CN108473874A

CN108473874A - Liquid-crystal composition and liquid crystal display element

Info

Publication number: CN108473874A
Application number: CN201780004337.1A
Authority: CN
Inventors: 斋藤将之
Original assignee: JNC Corp; Chisso Petrochemical Corp
Current assignee: JNC Corp; JNC Petrochemical Corp
Priority date: 2016-02-25
Filing date: 2017-01-24
Publication date: 2018-08-31
Also published as: KR20180113188A; TWI719139B; WO2017145611A1; TW201805409A; JPWO2017145611A1

Abstract

The present invention provides a kind of by the polymeric liquid-crystal composition for acting on the vertical orientation that may achieve liquid crystal molecule, the liquid crystal display element containing the composition.The present invention is a kind of nematic liquid-crystal composition, it contains the polar compound at least one polymerism base as the first additive and contains the polymerizable compound at least three polymerism bases as the second additive, and with negative dielectric anisotropy, the composition also contain the specific liquid crystal compounds with the big dielectric anisotropy born as first composition, contain the specific liquid crystal compounds with high ceiling temperature or small viscosity as second composition, and the present invention is a kind of liquid crystal display element containing the composition.

Description

Liquid-crystal composition and liquid crystal display element

Technical field

It is the liquid-crystal composition born, the liquid crystal display member containing the composition the present invention relates to a kind of dielectric anisotropy Part etc..More particularly to a kind of polar compound (or its condensate) containing with polymerism base and polymerizable compound (or institute State condensate) and may achieve by the effect of these compounds liquid crystal molecule vertical orientation liquid-crystal composition and liquid crystal Show element.

Background technology

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 row (twisted nematic, TN), STN Super TN (super twisted nematic, STN), electrically conerolled birefringence (electrically controlled birefringence, ECB), optical compensation curved (optically Compensated bend, OCB), in-plane switching (in-plane switching, IPS), vertical orientation (vertical Alignment, VA), fringing field switching (fringe field switching, FFS), electric field induction light reaction be orientated (field-induced photo-reactive alignment, FPA) isotype.Type of drive based on element is classified as Passive matrix (passive matrix, PM) and active matrix (active matrix, AM).PM is classified as static type (static) with multiplexing 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 non-crystalline silicon (amorphous silicon) and polysilicon (polycrystal silicon).The latter is classified as high temperature according to manufacturing step Type and low form.Based on light source be classified as using natural light reflection-type, using backlight infiltration type and utilize 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, the AM elements with superperformance are can get.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 elements.Nematic temperature range and element Workable temperature range is associated.Nematic preferred upper limit 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 is associated with the response time of element.In order to show dynamic image with element, Preferably the response time is short.Preferably it is shorter than 1 millisecond of response time.It is therefore preferable that the viscosity for composition is small.More preferably Viscosity under low temperature is small.

The characteristic of table 1. composition and AM elements

The optical anisotropy of composition is with the contrast of element than associated.According to the pattern of element, and need big Optical anisotropy or small optical anisotropy, i.e., optical anisotropy appropriate.Optical anisotropy (the Δ n) of composition It is designed to that contrast ratio is made to be maximum with the product (Δ n × d) of the cell gap (d) of element.The value of product appropriate depends on fortune The type of operation mode.In the element of VA patterns, the range that described value is about 0.30 μm to about 0.40 μm, IPS patterns or FFS mode Element in, range that described value is about 0.20 μm to about 0.30 μm.It is excellent for the element small to cell gap in the case of these It is selected as with big optically anisotropic composition.The big dielectric anisotropy of composition contributes to the low threshold in element electric Pressure, small consumption electric power and big contrast ratio.It is therefore preferable that being big dielectric anisotropy.The big specific resistance of composition Contribute to the big voltage retention of element and big contrast ratio.It is therefore preferable that in the starting stage not only at room temperature, And also there is the composition of big specific resistance at a temperature of close to nematic ceiling temperature.Preferably make for a long time With rear, not only at room temperature, but also the also combination with big specific resistance at a temperature of close to nematic ceiling temperature Object.Composition is associated with the service life of element to the stability of ultraviolet light or heat.When the stability is high, the service life of element It is long.Such characteristic is preferred for the AM elements for liquid crystal projection apparatus, LCD TV etc..

In general liquid crystal display element, the vertical orientation of liquid crystal molecule can be reached using specific alignment film of polyimide At.Polymer stabilizing is orientated in the liquid crystal display element of (polymer sustained alignment, PSA) type, is fully made With polymeric effect.First, the composition added with a small amount of polymerizable compound is injected into element.Then, right on one side Apply voltage between the substrate of the element, ultraviolet light is irradiated to composition on one side.Polymerizable compound is polymerize and in group It closes in object and generates polymeric reticular structure.In the composition, the orientation of liquid crystal molecule can be controlled using condensate, thus it is first The response time of part shortens, and the image retention of image is improved.Pattern with TN, ECB, OCB, IPS, VA, FFS, FPA etc It can be expected that polymeric such effect in element.

On the other hand, do not have in the liquid crystal display element of alignment films using containing condensate and without polymerism base The liquid-crystal composition of polar compound.First, by the composition added with a small amount of polymerizable compound and a small amount of polar compound It is injected into element.Herein, polar compound is adsorbed in substrate surface and is arranged.Liquid crystal molecule takes according to the arrangement To.Then, apply voltage between the substrate of the element on one side, ultraviolet light is irradiated to composition on one side.Herein, polymerism It closes object to be polymerize, and the orientation of liquid crystal molecule is made to stabilize.In the composition, can using condensate and polar compound come The orientation of liquid crystal molecule is controlled, therefore the response time of element shortens, the image retention of image is improved.In turn, do not have alignment films Element in the step of need not forming alignment films.Since there is no alignment films, therefore utilize the phase interaction of alignment films and composition With the resistance of element will not reduce.It can be expected that profit in the element of pattern with TN, ECB, OCB, IPS, VA, FFS, FPA etc With such effect of the combination of condensate and polar compound.

The composition with positive dielectric anisotropy is used in AM elements with TN patterns.AM members with VA patterns The composition with negative dielectric anisotropy is used in part.Use is with just in AM elements with IPS patterns or FFS mode Or the composition of negative dielectric anisotropy.In the AM elements of polymer stabilizing orientating type using have positive or negative dielectric respectively to Anisotropic composition.The example of liquid-crystal composition with negative dielectric anisotropy is disclosed in patent document 1 below to special In sharp document 6.In the present invention, by with polymerism base polar compound (or its condensate) and polymerizable compound (or The condensate) it is combined with liquid crystal compounds, and the composition is used for the liquid crystal display element without alignment films.

Existing technical literature

Patent document

Patent document 1：No. 2014/090362 specification of International Publication No.

Patent document 2：No. 2014/094959 specification of International Publication No.

Patent document 3：No. 2013/004372 specification of International Publication No.

Patent document 4：No. 2012/104008 specification of International Publication No.

Patent document 5：No. 2012/038026 specification of International Publication No.

Patent document 6：Japanese Patent Laid-Open No. Sho 50-35076 bulletins

Invention content

Problem to be solved by the invention

One object of the present invention is a kind of polar compound (or described condensate) containing with polymerism base and gathers The liquid-crystal composition of conjunction property compound (or described condensate), herein, polar compound and polymerizable compound has and liquid crystal The high compatibility of property compound.Another object is a kind of poly- by being generated by the polar compound and polymerizable compound Fit effect may achieve the liquid-crystal composition of the vertical orientation of liquid crystal molecule.Another object is a kind of liquid-crystal composition, The dielectric that nematic ceiling temperature is high, nematic lower limit temperature is low, viscosity is small, optical anisotropy is appropriate, negative is respectively to different Property the characteristics such as big, specific resistance is big, stability height high to the stability of ultraviolet light, to heat in, meet at least one characteristic.It is another Purpose is a kind of liquid-crystal composition with appropriate balance between at least two characteristics.Another object is that one kind containing described group Close the liquid crystal display element of object.A further object is a kind of with the response time is short, voltage retention is big, starting voltage is low, contrast Than the AM elements of the characteristics such as big, long lifespan.

Technical means to solve problem

Containing the polar compound at least one polymerism base the present invention relates to a kind of as the first additive and contain There is the polymerizable compound at least three polymerism bases as the second additive, and with negative dielectric anisotropy Liquid-crystal composition, and the liquid crystal display element containing the composition.

The effect of invention

An advantage of the invention is a kind of polar compound (or described condensate) containing with polymerism base and gathers The liquid-crystal composition of conjunction property compound (or described condensate), herein, polar compound and polymerizable compound has and liquid crystal The high compatibility of property compound.Another advantage is a kind of poly- by being generated by the polar compound and polymerizable compound Fit effect may achieve the liquid-crystal composition of the vertical orientation of liquid crystal molecule.Another advantage is a kind of liquid-crystal composition, The dielectric that nematic ceiling temperature is high, nematic lower limit temperature is low, viscosity is small, optical anisotropy is appropriate, negative is respectively to different Property the characteristics such as big, specific resistance is big, stability height high to the stability of ultraviolet light, to heat in, meet at least one characteristic.It is another Advantage is a kind of liquid-crystal composition with appropriate balance between at least two characteristics.Another advantage is that one kind containing described group Close the liquid crystal display element of object.Another advantage is a kind of with the response time is short, voltage retention is big, starting voltage is low, contrast Than the AM elements of the characteristics such as big, long lifespan.

Specific implementation mode

The application method of term in the specification is as described below.Sometimes by " liquid-crystal composition " and " liquid crystal display member The term of part " is briefly referred to as " composition " and " element "." liquid crystal display element " is liquid crystal display panel and liquid crystal display mode The general name of block." liquid crystal compounds " are the compounds for having the liquid crystalline phases such as nematic phase, smectic phase, though and without liquid crystalline phase But it is mixed in composition for the purpose for the characteristic for adjusting nematic temperature range, viscosity, dielectric anisotropy etc Compound general name.The compound has the hexatomic ring of such as 1 or 4 cyclohexylidene or Isosorbide-5-Nitrae-phenylene etc, molecule Structure is rodlike (rod like)." polymerizable compound " is for the change that makes to generate polymeric purpose in composition and add Close object.Liquid crystal compounds with alkenyl are not polymerism in terms of its meaning.

Liquid-crystal composition is prepared by mixing plurality of liquid crystals compound.It is regarded in the liquid-crystal composition Addition optically active compound, antioxidant, ultra-violet absorber, pigment, antifoaming agent, polymerizable compound, polymerization is needed to draw Send out the additive of agent, polymerization inhibitor, polar compound etc.Liquid crystal compounds or additive are mixed with the sequence.I.e. Just added with additive, the ratio (content) of liquid crystal compounds is also by based on the liquid crystal not comprising additive The weight percent (weight %) of the weight of composition indicates.The ratio (additive amount) of additive is by being based on not including addition The weight percent (weight %) of the weight of the liquid-crystal composition of object indicates.Sometimes parts per million by weight (ppm) is used.Polymerization The ratio of initiator and polymerization inhibitor is exceptionally to be indicated based on the weight of polymerizable compound.

Sometimes " nematic ceiling temperature " is referred to as " ceiling temperature ".Sometimes referred to as by " nematic lower limit temperature " For " lower limit temperature "." specific resistance is big " refer to composition in the starting stage not only at room temperature, but also close to upper limit temperature Also there is big specific resistance, and after prolonged use not only at room temperature at a temperature of degree, but also close to upper limit temperature Also there is big specific resistance at a temperature of degree." voltage retention is big " be finger element in the starting stage not only at room temperature, and And also there is big voltage retention at a temperature of close to ceiling temperature, and after prolonged use not only in room temperature Under, and also there is big voltage retention at a temperature of close to ceiling temperature.In composition or element, sometimes through when Variation experiment (including activated deterioration test) is front and back to study characteristic." improving dielectric anisotropy " is expressed in dielectric anisotropy For positive composition when, refer to that its value positively increases, when dielectric anisotropy is negative composition, refer to its value negatively Increase.

Sometimes the compound represented by formula (1) is referred to as " compound (1) ".Sometimes the change represented by formula (1) will be selected from It closes at least one of the group of object compound and is referred to as " compound (1) "." compound (1) " refers to one represented by formula (1) The mixture of the compound of kind of compound, the mixture of two kinds of compounds or three kinds or more.About the chemical combination represented by other formulas Object is also identical.The statement of " at least one ' A " ' refers to that the quantity of ' A ' is arbitrary.The table of " at least one ' A ' can replace through ' B ' " It refers to when the quantity of ' A ' is one to state, and the position of ' A ' is arbitrary, when the quantity of ' A ' is more than two, their position Can also unlimitedly it select.The rule applies also for the statement of " at least one ' A ' replaces through ' B ' ".

" at least one-CH₂Can replace through-O- " etc be expressed in the specification and use.In the case of described ,- CH₂-CH₂-CH₂Not adjacent-CH can be passed through₂Warp-O- replaces and is converted to-O-CH₂-O-.However, adjacent-CH₂It will not Replace through-O-.This is because generation-O-O-CH in the substitution₂(peroxide).That is, the statement refers to "-a CH₂- Can replace through-O- " and " at least two-CH not abutted₂Both can replace through-O- ".The rule is applicable not only to replace For-O- the case where, the case where applying also for being substituted by the bilvalent radical such as-CH=CH- or-COO- etc.In alkyl, sometimes at least One-CH₂Cycloalkylidene substitution through carbon number 3 to 8.The carbon number of alkyl is increased by the substitution.At this point, maximum carbon Number is 30.The rule is applicable not only to the monad radical of alkyl etc, applies also for the bilvalent radical of alkylidene etc.

In the chemical formula of component cpd, by terminal groups R¹Mark be used for multiple compounds.In these compounds, arbitrarily Two R¹Two represented bases can be identical, or also can be different.For example, there is the R of compound (1-1)¹For ethyl, and chemical combination The R of object (1-2)¹For ethyl the case where.Also there is the R of compound (1-1)¹For ethyl, and the R of compound (1-2)¹For the feelings of propyl Condition.The rule is suitable for other marks.In formula (1), when a is 2, there are two ring A.In the compound, two ring A institutes tables Two rings shown can be identical, or also can be different.The rule is also applied for any two ring As of a more than 2 when.The rule Suitable for other marks.The rule is also applied for two-Sp of compound (5-7)¹¹-P⁵Etc the case where.

The marks such as A, B, C, D surrounded with hexagon are correspondings with the rings such as ring A, ring B, ring C, ring D respectively, expression hexatomic ring, The rings such as condensed ring.In formula (3), the crosscutting oblique line of the hexagon is indicated that the arbitrary hydrogen on ring can be through-Sp¹-P¹Equal bases substitution. Subscripts such as ' k ' indicate the quantity for the base being substituted.When subscript ' k ' is 0, such substitution is not present.It is 2 or more in subscript ' k ' When, there are multiple-Sp on ring J¹-P¹。-Sp¹-P¹Represented multiple bases can be identical, or also can be different." ring A and ring C are only Be on the spot X, Y or Z " statement in, since subject is multiple, therefore use " independently ".When subject is " ring A ", due to subject For odd number, therefore " independently " is not used.When " ring A " in multiple formulas in use, the rule of " can be identical, or also can be different " is suitable For " ring A ".It is also the same for other bases.

Fluoro- Isosorbide-5-Nitrae-the phenylenes of 2- refer to following two kinds of bilvalent radicals.In chemical formula, fluorine can be or to be alternatively towards left (L) Towards right (R).It is non-that the rule applies also for being generated by removing two hydrogen from ring for oxinane -2,5- diyl etc Symmetrical bilvalent radical.The rule applies also for the divalent bond base of carbonyloxy group (- COO- or-OCO-) etc.

The alkyl of liquid crystal compounds is straight-chain or branch-like, does not include cyclic alkyl.Straight-chain alkyl is better than dividing Branch shape alkyl.These situations are also identical for terminal groups such as alkoxy, alkenyls.In order to improve ceiling temperature, with Isosorbide-5-Nitrae-Asia hexamethylene The relevant spatial configuration of base is that anti-configuration is better than cis-configuration.

The present invention is following items etc..

A kind of 1. liquid-crystal compositions of item contain the polar compound at least one polymerism base as the first addition Object and contain the polymerizable compound at least three polymerism bases as the second additive, and with negative dielectric respectively to It is anisotropic.

Liquid-crystal composition of the item 2. according to item 1, contains in the group selected from the compound represented by formula (1) extremely A kind of few compound as first composition,

In formula (1), R¹And R²It independently is the alkene of the alkyl of carbon number 1 to 12, the alkoxy of carbon number 1 to 12, carbon number 2 to 12 The alkenyl for the carbon number 2 to 12 that base, at least one hydrogen replace through fluorine or chlorine or the alkenyloxy group of carbon number 2 to 12；Ring A and ring C are independent Ground be 1 or 4 cyclohexylidene, Isosorbide-5-Nitrae-cyclohexadienylidene, oxinane -2,5- diyl, Isosorbide-5-Nitrae-phenylene, at least one hydrogen through fluorine or Naphthalene -2,6- diyl that Isosorbide-5-Nitrae-phenylene, naphthalene -2,6- diyl, at least one hydrogen of chlorine substitution replace through fluorine or chlorine, chromogen alkane -2, Chromogen alkane -2,6- diyl that 6- diyls or at least one hydrogen replace through fluorine or chlorine；Ring B be 2,3-, bis- fluoro- Isosorbide-5-Nitrae-phenylenes, Fluoro- Isosorbide-5-Nitrae-the phenylenes of the chloro- 3- of 2-, 2,3-, bis- fluoro- 5- methyl-1s, 4- phenylenes, 3,4,5- tri- fluoronaphthalene -2,6- diyls or 7,8- bis- Fluorine chromogen alkane -2,6- diyl；Z¹And Z²It independently is singly-bound ,-CH₂CH₂-、-CH₂O-、-OCH₂,-COO- or-OCO-；A is 1,2 Or 3, b is 0 or 1, and the sum of a and b are 3 or less.

3. liquid-crystal composition according to item 1 or item 2 contains represented by the formula (1-1) to formula (1-22) At least one of group of compound compound as first composition,

In formula (1-1) to formula (1-22), R¹And R²It independently is the alkyl of carbon number 1 to 12, the alkoxy of carbon number 1 to 12, carbon The alkenyl for the carbon number 2 to 12 that the alkenyl of number 2 to 12, at least one hydrogen replace through fluorine or chlorine or the alkenyloxy group of carbon number 2 to 12.

Liquid-crystal composition of the item 4. according to any one of item 1 to item 3, wherein the weight based on liquid-crystal composition, the The ratio of one ingredient is the range of 10 weight % to 90 weight %.

5. liquid-crystal composition according to any one of item 1 to item 4 contains the chemical combination represented by the formula (2) At least one of group of object compound as second composition,

In formula (2), R³And R⁴It independently is the alkene of the alkyl of carbon number 1 to 12, the alkoxy of carbon number 1 to 12, carbon number 2 to 12 The carbon number 2 that the alkyl or at least one hydrogen for the carbon number 1 to 12 that base, at least one hydrogen replace through fluorine or chlorine replace through fluorine or chlorine To 12 alkenyl；Ring D and ring E independently is the fluoro- Isosorbide-5-Nitrae-phenylene of 1 or 4 cyclohexylidene, Isosorbide-5-Nitrae-phenylene, 2- or 2, and 5- bis- is fluoro- Isosorbide-5-Nitrae-phenylene；Z³For singly-bound ,-CH₂CH₂-、-CH₂O-、-OCH₂,-COO- or-OCO-；C is 1,2 or 3.

Liquid-crystal composition of the item 6. according to any one of item 1 to item 5, contains selected from formula (2-1) to formula (2-13) At least one of represented group of compound compound as second composition,

In formula (2-1) to formula (2-13), R³And R⁴It independently is the alkyl of carbon number 1 to 12, the alkoxy of carbon number 1 to 12, carbon The alkyl or at least one hydrogen for the carbon number 1 to 12 that the alkenyl of number 2 to 12, at least one hydrogen replace through fluorine or chlorine are through fluorine or chlorine The alkenyl of substituted carbon number 2 to 12.

Liquid-crystal composition of the item 7. according to item 5 or item 6, wherein the weight based on liquid-crystal composition, second composition Ratio is the range of 10 weight % to 70 weight %.

8. liquid-crystal composition according to any one of item 1 to item 7, wherein the first additive be with selected from nitrogen, Heteroatomic polar compound in oxygen, sulphur and phosphorus.

Liquid-crystal composition of the item 9. according to any one of item 1 to item 8 contains represented selected from formula (3) and formula (4) At least one of the group of polar compound compound as the first additive,

In formula (3), R⁷For the alkyl of hydrogen, fluorine, chlorine or carbon number 1 to 25, in the alkyl, at least one-CH₂Can through- NR⁰,-O- ,-S- ,-CO- ,-CO-O- ,-O-CO- ,-O-CO-O- or carbon number 3 to 8 cycloalkylidene substitution, and it is at least one Tertiary carbon (＞ CH-) can replace through nitrogen (＞ N-), and in these bases, at least one hydrogen can replace through fluorine or chlorine, herein, R⁰For hydrogen or The alkyl of carbon number 1 to 12；R⁸Sulphur atom and level-one, two level or tertiary amine group for oxygen atom, SH structures with OH structures At least one of nitrogen-atoms polar group；Ring J, ring K and ring L independently be 1 or 4 cyclohexylidene, Isosorbide-5-Nitrae-cyclohexadienylidene, Isosorbide-5-Nitrae-phenylene, naphthalene -1,2- diyl, naphthalene -1,3- diyl, naphthalene-Isosorbide-5-Nitrae-diyl, naphthalene -1,5- diyl, naphthalene -1,6- diyl, naphthalene -1, 7- diyls, naphthalene -1,8- diyl, naphthalene -2,3- diyl, naphthalene -2,6- diyl, naphthalene -2,7- diyl, oxinane -2,5- diyl, 1,3- Dioxane -2,5- diyl, pyrimidine -2,5- diyl or pyridine -2,5- diyl, in these rings, at least one hydrogen can be through fluorine, 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；Z⁷And Z⁸It 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- substitutions, and at least one-CH₂CH₂It 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；P¹、P²And P³For polymerization Property base；Sp¹、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- ,-COO- ,-OCO- or-OCOO-, and at least one-CH₂CH₂It can replace through-CH=CH- or-C ≡ C-, this In a little bases, at least one hydrogen can replace through fluorine or chlorine；G and h independently is 0,1,2,3 or 4, and the sum of g and h are 0,1,2,3 Or 4；K and p independently is 0,1,2,3 or 4, o 1,2,3 or 4；

In formula (4), R⁹For hydrogen, the alkene of fluorine, chlorine, the alkyl of carbon number 1 to 12, the alkoxy of carbon number 1 to 12, carbon number 2 to 12 The carbon number 2 that the alkyl or at least one hydrogen for the carbon number 1 to 12 that base, at least one hydrogen replace through fluorine or chlorine replace through fluorine or chlorine To 12 alkenyl；R¹⁰For-OH ,-OR⁰、-NH₂、-NHR⁰Or-N (R⁰)₂Represented base, herein, R⁰For hydrogen or carbon number 1 to 12 Alkyl；Ring M and ring N independently is 1 or 4 cyclohexylidene, Isosorbide-5-Nitrae-cyclohexadienylidene, Isosorbide-5-Nitrae-phenylene, naphthalene -1,2- diyl, naphthalene -1, 3- diyls, naphthalene-Isosorbide-5-Nitrae-diyl, naphthalene -1,5- diyl, naphthalene -1,6- diyl, naphthalene -1,7- diyl, naphthalene -1,8- diyl, naphthalene -2,3- bis- Base, naphthalene -2,6- diyl, naphthalene -2,7- diyl, oxinane -2,5- diyl, 1,3- dioxanes -2,5- diyl, pyrimidine -2,5- bis- Base, pyridine -2,5- diyl, fluorenes -2,7- diyl, phenanthrene -2,7- diyl or anthracene -2,6- diyl, in these rings, at least one hydrogen can be through The carbon number 1 to 12 that fluorine, chlorine, the alkyl of carbon number 1 to 12, the alkoxy of carbon number 1 to 12 or at least one hydrogen replace through fluorine or chlorine Alkyl substitution；Z⁹For singly-bound ,-CH₂CH₂,-CH=CH- ,-C ≡ C- ,-COO- ,-OCO- ,-CF₂O-、-OCF₂-、-CH₂O-、- OCH₂Or-CF=CF-；Sp⁴And Sp⁵It independently is the alkylidene of singly-bound or carbon number 1 to 7, in the alkylidene, at least one- CH₂It can replace through-O- ,-COO- or-OCO-, at least one-CH₂CH₂It can replace through-CH=CH-, in these bases, at least one A hydrogen can be fluorine-substituted；J is 0,1,2,3 or 4.

10. liquid-crystal composition according to item 9, wherein in formula (3) according to item 9, R⁸To be selected from formula (A1) Base into the group of the polar group represented by formula (A4),

In formula (A1) to formula (A4), Sp⁶、Sp⁸And Sp⁹It independently is the alkylidene of singly-bound or carbon number 1 to 12, the alkylene In base, at least one-CH₂It can be through-O- ,-S- ,-NH- ,-N (R⁰)-、-CO-、-CO-O-、-O-CO、-O-CO-O-、-S-CO-、- CO-S-、-N(R⁰)-CO-O-、-O-CO-N(R⁰)-、-N(R⁰)-CO-N(R⁰- CH=CH- or-C ≡ C- substitutions)-, these bases In, at least one hydrogen can replace through fluorine or chlorine, herein, R⁰For hydrogen or the alkyl of carbon number 1 to 12；Sp⁷For ＞ CH-, ＞ CR⁰, ＞ N- or ＞ C ＜, herein, R⁰For hydrogen or the alkyl of carbon number 1 to 12；X¹⁷For-OH ,-OR⁰、-COOH、-NH₂、-NHR⁰、-N(R⁰)₂、- SH、-SR⁰、

Herein, R⁰For hydrogen or the alkyl of carbon number 1 to 12；X¹⁸For-O- ,-CO- ,-NH- ,-NR⁰,-S- or singly-bound, herein, R⁰ For hydrogen or the alkyl of carbon number 1 to 12；Z¹⁰For singly-bound or the alkylidene of carbon number 1 to 15, in the alkylidene, at least one-CH₂- It can replace through-C ≡ C- ,-CH=CH- ,-COO- ,-OCO- ,-CO- or-O-, in these bases, at least one hydrogen can take through fluorine or chlorine Generation；Ring P is the aryl of carbon number 6 to 25, and in the aryl, one to three hydrogen can be through-OH ,-(CH₂)_q- OH, fluorine, chlorine, carbon number 1 The alkyl of the carbon number 1 to 5 replaced to 5 alkyl or at least one hydrogen through fluorine or chlorine replaces, herein, q 1,2,3 or 4；N is 0,1,2 or 3；M is 1,2,3,4 or 5.

11. liquid-crystal composition according to item 9, wherein in formula (3) according to item 9, P¹、P²And P²Independently For the base in the group for the polymerism base being selected from represented by formula (P-1) to formula (P-5),

In formula (P-1) to formula (P-5), M¹、M²And M³It independently is hydrogen, fluorine, the alkyl of carbon number 1 to 5 or at least one The alkyl for the carbon number 1 to 5 that hydrogen replaces through fluorine or chlorine.

Liquid-crystal composition of the item 12. according to any one of item 1 to item 11, wherein the first additive is selected from formula (3- 1) at least one of the group of polar compound represented by formula (3-15) compound,

In formula (3-1) to formula (3-15), R⁷For the alkyl of hydrogen, fluorine, chlorine or carbon number 1 to 25, in the alkyl, at least one A-CH₂It can be through-NR⁰,-O- ,-S- ,-CO- ,-CO-O- ,-O-CO- ,-O-CO-O- or carbon number 3 to 8 cycloalkylidene substitution, And at least one tertiary carbon (＞ CH-) can replace through nitrogen (＞ N-), and in these bases, at least one hydrogen can replace through fluorine or chlorine, Herein, R⁰For hydrogen or the alkyl of carbon number 1 to 12；Sp²For singly-bound or the alkylidene of carbon number 1 to 10, in the alkylidene, at least one A-CH₂It can replace through-O- ,-COO- ,-OCO- or-OCOO-, and at least one-CH₂CH₂It can be through-CH=CH- or-C ≡ C- replaces, and in these bases, at least one hydrogen can replace through fluorine or chlorine；Sp¹⁰For singly-bound or the alkylidene of carbon number 1 to 10, the Asia In alkyl, at least one-CH₂It can replace through-O- ,-COO- ,-OCO- or-OCOO-, and at least one-CH₂CH₂Can through- CH=CH- or-C ≡ C- replace, and in these bases, at least one hydrogen can replace through fluorine or chlorine；L¹、L²、L³And L⁴Independently be hydrogen, Fluorine, methyl or ethyl；R¹¹And R¹²It independently is hydrogen or methyl.

Liquid-crystal composition of the item 13. according to any one of item 1 to item 12, wherein the first additive is selected from formula (4- 1) at least one of the group of polar compound represented by formula (4-9) compound,

In formula (4-1) to formula (4-9), R⁹For hydrogen, fluorine, chlorine, the alkyl of carbon number 1 to 12, the alkoxy of carbon number 1 to 12, carbon The alkyl or at least one hydrogen for the carbon number 1 to 12 that the alkenyl of number 2 to 12, at least one hydrogen replace through fluorine or chlorine are through fluorine or chlorine The alkenyl of substituted carbon number 2 to 12；Z⁹For singly-bound ,-CH₂CH₂,-CH=CH- ,-C ≡ C- ,-COO- ,-OCO- ,-CF₂O-、- OCF₂-、-CH₂O-、-OCH₂Or-CF=CF-；Sp⁴And Sp⁵It independently is the alkylidene of singly-bound or carbon number 1 to 7, the alkylidene In, at least one-CH₂It can replace through-O- ,-COO- or-OCO-, at least one-CH₂CH₂It can replace through-CH=CH-, these In base, at least one hydrogen can be fluorine-substituted；L⁵、L⁶、L⁷、L⁸、L⁹、L¹⁰、L¹¹、L¹²、L¹³、L¹⁴、L¹⁵And L¹⁶Independently be hydrogen, fluorine, Methyl or ethyl.

Liquid-crystal composition of the item 14. according to any one of item 1 to item 13, wherein the weight based on liquid-crystal composition, The ratio of first additive is the range of 0.05 weight % to 10 weight %.

15. liquid-crystal composition according to any one of item 1 to item 14 contains poly- represented by the formula (5) At least one of the group compound of conjunction property compound as the second additive,

In formula (5), ring T and ring V independently are cyclohexyl, cyclohexenyl group, phenyl, 1- naphthalenes, 2- naphthalenes, oxinane- 2- bases, 1,3- dioxane -2- bases, pyrimidine -2-base or pyridine -2- bases, 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； Ring U is 1 or 4 cyclohexylidene, Isosorbide-5-Nitrae-cyclohexadienylidene, Isosorbide-5-Nitrae-phenylene, naphthalene -1,2- diyl, naphthalene -1,3- diyl, naphthalene-Isosorbide-5-Nitrae-two Base, 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 pyridine -2,5- bis- Base, 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 one The alkyl for the carbon number 1 to 12 that a hydrogen replaces through fluorine or chlorine replaces；Z¹¹And Z¹²It 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-, and at least one-CH₂CH₂It can Through-CH=CH- ,-C (CH₃)=CH- ,-CH=C (CH₃)-or-C (CH₃)=C (CH₃)-replace, in these bases, at least one hydrogen It can replace through fluorine or chlorine；P⁴、P⁵And P⁶For polymerism base；Sp¹⁰、Sp¹¹And Sp¹²It independently is the alkylene of singly-bound or carbon number 1 to 10 Base, in the alkylidene, at least one-CH₂It can replace through-O- ,-COO- ,-OCO- or-OCOO-, and at least one- CH₂CH₂It can replace through-CH=CH- or-C ≡ C-, in these bases, at least one hydrogen can replace through fluorine or chlorine；T is 0,1 or 2；u、 V and w independently is 0,1,2,3 or 4, and the sum of u, v and w are 3 or more.

16. liquid-crystal composition according to item 15, wherein in formula (5) according to item 15, P⁴、P⁵And P⁶It is independent Ground is the base in the group selected from the polymerism base represented by formula (P-1) to formula (P-5),

Liquid-crystal composition of the item 17. according to any one of item 1 to item 16, contains selected from formula (5-1) to formula (5-7) At least one of represented group of polymerizable compound compound as the second additive,

In formula (5-1) to formula (5-7), P⁴、P⁵And P⁶It independently is the polymerism being selected from represented by formula (P-1) to formula (P-3) Base in the group of base,

Herein, M¹、M²And M³Hydrogen, fluorine, the alkyl of carbon number 1 to 5 or at least one hydrogen independently is through fluorine or chlorine to replace Carbon number 1 to 5 alkyl；Sp¹⁰、Sp¹¹And Sp¹²It 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-, and at least one-CH₂CH₂Can through-CH=CH- or- C ≡ C- replace, and in these bases, at least one hydrogen can replace through fluorine or chlorine.

Liquid-crystal composition of the item 18. according to any one of item 15 to item 17, wherein the weight based on liquid-crystal composition, The ratio of second additive is the range of 0.03 weight % to 10 weight %.

19. a kind of liquid crystal display elements of item, containing the liquid-crystal composition described in any one of with good grounds item 1 to item 18.

20. liquid crystal display element according to item 19, the wherein operating mode of liquid crystal display element be IPS patterns, VA patterns, FFS mode or FPA patterns, and the type of drive of liquid crystal display element is active matrix mode.

21. a kind of liquid crystal display elements of polymer stabilizing orientating type of item, containing with good grounds item 1 to any one of item 18 institute The liquid-crystal composition stated, and the first additive in the liquid-crystal composition and the second additive are polymerize.

22. a kind of liquid crystal display elements without alignment films of item, described in any one of with good grounds item 1 to item 18 Liquid-crystal composition, and the first additive in the liquid-crystal composition and the second additive are polymerize.

A kind of purposes of 23. liquid-crystal compositions according to any one of item 1 to item 18 of item is used for liquid crystal display member In part.

A kind of purposes of 24. liquid-crystal compositions according to any one of item 1 to item 18 of item, is used for polymer stabilizing In the liquid crystal display element of orientating type.

A kind of purposes of 25. liquid-crystal compositions according to any one of item 1 to item 18 of item is used to not have orientation In the liquid crystal display element of film.

The invention also includes the following termss.(a) manufacturing method of liquid crystal display element, by by above-mentioned liquid-crystal composition It is configured between two pieces of substrates, irradiation light in the state of applying voltage to the composition makes contained in the composition The compound with polymerism base polymerize, to manufacture above-mentioned liquid crystal display element.(b) above-mentioned liquid-crystal composition, to The ceiling temperature of row phase is 70 DEG C or more, and the optical anisotropy (being measured at 25 DEG C) under wavelength 589nm is 0.08 or more, and And the dielectric anisotropy (being measured at 25 DEG C) under frequency 1kHz is -2 or less.

The invention also includes the following termss.(c) above-mentioned composition, although Japanese Patent Laid-Open 2006-199941 bulletins Described in compound (5) to compound (7) be dielectric anisotropy be positive liquid crystal compounds, but above-mentioned composition contains At least one of group selected from these compounds compound.(d) above-mentioned group containing at least two above-mentioned polar compounds Close object.(e) also contain the above-mentioned composition of the polar compound different from above-mentioned polar compound.(f) above-mentioned composition contains A kind of, two kinds or at least three kinds optically active compounds, antioxidant, ultra-violet absorber, pigment, antifoaming agent, polymerisms Close the additive of object, polymerization initiator, polymerization inhibitor, polar compound etc.The additive can with the first additive or Second additive is identical, or also can be different.(g) the AM elements containing above-mentioned composition.(h) contain above-mentioned composition, and Element with TN patterns, ecb mode, ocb mode, IPS patterns, FFS mode, VA patterns or FPA patterns.(i) contain above-mentioned The infiltration type element of composition.(j) above-mentioned composition is used as to have nematic composition.(k) by above-mentioned composition Middle addition optically active compound and as the purposes of optical activity composition.

The composition of the present invention is illustrated in the following order.First, the composition of composition is illustrated.Second, Key property and the compound to component cpd are illustrated to the main effect that composition is brought.Third, to group The combination of ingredient in object, the preferred proportion of ingredient and its basis is closed to illustrate.4th, to the preferred shape of component cpd State illustrates.5th, preferred component cpd is shown.6th, pair additive that can be made an addition in composition illustrates. 7th, the synthetic method of component cpd is illustrated.Finally, the purposes of composition is illustrated.

First, the composition of composition is illustrated.The composition of the present invention is classified as composition A and composition B.Group Object A is closed other than containing the liquid crystal compounds being selected from compound (1) and compound (2), also can also contain other liquid crystal Property compound, additive etc.." other liquid crystal compounds " are the liquid crystal liquid crystal property chemical combination different from compound (1) and compound (2) Object.Such compound is mixed in composition for the purpose of further adjustment characteristic.Additive is optical activity chemical combination Object, antioxidant, ultra-violet absorber, pigment, antifoaming agent, polymerizable compound, polymerization initiator, polymerization inhibitor, polarity Compound etc..

Composition B substantially only includes the liquid crystal compounds in compound (1) and compound (2)." substantial " Though additive can be contained by referring to composition, other liquid crystal compounds are free of.Compared with composition A, the ingredient of composition B Quantity is few.In terms of reducing costs, composition B is better than composition A.Can by mix other liquid crystal compounds come Further for the viewpoint of adjustment characteristic, composition A is better than composition B.

Second, the main effect that key property and the compound to component cpd are brought to the characteristic of composition Fruit illustrates.Based on the effect of the present invention, the key property of component cpd is summarized in table 2.In the mark of table 2, L is Refer to big or height, M refers to moderate, and S refers to small or low.Mark L, M, S are based on the qualitative comparison between component cpd Classification, mark 0 refer to that value is zero, or close to zero.

The characteristic of 2. liquid crystal compounds of table

Characteristic	Compound (1)	Compound (2)
			Ceiling temperature	S~L	S~L
Viscosity	M~L	S~M
			Optical anisotropy	M~L	S~L
Dielectric anisotropy	M~L¹)	0
			Specific resistance	L	L

1) negative dielectric anisotropy

When component cpd is mixed in composition, main effect that component cpd is brought to the characteristic of composition It is as described below.Compound (1) improves dielectric anisotropy.Compound (2) improves ceiling temperature, or reduces viscosity.Chemical combination Object (3) and compound (4) are adsorbed in substrate surface by the effect of polar group, and control the orientation of liquid crystal molecule.In order to obtain Desired effect is obtained, these compounds there must be the high compatibility with liquid crystal compounds.These compounds have 1, The hexatomic ring of 4- cyclohexylidenes or Isosorbide-5-Nitrae-phenylene etc, and its molecular structure is rodlike, therefore it is most suitable for the purpose.Compound (5) it is to be made an addition in composition for the purpose for the element for being suitable for polymer stabilizing orientating type in turn.Compound (3) is changed It closes object (4) and compound (5) assigns condensate by polymerization.The condensate due to making the orientation of liquid crystal molecule stabilize, Therefore shorten the response time of element, and improve the image retention of image.

Third illustrates the combination of the ingredient in composition, the preferred proportion of ingredient and its basis.In composition Ingredient preferably be combined as compound (1)+compound (2).It is (or described by combining polar compound in the composition Condensate) and polymerizable compound (or described condensate) may achieve the vertical orientation of liquid crystal molecule." other liquid crystal liquid crystal property chemical combination Object " even if making an addition in the composition, also may achieve identical effect if a small amount of.

In order to improve dielectric anisotropy, compound (1) is preferably in a proportion of about 10 weight % or more, viscous in order to reduce Degree, compound (1) are preferably in a proportion of about 90 weight % or less.More preferable ratio is models of the about 15 weight % to about 80 weight % It encloses.Particularly preferred ratio is ranges of the about 20 weight % to about 70 weight %.

In order to improve ceiling temperature or in order to reduce viscosity, compound (2) is preferably in a proportion of about 10 weight % or more, is Raising dielectric anisotropy, compound (2) are preferably in a proportion of about 70 weight % or less.More preferable ratio is about 10 weight % To the range of about 65 weight %.Particularly preferred ratio is ranges of the about 15 weight % to about 60 weight %.

Compound (3) and compound (4) are made an addition in composition for the purpose of the orientation of control liquid crystal molecule.For Liquid crystal molecule is set to be orientated, compound (3) or compound (4) are preferably in a proportion of about 0.05 weight % or more, in order to anti- Only the display of element is bad, and compound (3) or compound (4) are preferably in a proportion of about 10 weight % or less.More preferable ratio is The range of about 0.1 weight % to about 7 weight %.Particularly preferred ratio is ranges of the about 0.5 weight % to about 5 weight %.

Compound (5) is made an addition in composition for the purpose for the element for being suitable for polymer stabilizing orientating type.For The long-term reliability of element is set to improve, compound (5) is preferably in a proportion of about 0.03 weight % or more, in order to prevent element Show bad, compound (5) is preferably in a proportion of about 10 weight % or less.More preferable ratio is about 0.1 weight % to about 2 weights Measure the range of %.Particularly preferred ratio is ranges of the about 0.2 weight % to about 1.0 weight %.

4th, the preferred configuration of component cpd is illustrated.In formula (1) and formula (2), R¹And R²It independently is carbon number 1 To the carbon number 2 that 12 alkyl, the alkoxy of carbon number 1 to 12, the alkenyl of carbon number 2 to 12, at least one hydrogen replace through fluorine or chlorine to 12 alkenyl or the alkenyloxy group of carbon number 2 to 12.In order to improve the stability to ultraviolet light or heat, preferred R¹Or R²For carbon number 1 to 12 alkyl, in order to improve dielectric anisotropy, preferred R¹Or R²For the alkoxy of carbon number 1 to 12.

R³And R⁴It independently is the alkyl of carbon number 1 to 12, the alkoxy of carbon number 1 to 12, the alkenyl of carbon number 2 to 12, at least one The alkene for the carbon number 2 to 12 that the alkyl or at least one hydrogen for the carbon number 1 to 12 that a hydrogen replaces through fluorine or chlorine replace through fluorine or chlorine Base.In order to improve the stability to ultraviolet light or heat, preferred R³Or R⁴For the alkyl of carbon number 1 to 12, in order to reduce lower limit temperature Or in order to reduce viscosity, preferred R³Or R⁴For the alkenyl of carbon number 2 to 12.

Preferred alkyl is methyl, ethyl, propyl, butyl, amyl, hexyl, heptyl or octyl.In order to reduce viscosity, more Preferred alkyl is ethyl, propyl, butyl, amyl or heptyl.

Preferred alkoxy is methoxyl group, ethyoxyl, propoxyl group, butoxy, amoxy, hexyloxy or oxygroup in heptan.In order to Viscosity is reduced, preferred alkoxy is methoxy or ethoxy.

Preferred alkenyl is vinyl, 1- acrylic, 2- acrylic, 1- cyclobutenyls, 2- cyclobutenyls, 3- cyclobutenyls, 1- penta Alkenyl, 2- pentenyls, 3- pentenyls, 4- pentenyls, 1- hexenyls, 2- hexenyls, 3- hexenyls, 4- hexenyls or 5- hexenes Base.In order to reduce viscosity, preferred alkenyl is vinyl, 1- acrylic, 3- cyclobutenyls or 3- pentenyls.In these alkenyls The preferred spatial configuration of-CH=CH- depend on the position of double bond.In order to reduce the reasons such as viscosity, in 1- acrylic, 1- butylene It is preferably anti-configuration in the alkenyl of base, 1- pentenyls, 1- hexenyls, 3- pentenyls, 3- hexenyls etc.2- cyclobutenyls, It is preferably cis-configuration in the alkenyl of 2- pentenyls, 2- hexenyls etc.

Preferred alkenyloxy group is ethyleneoxy, allyloxy, 3- butenyloxies, 3- amylenes oxygroup or 4- amylene oxygroups.For Reduction viscosity, preferred alkenyloxy group are allyloxy or 3- butenyloxies.

The preference for the alkyl that at least one hydrogen replaces through fluorine or chlorine is methyl fluoride, 2- fluoro ethyls, 3- fluoropropyls, 4- fluorine fourths Base, 5- fluorine amyl groups, 6- fluorine hexyl, 7- fluorine heptyl or 8- fluorine octyls.In order to improve dielectric anisotropy, more preferable example is 2- fluorine second Base, 3- fluoropropyls, 4- fluorine butyl or 5- fluorine amyl groups.

The preference for the alkenyl that at least one hydrogen replaces through fluorine or chlorine is 2,2- difluoroethylenes base, 3,3-, bis- fluoro- 2- propylene Base, 4,4-, bis- fluoro- 3- cyclobutenyls, 5,5-, bis- fluoro- 4- pentenyls or 6, bis- fluoro- 5- hexenyls of 6-.In order to reduce viscosity, more preferably Example is 2,2- difluoroethylenes base or 4, bis- fluoro- 3- cyclobutenyls of 4-.

Ring A and ring C independently is 1 or 4 cyclohexylidene, Isosorbide-5-Nitrae-cyclohexadienylidene, oxinane -2,5- diyl, Isosorbide-5-Nitrae-Asia Phenyl, at least one hydrogen Isosorbide-5-Nitrae-phenylene, naphthalene -2,6- diyl, at least one hydrogen through fluorine or chlorine substitution replace through fluorine or chlorine Chromogen alkane -2,6- diyl that naphthalene -2,6- diyl, chromogen alkane -2,6- diyl or at least one hydrogen replace through fluorine or chlorine.It is preferred that Ring A or ring C be 1 or 4 cyclohexylidene, Isosorbide-5-Nitrae-cyclohexadienylidene, oxinane -2,5- diyl, Isosorbide-5-Nitrae-phenylene, 2- fluoro- 1, 4- phenylenes, 2,3-, bis- fluoro- Isosorbide-5-Nitrae-phenylenes, 3,4,5- tri- fluoronaphthalene -2,6- diyls or 7,8- difluoro chromogen alkane -2,6- diyls. Preferred ring A or ring C is 1 or 4 cyclohexylidene or Isosorbide-5-Nitrae-phenylene.In these rings, in order to reduce viscosity, preferred ring A or Ring C is 1 or 4 cyclohexylidene, and in order to improve dielectric anisotropy, preferred ring A or ring C are oxinane -2,5- diyl, in order to Optical anisotropy is improved, preferred ring A or ring C are Isosorbide-5-Nitrae-phenylene.Oxinane -2,5- diyl is

Or

, preferably

Ring B is 2,3-, bis- fluoro- Isosorbide-5-Nitrae-phenylenes, the fluoro- Isosorbide-5-Nitrae-phenylenes of the chloro- 3- of 2-, 2,3-, bis- fluoro- 5- methyl-1s, and 4- is sub- Phenyl, 3,4,5- tri- fluoronaphthalene -2,6- diyls or 7,8- difluoro chromogen alkane -2,6- diyls.Preferred ring B is 2,3-, bis- fluoro- Isosorbide-5-Nitraes- Fluoro- Isosorbide-5-Nitrae-the phenylenes of the chloro- 3- of phenylene, 2- or 7,8- difluoro chromogen alkane -2,6- diyls.Preferred ring B is 2,3- bis- fluoro- 1, 4- phenylenes or the fluoro- Isosorbide-5-Nitrae-phenylenes of the chloro- 3- of 2-.There are 2,3-, bis- fluoro- Isosorbide-5-Nitrae-phenylenes by particularly preferred ring B.In these rings, In order to reduce viscosity, preferred ring B is 2,3-, bis- fluoro- Isosorbide-5-Nitrae-phenylenes, and in order to reduce optical anisotropy, preferred ring B is Fluoro- Isosorbide-5-Nitrae-the phenylenes of the chloro- 3- of 2-, in order to improve dielectric anisotropy, preferred ring B is 7,8- difluoro chromogen alkane -2,6- diyls.

Ring D and ring E independently is the fluoro- Isosorbide-5-Nitrae-phenylene of 1 or 4 cyclohexylidene, Isosorbide-5-Nitrae-phenylene, 2- or 2,5- bis- fluoro- 1, 4- phenylenes.In order to reduce viscosity, or in order to improve ceiling temperature, preferred ring D or ring E are 1 or 4 cyclohexylidene, in order to drop Low lower limit temperature, preferred ring D or ring E are Isosorbide-5-Nitrae-phenylene.

Z¹And Z²It independently is singly-bound ,-CH₂CH₂-、-CH₂O-、-OCH₂,-COO- or-OCO-.It is excellent in order to reduce viscosity The Z of choosing¹Or Z²For singly-bound, in order to reduce lower limit temperature, preferred Z¹Or Z²For-CH₂CH₂, in order to improve dielectric anisotropy, Preferred Z¹Or Z²For-CH₂O- or-OCH₂-。Z³For singly-bound ,-CH₂CH₂-、-CH₂O-、-OCH₂,-COO- or-OCO-.In order to drop Low viscosity, preferred Z³For singly-bound, in order to reduce lower limit temperature, preferred Z³For-CH₂CH₂, excellent in order to improve ceiling temperature The Z of choosing³For-COO- or-OCO-.

A is 1,2 or 3, and b is 0 or 1, and the sum of a and b are 3 or less.In order to reduce viscosity, preferred a is 1, in order to carry High ceiling temperature, preferred a are 2 or 3.In order to reduce viscosity, preferred b is 0, and in order to reduce lower limit temperature, preferred b is 1. C is 1,2 or 3.In order to reduce viscosity, preferred c is 1, and in order to improve ceiling temperature, preferred c is 2 or 3.

In formula (3), R⁸For polar group.In formula (4), R¹⁰For polar group.Compound (3) or compound (4) are preferably to purple Outside line or thermostabilization.When making an addition to compound (3) or compound (4) in composition, the preferably described compound will not drop The voltage retention of low element.Compound (3) or compound (4) preferably have low volatility.Preferably molal weight is 130g/mol or more.The range that preferred molal weight is 150g/mol to 500g/mol.Preferred compound (3) or chemical combination Object (4) has acryloxy (- OCO-CH=CH₂), methacryloxy (- OCO- (CH₃) C=CH₂) etc polymerism Base.

Polar group has the interaction with the non-covalently bonded on the surface of glass substrate or metal oxide film.Preferably Polar group has the hetero atom in the group selected from nitrogen, oxygen, sulphur and phosphorus.Preferred polar group has at least one or at least two These hetero atoms.Preferred polar group be by from selected from alcohol, level-one, two level and tertiary amine, ketone, carboxylic acid, mercaptan, ester, ether, Dehydrogenation is gone in compound in the group of thioether and these combination and derivative monad radical.The structure of these bases is alternatively straight chain Shape, branch-like, ring-type or these combination.Particularly preferred polar group have OH structures oxygen atom at least one or At least one of the nitrogen-atoms of level-one, two level or tertiary amine group.Most preferred polar group is hydroxyl (carbon-OH).

Polar group R⁸Example be formula (A1) to formula (A4) represented by base.

In formula (A1) to formula (A4), Sp⁶、Sp⁸And Sp⁹It independently is the alkylidene of singly-bound or carbon number 1 to 12, the alkylene In base, at least one-CH₂It can be through-O- ,-S- ,-NH- ,-N (R⁰)-、-CO-、-CO-O-、-O-CO、-O-CO-O-、-S-CO-、- CO-S-、-N(R⁰)-CO-O-、-O-CO-N(R⁰)-、-N(R⁰)-CO-N(R⁰- CH=CH- or-C ≡ C- substitutions)-, these bases In, at least one hydrogen can replace through fluorine or chlorine, herein, R⁰For hydrogen or the alkyl of carbon number 1 to 12.Sp⁷For ＞ CH-, ＞ CR⁰, ＞ N- or ＞ C ＜, herein, R⁰For hydrogen or the alkyl of carbon number 1 to 12.That is, referring to the Sp in formula (A2)⁷For ＞ CH-, ＞ CR⁰Or ＞ N-, the Sp in formula (A3)⁷For ＞ C ＜.

Preferred Sp⁶、Sp⁸Or Sp⁹For singly-bound ,-(CH₂)_p1-、-(CH₂)_p1-O-、-(CH₂CH₂O)_q1-CH₂CH₂-、- (CH₂)_p1-O-CO-、-(CH₂)_p1-O-CO-O-、-CH₂CH₂-S-CH₂CH₂Or-CH₂CH₂-NHCH₂CH₂, in addition, p1 is 1 to 12 Integer, q1 is integer of 1 to 3.Preferred Sp⁶、Sp⁸Or Sp⁹For ethylidene, propylidene, butylidene, pentylidene, it is sub- oneself Base, heptamethylene, octamethylene, nonylene, decylene, alkylene undecyl, sub-dodecyl, alkylene octadecyl, ethyleneoxy Asia second The thio ethylidene of base, methyleneoxybutylene, ethylene, ethylene-N- methyl-iminos ethylidene, 1- methyl alkylidene, sub- second Alkenyl, allylidene and butenylidene.

In formula (A1) to formula (A4), X¹⁷For-OH ,-OR⁰、-COOH、-NH₂、-NHR⁰、-N(R⁰)₂、-SH、-SR⁰、

Herein, R⁰For hydrogen or the alkyl of carbon number 1 to 12.

In formula (A1), X¹⁸For-O- ,-CO- ,-NH- ,-NR⁰,-S- or singly-bound, herein, R⁰For hydrogen or the alkane of carbon number 1 to 12 Base.Z¹⁰For singly-bound or the alkylidene of carbon number 1 to 15, in the alkylidene, at least one-CH₂It can be through-C ≡ C- ,-CH= CH- ,-COO- ,-OCO- ,-CO- or-O- replace, and in these bases, at least one hydrogen can replace through fluorine or chlorine.Ring P be carbon number 6 to 25 aryl, in the base, one to three hydrogen can be through-OH ,-(CH₂)_q- OH, fluorine, chlorine, the alkyl of carbon number 1 to 5 or at least The alkyl for the carbon number 1 to 5 that one hydrogen replaces through fluorine or chlorine replaces, herein, q 1,2,3 or 4.N be 0,1,2 or 3, m 1,2,3, 4 or 5.

Aryl is derivative monad radical by removing a hydrogen from aromatic hydrocarbon, does not include hetero atom.Aryl can be Monocycle or any one polycyclic.That is, there is aryl at least one ring, the ring can be condensed (such as naphthalene), two rings can Linked (such as xenyl) by covalent bond.Aryl can also have the combination of condensed ring and shackle.Aryl can be also substituted. The example of substituent group is-OH ,-(CH₂)_q- OH, fluorine, chlorine, the alkyl of carbon number 1 to 5 or at least one hydrogen replace through fluorine or chlorine The alkyl of carbon number 1 to 5, herein, q 1,2,3 or 4.

Preferred aryl is by from benzene, xenyl, terphenyl, [1,1 '：3 ', 1 "] terphenyl, naphthalene, anthracene, binaphthyl, Phenanthrene, pyrene, dihydropyrene,, aphthacene, pentacene, BaP, fluorenes, indenes, indenofluorene, in two fluorenes of spiral shell one hydrogen of removal and derive Monad radical.

In formula (3), R⁸Sulphur atom and level-one, two level or tertiary amine group for oxygen atom, SH structures with OH structures At least one of nitrogen-atoms polar group.Preferred R⁸For-OH ,-(CH₂)x-OH、-O-(CH₂)_n-OH、-[O- (CH₂)_n1-]_n2-OH、-COOH、-(CH₂)_n-COOH、-O-(CH₂)_n- COOH or-[O- (CH₂)_n1-]_n2-COOH.Herein, n, n1 and N2 is independently 1 to 12 integer, preferably 1,2,3 or 4.

Preferred R⁸It is alternatively-NH₂、-NH-(CH₂)_n3H、-(CH₂)_n-NH₂、-(CH₂)_n-NH-(CH₂)_n3H、-NH- (CH₂)_n-NH₂、-NH-(CH₂)_n-NH-(CH₂)_n3H、-(CH₂)_n1-NH-(CH₂)_n2-NH₂、-(CH₂)_n1-NH-(CH₂)_n2-NH- (CH₂)_n3H、-O-(CH₂)_n-NH₂、-(CH₂)_n1-O-(CH₂)_n-NH₂、-(CH₂)_n1-NH-(CH₂)_n2-OH、-O-(CH₂)_n1-NH- (CH₂)_n2-NH₂、-O-(CH₂)_n1-NH-(CH₂)_n2- OH or-(CH₂)_n1-NH-(CH₂)_n2-NH-(CH₂)_n3H.Herein, n, n1, n2 And n3 is independently 1 to 12 integer, preferably 1,2,3 or 4.

For the viewpoint of high solubility in a liquid crystal composition, R⁸Particularly preferably-OH or-NH₂.- OH is because having High anchor force, therefore it is better than-O- ,-CO- or-COO-.The particularly preferably base with multiple hetero atoms (nitrogen, oxygen).With such Even if the compound of polar group is low concentration, also effectively.

In formula (3), R⁷For the alkyl of hydrogen, fluorine, chlorine or carbon number 1 to 25, in the alkyl, at least one-CH₂Can through- NR⁰,-O- ,-S- ,-CO- ,-CO-O- ,-O-CO- ,-O-CO-O- or carbon number 3 to 8 cycloalkylidene substitution, and it is at least one Tertiary carbon (＞ CH-) can replace through nitrogen (＞ N-), and in these bases, at least one hydrogen can replace through fluorine or chlorine, herein, R⁰For hydrogen or The alkyl of carbon number 1 to 12.Preferred R⁷For the alkyl of carbon number 1 to 25.

In formula (3), P¹、P²And P³It independently is polymerism base.Preferred P¹、P²Or P³To be selected from formula (P-1) to formula (P-5) Base in the group of represented polymerism base.Preferred P¹、P²Or P³It is represented for formula (P-1), formula (P-2) or formula (P-3) Base.Particularly preferred P¹、P²Or P³For the base represented by formula (P-1) or formula (P-2).Most preferred P¹、P²Or P³For formula (P-1) Represented base.Preferred base represented by formula (P-1) is-OCO-CH=CH₂Or-OCO-C (CH₃)=CH₂.Formula (P-1) is to formula (P-5) wave indicates the position of bond.

In formula (P-1) to formula (P-5), M¹、M²And M³It independently is hydrogen, fluorine, the alkyl of carbon number 1 to 5 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 M¹、M²Or M³For hydrogen or methyl.More preferably M¹For hydrogen or methyl, and preferred M²Or M³For hydrogen.

In formula (3), Sp¹、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- ,-COO- ,-OCO- or-OCOO-, and at least one-CH₂CH₂It can be through-CH=CH- or-C ≡ C- replace, and in these bases, at least one hydrogen can replace through fluorine or chlorine.Preferred Sp¹、Sp²Or Sp³For singly-bound ,-CH₂CH₂-、- CH₂O-、-OCH₂,-COO- ,-OCO- ,-CO-CH=CH- or-CH=CH-CO-.Preferred Sp¹、Sp²Or Sp³For singly-bound.Its In, when ring J and ring L is phenyl, Sp¹And Sp³For singly-bound.

In formula (3), ring J, ring K and ring L independently be 1 or 4 cyclohexylidene, Isosorbide-5-Nitrae-cyclohexadienylidene, Isosorbide-5-Nitrae-phenylene, Naphthalene -1,2- diyl, naphthalene -1,3- diyl, naphthalene-Isosorbide-5-Nitrae-diyl, naphthalene -1,5- diyl, naphthalene -1,6- diyl, naphthalene -1,7- diyl, naphthalene -1, 8- diyls, 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 pyridine -2,5- diyl, in these rings, alkane that at least one hydrogen can be through fluorine, chlorine, carbon number 1 to 12 The alkyl for the carbon number 1 to 12 that base, the alkoxy of carbon number 1 to 12 or at least one hydrogen replace through fluorine or chlorine replaces.Preferred ring J, ring K or ring L is Isosorbide-5-Nitrae-phenylene or the fluoro- Isosorbide-5-Nitrae-phenylenes of 2-.

In formula (3), Z⁷And Z⁸It 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-, and at least one-CH₂CH₂It 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 ,-CH₂CH₂-、-CH₂O-、-OCH₂,-COO- or-OCO-.Preferred Z⁷Or Z⁸For singly-bound.

In formula (3), g and h independently are 0,1,2,3 or 4, and the sum of g and h are 0,1,2,3 or 4.Preferably g or h is 0, l or 2.K and p independently is 0,1,2,3 or 4.Preferred k or p is 1 or 2.O is 1,2,3 or 4.Preferred o is 1 or 2.

In formula (3-1) to formula (3-15), Sp¹⁰For singly-bound or the alkylidene of carbon number 1 to 10, in the alkylidene, at least one A-CH₂It can replace through-O- ,-COO- ,-OCO- or-OCOO-, and at least one-CH₂CH₂It can be through-CH=CH- or-C ≡ C- replaces, and in these bases, at least one hydrogen can replace through fluorine or chlorine.L¹、L²、L³And L⁴It independently is hydrogen, fluorine, methyl or ethyl. R¹¹And R¹²It independently is hydrogen or methyl.

In formula (4), R¹⁰For-OH ,-OR⁰、-NH₂、-NHR⁰Or-N (R⁰)₂Represented base, herein, R⁰For hydrogen or carbon number 1 to 12 alkyl.For the viewpoint of high solubility in a liquid crystal composition, R²Particularly preferably-OH or-NH₂.- OH is because of tool There is high anchor force, therefore is better than-O- ,-CO- or-COO-.The particularly preferably base with multiple hetero atoms (nitrogen, oxygen).With this Even if the compound of kind of polar group is low concentration, also effectively.

In formula (4), R⁹For hydrogen, the alkene of fluorine, chlorine, the alkyl of carbon number 1 to 12, the alkoxy of carbon number 1 to 12, carbon number 2 to 12 The carbon number 2 that the alkyl or at least one hydrogen for the carbon number 1 to 12 that base, at least one hydrogen replace through fluorine or chlorine replace through fluorine or chlorine To 12 alkenyl.Preferred R⁹For the alkyl of carbon number 1 to 12.

In formula (4), ring M and ring N independently are 1 or 4 cyclohexylidene, Isosorbide-5-Nitrae-cyclohexadienylidene, l, 4- phenylenes, naphthalene-l, 2- diyls, naphthalene-l, 3- diyl, naphthalene-Isosorbide-5-Nitrae-diyl, naphthalene-l, 5- diyl, naphthalene -1,6- diyl, naphthalene -1,7- diyl, naphthalene -1,8- bis- Base, 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, pyridine -2,5- diyl, fluorenes -2,7- diyl, phenanthrene -2,7- diyl or anthracene -2,6- diyl, in these rings, until Few hydrogen can take through fluorine, chlorine, the alkyl of carbon number 1 to 12, the alkoxy of carbon number 1 to 12 or at least one hydrogen through fluorine or chlorine The alkyl of the carbon number 1 to 12 in generation replaces.Preferred ring M or ring N is 1 or 4 cyclohexylidene, Isosorbide-5-Nitrae-phenylene or the fluoro- Isosorbide-5-Nitrae-Asias 2- Phenyl.

In formula (4), Z⁹For singly-bound ,-CH₂CH₂,-CH=CH- ,-C ≡ C- ,-COO- ,-OCO- ,-CF₂O-、-OCF₂-、- CH₂O-、-OCH₂Or-CF=CF-.Preferred Z⁹For singly-bound ,-CH₂CH₂-、-CH₂O-、-OCH₂,-COO- or-OCO-.It is more excellent The Z of choosing⁹For singly-bound.

In formula (4), Sp⁴And Sp⁵It independently is the alkylidene of singly-bound or carbon number 1 to 7, in the alkylidene, at least one- CH₂Can replace through-O- ,-COO- or-OCO-, at least one-CH₂CH₂It can replace through-CH=CH-, in these bases, at least one A hydrogen can be fluorine-substituted.Preferred Sp⁴Or Sp⁵For singly-bound.

In formula (4), j 0,1,2,3 or 4.Preferred j is 0,1 or 2.

In formula (4-1) to formula (4-9), L⁵、L⁶、L⁷、L⁸、L⁹、L¹⁰、L¹¹、L¹²、L¹³、L¹⁴、Lⁱ⁵And L¹⁶Independently be hydrogen, Fluorine, methyl or ethyl.Preferred L⁵To L¹⁶For hydrogen or fluorine.

In formula (5), P⁴、P⁵And P⁶It independently is polymerism base.Preferred P⁴、P⁵Or P⁶To be selected from formula (P-1) to formula (P-5) Base in the group of represented polymerism base.Preferred P⁴、P⁵Or P⁶It is represented for formula (P-1), formula (P-2) or formula (P-3) Base.Particularly preferred P⁴、P⁵Or P⁶For the base represented by formula (P-1) or formula (P-2).Most preferred P⁴、P⁵Or P⁶For formula (P-1) Represented base.Preferred base represented by formula (P-1) is-OCO-CH=CH₂Or-OCO-C (CH₃)=CH₂.Formula (P-1) is to formula (P-5) wave indicates the position of bond.

In formula (5), Sp¹⁰、Sp¹¹And Sp¹²It 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-, and at least one-CH₂CH₂Can through-CH=CH- or- C ≡ C- replace, and in these bases, at least one hydrogen can replace through fluorine or chlorine.Preferred Sp¹⁰、Sp¹¹Or Sp¹²For singly-bound ,- CH₂CH₂-、-CH₂O-、-OCH₂,-COO- ,-OCO- ,-CO-CH=CH- or-CH=CH-CO-.Preferred Sp¹⁰、Sp¹¹Or Sp¹²For singly-bound.

In formula (5), ring T and ring V independently are cyclohexyl, cyclohexenyl group, phenyl, 1- naphthalenes, 2- naphthalenes, oxinane- 2- bases, 1,3- dioxane -2- bases, pyrimidine -2-base or pyridine -2- bases, 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. Preferred ring T or ring V is phenyl.Ring U be 1 or 4 cyclohexylidene, Isosorbide-5-Nitrae-cyclohexadienylidene, Isosorbide-5-Nitrae-phenylene, naphthalene -1,2- diyl, Naphthalene -1,3- diyl, naphthalene-Isosorbide-5-Nitrae-diyl, naphthalene -1,5- diyl, naphthalene -1,6- diyl, naphthalene -1,7- diyl, naphthalene -1,8- diyl, naphthalene -2, 3- diyls, naphthalene -2,6- diyl, naphthalene -2,7- diyl, oxinane -2,5- diyl, 1,3- dioxanes -2,5- diyl, pyrimidine -2, 5- diyls 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 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.Preferred ring U is Isosorbide-5-Nitrae-Asia benzene Base or the fluoro- Isosorbide-5-Nitrae-phenylenes of 2-.

In formula (5), Z¹¹And Z¹²It 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-, and at least one-CH₂CH₂It 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 Z¹¹Or Z¹²For singly-bound ,-CH₂CH₂-、-CH₂O-、-OCH₂,-COO- or-OCO-.Preferred Z¹¹Or Z¹²For singly-bound.

In formula (5), t 0,1 or 2.Preferred t is 0 or 1.U, v and w independently is 0,1,2,3 or 4, and u, v and w it Be 3 or more.

5th, preferred component cpd is shown.Preferred compound (1) is the compound (1-1) described in item 3 to chemical combination Object (1-22).In these compounds, preferably at least one of first composition is compound (1-1), compound (1-3), chemical combination Object (1-4), compound (1-6), compound (1-8) or compound (1-10).Preferably at least two of first composition are chemical combination Object (1-1) and compound (1-6), compound (1-1) and compound (1-10), compound (1-3) and compound (1-6), chemical combination The group of object (1-3) and compound (1-10), compound (1-4) and compound (1-6) or compound (1-4) and compound (1-8) It closes.

Preferred compound (2) is the compound (2-1) described in item 6 to compound (2-13).In these compounds, preferably At least one for second composition is compound (2-1), compound (2-3), compound (2-5), compound (2-6), compound (2-8) or compound (2-9).Preferably at least two of second composition are compound (2-1) and compound (2-3), compound The combination of (2-1) and compound (2-5) or compound (2-1) and compound (2-6).

Preferred compound (3) is the compound (3-1) described in item 12 to compound (3-15).It is excellent in these compounds Be selected as the first additive at least one be compound (3-6), compound (3-8), compound (3-10), compound (3-11), Compound (3-13) or compound (3-15).Preferably at least two of the first additive are compound (3-1) and compound (3- Or the combination of compound (3-3) and compound (3-8) 11).

Preferred compound (4) is the compound (4-1) described in item 13 to compound (4-9).In these compounds, preferably At least one for the first additive is compound (4-1), compound (4-2), compound (4-3), compound (4-5) or chemical combination Object (4-6).Preferably at least two of the first additive are compound (4-1) and compound (4-2) or compound (4-1) and change Close the combination of object (4-4).

Preferred compound (5) is the compound (5-1) described in item 17 to compound (5-7).In these compounds, preferably At least one for the second additive is compound (5-2), compound (5-5) or compound (5-7).Preferably the second additive At least two for compound (5-1) and compound (5-2), compound (5-2) and compound (5-5) or compound (5-2) and The combination of compound (5-7).

6th, pair additive that can be made an addition in composition illustrates.Such additive is optically active compound, resists Oxidant, ultra-violet absorber, pigment, antifoaming agent, polymerizable compound, polymerization initiator, polymerization inhibitor, polar compound Deng.The purpose of torsion angle (torsion angle) is assigned for the helical structure of liquid crystal molecule is caused, and by optical activity Object is closed to make an addition in composition.The example of such compound is compound (6-1) to compound (6-5).Optically active compound Be preferably in a proportion of about 5 weight % or less.More preferable ratio is ranges of the about 0.01 weight % to about 2 weight %.

In order to prevent by the reduction of the specific resistance caused by the heating in air, or in order to be used for a long time by element Afterwards, not only at room temperature, big voltage retention but also at a temperature of close to ceiling temperature is also maintained, and by antioxidant It makes an addition in composition.The preference of antioxidant is the compound (7) of integer etc. that n is 1 to 9.

In compound (7), preferred n is 1,3,5,7 or 9.Preferred n is 7.The compound (7) that n is 7 is due to volatilization Property is small, therefore for after by element long-time use, not only at room temperature, but also also being tieed up at a temperature of close to ceiling temperature It holds for big voltage retention effectively.In order to obtain said effect, antioxidant is preferably in a proportion of about 50ppm or more, is Ceiling temperature is not reduced, or in order not to improve lower limit temperature, antioxidant is preferably in a proportion of about 600ppm or less.It is more excellent It is ranges of the about 100ppm to about 300ppm to select ratio.

The preference of ultra-violet absorber is benzophenone derivates, benzoate derivatives, triazole derivative etc..Separately Outside, amine etc with steric hindrance light stabilizer it is also preferred that.In order to obtain said effect, these absorbents or stabilizer Be preferably in a proportion of about 50ppm or more, in order not to reduce ceiling temperature, or in order not to improve lower limit temperature, these absorbents or Stabilizer is preferably in a proportion of about 10000ppm or less.More preferable ratio is ranges of the about 100ppm to about 10000ppm.

In order to be suitable for the element of host and guest (guest host, GH) pattern, and by azo system pigmen, anthraquinone system pigment etc. it The dichroism pigment (dichroic dye) of class makes an addition in composition.Pigment is preferably in a proportion of about 0.01 weight % to about 10 The range of weight %.It blisters in order to prevent, and the antifoaming agent such as dimethyl silicone oil, methylphenylsilicone oil is made an addition into composition In.In order to obtain said effect, antifoaming agent is preferably in a proportion of about 1ppm or more, show in order to prevent it is bad, antifoaming agent it is excellent It is about 1000ppm or less to select ratio.More preferable ratio is ranges of the about 1ppm to about 500ppm.

In order to be suitable for the element that polymer stabilizing is orientated (PSA) type, and use polymerizable compound.Compound (3) is changed It closes object (4) and compound (5) is suitable for the purpose.Also can by compound (3), compound (4) and compound (5) and with change Object (3), compound (4) and the different polymerizable compound of compound (5) is closed to make an addition in composition together.Such polymerism The preference for closing object is acrylate, methacrylate, vinyl compound, ethyleneoxy compounds, propenyl ether, epoxy The compounds such as compound (oxirane, oxetanes), vinyl ketone.More preferable example is acrylate or methacrylic acid Ester.Total weight based on polymerizable compound, compound (3), compound (4) and compound (5) are preferably in a proportion of about 10 weights Measure % or more.More preferable ratio is about 50 weight % or more.Particularly preferred ratio is about 80 weight % or more.Particularly preferred ratio Also it is 100 weight %.By change compound (3), the type of compound (4) and compound (5), or by with ratio appropriate So that other polymerizable compounds is combined with compound (3), compound (4) and compound (5), can adjust the anti-of polymerizable compound The pre-tilt angle of answering property or liquid crystal molecule.By by pre-dumping angle optimization, may achieve the short response time of element.Liquid crystal molecule It is orientated and stabilizes, therefore may achieve big contrast ratio or long-life.

Polymerizable compound is irradiated by ultraviolet light and polymerize.Also can exist in the initiator appropriate such as Photoepolymerizationinitiater initiater Under polymerize.The appropriate type and appropriate amount of felicity condition, initiator for being polymerize have been people in the art Known to member, and it is described in the literature.Such as gorgeous good solid (Irgacure) 651 (registered trademark as photoinitiator；BASF (BASF)), gorgeous good solid (Irgacure) 184 (registered trademark；BASF) or 1173 (registered trademarks of Da Luoka (Darocur)；Bar Si Fu) it is suitable for free radical polymerization.Total weight based on polymerizable compound, Photoepolymerizationinitiater initiater are preferably in a proportion of about 0.1 The range of weight % to about 5 weight %.More preferable ratio is ranges of the about 1 weight % to about 3 weight %.

In keeping polymerizable compound, it polymerize in order to prevent, can also adds polymerization inhibitor.Polymerizable compound is usual It is to be made an addition in composition with the state for not removing polymerization inhibitor.The example of polymerization inhibitor is hydroquinone, methyl to benzene Hydroquinone derivative, 4- tert-butyl catechols, 4- metoxyphenols, phenthazine of diphenol etc etc..

Polar compound is with polar organic compound.Herein, the compound with ionic bond is free of.Oxygen, sulphur and Electrically partially negative and tendency of the presence with partial negative charge of the atom of nitrogen etc.Carbon and hydrogen are neutral or exist with part The tendency of positive charge.Polarity is unequally distributed and generates between atom not of the same race because of Partial charge in compound.Example Such as, polar compound has-OH ,-COOH ,-SH ,-NH₂, ＞ NH, ＞ N- etc part-structure at least one.

7th, the synthetic method of component cpd is illustrated.These compounds can be synthesized using known method. Illustrate synthetic method.Compound (1-1) is synthesized using the method described in the flat 2-503441 bulletins of Japanese Patent Laid. Compound (2-1) is synthesized using the method described in Japanese Patent Laid-Open No. Sho 59-176221 bulletins.Compound (3-1) And the synthetic method of compound (4-1) is recorded in embodiment one.Compound (5-1) is to utilize International Publication 2013- Method described in No. 161576 bulletins synthesizes.A part for compound (7) is commercially available.The compound that the n of formula (7) is 1 can It is obtained from Sigma-Aldrich (Sigma-Aldrich Corporation).The compound (7) etc. that n is 7 is to utilize U.S. Method described in No. 3660505 specifications of state's patent synthesizes.

The compound for not recording synthetic method can be using synthesizing at the method described in book below：《Organic synthesis》 (Organic Syntheses, John Wei Li fathers and sons publishing company (John Wiley＆Sons, Inc.)),《Organic reaction》 (Organic Reactions, John Wei Li fathers and sons publishing company),《Comprehensive organic synthesis》(Comprehensive Organic Synthesis, Pei Geman publishing company (Pergamon Press)), new experimental chemistry lecture (ball kind) etc..Composition is to utilize Well known method is prepared by the compound obtained in the above described manner.For example, component cpd is mixed, then pass through heating And it is made to be mutually dissolved.

Finally, the purposes of composition is illustrated.Most composition have about -10 DEG C of lower limit temperatures below, The optical anisotropy of about 70 DEG C or more of ceiling temperature and the range of about 0.07 to about 0.20.Control composition can be passed through Close object ratio or by mixing other liquid crystal compounds, come prepare with about 0.08 to about 0.25 range optics Anisotropic composition.And then also there can be the optics of the range of about 0.10 to about 0.30 each to prepare by trial and error The composition of anisotropy.Element containing the composition has big voltage retention.The composition is suitable for AM elements. AM element of the composition particularly suitable for infiltration type.The composition can be used as having nematic composition, can pass through It adds optically active compound and is used as optical activity composition.

The composition can be used for AM elements.And then it can also be used for PM elements.The composition can be used for PC, TN, The AM elements and PM elements of STN, ECB, OCB, IPS, FFS, VA, FPA isotype.Particularly preferably be used for TN, OCB, The AM elements of IPS, FFS isotype.In AM elements with IPS patterns or FFS mode, when not applying voltage, liquid crystal molecule Orientation can be parallel with glass substrate, or be alternatively vertical.These elements can be reflection-type, infiltration type or semi-transmission type.It is excellent It is selected as the element for infiltration type.It can be additionally used in non-crystalline silicon-TFT elements or polysilicon-TFT elements.It can also be by the composition The nematic curved arrangement phase (nematic made for carrying out microencapsulation (microencapsulation) Curvilinear aligned phase, NCAP) type element or formed in the composition made of three-dimensional netted macromolecule gather Close the element of object dispersion (polymer dispersed, PD) type.

An example for manufacturing the method for the element of existing polymer stabilizing orientating type is as described below.Assembling includes two pieces of substrates Element, two pieces of substrates are referred to as array substrate and colored filter substrate.The substrate has alignment films.The substrate At least one piece have electrode layer.Liquid crystal compounds are mixed to prepare liquid-crystal composition.Add in the composition Add polymerizable compound.Additive can be optionally added in turn.The composition is injected into element.It is applied to the element Light irradiation is carried out in the state of making alive.Preferably ultraviolet light.It is irradiated by light by polymerizable compound is made to be polymerize.Pass through It is described polymerization and generate contain polymeric composition.The element of polymer stabilizing orientating type is sequentially to make as described above It makes.

In the sequence, when applying voltage, liquid crystal molecule is orientated by the effect of alignment films and electric field.According to described in It is orientated, the molecule of polymerizable compound is also orientated.Due to polymerizable compound be in this condition using ultraviolet light come It is polymerize, therefore generates the condensate for maintaining the orientation.By the polymeric effect, the response time of element shortens. Since the running that the image retention of image is liquid crystal molecule is bad, therefore by the polymeric effect, image retention is also improved simultaneously. In addition, also the polymerizable compound in composition can be made to be polymerize in advance, the composition is configured at liquid crystal display element Substrate between.

The polar compound with polymerism base of compound (3) and compound (4) etc is being used as polymerism chemical combination In the case of object, the substrate of element does not need alignment films.Element without alignment films is according to described in the paragraph before two paragraphs Sequence and manufactured from substrate without alignment films.

In the sequence, compound (3) or compound (4) are due to polar group and substrate surface occur to interact in substrate On arranged.Liquid crystal molecule is orientated according to the arrangement.When applying voltage, further promote the orientation of liquid crystal molecule. Since polymerism base is to be polymerize in this condition using ultraviolet light, therefore generate the condensate for maintaining the orientation.It is logical The polymeric effect is crossed, the orientation of liquid crystal molecule additionally stabilizes, and the response time of element shortens.It is residual due to image Running as being liquid crystal molecule is bad, therefore by the polymeric effect, image retention is also improved simultaneously.

Embodiment

The present invention is further described in detail by embodiment.The present invention is not restricted by the embodiments.This hair The bright mixture for including composition M1 and composition M2.The present invention also include by at least two of the composition of embodiment mixing and At mixture.Synthesized compound is by nuclear magnetic resonance (nuclear magnetic resonance, NMR) analysis etc. Method is identified.The characteristic of compound, composition and element is measured using following methods.

NMR is analyzed：The DRX-500 manufactured using this guest (Bruker BioSpin) company of Brooker Baier when measurement.¹H- In the measurement of NMR, sample is made to be dissolved in CDCl₃In equal deuterated solvents, at room temperature with 500MHz, the item that cumulative number is 16 times Part is measured.Using 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), and m refers to multiplet (multiplet), and br refers to broad peak (broad).

Gas chromatographic analysis：The GC-14B type gas chromatographs manufactured using Shimadzu Seisakusho Ltd. when measurement.Carrier gas is helium (2mL/min).Sample evaporation chamber is set as 280 DEG C, by detector (flame ionization detector (flame ionization Detector, FID)) it is set as 300 DEG C.It carries out using Anjelen Sci. ＆ Tech. Inc when the separation of component cpd Capillary column DB-1 (the length 30m, internal diameter 0.32mm, 0.25 μm of film thickness of (Agilent Technologies Inc.) manufacture； Fixed liquid phase is dimethyl polysiloxane；It is nonpolarity).After the tubing string is kept for 2 minutes at 200 DEG C, with the ratio of 5 DEG C/min It is warming up to 280 DEG C.After sample is prepared into acetone soln (0.1 weight %), its 1 μ L is injected into sample evaporation chamber.Record It is calculated as the C-R5A types chromatopac (Chromatopac) or its same product of Shimadzu Seisakusho Ltd.'s manufacture.The gas chromatogram of gained Show the retention time of peak value corresponding with component cpd and the area of peak value.

Chloroform, hexane etc. can be used in solvent for diluting sample.In order to detach component cpd, can be used as follows Capillary column.The HP-1 (length 30m, internal diameter 0.32mm, 0.25 μm of film thickness) of Anjelen Sci. ＆ Tech. Inc's manufacture, this auspicious Tyke The Rtx-1 (length 30m, internal diameter 0.32mm, 0.25 μm of film thickness) of company (Restek Corporation) manufacture, Australia BP-1 (length 30m, internal diameter 0.32mm, 0.25 μ of film thickness of SGE international corporations (SGE International Pty.Ltd) manufacture m).For the purpose for the overlapping for preventing compound peak value, the capillary column CBP1-M50-025 of Shimadzu Seisakusho Ltd.'s manufacture can be used (length 50m, internal diameter 0.25mm, 0.25 μm of film thickness).

The ratio of liquid crystal compounds contained in composition can be calculated using method as described below.Utilize gas phase Chromatograph (FID) analyzes the mixture of liquid crystal compounds.The area ratio of peak value in gas chromatogram is equivalent to The ratio of liquid crystal compounds.It, can be by the correction factor of various liquid crystal compounds when the capillary column that text is recorded in use It is considered as 1.Therefore, the ratio (weight %) of liquid crystal compounds can be calculated according to the area of peak value ratio.

Measure sample：When measuring the characteristic of composition and element, composition is directly used as sample.Measuring compound Characteristic when, prepare measurement sample in mother liquor brilliant (85 weight %) by the way that the compound (15 weight %) to be mixed in. According to the value obtained by measurement, the characteristic value of compound is calculated using extrapolation (extrapolation method). (extrapolated value)={ (measured value of sample) -0.85 × (measured value of mother liquor crystalline substance) }/0.15.Under the ratio, smectic phase When (or crystallization) is precipitated at 25 DEG C, by compound and the ratio of mother liquor crystalline substance with 10 weight %：90 weight %, 5 weight %：95 weights Measure %, 1 weight %：The sequence of 99 weight % changes.It is found out and the relevant ceiling temperature of compound, light using the extrapolation Learn anisotropy, the value of viscosity and dielectric anisotropy.

Use following mother liquors crystalline substance.The ratio of component cpd is indicated with weight %.

Assay 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； Referred to as JEITA) method described in the specified JEITA specifications (JEITAED-2521B) of review or side made of being modified Method.Thin film transistor (TFT) (TFT) is not installed on the TN elements of measurement.

(1) nematic ceiling temperature (NI；℃)：It is placed on the hot plate for the melting point apparatus for having petrographic microscope Sample is heated with the speed of 1 DEG C/min.Measure sample a part by nematic phase change be isotropic liquid when temperature Degree.Sometimes nematic ceiling temperature is referred to as " ceiling temperature ".

(2) nematic lower limit temperature (TC；℃)：Will have nematic sample be put into vial, 0 DEG C, -10 DEG C, -20 DEG C, take care of 10 days in the freezer units of -30 DEG C and -40 DEG C after, observe liquid crystalline phase.For example, when sample is kept at -20 DEG C Nematic state, and variation is for crystallization or when smectic phase at -30 DEG C, by T_CIt is recorded as ＜ -20 DEG C.It sometimes will be nematic Lower limit temperature is referred to as " lower limit temperature ".

(3) viscosity (bulk viscosity；η；It is measured at 20 DEG C；mPa·s)：Gauge share limited public affairs in Tokyo are used when measurement Take charge of the E type rotational viscometers of manufacture.

(4) viscosity (rotary viscosity；γ1；It is measured at 25 DEG C；mpa·s)：According to M. the presents well (M.Imai) et al.《Point Sub- crystal and liquid crystal》Note in (Molecular Crystals and Liquid Crystals) volume 259 page 37 (1995) The method of load is measured.Sample is injected in the VA elements that the interval (cell gap) of two panels glass substrate is 20 μm.It is right The element periodically applies voltage in the range of 39 volts to 50 volts as unit of 1 volt.Voltage 0.2 is not applied After second, only to apply 1 rectangular wave (rectangular pulse；0.2 second) it repeats to apply voltage with the condition for not applying (2 seconds).It measures logical It crosses the application and generates the peak point current (peak current) and time to peak of transient current (transient current) (peak time).Rotary viscosity is obtained by the calculating formula (8) of the paper page 40 of these measured values and M.Imai et al. Value.The required dielectric anisotropy of calculating is measured using the method measured described in (6).

(5) optical anisotropy (refractive anisotrop；Δn；It is measured at 25 DEG C)：The use of wavelength is the light of 589nm, It is measured using the Abbe refractometer for being equipped with polarizer on ocular lens.The surface of headprism is rubbed to a direction Afterwards, sample is added dropwise on headprism.Refractive index n//it is to be measured when the direction of polarisation is parallel with the direction of friction.Folding Penetrating rate n ⊥ is measured when the direction of polarisation is vertical with the direction of friction.Optically anisotropic value is according to Δ n= The formula of n//- n ⊥ calculates.

(6) dielectric anisotropy (Δ ε；It is measured at 25 DEG C)：Dielectric is calculated according to the formula of Δ ε=8//- ε ⊥ Anisotropic value.Dielectric constant (ε // and ε ⊥) is measured as follows.

1) measurement of dielectric constant (ε //)：Octadecyl triethoxysilicane is coated on the glass substrate through fully cleaning Ethyl alcohol (20mL) solution of alkane (octadecyl triethoxysilane) (0.16mL).Glass substrate is set to revolve using circulator After turning, heated 1 hour at 150 DEG C.It is put into examination in the VA elements that the interval (cell gap) of two panels glass substrate is 4 μm Sample, using the bonding agent hardened with ultraviolet light by the component seal.To the element apply sine wave (0.5V, 1kHz), the dielectric constant (ε //) on the long axis direction of liquid crystal molecule is measured after 2 seconds.

2) measurement of dielectric constant (ε ⊥)：It is coated with polyimide solution on the glass substrate through fully cleaning.It will be described After glass substrate calcining, friction treatment is carried out to the alignment films of gained.It is 9 μ at the interval (cell gap) of two panels glass substrate M, sample is injected in the TN elements that torsion angle is 80 degree.Sine wave (0.5V, 1kHz) is applied to the element, liquid is measured after 2 seconds The dielectric constant (ε ⊥) of the short-axis direction of brilliant molecule.

(7) starting voltage (Vth；It is measured at 25 DEG C；V)：It is manufactured using great Zhong electronics limited liability company when measurement LCD5100 type luminance meters.Light source is halogen lamp.At the interval (cell gap) of two panels glass substrate be 4 μm and frictional direction is It is put into sample in the antiparallel VA elements for normally showing black pattern (normally black mode), use is carried out with ultraviolet light The bonding agent of hardening is by the component seal.To the element apply voltage (60Hz, rectangular wave) be as unit of 0.02V from 0V periodically increases to 20V.At this point, measuring the light quantity through element to element irradiation light from vertical direction.It is formed in described Transmitance is 100% when light quantity reaches maximum, and voltage-transmittance curve that transmitance is 0% when the light quantity is minimum. Starting voltage is voltage when reaching 10% with transmitance to indicate.

(8) voltage retention (VHR-1；It is measured at 25 DEG C；%)：TN elements for measurement have orientation of polyimide Film, and the interval (cell gap) of two panels glass substrate is 5 μm.The element utilizes hard with ultraviolet light after injecting sample The bonding agent of change seals.Apply pulse voltage (5V, 60 microseconds) to the TN elements to charge.Existed using high speed potentiometer The voltage that decaying is measured in a period of 16.7 milliseconds finds out the area A between the voltage curve of unit period and horizontal axis.Area B Area when not decaying for voltage.Voltage retention is indicated relative to the percentage of area B by area A.

(9) voltage retention (VHR-2；It is measured at 80 DEG C；%)：Other than replacing 25 DEG C and being measured at 80 DEG C, With sequential determination voltage retention same as described above.The value of gained is indicated by VHR-2.

(10) voltage retention (VHR-3；It is measured at 25 DEG C；%)：After irradiating ultraviolet light, voltage retention is measured, is commented Stability of the valence to ultraviolet light.TN elements for measurement have alignment film of polyimide, and cell gap is 5 μm.Institute It states and injects sample in element, irradiation light 20 minutes.Light source is extra-high-pressure mercury vapour lamp USH-500D (oxtail (Ushio) motor systems Make), 20cm is divided between element and light source.In the measurement of VHR-3, decayed voltage is measured during 16.7 milliseconds.Have The composition of big VHR-3 has big stability to ultraviolet light.VHR-3 is preferably 90% or more, and more preferably 95% or more.

(11) voltage retention (VHR-4；It is measured at 25 DEG C；%)：The TN elements of sample will be injected in 80 DEG C of constant temperature After being heated 500 hours in slot, voltage retention is measured, evaluates the stability to heat.In the measurement of VHR-4, in 16.7 milliseconds of phases Between measure decayed voltage.Composition with big VHR-4 is to warm with big stability.

(12) response time (τ；It is measured at 25 DEG C；ms)：It is manufactured using great Zhong electronics limited liability company when measurement LCD5100 type luminance meters.Light source is halogen lamp.Low-pass filter (Low-pass filter) is set as 5kHz.In two sheet glass The interval (cell gap) of substrate is put into sample in being 3.5 μm and the VA elements without alignment films.It is carried out using with ultraviolet light The bonding agent of hardening is by the component seal.The voltage for applying 30V on one side to the element, irradiates 78mW/cm on one side² The ultraviolet light 449 seconds (35J) of (405nm).Rugged (EYE GRAPHICS) limited liability company of rock is used in ultraviolet irradiation The more metalized lamp M04-L41 of the UV hardening of manufacture.Rectangular wave (120Hz) is applied to the element.At this point, from vertical direction pair Element irradiation light measures the light quantity through element.It is considered as transmitance 100% when the light quantity reaches maximum, in the light quantity To be considered as transmitance 0% when minimum.The maximum voltage of rectangular wave is set in such a way that transmitance becomes 90%.Rectangular wave Minimum voltage be set to transmitance become 0% 2.5V.Response time is changed to needed for 90% from 10% by transmitance (rise time time wanted；rise time；Millisecond) it indicates.

(13) elastic constant (K11：Extend (spray) elastic constant, K33：It is bent (bend) elastic constant；At 25 DEG C It measures；pN)：The EC-1 type elastic constants manufactured using Dongyang technical concern Co., Ltd (TOYO Corporation) when measurement Analyzer.Sample is injected in the vertical orientation element that the interval (cell gap) of two panels glass substrate is 20 μm.To the member Part applies 20 volts to 0 volt of charge, measures electrostatic capacitance and applies voltage.It uses《Liquid-crystal apparatus handbook》(daily magazine work Retribution for sins society) formula (2.98) in page 75, formula (2.101) carry out the electrostatic capacitance (C) that is measured and the value for applying voltage (V) It is fitted (fitting), the value of elastic constant is obtained according to formula (2.100).

(14) specific resistance (ρ；It is measured at 25 DEG C；Ωcm)：Sample 1.0mL is put into the container for having electrode.To institute It states container and applies DC voltage (10V), the DC current after measuring 10 seconds.Specific resistance is calculated by following formula.(specific resistance)= { (voltage) × (capacitance of container) }/{ (DC current) × (dielectric constant of vacuum) }.

(15) pre-tilt angle (degree)：Using light splitting ellipsometer M-2000U, (J.A. Wu Lamu shares have in the measurement of pre-tilt angle Limit company (J.A.Woollam Co., Inc.) manufactures).

(16) orientation stability (liquid crystal aligning axis stability)：Evaluate the liquid crystal aligning axis of the electrode side of liquid crystal display element Variation.The liquid crystal aligning angle φ (before) of the electrode side before applying stress is measured, then, rectangular wave is applied to element 4.5V, 60Hz after twenty minutes, buffer 1 second, measure the liquid crystal aligning angle φ of electrode side again after 1 second and after five minutes (after).The changes delta φ of liquid crystal aligning angle after being calculated 1 second by these values and using following formula and after five minutes (deg.)。

Δ φ (deg.)=φ (after)-φ (before) (formula 2)

It covers special Bach, D. Bryants and P.J. with J. Xi Er Ficks, B. Jansens, the conspicuous Singhs of C., J.F. Chinese mugworts Germania, E. and wins This (J.Hilfiker, B.Johs, C.Herzinger, J.F.Elman, E.Montbach, D.Bryant, and P.J.Bos), 《Solid film》(Thin Solid Films), 455-456, (2004) 596-600 are with reference to carrying out these measurement.It may be said that The change rate of the smaller liquid crystal aligning axis of Δ φ is smaller, and the stability of liquid crystal aligning axis is better.

Synthesis example 1

Compound (3-1) is synthesized using following methods.

1st step

By compound (T-1) (4.98g), compound (T-2) (5.00g), potassium carbonate (6.88g), tetrakis triphenylphosphine palladium (0.289g) and isopropanol ((isopropyl alcohol, IPA)；It 100ml) is added into reactor, it is small that 2 is carried out at 80 DEG C When be heated to reflux.Reaction mixture is injected into water, after being neutralized using 1N hydrochloric acid, is extracted using ethyl acetate. The organic layer generated together is cleaned using saline solution, is dried using anhydrous magnesium sulfate.Under reduced pressure to described molten Liquid is concentrated, and is purified to residue using silica gel chromatography (toluene) and obtains compound (T-3) (6.38g；99%).

Second step

Sodium borohydride (1.88g) and methanol (90ml) are added into reactor, and are cooled to 0 DEG C.Thereto slowly Tetrahydrofuran (Tetrahydrofuran, THF) (40ml) solution of compound (T-3) (6.38g) is added dropwise, restores on one side to room Temperature stirs 8 hours on one side.Reaction mixture is injected into water, water layer is extracted using ethyl acetate.Utilize water pair one It acts the organic layer generated to be cleaned, be dried using anhydrous magnesium sulfate.The solution is concentrated under reduced pressure, is utilized (toluene: ethyl acetate=3: 1) volume ratio purifies residue silica gel chromatography.And then by from the mixed of heptane and toluene Close solvent (volume ratio, 1: 1) recrystallization and purified, to obtain compound (T-4) (5.50g；85%).

Third step

By compound (T-4) (0.600g), potassium carbonate (0.637g) and dimethylformamide (Dimethyl Formamide, DMF) (6ml) be added in reactor, stirred 1 hour at 80 DEG C.After reaction mixture is cooled to room temperature, The compound (T-5) synthesized according to method recorded in Japanese Patent Laid-Open 2013-177561 is slowly added dropwise DMF (6ml) solution of (0.983g), is stirred 8 hours at 80 DEG C.Reaction mixture is injected into water, using toluene to water Layer is extracted.The organic layer generated together is cleaned using water, is dried using anhydrous magnesium sulfate.It is right under reduced pressure The solution is concentrated, and using silica gel chromatography, (toluene: ethyl acetate=7: 1) volume ratio purifies residue and obtained Obtain compound (3-1) (0.350g；40%).

¹H-NMR：Chemical shift δ (ppm；CDCl₃)：7.35-7.29 (m, 2H), 7.15-7.10 (m, 1H), 7.07-6.94 (m, 3H), 6.14 (s, 1H), 5.60 (s, 1H), 4.71 (d, 6.6Hz, 2H), 4.58 (t, J=4.5Hz, 2H), 4.32 (t, J= 4.5Hz, 2H), 2.65-2.58 (m, 3H), 1.95 (s, 3H), 1.72-1.63 (m, 2H), 0.98 (t, J=7.5Hz, 3H)

Synthesis example 2

Compound (4-1) is synthesized using following methods.

1st step

By compound (T-11) (25.0g), acrylic acid (7.14g), 4-dimethylaminopyridine ((4- Dimethylaminopyridine, DMAP)；1.21g) and dichloromethane (300ml) is added into reactor, is cooled to 0 DEG C. 1,3- dicyclohexylcarbodiimides ((1,3-dicyclohexyl carbodiimide, DCC) are slowly added dropwise thereto； Dichloromethane (125ml) solution 24.5g), is stirred 12 hours while restoring to room temperature.Separation is filtered to insoluble matter Afterwards, reaction mixture is injected into water, water layer is extracted using dichloromethane.Using water to the organic layer that generates together It is cleaned, is dried using anhydrous magnesium sulfate.The solution is concentrated under reduced pressure, (is held using silica gel chromatography Product ratio, heptane: toluene=2：1) residue is purified.And then by from this (solmix) (registered trademark) of Sol Mick A-11 Recrystallization and purified, to obtain compound (T-12) (11.6g；38%).Furthermore Sol Mick this (solmix) (registered trademark) A-11 is the mixture of ethyl alcohol (85.5%), methanol (13.4%) and isopropanol (1.1%), is from Japanese alcohol pin Sell (stock) acquisition.

Second step

By paraformaldehyde (paraformaldehyde) (2.75g), Isosorbide-5-Nitrae-diazabicyclo [2.2.2] octane ((Isosorbide-5-Nitrae- Diazabicyclo [2.2.2] octane, DABCO)；4.62g) and water (40ml) is added into reactor, is stirred at room temperature 15 minutes.THF (90ml) solution of compound (T-12) (6.31g) is added dropwise thereto, is stirred at room temperature 72 hours.It will reaction Mixture is injected into water, is extracted to water layer using ethyl acetate.The organic layer generated together is cleaned using water, It is dried using anhydrous magnesium sulfate.The solution is concentrated under reduced pressure, using silica gel chromatography (volumetric ratio, toluene: Ethyl acetate=5: 1) residue is purified.And then pass through recrystallization (volumetric ratio, heptane: toluene=1：1) it is purified, To obtain compound (4-1) (1.97g；29%).

Compound (6-1)¹H-NMR：6 (ppm of chemical shift；CDCl₃)：6.23 (s, 1H), 5.79 (d, J=1.2Hz, 1H), 4.79-4.70 (m, 1H), 4.32 (d, J=6.7Hz, 2H), 2.29 (t, J=6.7Hz, 1H), 2.07-2.00 (m, 2H), 1.83-1.67 (m, 6H), 1.42-1.18 (m, 8H), 1.18-0.91 (m, 9H), 0.91-0.79 (m, 5H)

The embodiment of following presentation composition.Component cpd is indicated based on the definition of following Table 3 with mark.In table 3, It is anti-configuration with the relevant spatial configuration of 1 or 4 cyclohexylidene.Number table in the parantheses after the compound of signifying word Show the chemical formula belonging to compound.The mark of (-) refers to other liquid crystal compounds.The ratio (percentage) of liquid crystal compounds It is the weight percent (weight %) of the weight based on the liquid-crystal composition without additive.Finally conclude the characteristic of composition Value.

Table 3 uses the Description Method of the compound of mark

R-(A₁)-Z₁-…··-Z_n-(A_n)-R′

The embodiment of element

1. raw material

Composition of the injection added with polar compound into the element without alignment films.After irradiating ultraviolet light, grind Study carefully the vertical orientation of the liquid crystal molecule in the element.Raw material is illustrated first.Raw material is from composition M1 to composition M18, polar compound (PC-1) to polar compound (PC-22), polymerizable compound (RM-1) to polymerizable compound (RM- 7) it is suitably selected in.Composition is as described below.

[composition M1]

NI=73.2 DEG C；＜ -20 DEG C of Tc；Δ n=0.113；Δ ε=- 4.0；Vth=2.18V；η=22.6mPas.

[composition M2]

NI=82.8 DEG C；＜ -30 DEG C of Tc；Δ n=0.118；Δ ε=- 4.4；Vth=2.13V；η=22.5mPas.

[composition M3]

NI=78.1 DEG C；＜ -30 DEG C of Tc；Δ n=0.107；Δ ε=- 3.2；Vth=2.02V；η=15.9mPas.

[composition M4]

NI=88.5 DEG C；＜ -30 DEG C of Tc；Δ n=0.108；Δ ε=- 3.8；Vth=2.25V；η=24.6mPas； VHR-1=99.1%；VHR-2=98.2%；VHR-3=97.8%.

[composition M5]

NI=81.1 DEG C；＜ -30 DEG C of Tc；Δ n=0.119；Δ ε=- 4.5；Vth=1.69V；η=31.4mPas.

[composition M6]

NI=98.8 DEG C；＜ -30 DEG C of Tc；Δ n=0.111；Δ ε=- 3.2；Vth=2.47V；η=23.9mPas.

[composition M7]

NI=77.5 DEG C；＜ -30 DEG C of Tc；Δ n=0.084；Δ ε=- 2.6；Vth=2.43V；η=22.8mPas.

[composition M8]

NI=70.6 DEG C；＜ -20 DEG C of Tc；Δ n=0.129；Δ ε=- 4.3；Vth=1.69V；η=27.0mPas.

[composition M9]

NI=93.0 DEG C；＜ -30 DEG C of Tc；Δ n=0.123；Δ ε=- 4.0；Vth=2.27V；η=29.6mPas.

[composition M10]

NI=87.6 DEG C；＜ -30 DEG C of Tc；Δ n=0.126；Δ ε=- 4.5；Vth=2.21V；η=25.3mPas.

[composition M11]

NI=93.0 DEG C；＜ -20 DEG C of Tc；Δ n=0.124；Δ ε=- 4.5；Vth=2.22V；η=25.0mPas.

[composition M12]

NI=76.4 DEG C；＜ -30 DEG C of Tc；Δ n=0.104；Δ ε=- 3.2；Vth=2.06V；η=15.6mPas.

[composition M13]

NI=78.3 DEG C；＜ -20 DEG C of Tc；Δ n=0.103；Δ ε=- 3.2；Vth=2.17V；η=17.7mPas.

[composition M14]

NI=81.2 DEG C；＜ -20 DEG C of Tc；Δ n=0.107；Δ ε=- 3.2；Vth=2.11V；η=15.5mPas.

[composition M15]

NI=88.7 DEG C；＜ -30 DEG C of Tc；Δ n=0.115；Δ ε=- 1.9；Vth=2.82V；η=17.3mPas.

[composition M16]

NI=89.9 DEG C；＜ -20 DEG C of Tc；Δ n=0.122；Δ ε=- 4.2；Vth=2.16V；η=23.4mPas.

[composition M17]

NI=77.1 DEG C；＜ -20 DEG C of Tc；Δ n=0.101；Δ ε=- 3.0；Vth=2.04V；η=13.9mPas.

[composition M18]

NI=75.9 DEG C；＜ -20 DEG C of Tc；Δ n=0.114；Δ ε=- 3.9；Vth=2.20V；η=24.7mPas.

First additive is polar compound (PC-1) to polar compound (PC-22).

Second additive is polymerizable compound (RM-1) to polymerizable compound (RM-7).

2. the vertical orientation of liquid crystal molecule

Embodiment 1

Polar compound (PC-1) is made an addition to the ratio of 5 weight % in composition M1, and then by polymerizable compound (RM-1) it is made an addition in composition M1 with the ratio of 0.5 weight %.The mixture is injected into two on 100 DEG C of hot microscope carrier During the interval (cell gap) of sheet glass substrate is 4.0 μm and the element without alignment films.By using extra-high-pressure mercury vapour lamp USH-250-BY (oxtail (Ushio) motor manufacturing) is to element irradiation ultraviolet light (28J), to make polar compound (PC-1) It is polymerize with polymerizable compound (RM-1).The element configuration is shown in polarization element and the polarisation of analyzer orthogonal configuration Micro mirror, from lower section, to element irradiation light, to observe, whether there is or not light leakages.When light does not penetrate element, judge vertical orientation for " good ". Its reason is：It is speculated as liquid crystal molecule and has carried out abundant orientation.When observing the light through element, it is expressed as " bad ".

Embodiment 2 is to embodiment 22 and comparative example 1

The element without alignment films is made using the mixture of composition, polar compound and polymerizable compound. To observe, whether there is or not light leakages in the same manner as in Example 1.Result is summarized in table 4.In comparative example 1, in order to be compared, no Add the polar compound with polymerism base.

The vertical orientation of 4. liquid crystal molecule of table

It is such according to table 4, in embodiment 1 to embodiment 22, though change composition, polar compound or polymerism The type of compound, but light leakage is not observed.The result indicates that even if, No yield point film in the component, vertical orientation is also good, Liquid crystal molecule is steadily orientated.On the other hand, light leakage is observed in comparative example 1.The result indicates that vertical orientation is not Well.Therefore, it is known that by the condensate of polar compound and polymerizable compound generation with polymerism base to liquid crystal molecule Vertical orientation play an important role.

Industrial availability

The liquid-crystal composition of the present invention can be used for liquid crystal projection apparatus, LCD TV etc..

Claims

1. a kind of liquid-crystal composition contains the polar compound at least one polymerism base as the first additive and contains There is the polymerizable compound at least three polymerism bases as the second additive, and with negative dielectric anisotropy.

2. liquid-crystal composition according to claim 1 contains in the group selected from the compound represented by formula (1) extremely A kind of few compound as first composition,

In formula (1), R¹And R²It independently is the alkyl of carbon number 1 to 12, the alkoxy of carbon number 1 to 12, the alkenyl of carbon number 2 to 12, extremely The alkenyl for the carbon number 2 to 12 that few hydrogen replaces through fluorine or chlorine or the alkenyloxy group of carbon number 2 to 12；Ring A and ring C independently are 1 or 4 cyclohexylidene, Isosorbide-5-Nitrae-cyclohexadienylidene, oxinane -2,5- diyl, Isosorbide-5-Nitrae-phenylene, at least one hydrogen take through fluorine or chlorine Naphthalene -2,6- diyl that the Isosorbide-5-Nitrae-phenylene in generation, naphthalene -2,6- diyl, at least one hydrogen replace through fluorine or chlorine, chromogen alkane -2,6- bis- Chromogen alkane -2,6- diyl that base or at least one hydrogen replace through fluorine or chlorine；Ring B is 2,3-, bis- fluoro- Isosorbide-5-Nitrae-phenylenes, 2- is chloro- Fluoro- Isosorbide-5-Nitrae-the phenylenes of 3-, 2,3-, bis- fluoro- 5- methyl-1s, 4- phenylenes, 3,4,5- tri- fluoronaphthalene -2,6- diyls or 7,8- difluoro colors Former alkane -2,6- diyl；Z¹And Z²It independently is singly-bound ,-CH₂CH₂-、-CH₂O-、-OCH₂,-COO- or-OCO-；A is 1,2 or 3, B is 0 or 1, and the sum of a and b are 3 or less.

3. liquid-crystal composition according to claim 1 or 2, contain the change represented by the formula (1-1) to formula (1-22) At least one of the group compound of object is closed as first composition,

In formula (1-1) to formula (1-22), R¹And R²It independently is the alkyl of carbon number 1 to 12, the alkoxy of carbon number 1 to 12, carbon number 2 To the alkenyl of 12 carbon number 2 to 12 of alkenyl, at least one hydrogen through fluorine or chlorine substitution or the alkenyloxy group of carbon number 2 to 12.

4. liquid-crystal composition according to any one of claim 1 to 3, wherein the weight based on liquid-crystal composition, first The ratio of ingredient is the range of 10 weight % to 90 weight %.

5. liquid-crystal composition according to any one of claim 1 to 4, contain the compound represented by the formula (2) At least one of group compound as second composition,

In formula (2), R³And R⁴It independently is the alkyl of carbon number 1 to 12, the alkoxy of carbon number 1 to 12, the alkenyl of carbon number 2 to 12, extremely The carbon number 2 to 12 that the alkyl or at least one hydrogen for the carbon number 1 to 12 that few hydrogen replaces through fluorine or chlorine replace through fluorine or chlorine Alkenyl；Ring D and ring E independently is the fluoro- Isosorbide-5-Nitrae-phenylene of 1 or 4 cyclohexylidene, Isosorbide-5-Nitrae-phenylene, 2- or 2, the bis- fluoro- Isosorbide-5-Nitrae-Asias 5- Phenyl；Z³For singly-bound ,-CH₂CH₂-、-CH₂O-、-OCH₂,-COO- or-OCO-；C is 1,2 or 3.

6. liquid-crystal composition according to any one of claim 1 to 5 contains selected from formula (2-1) to formula (2-13) institute At least one of group of compound of expression compound as second composition,

In formula (2-1) to formula (2-13), R³And R⁴It independently is the alkyl of carbon number 1 to 12, the alkoxy of carbon number 1 to 12, carbon number 2 Replace to the alkyl of 12 carbon number 1 to 12 of alkenyl, at least one hydrogen through fluorine or chlorine substitution or at least one hydrogen through fluorine or chlorine Carbon number 2 to 12 alkenyl.

7. liquid-crystal composition according to claim 5 or 6, wherein the weight based on liquid-crystal composition, the ratio of second composition Example is the range of 10 weight % to 70 weight %.

8. liquid-crystal composition according to any one of claim 1 to 7, wherein the first additive be with selected from nitrogen, oxygen, Heteroatomic polar compound in sulphur and phosphorus.

9. liquid-crystal composition according to any one of claim 1 to 8, contain represented by the formula (3) and formula (4) At least one of group of polar compound compound as the first additive,

In formula (3), R⁷For the alkyl of hydrogen, fluorine, chlorine or carbon number 1 to 25, in the alkyl, at least one-CH₂It can be through-NR⁰-、- The cycloalkylidene substitution of O- ,-S- ,-CO- ,-CO-O- ,-O-CO- ,-O-CO-O- or carbon number 3 to 8, and at least one tertiary carbon (＞ CH-) can replace through nitrogen (＞ N-), and in these bases, at least one hydrogen can replace through fluorine or chlorine, herein, R⁰For hydrogen or carbon number 1 To 12 alkyl；R⁸For the sulphur atom and level-one of oxygen atom, SH structures with OH structures, the nitrogen of two level or tertiary amine group The polar group of at least one of atom；Ring J, ring K and ring L independently are 1 or 4 cyclohexylidene, Isosorbide-5-Nitrae-cyclohexadienylidene, Isosorbide-5-Nitrae- Phenylene, naphthalene -1,2- diyl, naphthalene -1,3- diyl, naphthalene-Isosorbide-5-Nitrae-diyl, naphthalene -1,5- diyl, naphthalene -1,6- diyl, naphthalene -1,7- bis- Base, naphthalene -1,8- diyl, naphthalene -2,3- diyl, naphthalene -2,6- diyl, naphthalene -2,7- diyl, oxinane -2,5- diyl, 1,3- bis- Evil Alkane -2,5- diyl, pyrimidine -2,5- diyl or pyridine -2,5- diyl, in these rings, at least one hydrogen can through fluorine, chlorine, carbon number 1 to The alkyl for the carbon number 1 to 12 that 12 alkyl, the alkoxy of carbon number 1 to 12 or at least one hydrogen replace through fluorine or chlorine replaces；Z⁷ And Z⁸It 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- substitutions, and at least one-CH₂CH₂It 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；P¹、P²And P³For polymerism base；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- substitutions, and at least one-CH₂CH₂It can replace through-CH=CH- or-C ≡ C-, in these bases, At least one hydrogen can replace through fluorine or chlorine；G and h independently is 0,1,2,3 or 4, and the sum of g and h are 0,1,2,3 or 4；K and p 0,1,2,3 or 4 independently are, o 1,2,3 or 4；

In formula (4), R⁹For hydrogen, fluorine, chlorine, the alkyl of carbon number 1 to 12, the alkoxy of carbon number 1 to 12, the alkenyl of carbon number 2 to 12, extremely The carbon number 2 to 12 that the alkyl or at least one hydrogen for the carbon number 1 to 12 that few hydrogen replaces through fluorine or chlorine replace through fluorine or chlorine Alkenyl；R¹⁰For-OH ,-OR⁰、-NH₂、-NHR⁰Or-N (R⁰)₂Represented base, herein, R⁰For hydrogen or the alkyl of carbon number 1 to 12；Ring M and ring N independently be 1 or 4 cyclohexylidene, Isosorbide-5-Nitrae-cyclohexadienylidene, Isosorbide-5-Nitrae-phenylene, naphthalene -1,2- diyl, naphthalene -1,3- diyl, Naphthalene-Isosorbide-5-Nitrae-diyl, naphthalene -1,5- diyl, naphthalene -1,6- diyl, naphthalene -1,7- diyl, naphthalene -1,8- diyl, naphthalene -2,3- diyl, naphthalene -2, 6- diyls, naphthalene -2,7- diyl, oxinane -2,5- diyl, 1,3- dioxanes -2,5- diyl, pyrimidine -2,5- diyl, pyridine - 2,5- diyls, fluorenes -2,7- diyl, phenanthrene -2,7- diyl or anthracene -2,6- diyl, in these rings, at least one hydrogen can be through fluorine, 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；Z⁹For singly-bound ,-CH₂CH₂,-CH=CH- ,-C ≡ C- ,-COO- ,-OCO- ,-CF₂O-、-OCF₂-、-CH₂O-、-OCH₂Or- CF=CF-；Sp⁴And Sp⁵It 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- substitutions, at least one-CH₂CH₂It can replace through-CH=CH-, in these bases, at least one hydrogen can be through fluorine Substitution；J is 0,1,2,3 or 4.

10. liquid-crystal composition according to claim 9, wherein in formula according to claim 9 (3), R⁸To be selected from formula Base in the group of polar group represented by (A1) to formula (A4),

In formula (A1) to formula (A4), Sp⁶、Sp⁸And Sp⁹It independently is the alkylidene of singly-bound or carbon number 1 to 12, in the alkylidene, At least one-CH₂It can be through-O- ,-S- ,-NH- ,-N (R⁰)-、-CO-、-CO-O-、-O-CO、-O-CO-O-、-S-CO-、-CO- S-、-N(R⁰)-CO-O-、-O-CO-N(R⁰)-、-N(R⁰)-CO-N(R⁰)-,-CH=CH- or-C ≡ C- replaced, in these bases, until Few hydrogen can replace through fluorine or chlorine, herein, R⁰For hydrogen or the alkyl of carbon number 1 to 12；Sp⁷For ＞ CH-, ＞ CR⁰, ＞ N- or ＞ C ＜, herein, R⁰For hydrogen or the alkyl of carbon number 1 to 12；X¹⁷For-OH ,-OR⁰、-COOH、-NH₂、-NHR⁰、-N(R⁰)₂、-SH、- SR⁰、

Herein, R⁰For hydrogen or the alkyl of carbon number 1 to 12；X¹⁸For-O- ,-CO- ,-NH- ,-NR⁰,-S- or singly-bound, herein, R⁰For hydrogen Or the alkyl of carbon number 1 to 12；Z¹⁰For singly-bound or the alkylidene of carbon number 1 to 15, in the alkylidene, at least one-CH₂Can through- C ≡ C- ,-CH=CH- ,-COO- ,-OCO- ,-CO- or-O- replace, and in these bases, at least one hydrogen can replace through fluorine or chlorine；Ring P is the aryl of carbon number 6 to 25, and in the aryl, one to three hydrogen can be through-OH ,-(CH₂)_q- OH, fluorine, chlorine, carbon number 1 to 5 The alkyl for the carbon number 1 to 5 that alkyl or at least one hydrogen replace through fluorine or chlorine replaces, herein, q 1,2,3 or 4；N is 0,1,2 Or 3；M is 1,2,3,4 or 5.

11. liquid-crystal composition according to claim 9, wherein in formula according to claim 9 (3), P¹、P²And P³ The base independently being in the group selected from the polymerism base represented by formula (P-1) to formula (P-5),

In formula (P-1) to formula (P-5), M¹、M²And M³It independently is hydrogen, fluorine, the alkyl of carbon number 1 to 5 or at least one hydrogen warp The alkyl of fluorine or the carbon number 1 to 5 of chlorine substitution.

12. liquid-crystal composition according to any one of claim 1 to 11, wherein the first additive is selected from formula (3-1) To at least one of the group of polar compound represented by formula (3-15) compound,

In formula (3-1) to formula (3-15), R⁷For the alkyl of hydrogen, fluorine, chlorine or carbon number 1 to 25, in the alkyl, at least one-CH₂- It can be through-NR⁰,-O- ,-S- ,-CO- ,-CO-O- ,-O-CO- ,-O-CO-O- or carbon number 3 to 8 cycloalkylidene substitution, Er Qiezhi A few tertiary carbon (＞ CH-) can replace through nitrogen (＞ N-), and in these bases, at least one hydrogen can replace through fluorine or chlorine, herein, R⁰ For hydrogen or the alkyl of carbon number 1 to 12；Sp²For singly-bound or the alkylidene of carbon number 1 to 10, in the alkylidene, at least one-CH₂- It can replace through-O- ,-COO- ,-OCO- or-OCOO-, and at least one-CH₂CH₂It can replace through-CH=CH- or-C ≡ C-, In these bases, at least one hydrogen can replace through fluorine or chlorine；Sp¹⁰For singly-bound or the alkylidene of carbon number 1 to 10, in the alkylidene, At least one-CH₂It can replace through-O- ,-COO- ,-OCO- or-OCOO-, and at least one-CH₂CH₂It can be through-CH=CH- Or-C ≡ C- replace, in these bases, at least one hydrogen can replace through fluorine or chlorine；L¹、L²、L³And L⁴It independently is hydrogen, fluorine, methyl Or ethyl；R¹¹And R¹²It independently is hydrogen or methyl.

13. liquid-crystal composition according to any one of claim 1 to 12, wherein the first additive is selected from formula (4-1) To at least one of the group of polar compound represented by formula (4-9) compound,

In formula (4-1) to formula (4-9), R⁹For hydrogen, fluorine, chlorine, the alkyl of carbon number 1 to 12, the alkoxy of carbon number 1 to 12, carbon number 2 to What the alkyl or at least one hydrogen for the carbon number 1 to 12 that 12 alkenyl, at least one hydrogen replace through fluorine or chlorine replaced through fluorine or chlorine The alkenyl of carbon number 2 to 12；Z⁹For singly-bound ,-CH₂CH₂,-CH=CH- ,-C ≡ C- ,-COO- ,-OCO- ,-CF₂O-、-OCF₂-、- CH₂O-、-OCH₂Or-CF=CF-；Sp⁴And Sp⁵It independently is the alkylidene of singly-bound or carbon number 1 to 7, in the alkylidene, until A few-CH₂It can replace through-O- ,-COO- or-OCO-, at least one-CH₂CH₂It can replace through-CH=CH-, in these bases, At least one hydrogen can be fluorine-substituted；L⁵、L⁶、L⁷、L⁸、L⁹、L¹⁰、L¹¹、L¹²、L¹³、L¹⁴、L¹⁵And L¹⁶It independently is hydrogen, fluorine, methyl Or ethyl.

14. liquid-crystal composition according to any one of claim 1 to 13, wherein the weight based on liquid-crystal composition, the The ratio of one additive is the range of 0.05 weight % to 10 weight %.

15. the liquid-crystal composition according to any one of claim 1 to 14, contain the polymerization represented by the formula (5) At least one of the group of property compound compound as the second additive,

In formula (5), ring T and ring V independently be cyclohexyl, cyclohexenyl group, phenyl, 1- naphthalenes, 2- naphthalenes, oxinane -2- bases, 1,3- dioxane -2- bases, pyrimidine -2-base or pyridine -2- bases, in these rings, at least one hydrogen can be through fluorine, chlorine, carbon number 1 to 12 The alkyl for the carbon number 1 to 12 that alkyl, the alkoxy of carbon number 1 to 12 or at least one hydrogen replace through fluorine or chlorine replaces；Ring U is 1 or 4 cyclohexylidene, Isosorbide-5-Nitrae-cyclohexadienylidene, Isosorbide-5-Nitrae-phenylene, naphthalene -1,2- diyl, naphthalene -1,3- diyl, naphthalene-Isosorbide-5-Nitrae-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- diyls, oxinane -2,5- diyl, 1,3- dioxanes -2,5- diyl, pyrimidine -2,5- diyl or pyridine -2,5- diyl, this In a little rings, at least one hydrogen can be passed through through fluorine, chlorine, the alkyl of carbon number 1 to 12, the alkoxy of carbon number 1 to 12 or at least one hydrogen The alkyl substitution of fluorine or the carbon number 1 to 12 of chlorine substitution；Z¹¹And Z¹²It independently is the alkylidene of singly-bound or carbon number 1 to 10, the Asia In alkyl, at least one-CH₂It can replace through-O- ,-CO- ,-COO- or-OCO-, and at least one-CH₂CH₂It can be through-CH =CH- ,-C (CH₃)=CH- ,-CH=C (CH₃)-or-C (CH₃)=C (CH₃)-substitution, in these bases, at least one hydrogen can be through Fluorine or chlorine substitution；P⁴、P⁵And P⁶For polymerism base；Sp¹⁰、Sp¹¹And Sp¹²It 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- ,-COO- ,-OCO- or-OCOO-, and at least one-CH₂CH₂It can Replace through-CH=CH- or-C ≡ C-, in these bases, at least one hydrogen can replace through fluorine or chlorine；T is 0,1 or 2；U, v and w is independent Ground is 0,1,2,3 or 4, and the sum of u, v and w are 3 or more.

16. liquid-crystal composition according to claim 15, wherein in formula according to claim 15 (5), P⁴、P⁵And P⁶The base independently being in the group selected from the polymerism base represented by formula (P-1) to formula (P-5),

17. the liquid-crystal composition according to any one of claim 1 to 16 contains selected from formula (5-1) to formula (5-7) institute At least one of group of polymerizable compound of expression compound as the second additive,

In formula (5-1) to formula (5-7), P⁴、P⁵And P⁶It independently is and is selected from the polymerism base represented by formula (P-1) to formula (P-3) Base in group,

Herein, M¹、M²And M³It 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；Sp¹⁰、Sp¹¹And Sp¹²It 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- ,-COO- ,-OCO- or-OCOO-, and at least one-CH₂CH₂It can be through-CH=CH- or-C ≡ C- replaces, and in these bases, at least one hydrogen can replace through fluorine or chlorine.

18. the liquid-crystal composition according to any one of claim 15 to 17, wherein the weight based on liquid-crystal composition, the The ratio of two additives is the range of 0.03 weight % to 10 weight %.

19. a kind of liquid crystal display element, containing the liquid-crystal composition described in any one of with good grounds claim 1 to 18.

20. liquid crystal display element according to claim 19, wherein the operating mode of liquid crystal display element is in-plane switching Pattern, vertical alignment mode, fringe field switching mode or electric field induction light reaction alignment mode, and the driving of liquid crystal display element Mode is active matrix mode.

21. a kind of liquid crystal display element of polymer stabilizing orientating type, described in any one of with good grounds claim 1 to 18 Liquid-crystal composition, and the first additive in the liquid-crystal composition and the second additive are polymerize.

22. a kind of liquid crystal display element without alignment films, containing the liquid described in any one of with good grounds claim 1 to 18 Crystal composite, and the first additive in the liquid-crystal composition and the second additive are polymerize.

23. a kind of purposes of liquid-crystal composition according to any one of claim 1 to 18, is used for liquid crystal display element In.

24. a kind of purposes of liquid-crystal composition according to any one of claim 1 to 18, is used for polymer stabilizing and takes Into the liquid crystal display element of type.

25. a kind of purposes of liquid-crystal composition according to any one of claim 1 to 18 is used to not have alignment films Liquid crystal display element in.