CN109997074A

CN109997074A - The manufacturing method of liquid crystal display element without alignment films

Info

Publication number: CN109997074A
Application number: CN201780073225.1A
Authority: CN
Inventors: 平井吉治; 片野裕子; 近藤史尚; 荻田和寛; 远藤浩史; 黄名鸿; 宋依霖; 谢松年
Original assignee: JNC Corp
Current assignee: JNC Corp
Priority date: 2016-11-28
Filing date: 2017-11-20
Publication date: 2019-07-09
Anticipated expiration: 2037-11-20
Also published as: JPWO2018097093A1; TW201820009A; CN109997074B; WO2018097093A1

Abstract

The present invention provides a kind of method for forming tropism control layer, and the tropism control layer is effective for being orientated liquid crystal molecule equably when making to make an addition to the polymerism polar compound polymerization in liquid-crystal composition.With first substrate, the multiple pixel electrodes for being formed in the first substrate, the second substrate, be formed in the second 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, to polymerism polar compound contained in the liquid crystal layer, do not apply voltage in the first phase and ultraviolet light is irradiated with specific illumination, and withs in second stage specific illumination while the voltage as defined in applies to irradiate ultraviolet light.

Description

The manufacturing method of liquid crystal display element without alignment films

Technical field

The present invention relates to a kind of manufacturing methods of liquid crystal display element without alignment films.Further specifically, originally Invention is related to a kind of with containing polymerism polar compound and dielectric anisotropy is the liquid crystal of positive or negative liquid-crystal composition The manufacturing method of display element.

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 high temperature according to manufacturing process Type and low form.Based on light source be classified as using natural light reflection-type, using backlight infiltration type and using natural light with The semi-transmission type of both backlights.

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 superperformance.Association in the characteristic of the two 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, and 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 As (moving image), the preferably response time is short.Preferably it is shorter than 1 millisecond of response time.It is therefore preferable that being composition Viscosity it is small.Viscosity more preferably at low temperatures 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 such as element of TN mode.In the element of VA mode, described value be about 0.30 μm extremely About 0.40 μm of range, in the element of IPS mode or FFS mode, range that described value is about 0.20 μm to about 0.30 μm.This In a little situations, for the element small for cell gap, it is however preferred to have big optically anisotropic composition.Composition Big dielectric anisotropy helps to make that the starting voltage of element is low, electric power is small and contrast is than big for consumption.It is therefore preferable that be positive or Negative dielectric anisotropy is big.The specific resistance of composition facilitates greatly the voltage retention of element greatly with contrast than big.Therefore, With the composition of big specific resistance preferably in the initial stage.Preferably there is big specific resistance after prolonged use Composition.Composition is associated with the service life of element to the stability of ultraviolet light and heat.When the stability is high, the longevity of element Life length.Such characteristic is preferred for the AM element for LCD monitor, LCD TV etc..

In general liquid crystal display element, the vertical orientation of liquid crystal molecule can be reached by specific alignment film of polyimide At.Polymer stabilizing is orientated in the liquid crystal display element of (polymer sustained alignment, PSA) type, makes polymer It is combined with alignment films.Firstly, the composition added with a small amount of polymerizable compound is injected into the element with alignment films In.Secondly, applying voltage between the substrate of the element on one side, ultraviolet light is irradiated to composition on one side.Polymerizable compound It is polymerize and is generated in the composition the reticular structure of polymer.In the composition, liquid crystal can be controlled by polymer The orientation of molecule, therefore the response time of element shortens, the image retention of image is improved.Alignment film of polyimide so has With, but when element is big, it is difficult to the solution of polyimide precursor is uniformly applied on substrate and is difficult to obtain by calcining Uniform film.

On the other hand, using containing polymer and not in the liquid crystal display element without alignment films as polyimides The liquid-crystal composition of polar compound with polymerism base.Firstly, a small amount of polymerizable compound and a small amount of polarity will be added with The composition of compound is injected into element.Herein, polar compound is adsorbed in substrate surface and is arranged.According to the row Column, liquid crystal molecule are orientated.Secondly, applying voltage between the substrate of the element on one side, composition is irradiated on one side purple Outside line.Herein, polymerizable compound is polymerize, and stabilizes the orientation of liquid crystal molecule.It, can be by poly- in the composition Object and polar compound are closed to control the orientation of liquid crystal molecule, therefore the response time of element shortens, the image retention of image is changed It is kind.In turn, the process that the element without alignment films not necessarily forms alignment films.Since there is no alignment films, therefore there is no members The case where resistance of part is reduced because of the interaction of alignment films and composition.With TN, ECB, OCB, IPS, VA, FFS, It can be expected that such effect of the combination using polymer and polar compound in the element of the mode of FPA etc.

In the manufacture for the element for not having alignment films as polyimides, in order to reduce the orientation defect of liquid crystal molecule And disclose two methods below.1) it is purple that the liquid-crystal composition irradiation comprising polymerizable compound is directed at while applying voltage Outside line, and then do not apply voltage but the method that carries out the liquid crystal display device of additional ultraviolet light irradiation.2) apply electricity on one side Pressure irradiates ultraviolet light to the liquid-crystal composition comprising polymerizable compound on one side, and then applies substantially do not make liquid crystal molecule on one side The voltage of driving carries out the method (patent document 1) of the liquid crystal display device of additional ultraviolet light irradiation on one side.In such element Manufacture in, according to the condition of manufacturing process, vertically oriented uniformity can change (patent document 2, patent document 3). In the present invention, instead of polymer and polar compound and by with polymerism base polar compound and liquid crystal compounds group It closes, and the composition is efficiently used, thus research has the manufacturing method of the liquid crystal display element without alignment films.

Existing technical literature

Patent document

Patent document 1: Japanese Patent Laid-Open 2008-134668 bulletin

Patent document 2: Japanese Patent Laid-Open 2005-181582 bulletin

Patent document 3: Japanese Patent Laid-Open 2006-58755 bulletin

Summary of the invention

Problem to be solved by the invention

It is an object of the present invention to provide a kind of method, the method is in the liquid for not having alignment films as polyimides In the manufacture of crystal display element, changes ultraviolet light irradiation in order to obtain uniform orientation from the prior art and apply with voltage Sequence method.Another object is to provide a kind of method for manufacturing liquid crystal display element, and the method passes through in liquid crystal combination Addition has high chemical stability, the high ability for making liquid crystal molecular orientation and high dissolution in a liquid crystal composition in object The polymerism polar compound of degree simultaneously makes its polymerization, and manufactures to have and can be used the wide temperature range of element, response time short, electric The liquid crystal display element for the characteristic for pressing that conservation rate is high, starting voltage is low, contrast is longer than big, service life etc.Another object is to provide A method of the liquid crystal display element with liquid-crystal composition being manufactured, the liquid-crystal composition meets nematic ceiling temperature High, nematic lower limit temperature is low, viscosity is small, optical anisotropy is appropriate, positive or negative dielectric anisotropy is big, specific resistance Greatly, at least one of the characteristics such as high to the stability of ultraviolet light, big to stability height, the elastic constant of heat.

Technical means to solve problem

The inventors of the present invention people in order to solve the problem, studied by the sequence applied with regard to ultraviolet light irradiation with voltage, and Polymerism pole with the mesogen position that at least one ring is made of of the addition as orientation monomer in a liquid crystal composition Property compound and studied, as a result, it has been found that by with specific condition make its polymerization can to solve the problem, so as to complete The present invention.The present invention includes following proposal etc..

[1] a kind of manufacturing method of liquid crystal display element, wherein with first substrate, be formed in the first substrate Multiple pixel electrodes, the second substrate are formed in the second substrate and opposite electrode and folder with the pixel electrode in opposite directions It is held in the liquid crystal display element of the liquid crystal layer between the pixel electrode and the opposite electrode, the liquid crystal layer includes liquid crystal Composition, the liquid-crystal composition contain as the poly- with the mesogen position being made of at least one ring of orientation monomer Conjunction property polar compound and liquid crystal compounds；The manufacturing method of the liquid crystal display element is characterized in that: first to described Liquid-crystal composition does not apply voltage or application does not make the voltage of liquid-crystal composition driving and substantially with 1J/cm²To 60J/cm²'s Range illumination illumination is 2mW/cm²To 200mW/cm²Range the first ultraviolet light, secondly, being applied on one side to the liquid-crystal composition Add starting voltage or more and 30V voltage below is on one side with 5J/cm²To 100J/cm²Range illumination illumination be 2mW/cm²Extremely 200mW/cm²Range the second ultraviolet light, to be formed comprising being generated and polymerizeing the polymerism polar compound Polymer tropism control layer.

[2] manufacturing method of the liquid crystal display element according to [1], wherein in ultraviolet light irradiation described in [1], it is first First, the liquid-crystal composition is not applied voltage or applied does not make the voltage of liquid-crystal composition driving and substantially with 3J/cm² To 50J/cm²Range illumination illumination be 2mW/cm²To 100mW/cm²Range the first ultraviolet light, secondly, on one side to described Liquid-crystal composition applies starting voltage or more and 30V voltage below on one side with 5J/cm²To 55J/cm²Range illumination illumination be 2mW/cm²To 100mW/cm²Range the second ultraviolet light.

[3] manufacturing method of the liquid crystal display element according to [1] or [2], wherein ultraviolet described in [1] or [2] In line irradiation, after the irradiation of the second ultraviolet light, and then does not apply voltage to liquid-crystal composition or apply and substantially do not make liquid crystal group Close the voltage of object driving and with 1J/cm²To 60J/cm²Range illumination illumination be 2mW/cm²To 200mW/cm²Range Three ultraviolet lights.

[4] manufacturing method of the liquid crystal display element according to any one of [1] to [3], wherein the orientation list Body is compound represented by formula (1 α)；

In formula (1 α),

R¹For the alkyl of carbon number 1 to 15, in the alkyl, at least one-CH₂It can replace through-O- or-S-, 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；

MES is the liquid crystal former base at least one ring；

Sp¹For singly-bound or the alkylidene of carbon number 1 to 10, in the alkylidene, at least one-CH₂Can through-O- ,-CO- ,- COO- ,-OCO- or-OCOO- replace, 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；

M¹And M²It independently is the carbon number 1 that hydrogen, fluorine, chlorine, the alkyl of carbon number 1 to 5 or at least one hydrogen replace through fluorine or chlorine To 5 alkyl；

R²For base represented by formula (1 α a), formula (1 α b) or formula (1 α c):

In formula (1 α a), formula (1 α b) and formula (1 α c),

Sp²And Sp³It independently is the alkylidene of singly-bound or carbon number 1 to 10, in the alkylidene, at least one-CH₂Can through- O- ,-NH- ,-CO- ,-COO- ,-OCO- or-OCOO- replace, 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；

S¹For > CH- or > N-；

S²For > C < or > Si <；

X¹It independently is-OH ,-NH₂、-OR³、-N(R³)₂, formula (x1) ,-COOH ,-SH ,-B (OH)₂Or-Si (R³)₃It is represented Base, herein, R³For hydrogen or the alkyl of carbon number 1 to 10, in the alkyl, at least one-CH₂It can replace through-O-, at least one A-(CH₂)₂Can replace through-CH=CH-, in these bases, at least one hydrogen can replace through fluorine or chlorine, the w in formula (x1) is 1,2, 3 or 4；

[5] manufacturing method of the liquid crystal display element according to any one of [1] to [3], wherein the orientation list Body is compound represented by formula (1 β)；

In formula (1 β),

MES is the liquid crystal former base at least one ring；

R²、M¹、M²And M³It independently is the alkyl of hydrogen, fluorine, chlorine or carbon number 1 to 10, in the alkyl, at least one-CH₂- It can replace through-O- or-S-, at least one-(CH₂)₂It can replace through-CH=CH- or-C ≡ C-, in these bases, at least one hydrogen It can replace through fluorine or chlorine.

[6] manufacturing method of the liquid crystal display element according to any one of [1] to [3], wherein the orientation list Body is compound represented by formula (1 γ)；

In formula (1 γ),

R¹、R²And R³It independently is the alkyl of hydrogen or carbon number 1 to 15, in the alkyl, at least one-CH₂Can through-O- ,- S- or-NH- replaces, at least one-(CH₂)₂It can replace through-CH=CH-, in these bases, at least one hydrogen can take through fluorine or chlorine Generation；

N independently is 0,1 or 2；

Ring A⁴It is disliked for cyclohexylidene, cyclohexadienylidene, phenylene, naphthalene, decahydronaphthalene, naphthane, oxinane, 1,3- bis- Alkane, pyrimidine or pyridine, ring A¹And ring A⁵It 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, the alkenyl of carbon number 2 to 12, carbon number 1 to 11 alkoxy or carbon number 2 to 11 alkenyloxy group replaces, and in these bases, at least one hydrogen can replace through fluorine or chlorine；

Z¹And Z⁵It independently is the alkylidene of singly-bound or carbon number 1 to 10, in the alkylidene, at least one-CH₂Can through- O- ,-COO- ,-OCO- or-OCOO- replace, 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；

Sp¹、Sp²And Sp³It independently is the alkylidene of singly-bound or carbon number 1 to 10, in the alkylidene, at least one-CH₂- It can replace through-O- ,-COO- ,-OCO- or-OCOO-, at least one-(CH₂)₂It can replace through-CH=CH- or-C ≡ C-, these In base, at least one hydrogen can replace through fluorine or chlorine；

A and b independently is 0,1,2,3 or 4, and a and b's and be 1,2,3 or 4；

C, d and e independently is 0,1,2,3 or 4；

C, d and e's and be 2,3 or 4；

P¹、P²And P³It independently is polymerism base represented by formula (P-1)；

In formula (P-1),

R⁴For the base in the group of the base represented by formula (1 γ a), formula (1 γ b) and the formula (1 γ c)；

In formula (1 γ a), formula (1 γ b) and formula (1 γ c),

Sp⁵And Sp⁶It independently is the alkylidene of singly-bound or carbon number 1 to 10, in the alkylidene, at least one-CH₂It can Replace through-O- ,-NH- ,-CO- ,-COO- ,-OCO- or-OCOO-, at least one-(CH₂)₂It can be taken through-CH=CH- or-C ≡ C- In generation, in these bases, at least one hydrogen can replace through fluorine or chlorine；

S¹For > CH- or > N-；

S²For > C < or > Si <；

X¹It independently is-OH ,-NH₂、-OR⁵、-N(R⁵)₂、-COOH、-SH、-B(OH)₂Or-Si (R⁵)₃Represented base, this Place, R⁵For hydrogen or the alkyl of carbon number 1 to 10, in the alkyl, at least one-CH₂It can replace through-O-, at least one- (CH₂)₂It can replace through-CH=CH-, in these bases, at least one hydrogen can replace through fluorine or chlorine.

[7] manufacturing method of the liquid crystal display element according to any one of [1] to [6], wherein having by least In the orientation monomer at the mesogen position that one ring is constituted, the mesogen position includes cyclohexane ring.

[8] manufacturing method of the liquid crystal display element according to any one of [1] to [3], wherein the orientation list Body is compound represented by formula (1-1)；

In formula (1-1),

R¹For the alkyl of carbon number 1 to 15, the R¹In, at least one-CH₂It can replace through-O- or-S-, at least one- CH₂CH₂It can replace through-CH=CH- or-C ≡ C-, at least one hydrogen can replace through halogen；

Ring A¹And ring A²Independently be 1,4- cyclohexylidene, 1,4- cyclohexadienylidene, 1,4- phenylene, naphthalene -2,6- diyl, Decahydronaphthalene -2,6- diyl, 1,2,3,4- naphthane -2,6- diyl, oxinane -2,5- diyl, 1,3- dioxanes -2,5- two Base, pyrimidine -2,5- diyl, pyridine -2,5- diyl, fluorenes -2,7- diyl, phenanthrene -2,7- diyl, anthracene -2,6- diyl, perhydro cyclopentano [a] phenanthrene -3,17- diyl or ten tetrahydro cyclopentyl of 2,3,4,7,8,9,10,11,12,13,14,15,16,17- simultaneously [a] phenanthrene -3,17- Diyl, in these rings, at least one hydrogen can be through fluorine, chlorine, the alkyl of carbon number 1 to 12, the alkenyl of carbon number 2 to 12, carbon number 1 to 11 The alkenyloxy group of alkoxy or carbon number 2 to 11 replaces, and in these bases, at least one hydrogen can replace through fluorine or chlorine；

A is 0,1,2,3 or 4；

Z¹For singly-bound or the alkylidene of carbon number 1 to 6, the Z¹In, at least one-CH₂Can through-O- ,-CO- ,-COO- ,- OCO- or-OCOO- replaces, at least one-CH₂CH₂It can replace through-CH=CH- or-C ≡ C-, in these bases, at least one hydrogen It can replace through fluorine or chlorine；

Sp¹For singly-bound or the alkylidene of carbon number 1 to 10, the Sp¹In, at least one-CH₂Can through-O- ,-CO- ,- COO- ,-OCO- or-OCOO- replace, at least one-CH₂CH₂It can replace through-CH=CH- or-C ≡ C-, in these bases, at least One hydrogen can replace through halogen, and in these bases, at least one hydrogen passes through the base being selected from base represented by formula (1a) and replaces；

In formula (1a),

Sp¹²For singly-bound or the alkylidene of carbon number 1 to 10, the Sp¹²In, at least one-CH₂Can through-O- ,-CO- ,- COO- ,-OCO- or-OCOO- replace, at least one-CH₂CH₂It can replace through-CH=CH- or-C ≡ C-, in these bases, at least One hydrogen can replace through halogen；

M¹¹And M¹²Independently be hydrogen, carbon number 1 that halogen, the alkyl of carbon number 1 to 5 or at least one hydrogen replace through halogen to 5 alkyl:

R¹²For the alkyl of carbon number 1 to 15, the R¹²In, at least one-CH₂It can replace through-O- or-S-, at least one- CH₂CH₂It can replace through-CH=CH- or-C ≡ C-, at least one hydrogen can replace through halogen:

In formula (1-1),

P¹¹For the base in the base represented by the formula (1e) and formula (1f)；

In formula (1e) and formula (1f),

Sp¹³For singly-bound or the alkylidene of carbon number 1 to 10, the Sp¹³In, at least one-CH₂Can through-O- ,-NH- ,- CO- ,-COO- ,-OCO- or-OCOO- replace, at least one-CH₂CH₂It can replace through-CH=CH- or-C ≡ C-, these bases In, at least one hydrogen can replace through halogen；

M¹³And M¹⁴Independently be hydrogen, carbon number 1 that halogen, the alkyl of carbon number 1 to 5 or at least one hydrogen replace through halogen to 5 alkyl；

R¹³For the base in the base represented by formula (1g), formula (1h) and the formula (1i)；

In formula (1g), formula (1h) and formula (1i),

Sp¹⁴And Sp¹⁵It independently is the alkylidene of singly-bound or carbon number 1 to 10, in the alkylidene, at least one-CH₂It can Replace through-O- ,-NH- ,-CO- ,-COO- ,-OCO- or-OCOO-, at least one-CH₂CH₂It can be through-CH=CH- or-C ≡ C- Replace, at least one hydrogen can replace through halogen；

In formula (1g) and formula (1i), S¹For > CH- or > N-, S²For > C < or > Si <；

X¹For-OH ,-NH₂、-OR¹⁵、-N(R¹⁵)₂、-COOH、-SH、-B(OH)₂Or-Si (R¹⁵)₃；

-OR¹⁵、-N(R¹⁵)₂And-Si (R¹⁵)₃In,

R¹⁵For hydrogen or the alkyl of carbon number 1 to 10, the R¹⁵In, at least one-CH₂It can replace through-O-, at least one- CH₂CH₂It can replace through-CH=CH-, in these bases, at least one hydrogen can replace through halogen.

[9] manufacturing method of the liquid crystal display element according to [8], wherein orientation monomer be selected from formula (1-2) extremely At least one of the group of compound represented by formula (1-3) polymerizable compound；

In formula (1-2) and formula (1-3),

R¹For the alkyl of carbon number 1 to 12, in the alkyl, at least one-CH₂It can replace through-O-, at least one- CH₂CH₂It can replace through-CH=CH- or-C ≡ C-, in these bases, at least one hydrogen can be fluorine-substituted；

Ring A¹And ring A²Independently be 1,4- cyclohexylidene, 1,4- cyclohexadienylidene, 1,4- phenylene, naphthalene -2,6- diyl, Oxinane -2,5- diyl, 1,3- dioxanes -2,5- diyl, fluorenes -2,7- diyl, phenanthrene -2,7- diyl, perhydro cyclopentano [a] Phenanthrene -3,17- diyl or ten tetrahydro cyclopentyl of 2,3,4,7,8,9,10,11,12,13,14,15,16,17- simultaneously [a] phenanthrene -3,17- two Base, in these rings, at least one hydrogen can through fluorine, the alkyl of carbon number 1 to 8, the alkenyl of carbon number 2 to 8, carbon number 1 to 7 alkoxy, Or the alkenyloxy group of carbon number 2 to 7 replaces, in these bases, at least one hydrogen can be fluorine-substituted；

A is 0,1,2,3 or 4；

L is 0,1,2,3,4,5 or 6, at least one-CH of the alkylidene₂Can through-O- ,-CO- ,-COO- ,-OCO-, Or-OCOO- replaces, at least one-CH₂CH₂It can replace through-CH=CH- or-C ≡ C-, in these bases, at least one hydrogen can be through Fluorine replaces；

Sp¹²For singly-bound or the alkylidene of carbon number 1 to 5, in the alkylidene, at least one-CH₂Can through-O- ,-CO- ,- COO- ,-OCO- or-OCOO- replace, at least one-CH₂CH₂It can replace through-CH=CH- or-C ≡ C-, in these bases, at least One hydrogen can be fluorine-substituted；

M¹¹And M¹²It independently is hydrogen, fluorine, methyl, ethyl or trifluoromethyl；

R¹²For hydrogen or the alkyl of carbon number 1 to 5, in the alkyl, at least one-CH₂It can replace through-O- or-S-, at least One-(CH₂)₂It can replace through-CH=CH- or-C ≡ C-, in these bases, at least one hydrogen can be fluorine-substituted；

Sp¹³For singly-bound or the alkylidene of carbon number 1 to 5, in the alkylidene, at least one-CH₂Can through-O- ,-CO-, Or-COO- replaces, at least one-CH₂CH₂It can replace through-CH=CH- or-C ≡ C-, in these bases, at least one hydrogen can be through fluorine Replace；

M¹³And M¹⁴It independently is hydrogen, fluorine, methyl, ethyl or trifluoromethyl；

Sp¹⁴For singly-bound or the alkylidene of carbon number 1 to 5, in the alkylidene, at least one-CH₂Can through-O- ,-CO-, Or-COO- replaces, at least one-CH₂CH₂It can replace through-CH=CH- or-C ≡ C-, in these bases, at least one hydrogen can be through fluorine Replace；

X¹For-OH or-N (R¹⁵)₂；

-N(R¹⁵)₂In,

R¹⁵For hydrogen or the alkyl of carbon number 1 to 5, in the alkyl, at least one-CH₂It can replace through-O-, at least one- CH₂CH₂It can replace through-CH=CH-, in these bases, at least one hydrogen can be fluorine-substituted.

[10] manufacturing method of the liquid crystal display element according to [8], wherein orientation monomer be selected from formula (1-4) extremely At least one of the group of compound represented by formula (1-60) polymerizable compound；

Formula (1-4) into formula (1-60),

R¹For the alkyl of carbon number 1 to 10；

Z¹、Z¹²And Z¹³It independently is singly-bound ,-CH₂CH₂Or-(CH₂)₄-；

Sp¹²、Sp¹³And Sp¹⁴It independently is the alkylidene of singly-bound or carbon number 1 to 5, in the alkylidene, at least one- CH₂It can replace through-O-；

L¹、L²、L³、L⁴、L⁵、L⁶、L⁷、L⁸、L⁹、L¹⁰、L¹¹And L¹²It independently is hydrogen, fluorine, methyl or ethyl；

L is 0,1,2,3,4,5 or 6.

[11] manufacturing method of the liquid crystal display element according to any one of [1] to [10], wherein the liquid crystal group It closes object and then 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 the 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-.

[12] manufacturing method of the liquid crystal display element according to any one of [1] to [11], wherein the liquid crystal group It closes object 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 the 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- ,-C ≡ C- ,-COO- ,-CF₂O-、-OCF₂-、- CH₂O- or-(CH₂)₄-；

L¹¹And L¹²It independently is hydrogen or fluorine.

[13] manufacturing method of the liquid crystal display element according to any one of [1] to [12], wherein the liquid crystal group It closes object 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 the 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.

[14] manufacturing method of the liquid crystal display element according to any one of [1] to [13], wherein the liquid crystal group It closes object 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 the 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 the 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.

[15] manufacturing method of the liquid crystal display element according to any one of [1] to [14], wherein the liquid crystal group It closes object and then contains polymerizable compound represented by the formula (16 α) as reactive monomer, and to be 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- 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.

[16] manufacturing method of the liquid crystal display element according to [15], wherein in formula (16 α) described in [15], P¹¹、P¹²And P¹³It independently is the base being selected from the group of polymerism base represented by formula (P-1) to formula (P-5)；

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

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

[17] manufacturing method of the liquid crystal display element according to any one of [1] to [16], wherein the liquid crystal group Closing object has negative dielectric anisotropy.

[18] manufacturing method of the liquid crystal display element according to any one of [1] to [17], wherein the orientation is controlled Preparative layer has the film thickness of 10nm to 100nm, and the partial size of the polymer in the tropism control layer is the range of 1nm to 90nm.

[19] manufacturing method of the liquid crystal display element according to any one of [1] to [18], wherein the orientation is controlled The partial size of polymer in preparative layer is the range of 1nm to 70nm.

[20] manufacturing method of the liquid crystal display element according to any one of [1] to [19], wherein the liquid crystal liquid crystal property Being oriented to for the molecule of compound is vertical, and the angle of the molecule and the substrate is 90 ° ± 10 °.

[21] manufacturing method of the liquid crystal display element according to any one of [1] to [20], wherein the liquid crystal liquid crystal property The orientation of the molecule of compound orientation segmentation according to each pixel.

[22] a kind of display device has through the liquid crystal display element according to any one of [1] to [21] Liquid crystal display element manufactured by manufacturing method and backlight.

The effect of invention

Advantages of the present invention is a kind of method that provides, and the method is in the liquid for not having alignment films as polyimides For obtaining uniform orientation in the manufacture of crystal display element.Another advantage is to provide a kind of side for manufacturing liquid crystal display element Method, the method by a liquid crystal composition addition have high chemical stability, the high ability for making liquid crystal molecular orientation, And high-dissolvability in a liquid crystal composition polymerism polar compound and make its polymerization, and manufacture to have and element can be used The liquid crystal of wide temperature range, the characteristic that the response time is short, voltage retention is high, starting voltage is low, contrast is longer than big, service life etc Display element.Another advantage is to provide a kind of method of liquid crystal display element of the manufacture with liquid-crystal composition, the liquid crystal group It closes object and meets that nematic ceiling temperature is high, nematic lower limit temperature is low, viscosity is small, optical anisotropy is appropriate, positive or negative The characteristics such as 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 At least one.

Detailed description of the invention

[Fig. 1] is the polymerism polarity indicated by the interaction of polar group and substrate surface as orientation monomer Compound 5 is arranged in the skeleton diagram (electrode not shown of the element 11 of the state in colored filter substrate 1 and array substrate 2 Layer), and the tropism control layer of polymer is formed by polymerization.

[Fig. 2] is the polymerism polarity indicated by the interaction of polar group and substrate surface as orientation monomer Compound 5 and polymerizable compound 6 as reactive monomer are arranged in the shape in colored filter substrate 1 and array substrate 2 The skeleton diagram (electrode layer not shown) of the element 12 of state, and the tropism control layer of copolymer is formed by polymerizeing.

[Fig. 3] be it is existing with alignment films 7 and include polymerizable compound element 21 skeleton diagram (electrode not shown Layer).

Specific embodiment

The application method of term in the specification is as described below.Sometimes by " liquid-crystal composition " and " liquid crystal display The term of element " is briefly referred to as " composition " and " element "." liquid crystal display element " is liquid crystal display panel and liquid crystal display The general name of module." liquid crystal compounds " are the compounds with liquid crystalline phases such as nematic phase, smectic phases, though and without liquid crystal Phase, but composition is mixed in for the purpose for the characteristic for adjusting nematic temperature range, viscosity, dielectric anisotropy etc In compound general name.The compound has the hexatomic ring of such as 1 or 4 cyclohexylidene or Isosorbide-5-Nitrae-phenylene etc, and its Molecular structure is rodlike (rod like)." polymerizable compound " is added for the purpose for generating polymer in composition is made Compound." polar compound " is to occur to interact to help liquid crystal molecule to be arranged with substrate surface by polar group Column.

Liquid-crystal composition is prepared by mixing plurality of liquid crystals compound.In the liquid-crystal composition optionally Add optically active compound, antioxidant, ultraviolet absorbing agent, pigment, defoaming agent, polymerizable compound, polymerization initiator, The additive of polymerization inhibitor, polar compound etc.Even if in the case where being added with additive, the ratio of liquid crystal compounds Example is also to be indicated by the weight percent (weight %) of the weight based on the liquid-crystal composition without additive.The ratio of additive It is to be indicated by the weight percent (weight %) of the weight based on the liquid-crystal composition without additive.That is, liquid crystal compounds Or the ratio of additive is the total weight based on liquid crystal compounds and calculates.Sometimes also parts per million by weight (ppm) is used.It is poly- The ratio for closing initiator and polymerization inhibitor is exceptionally indicated based on the weight of polymerizable compound.

Sometimes compound represented by formula (1) is referred to as " compound (1) ".Compound (1) refers to represented by formula (1) 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 for being selected from At least one of the group of compound represented by formula (2) compound etc..The B surrounded by hexagon¹、C¹, the marks difference such as F Corresponding to ring B¹, ring C¹, ring F etc..Hexagon indicate the hexatomic ring as cyclohexane ring or phenyl ring or as naphthalene nucleus it is thick Ring.In formula (1 γ), the straight line on one side of crosscutting hexagon is to indicate that the arbitrary hydrogen on ring can be through-Sp¹-P¹Equal bases replace.‘c' Etc. subscripts indicate the quantity of base being substituted.When being designated as 0 under, such substitution is not present.When subscript ' c ' is 2 or more, in ring A¹On there are multiple-Sp¹-P¹。-Sp¹-P¹The multiple bases indicated can be identical, or can also be different.In formula (1 γ), (R is used¹)n、 (R²) n and (R³) n mark.3 numbers can be identical represented by 3 ' n ', or can also be different.These rules are also applied for it In his formula.In the statement of " ring A and ring B independently are X, Y or Z ", since subject is multiple, therefore " independently " is used.In subject When for " ring A ", since subject is odd number, therefore " independently " is not used.

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 the feelings of ethyl Condition.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 for other The mark of terminal groups, ring, bond base etc..In formula (8), when i is 2, there are two ring D¹.In the compound, two ring D¹Institute Two bases indicated can be identical, or can also be different.The rule is also applied for arbitrary two ring D of the i greater than 2 when¹.The rule Then it is also applied for the mark of 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 ' " Refer to ' A ' quantity be one when, the position of ' A ' be it is any, ' A ' quantity for two or more when, their position It can unlimitedly select.The rule is also applied for the statement of " at least one ' A ' replaces through ' B ' "." at least one A can be through B, C Or D replaces " statement refer to and include the case where following situations: at least one A replaces through B；The case where at least one A replaces through C； And at least one A the case where replacing through D；In turn, the case where multiple A replace through at least the two of B, C, D.For example, at least one- CH₂(or-(CH₂)₂) can through-O- (or-CH=CH-) replace alkyl include: alkyl, alkenyl, alkoxy, alkoxyalkyl, Alkoxyalkenyl, alkenyloxy group alkyl.Furthermore continuous two-CH₂Replaced by-O- and is become the situation as-O-O- and owe It is good.In alkyl etc., methyl moiety (- CH₂- H)-CH₂The case where warp-O- is substituted by-O-H be not good enough yet.

In liquid crystal compounds, it does not include cyclic alkyl that alkyl, which is straight-chain or branch-like,.Straight-chain alkyl is typically superior to Branch-like alkyl.For the terminal groups such as alkoxy, alkenyl, the situation is similarly such.In order to promote the nematic upper limit Temperature, spatial configuration relevant to 1 or 4 cyclohexylidene are trans- better than cis-.The fluoro- 1,4- phenylene of 2- refers to following two kinds Bilvalent radical.In chemical formula, fluorine can also be able to be towards right (R) for towards left (L).The rule is also applied for such as oxinane -2,5- two The such asymmetrical bilvalent radical generated and removing two hydrogen from ring of base.

In the manufacturing method of liquid crystal display element of the invention, polymerism polar compound will be added in a liquid crystal composition Made of liquid-crystal composition enclose element in.Polymerism polar compound has the function of as orientation monomer.The chemical combination The polar group and substrate surface of object have interaction, therefore help to be orientated.The compound has by least one ring structure At mesogen position.At least one ring is preferably cyclohexane ring.Mesogen position, which refers to, helps to show the upright and outspoken of liquid crystal liquid crystal property Part.The compound is polymerism, and provides polymer by polymerization.The polymer facilitates taking for liquid crystal molecule To.Polar compound is with polar organic compound.Herein, without the compound with ionic bond.Oxygen, sulphur and nitrogen etc Atom electrical property it is partially negative and there is the tendency with partial negative charge.Carbon and hydrogen are neutral or exist with part positive charge Tendency.Polarity is unequally distributed and generates between atom not of the same race because of Partial charge in compound.For example, polarity Compound has-OH ,-COOH ,-SH ,-NH₂, > NH, > N- etc part-structure at least one.

The polymerism polar compound is referred to as compound (1) in the present specification.In turn, depending on referring to structural details Occasion etc. needs, and is hereinafter referred to as compound (1 α), compound (1 β), compound (1 γ), compound (1-1)~compound (1- 60).Hereinafter, the successively conjunction to the synthesis of 1. compounds (1 α), 2. compounds (1 α), 3. compounds (1 β), 4. compounds (1 β) At, 5. compounds (1 γ), the synthesis of 6. compounds (1 γ), 7. compounds (1-1)~compound (1-60), 8. compound (1- 1) synthesis of~compound (1-60), as the composition comprising compound (1) 9. liquid-crystal compositions, as contain described group 10. liquid crystal display elements for closing the element of object are illustrated.

1. compound (1 α)

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

This illustration includes following items etc..

A kind of 1. compounds of item, are indicated by formula (1 α)；

In formula (1 α),

MES is the liquid crystal former base at least one ring；

M¹And M²It independently is the carbon number that hydrogen, fluorine, chlorine, the alkyl of carbon number 1 to 5 or at least one hydrogen replace through fluorine or chlorine 1 to 5 alkyl；

R²For base represented by formula (1 α a), formula (1 α b) or formula (1 α c)；

In formula (1 α a), formula (1 α b) and formula (1 α c),

Sp²And Sp³It independently is the alkylidene of singly-bound or carbon number 1 to 10, in the alkylidene, at least one-CH₂It can Replace through-O- ,-NH- ,-CO- ,-COO- ,-OCO- or-OCOO-, at least one-(CH₂)₂It can be taken through-CH=CH- or-C ≡ C- In generation, in these bases, at least one hydrogen can replace through fluorine or chlorine；

S¹For > CH- or > N-；

S²For > C < or > Si <；

2. compounds according to item 1 of item, are indicated by formula (1 α -1)；

In formula (1 α -1),

Ring A¹And ring A⁴Independently be 1,4- cyclohexylidene, 1,4- cyclohexadienylidene, 1,4- phenylene, naphthalene -2,6- diyl, Decahydronaphthalene -2,6- diyl, 1,2,3,4- naphthane -2,6- diyl, oxinane -2,5- diyl, 1,3- dioxanes -2,5- two Base, pyrimidine -2,5- diyl, pyridine -2,5- diyl, fluorenes -2,7- diyl, phenanthrene -2,7- diyl, anthracene -2,6- diyl, perhydro cyclopentano [a] phenanthrene -3,17- diyl or ten tetrahydro cyclopentyl of 2,3,4,7,8,9,10,11,12,13,14,15,16,17- simultaneously [a] phenanthrene -3,17- Diyl, in these rings, at least one hydrogen can be through fluorine, chlorine, the alkyl of carbon number 1 to 12, the alkenyl of carbon number 2 to 12, carbon number 1 to 11 The alkenyloxy group of alkoxy or carbon number 2 to 11 replaces, and in these bases, at least one hydrogen can replace through fluorine or chlorine；

Z¹For singly-bound or the alkylidene of carbon number 1 to 10, in the alkylidene, at least one-CH₂Can through-O- ,-CO- ,- COO- ,-OCO- or-OCOO- replace, 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；

A is 0,1,2,3 or 4；

R²For base represented by formula (1 α a) or formula (1 α b)；

In formula (1 α a) and formula (1 α b),

S¹For > CH- or > N-；

3. compounds according to item 1 or item 2 of item, are indicated by formula (1 α -2)；

In formula (1 α -2),

R¹For the alkyl of carbon number 1 to 15, the alkenyl of carbon number 2 to 15, the alkoxy of carbon number 1 to 14 or the alkene of carbon number 2 to 14 Oxygroup, in these bases, at least one hydrogen can replace through fluorine or chlorine；

Ring A¹And ring A⁴Independently be 1,4- cyclohexylidene, 1,4- cyclohexadienylidene, 1,4- phenylene, naphthalene -2,6- diyl, Decahydronaphthalene -2,6- diyl, 1,2,3,4- naphthane -2,6- diyl, oxinane -2,5- diyl, 1,3- dioxanes -2,5- two Base, pyrimidine -2,5- diyl, pyridine -2,5- diyl, perhydro cyclopentano [a] phenanthrene -3,17- diyl or 2,3,4,7,8,9,10,11, 12,13,14,15,16,17- ten tetrahydro cyclopentyls simultaneously [a] phenanthrene -3,17- diyl, in these rings, at least one hydrogen can be through fluorine, chlorine, carbon The alkenyloxy group substitution of the alkyl of number 1 to 2, the alkenyl of carbon number 2 to 12, the alkoxy of carbon number 1 to 11 or carbon number 2 to 11, these bases In, at least one hydrogen can replace through fluorine or chlorine；

Z¹For singly-bound ,-(CH₂)₂,-CH=CH- ,-C ≡ C- ,-COO- ,-OCO- ,-CF₂O-、-OCF₂-、-CH₂O-、- OCH₂Or-CF=CF-；

Sp¹And Sp²It 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- or-OCO-, at least one-(CH₂)₂It can replace through-CH=CH-, in these bases, at least one hydrogen can Replace through fluorine or chlorine；

M¹And M²It independently is hydrogen, fluorine, the alkyl of carbon number 1 to 5 or the fluorine-substituted carbon number 1 to 5 of at least one hydrogen Alkyl；

X¹For-OH ,-NH₂、-OR³、-N(R³)₂, formula (x1) ,-COOH ,-SH ,-B (OH)₂Or-Si (R³)₃Represented base, Herein, R³For hydrogen or the alkyl of carbon number 1 to 10, in the alkyl, at least one-CH₂It can replace through-O-, at least one- (CH₂)₂Can replace through-CH=CH-, in these bases, at least one hydrogen can replace through fluorine or chlorine, the w in formula (x1) be 1,2,3 or 4；

A is 0,1,2,3 or 4.

4. compounds according to any one of item 1 to item 3 of item, by any one table of formula (1 α -3) to formula (1 α -6) Show；

Formula (1 α -3) into formula (1 α -6),

R¹For the alkyl of carbon number 1 to 15, the alkenyl of carbon number 2 to 15, the alkoxy of carbon number 1 to 14 or the alkene of carbon number 2 to 14 Oxygroup, in these bases, at least one hydrogen can be fluorine-substituted；

Ring A¹, ring A², ring A³And ring A⁴It independently is 1,4- cyclohexylidene, 1,4- cyclohexadienylidene, 1,4- phenylene, naphthalene- 2,6- diyl, decahydronaphthalene -2,6- diyl, oxinane -2,5- diyl, 1,3- dioxanes -2,5- diyl, perhydro cyclopentano [a] Phenanthrene -3,17- diyl or ten tetrahydro cyclopentyl of 2,3,4,7,8,9,10,11,12,13,14,15,16,17- simultaneously [a] phenanthrene -3,17- two Base, in these rings, at least one hydrogen can be through the alcoxyl of fluorine, chlorine, the alkyl of carbon number 1 to 7, the alkenyl of carbon number 2 to 7 or carbon number 1 to 6 Base replaces；

Z¹、Z²And Z³It independently is singly-bound ,-(CH₂)₂,-CH=CH- ,-C ≡ C- ,-COO- ,-OCO- ,-CF₂O-、- OCF₂-、-CH₂O-、-OCH₂Or-CF=CF-；

Sp¹And Sp²It independently is the alkylidene of singly-bound or carbon number 1 to 7, in the alkylidene, at least one-CH₂Can through- O- ,-COO- or-OCO- replace, at least one-(CH₂)₂It can replace through-CH=CH-, in these bases, at least one hydrogen can be through Fluorine replaces；

M¹And M²It independently is hydrogen, fluorine, methyl, ethyl or trifluoromethyl；

X¹For-OH ,-NH₂、-OR³、-N(R³)₂, formula (x1) or-Si (R³)₃Represented base, herein, R³For hydrogen or carbon number 1 To 5 alkyl, in the alkyl, at least one-CH₂It can replace through-O-, at least one-(CH₂)₂It can be taken through-CH=CH- In generation, in these bases, at least one hydrogen can be fluorine-substituted, and the w in formula (x1) is 1,2,3 or 4；

5. compounds according to any one of item 1 to item 4 of item, by any one of formula (1 α -7) to formula (1 α -10) It indicates；

Formula (1 α -7) into formula (1 α -10),

R¹For the alkoxy of the alkyl of carbon number 1 to 10, the alkenyl of carbon number 2 to 10 or carbon number 1 to 9, in these bases, until Few hydrogen can be fluorine-substituted；

Ring A¹, ring A², ring A³And ring A⁴It independently is 1,4- cyclohexylidene, 1,4- cyclohexadienylidene, 1,4- phenylene, four Hydrogen pyrans -2,5- diyl, 1,3- dioxanes -2,5- diyl, perhydro cyclopentano [a] phenanthrene -3,17- diyl or 2,3,4,7,8,9, 10,11,12,13,14,15,16,17- ten tetrahydro cyclopentyls simultaneously [a] phenanthrene -3,17- diyl, in these rings, at least one hydrogen can be through The alkoxy substitution of fluorine, chlorine, 1 to 5 alkyl of carbon number, the alkenyl of carbon number 2 to 5 or carbon number 1 to 4；

Z¹、Z²And Z³It independently is singly-bound ,-(CH₂)₂Or-CH=CH-；

Sp¹For singly-bound or the alkylidene of carbon number 1 to 7, in the alkylidene, at least one-CH₂It can replace through-O-, at least One-(CH₂)₂It can replace through-CH=CH-；

Sp²For the alkylidene of carbon number 1 to 7, in the alkylidene, at least one-CH₂It can replace through-O-；

X¹For-OH ,-NH₂Or-N (R³)₂, herein, R³For hydrogen or the alkyl of carbon number 1 to 5, in the alkyl, at least one- CH₂It can replace through-O-, at least one-(CH₂)₂It can replace through-CH=CH-, in these bases, at least one hydrogen can take through fluorine Generation.

6. compounds according to any one of item 1 to item 5 of item, by any one of formula (1 α -11) to formula (1 α -14) It indicates；

Formula (1 α -11) into formula (1 α -14),

Ring A¹, ring A², ring A³And ring A⁴It independently is 1,4- cyclohexylidene, 1,4- phenylene, perhydro cyclopentano [a] phenanthrene -3, 17- diyl or 2,3,4,7,8,9,10,11,12,13,14,15,16,17- ten tetrahydro cyclopentyls simultaneously [a] phenanthrene -3,17- diyl, these In ring, at least one hydrogen can replace through the alkyl of fluorine or carbon number 1 to 5；

Z¹、Z²And Z³It independently is singly-bound or-(CH₂)₂-；

Sp¹For singly-bound or the alkylidene of carbon number 1 to 5, in the alkylidene, at least one-CH₂It can replace through-O-；

Sp²For the alkylidene of carbon number 1 to 5, in the alkylidene, at least one-CH₂It can replace through-O-；

7. compounds according to any one of item 1 to item 6 of item, by any one of formula (1 α -15) to formula (1 α -31) It indicates；

Formula (1 α -15) into formula (1 α -31),

Z¹、Z²And Z³It independently is singly-bound or-(CH₂)₂-；

L¹、L²、L³、L⁴、L⁵、L⁶、L⁷、L⁸、L⁹And L¹⁰It independently is hydrogen, fluorine, methyl or ethyl；

Y¹、Y²、Y³And Y⁴It independently is hydrogen or methyl；

X¹For-OH ,-NH₂Or-N (R³)₂, herein, R³For hydrogen or the alkyl of carbon number 1 to 4, in the alkyl, at least one- CH₂It can replace through-O-, in these bases, at least one hydrogen can be fluorine-substituted.

8. compounds according to any one of item 1 to item 7 of item, by any one of formula (1 α -32) to formula (1 α -43) It indicates；

Formula (1 α -32) into formula (1 α -43),

R¹For the alkyl of carbon number 1 to 10；

Sp¹For singly-bound or the alkylidene of carbon number 1 to 5, in the alkylidene, at least one-CH₂It can replace through-O-, these In base, at least one hydrogen can be fluorine-substituted；

L¹、L²、L³、L⁴、L⁵、L⁶、L⁷、L⁸And L⁹It independently is hydrogen, fluorine, methyl or ethyl；

Y¹And Y²It independently is hydrogen or methyl；

X¹For-OH ,-NH₂Or-N (R³)₂, herein, R³For hydrogen or the alkyl of carbon number 1 to 4, in the alkyl, at least one- CH₂It can replace through-O-.

9. compounds according to any one of item 1 to item 8 of item, by any one of formula (1 α -44) to formula (1 α -63) It indicates；

Formula (1 α -44) into formula (1 α -63),

R¹For the alkyl of carbon number 1 to 10；

Sp¹For singly-bound or the alkylidene of carbon number 1 to 3, in the alkylidene, at least one-CH₂It can replace through-O-, these In base, at least one hydrogen can be fluorine-substituted；

L¹、L²、L³、L⁴And L⁵It independently is hydrogen, fluorine, methyl or ethyl；

Y¹And Y²It independently is hydrogen or methyl；

R³It independently is hydrogen, methyl or ethyl.

A kind of 10. liquid-crystal compositions of item contain at least one compound according to any one of item 1 to item 9 and make For orientation monomer.

11. liquid-crystal compositions according to item 10, and then contain the chemical combination represented by the formula (2) to formula (4) At least one of group of object compound；

Formula (2) into formula (4),

12. liquid-crystal compositions according to item 10 or item 11 of item, and then contain represented to formula (7) selected from formula (5) At least one of the group of compound compound；

Formula (5) into formula (7),

L¹¹And L¹²It independently is hydrogen or fluorine.

13. liquid-crystal compositions according to item 10 or item 11, and then contain the compound represented by formula (8) At least one of group compound；

In formula (8),

X¹²For-C ≡ N or-C ≡ C-C ≡ N；

L¹³And L¹⁴It independently is hydrogen or fluorine；

I is 1,2,3 or 4.

14. liquid-crystal compositions according to item 10 or item 11 of item, and then contain represented to formula (15) selected from formula (9) At least one of the group of compound compound；

Formula (9) into formula (15),

L¹⁵And L¹⁶It independently is fluorine or chlorine；

S¹¹For hydrogen or methyl；

X independently is-CHF- or-CF₂-；

15. liquid-crystal compositions according to any one of item 10 to item 14 contain represented by formula (16 α) At least one of group of polymerizable compound compound is as reactive monomer；

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-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；

P¹¹、P¹²And P¹³It independently is polymerism base；

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.

16. liquid-crystal compositions according to item 15 of item, wherein in the formula described in item 15 (16 α), P¹¹、P¹²And P¹³Solely It is on the spot the base in the group of the polymerism base represented by the formula (P-1) to formula (P-5)；

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

17. liquid-crystal compositions according to any one of item 10 to item 16 of item, contain selected from formula (16 α -1) to formula At least one of the group of compound represented by (16 α -27) polymerizable compound；

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), this Place, M¹¹、M¹²And M¹³Independently be 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.

18. liquid-crystal compositions according to any one of item 10 to item 17, so contain selected from formula (1 α) and The different polymerizable compound of polymerizable compound represented by formula (16 α), polymerization initiator, polymerization inhibitor, optical activity At least one of compound, antioxidant, ultraviolet absorbing agent, light stabilizer, heat stabilizer and defoaming agent.

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) a kind of polymerizable composition, polymerizable composition, passing through will be different from compound (1 α) or compound (16 α) Polymerizable compound make an addition in the liquid-crystal composition and prepare.(c) a kind of polymerizable composition, polymerizable composition, by by compound (1 α) and compound (16 α) makes an addition in the liquid-crystal composition and prepares.(d) a kind of liquid crystal composite, by making to polymerize Property composition polymerization and prepare.(e) a kind of element of polymer stabilizing orientating type, contains the liquid crystal composite.(f) a kind of The element of polymer stabilizing orientating type is made by using following polymerizable composition, polymerizable composition, and the polymerizable composition, polymerizable composition passes through Compound (1 α) is made an addition to from compound (16 α) and the polymerizable compound different with compound (1 α) or compound (16 α) It is prepared in the liquid-crystal composition.

The form of 1-2. compound (1 α)

Compound (1 α) is characterized by having the mesogen position being made of at least one ring and through poles such as hydroxy alkyls Property base replace acryloxy.Due to polar group phase interaction occurs with substrate surface in a manner of non-covalent bond for compound (1 α) With, therefore it is useful.One of purposes is the additive of liquid-crystal composition used in liquid crystal display element.Compound (1 α) be with It is added for the purpose of the orientation of control liquid crystal molecule.Such additive be preferably have high-dissolvability in a liquid crystal composition and Chemical stabilization under conditions of being sealed in element, and be used for liquid crystal display element when voltage retention it is big.Compound (1 α) considerably meet such characteristic.

The preference of compound (1 α) is illustrated.R in compound (1 α)¹、MES、Sp¹、R²、M¹Or M²Preference It is also applied for the hypogyny of compound (1 α).In compound (1 α), can arbitrarily it be adjusted and being appropriately combined the type of these bases Whole characteristic.Since, without big difference, compound (1 α) contains more naturally occurring ratio in terms of the characteristic of compound More than amount²H (deuterium),¹³The isotopes such as C.

In formula (1 α), R¹For the alkyl of carbon number 1 to 15, in the alkyl, at least one-CH₂It can replace through-O- or-S-, 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.

In formula (1 α), preferred R¹For the alkyl of carbon number 1 to 15, the alkenyl of carbon number 2 to 15, carbon number 1 to 14 alkoxy, Or the alkenyloxy group of carbon number 2 to 14.And then preferred R¹For the alkyl of carbon number 1 to 10, the alkenyl of carbon number 2 to 10 or carbon number 1 to 9 Alkoxy.Particularly preferred R¹For the alkyl of carbon number 1 to 10.

In formula (1 α), MES is the liquid crystal former base at least one ring.Liquid crystal former base is ripe for those skilled in the art Know.Liquid crystal former base refers to, when compound has liquid crystalline phase (interphase), facilitates the part of the formation of liquid crystalline phase.Compound The preference of (1 α) is compound (1 α -1).

In formula (1 α -1), preferred ring A¹Or ring A⁴For 1,4- cyclohexylidene, 1,4- cyclohexadienylidene, 1,4- phenylene, Naphthalene -2,6- diyl, decahydronaphthalene -2,6- diyl, 1,2,3,4- naphthane -2,6- diyl, oxinane -2,5- diyl, 1,3- bis- Oxane -2,5- diyl, pyrimidine -2,5- diyl, pyridine -2,5- diyl, perhydro cyclopentano [a] phenanthrene -3,17- diyl or 2,3,4,7, 8,9,10,11,12,13,14,15,16,17- ten tetrahydro cyclopentyls simultaneously [a] phenanthrene -3,17- diyl, in these rings, at least one hydrogen can Alkenyloxy group through fluorine, chlorine, the alkyl of carbon number 1 to 12, the alkenyl of carbon number 2 to 12, the alkoxy of carbon number 1 to 11 or carbon number 2 to 11 Replace, in these bases, at least one hydrogen can replace through fluorine or chlorine.And then preferred ring A¹Or ring A⁴For 1,4- cyclohexylidene, 1,4- Ten tetrahydro of phenylene, perhydro cyclopentano [a] phenanthrene -3,17- diyl or 2,3,4,7,8,9,10,11,12,13,14,15,16,17- Cyclopentano [a] phenanthrene -3,17- diyl, in these rings, at least one hydrogen can replace through the alkyl of fluorine or carbon number 1 to 5.Particularly preferably Ring A¹Or ring A⁴For 1 or 4 cyclohexylidene, Isosorbide-5-Nitrae-phenylene, perhydro cyclopentano [a] phenanthrene -3,17- diyl, in these rings, such as Such as 1- methyl-1,4- cyclohexylidene, 2- ethyl -1 or 4 cyclohexylidene, the fluoro- Isosorbide-5-Nitrae-phenylene of 2- are such, at least one hydrogen can be through Fluorine, methyl or ethyl replace.

In formula (1 α -1), Z¹For singly-bound or the alkylidene of carbon number 1 to 10, in the alkylidene, at least one-CH₂Can through- O- ,-CO- ,-COO- ,-OCO- or-OCOO- replace, at least one-(CH₂)₂It can replace through-CH=CH- or-C ≡ C-, these In base, at least one hydrogen can replace through fluorine or chlorine.

In formula (1 α -1), preferred Z¹For singly-bound ,-(CH₂)₂,-CH=CH- ,-C ≡ C- ,-COO- ,-OCO- ,- CF₂O-、-OCF₂-、-CH₂O-、-OCH₂Or-CF=CF-.And then preferred Z¹For singly-bound ,-(CH₂)₂Or-CH=CH-.It is special Not preferred Z¹For singly-bound.

In formula (1 α -1), a 0,1,2,3 or 4.Preferred a is 0,1,2 or 3.And then preferred a is 0,1 or 2.

In formula (1 α) and formula (1 α -1), Sp¹For singly-bound or the alkylidene of carbon number 1 to 10, in the alkylidene, at least one A-CH₂It can replace through-O- ,-CO- ,-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.

In formula (1 α), preferred Sp¹For singly-bound, the alkylidene of carbon number 1 to 5 or-a CH₂The carbon number 1 that warp-O- replaces To 5 alkylidene.And then preferred Sp¹For singly-bound, the alkylidene of carbon number 1 to 3 or-a CH₂Warp-O- replace carbon number 1 to 3 alkylidene.

In formula (1 α) and formula (1 α -1), M¹And M²It independently is the alkyl or at least one hydrogen of hydrogen, fluorine, chlorine, carbon number 1 to 5 The alkyl of the carbon number 1 to 5 replaced through fluorine or chlorine.Preferred M¹Or M²For hydrogen, fluorine, methyl, ethyl or trifluoromethyl.And then preferably M¹Or M²For hydrogen.

In formula (1 α) and formula (1 α -1), R²For base represented by formula (1 α a), formula (1 α b) or formula (1 α c).Preferred R²For formula Base represented by (1 α a) or formula (1 α b).And then preferred R²For base represented by formula (1 α a).

In formula (1 α a), formula (1 α b) and formula (1 α c), Sp²And Sp³It independently is the alkylidene of singly-bound or carbon number 1 to 10, institute It states in alkylidene, at least one-CH₂It can replace through-O- ,-NH- ,-CO- ,-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.

In formula (1 α a), formula (1 α b) and formula (1 α c), preferred Sp²Or Sp³For the alkylidene of carbon number 1 to 7 or one- CH₂The alkylidene for the carbon number 1 to 5 that warp-O- replaces.And then preferred Sp²Or Sp³For the alkylidene of carbon number 1 to 5 or one- CH₂The alkylidene for the carbon number 1 to 5 that warp-O- replaces.Particularly preferred Sp²Or Sp³For-CH₂-。

In formula (1 α a), formula (1 α b) and formula (1 α c), S¹For > CH- or > N-；S²For > C < or > Si <.Preferred S¹ For > CH- or > N-, preferred S²For > C <.Formula (1b) is better than formula (1c).

In formula (1 α a), formula (1 α b) and formula (1 α c), X¹It independently is-OH ,-NH₂、-OR³、-N(R³)₂, formula (x1) ,- COOH、-SH、-B(OH)₂Or-Si (R³)₃Represented base, herein, R³For hydrogen or the alkyl of carbon number 1 to 10, in the alkyl, At least one-CH₂It can replace through-O-, at least one-(CH₂)₂It can replace through-CH=CH-, in these bases, at least one hydrogen It can replace through fluorine or chlorine, the w in formula (x1) is 1,2,3 or 4.

In formula (1 α a), formula (1 α b) and formula (1 α c), preferred X¹For-OH ,-NH₂、-OR³、-N(R³)₂, formula (x1) or-Si (R³)₃Represented base, herein, R³For hydrogen or the alkyl of carbon number 1 to 5, in the alkyl, at least one-CH₂It can be taken through-O- Generation, at least one-(CH₂)₂It can replace through-CH=CH-, in these bases, at least one hydrogen can be fluorine-substituted, the w in formula (x1) It is 1,2,3 or 4.And then preferred X¹For-OH ,-NH₂Or-N (R³)₂.Particularly preferred X¹For-OH.

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.

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) swash Indicate the position of bond.

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.Into And 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, and f, g and h And be 1 or more.Preferred f, g or h are 1 or 2.

2. the synthesis of compound (1 α)

The synthetic method of compound (1 α) is illustrated.Compound (1 α) is using International Publication No. 2016/129490 The method recorded in handbook synthesizes.In addition, can also be closed by the way that the method for well known Synthetic Organic Chemistry to be appropriately combined At.Can also 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 publishing company (Pergamon Press)), " new experimental chemistry lecture " (ball is kind) etc. is at book.

3. compound (1 β)

3-1. compound (1 β), using its liquid-crystal composition illustration

This illustration includes following items etc..

A kind of 21. compounds of item, are indicated by formula (1 β)；

In formula (1 β),

MES is the liquid crystal former base at least one ring；

22. compounds according to item 21 of item, are indicated by formula (1 β -1)；

In formula (1 β -1),

Z¹For singly-bound or the alkylidene of carbon number 1 to 4, in the alkylidene, at least one-CH₂Can through-O- ,-CO- ,- COO- ,-OCO- or-OCOO- replace, 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；

R²、M¹、M²And M³It independently is the alkyl of hydrogen, fluorine, chlorine or carbon number 1 to 8, in the alkyl, at least one-CH₂It can Replace through-O- or-S-, 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；

A is 0,1,2,3 or 4；

It is 0 and ring A in a⁴When for 1 or 4 cyclohexylidene or Isosorbide-5-Nitrae-phenylene, R¹For the alkyl of carbon number 5 to 15, the alkyl In, at least one-CH₂It can replace through-O- or-S-, at least one-(CH₂)₂It can replace through-CH=CH- or-C ≡ C-, these In base, at least one hydrogen can replace through fluorine or chlorine；

It is 0 and ring A in a⁴For perhydro cyclopentano [a] phenanthrene -3,17- diyl or 2,3,4,7,8,9,10,11,12,13,14, 15,16,17- ten tetrahydro cyclopentyls simultaneously [a] phenanthrene -3,17- diyl when, M¹For the alkyl of fluorine, chlorine or carbon number 1 to 8, in the alkyl, At least one-CH₂It can replace through-O- or-S-, 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.

23. compounds according to item 21 or item 22 of item, by any one expression of formula (1 β -3) to formula (1 β -6)；

Formula (1 β -3) into formula (1 β -6),

Sp¹For singly-bound or the alkylidene of carbon number 1 to 7, in the alkylidene, at least one-CH₂Can through-O- ,-COO- or- OCO- replaces, at least one-(CH₂)₂It can replace through-CH=CH-, in these bases, at least one hydrogen can be fluorine-substituted；

R²、M¹、M²And M³It independently is the alkyl of hydrogen or carbon number 1 to 8, in the alkyl, at least one-CH₂It can be through-O- Replace, at least one-(CH₂)₂It can replace through-CH=CH-, in these bases, at least one hydrogen can replace through fluorine or chlorine；

In formula (1 β -3), in ring A⁴When for 1 or 4 cyclohexylidene or Isosorbide-5-Nitrae-phenylene, R¹Alkyl, carbon number for carbon number 5 to 15 The alkenyloxy group of 5 to 15 alkenyl, the alkoxy of carbon number 4 to 14 or carbon number 4 to 14, in these bases, at least one hydrogen can take through fluorine Generation；

In formula (1 β -3), in ring A⁴For perhydro cyclopentano [a] phenanthrene -3,17- diyl or 2,3,4,7,8,9,10,11,12, 13,14,15,16,17- ten tetrahydro cyclopentyls simultaneously [a] phenanthrene -3,17- diyl when, M¹For the alkyl of carbon number 1 to 8, in the alkyl, until A few-CH₂It can replace through-O-, at least one-(CH₂)₂It can replace through-CH=CH-, in these bases, at least one hydrogen can Replace through fluorine or chlorine.

24. compounds according to any one of item 21 to item 23 of item, by any of formula (1 β -3) to formula (1 β -6) Person indicates；

Formula (1 β -3) into formula (1 β -6),

M²And M³For hydrogen；

R¹For the alkoxy of the alkyl of carbon number 1 to 10, the alkenyl of carbon number 2 to 10 or carbon number 1 to 9；

Z¹、Z²And Z³It independently is singly-bound or-(CH₂)₂-；

M¹And R²It independently is the alkyl of hydrogen or carbon number 1 to 5, in the alkyl, at least one-CH₂It can replace through-O-；

In formula (1 β -3), in ring A⁴When for 1 or 4 cyclohexylidene or Isosorbide-5-Nitrae-phenylene, R¹Alkyl, carbon number for carbon number 5 to 10 5 to 10 alkenyl or the alkoxy of carbon number 4 to 9；

In formula (1 β -3), in ring A⁴For perhydro cyclopentano [a] phenanthrene -3,17- diyl or 2,3,4,7,8,9,10,11,12, 13,14,15,16,17- ten tetrahydro cyclopentyls simultaneously [a] phenanthrene -3,17- diyl when, M¹For the alkyl of carbon number 1 to 5, in the alkyl, until A few-CH₂It can replace through-O-.

25. compounds according to any one of item 21 to item 24 of item, by any of formula (1 β -7) to formula (1 β -20) Person indicates；

Formula (1 β -7) into formula (1 β -20),

Z¹、Z²And Z³It independently is singly-bound or-(CH₂)₂-；

L¹、L²、L³、L⁴、L⁵、L⁶、L⁷、L⁸、L⁹、L¹⁰、L¹¹、L¹²、L¹³And L¹⁴It independently is hydrogen, fluorine, methyl or ethyl；

Y¹、Y²、Y³And Y⁴It independently is hydrogen or methyl,

M¹For hydrogen or the alkyl of carbon number 1 to 5；

M⁴For the alkyl of carbon number 1 to 5；

R²For hydrogen, methyl or ethyl.

26. compounds according to any one of item 21 to item 24 of item, by appointing for formula (1 β -21) to formula (1 β -29) One indicates；

Formula (1 β -21) into formula (1 β -29),

R¹For the alkyl of carbon number 1 to 10；

Y¹And Y²It independently is hydrogen or methyl；

M¹For hydrogen, methyl or ethyl；

M⁴For methyl or ethyl；

R²For hydrogen or methyl.

27. compounds according to any one of item 21 to item 24 of item, by appointing for formula (1 β -30) to formula (1 β -36) One indicates；

Formula (1 β -30) into formula (1 β -36),

R¹For the alkyl of carbon number 1 to 10；

Sp¹For singly-bound or the alkylidene of carbon number 1 to 3, in the alkylidene, at least one-CH₂It can replace through-O-；

Y¹And Y²It independently is hydrogen or methyl；

R²For hydrogen or methyl.

A kind of 28. liquid-crystal compositions of item, contain at least one compound according to any one of item 21 to item 27 As orientation monomer.

29. liquid-crystal compositions according to item 28, and then contain the chemical combination represented by the formula (2) to formula (4) At least one of group of object compound.Furthermore it is recorded in the definition of the structural formula and mark of these compounds and item 11 It is identical.

30. liquid-crystal compositions according to item 28 or item 29 of item, and then contain represented to formula (7) selected from formula (5) At least one of the group of compound compound.Furthermore in the definition of the structural formula and mark of these compounds and item 12 That records is identical.

31. liquid-crystal compositions according to item 28 or item 29, and then contain the compound represented by formula (8) At least one of group compound.Furthermore the phase recorded in the definition of the structural formula and mark of these compounds and item 13 Together.

32. liquid-crystal compositions according to item 28 or item 29 of item, and then contain represented to formula (15) selected from formula (9) At least one of the group of compound compound.Furthermore in the definition of the structural formula and mark of these compounds and item 14 That records is identical.

33. liquid-crystal compositions according to any one of item 28 to item 32 of item, and then contain selected from formula (16 α) institute table At least one of group of polymerizable compound shown compound is as reactive monomer.Furthermore the structure of these compounds It is recorded in the definition of formula and mark and item 15 identical.The preferred configuration of compound (16 α) is as the form recorded.

34. liquid-crystal compositions according to item 33 of item, wherein in the formula described in item 33 (16 α), P¹¹、P¹²And P¹³Solely It is on the spot the base in the group of the polymerism base represented by the formula (P-1) to formula (P-5).Furthermore the structure of these compounds It is recorded in the definition of formula and mark and item 16 identical.

35. liquid-crystal compositions according to any one of item 28 to item 34 of item, contain selected from formula (16 α -1) to formula At least one of the group of polymerizable compound represented by (16 α -27) compound.Furthermore the structural formula of these compounds And it is recorded in the definition of mark and item 17 identical.

36. liquid-crystal compositions according to any one of item 28 to item 35, so contain selected from by with formula (1 α) And the different polymerizable compound of polymerizable compound represented by formula (16 α), polymerization initiator, polymerization inhibitor, optics are living In group composed by property compound, antioxidant, ultraviolet absorbing agent, light stabilizer, heat stabilizer and defoaming agent at least It is a kind of.

This illustration also in next paragraph comprising item 18 (a) item for recording to (f) item.

The form of 3-2. compound (1 β)

Compound (1 β) is characterized by having the mesogen position being made of at least one ring and acrylamido.Change Conjunction object (1 β) is useful since polar group and substrate surface are interacted in a manner of non-covalent bond.One of purposes is The additive of liquid-crystal composition used in liquid crystal display element.Compound (1 β) is to control being oriented to for liquid crystal molecule Purpose and add.Such additive preferably has high-dissolvability in a liquid crystal composition and in the item being sealed in element Chemical stabilization under part, and be used for liquid crystal display element when voltage retention it is big.Compound (1 β) considerably meets Such characteristic.

The preference of compound (1 β) is illustrated.R in compound (1 β)¹、MES、Sp¹、M¹、R²、M²Or M³It is excellent Example is selected to be also applied for the hypogyny of compound (1 β).In compound (1 β), it can be appointed and being appropriately combined the type of these bases Meaning adjustment characteristic.Since, without big difference, compound (1 β) can also contain more naturally occurring in terms of the characteristic of compound More than the amount of ratio²H (deuterium),¹³The isotopes such as C.

In formula (1 β), R¹For the alkyl of carbon number 1 to 15, in the alkyl, at least one-CH₂It can replace through-O- or-S-, 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.

In formula (1 β), preferred R¹For the alkyl of carbon number 1 to 15, the alkenyl of carbon number 2 to 15, carbon number 1 to 14 alkoxy, Or the alkenyloxy group of carbon number 2 to 14.And then preferred R¹For the alkyl of carbon number 1 to 10, the alkenyl of carbon number 2 to 10 or carbon number 1 to 9 Alkoxy.Particularly preferred R¹For the alkyl of carbon number 1 to 10.

In formula (1 β), MES is the liquid crystal former base at least one ring.Liquid crystal former base is ripe for those skilled in the art Know.Liquid crystal former base refers to, when compound has liquid crystalline phase (interphase), facilitates the part of the formation of liquid crystalline phase.Compound The preference of (1 β) is compound (1 β -1).

In formula (1 β -1), preferred ring A¹Or ring A⁴For 1,4- cyclohexylidene, 1,4- cyclohexadienylidene, 1,4- phenylene, Naphthalene -2,6- diyl, decahydronaphthalene -2,6- diyl, 1,2,3,4- naphthane -2,6- diyl, oxinane -2,5- diyl, 1,3- bis- Oxane -2,5- diyl, pyrimidine -2,5- diyl, pyridine -2,5- diyl, perhydro cyclopentano [a] phenanthrene -3,17- diyl or 2,3,4,7, 8,9,10,11,12,13,14,15,16,17- ten tetrahydro cyclopentyls simultaneously [a] phenanthrene -3,17- diyl, in these rings, at least one hydrogen can Alkenyloxy group through fluorine, chlorine, the alkyl of carbon number 1 to 12, the alkenyl of carbon number 2 to 12, the alkoxy of carbon number 1 to 11 or carbon number 2 to 11 Replace, in these bases, at least one hydrogen can replace through fluorine or chlorine.And then preferred ring A¹Or ring A⁴For 1,4- cyclohexylidene, 1,4- Ten tetrahydro of phenylene, perhydro cyclopentano [a] phenanthrene -3,17- diyl or 2,3,4,7,8,9,10,11,12,13,14,15,16,17- Cyclopentano [a] phenanthrene -3,17- diyl, in these rings, at least one hydrogen can replace through the alkyl of fluorine or carbon number 1 to 5.Particularly preferably Ring A¹Or ring A⁴For 1 or 4 cyclohexylidene, Isosorbide-5-Nitrae-phenylene, perhydro cyclopentano [a] phenanthrene -3,17- diyl, in these rings, at least One hydrogen can replace through fluorine, methyl or ethyl.

In formula (1 β -1), Z¹For singly-bound or the alkylidene of carbon number 1 to 10, in the alkylidene, at least one-CH₂Can through- O- ,-CO- ,-COO- ,-OCO- or-OCOO- replace, at least one-(CH₂)₂It can replace through-CH=CH- or-C ≡ C-, these In base, at least one hydrogen can replace through fluorine or chlorine.

In formula (1 β -1), preferred Z¹For singly-bound ,-(CH₂)₂,-CH=CH- ,-C ≡ C- ,-COO- ,-OCO- ,- CF₂O-、-OCF₂-、-CH₂O-、-OCH₂Or-CF=CF-.And then preferred Z¹For singly-bound ,-(CH₂)₂Or-CH=CH-.It is special Not preferred Z¹For singly-bound.

In formula (1 β -1), a 0,1,2,3 or 4.Preferred a is 0,1,2 or 3.And then preferred a is 0,1 or 2.

Formula (1 β) is into formula (1 β -1), Sp¹For singly-bound or the alkylidene of carbon number 1 to 10, in the alkylidene, at least one A-CH₂It can replace through-O- ,-CO- ,-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.

In formula (1 β), preferred Sp¹For singly-bound, the alkylidene of carbon number 1 to 5 or-a CH₂The carbon number 1 that warp-O- replaces To 5 alkylidene.And then preferred Sp¹For singly-bound, the alkylidene of carbon number 1 to 3 or-a CH₂Warp-O- replace carbon number 1 to 3 alkylidene.

In formula (1 β) and formula (1 β -1), M²And M³It independently is the alkyl or at least one hydrogen of hydrogen, fluorine, chlorine, carbon number 1 to 5 The alkyl of the carbon number 1 to 5 replaced through fluorine or chlorine.Preferred M²Or M³For hydrogen, fluorine, methyl, ethyl or trifluoromethyl.And then preferably M²Or M³For hydrogen.

In formula (1 β) and formula (1 β -1), R²It is hydrogen, fluorine, chlorine, the alkyl of carbon number 1 to 5 or at least one hydrogen through fluorine or chlorine The alkyl of substituted carbon number 1 to 5.Preferred R²For hydrogen, methyl, ethyl.And then preferred R²For hydrogen.

In formula (1 β) and formula (1 β -1), M¹It is hydrogen, fluorine, chlorine, the alkyl of carbon number 1 to 5 or at least one hydrogen through fluorine or chlorine The alkyl of substituted carbon number 1 to 5.Preferred M¹For hydrogen, fluorine, methyl, ethyl or trifluoromethyl.And then preferred M¹For methyl.

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.In formula (16 α), preferred configuration is as the form recorded.

4. the synthesis of compound (1 β)

The synthetic method of compound (1 β) is illustrated.Compound (1 β) is using International Publication handbook the 2017/th The method recorded in No. 014013 synthesizes.In addition, can also be by the way that the method for well known Synthetic Organic Chemistry be appropriately combined To synthesize.It can also 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 publishing company (Pergamon Press)), " new experimental chemistry lecture " (ball is kind) etc. is at book.

5. compound (1 γ)

5-1. compound (1 γ), using its liquid-crystal composition illustration

This illustration includes following items etc..

A kind of 41. compounds of item, are indicated by formula (1 γ)；

In formula (1 γ),

N independently is 0,1 or 2；

A and b independently is 0,1,2,3 or 4, and a and b's and be 1,2,3 or 4；

C, d and e independently is 0,1,2,3 or 4；

C, d and e's and be 2,3 or 4；

In formula (P-1),

In formula (1 γ a), formula (1 γ b) and formula (1 γ c),

S¹For > CH- or > N-；

S²For > C < or > Si <；

42. compounds according to item 41 of item, wherein in formula (P-1), R⁴For by formula (1 γ a) or formula (1 γ b) table The base shown.

43. compounds according to item 41 or item 42 of item, wherein in formula (1 γ), R⁴It is indicated by formula (1 γ a), and c, D and e be 0,1,2 or 3, c, d and e and be 2,3 or 4.

44. compounds according to any one of item 41 to item 43 of item, by appointing for formula (1 γ -1) to formula (1 γ -6) One indicates；

Formula (1 γ -1) into formula (1 γ -6),

R¹、R²And R³It independently is the alkoxy of hydrogen, the alkyl of carbon number 1 to 12, the alkenyl of carbon number 2 to 12, carbon number 1 to 11 Or the alkenyloxy group of carbon number 2 to 11, in these bases, at least one hydrogen can be fluorine-substituted；

Ring A¹, ring A², ring A³, ring A⁴, ring A⁵And ring A⁶It independently is cyclohexylidene, cyclohexadienylidene, phenylene, naphthalene, four Hydrogen pyrans or 1,3- dioxanes, in these rings, at least one hydrogen can be through fluorine, chlorine, the alkyl of carbon number 1 to 10, carbon number 2 to 10 The alkenyloxy group of alkenyl, the alkoxy of carbon number 1 to 9 or carbon number 2 to 9 replaces, and in these bases, at least one hydrogen can take through fluorine or chlorine Generation；

Z¹、Z²、Z³、Z⁵And Z⁶It independently is the alkylidene of singly-bound or carbon number 1 to 8, in the alkylidene, at least one- CH₂It can replace through-O- ,-COO- or-OCO-, 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；

Sp¹、Sp²、Sp³And Sp⁴It independently is the alkylidene of singly-bound or carbon number 1 to 8, in the alkylidene, at least one- CH₂It can replace through-O- ,-COO- or-OCO-, 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；

C, d, e and f independently are 0,1,2 or 3, c, d, e and f and be 2,3 or 4；Wherein, formula (1 γ -1) is to formula (1 γ -3) in, d is 2 or 3；

P¹、P²、P³And P⁴It independently is polymerism base represented by formula (P-1)；

In formula (P-1),

M¹And M²It independently is the carbon number that hydrogen, fluorine, chlorine, the alkyl of carbon number 1 to 4 or at least one hydrogen replace through fluorine or chlorine 1 to 4 alkyl；

Sp⁵For singly-bound or the alkylidene of carbon number 1 to 8, in the alkylidene, at least one-CH₂Can through-O- ,-CO- ,- COO- or-OCO- replaces, 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；

X¹For-OH ,-NH₂、-OR⁵、-N(R⁵)₂Or-Si (R⁵)₃Represented base, herein, R⁵For hydrogen or the alkane of carbon number 1 to 8 Base, in the alkyl, at least one-CH₂It can replace through-O-, at least one-(CH₂)₂It can replace through-CH=CH-, these bases In, at least one hydrogen can replace through fluorine or chlorine.

Item 45. is compound described in item 44, and in formula (1 γ -1) into formula (1 γ -6), R¹、R²And R³It independently is The alkenyloxy group of hydrogen, the alkyl of carbon number 1 to 10, the alkenyl of carbon number 2 to 10, the alkoxy of carbon number 1 to 9 or carbon number 2 to 9, these bases In, at least one hydrogen can be fluorine-substituted；

Ring A¹, ring A², ring A³, ring A⁴, ring A⁵And ring A⁶Independently be cyclohexylidene, cyclohexadienylidene, phenylene, naphthalene or Oxinane, in these rings, at least one hydrogen can through fluorine, chlorine, the alkyl of carbon number 1 to 6, the alkenyl of carbon number 2 to 6 or carbon number 2 to 5 alkoxy replaces, and in these bases, at least one hydrogen can replace through fluorine or chlorine；

Z¹、Z²、Z³、Z⁵And Z⁶It independently is the alkylidene of singly-bound or carbon number 1 to 6, in the alkylidene, at least one- CH₂It can replace through-O- ,-COO- or-OCO-, at least one-(CH₂)₂It can replace through-CH=CH- or-C ≡ C-, these bases In, at least one hydrogen can be fluorine-substituted；

Sp¹、Sp²、Sp³And Sp⁴It independently is the alkylidene of singly-bound or carbon number 1 to 6, in the alkylidene, at least one- CH₂It can replace through-O-, at least one-(CH₂)₂It can replace through-CH=CH-, in these bases, at least one hydrogen can take through fluorine Generation；

C, d, e and f independently are 0,1,2,3, c, d, e and f and be 2,3 or 4；Wherein, formula (1-1) is into formula (1-3), D is 2,3；

In formula (P-1),

M¹And M²It independently is the alkane for the carbon number 1 or 3 that hydrogen, the alkyl of carbon number 1 or 3 or at least one hydrogen replace through fluorine or chlorine Base；

Sp⁵For singly-bound or the alkylidene of carbon number 1 to 6, in the alkylidene, at least one-CH₂It can replace through-O-, at least One-(CH₂)₂It can replace through-CH=CH- or-C ≡ C-, in these bases, at least one hydrogen can be fluorine-substituted,

X¹For-OH ,-NH₂Represented base.

46. compounds according to any one of item 41 to item 45 of item, by appointing for formula (1 γ -7) to formula (1 γ -21) One indicates；

Formula (1 γ -7) into formula (1 γ -21),

R¹、R²And R³It independently is the alkoxy or carbon of hydrogen, the alkyl of carbon number 1 to 8, the alkenyl of carbon number 2 to 8, carbon number 1 to 7 The alkenyloxy group of number 2 to 7；

Ring A¹, ring A², ring A³, ring A⁴And ring A⁵It independently is cyclohexylidene, cyclohexadienylidene or phenylene, in these rings, At least one hydrogen can replace through the alkoxy of fluorine, chlorine, the alkyl of carbon number 1 to 5, the alkenyl of carbon number 2 to 5 or carbon number 1 to 4, these In base, at least one hydrogen can be fluorine-substituted；

L¹、L²、L³、L⁴、L⁵、L⁷、L⁸、L¹⁰、L¹²、L¹³、L¹⁵、L¹⁶、L¹⁷、L¹⁸、L¹⁹And L²⁰It independently is fluorine, methyl or second Base；

Sp¹、Sp²、Sp³And Sp⁴It independently is the alkylidene of singly-bound or carbon number 1 to 5, in the alkylidene, at least one- CH₂It can replace through-O-；

C, d, e and f independently are 0,1 or 2, c, d, e and f and be 2,3 or 4；Wherein, formula (1 γ -7) is to formula (1 γ - 9) in, d 2；

In formula (P-1),

Sp⁵For singly-bound or the alkylidene of carbon number 1 to 5, in the alkylidene, at least one-CH₂It can replace through-O-；

X¹For-OH ,-NH₂Represented base.

Item 47. is compound described in item 46, and in formula (1 γ -7) into formula (1 γ -21), R¹、R²And R³It independently is The alkenyloxy group of hydrogen, the alkyl of carbon number 1 to 8, the alkenyl of carbon number 2 to 8, the alkoxy of carbon number 1 to 7 or carbon number 2 to 7；

Ring A¹, ring A², ring A³, ring A⁴And ring A⁵It independently is cyclohexylidene, cyclohexadienylidene or phenylene, in these rings, At least one hydrogen can replace through the alkoxy of fluorine, the alkyl of carbon number 1 to 3, the alkenyl of carbon number 2 to 3 or carbon number 1 to 2, these bases In, at least one hydrogen can be fluorine-substituted；

In formula (P-1),

M¹And M²It independently is hydrogen, fluorine, methyl or ethyl；

X¹For-OH ,-NH₂Represented base.

48. compounds according to any one of item 41 to item 47 of item, by formula (1 γ -22) to formula (1 γ -34) Any one is indicated；

Formula (1 γ -22) into formula (1 γ -34),

R¹And R²It independently is the alkoxy or carbon number 2 to 6 of the alkyl of carbon number 1 to 7, the alkenyl of carbon number 2 to 7, carbon number 1 to 6 Alkenyloxy group；

L⁶、L⁷、L⁸、L⁹、L¹⁰、L¹¹、L¹³、L¹⁵、L¹⁶、L¹⁷、L¹⁸、L¹⁹、L²⁰、L²¹、L²²And L²³It independently is hydrogen, fluorine, methyl Or ethyl；

Sp¹、Sp²And Sp³It independently is the alkylidene of singly-bound or carbon number 1 to 3, in the alkylidene, at least one-CH₂- It can replace through-O-；

In formula (P-1),

M¹And M²It independently is hydrogen, fluorine or methyl；

Sp⁵For singly-bound or the alkylidene of carbon number 1 to 3, in the alkylidene, at least one-CH₂It can replace through-O-.

A kind of 49. liquid-crystal compositions of item, contain at least one compound according to any one of item 41 to item 48 As orientation monomer.

50. liquid-crystal compositions according to item 49, and then contain the chemical combination represented by the formula (2) to formula (4) At least one of group of object compound.Furthermore it is recorded in the definition of the structural formula and mark of these compounds and item 11 It is identical.

51. liquid-crystal compositions according to item 49 or item 50 of item, and then contain represented to formula (7) selected from formula (5) At least one of the group of compound compound.Furthermore in the definition of the structural formula and mark of these compounds and item 12 That records is identical.

52. liquid-crystal compositions according to item 49 or item 50, and then contain the compound represented by formula (8) At least one of group compound.Furthermore the phase recorded in the definition of the structural formula and mark of these compounds and item 13 Together.

53. liquid-crystal compositions according to item 49 or item 50 of item, and then contain represented to formula (15) selected from formula (9) At least one of the group of compound compound.Furthermore in the definition of the structural formula and mark of these compounds and item 14 That records is identical.

54. liquid-crystal compositions according to any one of item 49 to item 53 contain represented by formula (16 α) At least one of group of polymerizable compound compound is as reactive monomer.Furthermore the structural formula of these compounds and It is recorded in the definition of mark and item 15 identical.

55. liquid-crystal compositions according to item 54 of item, wherein in formula (16 α), P¹、P²And P³It independently is selected from formula (P- 2) base into the group of polymerism base represented by formula (P-6).Furthermore the definition of the structural formula and mark of these compounds with It is recorded in item 16 identical.

56. liquid-crystal compositions according to any one of item 49 to item 55 of item, contain selected from formula (16 α -1) to formula At least one of the group of polymerizable compound represented by (16 α -27) compound.Furthermore the structural formula of these compounds And it is recorded in the definition of mark and item 17 identical.

57. liquid-crystal compositions according to any one of item 49 to item 56, so contain selected from by with formula (1 α) And the different polymerizable compound of polymerizable compound represented by formula (16 α), polymerization initiator, polymerization inhibitor, optics are living In group composed by property compound, antioxidant, ultraviolet absorbing agent, light stabilizer, heat stabilizer and defoaming agent at least It is a kind of.

The form of 5-2. compound (1 γ)

Compound (1 γ) is characterized by having the mesogen position being made of at least one ring and multiple polar groups.Change Conjunction object (1 γ) is useful since polar group and substrate surface are interacted in a manner of non-covalent bond.One of purposes is The additive of liquid-crystal composition used in liquid crystal display element.Compound (1 γ) is the orientation to control liquid crystal molecule For the purpose of and add.Such additive preferably has high-dissolvability in a liquid crystal composition and in being sealed in element Under the conditions of chemical stabilization, and be used for liquid crystal display element when voltage retention it is big.Compound (1 γ) is considerably full Such characteristic of foot.

The preference of compound (1 γ) is illustrated.R in compound (1 γ)¹、R²、R³、Z¹、Z²、Z³、A¹、A⁴、A⁵、 Sp¹、Sp²、Sp³、P¹、P²、P³Preference be also applied for the hypogyny of compound (1 γ).It, can be by suitable in compound (1 γ) It combines the type of these bases and arbitrarily adjusts characteristic in locality.Due in terms of the characteristic of compound without big difference, chemical combination More than amount of the object (1 γ) containing more naturally occurring ratio²H (deuterium),¹³The isotopes such as C.

In formula (1 γ), R¹、R²And R³It independently is the alkyl of carbon number 1 to 15, in the alkyl, at least one-CH₂It can Replace through-O- or-S-, 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.

In formula (1 γ), preferred R¹、R²Or R³For the alkyl of carbon number 1 to 15, the alkenyl of carbon number 2 to 15, carbon number 1 to 14 The alkenyloxy group of alkoxy or carbon number 2 to 14.And then preferred R¹For the alkyl of carbon number 1 to 10, the alkenyl of carbon number 2 to 10 or carbon The alkoxy of number 1 to 9.Particularly preferred R¹For the alkyl of carbon number 1 to 10.

In formula (1 γ), ring A¹, ring A⁴And ring A⁵Independently be cyclohexylidene, cyclohexadienylidene, phenylene, naphthalene, decahydronaphthalene, Naphthane, oxinane, 1,3- dioxanes, pyrimidine or pyridine, in these rings, at least one hydrogen can be through fluorine, chlorine, carbon number 1 to 12 Alkyl, carbon number 1 to 12 alkoxy or the alkyl of carbon number 1 to 12 that replaces through fluorine or chlorine of at least one hydrogen replace.

In formula (1 γ), preferred ring A¹, ring A⁴Or ring A⁵For cyclohexylidene, cyclohexadienylidene, phenylene, naphthalene, tetrahydro pyrrole It mutters or 1,3- dioxanes, in these rings, at least one hydrogen can be through the alcoxyl of fluorine, chlorine, the alkyl of carbon number 1 to 5 or carbon number 1 to 4 Base replaces.And then preferred ring A¹, ring A⁴Or ring A⁵For the fluorine-substituted phenylene of cyclohexylidene, phenylene, at least one hydrogen, Or alkyl-substituted phenylene of at least one hydrogen through carbon number 1 to 3.Particularly preferred ring A¹, ring A⁴Or ring A⁵For cyclohexylidene, The phenylene that phenylene, at least one hydrogen replace through methyl substituted phenylene or at least one hydrogen through ethyl.

In formula (1 γ), Z¹And Z⁵It 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.

In formula (1 γ), preferred Z¹Or Z⁵For singly-bound ,-(CH₂)₂,-CH=CH- ,-C ≡ C- ,-COO- ,-OCO- ,- CF₂O-、-OCF₂-、-CH₂O-、-OCH₂Or-CF=CF-.And then preferred Z¹Or Z⁵For singly-bound.

In formula (1 γ), Sp¹、Sp²Or Sp³It independently is the alkylidene of singly-bound or carbon number 1 to 10, in the alkylidene, until A few-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.

In formula (1 γ), preferred Sp¹、Sp²Or Sp³For singly-bound, the alkylidene of carbon number 1 to 5 or-a CH₂Warp-O- takes The alkylidene of the carbon number 1 to 5 in generation.And then preferred Sp¹、Sp²Or Sp³For singly-bound, the alkylidene of carbon number 1 to 3 or-a CH₂- The alkylidene of the carbon number 1 to 3 replaced through-O-.Particularly preferred Sp¹、Sp²Or Sp³For-CH₂-、-(CH₂)₂-、-(CH₂)₃Or-O (CH₂)₂-。

In formula (1 γ), P¹、P²And P³It independently is polymerism base represented by formula (P-1).

In formula (P-1), M¹And M²Hydrogen, fluorine, chlorine, 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.In order to improve reactivity, preferred M¹Or M²For hydrogen or methyl.And then preferred M¹Or M²For hydrogen.

In formula (P-1), R⁴For base represented by formula (1 γ a), formula (1 γ b) and formula (1 γ c).

Preferred R⁴For base represented by formula (1 γ a) or formula (1 γ b).Preferred R⁴For base represented by formula (1 γ a).

In formula (1 γ a), formula (1 γ b) and formula (1 γ c), Sp⁵And Sp⁶It independently is the alkylidene of singly-bound or carbon number 1 to 10, In the alkylidene, at least one-CH₂It can replace through-O- ,-NH- ,-CO- ,-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.

In formula (1 γ a), formula (1 γ b) and formula (1 γ c), preferred Sp⁵And Sp⁶For singly-bound, carbon number 1 to 5 alkylidene or One-CH₂The alkylidene for the carbon number 1 to 5 that warp-O- replaces.And then preferred Sp⁵Or Sp⁶For singly-bound, the alkylidene of carbon number 1 to 5 An or-CH₂The alkylidene for the carbon number 1 to 5 that warp-O- replaces.Particularly preferred Sp⁵And Sp⁶For singly-bound ,-CH₂-、- (CH₂)₂-、-(CH₂)₃Or-O (CH₂)₂-。

In formula (1 γ a), formula (1 γ b) and formula (1 γ c), S¹For > CH- or > N-, S²For > C < or > Si <.Preferably S¹For > CH- or > N-, preferred S²For > C <.S¹Better than S²。

In formula (1 γ a), formula (1 γ b) and formula (1 γ c), X¹It independently is-OH ,-NH₂、-OR³、-N(R³)₂、-COOH、- SH、-B(OH)₂Or-Si (R³)₃Represented base, herein, R³For hydrogen or the alkyl of carbon number 1 to 10, in the alkyl, at least one A-CH₂It can replace through-O-, at least one-(CH₂)₂It can replace through-CH=CH-, in these bases, at least one hydrogen can be through fluorine Or chlorine replaces.

In formula (1 γ a), formula (1 γ b) and formula (1 γ c), preferred X¹For-OH ,-NH₂Or-Si (R³)₃Represented base, Herein, R³For the alkyl of carbon number 1 to 5 or the alkoxy of carbon number 1 to 4.And then preferred X¹For-OH ,-NH₂、-Si(OCH₃)₃Or- Si(OC₂H₅)3.Particularly preferred X¹For-OH.

In formula (1 γ), a and b independently are 0,1,2,3 or 4, and a and b's and be 1,2,3 or 4.Preferred a's and b Group is combined into (a=1, b=0), (a=0, b=1), (a=2, b=0), (a=1, b=1), (a=0, b=2), (a=3, b= 0), (a=2, b=1), (a=1, b=2) or (a=0, b=3).And then the group of preferred a and b is combined into (a=1, b=0), (a =2, b=0), (a=1, b=1), (a=3, b=0), (a=2, b=1) or (a=1, b=2).The group of particularly preferred a and b It is combined into (a=1, b=0) or (a=2, b=0).

In formula (1 γ), d 0,1,2,3 or 4.Preferred d is 2 or 3, and then preferred d is 2.

In formula (1 γ), c and e independently are 0,1,2,3 or 4.Preferred c or e is 0.

6. the synthesis of compound (1 γ)

The synthetic method of compound (1 γ) is illustrated.Compound (1 γ) is using International Publication 2017/047177 The method recorded in handbook synthesizes.In addition, can also be closed by the way that the method for well known Synthetic Organic Chemistry to be appropriately combined At.Can also 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 publishing company (Pergamon Press)), " new experimental chemistry lecture " (ball is kind) etc. is at book.

7. compound (1-1)~compound (1-60)

7-1. compound (1-1)~compound (1-60), using its liquid-crystal composition illustration

Compound (1-1)~compound (1-60) is such shown in [8]~[10].As using compound The liquid-crystal composition of (1-1)~compound (1-60), it is preferably identical to item 18. with the item 11. illustrated in compound (1 α) Combination.In addition, this illustration also includes following item.(a) and then contain polymerizable compound, polymerization initiator, polymerization inhibitor, light Learn the additive of reactive compound, antioxidant, ultraviolet absorbing agent, light stabilizer, heat stabilizer, defoaming agent etc at least Two kinds of the liquid-crystal composition.(b) a kind of polymerizable composition, polymerizable composition, passing through will be with compound (1-1)~compound (1-60) Or compound (16 α) different polymerizable compound makes an addition in the liquid-crystal composition and prepares.(c) a kind of polymerism combination Object, by the way that compound (1-1)~compound (1-60) and compound (16 α) are made an addition to and system in the liquid-crystal composition It is standby.(d) a kind of liquid crystal composite is prepared and polymerizeing polymerizable composition, polymerizable composition.(e) a kind of polymer stabilizing orientating type Element contains the liquid crystal composite.(f) a kind of element of polymer stabilizing orientating type, by using following polymerism Composition and make, the polymerizable composition, polymerizable composition by by compound (1-1)~compound (1-60) and compound (16 α) and with Compound (1-1)~compound (1-60) or compound (16 α) different polymerizable compound make an addition to the liquid-crystal composition In and prepare.

7-2. compound (1-1)~compound (1-60) form

Compound (1-1)~compound (1-60) has the acryloxy replaced by hydroxy alkyl isopolarity base, therefore It is adsorbed in substrate surface and controls the orientation of liquid crystal molecule.In order to obtain desired effect, compound (1-1)~compound (1-60) must have the high compatibility with liquid crystal compounds.It is believed that compound (1-1)~compound (1-60) has The hexatomic ring of 1 or 4 cyclohexylidene or Isosorbide-5-Nitrae-phenylene etc and there is rodlike molecular structure, and at single end of molecular structure It holds the structure with branch-like and compatibility can be improved, therefore be most suitable for the purpose.Compound (1-1)~compound (1-60) Polymer is provided by polymerization.The polymer shortens the response of element due to stabilizing the orientation of liquid crystal molecule Time, and improve the image retention of image.The polymer preferably chemical stabilization under conditions of being sealed in element, and use Voltage retention when liquid crystal display element is big.Compound (1-1)~compound (1-60) considerably meets such spy Property.

About preferred compound (1-1)~compound (1-60), it is illustrated by taking compound (1-1) as an example.

In formula (1-1), the X of formula (1f), formula (1g), formula (1h) and formula (1i)¹For polar group.Compound (1-1) is because of addition Stablize in composition, therefore preferably.When making an addition to compound (1-1) in composition, the preferably described compound is not The voltage retention of element can be reduced.Compound (1-1) preferably has low volatility.Preferred molal weight is 130g/ Mol or more.And then the range that preferred molal weight is 150g/mol to 800g/mol.Preferred compound (1-1) has third Alkene acyloxy (- OCO-CH=CH₂), methacryloxy (- OCO- (CH₃) C=CH₂), acrylic acid Alpha-hydroxy Arrcostab etc Polymerism base.

In formula (1f), formula (1g), formula (1h) and formula (1i), X¹For-OH ,-NH₂、-OR¹⁵、-N(R¹⁵)₂、-COOH、-SH、-B (OH)₂Or-Si (R¹⁵)₃Represented base, herein, R¹⁵For hydrogen or the alkyl of carbon number 1 to 5, in the alkyl, at least one- CH₂It can replace through-O-, at least one-CH₂CH₂It can replace through-CH=CH-, in these bases, at least one hydrogen can take through fluorine Generation.For the viewpoint of high-dissolvability in a liquid crystal composition, X¹Particularly preferably-OH or-NH₂.- OH is because having high anchor Gu power, therefore it is better than-O- ,-CO- or-COO-.Particularly preferably with the base of multiple hetero atoms (nitrogen, oxygen).With such pole Even if the compound of property base is low concentration, also effectively.

In formula (1-1), R¹For the alkyl of carbon number 1 to 15, the R¹In, at least one-CH₂It can replace through-O- or-S-, At least one-CH₂CH₂It can replace through-CH=CH- or-C ≡ C-, at least one hydrogen can replace through halogen.

Ring A¹And ring A²Independently be 1,4- cyclohexylidene, 1,4- cyclohexadienylidene, 1,4- phenylene, naphthalene -2,6- diyl, Decahydronaphthalene -2,6- diyl, 1,2,3,4- naphthane -2,6- diyl, oxinane -2,5- diyl, 1,3- dioxanes -2,5- two Base, pyrimidine -2,5- diyl, pyridine -2,5- diyl, fluorenes -2,7- diyl, phenanthrene -2,7- diyl, anthracene -2,6- diyl, perhydro cyclopentano [a] phenanthrene -3,17- diyl or ten tetrahydro cyclopentyl of 2,3,4,7,8,9,10,11,12,13,14,15,16,17- simultaneously [a] phenanthrene -3,17- Diyl, in these rings, at least one hydrogen can be through fluorine, chlorine, the alkyl of carbon number 1 to 12, the alkenyl of carbon number 2 to 12, carbon number 1 to 11 The alkenyloxy group of alkoxy or carbon number 2 to 11 replaces, and in these bases, at least one hydrogen can replace through fluorine or chlorine.Preferred ring A¹Or Ring A²For 1,4- cyclohexylidene, 1,4- phenylene, the fluoro- 1,4- phenylene of 2-, naphthalene -2,6- diyl or the Asia 3- ethyl -1,4- benzene Base.

In formula (1-1), Z¹For singly-bound or the alkylidene of carbon number 1 to 6, the Z¹In, at least one-CH₂Can through-O- ,- CO- ,-COO- ,-OCO- or-OCOO- replace, at least one-CH₂CH₂It can replace through-CH=CH- or-C ≡ C-, at least one Hydrogen can replace through fluorine or chlorine.Preferred Z¹For singly-bound ,-CH₂CH₂-、-CH₂O-、-OCH₂,-COO- or-OCO-.And then it is preferred Z¹For singly-bound.

In formula (1-1), a 0,1,2,3 or 4.Preferred a is 0,1,2 or 3.And then preferred a is 0,1 or 2.Especially Preferred a is 1 or 2.

In formula (1-1), Sp¹For singly-bound or the alkylidene of carbon number 1 to 10, the Sp¹In, at least one-CH₂Can through- O- ,-CO- ,-COO- ,-OCO- or-OCOO- replace, at least one-CH₂CH₂It can replace through-CH=CH- or-C ≡ C-, at least One hydrogen can replace through halogen, and in these bases, at least one hydrogen passes through the base being selected from base represented by formula (1a) and replaces；

In formula (1a),

Sp¹²For singly-bound or the alkylidene of carbon number 1 to 10, the Sp¹²In, at least one-CH₂Can through-O- ,-CO- ,- COO- ,-OCO- or-OCOO- replace, at least one-CH₂CH₂It can replace through-CH=CH- or-C ≡ C-, at least one hydrogen can Replace through halogen.Preferred Sp¹²For singly-bound, the alkylidene of carbon number 1 to 5 or-a CH₂The carbon number 1 to 5 that warp-O- replaces Alkylidene.And then preferred Sp¹²For singly-bound, the alkylidene of carbon number 1 to 3 or-a CH₂The carbon number 1 to 3 that warp-O- replaces Alkylidene.

M¹¹And M¹²Independently be hydrogen, carbon number 1 that halogen, the alkyl of carbon number 1 to 5 or at least one hydrogen replace through halogen to 5 alkyl.In order to improve reactivity, preferred M¹¹Or M¹²For hydrogen or methyl.And then preferred M¹¹Or M¹²For hydrogen.

R¹²For the alkyl of carbon number 1 to 15, the R¹²In, at least one-CH₂It can replace through-O- or-S-, at least one- CH₂CH₂It can replace through-CH=CH- or-C ≡ C-, at least one hydrogen can replace through halogen.Preferred R¹²For hydrogen or carbon number 1 to 5 alkylidene or-a CH₂The alkylidene for the carbon number 1 to 5 that warp-O- replaces.And then preferred R¹²For hydrogen or carbon number 1 to 3 Alkylidene or-a CH₂The alkylidene for the carbon number 1 to 3 that warp-O- replaces.Particularly preferred R¹²For hydrogen or methyl.In R¹² For-CH₂In the case where-OH, due to there is the effect of two hydroxyls in the molecule it can be expected that the vertical orientation of low concentration addition.

In formula (1-1), preferred Sp¹For the alkylidene of carbon number 1 to 5 or-a CH₂The carbon number 1 to 5 that warp-O- replaces Alkylidene.And then preferred Sp¹For the alkylidene of carbon number 1 to 3 or-a CH₂The alkylidene for the carbon number 1 to 3 that warp-O- replaces, In these bases, at least one hydrogen can replace through polymerism base represented by formula (1a).

P¹¹For the base in the base represented by the formula (1e) and formula (1f),

In formula (1e), R¹³For the base in the base represented by formula (1g), formula (1h) and the formula (1i).

In formula (1e) and formula (1f),

Sp¹³For singly-bound or the alkylidene of carbon number 1 to 10, the Sp¹³In, at least one-CH₂Can through-O- ,-NH- ,- CO- ,-COO- ,-OCO- or-OCOO- replace, at least one-CH₂CH₂It can replace through-CH=CH- or-C ≡ C-, these bases In, at least one hydrogen can replace through halogen.Preferred Sp¹³For the alkylidene of carbon number 1 to 7 or-a CH₂What warp-O- replaced The alkylidene of carbon number 1 to 5.And then preferred Sp¹³For the alkylidene of carbon number 1 to 5 or-a CH₂The carbon number 1 that warp-O- replaces To 5 alkylidene.Particularly preferred Sp¹³For-CH₂-。

In formula (1e), M¹³And M¹⁴Hydrogen, halogen, the alkyl of carbon number 1 to 5 or at least one hydrogen independently is to replace through halogen Carbon number 1 to 5 alkyl, in order to improve reactivity, preferred M¹³Or M¹⁴For hydrogen or methyl.And then preferred M¹³Or M¹⁴For hydrogen.

In formula (1e), R¹³For the base in the group of the polar group represented by formula (1g), formula (1h) and the formula (1i), preferably R¹³For polar group represented by formula (1g) or formula (1h).And then preferred R¹³For polar group represented by formula (1g).

In formula (1g), formula (1h) and formula (1i), Sp¹⁴And Sp¹⁵It independently is the alkylidene of singly-bound or carbon number 1 to 10, it is described Sp¹⁴And Sp¹⁵In, at least one-CH₂It can replace through-O- ,-NH- ,-CO- ,-COO- ,-OCO- or-OCOO-, at least one- CH₂CH₂It can replace through-CH=CH- or-C ≡ C-, in these bases, at least one hydrogen can replace through halogen.Preferred Sp¹⁴Or Sp¹⁵For the alkylidene of carbon number 1 to 7 or-a CH₂The alkylidene for the carbon number 1 to 5 that warp-O- replaces.And then preferred Sp¹⁴Or Sp¹⁵For the alkylidene of carbon number 1 to 5 or-a CH₂The alkylidene for the carbon number 1 to 5 that warp-O- replaces.Particularly preferred Sp¹⁴Or Sp¹⁵For-CH₂-。

In formula (1h) and formula (1i), S¹For > CH- or > N-, and S²For > C < or > Si <.Preferred S¹For > CH-, preferred S²For > C <.

In formula (1f), formula (1g) and formula (1i), X¹For-OH ,-NH₂、-OR⁵、-N(R¹⁵)₂、-COOH、-SH、-B(OH)₂、 Or-Si (R¹⁵)₃, herein, R¹⁵For hydrogen or the alkyl of carbon number 1 to 10, in the alkyl, at least one-CH₂It can replace through-O-, At least one-CH₂-CH₂It can replace through-CH=CH-, in these bases, at least one hydrogen can replace through fluorine or chlorine.Preferred X¹ For-OH ,-NH₂Or-N (R¹⁵)₂, herein, R¹⁵For hydrogen or the alkyl of carbon number 1 to 10, the R¹⁵In, at least one-CH₂Can through- O- replaces, at least one-CH₂CH₂It can replace through-CH=CH-, at least one hydrogen can replace through halogen.Preferred X¹For carbon number 1 To 5 alkyl or the alkoxy of carbon number 1 to 4.And then preferred X¹For-OH ,-NH₂Or-N (R¹⁵)₂.Particularly preferred X¹For- OH。

Preferred ring A in compound (1-2)~compound (1-3)¹, ring A²、a、M¹¹、M¹²、X¹、R¹²With compound (1- 1) the ring A in¹, ring A²、a、M¹¹、M¹²、X¹、R¹²Identical, preferred l is 0,1,2,3,4,5 or 6.Preferred l is 0,1,2,3, 4。

Formula (1-2) into formula (1-60),

R¹For the alkyl of carbon number 1 to 10；

L¹、L²、L³、L⁴、L⁵、L⁶、L⁷、L⁸、L⁹、L¹⁰、L¹¹And L¹²It independently is hydrogen, fluorine, methyl or ethyl.

8. the synthesis of compound (1-1)~compound (1-60)

Compound (1-1)~compound (1-60) synthetic method is illustrated.Compound (1-1)~compound (1-60) It can be with reference to synthesizing in aftermentioned method.In addition, can also be by the way that the method for well known Synthetic Organic Chemistry be appropriately combined To synthesize.It can also 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 publishing company (Pergamon Press)), " new experimental chemistry lecture " (ball is kind) etc. is at book.

9. liquid-crystal composition

9-1. ingredient B to ingredient E

Liquid-crystal composition contains polymerism polar compound (1) as orientation monomer.Compound (1) has by least one The mesogen position that a ring is constituted.The example of compound (1) be compound (1 α), compound (1 β), compound (1 γ) or change It closes object (1-1)~compound (1-60).Compound (1) is come by the interaction of the non-covalent bond mode of the substrate with element Control the orientation of liquid crystal molecule.The composition preferably includes compound (1) as ingredient A, and in turn comprising selected from following Shown in liquid crystal compounds in ingredient B, ingredient C, ingredient D and ingredient E.Ingredient B is compound (2) to compound (4). Ingredient C is compound (5) to compound (7).Ingredient D is compound (8).Ingredient E is compound (9) to compound (15).Institute Stating composition also may include other liquid crystal compounds different from compound (2) to compound (15).Preparing the combination When object, preferably selection component B, ingredient C, ingredient D and ingredient E in view of size etc. of positive or negative dielectric anisotropy. Properly selected ingredient composition have high ceiling temperature, low lower limit temperature, small viscosity, optics appropriate respectively to Anisotropic (that is, optical anisotropy is big or optical anisotropy is small), big positive or negative dielectric anisotropy, big specific resistance, To the stability and elastic constant appropriate (that is, elastic constant is big or elastic constant is small) of heat or ultraviolet light.It is reacted for improving The purpose of property (polymerism), can also add the polymerizable compound having the function of as reactive monomer in the composition (16)。

About the preferred proportion of compound (1), in order to maintain the high stability to ultraviolet light and be about 0.01 weight % with On, it is about 5 weight % or less to make it dissolve in liquid-crystal composition.And then preferred ratio be about 0.05 weight % extremely The range of about 3 weight %.Most preferred ratio is range of the about 0.05 weight % to about 1 weight %.Compound is being added in turn (16) in the case where, preferred ratio is range of the about 0.01 weight % to about 1.0 weight %.

Ingredient B is the compound that two terminal groups are alkyl etc..The preference of ingredient B can be enumerated: 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 since 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.

Increase the content of ingredient B, then the dielectric anisotropy of composition reduces therewith, but viscosity reduces.Therefore, as long as it is full The required value of the starting voltage of sufficient element, then the more content the better.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 is in right end with fluorine, chlorine or containing fluorine-based compound.The preference of ingredient C can enumerate compound (5- 1) to compound (5-16), compound (6-1) to compound (6-113), compound (7-1) to compound (7-57).Ingredient C's In compound, R¹³For the alkyl of carbon number 1 to 10 or the alkenyl of carbon number 2 to 10, in the alkyl and the 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。

Ingredient C is very excellent to the stability of heat, light etc. since dielectric anisotropy is positive, thus be used to prepare IPS, The case where FFS, OCB isotype composition.Weight based on liquid-crystal composition, the content of ingredient C suitably 1 weight % is extremely The range of 99 weight %, preferably 10 weight % are to the range of 97 weight %, and then preferably 40 weight % are to 95 weight %'s Range.In the case where ingredient C is made an addition in the composition that dielectric anisotropy is negative, the weight based on liquid-crystal composition, The content of ingredient C is preferably 30 weight % or less.By adding ingredient C, the elastic constant of composition can adjust, adjustment element Voltage-transmittance curve.

Ingredient D is the compound (8) that right terminal groups are-C ≡ N or-C ≡ C-C ≡ N.The preference of ingredient D can enumerate chemical combination Object (8-1) is to compound (8-64).In the compound of ingredient D, R¹⁴For the alkyl of carbon number 1 to 10 or the alkenyl of carbon number 2 to 10, institute It states in alkyl and the 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.

Ingredient D is since dielectric anisotropy is positive, and its value is big, therefore mainly for the preparation of the composition of TN isotype The case where.The dielectric anisotropy of composition can be increased by adding the ingredient D.Ingredient D has the temperature for expanding liquid crystalline phase Spend range, adjustment viscosity or the optically anisotropic effect of adjustment.Ingredient D can also be used for voltage-transmitance of adjustment element Curve.

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 making an addition to ingredient D 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 is compound (9) to compound (15).Fluoro- Isosorbide-5-Nitrae-the phenylene of these compounds such as 2,3- bis- is such, has The phenylene that side position replaces through 2 fluorine or chlorine.The preference of ingredient E can enumerate compound (9-1) to compound (9-8), chemical combination Object (10-1) is to compound (10-17), compound (11-1), compound (12-1) to compound (12-3), compound (13-1) To compound (13-11), compound (14-1) to compound (14-3) and compound (15-1) to compound (15-3).Ingredient E Compound in, R¹⁵And R¹⁶It independently is the alkyl of carbon number 1 to 10 or the alkenyl of carbon number 2 to 10, the alkyl and the alkenyl In, at least one-CH₂It can replace through-O-, at least one hydrogen can be fluorine-substituted；R¹⁷For hydrogen, fluorine, carbon number 1 to 10 alkyl or In the alkenyl of carbon number 2 to 10, the alkyl and the alkenyl, at least one-CH₂It can replace through-O-, at least one hydrogen can be through Fluorine replaces.

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.Increase the content of ingredient E, then the dielectric anisotropy of composition is negative and increases therewith, but viscosity becomes larger.Therefore, As long as meeting the required value of the starting voltage of element, content to be preferred less.If in view of dielectric anisotropy is -5 or so, for Carry out sufficient voltage driving, preferably content are 40 weight % or more.

In ingredient E, compound (9) be bicyclic compound, therefore mainly reduce viscosity, adjustment optical anisotropy or The aspect that person increases dielectric anisotropy is effective.Compound (10) and compound (11) are tricyclic compound, therefore have and mention High ceiling temperature increases optical anisotropy or increases the effect of dielectric anisotropy.Compound (12) is to compound (15) Have the effect of increasing dielectric 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 made an addition into 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.The elastic constant of composition, voltage-transmittance curve of adjustment element can be adjusted by adding ingredient E.

By the way that above-described ingredient B, ingredient C, ingredient D and ingredient E is appropriately combined, it can prepare and meet following characteristic At least one liquid-crystal composition: Jie that ceiling temperature is high, lower limit temperature is low, viscosity is small, optical anisotropy is appropriate, positive or negative Electrical 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..Optionally The liquid crystal compounds different from ingredient B, ingredient C, ingredient D and ingredient E can be added.

9-2. additive

Liquid-crystal composition is prepared by well known method.Such as mix component cpd, then 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 be polymerizable compound, Polymerization initiator, polymerization inhibitor, optically active compound, antioxidant, ultraviolet absorbing agent, light stabilizer, heat stabilizer, Defoaming agent etc..Such additive has been well known to those skilled in the art, and is had been described in the literature.

Polymerizable compound is added for the purpose for generating polymer in liquid-crystal composition is made.Compound (1) can also It is used alone.Copolymer can also be generated by compound (1) and compound (16).Compound (1) polar group and substrate surface with It is fixed in the state that the mode of non-covalent bond interacts.It is further in the ability of the orientation of liquid crystal molecule as a result, While promotion, prevent compound (1) from spreading in a liquid crystal composition.Compound (1) provides polymer by polymerization.It is described Polymer is arranged, therefore in substrate surface, assigns pre-tilt angle appropriate to liquid crystal molecule.The polymer makes liquid crystal molecule Orientation stabilize, therefore shorten element response time, and improve image image retention.The preference of polymerizable compound is Acrylate, methacrylate, vinyl compound, vinyl oxo-compound, propenyl ether, epoxide (oxa- Cyclopropane, oxetanes) and vinyl ketone.And then preferred example be compound at least one acryloxy and Compound at least one methacryloxy.And then also including having acryloxy and methyl in preferred example The compound of both acryloxies.

Polymerizable compound can promptly be polymerize by addition polymerization initiator.By keeping reaction temperature most suitable Change, the amount of the polymerizable compound of remaining can be reduced.The example of optical free radical polymerization initiator is BASF (BASF) company Up to TPO, 1173 and 4265 in Luo Gu (Darocure) series and 184 in gorgeous good solid (Irgacure) series, 369, 500,651,784,819,907,1300,1700,1800,1850 and 2959.

The addition example of optical free radical polymerization initiator is bis- (trichloromethyl) triazines of 4- methoxyphenyl -2,4-, 2- (4- fourth Oxygroup styryl) -5- trichloromethyl -1,3,4- oxadiazoles, 9- phenylacridine, 9,10- phenonaphthazine, benzophenone/Michaelis Alcohol/ketone mixtures, six aryl bisglyoxalines/mercaptobenzimidazole mixture, 1- (4- isopropyl phenyl) -2- hydroxy-2-methyl propane - 1- ketone, benzyl dimethyl ketal, 2- methyl-1-[4- (methyl mercapto) phenyl]-2- morpholinopropane-1- ketone, 2,4- diethyl oxygen Miscellaneous anthrone/ESCAROL 507 mixtures of methyl esters, benzophenone/methyl triethanol amine blends.

After adding optical free radical polymerization initiator into liquid-crystal composition, ultraviolet light is irradiated in the state of applying electric field, Thus it may be polymerized.But the decomposition product of unreacted polymerization initiator or polymerization initiator in element there is a possibility that produce The displays such as the image retention of raw image are bad.The situation in order to prevent can also carry out light in the state of not adding polymerization initiator Polymerization.The preferred wavelength of the light irradiated is the range of 150nm to 500nm.And then preferred wavelength is 250nm to 450nm Range, most preferred wavelength be 300nm to 400nm range.

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

Optically active compound, which has, assigns required torsion angle and inducing helical structure in liquid crystal molecule to prevent Non-return this effect of torsion.By adding optically active compound, adjustable even pitch.It can also be interdependent for the temperature for adjusting screw pitch The purpose of property and add two or more optically active compounds.As the preference of optically active compound, can enumerate following Compound (Op-1) to compound (Op-18).In compound (Op-18), ring J is 1 or 4 cyclohexylidene or Isosorbide-5-Nitrae-Asia benzene Base, 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, easy fine jade Northey (IRGANOX) 565, easy fine jade Northey (IRGANOX) 1010, easy fine jade Northey (IRGANOX) 1035, easy fine jade Northey (IRGANOX) 3114 and easy fine jade Northey (IRGANOX) 1098 (trade name；BASF (BASF) company).Ultraviolet absorbing agent is for the decline for preventing ceiling temperature Effectively.The preference of ultraviolet absorbing agent are as follows: benzophenone derivates, benzoate derivatives, triazole derivative etc..Concrete example Following compounds (AO-3) and compound (AO-4) can be enumerated；Refined (TINUVIN) 329 of ground slave, refined (TINUVIN) P of slave, slave Refined (TINUVIN) 326, refined (TINUVIN) 234 of slave, refined (TINUVIN) 213 of slave, refined (TINUVIN) 400 of slave, slave Refined (TINUVIN) 328 and refined (TINUVIN) 99-2 (trade name of ground slave；BASF (BASF) company)；And 1,4- diazabicyclo [2.2.2] octane (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)；Refined (TINUVIN) 144 of ground slave, slave it is refined (TINUVIN) 765 and refined (TINUVIN) 770DF (trade name of ground slave；BASF (BASF) company).Heat stabilizer is also for maintaining big For voltage retention effectively, preference can enumerate easy 168 (trade name of fine jade Floex (IRGAFOS)；BASF (BASF) company). Defoaming agent is effective for preventing blistering.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), R⁴³It is 1 or 4 cyclohexylidene or Isosorbide-5-Nitrae-Asia for hydrogen, methyl or O (oxygen radical), ring G Phenyl, z 1,2 or 3.

9. 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-permeable Any type of type.

The composition can also be used for nematic crystal carrying out nematic curved arrangement phase made by microencapsulation (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).It is being based on The weight of liquid-crystal composition can make the liquid crystal of PSA mode when the additive amount of polymerizable compound is about 10 weight % or less Show element.Preferred ratio is range of the about 0.1 weight % to about 2 weight %.And then preferred ratio be about 0.2 weight % extremely The range of about 1.0 weight %.The element of PSA mode can be driven with as active matrix, passive matrix driving method.This Kind of element can also be applied to reflection-type, infiltration type, semi-transmission type any kind.By the addition for increasing polymerizable compound Amount can also make the element of polymer dispersion (polymer dispersed) mode.

Alignment films are the film for arranging liquid crystal molecule in a certain direction.Generally use the film of polyimides.? In liquid crystal display element without such alignment films, the composition for containing polymerism polar compound (1) is used.Compound (1) polymer is provided by polymerization.The polymer has the function of alignment films, therefore can replace alignment films and use.System An example for making the method for such element is as described below.Prepare to have and is referred to as array substrate and both bases of colored filter substrate The element of plate.The substrate does not have alignment films.At least one piece of the substrate has electrode layer.Liquid crystal compounds are carried out Mixing is to prepare liquid-crystal composition.Add compound (1) in the composition.Additive can be optionally added in turn.By institute Composition is stated to be injected into element.Substantially drive liquid-crystal composition the element no applied voltage or application The light irradiation of first stage is carried out in the state of voltage, secondly, in the state of applying starting voltage or more and 30V voltage below Carry out the light irradiation of second stage.Preferably ultraviolet light.It polymerize polymerizable compound by light irradiation.By such Two stage polymerization generates and induces uniform vertically oriented tropism control layer in liquid crystal molecule, to make object component.

In the sequence, compound (1) passes through no applied voltage because polar group and substrate surface interact Or applies the voltage for substantially driving liquid-crystal composition and be easy equably to arrange on substrate.It carries out in this condition The ultraviolet light of first stage irradiates, and orientation is subject to immobilization.The polymer is orientated liquid crystal molecule equably.Secondly, When applying starting voltage or more and 30V voltage below, pass through the orientation of the effect promotion liquid crystal molecule of electric field.According to described Orientation, unreacted compound are also orientated.In this condition, compound is irradiated big by the ultraviolet light of second stage Polymerization completely is caused, therefore generates the polymer for maintaining orientation.By the effect of the polymer, the orientation of liquid crystal molecule is additional Ground stabilizes, therefore the response time of element shortens.Due to the image retention of image be liquid crystal molecule running it is bad, pass through institute The effect for stating polymer can also improve image retention simultaneously.It is polymerize with such two stages, therefore unreacted reactant is few.Therefore, may be used Obtain the big element of voltage retention.

It is illustrated about the ultraviolet light irradiation to substrate.In the present invention, ultraviolet light is irradiated at least two stages.First In stage, between do not apply substrate voltage or apply substantially do not make liquid-crystal composition drive voltage and be irradiated.It is preferred that Illumination be about 2mW/cm²To about 200mW/cm²Range, preferred light exposure (product of illumination and irradiation time) be 1J/cm² To 60J/cm²Range.Sometimes the ultraviolet light is known as " the first ultraviolet light ".Pass through the most polymerization of the ultraviolet light Property compound is polymerize.In first ultraviolet light, and then preferred illumination is about 2mW/cm²To about 100mW/cm²Range, into And preferred light exposure is 3J/cm²To 50J/cm²Range.

In second stage, ultraviolet light is irradiated while between starting voltage or more and 30V voltage below is applied substrate.It is excellent The illumination of choosing is about 2mW/cm²To about 200mW/cm²Range, preferred light exposure be 5J/cm²To 100J/cm²Range.Have When by the ultraviolet light be known as " the second ultraviolet light ".Polymer is converted to by the unreacted compound of the ultraviolet light (1). In second ultraviolet light, and then preferred illumination is about 2mW/cm²To about 100mW/cm²Range, and then preferred light exposure is 5J/cm²To 55J/cm²Range.Though in the case where carrying out the ultraviolet light irradiation of second stage but also remaining unreacted reactant, this The ultraviolet light irradiation of phase III can also be added in invention.In the phase III, between do not apply substrate voltage or apply essence On do not make liquid-crystal composition drive voltage and be irradiated.Preferred illumination is about 2mW/cm²To about 200mW/cm²Range, Preferred light exposure (product of illumination and irradiation time) is 1J/cm²To 60J/cm²Range.Sometimes the ultraviolet light is known as " third ultraviolet light ".It is polymerize by the most polymerizable compound of the ultraviolet light.In third ultraviolet light, in turn Preferred illumination is about 2mW/cm²To about 100mW/cm²Range, and then preferred light exposure is 3J/cm²To 50J/cm²Model It encloses.

Colour is arranged in Fig. 1 shows the interaction polymerism polar compound (1) by polar group and substrate surface The element 11 of state on filter sheet base plate 1 and array substrate 2.Compound (1) forms tropism control layer by polymerization.Fig. 2 It indicates to arrange by the interaction polymerism polar compound (1) of polar group and substrate surface and polymerizable compound (16) In the element 12 of the state on colored filter substrate 1 and array substrate 2.Compound (1) passes through the copolymerization with compound (16) And form tropism control layer.Fig. 3 be it is existing with alignment films and include polymerizable compound element 21 skeleton diagram.Again Person, liquid crystal display element of the invention are not limited to such with array substrate and colored filter shown in Fig. 1 or Fig. 2 The element of the structure of both substrates of substrate.Another example be formed on the tft substrate colored filter (Color Filter, The element etc. of colorful optical filter array (Color Filter On Array, COA) structure CF).

Tropism control layer is viewed as having small concave-convex film according to using scanning electron microscope, can be considered grain The set of son.The section of the film is wavy.The interval of wave crest point and adjacent wave crest point is defined as the tropism control The partial size (hereinafter sometimes referred to simply as " partial size ") of polymer in layer.Partial size average out to about 1nm is to about 90nm, preferably from about 1nm To about 70nm.When partial size is such range, it is believed that liquid crystal molecule is equably vertically oriented and prevents light leakage.Tropism control layer Film thickness is about 10nm to about 100nm, preferably from about 10nm to about 80nm, even more preferably about 20nm to about 80nm.It is about in film thickness When 10nm or more, electrical characteristics can be maintained, therefore preferably.When film thickness is 100nm or less, driving voltage can be suitably reduced, because This is preferably.

In vertically oriented (VA) type element, in no applied voltage, liquid crystal molecule relative to real estate generally perpendicularly Orientation.In general, in order to keep liquid crystal molecule vertically oriented, as shown in figure 3, between colored filter substrate 1 and liquid crystal layer 3 or battle array Vertical alignment layer as polyimides, polyamide, polysiloxanes is configured between column substrate 2 and liquid crystal layer 3.On the other hand, exist In element without alignment films, such alignment films are not needed.In the element, pass through the effect of tropism control layer, liquid crystal Molecule is vertically oriented relative to substrate.The angle (i.e. pre-tilt angle) of liquid crystal molecule and substrate be 90 ° ± 10 °, preferably 90 ° ± 5 °, more preferably 90 ° ± 3 °.It, can by combining such vertically oriented pixel electrode with slit and through pixel segmentation Reach wide viewing angle.

Embodiment

By embodiment (including synthesis example, use example), the present invention will be described in more detail.The present invention is not by these The limitation of embodiment.The present invention includes the mixture of the composition of use example 1 Yu the composition of use example 2.The present invention also includes The mixture prepared and being mixed 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 (1) is by shown in synthesis example etc. Sequence synthesizes.Synthesized compound is by nuclear magnetic resonance (nuclear magnetic resonance, NMR) analysis etc. Method is identified.Characteristic can be measured by following methods.

NMR analysis: the DRX-500 manufactured in the assay using this guest (Bruker BioSpin) company of Brooker Baier.¹In the measurement of H-NMR, sample is made to be dissolved in CDCl₃Etc. in deuterates solvent, at room temperature, 500MHz, cumulative number 16 times items 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 For 0.25mm, film thickness is 0.25 μm).Use helium (1ml/ minutes) as carrier gas.The temperature of sample evaporation chamber is set as 300 DEG C, the temperature that will test the part device (flame ionization detector (flame ionization detector, FID)) is set as 300℃.Sample is dissolved in acetone and prepares in a manner of as the solution of 1 weight %, and the resulting solution of 1 μ l is injected Into sample evaporation chamber.Recording gauge is GC dissolution (GC Solution) system etc. manufactured using Shimadzu Seisakusho Ltd..

High performance liquid chromatography (High Performance Liquid Chromatography, HPLC) analysis: when measurement Pu Luominsi (the Prominence) (LC-20AD manufactured using Shimadzu Seisakusho Ltd.；SPD-20A).Tubing string uses YMC manufacture YMC-Pack ODS-A (length 150mm, internal diameter 4.6mm, 5 μm of partial size).Dissolution fluid is to properly mix acetonitrile to use with water. Detector suitably use ultraviolet light (Ultraviolet, UV) detector, refractive index (Refractive Index, RI) detector, Corona detection device (CORONA detector) etc..Using UV detector, Detection wavelength is set as 254nm.Sample is It is dissolved in acetonitrile and is prepared in a manner of as the solution of 0.1 weight %, the solution of 1 μ L is directed into sample chamber. The C-R7Aplus that recording gauge uses Shimadzu Seisakusho Ltd. to manufacture.

UV, visible light spectrum analysis: method Ma Spike (PharmaSpec) UV- that measurement is manufactured using Shimadzu Seisakusho Ltd. 1700.It will test wavelength and be set as 190nm to 700nm.Sample is dissolved in acetonitrile and with the solution as 0.01mmol/L Prepared by mode, and be added and be measured into quartz cell (optical path length 1cm).

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

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

(1) phase structure

In hot plate (Mei Tele (Mettler) company, the heating of FP-52 type of the melting point apparatus for having petrographic microscope Platform) on place sample.The sample is heated with 3 DEG C/min of speed on one side, is observed on one side using petrographic microscope Phase state and its variation determine the type of phase.

(2) transition temperature (DEG C)

In measurement, the scanning calorimeter, the diamond that are manufactured using Pa Jinaierma (Perkin Elmer) company (Diamond) differential scanning calorimetry (Differential Scanning Calorimeter, DSC) system or SSI nanometers of sections The high sensitivity differential scanning calorimetry X-DSC7000 of skill (SSI Nanotechnology) company manufacture.To sample with 3 DEG C/minute The speed of clock carries out heating and cooling, and the starting of the endothermic peak along with the phase change of sample or the peak value that generates heat is found out by extrapolation Point, determines transition temperature.Fusing point, the polymerization initiating temperature of compound are also to be measured using described device.Sometimes by compound The temperature for being changed into the liquid crystalline phases such as smectic phase, nematic phase from solid is referred to as " lower limit temperature of liquid crystalline phase ".Sometimes by compound " brocken spectrum " is referred to as from the temperature that liquid crystal phase transition is liquid.

Crystallization is expressed as C.In the case where being distinguished to the type of crystallization, it is expressed as C₁、C₂.Smectic phase indicates For S, nematic phase is expressed as N.In smectic phase, what is be distinguished to smectic C, smectic B, smectic C phase or smectic F phase In the case of, it is expressed as S_A、S_B、S_COr S_F.Liquid (isotropism) is expressed as I.Transition temperature is for example expressed as " C 50.0N 100.0I".This is indicated, crystallizes to that nematic transition temperature is 50.0 DEG C certainly, the transformation temperature from nematic phase to liquid Degree is 100.0 DEG C.

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

Sample is placed on the hot plate for the melting point apparatus for having petrographic microscope, the speed with 1 DEG C/min is added Heat.Measure sample a part from nematic phase change be isotropic liquid when temperature.Sometimes by nematic ceiling temperature Referred to as " ceiling temperature ".When sample is the mixture of liquid crystal compounds and mother liquor crystalline substance, with mark T_NIIt indicates.It is in sample When the mixture of the compound of liquid crystal compounds and ingredient B, ingredient C, ingredient D etc, 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)

It is measured using the E type rotational viscometer that Tokyo gauge limited liability company manufactures.

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

The light for the use of wavelength being 589nm, utilizes the Abbe refractometer (abbe that polarizer is equipped on eyepiece 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 by 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 that the sample and dielectric anisotropy being positive for dielectric anisotropy are negative, the measuring method of characteristic is not sometimes Together.It is to be recorded in item (8a) into item (12a) in the measuring method that dielectric anisotropy is timing.It is negative in dielectric anisotropy In the case of, measuring method is to be recorded in item (8b) into item (12b).

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

Positive dielectric anisotropy: measurement is " molecular crystal and the liquid crystal according to M. the present well (M.Imai) et al. (Molecular Crystals and Liquid Crystals) " (Vol.259,37 (1995)) middle method recorded.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 Periodically apply voltage as unit of 0.5V in the range of 16V to 19.5V.After not applying voltage 0.2 second, only to apply one A rectangular wave (rectangular pulse；0.2 second) with the condition for not applying voltage (2 seconds) apply voltage repeatedly.It is produced to because of the application The peak point current (peak current) and time to peak (peak time) of raw transient current (transient current) It is measured.It is viscous that rotation is obtained according to paper page 40 of calculating formula (8) of these measured values and M. the present well (M.Imai) et al. The value of degree.The value of dielectric anisotropy necessary to the calculating is using determining the element of the rotary viscosity using following The method of record and find out.

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

Negative dielectric anisotropy: measurement is " molecular crystal and the liquid crystal according to M. the present well (M.Imai) et al. (Molecular Crystals and Liquid Crystals) " method for recording in (Vol.259,37 (1995)) come into Row.Sample is put into the VA element that the interval (cell gap) of two pieces of glass substrates is 20 μm.To the element at 39 volts To in the range of 50 volts, periodically apply voltage as unit of 1 volt.After not applying voltage 0.2 second, only to apply one A rectangular wave (rectangular pulse；0.2 second) with the condition for not applying voltage (2 seconds) apply voltage repeatedly.It is produced to because of the application The peak point current (peak current) and time to peak (peak time) of raw transient current (transient current) It is measured.It is viscous that rotation is obtained according to paper page 40 of calculating formula (8) of these measured values and M. the present well (M.Imai) et al. The value of degree.The value of dielectric anisotropy necessary to the calculating is the value measured in 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, it is viscous using being hardened with ultraviolet light Agent is connect by the component seal.Sine wave (0.5V, 1kHz) is applied to the element, the long axis side of liquid crystal molecule is measured after 2 seconds To dielectric constant (ε ∥).

2) measurement of dielectric constant (ε ⊥): polyimide solution is coated on the glass substrate through sufficiently cleaning.It will be described After glass substrate calcining, friction treatment is carried out to resulting alignment films.It is 9 μ at the interval (cell gap) of two pieces of glass substrates M, and torsion angle is to be put into sample in 80 degree of TN element.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: Yokogawa Hewlett-Packard (YokogawaHewlett-Packard) share is used when measurement The HP4284A type LCR meter of Co., Ltd's manufacture.The horizontal alignment member for being 20 μm at the interval (cell gap) of two pieces of glass substrates Sample is put into part.Apply 0 volt to 20 volts of charge to the element, measure electrostatic capacitance and applies voltage.Use " liquid Brilliant device handbook " (daily magazine Jndustrial News company) page 75 formula (2.98), formula (2.101), by the electrostatic capacitance measured (C) It is fitted with the value for applying voltage (V), K is obtained according to formula (2.99)₁₁And K₃₃Value.Then, the formula in page 171 (3.18) In, use the K first found out₁₁And K₃₃Value calculate K₂₂.Elastic constant K is the K so to find out₁₁、K₂₂And K₃₃Be averaged Value indicates.

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

Negative dielectric anisotropy: it is manufactured when measurement using Dongyang technical concern Co., Ltd (TOYO Corporation) EC-1 type spring constant testing device.It is put in the vertically oriented element that the interval (cell gap) of two pieces of glass substrates is 20 μm Enter sample.Apply 20 volts to 0 volt of charge to the element, measure electrostatic capacitance and applies voltage.Use " liquid crystal dress Set handbook " formula (2.98), the formula (2.101) of (Nikkan Kogyo Shimbun) page 75, by electrostatic capacitance (C) and apply voltage (V) Value fitting, the value of elastic constant is obtained according to formula (2.100).

(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.At the interval (cell gap) of two pieces of glass substrates be 0.45/ Δ n (μm) and torsion angle is 80 degree Sample is put into the TN element of normal whitening mode (normally white mode).The voltage that the element is applied (32Hz, rectangular wave) is periodically to increase to 10V from 0V as unit of 0.02V.At this point, being irradiated from vertical direction to element Light, measurement penetrate the light quantity of element.Being formed in transmitance when the light quantity reaches maximum is 100%, and is most in the light quantity Voltage-transmittance curve that hour transmitance is 0%.Starting voltage is voltage when reaching 90% with 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.It is 4 μm and frictional direction at the interval (cell gap) of two pieces of glass substrates is antiparallel normally to show black It is put into sample in the VA element of mode (normally black mode), uses the bonding agent that is hardened with ultraviolet light by institute State component seal.The voltage (60Hz, rectangular wave) applied to the element is periodically to be increased as unit of 0.02V from 0V To 20V.At this point, from vertical direction to element irradiation light, measurement penetrates the light quantity of element.When being formed in the light quantity and reaching maximum Transmitance is 100%, and voltage-transmittance curve that transmitance is 0% when the light quantity is minimum.Starting voltage is to penetrate Voltage when rate reaches 10% indicates.

(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) be the normal whitening mode (normally white mode) that 5.0 μm and torsion angle are 80 degree TN element in put Enter sample.Rectangular wave (60Hz, 5V, 0.5 second) is applied to the element.At this point, from vertical direction to element irradiation light, measurement is saturating Cross the light quantity of element.Being considered as transmitance when the light quantity reaches maximum is 100%, is considered as transmission when the light quantity is minimum Rate is 0%.Rise time (τ r:rise time；Millisecond) be transmitance from 90% variation be 10% required for the time.Decline Time (τ f:fall time；Millisecond) be transmitance from 10% variation be 90% required for the time.Response time is by with institute The sum of rise time and fall time that the mode of stating 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, and frictional direction is antiparallel normally to show the having through scheming of black mode (normally black mode) Sample is put into the VA element of the electrode structure of case.The element is sealed using the bonding agent hardened with ultraviolet light. Apply voltage 1 minute for being just over starting voltage degree to the element, is then irradiated while applying the voltage of 5.6V 23.5mW/cm²Ultraviolet light 8 minutes.Rectangular wave (60Hz, 10V, 0.5 second) is applied to the element.At this point, from vertical direction To element irradiation light, measurement penetrates the light quantity of element.Being considered as transmitance when the light quantity reaches maximum is 100%, described Being considered as transmitance when light quantity is minimum is 0%.Response time be as transmitance from 90% variation for the time required for 10% (under Time drops；fall time；Millisecond) it indicates.

(13) voltage retention

Use black light (black light), the F40T10 (peak value of outstanding (EyeGraphics) the limited liability company manufacture of rock Wavelength is 335nm) irradiate ultraviolet light, thus it polymerize polymerizable compound.Arteries and veins is applied at 60 DEG C to the element Voltage (1V, 60 microseconds) is rushed to charge.The voltage of decaying is measured in a period of 1.67 seconds using high speed potentiometer, and is asked Area A between voltage curve and horizontal axis in unit period out.Area B is area when not decaying.Voltage retention be by Area A is indicated relative to the percentage of area B.

(14) illumination

In the measurement of ultraviolet light illumination, the ultraviolet light illumination of oxtail (USHIO) Electric Co., Ltd manufacture is used It counts UIT-250 type (sensor: UVD-S365).

(15) vertical orientation

Element obtained is set on petrographic microscope, from lower to element irradiation light, whether there is or not light leakages for observation.In liquid crystal In the case that molecule is fully orientated, and light is not through element, vertical orientation is judged as " good ".It is observing through member When the light of part, " having orientation defect " is expressed as.

(16) pre-tilt angle (degree)

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

(17) film thickness and partial size

The measurement of the film thickness and partial size of tropism control layer is using SEM (scanning electron microscope) (SU-70 that scanning electron microscope, new and high technology limited liability company, Hitachi manufacture) Lai Jinhang.

Synthesize following compounds.Compound (1 α -3-A), compound (1 α -4-A) to compound (1 α -4-J), compound The synthetic method and applicable chemical combination of (1 α -5-A) to compound (1 α -5-B), compound (1 α -6-A) to compound (1 α -6-J) The concrete example of object is disclosed in International Publication 2016-129490 handbook.About compound (1 β -4-A) and compound (1 γ -2- A synthetic method) is disclosed in International Publication 2017-014013 handbook and International Publication 2017-047177 handbook In.

[synthesis example of compound (1-4-3)]

1st process

By compound (T-7), 3,4- dihydro -2H- pyrans (23.3g), pyridinium p-toluenesulfonate (Pyridinium p- Toluenesulfonate, PPTS) (5.80g) be put into reactor and stir 10 hours at 50 DEG C.Insoluble matter is filtered After separation, reaction mixture is injected into water, and water layer is extracted using methylene chloride.Using water to mixing Organic layer is cleaned, and is dried using anhydrous magnesium sulfate.The solution is concentrated under reduced pressure, silica gel chromatography is utilized (volumetric ratio, heptane: ethyl acetate=2:1) purifies residue, and obtains compound (T-21) (39.5g；80%).

2nd process

Compound (T-21) (39.5g), THF (400ml) and water (400ml) are put into reactor, are cooled to 0 DEG C. Lithium hydroxide monohydrate (15.4g) is added thereto, restore to room temperature and stirs 12 hours.Reaction mixture is injected into In water, and 6N hydrochloric acid (60ml) is slowly added into after becoming acid, water layer is extracted using ethyl acetate.Utilize water pair The organic layer to mix is cleaned, and is dried using anhydrous magnesium sulfate.The solution is concentrated under reduced pressure, and is obtained Obtain compound (T-22) (32.6g；95%).

3rd process

By compound (1-23-2) (2.0g), compound (T-22) (1.18g), DMAP (0.32g) and methylene chloride (100ml) is put into reactor, is cooled to 0 DEG C.The methylene chloride (60ml) that DCC (1.30g) is slowly added dropwise thereto is molten Liquid restores to room temperature and stirs 12 hours.After insoluble matter is separated by filtration, reaction mixture is injected into water, and is utilized Methylene chloride extracts water layer.The organic layer to mix is cleaned using water, and is carried out using anhydrous magnesium sulfate It is dry.The solution is concentrated under reduced pressure, using silica gel chromatography (volumetric ratio, toluene: ethyl acetate=19:1) by residue Purifying, and obtain compound (T-23) (2.37g；82%).

4th process

By compound (T-23) (2.37g), pyridinium p-toluenesulfonate (PPTS) (0.54g), THF (50ml) and methanol (50ml) is put into reactor, is stirred 5 hours at 50 DEG C.After insoluble matter is separated by filtration, reaction mixture is injected into In water, and water layer is extracted using ethyl acetate.The organic layer to mix is cleaned using water, and is utilized anhydrous Magnesium sulfate is dried.The solution is concentrated under reduced pressure, using silica gel chromatography (volumetric ratio, toluene: ethyl acetate=9: 1) residue is purified, and obtains compound (1-4-3) (1.50g；75%).

The NMR assay value of resulting compound (1-4-3) is as described below.

¹H-NMR: chemical shift δ (ppm；CDCl₃): 6.24 (s, 1H), 6.09 (s, 1H), 5.84 (s, 1H), 5.57 (s, 1H)、4.33-4.27(m,4H)、4.20-4.16(m,2H)、2.34-2.31(m,1H)、1.97-1.90(m,4H)、1.82-1.67 (m,8H)、1.43-1.39(m,1H)、1.31-1.18(m,6H)、1.15-0.75(m,16H).

The physical property of compound (1-4-3) is as described below.

Transition temperature: C 66.5I.

[synthesis example of compound (1-23-3)]

1st process

Three phenyl-bromide Phosphonium (103.7g) of 2- (1,3- dioxanes -2- base) second base and THF (500ml) are put into reactor In, -30 DEG C are cooled to, is added potassium tert-butoxide (25.4g), and is stirred 1 hour.Compound (T-35) slowly is added dropwise thereto THF (300ml) solution of (50.0g) restores to room temperature and stirs 6 hours.After insoluble matter is separated by filtration, reaction is mixed Object is injected into water, and is extracted using toluene to water layer.The organic layer to mix is cleaned using water, and is utilized Anhydrous magnesium sulfate is dried.The solution is concentrated under reduced pressure, using silica gel chromatography (volumetric ratio, toluene: heptane=1: 1) residue is purified, and obtains compound (T-36) (63.0g；92%).

2nd process

Compound (T-36) (63.0g), toluene (500ml), IPA (500ml) and Pd/C (0.55g) are put into reactor In, and stirred 16 hours under hydrogen environment.After insoluble matter is separated by filtration, reaction mixture is injected into water, and toluene Water layer is extracted.The organic layer to mix is cleaned using water, and is dried using anhydrous magnesium sulfate.By institute It states solution to be concentrated under reduced pressure, is purified residue using silica gel chromatography (volumetric ratio, toluene: heptane=1:1), and obtain chemical combination Object (T-37) (60.1g；95%).

3rd process

Compound (T-37) (60.1g), formic acid (75.8g) and toluene (1000ml) are put into reactor, and It is stirred 6 hours at 100 DEG C.It after insoluble matter is separated by filtration, is neutralized using sodium bicarbonate aqueous solution, and using toluene to water Layer is extracted.The organic layer to mix is cleaned using water, and is dried using anhydrous magnesium sulfate.It will be described molten Liquid is concentrated under reduced pressure, and purifies residue using silica gel chromatography and using toluene, and obtains compound (T-38) (45.0g； 89%).

4th process

By compound (T-38) (45.0g), permonosulphuric acid potassium (OXONE) (108.3g) and DMF (1000ml) be put into In reactor, and it is stirred at room temperature 8 hours.

After insoluble matter is separated by filtration, reaction mixture is injected into water, and ethyl acetate extracts water layer.Benefit The organic layer to mix is cleaned with water, and is dried using anhydrous magnesium sulfate.The solution is dense under reduced pressure Contracting, and obtain compound (T-39) (28.5g；60%).

5th process

Compound (T-39) (28.5g), sulfuric acid (0.5ml) and methanol (500ml) are put into reactor, and at 60 DEG C Lower stirring 5 hours.It after insoluble matter is separated by filtration, is concentrated, residue is carried out using silica gel chromatography and using toluene pure Change, and obtains compound (T-40) (22.3g；75%).

6th process

Use compound (T-40) (22.3g) as raw material, is obtained and method identical with the 1st process of synthesis example 4 Obtain compound (T-41) (18.3g；70%).

7th process

Use compound (T-41) (18.3g) as raw material, is obtained and method identical with the 2nd process of synthesis example 4 Obtain compound (T-42) (5.9g；38%).

8th process

Use compound (T-42) (5.9g) as raw material, is obtained and method identical with the 3rd process of synthesis example 4 Compound (1-23-3) (2.4g；34%).

The NMR assay value of resulting compound (1-23-3) is as described below.

¹H-NMR: chemical shift δ (ppm；CDCl₃): 6.11 (s, 1H), 5.81 (s, 1H), 4.31-4.28 (m, 1H), 4.17-4.14(m,1H)、3.63-3.58(m,1H)、3.54-3.49(m,1H)、1.98-1.95(m,4H)、1.84-1.69(m, 9H)、1.41-1.18(m,10H)、1.15-1.06(m,4H)、1.02-0.80(m,13H).

The physical property of compound (1-23-3) is as described below.

Transition temperature: C 33.6S_A 101I.

[synthesis example of compound (1-4-4)]

1st process

Use compound (1-23-3) (2.0g) as raw material, is obtained and method identical with the 3rd process of synthesis example 5 Obtain compound (T-43) (2.1g；74%).

2nd process

Use compound (T-43) (2.1g) as raw material, is obtained and method identical with the 4th process of synthesis example 5 Compound (1-4-4) (1.3g；72%).

The NMR assay value of resulting compound (1-4-4) is as described below.

¹H-NMR: chemical shift δ (ppm；CDCl₃): 6.25 (s, 1H), 6.10 (s, 1H), 5.85 (d, J=1.1Hz, 1H), 5.57 (s, 1H), 4.33 (d, J=6.5Hz, 2H), 4.24-4.11 (m, 4H), 2.28 (t, J=6.6Hz, 1H), 2.09-2.03 (m,1H)、1.94(s,3H)、1.75-1.67(m,8H)、1.44-1.39(m,2H)、1.32-1.18(m,8H)、1.15-1.06 (m,4H)、1.02-0.79(m,13H).

The physical property of compound (1-4-4) is as described below.

Transition temperature: C 71.4I.

Compound in composition is 1 based on following table 2)~5) definition and indicated using mark.In table 2, with The relevant spatial configuration of 1,4- cyclohexylidene is anti-configuration.Number and the number phase of compound in the parantheses after mark It is corresponding.The mark of (-) refers to other liquid crystal compounds.The ratio (percentage) of liquid crystal compounds is based on liquid-crystal composition Weight weight percent (weight %).Finally, concluding the characteristic value of liquid-crystal composition.Characteristic is the side recorded according to before Method measures, directly record measured value (not extrapolating).

Table 2 uses the expression method of the compound of mark

R-(A₁)-Z₁-……Zn-(A_n)-R’

[composition (i)]

NI=76.1 DEG C；η=16.1mPas；Δ n=0.100；Δ ε=- 2.5；Vth=2.4V.

[composition (ii)]

NI=74.2 DEG C；< -20 DEG C of Tc；Δ n=0.103；Δ ε=- 2.5；Vth=2.36V；η=18.4mPas.

[composition (iii)]

NI=74.9 DEG C；< -20 DEG C of Tc；Δ n=0.102；Δ ε=- 2.8；Vth=2.30V；η=19.2mPas.

[composition (iv)]

NI=76.5 DEG C；< -20 DEG C of Tc；Δ n=0.098；Δ ε=- 3.0；Vth=2.15V；η=16.2mPas.

[composition (v)]

NI=75.3 DEG C；Tc<-20℃；Δ n=0.102；Δ ε=- 2.6；Vth=2.41V；η=17.5mPas.

[embodiment 1]

Following compounds (1 α -4-A) are added as polymerism polarity using the ratio of 3 parts by weight in the composition (i) Compound.

In addition, adding following compounds (16-6-1-A) as polymerizable compound using the ratio of 0.3 parts by weight.It will be described Composition is injected into the element without alignment films that the interval (cell gap) of two pieces of glass substrates is 3.5 μm and makes member Part (1A) does not apply voltage to made element (1A) and irradiates 29.7J/cm²Dominant wavelength be 365nm ultraviolet light (90mW/cm²).In ultraviolet irradiation, irradiated using the ultraviolet light of outstanding (EyeGraphics) the limited liability company manufacture of rock Device US4-X0401-FKTN type (metal halide lamp M04-L41).Secondly, rising to voltage with the speed of 0.05V per second 3V and apply 5.4V to the element with the speed of 0.15V per second voltage with rising to 5.4V, in this condition, using same One device irradiates 29.7J/cm²Dominant wavelength be 365nm ultraviolet light (90mW/cm²).The pre-tilt angle of liquid crystal is measured, is tied Fruit is 88.9 °.Observed using petrographic microscope, as a result without light leakage and vertical orientation it is good.It is aobvious using scanning electron Micro mirror observes tropism control layer present on colored filter substrate, and as a result film thickness is 50nm and partial size is 70nm.

[embodiment 2]

Using the element (1A) made by method same as Example 1, does not apply voltage and irradiate 5.0J/cm² Dominant wavelength be 335nm ultraviolet light (3mW/cm²).In ultraviolet irradiation, had using outstanding (EyeGraphics) share of rock Black light (black light), the F40T10 (peak wavelength 335nm) of limit company manufacture.Secondly, by being recorded with embodiment 1 Voltage apply the voltage that identical method applies 5.4V to the element, and in this condition, irradiate 9.9J/cm²Master Wavelength is the ultraviolet light (3mW/cm of 335nm²).The pre-tilt angle of liquid crystal molecule is measured, result is 88.8 °.The element Without light leakage and vertical orientation it is good.The film thickness of tropism control layer is 50nm present on colored filter substrate and partial size is 50nm。

[embodiment 3]

Using the element (1A) made by method same as Example 1, does not apply voltage and irradiate 5.0J/cm² Dominant wavelength be 335nm ultraviolet light (3mW/cm²).In ultraviolet irradiation, had using outstanding (EyeGraphics) share of rock Black light (black light), the F40T10 (peak wavelength 335nm) of limit company manufacture.Secondly, by being recorded with embodiment 1 Voltage apply the voltage that identical method applies 5.4V to the element, and in this condition, irradiate 49.5J/cm²Master Wavelength is the ultraviolet light (90mW/cm of 365nm²).The pre-tilt angle of liquid crystal is measured, result is 89.4 °.The element is without leakage Light and vertical orientation is good.The film thickness of tropism control layer present on colored filter substrate is 50nm and partial size is 65nm.

[embodiment 4]

The additive amount of compound (16-6-1-A) is changed to 0.05 parts by weight, in addition to this, to by with 1 phase of embodiment The element (1B) of same method production, does not apply voltage and irradiates 19.8J/cm²Dominant wavelength be 365nm ultraviolet light (90mW/cm²).Secondly, applying the electricity that identical method applies 5.4V to the element by the voltage recorded with embodiment 1 Pressure, and in this condition, irradiate 13.2J/cm²Dominant wavelength be 335nm ultraviolet light (3mW/cm²).To the pre-tilt angle of liquid crystal It is measured, result is 89.0 °.The element without light leakage and vertical orientation it is good.It is taken present on colored filter substrate To the film thickness of control layer be 55nm and partial size is 65nm.

[embodiment 5]

Using the element (1A) made by method same as Example 1, does not apply voltage and irradiate 10.0J/cm² Dominant wavelength be 365nm ultraviolet light (90mW/cm²).Secondly, applying identical method by the voltage recorded with embodiment 1 Apply the voltage of 5.4V to the element, and in this condition, irradiates 5.1J/cm²Dominant wavelength be 365nm ultraviolet light (90mW/cm²).In turn, voltage is not applied to the element and irradiates 10.8J/cm²Dominant wavelength be 335nm ultraviolet light (3mW/cm²).The pre-tilt angle of liquid crystal is measured, result is 87.8 °.The element without light leakage and vertical orientation it is good. The film thickness of tropism control layer present on colored filter substrate is 50nm and partial size is 55nm.

[comparative example 1]

Using the element (1A) made by method same as Example 1, and the voltage by recording with embodiment 1 is applied Add identical method to apply the voltage of 5.4V, and in this condition, irradiates 49.5J/cm while applying voltage²Main wave Ultraviolet light (the 90mW/cm of a length of 365nm²).Secondly, not applying voltage to the element and irradiating 9.9J/cm²Dominant wavelength be Ultraviolet light (the 3mW/cm of 335nm²).The pre-tilt angle of liquid crystal is measured, result is 89.0 °.The element has light leakage, is The result of " having orientation defect ".The film thickness of tropism control layer present on colored filter substrate is 50nm and partial size is 110nm.

The element of embodiment 1 to embodiment 5 has no light leakage.On the other hand, it observed light leakage in comparative example 1.Think to leak Light is generated because being orientated defect.The partial size of the partial size and comparative example of learning embodiment is in comparison small.Think that small particle helps In uniform vertically oriented.Even if the constituent of liquid-crystal composition or the type of orientation monomer are different, can also similarly obtain Obtain same effect.Therefore, it can show that the liquid crystal display element manufactured by means of the present invention has uniformly vertically to take To conclusion.In the element, light leakage can be prevented, therefore is the excellents such as contrast.

Industrial availability

The liquid crystal display element manufactured using method of the invention can be used for LCD monitor, LCD TV etc..

The explanation of symbol

1: colored filter substrate

2: array substrate

3: liquid-crystal composition

4: liquid crystal compounds (liquid crystal molecule)

5: polymerism polar compound (1) (as orientation monomer)

6: polymerizable compound (16) (as reactive monomer)

7: alignment films

8: polymerizable compound

Claims

1. a kind of manufacturing method of liquid crystal display element, the liquid crystal display element include

First substrate；

It is formed in multiple pixel electrodes of the first substrate；

The second substrate；

It is formed in the opposite electrode opposite with the pixel electrode of the second substrate；And

The liquid crystal layer being held between the pixel electrode and the opposite electrode,

The liquid crystal layer includes liquid-crystal composition,

The liquid-crystal composition contains the polymerization with the mesogen position being made of at least one ring as orientation monomer Property polar compound and liquid crystal compounds,

The manufacturing method of the liquid crystal display element is characterized in that:

Firstly, voltage is not applied to the liquid-crystal composition or applies the voltage for substantially driving liquid-crystal composition, and with 1J/cm²To 60J/cm²Range illumination illumination be 2mW/cm²To 200mW/cm²Range the first ultraviolet light；

Secondly, applying starting voltage or more and 30V voltage below to the liquid-crystal composition on one side, on one side with 5J/cm²To 100J/ cm²Range illumination illumination be 2mW/cm²To 200mW/cm²Range the second ultraviolet light；

To form tropism control layer, the tropism control layer includes to be generated and polymerizeing the polymerism polar compound Polymer.

2. the manufacturing method of liquid crystal display element according to claim 1, wherein firstly, not to the liquid-crystal composition Apply voltage or apply the voltage for substantially driving liquid-crystal composition, and with 3J/cm²To 50J/cm²Range illumination shine Degree is 2mW/cm²To 100mW/cm²Range the first ultraviolet light；Secondly, on one side to the liquid-crystal composition apply starting voltage with Upper and 30V voltage below, on one side with 5J/cm²To 55J/cm²Range illumination illumination be 2mW/cm²To 100mW/cm²Model The second ultraviolet light enclosed.

3. the manufacturing method of liquid crystal display element according to claim 1, wherein after the irradiation of the second ultraviolet light, in turn Do not apply voltage to liquid-crystal composition or apply the voltage for substantially driving liquid-crystal composition, and with 1J/cm²To 60J/ cm²Range illumination illumination be 2mW/cm²To 200mW/cm²Range third ultraviolet light.

4. the manufacturing method of liquid crystal display element according to any one of claim 1 to 3, wherein the orientation monomer For compound represented by formula (1 α).

In formula (1 α),

MES is the liquid crystal former base at least one ring；

M¹And M²It independently is the carbon number 1 to 5 that hydrogen, fluorine, chlorine, the alkyl of carbon number 1 to 5 or at least one hydrogen replace through fluorine or chlorine Alkyl；

In formula (1 α a), formula (1 α b) and formula (1 α c),

S¹For > CH- or > N-；

S²For > C < or > Si <；

X¹It independently is-OH ,-NH₂、-OR³、-N(R³)₂, formula (x1) ,-COOH ,-SH ,-B (OH)₂Or-Si (R³)₃Represented Base, herein, R³For hydrogen or the alkyl of carbon number 1 to 10, in the alkyl, at least one-CH₂It can replace through-O-, at least one- (CH₂)₂Can replace through-CH=CH-, in these bases, at least one hydrogen can replace through fluorine or chlorine, the w in formula (x1) be 1,2,3 or 4,

5. the manufacturing method of liquid crystal display element according to any one of claim 1 to 3, the orientation monomer is formula Compound represented by (1 β).

In formula (1 β),

MES is the liquid crystal former base at least one ring；

R²、M¹、M²And M³It independently is the alkyl of hydrogen, fluorine, chlorine or carbon number 1 to 10, in the alkyl, at least one-CH₂Can through- O- or-S- replaces, at least one-(CH₂)₂It can replace through-CH=CH- or-C ≡ C-, in these bases, at least one hydrogen can be through fluorine Or chlorine replaces.

6. the manufacturing method of liquid crystal display element according to any one of claim 1 to 3, the orientation monomer is formula Compound represented by (1 γ).

In formula (1 γ),

R¹、R²And R³It independently is the alkyl of hydrogen or carbon number 1 to 15, in the alkyl, at least one-CH₂Can through-O- ,-S- or- NH- replaces, at least one-(CH₂)₂It can replace through-CH=CH-, in these bases, at least one hydrogen can replace through fluorine or chlorine；

N independently is 0,1 or 2；

Ring A⁴For cyclohexylidene, cyclohexadienylidene, phenylene, naphthalene, decahydronaphthalene, naphthane, oxinane, 1,3- dioxanes, pyrimidine Or pyridine, ring A¹And ring A⁵It 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, the alkenyl of carbon number 2 to 12, the alkoxy of carbon number 1 to 11 or carbon number 2 to 11 alkenyloxy group replaces, and in these bases, at least one hydrogen can replace through fluorine or chlorine；

Z¹And Z⁵It independently is the alkylidene of singly-bound or carbon number 1 to 10, in the alkylidene, at least one-CH₂Can through-O- ,- COO- ,-OCO- or-OCOO- replace, 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；

Sp¹、Sp²And Sp³It independently is the alkylidene of singly-bound or carbon number 1 to 10, in the alkylidene, at least one-CH₂Can through- O- ,-COO- ,-OCO- or-OCOO- replace, 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；

A and b independently is 0,1,2,3 or 4, and a and b's and be 1,2,3 or 4；

C, d and e independently is 0,1,2,3 or 4；

C, d and e's and be 2,3 or 4；

In formula (P-1),

R⁴For the base in the group of the base represented by formula (1 γ a), formula (1 γ b) and the formula (1 γ c).

In formula (1 γ a), formula (1 γ b) and formula (1 γ c),

Sp⁵And Sp⁶It independently is the alkylidene of singly-bound or carbon number 1 to 10, in the alkylidene, at least one-CH₂Can through- O- ,-NH- ,-CO- ,-COO- ,-OCO- or-OCOO- replace, 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；

S¹For > CH- or > N-；

S²For > C < or > Si <；

X¹It independently is-OH ,-NH₂、-OR⁵、-N(R⁵)₂、-COOH、-SH、-B(OH)₂Or-Si (R⁵)₃Represented base, herein, R⁵For hydrogen or the alkyl of carbon number 1 to 10, in the alkyl, at least one-CH₂It can replace through-O-, at least one-(CH₂)₂It can Replace through-CH=CH-, in these bases, at least one hydrogen can replace through fluorine or chlorine.

7. the manufacturing method of liquid crystal display element according to any one of claim 1 to 6, wherein having by least one In the orientation monomer at the mesogen position that a ring is constituted, the mesogen position includes cyclohexane ring.

8. the manufacturing method of liquid crystal display element according to any one of claim 1 to 3, wherein the orientation monomer For compound represented by formula (1-1).

In formula (1-1),

R¹For the alkyl of carbon number 1 to 15, the R¹In, at least one-CH₂It can replace through-O- or-S-, at least one-CH₂CH₂- It can replace through-CH=CH- or-C ≡ C-, at least one hydrogen can replace through halogen；

Ring A¹And ring A²It independently is 1,4- cyclohexylidene, 1,4- cyclohexadienylidene, 1,4- phenylene, naphthalene -2,6- diyl, decahydro It is naphthalene -2,6- diyl, 1,2,3,4- naphthane -2,6- diyl, oxinane -2,5- diyl, 1,3- dioxanes -2,5- diyl, phonetic Pyridine -2,5- diyl, pyridine -2,5- diyl, fluorenes -2,7- diyl, phenanthrene -2,7- diyl, anthracene -2,6- diyl, perhydro cyclopentano [a] Phenanthrene -3,17- diyl or ten tetrahydro cyclopentyl of 2,3,4,7,8,9,10,11,12,13,14,15,16,17- simultaneously [a] phenanthrene -3,17- two Base, in these rings, at least one hydrogen can through fluorine, chlorine, the alkyl of carbon number 1 to 12, the alkenyl of carbon number 2 to 12, carbon number 1 to 11 alkane Oxygroup or the alkenyloxy group of carbon number 2 to 11 replace, and in these bases, at least one hydrogen can replace through fluorine or chlorine；

A is 0,1,2,3 or 4；

Z¹For singly-bound or the alkylidene of carbon number 1 to 6, the Z¹In, at least one-CH₂Can through-O- ,-CO- ,-COO- ,-OCO-, Or-OCOO- replaces, at least one-CH₂CH₂It can replace through-CH=CH- or-C ≡ C-, in these bases, at least one hydrogen can be through Fluorine or chlorine replace；

Sp¹For singly-bound or the alkylidene of carbon number 1 to 10, the Sp¹In, at least one-CH₂Can through-O- ,-CO- ,-COO- ,- OCO- or-OCOO- replaces, at least one-CH₂CH₂It can replace through-CH=CH- or-C ≡ C-, in these bases, at least one hydrogen It can replace through halogen, in these bases, at least one hydrogen passes through the base being selected from base represented by formula (1a) and replaces,

In formula (1a),

Sp¹²For singly-bound or the alkylidene of carbon number 1 to 10, the Sp¹²In, at least one-CH₂Can through-O- ,-CO- ,-COO- ,- OCO- or-OCOO- replaces, at least one-CH₂CH₂It can replace through-CH=CH- or-C ≡ C-, in these bases, at least one hydrogen It can replace through halogen；

M¹¹And M¹²It independently is the alkane of hydrogen, the carbon number 1 to 5 that halogen, the alkyl of carbon number 1 to 5 or at least one hydrogen replace through halogen Base:

In formula (1-1),

P¹¹For the base in the base represented by the formula (1e) and formula (1f),

In formula (1e) and formula (1f),

Sp¹³For singly-bound or the alkylidene of carbon number 1 to 10, the Sp¹³In, at least one-CH₂Can through-O- ,-NH- ,-CO- ,- COO- ,-OCO- or-OCOO- replace, at least one-CH₂CH₂It can replace through-CH=CH- or-C ≡ C-, in these bases, at least One hydrogen can replace through halogen；

M¹³And M¹⁴It independently is the alkane of hydrogen, the carbon number 1 to 5 that halogen, the alkyl of carbon number 1 to 5 or at least one hydrogen replace through halogen Base；

In formula (1g), formula (1h) and formula (1i),

Sp¹⁴And Sp¹⁵It independently is the alkylidene of singly-bound or carbon number 1 to 10, in the alkylidene, at least one-CH₂Can through- O- ,-NH- ,-CO- ,-COO- ,-OCO- or-OCOO- replace, at least one-CH₂CH₂It can be taken through-CH=CH- or-C ≡ C- Generation, at least one hydrogen can replace through halogen；

-OR¹⁵、-N(R¹⁵)₂And-Si (R¹⁵)₃In,

R¹⁵For hydrogen or the alkyl of carbon number 1 to 10, the R¹⁵In, at least one-CH₂It can replace through-O-, at least one-CH₂CH₂- It can replace through-CH=CH-, in these bases, at least one hydrogen can replace through halogen.

9. the manufacturing method of liquid crystal display element according to claim 8, wherein orientation monomer be selected from formula (1-2) extremely At least one of the group of compound represented by formula (1-3) polymerizable compound.

In formula (1-2) and formula (1-3),

R¹For the alkyl of carbon number 1 to 12, in the alkyl, at least one-CH₂It can replace through-O-, at least one-CH₂CH₂It can Replace through-CH=CH- or-C ≡ C-, in these bases, at least one hydrogen can be fluorine-substituted；

Ring A¹And ring A²It independently is 1,4- cyclohexylidene, 1,4- cyclohexadienylidene, 1,4- phenylene, naphthalene -2,6- diyl, tetrahydro Pyrans -2,5- diyl, 1,3- dioxanes -2,5- diyl, fluorenes -2,7- diyl, phenanthrene -2,7- diyl, perhydro cyclopentano [a] phenanthrene -3, 17- diyl or 2,3,4,7,8,9,10,11,12,13,14,15,16,17- ten tetrahydro cyclopentyls simultaneously [a] phenanthrene -3,17- diyl, this In a little rings, at least one hydrogen can through fluorine, the alkyl of carbon number 1 to 8, the alkenyl of carbon number 2 to 8, carbon number 1 to 7 alkoxy or carbon number 2 to 7 alkenyloxy group replaces, and in these bases, at least one hydrogen can be fluorine-substituted；

A is 0,1,2,3 or 4；

L is 0,1,2,3,4,5 or 6, at least one-CH of the alkylidene₂Can through-O- ,-CO- ,-COO- ,-OCO- or- OCOO- replaces, at least one-CH₂CH₂It can replace through-CH=CH- or-C ≡ C-, in these bases, at least one hydrogen can take through fluorine Generation；

R¹²For hydrogen or the alkyl of carbon number 1 to 5, in the alkyl, at least one-CH₂It can replace through-O- or-S-, at least one- (CH₂)₂It can replace through-CH=CH- or-C ≡ C-, in these bases, at least one hydrogen can be fluorine-substituted；

Sp¹³For singly-bound or the alkylidene of carbon number 1 to 5, in the alkylidene, at least one-CH₂Can through-O- ,-CO- or- COO- replaces, at least one-CH₂CH₂It can replace through-CH=CH- or-C ≡ C-, in these bases, at least one hydrogen can take through fluorine Generation；

Sp¹⁴For singly-bound or the alkylidene of carbon number 1 to 5, in the alkylidene, at least one-CH₂Can through-O- ,-CO- or- COO- replaces, at least one-CH₂CH₂It can replace through-CH=CH- or-C ≡ C-, in these bases, at least one hydrogen can take through fluorine Generation；

X¹For-OH or-N (R¹⁵)₂；

-N(R¹⁵)₂In,

10. the manufacturing method of liquid crystal display element according to claim 8, wherein orientation monomer is selected from formula (1-4) To at least one of the group of compound represented by formula (1-60) polymerizable compound.

Formula (1-4) into formula (1-60),

R¹For the alkyl of carbon number 1 to 10；

Sp¹²、Sp¹³And Sp¹⁴It independently is the alkylidene of singly-bound or carbon number 1 to 5, in the alkylidene, at least one-CH₂It can Replace through-O-；

L is 0,1,2,3,4,5 or 6.

11. the manufacturing method of liquid crystal display element according to any one of claim 1 to 10, wherein the liquid crystal combination Object contains at least one of the group of compound represented by the formula (2) to formula (4) compound in turn.

Formula (2) into formula (4),

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；

12. the manufacturing method of liquid crystal display element according to any one of claim 1 to 11, wherein the liquid crystal combination Object 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 the alkenyl, at least one-CH₂It can Replace through-O-, 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- ,-C ≡ C- ,-COO- ,-CF₂O-、-OCF₂-、-CH₂O-、 Or-(CH₂)₄-；

L¹¹And L¹²It independently is hydrogen or fluorine.

13. the manufacturing method of liquid crystal display element according to any one of claim 1 to 12, wherein the liquid crystal combination Object 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 the alkenyl, at least one-CH₂- It 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- 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.

14. the manufacturing method of liquid crystal display element according to any one of claim 1 to 13, wherein the liquid crystal combination Object contains at least one of the group of compound represented by the formula (9) to formula (15) compound in turn.

Formula (9) into formula (15),

R¹⁷For the alkenyl of hydrogen, fluorine, the alkyl of carbon number 1 to 10 or carbon number 2 to 10, in the alkyl and the 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 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-；

15. according to claim 1 to the manufacturing method of liquid crystal display element described in any one of 14, wherein the liquid crystal combination Object contains polymerizable compound represented by the formula (16 α) as reactive monomer in turn, and to be formed comprising by making These compounds polymerize and the tropism control layer of 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 of carbon number 1 to 12 of at least one hydrogen through fluorine or chlorine substitution 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.

16. the manufacturing method of liquid crystal display element according to claim 15, wherein in formula (16 α), P¹¹、P¹²And P¹³Solely It is on the spot the base in the group of the polymerism base represented by the formula (P-1) to formula (P-5).

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

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.

17. according to claim 1 to the manufacturing method of liquid crystal display element described in any one of 16, wherein the liquid crystal combination Object has negative dielectric anisotropy.

18. according to claim 1 to the manufacturing method of liquid crystal display element described in any one of 17, wherein the tropism control Layer has the film thickness of 10nm to 100nm, and the partial size of the polymer in the tropism control layer is the range of 1nm to 90nm.

19. according to claim 1 to the manufacturing method of liquid crystal display element described in any one of 18, wherein the tropism control The partial size of polymer in layer is the range of 1nm to 70nm.

20. according to claim 1 to the manufacturing method of liquid crystal display element described in any one of 19, wherein the liquid crystal liquid crystal property It is vertical to close being oriented to for the molecule of object, and the angle of the molecule and the substrate is 90 ° ± 10 °.

21. according to claim 1 to the manufacturing method of liquid crystal display element described in any one of 20, wherein the liquid crystal liquid crystal property The orientation of the molecule of conjunction object orientation segmentation according to each pixel.

22. a kind of display device comprising pass through the manufacture of the liquid crystal display element as described in any one of claim 1 to 21 Liquid crystal display element manufactured by method and backlight.