CN108603120A

CN108603120A - Liquid-crystal composition and liquid crystal display element

Info

Publication number: CN108603120A
Application number: CN201680079899.8A
Authority: CN
Inventors: 斋藤将之
Original assignee: JNC Corp; Chisso Petrochemical Corp
Current assignee: JNC Corp; JNC Petrochemical Corp
Priority date: 2016-01-29
Filing date: 2016-12-02
Publication date: 2018-09-28
Anticipated expiration: 2036-12-02
Also published as: KR20180103856A; CN108603120B; WO2017130566A1; JP6747456B2; TW201739906A; JPWO2017130566A1; TWI713651B

Abstract

The present invention provides the liquid-crystal composition that a kind of effect by polar compound and polymer may achieve the vertical orientation of liquid crystal molecule, the liquid crystal display element containing the composition.The present invention is a kind of nematic liquid-crystal composition, it contains polar compound 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 one kind containing polar compound and polymerizable compound (or its polymer) and passing through these compounds Effect may achieve the liquid-crystal composition and liquid crystal display element of the vertical orientation of liquid crystal molecule.

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 small for the viscosity in composition.And then it is excellent The viscosity being selected as 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.Big dielectric anisotropy in composition contributes to the low threshold in element Voltage, small consumption electric power and big contrast ratio.It is therefore preferable that being big dielectric anisotropy.The big ratio electricity of composition Resistance contributes to the big voltage retention of element and big contrast ratio.It is therefore preferable that in the starting stage not only in room temperature Under, and the also composition with big specific resistance at a temperature of close to nematic ceiling temperature.Preferably when long Between after use, not only at room temperature, but also also with big specific resistance at a temperature of close to nematic ceiling temperature Composition.Composition is associated with the service life of element to the stability of ultraviolet light or heat.When the stability is high, the longevity of element Life length.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, uses polymerization The effect of object.First, the composition added with a small amount of polymerizable compound is injected into element.Then, on one side to the member Apply voltage between the substrate of part, ultraviolet light is irradiated to composition on one side.Polymerizable compound polymerize and in the composition Generate the reticular structure of polymer.In the composition, the orientation of liquid crystal molecule can be controlled using polymer, therefore the sound of element Shorten between seasonable, the image retention of image is improved.In the element of pattern with TN, ECB, OCB, IPS, VA, FFS, FPA etc It can be expected that such effect of polymer.

On the other hand, the liquid crystal containing polymer and polar compound is used in the liquid crystal display element for not having alignment films Composition.First, the composition added with a small amount of polymerizable compound and a small amount of polar compound is injected into element.This Place, polar compound are adsorbed in substrate surface and are arranged.Liquid crystal molecule is orientated according to the arrangement.Then, right on one side Apply voltage between the substrate of the element, ultraviolet light is irradiated to composition on one side.Herein, polymerizable compound is polymerize, And the orientation of liquid crystal molecule is made to stabilize.In the composition, liquid crystal molecule can be controlled using polymer and polar compound Orientation, therefore the response time of element shorten, the image retention of image improved.In turn, it is not required in the element without alignment films The step of forming alignment films.Since there is no alignment films, therefore utilize the interaction of alignment films and composition, the resistance of element It will not reduce.It can be expected that utilizing polymer and pole in the element of pattern with TN, ECB, OCB, IPS, VA, FFS, FPA etc Such effect of the combination of property 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 polar compound and polymerizable compound (or its polymer) and liquid crystal compounds group It closes, 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 liquid containing polar compound and polymerizable compound (or described polymer) Crystal composite, herein, polar compound and polymerizable compound have the high compatibility with liquid crystal compounds.Another object It may achieve the liquid-crystal composition of the vertical orientation of liquid crystal molecule for a kind of effect using the polymer.Another object is one kind Liquid-crystal composition, nematic ceiling temperature is high, nematic lower limit temperature is low, viscosity is small, optical anisotropy is appropriate, In the characteristics such as negative dielectric anisotropy is big, specific resistance is big, stability height high to the stability of ultraviolet light, to heat, meet extremely A kind of few characteristic.Another object is a kind of liquid-crystal composition with appropriate balance between at least two characteristics.Another object For a kind of liquid crystal display element containing the composition.A further object is short with the response time for one kind, voltage retention is big, Starting voltage is low, contrast than the characteristics such as big, long lifespan AM elements.

Technical means to solve problem

The present invention is a kind of polar compound that contains as the first additive and containing at least three polymerism bases Polymerizable compound has the liquid-crystal composition of negative dielectric anisotropy as the second additive, and contains described group Close the liquid crystal display element of object.

The effect of invention

An advantage of the invention is a kind of liquid containing polar compound and polymerizable compound (or described polymer) Crystal composite, herein, polar compound and polymerizable compound have the high compatibility with liquid crystal compounds.Another advantage It may achieve the liquid-crystal composition of the vertical orientation of liquid crystal molecule for a kind of effect by the polymer.Another advantage is one kind Liquid-crystal composition, nematic ceiling temperature is high, nematic lower limit temperature is low, viscosity is small, optical anisotropy is appropriate, In the characteristics such as negative dielectric anisotropy is big, specific resistance is big, stability height high to the stability of ultraviolet light, to heat, meet extremely A kind of few characteristic.Another advantage is a kind of liquid-crystal composition with appropriate balance between at least two characteristics.Another advantage For a kind of liquid crystal display element containing the composition.Another advantage is short with the response time for one kind, voltage retention is big, Starting voltage is low, contrast than the characteristics such as big, long lifespan AM elements.

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 six membered 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 for making the purpose for generating polymer in composition and adding 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 Also it can unlimitedly select.The rule is also applied 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 being also applied 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, is also applied 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)¹⁰-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 six membered ring, The rings such as condensed ring.In formula (5), the crosscutting oblique line of the hexagon is indicated that the arbitrary hydrogen on ring can be through-Sp¹⁰-P⁵Equal bases substitution. Subscripts such as ' v ' indicate the quantity for the base being substituted.When subscript ' v ' is 0, such substitution is not present.It is 2 or more in subscript ' v ' When, there are multiple-Sp on ring U¹⁰-P⁵。-Sp¹⁰-P⁵Represented multiple bases can be identical, or also can be different." ring A and ring C It independently is in the statement of X, Y or Z ", since subject is multiple, therefore uses " independently ".When subject is " ring A ", due to master Language is odd number, therefore does not use " independently ".When " ring A " in multiple formulas in use, the rule of " can be identical, or also can be different " Suitable for " ring A ".It is also the same for other bases.

The fluoro- 1,4- 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-right that the rule is generated suitable for oxinane -2,5- diyls etc by two hydrogen of removal from ring The bilvalent radical of title.The rule is also applied 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 polar compound as the first additive and containing at least three The polymerizable compound of a polymerism base has negative dielectric anisotropy as the second additive.

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 1,4- cyclohexylidenes, 1,4- cyclohexadienylidenes, oxinane -2,5- diyls, 1,4- phenylenes, at least one hydrogen through fluorine or Naphthalene -2,6- diyls that 1,4- phenylenes, naphthalene -2,6- diyls, at least one hydrogen of chlorine substitution replace through fluorine or chlorine, chromogen alkane (chroman) the chromogen alkane -2,6- diyls that -2,6- diyls or at least one hydrogen replace through fluorine or chlorine；Ring B is that 2,3- bis- is fluoro- The fluoro- 1,4- phenylenes of the chloro- 3- of 1,4- phenylenes, 2-, bis- fluoro- 5- methyl-1s of 2,3-, 4- phenylenes, tri- fluoronaphthalene -2,6- of 3,4,5- Diyl or 7,8- difluoro chromogen alkane -2,6- diyls；Z¹And Z²It independently is singly-bound ,-CH₂CH₂-、-CH₂O-、-OCH₂-、-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.

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- 1,4- phenylenes of 1,4- cyclohexylidenes, 1,4- phenylenes, 2- or 2,5- bis- is fluoro- 1,4- phenylenes；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 %.

Liquid-crystal composition of the item 8. according to any one of item 1 to item 7 contains polar compound as the first addition Object, the polar compound contain with the heteroatomic polar group in nitrogen, 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,

MES-R⁶ (3)

(R⁵)_xR⁶ (4)

In formula (3), MES is the liquid crystal former base at least one ring；In formula (4), R⁵For the alkyl of carbon number 4 to 20, institute It states in alkyl, at least one-CH₂It can be through the sub- cycloalkanes of-CH=CH- ,-CF=CH- ,-CH=CF- ,-C ≡ C- or carbon number 3 to 8 Base replaces, and in these bases, at least one hydrogen can replace through fluorine or chlorine；In formula (3) and formula (4), R⁶It is former for the oxygen with OH structures The polar group of at least one of the nitrogen-atoms of son, the sulphur atom of SH structures and level-one, two level or tertiary amine structure；X is 1 or 2.

10. liquid-crystal composition according to any one of item 1 to item 9 contains the pole represented by the formula (3-1) At least one of the group of property compound compound as the first additive,

In formula (3-1), 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；R⁸For the alkyl of carbon number 1 to 25, in the alkyl, at least one-CH₂It can be through-NR⁰-、-O-、- The cycloalkylidene substitution of S- ,-CO- ,-COO- ,-OCO- ,-OCOO- or carbon number 3 to 8, at least one tertiary carbon (＞ CH-) can be through Nitrogen (＞ N-) replaces, 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, Wherein, R⁸In the sulphur atom of oxygen atom, SH structures or the nitrogen-atoms of level-one, two level or tertiary amine structure with OH structures At least one；Ring F and ring G independently be the aromatic series base of carbon number 6 to 25, the heteroaromatic base of carbon number 5 to 25, carbon number 3 to 25 ester ring type base or the heterolipid cyclic group of carbon number 4 to 25, these bases can be condensed ring, and in these bases, at least one hydrogen can be through Base T substitutions, herein, base T is-OH ,-(CH₂)_i- OH, fluorine, chlorine ,-CN ,-NO₂,-NCO ,-NCS ,-OCN ,-SCN ,-C (=O) N (R⁰)₂,-C (=O) R⁰、-N(R⁰)₂、-(CH₂)_i-N(R⁰)₂, the aryl of carbon number 6 to 20, the heteroaryl of carbon number 6 to 20, carbon number 1 to 25 alkyl, the alkoxy of carbon number 1 to 25, the alkyl-carbonyl of carbon number 2 to 25, the alkoxy carbonyl of carbon number 2 to 25, carbon number 2 to 25 alkyl carbonyl oxy or the alkoxy carbonyloxy group of carbon number 2 to 25, in these bases, at least one hydrogen can replace through fluorine or chlorine, this Place, R⁰For hydrogen or the alkyl of carbon number 1 to 12, and i is 1,2,3 or 4；Z⁴For-O- ,-S- ,-CO- ,-CO-O- ,-OCO- ,-O- CO-O-、-OCH₂-、-CH₂O-、-SCH₂-、-CH₂S-、-CF₂O-、-OCF₂-、-CF₂S-、-SCF₂-、-(CH₂)_i-、-CF₂CH₂-、- CH₂CF₂-、-(CF₂)_i,-CH=CH- ,-CF=CF- ,-C ≡ C- ,-CH=CH-COO- ,-OCO-CH=CH- ,-C (R⁰)₂Or Singly-bound, herein, R⁰For hydrogen or the alkyl of carbon number 1 to 12, and i is 1,2,3 or 4；D is 0,1,2,3,4 or 5.

11. liquid-crystal composition according to any one of item 1 to item 10 contains represented by the formula (4-1) At least one of group of polar compound compound as the first additive,

R⁹-R¹⁰ (4-1)

In formula (4-1), R⁹For the alkyl of carbon number 4 to 20, in the alkyl, at least one-CH₂It can be through-CH=CH- ,-CF The cycloalkylidene substitution of=CH- ,-CH=CF- ,-C ≡ C- or carbon number 3 to 8, in these bases, at least one hydrogen can take through fluorine or chlorine Generation；R¹⁰For the alkyl of carbon number 1 to 25, in the alkyl, at least one-CH₂It can be through-NR⁰-、-O-、-S-、-CO-、-COO-、- The cycloalkylidene of OCO- ,-OCOO- or carbon number 3 to 8 replaces, at least one tertiary carbon (>CH-) can through nitrogen (>N-) replace, these In base, at least one hydrogen can replace through fluorine or chlorine, herein, R⁰For hydrogen or the alkyl of carbon number 1 to 12, wherein R¹⁰With OH structures Oxygen atom, the sulphur atom and level-ones of SH structures, two level or tertiary amine structure at least one of nitrogen-atoms.

12. liquid-crystal composition according to item 9, wherein in formula (3) and formula (4) according to item 9, R⁶To be selected from Base in the group of polar group represented by formula (A1) to formula (A4),

In formula (A1) to formula (A4), Sp⁴、Sp⁶And Sp⁷It independently is singly-bound or base (- Sp "-X " -), herein, Sp " is carbon number 1 to 20 alkylidene, 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- substitution, in these bases, at least one hydrogen can replace through fluorine, chlorine or-CN, and X " is-O- ,-S- ,-CO- ,- CO-O-、-O-CO-、-O-CO-O-、-CO-N(R⁰)-、-N(R⁰)-CO-、-N(R⁰)-CO-N(R⁰)-、-OCH₂-、-CH₂O-、- SCH₂-、-CH₂S-、-CF₂O-、-OCF₂-、-CF₂S-、-SCF₂-、-CF₂CH₂-、-CH₂CF₂-、-CF₂CF₂,-CH=N- ,-N= CH- ,-N=N- ,-CH=CR⁰-、-CY²=CY³,-C ≡ C- ,-CH=CH-CO-O- ,-O-CO-CH=CH- or singly-bound, herein, R⁰For hydrogen or the alkyl of carbon number 1 to 12, and Y²And Y³It independently is hydrogen, fluorine, chlorine or-CN；Sp⁵For>CH-、>CR^a1-、>N- or> C<；X¹For-OH ,-OR^a1、-COOH、-NH₂、-NHR^a1、-N(R^a1)₂、-SH、-SR^a1、

Herein, R⁰For hydrogen or the alkyl of carbon number 1 to 12；X²For-O- ,-CO- ,-NH- ,-NR^a1,-S- or singly-bound；Z⁹For carbon The alkylidene of number 1 to 15, the ester ring type base of carbon number 5 or 6 or these combination, in these bases, at least one hydrogen can through- OH、-OR^a1、-COOH、-NH₂、-NHR^a1、-N(R^a1)₂, fluorine or chlorine substitution；Herein, R^a1For the alkyl of carbon number 1 to 15, the alkane In base, at least one-CH₂It can replace through-C ≡ C- ,-CH=CH- ,-COO- ,-OCO- ,-CO- or-O-, in these bases, at least One hydrogen can replace through fluorine or chlorine；Ring P is the aromatic series base of carbon number 6 to 25 or the ester ring type base of carbon number 3 to 25, these bases can be Condensed ring, in these bases, one to three hydrogen can be through R^LSubstitution, herein, R^LFor-OH ,-(CH₂)_r- OH, fluorine, chlorine ,-CN ,-NO₂、- NCO ,-NCS ,-OCN ,-SCN ,-C (=O) N (R⁰)₂,-C (=O) R⁰、-N(R⁰)₂、-(CH₂)_r-N(R⁰)₂、-SH、-SR⁰, carbon number 6 To 20 aryl, the alkane of the heteroaryl of carbon number 6 to 20, the alkyl of carbon number 1 to 25, the alkoxy of carbon number 1 to 25, carbon number 2 to 25 The alkoxy carbonyloxy group of base carbonyl, the alkoxy carbonyl of carbon number 2 to 25, the alkyl carbonyl oxy of carbon number 2 to 25 or carbon number 2 to 25, 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, and r be 1,2,3 or 4；P is 0,1,2 or 3；Q is 2,3,4 or 5.

Liquid-crystal composition of the item 13. according to item 9 or item 10, wherein the first additive is selected from formula (3-1-1) to formula At least one of the group of polar compound represented by (3-1-4) compound,

In formula (3-1-1) to formula (3-1-4), R¹⁵For the alkyl or fluorine of carbon number 1 to 8；Ring Q and ring R independently is the Asias 1,4- The fluoro- 1,4- phenylenes of cyclohexyl, 1,4- phenylenes, 2-, the fluoro- 1,3- phenylenes of 2-, 2- ethyl -1,4- phenylenes, 2,6- diethyls Base -1,4- phenylenes, 2- Trifluoromethyl-1s, 4- phenylenes, bis- fluoro- 1,4- phenylenes of 2,3-, bis- fluoro- 1,4- phenylenes of 2,5-, Tetra- fluoro- 1,4- phenylenes of bis- fluoro- 1,4- phenylenes of 2,6- or 2,3,5,6-；Ring S is cyclohexyl or phenyl；Z¹⁰For singly-bound ,- CH₂CH₂,-COO- or-OCO-；Z¹¹For singly-bound, the alkylidene of carbon number 1 to 15, carbon number 5 or 6 ester ring type base or these It combines, in these bases, at least one hydrogen can be through-OH ,-OR^a1、-COOH、-NH₂、-NHR^a1、-N(R^a1)₂, fluorine or chlorine substitution, this Place, R^a1For the alkyl of carbon number 1 to 15, in the alkyl, 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；Sp⁴For singly-bound ,-CH₂CH₂-、- CH₂CH₂CH₂-、-CH₂O- or-OCH₂-；Sp⁷For singly-bound or the alkylidene of carbon number 1 to 5, in the alkylidene ,-CH₂It can be through-O- Or-NH- substitutions；S is 0,1,2,3,4 or 5；X³For-OH ,-COOH ,-SH ,-OCH₃Or-NH₂；X⁴For singly-bound or-O-.

Liquid-crystal composition of the item 14. according to item 9 or item 11, wherein the first additive is selected from formula (4-1-1) to formula At least one of the group of polar compound represented by (4-1-29) compound,

R⁹-OH (4-1-1)

R⁹-COOH (4-1-9)

R⁹-NH₂ (4-1-11)

In formula (4-1-1) to formula (4-1-29), R⁹For the alkyl of carbon number 4 to 20, in the alkyl, at least one-CH₂It can Cycloalkylidene through-CH=CH- ,-CF=CH- ,-CH=CF- ,-C ≡ C- or carbon number 3 to 8 replaces, at least one in these bases Hydrogen can replace through fluorine or chlorine.

Liquid-crystal composition of the item 15. according to any one of item 1 to item 14, wherein the weight based on liquid-crystal composition, The ratio of first additive is the range of 0.05 weight % to 10 weight %.

16. liquid-crystal composition according to any one of item 1 to item 15 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 1,4- cyclohexylidenes, 1,4- cyclohexadienylidenes, 1,4- phenylenes, naphthalene -1,2- diyls, naphthalene -1,3- diyls, naphthalene -1,4- two Base, naphthalene -1,5- diyls, naphthalene -1,6- diyls, naphthalene -1,7- diyls, naphthalene -1,8- diyls, naphthalene -2,3- diyls, naphthalene -2,6- diyls, Naphthalene -2,7- diyls, oxinane -2,5- diyls, 1,3- dioxane -2,5- diyls, pyrimidine -2,5- diyls or pyridine -2,5- two 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；Z¹²And Z¹³It 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；Sp⁹、Sp¹⁰And Sp¹¹It 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.

17. liquid-crystal composition according to item 16, wherein in formula (5) according to item 16, 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),

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 18. according to any one of item 1 to item 17, 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；Sp⁹、Sp¹⁰And Sp¹¹It 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 19. according to any one of item 16 to item 18, wherein the weight based on liquid-crystal composition, The ratio of second additive is the range of 0.03 weight % to 10 weight %.

20. 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 19.

21. liquid crystal display element according to item 20, 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.

22. 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 19 institute The liquid-crystal composition stated, and the polymerizable compound in the liquid-crystal composition is polymerize.

23. a kind of liquid crystal display elements without alignment films of item, described in any one of with good grounds item 1 to item 19 Liquid-crystal composition, and the polymerizable compound in the liquid-crystal composition is polymerize.

A kind of purposes of 24. liquid-crystal compositions according to any one of item 1 to item 19 of item is used for liquid crystal display member In part.

A kind of purposes of 25. liquid-crystal compositions according to any one of item 1 to item 19 of item, is used for polymer stabilizing In the liquid crystal display element of orientating type.

A kind of purposes of 26. liquid-crystal compositions according to any one of item 1 to item 19 of item is used to not have orientation In the liquid crystal display element of film.

The present invention also includes the following terms.(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 Polymerizable compound polymerize, to manufacture above-mentioned liquid crystal display element.(b) above-mentioned liquid-crystal composition, it is nematic on It is 70 DEG C or more to limit temperature, and the optical anisotropy (being measured at 25 DEG C) under wavelength 589nm is 0.08 or more, and frequency Dielectric anisotropy (being measured at 25 DEG C) under 1kHz is -2 or less.

The present invention also includes the following terms.(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.(g) the AM elements containing above-mentioned composition. (h) contain above-mentioned composition, and there is TN patterns, ecb mode, ocb mode, IPS patterns, FFS mode, VA patterns or FPA The element of pattern.(i) the infiltration type element containing above-mentioned composition.(j) above-mentioned composition is used as to have nematic combination Object.(k) purposes by adding optically active compound in above-mentioned composition as 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) or compound (4) are adsorbed in substrate surface using 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.Compound (5) passes through polymerization And form polymer.The polymer shortens the response time of element, Er Qiegai due to making the orientation of liquid crystal molecule stabilize The image retention of kind 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).By combining polar compound and polymerization in the composition Property compound (or its polymer) may achieve the vertical orientation of liquid crystal molecule." other liquid crystal compounds " if a small amount of, even if It makes an addition in the composition, also may achieve identical effect.

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.And then about 15 weight % are preferably in a proportion of to about 80 weight %'s Range.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.And then it is preferably in a proportion of about 10 weights Measure the range of % to 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.And then preferred proportion It is ranges of the 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.And then about 0.1 weight % is preferably in a proportion of 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, into And 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, and then 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, and then 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, and then preferred alkenyloxy group is 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, and then preference is 2- fluorine Ethyl, 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, bis- fluoro- 2- propylene of 3,3- Base, bis- fluoro- 5- hexenyls of bis- fluoro- 3- cyclobutenyls of 4,4-, bis- fluoro- 4- pentenyls of 5,5- or 6,6-.In order to reduce viscosity, Jin Eryou It is bis- fluoro- 3- cyclobutenyls of 2,2- difluoroethylenes base or 4,4- to select example.

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

Or

, preferably

Ring B is bis- fluoro- 1,4- phenylenes of 2,3-, the fluoro- 1,4- phenylenes of the chloro- 3- of 2-, bis- fluoro- 5- methyl-1s of 2,3-, and 4- is sub- Phenyl, tri- fluoronaphthalene -2,6- diyls of 3,4,5- or 7,8- difluoro chromogen alkane -2,6- diyls.Preferred ring B is bis- fluoro- 1,4- of 2,3- The fluoro- 1,4- phenylenes of the chloro- 3- of phenylene, 2- or 7,8- difluoro chromogen alkane -2,6- diyls.And then preferred ring B is that 2,3- bis- is fluoro- 1,4- phenylenes or the fluoro- 1,4- phenylenes of the chloro- 3- of 2-.Particularly preferred ring B is bis- fluoro- 1,4- phenylenes of 2,3-.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 color alkane -2,6- diyls.

Ring D and ring E independently is the fluoro- 1,4- phenylenes of 1,4- cyclohexylidenes, 1,4- phenylenes, 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), MES is the liquid crystal former base at least one ring.Liquid crystal former base is well known to those skilled in the art. Liquid crystal former base refers to, when compound has liquid crystalline phase (interphase), contributing to the part (moiety) of the formation of liquid crystalline phase.Change The preference for closing object (3) is compound (3-1).

In formula (4), R⁵For the alkyl of carbon number 4 to 20, in the alkyl, at least one-CH₂It can be through-CH=CH- ,-CF= The cycloalkylidene substitution of CH- ,-CH=CF- ,-C ≡ C- or carbon number 3 to 8, in these bases, at least one hydrogen can take through fluorine or chlorine Generation.X is 1 or 2, preferably 1.

Preferred R⁵For the alkyl of carbon number 4 to 20.And then preferred R⁵For the alkyl of carbon number 6 to 18.At least one-CH₂- Can be through-CH=CH- ,-CF=CH- ,-CH=CF- ,-C ≡ C- or-O- substitutions, and at least one hydrogen can replace through fluorine or chlorine.

In formula (3) and formula (4), R⁶For polar group.Compound (3) and compound (4) because making an addition in composition, therefore it is preferred that For to ultraviolet light or thermostabilization.When compound (3) and compound (4) are made an addition in composition, the preferably described compound The voltage retention of element will not be reduced.Compound (3) and compound (4) preferably have low volatility.Preferred mole Quality is 130g/mol or more.And then the range that preferred molal weight is 150g/mol to 500g/mol.

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.And then preferred polar group be by from selected from alcohol, level-one, two level and tertiary amine, ketone, carboxylic acid, mercaptan, ester, Dehydrogenation is gone in compound in the group of ether, thioether and these combination and derivative monad radical.The structure of these bases is alternatively Straight-chain, branch-like, ring-type or these combination.Particularly preferred polar group has oxygen atom or level-one, two of OH structures At least one of the nitrogen-atoms of grade or tertiary amine structure.Most preferred polar group is hydroxyl (carbon-OH).

Polar group R⁶Example be formula (A1) to formula (A4) represented by base.

In formula (A1) to formula (A4), Sp⁴、Sp⁶And Sp⁷It independently is singly-bound or base (- Sp "-X " -), and X " is bonded to ring P.Sp " is the alkylidene of carbon number 1 to 20, the preferably alkylidene of carbon number 1 to 12, in the alkylidene, at least one-CH₂It can 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, and in these bases, at least one hydrogen can be through fluorine, chlorine Or-CN substitutions, X " are-O- ,-S- ,-CO- ,-CO-O- ,-O-CO- ,-O-CO-O- ,-CO-N (R⁰)-、-N(R⁰)-CO-、-N (R⁰)-CO-N(R⁰)-、-OCH₂-、-CH₂O-、-SCH₂-、-CH₂S-、-CF₂O-、-OCF₂-、-CF₂S-、-SCF₂-、-CF₂CH₂-、- CH₂CF₂-、-CF₂CF₂,-CH=N- ,-N=CH- ,-N=N- ,-CH=CR⁰-、-CY²=CY³,-C ≡ C- ,-CH=CH-CO- O- ,-O-CO-CH=CH- or singly-bound, herein, R⁰For hydrogen or the alkyl of carbon number 1 to 12, Y²And Y³Independently be hydrogen, fluorine, chlorine or- CN.Preferred X " is-O- ,-S- ,-CO- ,-COO- ,-OCO- ,-O-COO- ,-CO-NR⁰-、-NR⁰-CO-、-NR⁰-CO-NR⁰Or Singly-bound.Sp⁵For>CH-、>CR^a1-、>N- or>C<.That is, the Sp in formula (A2)⁵For>CH-、>CR^a1Or>N-, the Sp in formula (A3)⁵ Refer to>C<.

Preferred Sp " is-(CH₂)_p1-、-(CH₂CH₂O)_q1-CH₂CH₂-、-CH₂CH₂-S-CH₂CH₂Or-CH₂CH₂- NHCH₂CH₂, herein, the integer that p1 is 1 to 12, q1 is integer of 1 to 3.Preferred base (- Sp "-X " -) it is-(CH₂)_p1-、- (CH₂)_p1-O-、-(CH₂)_p1-O-CO-、-(CH₂)_p1- O-CO-O-, herein, p1 and q1 have meaning illustrated above.And then it is excellent The base Sp " of choosing is ethylidene, propylidene, butylidene, pentylidene, hexylidene, heptamethylene, octamethylene, nonylene, decylene, Asia The thio sub- second of undecyl, sub-dodecyl, alkylene octadecyl, ethyleneoxy ethylidene, methyleneoxybutylene, ethylene Base, ethylene-N- methyl-iminos ethylidene, 1- methyl alkylidene, ethenylidene, allylidene and butenylidene.

X¹For-NH₂、-NHR^a1、-N(R^a1)₂、-OR^a1、-OH、-COOH、-SH、-SR^a1、

Herein, R^a1For the alkyl of carbon number 1 to 15, in the alkyl, 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, R⁰For hydrogen or carbon number 1 To 12 alkyl.

X²For-O- ,-CO- ,-NH- ,-NR^a1,-S- or singly-bound, Z⁹Indicate the alkylidene of carbon number 1 to 15, carbon number 5 to 6 The combination of ester ring type base or at least one ring and alkylidene, in these bases, at least one hydrogen can be through-OH ,-OR^a1、-COOH、- NH₂、-NHR^a1、-N(R^a1)₂, fluorine or chlorine substitution, herein, R^a1With meaning illustrated above.P is 0,1,2 or 3.Q be 2,3,4 or 5。

Ring P is the aromatic series base of carbon number 6 to 25 or the ester ring type base of carbon number 3 to 25, these bases can be condensed ring, these bases In, one to three hydrogen can be through R^LSubstitution.R^LFor-OH ,-(CH₂)_r- OH, fluorine, chlorine ,-CN ,-NO₂、-NCO、-NCS、-OCN、- SCN ,-C (=O) N (R⁰)₂,-C (=O) R⁰、-N(R⁰)₂、-(CH₂)_r-N(R⁰)₂、-SH、-SR⁰, carbon number 6 to 20 aryl, carbon number 6 to 20 heteroaryl, the alkyl of carbon number 1 to 25, the alkoxy of carbon number 1 to 25, the alkyl-carbonyl of carbon number 2 to 25, carbon number 2 to 25 Alkoxy carbonyl, the alkyl carbonyl oxy of carbon number 2 to 25 or the alkoxy carbonyloxy group of carbon number 2 to 25, it is at least one in these bases Hydrogen can replace through fluorine or chlorine, herein, R⁰For hydrogen or the alkyl of carbon number 1 to 12.

Particularly preferred nitrogenous base R⁶For-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.

Particularly preferred non-nitrogen containing base R⁶For-OH ,-(CH₂)_n-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 independently 1 to 12 integer, preferably 1,2,3 or 4.

For the viewpoint of high solubility in a liquid crystal composition, R⁶Particularly 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 (3-1), R⁷For hydrogen, the alkyl of fluorine, chlorine, 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 through nitrogen (>N-) replacing, in these bases, at least one hydrogen can replace through fluorine or chlorine, herein, R⁰For hydrogen or carbon The alkyl of number 1 to 12.

R⁸For the alkyl of carbon number 1 to 25, in the alkyl, at least one-CH₂It can be through-NR⁰-、-O-、-S-、-CO-、- The cycloalkylidene substitution of COO- ,-OCO- ,-OCOO- or carbon number 3 to 8, herein, R⁰For hydrogen or the alkyl of carbon number 1 to 12, at least one A tertiary carbon (>CH-) can through nitrogen (>N-) replace, and at least one hydrogen can replace through fluorine or chlorine, wherein R⁸With OH structures Oxygen atom, the sulphur atom or level-ones of SH structures, two level or tertiary amine structure at least one of nitrogen-atoms.

Ring F and ring G independently is the aromatic series base of carbon number 6 to 25, the heteroaromatic base of carbon number 5 to 25, carbon number 3 to 25 The heterolipid cyclic group of ester ring type base or carbon number 4 to 25, these bases can be condensed ring, and in these bases, at least one hydrogen can take through base T Generation, herein, base T are-OH ,-(CH₂)_i- OH, fluorine, chlorine ,-CN ,-NO₂,-NCO ,-NCS ,-OCN ,-SCN ,-C (=O) N (R⁰)₂、-C (=O) R⁰、-N(R⁰)₂、-(CH₂)_i-N(R⁰)₂, the aryl of carbon number 6 to 20, the heteroaryl of carbon number 6 to 20, carbon number 1 to 25 alkane The alkane of base, the alkoxy of carbon number 1 to 25, the alkyl-carbonyl of carbon number 2 to 25, the alkoxy carbonyl of carbon number 2 to 25, carbon number 2 to 25 The alkoxy carbonyloxy group of base carbonyloxy group or carbon number 2 to 25, in these bases, at least one hydrogen can replace through fluorine or chlorine, herein, R⁰For The alkyl of hydrogen or carbon number 1 to 12, i 1,2,3 or 4.

Z⁴For-O- ,-S- ,-CO- ,-CO-O- ,-OCO- ,-O-CO-O- ,-OCH₂-、-CH₂O-、-SCH₂-、-CH₂S-、- CF₂O-、-OCF₂-、-CF₂S-、-SCF₂-、-(CH₂)_i-、-CF₂CH₂-、-CH₂CF₂-、-(CF₂)_i,-CH=CH- ,-CF= CF- ,-C ≡ C- ,-CH=CH-COO- ,-OCO-CH=CH- ,-C (R⁰)₂Or singly-bound, herein, R⁰For hydrogen or the alkane of carbon number 1 to 12 Base, i 1,2,3 or 4.

D is 0,1,2,3,4 or 5.

In formula (4-1), R⁹For the alkyl of carbon number 4 to 20, in the alkyl, at least one-CH₂It can be through-CH=CH- ,-CF The cycloalkylidene substitution of=CH- ,-CH=CF- ,-C ≡ C- or carbon number 3 to 8, in these bases, at least one hydrogen can take through fluorine or chlorine Generation.

R¹⁰For the alkyl of carbon number 1 to 25, in the alkyl, at least one-CH₂It can be through-NR⁰-、-O-、-S-、-CO-、- The cycloalkylidene substitution of COO- ,-OCO- ,-OCOO- or carbon number 3 to 8, herein, R⁰For hydrogen or the alkyl of carbon number 1 to 12, at least one A tertiary carbon (>CH-) can through nitrogen (>N-) replace, and at least one hydrogen can replace through fluorine or chlorine, wherein R¹⁰With OH structures Oxygen atom, the sulphur atom and level-ones of SH structures, two level or tertiary amine structure at least one of nitrogen-atoms.

In formula (3-1-1) to formula (3-1-4), R¹⁵For the alkyl or fluorine of carbon number 1 to 8.Ring Q and ring R independently is the Asias 1,4- The fluoro- 1,4- phenylenes of cyclohexyl, 1,4- phenylenes, 2-, the fluoro- 1,3- phenylenes of 2-, 2- ethyl -1,4- phenylenes, 2,6- diethyls Base -1,4- phenylenes, 2- Trifluoromethyl-1s, 4- phenylenes, bis- fluoro- 1,4- phenylenes of 2,3-, bis- fluoro- 1,4- phenylenes of 2,5-, Tetra- fluoro- 1,4- phenylenes of bis- fluoro- 1,4- phenylenes of 2,6- or 2,3,5,6-.Ring S is cyclohexyl or phenyl.

Z¹⁰For singly-bound ,-CH₂CH₂,-COO- or-OCO-.Z¹¹For singly-bound, the alkylidene of carbon number 1 to 15, carbon number 5 or 6 Ester ring type base or these combination, in these bases, at least one hydrogen can be through-OH ,-OR^a1、-COOH、-NH₂、-NHR^a1、-N (R^a1)₂, fluorine or chlorine substitution, herein, R^a1For the alkyl of carbon number 1 to 15, in the alkyl, 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.

Sp⁴For singly-bound ,-CH₂CH₂-、-CH₂CH₂CH₂-、-CH₂O- or-OCH₂-。Sp⁷For singly-bound or the alkylene of carbon number 1 to 5 Base, in the alkylidene ,-CH₂It can replace through-O- or-NH-.X³For-OH ,-COOH ,-SH ,-OCH₃Or-NH₂。X⁴For singly-bound Or-O-.S is 0,1,2,3,4 or 5.

Aromatic series base refers to aryl or the aryl being substituted.Heteroaryl refers to having at least one heteroatomic aromatic series Base.Aryl and heteroaryl can be monocycle or any one polycyclic.That is, there is these bases at least one ring, the ring can contract It closes (such as naphthalene), two rings can be linked (such as xenyl) by covalent bond, or can be with condensed ring and shackle Combination.Preferred heteroaryl has at least one of the group selected from nitrogen, oxygen, sulphur and phosphorus hetero atom.

Preferred aryl or heteroaryl have carbon number 6 to 25 or five-membered ring, six membered ring or seven Yuans rings.Preferred virtue Base or heteroaryl can be monocycle, and be alternatively two rings or tricyclic.These bases can be condensed ring, can also be substituted.

Preferred aryl is by from benzene, xenyl, terphenyl, [1,1'：3', 1 "] terphenyl, naphthalene, anthracene, binaphthyl, Phenanthrene, pyrene (pyrene), dihydropyrene (dihydropyrene),(chrysene), (perylene), aphthacene (tetracene), pentacene (pentacene), BaP, fluorenes (fluorene), indenes (indene), indenofluorene (indenofluorene), one hydrogen of removal and derivative monad radical in two fluorenes of spiral shell (spirobifluorene).

Preferred heteroaryl is by from pyrroles, pyrazoles, imidazoles, 1,2,3- triazoles, 1,2,4- triazoles, tetrazolium, furans, thiophene Pheno, selenophen, oxazole, isoxazoles, 1,2- thiazoles, 1,3- thiazoles, 1,2,3- oxadiazoles, 1,2,4- oxadiazoles, 1,2,5- oxadiazoles, The five-membered rings chemical combination such as 1,3,4- oxadiazoles, 1,2,3- thiadiazoles, 1,2,4- thiadiazoles, 1,2,5- thiadiazoles, 1,3,4- thiadiazoles Object or pyridine, pyridazine, pyrimidine, pyrazine, 1,3,5- triazines, 1,2,4- triazines, 1,2,3- triazines, 1,2,4,5- tetrazines, 1,2,3, A hydrogen and derivative monad radical are removed in the six-membered ring compounds such as 4- tetrazines, 1,2,3,5- tetrazines.

Preferred heteroaryl be also by from indoles, iso-indoles, indolizine, indazole, benzimidazole, benzotriazole, purine, Naphtho- imidazoles, phenanthro- imidazoles, pyridine-imidazole (pyridimidazole), pyrazine and imidazoles, quinoxaline and imidazoles, Ben Bing Evil Azoles, Nai Bing oxazoles, En Bing oxazoles, Fei Bing oxazole, isoxazoles, benzothiazole, benzofuran, isobenzofuran, dibenzofurans, Quinoline, isoquinolin, dish pyridine, benzo -5,6- quinoline, benzo -6,7- quinoline, benzo -7,8- quinoline, benzisoquinoline, acridine, pheno Thiazine, phenoxazines, benzo pyridazine, benzo pyrimidine, quinoxaline, coffee piperazine, naphthyridines, azepine carbazole, benzo carboline, phenanthridines, phenanthroline, Thieno [2,3b] thiophene, thieno [3,2b] thiophene, dithienothiophene, isothiophene, dibenzothiophenes, benzo thiophene two A hydrogen and derivative monad radical are removed in the condensed-cyclic compounds such as azoles thiophene.Preferred heteroaryl is also by that will be selected from this certainly The ring that two bases in a little five-membered ring, six membered ring, condensed rings are composed removes a hydrogen and derivative monad radical.These heteroaryls Base can replace through alkyl, alkoxy, alkylthio, fluorine, fluoroalkyl, aryl or heteroaryl.

Ester ring type base can be saturation, or be alternatively unsaturation.That is, these bases can only have singly-bound, or can also have The combination of singly-bound and multikey.The ring of saturation is better than undersaturated ring.

Ester ring type base can be a ring, or be alternatively multiple rings.The preference of these bases be carbon number 3 to 25 monocycle, Two rings or tricyclic, these bases can be condensed ring, can also be substituted.The preference of these bases be five-membered ring, six membered ring, seven Yuans rings or Eight Yuans rings, in these bases, at least one carbon can replace through silicon, at least one>CH- can be through>N- replaces, and at least one- CH₂It can replace through-O- or-S-.

Preferred ester ring type base is by from five-membered rings, rings such as pentamethylene, tetrahydrofuran, tetrahydrochysene thio-furan, pyrrolidines Six membered rings, the cycloheptane such as hexane, cyclohexene, oxinane, tetrahydrochysene thio-pyrylium, 1,3- dioxanes, 1,3- dithiane, piperidines etc. Seven Yuans rings, naphthane, decahydronaphthalene, indane, bicyclic [1.1.1] pentane, bicyclic [2.2.2] octane, loop coil [3.3] heptane, octahydro- Two hydrogen and derivative bilvalent radical are removed in the condensed rings such as 4,7- methylene indanes.

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.And then preferred P⁴、P⁵Or P⁶For formula (P-1), formula (P-2) or formula (P-3) institute table The base shown.Particularly preferred P⁴、P⁵Or P⁶For the base represented by formula (P-1) or formula (P-2).Most preferred P⁴、P⁵Or P⁶For formula (P- 1) base represented by.Preferred base represented by formula (P-1) is-OCO-CH=CH₂Or-OCO-C (CH₃)=CH₂.Formula (P-1) is extremely The wave of formula (P-5) 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.And then it is excellent The M of choosing¹For hydrogen or methyl, and preferred M in turn²Or M³For hydrogen.

Sp⁹、Sp¹⁰And Sp¹¹It 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 taken through-CH=CH- or-C ≡ C- In generation, in these bases, at least one hydrogen can replace through fluorine or chlorine.Preferred Sp⁹、Sp¹⁰Or Sp¹¹For singly-bound ,-CH₂CH₂-、- CH₂O-、-OCH₂,-COO- ,-OCO- ,-CO-CH=CH- or-CH=CH-CO-.And then preferred Sp⁹、Sp¹⁰Or Sp¹¹For list Key.

Ring T and ring V independently is 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, 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 T or ring V is phenyl.Ring U is 1,4- cyclohexylidenes, 1,4- cyclohexadienylidenes, 1,4- phenylenes, naphthalene -1,2- diyls, naphthalene -1,3- Diyl, naphthalene -1,4- diyls, naphthalene -1,5- diyls, naphthalene -1,6- diyls, naphthalene -1,7- diyls, naphthalene -1,8- diyls, naphthalene -2,3- diyls, Naphthalene -2,6- diyls, naphthalene -2,7- diyls, oxinane -2,5- diyls, 1,3- dioxane -2,5- diyls, pyrimidine -2,5- diyls or Pyridine -2,5- diyl, in these rings, at least one hydrogen can through fluorine, chlorine, the alkyl of carbon number 1 to 12, carbon number 1 to 12 alkoxy, Or the alkyl of carbon number 1 to 12 of at least one hydrogen through fluorine or chlorine substitution replaces.Preferred ring U is that 1,4- phenylenes or 2- are fluoro- 1,4- phenylenes.

Z¹²And Z¹³It 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.Preferred Z¹²Or Z¹³For Singly-bound ,-CH₂CH₂-、-CH₂O-、-OCH₂,-COO- or-OCO-.And then preferred Z¹²Or Z¹³For singly-bound.

T is 0,1 or 2.Preferred t is 0 or 1.U, v and w independently is 0,1,2,3 or 4, and the sum of u, v and w be 3 with On.Preferred u, v or w are 1 or 2.

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 (3-1-1) described in item 13 to compound (3-1-4).In these compounds, Preferably at least one of the first additive is compound (3-1-1).Preferably at least two of the first additive are compound The combination of (3-1-1) and compound (3-1-2).

Preferred compound (4) is the compound (4-1-1) described in item 14 to compound (4-1-29).In general, changing It closes object (3) and is better than compound (4).

Particularly preferred compound (3-1) is in following compound.

In formula (3-1-1-1) to formula (3-1-4-4), R¹⁵For the alkyl or fluorine of carbon number 1 to 8.

Particularly preferred compound (4-1) is selected from following compound (4-1-1-1) to compound (4-1-29-1).

Preferred compound (5) is the compound (5-1) described in item 18 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.And then about 0.01 weight % is preferably in a proportion of to the range of 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.And then preferred n is 7.The compound (7) that n is 7 is due to waving Hair property is small, therefore for after by element long-time use, not only at room temperature, but also at a temperature of close to ceiling temperature It maintains for big voltage retention effectively.In order to obtain said effect, antioxidant is preferably in a proportion of about 50ppm or more, In order not to reducing ceiling temperature, or in order not to improve lower limit temperature, antioxidant is preferably in a proportion of about 600ppm or less.Into And about 100ppm is preferably in a proportion of to the range of about 300ppm.

The preference of ultra-violet absorber is benzophenone derivates, benzoate derivatives, triazole derivative etc..Separately Outside, ammonia etc with steric hindrance light stabilizer it is also preferred that.In order to obtain said effect, these absorbents or stabilizer it is preferred Ratio is about 50ppm or more, in order not to reduce ceiling temperature, or in order not to improve lower limit temperature, these absorbents or stabilization Agent is preferably in a proportion of about 10000ppm or less.And then about 100ppm is preferably in a proportion of to the range of 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.And then about 1ppm is preferably in a proportion of to the range of about 500ppm.

In order to be suitable for the element that polymer stabilizing is orientated (PSA) type, and use polymerizable compound.Compound (5) is suitable Together in the purpose.Also composition will can be made an addition to together with compound (5) and the polymerizable compound different with compound (5) In.The preference of such polymerizable compound is acrylate, methacrylate, vinyl compound, ethyleneoxy chemical combination The compounds such as object, propenyl ether, epoxide (oxirane, oxetanes), vinyl ketone.And then preference is third Olefin(e) acid ester or methacrylate.Total weight based on polymerizable compound, compound (5) are preferably in a proportion of about 10 weight % More than.And then it is preferably in a proportion of about 50 weight % or more.Particularly preferred ratio is about 80 weight % or more.Particularly preferred ratio For 100 weight %.By the type of change compound (5), or by making other polymerizable compounds with ratio appropriate and changing It closes object (5) to combine, can adjust the reactivity of polymerizable compound or the pre-tilt angle of liquid crystal molecule.By the way that pre-tilt angle is optimized, It may achieve the short response time of element.The orientation of liquid crystal molecule 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 %.And then about 1 weight % is preferably in a proportion of to the range of 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、>At least one of the part-structure of N- etc.

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) It is to be synthesized using the method described in International Publication 2012-038026 bulletins.A part for compound (4) is commercially available.Change Closing object (5-1) is synthesized using the method described in International Publication 2013-161576 bulletins.A part for compound (7) It is commercially available.The compound that the n of formula (7) is 1 can be obtained from Sigma-Aldrich (Sigma-Aldrich Corporation) It takes.The compound (7) etc. that n is 7 is synthesized using the method described in No. 3660505 specifications of United States Patent (USP).

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 is kind) etc..Composition is profit With well known method, prepared by the compound obtained in the above described manner.For example, component cpd is mixed, then by adding Heat and so that it is 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 also be used for non-crystalline silicon-TFT elements or polysilicon-TFT elements.It also can 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 the composition containing polymer.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 polymer for maintaining the orientation.By the effect of the polymer, the response time of element shortens. Since the running that the image retention of image is liquid crystal molecule is bad, therefore by the effect of the polymer, 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.

An example of the method for element of the manufacture without alignment films is as described below.By liquid crystal compounds, polymerism chemical combination The mixture of object and polar compound is injected into the element without alignment films.In the state of applying voltage to the element Carry out light irradiation.It is irradiated by light by polymerizable compound is made to be polymerize.To include polymer and polarity by the polymerization The layer of the composition of compound is formed on substrate.

In the sequence, polar compound occurs to be arranged on substrate due to interaction because of polar group with substrate surface Row.The polar compound makes liquid crystal molecule be orientated.When applying voltage, further promote the orientation of liquid crystal molecule, according to According to the orientation, polymerizable compound is also orientated.Due to polymerizable compound be in this condition using ultraviolet light come It is polymerize, therefore generates the polymer for maintaining the orientation.By the effect of the polymer, the orientation of liquid crystal molecule is additionally It stabilizes, the response time of element shortens.Since the running that the image retention of image is liquid crystal molecule is bad, therefore pass through the polymer Effect, image retention also simultaneously improved.

[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 includes to be mixed at least two of the composition of embodiment Mixture made of conjunction.Synthesized compound is by nuclear magnetic resonance (nuclear magnetic resonance, NMR) point The methods of analysis is identified.The characteristic of compound, composition and element is measured by 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 limited using Agilent Technologies when the separation of component cpd Capillary column DB-1 (length 30m, internal diameter 0.32mm, the film thickness 0.25 of company (Agilent Technologies Inc.) manufacture μm；Fixed liquid phase is dimethyl polysiloxane；It is nonpolarity).After the tubing string is kept for 2 minutes at 200 DEG C, with 5 DEG C/min's Ratio 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 is calculated as the C-R5A types chromatopac (Chromatopac) or its same product of Shimadzu Seisakusho Ltd.'s manufacture.The gas phase color of gained Spectrogram shows 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 by the method described in measurement (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 ∥ are 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=n The formula of ∥-n ⊥ calculates.

(6) dielectric anisotropy (Δ ε；It is measured at 25 DEG C)：Dielectric is calculated according to the formula of Δ ε=ε ∥-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 (threshold voltage) (Vth；It is measured at 25 DEG C；V)：Big tomb electronics shares are used when measurement The LCD5100 type luminance meters of part Co., Ltd manufacture.Light source is halogen lamp.It is at the interval (cell gap) of two panels glass substrate 4 μm and frictional direction are to be put into sample in antiparallel VA elements for normally showing black pattern (normally black mode), are made The bonding agent hardened to ultraviolet light is by the component seal.To the element apply voltage (60Hz, rectangular wave) be As unit of 0.02V 20V is periodically increased to from 0V.At this point, measuring element irradiation light through element from vertical direction Light quantity.It is 100% to be formed in transmitance when the light quantity reaches maximum, and transmitance is 0% when the light quantity is minimum Voltage-transmittance curve.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, so preferably 95% with On.

(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.

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 1,4- cyclohexylidenes.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 combination Object (M18), polar compound (PC-1) to polar compound (PC-33), 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；Tc<-20℃；Δ n=0.113；Δ ε=- 4.0；Vth=2.18V；η=22.6mPas.

[composition (M2)]

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

[composition (M3)]

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

[composition (M4)]

NI=88.5 DEG C；Tc<-30℃；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；Tc<-30℃；Δ n=0.119；Δ ε=- 4.5；Vth=1.69V；η=31.4mPas.

[composition (M6)]

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

[composition (M7)]

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

[composition (M8)]

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

[composition (M9)]

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

[composition (M10)]

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

[composition (M11)]

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

[composition (M12)]

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

[composition (M13)]

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

[composition (M14)]

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

[composition (M15)]

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

[composition (M16)]

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

[composition (M17)]

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

[composition (M18)]

NI=75.9 DEG C；Tc<-20℃；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-33).

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

2. the vertical orientation of liquid crystal molecule

Embodiment 1

By polar compound (PC-1) with the ratio of 5 weight % and by polymerizable compound (RM-1) with 0.5 weight %'s Ratio makes an addition in composition (M1).The mixture is injected into the interval of two panels glass substrate on 100 DEG C of hot microscope carrier During (cell gap) is 4.0 μm and the element without alignment films.By using extra-high-pressure mercury vapour lamp USH-250-BY (oxtails (Ushio) motor manufacturing) to element irradiation ultraviolet light (28J), to make polymerizable compound be polymerize.By the element It is configured at the petrographic microscope of polarization element and analyzer orthogonal configuration, whether there is or not light leakages to observe to element irradiation light from lower section. When liquid crystal molecule is fully orientated, light does not penetrate element, judge vertical orientation for " good ".Observing the light through element When, it is expressed as " bad ".

Embodiment 2 is to embodiment 33 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 polymerizable compound.

The vertical orientation of 4. molecule of table

It is such according to table 4, in embodiment 1 to embodiment 33, 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 the polymer generated by polymerizable compound plays an important role to the vertical orientation of liquid crystal molecule.

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 polar compound as the first additive and containing at least three polymerism bases Polymerizable compound 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 1,4- cyclohexylidenes, 1,4- cyclohexadienylidenes, oxinane -2,5- diyls, 1,4- phenylenes, at least one hydrogen take through fluorine or chlorine Naphthalene -2,6- diyls that the 1,4- phenylenes in generation, naphthalene -2,6- diyls, at least one hydrogen replace through fluorine or chlorine, chromogen alkane -2,6- two Chromogen alkane -2,6- the diyls that base or at least one hydrogen replace through fluorine or chlorine；Ring B is bis- fluoro- 1,4- phenylenes of 2,3-, 2- is chloro- The fluoro- 1,4- phenylenes of 3-, bis- fluoro- 5- methyl-1s of 2,3-, 4- phenylenes, tri- fluoronaphthalene -2,6- diyls of 3,4,5- or 7,8- difluoro colors Former alkane -2,6- diyls；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- 1,4- phenylenes of 1,4- cyclohexylidenes, 1,4- phenylenes, 2- or bis- fluoro- 1,4- of 2,5- are sub- 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 contains polar compound as the first addition Object, the polar compound contain with the heteroatomic polar group in nitrogen, oxygen, 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,

MES-R⁶ (3)

(R⁵)_x-R⁶ (4)

In formula (3), MES is the liquid crystal former base at least one ring；In formula (4), R⁵For the alkyl of carbon number 4 to 20, the alkyl In, at least one-CH₂It can be taken through the cycloalkylidene of-CH=CH- ,-CF=CH- ,-CH=CF- ,-C ≡ C- or carbon number 3 to 8 In generation, in these bases, at least one hydrogen can replace through fluorine or chlorine；In formula (3) and formula (4), R⁶For oxygen atom, SH with OH structures The polar group of at least one of the sulphur atom and level-one of structure, the nitrogen-atoms of two level or tertiary amine structure；X is 1 or 2.

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

In formula (3-1), 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 through nitrogen (>N-) replacing, in these bases, at least one hydrogen can replace through fluorine or chlorine, herein, R⁰For hydrogen or carbon The alkyl of number 1 to 12；R⁸For the alkyl of carbon number 1 to 25, in the alkyl, at least one-CH₂It can be through-NR⁰-、-O-、-S-、- The cycloalkylidene substitution of CO- ,-COO- ,-OCO- ,-OCOO- or carbon number 3 to 8, at least one tertiary carbon (>CH-) can through nitrogen (> N-) replacing, 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, wherein R⁸ At least one in the sulphur atom of oxygen atom, SH structures or the nitrogen-atoms of level-one, two level or tertiary amine structure with OH structures Kind；Ring F and ring G independently be the aromatic series base of carbon number 6 to 25, the heteroaromatic base of carbon number 5 to 25, carbon number 3 to 25 alicyclic ring The heterolipid cyclic group of formula base or carbon number 4 to 25, these bases can be condensed ring, and in these bases, at least one hydrogen can replace through base T, Herein, base T is-OH ,-(CH₂)_i- OH, fluorine, chlorine ,-CN ,-NO₂,-NCO ,-NCS ,-OCN ,-SCN ,-C (=O) N (R⁰)₂,-C (= O)R⁰、-N(R⁰)₂、-(CH₂)_i-N(R⁰)₂, the aryl of carbon number 6 to 20, the heteroaryl of carbon number 6 to 20, carbon number 1 to 25 alkyl, The alkyl oxycarbonyl of the alkoxy of carbon number 1 to 25, the alkyl-carbonyl of carbon number 2 to 25, the alkoxy carbonyl of carbon number 2 to 25, carbon number 2 to 25 The alkoxy carbonyloxy group of oxygroup or carbon number 2 to 25, 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, and i is 1,2,3 or 4；Z⁴For-O- ,-S- ,-CO- ,-CO-O- ,-OCO- ,-O-CO-O- ,- OCH₂-、-CH₂O-、-SCH₂-、-CH₂S-、-CF₂O-、-OCF₂-、-CF₂S-、-SCF₂-、-(CH₂)_i-、-CF₂CH₂-、- CH₂CF₂-、-(CF₂)_i,-CH=CH- ,-CF=CF- ,-C ≡ C- ,-CH=CH-COO- ,-OCO-CH=CH- ,-C (R⁰)₂Or Singly-bound, herein, R⁰For hydrogen or the alkyl of carbon number 1 to 12, and i is 1,2,3 or 4；D is 0,1,2,3,4 or 5.

11. liquid-crystal composition according to any one of claim 1 to 10, contain the pole represented by the formula (4-1) At least one of the group of property compound compound as the first additive,

R⁹-R¹⁰ (4-1)

In formula (4-1), R⁹For the alkyl of carbon number 4 to 20, in the alkyl, at least one-CH₂It can be through-CH=CH- ,-CF= The cycloalkylidene substitution of CH- ,-CH=CF- ,-C ≡ C- or carbon number 3 to 8, in these bases, at least one hydrogen can take through fluorine or chlorine Generation；R¹⁰For the alkyl of carbon number 1 to 25, in the alkyl, at least one-CH₂It can be through-NR⁰-、-O-、-S-、-CO-、-COO-、- The cycloalkylidene of OCO- ,-OCOO- or carbon number 3 to 8 replaces, at least one tertiary carbon (>CH-) can through nitrogen (>N-) replace, these In base, at least one hydrogen can replace through fluorine or chlorine, herein, R⁰For hydrogen or the alkyl of carbon number 1 to 12, wherein R¹⁰With OH structures Oxygen atom, the sulphur atom and level-ones of SH structures, two level or tertiary amine structure at least one of nitrogen-atoms.

12. liquid-crystal composition according to claim 9, wherein in formula according to claim 9 (3) and formula (4), R⁶ For the base in the group for the polar group being selected from represented by formula (A1) to formula (A4),

In formula (A1) to formula (A4), Sp⁴、Sp⁶And Sp⁷Independently be singly-bound or base (- Sp "-X " -), herein, Sp " be carbon number 1 to 20 alkylidene, 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- replace, in these bases, at least one hydrogen can replace through fluorine, chlorine or-CN, and X " is-O- ,-S- ,-CO- ,-CO- O-、-O-CO-、-O-CO-O-、-CO-N(R⁰)-、-N(R⁰)-CO-、-N(R⁰)-CO-N(R⁰)-、-OCH₂-、-CH₂O-、- SCH₂-、-CH₂S-、-CF₂O-、-OCF₂-、-CF₂S-、-SCF₂-、-CF₂CH₂-、-CH₂CF₂-、-CF₂CF₂,-CH=N- ,-N= CH- ,-N=N- ,-CH=CR⁰-、-CY²=CY³,-C ≡ C- ,-CH=CH-CO-O- ,-O-CO-CH=CH- or singly-bound, herein, R⁰For hydrogen or the alkyl of carbon number 1 to 12, and Y²And Y³It independently is hydrogen, fluorine, chlorine or-CN；Sp⁵For>CH-、>CR^a1-、>N- or> C<；X¹For-OH ,-OR^a1、-COOH、-NH₂、-NHR^a1、-N(R^a1)₂、-SH、-SR^a1、

Herein, R⁰For hydrogen or the alkyl of carbon number 1 to 12；X²For-O- ,-CO- ,-NH- ,-NR^a1,-S- or singly-bound；Z⁹For carbon number 1 to 15 alkylidene, the ester ring type base of carbon number 5 or 6 or these combination, in these bases, at least one hydrogen can through-OH ,- OR^a1、-COOH、-NH₂、-NHR^a1、-N(R^a1)₂, fluorine or chlorine substitution；Herein, R^a1For the alkyl of carbon number 1 to 15, in the alkyl, At least one-CH₂It can replace through-C ≡ C- ,-CH=CH- ,-COO- ,-OCO- ,-CO- or-O-, it is at least one in these bases Hydrogen can replace through fluorine or chlorine；Ring P is the aromatic series base of carbon number 6 to 25 or the ester ring type base of carbon number 3 to 25, these bases can be condensation Ring, in these bases, one to three hydrogen can be through R^LSubstitution, herein, R^LFor-OH ,-(CH₂)_r- OH, fluorine, chlorine ,-CN ,-NO₂、- NCO ,-NCS ,-OCN ,-SCN ,-C (=O) N (R⁰)₂,-C (=O) R⁰、-N(R⁰)₂、-(CH₂)_r-N(R⁰)₂、-SH、-SR⁰, carbon number 6 To 20 aryl, the alkane of the heteroaryl of carbon number 6 to 20, the alkyl of carbon number 1 to 25, the alkoxy of carbon number 1 to 25, carbon number 2 to 25 The alkoxy carbonyloxy group of base carbonyl, the alkoxy carbonyl of carbon number 2 to 25, the alkyl carbonyl oxy of carbon number 2 to 25 or carbon number 2 to 25, 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, and r be 1,2,3 or 4；P is 0,1,2 or 3；Q is 2,3,4 or 5.

13. liquid-crystal composition according to claim 9 or 10, wherein the first additive is selected from formula (3-1-1) to formula (3- At least one of group of polar compound represented by 1-4) compound,

In formula (3-1-1) to formula (3-1-4), R¹⁵For the alkyl or fluorine of carbon number 1 to 8；Ring Q and ring R independently is the Asias 1,4- hexamethylene The fluoro- 1,4- phenylenes of base, 1,4- phenylenes, 2-, the fluoro- 1,3- phenylenes of 2-, 2- ethyl -1,4- phenylenes, diethyl -1 2,6-, 4- phenylenes, 2- Trifluoromethyl-1s, 4- phenylenes, bis- fluoro- 1,4- phenylenes of 2,3-, bis- fluoro- 1,4- phenylenes of 2,5-, 2,6- bis- Tetra- fluoro- 1,4- phenylenes of fluoro- 1,4- phenylenes or 2,3,5,6-；Ring S is cyclohexyl or phenyl；Z¹⁰For singly-bound ,-CH₂CH₂-、- COO- or-OCO-；Z¹¹For singly-bound, the alkylidene of carbon number 1 to 15, the ester ring type base of carbon number 5 or 6 or these combination, these In base, at least one hydrogen can be through-OH ,-OR^a1、-COOH、-NH₂、-NHR^a1、-N(R^a1)₂, fluorine or chlorine substitution, herein, R^a1For carbon The alkyl of number 1 to 15, in the alkyl, at least one-CH₂Can through-C ≡ C- ,-CH=CH- ,-COO- ,-OCO- ,-CO- or- O- replaces, and in these bases, at least one hydrogen can replace through fluorine or chlorine；Sp⁴For singly-bound ,-CH₂CH₂-、-CH₂CH₂CH₂-、-CH₂O- Or-OCH₂-；Sp⁷For singly-bound or the alkylidene of carbon number 1 to 5, in the alkylidene ,-CH₂It can replace through-O- or-NH-；S be 0, 1,2,3,4 or 5；X³For-OH ,-COOH ,-SH ,-OCH₃Or-NH₂；X⁴For singly-bound or-O-.

14. the liquid-crystal composition according to claim 9 or 11, wherein the first additive is selected from formula (4-1-1) to formula (4- At least one of group of polar compound represented by 1-29) compound,

In formula (4-1-1) to formula (4-1-29), R⁹For the alkyl of carbon number 4 to 20, in the alkyl, at least one-CH₂Can through- The cycloalkylidene substitution of CH=CH- ,-CF=CH- ,-CH=CF- ,-C ≡ C- or carbon number 3 to 8, in these bases, at least one hydrogen It can replace through fluorine or chlorine.

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

16. the liquid-crystal composition according to any one of claim 1 to 15, 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 1,4- cyclohexylidenes, 1,4- cyclohexadienylidenes, 1,4- phenylenes, naphthalene -1,2- diyls, naphthalene -1,3- diyls, naphthalene -1,4- diyls, Naphthalene -1,5- diyls, naphthalene -1,6- diyls, naphthalene -1,7- diyls, naphthalene -1,8- diyls, naphthalene -2,3- diyls, naphthalene -2,6- diyls, 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；Z¹²And Z¹³It 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；Sp⁹、Sp¹⁰And Sp¹¹It 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.

17. liquid-crystal composition according to claim 16, wherein in formula according to claim 16 (5), P⁴、P⁵And P⁶The 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.

18. the liquid-crystal composition according to any one of claim 1 to 17 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；Sp⁹、Sp¹⁰And Sp¹¹It 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.

19. the liquid-crystal composition according to any one of claim 16 to 18, wherein the weight based on liquid-crystal composition, the The ratio of two additives is the range of 0.03 weight % to 10 weight %.

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

21. liquid crystal display element according to claim 20, the wherein operating mode of liquid crystal display element are 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.

22. a kind of liquid crystal display element of polymer stabilizing orientating type, described in any one of with good grounds claim 1 to 19 Liquid-crystal composition, and the polymerizable compound in the liquid-crystal composition is polymerize.

23. a kind of liquid crystal display element without alignment films, containing the liquid described in any one of with good grounds claim 1 to 19 Crystal composite, and the polymerizable compound in the liquid-crystal composition is polymerize.

24. a kind of purposes of liquid-crystal composition according to any one of claim 1 to 19, is used for liquid crystal display element In.

25. a kind of purposes of liquid-crystal composition according to any one of claim 1 to 19, is used for polymer stabilizing and takes Into the liquid crystal display element of type.

26. a kind of purposes of liquid-crystal composition according to any one of claim 1 to 19 is used to not have alignment films Liquid crystal display element in.