CN110383157A

CN110383157A - The manufacturing method of liquid crystal display element

Info

Publication number: CN110383157A
Application number: CN201880015641.0A
Authority: CN
Inventors: 平井吉治; 荻田和寛; 近藤史尚
Original assignee: Chisso Petrochemical Corp
Current assignee: JNC Petrochemical Corp
Priority date: 2017-06-28
Filing date: 2018-06-12
Publication date: 2019-10-25
Also published as: TW201905564A; WO2019003894A1; JPWO2019003894A1

Abstract

The present invention provides a kind of method for when making to be added to the tropism control layer formation monomer polymerization in liquid-crystal composition, forming tropism control layer effective for making liquid crystal molecule equably be horizontally oriented.There is the 1st substrate, the multiple pixel electrodes for being formed in the 1st substrate, the 2nd substrate, be formed in the 2nd substrate and in the liquid crystal display element of the opposite electrode opposite with the pixel electrode and the liquid crystal layer being held between the pixel electrode and the opposite electrode, monomer is formed for tropism control layer contained in the liquid crystal layer, with specific wavelength and illumination irradiation ultraviolet light on one side on one side carrying out heating polarisation in the first phase, in the non-heated lower non-polarized ultraviolet light for irradiating specific wavelength and illumination in second stage.

Description

The manufacturing method of liquid crystal display element

Technical field

The present invention relates to a kind of manufacturing methods of horizontally oriented type liquid crystal display element.More particularly to a kind of following liquid of utilization The manufacturing method of the liquid crystal display element of brilliant composition, in the liquid-crystal composition contains with light is generated not by light irradiation This tropism control layer for resetting the aromatic ester of (photo Fries rearrangement) forms monomer, and passes through describedization Close the effect of object and the horizontal alignment of liquid crystal molecule can be reached without using the alignment films of polyimides etc, and dielectric respectively to The opposite sex is positive or negative.

Background technique

In liquid crystal display element, the operating mode based on liquid crystal molecule is classified as phase transformation (phase change, PC), turns round Turn to column (twisted nematic, TN), STN Super TN (super twisted nematic, STN), electrically conerolled birefringence (electrically controlled birefringence, ECB), optical compensation curved (optically Compensated bend, OCB), coplanar switching (in-plane switching, IPS), vertical orientation (vertical Alignment, VA), fringing field switching (fringe field switching, FFS), electric field induction light reaction orientation (field-induced photo-reactive alignment, FPA) isotype.Driving method based on element is classified as Passive matrix (passive matrix, PM) and active matrix (active matrix, AM).PM is classified as static type (static), multiplex formula (multiplex) etc., AM be classified as thin film transistor (TFT) (thin film transistor, TFT), metal-insulator-metal type (metal insulator metal, MIM) etc..TFT's is classified as amorphous silicon (amorphous silicon) and polysilicon (polycrystal silicon).The latter is classified as height according to manufacturing step Warm type and low form.The reflection-type using natural light, the infiltration type using backlight are classified as and using nature based on light source The semi-transmission type of both light and backlight.

Liquid crystal display element contains with nematic liquid-crystal composition.The composition has characteristic appropriate.Pass through The characteristic of the composition is improved, can get the AM element with good characteristic.Association in two kinds of characteristics is summarized in down It states in table 1.The characteristic of composition is further illustrated based on commercially available AM element.Nematic temperature range and element Workable temperature range is associated.Nematic preferred ceiling temperature is about 70 DEG C or more, moreover, nematic preferred Lower limit temperature is about -10 DEG C or less.The viscosity of composition and the response time of element are associated.In order to show Dynamic Graph with element Picture, preferably response time are short.Preferably it is shorter than 1 millisecond of response time.It is therefore preferable that the viscosity for composition is small.It is more excellent The viscosity being selected as under low temperature is small.

The characteristic of 1. composition of table and the characteristic of AM element

The optical anisotropy of composition and the contrast of element are than associated.According to the mode of element, and need optics Anisotropy is big or optical anisotropy is small, i.e., optical anisotropy is appropriate.Optical anisotropy (Δ n) and the element of composition The product (Δ n × d) of cell gap (d) be designed to make contrast ratio maximum.The value of product appropriate depends on operating mode Type.Described value is about 0.45 μm in the element of the mode of TN etc.Described value is about 0.30 μ in the element of VA mode M to about 0.40 μm of range, the range for being about 0.20 μm to about 0.30 μm in the element of IPS mode or FFS mode.These feelings Under condition, preferably with big optically anisotropic composition for the element small to cell gap.The dielectric of composition is each The starting voltage that anisotropy facilitates greatly element is low, consumption electric power is small big with contrast ratio.It is therefore preferable that each for positive or negative dielectric Anisotropy is big.The specific resistance of composition facilitates greatly the voltage retention of element greatly with contrast than big.It is therefore preferable that being initial With the composition of big specific resistance in stage.Preferably after prolonged use with the composition of big specific resistance.Combination Object is associated with the service life of element to the stability of ultraviolet light and heat.When the stability is high, the service life of element is long.Such spy Property for the AM element for LCD monitor, LCD TV etc. preferably.

The composition with positive dielectric anisotropy is used in AM element with TN mode.AM member with VA mode The composition with negative dielectric anisotropy is used in part.Using with just in AM element with IPS mode or FFS mode Or the composition of negative dielectric anisotropy.Polymer stabilizing is orientated (polymer sustained alignment, PSA) type AM element in using with positive or negative dielectric anisotropy composition.Polymer stabilizing is orientated (polymer Sustained alignment, PSA) type liquid crystal display element in, use the liquid-crystal composition containing polymer.Firstly, will Composition added with a small amount of polymerizable compound is injected into element.Secondly, applying on one side between the substrate of the element Voltage irradiates ultraviolet light to composition on one side.Polymerizable compound is polymerize and generates the netted of polymer in the composition Structure.In the composition, the orientation of liquid crystal molecule can be controlled using polymer, therefore the response time of element shortens, figure The image retention of picture is improved.It can be expected that polymer in the element of mode with TN, ECB, OCB, IPS, VA, FFS, FPA etc Such effect.

IPS mode, FFS mode in ecb mode, need to make liquid crystal molecule in no applied voltage relative to the master of substrate Face is orientated in a generally horizontal direction.In order to realize the tropism control of such liquid crystal molecule, always using polyimides etc Alignment films.In recent years, the then width of the narrow frameization progress of liquid crystal display panel, alignment films and sealant narrows and Bonding strength Weaken, the interface of auto-orientation film and sealant is removed sometimes.Such problem in order to prevent, proposition have and without using existing The method of the alignment films of polyimides etc.(1~patent document of patent document 4)

On the other hand, in VA mode, it was also proposed that have the liquid crystal display element for the PSA type for not being previously formed alignment films.Institute Technology and the alignment films without using existing polyimides etc are stated, therefore are not easy to obtain uniform vertical orientation.In order to solve Such problem, proposition, which has, to be changed intensity or wavelength and carries out repeatedly for the purple of polymerizable compound contained in liquid-crystal composition The method of outer line exposing.(5~patent document of patent document 6)

Existing technical literature

Patent document

Patent document 1: International Publication No. 2015/146369

Patent document 2: International Publication No. 2017/057162

Patent document 3: Japanese Patent Laid-Open 2015-64465 bulletin

Patent document 4: Japanese Patent Laid-Open 2015-125151 bulletin

Patent document 5: Japanese Patent Laid-Open 2005-181582 bulletin

Patent document 6: No. 2010/053527 bulletin of U.S. Patent Publication

Summary of the invention

Problem to be solved by the invention

Project of the invention is to provide a kind of horizontally oriented type in the alignment films for not being previously formed polyimides etc In the manufacture of liquid crystal display element, in turn to the ultraviolet exposure step for the liquid-crystal composition comprising the controlling agent that is horizontally oriented Additional UV irradiation step, thus improves the method for the uniformity of the horizontal alignment of liquid crystal molecule.

There are as below methods for report: instead of the alignment films of polyimides etc using degraded with cinnamic acid ester group It closes object or polyvinyl cinnamate, the low molecular compound with chalcone structure or polymerizable compound, there is azobenzene The low molecular compound or dendritic (dendrimer) of structure come control liquid crystal orientation (patent document 1 and patent text It offers 2).In the method for patent document 1 and patent document 2, firstly, making the low molecular compound, polymerizable compound or polymerization Object is dissolved in liquid-crystal composition as additive.Secondly, packet is generated on substrate and separating the additive mutually Film containing the additive.Finally, irradiating linear polarization to be higher than the temperature of the ceiling temperature of liquid-crystal composition to substrate.? When low molecular compound or polymer carry out dimerization or isomerization by the linear polarization, molecule is on fixed-direction It is arranged.In the method, by selecting the type of additive, the member of the horizontal alignment mode of IPS or FFS etc can be manufactured The element of the vertical alignment mode of part and VA etc.In the method, it is important that additive is easy be higher than liquid-crystal composition Ceiling temperature at a temperature of dissolve, when restoring to room temperature, the compound is easy mutually to be separated from liquid-crystal composition.Its In, it is difficult to ensure the compatibility of additive and liquid-crystal composition.

In the method for patent document 3 and patent document 4, make that there is azobenzene to make as the dendritic of part-structure It is dissolved in liquid-crystal composition for additive.Secondly, by making the compound generate describedization on substrate and mutually separation Close the film of object.At this point, liquid-crystal composition is vertically oriented relative to substrate.Secondly, not heating the substrate and irradiating Linear polarization.When dendritic carries out dimerization or isomerization by the linear polarization, molecule is relative to base Plate and arranged on horizontal direction.The element of the horizontal alignment mode of IPS or FFS etc can be manufactured.In the method, Also must by dendritic and liquid-crystal composition it is appropriately combined be easy to carry out the dissolution of dendritic with mutually separate. In the case where using the dendritic with azobenzene as part-structure, there are asking for the coloring for being originated from azobenzene Topic.

The liquid crystal to the liquid-crystal composition comprising the polymerizable compound with non-liquid crystal property is disclosed in patent document 5 Show the method that element carries out 3 polymerization speeds ultraviolet exposure different from each other.The liquid crystal aligning applied herein is vertical orientation, And for vertical alignment-type liquid crystal display device relative, have no in the horizontally oriented type liquid crystal display element of the application Using relevant hint or record.It is disclosed in patent document 6 to comprising different from each other with ultraviolet radiation absorption peak wavelength The liquid crystal display element of the liquid-crystal composition of plural polymerizable compound carries out 2 wave-length coverages ultraviolet exposure different from each other Method.The liquid crystal aligning applied herein be vertical orientation, and for vertical alignment-type liquid crystal display device relative, have no with In the horizontally oriented type liquid crystal display element of the application using relevant hint or record.

Technical means to solve problem

Present invention discover that its polymerization is made by ultraviolet exposure using following liquid-crystal composition and under given conditions, by This can to solve the problem, so as to complete the present invention, the liquid-crystal composition contain have by ultraviolet light irradiate generate The tropism control layer of the aromatic ester of light Fries rearrangement forms monomer and has positive or negative dielectric anisotropy.This hair It is bright to include following forms etc..

[1] a kind of manufacturing method of horizontally oriented type liquid crystal display element, the horizontally oriented type liquid crystal display element are Liquid crystal layer is clamped between opposite a pair of of the substrate for configuring and being bonded via sealant, in the pair of substrate and the liquid crystal layer Between have to liquid crystal molecule carry out tropism control tropism control layer,

The liquid crystal layer includes liquid-crystal composition；And in the manufacturing method of the horizontally oriented type liquid crystal display element,

The liquid-crystal composition contains liquid crystal compounds, has positive or negative dielectric anisotropy, has from nematic phase To the transition temperature T of isotropic phase_NI, and containing it is at least one by light irradiation generate light Fries rearrangement, photoisomerization, The tropism control layer of any one of photodimerization, photodegradation forms monomer as the first additive；

Liquid crystal layer is remained into T_NIAbove temperature range, and to liquid crystal layer

It is 2mW/cm with illumination²To 200mW/cm²Range and be 1J/cm²To 15J/cm²Light exposure range polarisation 280nm is radiated at into 340nm with the first ultraviolet light of peak value；

Secondly, liquid crystal layer is remained room temperature (25 DEG C) to T_NITemperature range, be 1mW/cm with illumination²To 200mW/ cm²Range and be 1J/cm²To 15J/cm²Light exposure range illumination 330nm into 400nm with peak value second Ultraviolet light；

The tropism control layer is formed and making the tropism control layer form monomer polymerization.

[2] manufacturing method of the horizontally oriented type liquid crystal display element according to [1], wherein according to [1] One additive is tropism control layer represented by the formula (A) with the aromatic ester for generating light Fries rearrangement by light irradiation Monomer is formed,

In formula (A),

P¹⁰And P²⁰Independently indicate polymerism base；

Sp¹⁰And Sp²⁰It independently is the alkylidene of singly-bound or carbon number 1 to 12, at least one hydrogen of the alkylidene can be through fluorine Or hydroxyl replaces, at least one-CH₂It can replace through-O- ,-COO- ,-OCO- or formula (Q-1), at least one-CH₂-CH₂It can Replace through-CH=CH- or-C ≡ C-；

In formula (Q-1), M¹⁰、M²⁰And M³⁰Independently be hydrogen, fluorine, the alkyl of carbon number 1 to 5 or at least one hydrogen through fluorine or The alkyl for the carbon number 1 to 5 that chlorine replaces；Sp¹¹At least one hydrogen for singly-bound or the alkylidene of carbon number 1 to 12, the alkylidene can Replace through fluorine or hydroxyl, at least one-CH₂It can replace through-O- ,-COO- or-OCO-, at least one-CH₂-CH₂It can be through-CH =CH- or-C ≡ C- replaces；

Z¹⁰、Z²⁰And Z³⁰It independently is singly-bound ,-COO- ,-OCO- ,-OCOO ,-OCO-CH₂CH₂-、-CH₂CH₂-COO-、- CH₂O-、-OCH₂-、-CF₂O-、-OCF₂-、-C≡C-、-CONH-、-NHCO-、-(CH₂)₄-、-CH₂CH₂Or-CF₂CF₂-；

A¹⁰And A³⁰Independently be 1,4- phenylene, 1,4- cyclohexylidene, pyridine -2,5- diyl, pyrimidine -2,5- diyl, Naphthalene -2,6- diyl, naphthalene -1,5- diyl, naphthane -2,6- diyl, fluorenes -2,7- diyl, sub- biphenyl -4,4'- diyl or 1,3- bis- Oxane -2,5- diyl, in the Isosorbide-5-Nitrae-phenylene, arbitrary hydrogen can be through fluorine, chlorine, cyano, hydroxyl, formoxyl, acetoxyl group, second Acyl group, trifluoroacetyl group, difluoromethyl, trifluoromethyl, the alkyl of carbon number 1 to 5, carbon number 1 to 5 alkoxy or P¹⁰-Sp¹⁰- Z¹⁰Replace, in fluorenes -2,7- diyl, arbitrary hydrogen can replace through the alkyl of fluorine, carbon number 1 to 5, the Asia biphenyl -4,4'- In diyl, arbitrary hydrogen can take through the alkoxy of fluorine, difluoromethyl, trifluoromethyl, the alkyl of carbon number 1 to 5 or carbon number 1 to 5 Generation；

A²⁰For 1,4- phenylene represented by formula (A20-1), pyridine -2,5- diyl, pyrimidine -2,5- diyl, formula (A20-2) Represented naphthalene -2,6- diyl, naphthalene -1,5- diyl, sub- biphenyl -4,4'- diyl or formula (A20-4) represented by formula (A20-3) Represented fluorenes -2,7- diyl,

In Isosorbide-5-Nitrae-phenylene represented by formula (A20-1), Y¹⁰、Y¹¹、Y¹²And Y¹³Separately for hydrogen, fluorine, chlorine, cyano, Hydroxyl, formoxyl, acetoxyl group, acetyl group, trifluoroacetyl group, difluoromethyl, trifluoromethyl, carbon number 1 to 5 alkyl or carbon The alkoxy of number 1 to 5, Y¹⁰With Y¹³At least one be hydrogen,

In naphthalene -2,6- diyl represented by formula (A20-2), Y¹⁴、Y¹⁵、Y¹⁶、Y¹⁷、Y¹⁸And Y¹⁹Separately for hydrogen, fluorine, The alkyl of carbon number 1 to 5 or the alkoxy of carbon number 1 to 5, Y¹⁴With Y¹⁹At least one be hydrogen,

In sub- biphenyl -4,4'- diyl represented by formula (A20-3), Y²⁰、Y²¹、Y²²、Y²³、Y²⁴、Y²⁵、Y²⁶And Y²⁷It is only respectively It is on the spot the alkoxy of hydrogen, fluorine, difluoromethyl, trifluoromethyl, the alkyl of carbon number 1 to 5 or carbon number 1 to 5, Y²⁰With Y²⁷At least One is hydrogen,

In fluorenes -2,7- diyl represented by formula (A20-4), Y²⁸、Y²⁹、Y³⁰、Y³¹、Y³²And Y³³Separately for hydrogen, fluorine, The alkyl of carbon number 1 to 5, Y²⁸With Y³¹At least one be hydrogen；

n¹⁰Independently 0 to 3 integer；

In ultraviolet light irradiation, liquid crystal layer is remained into T_NIUp to T_NI+ 5 DEG C of temperature ranges below, are 2mW/ with illumination cm²To 100mW/cm²Range and be 1J/cm²To 13J/cm²The range polarisation of light exposure be radiated at 280nm into 340nm The first ultraviolet light with peak value；

Secondly, liquid crystal layer is remained room temperature (25 DEG C) to less than T_NITemperature range, be 1mW/cm with illumination²Extremely 100mW/cm²Range and be 1J/cm²To 14J/cm²Light exposure range illumination 330nm into 400nm have peak value The second ultraviolet light.

[3] manufacturing method of the horizontally oriented type liquid crystal display element according to [1], wherein the purple according to [1] In outside line irradiation, liquid crystal layer is remained into T_NIUp to T_NI+ 5 DEG C of temperature ranges below, are 2mW/cm with illumination²To 100mW/ cm²Range and be 1J/cm²To 11J/cm²The range polarisation of light exposure be radiated at 280nm into 340nm with peak value First ultraviolet light；

It is 1mW/cm with illumination secondly, liquid crystal layer is remained room temperature (25 DEG C) to 45 DEG C of temperature ranges below²Extremely 50mW/cm²Range and be 1J/cm²To 14J/cm²Light exposure range illumination in 330nm into 400nm with peak value Second ultraviolet light.

[4] manufacturing method of the horizontally oriented type liquid crystal display element according to [2], wherein the formula according to [2] (A) in,

P¹⁰And P²⁰Independently indicate acryloxy, methacryloxy, α-fluorinated monomer, trifluoromethyl propylene Acid esters, vinyl, vinyl oxygroup, epoxy group；

Sp¹⁰And Sp²⁰It independently is the alkylidene of singly-bound or carbon number 1 to 12, at least one hydrogen of the alkylidene can be through fluorine Or hydroxyl replaces, at least one-CH₂It can replace through-O- ,-COO- or-OCO-, at least one-CH₂-CH₂It can be through-CH= CH- or-C ≡ C- replaces；

Z¹⁰、Z²⁰And Z³⁰It independently is singly-bound ,-COO- ,-OCO- ,-OCOO- ,-OCO-CH₂CH₂-、-CH₂CH₂-COO-、- CH₂O-、-OCH₂-、-CF₂O-、-OCF₂-、-C≡C-、-CONH-、-NHCO-、-(CH₂)₄-、-CH₂CH₂Or-CF₂CF₂-；

A¹⁰And A³⁰It independently is 1,4- phenylene, 1,4- cyclohexylidene, naphthalene -2,6- diyl, naphthalene -1,5- diyl, fluorenes -2, 7- diyl, sub- biphenyl -4,4'- diyl, in the Isosorbide-5-Nitrae-phenylene, arbitrary hydrogen can be through fluorine, cyano, hydroxyl, acetoxyl group, second Acyl group, trifluoroacetyl group, difluoromethyl, trifluoromethyl, the alkyl of carbon number 1 to 5, carbon number 1 to 5 alkoxy or P¹⁰-Sp¹⁰- Z¹⁰Replace, in fluorenes -2,7- diyl, arbitrary hydrogen can replace through the alkyl of fluorine, carbon number 1 to 5, the Asia biphenyl -4,4'- In diyl, arbitrary hydrogen can take through the alkoxy of fluorine, difluoromethyl, trifluoromethyl, the alkyl of carbon number 1 to 5 or carbon number 1 to 5 Generation；

A²⁰For naphthalene -2,6- diyl, formula (A20- represented by 1,4- phenylene represented by formula (A20-1), formula (A20-2) 3) fluorenes -2,7- diyl represented by sub- biphenyl -4, the 4'- diyl or formula (A20-4) represented by,

In Isosorbide-5-Nitrae-phenylene represented by formula (A20-1), Y¹⁰、Y¹¹、Y¹²And Y¹³It separately can be through hydrogen, fluorine, chlorine, cyanogen Base, hydroxyl, formoxyl, acetoxyl group, acetyl group, trifluoroacetyl group, difluoromethyl, trifluoromethyl, carbon number 1 to 5 alkyl or The alkoxy of carbon number 1 to 5 replaces, Y¹⁰With Y¹³At least one be hydrogen,

In naphthalene -2,6- diyl represented by formula (A20-2), Y¹⁴、Y¹⁵、Y¹⁶、Y¹⁷、Y¹⁸And Y¹⁹Separately can through hydrogen, The alkoxy of fluorine, the alkyl of carbon number 1 to 5 or carbon number 1 to 5 replaces, Y¹⁴With Y¹⁹At least one be hydrogen,

In sub- biphenyl -4,4'- diyl represented by formula (A20-3), Y²⁰、Y²¹、Y²²、Y²³、Y²⁴、Y²⁵、Y²⁶And Y²⁷It is only respectively It can on the spot replace through the alkoxy of hydrogen, fluorine, difluoromethyl, trifluoromethyl, the alkyl of carbon number 1 to 5 or carbon number 1 to 5, Y²⁰With Y²⁷ At least one be hydrogen,

n¹⁰Independently 0 to 3 integer.

[5] manufacturing method of the horizontally oriented type liquid crystal display element according to any one of [1] to [4], wherein institute State tropism control layer formed monomer by formula (A-1) to formula (A-3) any one represented by；

Formula (A-1) into formula (A-3),

R¹⁰It independently is hydrogen, fluorine, methyl or trifluoromethyl；

R³¹It independently is hydrogen or methyl；

A²⁰It independently is sub- biphenyl -4,4'- two represented by 1,4- phenylene represented by formula (A20-1), formula (A20-3) Fluorenes -2,7- diyl represented by base or formula (A20-4),

In Isosorbide-5-Nitrae-phenylene represented by formula (A20-1), Y¹⁰、Y¹¹、Y¹²And Y¹³Separately can through hydrogen, fluorine, hydroxyl, The alkoxy substitution of difluoromethyl, trifluoromethyl, the alkyl of carbon number 1 to 5 or carbon number 1 to 5, Y¹⁰With Y¹³At least one be Hydrogen,

A³⁰It independently is 1,4- phenylene, naphthalene -2,6- diyl, naphthalene -1,5- diyl, fluorenes -2,7- diyl, sub- biphenyl -4,4'- Diyl, in the Isosorbide-5-Nitrae-phenylene, arbitrary hydrogen can through fluorine, hydroxyl, difluoromethyl, trifluoromethyl, carbon number 1 to 5 alkyl or The alkoxy of carbon number 1 to 5 replaces, and in fluorenes -2,7- diyl, arbitrary hydrogen can replace through the alkyl of fluorine, carbon number 1 to 5, described In sub- biphenyl -4,4'- diyl, arbitrary hydrogen can through fluorine, difluoromethyl, trifluoromethyl, carbon number 1 to 5 alkyl or carbon number 1 to 5 Alkoxy replace；

L¹⁰Independently be hydrogen, fluorine, difluoromethyl, trifluoromethyl, the alkyl of carbon number 1 to 5, carbon number 1 to 5 alkoxy or P¹⁰-Sp¹⁰-Z¹⁰-；

n¹¹Independently 0 to 4 integer.

[6] manufacturing method of the horizontally oriented type liquid crystal display element according to any one of [1] to [5], wherein When the total amount of liquid crystal compounds is set as 100 parts by weight, the ratio that the tropism control layer forms monomer is 0.1 parts by weight To the range of 10.0 parts by weight.

[7] manufacturing method of the horizontally oriented type liquid crystal display element according to any one of [1] to [6], wherein institute It states liquid-crystal composition and contains at least one of the group of compound represented by the formula (2) to formula (4) compound；

Formula (2) into formula (4),

R¹¹And R¹²It independently is the alkyl of carbon number 1 to 10 or the alkenyl of carbon number 2 to 10, in the alkyl and alkenyl, at least One-CH₂It can replace through-O-, at least one hydrogen can be fluorine-substituted；

Ring B¹, ring B², ring B³And ring B⁴It independently is the fluoro- 1,4- phenylene of 1,4- cyclohexylidene, 1,4- phenylene, 2-, 2, The fluoro- 1,4- phenylene of 5- bis- or pyrimidine -2,5- diyl；

Z¹¹、Z¹²And Z¹³It independently is singly-bound ,-(CH₂)₂,-CH=CH- ,-C ≡ C- or-COO-.

[8] manufacturing method of the horizontally oriented type liquid crystal display element according to any one of [1] to [7], wherein institute It states liquid-crystal composition and then contains at least one of the group of compound represented by the formula (5) to formula (7) compound；

Formula (5) into formula (7),

R¹³For the alkyl of carbon number 1 to 10 or the alkenyl of carbon number 2 to 10, in the alkyl and alkenyl, at least one-CH₂It can Replace through-O-, at least one hydrogen can be fluorine-substituted；

X¹¹For fluorine, chlorine ,-OCF₃、-OCHF₂、-CF₃、-CHF₂、-CH₂F、-OCF₂CHF₂Or-OCF₂CHFCF₃；

Ring C¹, ring C²And ring C³Independently be 1,4- cyclohexylidene, the 1,4- phenylene that at least one hydrogen can be fluorine-substituted, Oxinane -2,5- diyl, 1,3- dioxanes -2,5- diyl or pyrimidine -2,5- diyl；

Z¹⁴、Z¹⁵And Z¹⁶It independently is singly-bound ,-(CH₂)₂,-CH=CH- ,-CH=CF- ,-CF=CF- ,-C ≡ C- ,- COO-、-CF₂O-、-OCF₂-、-CH₂O- ,-CH=CF-CF₂O- ,-CF=CF-CF₂O- or-(CH₂)₄-；

L¹¹And L¹²It independently is hydrogen or fluorine.

[9] manufacturing method of the horizontally oriented type liquid crystal display element according to any one of [1] to [8], wherein institute It states liquid-crystal composition and then contains at least one of the group of compound represented by formula (8) compound；

In formula (8),

R¹⁴For the alkyl of carbon number 1 to 10 or the alkenyl of carbon number 2 to 10, in the alkyl and alkenyl, at least one-CH₂It can Replace through-O-, at least one hydrogen can be fluorine-substituted；

X¹²For-C ≡ N or-C ≡ C-C ≡ N；

Ring D¹For 1,4- cyclohexylidene, at least one hydrogen can be fluorine-substituted 1,4- phenylene, oxinane -2,5- two Base, 1,3- dioxanes -2,5- diyl or pyrimidine -2,5- diyl；

Z¹⁷For singly-bound ,-(CH₂)₂-、-C≡C-、-COO-、-CF₂O-、-OCF₂Or-CH₂O-；

L¹³And L¹⁴It independently is hydrogen or fluorine；

I is 1,2,3 or 4.

[10] manufacturing method of the horizontally oriented type liquid crystal display element according to any one of [1] to [9], wherein institute It states liquid-crystal composition and then contains at least one of the group of compound represented by the formula (9) to formula (15) compound；

Formula (9) into formula (15),

R¹⁵And R¹⁶It independently is the alkyl of carbon number 1 to 10 or the alkenyl of carbon number 2 to 10, in the alkyl and alkenyl, at least One-CH₂It can replace through-O-, at least one hydrogen can be fluorine-substituted；

R¹⁷For the alkenyl of hydrogen, fluorine, the alkyl of carbon number 1 to 10 or carbon number 2 to 10, in the alkyl and alkenyl, at least one- CH₂It can replace through-O-, at least one hydrogen can be fluorine-substituted；

Ring E¹, ring E², ring E³And ring E⁴Independently being 1,4- cyclohexylidene, 1,4- cyclohexadienylidene, at least one hydrogen can be through Fluorine-substituted 1,4- phenylene, oxinane -2,5- diyl or decahydronaphthalene -2,6- diyl；

Ring E⁵And ring E⁶It independently is 1,4- cyclohexylidene, 1,4- cyclohexadienylidene, 1,4- phenylene, oxinane -2,5- Diyl or decahydronaphthalene -2,6- diyl；

Z¹⁸、Z¹⁹、Z²⁰And Z²¹It independently is singly-bound ,-(CH₂)₂-、-COO-、-CH₂O-、-OCF₂Or-OCF₂CH₂CH₂-；

L¹⁵And L¹⁶It independently is fluorine or chlorine；

S¹¹For hydrogen or methyl；

X independently is-CHF- or-CF₂-；

J, k, m, n, p, q, r and s independently are 0 or 1, k, m, n and p and be 1 or 2, q, r and s and be 0,1,2 or 3, T is 1,2 or 3.

[11] manufacturing method of the horizontally oriented type liquid crystal display element according to any one of [1] to [10], wherein The liquid-crystal composition contains polymerizable compound represented by formula (16 α) as the second additive in turn, and is formed comprising logical Cross the tropism control layer for making the polymerization of these compounds and the copolymer of generation；

In formula (16 α),

Ring F and ring I independently is cyclohexyl, cyclohexenyl group, phenyl, 1- naphthalene, 2- naphthalene, oxinane -2- base, 1,3- Dioxanes -2- base, pyrimidine -2-base or pyridine -2- base, in these rings, at least one hydrogen can through fluorine, chlorine, carbon number 1 to 12 alkane The alkyl for the carbon number 1 to 12 that base or at least one hydrogen replace through fluorine or chlorine replaces；

Ring G be 1,4- cyclohexylidene, 1,4- cyclohexadienylidene, 1,4- phenylene, naphthalene -1,2- diyl, naphthalene -1,3- diyl, Naphthalene -1,4- diyl, naphthalene -1,5- diyl, naphthalene -1,6- diyl, naphthalene -1,7- diyl, naphthalene -1,8- diyl, naphthalene -2,3- diyl, naphthalene -2, 6- diyl, naphthalene -2,7- diyl, oxinane -2,5- diyl, 1,3- dioxanes -2,5- diyl, pyrimidine -2,5- diyl or pyrrole Pyridine -2,5- diyl, in these rings, at least one hydrogen can through fluorine, chlorine, the alkyl of carbon number 1 to 12, carbon number 1 to 12 alkoxy or The alkyl for the carbon number 1 to 12 that at least one hydrogen replaces through fluorine or chlorine replaces；

Z²²And Z²³It independently is the alkylidene of singly-bound or carbon number 1 to 10, in the alkylidene, at least one-CH₂Can through- O- ,-CO- ,-COO- or-OCO- replace, at least one-(CH₂)₂It can be through-CH=CH- ,-C (CH₃)=CH- ,-CH=C (CH₃)-or-C (CH₃)=C (CH₃)-replace, in these bases, at least one hydrogen can replace through fluorine or chlorine；

P¹¹、P¹²And P¹³It independently is polymerism base；

Sp¹¹、Sp¹²And Sp¹³It independently is the alkylidene of singly-bound or carbon number 1 to 10, in the alkylidene, at least one- CH₂It can replace through-O- ,-COO- ,-OCO- or-OCOO-, at least one-(CH₂)₂It can replace through-CH=CH- or-C ≡ C-, In these bases, at least one hydrogen can replace through fluorine or chlorine；

U is 0,1 or 2；

F, g and h independently is 0,1,2,3 or 4, and f, g and h and be 2 or more.

[12] manufacturing method of the horizontally oriented type liquid crystal display element according to [11], wherein according to [11] In formula (16 α), P¹¹、P¹²And P¹³It independently is in the group for being selected from polymerism base represented by formula (P-1) to formula (P-5) Base；

Formula (P-1) into formula (P-5),

M¹¹、M¹²And M¹³It independently is the carbon number that hydrogen, fluorine, the alkyl of carbon number 1 to 5 or at least one hydrogen replace through fluorine or chlorine 1 to 5 alkyl.

[13] manufacturing method of the horizontally oriented type liquid crystal display element according to any one of [11] to [12], wherein When the total amount of liquid crystal compounds is set as 100 parts by weight, the ratio of the second additive in liquid-crystal composition is 0.03 Parts by weight to 10 parts by weight range.

[14] a kind of display device, including what is obtained by the manufacturing method according to any one of [1] to [13] Horizontally oriented type liquid crystal display element；And backlight.

This illustration also includes following item.(a) and then contain polymerizable compound, polymerization initiator, polymerization inhibitor, optics At least the two of the additive of reactive compound, antioxidant, ultraviolet absorbing agent, light stabilizer, heat stabilizer, defoaming agent etc The liquid-crystal composition of kind.(b) different from compound (A) or compound (16 α) by being added in the liquid-crystal composition Polymerizable compound and the polymerizable composition, polymerizable composition for preparing.(c) by adding compound (A) in the liquid-crystal composition and changing The polymerizable composition, polymerizable composition for closing object (16 α) and preparing.(d) the liquid crystal complex prepared and polymerizeing polymerizable composition, polymerizable composition.(e) The element of polymer stabilizing orientating type containing the liquid crystal complex.(f) by adding chemical combination in the liquid-crystal composition Object (A) prepares polymerism group from compound (16 α) and with compound (A) or compound (16 α) different polymerizable compound Close object, the element of the polymer stabilizing orientating type made by using prepared polymerizable composition, polymerizable composition.

The effect of invention

According to the present invention, by the liquid crystal display element for including the liquid-crystal composition comprising tropism control layer formation monomer Carry out the ultraviolet exposure of condition different from each other, it can be achieved that light transmission rate or contrast than excellent horizontally oriented type liquid Crystal display element.

In turn, the forming step that alignment films are not needed in the manufacture of the liquid crystal display element of horizontally oriented type, can cut down liquid The manufacturing cost of crystal display element.

Specific embodiment

The application method of term in the specification is as described below.Sometimes by " liquid-crystal composition " and " liquid crystal display member The term of part " is briefly referred to as " composition " and " element "." liquid crystal display element " is liquid crystal display panel and liquid crystal display mode The general name of block." liquid crystal compounds " be compound with liquid crystalline phases such as nematic phase, smectic phases and do not have liquid crystalline phase but The change into composition is mixed for the purpose of the characteristic for adjusting nematic temperature range, viscosity, dielectric anisotropy etc Close the general name of object.The compound has the six membered ring of such as 1 or 4 cyclohexylidene or Isosorbide-5-Nitrae-phenylene etc, molecular structure For rodlike (rod like)." polymerizable compound " is the compound of addition for the purpose of generating polymer in the composition.

Liquid-crystal composition is prepared by mixing plurality of liquid crystals compound.In the liquid-crystal composition optionally To add optically active compound, antioxidant, ultraviolet absorbing agent, pigment, defoaming agent, polymerizable compound, polymerization initiation The additive of agent, polymerization inhibitor, polar compound etc.Even if in the case where being added with additive, liquid crystal compounds Ratio be also by being indicated based on the weight percent (weight %) of the weight for the liquid-crystal composition for not including additive.Addition The ratio of object is by being indicated based on the weight percent (parts by weight) of the weight for the liquid-crystal composition for not including additive.That is, The ratio of liquid crystal compounds or additive is the total weight based on liquid crystal compounds and calculates.Sometimes weight million is also used Divide rate (ppm).The ratio of polymerization initiator is exceptionally to be indicated based on the weight of polymerizable compound.

Sometimes compound represented by formula (A) is referred to as " compound (A) ".Compound (A) refers to represented by formula (A) A kind of mixture of the compound of compound, the mixture of two kinds of compounds or three kinds or more.The rule is also applied to be selected from By at least one of the group of compound represented by formula (2) compound etc..The B surrounded by hexagon¹、C¹、D¹、E¹Deng note Number correspond respectively to ring B¹, ring C¹, ring F etc..Hexagon indicates the contracting of the six membered ring or naphthalene nucleus etc of cyclohexane ring or phenyl ring etc Cyclization.The crosscutting straight line in one side of hexagon, formula (A-3), in formula (16 α), is indicated any on ring at formula (A-2) by formula (A-1) Hydrogen can be through-(L¹⁰)n¹¹Or-Sp¹-P¹Equal bases replace.Subscripts such as ' f ' indicate the quantity for the base being substituted.When being designated as 0 under, There is no such substitutions.When subscript ' f ' is 2 or more, there are multiple-Sp on ring F¹-P¹。-Sp¹-P¹Represented multiple bases Can be identical, or can also be different.These rules are also applied in other formulas.The statement of " ring F and ring G independently are X, Y or Z " In, because subject is multiple, therefore use " independently ".When subject is " ring F ", because subject is odd number, therefore without using " independent Ground ".

By terminal groups R¹¹Mark be used for Multiple components compound.In these compounds, arbitrary two R¹¹Represented Two bases can be identical, or can also be different.For example, there is the R of compound (2)¹¹For ethyl, and the R of compound (3)¹¹For ethyl Situation.Also there is the R of compound (2)¹¹For ethyl, and the R of compound (3)¹¹The case where for propyl.The rule is also applied to it The mark of his terminal groups, ring, bond base etc..In formula (8), when i is 2, there are two ring D¹.In the compound, two ring D¹ Two represented bases can be identical, or can also be different.The rule is also applied to arbitrary two ring D of the i greater than 2 when¹.Institute State the mark that rule is also applied to other rings, bond base etc..

The statement of " at least one ' A ' " refers to that the quantity of ' A ' is any.The statement of " at least one ' A ' can replace through ' B ' " ' A ' quantity be one when, refer to the position of ' A ' be it is any, ' A ' quantity for two or more when, these position It can unlimitedly select.The rule is also applied to the statement of " at least one ' A ' replaces through ' B ' "." at least one A can be through B, C Or D replace " statement refer to include the case where the case where at least one A replaces through B, at least one A replaces through C and at least one The case where A replaces through D, and then include the case where at least two substitutions of multiple A through B, C, D.For example, at least one-CH₂- (or-(CH₂)₂) can include through the alkyl of-O- (or-CH=CH-) substitution: alkyl, alkenyl, alkoxy, alkoxyalkyl, alcoxyl Base alkenyl, alkenyloxy group alkyl.Furthermore continuous two-CH₂The case where warp-O- replaces and becomes-O-O-, is bad.Alkyl etc. In, methyl moiety (- CH₂- H)-CH₂The case where warp-O- replaces and becomes-O-H, is also bad.

In liquid crystal compounds, alkyl is straight-chain or branch-like, does not include cyclic alkyl.Straight-chain alkyl is typically superior to Branch-like alkyl.About terminal groups such as alkoxy, alkenyls, these situations are also the same.In order to improve nematic ceiling temperature, with The relevant spatial configuration of 1,4- cyclohexylidene is trans- better than cis-.The fluoro- 1,4- phenylene of 2- refers to two kinds of following bilvalent radicals. In chemical formula, fluorine can be for the left (L), can also be for the right (R).The rule is also applied to oxinane -2,5- diyl etc The asymmetrical bilvalent radical generated and removing two hydrogen from ring.

In the manufacturing method of horizontally oriented type liquid crystal display element of the invention, enclose in the component in a liquid crystal composition Addition generates the tropism control layer of any one of light Fries rearrangement, photoisomerization, photodimerization, photodegradation by light irradiation Form liquid-crystal composition made of monomer.

Tropism control layer forms monomer and is changed by polarisation irradiation structure with directionality, therefore facilitates liquid The tropism control of brilliant molecule.In addition, because having polymerism base, therefore include that tropism control layer forms the polymer of monomer with work For the effect of tropism control film.

The compound for having the aromatic ester for generating light Fries rearrangement is illustrated.With generation light Fries rearrangement The compound of aromatic ester refer to that absorbing ultraviolet light and aromatic ester position carries out free radical cracking and generate for hydroxy-ketone Rearrangement compound, be compound represented by formula (A) and formula (A-1) to formula (A-3) in the present invention.Preferably formula (A- 1), compound, more preferably compound represented by formula (A-1) represented by formula (A-2) and formula (A-3).

Compound with aromatic ester and with polymerism base carries out light by irradiating ultraviolet light aromatic ester position It decomposes, free radical is consequently formed, and generate light Fries rearrangement.In light Fries rearrangement, the photodegradation at aromatic ester position exists The long axis direction at the polarization direction of polarisation ultraviolet light and aromatic ester position is to generate in the case where the same direction.After photodegradation, It is bonded again and hydroxyl is generated by tautomerization in the molecule.Think to generate substrate interface by the hydroxyl Interaction, tropism control layer formed monomer substrate interface side have anisotropy and be easy absorption.In addition, poly- because having Conjunction property base, therefore by polymerizeing immobilization.It can make the film of liquid crystal molecular orientation using property preparation.In order to make The standby film, the ultraviolet light of irradiation suitably linear polarization.Firstly, in a liquid crystal composition, by liquid crystal compounds Range of total amount when being set as 100 parts by weight for 0.1 parts by weight to 10 parts by weight add tropism control layer and form monomer, and be Tropism control layer is set to form monomer dissolution and heat to composition.The composition is injected into without alignment films In element.Secondly, linear polarization is irradiated while heating to element, in so that tropism control layer is formed monomer progress light not This is reset and makes its polymerization.

Tropism control layer through light Fries rearrangement forms monomer and arranges on fixed-direction, and the film formed after polymerizeing With the function as liquid crystal orientation film.

Tropism control layer forms monomer and is referred to as compound (A) in the present specification.In turn, in the details for referring to structure In the case of etc., optionally it is distinguished referred to as compound (A-1), compound (A-2), compound (A-3).Hereinafter, sequentially illustrating 1. Compound (A), the synthesis of 2. compounds (A), as 3. liquid-crystal compositions of the composition comprising compound (A), as containing 4. liquid crystal display elements of the element of the composition.

1. compound (A)

1-1. compound (A), using its liquid-crystal composition illustration

Compound represented by a kind of formula (A).

Formula (A), formula (A-1) into formula (A-3),

P¹⁰And P²⁰Independently be polymerism base, preferably acryloxy, methacryloxy, α-fluorinated monomer, Trifluoromethyl acrylate ester, vinyl, vinyl oxygroup, epoxy group.

Sp¹⁰And Sp²⁰It independently is the alkylidene of singly-bound or carbon number 1 to 12, at least one hydrogen of the alkylidene can be through fluorine Or hydroxyl replaces, at least one-CH₂It can replace through-O- ,-COO- ,-OCO- or formula (Q-1), at least one-CH₂-CH₂It can Replace through-CH=CH- or-C ≡ C-.

In formula (Q-1), M¹⁰、M²⁰And M³⁰Independently be hydrogen, fluorine, the alkyl of carbon number 1 to 5 or at least one hydrogen through fluorine or The alkyl for the carbon number 1 to 5 that chlorine replaces, Sp¹¹At least one hydrogen for singly-bound or the alkylidene of carbon number 1 to 12, the alkylidene can Replace through fluorine or hydroxyl, at least one-CH₂It can replace through-O- ,-COO- or-OCO-, at least one-CH₂-CH₂It can be through-CH =CH- or-C ≡ C- replaces.

Z¹⁰、Z²⁰And Z³⁰It independently is singly-bound ,-COO- ,-OCO- ,-OCOO ,-OCO-CH₂CH₂-、-CH₂CH₂-COO-、- CH₂O-、-OCH₂-、-CF₂O-、-OCF₂-、-C≡C-、-CONH-、-NHCO-、-(CH₂)₄-、-CH₂CH₂Or-CF₂CF₂, preferably For

Singly-bound ,-COO- ,-OCO- ,-OCO-CH₂CH₂-、-CH₂CH₂-COO-、-CH₂O-、-OCH₂-、-CF₂O-、-OCF₂-、- C ≡ C- or-CH₂CH₂-。

A¹⁰And A³⁰Independently be 1,4- phenylene, 1,4- cyclohexylidene, pyridine -2,5- diyl, pyrimidine -2,5- diyl, Naphthalene -2,6- diyl, naphthalene -1,5- diyl, naphthane -2,6- diyl, fluorenes -2,7- diyl, sub- biphenyl -4,4'- diyl or 1,3- bis- Oxane -2,5- diyl, in the Isosorbide-5-Nitrae-phenylene, arbitrary hydrogen can be through fluorine, chlorine, cyano, hydroxyl, formoxyl, acetoxyl group, second Acyl group, trifluoroacetyl group, difluoromethyl, trifluoromethyl, the alkyl of carbon number 1 to 5, carbon number 1 to 5 alkoxy or P¹⁰-Sp¹⁰- Z¹⁰Replace, in fluorenes -2,7- diyl, arbitrary hydrogen can replace through the alkyl of fluorine, carbon number 1 to 5, the Asia biphenyl -4,4'- In diyl, arbitrary hydrogen can take through the alkoxy of fluorine, difluoromethyl, trifluoromethyl, the alkyl of carbon number 1 to 5 or carbon number 1 to 5 Generation, preferably Isosorbide-5-Nitrae-phenylene, 1 or 4 cyclohexylidene, naphthalene -2,6- diyl, naphthalene -1,5- diyl, fluorenes -2,7- diyl, sub- biphenyl - 4,4'- diyls, in the Isosorbide-5-Nitrae-phenylene, arbitrary hydrogen can be through fluorine, cyano, hydroxyl, acetoxyl group, acetyl group, trifluoroacetyl Base, difluoromethyl, trifluoromethyl, the alkyl of carbon number 1 to 5 or carbon number 1 to 5 alkoxy replace, in fluorenes -2,7- diyl, Arbitrary hydrogen can replace through the alkyl of fluorine, carbon number 1 to 5, and in Asia biphenyl -4,4'- diyl, arbitrary hydrogen can be through fluorine, difluoro The alkoxy substitution of methyl, trifluoromethyl, the alkyl of carbon number 1 to 5 or carbon number 1 to 5.

A²⁰It independently is 1,4- phenylene represented by formula (A20-1), pyridine -2,5- diyl, pyrimidine -2,5- diyl, formula (A20-2) sub- biphenyl -4,4'- diyl or formula represented by the naphthalene -2,6- diyl, naphthalene -1,5- diyl, formula (A20-3) represented by (A20-4) fluorenes -2,7- diyl represented by, preferably Isosorbide-5-Nitrae-phenylene, formula (A20-2) represented by formula (A20-1) are represented Naphthalene -2,6- diyl, fluorenes -2,7- two represented by sub- biphenyl -4,4'- diyl or formula (A20-4) represented by formula (A20-3) Isosorbide-5-Nitrae-phenylene represented by base, more preferably formula (A20-1), sub- biphenyl -4,4'- diyl or formula represented by formula (A20-3) (A20-4) fluorenes -2,7- diyl represented by.

In Isosorbide-5-Nitrae-phenylene represented by formula (A20-1), Y¹⁰、Y¹¹、Y¹²And Y¹³Separately for hydrogen, fluorine, chlorine, cyano, Hydroxyl, formoxyl, acetoxyl group, acetyl group, trifluoroacetyl group, difluoromethyl, trifluoromethyl, carbon number 1 to 5 alkyl or carbon The alkoxy of number 1 to 5, Y¹⁰With Y¹³At least one be hydrogen.Preferably Y¹⁰、Y¹¹、Y¹²And Y¹³Separately for hydrogen, fluorine, chlorine, Cyano, hydroxyl, formoxyl, acetoxyl group, acetyl group, trifluoroacetyl group, difluoromethyl, trifluoromethyl, carbon number 1 to 5 alkyl, Or the alkoxy of carbon number 1 to 5, Y¹⁰With Y¹³At least one be hydrogen.More preferably Y¹⁰、Y¹¹、Y¹²And Y¹³Be separately hydrogen, Fluorine, hydroxyl, difluoromethyl, trifluoromethyl, the alkyl of carbon number 1 to 5 or carbon number 1 to 5 alkoxy, Y¹⁰With Y¹³At least one For hydrogen.

In naphthalene -2,6- diyl represented by formula (A20-2), Y¹⁴、Y¹⁵、Y¹⁶、Y¹⁷、Y¹⁸And Y¹⁹Separately for hydrogen, fluorine, The alkyl of carbon number 1 to 5 or the alkoxy of carbon number 1 to 5, Y¹⁴With Y¹⁹At least one be hydrogen.

In sub- biphenyl -4,4'- diyl represented by formula (A20-3), Y²⁰、Y²¹、Y²²、Y²³、Y²⁴、Y²⁵、Y²⁶And Y²⁷It is only respectively It is on the spot the alkoxy of hydrogen, fluorine, difluoromethyl, trifluoromethyl, the alkyl of carbon number 1 to 5 or carbon number 1 to 5, Y²⁰With Y²⁷At least One is hydrogen.

In fluorenes -2,7- diyl represented by formula (A20-4), Y²⁸、Y²⁹、Y³⁰、Y³¹、Y³²And Y³³Separately for hydrogen, fluorine, The alkyl of carbon number 1 to 5, Y²⁸With Y³¹At least one be hydrogen.

n¹⁰Independently 0 to 3 integer.

Formula (A-1) into formula (A-3),

R¹⁰For hydrogen, fluorine or methyl, preferably hydrogen or methyl.

R³¹For hydrogen or methyl, preferably hydrogen.

L¹⁰It independently is the alkoxy of hydrogen, fluorine, difluoromethyl, trifluoromethyl, the alkyl of carbon number 1 to 5 or carbon number 1 to 5, The preferably alkoxy of hydrogen, fluorine, trifluoromethyl, the alkyl of carbon number 1 to 5 or carbon number 1 to 5.

n¹¹Independently 0 to 4 integer, preferably 0 to 2 integer, more preferably 0 or 1.

The form of 1-2. compound (A)

Compound (A) is characterized by having generating aromatic ester position and the polymerism base of light Fries rearrangement.Change Object (A) is closed if generating light Fries rearrangement, polar group and substrate surface by ultraviolet light irradiation with the side of non-covalently bonded Formula interacts, therefore useful.One of purposes is liquid-crystal composition additive used in liquid crystal display element.Change Closing object (A) is added for the purpose of the orientation for controlling liquid crystal molecule.Such additive preferably has in a liquid crystal composition High solubility, and the chemical stabilization and in the case where liquid crystal display element under conditions of being enclosed within element Voltage retention is big.Compound (A) largely sufficiently meets such characteristic.

The preference of compound (A) is illustrated.It is chemical combination that preferred tropism control layer forms monomer as described below Object (A-1-1) is to compound (A-1-10), compound (A-2-1), compound (A-2-2) and compound (A-3-1).Following chemical combination N and m in object independently are 2 to 6, R¹⁰It independently is hydrogen, methyl, fluorine or trifluoromethyl.Y¹⁰For hydrogen, fluorine, carbon number 1 to 5 alkane The alkoxy of base or carbon number 1 to 5.Y²⁰For the alkoxy of hydrogen, fluorine, the alkyl of carbon number 1 to 5 or carbon number 1 to 5.

Formula (2) shows the component cpd of liquid-crystal composition into formula (15).Compound (2) to compound (4) have small Dielectric anisotropy.Compound (5) to compound (7) have positive big dielectric anisotropy.Compound (8) has cyanogen Base, therefore there is positive bigger dielectric anisotropy.Compound (9) to compound (15) have negative big dielectric respectively to different Property.The concrete example of these compounds will be described later.

2. the synthesis of compound (A)

The synthetic method of compound (A) is illustrated.Compound (A) can according to International Publication No. 1995/22586, Japanese Patent Laid-Open 2005-206579 bulletin, International Publication No. 2006/049111, " macromolecular (Macromolecules) " (26,1244-1247 (1993)), Japanese Patent Laid-Open 2003-238491 bulletin, International Publication No. 2010/133278, Japanese Patent Laid-Open 2000-178233 bulletin, Japanese Patent Laid-Open 2012-1623 bulletin, day The method recorded in this patent special open 2011-227187 bulletin synthesizes.

It is according in Japanese Patent Laid-Open 2005-112850 bulletin with α-perfluoroalkyl acrylate ester group tropism control monomer The method of record synthesizes.It is according to Japanese Patent Laid-Open with α-trifluoromethyl acrylate ester group tropism control monomer The method recorded in 2004-175728 bulletin synthesizes.Compound (A) with tolans structure is according to International Publication No. 2001/053248 synthesizes.The compound for recording synthetic method can be by by the side of well known Synthetic Organic Chemistry Method is appropriately combined to be synthesized.It can refer to " organic synthesis " (Organic Syntheses, John Wei Li father and son publishing company (John Wiley&Sons, Inc)), " organic reaction " (Organic Reactions, John Wei Li father and son publishing company (John Wiley&Sons, Inc)), " comprehensive organic synthesis " (Comprehensive Organic Synthesis, Pei Geman publish public Take charge of (Pergamon Press)), " new experimental chemistry lecture " (ball kind) etc. at book.

3. liquid-crystal composition

Liquid-crystal composition contains compound (A) as tropism control layer and forms monomer.Compound (A), which at least has, passes through light Irradiate and generate the aromatic ester of light Fries rearrangement.The example of compound (A) be compound (A-1), compound (A-2) or Compound (A-3).Compound (A) is by having the different of the light Fries rearrangement bring directionality generated by polarisation irradiation Structure and interaction with the non-covalently bonded mode of the substrate of element, control the orientation of liquid crystal molecule.The composition It is used as ingredient A comprising compound (A), and in turn comprising in ingredient B as shown below, ingredient C, ingredient D and ingredient E Liquid crystal compounds.

About the preferred ratio of compound (A), in order to obtain the high response for ultraviolet light, by liquid crystal liquid crystal property chemical combination When the total amount of object is set as 100 parts by weight, it is about 0.1 parts by weight or more, is about 7 to make it dissolve in liquid-crystal composition Below parts by weight.And then preferred ratio is range of about 0.3 parts by weight to about 7 parts by weight.Most preferred ratio is about 0.3 weight Measure the range of part to about 5 parts by weight.So add compound (16 α) in the case where, preferred ratio be about 0.3 parts by weight extremely The range of about 7 parts by weight.

3-1. ingredient B to ingredient E

Ingredient B as liquid crystal compounds is compound (2) to compound (4).Ingredient C is compound (5) to chemical combination Object (7).Ingredient D is compound (8).Ingredient E is compound (9) to compound (15).The composition also may include and chemical combination Object (2) other liquid crystal compounds different to compound (15).When preparing the composition, preferably in view of positive or negative The size of dielectric anisotropy etc. and selection component B, ingredient C, ingredient D and ingredient E.The composition of ingredient is properly selected With high ceiling temperature, low lower limit temperature, small viscosity, optical anisotropy appropriate (that is, optical anisotropy it is big or Optical anisotropy is small), positive or negative big dielectric anisotropy, big specific resistance, to the stability of heat or ultraviolet light and suitable When elastic constant (that is, elastic constant is big or elastic constant is small).

Ingredient B is the compound that two terminal groups are alkyl etc..The preference of ingredient B can enumerate compound (2-1) to change Close object (2-11), compound (3-1) to compound (3-19) and compound (4-1) to compound (4-7).The compound of ingredient B In, R¹¹And R¹²It independently is the alkyl of carbon number 1 to 10 or the alkenyl of carbon number 2 to 10, in the alkyl or alkenyl, at least one- CH₂It can replace through-O-, at least one hydrogen can be fluorine-substituted.

Ingredient B is close neutral compound because the absolute value of dielectric anisotropy is small.Compound (2) mainly exists Reduce viscosity or the optically anisotropic aspect of adjustment is effective.Compound (3) and compound (4) have by improving ceiling temperature And expand the effect of nematic temperature range, or effective adjusting optically anisotropic aspect.

With the content for increasing ingredient B, the dielectric anisotropy of composition becomes smaller, but viscosity becomes smaller.Therefore, as long as it is full The required value of the starting voltage of sufficient element, then content is with mostly good.In the case where preparing the composition of IPS, VA isotype, base In the weight of liquid-crystal composition, the content of ingredient B is preferably 30 weight % or more, and then preferably 40 weight % or more.

Ingredient C as liquid crystal compounds is the compound for having fluorine, chlorine or the base containing fluorine in right end.Ingredient C Preference can enumerate compound (5-1) to compound (5-16), compound (6-1) to compound (6-113), compound (7- 1) to compound (7-61).In the compound of ingredient C, R¹³For the alkyl of carbon number 1 to 10 or the alkenyl of carbon number 2 to 10, the alkane In base and alkenyl, at least one-CH₂It can replace through-O-, at least one hydrogen can be fluorine-substituted；X¹¹For fluorine, chlorine ,-OCF₃、- OCHF₂、-CF₃、-CHF₂、-CH₂F、-OCF₂CHF₂Or-OCF₂CHFCF₃。

The dielectric anisotropy of ingredient C is positive, and very excellent to the stability of heat, light etc., therefore can be used for preparing The case where composition of IPS, FFS, OCB isotype.Weight based on liquid-crystal composition, the content of ingredient C suitably 1 weight Measure the range of % to 99 weight %, the range of preferably 10 weight % to 97 weight %, and then preferably 40 weight % to 95 weights Measure the range of %.In the case where ingredient C to be added in the composition that dielectric anisotropy is negative, based on liquid-crystal composition Weight, the content of ingredient C are preferably 30 weight % or less.By adding ingredient C, the elastic constant of composition, adjustment can adjust Voltage-transmittance curve of element.

Ingredient D as liquid crystal compounds is the compound (8) that right terminal groups are-C ≡ N or-C ≡ C-C ≡ N.Ingredient D Preference can enumerate compound (8-1) to compound (8-64).In the compound of ingredient D, R¹⁴For carbon number 1 to 10 alkyl or The alkenyl of carbon number 2 to 10, in the alkyl and alkenyl, at least one-CH₂It can replace through-O-, at least one hydrogen can take through fluorine Generation；-X¹²For-C ≡ N or-C ≡ C-C ≡ N.

The dielectric anisotropy of ingredient D is positive, and its value is big, therefore is primarily useful for preparing the composition of TN isotype The case where.By adding the ingredient D, it is possible to increase the dielectric anisotropy of composition.Ingredient D has the temperature model for expanding liquid crystalline phase It encloses, adjust viscosity or the optically anisotropic effect of adjustment.Ingredient D is also useful for voltage-transmittance curve of adjustment element.

In the case where preparing the composition of TN isotype, the content of the weight based on liquid-crystal composition, ingredient D is suitable Be range of the 1 weight % to 99 weight %, the range of preferably 10 weight % to 97 weight %, and then preferably 40 weight % To the range of 95 weight %.In the case where ingredient D to be added in the composition that dielectric anisotropy is negative, it is based on liquid crystal group The weight of object is closed, the content of ingredient D is preferably 30 weight % or less.By adding ingredient D, the elasticity of composition can adjust often Number, voltage-transmittance curve of adjustment element.

Ingredient E as liquid crystal compounds is compound (9) to compound (15).These compounds such as 2,3- bis- is fluoro- The phenylene that there is 1,4- phenylene side position (lateral position) to replace through two fluorine or chlorine like that.Ingredient E's is preferred Example can enumerate compound (9-1) to compound (9-8), compound (10-1) to compound (10-17), compound (11-1), change Object (12-1) is closed to compound (12-3), compound (13-1) to compound (13-11), compound (14-1) to compound (14- 3) and compound (15-1) is to compound (15-3).In the compound of ingredient E, R¹⁵And R¹⁶It independently is the alkyl of carbon number 1 to 10 Or the alkenyl of carbon number 2 to 10, in the alkyl and alkenyl, at least one-CH₂It can replace through-O-, at least one hydrogen can be through fluorine Replace；R¹⁷For the alkenyl of hydrogen, fluorine, the alkyl of carbon number 1 to 10 or carbon number 2 to 10, in the alkyl and alkenyl, at least one- CH₂It can replace through-O-, at least one hydrogen can be fluorine-substituted.

The dielectric anisotropy of ingredient E is negative and greatly.Ingredient E can be used for preparing the composition of IPS, VA, PSA isotype The case where.With the content for increasing ingredient E, the dielectric anisotropy of composition is negative and becomes larger, but viscosity becomes larger.Therefore, only Meet the required value of the starting voltage of element, then content to be preferred less.If in view of dielectric anisotropy is -5 or so, in order to Sufficient voltage driving is carried out, preferably content is 40 weight % or more.

In ingredient E, compound (9) is bicyclic compound, therefore is mainly reducing viscosity, adjustment optical anisotropy or increasing Add the aspect of dielectric anisotropy effective.Compound (10) and compound (11) are tricyclic compound, therefore are improved the upper limit Temperature increases optical anisotropy or increases the effect of dielectric anisotropy.Compound (12) to compound (15) has increase to be situated between The effect of electrical anisotropy.

In the case where preparing the composition of IPS, VA, PSA isotype, the weight based on liquid-crystal composition, ingredient E's Content is preferably 40 weight % or more, and then the range of preferably 50 weight % to 95 weight %.Ingredient E is being added to dielectric In the case where in the composition that anisotropy is positive, the weight based on liquid-crystal composition, the content of ingredient E is preferably 30 weight % Below.By adding ingredient E, the elastic constant of composition, voltage-transmittance curve of adjustment element can adjust.

By the way that above-described ingredient B, ingredient C, ingredient D and ingredient E is appropriately combined, can prepare sufficiently meet it is following special Property at least one liquid-crystal composition: ceiling temperature is high, lower limit temperature is low, viscosity is small, optical anisotropy is appropriate, positive or negative Dielectric anisotropy is big, specific resistance is big, high to the stability of ultraviolet light, high to the stability of heat, elastic constant is big etc..Depending on needing The liquid crystal compounds different from ingredient B, ingredient C, ingredient D and ingredient E can also be added.

The second additive of 3-2.

It can also be improved for the purpose of reactive (polymerism) and add has as reactive monomer in the composition Effect second additive, that is, polymerizable compound (16 α).

In formula (16 α), P¹¹、P¹²And P¹³It independently is polymerism base.Preferred P¹¹、P¹²Or P¹³For selected from formula (P-1) extremely Polymerism base in the group of base represented by formula (P-5).And then preferred P¹¹、P¹²Or P¹³For base (P-1), base (P-2) or base (P-3).Particularly preferred base (P-1) is-OCO-CH=CH₂Or-OCO-C (CH₃)=CH₂.Base (P-1) to base (P-5) wave Line indicates the position being bonded.

Base (P-1) is into base (P-5), M¹¹、M¹²And M¹³Independently be hydrogen, fluorine, carbon number 1 to 5 alkyl or at least one The alkyl for the carbon number 1 to 5 that hydrogen replaces through fluorine or chlorine.In order to improve reactivity, preferred M¹¹、M¹²Or M¹³For hydrogen or methyl.In turn Preferred M¹¹For methyl, and then preferred M¹²Or M¹³For hydrogen.

In formula (16 α), Sp¹¹、Sp¹²And Sp¹³It independently is the alkylidene of singly-bound or carbon number 1 to 10, in the alkylidene, At least one-CH₂It can replace through-O- ,-COO- ,-OCO- or-OCOO-, at least one-(CH₂)₂It can be through-CH=CH- or-C ≡ C- replaces, and in these bases, at least one hydrogen can replace through fluorine or chlorine.Preferred Sp¹¹、Sp¹²Or Sp¹³For singly-bound.

In formula (16 α), ring F and ring I independently are cyclohexyl, cyclohexenyl group, phenyl, 1- naphthalene, 2- naphthalene, tetrahydro pyrrole It mutters -2- base, 1,3- dioxanes -2- base, pyrimidine -2-base or pyridine -2- base, in these rings, at least one hydrogen can be through fluorine or chlorine, carbon The alkyl for the carbon number 1 to 12 that the alkyl of number 1 to 12, the alkoxy of carbon number 1 to 12 or at least one hydrogen replace through fluorine or chlorine takes Generation.Preferred ring F or ring I is phenyl.Ring G is 1,4- cyclohexylidene, 1,4- cyclohexadienylidene, 1,4- phenylene, naphthalene -1,2- two Base, naphthalene -1,3- diyl, naphthalene -1,4- diyl, naphthalene -1,5- diyl, naphthalene -1,6- diyl, naphthalene -1,7- diyl, naphthalene -1,8- diyl, It is naphthalene -2,3- diyl, naphthalene -2,6- diyl, naphthalene -2,7- diyl, oxinane -2,5- diyl, 1,3- dioxanes -2,5- diyl, phonetic Pyridine -2,5- diyl or pyridine -2,5- diyl, in these rings, at least one hydrogen can be through fluorine, chlorine, the alkyl of carbon number 1 to 12, carbon number The alkyl for the carbon number 1 to 12 that 1 to 12 alkoxy or at least one hydrogen replace through fluorine or chlorine replaces.Particularly preferred ring G is 1, 4- phenylene or the fluoro- 1,4- phenylene of 2-.

In formula (16 α), Z²²And Z²³It independently is the alkylidene of singly-bound or carbon number 1 to 10, in the alkylidene, at least one A-CH₂It can replace through-O- ,-CO- ,-COO- or-OCO-, at least one-(CH₂)₂It can be through-CH=CH- ,-C (CH₃)= CH- ,-CH=C (CH₃)-or-C (CH₃)=C (CH₃)-replace, in these bases, at least one hydrogen can replace through fluorine or chlorine.It is preferred that Z⁷Or Z⁸For singly-bound ,-(CH₂)₂-、-CH₂O-、-OCH₂,-COO- or-OCO-.And then preferred Z²²Or Z²³For singly-bound.

In formula (16 α), u 0,1 or 2.Preferred u is 0 or 1.F, g and h independently is 0,1,2,3 or 4, moreover, f, g and H's and be 1 or more.Preferred f, g or h are 1 or 2.

Preferred second additive is compound represented by formula (16 α -1) to formula (16 α -27).

Formula (16 α -1) into formula (16 α -27),

P¹¹、P¹²And P¹³It independently is the base being selected from the group of polymerism base represented by formula (P-1) to formula (P-3), Herein, M¹¹、M¹²And M¹³It independently is the carbon number 1 that hydrogen, fluorine, the alkyl of carbon number 1 to 5 or at least one hydrogen replace through fluorine or chlorine To 5 alkyl；

Sp¹¹、Sp¹²And Sp¹³It independently is the alkylidene of singly-bound or carbon number 1 to 10, in the alkylidene, at least one- CH₂It can replace through-O- ,-COO- ,-OCO- or-OCOO-, at least one-(CH₂)₂It can replace through-CH=CH- or-C ≡ C-, In these bases, at least one hydrogen can replace through fluorine or chlorine.

The polymerizable compound of first additive or the second additive used in this case liquid-crystal composition etc be with It is added in liquid-crystal composition for the purpose of generation polymer.Compound (A) can be used alone or be used in combination of two or more. Copolymer can also be generated by compound (A) and compound (16 α).Compound (A) is with polar group and substrate surface with non-covalent bond State that the mode of knot interacts and immobilization.It is further increased as a result, in the ability that liquid crystal molecule is orientated Meanwhile preventing compound (A) from spreading in a liquid crystal composition.Compound (A) forms polymer by polymerization.The polymer It is arranged, therefore pre-tilt angle appropriate can be assigned to liquid crystal molecule in substrate surface.The polymer makes liquid crystal molecule Orientation stabilizes, therefore shortens the response time of element, and improves the image retention of image.The preference of compound (16 α) is third Enoic acid ester compounds, methacrylate compound, vinyl compound, vinyl oxo-compound, propenyl ether compounds, Epoxide (oxirane, oxetanes) and vinyl ketone compound.And then preferred example is at least one The compound of a acryloxy and compound at least one methacryloxy.And then preferred example also includes Compound with both acryloxy and methacryloxy.

3-3. additive

Liquid-crystal composition is prepared by well known method.For example, component cpd is mixed, and made by heating It is soluble in one another.Additive can also be added depending on the application and in the composition.The example of additive is polymerization initiator, gathers Close inhibitor, optically active compound, antioxidant, ultraviolet absorbing agent, light stabilizer, heat stabilizer, defoaming agent etc..It is such Additive has been well known to those skilled in the art, and is described in the literature.

Polymerizable compound can be made to polymerize rapidly by adding polymerization initiator.It, can by optimizing reaction temperature Reduce the amount of the polymerizable compound of remaining.The example of optical free radical polymerization initiator is IGM resin (IGM Resins) company Meter La De difficult to understand (Omnirad) series in TPO, 1173,4265,184,369,500,651,784,819,907,1300, 1700,1800,1850 and 2959.

The addition example of optical free radical polymerization initiator are as follows: bis- (trichloromethyl) triazines of 4- methoxyphenyl -2,4-, 2- (4- Butyl phenyl ether vinyl) -5- trichloromethyl -1,3,4- oxadiazoles, 9- phenylacridine, 9,10- phenonaphthazine (9,10- Benzophenazine), benzophenone/michaelis ketone (benzophenone/michler's ketone) mixture, six aryl connection Imidazoles/mercaptobenzimidazole mixture, 1- (4- isopropyl phenyl) -2- hydroxy-2-methyl propane -1- ketone, benzil dimethyl Ketal, 2- methyl-1-[4- (methyl mercapto) phenyl]-2- morpholinopropane-1- ketone, 2,4- diethyl xanthone/to dimethyl Methyl anthranilate mixture, benzophenone/methyl triethanol amine blends.

After can be by adding optical free radical polymerization initiator in a liquid crystal composition, ultraviolet light be irradiated to be polymerize.So And perhaps the decomposition product of unreacted polymerization initiator or polymerization initiator can cause image retention of image etc. to show in the component It is bad.The situation in order to prevent can also carry out photopolymerization in the state of not adding polymerization initiator.The light of irradiation it is preferred Wavelength will be described later.

In keeping polymerizable compound, it polymerize in order to prevent, polymerization inhibitor can also be added.Polymerizable compound is usual It is to be added in composition in the state of not removing polymerization inhibitor.The example of polymerization inhibitor be quinhydrones, methylnaphthohydroquinone it Hydroquinone derivatives, 4- tert-butyl catechol, 4- metoxyphenol, phenthazine of class etc..

Optically active compound have by make liquid crystal molecule cause helical structure come assign required twist angle and prevent The effect of inverse distortion.It can adjust screw pitch (helical pitch) by addition optically active compound.To adjust spiral For the purpose of the temperature dependency of pitch, two or more optically active compounds can also be added.Optically active compound it is preferred Example can enumerate following compounds (Op-1) to compound (Op-18).In compound (Op-18), ring J be 1 or 4 cyclohexylidene or Isosorbide-5-Nitrae-phenylene, R²⁸For the alkyl of carbon number 1 to 10.

Antioxidant is effective for maintaining big voltage retention.The preference of antioxidant can be enumerated: Xia Shuhua Close object (AO-1) and compound (AO-2)；Easy fine jade Northey (IRGANOX) 415, IRGANOX 565, IRGANOX 1010, IRGANOX 1035, IRGANOX 3114 and IRGANOX 1098 (trade name: BASF (BASF) company).Ultraviolet light is inhaled It is effective for the decline for preventing ceiling temperature to receive agent.The preference of ultraviolet absorbing agent is benzophenone derivates, benzene first Acid ester derivant, triazole derivative etc..Concrete example can be enumerated: following compounds (AO-3) and compound (AO-4)；Ground slave is refined (TINUVIN)329、TINUVIN P、TINUVIN 326、TINUVIN 234、TINUVIN 213、TINUVIN 400、 TINUVIN 328 and TINUVIN 99-2 (trade name: BASF (BASF) company)；And 1,4- diazabicyclo [2.2.2] is pungent Alkane (Isosorbide-5-Nitrae-diazabicyclo [2.2.2] octane, DABCO).

In order to maintain big voltage retention, it is however preferred to have the light stabilizer of amine of steric hindrance etc.Light stabilizer it is excellent Select example that can enumerate: following compounds (AO-5) and compound (AO-6)；TINUVIN 144, TINUVIN 765 and TINUVIN 770DF (trade name: BASF (BASF) company).Heat stabilizer is also for maintaining for big voltage retention effectively, preferably Example can enumerate easy fine jade Floex (IRGAFOS) 168 (trade name: BASF (BASF) company).Defoaming agent is for preventing blistering Effectively.The preference of defoaming agent is dimethyl silicone oil, methylphenylsilicone oil etc..

In compound (AO-1), R⁴⁰For the alkyl of carbon number 1 to 20, the alkoxy ,-COOR of carbon number 1 to 20⁴¹Or- CH₂CH₂COOR⁴¹, herein, R⁴¹For the alkyl of carbon number 1 to 20.In compound (AO-2) and compound (AO-5), R⁴²For carbon number 1 To 20 alkyl.In compound (AO-5), R⁴³For hydrogen, methyl or O^·(oxygen radical), ring K are 1 or 4 cyclohexylidene or Isosorbide-5-Nitrae-Asia Phenyl, z 1,2 or 3.

4. liquid crystal display element

The liquid-crystal composition can be used for operating modes such as PC, TN, STN, OCB, PSA, and in a manner of active matrix The liquid crystal display element driven.The composition can also be used for operating modes such as PC, TN, STN, OCB, VA, IPS and The liquid crystal display element driven in a manner of passive matrix.These elements can also be applied to reflection-type, infiltration type, semi-transmission type Any type.

The composition can also be used for carrying out nematic curved arrangement phase made by microencapsulation to nematic crystal (nematic curvilinear aligned phase, NCAP) element is formed made by three-dimensional netted macromolecule in liquid crystal Polymer-dispersed liquid crystal display element (Polymer Dispersed Liquid Crystal Display, PDLCD), with And polymer network liquid crystal display element (Polymer Network Liquid Crystal Display, PNLCD).By liquid It is about 10 parts by weight or less when system in the additive amount of polymerizable compound when the total amount of crystalline compound is set as 100 parts by weight Make the liquid crystal display element of PSA mode.The element of PSA mode can by the driving method of active matrix, passive matrix etc come It is driven.Such element can also be applied to any type of reflection-type, infiltration type, semi-transmission type.By increasing polymerism The additive amount of compound can also make the element of macromolecule dispersion (polymer dispersed) mode.

Alignment films are the film arrange liquid crystal molecule on fixed-direction.Usually using the film of polyimides.No In liquid crystal display element with such alignment films, the combination for forming monomer as tropism control layer containing compound (A) is used Object.Compound (A) forms polymer by polymerization.The polymer has the function of alignment films, therefore can replace alignment films And it uses.An example for manufacturing the method for such element is as follows.Prepare to have and is referred to as array substrate and colorized optical filtering chip base The element of two substrates of plate.The substrate does not have alignment films.At least one of the substrate is with electrode layer.By liquid crystal liquid crystal property Compound mixes to prepare liquid-crystal composition.Add compound (A) in the composition.Addition can be optionally added in turn Object.The composition is injected into element.The element is heated to from the opposite isotropic phase of the nematic of liquid-crystal composition Transition temperature (T_NI) more than, make liquid-crystal composition variation for after isotropic phase state, the polarisation for carrying out the first stage is ultraviolet Line irradiation.The polarisation irradiated herein is the ultraviolet light in the range of wavelength 280nm to wavelength 340nm with peak value.Secondly, not Liquid-crystal composition is heated, in room temperature (25 DEG C) to less than T_NIIn the state of temperature, the light irradiation of second stage is carried out.This Place, the preferably ultraviolet light of non-polarized.The ultraviolet light of preferred non-polarized can also be in wavelength 330nm to the model of wavelength 400nm There is peak value in enclosing.Polymerizable compound is reacted by ultraviolet light irradiation.By such two stage reaction, generation makes liquid Brilliant molecule causes the tropism control layer being uniformly horizontally oriented, and makes object component.

In the sequence, if liquid crystal layer is remained the transition temperature (T to the isotropy phase of liquid-crystal composition_NI) more than Temperature range and using in the range of wavelength 280nm to wavelength 340nm with peak value first stage polarisation ultraviolet light It is irradiated, then the aromatic ester position of compound (A) carries out photodegradation, forms free radical, and carry out light Fries rearrangement.Light In Fries rearrangement, the photodegradation at aromatic ester position is in the polarization direction of polarisation ultraviolet light and the long axis side at aromatic ester position To generating in the case where for the same direction.After photodegradation, then it is bonded and is generated in the molecule by tautomerization Hydroxyl.Think the interaction that substrate interface is generated by the hydroxyl, tropism control layer forms monomer to be had in substrate interface side There is anisotropy and is easy absorption.In addition, because having polymerism base, therefore by polymerizeing immobilization.The polymer is to make The tropism control layer that liquid crystal molecule is uniformly directed.Next is thought, if liquid crystal layer is remained room temperature (25 DEG C) to less than T_NITemperature Degree range is simultaneously radiated at wavelength 330nm into wavelength 400nm with the second ultraviolet light of peak value with non-polarized state, then is orientated control Remaining aromatic ester position carries out light Fries rearrangement in preparative layer or unreacted tropism control layer forms monomer along orientation Control layer is polymerize.Light Fries rearrangement herein is generated in the inside of the polymer oriented by the first ultraviolet light, because This thinks have the tendency that in the enterprising rearrangement reaction in the direction that the anisotropy of tropism control layer improves.Think unreacted orientation The additional polymerization that control layer forms monomer also contributes to assigning the anisotropy of tropism control layer.Such tropism control layer it is each to Anisotropic rising, which refers to, becomes larger to the orientation restraint that liquid crystal molecule plays a role.Pass through the effect of such polymer, liquid crystal point The orientation of son additionally stabilizes, therefore the contrast of element improves.Response time shortens.The image retention of image is liquid crystal molecule Running it is bad, therefore image retention is also improved simultaneously by the effect of the polymer.Because being polymerize with such two stages, because This unreacted reactant is few.Therefore, it can get the big element of voltage retention.

It is illustrated about the ultraviolet light irradiation for substrate.Ultraviolet light is irradiated in the present invention at least two stages.First The preferred illumination of the ultraviolet light in stage is about 2mW/cm²To about 200mW/cm²Range, preferred light exposure (illumination (unit: mW/cm²) with the product of irradiation time (unit: second)) be 1J/cm²To 15J/cm²Range.Preferably in 280nm to 340nm's There is peak value in range and there is the ultraviolet light of peak value near 313nm and near 335nm.Sometimes the ultraviolet light is known as " the first ultraviolet light ".It is polymerize by the most polymerizable compound of the ultraviolet light.In first ultraviolet light, Jin Eryou The illumination of choosing is about 2mW/cm²To about 100mW/cm²Range, and then preferred light exposure is 1J/cm²To 13J/cm²Model It encloses.Preferred illumination is about 2mW/cm²To about 100mW/cm²Range, preferred light exposure be 1J/cm²To 11J/cm² Range.

The illumination of the preferred ultraviolet light of second stage is about 1mW/cm²To about 200mW/cm²Range, it is preferred to expose Amount is 1J/cm²To 15J/cm²Range.Preferred illumination is about 1mW/cm²To about 100mW/cm²Range, more preferably Light exposure is 1J/cm²To 14J/cm²Range.And then preferred illumination is about 1mW/cm²To about 50mW/cm²Range, in turn Preferred light exposure is 1J/cm²To 14J/cm²Range.Preferably in the range of 330nm to 400nm have peak value and 335nm nearby and near 365nm has the ultraviolet light of peak value.Sometimes the ultraviolet light is known as " the second ultraviolet light ".Pass through institute Ultraviolet light is stated, can produce additional Fries rearrangement.In addition, unreacted tropism control layer can also be formed to monomer (A) conversion For polymer.

According to the observation using scanning electron microscope, tropism control layer is comprising small concave-convex film.It is viewed as Play accumulation and the layer of formation in the polymer self-reference substrate face of polymerizable compound.The height of the section of the film is defined as being orientated The film thickness of control layer.Film thickness is to be averagely calculated as about 1nm to about 100nm, preferably from about 5nm to about 70nm.Film thickness be about 5nm with When upper, can maintenance level be orientated characteristic, therefore preferably.When film thickness is 100nm or less, driving voltage can be suitably reduced, therefore It is preferred that.

In horizontally oriented type element, in no applied voltage, liquid crystal molecule is relative to real estate generally horizontal orientation.It is logical Often, in order to so that liquid crystal molecule is horizontally oriented and between colored filter substrate and liquid crystal layer or array substrate and liquid crystal layer it Between configure the horizontal alignment film of polyimides etc.On the other hand, in horizontally oriented type element of the invention, at least one base Plate side is not necessarily to such alignment films.In the element, by the effect of tropism control layer, liquid crystal molecule takes relative to substrate level To.The angle (i.e. pre-tilt angle) of liquid crystal molecule and substrate is 0 ° or more and 5 ° or less.Preferably 0 ° or more and 3 ° or less.Passing through will Such horizontal alignment is combined with comb-type electrode may achieve wide viewing angle.

[embodiment]

The present invention is described in more detail by embodiment (including synthesis example, use example).The present invention is not by these realities Apply the limitation of example.The present invention also includes the mixture prepared and mixing at least two of the composition of use example.

As long as recording without special, reaction is to carry out in a nitrogen environment.Compound (A) is by shown in synthesis example etc. Sequence synthesize.Synthesized compound is analyzed using nuclear magnetic resonance (nuclear magnetic resonance, NMR) The methods of identified.Characteristic is measured by following methods.

NMR analysis: the DRX-500 manufactured when measurement using this guest (Bruker BioSpin) company of Brooker Baier.¹H- In the measurement of NMR, sample is made to be dissolved in CDCl₃Etc. in deuterates solvent, at room temperature with 500MHz, the item that cumulative number is 16 times Part is measured.Use tetramethylsilane as internal standard.¹⁹In the measurement of F-NMR, CFCl is used₃As internal standard, with Cumulative number 24 times carries out.In the explanation of NMR spectrum, s refers to unimodal (singlet), and d refers to doublet (doublet), t refers to triplet (triplet), and q refers to quartet (quartet), and quin refers to quintet (quintet), Sex refers to sextet (sextet) that m refers to multiplet (multiplet), and br refers to broad peak (broad).

Gas chromatographic analysis: the GC-2010 type gas chromatograph manufactured when measurement using Shimadzu Seisakusho Ltd..Tubing string uses peace Capillary column DB-1 (length 60m, the internal diameter of prompt Lun Science & technology Co., Ltd (Agilent Technologies Inc.) manufacture 0.25mm, 0.25 μm of film thickness).As carrier gas, use helium (1ml/ minutes).The temperature of sample evaporation chamber is set as 300 DEG C, it will test the temperature setting of the part device (flame ionization detector (flame ionization detector, FID)) It is 300 DEG C.It is dissolved in sample in acetone, is prepared into the solution of 1 weight %, 1 μ l of solution obtained is injected into sample gas Change in room.Recording gauge is the gas-chromatography solution system (GC Solution system) etc. manufactured using Shimadzu Seisakusho Ltd..

High performance liquid chromatography (High Performance Liquid Chromatography, HPLC) analysis: measurement When use Shimadzu Seisakusho Ltd. to manufacture Pu Luo meter can this (Prominence) (LC-20AD；SPD-20A).Tubing string is manufactured using YMC YMC-Pack ODS-A (length 150mm, internal diameter 4.6mm, 5 μm of partial size).It is suitable for mixing and making that dissolution fluid, which is by acetonitrile and water, With.As detector, be suitable for using ultraviolet light (Ultraviolet, UV) detector, refractive index (Refractive Index, RI) detector, corona (CORONA) detector etc..When using UV detector, it will test wavelength and be set as 254nm.Keep sample molten Solution is prepared into the solution of 0.1 weight % in acetonitrile, and the 1 μ L of solution is directed into sample chamber.As recording gauge, make The C-R7Aplus manufactured with Shimadzu Seisakusho Ltd..

UV, visible light spectrum analysis: Fa Masipeiku (PharmaSpec) UV- manufactured when measurement using Shimadzu Seisakusho Ltd. 1700.It will test wavelength and be set as 190nm to 700nm.It is dissolved in sample in acetonitrile, is prepared into the solution of 0.01mmol/L, puts Enter into quartz cell (optical path length 1cm) and is measured.

Measure sample: when measuring phase structure and transition temperature (brocken spectrum, fusing point, polymerization initiation temperature etc.), by chemical combination Object itself serves as sample.

Measuring method: the measurement of characteristic is carried out by following methods.These methods are Japan Electronics information technology mostly Industry association (JEITA；Japan Electronics and Information Technology Industries Association it) reviews documented method in the JEITA specification (JEITAED-2521B) formulated or is repaired Method made of decorations.Thin film transistor (TFT) (TFT) is not installed on the TN element of measurement.

(1) phase structure

Sample is placed in have the melting point apparatus of petrographic microscope hot plate (Mei Tele (Mettler) company FP-52 type high temperature microscope carrier) on.The sample is heated with 3 DEG C/min of speed on one side, utilizes petrographic microscope on one side Observation phase state changes with it, to determine the type of phase.

(2) transition temperature (DEG C)

The scanning calorimeter Dai Mengde (Diamond) manufactured when measurement using PerkinElmer (PerkinElmer) company DSC system or the high sensitivity differential scanning calorimeter X- of SSI nanotechnology (SSI Nanotechnology) company manufacture DSC7000.Make sample heating and cooling with 3 DEG C/min of speed, and finds out by extrapolating the endothermic peak of the phase change with sample Or the starting point of exothermic peak, determine transition temperature.Fusing point, the polymerization initiation temperature of compound are also surveyed using described device It is fixed.Sometimes compound is shifted from solid and is referred to as " the lower limit temperature of liquid crystalline phase for the temperature of the liquid crystalline phases such as smectic phase, nematic phase Degree ".Sometimes compound is referred to as " brocken spectrum " from the temperature that liquid crystal phase transfer is liquid.

Crystallization is expressed as C.In the case where being distinguish to the type of crystallization, it is expressed as C₁、C₂.By smectic phase table It is shown as S, nematic phase is expressed as N.In smectic phase, it is added to smectic C, smectic B, smectic C phase or smectic F with area In the case where point, it is expressed as S_A、S_B、S_COr S_F.Liquid (isotropism) is expressed as I.Transition temperature is for example stated For " C 50.0N 100.0I ".It indicates to be 50.0 DEG C from crystallizing to nematic transition temperature, from turning for the opposite liquid of nematic Moving temperature is 100.0 DEG C.

(3) nematic ceiling temperature (T_NIOr NI；℃)

Sample is placed on the hot plate for having the melting point apparatus of petrographic microscope, is carried out with 1 DEG C/min of speed Heating.Measure sample a part from nematic phase change be isotropic liquid when temperature.Sometimes by nematic upper limit temperature Degree is referred to as " ceiling temperature ".When sample is the mixture of liquid crystal compounds and mother liquor crystalline substance, with mark T_NIIt indicates.In sample For liquid crystal compounds and the compound of ingredient B, ingredient C, ingredient D etc mixture when, indicated with mark NI.

(4) nematic lower limit temperature (T_C；℃)

After being taken care of 10 days in 0 DEG C, -10 DEG C, -20 DEG C, -30 DEG C and -40 DEG C of freezer unit with nematic sample, Observe liquid crystalline phase.For example, be nematic state at -20 DEG C in sample, and variation is crystallization or smectic phase at -30 DEG C When, by T_CJi Zai Wei≤- 20 DEG C.Sometimes nematic lower limit temperature is referred to as " lower limit temperature ".

(5) viscosity (bulk viscosity；η；It is measured at 20 DEG C；mPa·s)

The E type rotational viscometer manufactured when measurement using Tokyo gauge limited liability company.

(6) optical anisotropy (refractive anisotrop；It is measured at 25 DEG C；Δn)

Using the light of wavelength 589nm, the Abbe refractometer (abbe that polarizer is equipped on ocular lens is utilized Refractometer it) is measured.After the surface of headprism is rubbed to a direction, sample is added dropwise on headprism. Refractive index (n ∥) is the measurement at the direction of polarisation and the parallel direction of friction.Refractive index (n ⊥) be polarisation direction with rub It is measured when the direction of wiping is vertical.(value of Δ n) is calculated according to the formula of Δ n=n ∥-n ⊥ to optical anisotropy.

(7) specific resistance (ρ；It is measured at 25 DEG C；Ωcm)

Sample 1.0mL is injected in the container for having electrode.DC voltage (10V) is applied to the container, is measured 10 seconds DC current afterwards.Specific resistance is to calculate according to the following formula.(specific resistance)={ (voltage) × (capacitor of container) }/{ (direct current Stream) × (dielectric constant of vacuum) }.

The sample and negative sample being positive for dielectric anisotropy, the measuring method of characteristic is different sometimes.Dielectric respectively to The opposite sex is that the measuring method of timing is recorded in item (8a) into item (12a).The case where dielectric anisotropy is negative is recorded in item (8b) is into item (12b).

(8a) viscosity (rotary viscosity；γ1；It is measured at 25 DEG C；mPa·s)

Positive dielectric anisotropy: " molecular crystal and liquid crystal (Molecular according to M. the present well (M.Imai) et al. Crystals and Liquid Crystals) " documented method is measured in (Vol.259,37 (1995)).It is turning round Corner is to be put into sample in TN element that the interval (cell gap) of 0 degree and two pieces glass substrate is 5 μm.To the element In the range of 16V to 19.5V, periodically apply voltage as unit of 0.5V.After not applying voltage 0.2 second, only to apply Add a rectangular wave (rectangular pulse；0.2 second) apply repeatedly with the condition for not applying voltage (2 seconds).Measurement passes through the application And the peak point current (peak current) and time to peak (peak of the transient current (transient current) generated time).Rotary viscosity is obtained by the paper of these measured values and M. the present well (M.Imai) et al. page 40 of calculating formula (8) Value.The value of dielectric anisotropy needed for the calculating is using the element for determining the rotary viscosity and by following institute The method of record and find out.

(8b) viscosity (rotary viscosity；γ1；It is measured at 25 DEG C；mPa·s)

Negative dielectric anisotropy: " molecular crystal and liquid crystal (Molecular according to M. the present well (M.Imai) et al. Crystals and Liquid Crystals) " documented method is measured in (Vol.259,37 (1995)).Two Sample is put into the VA element that the interval (cell gap) of block glass substrate is 20 μm.To the element at 39 volts to 50 volts In the range of, periodically apply voltage as unit of 1 volt.After not applying voltage 0.2 second, only to apply a rectangular wave (rectangular pulse；0.2 second) apply repeatedly with the condition for not applying voltage (2 seconds).Measurement applies the transient state generated by described The peak point current (peak current) and time to peak (peak time) of electric current (transient current).By these surveys The calculating formula (8) of page 40 in the paper of definite value and M. the present well (M.Imai) et al. and the value for obtaining rotary viscosity.The calculating The value that required dielectric anisotropy is measured in the item using following dielectric anisotropies.

(9a) dielectric anisotropy (Δ ε；It is measured at 25 DEG C)

Positive dielectric anisotropy: at the interval (cell gap) of two pieces of glass substrates be 9 μm and torsion angle is 80 degree TN element in be put into sample.Sine wave (10V, 1kHz) is applied to the element, the long axis direction of liquid crystal molecule is measured after 2 seconds On dielectric constant (ε ∥).Sine wave (0.5V, 1kHz) is applied to the element, the short-axis direction of liquid crystal molecule is measured after 2 seconds On dielectric constant (ε ⊥).The value of dielectric anisotropy is calculated according to the formula of Δ ε=ε ∥-ε ⊥.

(9b) dielectric anisotropy (Δ ε；It is measured at 25 DEG C)

Negative dielectric anisotropy: the value of dielectric anisotropy is calculated according to the formula of Δ ε=ε ∥-ε ⊥.Dielectric Constant (ε ∥ and ε ⊥) measures as follows.

1) measurement of dielectric constant (ε ∥): by ethyl alcohol (20mL) solution of octadecyltriethoxy silane (0.16mL) It is coated on the glass substrate through sufficiently cleaning.After rotating glass substrate using rotator, heated 1 hour at 150 DEG C.? It is put into sample in the VA element that the interval (cell gap) of two pieces of glass substrates is 4 μm, is connect using what is hardened by ultraviolet light Agent the element is closed.Sine wave (0.5V, 1kHz) is applied to the element, the long axis side of liquid crystal molecule is measured after 2 seconds Upward dielectric constant (ε ∥).

2) measurement of dielectric constant (ε ⊥): polyimide solution is coated on the glass substrate through sufficiently cleaning.By institute After stating glass substrate calcining, friction treatment is carried out to alignment films obtained.At the interval (cell gap) of two pieces of glass substrates Sample is put into the TN element for being 80 degree for 9 μm, torsion angle.Sine wave (0.5V, 1kHz) is applied to the element, is surveyed after 2 seconds Determine the dielectric constant (ε ⊥) on the short-axis direction of liquid crystal molecule.

(10a) elastic constant (K；It is measured at 25 DEG C；pN)

Positive dielectric anisotropy: had when measurement using Yokogawa Hewlett-Packard (Yokogawa Hewlett-Packard) share The HP4284A type LCR meter of limit company manufacture.The horizontal alignment element for being 20 μm at the interval (cell gap) of two pieces of glass substrates In be put into sample.0 volt to 20 volts charge is applied to the element, measure electrostatic capacitance and applies voltage.Use " liquid crystal device Part handbook " (daily magazine Jndustrial News company) page 75 formula (2.98), formula (2.101), by the electrostatic capacitance measured (C) with apply The value of making alive (V) is fitted, and obtains K according to formula (2.99)₁₁And K₃₃Value.Secondly, in the formula (3.18) in page 171, Use the K first found out₁₁And K₃₃Value calculate K₂₂.Elastic constant K is the K so to find out₁₁、K₂₂And K₃₃Average value table Show.

(10b) elastic constant (K₁₁And K₃₃；It is measured at 25 DEG C；pN)

Negative dielectric anisotropy: it is surveyed when measurement using the EC-1 type elastic constant that Dongyang technical concern Co., Ltd manufactures Determine device.Sample is put into the vertically oriented element that the interval (cell gap) of two pieces of glass substrates is 20 μm.To the element Apply 20 volts to 0 volt charges, measure electrostatic capacitance and applies voltage.Use " liquid crystal device handbook " (daily magazine Jndustrial News Company) page 75 formula (2.98), formula (2.101), electrostatic capacitance (C) and the value for applying voltage (V) are fitted, according to formula (2.100) value of elastic constant is obtained.

(11a) starting voltage (Vth；It is measured at 25 DEG C；V)

Positive dielectric anisotropy: the LCD5100 type luminance meter manufactured when measurement using great Zhong electronics limited liability company. Light source is halogen lamp.In the Chang Bai that the interval (cell gap) of two pieces of glass substrates is 0.45/ Δ n (μm), torsion angle is 80 degree Sample is put into the TN element of mode (normally white mode).The voltage (32Hz, rectangular wave) that the element is applied It is that 10V is periodically increased to from 0V with each 0.02V.At this point, from vertical direction to element irradiation light, and measure through element Light quantity.The electricity that transmitance when the light quantity reaches maximum is 100% and transmitance is 0% when the light quantity is minimum is made Pressure-transmittance curve.Starting voltage is voltage when reaching 90% by transmitance to indicate.

(11b) starting voltage (Vth；It is measured at 25 DEG C；V)

Negative dielectric anisotropy: the LCD5100 type luminance meter manufactured when measurement using great Zhong electronics limited liability company. Light source is halogen lamp.The interval (cell gap) of two pieces of glass substrates be 4 μm, frictional direction be antiparallel normally black mode It is put into sample in the VA element of (normally black mode), using the solid hardened by ultraviolet light by the member Part is closed.The voltage (60Hz, rectangular wave) applied to the element is periodically to increase to 20V from 0V with each 0.02V.This When, from vertical direction to element irradiation light, and measure the light quantity through element.The transmitance when light quantity reaches maximum, which is made, is 100% and light quantity voltage-transmittance curve that transmitance is 0% when being minimum.Starting voltage is to reach 10% by transmitance When voltage indicate.

(12a) response time (τ；It is measured at 25 DEG C；ms)

Positive dielectric anisotropy: the LCD5100 type luminance meter manufactured when measurement using great Zhong electronics limited liability company. Light source is halogen lamp.Low-pass filter (Low-pass filter) is set as 5kHz.In the interval (unit of two pieces of glass substrates Gap) it is 5.0 μm, is put into sample in the TN element for the normal white mode (normally white mode) that torsion angle is 80 degree.It is right The element applies rectangular wave (60Hz, 5V, 0.5 second).At this point, from vertical direction to element irradiation light, and measure through element Light quantity.It is 100% that transmitance is regarded as when the light quantity reaches maximum, and being regarded as transmitance when the light quantity is minimum is 0%.Rise time (τ r:rise time；Millisecond) be transmitance from 90% variation be 10% required for the time.Fall time (τ f:fall time；Millisecond) be transmitance from 10% variation be 90% required for the time.Response time is by with the side The sum of rise time and fall time that formula is found out indicates.

(12b) response time (τ；It is measured at 25 DEG C；ms)

Negative dielectric anisotropy: the LCD5100 type luminance meter manufactured when measurement using great Zhong electronics limited liability company. Light source is halogen lamp.Low-pass filter (Low-pass filter) is set as 5kHz.In the interval (unit of two pieces of glass substrates Gap) it is 3.2 μm, the pattern vertical orientation that frictional direction is antiparallel normally black mode (normally black mode) Sample is put into (Patterned Vertical Alignment, PVA) element.Use the solid hardened by ultraviolet light The element is closed.Apply voltage 1 minute for slightly exceeding starting voltage degree to the element, secondly applies 5.6V's on one side Voltage irradiates 23.5mW/cm on one side²Ultraviolet light 8 minutes.Rectangular wave (60Hz, 10V, 0.5 second) is applied to the element.This When, from vertical direction to element irradiation light, and measure the light quantity through element.Transmitance is regarded as when the light quantity reaches maximum It is 100%, it is 0% that transmitance is regarded as when the light quantity is minimum.Response time is from 90% variation by transmitance for 10% Required (fall time time；fall time；Millisecond) it indicates.

(13) voltage retention

Apply pulse voltage (1V and 60 microseconds) Lai Jinhang at 60 DEG C to the element for making polymerizable compound be polymerized Charging.The voltage of decaying is measured in a period of 1.67 seconds using high speed potentiometer, and finds out the voltage curve in unit period Area A between horizontal axis.Area B is area when not decaying.Voltage retention is the percentage by area A relative to area B Rate indicates.

(14) illumination

When the measurement of ultraviolet light illumination using oxtail (USHIO) Electric Co., Ltd manufacture ultraviolet light illumination photometer, UIT-250 type (sensor: UVD-S313 and UVD-S365).

(15) horizontal alignment property

Element obtained is set on petrographic microscope, observes element irradiation light that whether there is or not light leakages from lower section.? In the case that liquid crystal molecule is sufficiently orientated and light does not pass through element, it is judged as horizontal alignment property for " good ".Pass through observing In the case where the light of element, " having orientation defect " is expressed as.

(16) pre-tilt angle (degree)

The Opti-Pro of scientific and technological (Shintech) the limited liability company manufacture of SHIN-ETSU HANTOTAI is used when the measurement of pre-tilt angle.

(17) film thickness

The film thickness measuring of tropism control layer is using SEM (scanning electron microscope (scanning electron Microscope), the SU-70 of Hitachi's high and new technology (Hitachi High-technologies) limited liability company manufacture) into Row.

First additive is in compound shown below.

Compound in composition is 1 based on following table 2)~5) definition, indicated using mark.In table 2, and 1, The relevant spatial configuration of 4- cyclohexylidene is trans-.Number in the parantheses after mark is corresponding with the number of compound.Note Number (-) refers to other liquid crystal compounds.The ratio (percentage) of liquid crystal compounds is the weight based on liquid-crystal composition Weight percent (weight %).Finally, summarizing the characteristic value of liquid-crystal composition.Characteristic is the method for the record according to before to carry out Measurement directly records measured value (not extrapolating).

Table 2 uses the expression method of the compound of mark

R-(A₁)-Z₁-·····Z_n-(A_n)-R'

[composition (M1)]

NI=80.8 DEG C；< -20 DEG C of Tc；Δ n=0.108；Δ ε=- 3.8；Vth=2.02V；η=19.8mPas.

[composition (M2)]

NI=78.4 DEG C；< -20 DEG C of Tc；Δ n=0.108；Δ ε=10.4；Vth=1.35V；η=17.8mPas；γ 1=79.9mPas.

[composition (M3)]

NI=87.5 DEG C；< -20 DEG C of Tc；Δ n=0.100；Δ ε=- 3.4；Vth=2.25V

[embodiment 1]

Using the ratios of 0.5 parts by weight addition compound (A-1-3-1) as taking in 100 parts by weight of the composition (M1) Monomer is formed to control layer.As antioxidant, R is added with the ratio of 150ppm⁴⁰For heptyl (C₇H₁₅) compound (AO- 1).The composition is injected into the interval of two pieces of glass substrates (between unit under 90 DEG C (more than nematic ceiling temperature) Gap) be 3.2 μm and do not have alignment films and with comb electrodes liquid crystal cell (hereinafter, sometimes referred to as IPS element or referred to as Element) in.Liquid crystal layer is remained 90 DEG C on one side, 10J/cm is irradiated to element from normal direction on one side²As the first ultraviolet light The polarisation ultraviolet light at wavelength 313nm, wavelength 335nm and wavelength 365nm with peak value (illumination under wavelength 313nm is 3mW/cm².The UIT-150 and UVD-S313 manufactured using oxtail (USHIO) Motor Corporation is measured).Ultraviolet irradiation Lamp is the USH-250BY manufactured using oxtail (USHIO) Electric Co., Ltd.Exposure machine unit (unit) is using oxtail (USHIO) ML-251A/B of Electric Co., Ltd's manufacture.Polarisation ultraviolet light is using wiregrating (wire grid) polarizer (Pu Ruofulusi (ProFlux) UVT260A of Bora (Polatechno) company (stock) manufacture) is formed.

IPS element is cooled to room temperature (25 DEG C), liquid crystal layer is remained into room temperature (25 DEG C) on one side, on one side used as Black light (black light) F40T10 (peak value wave of Ai Gufei (Eyegraphics) the limited liability company manufacture of two ultraviolet lights Long 335nm and 365nm), 5.4J/cm is carried out to element from normal direction with non-polarized state (unused wire-grid polarizer)²According to Penetrate that (illumination under wavelength 365nm is 3mW/cm².The UIT-150 and UVD-S365 manufactured using oxtail (USHIO) Motor Corporation It is measured), carry out the horizontal alignment processing of element.

Secondly, the element for being formed with tropism control layer to be set to the state of orientation on petrographic microscope and observing liquid crystal. The polarizer of petrographic microscope with analyzer is configured in the orthogonal mode of respective transmission axis.Firstly, taking with liquid crystal molecule To the direction mode parallel with the transmission axis of the polarizer of petrographic microscope, the i.e. differently- oriented directivity and petrographic microscope of liquid crystal molecule The transmission axis angulation of polarizer be 0 degree of mode, element is set on the horizontal rotating table of petrographic microscope.From The downside of element, i.e. polarizer side irradiation light, whether there is or not the light through analyzer for observation.Because almost not observing through analyzer Light, therefore, it is determined that be oriented to " good ".Furthermore in same observation, in the case where observing the light through analyzer, sentence It is set to and is oriented to " bad ".Secondly, rotating element on the horizontal rotating table of petrographic microscope, make the polarization of petrographic microscope The transmission axis of device and the differently- oriented directivity angulation of liquid crystal molecule change from 0 degree.It confirms: through the light of analyzer Intensity is increased as the transmission axis of the polarizer of petrographic microscope and the differently- oriented directivity angulation of liquid crystal molecule become larger, It is substantially maximum when the angle ranging from 45 degree.By obtaining in element above, liquid crystal molecule is in the substrate relative to element Interarea and be orientated in substantially horizontal direction, be judged to " being horizontally oriented ".

In order to evaluate the uniformity of horizontal alignment, surveyed using the multi-media display that Yokogawa Motor limited liability company manufactures It tries device (multimedia display tester) 3298 and obtains the differently- oriented directivity of liquid crystal molecule and the polarization of petrographic microscope Brightness when the transmission axis angulation of device is 0 degree, ((light penetrates the light under state and penetrates with the ratio of brightness when being 45 degree Intensity)/(light penetrate intensity) under black state), result is about 1300 and good.

The tropism control layer on device substrate is observed using scanning electron microscope, as a result film thickness is about 8nm, Tropism control layer forms monomer and is largely consumed.

[comparative example 1]

Composition used in embodiment 1 is injected into two pieces of glass bases under 90 DEG C (more than nematic ceiling temperature) The interval (cell gap) of plate is 3.2 μm and does not have in the IPS element of alignment films.Liquid crystal layer is remained 90 DEG C on one side, one While irradiating 10J/cm to element from normal direction²As the first ultraviolet light in wavelength 313nm, wavelength 335nm and wavelength 365nm (illumination under wavelength 313nm is 3mW/cm to the polarisation ultraviolet light with peak value down²), only thus at the horizontal alignment of progress element Reason.

Secondly, the element for being formed with tropism control layer is set on petrographic microscope and is observed similarly to Example 1 The state of orientation of liquid crystal.From the downside of element, i.e. polarizer side irradiation light, whether there is or not the light through analyzer for observation.Because slightly seeing The light through analyzer is observed, therefore, it is determined that be oriented to " slightly bad ".Secondly, making element in the level rotation of petrographic microscope It is rotated on turntable, the differently- oriented directivity angulation of the transmission axis and liquid crystal molecule that make the polarizer of petrographic microscope is sent out from 0 degree Changing, result are tendency similarly to Example 1, are judged to " being horizontally oriented ".

In order to evaluate the uniformity of horizontal alignment, the orientation side of liquid crystal molecule is obtained by method similarly to Example 1 Brightness when to the transmission axis angulation of the polarizer with petrographic microscope being 0 degree, the ratio with brightness when being 45 degree, knot Fruit is about 860 and poorer than embodiment 1.

[comparative example 2]

Composition used in embodiment 1 is injected into two pieces of glass bases under 90 DEG C (more than nematic ceiling temperature) The interval (cell gap) of plate is 3.2 μm and does not have in the IPS element of alignment films.Liquid crystal layer is remained 90 DEG C on one side, one While irradiating 10J/cm to element from normal direction²As the first ultraviolet light in wavelength 313nm, wavelength 335nm and wavelength 365nm (illumination under wavelength 313nm is 3mW/cm to the polarisation ultraviolet light with peak value down²)。

IPS element is cooled to room temperature (25 DEG C), and use light source identical with the first ultraviolet light to element from normal side To with 5.4J/cm²Non-polarized is irradiated that (illumination under wavelength 313nm is 8mW/cm²) and carry out the exposure of second stage, into The horizontal alignment of units is handled.

In order to evaluate the uniformity of horizontal alignment, the orientation side of liquid crystal molecule is obtained by method similarly to Example 1 Brightness when to the transmission axis angulation of the polarizer with petrographic microscope being 0 degree, the ratio with brightness when being 45 degree, knot Fruit is about 720 and poorer than embodiment 1.

[comparative example 3]

Composition used in embodiment 1 is injected into two pieces of glass bases under 90 DEG C (more than nematic ceiling temperature) The interval (cell gap) of plate is 3.2 μm and does not have in the IPS element of alignment films.Liquid crystal layer is remained 90 DEG C on one side, one While irradiating 10J/cm to element from normal direction²As the first ultraviolet light in wavelength 313nm, wavelength 335nm and wavelength 365nm (illumination under wavelength 313nm is 8mW/cm to the ultraviolet light of the non-polarized with peak value down²)。

Liquid crystal layer is remained 90 DEG C on one side, uses light source identical with the first ultraviolet light to element from normal direction on one side Carry out 5.4J/cm²(illumination under wavelength 313nm is 3mW/cm for polarisation irradiation²) and carry out the exposure of second stage, carry out element Horizontal alignment processing.

In order to evaluate the uniformity of horizontal alignment, the orientation side of liquid crystal molecule is obtained by method similarly to Example 1 Brightness when to the transmission axis angulation of the polarizer with petrographic microscope being 0 degree, the ratio with brightness when being 45 degree, knot Fruit is about 800 and poorer than embodiment 1.

[embodiment 2]

In addition to by be used as tropism control layer formed monomer compound (A-1-3-4) be set as 3 parts by weight other than, by with reality It applies the same method of example 1 and IPS element is made.In addition, irradiating the first ultraviolet light and the second purple by method similarly to Example 1 Outside line carries out horizontal alignment processing.The uniformity of the orientation of element obtained is " good " similarly to Example 1, is " water Flat orientation ".Obtain the uniformity of horizontal alignment by method similarly to Example 1, the ratio of as a result brightness is about 1000 and good It is good.The tropism control layer on device substrate is observed using scanning electron microscope, as a result film thickness is about 48nm, orientation Control layer forms monomer and is largely consumed.

[embodiment 3]

In addition to by be used as tropism control layer formed monomer compound (A-1-3-14) be set as 3 parts by weight other than, by with IPS element is made in the same method of embodiment 1.In addition, irradiating the first ultraviolet light and second by method similarly to Example 1 Ultraviolet light carries out horizontal alignment processing.The uniformity of the orientation of element obtained is " good " similarly to Example 1, is " horizontal alignment ".Obtain the uniformity of horizontal alignment by method similarly to Example 1, the ratio of as a result brightness be about 1040 and Well.The tropism control layer on device substrate is observed using scanning electron microscope, as a result film thickness is about 48nm, is taken Monomer is formed to control layer to be largely consumed.

[embodiment 4]

In addition to by be used as tropism control layer formed monomer compound (A-2-2-2) be set as 0.5 parts by weight other than, by with IPS element is made in the same method of embodiment 1.In addition, in addition to the light exposure of the first ultraviolet light is set as 0.9J/cm²In addition, lead to The method crossed similarly to Example 1 irradiates the second ultraviolet light, carries out horizontal alignment processing.The orientation of element obtained it is uniform Property be similarly to Example 1 " good ", be " horizontal alignment ".Horizontal alignment is obtained by method similarly to Example 1 The uniformity, the ratio of as a result brightness are about 1100 and good.Using scanning electron microscope to the tropism control on device substrate Layer is observed, and as a result film thickness is about 8nm, and tropism control layer forms monomer and is largely consumed.

[embodiment 5]

In addition to by be used as tropism control layer formed monomer compound (A-2-2-2) be set as 10 parts by weight other than, by with IPS element is made in the same method of embodiment 4.In addition, irradiating the first ultraviolet light and second by method similarly to Example 1 Ultraviolet light carries out horizontal alignment processing.The uniformity of the horizontal alignment of element obtained is tendency similarly to Example 1.

The element of embodiment 1 is almost without light leakage.On the other hand, comparative example 1 slightly observes light leakage into comparative example 3. Think that light leakage is generated because of the orientation restraint of tropism control layer deficiency.It is observed according to the thickness of tropism control layer, it is believed that real The substantially total amount for applying the tropism control layer formation monomer in example and comparative example is converted into polymer.Speculate in embodiment and comparative example Brightness ratio difference the reason of are as follows: irradiated by the second ultraviolet light, in tropism control layer remaining aromatic ester position into The Fries rearrangement of row light or unreacted tropism control layer form monomer along tropism control layers of polymer, therefore tropism control layer Anisotropy (orientation restraint) get higher.Think that the second UV irradiation step of the invention helps to improve horizontal alignment Uniformity.Same effect can also be obtained in the case where the dielectric anisotropy of liquid-crystal composition is positive.Therefore, it can obtain logical The liquid crystal display element crossing method of the invention and manufacturing has the conclusion being uniformly horizontally oriented.The element prevents light leakage, It therefore is the excellents such as contrast.

Industrial availability

The liquid crystal display element manufactured by means of the present invention can be used for LCD monitor, LCD TV etc..

Claims

1. a kind of manufacturing method of horizontally oriented type liquid crystal display element, the horizontally oriented type liquid crystal display element is opposite Liquid crystal layer is clamped between configuration and a pair of of the substrate being bonded via sealant,

There is the tropism control layer that tropism control is carried out to liquid crystal molecule between the pair of substrate and the liquid crystal layer,

The liquid-crystal composition contains liquid crystal compounds, has positive or negative dielectric anisotropy, has each in opposite directions from nematic To the transition temperature T of same sex phase_NI, and light Fries rearrangement, photoisomerization, light two are generated by light irradiation containing at least one The tropism control layer of any one of dimerization, photodegradation forms monomer as the first additive；

It is 2mW/cm with illumination²To 200mW/cm²Range and be 1J/cm²To 15J/cm²Light exposure range polarisation irradiation In 280nm into 340nm with the first ultraviolet light of peak value；

Secondly, liquid crystal layer is remained room temperature (25 DEG C) to T_NITemperature range, be 1mW/cm with illumination²To 200mW/cm²Model It encloses and is 1J/cm²To 15J/cm²Light exposure range illumination 330nm into 400nm with peak value the second ultraviolet light；

2. the manufacturing method of horizontally oriented type liquid crystal display element according to claim 1, wherein as described in claim 1 The first additive be with by light irradiation generate light Fries rearrangement aromatic ester formula (A) represented by orientation control Preparative layer forms monomer,

In formula (A),

P¹⁰And P²⁰Independently indicate polymerism base；

Sp¹⁰And Sp²⁰It independently is the alkylidene of singly-bound or carbon number 1 to 12, at least one hydrogen of the alkylidene can be through fluorine or hydroxyl Base replaces, at least one-CH₂It can replace through-O- ,-COO- ,-OCO- or formula (Q-1), at least one-CH₂-CH₂It can be through-CH =CH- or-C ≡ C- replaces；

In formula (Q-1), M¹⁰、M²⁰And M³⁰Hydrogen, fluorine, the alkyl of carbon number 1 to 5 or at least one hydrogen independently is to take through fluorine or chlorine The alkyl of the carbon number 1 to 5 in generation；Sp¹¹At least one hydrogen for singly-bound or the alkylidene of carbon number 1 to 12, the alkylidene can be through fluorine Or hydroxyl replaces, at least one-CH₂It can replace through-O- ,-COO- or-OCO-, at least one-CH₂-CH₂It can be through-CH= CH- or-C ≡ C- replaces；

Z¹⁰、Z²⁰And Z³⁰It independently is singly-bound ,-COO- ,-OCO- ,-OCOO ,-OCO-CH₂CH₂-、-CH₂CH₂-COO-、-CH₂O-、- OCH₂-、-CF₂O-、-OCF₂-、-C≡C-、-CONH-、-NHCO-、-(CH₂)₄-、-CH₂CH₂Or-CF₂CF₂-；

A¹⁰And A³⁰It independently is 1,4- phenylene, 1,4- cyclohexylidene, pyridine -2,5- diyl, pyrimidine -2,5- diyl, naphthalene -2,6- Diyl, naphthalene -1,5- diyl, naphthane -2,6- diyl, fluorenes -2,7- diyl, sub- biphenyl -4,4'- diyl or dioxanes -2 1,3-, 5- diyl, in the Isosorbide-5-Nitrae-phenylene, arbitrary hydrogen can be through fluorine, chlorine, cyano, hydroxyl, formoxyl, acetoxyl group, acetyl group, three Acetyl fluoride base, difluoromethyl, trifluoromethyl, the alkyl of carbon number 1 to 5, carbon number 1 to 5 alkoxy or P¹⁰-Sp¹⁰-Z¹⁰Replace, In fluorenes -2,7- diyl, arbitrary hydrogen can replace through the alkyl of fluorine, carbon number 1 to 5, in Asia biphenyl -4,4'- diyl, appoint The hydrogen of meaning can replace through the alkoxy of fluorine, difluoromethyl, trifluoromethyl, the alkyl of carbon number 1 to 5 or carbon number 1 to 5；

A²⁰For 1,4- phenylene represented by formula (A20-1), pyridine -2,5- diyl, pyrimidine -2,5- diyl, formula (A20-2) institute table Naphthalene -2,6- the diyl shown, naphthalene -1,5- diyl, sub- biphenyl -4,4'- diyl or formula (A20-4) institute table represented by formula (A20-3) Fluorenes -2, the 7- diyl shown,

In Isosorbide-5-Nitrae-phenylene represented by formula (A20-1), Y¹⁰、Y¹¹、Y¹²And Y¹³It is separately hydrogen, fluorine, chlorine, cyano, hydroxyl Base, formoxyl, acetoxyl group, acetyl group, trifluoroacetyl group, difluoromethyl, trifluoromethyl, the alkyl of carbon number 1 to 5 or carbon number 1 To 5 alkoxy, Y¹⁰With Y¹³At least one be hydrogen,

In naphthalene -2,6- diyl represented by formula (A20-2), Y¹⁴、Y¹⁵、Y¹⁶、Y¹⁷、Y¹⁸And Y¹⁹It is separately hydrogen, fluorine, carbon number 1 to 5 alkyl or the alkoxy of carbon number 1 to 5, Y¹⁴With Y¹⁹At least one be hydrogen,

In sub- biphenyl -4,4'- diyl represented by formula (A20-3), Y²⁰、Y²¹、Y²²、Y²³、Y²⁴、Y²⁵、Y²⁶And Y²⁷Separately For the alkoxy of hydrogen, fluorine, difluoromethyl, trifluoromethyl, the alkyl of carbon number 1 to 5 or carbon number 1 to 5, Y²⁰With Y²⁷At least one For hydrogen,

In fluorenes -2,7- diyl represented by formula (A20-4), Y²⁸、Y²⁹、Y³⁰、Y³¹、Y³²And Y³³It is separately hydrogen, fluorine, carbon number 1 to 5 alkyl, Y²⁸With Y³¹At least one be hydrogen；

n¹⁰Independently 0 to 3 integer；

In ultraviolet light irradiation, liquid crystal layer is remained into T_NIUp to T_NI+ 5 DEG C of temperature ranges below, are 2mW/cm with illumination²Extremely 100mW/cm²Range and be 1J/cm²To 13J/cm²The range polarisation of light exposure be radiated at 280nm and have into 340nm First ultraviolet light of peak value；

Secondly, liquid crystal layer is remained room temperature (25 DEG C) to less than T_NITemperature range, be 1mW/cm with illumination²To 100mW/cm² Range and be 1J/cm²To 14J/cm²Light exposure range illumination it is second ultraviolet with peak value into 400nm in 330nm Line.

3. the manufacturing method of horizontally oriented type liquid crystal display element according to claim 1, wherein as described in claim 1 Ultraviolet light irradiation in, liquid crystal layer is remained into T_NIUp to T_NI+ 5 DEG C of temperature ranges below, are 2mW/cm with illumination²Extremely 100mW/cm²Range and be 1J/cm²To 11J/cm²The range polarisation of light exposure be radiated at 280nm and have into 340nm First ultraviolet light of peak value；

It is 1mW/cm with illumination secondly, liquid crystal layer is remained room temperature (25 DEG C) to 45 DEG C of temperature ranges below²To 50mW/ cm²Range and be 1J/cm²To 14J/cm²Light exposure range illumination 330nm into 400nm with peak value second Ultraviolet light.

4. the manufacturing method of horizontally oriented type liquid crystal display element according to claim 2, wherein as claimed in claim 2 Formula (A) in,

P¹⁰And P²⁰Independently indicate acryloxy, methacryloxy, α-fluorinated monomer, trifluoromethyl acrylate ester, Vinyl, vinyl oxygroup, epoxy group；

Sp¹⁰And Sp²⁰It independently is the alkylidene of singly-bound or carbon number 1 to 12, at least one hydrogen of the alkylidene can be through fluorine or hydroxyl Base replaces, at least one-CH₂It can replace through-O- ,-COO- or-OCO-, at least one-CH₂-CH₂Can through-CH=CH- or- C ≡ C- replaces；

A¹⁰And A³⁰It independently is 1,4- phenylene, 1,4- cyclohexylidene, naphthalene -2,6- diyl, naphthalene -1,5- diyl, fluorenes -2,7- two Base, sub- biphenyl -4,4'- diyl, in the Isosorbide-5-Nitrae-phenylene, arbitrary hydrogen can be through fluorine, cyano, hydroxyl, acetoxyl group, acetyl Base, trifluoroacetyl group, difluoromethyl, trifluoromethyl, the alkyl of carbon number 1 to 5, carbon number 1 to 5 alkoxy or P¹⁰-Sp¹⁰-Z¹⁰- Replace, in fluorenes -2,7- diyl, arbitrary hydrogen can replace through the alkyl of fluorine, carbon number 1 to 5, Asia biphenyl -4,4'- diyl In, arbitrary hydrogen can replace through the alkoxy of fluorine, difluoromethyl, trifluoromethyl, the alkyl of carbon number 1 to 5 or carbon number 1 to 5；

A²⁰For naphthalene -2,6- diyl represented by 1,4- phenylene represented by formula (A20-1), formula (A20-2), formula (A20-3) institute Fluorenes -2,7- diyl represented by sub- biphenyl -4, the 4'- diyl or formula (A20-4) of expression,

In Isosorbide-5-Nitrae-phenylene represented by formula (A20-1), Y¹⁰、Y¹¹、Y¹²And Y¹³It separately can be through hydrogen, fluorine, chlorine, cyano, hydroxyl Base, formoxyl, acetoxyl group, acetyl group, trifluoroacetyl group, difluoromethyl, trifluoromethyl, the alkyl of carbon number 1 to 5 or carbon number 1 Alkoxy to 5 replaces, Y¹⁰With Y¹³At least one be hydrogen,

In naphthalene -2,6- diyl represented by formula (A20-2), Y¹⁴、Y¹⁵、Y¹⁶、Y¹⁷、Y¹⁸And Y¹⁹It separately can be through hydrogen, fluorine, carbon The alkyl of number 1 to 5 or the alkoxy of carbon number 1 to 5 replace, Y¹⁴With Y¹⁹At least one be hydrogen,

In sub- biphenyl -4,4'- diyl represented by formula (A20-3), Y²⁰、Y²¹、Y²²、Y²³、Y²⁴、Y²⁵、Y²⁶And Y²⁷Separately It can replace through the alkoxy of hydrogen, fluorine, difluoromethyl, trifluoromethyl, the alkyl of carbon number 1 to 5 or carbon number 1 to 5, Y²⁰With Y²⁷Extremely Few one is hydrogen,

n¹⁰Independently 0 to 3 integer.

5. the manufacturing method of horizontally oriented type liquid crystal display element according to any one of claim 1 to 4, wherein described Tropism control layer formed monomer by formula (A-1) to formula (A-3) any one represented by；

Formula (A-1) into formula (A-3),

R¹⁰It independently is hydrogen, fluorine, methyl or trifluoromethyl；

R³¹It independently is hydrogen or methyl；

A²⁰Independently be sub- biphenyl -4,4'- diyl represented by 1,4- phenylene represented by formula (A20-1), formula (A20-3) or Fluorenes -2,7- diyl represented by formula (A20-4),

In Isosorbide-5-Nitrae-phenylene represented by formula (A20-1), Y¹⁰、Y¹¹、Y¹²And Y¹³It separately can be through hydrogen, fluorine, hydroxyl, difluoro The alkoxy substitution of methyl, trifluoromethyl, the alkyl of carbon number 1 to 5 or carbon number 1 to 5, Y¹⁰With Y¹³At least one be hydrogen,

A³⁰It independently is 1,4- phenylene, naphthalene -2,6- diyl, naphthalene -1,5- diyl, fluorenes -2,7- diyl, sub- biphenyl -4,4'- two Base, in the Isosorbide-5-Nitrae-phenylene, arbitrary hydrogen can through fluorine, hydroxyl, difluoromethyl, trifluoromethyl, carbon number 1 to 5 alkyl or carbon The alkoxy of number 1 to 5 replaces, and in fluorenes -2,7- diyl, arbitrary hydrogen can replace through the alkyl of fluorine, carbon number 1 to 5, the Asia In biphenyl -4,4'- diyl, arbitrary hydrogen can be through fluorine, difluoromethyl, trifluoromethyl, the alkyl of carbon number 1 to 5 or carbon number 1 to 5 Alkoxy replaces；

L¹⁰It independently is the alkoxy or P of hydrogen, fluorine, difluoromethyl, trifluoromethyl, the alkyl of carbon number 1 to 5, carbon number 1 to 5¹⁰- Sp¹⁰-Z¹⁰-；

n¹¹Independently 0 to 4 integer.

6. the manufacturing method of horizontally oriented type liquid crystal display element according to any one of claim 1 to 5, wherein will When the total amount of liquid crystal compounds is set as 100 parts by weight, the tropism control layer formed monomer ratio be 0.1 parts by weight extremely The range of 10.0 parts by weight.

7. the manufacturing method of horizontally oriented type liquid crystal display element according to any one of claim 1 to 6, wherein described Liquid-crystal composition contains at least one of the group of compound represented by the formula (2) to formula (4) compound；

Formula (2) into formula (4),

R¹¹And R¹²It independently is the alkyl of carbon number 1 to 10 or the alkenyl of carbon number 2 to 10, in the alkyl and alkenyl, at least one- CH₂It can replace through-O-, at least one hydrogen can be fluorine-substituted；

Ring B¹, ring B², ring B³And ring B⁴It independently is the fluoro- 1,4- phenylene of 1,4- cyclohexylidene, 1,4- phenylene, 2-, 2,5- bis- Fluoro- 1,4- phenylene or pyrimidine -2,5- diyl；

8. the manufacturing method of horizontally oriented type liquid crystal display element according to any one of claim 1 to 7, wherein described Liquid-crystal composition contains at least one of the group of compound represented by the formula (5) to formula (7) compound in turn；

Formula (5) into formula (7),

R¹³For the alkyl of carbon number 1 to 10 or the alkenyl of carbon number 2 to 10, in the alkyl and alkenyl, at least one-CH₂Can through- O- replaces, at least one hydrogen can be fluorine-substituted；

Ring C¹, ring C²And ring C³It independently is 1,4- cyclohexylidene, the 1,4- phenylene that at least one hydrogen can be fluorine-substituted, tetrahydro Pyrans -2,5- diyl, 1,3- dioxanes -2,5- diyl or pyrimidine -2,5- diyl；

Z¹⁴、Z¹⁵And Z¹⁶It independently is singly-bound ,-(CH₂)₂,-CH=CH- ,-CH=CF- ,-CF=CF- ,-C ≡ C- ,-COO- ,- CF₂O-、-OCF₂-、-CH₂O- ,-CH=CF-CF₂O- ,-CF=CF-CF₂O- or-(CH₂)₄-；

L¹¹And L¹²It independently is hydrogen or fluorine.

9. the manufacturing method of horizontally oriented type liquid crystal display element according to any one of claim 1 to 8, wherein described Liquid-crystal composition contains at least one of the group of compound represented by formula (8) compound in turn；

In formula (8),

R¹⁴For the alkyl of carbon number 1 to 10 or the alkenyl of carbon number 2 to 10, in the alkyl and alkenyl, at least one-CH₂Can through- O- replaces, at least one hydrogen can be fluorine-substituted；

X¹²For-C ≡ N or-C ≡ C-C ≡ N；

Ring D¹For 1,4- cyclohexylidene, at least one hydrogen can be fluorine-substituted 1,4- phenylene, oxinane -2,5- diyl, 1,3- Dioxanes -2,5- diyl or pyrimidine -2,5- diyl；

L¹³And L¹⁴It independently is hydrogen or fluorine；

I is 1,2,3 or 4.

10. the manufacturing method of horizontally oriented type liquid crystal display element according to any one of claim 1 to 9, wherein institute It states liquid-crystal composition and then contains at least one of the group of compound represented by the formula (9) to formula (15) compound；

Formula (9) into formula (15),

R¹⁵And R¹⁶It independently is the alkyl of carbon number 1 to 10 or the alkenyl of carbon number 2 to 10, in the alkyl and alkenyl, at least one- CH₂It can replace through-O-, at least one hydrogen can be fluorine-substituted；

R¹⁷For the alkenyl of hydrogen, fluorine, the alkyl of carbon number 1 to 10 or carbon number 2 to 10, in the alkyl and alkenyl, at least one-CH₂- It can replace through-O-, at least one hydrogen can be fluorine-substituted；

Ring E¹, ring E², ring E³And ring E⁴Independently being 1,4- cyclohexylidene, 1,4- cyclohexadienylidene, at least one hydrogen can take through fluorine 1,4- phenylene, oxinane -2,5- diyl or the decahydronaphthalene -2,6- diyl in generation；

L¹⁵And L¹⁶It independently is fluorine or chlorine；

S¹¹For hydrogen or methyl；

X independently is-CHF- or-CF₂-；

11. the manufacturing method of horizontally oriented type liquid crystal display element according to any one of claim 1 to 10, wherein institute It states liquid-crystal composition and then contains polymerizable compound represented by formula (16 α) as the second additive, and formed comprising passing through Make the tropism control layer of the polymerization of these compounds and the copolymer of generation；

In formula (16 α),

Ring F and ring I independently is cyclohexyl, cyclohexenyl group, phenyl, 1- naphthalene, 2- naphthalene, oxinane -2- base, 1,3- bis- and dislikes Alkane -2- base, pyrimidine -2-base or pyridine -2- base, in these rings, at least one hydrogen can through fluorine, chlorine, carbon number 1 to 12 alkyl or The alkyl for the carbon number 1 to 12 that at least one hydrogen replaces through fluorine or chlorine replaces；

Ring G be 1,4- cyclohexylidene, 1,4- cyclohexadienylidene, 1,4- phenylene, naphthalene -1,2- diyl, naphthalene -1,3- diyl, naphthalene -1, 4- diyl, naphthalene -1,5- diyl, naphthalene -1,6- diyl, naphthalene -1,7- diyl, naphthalene -1,8- diyl, naphthalene -2,3- diyl, naphthalene -2,6- two Base, naphthalene -2,7- diyl, oxinane -2,5- diyl, 1,3- dioxanes -2,5- diyl, pyrimidine -2,5- diyl or pyridine -2, 5- diyl, in these rings, at least one hydrogen can be through fluorine, chlorine, the alkyl of carbon number 1 to 12, the alkoxy of carbon number 1 to 12 or at least The alkyl for the carbon number 1 to 12 that one hydrogen replaces through fluorine or chlorine replaces；

Z²²And Z²³It independently is the alkylidene of singly-bound or carbon number 1 to 10, in the alkylidene, at least one-CH₂Can through-O- ,- CO- ,-COO- or-OCO- replace, at least one-(CH₂)₂It can be through-CH=CH- ,-C (CH₃)=CH- ,-CH=C (CH₃)-、 Or-C (CH₃)=C (CH₃)-replace, in these bases, at least one hydrogen can replace through fluorine or chlorine；

P¹¹、P¹²And P¹³It independently is polymerism base；

Sp¹¹、Sp¹²And Sp¹³It independently is the alkylidene of singly-bound or carbon number 1 to 10, in the alkylidene, at least one-CH₂It can Replace through-O- ,-COO- ,-OCO- or-OCOO-, at least one-(CH₂)₂It can replace through-CH=CH- or-C ≡ C-, these bases In, at least one hydrogen can replace through fluorine or chlorine；

U is 0,1 or 2；

F, g and h independently is 0,1,2,3 or 4, and f, g and h and be 2 or more.

12. the manufacturing method of horizontally oriented type liquid crystal display element according to claim 11, wherein such as claim 11 In the formula (16 α), P¹¹、P¹²And P¹³It independently is the group for being selected from polymerism base represented by formula (P-1) to formula (P-5) In base；

Formula (P-1) into formula (P-5),

M¹¹、M¹²And M¹³It independently is the carbon number 1 to 5 that hydrogen, fluorine, the alkyl of carbon number 1 to 5 or at least one hydrogen replace through fluorine or chlorine Alkyl.

13. the manufacturing method of horizontally oriented type liquid crystal display element described in any one of 1 to 12 according to claim 1, wherein When the total amount of liquid crystal compounds is set as 100 parts by weight, the ratio of the second additive in liquid-crystal composition is 0.03 Parts by weight to 10 parts by weight range.

14. a kind of display device, including the level obtained by the manufacturing method as described in any one of claims 1 to 13 Alignment-type liquid crystal display device；And backlight.