chemical combination in liquid crystalline phase Object mutually generates and grows up as the core of numerous island, which is by the dense of liquid crystalline phase and polymerizable compound phase Degree fluctuates and causes to be separated.The polymer network caused by bimodal decomposition is formed, preferably makes the content of low molecular weight liquid crystal extremely It is that it is small to will produce numerous size by using the fast compound of the reaction speed of polymerizable compound by 85 mass % or more less In the core of the polymerizable compound of visible wavelength, nano level phase separation structure is formed, thus preferably.If as a result, polymerism Polymerization in compound phase carries out, then the polymeric web that gapping interval is less than visible wavelength is formed depending on phase separation structure Network, on the other hand, if caused by phase separation of the gap of polymer network by low molecular weight liquid crystal phase, and the size in the gap It is less than visible wavelength, then non-light-scattering and be high contrast, and the influence of the anchorage force from polymer network can become strong, Fall time can shorten, and obtain the liquid crystal display element of high-speed response, so particularly preferably.The polymerism chemical combination of bimodal decomposition The karyogenesis of object phase can by caused by the difference of classes of compounds, combination intermiscibility change or reaction speed, temperature The influence of the parameters such as degree, is preferably adjusted as suitably desired.It is depended in polymerizable ultraviolet about reaction speed The functional group of polymerizable compound, the type and content of photoinitiator, ultraviolet irradiation intensity, as long as suitably adjusting ultraviolet light Irradiation condition is to promote reactivity, preferably at least 20mW/cm²Above ultraviolet irradiation intensity.In low molecular weight liquid crystal For 85 mass % or more when, form polymer network preferably by the phase separation structure caused by spinodal decomposition, spinodal decomposition by In available by the phase separation fine structure caused by the fluctuation of concentration with periodic two-phase, therefore it is easily formed than visible The small and uniform gapping interval of optical wavelength, thus preferably.It is preferred that being formed with polymer network.If the ratio of polymerizable compound is small In 15 mass %, it is preferably formed as the phase separation structure caused by bimodal decomposition, if 15 mass % or more, is then preferably formed as by revolving Phase separation structure caused by section decomposes.If polymerizable compound content increases, there are low molecular weight liquid crystal phases and polymerism chemical combination The phase transition temperature of two-phase laminated flow mutually occurs under the influence of the temperature for object.In the temperature higher than two-phase laminated flow transition temperature, can be in Existing isotropic phase (isotropic phase), if but be less than the temperature, it can detach, uniform phase point can not be obtained From structure, not preferably.When two-phase laminated flow occurs because of temperature, preferably phase point is formed in the temperature higher than two-phase laminated flow temperature From structure.No matter in which kind of above-mentioned situation, the same of state of orientation identical with the state of orientation of low molecular weight liquid crystal is being kept When form polymer network.Be formed by polymer network shown in a manner of the orientation for copying low molecular weight liquid crystal optics respectively to It is anisotropic.As the form of the liquid crystal layer in polymer network, can enumerate：Liquid-crystal composition is in the tridimensional network of polymer Form the structure of pantostrat, the structure that the structure, or both of the droplet distribution of liquid-crystal composition in polymer is mixed, And only has the knot of liquid crystal layer using two substrates face as starting point there are polymeric web network layers and in the immediate vicinity with opposing substrate Structure.At all events plant structure, it is preferably to by the effect of polymer network come induce relative to liquid crystal cell substrate interface in 0~ 90 ° of pre-tilt angle.The polymer network of formation, which preferably has, makes the low molecular weight liquid crystal coexisted be in along the alignment films of liquid crystal cells The function that existing differently- oriented directivity is orientated, further, it is also preferred that with making low molecular weight liquid crystal occur relative to polymer interface direction The function of pre-tilt.It is right if importing the polymerizable compound for making low molecular weight liquid crystal that pre-tilt occur relative to polymer interface It is useful to promote transmissivity, the driving voltage of reduction liquid crystal cell, thus preferably.In addition, about can have refractive anisotrop, Make the function that liquid crystal is orientated towards differently- oriented directivity, it is preferable to use the polymerizable compound with liquid crystal base.In addition, also can be by applying Making alive and ultraviolet light is irradiated simultaneously etc. to form polymer network, form pre-tilt.

For the vertical orientation unit of VA patterns etc., it is possible to use vertical orientation can be induced and had without liquid crystal base There is the polymerizable compound of multivalence alkyl or multivalence branched alkylene groups, it is also preferred that being closed with the polymerizable compound with liquid crystal base And it uses.When using above-mentioned polymerizable liquid crystal compound, it is polymerize by being separated by forms polymer in vertical orientation unit When network, preferably fiber is formed in the direction substantially common direction vertical relative to liquid crystal cell substrate with low molecular weight liquid crystal Shape or process for preparing column type polymer network.In addition, implementing friction treatment etc. to the vertical alignment layer positioned at unit substrate surface to induce liquid Brilliant tilted alignment is to induce pre-tilt angle, when using such vertical alignment layer, preferably fibrous or columnar polymerization Object network is formed obliquely on direction identical with the low molecular weight liquid crystal that pre-tilt is orientated.It can also be according to polymer network Tilt the selected polymerizable compound of mode for spontaneously occurring in substrate interface.Liquid crystal is set to be to tilt in addition, can also apply voltage State of orientation irradiates ultraviolet light etc. and forms polymer network.

It further, can be than polymerizable liquid crystal compound as the method for inducing pre-tilt angle while applying voltage The low 0.9V of threshold voltage or so voltage to the voltage of high 2V or so in the range of make its polymerization while apply voltage, or It can be set as being less than threshold after voltage several seconds~tens of seconds that the short time applies threshold voltage or more in polymer network forming process Threshold voltage forms polymer network.Since threadiness or process for preparing column type polymer network are formed obliquely to induce relative to transparent base Plate plane is in 90 degree~80 degree of pre-tilt angle, therefore it is further preferred that preferably 90 degree~85 degree of pre-tilt angle, preferably 89.9 degree~85 The pre-tilt angle of degree, preferably 89.9 degree~87 degree of pre-tilt angle, preferably 89.9 degree~88 degree of pre-tilt angle.Shape in any method At threadiness or process for preparing column type polymer network be characterized in that, will be connected between two blade unit substrates.The thermostabilization of pre-tilt angle as a result, Property can be promoted, and the reliability of liquid crystal display element can be improved.

In addition, inducing low molecular weight liquid crystal as by being formed with making threadiness or process for preparing column type polymer network tilted alignment The method of pre-tilt angle can enumerate following methods：By between functional group and liquid crystal base and the carbon atom number of alkylidene be 6 or more And the small bifunctional acrylate of induction angle of pre-tilt angle and between liquid crystal base and the carbon atom number of alkylidene be 5 with The big bifunctional acrylate of upper and pre-tilt angle induction angle is applied in combination.Can by adjusting the match ratio of these compounds, Desired pre-tilt angle is induced near interface.

Further, can enumerate has the function of invertibity light orientation at least 0.01% or more and 1% range addition below Polymerizable compound to formed threadiness or process for preparing column type polymer network method.It in this case, can be in trans- body For rod-like morphology identical with low molecular weight liquid crystal, the state of orientation of low molecular weight liquid crystal is impacted.Polymerization about the present invention Property liquid-crystal composition contained by the trans- body, if irradiating ultraviolet light as directional light from unit upper surface, this is rodlike Molecular long axis direction can unanimously be parallel to ultraviolet light direction of travel, and low molecular weight liquid crystal is also orientated to unanimously towards the trans- body simultaneously Molecular long axis direction.If obliquely irradiating ultraviolet light to unit, the molecular long axis of the trans- body can be obliquely oriented, and be made The inclined direction of liquid crystal towards ultraviolet light is orientated.That is, pre-tilt angle can be induced, light orientation function is shown.If in this stage Polymerizable compound is set to be crosslinked, then the pre-tilt angle meeting reason polymerization phase separation through induction is formed by threadiness or process for preparing column type polymer Network and immobilization., can be as needed accordingly, with respect to the induction of important pre-tilt angle in VA patterns, it is made using following methods Make the liquid crystal cell of the present invention：The method that polymerization phase separation is carried out while applying voltage；Add the different pre-dumpings of a variety of inductions The method that the polymerizable compound at angle carries out polymerization phase separation；Utilize the polymerizable compound institute with invertibity light orientation function The light orientation function of showing, makes low molecular weight liquid crystal and polymerizable liquid crystal compound are orientated towards ultraviolet light direction of travel, is gathered The method for closing phase separation.

Polymerizable compound with light orientation function is preferably the photoisomerization that can be absorbed ultraviolet light and become trans- body Object is closed, the reaction speed of the further preferred polymerizable compound with light orientation function is slower than the polymerization with light orientation function The reaction speed of polymerizable compound other than property compound.If being irradiated with, the polymerization with light orientation function Property compound can be immediately turned into trans- body and is orientated along light direction of travel, so, around containing polymerizable compound Liquid-crystal compounds can be also orientated in the same direction.At this point, polymerization phase separation carries out, low molecular weight liquid crystal long axis direction and polymer The easy orientation axis direction of network can be unanimously towards side identical with the easy axis of orientation of the polymerizable compound with light orientation function To towards ultraviolet direction of travel induction pre-tilt angle.

Further, in the parallel-oriented unit of IPS, FFS mode etc., using polymerizable liquid crystal compound, pass through phase point Threadiness or process for preparing column type polymer network are formed from polymerization, wherein low molecular weight liquid crystal is relative to taking positioned at liquid crystal cell substrate face Differently- oriented directivity to film is parallel-oriented, is preferably formed by the refractive anisotrop or easy of threadiness or process for preparing column type polymer network The differently- oriented directivity for being orientated axis direction and low molecular weight liquid crystal is substantially common direction.Further, threadiness or process for preparing column type polymer net Network more preferably substantially exists in unit entirety other than the gap for being dispersed with low molecular weight liquid crystal.In order to relative to polymer Interface direction induces the pre-tilt angle, it is preferable to use having the polymerism of multivalence alkyl or polyvalent alkylene without liquid crystal base Compound and polymerizable compound with liquid crystal base.

Further, electro-optic properties can be by the gapping interval of the surface area and polymer network at polymer network interface It influences, light scattering will not occur and be important, average void interval is preferably made to be less than visible wavelength.Such as in order to expand the boundary The surface area in face and the gapping interval is reduced, there is the method for increasing monomer composition content.As a result, send out polymerization phase separation structure Changing, the gapping interval become fine, to form polymer network, driving electricity in a manner of the surface area for increasing the interface Pressure and fall time tail off.Polymerization phase separation structure is also influenced by polymerization temperature.

In the present invention, it is preferred to make its polymerization obtain the phase separation knot with fine voids by accelerating phase separation speed Structure.Phase separation speed can be by the very big influence of the intermiscibility of low molecular weight liquid crystal and polymerizable compound, polymerization speed.Due to very Molecular structure, the content of compound are depended in big degree, therefore preferably properly adjustment forms to use.In intermiscibility height When, it is preferable to use the fast polymerizable compound of the polymerization speed, it is and in polymerizable ultraviolet, then preferred to improve uitraviolet intensity. In addition, it is also preferred that increasing the content of the polymerizable compound in polymerizable liquid crystal compound.When intermiscibility is low, phase separation speed Become sufficiently fast, therefore is beneficial to make the liquid crystal cell of the present invention.As the method for reducing intermiscibility, can enumerate makes in low temperature Its method polymerizeing.If being in low temperature, the orientation degree of order of liquid crystal can be promoted, the intermiscibility of liquid crystal and monomer can under Drop, therefore can accelerate to polymerize phase separation speed.Further, as other methods, can also enumerate make polymerizable liquid crystal compound at For the method being polymerize in the temperature of supercooling state.In this case, as long as slightly less than polymerizable liquid crystal compound Fusing point, therefore temperature several times is only reduced, it can also accelerate to be separated, be preferred.It is formed to be equivalent to as a result, and contains tens of % The monomer composition of amount makes an addition to polymerization phase separation structure when liquid crystal, that is, the structure for making fall time shorten that plays a role The polymer network structure that i.e. surface area at polymer network interface increases and the gapping interval is fine.Accordingly, with respect to the present invention Polymerizable liquid crystal compound, preferably in the way of so that fall time is shortened, it is contemplated that be orientated function, crosslink density, anchoring Power, gapping interval, the appropriate composition for adjusting polymerizable liquid crystal.

It, must in order to obtain the display of high contrast in the liquid crystal cell using the polymerizable liquid crystal compound of the present invention Light scattering must will not occur, it is important that, it is contemplated that the above method, it is special according to acquisition target voltage-transmission characteristics and switching The mode of property controls phase separation structure, forms polymeric web network layers structure appropriate.If specifically describing polymeric web network layers knot Structure, then as described below.

It is excellent to be formed with polymeric web network layers and the consecutive structure of liquid crystal in liquid crystal display element whole face in liquid crystalline phase It is the easy axis of orientation substantially common direction with low molecular weight liquid crystal to select the easy axis of orientation of polymer network, uniaxial optic axis, excellent Choosing forms polymer network in a manner of the pre-tilt angle for inducing low molecular weight liquid crystal, by the average void interval for making polymer network Less than the size of visible wavelength, at least below 450nm, to which light scattering will not occur, thus preferably.Further, in order to logical Crossing the repercussion effect (anchorage force) of polymer network and low molecular weight liquid crystal makes the fall time of response be shorter than low molecular weight liquid crystal The response time of simple substance is preferably set to the range of 50nm~450nm.In order to make the element thickness of liquid crystal to the influence of fall time Become smaller, even if element thickness is thick, also shows that the fall time same with thin thickness, be preferably at least in average void interval Lower limit is near 200nm and the upper limit is the range near 450nm.If reducing average void interval, there are driving voltage increases Project, in order to by the increase of driving voltage inhibit 25V or less and shorten decline the response time, as long as making average void interval It can improve the range to about 5msec to about 1msec to the range of 450nm, decline response time near 250nm, because And it is preferred that.In addition, in order to inhibit the increase of driving voltage within 5V or so, average void interval is preferably made to be in 300nm Nearby to the range of 450nm.Further, the average void interval that also can control polymer network, makes the decline response time be 1msec high-speed responses below.Though driving voltage can increase to 30V or more sometimes, but as long as average void is made to be spaced in 50nm Nearby between near 250nm, in order to reach 0.5msec hereinafter, it is preferred that average void is made to be spaced in 50nm nearby extremely Near 200nm.About the average diameter of polymer network, with average void interval rather, it is preferred to the model in 20nm to 700nm It encloses.If the content of polymerizable compound increases, average diameter has increased tendency.If improving reactivity, accelerating polymerization phase point From speed, then since the density of polymer network increases, the average diameter of polymer network can reduce, as long as needed Adjust phase separation.When polymerizable compound content is 10% or less, preferred average diameter is in 20nm extremely 160nm, when average void interval is in 200nm to 450nm ranges, preferred average diameter is the range of 40nm to 160nm.If Polymerizable compound content is more than 10%, then the range of preferably 50nm to 700nm, the range of more preferably 50nm to 400nm.

Polymeric web network layers and the consecutive structure of liquid crystal are formed with relative in liquid crystal display element whole face, if polymerism Compounds content is lower, the coating unit of polymeric web network layers is not achieved whole required amount, then polymeric web network layers can be discontinuous Ground is formed.If the polarity of the substrate surfaces such as alignment film of polyimide is high, polymerizable compound is easily gathered in liquid crystal cell substrate Near interface, polymer network can grow up from substrate surface and form polymeric web network layers in a manner of being attached to substrate interface, The shape in a manner of stacking gradually polymeric web network layers, liquid crystal layer, polymeric web network layers, opposite substrate from unit substrate surface At.If the stepped construction of polymeric web network layers/liquid crystal layer/polymeric web network layers is presented and is formed with relative to unit section direction At least polymeric web network layers of 0.5% or more, preferably 1% or more, more preferable 5% or more thickness of element thickness, then can The effect that fall time shortens is shown because of the effect of polymer network and the anchorage force of low molecular weight liquid crystal, is shown preferred Tendency.Wherein, since the influence of element thickness becomes larger, when fall time is elongated if adding unit thickness, as long as root According to the thickness for needing increase polymeric web network layers.About the structure of the polymer network in polymeric web network layers, as long as low Molecular liquid crystal and easy axis of orientation, uniaxial optic axis are all towards substantially common direction, as long as being induced with low molecular weight liquid crystal The mode of pre-tilt angle is formed.Average void is preferably spaced the range of 90nm to 450nm.

Such as make polymerizable compound content be 1 mass % to 6 mass % when, it is preferable to use anchorage force it is high have liquid The bifunctional monomer of brilliant base, it is preferable to use the fast bifunctional monomer of the structure and polymerization speed short as distance between functional group, It is preferred that forming polymerization phase separation structure in 0 DEG C of low temperature below.When make polymerizable compound content be 6 mass % to less than 10 matter When measuring %, the preferably combination of the bifunctional monomer and the weak monofunctional monomer of anchorage force, preferably as needed at 25 DEG C~-20 DEG C Range formed polymerization phase separation structure.Further, if the fusing point is room temperature or more, if making its 5 DEG C of left side lower than the fusing point The right side can then obtain effect identical with low temperature polymerization, therefore preferably.When make polymerizable compound content be 10 mass % to 40 matter When measuring %, since polymer adhesive or polymer network can seriously affect the orientation of low molecular weight liquid crystal, driving voltage, make driving Voltage increases, it is therefore preferable that using have the function of the orientation of low molecular weight liquid crystal and anchorage force it is relatively weak with liquid crystal base Polymerizable compound.Such as about anchorage force it is weak and with liquid crystal base polymerizable compound, increase be located at functional group with The carbon number of alkylidene between liquid crystal base is effective, and preferably carbon number is 5~10.In addition, if polymerizable compound is more than 30 Quality %, then also become the state for being dispersed with liquid crystal drop in polymer adhesive sometimes preferably also has in this case The polymer adhesive of refractive anisotrop, and the light of differently- oriented directivity and polymer adhesive that the alignment films of real estate are shown Axis direction is consistent.

The concentration of polymerizable compound in polymerizable liquid crystal compound is higher, the anchor of liquid-crystal composition and polymer interface It is bigger to determine power, τ d get over high speed.On the other hand, if the anchorage force of liquid-crystal composition and polymer interface becomes larger, τ r can low speed Change.In order to make the sum of τ d and τ r be less than 1.5ms, a concentration of 1 mass % of the polymerizable compound in polymerizable liquid crystal compound Less than 40 mass %, preferably 2 mass % or more and 15 mass % hereinafter, more preferably 3 mass % or more and 8 matter Measure % or less.

When driving liquid crystal display element for TFT, it is necessary to inhibit flicker (flicker) and be promoted caused by burn-in The reliability of ghost etc., voltage retention become important characteristic.The reason of thinking that voltage retention is made to reduce is polymerism Contained ionic impurity in liquid-crystal composition.Especially removable ion can seriously affect voltage retention.It is therefore preferable that with It can get at least 10¹⁴The mode of the resistivity of Ω cm or more implements purification process etc., by removable ion remaval.If in addition, Polymer network is formed by free radical polymerization, then sometimes because ionic impurity caused by Photoepolymerizationinitiater initiater etc. leads to electricity Press conservation rate to reduce, preferably selected organic acid, low molecule by-product the few polymerization initiator of production quantity.

[liquid crystal display element]

In the liquid crystal display element of the present invention, the liquid crystal between being held at least one 2 transparent substrate with electrode Contain polymer or copolymer in composition, the content of the polymer or copolymer is the liquid-crystal composition and the polymer or altogether 0.5 mass % of total quality of polymers forms polymer network less than 40 mass %, the polymer or copolymer, should Polymer network has the refractive anisotrop of uniaxiality or easy axis of orientation, and has different state of orientation of more than two kinds. The liquid crystal display element of the present invention preferably has the orientation to make liquid-crystal composition be orientated on the transparent substrate of at least one party Film.Apply voltage to being set to the alignment films of substrate and being set to the electrode of substrate, can control the orientation of liquid crystal molecule.Polymerization Object network or polymer adhesive have the refractive anisotrop of uniaxiality or are easily orientated axis direction, preferred polymers network or The optical axis direction of polymer adhesive is easily orientated the easy orientation axis direction of axis direction and low molecular weight liquid crystal as the same direction.With regard to this Point for, with without uniaxiality refractive anisotrop or easily be orientated axis direction light scattering type polymer network liquid crystal, Polymer dispersion type liquid crystal is different.

Further, the easy easy axis of orientation side for being orientated axis direction and polymer network or polymer adhesive of preferred orientation film To identical.By having polarizer, phase difference film etc., shown using this state of orientation.As liquid crystal display element, can answer For operating modes such as TN, STN, ECB, VA, VA-TN, IPS, FFS, π unit, OCB, cholesteryl liquid crystals.Wherein, particularly preferably For VA, IPS, FFS, VA-TN, TN, ECB.It should be noted that in liquid crystal display element of the invention, with regard to containing in liquid-crystal composition For the aspect for having polymer or copolymer, with the PSA (Polymer with polymer or copolymer in alignment films Sustained Alignment, macromolecule maintain to be orientated) type liquid crystal display element difference.

The content of polymer or copolymer in liquid-crystal composition is the liquid-crystal composition and the polymer or copolymer 0.5 mass % of total quality is less than 40 mass %, as lower limiting value, preferably 0.7 mass % or more, preferably 0.9 mass % or more, as upper limit value, preferably smaller than 30 mass %, preferably smaller than 20 mass %.

In PSA type liquid crystal display element, a plurality of slit of 3~5 μm of width is arranged in electrode makes liquid crystal towards slit direction Thus tilted alignment omits orientation process to replace friction orientation to handle.In volume production technical aspect, if applying some tens of volts Voltage, and irradiate ultraviolet light simultaneously, then the orientation of liquid crystal can be to obtain pre-tilt angle (relative to inclining for substrate normal in substrate interface Oblique angle) mode it is polymer-stabilized, form the film of polymer.Pre-tilt angle can be lured because of the effect of the macromolecule membrane Hair, using this phenomenon, and can be used in PSVA (polymer-stabilized vertical alignment, polymer stabilizing Vertical orientation) LCD or PSALCD manufacture.In addition, in order to promote angle of visibility, and use the pattern electricity for being designed as to be formed multiple domain Pre-dumping angular direction in one pixel is divided into multiple by pole.When using with negative dielectric anisotropic liquid crystal when, if with from Voltage more than saturation voltage is applied to by the mode that the vertical orientation of liquid crystal is converted to curved orientation (bend alignment) Unit simultaneously irradiates ultraviolet light, then when the micro monomer made an addition in liquid crystal polymerize on vertical alignment layer, can form alignment films, The alignment films make to occur polymer-stabilized as flexural deformation end and the orientation of liquid crystal that is slightly tilted and induce pre-tilt angle.By This, if terminating irradiation ultraviolet light, interrupting application voltage, (pre-tilt) vertical orientation that can be slightly tilted.If however, will The method is applied to that polymer network etc. can be integrally formed in unit and the liquid crystal display element that improves the relaxation time of response, then Due to the voltage for some tens of volts for applying saturation voltage or more, ultraviolet light irradiation is carried out, polymer network can make liquid crystal exist Stabilizing polymer under parallel-oriented state.In this way, due to can be formed in such a way that liquid crystal molecule is held in parallel-oriented state The refraction ansiotropy of polymer network or easy axis of orientation, therefore vertical orientation can be unable to get.

For the LCD of vertical orientating type, in order to make the well azimuth of tilted alignment consistently court by applying voltage Certain orientation, by assigning the pre-tilt angle relative to unit normal direction within 2 degree, come when seeking to improve transmissivity, response Between equal electro-optic properties.However, in order to form the polymer network being slightly tilted in a manner of inducing pre-tilt angle, it is believed that apply The voltage of the threshold voltage of a little higher than liquid crystal makes liquid crystal be formed in the state of tilted alignment within 2 degree.However, in PVA (Patterned vertical alignment pattern vertical orientation) etc. makes tilted alignment direction fix by electrode shape In consistent liquid crystal display element, if the refraction ansiotropy for applying the low-voltage of near threshold voltage, forming polymer network Or easy axis of orientation, then it can be not fixed because of the tilted alignment orientation of liquid crystal, and transmissivity is declined.Its reason is：If applying The voltage of near threshold voltage, then simply because curved orientation is slightly distorted into, one end of the alignment films side of flexural deformation is substantially hung down Directly, the influence of vertical alignment layer is big, therefore the liquid crystal near substrate interface can become vertical orientation, therefore attached in substrate interface Tilted alignment orientation can not closely be provided, towards certain orientation, to become unstable.On the other hand, if applying the full of electro-optic properties With high voltage more than voltage, then the liquid crystal near substrate interface can become inclined state of orientation, and electric-field strength, therefore, by scheming The influence of field distribution caused by pattern electrode can become larger, and tilted alignment orientation becomes certain orientation, can help to promote transmissivity. However, since parallel-oriented polymer network can be formed in unit entirety, vertically taken as described above, can be unable to get To.

Type of the tilted alignment orientation due to largely depending on electrode pattern, such as shown in Figure 13 Fish-bone (Fishbone) type electrode, alternatively repeat fine line electrode configured with a plurality of 3~5 μm or so width and with line electricity The linear slit of extremely same width, the tilted alignment orientation of liquid crystal is in the pattern electrode, and the liquid crystal on line electrode can be orientated At parallel generally towards slit direction.Make towards the fixed orientation memory of slit direction therefore, it is necessary to make it have tilted alignment orientation Refraction ansiotropy for polymer network or easy axis of orientation.In addition, working as axial symmetry vertical orientation (Axially Symmetric Vertical Alignment) pattern electrode in the case of, to be made of the counter electrode of point electrode and approximating square Sub-pixel structure.Though central shaft perpendicular orientation applying voltage, using the point electrode of central shaft as starting point, liquid crystal is axial (liquid crystal director) tilted alignment is at radial.When element seen from above, tilted alignment orientation is, Liquid crystal is axially continuously orientated from central shaft with radial 360 degree.If by applying high voltage, in a part for polymer network So that state of orientation is occurred polymer-stabilized, then can form one in such a way that the generation of radial tilted alignment orientation is stabilized Partial polymer network.If making voltage be less than threshold voltage in ultraviolet light irradiation, to make liquid crystal revert to substantially vertical take To, and continue to irradiate ultraviolet light in this case, then the folding of polymer network can be formed in a manner of as being approximately vertically oriented Anisotropy or easy axis of orientation are penetrated, radial tilted alignment orientation can remain on polymer network, Neng Goutong in the form of track When take into account apply voltage when tropism control with without apply voltage when vertical orientation.

That is, in the liquid crystal display element of PVA, coexisting two different makes the poly- of liquid crystal aligning in stable conditionization Polymeric network, above two different polymer different to the influence power of liquid crystal aligning to the polymer network of each self-forming Network is respectively：In order to keep the obtained state of orientation of the voltage of application threshold voltage or more polymer-stabilized, with liquid crystal The consistent mode of state of orientation forms the case where refractive anisotrop of polymer network or easy axis of orientation；And in order to make to apply Add, by with liquid crystal aligning state consistency in a manner of shape polymer-stabilized less than the obtained state of orientation of voltage of threshold voltage At polymer network refractive anisotrop or easy axis of orientation the case where.If for example, only forming the liquid made less than threshold voltage The brilliant stabilized polymer network of state of orientation, then when making liquid crystal aligning change by switching voltage, due to being carried out autohemagglutination The state of orientation of the influence of polymeric network, liquid crystal can be different from the liquid crystal aligning state needed for liquid crystal display element script, therefore The orientation after changing is orientated when the switch of PVA units to deform, and be unable to get desired state of orientation, and is imitated to electrooptics Fruit impacts, the declines such as contrast, transmissivity.Therefore, apply threshold voltage or more by making to have coexisted in polymer network The obtained state of orientation of voltage be less than the obtained state of orientation of voltage of threshold voltage both state of orientation with applying, The orientation between two states may make to become easy, display characteristic becomes good.Therefore, in order to make the liquid crystal of threshold voltage or more State of orientation is polymer-stabilized with the liquid crystal aligning state for being less than threshold voltage, is mixed according to both state of orientation Mode is formed in polymer network, it is preferable that a part for the polymerizable compound contained in polymerizable liquid crystal compound is used for Liquid crystal aligning in stable conditionization of threshold voltage or more, remaining polymerizable compound is set to be used in so that less than threshold voltage The polymer network that the mode of liquid crystal aligning in stable conditionization is formed.If after the voltage for applying threshold voltage or more, in ultraviolet light Apply the voltage less than threshold voltage in polymerization, though the transformation of liquid crystal aligning can then occur, when changing herein sometimes It is orientated defect, if this is orientated defect by polymer-stabilized, is less than the homogeneity meeting of the liquid crystal aligning state of threshold voltage It is impaired, become the decrease reason of contrast, transmissivity, it is not preferable.Voltage especially more than threshold voltage is saturation electricity When pressing above, if making it become less than the voltage of threshold voltage during irradiating ultraviolet light, causes liquid crystal aligning to change, then can A large amount of orientation defects occur.Therefore, it is necessary to by applying saturation voltage voltage below, to be orientated when inhibiting orientation transition Defect (to wrong (disclination)), but simultaneously as above-mentioned, since the inclination of the liquid crystal of substrate interface dies down, well azimuth side To becoming unstable, it is not preferable.In order to inhibit the orientation defect occurred by the orientation transition in polymerizable ultraviolet, apply from Voltage drop more than threshold voltage in polymerizable ultraviolet at least applies liquid down to the medium voltage of threshold voltage voltage below Brilliant the time more than response time, the time that the formation of polymer network will not be preferably impacted, as long as that can press down The time for being orientated defect occurs for system, as long as the time that orientation defect will not be made polymer-stabilized, depends on liquid The reactivity of polymerizable compound in crystalline substance, within preferably at least 5 seconds.In addition, medium voltage is preferably at least in threshold voltage Above and in saturation voltage hereinafter, being middle gray voltage.The preferably rectangular wave of waveform, preferably voltage according to threshold voltage with On voltage, medium voltage, threshold voltage voltage below the stage shape waveform that is lower of sequential stages ground.In addition, intermediate Voltage is alternatively the voltage drop that makes voltage continuously more than threshold voltage down to the oblique wave (ramp of threshold voltage voltage below wave).Further, in order to make orientation defect not remained by after polymer-stabilized to apply the method other than medium voltage, Midway can be irradiated in ultraviolet light, cut off the voltage of threshold voltage or more, irradiated with ultraviolet light is interrupted with applying voltage synchronous, again Applying liquid crystal aligning can be as such threshold voltage voltage below be approximately vertically oriented, with voltage synchronous again at this moment Irradiate ultraviolet light.That is, when continuously irradiating ultraviolet light, apply medium voltage when the liquid crystal aligning transformation in irradiation ?.And when discontinuously irradiating ultraviolet light, then ultraviolet light irradiation is being interrupted in a flash when liquid crystal aligning changes, and turning Ultraviolet light is irradiated again at the time of becoming end.

Further, there is the polymeric web for the stabilized effect of state of orientation for respectively keeping both different due to that can become The state that network is mixed, therefore, forming liquid crystal aligning state of element when without voltage is applied after polymer network can be by To the influence of the polymer network of two kinds of different orientation states of desired holding, the equilibrium of the influence power of each polymer network can determine Liquid crystal aligning state when without application voltage.For example, in the liquid crystal display element of vertical alignment mode, if enhancing makes to be less than threshold The influence power of the polymer network of liquid crystal aligning in stable conditionization of threshold voltage, then liquid crystal display element can show needed for script Vertical orientation improves the contrast of liquid crystal display, thus preferably.On the contrary, if the liquid crystal aligning of threshold voltage or more is made to stablize The influence power of the polymer network of change is too strong, and there will be the tendencies that the increase of the pre-tilt angle of liquid crystal, contrast decline.In order to improve liquid Transmissivity, the contrast of crystal display element are promoted and show quality, make the polymer of two different liquid crystal aligning in stable conditionization The balanced adjustment of the respective influence power of network is important, such as in PVA units, if according to the liquid crystal for making threshold voltage or more Polymer network its influence power that the stabilized mode of state of orientation acts on is too strong, black although then maximum transmission rate can be promoted Level can increase, and contrast is caused to decline.If in addition, in the way of making liquid crystal aligning in stable conditionization less than threshold voltage Its influence power of the polymer network of effect is too strong, though good black level then can be obtained, maximum transmission rate can be caused to decline, Contrast reduces, not preferably.

If apply curved orientation deformation etc. liquid crystal can inclined voltage, so that the orientation of the tilted alignment of liquid crystal is fixed, then most Big transmissivity can be promoted, therefore, if first according to make tilted alignment orientation as fixed mode, so that make threshold voltage with On liquid crystal aligning in stable conditionization and formed polymer network influence it is minimum, then ultraviolet light irradiate midway apply be less than The voltage of threshold voltage forms polymer network, so as to substantially perpendicular orientation in stable conditionization of good black level can be obtained, Good black level can then be become, the orientation of tilted alignment, which can become, to be fixed, and maximum transmission rate can be got higher, and therefore, height can be obtained Contrast, display quality is promoted, to preferably.At this point, in order to make according to make tilted alignment orientation become fixed mode The influence power of the polymer network of formation is minimum, preferably applies the voltage of threshold voltage or more to form polymer network, and And voltage application time is that tilted alignment is made by the completely polymer-stabilized time, can not to apply in ultraviolet light irradiation When threshold voltage voltage below, continue to irradiate ultraviolet light in the way of it can be approximately vertically oriented.

[manufacturing method of liquid crystal display element and the effect of polymer network]

The manufacturing method of the liquid crystal display element of the present invention, for the method containing following processes：To being held at least one Polymerizable liquid crystal compound between 2 transparent substrates with electrode, apply the threshold voltage of the polymerizable liquid crystal compound with On voltage and irradiate ultraviolet light simultaneously, carry out polymerization phase separation process；And then make in the state of irradiating ultraviolet light Voltage is less than threshold voltage, and further irradiates the process of ultraviolet light.It is following method as a result,：It is formed respectively by threshold value The state of orientation of liquid crystal more than voltage with less than threshold voltage liquid crystal the stabilized polymer network of state of orientation, make by The polymer network of two kinds of different liquid crystal aligning in stable conditionization is formed with being mixed.In addition, when being to contain pattern electrode list When the vertical alignment mode liquid crystal display element of member etc., the electricity preferably more than the threshold voltage for applying polymerizable liquid crystal compound It presses and irradiates simultaneously in the process that ultraviolet light carries out polymerization phase separation, it is preferable that under curved orientation deformation, polymerizable liquid crystal group The liquid crystal molecule closed in object is obliquely taken relative to transparent substrate plane with 0 degree to 30 degree of range near transparent substrate plane To, and so that aforesaid voltage is less than in threshold voltage and the further process of irradiation ultraviolet light in the state of irradiating ultraviolet light, greatly Cause vertical orientation, near transparent substrate plane, foregoing liquid crystal molecule relative to transparent substrate plane tilt 80 degree to 90 degree and It is orientated.It is pair of liquid crystal with the state of 0 degree to 30 degree of range tilted alignment relative to transparent substrate plane about liquid crystal molecule Increased state is presented because applying voltage in refractive index, double if the state of orientation of liquid crystal is 0 degree relative to transparent substrate plane Refractive index can be maximum, is preferred, even if be tilt 30 degree relative to base plan and be orientated, it is also preferred that.It is especially mono- in PVA In member, since well azimuth can be made to be fixation, thus preferably.No matter which kind of situation, all preferably according to application voltage is made caused by LC tilt orientation becomes the mode of fixed-direction, and formation makes the stabilized polymer network of orientation.

At this point, in order to make the influence power pole for becoming the polymer network that fixed mode is formed according to tilted alignment orientation It is small, apply the voltage of threshold voltage or more in ultraviolet light irradiation, so that liquid crystal is generated curved orientation deformation, but preferably make this state Time be less than apply threshold voltage voltage below time, as long as when terminate apply threshold voltage more than voltage when for hair The state of raw orientation transition.When the influence for making to become the polymer network that certain mode is formed according to tilted alignment orientation When power is strong, pre-tilt angle can increase and be unable to get required black level, therefore, in order to avoid such case, if being shone in ultraviolet light It hits and applies threshold voltage voltage below, then can be deformed from curved orientation to being approximately vertically oriented transformation, and it is purple to continue irradiation Outside line preferably makes do not have remaining polymerizable compound in liquid crystal.It is preferred that making aforementioned electricity in the state of irradiating ultraviolet light Pressure is less than threshold voltage and further irradiates in the process of ultraviolet light, and main polymer network is made to be formed.At this point, pre-tilt angle Size can depend on applying the ratio of the time and the time for applying threshold voltage voltage below of the voltage of threshold voltage or more, Apply threshold voltage more than time, be do not formed completely from liquid crystal in polymerize phase separation polymer network at the beginning of Beginning state to polymerization is separated at first until at the time of a part is formed with polymer network, if preferably stopping applying electricity Pressure then can be from curved orientation recoverable force at the state being approximately vertically oriented.Apply the time of the voltage of threshold voltage or more, it is excellent It is selected as 1 second to 15 seconds.When changing to next process from this process, orientation transition preferably is occurring as the shape being approximately vertically oriented Apply threshold voltage voltage below under state and irradiate ultraviolet light, be preferably formed entirely of polymer network, make it is not residual in liquid crystal The polymerizable compound stayed.The state for applying threshold voltage voltage below is the state that is approximately vertically oriented, but is alternatively slightly Curved orientation deformation, adjust voltage as needed required black level and tilted alignment orientation made to become and fix.It should be noted It is that the time for applying threshold voltage voltage below can be until the formation of polymer network substantially terminates, when remaining on It can not apply if amount of monomer in liquid crystal is to be micro and when will not impact electro-optic properties residual monomer polymerize Threshold voltage voltage below.

Further, it is aforementioned application threshold voltage more than voltage and irradiate simultaneously ultraviolet light carry out polymerization phase separation work Sequence and between then making in the state of irradiating ultraviolet light voltage be less than threshold voltage and irradiating the process of ultraviolet light, may also set up Apply in the state of irradiating ultraviolet light at least more than threshold voltage and the process of saturation voltage middle gray voltage below. Middle gray voltage is preferably smaller than the application voltage of initial process and more than threshold voltage.Middle gray voltage is in order to postpone It deforms to the transformation being approximately vertically oriented and applies from curved orientation.The hair of defect is orientated due to can inhibit by carryover effects It is raw, therefore preferably apply as needed.

The shape for tilting 80 degree to 90 degree in the form of pre-tilt angle relative to transparent substrate plane about liquid crystal molecule and being orientated State, if liquid crystalline phase is orientated transparent substrate plane in 90 degree when without voltage is applied, birefringence can become minimum, right It is useful and preferred in the high contrastization of liquid crystal display element, but taken to make it tilt towards fixed-direction when applying voltage To, more preferably in the form of pre-tilt angle relative to base plan tilt 89.9 degree to 85 degree within.If relative to base plan More than 80 degree, then since birefringence and light transmission capacity can increase, and so that the contrast of display declines, not preferably, relative to For base plan at 85 degree or more, the black level of display can become good, high contrast can be obtained, therefore preferably.In addition, IPS (In-plane switching, in-plane switching) display pattern, FFS (cut by Fringe Field Switching, fringing field Change) pattern, TN (Twisted Nematic, twisted-nematic) pattern liquid crystal display element in, preferably also：It polymerize applying Property liquid-crystal composition threshold voltage more than voltage and irradiate simultaneously ultraviolet light carry out polymerization phase separation process in, polymerism Liquid crystal molecule in liquid-crystal composition depends on applying voltage and the range relative to transparent substrate plane at 0 degree to 90 degree tilts And be orientated, so that aforesaid voltage is less than threshold voltage in the state of irradiating ultraviolet light and further irradiates the process of ultraviolet light In, foregoing liquid crystal molecule depends on applying voltage and tilting 0 degree to 30 degree in the form of pre-tilt angle relative to transparent substrate plane And it is orientated.

It tilts and is orientated in 0 degree to 90 degree of range relative to transparent substrate plane about liquid crystal molecule, according to making application The state of orientation stabilized mode of the liquid crystal of voltage forms polymer network.But precondition is electric when stopping applying When pressure, the liquid crystal aligning state corresponded to less than threshold voltage can be become.In IPS patterns, alignment films used in element The angle of inclination of property influences very big, can contain the liquid crystal molecule of twisted-oriented in 1 degree to 2 degree or so of range, pre-tilt angle Angle of inclination is preferably 0.5 degree to 3 degree, within preferably 0 degree to 2 degree.In the threshold voltage for applying polymerizable liquid crystal compound It above voltage and irradiates simultaneously in the process that ultraviolet light carries out polymerization phase separation, preferably applies the state that can become torsional deformation Voltage, and make in the state of irradiating ultraviolet light aforesaid voltage be less than threshold voltage and further irradiation ultraviolet light process In, so that voltage is less than threshold voltage in the state that torsional deformation is not polymer-stabilized, with as parallel-oriented black The condition of display makes its polymerization.In FFS mode, if applying the voltage of threshold voltage or more, in the state of orientation of liquid crystal, meeting Injection (spray) orientation, curved orientation, twisted-oriented state, but main table have coexisted depending on the field distribution in element Reveal injection to be orientated and twisted-oriented state.Inclination angle under the liquid crystal molecular orientation state of these states is at 0 degree to 45 degree Range, it is preferably stabilized with same range if making orientation stabilize with polymer network.But precondition is When stop apply voltage when, become corresponding to less than threshold voltage liquid crystal state of orientation, preferably from these states restore to As parallel-oriented state, and irradiate ultraviolet light.And in TN patterns, preferably 45 degree of angles of inclination to 90 degree of ranges.

On the other hand, though applying the voltage less than threshold voltage, according to making the stabilized mode shape of the state of orientation of liquid crystal At polymer network, but in the case of IPS patterns, FFS mode and TN patterns, due to friction orientation processing, in substrate interface Pre-tilt angle be 1 degree~3 degree or so, it is therefore preferable that according to the liquid crystal aligning state for making to be applied with the voltage less than threshold voltage Stabilized mode forms polymer network, and the angle of liquid crystal aligning can also tilt in the range, using optical alignment film etc. its His method for orientation treatment, the angle of inclination for the liquid crystal molecule that pre-tilt angle contains twisted-oriented is preferably 0.5 degree to 3 degree, and 0 degree extremely It is useful for obtaining wide angle of visibility within 2 degree, more preferably.

Furthermore it is preferred that apply voltage be AC wave shape, and with polymerizable liquid crystal compound show dielectric respectively to The frequency of anisotropic range.Waveform is preferably the rectangular wave that effective voltage can be made high when peak voltage is set as fixed.Frequency it is upper Be limited to be transferred to by the driving circuit used in liquid crystal display element pixel signal will not decay in the range of frequency , preferably at least frequency is in 2kHz or less.The dielectric constant shown about the polymerizable liquid crystal compound before irradiation ultraviolet light Frequency dependence, the frequency meter shown with dielectric anisotropy is in 10kHz or less.About lower limiting value, work as driving element When will produce flicker sometimes, lower limiting value is to make to flicker minimum frequency at this time, preferably at least in 20Hz or more.

The manufacturing method of the liquid crystal display element of the present invention has as described above according to two kinds of liquid crystal aligning states of holding Mode form the feature of polymer network, in order to which the polymer network for keeping each liquid crystal aligning state and being formed is formed as poly- The refractive anisotrop of polymeric network or easy axis of orientation with it is more than threshold voltage liquid crystal aligning direction or be less than threshold voltage Liquid crystal aligning direction it is consistent.Generating as a result, makes the stabilized polymer network of liquid crystal aligning when application voltage be applied with nothing is made The state that the stabilized polymer network of liquid crystal aligning when making alive coexists, liquid crystal aligning when can inhibit from without application voltage The orientation that state occurs when making it be orientated deformation by applying voltage distorts, and can promote contrast etc. improves display characteristic.It is another Aspect, only for the polymer network that is formed in the way of keeping without liquid crystal aligning state when applying voltage, when to applying When liquid crystal aligning state transformation when making alive, the polymer that is formed in the way of the liquid crystal aligning for remaining less than threshold voltage The influence power of network is strong, therefore, when changing to liquid crystal aligning state more than threshold voltage, will produce orientation distortion, becomes The reason of making transmissivity decline.Keep liquid crystal aligning when application voltage stabilized by making a part for polymer network be formed Polymer network can inhibit the distortion that the orientation occurred by switch changes, the change of the liquid crystal aligning needed for script can be obtained, Promote transmissivity.It should be noted that according to when making application voltage and without each liquid crystal aligning in stable conditionization when applying voltage The polymer network that mode is formed is characterized in that, polymer network is formed in the way of along two different liquid crystal alignings Refractive anisotrop or easy axis of orientation.

Further, the application time of the voltage more than threshold voltage in being irradiated according to ultraviolet light, in order to make threshold voltage Above mesomorphic state stabilizes and the influence power of the polymer network of formation changes, and electro-optic properties can be changed.For example, It is comprising the parallel-oriented of the tilted alignment for being in 0 degree to 30 degree relative to base plan to make liquid crystal aligning state when application voltage And in the case of forming polymer network, if shortening the application time of the voltage of the threshold voltage in ultraviolet light irradiation or more, The effect that keeping parallelism is orientated is minimum, therefore liquid crystal is orientated under the action of keeping the polymer network of vertical orientation.Further, Carry out the influence power equilibrium that the polymer network of two kinds of different orientations of self-sustaining is orientated for two, relative to transparent substrate normal side To the pre-tilt of the angle within as low as 1 degree of induction.When the application of the voltage more than threshold voltage in being irradiated with ultraviolet light Between increase, the influence of polymer network that keeping parallelism is orientated can become strong, thus pre-tilt angle can because keep the power of vertical orientation with Keeping parallelism be orientated power between equilibrium and increase, can increase pre-tilt angle and relative to transparent substrate normal direction 10 degree with On.In addition, the application time of voltage more than threshold voltage in ultraviolet light irradiation be heavily dependent on used in it is poly- The reactivity that conjunction property liquid-crystal composition has, therefore be preferably properly adjusted to obtain desired pre-tilt angle.Particularly preferably It is adjusted to obtaining pre-tilt angle in 80 degree to 90 degree of range relative to base plan, is more preferably adjusted to 85 degree to 89.9 degree, Further preferably it is adjusted to 87 degree to 89.9 degree.

About in order to keep by apply threshold voltage more than voltage obtained from liquid crystal state of orientation by formed Polymer network is desired for parallel-oriented in the liquid crystal display element using the vertical alignment mode of negative dielectric anisotropic The fixed tilted alignment of state or azimuth.It is preferably substantially vertical with the state of orientation obtained less than the voltage of threshold voltage It is orientated, is particularly preferably in 80 degree to 90 degree of substantially perpendicular orientation relative to base plan, preferably shows as can be obtained The state of orientation of good black level as high contrast.Using utilizing negative dielectric anisotropic or positive dielectric anisotropy In IPS (In-plane switching, in-plane switching) display pattern of transverse electric field, apply the threshold value electricity in ultraviolet light irradiation The obtained liquid crystal aligning state of voltage more than pressure is preferably twisted-oriented.The orientation obtained with the voltage less than threshold voltage State is preferably that azimuth is fixed parallel-oriented.In FFS (Fringe Field Switching, fringing field switching) pattern In, the obtained state of orientation of voltage for preferably applying threshold voltage or more in ultraviolet light irradiation is at least curved orientation, injection It is orientated, any one or a variety of state of orientation being mixed of tilted alignment.Less than under threshold voltage, preferably substantially put down Row is orientated.After forming polymer network by way of the state of orientation of liquid crystal when according to keeping applying voltage, make to be less than The state of orientation of the liquid crystal of threshold voltage is polymer-stabilized, so as to easily to polymer network formed after be applied with The state of orientation of liquid crystal when voltage carries out orientation deformation, can take into account high-transmission rate and high-speed response simultaneously.

Applications voltage when irradiating ultraviolet light is preferred to carry out the appropriate liquid crystal being adjusted so that after polymer network is formed Show that the display of element becomes high contrast, due to being heavily dependent on the polymerizable liquid crystal compound before irradiating ultraviolet light The characteristic of electrooptics effect, therefore, it is necessary to be matched with the voltage-transmission rate characteristic shown by polymerizable liquid crystal compound.Make For voltage more than threshold voltage, preferably voltage V10 or more, wherein electricity of the voltage V10 relative to polymerizable liquid crystal compound Transmissivity total variation in pressure-transmission characteristics voltage is 10% or more, more preferable voltage V20 or more, wherein voltage V20's Transmissivity total variation is 20% or more, more preferably voltage V50 or more, and the wherein transmissivity total variation of voltage V50 is 50% or more.However, it is preferred to for 6 times of voltages below of critical voltage.About the threshold voltage applied in ultraviolet light irradiation Above voltage preferably applies alternating voltage, preferably applies rectangular wave.Frequency is preferably to go out the frequency of flicker with visual None- identified Rate, when being formed with the electronic circuits such as TFT substrate on the glass substrate, as long as the frequency of coincidence voltage attenuation will not occur i.e. Can, preferably 30Hz to 5kHz or so.

Although the voltage applied in ultraviolet light irradiation way is made to become smaller than threshold voltage more than threshold voltage, make For the voltage less than threshold voltage, as long as the range that will not change by voltage of orientation of liquid crystal, preferably 0V or more And less than 90% voltage of threshold voltage, preferably less than 80% voltage, more preferably 70% or less.Though in addition, in purple Application voltage is set to be threshold voltage in outside line irradiation hereinafter, but liquid crystal when being preferably restored to liquid crystal display element OFF at this time State of orientation, for example, vertical orientation can be reverted in vertical alignment mode as described above, FFS mode, IPS patterns then It can become parallel-oriented.In order to be restored to liquid crystal aligning state when liquid crystal display element OFF, preferably when making application voltage The stabilized polymer network of liquid crystal aligning its influence power it is minimum in the state of reduce into the voltage less than threshold voltage.

Ultraviolet light is irradiated after the voltage for applying threshold voltage or more, if but voltage application time becomes in ultraviolet light irradiation Long, then the influence power of the stabilized polymer network of liquid crystal aligning when applying voltage in making ultraviolet light irradiate will increase, will not Liquid crystal aligning state when required liquid crystal display element OFF is reverted to, not preferably.It is therefore preferable that by most suitable ultraviolet Voltage in line irradiation suitably optimizes, to manufacture the liquid crystal display element of the present invention.In addition, the voltage in making ultraviolet light irradiate When less than threshold voltage, it has been alternatively the response relaxation time of the liquid crystal of adjustment polymerizable liquid crystal compound, and has been shone in ultraviolet light Penetrate reduces voltage at leisure on the way, makes to apply response relaxation time of the alive fall time than the liquid crystal in ultraviolet light irradiation Long, it is bottom line so that response is mitigated the influence of the adverse current (back flow) generated in the process, when applying alive decline Between preferably 10ms within 1000ms.In addition, on the contrary, the case where rapid decrease is also possible, preferably at least set Short, the preferably 100ms or less for relaxation time for being shown than polymerizable liquid crystal compound.

By irradiating ultraviolet light in the state of applying the voltage of threshold voltage or more, thus it is partly formed parallel-oriented The polymer network of ingredient continues to irradiate ultraviolet light and voltage is made to be less than threshold voltage simultaneously, liquid crystal is thus made to revert to vertically It is orientated, to complete polymerization phase separation.In fish bone well electrode liquid crystal cells, it can be taken with vertical by above-mentioned parallel-oriented ingredient Change pre-tilt angle to the ratio of ingredient, voltage is removed if being formed in initial procedure in polymer network, tilted alignment orientation will It can be fixed up, then vertical orientation is formed with residual monomer, vertical orientation and tilted alignment orientation can be taken into account as a result, be nanometer The tropism control technology of phase separation liquid crystal.

It should be noted that so-called parallel-oriented state, means and applies voltage to which negative dielectric anisotropy liquid crystal becomes It is oriented generally parallel state, the range preferably with respect to real estate at 0.1 degree to 30 degree, preferably with 0.1 degree to 10 degree of range Tilted alignment.Vertical orientation when the so-called voltage without application, mean becomes substantially vertical because of the effect of vertical alignment layer takes To state, the orientation of liquid crystal tilts 80 to 89.9 degree preferably with respect to base plan and is orientated, and more preferably tilts 85 degree to 89.9 Degree.

In the case of positive dielectric anisotropy liquid crystal, if applying voltage, though vertical orientation, liquid crystal aligning can be obtained State also include liquid crystalline phase for base plan with 45 degree to 89.9 degree of range tilted alignment.

Without parallel-oriented when applying voltage, mean to become because of the effect of parallel-oriented film and be oriented generally parallel shape State, the orientation of liquid crystal include tilting 0.1 to 30 degree relative to base plan and being orientated.

Therefore, the manufacturing method of liquid crystal display element of the present invention preferably has following processes：Light irradiation process, it is right The polymerizable liquid crystal compound irradiation ultraviolet light being held between at least one 2 transparent substrate with electrode；And voltage is applied Sequence is processed, between polymerizable liquid crystal compound of the aforesaid clip at least one 2 transparent substrate with electrode, it is poly- to apply this The voltage more than threshold voltage of conjunction property liquid-crystal composition.It is preferred that at the time of stating light irradiation process before start, apply aforementioned electricity Press the voltage of applying step.Therefore, aforesaid voltage applying step is penetrated process with abovementioned light and can be carried out at the same time, and can also be to be later than Aforesaid voltage applying step and start abovementioned light and penetrate process.Furthermore it is preferred that occur when orientation transition when applying voltage It is orientated the stage that defect has disappeared, starts abovementioned light and penetrates process.

For example, in the case that orientation defect hardly happens when applying voltage, it is aforementioned that (or progress) can be started simultaneously at Voltage applying step penetrates process with abovementioned light, also interrupting or stopping aforesaid voltage applying step can penetrate work with abovementioned light simultaneously Sequence can carry out as follows：Abovementioned light is carried out under the ON states of liquid crystal cell penetrates process, in the midway of polymerization process, Before the orientation of ON states will be stabilized because forming polymer network, aforesaid voltage applying step is interrupted, in liquid crystal cell OFF state under, only carry out abovementioned light and penetrate process, make to remain on polymerizable compound in liquid crystal and disappear.In addition, from ON shapes State preferably interrupts ultraviolet light irradiation, prevents polymer network from being formed between the orientation transition of OFF state.

During following (time)：To being held at least one 2 transparent substrate with electrode Between polymerizable liquid crystal compound apply the voltage of the threshold voltage of the polymerizable liquid crystal compound or more in the state of, irradiation is purple Outside line applies the voltage of the threshold voltage of the polymerizable liquid crystal compound or more.In other words, have to being held at least one Polymerizable liquid crystal compound between 2 transparent substrates of electrode applies the electricity of the threshold voltage of the polymerizable liquid crystal compound or more It presses and irradiates ultraviolet light simultaneously and polymerize in the process of phase separation, it can be when carrying out aforesaid voltage applying step It carries out abovementioned light and penetrates process, preferably abovementioned light is be overlapped with during aforesaid voltage applying step during penetrating process.

The preferred embodiment of liquid crystal display element manufacturing method of the present invention is to have electricity to being held at least one In the light irradiation process of polymerizable liquid crystal compound irradiation ultraviolet light between 2 transparent substrates of pole, as long as being irradiated purple Outside line and can from ON states to OFF state occur orientation transition, voltage applying step is preferably 3~30 seconds, more excellent It is selected as 5~10 seconds, being preferably arranged to voltage applying step when interrupting light irradiation, during the interruption of ultraviolet light irradiation just terminates Afterwards.Can terminate in liquid crystal aligning transition process, state of orientation be in balance in the state of restart ultraviolet light irradiation, terminate aforementioned light Irradiation process.

The present invention liquid crystal display element manufacturing method in, it is preferable that be held on it is aforementioned at least one have electricity Polymerizable liquid crystal compound between 2 transparent substrates of pole applies the voltage of the threshold voltage of the polymerizable liquid crystal compound or more Time transfer receiver be held on polymerizable liquid crystal compound between at least one 2 transparent substrate with electrode irradiation ultraviolet light Time is short.

It is transparent to being held at least one 2 with electrode in the manufacturing method of the liquid crystal display element of the present invention The voltage that polymerizable liquid crystal compound between substrate applies the voltage of the threshold voltage of the polymerizable liquid crystal compound or more applies 1 time or more multiple (2 times, 3 times or more 10 times or less) can be arranged in process.At this time apply alive size respectively can it is identical or It is different.It is preferably different.As the mode of the voltage applying step, preferably following manner：To being held at least one tool In the state of having the polymerizable liquid crystal compound irradiation ultraviolet light between 2 transparent substrates of electrode, it is poly- that this is applied with the stipulated time 1 time more than threshold voltage of conjunction property liquid-crystal composition voltage (V₁) as after 1 voltage, in the state of irradiating ultraviolet light, Apply threshold voltage or more and 1 voltage (V₁) medium voltage (V below_m)。

In the manufacturing method of liquid crystal display element of the present invention, multiple (2 times, 3 times of 1 time or more can be also carried out Above 10 times or less) following voltage applying steps：Apply above-mentioned polymerizable liquid crystal compound in the state of irradiating ultraviolet light Threshold voltage voltage below.Alive size of applying at this time respectively may be the same or different.In addition, when applying threshold voltage When voltage below, can periodically by apply voltage drop be carried out down to threshold voltage voltage below, also can continuously by Apply voltage drop to carry out down to threshold voltage voltage below.

In above-mentioned preferred embodiment, if after the voltage for applying threshold voltage or more, apply in polymerizable ultraviolet small In the voltage of threshold voltage, then occur to be orientated defect when the transformation of liquid crystal aligning can occur, but sometimes herein changing, if this takes To defect by polymer-stabilized, then the homogeneity of liquid crystal aligning state when being less than threshold voltage can be damaged, and as pair Than degree, the decrease reason of transmissivity, it is not preferable.When voltage especially more than threshold voltage is saturation voltage or more, if The voltage less than threshold voltage is changed into ultraviolet light irradiation, causes liquid crystal aligning to change, then can occur largely to be orientated defect.Cause This, it is necessary to is by applying saturation voltage voltage below, to occur to be orientated defect (to mistake) when inhibiting orientation transition, but simultaneously such as Above-mentioned such, the inclination of the liquid crystal of substrate interface can die down, and well azimuth direction becomes unstable, and it is not preferable.In order to inhibit The orientation defect occurred when orientation transition in polymerizable ultraviolet applies the voltage more than the threshold voltage in polymerizable ultraviolet The medium voltage reduced to threshold voltage voltage below, applies the time more than response time of at least liquid crystal, preferably not The time that can be impacted to the formation of polymer network can be the time that can inhibit to occur to be orientated defect, can be not Orientation defect can be made to carry out the polymer-stabilized time, the reactivity of the polymerizable compound in liquid crystal is depended on, preferably exist Within at least 5 seconds.In addition, medium voltage is at least more than threshold voltage and in saturation voltage hereinafter, preferably middle gray electricity Pressure.The preferably rectangular wave of waveform, preferably following stage shape waveform：Voltage is according to voltage, intermediate more than threshold voltage The sequential stages of voltage, threshold voltage voltage below it is lower.Can be to make voltage from threshold value in addition, about intermediate voltage Voltage more than voltage is continuously reduced to the oblique wave of threshold voltage voltage below.Further, it to utilize and apply medium voltage Method in addition make orientation defect do not occur it is polymer-stabilized and when remaining, irradiate midway in ultraviolet light, cut off threshold voltage Above voltage, but with apply voltage synchronous interrupt ultraviolet light irradiation, again apply threshold voltage voltage below so that Liquid crystal aligning, which becomes, to be approximately vertically oriented, and with voltage synchronous can irradiate ultraviolet light again at this moment.That is, continuously When irradiating ultraviolet light, apply medium voltage when the liquid crystal aligning transformation in irradiation.And when discontinuously irradiating ultraviolet light, When liquid crystal aligning changes, then instantaneous interruption ultraviolet light irradiates, and irradiates ultraviolet light again at the time of transformation finishes.

It is preferably formed as making the stabilized polymer network of orientation, so that the LC tilt orientation for applying voltage formation is Fixed-direction.At this point, in order to make the influence power pole for becoming the polymer network that fixed mode is formed according to tilted alignment orientation It is small, apply the voltage of threshold voltage or more in ultraviolet light irradiation, so that liquid crystal is generated curved orientation deformation, but preferably make this state Time be less than apply threshold voltage voltage below time, when terminate apply threshold voltage more than voltage when, for occur The state of orientation transition.When the influence power for becoming the polymer network that certain mode is formed according to tilted alignment orientation is strong When, it is unable to get required black level since pre-tilt angle can increase, in order to avoid such case, if being shone in ultraviolet light It hits and applies threshold voltage voltage below, then can be from curved orientation deformation at being approximately vertically oriented, and continue to irradiate Ultraviolet light preferably makes to remain on the polymerizable compound in liquid crystal and disappears.It is preferred that before making in the state of irradiating ultraviolet light Voltage is stated less than threshold voltage and is further irradiated in the process of ultraviolet light, main polymer network is made to be formed.At this point, pre-dumping The size at angle can depend on applying the time of the voltage of threshold voltage or more and the time for applying threshold voltage voltage below Ratio, the time for applying threshold voltage or more are not form polymer network completely in liquid crystal from polymerization phase separation Original state to polymerization be separated at first at the time of a part is formed with polymer network, if preferably stop apply electricity Pressure then can be from curved orientation recoverable force at the state being approximately vertically oriented.The time for applying the voltage of threshold voltage or more is preferred It is 1 second to 15 seconds.When changing to next process from the process, preferably in the state of to generation orientation transition is approximately vertically oriented Apply threshold voltage or less and irradiates ultraviolet light, be preferably formed entirely of polymer network and make remaining polymerism in liquid crystal Object is closed to disappear.It is the state that is approximately vertically oriented to apply threshold voltage state below, but is alternatively curved orientation deformation slightly, Voltage is adjusted as needed as fixed mode with tilted alignment orientation according to required black level is made.It should be noted that applying Add the time of threshold voltage voltage below can be until the formation of polymer network substantially terminates, when remaining in liquid crystal Amount of monomer is micro and when will not be impacted to electro-optic properties residual monomer polymerize if can not apply threshold voltage Voltage below.

Further, the voltage of threshold voltage or more is stated before the application and is irradiated ultraviolet light simultaneously and is carried out polymerization phase separation Process and between then making in the state of irradiating ultraviolet light voltage be less than threshold voltage and irradiating the process of ultraviolet light, It may be provided in the state of irradiation ultraviolet light and apply at least more than threshold voltage and saturation voltage middle gray voltage below Process.Middle gray voltage is preferably smaller than the application voltage of initial process and more than threshold voltage.Middle gray voltage Apply to postpone to deform to the transformation being approximately vertically oriented from curved orientation.It is lacked due to can inhibit orientation by carryover effects Sunken generation, therefore preferably apply as needed.

One of preferred embodiment of liquid crystal display element manufacturing method of the present invention has to being held at least one Before the light irradiation process of polymerizable liquid crystal compound irradiation ultraviolet light between person's 2 transparent substrates with electrode and application The voltage applying step of the voltage of the threshold voltage of polymerizable liquid crystal compound or more is stated, and containing in aforesaid voltage application work Start abovementioned light in sequence to penetrate process and voltage is made to be less than threshold voltage and further irradiation purple in the state of irradiating ultraviolet light The process of outside line.Moreover it is preferred that applying the threshold voltage of the polymerizable liquid crystal compound to aforementioned polymeric liquid-crystal composition The Time transfer receiver of above voltage is held on the photograph of the polymerizable liquid crystal compound between at least one 2 transparent substrate with electrode The time for penetrating ultraviolet light is short.

As a result, since its state of orientation more than threshold voltage can be made to be transformed into threshold voltage state of orientation below, Two kinds of liquid crystal aligning states can be irradiated with ultraviolet light, thus preferably.

The variation of above-mentioned preferred embodiment has between being held at least one 2 transparent substrate with electrode Polymerizable liquid crystal compound irradiation ultraviolet light light irradiation process, apply aforementioned polymeric liquid-crystal composition threshold voltage with On the 1st voltage (V1) the 1st voltage applying step and apply aforementioned polymeric liquid-crystal composition threshold voltage more than and 2nd voltage applying step of aforementioned 1st voltage (V1) the 2nd voltage (V2) below, and containing in aforementioned 1st voltage application work Start abovementioned light in sequence and/or the 2nd voltage applying step to penetrate process and voltage is made to be less than threshold in the state of irradiating ultraviolet light Threshold voltage and the process for further irradiating ultraviolet light.Moreover it is preferred that applying the polymerism to aforementioned polymeric liquid-crystal composition The Time transfer receiver of the voltage more than threshold voltage of liquid-crystal composition is held between at least one 2 transparent substrate with electrode Polymerizable liquid crystal compound irradiation ultraviolet light time it is short.

One of other preferred embodiments of manufacturing method of the present invention are the liquid crystal display member with following characteristics Part manufacturing method：With between the polymerizable liquid crystal compound application being held at least one 2 transparent substrate with electrode The voltage applying step of the voltage more than threshold voltage of the polymerizable liquid crystal compound and in aforesaid voltage applying step Start the light irradiation process that abovementioned light penetrates process and irradiates ultraviolet light to aforementioned polymeric liquid-crystal composition, abovementioned light penetrates work During sequence has the ultraviolet light irradiation interruption for interrupting ultraviolet light irradiation, voltage is made to be less than threshold value in the state of irradiating ultraviolet light Voltage, and further irradiate ultraviolet light.Moreover it is preferred that applying the polymerizable liquid crystal group to aforementioned polymeric liquid-crystal composition The Time transfer receiver for closing the voltage of the threshold voltage of object or more is held on the polymerization between at least one 2 transparent substrate with electrode Property liquid-crystal composition irradiation ultraviolet light time it is short.Though the polymerization for the state of orientation for keeping threshold voltage or more can be formed as a result, Object network, but influence power can be made minimum, the polymer network for keeping threshold voltage state below can be mainly formed, it can be enhanced Influence power, thus preferably.In the liquid crystal cell further made, the state of orientation and threshold voltage of threshold voltage or more can be made Two states of state of orientation below are converted.If when more than the threshold voltage of polymerizable liquid crystal compound application voltage Between it is long, then can keep the state of orientation of threshold voltage or more, threshold voltage state of orientation below can not be reverted to, be unable to get The conversion of ON-OFF, it is thus not preferred.

The variation of above-mentioned preferred embodiment is the liquid crystal display element manufacturing method with following characteristics：With to folder The polymerizable liquid crystal compound being held between at least one 2 transparent substrate with electrode applies the polymerizable liquid crystal compound The voltage applying step of voltage more than threshold voltage and in aforesaid voltage applying step start abovementioned light penetrate process and To aforementioned polymeric liquid-crystal composition irradiate ultraviolet light light irradiation process, also, at the same time stop abovementioned light penetrating process with After aforesaid voltage applying step, restart abovementioned light and penetrate process, voltage is made to be less than threshold voltage in the state of irradiating ultraviolet light, And further irradiate ultraviolet light.Though in addition, can be between the polymerism liquid being held at least one 2 transparent substrate with electrode Crystal composite irradiates ultraviolet light and interrupts, but preferably total irradiation time compares aforementioned polymeric liquid-crystal composition and applies the polymerism The time of the voltage more than threshold voltage of liquid-crystal composition is long.As a result, due to that can prevent more than threshold voltage to threshold value electricity It presses the polymer network that the orientation defect occurred when orientation transition below is formed to keep, high contrast can be obtained and high speed is rung The liquid crystal cell answered, thus preferably.

One of other preferred embodiments of manufacturing method of the present invention have the liquid crystal display element of following processes Manufacturing method：The polymerization is applied between the polymerizable liquid crystal compound being held at least one 2 transparent substrate with electrode The voltage applying step of the voltage more than threshold voltage of property liquid-crystal composition；Start aforementioned light in aforesaid voltage applying step Irradiation process, and the light irradiation process of ultraviolet light is irradiated to aforementioned polymeric liquid-crystal composition；In the state of irradiating ultraviolet light, It is the 3rd voltage (V3) less than threshold voltage to make voltage, and further irradiates the process of ultraviolet light；And in irradiation ultraviolet light Under state, make voltage for the 4th voltage (V4) less than the 3rd voltage (V3) (the 3rd voltage (V3) is less than threshold voltage), and further Irradiate the process of ultraviolet light.Moreover it is preferred that applying the threshold of the polymerizable liquid crystal compound to aforementioned polymeric liquid-crystal composition The Time transfer receiver of voltage more than threshold voltage is held on the polymerizable liquid crystal group between at least one 2 transparent substrate with electrode The time for closing object irradiation ultraviolet light is short.

Orientation about the orientation and OFF state of the liquid crystal ON states of obtained liquid crystal cell as a result, even if forming polymerization Object network, can also make its liquid crystal being similar to before polymerization is individually oriented state, and high contrast can be obtained and show that high speed is rung The liquid crystal cell answered, thus preferably.

It should be noted that the scope of the present invention is not limited to the preferred embodiment of the present invention of above-mentioned record. In addition, above-mentioned light irradiation process (including the 1st, the 2nd) and voltage applying step with of the present invention due to polymerizeing phase separation Process explanation it is identical, therefore, omit herein.

Distance (d) between the substrate of the liquid crystal display element of the present invention is preferably 2~5 μm of range, more preferably 3.5 μm Below.In general, can birefringence be adjusted so that the birefringence of liquid-crystal composition and the product of element thickness are attached 0.275 Closely, but since the polymerizable liquid crystal compound of the present invention can form polymer network after polymerization is separated, so apply electric field When the birefringence of liquid crystal display element can be due to the anchoring force effect of polymer network and the optical property of polymer network It is lower, accordingly, with respect to the two-fold of the liquid-crystal composition contained by liquid-crystal composition and polymeric compositions or polymerizable liquid crystal compound The product of rate (△ n) and base distance between plates (d) is penetrated, if driving voltage has the increase within 5V or so because forming polymer network, Then it is particularly preferably 0.3~0.4 μm of range, if there is the increase within 3V or so, further preferably 0.30~0.35 μm Range, if driving voltage has the increase within 1V, particularly preferably 0.29~0.33 μm of range.By making liquid crystal display The birefringence (△ n) of distance (d) and liquid-crystal composition between the substrate of element between substrate at a distance from (d) integral not above-mentioned In range, transmissivity is high and can be equal to the case where only low molecular weight liquid crystal, can get high-speed response and color reprodubility is good Display.Relative to the product 0.275 of element thickness (d) and birefringence (△ n), it is preferable to use in the liquid of polymerizable liquid crystal compound The birefringence of crystal composite is 1~1.9 times.

The driving voltage of the liquid crystal display element of the present invention is not dielectric anisotropy, the bullet for being only dependent upon liquid-crystal composition Property constant, also can be by the prodigious influence of the anchorage force acted between liquid-crystal composition and polymer interface.

Such as the description as the driving voltage about high-molecular dispersed liquid crystal display element, Japanese Unexamined Patent Publication 6- The relationship of following formula is shown in No. 222320 bulletins.

(Vth indicates that threshold voltage, 1Kii and 2Kii indicate that elastic constant, i indicate that 1,2 or 3, △ ε indicate that dielectric constant is each Anisotropy,<r>Indicate that the average void interval at transparent polymer substance interface, A indicate transparent polymer confrontation liquid crystal The anchorage force of composition, d indicate the distance for having between the substrate of transparent electrode.)

Accordingly, the driving voltage of light scattering type liquid crystal display element depends on the average sky at transparent polymer substance interface The elastic constant or dielectric constant anisotropy and liquid-crystal composition of distance, liquid-crystal composition between gap interval, substrate with thoroughly Anchoring energy between bright property polymer substance.

Wherein, anchoring of the parameter of liquid crystal display element control that can be through the invention between liquid crystal physical property and polymer Power.The molecular structure of the polymer and the molecular structure of low molecular weight liquid crystal are heavily dependent on due to anchorage force, if so The strong polymerizable compound of selected anchorage force, then can will speed to 1.5ms hereinafter, but driving voltage can increase simultaneously the response time To 30V or more, it is therefore preferable that by driving voltage become 30V or less and response speed become 1.5ms it is below in a manner of it is suitably selected Liquid-crystal compounds and polymerizable compound, adjustment composition.It is preferred that suitably cooperation anchorage force strong polymer precursor and anchorage force is weak Polymer precursor and being adjusted in the way of obtaining the balance between driving voltage and response speed form.On the other hand, as Reduce driving voltage required by liquid-crystal composition physical property, particularly preferably for p-type liquid crystal make dielectric anisotropy become 6 with On, so that dielectric anisotropy is become -3 or less in N-type liquid crystal.Furthermore it is preferred that birefringence is made to be 0.09 or more.Further, If make the birefringence of liquid-crystal composition and threadiness or the refractive index of process for preparing column type polymer network close to and eliminate light Scattering, then more preferably.Wherein, polymer precursor concentration can influence the delay (retardation) of liquid crystal cell, so it is preferred that with The mode that can get required delay suitably increases and decreases the birefringence of liquid-crystal composition and uses.

The liquid crystal display element of the present invention preferably obtains in the following manner：Above-mentioned liquid-crystal composition is set to become -50 DEG C on one side ~30 DEG C of one side irradiation energy rays make polymerizable compound polymerize and be formed in a liquid crystal composition with refractive index respectively to different Property or easily be orientated axis direction polymer network.The upper limit of polymerization temperature is 30 DEG C, preferably 20 DEG C~-10 DEG C.Such as following reality It applies described in example, the inventors discovered that being formed depending on polymerizable compound, makes τ d into one by low temperature polymerization and polymerized at normal temperature Walk high speed.Think itself reason for this is that：1) it is polymerize in the state that the degree of orientation of liquid crystal molecule rises because of low temperature；2) lead to The intermiscibility of polymer and liquid-crystal composition crossed low temperature polymerization and polymerize declines so that phase separation becomes easy, polymerization phase point Accelerate from speed, the gapping interval of polymer network becomes fine；3) even with the relatively low polymerism chemical combination of anchorage force Object, also because gapping interval is fine, and the influence power for forming anchorage force becomes strong such refractive anisotrop polymer network； Deng.

Further, liquid crystal display element of the invention is preferably formed into, and is had uniaxiality refractive anisotrop or is easily taken The optical axis direction of polymer network or polymer adhesive axially or easily orientation axis direction are formed relative to transparent substrate Pre-tilt angle, and constituted preferably by obtained from following：By adjusting electric field strength control low molecular weight liquid crystal be orientated so that It is tilted relative to real estate, applies voltage and simultaneously irradiation energy ray to above-mentioned liquid crystal layer, to make polymerizable compound Producing high-molecular occurs, obtains the polymer for refractive anisotrop or being easily orientated axis direction in a liquid crystal composition.It is hanging down In the VA patterns being directly orientated, applies voltage in a manner of being become within 20 degree relative to substrate normal direction by pre-tilt angle and make it It polymerize, not only the fine polymer with protrusion (protrusion) being equivalent to used in current VA mode units etc., PSA liquid crystal The effect of protrusion, and show the high-speed response that PSA cannot achieve, therefore particularly preferably.In addition, by from multiple directions Applying electric field makes its producing high-molecular, can form multiple domain, and angle of visibility can be improved, thus more preferably.Further, to hang down in substrate interface The straight membrane interface that is orientated makes the mode that low molecular weight liquid crystal induces pre-tilt angle implement light orientation processing, friction orientation processing to the alignment films Deng, to could dictate that the inclined direction of low molecular weight liquid crystal orientation, inhibit to generate orientation defect when switching, thus preferably, Huo Zheye It is preferable to use tilt such pattern electrode to multiple directions to implement the orientation process.About liquid crystal display layer, to containing polymerization Property compound liquid-crystal composition suitably apply AC field in -50 DEG C~30 DEG C of temperature range, and irradiate ultraviolet light simultaneously Or electron ray, thus make there is the polymer network of refractive anisotrop to be formed relative to real estate with its optical axis direction pre- The mode at inclination angle is formed in liquid crystal.If inducing pre-dumping by applying electric field in the dielectric anisotropy using low molecular weight liquid crystal Polymerization phase separation is carried out under the state of orientation at angle, then can get makes the optical axis of the polymer network after polymerization incline relative to real estate Oblique liquid crystal cell more preferably makes aforementioned polymeric compound realize the composition of producing high-molecular.Further, it is also preferred that will make to apply Polymer network obtained by state of orientation after making alive stabilizes and obtained by making the state of orientation of no applied voltage stabilize Polymer network Composite induces pre-tilt angle.

Two plate bases used in the liquid crystal display element of the present invention can be used glass or have flexibility as plastics Transparent material.Transparent substrate with transparent electrode layer by indium tin oxide (ITO) such as can be by sputtering at glass plate It is obtained on transparent substrate.

Colour filter is such as can pass through making pigment dispersion method, print process, galvanoplastic or decoration method.If to pass through pigment point Illustrate as an example of the colour filter production method that arching pushing carries out, then the curing colouration composition of colour filter is coated on this thoroughly On bright substrate, implement patterned process, its solidification is then made by heating or irradiation.For three kinds of colors of red, green, blue respectively into This process of row, thus can make the pixel portion of colour filter.In addition can also be arranged on the substrate equipped with TFT, thin film diode The pixel electrode of equal active components.

Keep the mode that aforesaid substrate becomes inside with transparent electrode layer opposite.Substrate can be adjusted via spacer at this time Interval.Preferably it is adjusted to make the thickness of the light modulation layer of acquisition to become 1~100 μm at this time.It more preferably 1.5 to 10 μm, is using When polarizer, preferably by contrast become it is maximum in a manner of adjust liquid crystal refractive anisotrop △ n and element thickness d it Product, and the 1/2 or 1/4 of 550nm is set as according to display pattern.In addition, when with two panels polarizer, each polarisation also can adjust The polarizing axis of plate and be good by angle of visibility, setting contrast.Further, it is possible to use to expand the phase difference of angle of visibility Film.As spacer, such as glass particle can be enumerated, plastic pellet, aluminium oxide particles, be made of photo anti-corrosion agent material etc. Column spacer etc..Then, the sealants such as epoxy heat-curable composition are printed with the shape halftone that liquid crystal injecting port is arranged It brushes in the substrate, which is bonded each other, heats and makes sealant heat cure.

About making polymerizable liquid crystal compound be held on the method between two plate bases, can be used common vacuum impregnation or ODF methods etc..In the liquid crystal display element manufacturing process of ODF methods, using dispenser by epoxy photo-thermal and with curability etc. Sealant is depicted in any substrate in backboard or foreboard with closed loop dykes and dams shape, and the polymerization of specified amount is added dropwise thereto under degasification After property liquid-crystal composition, foreboard is engaged with backboard, thus can manufacture liquid crystal display element.The polymerism liquid used in the present invention Dropwise addition of the crystal composite due to can steadily carry out liquid crystal-monomer composition in ODF processes, can properly use.

As the method for making polymerizable compound polymerize, the in order to obtain good orientation characteristic of liquid crystal, it is expected that appropriate is poly- Sum velocity, thus preferably by it is single or be used in combination successively irradiation as active energy beam ultraviolet light or electron ray with The method of polymerization.When using ultraviolet light, polarization light source can be used, it is possible to use non-polarized light source.In addition, when making polymerization Property liquid-crystal composition be held between two plate bases in the state of when being polymerize, the substrate at least irradiating surface side must be to active energy Measuring ray has the transparency of appropriateness.Furthermore it is preferred that the liquid-crystal composition containing polymerizable compound, by polymerizable liquid crystal group The temperature range that object is closed at -50 DEG C~20 DEG C applies AC field, and irradiates ultraviolet light or electron ray simultaneously.The friendship applied Galvanic electricity field is preferably the exchange of frequency 10Hz~10kHz, more preferably frequency 100Hz to 5kHz, and voltage depends on liquid crystal display Element desired pre-tilt angle is selected.That is, the pre-dumping of liquid crystal display element can be controlled by the voltage of application Angle.In the liquid crystal display element of lateral electric-field type MVA patterns, from orientation stability and the viewpoint of contrast, preferably by pre-dumping Angle is controlled at 80 degree~89.9 degree.

Temperature when irradiation is preferably the temperature range that polymerizable liquid crystal compound is -50 DEG C~30 DEG C.It is purple as generating Metal halide lamp, high-pressure mercury-vapor lamp, extra-high-pressure mercury vapour lamp etc. can be used in the lamp of outside line.In addition, ultraviolet light as irradiation Wavelength, preferably illumination wavelength region in the ultraviolet light in the absorbing wavelength domain of liquid-crystal composition, will preferably not be less than as needed It is used after the ultraviolet filter of 365nm.The intensity of the ultraviolet light of irradiation is preferably 0.1mW/cm²~100W/cm², more preferably 2mW/cm²~50W/cm².The amount of the energy of the ultraviolet light of irradiation can be adjusted suitably, preferably 10mJ/cm²To 500J/cm², more Preferably 100mJ/cm²To 200J/cm².When irradiating ultraviolet light, intensity also can be changed.The time for irradiating ultraviolet light can be according to photograph The uitraviolet intensity penetrated makees appropriate selection, preferably 10 seconds to 3600 seconds, more preferably 10 seconds to 600 seconds.

(lateral electric-field type)

First, the liquid crystal display element of an embodiment of the present invention is illustrated while with reference to attached drawing.Fig. 1 is to indicate this hair The schematic sectional view of bright liquid crystal display element an example.The liquid crystal display element 10 of an embodiment of the present invention has in surface shape At the first substrate 2 for having oriented layer 4, separately positioned and be formed with the second substrate of light redirecting layer on surface with aforementioned first substrate 7 and the liquid crystal layer 5 that is filled between aforementioned first substrate 2 and second substrate 7 and is abutted with aforementioned a pair of of oriented layer, preceding Stating, there is electrode layer 3, the electrode layer 3 to have between oriented layer 4 (4a, 4b) and aforementioned first substrate 2 as the thin of active component Film transistor, common electrode 22 and pixel electrode.

Fig. 1 is the figure for the composition for schematically showing liquid crystal display element.For convenience of description and by each integral part in Fig. 1 Separation is recorded.The composition of the liquid crystal display element 10 of one embodiment of the present invention is held on opposite direction as recorded in Fig. 1 to have Polymerizable liquid crystal compound (or liquid crystal layer 5) between the first transparent insulation substrate 2 and the second transparent insulation substrate 7 of configuration Transverse electric-field type (in figure an example be as IPS a form FFS mode) liquid crystal display element.First transparent insulation base Plate 2 is formed with electrode layer 3 on the surface of 5 side of liquid crystal layer.In addition, between liquid crystal layer 5 and the first transparent insulation substrate 2 and liquid crystal It is respectively provided between layer 5 and the second transparent insulation substrate 7 and directly abuts and lure with the polymerizable liquid crystal compound for constituting liquid crystal layer 5 A pair of of alignment films 4 (4a, 4b) that homogeneous is orientated are sent out, quilt when without voltage is applied of the liquid crystal molecule in the polymerizable liquid crystal compound It is orientated to substantially parallel relative to aforesaid base plate 2,7.As shown in Figures 1 and 3, aforementioned second substrate 7 and aforementioned first substrate 2 It can be clamped by a pair of of polarizer 1,8.Further, in Fig. 1, it is provided with colour filter between aforementioned second substrate 7 and alignment films 4 6.It should be noted that form or so-called integrated colour filter (COA) as liquid crystal display element of the present invention, Colour filter can be set between the electrode layer and liquid crystal layer containing thin film transistor (TFT), or the electrode of thin film transistor (TFT) can be contained at this Colour filter is set between layer and second substrate.

That is, the liquid crystal display element 10 of one embodiment of the present invention is to be sequentially laminated with the first polarizer 1, first substrate 2, the electrode layer 3 containing thin film transistor (TFT), alignment films 4, the liquid crystal layer 5 containing polymerizable liquid crystal compound, alignment films 4, colour filter The composition of device 6, second substrate 7 and the second polarizer 8.

Glass or the transparent material with flexibility as plastics can be used with second substrate 7 in first substrate 2, wherein one Person is alternatively the opaque materials such as silicon.Two plate bases 2,7 are close by the epoxy heat-curable composition that is configured at neighboring area etc. Envelope (seal) material and package material stick together, and can also be configured the grain such as glass particle, plastic pellet, aluminium oxide particles therebetween Shape spacer or the spacer being made of resin formed by photoetching process, to keep base distance between plates.

Fig. 2 is by the vertical view for the region amplification gained of the electrode layer 3 being formed in Fig. 1 on substrate 2 surrounded by II lines. Fig. 3 for along Fig. 2 III-III lines direction cut the sectional view that liquid crystal display element shown in FIG. 1 is obtained.As shown in Fig. 2, shape At in the electrode layer 3 containing thin film transistor (TFT) on 2 surface of first substrate, to supply a plurality of gate wirings 24 of scanning signal With to supply display signal a plurality of data wiring 25 be configured to intersecting it is rectangular.It should be noted that only aobvious in Fig. 2 Show a pair of of gate wirings 24 and a pair of of data wiring 25.

The unit of liquid crystal display device is formed using the region surrounded by a plurality of gate wirings 24 and a plurality of data wiring 25 Pixel is formed with pixel electrode 21 and common electrode 22 in the unit pixel.It is mutual in gate wirings 24 and data wiring 25 Near the cross part of intersection, it is provided with the thin film transistor (TFT) containing source electrode 27, drain electrode 26 and gate electrode 28.This is thin Film transistor is connect as the switch element for supplying display signal to pixel electrode 21 with pixel electrode 21.In addition, and grid Wiring 24 has been set in parallel bridging line (not shown).The bridging line is connect with common electrode 22 with total to the supply of common electrode 22 Use signal.

One preferred embodiment of thin-film transistor structure is for example as shown in figure 3, with the gate electrode for being formed in 2 surface of substrate 11, the gate insulating layer 12 that is arranged in a manner of the coating gate electrode 11 and 2 substantially entire surface of coating aforesaid base plate, before being formed in State the surface of gate insulating layer 12 and the semiconductor layer 13 opposite with aforementioned gate electrode 11, with coating aforementioned semiconductor layer 13 1 Protective layer 14 that the mode of part surface is arranged, with a side end of coating aforementioned protective layer 14 and aforementioned semiconductor layer 13 and Drain electrode 16 that the mode contacted with the aforementioned gate insulating layer 12 for being formed in 2 surface of aforesaid base plate is arranged, with coating aforementioned Another side end of protective layer 14 and aforementioned semiconductor layer 13 and with the aforementioned gate insulating layer that is formed in 2 surface of aforesaid base plate The source electrode 17 and set in a manner of coating aforementioned drain electrode 16 and aforementioned source electrode 17 that the mode of 12 contacts is arranged The insulating protective layer 18 set.Also anodic oxidation coating (not shown) can be formed on the surface of gate electrode 11, with elimination and grid The segment difference etc. of electrode.

Non-crystalline silicon, polysilicon etc. can be used in aforementioned semiconductor layer 13, if but using ZnO, IGZO (In-Ga-Zn-O), ITO Etc. transparent semiconductor films, then can inhibit the harm of the photocarrier due to light absorption, from increase element aperture opening ratio viewpoint and Speech, it is also preferred that.

It further, also can be in semiconductor layer 13 and drain electrode 16 or source in order to reduce width, the height of Schottky energy barrier Ohmic contact layer 15 is set between pole electrode 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.

Gate wirings 26, data wiring 25, bridging line 29 be preferably metal film, more preferably Al, Cu, Au, Ag, Cr, Ta, The case where Ti, Mo, W, Ni or its alloy, the particularly preferred wiring for using Al or its alloy.In addition, insulating protective layer 18 be with The layer of insulation function, by formation such as silicon nitride, silica, silicon oxynitride films.

In Fig. 2 and embodiment shown in Fig. 3, common electrode 22 is to be formed in 12 substantially entire surface of gate insulating layer Planar electrode, on the other hand, pixel electrode 21 are the comb shape electricity being formed on the insulating protective layer 18 of coating common electrode 22 Pole.That is, common electrode 22 is configured in than pixel electrode 21 closer to the position of first substrate 2, these electrodes across Insulating protective layer 18 overlaps the to each other configuration.Pixel electrode 21 is with common electrode 22 for example by tin indium oxide (ITO, Indium Tin Oxide), indium zinc oxide (IZO, Indium Zinc Oxide), indium oxide zinc-tin (IZTO, Indium Zinc Tin ) etc. Oxide transparent conductive materials are formed.Since pixel electrode 21 and common electrode 22 are formed by transparent conductive material, therefore And the area of the opening in unit pixel area becomes larger, aperture opening ratio and transmissivity increase.

In addition, about pixel electrode 21 and common electrode 22, in order to form fringe field between these electrodes, by pixel electricity Interelectrode distance (also referred to as minimum separation distances) between pole 21 and common electrode 22：R is formed as less than first substrate 2 and The distance of two substrates 7：G.Herein, interelectrode distance：R is indicated between each electrode at a distance from the direction with substrate level.Fig. 3 In, since tabular common electrode 22 is Chong Die with the pixel electrode 21 of pectination, therefore illustrate interelectrode distance：The example of R=0 Son, due to minimum separation distances：R is less than first substrate 2 (i.e. cell gap) at a distance from second substrate 7：G, so form side Edge electric field E.Therefore, shape on the available direction vertical with the line of comb shape of pixel electrode 21 is formed of FFS types liquid crystal display element At horizontal direction electric field and parabolic shape electric field.The electrode width of the comb section of pixel electrode 21：L and pixel electrode 21 Comb section gap width：The electric field that m is preferably formed into generation can be such that the liquid crystal molecule in liquid crystal layer 5 is all driven Degree width.In addition, pixel electrode and the minimum separation distances R of common electrode can be used as (average) of gate insulating layer 12 Film thickness is adjusted.In addition, liquid crystal display element of the present invention may also differ from Fig. 3, be formed as pixel electrode 21 together With the interelectrode distance (also referred to as minimum separation distances) between electrode 22：R is more than first substrate 2 at a distance from second substrate 7： G (IPS modes).In this case, such as the pixel electrode of pectination and the common electrode of pectination can be enumerated in substantially same plane The composition etc. of interior interaction setting.

One preferred embodiment of liquid crystal display element of the present invention is preferably the liquid in the way of the FFS of fringe field Crystal display element, if the most short spacing distance d that common electrode 22 and pixel electrode 21 abut is shorter than alignment films 4 each other (between substrate Distance) most short spacing distance D, then can form fringe field between common electrode and pixel electrode, can efficiently utilize liquid The horizontal direction of brilliant molecule and the orientation of vertical direction.In the case of the FFS mode liquid crystal display elements of the present invention, if to pressing Apply voltage according to the liquid crystal molecule that the long axis direction mode parallel with the differently- oriented directivity of oriented layer configures, then it can be in pixel electrode 21 Between common electrode 22, the equipotential line of parabola shaped electric field is formed to the top of pixel electrode 21 and common electrode 22, liquid crystal The long axis edge of liquid crystal molecule in layer 5 is formed by electric field alignment.Therefore, even low dielectric anisotropy, liquid can also be driven Brilliant molecule.

For the viewpoint for preventing light leakage, colour filter 6 of the present invention preferably with thin film transistor (TFT) and storage capacitance 23 corresponding part of device forms black matrix (not shown).In addition, in colour filter 6, usually by 3 kinds of colour filters of R (red) G (green) B (indigo plant) Device pixel constitutes 1 point of image, image, such as 3 kinds of colour filters are arranged along the extending direction of gate wirings.The colour filter 6 Such as the making such as pigment dispersion method, print process, electrodeposition process or decoration method can be passed through.If with the filter carried out by pigment dispersion method It is illustrated as an example of color device production method, is then that the curing colouration composition of colour filter is coated on the transparent substrate On, implement patterned process, and its solidification is made by heating or irradiation light.This is carried out respectively for three kinds of colors of red, green, blue Thus process can make the pixel portion of colour filter.In addition or it is arranged on the substrate and is equipped with TFT, thin film diode etc. The so-called integrated colour filter of the pixel electrode of active component.

May be provided on electrode layer 3 and colour filter 6 with constitute liquid crystal layer 5 polymerizable liquid crystal compound directly abut and Induce a pair of of alignment films 4 that homogeneous is orientated.

In addition, about polarizer 1 and polarizer 8, it can adjust the polarizing axis of each polarizer and be adjusted to make angle of visibility, comparison Degree becomes good, has preferably in such a way that these axis of homology work under normally-black (normally black) pattern and is mutually perpendicular to The axis of homology.Any one of particularly preferred polarizer 1 and polarizer 8 are with parallel with the differently- oriented directivity of liquid crystal molecule saturating The mode for penetrating axis configures.Furthermore it is preferred that adjusting the refractive anisotrop △ n and list of liquid crystal in such a way that contrast becomes maximum The product of first thickness d.Further, it is possible to use to expand the phase difference film of angle of visibility.

In addition, the embodiment as other liquid crystal display elements is neighbouring shared electricity in the case of IPS modes Most short spacing distance d between pole and pixel electrode is more than the condition of the most short spacing distance G between liquid crystal orientation film, such as can enumerate Following compositions etc.：It is formed on same substrate with pixel electrode in common electrode and the common electrode interacts with the pixel electrode and matches In the case of setting, most short spacing distance d between neighbouring common electrode and pixel electrode is more than between most short between liquid crystal orientation film Gauge is from G.

In the manufacturing method of liquid crystal display element of the present invention, preferably in substrate and/or base with electrode layer Plate surface formed envelope after, by the envelope become inside in a manner of make a pair of of substrate discretely relatively after, the filling liquid between substrate Crystal composite.At this point, preferably via spacer adjustment substrate interval.

Distance (for the average thickness of the liquid crystal layer of acquisition, the also referred to as spacing distance between envelope) between aforesaid base plate is preferred It is adjusted to 1~100 μm.Average distance between aforementioned envelope is more preferably 1.5~10 μm.

In the present invention, as adjusting the spacer of base distance between plates, such as can enumerate glass particle, plastic pellet, Aluminium oxide particles, the column spacer etc. being made of photo anti-corrosion agent material etc..

As an example of the FFS type liquid crystal display elements illustrated using Fig. 1~Fig. 3, as long as without departing from the technological thought of the present invention, Then can also other various modes implement.

Fig. 4 and Fig. 5 used below, illustrate the other embodiment of liquid crystal display element of the present invention.

Such as Fig. 4 is bowing the region amplification gained of the electrode layer 3 being formed in Fig. 1 on substrate 2 surrounded by II lines The other embodiment of view.As shown in figure 4, can also be set as pixel electrode 21 has the composition of slit.In addition it is also possible to opposite There is the pattern that the mode at inclination angle forms slit in gate wirings 24 or data wiring 25.

The pixel electrode 21 shown in Fig. 4 is that the electrode of pairing approximation rectangular flat plate body cuts out the notch of approximate rectangular frame-shaped Shape made of portion.In addition, being formed with comb on one side across insulating protective layer 18 (not shown) at the back side of the pixel electrode 21 Dentation common electrode 22.Further, it is less than oriented layer each other in the most short spacing distance R of adjacent common electrode and pixel electrode Most short spacing distance G when can become FFS modes, and R be more than G when can then become IPS modes.In addition, in aforementioned pixel electricity The surface of pole is preferably coating by protection insulating film and orientation film layer.It should be noted that also can be as described above by aforementioned more Root gate wirings 24 are arranged with the region that more single data wirings 25 surround is subject to the display signal supplied via data wiring 25 The storage 23 of preservation.It should be noted that there is no particular restriction for the shape of notch, approximate square only not shown in Fig. 4 Shape, it is possible to use the notch of shape known in ellipse, circle, rectangle, diamond shape, triangle or parallelogram etc..In addition, When the most short spacing distance R of adjacent common electrode and pixel electrode is more than oriented layer mutual most short spacing distance G, it can become The display element of IPS modes.

Fig. 5 is the embodiment for being different from Fig. 3, for the III-III lines direction cutting liquid crystal display shown in FIG. 1 along Fig. 2 Another example for the sectional view that element is obtained.Surface is formed with the first of oriented layer 4 and the electrode layer 3 containing thin film transistor (TFT) 20 Substrate 2 and surface are formed with the second substrate 8 of oriented layer 4 to be separated into oriented layer relative to each other by D at predetermined intervals, are filled out in this space Filled with the liquid crystal layer 5 containing liquid-crystal composition.A part on 2 surface of first substrate is sequentially laminated with gate insulating layer 12, is total to With electrode 22, insulating protective layer 18, pixel electrode 21 and oriented layer 4.In addition, also as shown in figure 4, pixel electrode 21 is in tablet The central portion of body and both ends cut out the notch of triangle and cut out shape made of rectangular notch in remaining region Shape, and common electrode 22 is following construction：The common electrode of comb teeth-shaped and the approximate ellipsoidal of aforementioned pixel electrode 21 Notch is configured at substantially in parallel than aforementioned pixel electrode closer to first substrate side.

Common electrode 22 using there is pectination or with slit in the example shown in FIG. 5, the electricity consumption together of pixel electrode 21 The interelectrode distance R=α (it should be noted that the horizontal component of interelectrode distance is denoted as R for convenience in Fig. 5) of pole 22. Further, in figure 3, though showing the example for being formed with common electrode 22 on gate insulating layer 12, also can as shown in Figure 5 that Sample forms common electrode 22 on the first substrate 2, and pixel electrode 21 is arranged across gate insulating layer 12.The electrode of pixel electrode 21 Width：L, the electrode width of common electrode 22：N and interelectrode distance：The electric field that R is preferably suitably adjusted to generate can make liquid crystal layer The width of the whole driven degree of liquid crystal molecule in 5.As the most short spacing distance R of adjacent common electrode and pixel electrode When most short spacing distance G mutual less than oriented layer, FFS modes can be become, and when R is more than G, then it can become IPS modes.Into One step, in Figure 5, pixel electrode 21 are different from the position of common electrode 22 in a thickness direction, but also can be by two electrodes in thickness Position on degree direction is set as identical or common electrode is set to 5 side of liquid crystal layer.

(vertical electric field type)

Currently preferred other embodiment is the vertical electric field type liquid crystal display element using liquid-crystal composition.Fig. 6 For schematically show vertical electric field type liquid crystal display element composition figure.In addition, in Fig. 7 for convenience of explanation, and will be each Inscape separation is recorded.Fig. 7 be by be formed in the Fig. 6 on substrate containing thin film transistor (TFT) electrode layer 300 (or Also referred to as tft layer 300) region that is surrounded by VII lines amplifies obtained vertical view.Fig. 8 is the VIII- along Fig. 7 Cut the sectional view that liquid crystal display element shown in fig. 6 is obtained in VIII lines direction.Illustrate that the present invention relates to referring to Fig. 6~9 And vertical electric field type liquid crystal display element.

It is following liquid crystal as recorded in Fig. 6 about the composition of liquid crystal display element 1000 of the present invention Display element：With second substrate 800, first substrate 200 and it is held between aforementioned first substrate 200 and second substrate 800 Polymerizable liquid crystal compound (or liquid crystal layer 500), and the liquid crystal molecule in the polymerizable liquid crystal compound is when without voltage is applied Be oriented approximately perpendicular to aforesaid base plate 200,800, wherein aforementioned second substrate 800 has to be made of transparent conductive material Transparent electrode (layer) 600 (or also referred to as common electrode 600), aforementioned first substrate 200 contain by transparent conductive material structure At pixel electrode and be formed with the thin film transistor (TFT) that the aforementioned pixel electrode that each pixel has is controlled film it is brilliant Body tube layer 300.In addition, as shown in Fig. 6 and Fig. 8, aforementioned second substrate 800 also can be by a pair of of polarisation with aforementioned first substrate 200 Plate 100,900 is clamped.Further, in figure 6, it is provided with colour filter between aforementioned first substrate 200 and common electrode 600 700.In addition further, on 600,1400 surface of transparent electrode (layer), according to the adjoining of the liquid crystal layer 500 of the present invention and with composition The mode that the polymerizable liquid crystal compound of the liquid crystal layer 500 is in direct contact is formed with a pair of of alignment films 400.

That is, liquid crystal display element 1000 of the present invention is to be sequentially laminated with the first polarizer 100, the first base Plate 200, optical alignment film 400, contains liquid crystal group at the electrode layer (or also referred to as tft layer) 300 containing thin film transistor (TFT) Close the layer 500 of object, the composition of alignment films 400, common electrode 600, colour filter 700, second substrate 800 and the second polarizer 900. It should be noted that alignment films 400 are preferably optical alignment film.

Alignment films are in the liquid crystal list manufactured using orientation process (mask friction (mask rubbing) or light orientation) In member, in the inside (liquid crystal layer side) of the transparent electrode of liquid crystal cells, be formed with relative to glass substrate normal direction slightly Tilt the vertical alignment layer of (0.1~5.0 °).

Polymerizable monomer is vertically arranged by the orientation regulation power of vertical alignment layer, by irradiating ultraviolet Make polymerizable monomer polymerization and immobilization and forms polymer network.It is as follows to infer that the polymer network formed by this method has About 4 kinds of structure：(1) polymer network is formed across upper and lower base plate；(2) it is formed from upper (lower) substrate towards liquid crystal orientation poly- Polymeric network, but formed to midway；(3) only polymer network (predominantly monofunctional monomer is formed about on the surface of alignment films The case where)；(4) it is connected to each other and (does not float (Floating)) in liquid crystal layer interpolymer network.In these modes, all mixing are deposited There is the stabilized polymer network of state of orientation for keeping the following two kinds different：The refractive anisotrop of polymer network is easy Axis of orientation be formed to make the stabilized situation of the state of orientation of threshold voltage or more and the refractive index of polymer network respectively to Anisotropic or easily axis of orientation is formed to make the stabilized situation of threshold voltage state of orientation below.

That thinks to be formed by this method there is anisotropic polymer network can be substantially kept completely separate with liquid crystal layer, liquid crystal Molecule orientations between these macromolecule networks.It has a structure which, is mixed with liquid crystal molecule and macromolecule network And the molecule arranging structure for the so-called polymer network type liquid crystal that light scattering occurs when without voltage is applied is significantly different, and Also entirely different with the structure for the orientation sustaining layer being biased against used by PSA etc. near alignment films.

As illustration, the polymer network and the Liquid Crystal Molecules Alignment knot that are obtained shown with the method by using alignment films Structure.On the other hand, even if in so-called MVA modes, PVA with structures such as rib, slits etc., only substrate interface is attached The pre-tilt of close polymer network, liquid crystal molecule can be due tos the oblique electric field intensity etc. applied via structure, slit slightly It is different, infer the structure of inherently figure as above.

It is filled in the VA type liquid crystal displays with the Liquid Crystal Molecules Alignment being made of such polymer network and liquid crystal molecule In setting, it is no can be because of the association for the anchorage force that liquid crystal orientation film and polymer network have to the anchorage force of liquid crystal molecule when applying voltage Same-action and more strongly act on, as a result can accelerate response speed when voltage OFF.

(transverse direction/oblique electric field type)

It can be by being only dedicated to electrode structure as complicated process such as friction, mask irradiation is not masked to alignment films The short-cut method made carries out liquid crystal display area the novel display technologies for being orientated segmentation, and proposing to have makes oblique electric field and laterally electricity Field action is in the method for liquid crystal layer.

Figure 11 is the minimum unit in the pixel PX that outlined using the TFT liquid crystal display elements for having above-mentioned technology Constitute the vertical view of body.The construction of simple declaration transverse direction/oblique electric field mode LCD and running below.

Pixel electrode PE has main pixel electrode PA and sub-pixel electrode PB.These main pixel electrode PA and sub-pixel electrode PB is electrically connected to each other, these main pixel electrode PA and sub-pixel electrode PB are arranged at array substrate AR.Main pixel electrode PA Extend along the 2nd direction Y, sub-pixel electrode PB extends along the 1st direction X different from the 2nd direction Y.In the example in the figures, pixel Electrode PE is formed as approximate crosswise.Sub-pixel electrode PB is incorporated into the substantially central portion of main pixel electrode PA, from main pixel electricity Pole PA extends to the left side of its both sides, that is, pixel PX and right side.These main pixel electrode PA and sub-pixel electrode PB are each other substantially just It hands over.Pixel electrode PE is electrically connected with the switch element of the illustration omitted in pixel electrode PB.

Common electrode CE has main common electrode CA and pair common electrode CB, these main common electrode CA and secondary common electrode CB is electrically connected to each other.Common electrode CE is electrically insulated with pixel electrode PE.In common electrode CE, main common electrode CA and secondary shared electricity At least part of pole CB is arranged at opposite substrate CT.Main common electrode CA extends along the 2nd direction Y.The main common electrode CA It is configured in the both sides for clipping main pixel electrode PA.At this point, in X-Y plane, any main common electrode CA not with main pixel Electrode PA is overlapped, and roughly equal interval is formed between each main common electrode CA and main pixel electrode PA.That is, main Pixel electrode PA is located at the approximately mid way between of adjacent main common electrode CA.Secondary common electrode CB extends along the 1st direction X.It is secondary Common electrode CB is configured in the both sides for clipping sub-pixel electrode PB.At this point, in X-Y plane, any pair common electrode CB is equal It is not overlapped with sub-pixel electrode PB, roughly equal interval is formed between each pair common electrode CB and sub-pixel electrode PB. That is, sub-pixel electrode PB is located at the approximately mid way between of adjacent secondary common electrode CB.

In the example in the figures, main common electrode CA is formed as linearly extending along the 2nd direction Y band-like.Pair shares electricity Pole CB is then formed as linearly extended band-like along the 1st direction X.It should be noted that main common electrode CA is between the 1st direction X is separated It is arranged in parallel two-by-two every ground, the main common electrode in left side in figure is known as CAL in order to distinguish them below, by right side in figure Main common electrode is known as CAR.In addition, pair common electrode CB is arranged in parallel two-by-two at spaced intervals along the 2nd direction Y, below in order to It distinguishes them and the secondary common electrode of upside in figure is known as CBU, the secondary common electrode of downside in figure is known as CBB.It is main to share Electrode CAL and main common electrode CAR and pair common electrode CBU and secondary common electrode CBB is same current potential.In the example in the figures, Main common electrode CAL and main common electrode CAR is connect with secondary common electrode CBU and pair common electrode CBB respectively.

Main common electrode CAL and main common electrode CAR is configured in respectively between pixel PX and the pixel of left and right adjoining. That is, main common electrode CAL is configured as across the boundary of the pixel PX and the pixel (not shown) on the left of it of diagram, it is main to share Electrode CAR is configured as across the boundary of the pixel PX and the pixel (not shown) on the right side of it of diagram.Secondary common electrode CBU and Secondary common electrode CBB is respectively arranged between pixel PX and pixel adjacent up and down.That is, pair common electrode CBU is configured as Across the boundary of the pixel PX and the pixel (not shown) on the upside of it of diagram, secondary common electrode CBB is configured as across diagram Pixel PX with its on the downside of pixel (not shown) boundary.

In the example in the figures, in a pixel PX, 4 regions divided by pixel electrode PE and common electrode CE are by shape At as opening portion, the transmissive portions for mainly helping display.In this instance, the initial orientation direction of liquid crystal molecule LM is and the 2nd Direction substantially parallel direction Y.1st alignment films AL1 be configured at array substrate AR it is opposite with opposite substrate CT to face, big It causes to extend in entire active region ACT.The coating pixel electrode PE of 1st alignment films AL1, are also configured at the 2nd interlayer dielectric 13 On.Such 1st alignment films AL1 is by showing that the material of horizontal alignment property is formed.It should be noted that array substrate AR is sometimes It is further equipped with the 1st main common electrode and the 1st secondary common electrode of the part as common electrode.

Figure 12 is the electrode structure schematic diagram for the oblique electric field mode liquid crystal cell for being divided into 8 parts.In this way 1 pixel is divided into 8 parts, it can be achieved that further width visual field angling.

Next, illustrating the running of the liquid crystal display panel of above-mentioned composition.In the state of not applying voltage to liquid crystal layer, Be not formed between pixel electrode PE and common electrode CE electric field without electric field when (when OFF), as shown in phantom in Figure 11, liquid The liquid crystal molecule LM of crystal layer LQ is with the 1st orientation process direction PD1 and the 2nd alignment films AL2 of the 1st alignment films AL1 of its long axis direction The mode of the 2nd orientation process direction PD2 be orientated.It is equivalent to initial orientation state when such OFF, liquid crystal molecule when OFF The differently- oriented directivity of LM is equivalent to initial orientation direction.Strictly speaking, liquid crystal molecule LM is not only parallel to X-Y plane orientation, more There is pre-tilt in the case of number.Therefore, the liquid crystal molecule when initial orientation directions of liquid crystal molecule LM in a strict sense are by OFF The direction that differently- oriented directivity orthographic projection to the X-Y plane of LM is obtained.

1st orientation process direction PD1 and the 2nd orientation process direction PD2 is the direction substantially parallel with the 2nd direction Y.? When OFF, liquid crystal molecule LM as shown in phantom in Figure 11, with its long axis towards the direction substantially parallel with the 2nd direction Y side Formula carries out initial orientation.That is, the initial orientation direction of liquid crystal molecule LM is parallel with the 2nd direction Y (or is in relative to the 2nd direction Y 0°)。

As illustrated in the example, when the 1st orientation process direction PD1 and the 2nd orientation process direction PD2 is parallel and towards phase Meanwhile in the section of liquid crystal layer LQ, liquid crystal molecule LM is approximate horizontal near the middle part of liquid crystal layer LQ, and (pre-tilt angle is about Zero) it is orientated, with herein for boundary, near the 1st alignment films AL1 and near the 2nd alignment films AL2 in a manner of becoming symmetrical It is orientated with pre-tilt angle (injection is orientated).Liquid crystal molecule LM by this method spray orientation in the state of, even if relative to On the inclined direction in substrate normal direction, also can by near the 1st alignment films AL1 liquid crystal molecule LM and the 2nd alignment films AL2 it is attached The optical compensation of close liquid crystal molecule LM.Therefore, when the 1st orientation process direction PD1 and the 2nd orientation process direction PD2 are mutually flat Row and towards it is identical when, light leakage is few, it can be achieved that high contrast, can carry high display quality when black display.It should be noted that when 1 orientation process direction PD1 and the 2nd orientation process direction PD2 be mutually parallel and towards it is opposite when, in the section of liquid crystal layer LQ, Liquid crystal molecule LM near the 1st alignment films AL1, near the 2nd alignment films AL2 and the middle part of liquid crystal layer LQ have substantially Even pre-tilt angle and be orientated (homogeneous orientation).A part for backlight light from backlight 4 can enter across the 1st polarizer PL1 It is incident upon liquid crystal display panel LPN.The light for being incident to liquid crystal display panel LPN be with the 1st polarizing axis AX1 of the 1st polarizer PL1 just The linear polarization of friendship.Almost without change when liquid crystal display panel LPN of the polarized condition of such linear polarization when passing through OFF Change.Therefore, it can be in intersect Niccol (cross with the 1st polarizer PL1 to pass through the linear polarization of liquid crystal display panel LPN Nicol) the 2nd polarizer PL2 of position relationship absorbs (black display).

On the other hand, it in the state of applying voltage to liquid crystal layer LQ, is i.e. formed between pixel electrode PE and common electrode CE Have in the state of potential difference (when ON), the transverse direction substantially parallel with substrate can be formed between pixel electrode PE and common electrode CE Electric field (or oblique electric field).Liquid crystal molecule LM can be influenced by electric field and its long axis as shown by the solid line in the drawings like that with X-Y The substantially parallel plane internal rotation of plane.

In the example shown in Figure 11, in the region between pixel electrode PE and main common electrode CAL, in lower half side region Liquid crystal molecule LM be rotated in a clockwise direction relative to the 2nd direction Y, and be orientated to towards the lower left in figure, in addition, upper half Liquid crystal molecule LM in side region is rotated in the counterclockwise direction relative to the 2nd direction Y, and is orientated to towards the upper left side in figure. In region between pixel electrode PE and main common electrode CAR, the liquid crystal molecule LM in lower half side region is relative to the 2nd direction Y It is rotated in the counterclockwise direction, and is orientated to towards the lower right in figure, the liquid crystal molecule LM in upper half side region is relative to the 2nd side It is rotated in a clockwise direction, and is orientated to towards the upper right side in figure to Y.By this method, in each pixel PX, in pixel electrode PE In the state of being formed with electric field between common electrode CE, the differently- oriented directivity of liquid crystal molecule LM is with the position Chong Die with pixel electrode PE It sets as boundary and is divided into multiple directions, domain (domain) is formed in each differently- oriented directivity.That is, the shape in a pixel PX At multiple domains.

In such ON, the linear polarization orthogonal with the 1st polarizing axis AX1 of the 1st polarizer PL1 can be incident to liquid crystal Show that panel LPN, polarized condition can change when by liquid crystal layer LQ according to the state of orientation of liquid crystal molecule LM.Such When ON, the 2nd polarizer PL2 (white display) is passed through by least part of the light of liquid crystal layer LQ.If according to such construction, Since 4 domains can be formed in a pixel, optical compensation can be carried out to the angle of visibility in 4 directions, and realize wide angle of visibility Change.Therefore, it can be achieved that reverse without gradual change and high-transmission rate display, is capable of providing the second best in quality liquid crystal display device of display. In addition, by the way that the area of each opening portion in 4 regions divided by pixel electrode PE and common electrode CE is set in a pixel To be roughly the same, the transmissivity in each region can be made roughly the same, the light across each opening portion carry out optical compensation each other and Uniform display is realized in entire wide viewing angle.

(fish bone well electrode)

Figure 13 indicates the fish bone well electrode structure recorded.With the opposite 2 sheet glass bases that are bonded of ground of scheduled cell gap Liquid crystal layer is packaged between plate.It is each formed with the transparent electrode being made of ITO in the opposite surface of 2 opposite plate bases.It uses The glass substrate of the thickness of 0.7mm or so, forms common electrode on opposite substrate.Removal electrode is provided in transparent electrode Slit portion 512c made of a part for material (ITO).According to by the crosswise of each opposite side midpoint connection of rectangular elements, The slit portion 512c that 3~5 μm or so of width is functioned as regulation works is orientated, and is tilted along from slit portion 512c The slit portion 512c for 5 μm of the width that 45 ° of directions extend is formed with multiple, side when they can be tilted as inhibition for 8 μm with spacing The auxiliary tropism control factor of parallactic angle direction confusion and function.The width of the pixel electrode of display is 3 μm.Pixel cadre Electrode 512a and pixel branch portion electrode 512b has 45 degree of angle, and has simultaneously using pixel center as symmetrical centre and every 90 degree of different 4 direction is extended with a structure for portion's electrode.Though liquid crystal molecule can because applying voltage due to tilted alignment, due to Meeting tilted alignment is consistent at 4 directions in orientation and this of tilted alignment, therefore, makes to form the domain for being divided into 4 in a pixel To increase the angle of visibility of display.

Embodiment

The present invention is described in more detail by the following examples, but the present invention is not limited to these embodiments.In addition, following Examples and Comparative Examples composition in " % " mean " quality % ".

[embodiment 1]

It prepares composition shown in following (LCN-1) (Δ n 0.103, sticky η 16.5, Δ ε -3.1) and is used as N-type liquid crystal group Close object.N-type liquid-crystal composition (LCN-1) is heated to 60 DEG C, by solid-state polymerization compound (V1-1-1) and polymerism chemical combination Object (V1-1-2) is mixed and is made it dissolve.Make polymerizable compound (V1-1-1) and (V1-1-2) uniform dissolution in room temperature, with inclined Light microscope confirmation shows nematic liquid crystal phase.The mixed polymerization photoinitiator Irgacure 651 in the solution prepares polymerization Property liquid-crystal composition.The composition table of the polymerizable liquid crystal compound of preparation is recorded in table 1.

In a manner of the uniaxial orientation (horizontal alignment) that liquid crystal can be obtained, polyamides is coated with using 3.6 μm of cell gap The unit of the fish bone well pattern electrode vertical orientation (PVA) of imines vertical alignment layer, the polymerization that will be obtained by vacuum impregnation Property liquid-crystal composition is flow into unit.It is carved with a plurality of slit in the cells so that liquid crystal can be due to applying voltage towards slit direction Tilted alignment.The line electrode width of fish bone well pattern electrode and slit width are all 3.5 μm, and the length of line electrode is 100 μm.

After injection, inlet is sealed with sealing compound 3026E (Threebond corporations).Apply 2.45V with frequency 1kHz Square-wave voltage, and simultaneously use wavelength 365nm ultraviolet light LED light source irradiation exposure intensity be 15mW/cm²It is ultraviolet After line 12 seconds, in the state of prolonged exposure ultraviolet light, it is 0V to make voltage, is restored to vertical orientation, from make voltage restore to Start to irradiate ultraviolet light 68 seconds at the time of 0V, and fish bone well PVA units are made.Thus the poly- of parallel-oriented ingredient is formed it into The polymer network of polymeric network and vertical orientation ingredient.It should be noted that ultraviolet irradiation time is made to be calculated as 80 seconds with whole.

After ultraviolet light irradiates, voltage is applied to unit, slit side is configured in such a way that bright-field becomes most bright To any one relative to 2 polarizing axis for intersecting Niccol polarizer at 45 degree, with the liquid crystal of polarized light microscope observing unit State of orientation.About alive state is not applied, dark field can be confirmed as and be approximately vertically oriented state completely.If rising at leisure High voltage is applied, then confirms that the part of slit can be changing into tilted alignment from vertical orientation, brightness gradually increases.It is single herein In member, in order to confirm the tilted alignment orientation of liquid crystal, in the state that the voltage for applying 7.5V becomes inclined orientation, with transmissivity As least way make slit direction relative to 2 polarizing axis for intersecting Niccol polarizer any one is parallel.Such as Fig. 9 Shown in petrographic microscope photo, if tilted alignment orientation can consistently be seen unanimously towards slit direction with slit and line electrode Black line is observed, if keeping polarization direction consistent with slit direction, can be consistently observed with slit and line electrode without several black lines, Confirm the orientation of tilted alignment unanimously towards slit direction.If it can thus be appreciated that make LC tilt be orientated liquid crystal applied voltages, Due to can be tilted towards slit direction, transmissivity can be promoted.

Apply the rectangular wave of 60Hz, measure voltage-transmission rate characteristic, as a result, maximum transmission rate T100 is 65%, is and liquid The close value of transmissivity 69% that brilliant simple substance is shown.

[table 1]

[table 2]

<LCN-1>

[comparative example 1]

The composition of the comparative example 1 of table 1 is flow into unit in a manner of similarly to Example 1.Carrying out ultraviolet light photograph Before penetrating, apply the voltage of 15V, waits for several minutes and disappearing until being orientated defect.Then, it is 0V to make voltage.Then, with polarized light microscopy After mirror confirms that liquid crystal is unanimously orientated towards slit direction, irradiation ultraviolet light 80 seconds.After irradiation, to being formed with polymeric web The unit of network applies the voltage of 9V, so that LC tilt is orientated, in polarized light microscope observing, if making polarization direction and slit direction Unanimously, then it can observe that the orientation of tilted alignment is unanimously towards the part of slit direction and inclination without several black lines in some The light that orientation deviates from slit direction is mixed, and slit will not integrally become black line, observe tilted alignment Orientation is different.If slowly increasing voltage and measuring transmissivity, maximum transmission rate T100 is low, is 36.1%.

[comparative example 2-3]

The composition of the comparative example of table 12,3 is flow into unit in a manner of similarly to Example 1.Carrying out ultraviolet light Pre-irradiation applies unit the voltage of 15V, waits for several minutes and disappearing until being orientated defect.Then, table 2 is applied to each unit Voltage confirms that liquid crystal unanimously towards slit direction tilted alignment, irradiates ultraviolet light in the state of applying voltage with petrographic microscope 80 seconds.In order to use the orientation of polarized light microscope observing liquid crystal, after irradiation, applies the voltage of 9V to unit, make liquid Brilliant tilted alignment can observe in some without several black lines if keeping polarization direction consistent with slit direction, tilted alignment The light that orientation unanimously deviates with tilted alignment orientation from slit direction towards the part of slit direction is mixed, slit Entirety will not become black line, and the petrographic microscope photo of comparative example 2 as shown in Figure 10 is such, observes tilted alignment orientation not Equally.If slowly increasing voltage and measuring transmissivity, maximum transmission rate T100 is 40.3% in comparative example 2, in comparative example 3 In be 36.1%, compared to comparative example 1, though T100 is promoted, the tilted alignment orientation of liquid crystal is not all unanimously towards slit Direction is low.

[comparative example 4]

The composition of the comparative example 4 of table 1 is flow into unit in a manner of similarly to Example 1.Carrying out ultraviolet light photograph Before penetrating, apply the voltage of 15V to unit, waits for several minutes and disappearing until being orientated defect.Then, apply the voltage of table 2 to unit, Liquid crystal is confirmed unanimously towards slit direction tilted alignment with petrographic microscope, in the state of applying voltage, irradiates ultraviolet light 80 seconds Clock.If using the orientation of polarized light microscope observing liquid crystal, bright-field is shown in the state of no applied voltage, if measuring most Small transmissivity T0 is then 39.6%, and polymer network is formed to keep the state of orientation of threshold voltage or more, substantially parallel Liquid crystal aligning state is stabilized, and the black of dark field is unable to get.If applying voltage and measuring maximum transmission rate T100, It is 60.3%.

[embodiment 2~5]

The composition of the embodiment 2~5 of table 1 is flow into unit in a manner of similarly to Example 1.

Glass unit is taken out after injection, is sealed inlet with sealing compound 3026E (Threebond corporations).It uses The ultraviolet light LED light source of wavelength 365nm, it is 15mW/cm that exposure intensity is irradiated at 25 DEG C²Ultraviolet light 80 seconds.With frequency The rectangular wave of 1kHz and 2.39V~7.5V as voltage, the appropriate adjustment time from the time of starting to irradiate ultraviolet light and apply 5 Second~after 15 seconds, in the state of irradiating ultraviolet light, it is 0V to make polymerization voltage, restores to vertical orientation, fish bone well PVA is made Unit.Thus the polymer network of the polymer network and vertical orientation ingredient of parallel-oriented ingredient is formed it into.

After ultraviolet light irradiates, slit direction is configured to relative to any one inclination 45 for intersecting Niccol polarizer Degree, with the liquid crystal aligning state of polarized light microscope observing unit.About the state of no applied voltage, dark field and complete can be confirmed as It is all the state of being approximately vertically oriented.If increasing voltage at leisure to be applied, confirm that the part of slit can become from vertical orientation It is melted into tilted alignment, brightness gradually increases.In order to confirm tilted alignment orientation, applying the voltage of 7.5V makes it be tilted alignment shape State, becoming least way with transmissivity keeps slit direction consistent with polarizer direction.If tilted alignment orientation is unanimously towards narrow Direction is stitched, then is consistently observed black line with slit and line electrode.If keeping polarization direction consistent with slit direction, with slit and Line electrode is consistently observed the orientation that tilted alignment is confirmed without several black lines unanimously towards slit direction.

Apply the rectangular wave of 60Hz, measure voltage-transmission rate characteristic, as a result, maximum transmission rate T100 is 60% or more, is The close value of the transmissivity 69% that shows with liquid crystal simple substance.

[embodiment 6]

The composition of the embodiment 6 of table 1 is flow into unit in a manner of similarly to Example 1.

Glass unit is taken out after injection, is sealed inlet with sealing compound 3026E (Threebond corporations).It uses The ultraviolet light LED light source of wavelength 365nm, it is 15mW/cm that exposure intensity is irradiated at 25 DEG C²Ultraviolet light 80 seconds.With frequency The rectangular wave of 1kHz and 2.45V are as voltage, after applying 12 seconds from the time of starting to irradiate ultraviolet light, in irradiation ultraviolet light In the state of, it is 0V to make voltage, restores to vertical orientation, fish bone well PVA units are made.Thus parallel-oriented ingredient is formed it into Polymer network and vertical orientation ingredient polymer network.

After ultraviolet light irradiates, slit direction is configured to relative to any one inclination 45 for intersecting Niccol polarizer Degree, with the liquid crystal aligning state of polarized light microscope observing unit.About the state of no applied voltage, dark field and complete can be confirmed as It is all the state of being approximately vertically oriented.If increasing voltage at leisure to be applied, confirm that the part of slit can become from vertical orientation It is melted into tilted alignment, brightness gradually increases.In order to confirm tilted alignment orientation, applying the voltage of 7.5V makes it be tilted alignment shape State, becoming least way with transmissivity keeps slit direction consistent with polarizer direction.Even if changing polymerizable compound, liquid crystal Composition, if tilted alignment orientation can be consistently observed black line unanimously towards slit direction with slit and line electrode.If making partially Light direction is consistent with slit direction, then can be consistently observed without several black lines with slit and line electrode, confirm tilted alignment Orientation is unanimously towards slit direction.

[embodiment 7]

The composition of the embodiment 7 of table 1 is flow into unit in a manner of similarly to Example 1.

Glass unit is taken out after injection, is sealed inlet with sealing compound 3026E (Threebond corporations).It uses The ultraviolet light LED light source of wavelength 365nm, it is 15mW/cm that exposure intensity is irradiated at 25 DEG C²Ultraviolet light 80 seconds.With frequency The rectangular wave of 1kHz and 2.45V are as voltage, after applying 8 seconds from the time of starting to irradiate ultraviolet light, in irradiation ultraviolet light In the state of, it is 0V to make voltage, restores to vertical orientation, fish bone well PVA units are made.Thus parallel-oriented ingredient is formed it into Polymer network and vertical orientation ingredient polymer network.After ultraviolet light irradiates, it is configured to the rectilinear direction of slit Relative to any one 45 degree of the inclination for intersecting Niccol polarizer, with the liquid crystal aligning state of polarized light microscope observing unit.It closes In the state of no applied voltage, dark field can be confirmed as and be entirely to be approximately vertically oriented state.If at leisure increase voltage into Row applies, then confirms that the part of slit can be changing into tilted alignment from vertical orientation, brightness gradually increases.In order to confirm that inclination takes To orientation, applying the voltage of 7.5V makes it be tilted alignment state, with transmissivity become least way make slit direction with partially Tabula rasa direction is consistent.Even if changing polymerizable compound, liquid crystal composition, if tilted alignment orientation unanimously towards slit direction, It can be consistently observed black line with slit and line electrode.It, can be with slit and line electricity if keeping polarization direction consistent with slit direction Pole is consistently observed the orientation that tilted alignment is confirmed without several black lines unanimously towards slit direction.

Applying the rectangular wave of 60Hz, measures voltage-transmission rate characteristic, as a result, maximum transmission rate T100 is 65.4% or more, For the close value of the transmissivity 69% shown with liquid crystal simple substance.

[embodiment 8]

The composition of the embodiment 8 of table 1 is flow into unit in a manner of similarly to Example 1.

Glass unit is taken out after injection, is sealed inlet with sealing compound 3026E (Threebond corporations).It uses The ultraviolet light LED light source of wavelength 365nm, it is 15mW/cm that exposure intensity is irradiated at 25 DEG C²Ultraviolet light 1200 seconds.With frequency The rectangular wave of 1kHz and 3.4V are as voltage, after applying 100 seconds from the time of starting to irradiate ultraviolet light, in irradiation ultraviolet light In the state of, it is 0V to make voltage, restores to vertical orientation, fish bone well PVA units are made.Thus parallel-oriented ingredient is formed it into Polymer network and vertical orientation ingredient polymer network.

Similarly to Example 7 in order to confirm tilted alignment orientation, applying the voltage of 7.5V makes it be tilted alignment state, Becoming least way with transmissivity keeps slit direction consistent with polarizer direction.Even if changing polymerizable compound, liquid crystal group At if tilted alignment orientation can be consistently observed black line unanimously towards slit direction with slit and line electrode.If making polarisation Direction is consistent with slit direction, then the side that tilted alignment is confirmed without several black lines can be consistently observed with slit and line electrode Position is unanimously towards slit direction.

Apply 60Hz rectangular wave, measure voltage-transmission rate characteristic, as a result, maximum transmission rate T100 be 64.3%, for The close value of transmissivity 69% that liquid crystal simple substance is shown.

[embodiment 9]

The composition of the embodiment 9 of table 1 is adjusted in a manner of similarly to Example 1.

It is opposite with pre-tilt angle after being coated with alignment film of polyimide in a manner of the vertical orientation (being orientated in the same direction) for obtaining liquid crystal The mode for being 1 ° or so in real estate normal direction implements friction orientation processing, uses the list of the parallel friction orientation with ITO Member is flow into obtained polymerizable liquid crystal compound in unit by vacuum impregnation.Glass unit is taken out after injection, with Sealing compound 3026E (Threebond corporations) seals inlet.It is 15mW/cm that exposure intensity is irradiated at 25 DEG C²Ultraviolet light 80 seconds.Using the rectangular wave of frequency 1kHz and 12V as voltage, changed from 2 seconds to 10 from the time of starting to irradiate ultraviolet light After the time of second is applied, in the state of irradiating ultraviolet light, it is 0V to make voltage, restores to vertical orientation, fish bone well is made PVA units.Thus two kinds of the polymer network of the polymer network and vertical orientation ingredient that form it into parallel-oriented ingredient is not With the polymer network being orientated.After ultraviolet light irradiates, it is configured to friction orientation axis direction and is parallel to intersection Niccol polarisation Any one of plate, with the liquid crystal aligning state of polarized light microscope observing unit.

Element number 1~2 is dark field, even if by unit rotation with towards the black level of azimuth direction dark field It is unchanged, to be orientated in the same direction, confirm that polymer network optical axis direction is easily orientated axis direction with liquid crystal and is formed as orthogonal with elemental area. And in element number 3~4, even if unit rotation is had available and element number 1 towards azimuth direction, to also show that The orientation of~2 same dark fields slightly becomes bright orientation with dark field.Element number 5 is different from other units, even if will Unit rotation is with towards azimuth direction, the azimuth also without display dark field becomes compared to the dark field of element number 1~4 It obtains slightly bright.It confirms, due to what is formed according to the mode for keeping polymer network optical axis direction consistent with the easy axis of orientation of liquid crystal The effect of the anchorage force of polymer network so that fall time shortens.Element number 1~5 is configured to relative to intersection Nico Any one 45 degree of inclination of your polarizer, with the liquid crystal aligning state of polarized light microscope observing unit.Under without voltage is applied, show Show dark field (in addition to element number 5), applies if slowly increasing voltage, be changing into bright-field.In the configuration status of the unit Under, electro-optic properties are measured, result is summarized in table 3.

If changing the voltage application time during irradiation ultraviolet light to 10 seconds from 2 seconds, pre-tilt angle increases from 1.9 ° To 22.4 °.As pre-tilt angle increases, Toff (relaxation time) increases to 7.7ms from 3.8ms, and minimum transmittance T0 is from 0.01% Increase to 5.26%.If especially voltage application time becomes 10 seconds, T0 can be sharply increased.On the other hand, driving voltage V90 from 8.1V is reduced to 5.5V.At the time of starting to irradiate ultraviolet light, applies and show parallel-oriented voltage 12V, leaving makes parallel take To the track of stabilized polymer network, if making voltage be 0V on the way in irradiation ultraviolet light, though can be formed makes vertical orientation Stabilized polymer network, but can be mixed and show that (a) makes parallel-oriented stabilized ingredient and (b) make vertical orientation The polymer network of stabilized ingredient, as voltage application time is elongated, the influence power of (a) gradually increases, and pre-tilt angle increases. This result illustrates to want to become the anchorage force of parallel-oriented polymer network and wants to become the polymeric web of vertical orientation The balance of the anchorage force of network can determine pre-tilt angle.If applying voltage time becomes 10 seconds or more, the influence power of (a) can become larger, Can be towards parallel-oriented direction, T0 can be 0.1% or more, and contrast can decline.If polymerizeing voltage application time at 7 seconds or less If, then the influence power of (a) is minimum, and therefore, high contrast can be obtained 0.1% hereinafter, show good value in T0.

[table 3]

[embodiment 10]

Using the polymerizable liquid crystal compound of embodiment 6, the making of unit is same as Example 7.As shown in table 4, it is applying Stop irradiation ultraviolet light after the making alive time, after the voltage-transmission rate characteristic for measuring ultraviolet light irradiation midway, with total irradiation time Ultraviolet light is irradiated with the remaining time as 80 seconds modes, measures the voltage-transmission rate characteristic after ultraviolet light irradiation.It is logical The voltage-transmission rate for measuring ultraviolet light irradiation midway is crossed, shows that (a) makes parallel-oriented stabilized ingredient and (b) to investigate Make the influence of the polymer network of the stabilized ingredient of vertical orientation.By the voltage-transmission rate after the application voltage of same unit Characteristic and response time and make to polymerize the voltage-transmission rate characteristic after voltage uses the remaining time to irradiate ultraviolet light for 0V It is shown in table 4 with the response time.If comparing unit number 1 to 5 apply voltage after voltage-transmission rate characteristic (V90, T0, T100), then almost the same characteristic is shown.In addition, ultraviolet light irradiate after voltage-transmission rate characteristic (V90, T0, T100) also roughly the same.However, T0 and pre-tilt angle after the application voltage of element number 6 are drastically compared to element number 1~5 Ground increases.This increases due to the parallel-oriented stabilisation ingredient of (a).Therefore, the dark of good black level is shown in order to obtain The visual field, it is necessary to which being suitably adjusted to T0 will not increased polymerization voltage application time.In embodiment 10, when preferably polymerization being made to apply Between within 10 seconds.If the voltage-transmission rate characteristic after the ultraviolet light irradiation of comparing unit number 1 to 5, can be obtained 0.1% good T0 below, but the T0 after the polymerization voltage application of element number 6 further increases, the influence of (a) Power increases.As a result since pre-tilt angle is big so that the response time is also elongated, is not suitable for display element.That is, in vertical orientation In the case of unit, polymerization voltage application time is adjusted in a manner of as the range (0.1% or less) for not sacrificing black level, by This obtain Toff 4ms or less and maximum transmission rate T100 high voltage-transmission rate characteristic.

[table 4]

[embodiment 11]

Using the polymerizable liquid crystal compound of embodiment 1, the making of unit is also same as Example 1.

After injection, inlet is sealed with sealing compound 3026E (Threebond corporations).Apply frequency 1kHz and 2.45V Square-wave voltage, and simultaneously use wavelength 365nm ultraviolet light LED light source, irradiation exposure intensity be 15mW/cm²It is ultraviolet After line 12 seconds, in the state of prolonged exposure ultraviolet light, it is 0.9V to make voltage, restores to vertical orientation, restores from voltage is made For 0.9V at the time of from irradiation ultraviolet light 68 seconds, fish bone well PVA units are made.Thus the poly- of parallel-oriented ingredient is formed it into The polymer network of polymeric network and vertical orientation ingredient.

After ultraviolet light irradiates, slit direction is configured to relative to any one inclination 45 for intersecting Niccol polarizer Degree, with the liquid crystal aligning state of polarized light microscope observing unit.About alive state is not applied, dark field and complete can be confirmed as It is approximately vertically oriented state entirely.If increasing voltage at leisure to be applied, confirm that the part of slit can change from vertical orientation At tilted alignment, brightness gradually increases.In order to confirm tilted alignment orientation, applying the voltage of 7.5V makes it be tilted alignment shape State, becoming least way with transmissivity keeps slit direction consistent with polarizer direction.If tilted alignment orientation is unanimously towards narrow Direction is stitched, then can be consistently observed black line with slit and line electrode.If keeping polarization direction consistent with slit direction, can with it is narrow Seam and line electrode are consistently observed the orientation that tilted alignment is confirmed without several black lines unanimously towards slit direction.

Applying the rectangular wave of 60Hz and measures voltage-transmission rate characteristic, as a result, maximum transmission rate T100 is 63% or more, For the close value of the transmissivity 69% shown with liquid crystal simple substance.

[embodiment 12-15]

Glass unit is taken out after injection, is sealed inlet with sealing compound 3026E (Threebond corporations).About Ultraviolet light irradiation condition, using the ultraviolet light LED light source of wavelength 365nm, it is 15mW/cm that exposure intensity is irradiated at 25 DEG C²Purple Outside line 80 seconds.On the other hand, it is then to apply frequency under the conditions of aforementioned irradiation ultraviolet light and be 1kHz and be that voltage, which applies condition, The square-wave voltage as primary voltage that table 5 is recorded is irradiating after applying 6 seconds from the time of starting to irradiate ultraviolet light The primary voltage that aforementioned table 5 is recorded is changed into medium voltage that table 5 is recorded in the state of ultraviolet light, and after applying 1 second, irradiation is purple Outside line and simultaneously by the medium voltage that aforementioned table 5 is recorded change into 5 manufacturing conditions of table record secondary voltage (liquid crystal threshold voltage with Under), in the state of reverting to vertical orientation, fish bone well PVA units are made.Thus the polymerization of parallel-oriented ingredient is formed it into The polymer network of object network and vertical orientation ingredient.

After ultraviolet light irradiates, slit direction is configured to relative to any one inclination 45 for intersecting Niccol polarizer Degree, with the liquid crystal aligning state of polarized light microscope observing unit.About the state of no applied voltage, dark field and complete can be confirmed as It is all the state of being approximately vertically oriented.If increasing voltage at leisure to be applied, confirm that the part of slit can become from vertical orientation It is melted into tilted alignment, brightness gradually increases.In order to confirm tilted alignment orientation, applying the voltage of 7.5V makes it be tilted alignment shape State, becoming least way with transmissivity keeps slit direction consistent with polarizer direction.If tilted alignment orientation is unanimously towards narrow Direction is stitched, then can be consistently observed black line with slit and line electrode.If voltage is removed, the orientation occurred sometimes can be confirmed Defect is not affected by polymer-stabilized.If keeping polarization direction consistent with slit direction, can consistently be seen with slit and line electrode The orientation that tilted alignment is confirmed without several black lines is observed unanimously towards slit direction.Apply the rectangular wave of 60Hz and measures voltage- Transmission characteristics, as a result, maximum transmission rate T100 such as 5 element characteristics of table are recorded, and show the transmissivity shown with liquid crystal simple substance 69% close value.

[embodiment 16-18]

The composition of the embodiment 6 of table 1 is flow into unit in such a way that embodiment 1 is same.

Glass unit is taken out after injection, is sealed inlet with sealing compound 3026E (Threebond corporations).About Ultraviolet light irradiation condition, using the ultraviolet light LED light source of wavelength 365nm, it is 15mW/cm that exposure intensity is irradiated at 25 DEG C²Purple Outside line 80 seconds, as be described hereinafter, (it should be noted that being free of for 80 seconds in irradiation ultraviolet light during the interruption of setting irradiation ultraviolet light During disconnected).On the other hand, it is then to apply frequency under aforementioned ultraviolet light irradiation condition and be 1kHz and be table 5 that voltage, which applies condition, The square-wave voltage as primary voltage that manufacturing conditions are recorded, after applying 10 seconds from the time of starting to irradiate ultraviolet light, Voltage is removed simultaneously with ultraviolet light, in the state of not applying the medium voltage of the record of table 5, ultraviolet light irradiation is interrupted one second Zhong Hou only irradiates ultraviolet light in the state of reverting to vertical orientation, and fish bone well PVA units are made.Thus it forms it into parallel The polymer network of the polymer network and vertical orientation ingredient of orientation component.

After ultraviolet light irradiates, slit direction is configured to relative to any one inclination 45 for intersecting Niccol polarizer Degree, with the liquid crystal aligning state of polarized light microscope observing unit.About the state of no applied voltage, dark field and complete can be confirmed as It is all the state of being approximately vertically oriented.If increasing voltage at leisure to be applied, confirm that the part of slit can become from vertical orientation It is melted into tilted alignment, brightness gradually increases.In order to confirm tilted alignment orientation, applying the voltage of 7.5V makes it be tilted alignment shape State, becoming least way with transmissivity keeps slit direction consistent with polarizer direction.If tilted alignment orientation is unanimously towards narrow Direction is stitched, then can be consistently observed black line with slit and line electrode.If voltage is removed, the orientation occurred sometimes can be confirmed Defect is not affected by polymer-stabilized.If keeping polarization direction consistent with slit direction, can consistently be seen with slit and line electrode The orientation that tilted alignment is confirmed without several black lines is observed unanimously towards slit direction.Apply the rectangular wave of 60Hz and measures voltage- Transmission characteristics, as a result, maximum transmission rate T100 such as tables 5 are recorded, and show that the transmissivity 69% shown with liquid crystal simple substance is close Value.

(5 manufacturing conditions of table)

[table 5]

(6 element characteristic of table)

[table 6]

	V90	T100	To	Toff	Ton	Gap
							Embodiment 12	8.1	62.8	0.02	3.9	3.1	3.62
Embodiment 13	8.1	62.3	0.01	3.1	3.9	3.61
							Embodiment 14	8.2	62.9	0.03	2.9	4.9	3.65
Embodiment 15	8.2	61.2	0.04	2.7	6.6	3.67
							Embodiment 16	7.7	65.3	0.01	3.6	3.4	3.57
Embodiment 17	7.2	64.9	0.02	3.2	3.9	3.65
							Embodiment 18	7.7	65.1	0.01	3.3	4.7	3.98

It should be noted that in this specification, in embodiment, the abbreviation " Gap " of the table of embodiment indicates cell gap (μm), " V90 " indicates driving voltage (V), Ton (opening time millisecond), Toff (shut-in time millisecond).The application quotes addition conduct Basis application on April in 2016 5 Japanese publication Patent 2016-075809 full content.

Symbol description

1 ... polarizer, 2 ... first transparent insulation substrates, 3 ... electrode layers, 4 ... alignment films, 4a ... differently-s oriented directivity, 5 ... liquid Crystal layer, liquid crystal molecule when 5a ... is without application voltage, 5b ... apply liquid crystal molecule when voltage, and 6 ... colour filters, 7 ... second thoroughly Bright insulating substrate, 8 ... polarizers, 9 ... continuous or discontinuous polymer networks, 10 ... liquid crystal display elements, 11 ... grids electricity Pole, 12 ... gate insulating layers, 13 ... semiconductor layers, 14 ... protective layers, 15 ... ohmic contact layers, 16 ... drain electrodes, 17 ... sources Pole electrode, 18 ... insulating protective layers, 21 ... pixel electrodes, 22 ... common electrodes, 23 ... storages, 24 ... gate wirings, 25 ... data wirings, 26 ... drain electrodes, 27 ... source electrodes, 28 ... gate electrodes, 29 ... bridging lines, 100 ... polarizers, 110 ... gate electrodes, 120 ... gate insulating layers, 130 ... semiconductor layers, 140 ... protective layers, 160 ... drain electrodes, 190b ... Organic insulating film, 200 ... first substrates, 210 ... pixel electrodes, 220 ... storages, 230 ... drain electrodes, 240 ... numbers According to wiring, 250 ... gate wirings, 260 ... source electrodes, 270 ... gate electrodes, 300 ... tft layers, 400 ... are orientated Film, 500 ... liquid crystal layers, 510 ... liquid crystal display devices, 512 ... pixel electrodes, 512a ... pixel cadre's electrodes, 512b ... pixels Branch portion electrode, 512c ... pixel slits, 516 ... scan wirings, 517 ... signal wirings, 600 ... common electrodes, 700 ... colour filters Device, 800 ... second substrates, 900 ... polarizers, 1000 ... liquid crystal display elements, 1400 ... transparent electrodes (layer), PX ... pixels, PE ... pixel electrodes, the main pixel electrodes of PA ..., PB ... sub-pixel electrodes, CE ... common electrodes, the main common electrodes of CA ..., CAL ... The main common electrode in left side, the main common electrode in the right sides CAR ..., the secondary common electrodes of CB ..., the upsides CBU ... pair common electrode, under CBB ... Side pair common electrode.

Claims

1. a kind of manufacturing method of liquid crystal display element, contains：

For the polymerizable liquid crystal compound being held between at least one 2 transparent substrate with electrode, apply the polymerism More than the threshold voltage of liquid-crystal composition voltage and the process that ultraviolet light carries out polymerization phase separation is irradiated simultaneously, and

Then so that voltage is less than threshold voltage in the state of irradiating ultraviolet light, and further irradiate the process of ultraviolet light.

2. the manufacturing method of liquid crystal display element according to claim 1, in the threshold value for applying polymerizable liquid crystal compound It more than voltage voltage and irradiates simultaneously in the process that ultraviolet light carries out polymerization phase separation, the liquid crystal in polymerizable liquid crystal compound Molecule is orientated relative to transparent substrate plane with 0 degree to 30 degree of range inclination, and makes institute in the state of irradiating ultraviolet light Voltage is stated less than threshold voltage and is further irradiated in the process of ultraviolet light, the liquid crystal molecule inclines relative to transparent substrate plane Oblique 80 degree to 90 degree and be orientated.

3. the manufacturing method of liquid crystal display element according to claim 1 or 2, in the threshold for applying polymerizable liquid crystal compound It more than threshold voltage voltage and irradiates simultaneously in the process that ultraviolet light carries out polymerization phase separation, the liquid in polymerizable liquid crystal compound Brilliant molecule is orientated relative to transparent substrate plane with 0 degree to 90 degree of range inclination, and is made in the state of irradiating ultraviolet light The voltage is less than in threshold voltage and the further process of irradiation ultraviolet light, and the liquid crystal molecule is relative to transparent substrate plane It tilts 0 degree to 30 degree and is orientated.

4. the voltage of the manufacturing method of liquid crystal display element according to any one of claim 1 to 3, application is waves AC Shape shows the frequency of the range of dielectric anisotropy with polymerizable liquid crystal compound.

5. the manufacturing method of liquid crystal display element according to any one of claim 1 to 4, voltage more than threshold voltage For voltage V10 or more, wherein voltage V10 is relative to the transmission in the voltage-transmission rate characteristic voltage of polymerizable liquid crystal compound Rate total variation is 10% or more.

6. the manufacturing method of liquid crystal display element according to any one of claim 1 to 5 is less than the voltage of threshold voltage It is 0V less than 90% voltage of threshold voltage.

7. the manufacturing method of liquid crystal display element according to any one of claim 1 to 6 is combined as polymerizable liquid crystal Polymerizable compound in object, using one kind or two or more in the compound selected from the following general formula (V) and the expression of logical formula (VI) Compound,

[changing 1]

In formula, X¹And X²Each independently represent hydrogen atom or methyl, Sp¹And Sp²Each independently represent singly-bound, carbon atom number 1 ~12 alkylidene or-O- (CH₂)_s, in formula, s indicates that 1~11 integer, oxygen atom are connected to aromatic rings, and U indicates carbon atom The straight chain or branch's polyvalent alkylene of number 2~20 or the multivalence cyclic substituents of carbon atom number 5~30, in polyvalent alkylene Alkylidene can be replaced in the range that oxygen atom does not abut by oxygen atom, or can be taken by the alkyl of carbon atom number 5~20 or ring-type Replace for base, the alkylidene in the alkyl of the carbon atom number 5~20 can be taken in the range that oxygen atom does not abut by oxygen atom Generation, k indicate 1~5 integer, and arbitrary hydrogen atom can be substituted by-CH in all Isosorbide-5-Nitrae-phenylenes in formula₃、-OCH₃, fluorine it is former Son or cyano,

[changing 2]

In formula, X³Indicate hydrogen atom or methyl, Sp³The alkylidene or-O- (CH of expression singly-bound, carbon atom number 1~12₂)_t, formula-O- (CH₂)_tIn, t indicates that 2~11 integer, oxygen atom are connected to aromatic rings, and V indicates straight chain or the branch of carbon atom number 2~20 The multivalence cyclic substituents of polyvalent alkylene or carbon atom number 5~30, the alkylidene in polyvalent alkylene can be not adjacent in oxygen atom Replaced by oxygen atom in the range of connecing, or can be replaced by the alkyl of carbon atom number 5~20 or cyclic substituents, the carbon atom number Alkylidene in 5~20 alkyl can be replaced in the range that oxygen atom does not abut by oxygen atom, and W indicates hydrogen atom, halogen atom Or the alkyl of carbon atom number 1~15；Arbitrary hydrogen atom can be substituted into-CH in all 1,4- phenylenes in formula₃、-OCH₃、 Fluorine atom or cyano.

8. the manufacturing method of liquid crystal display element according to claim 7 uses general formula as the polymerizable compound (V) Sp indicated¹With Sp²Identical one kind or two or more compound.

9. the manufacturing method of liquid crystal display element according to claim 7 or 8 is used as the polymerizable compound The Sp that logical formula (V) indicates¹With Sp²Identical compound of more than two kinds, wherein the mutual Sp of compound of more than two kinds¹And Sp²It is different.

10. the manufacturing method of liquid crystal display element according to any one of claim 1 to 9, as polymerizable liquid crystal group The liquid-crystal compounds in object is closed, the liquid-crystal compounds indicated using the following general formula (LC),

[changing 3]

In general formula (LC), R^LCIndicate the alkyl of carbon atom number 1~15,1 or 2 or more CH in the alkyl₂Base can be with oxygen The mode that atom does not abut directly against is replaced by-O- ,-CH=CH- ,-CO- ,-OCO- ,-COO- or-C ≡ C-, 1 in the alkyl Or 2 or more hydrogen atoms can arbitrarily be substituted into halogen atom, A^LC1And A^LC2It each independently represents selected from by following bases Group in the group of group (a), group (b) and group (c) composition,

(a) anti-form-1,4- cyclohexylidenes, 1 CH being present in the group₂Base or 2 or more not adjacent CH₂Base can quilt Oxygen atom or sulphur atom substitution,

(b) Isosorbide-5-Nitrae-phenylene, 1 CH base being present in the group or 2 or more not adjacent CH bases can be taken by nitrogen-atoms Generation,

(c) bicyclic (2.2.2) octamethylenes of 1,4-, naphthalene -2,6- diyls, decahydronaphthalene -2,6- diyls, 1,2,3,4- naphthanes -2,6- Diyl or chroman -2,6- diyl,

1 or 2 or more hydrogen atom contained by the group (a), group (b) or group (c) respectively can be former by fluorine atom, chlorine Son ,-CF₃Or-OCF₃Substitution,

Z^LCIndicate singly-bound ,-CH=CH- ,-CF=CF- ,-C ≡ C- ,-CH₂CH₂-、-(CH₂)₄-、-OCH₂-、-CH₂O-、- OCF₂-、-CF₂O- ,-COO- or-OCO-,

Y^LCThe alkyl for indicating hydrogen atom, fluorine atom, chlorine atom, cyano and carbon atom number 1~15,1 or 2 in the alkyl with On CH₂Base can in such a way that oxygen atom does not abut directly against by-O- ,-CH=CH- ,-CO- ,-OCO- ,-COO- ,-C ≡ C- ,- CF₂O-、-OCF₂Replacing, 1 or 2 or more hydrogen atom in the alkyl can arbitrarily be replaced by halogen atom,

A indicates 1~4 integer, and when a expressions 2,3 or 4, there are multiple A in general formula (LC)^LC1When, multiple A^LC1It can It is identical or different, when there are multiple Z^LCWhen, multiple Z^LCIt may be the same or different.

11. the manufacturing method of liquid crystal display element according to any one of claim 1 to 10, the list of liquid crystal display element Meta structure is VA patterns, IPS patterns, FFS mode, VA-TN patterns, TN patterns or ecb mode.

12. a kind of liquid crystal display element, in the liquid-crystal composition between being held at least one 2 transparent substrate with electrode Containing polymer or copolymer, the content of the polymer or copolymer is the conjunction of the liquid-crystal composition and the polymer or copolymer The 0.5 mass % for counting quality forms polymer network, the polymeric web less than 40 mass %, the polymer or copolymer Network has the refractive anisotrop of uniaxiality or easy axis of orientation, and has different state of orientation of more than two kinds.

13. liquid crystal display element according to claim 12, the different orientation shapes of more than two kinds as polymer network State has relative to transparent substrate plane in the tilted alignment of 0 degree to 30 degree of range and exists relative to transparent substrate plane The tilted alignment of 80 degree to 90 degree of range.

14. liquid crystal display element according to claim 12 or 13, having can will be in the display pixel of liquid crystal display element It is divided into the electrode of the shape in multiple domains, in a domain being divided out according to electrode shape, as polymer network Different state of orientation of more than two kinds, has：Relative to transparent substrate plane 0 degree to 30 degree of range tilted alignment, and The tilted alignment azimuth direction of the tilted alignment is fixed；And relative to transparent substrate plane in 80 degree to 90 degree of range Tilted alignment,

15. the liquid crystal display element according to any one of claim 12 to 14, according to the optical axis direction of polymer network Or be easily orientated the axis direction mode consistent with the liquid crystal molecular orientation in liquid-crystal composition and be orientated, as different of more than two kinds State of orientation has：Relative to transparent substrate plane 0 degree to 30 degree of range tilted alignment, and relative to transparent base Tilted alignment of the plate plane at 80 degree to 90 degree,

When without voltage is applied, liquid crystal molecule in liquid-crystal composition is pre- with 0 degree~90 degree relative to transparent substrate plane Inclination angle.

16. according to liquid crystal display element described in any one of claim 12 to 15, relative to unit section direction, it is formed with At least polymeric web network layers of 0.5% or more thickness of element thickness.

17. the liquid crystal display element according to any one of claim 12 to 16, as in polymerizable liquid crystal compound Polymerizable compound, using selected from by the one kind or two or more change in the following general formula (V) and the compound of logical formula (VI) expression Object is closed,

[changing 4]

In formula, X¹And X²Each independently represent hydrogen atom or methyl, Sp¹And Sp²Each independently represent singly-bound, carbon atom number 1 ~12 alkylidene or-O- (CH₂)_s, formula-O- (CH₂)_sIn, s indicates that 1~11 integer, oxygen atom are connected to aromatic rings, U Indicate the straight chain of carbon atom number 2~20 or the multivalence cyclic substituents of branch's polyvalent alkylene or carbon atom number 5~30, multivalence Alkylidene in alkylidene can be replaced in the range that oxygen atom does not abut by oxygen atom, or can be by the alkane of carbon atom number 5~20 Base or cyclic substituents replace, and the alkylidene in the alkyl of carbon atom number 5~20 can be in the range that oxygen atom does not abut by oxygen Atom replaces, the integer of k expressions 1~5, and arbitrary hydrogen atom can be substituted by-CH in all Isosorbide-5-Nitrae-phenylenes in formula₃、- OCH₃, fluorine atom or cyano,

[changing 5]

In formula, X³Indicate hydrogen atom or methyl, Sp³The alkylidene or-O- (CH of expression singly-bound, carbon atom number 1~12₂)_t, formula-O- (CH₂)_tIn, t indicates that 2~11 integer, oxygen atom are connected to aromatic rings, and V indicates straight chain or the branch of carbon atom number 2~20 The multivalence cyclic substituents of polyvalent alkylene or carbon atom number 5~30, the alkylidene in polyvalent alkylene can be not adjacent in oxygen atom Replaced by oxygen atom in the range of connecing, or can be replaced by the alkyl of carbon atom number 5~20 or cyclic substituents, carbon atom number 5~ Alkylidene in 20 alkyl can be replaced in the range that oxygen atom does not abut by oxygen atom, and W indicates hydrogen atom, halogen atom or carbon The alkyl of atomicity 1~15, arbitrary hydrogen atom can be substituted by-CH in all Isosorbide-5-Nitrae-phenylenes in formula₃、-OCH₃, fluorine it is former Son or cyano.

18. liquid crystal display element according to claim 17 is indicated as the polymerizable compound using logical formula (V) Sp¹With Sp²Identical one kind or two or more compound.

19. the liquid crystal display element according to claim 17 or 18 uses logical formula (V) as the polymerizable compound The Sp of expression¹With Sp²Identical compound of more than two kinds, wherein the mutual Sp of compound of more than two kinds¹And Sp²It is different.

20. the liquid crystal display element according to any one of claim 12 to 19, as in polymerizable liquid crystal compound Liquid-crystal compounds, the liquid-crystal compounds indicated using the following general formula (LC),

[changing 6]

Y^LCIndicate the alkyl of hydrogen atom, fluorine atom, chlorine atom, cyano and carbon atom number 1~15；1 or 2 in the alkyl with On CH₂Base can in such a way that oxygen atom does not abut directly against by-O- ,-CH=CH- ,-CO- ,-OCO- ,-COO- ,-C ≡ C- ,- CF₂O-、-OCF₂Replacing, 1 or 2 or more hydrogen atom in the alkyl can arbitrarily be replaced by halogen atom,

21. the liquid crystal display element according to any one of claim 12 to 20, cellular construction be VA patterns, IPS patterns, FFS mode, VA-TN patterns, TN patterns or ecb mode.