CN107109233A

CN107109233A - Liquid-crystal composition and liquid crystal display cells

Info

Publication number: CN107109233A
Application number: CN201580072430.7A
Authority: CN
Inventors: 松田尚子; 斋藤将之
Original assignee: JNC Corp; Chisso Petrochemical Corp
Current assignee: JNC Corp; JNC Petrochemical Corp
Priority date: 2015-01-20
Filing date: 2015-12-24
Publication date: 2017-08-29
Also published as: JP2020073701A; KR20170107436A; TW201627409A; WO2016117271A1; TWI672332B; JP6729395B2; JPWO2016117271A1

Abstract

The present invention provides one kind comprising polymerizable compound (or its polymer) and polar compound and can reach the vertical orientated liquid-crystal composition of liquid crystal molecule, the liquid crystal display cells containing the composition using the effect of these compounds.The composition meets at least one characteristic in the characteristics such as high ceiling temperature, low lower limit temperature, small viscosity, appropriate optical anisotropy, negative big dielectric anisotropy, or at least two characteristics with appropriate balance.The present invention is a kind of to contain polymerizable compound as the first additive and contain polar compound as the second additive and with the nematic liquid-crystal composition of negative dielectric anisotropy, the composition can also contain the specific liquid crystal compounds with negative big dielectric anisotropy and the specific liquid crystal compounds with high ceiling temperature or small viscosity, and be a kind of liquid crystal display cells containing the composition.

Description

Liquid-crystal composition and liquid crystal display cells

Technical field

The present invention relates to a kind of liquid-crystal composition, liquid crystal display cells containing the composition etc..More particularly to it is a kind of It can reach liquid crystal point comprising polar compound and polymerizable compound (or its polymer) and using the effect of these compounds The vertical orientated dielectric anisotropy of son is negative liquid-crystal composition, and liquid crystal display cells.

Background technology

In liquid crystal display cells, the operating mode based on liquid crystal molecule be categorized as phase transformation (phase change, PC), torsion Qu Xianglie (twisted nematic, TN), super twisted nematic (super twisted nematic, STN), electrically conerolled birefringence (electrically controlled birefringence, ECB), optical compensation curved (optically Compensated bend, OCB), it is coplanar switching (in-plane switching, IPS), vertical orientated (vertical Alignment, VA), fringing field switching (fringe field switching, FFS), electric field induction light reaction orientation (field-induced photo-reactive alignment, FPA) isotype.Type of drive based on element is categorized 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 categorized as non-crystalline silicon (amorphous silicon) and polysilicon (polycrystal silicon).The latter is categorized as high temperature according to manufacturing step Type and low form.Being categorized as using the reflection-type of natural light, the infiltration type using backlight based on light source and utilize natural light With the semi-transmission type of both backlights.

Liquid crystal display cells contain with nematic liquid-crystal composition.The composition has appropriate characteristic.Pass through The characteristic of the composition is improved, the AM elements with superperformance can be obtained.Association in both characteristics is summarized in down State in table 1.It is further illustrated based on commercially available AM elements come the characteristic to composition.Nematic temperature range and element Workable temperature range is associated.Nematic preferred upper limit temperature is more than about 70 DEG C, moreover, nematic preferred lower limit Temperature is less than about -10 DEG C.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 of composition.Particularly preferably It is small for the viscosity under low temperature.

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

In general liquid crystal display cells, the vertical orientated of liquid crystal molecule reaches using specific alignment film of polyimide Into.In the liquid crystal display cells of polymer stabilizing orientation (polymer sustained alignment, PSA) type, effectively make With the effect of polymer.First, the composition added with a small amount of polymerizable compound is injected into element.Then, it is right on one side Apply voltage between the substrate of the element, while to composition irradiation ultraviolet radiation.Polymerizable compound is polymerize and in group The network structure of polymer is generated in compound.In the composition, the orientation of liquid crystal molecule can be controlled using polymer, therefore The response time of element shortens, and the image retention of image is improved.Pattern with TN, ECB, OCB, IPS, VA, FFS, FPA etc Element in can expect such a effect of polymer.

On the other hand, the liquid crystal containing polymer and polar compound is used in the liquid crystal display cells without 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 is adsorbed in substrate surface and arranged.Liquid crystal molecule is orientated according to the arrangement.Then, it is right on one side Apply voltage between the substrate of the element, while to composition irradiation ultraviolet radiation.Herein, polymerizable compound is polymerize, And stabilize the orientation of liquid crystal molecule.In the composition, liquid crystal point can be controlled using polymer and polar compound The orientation of son, therefore the shortening of the response time of element, the image retention of image are improved.And then, in the element without alignment films not The step of needing to form alignment films.Due in the absence of alignment films, therefore utilize the interaction of alignment films and composition, the electricity of element Resistance will not be reduced.Can expect in the element of pattern with TN, ECB, OCB, IPS, VA, FFS, FPA etc using polymer with Such a effect of the combination of polar compound.

The composition with positive dielectric anisotropy is used in AM elements with TN patterns.AM members with VA patterns The composition with negative dielectric anisotropy is used in part.Being used in AM elements with IPS patterns or FFS mode has just Or the composition of negative dielectric anisotropy.Used in the AM elements of polymer stabilizing orientating type have positive or negative dielectric each to The composition of the opposite sex.The example of liquid-crystal composition with negative dielectric anisotropy is disclosed in following patent document 1 to special In sharp document 3.

Prior art literature

Patent document

The Japanese Patent Laid-Open 2003-307720 publications of patent document 1

The Japanese Patent Laid-Open 2004-131704 publications of patent document 2

Patent document No. 1889894 specifications of 3 European Patent Application Publication

The content of the invention

Invent problem to be solved

One object of the present invention includes polymerizable compound (or its polymer) and polar compound and utilization to be a kind of The effect of these compounds can reach the vertical orientated liquid-crystal composition of liquid crystal molecule.Another object is a kind of liquid crystal combination Thing, its nematic high ceiling temperature, nematic low lower limit temperature, small viscosity, appropriate optical anisotropy, Negative big dielectric anisotropy, big ratio resistance, the high stability to ultraviolet, in the characteristics such as the high stability of heat, meeting At least one characteristic.Another object is a kind of liquid-crystal composition with appropriate balance between at least two characteristics.Another mesh For a kind of liquid crystal display cells containing such a composition.A further object has short response time, big voltage to be a kind of The AM elements of conservation rate, low starting voltage, big contrast than characteristics such as, long-lives.

The technological means solved the problems, such as

The present invention contains selected from least one of the group of compound represented by formula (1) polymerizable compound to be a kind of As the first additive, contain at least one polar compound as the second additive and with negative dielectric anisotropy Liquid-crystal composition, and liquid crystal display cells containing the composition.

In formula (1), ring A and ring C independently be cyclohexyl, cyclohexenyl group, phenyl, 1- naphthyls, 2- naphthyls, oxinane- In 2- bases, 1,3- dioxane -2- bases, pyrimidine -2-base or pyridine -2- bases, these rings, at least one hydrogen can be through fluorine, chlorine, carbon number 1 The alkyl for the carbon number 1 to 12 that the alkoxy or at least one hydrogen of alkyl, carbon number 1 to 12 to 12 replace through fluorine or chlorine replaces；Ring B 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 In base, these rings, at least one hydrogen can 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 hydrogen replaces through fluorine or chlorine replaces；Z¹And Z²The alkylidene of singly-bound or carbon number 1 to 10 independently is, it is described In alkylidene, at least one-CH₂- can replace through-O- ,-CO- ,-COO- or-OCO-, moreover, at least one-CH₂-CH₂- can Through-CH=CH- ,-C (CH₃)=CH- ,-CH=C (CH₃)-or-C (CH₃)=C (CH₃In)-substitution, these bases, at least one Hydrogen can replace through fluorine or chlorine；P¹、P²And P³For polymerism base；Sp¹、Sp²And Sp³It independently is the Asia of singly-bound or carbon number 1 to 10 In alkyl, the alkylidene, at least one-CH₂- can replace through-O- ,-COO- ,-OCO- or-OCOO-, moreover, at least one Individual-CH₂-CH₂- can replace through-CH=CH- or-C ≡ C-, in these bases, at least one hydrogen can replace through fluorine or chlorine；A be 0,1, Or 2；B, c and d independently are 0,1,2,3 or 4；Wherein, when ring A and ring C is phenyl, a is 1 or 2, and when a is 1, Sp¹And Sp³For singly-bound.

The effect of invention

An advantage of the invention includes polymerizable compound (or its polymer) and polar compound and utilization to be a kind of The effect of these compounds can reach the vertical orientated liquid-crystal composition of liquid crystal molecule.Another advantage is a kind of liquid crystal combination Thing, its nematic high ceiling temperature, nematic low lower limit temperature, small viscosity, appropriate optical anisotropy, Negative big dielectric anisotropy, big ratio resistance, the high stability to ultraviolet, in the characteristics such as the high stability of heat, meeting At least one characteristic.Another advantage is the liquid-crystal composition with appropriate balance between at least two characteristics.Another advantage is Liquid crystal display cells containing such a composition.Another advantage is with short response time, big voltage retention, low threshold The AM elements of voltage, big contrast than characteristics such as, long-lives.

Embodiment

The application method of term in this specification is as described below.Sometimes by " liquid-crystal composition " and " liquid crystal display cells " Term be briefly referred to as " composition " and " element "." liquid crystal display cells " are liquid crystal display panel and LCD MODULE General name." liquid crystal compounds " are the compounds with nematic phase, the equal liquid crystalline phase of stratose, though and do not have liquid crystalline phase and go out The change in composition is mixed in the purpose for the characteristic for adjusting nematic temperature range, viscosity, dielectric anisotropy etc The general name of compound.The compound has the six membered ring of such as Isosorbide-5-Nitrae-cyclohexylidene or Isosorbide-5-Nitrae-phenylene etc, its molecular structure For bar-shaped (rod like)." polymerizable compound " is in order at the chemical combination for making the purpose of generation polymer in composition and adding Thing.

Liquid-crystal composition is prepared by the way that plurality of liquid crystals compound is mixed.Regarded in the liquid-crystal composition Addition optically active compound, antioxidant, ultra-violet absorber, pigment, defoamer, 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 such a order.I.e. Just in the case of 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 is represented.The ratio (addition) of additive is by based on not comprising addition The weight percent (weight %) of the weight of the liquid-crystal composition of thing is represented.Sometimes parts per million by weight (ppm) is used.Polymerization The ratio of initiator and polymerization inhibitor is that exceptionally weight based on polymerizable compound is represented.

Sometimes " nematic ceiling temperature " is referred to as " ceiling temperature ".Sometimes by " nematic lower limit temperature " referred to as For " lower limit temperature "." ratio resistance is big " refer to composition in the starting stage not only at room temperature, and close to upper limit temperature Also there is big ratio resistance, moreover, after a long time use not only at room temperature, and close to upper limit temperature at a temperature of degree Also there is big ratio 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, moreover, after a long time use not only in room temperature Under, and also with big voltage retention at a temperature of close to ceiling temperature.In composition or element, sometimes through when Research characteristic before and after change experiment (including activated deterioration test)." raising dielectric anisotropy " is expressed in dielectric anisotropy During for positive composition, 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 will be selected from the change represented by formula (1) At least one of group of compound compound is referred to as " compound (1) "." compound (1) " refers to one represented by formula (1) The mixture of kind of compound, the mixture of two kinds of compounds or more than three kinds of compound.On the chemical combination represented by other formulas Thing is also identical.The statement of " at least one ' A ' " refers to that the quantity of ' A ' is any.The table of " at least one ' A ' can replace through ' B ' " State and refer to when the quantity of ' A ' is one, the position of ' A ' is any, when the quantity of ' A ' is two or more, their position Also can unrestrictedly it select.This rule is also applied for the statement of " at least one ' A ' replaces through ' B ' ".

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 compound (2-1) R¹For ethyl, and chemical combination The R of thing (2-2)¹For the situation of ethyl.Also there is compound (2-1) R¹For ethyl, and the R of compound (2-2)¹For the feelings of propyl group Condition.This rule is also applied for the mark of other terminal groups etc..In formula (2), when e is 2, there are two ring D.The compound In, two rings represented by two ring D can be identical, or also can be different.Any two when this rule is also applied for e more than 2 Individual ring D.This rule is also applied for other marks.This rule is also applied for two-Sp of compound (1-11)²-P²Feelings Condition.

The marks such as A, B, C, the D surrounded with hexagon are corresponding with the ring such as ring A, ring B, ring C, ring D respectively, represent six membered ring, The rings such as condensed ring.In formula (1), the crosscutting oblique line of the hexagon being represented to, any hydrogen on ring can be through-Sp¹-P¹Deng base substitution. Subscripts such as ' b ' represents the quantity for the base being substituted.When subscript ' b ' is 0, represent that such a substitution is not present.It is 2 in subscript ' b ' During the above, there are multiple-Sp on ring A¹-P¹。-Sp¹-P¹Represented multiple bases can be identical, or also can be different.

The fluoro- 1,4- phenylenes of 2- refer to two kinds of following bilvalent radicals.In chemical formula, fluorine can be towards left (L), or towards the right side (R).This rule is also applied for the asymmetric by what is removed two hydrogen from ring and generate of oxinane -2,5- diyls etc Bilvalent radical.This rule is also applied for the divalence bond base of carbonyloxy group (- COO- or-OCO-) etc.

" at least one-CH₂- can replace through-O- " etc statement use in this description.Under this case ,-CH₂- CH₂-CH₂- not adjacent-CH can be passed through₂- warp-O- replaces and is converted to-O-CH₂-O-.However, adjacent-CH₂- will not be through-O- Substitution.Because generation-O-O-CH in this substitution₂- (peroxide).That is, this statement refers to "-a CH₂- can be taken through-O- Generation " and " at least two-CH not abutted₂Both-can replace through-O- ".This rule is not only applicable to be substituted by-O- feelings Condition, is also applied to be substituted by the situation of the bilvalent radical such as-CH=CH- or-COO- etc.In formula (5), R⁵For carbon number 4 to 20 At least one-CH in alkyl, the alkyl₂- can replace through-CH=CH- etc..Pass through the substitution, the carbon number increase of alkyl.This When, maximum carbon number is 30.This rule is also applied for alkylidene, cycloalkylidene etc..

The alkyl of liquid crystal compounds is straight-chain or branch-like, not comprising cyclic alkyl.Straight-chain alkyl is better than dividing Branch shape alkyl.These situations are also identical for terminal groups such as alkoxy, alkenyls.The spatial configuration related to 1,4- cyclohexylidenes leads to It is often that anti-configuration is better than cis-configuration.Halogen refers to fluorine, chlorine, bromine, iodine.It is preferred that halogen be fluorine or chlorine.Especially preferred halogen Element is fluorine.

The present invention is following items etc..

A kind of 1. liquid-crystal compositions of item, it contains poly- selected from least one of group of compound represented by formula (1) Conjunction property compound contains at least one polar compound as the second additive as the first additive, and with negative Jie Electrical anisotropy,

2. liquid-crystal composition according to item 1 of item, wherein, in formula (1), P¹、P²And P³It independently is selected from formula (P-1) Polymerism base into the group of the base represented by formula (P-5),

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

3. liquid-crystal composition according to item 1 or item 2 of item, wherein, the first additive is selected from formula (1-1) to formula (1- 12) at least one of group of compound represented by polymerizable compound,

Formula (1-1) is into formula (1-12), P¹、P²And P³It independently is selected from the base represented by formula (P-1) to formula (P-3) Polymerism base in group, herein, M¹、M²And M³Hydrogen, fluorine, the alkyl of carbon number 1 to 5 or at least one hydrogen independently are through fluorine Or the alkyl of the carbon number 1 to 5 of chlorine substitution；

Sp¹、Sp²And Sp³It independently is in the alkylidene of singly-bound or carbon number 1 to 10, the alkylidene, at least one- CH₂- can replace through-O- ,-COO- ,-OCO- or-OCOO-, moreover, at least one-CH₂-CH₂- can be through-CH=CH- or-C ≡ C- replaces, in these bases, and at least one hydrogen can replace through fluorine or chlorine.

4. liquid-crystal composition according to any one of item 1 to item 3 of item, wherein, the weight based on liquid-crystal composition, the The ratio of one additive is 0.03 weight % to 10 weight % scope.

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

In formula (2), R¹And R²It independently is the alkyl, the alkoxy of carbon number 1 to 12, the alkene of carbon number 2 to 12 of carbon number 1 to 12 The alkenyloxy group of base or carbon number 2 to 12；Ring D and ring F independently are the sub- benzene of 1,4- cyclohexylidenes, 1,4- cyclohexadienylidenes, 1,4- 1,4- phenylenes or oxinane -2,5- diyls that base, at least one hydrogen replace through fluorine or chlorine；Ring E is the fluoro- 1,4- of 2,3- bis- The fluoro- 1,4- phenylenes of the chloro- 3- of phenylene, 2-, the fluoro- 5- methyl isophthalic acids of 2,3- bis-, 4- phenylenes, the fluoronaphthalene -2,6- diyls of 3,4,5- tri-, Or 7,8- difluoros chroman (chroman) -2,6- diyls；Z³And Z⁴It independently is singly-bound ,-CH₂CH₂-、-CH₂O-、-OCH₂-、- COO- or-OCO-；E is 1,2 or 3, f are 0 or 1, moreover, e and f's and for less than 3.

6. liquid-crystal composition according to any one of item 1 to item 5 of item, it contains selected from formula (2-1) to formula (2-21) At least one of represented group of compound compound as first composition,

Formula (2-1) is into formula (2-21), R¹And R²It independently is the alkyl, the alkoxy of carbon number 1 to 12, carbon of carbon number 1 to 12 The alkenyl of number 2 to 12 or the alkenyloxy group of carbon number 2 to 12.

7. liquid-crystal composition according to item 5 or item 6 of item, wherein, the weight based on liquid-crystal composition, first composition Ratio is 10 weight % to 90 weight % scope.

8. liquid-crystal composition according to any one of item 1 to item 7 of item, it contains selected from the chemical combination represented by formula (3) At least one of group of thing compound as second composition,

In formula (3), R³And R⁴It independently is the alkyl, the alkoxy of carbon number 1 to 12, the alkene of carbon number 2 to 12 of carbon number 1 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 G and ring I independently are the fluoro- 1,4- phenylenes of 1,4- cyclohexylidenes, 1,4- phenylenes, 2- or 2,5- bis- is fluoro- 1,4- phenylenes；Z⁵For singly-bound ,-CH₂CH₂-、-CH₂O-、-OCH₂- ,-COO- or-OCO-；G is 1,2 or 3.

9. liquid-crystal composition according to any one of item 1 to item 8 of item, it contains selected from formula (3-1) to formula (3-13) At least one of represented group of compound compound as second composition,

Formula (3-1) is into formula (3-13), R³And R⁴It independently is the alkyl, the alkoxy of carbon number 1 to 12, carbon of carbon number 1 to 12 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 take through fluorine or chlorine The alkenyl of the carbon number 2 to 12 in generation.

10. liquid-crystal composition according to item 8 or item 9 of item, wherein, the weight based on liquid-crystal composition, second composition Ratio be 10 weight % to 90 weight % scope.

11. liquid-crystal composition according to any one of item 1 to item 10, wherein, the second additive be containing with The polar compound of heteroatomic polar group in nitrogen, oxygen, sulphur and phosphorus.

12. liquid-crystal composition according to any one of item 1 to item 11 of item, it contains selected from formula (4) and formula (5) institute table At least one of group of compound shown polar compound as the second additive,

MES-R⁶ (4)

(R⁵)_h-R⁶ (5)

In formula (4), MES is the mesomorphic base with least one ring；In formula (5), R⁵It is described for the alkyl of carbon number 4 to 20 In alkyl, at least one-CH₂- can the sub- cycloalkanes through-CH=CH- ,-CF=CH- ,-CH=CF- ,-C ≡ C- or carbon number 3 to 8 Base replaces, in these bases, and at least one hydrogen can replace through fluorine or chlorine；In formula (4) and formula (5), R⁶It is former for the oxygen with OH structures The polar group of at least one of son, the sulphur atom of SH structures and one-level, the nitrogen-atoms of two grades or tertiary amine group；H be 1 or 2。

13. liquid-crystal composition according to any one of item 1 to item 12 of item, it contains selected from represented by formula (4-1) At least one of group of compound compound as the second additive,

In formula (4-1), ring J and ring K independently be the aromatic series base of carbon number 6 to 25, the heteroaromatic base of carbon number 5 to 25, The ester ring type base of carbon number 3 to 25 or the heterolipid cyclic group of carbon number 4 to 25, these bases can be condensed ring, in these bases, at least one Individual hydrogen can replace through base T, herein, and base T is-OH ,-(CH₂)_j- OH, halogen ,-CN ,-NO₂、-NCO、-NCS、-OCN、-SCN、-C (=O) N (R⁰)₂,-C (=O) R⁰、-N(R⁰)₂、-(CH₂)_j-N(R⁰)₂, the aryl of carbon number 6 to 20, the heteroaryl of carbon number 6 to 20, 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, the alkoxy carbonyl of carbon number 2 to 25, In the alkyl carbonyl oxy of carbon number 2 to 25 or the alkoxy carbonyloxy group of carbon number 2 to 25, these bases, at least one hydrogen can be through fluorine or chlorine Substitution, herein, R⁰For hydrogen or the alkyl of carbon number 1 to 12, j is 1,2,3 or 4；Z⁶For-O- ,-S- ,-CO- ,-CO-O- ,-OCO- ,- O-CO-O-、-OCH₂-、-CH₂O-、-SCH₂-、-CH₂S-、-CF₂O-、-OCF₂-、-CF₂S-、-SCF₂-、-(CH₂)_j-、- CF₂CH₂-、-CH₂CF₂-、-(CF₂)_j- ,-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, j is 1,2,3 or 4；R⁶For the alkyl of carbon number 1 to 25, institute State in alkyl, at least one-CH₂- can be through-NR⁰-, the Asia of-O- ,-S- ,-CO- ,-COO- ,-OCO- ,-OCOO- or carbon number 3 to 8 Cycloalkyl replaces, herein, R⁰For hydrogen or the alkyl of carbon number 1 to 12, at least one tertiary carbon (>CH-) can through nitrogen (>N-) replace, Moreover, at least one hydrogen can replace through fluorine or chlorine, wherein, R⁶Oxygen atom with OH structures, the sulphur atom of SH structures or one At least one of level, nitrogen-atoms of two grades or tertiary amine group；R⁷For hydrogen, halogen, carbon number 1 to 25 alkyl, the alkyl In, at least one-CH₂- can be through-NR⁰-, the sub- ring of-O- ,-S- ,-CO- ,-CO-O- ,-O-CO- ,-O-CO-O- or carbon number 3 to 8 Alkyl replaces, moreover, at least one tertiary carbon (>CH-) can through nitrogen (>N-) replace, in these bases, at least one hydrogen can through fluorine or Chlorine replaces, herein, R⁰For hydrogen or the alkyl of carbon number 1 to 12；I is 0,1,2,3,4 or 5.

14. liquid-crystal composition according to any one of item 1 to item 12 of item, it contains selected from represented by formula (5-1) At least one of group of compound polar compound as the second additive,

R⁵-R⁶ (5-1)

In formula (5-1), R⁵For the alkyl of carbon number 4 to 20, in the alkyl, at least one-CH₂- can be through-CH=CH- ,-CF In=CH- ,-CH=CF-, the cycloalkylidene substitution of-C ≡ C- or carbon number 3 to 8, these bases, at least one hydrogen can be through fluorine or chlorine Substitution；R⁶For the alkyl of carbon number 1 to 25, in the alkyl, at least one-CH₂- can be through-NR⁰-、-O-、-S-、-CO-、- COO- ,-OCO-, the cycloalkylidene substitution of-OCOO- or carbon number 3 to 8, herein, R⁰For hydrogen or the alkyl of carbon number 1 to 12, at least One tertiary carbon (>CH-) can through nitrogen (>N-) replace, moreover, at least one hydrogen can also replace through fluorine or chlorine, wherein, R⁶With OH At least one of oxygen atom, the sulphur atom of SH structures or the one-level of structure, the nitrogen-atoms of two grades or tertiary amine group.

15. liquid-crystal composition according to any one of item 12 to item 14 of item, formula (4) and formula according to item 12 (5) in, R⁶For the base represented by formula (A1) to any one of formula (A4),

Formula (A1) is into formula (A4), Sp⁴、Sp⁶And Sp⁷Singly-bound or base (- Sp "-X " -) independently are, herein, Sp " is carbon In the alkylidene of number 1 to 20, the alkylidene, at least one-CH₂- 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, and at least one hydrogen can replace through fluorine, chlorine or-CN, moreover, X " be-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 single Key, herein, R⁰For hydrogen or the alkyl of carbon number 1 to 12, Y²And Y³It independently is hydrogen, fluorine, chlorine or-CN；Sp⁵For>CH-、>CR¹¹-、> N- or>C<；X¹For-OH ,-OR¹¹、-COOH、-NH₂、-NHR¹¹、-N(R¹¹)₂、-SH、-SR¹¹、

Herein, R⁰For hydrogen or the alkyl of carbon number 1 to 12；X²For-O- ,-CO- ,-NH- ,-NR¹¹- ,-S- or singly-bound；Z⁷For carbon In alkylidene, the ester ring type base of carbon number 5 or 6 or the combinations thereof of number 1 to 15, these bases, at least one hydrogen can through-OH ,- OR¹¹、-COOH、-NH₂、-NHR¹¹、-N(R¹¹)₂, fluorine or chlorine substitution；R¹¹For the alkyl of carbon number 1 to 15, in the alkyl, at least One-CH₂- 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 L is the aromatic series base of carbon number 6 to 25 or the ester ring type base of carbon number 3 to 25, and these bases can be condensed ring, In these bases, 1 to 3 hydrogen can be through R^LSubstitution；R^LFor-OH ,-(CH₂)_j- OH, fluorine, chlorine ,-CN ,-NO₂、-NCO、-NCS、- OCN ,-SCN ,-C (=O) N (R⁰)₂,-C (=O) R⁰、-N(R⁰)₂、-(CH₂)_j-N(R⁰)₂、-SH、-SR⁰, carbon number 6 to 20 virtue Base, the heteroaryl of carbon number 6 to 20, 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 In the alkoxy carbonyloxy group of the alkoxy carbonyl of number 2 to 25, the alkyl carbonyl oxy of carbon number 2 to 25 or carbon number 2 to 25, these bases, At least one hydrogen can replace through fluorine or chlorine, herein, R⁰For hydrogen or the alkyl of carbon number 1 to 12, j is 1,2,3 or 4；K be 0,1,2, Or 3；M is 2,3,4 or 5.

16. liquid-crystal composition according to item 13 of item, wherein, the second additive is selected from formula (4-1-1) to formula (4-1- 4) at least one of group of compound represented by compound,

In formula (4-1-1) and formula (4-1-4), it is fluoro- that ring J and ring K independently are Isosorbide-5-Nitrae-cyclohexylidene, Isosorbide-5-Nitrae-phenylene, 2- The fluoro- 1,3- phenylenes of 1,4- phenylenes, 2-, 2- ethyl -1,4- phenylenes, 2,6- diethyl -1,4- phenylenes, 2- fluoroforms The fluoro- 1,4- phenylenes of base -1,4- phenylenes, 2,3- bis-, the fluoro- 1,4- phenylenes of 2,5- bis-, the fluoro- 1,4- phenylenes of 2,6- bis- or The fluoro- 1,4- phenylenes of 2,3,5,6- tetra-；Ring L is cyclohexyl or phenyl；Z⁶For singly-bound, ethylidene or carbonyloxy group；Z⁷For singly-bound, carbon In alkylidene, the ester ring type base of carbon number 5 or 6 or the combinations thereof of number 1 to 15, these bases, at least one hydrogen can through-OH ,- OR¹¹、-COOH、-NH₂、-NHR¹¹、-N(R¹¹)₂Or halogen substitution, R¹¹For the alkyl of carbon number 1 to 15, in the base, at least one Individual-CH₂- can replace through-C ≡ C- ,-CH=CH- ,-COO- ,-OCO- ,-CO- ,-O- or-NH-；Sp⁴For singly-bound, ethylidene, Asia Propyl group or methylene epoxide, Sp⁷For singly-bound or the alkylidene of carbon number 1 to 5, in the alkylidene ,-CH₂- can be through-O- or-NH- Substitution；R⁷For the alkyl or fluorine of carbon number 1 to 8；I is 0,1,2,3,4 or 5；X¹For-OH ,-COOH ,-SH ,-OCH₃Or-NH₂；X² For singly-bound or-O-.

17. liquid-crystal composition according to item 14 of item, wherein, the second additive is selected from formula (5-1-1) to formula (5-1- 29) at least one of group of compound represented by compound,

R⁵-OH (5-1-1)

R⁵-COOH (5-1-9)

R⁵-NH₂ (5-1-11)

Formula (5-1-1) is into formula (5-1-29), R⁵For the alkyl of carbon number 4 to 20, in the alkyl, at least one-CH₂- can In cycloalkylidene substitution through-CH=CH- ,-CF=CH- ,-CH=CF- ,-C ≡ C- or carbon number 3 to 8, these bases, at least one Individual hydrogen can replace through fluorine or chlorine.

18. liquid-crystal composition according to any one of item 1 to item 17 of item, wherein, the weight based on liquid-crystal composition, The ratio of second additive is less than 10 weight %.

A kind of 19. liquid crystal display cells of item, it is containing with good grounds item 1 to the liquid-crystal composition any one of item 18.

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

A kind of 21. liquid crystal display cells of polymer stabilizing orientating type of item, it is containing with good grounds item 1 to any one of item 18 institute Polymerizable compound in the liquid-crystal composition stated, and the liquid-crystal composition is polymerize.

A kind of 22. liquid crystal display cells without alignment films of item, it is containing any one of with good grounds item 1 to item 18 Polymerizable compound in liquid-crystal composition, and the liquid-crystal composition is polymerize.

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

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

A kind of purposes of 25. liquid-crystal compositions according to any one of item 1 to item 18 of item, it is used for without orientation In the liquid crystal display cells of film.

The present invention also includes the following.(a) manufacture method of liquid crystal display cells, it is by by above-mentioned liquid-crystal composition It is configured between 2 pieces of substrates, the irradiation light in the state of voltage is applied to the composition, makes in the composition contained Polymerizable compound is polymerize, to manufacture above-mentioned liquid crystal display cells.(b) above-mentioned liquid-crystal composition, its nematic upper limit Temperature is that the optical anisotropy (being determined at 25 DEG C) under more than 70 DEG C, wavelength 589nm is more than 0.08, moreover, frequency Dielectric anisotropy (being determined at 25 DEG C) under 1kHz is below -2.

The present invention also includes the following.(c) above-mentioned composition, although Japanese Patent Laid-Open 2006-199941 publications Described in compound (5) to compound (7) be that dielectric anisotropy is positive liquid crystal compounds, but above-mentioned composition contains At least one of group selected from these compounds compound.(d) it is upper containing at least two above-mentioned polymerizable compounds (1) State composition.(e) above-mentioned composition of the polymerizable compound different from above-mentioned polymerizable compound (1) is also contained.(f) it is above-mentioned Composition, contains a kind of, two kinds or at least three kinds optically active compounds, antioxidant, ultra-violet absorber, pigment, froth breakings The additive of agent, polymerizable compound, polymerization initiator, polymerization inhibitor, polar compound etc.(g) combinations thereof is contained The AM elements of thing.(h) above-mentioned composition, and the element with TN, ECB, OCB, IPS, FFS, VA or FPA pattern are contained. (i) the infiltration type element containing above-mentioned composition.(j) above-mentioned composition is used as to have nematic composition.(k) by Optically active compound is added in above-mentioned composition and is used as the purposes of optical activity composition.

The composition of the present invention is illustrated in the following order.First, the composition to composition is illustrated.Second, Key property and the compound to component cpd are illustrated to the main efficacy results that composition is brought.3rd, to group The combination of composition in compound, the preferred proportion of composition and its basis are illustrated.4th, to the preferred shape of component cpd State is illustrated.5th, preferred component cpd is shown.6th, pair additive that can be made an addition in composition is illustrated. 7th, the synthetic method to component cpd is illustrated.Finally, the purposes to composition is illustrated.

First, the composition to composition is illustrated.The composition of the present invention is classified as composition A and composition B.Group Compound A also can also contain other liquid crystal in addition to containing the liquid crystal compounds in compound (2) and compound (3) Property compound, additive etc.." other liquid crystal compounds " are the liquid crystal liquid crystal property chemical combination different from compound (2) and compound (3) Thing.Such a compound is in order at the further purpose of adjustment characteristic and is mixed in composition.Additive is optical activity chemical combination Thing, antioxidant, ultra-violet absorber, pigment, defoamer, polymerizable compound, polymerization initiator, polymerization inhibitor, polarity Compound etc..

Composition B substantially only includes the liquid crystal compounds in compound (2) and compound (3)." substantial " Though referring to that composition can contain additive, other liquid crystal compounds are free of.Compared with composition A, composition B composition Quantity is few.For the viewpoint for reducing cost, 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 high, 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 refers to that value is zero or close to zero.

The characteristic of the compound of table 2.

Characteristic	Compound (2)	Compound (3)
			Ceiling temperature	S~L	S~L
Viscosity	M~L	S~M
			Optical anisotropy	M~L	S~L
Dielectric anisotropy	M~L¹⁾	0
			Ratio resistance	L	L

1) value of dielectric anisotropy is negative, and mark represents the size of absolute value.

When component cpd is mixed in composition, the main efficacy results that component cpd is brought to the characteristic of composition To be as described below.Compound (1) forms polymer by polymerization.The polymer is due to making the orientation of liquid crystal molecule stable Change, therefore shorten the response time of element, and improve the image retention of image.Compound (2) improves dielectric anisotropy, and reduction Lower limit temperature.Compound (3) reduces viscosity.Compound (4) and compound (5) are adsorbed in substrate table because of the effect of polar group Face, and control the orientation of liquid crystal molecule.For the viewpoint of the orientation of liquid crystal molecule, the polymer of compound (1) is effective.Change Compound (4) or compound (5) are also effective.The combination of compound (1) and compound (4) or compound (1) and compound (5) More effective fruit.Using the combination, multiplication effect can be expected.Compared to only compound (4) or only feelings of compound (5) For condition, the combination can expect better long-time stability.

3rd, the preferred proportion of combination, composition to the composition in composition and its basis are illustrated.In composition Composition preferred compositions be compound (1)+compound (2)+compound (3)+compound (4), compound (1)+compound (2) + compound (3)+compound (5) or compound (1)+compound (2)+compound (3)+compound (4)+compound (5).Especially Preferably it is combined as compound (1)+compound (2)+compound (3)+compound (4).

Compound (1) is in order at the purpose for the element for being suitable for polymer stabilizing orientating type and made an addition in composition.For Improve the long-term reliability of element, compound (1) is preferably in a proportion of more than about 0.03 weight %, in order to prevent element Display is bad, and compound (1) is preferably in a proportion of below about 10 weight %.Especially preferred ratio is about 0.1 weight % to about 2 Weight % scope.Ratio particularly preferably is scopes of the about 0.2 weight % to about 1.0 weight %.

In order to improve dielectric anisotropy, compound (2) is preferably in a proportion of more than about 10 weight %, in order to reduce lower limit Temperature, compound (2) is preferably in a proportion of below about 90 weight %.Especially preferred ratio is about 20 weight % to about 85 weights Measure % scope.Ratio particularly preferably is scopes of the about 30 weight % to about 85 weight %.

In order to improve ceiling temperature or in order to reduce lower limit temperature, compound (3) be preferably in a proportion of about 10 weight % with On, in order to improve dielectric anisotropy, compound (3) is preferably in a proportion of below about 90 weight %.Especially preferred ratio is About 15 weight % to about 75 weight % scope.Ratio particularly preferably is scopes of the about 15 weight % to about 60 weight %.

Compound (4) or compound (5) are in order at the purpose of the orientation of control liquid crystal molecule and made an addition in composition.For It is orientated liquid crystal molecule, compound (4) or compound (5) are preferably in a proportion of more than about 0.05 weight %, in order to anti- Only the display of element is bad, and compound (4) or compound (5) are preferably in a proportion of below about 10 weight %.Especially preferred ratio Example is scopes of the about 0.1 weight % to about 7 weight %.Ratio particularly preferably is scopes of the about 0.5 weight % to about 5 weight %.

4th, the preferred configuration to component cpd is illustrated.In formula (1), P¹、P²And P³It independently is polymerism Base.It is preferred that P¹、P²Or P³For the polymerism base in the group selected from the base represented by formula (P-1) to formula (P-5).Particularly preferably P¹、P²Or P³For the base represented by formula (P-1), formula (P-2) or formula (P-3).P particularly preferably¹、P²Or P³For formula (P-1) or Base represented by formula (P-2).Most preferred P¹、P²Or P³For the base represented by formula (P-1).It is preferred represented by formula (P-1) Base is-OCO-CH=CH₂Or-OCO-C (CH₃)=CH₂.The wave of formula (P-1) to formula (P-5) represents the position of bond.

Formula (P-1) is into formula (P-5), M¹、M²And M³It independently is hydrogen, fluorine, the alkyl of carbon number 1 to 5 or at least one hydrogen The alkyl of the carbon number 1 to 5 replaced through fluorine or chlorine.In order to improve reactivity, M preferably¹、M²Or M³For hydrogen or methyl.It is especially excellent The M of choosing¹For hydrogen or methyl, and especially preferred M²Or M³For hydrogen.

Sp¹、Sp²And Sp³It independently is in the alkylidene of singly-bound or carbon number 1 to 10, the alkylidene, at least one- CH₂- can replace through-O- ,-COO- ,-OCO- or-OCOO-, moreover, at least one-CH₂-CH₂- can be through-CH=CH- or-C ≡ C- replaces, in these bases, and at least one hydrogen can replace through fluorine or chlorine.It is preferred that Sp¹、Sp²Or Sp³For singly-bound ,-CH₂CH₂-、- CH₂O-、-OCH₂- ,-COO- ,-OCO- ,-CO-CH=CH- or-CH=CH-CO-.Especially preferred Sp¹、Sp²Or Sp³For list Key.Wherein, when ring A and ring C is phenyl, Sp¹And Sp³For singly-bound.

Ring A and ring C independently are cyclohexyl, cyclohexenyl group, phenyl, 1- naphthyls, 2- naphthyls, oxinane -2- bases, 1,3- In dioxane -2- bases, pyrimidine -2-base or pyridine -2- bases, these rings, at least one hydrogen can through fluorine, chlorine, carbon number 1 to 12 alkane The alkyl for the carbon number 1 to 12 that base, the alkoxy of carbon number 1 to 12 or at least one hydrogen replace through fluorine or chlorine replaces.It is preferred that ring A Or ring C is phenyl.Ring B is 1,4- cyclohexylidenes, 1,4- cyclohexadienylidenes, 1,4- phenylenes, naphthalene -1,2- diyls, naphthalene -1,3- two Base, 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 alcoxyl The alkyl for the carbon number 1 to 12 that base or at least one hydrogen replace through fluorine or chlorine replaces.It is preferred that ring B for 1,4- phenylenes or 2- it is fluoro- 1,4- phenylenes.

Z¹And Z²It independently is in the alkylidene of singly-bound or carbon number 1 to 10, the alkylidene, at least one-CH₂- can through- O- ,-CO- ,-COO- or-OCO- substitutions, moreover, at least one-CH₂-CH₂- can be through-CH=CH- ,-C (CH₃)=CH- ,-CH =C (CH₃)-or-C (CH₃)=C (CH₃In)-substitution, these bases, at least one hydrogen can replace through fluorine or chlorine.It is preferred that Z¹Or Z² For singly-bound ,-CH₂CH₂-、-CH₂O-、-OCH₂- ,-COO- or-OCO-.Especially preferred Z¹Or Z²For singly-bound.

A is 0,1 or 2.It is preferred that a be 0 or 1.B, c and d independently are 0,1,2,3 or 4, moreover, b, c and d sum For more than 1.It is preferred that b, c and d be 1 or 2.Wherein, when ring A and ring C is phenyl, a is 1 or 2.Therefore, with xenyl bone Except the polymerizable compound of frame.

In formula (2) and formula (3), R¹And R²Independently be the alkyl, the alkoxy of carbon number 1 to 12, carbon number 2 of carbon number 1 to 12 to 12 alkenyl or the alkenyloxy group of carbon number 2 to 12.In order to improve the stability to ultraviolet or heat, R preferably¹Or R²For carbon number 1 To 12 alkyl, in order to improve dielectric anisotropy, R preferably¹Or R²For the alkoxy of carbon number 1 to 12.R³And R⁴It independently is The carbon that 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 hydrogen replace through fluorine or chlorine The alkenyl for the carbon number 2 to 12 that the alkyl of number 1 to 12 or at least one hydrogen replace through fluorine or chlorine.In order to reduce viscosity, R preferably³ Or R⁴For the alkenyl of carbon number 2 to 12, in order to improve the stability to ultraviolet or heat, R preferably³Or R⁴For the alkane of carbon number 1 to 12 Base.The alkyl of liquid crystal compounds is straight-chain or branch-like, not comprising cyclic alkyl.Straight-chain alkyl is better than branch-like alkane Base.These situations are also identical for terminal groups such as alkoxy, alkenyls.

It is preferred that alkyl be methyl, ethyl, propyl group, butyl, amyl group, hexyl, heptyl or octyl group.In order to reduce viscosity, especially Its preferred alkyl is ethyl, propyl group, butyl, amyl group or heptyl.

It is preferred that alkoxy be methoxyl group, ethyoxyl, propoxyl group, butoxy, amoxy, hexyloxy or epoxide in heptan.In order to Viscosity is reduced, especially preferred alkoxy is methoxy or ethoxy.

It is preferred that alkenyl be 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, especially preferred alkenyl is vinyl, 1- acrylic, 3- cyclobutenyls or 3- pentenyls.These alkenyls In-CH=CH- preferred spatial configuration depend on the position of double bond.In order to reduce the reasons such as viscosity, in 1- acrylic, 1- It is preferably anti-configuration in the alkenyl of cyclobutenyl, 1- pentenyls, 1- hexenyls, 3- pentenyls, 3- hexenyls etc.In 2- butylene It is preferably cis-configuration in the alkenyl of base, 2- pentenyls, 2- hexenyls etc.

It is preferred that alkenyloxy group be ethyleneoxy, allyloxy, 3- butenyloxies, 3- amylenes epoxide or 4- amylene epoxides.For Reduction viscosity, especially 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 octyl groups.In order to improve dielectric anisotropy, especially preferred example For 2- fluoro ethyls, 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, the fluoro- 2- propylene of 3,3- bis- The fluoro- 3- cyclobutenyls of base, 4,4- bis-, the fluoro- 4- pentenyls of 5,5- bis- or the fluoro- 5- hexenyls of 6,6- bis-.In order to reduce viscosity, especially It is preferred that example be 2,2- difluoroethylenes base or the fluoro- 3- cyclobutenyls of 4,4- bis-.

Ring D and ring F independently are 1,4- cyclohexylidenes, 1,4- cyclohexadienylidenes, 1,4- phenylenes, at least one hydrogen through fluorine Or the 1,4- phenylenes or oxinane -2,5- diyls of chlorine substitution." the 1,4- phenylenes that at least one hydrogen replaces through fluorine or chlorine " Preference be the fluoro- 1,4- phenylenes of 2-, the fluoro- 1,4- phenylenes of 2,3- bis- or the fluoro- 1,4- phenylenes of the chloro- 3- of 2-.In order to reduce Viscosity, ring D or ring F preferably are Isosorbide-5-Nitrae-cyclohexylidene, and in order to improve dielectric anisotropy, ring D or ring F preferably are tetrahydrochysene pyrrole Mutter -2,5- diyls, in order to improve optical anisotropy, ring D or ring F preferably are Isosorbide-5-Nitrae-phenylene.In order to improve ceiling temperature, The spatial configuration related to 1,4- cyclohexylidenes is that anti-configuration is better than cis-configuration.Oxinane -2,5- diyls are

Preferably

Ring E is the fluoro- 1,4- phenylenes of 2,3- bis-, the fluoro- 1,4- phenylenes of the chloro- 3- of 2-, the fluoro- 5- methyl isophthalic acids of 2,3- bis-, and 4- is sub- Phenyl, the fluoronaphthalene -2,6- diyls of 3,4,5- tri- or 7,8- difluoro chroman -2,6- diyls.In order to reduce viscosity, ring E preferably is 2, Fluoro- Isosorbide-5-Nitrae-the phenylenes of 3- bis-, in order to reduce optical anisotropy, ring E preferably is the fluoro- Isosorbide-5-Nitrae-phenylenes of the chloro- 3- of 2-, in order to carry High dielectric anisotropy, ring E preferably is 7,8- difluoro chroman -2,6- diyls.

Ring G and ring I independently are 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, ring G or ring I preferably are Isosorbide-5-Nitrae-cyclohexylidene, in order to Lower limit temperature is reduced, ring G or ring I preferably are Isosorbide-5-Nitrae-phenylene.It is related to Isosorbide-5-Nitrae-cyclohexylidene in order to improve ceiling temperature Spatial configuration is that anti-configuration is better than cis-configuration.

Z³、Z⁴And Z⁵It independently is singly-bound ,-CH₂CH₂-、-CH₂O-、-OCH₂- ,-COO- or-OCO-.It is viscous in order to reduce Degree, Z preferably³Or Z⁴For singly-bound, in order to reduce lower limit temperature, Z preferably³Or Z⁴For-CH₂CH₂-, in order to improve dielectric it is each to The opposite sex, Z preferably³Or Z⁴For-CH₂O- or-OCH₂-.In order to reduce viscosity, Z preferably⁵For singly-bound, in order to reduce lower limit temperature, It is preferred that Z⁵For-CH₂CH₂-, in order to improve ceiling temperature, Z preferably⁵For-COO- or-OCO-.

E is 1,2 or 3, f are 0 or 1, moreover, e and f's and for less than 3.In order to reduce viscosity, e preferably is 1, in order to Ceiling temperature is improved, e preferably is 2 or 3.In order to reduce viscosity, f preferably is 0, and in order to reduce lower limit temperature, f preferably is 1.G is 1,2 or 3.In order to reduce viscosity, g preferably is 1, and in order to improve ceiling temperature, g preferably is 2 or 3.

In formula (4) and formula (5), R⁶For polar group.Polar compound with polar group is therefore excellent because added in composition Elect stabilization as.When polar compound is added in composition, the voltage that preferably described compound will not reduce element is protected Holdup.Polar compound is preferably to have low volatility.It is preferred that molal weight be more than 130g/mol.It is especially preferred to rub The scope that your quality is 150g/mol to 500g/mol.It is preferred that polar compound do not have acryloxy (- OCO-CH= CH₂), methacryloxy (- OCO- (CH₃) C=CH₂) etc polymerism base.

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

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

Formula (A1) is into formula (A4), Sp⁴、Sp⁶And Sp⁷Singly-bound or base (- Sp "-X " -) independently are, moreover, X " is bonded to MES bases or R⁵.Sp " for the alkylidene, preferably carbon number 1 to 12 of carbon number 1 to 20 alkylidene, in the alkylidene, at least one Individual-CH₂- 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(R⁰In-CH=CH- or-C ≡ C- substitutions)-, these bases, at least one Individual 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, Y²And Y³Solely It is on the spot hydrogen, fluorine, chlorine or-CN.It is preferred that X " be-O- ,-S- ,-CO- ,-COO- ,-OCO- ,-O-COO- ,-CO-NR⁰-、-NR⁰- CO-、-NR⁰-CO-NR⁰- or singly-bound.Sp⁵For>CH-、>CR¹¹-、>N- or>C<.That is, the Sp in formula (A2)⁵For>CH-、> CR¹¹- or>Sp in N-, formula (A3)⁵Refer to>C<.

It is preferred that Sp " be-(CH₂)_p1-、-(CH₂CH₂O)_q1-CH₂CH₂-、-CH₂CH₂-S-CH₂CH₂- or-CH₂CH₂- NHCH₂CH₂-, herein, p1 is 1 to 12 integer, and q1 is 1 to 3 integer.It is preferred that base (- Sp "-X " -) be-(CH₂)_p1-、- (CH₂)_p1-O-、-(CH₂)_p1-O-CO-、-(CH₂)_p1- O-CO-O-, herein, p1 and q1 have meaning illustrated above.It is especially excellent The base Sp " of choosing is ethylidene, propylidene, butylidene, pentylidene, hexylidene, heptamethylene, octamethylene, nonylene, decylene, Asia Undecyl, sub- dodecyl, alkylene octadecyl, ethyleneoxy ethylidene, methylene epoxide butylidene, the thio ethylidene of ethene, Ethene-N- methyl-iminos ethylidene, 1- methyl alkylidene, ethenylidene, allylidene and butenylidene.

X¹For-NH₂、-NHR¹¹、-N(R¹¹)₂、-OR¹¹、-OH、-COOH、-SH、-SR¹¹、

Herein, R¹¹For the alkyl of carbon number 1 to 15, in the alkyl, at least one-CH₂- can be through-C ≡ C- ,-CH= In CH- ,-COO- ,-OCO- ,-CO- or-O- substitutions, 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- ,-NR¹¹- ,-S- or singly-bound, Z⁷Represent the alkylidene of carbon number 1 to 15, carbon number 5 to 6 In the combination of ester ring type base or at least one ring and alkylidene, these bases, at least one hydrogen can be through-OH ,-OR¹¹、-COOH、- NH₂、-NHR¹¹、-N(R¹¹)₂, fluorine or chlorine substitution, herein, R¹¹With meaning illustrated above.K is 0,1,2 or 3.

Nitrogenous base R particularly preferably⁶For-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.

Non-nitrogen containing base R particularly preferably⁶For-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 are 1 To 12 integer, preferably 1,2,3 or 4.

For the viewpoint of the high solubility in liquid-crystal composition, R⁶It is particularly preferably-OH or-NH₂.- OH is because with height Anchor force, therefore better than-O- ,-CO- or-COO-.It is particularly preferably the base with multiple hetero atoms (nitrogen, oxygen).With such a pole Even if the compound of property base is low concentration, also effectively.

In formula (4), MES is the mesomorphic base with least one ring.Mesomorphic base is well known to those skilled in the art.Mesomorphic Base refers to, when compound has liquid crystalline phase (interphase), contributes to the part of the formation of liquid crystalline phase.Compound (4) it is preferred Example is compound (4-1).

In formula (4-1), ring J and ring K independently be the aromatic series base of carbon number 6 to 25, the heteroaromatic base of carbon number 5 to 25, The ester ring type base of carbon number 3 to 25 or the heterolipid cyclic group of carbon number 4 to 25, these bases can be condensed ring, in these bases, at least one Individual hydrogen can replace through base T, in these bases, and preferred carbon number is 4 to 25, during these bases can be condensed ring, these bases, at least one Hydrogen can replace through base T.Base T meaning is described in the last of this paragraph.It is preferred that ring J or ring K be 1,4- phenylenes, naphthalene- Isosorbide-5-Nitrae-diyl or naphthalene -2,6- diyl (in these 3 bases, at least one tertiary carbon (>CH-) can through nitrogen (>N-) replace), 1,4- Cyclohexylidene (in the base, at least one-CH₂- can replace through-O- or-S-), the bicyclic butylidenes of 3,3'-, the sub- cyclohexene of 1,4- Base, bicyclic [1.1.1] pentane -1,3- diyls, bicyclic [2.2.2] octane -1,4- diyls, loop coil [3.3] heptane -2,6- diyls, Piperidines -1,4- diyls, decahydronaphthalene -2,6- diyls, 1,2,3,4- naphthane -2,6- diyls, indane -2,5- diyls, octahydro -4,7- Methylene indane -2,5- diyl or perhydro cyclopenta [a] phenanthrene -3,17- diyls (especially gonane -3,17- diyl), these In base, at least one hydrogen can replace through base T, herein, and base T is-OH- ,-(CH₂)_j- OH, halogen ,-CN ,-NO₂、-NCO、-NCS、- OCN ,-SCN ,-C (=O) N (R⁰)₂,-C (=O) R⁰、-N(R⁰)₂、-(CH₂)_j-N(R⁰)₂, carbon number 6 to 20 aryl or heteroaryl, Alkyl, alkoxy, the alkyl-carbonyl of carbon number 2 to 25, alkoxy carbonyl, alkyl carbonyl oxy or the alkoxy carbonyl oxygen of carbon number 1 to 25 In base, these bases, at least one hydrogen can replace through fluorine or chlorine, herein, R⁰For hydrogen or the alkyl of carbon number 1 to 12, j be 1,2,3 or 4。

Z⁶For singly-bound ,-O- ,-S- ,-CO- ,-CO-O- ,-OCO- ,-O-CO-O- ,-OCH₂-、-CH₂O-、-SCH₂-、- CH₂S-、-CF₂O-、-OCF₂-、-CF₂S-、-SCF₂-、-(CH₂)_j-、-CF₂CH₂-、-CH₂CF₂-、-(CF₂)_j- ,-CH=CH- ,- CF=CF- ,-C ≡ C- ,-CH=CH-COO- ,-OCO-CH=CH- or-C (R⁰)₂-。R⁰For hydrogen or the alkyl of carbon number 1 to 12, j For 1,2,3 or 4.It is preferred that Z⁶For singly-bound.

R⁶For the alkyl of carbon number 1 to 25, in the alkyl, at least one-CH₂- can be through-NR⁰-、-O-、-S-、-CO-、- COO- ,-OCO-, the cycloalkylidene substitution of-OCOO- or carbon number 3 to 8, herein, R⁰For hydrogen or the alkyl of carbon number 1 to 12, at least One tertiary carbon (>CH-) can through nitrogen (>N-) replace, moreover, at least one hydrogen can replace through fluorine or chlorine, wherein, R⁶With OH knots At least one of oxygen atom, the sulphur atom of SH structures and the one-level of structure, the nitrogen-atoms of two grades or tertiary amine group.It is preferred that R⁶With at least one>NH ,-OH or-SH.R⁷For hydrogen, halogen, carbon number 1 to 25 alkyl, in the alkyl, at least one- CH₂- can be through-NR⁰-, the cycloalkylidene substitution of-O- ,-S- ,-CO- ,-CO-O- ,-O-CO- ,-O-CO-O- or carbon number 3 to 8, and And, at least one tertiary carbon (>CH-) can through nitrogen (>N-) replace, 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.It is preferred that R⁷For alkyl.

The aryl that aromatic series base refers to aryl or is substituted.The heteroaryl that heteroaromatic base refers to heteroaryl or is substituted. Heteroaryl refers to there is at least one heteroatomic aromatic series base.Aryl and heteroaryl can be monocyclic or any one polycyclic.That is, These bases have at least one ring, and the ring can be condensed (such as naphthyl), and two rings can be linked (for example using covalent bond Xenyl), or can have the combination of condensed ring and shackle.It is preferred that heteroaryl have selected from nitrogen, oxygen, sulphur and phosphorus group At least one hetero atom in group.

It is preferred that aryl or heteroaryl there are carbon number 6 to 25, or five-membered ring, six membered ring or seven Yuans rings.It is preferred that virtue Base or heteroaryl can be monocyclic, or two rings or three rings.These bases can be condensed ring, can also be substituted.

It is preferred that aryl be by from benzene, xenyl, terphenyl, [1,1'：3', 1 "] terphenyl, naphthalene, anthracene, binaphthyl, Phenanthrene, pyrene, dihydropyrene,A hydrogen is removed in perylene, aphthacene, pentacene, BaP, fluorenes, indenes, indenofluorene, the fluorenes of spiral shell two and is spread out Raw monad radical.

It is preferred that heteroaryl be by from pyrroles, pyrazoles, imidazoles, 1,2,3- triazoles, 1,2,4- triazoles, tetrazolium, furans, thiophene Fen, selenophen, oxazole, isoxazoles, 1,2- thiazoles, 1,3- thiazoles, 1,2,3- oxadiazoles, 1,2,4- oxadiazoles, 1,2,5- oxadiazoles, The five-membered ring chemical combination such as 1,3,4- oxadiazoles, 1,2,3- thiadiazoles, 1,2,4- thiadiazoles, 1,2,5- thiadiazoles, 1,3,4- thiadiazoles Thing 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.

It is preferred that heteroaryl also be by from indoles, iso-indoles, indolizine, indazole, benzimidazole, BTA, purine, Naphtho- imidazoles, phenanthro- imidazoles, pyridine-imidazole, pyrazine and imidazoles, quinoxalos imidazoles, benzoxazole, Nai Bing oxazoles, En Bing Evil Azoles, Fei Bing oxazole, isoxazoles, benzothiazole, benzofuran, isobenzofuran, dibenzofurans, quinoline, isoquinolin, pyridine of talking endlessly, Benzo -5,6- quinoline, benzo -6,7- quinoline, benzo -7,8- quinoline, benzisoquinoline, acridine, phenthazine, phenoxazines, benzo Pyridazine, benzo pyrimidine, quinoxalines, azophenlyene, naphthyridines, azepine carbazole, benzo carboline, phenanthridines, phenanthroline, thieno [2,3b] thiophene The condensed rings such as fen, thieno [3,2b] thiophene, dithienothiophene, isothiophene, dibenzothiophenes, diazosulfide thiophene A hydrogen and derivative monad radical are removed in compound.It is preferred that heteroaryl also be by from will selected from these rings, six membered ring, Ring that two bases in condensed ring are combined removes a hydrogen and derivative monad radical.These heteroaryls can be through alkyl, alcoxyl Base, alkylthio, fluorine, fluoroalkyl, aryl or heteroaryl substitution.

Ester ring type base and heterolipid cyclic group can be saturation, or unsaturated.That is, these bases can only have singly-bound, also may be used Combination with singly-bound and multikey.The ring of saturation is better than undersaturated ring.It is preferred that heterolipid cyclic group have selected from nitrogen, oxygen, sulphur, And at least one hetero atom in phosphorus.

Ester ring type base and heterolipid cyclic group can be a ring, or multiple rings.The preference of these bases is carbon number 3 to 25 Monocyclic, two rings or three rings, these bases can be condensed ring, can also be substituted.The preference of these bases be five-membered ring, six membered ring, In seven Yuans rings or eight Yuans rings, these bases, at least one carbon can replace through silicon, at least one>CH- can be through>N- replaces, moreover, extremely A few-CH₂- can replace through-O- or-S-.

It is preferred that ester ring type base and heterolipid cyclic group be by from pentamethylene, tetrahydrofuran, tetrahydrochysene thio-furan, pyrrolidines Deng six members such as five-membered ring, hexamethylene, cyclohexene, oxinane, tetrahydrochysene thio-pyrylium, 1,3- dioxanes, 1,3- dithiane, piperidines Seven Yuans rings such as ring, cycloheptane, naphthane, decahydronaphthalene, indane, bicyclic [1.1.1] pentane, bicyclic [2.2.2] octane, loop coil [3.3] two hydrogen and derivative bilvalent radical are removed in the condensed ring such as heptane, octahydro -4,7- methylene indanes.

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

In formula (5), R⁵For the alkyl of carbon number 4 to 20, in the alkyl, at least one-CH₂- can be through-CH=CH- ,-CF= CH- ,-CH=CF-, the cycloalkylidene substitution of-C ≡ C- or carbon number 3 to 8, moreover, at least one hydrogen can replace through fluorine or chlorine.h For 1 or 2, preferably 1.

It is preferred that R⁵For the alkyl of carbon number 4 to 20.Especially preferred R⁵For the alkyl of carbon number 6 to 18.At least one-CH₂- It can replace through-CH=CH- ,-CF=CH- ,-CH=CF- ,-C ≡ C- or-O-, moreover, at least one hydrogen can take through fluorine or chlorine Generation.

Compound (4-1) particularly preferably is in following compound.

Formula (4-1-1-1) is into formula (4-1-4-4), R⁷For the alkyl or fluorine of carbon number 1 to 8.

Compound (5-1) particularly preferably is selected from following compound (5-1-1-1) into compound (5-1-29-1).

5th, preferred component cpd is shown.It is preferred that compound (1) be the compound (1-1) described in item 3 to chemical combination Thing (1-12).In these compounds, preferably at least one of the first additive is compound (1-7), compound (1-8), changed Compound (1-9) or compound (1-10).Preferably at least two of the first additive are compound (1-8) and compound (1- 9) or compound (1-2) and compound (1-7) combination.

It is preferred that compound (2) be the compound (2-1) described in item 6 to compound (2-21).In these compounds, preferably It is compound (2-1), compound (2-4), compound (2-5), compound (2-7), compound at least one of first composition (2-10) or compound (2-15).Preferably at least two of first composition are compound (2-1) and compound (2-7), chemical combination Thing (2-1) and compound (2-15), compound (2-4) and compound (2-7), compound (2-4) and compound (2-15) are changed The combination of compound (2-5) and compound (2-10).

It is preferred that compound (3) be the compound (3-1) described in item 9 to compound (3-13).In these compounds, preferably It is compound (3-1), compound (3-3), compound (3-5), compound (3-6), compound at least one of second composition (3-7) or compound (3-8).Preferably at least two of second composition are compound (3-1) and compound (3-3), compound (3-1) and compound (3-5) or compound (3-1) and compound (3-6) combination.

It is preferred that compound (4) be the compound (4-1) described in item 13.Especially preferred compound (4) is described in item 16 Compound (4-1-1) to compound (4-1-4).It is preferred that compound (5) be the compound (5-1) described in item 14.It is especially excellent The compound (5) of choosing is the compound (5-1-1) described in item 17 to compound (5-1-29).As a rule, compound (4) is better than Compound (5).

6th, pair additive that can be made an addition in composition is illustrated.Such a additive is optically active compound, resisted Oxidant, ultra-violet absorber, pigment, defoamer, polymerizable compound, polymerization initiator, polymerization inhibitor, polar compound Deng.Assign torsional angle (torsion angle) purpose for the helical structure of liquid crystal molecule is caused, and by optical activity chemical combination Thing is made an addition in composition.The example of such a compound is compound (6-1) to compound (6-5).Optically active compound It is preferably in a proportion of below about 5 weight %.Especially preferred ratio is scopes of the about 0.01 weight % to about 2 weight %.

In order to prevent as the reduction of the ratio 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 and at a temperature of close to ceiling temperature is also maintained, and by antioxidant Make an addition in composition.The preference of antioxidant is compound (7) of integer that n is 1 to 9 etc..

In compound (7), n preferably is 1,3,5,7 or 9.Especially 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, and at a temperature of close to ceiling temperature For the big voltage retention of maintenance effectively.In order to obtain the effect above, antioxidant is preferably in a proportion of about more than 50ppm, In order to not reduce ceiling temperature, or in order to not improve lower limit temperature, antioxidant is preferably in a proportion of about below 600ppm.Especially Its preferred ratio is scopes of the about 100ppm to about 300ppm.

The preference of ultra-violet absorber is benzophenone derivates, benzoate derivatives, triazole derivative etc..Separately Outside, amine with steric hindrance etc light stabilizer it is also preferred that.In order to obtain the effect above, these absorbents or stabilizer it is preferred Ratio is about more than 50ppm, in order to not reduce ceiling temperature, or in order to not improve lower limit temperature, these absorbents or stably Agent is preferably in a proportion of about below 10000ppm.Especially preferred ratio is scopes of the about 100ppm to about 10000ppm.

In order to be suitable for the element of host and guest (guest host, GH) pattern, and by azo system pigmen, anthraquinone system pigment etc. it The dichroism pigment (dichroic dye) of class is made an addition in composition.Pigment is preferably in a proportion of about 0.01 weight % to about 10 Weight % scope.In order to prevent bubbling, and the defoamers such as dimethyl silicone oil, methylphenylsilicone oil are made an addition into composition In.In order to obtain the effect above, defoamer is preferably in a proportion of about more than 1ppm, in order to prevent display bad, defoamer it is excellent It is about below 1000ppm to select ratio.Especially preferred ratio is scopes of the about 1ppm to about 500ppm.

The element of (PSA) type is orientated in order to be suitable for polymer stabilizing, and uses polymerizable compound.Compound (1) is fitted Together in the purpose.Also combination will can be made an addition to together with compound (1) and other polymerizable compounds different with compound (1) In thing.The preference of other polymerizable compounds is acrylate, methacrylate, vinyl compound, ethyleneoxy The compounds such as compound, propenyl ether, epoxide (oxirane, oxetanes), vinyl ketone.Especially preferred example Son is acrylate or methacrylate.Gross weight based on polymerizable compound, compound (1) is preferably in a proportion of about 10 More than weight %.Particularly preferred ratio is more than about 50 weight %.Ratio particularly preferably is more than about 80 weight %.Particularly preferably compare Example is also 100 weight %.By changing the species of compound (1), or by making other polymerizable compounds with appropriate ratio Combined with compound (1), can adjust the reactivity of polymerizable compound or the pre-tilt angle of liquid crystal molecule.By the way that pre-tilt angle is optimal Change, may achieve the short response time of element.The orientation of liquid crystal molecule is stabilized, therefore may achieve big contrast ratio or longevity Life.

The polymerizable compound of compound (1) etc is irradiated and polymerize by ultraviolet.Also can be in Photoepolymerizationinitiater initiater etc. It is polymerize in the presence of appropriate initiator.For felicity condition, the appropriate type of initiator and the appropriate amount being polymerize It is known to those skilled in the art, and be described in the literature.For example as gorgeous good solid (Irgacure) 651 of light trigger (registration mark；BASF (BASF)), gorgeous good solid (Irgacure) 184 (registration mark；BASF) or moral it is firm (Darocur) 1173 (registration mark；BASF) it is suitable for radical polymerization.Gross weight based on polymerizable compound, light gathers That closes initiator is preferably in a proportion of about 0.1 weight % to about 5 weight % scope.Especially preferred ratio be about 1 weight % extremely About 3 weight % scope.

In the polymerizable compound of keeping compound (1) etc, in order to prevent polymerization, polymerization inhibitor can be also added. Polymerizable compound is typically to be made an addition to the state for not removing polymerization inhibitor in composition.The example of polymerization inhibitor for pair The hydroquinone derivative of benzenediol, methyl hydroquinone etc, 4- tert-butyl catechols, 4- metoxyphenols, phenthazine Deng.

7th, the synthetic method to component cpd is illustrated.These compounds can be synthesized using known method. Illustrate synthetic method.Compound (1-2) is synthesized using the method described in Japanese Patent Laid-Open 7-101900 publications. Compound (2-1) is synthesized using the method described in the flat 2-503441 publications of Japanese Patent Laid.Compound (3-5) is Synthesized using the method described in Japanese Patent Laid-Open No. Sho 57-165328 publications.Compound (4-1) is to utilize International Publication Method described in 2012-038026 publications is synthesized.A part for compound (5) is commercially available.The n of formula (7) is 1 chemical combination Thing can be obtained from Sigma-Aldrich (Sigma-Aldrich Corporation).N is that 7 compound (7) etc. is profit Synthesized with the method described in No. 3660505 specifications of United States Patent (USP).

Not recording the compound of synthetic method can synthesize using below into the method described in book：《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 be apt to) etc..Composition is to utilize Known method, is prepared by the compound obtained in the above described manner.For example, component cpd is mixed, then pass through heating And it is mutually dissolved it.

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

The composition can be used in AM elements.And then also can be used in PM elements.The composition can be used in having The AM elements and PM elements of PC, TN, STN, ECB, OCB, IPS, FFS, VA, FPA isotype.Particularly preferably be for TN, The AM elements of OCB, IPS pattern or FFS mode.In AM elements with IPS patterns or FFS mode, when not applying voltage, liquid The orientation of brilliant molecule can be parallel with glass substrate, or is alternatively vertical.These elements can be reflection-type, infiltration type or semi-permeable Type.It is preferably used for the element of infiltration type.Also it can be used in non-crystalline silicon-TFT elements or polysilicon-TFT elements.Also can will be described Composition is used for the nematic curved arrangement phase (nematic for carrying out microencapsulation (microencapsulation) and making Curvilinear aligned phase, NCAP) type element or form three-dimensional netted macromolecule in the composition Polymer disperses the element of (polymer dispersed, PD) type.

Manufacture the method for the element of existing polymer stabilizing orientating type one is for example lower described.Assembling includes 2 pieces of substrates Element, 2 pieces of substrates are referred to as array base palte 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 Plus polymerizable compound.It and then can optionally add additive.The composition is injected into element.Applied to the element Light irradiation is carried out in the state of making alive.Preferably ultraviolet.It is polymerize polymerizable compound by light irradiation.Utilize It is described polymerization and generate the composition containing polymer.The element of polymer stabilizing orientating type is sequentially to make as described above Make.

In the order, when applying voltage, liquid crystal molecule is orientated using the effect of alignment films and electric field.According to described Orientation, the molecule of polymerizable compound is also orientated.Due to polymerizable compound be in this condition using ultraviolet come It is polymerize, therefore generation maintains the polymer of the orientation.Using the effect of the polymer, the response time of element shortens. Because the image retention of image is bad for the running of liquid crystal molecule, therefore the effect of the polymer is utilized, image retention is also improved simultaneously. It is further possible to make the polymerizable compound in composition be polymerize in advance, the composition is configured at liquid crystal display member Between the substrate of part.

The one of the method for element of the manufacture without alignment films is for example lower described.Preparation includes the element of 2 pieces of substrates, described 2 pieces of substrates are referred to as array base palte and colored filter substrate.The substrate does not have alignment films.At least one piece of the substrate With electrode layer.Liquid crystal compounds are mixed to prepare liquid-crystal composition.Polymerism is added in the composition Compound and polar compound.It and then can optionally add additive.The composition is injected into element.To the element Light irradiation is carried out in the state of application voltage.Preferably ultraviolet.It is polymerize polymerizable compound by light irradiation.It is logical The polymerization is crossed, the layer comprising polymer and the composition of polar compound is formed on substrate.

In the order, polar compound is because polar group occurs interaction with substrate surface and is arranged on substrate Row.According to the arrangement, liquid crystal molecule is orientated.When applying voltage, further promote the orientation of liquid crystal molecule, according to institute Orientation is stated, polymerizable compound is also orientated.Because polymerizable compound is to be carried out in this condition using ultraviolet Polymerization, therefore generation maintains the polymer of the orientation.Using the effect of the polymer, the orientation of liquid crystal molecule is additionally stablized Change, the response time of element shortens.Because the image retention of image is bad for the running of liquid crystal molecule, therefore utilize the effect of the polymer Really, image retention is also improved simultaneously.

[embodiment]

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

NMR is analyzed：The DRX-500 manufactured during measure using this guest (Bruker BioSpin) company of Brooker Baier.¹H- In NMR measure, sample is set to be dissolved in CDCl₃Deng in deuterated solvents, at room temperature using 500MHz, cumulative number as the bar of 16 times Part is measured.Internal standard is used as using tetramethylsilane.¹⁹In F-NMR measure, CFCl is used₃As internal standard, with Cumulative number 24 times is carried 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 during measure using Shimadzu Seisakusho Ltd..Vector gas are 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.Carry out limited using Agilent Technologies during the separation of component cpd Capillary column DB-1 (length 30m, internal diameter 0.32mm, the 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.Sample is prepared into after 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 equal product of Shimadzu Seisakusho Ltd.'s manufacture.The gas phase of gained Chromatogram 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 which component cpd is separated, it can be used as follows Capillary column.The HP-1 (length 30m, internal diameter 0.32mm, 0.25 μm of thickness) of Anjelen Sci. ＆ Tech. Inc's manufacture, this auspicious Tyke The Rtx-1 (length 30m, internal diameter 0.32mm, 0.25 μm of thickness) of company (Restek Corporation) manufacture, Australia BP-1 (length 30m, internal diameter 0.32mm, the μ of thickness 0.25 of SGE international corporations (SGE International Pty.Ltd) manufacture m).For the overlapping purpose of compound peak value is prevented, 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 thickness).

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

Determine sample：When determining the characteristic of composition and element, composition is directly used as sample.Determining compound Characteristic when, by the way that the compound (15 weight %) is mixed in mother liquor brilliant (85 weight %) come formation determination sample. According to the value obtained by measure, the characteristic value of compound is calculated using extrapolation (extrapolation method). (extrapolated value)={ (measured value of sample) -0.85 × (the brilliant measured value of mother liquor) }/0.15.When under the ratio, smectic phase When (or crystallization) is separated out at 25 DEG C, by compound and the brilliant ratio of mother liquor with 10 weight %：90 weight %, 5 weight %：95 weights Measure %, 1 weight %：99 weight % order change.The ceiling temperature related to compound, light are obtained using the extrapolation Learn the value of anisotropy, viscosity and dielectric anisotropy.

It is brilliant using following mother liquors.The ratio of component cpd is represented with weight %.

Assay method：The measure of characteristic is carried out using following methods.These methods are JEOL's information technology mostly Industry association (Japan Electronics and Information Technology Industries Association； Referred to as JEITA) review the method described in the JEITA specifications (JEITAED-2521B) specified or the side modified Method.Thin film transistor (TFT) (TFT) is not installed on the TN elements of measure.

(1) nematic ceiling temperature (NI；℃)：Placed on the hot plate for the melting point apparatus for possessing petrographic microscope Sample, is heated with 1 DEG C/min speed.A temperature when part for measure sample is isotropic liquid by nematic phase change Degree.Sometimes nematic ceiling temperature is referred to as " ceiling temperature ".

(2) nematic lower limit temperature (T_C；℃)：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 unit of -30 DEG C and -40 DEG C after, observe liquid crystalline phase.For example, when sample is protected at -20 DEG C Nematic state is held, and when change turns to crystallization or smectic phase at -30 DEG C, TC is recited as ＜ -20 DEG C.Sometimes by nematic phase Lower limit temperature be referred to as " lower limit temperature ".

(3) viscosity (bulk viscosity；η；Determined at 20 DEG C；mPa·s)：Gauge share limited public affairs in Tokyo are used during measure Take charge of the E type rotation viscometers of manufacture.

(4) viscosity (rotary viscosity；γ1；Determined at 25 DEG C；mPa·s)：According to the modern wells (M.Imai) of M. et al.《Point Sub- crystal and liquid crystal》Remember in (Molecular Crystals and Liquid Crystals) volume 259 page 37 (1995) The method of load is measured.Sample is injected in 20 μm of VA elements is in the interval (cell gap) of 2 sheet glass substrates.To institute Element is stated in the range of 39 volts to 50 volts, voltage is periodically applied in units of 1 volt.Voltage is not applied 0.2 second Afterwards, only to apply 1 square wave (rectangular pulse；0.2 second) repeat to apply voltage with not applying the condition of (2 seconds).Measure passes through The application and produce transient current (transient current) peak point current (peak current) and time to peak (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.Dielectric anisotropy required for the calculating is measured using the method determined described in (6).

(5) optical anisotropy (refractive anisotrop；Δn；Determined at 25 DEG C)：Using the light that wavelength is 589nm, It is measured using the Abbe refractometer of Polarizer is provided with eyepiece.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 rubbed.Folding Penetrating rate n ⊥ is measured when the direction of polarisation is vertical with the direction rubbed.Optically anisotropic value is according to Δ n=n ∥-n ⊥ formula is calculated.

(6) dielectric anisotropy (Δ ε；Determined at 25 DEG C)：Dielectric is calculated according to Δ ε=ε ∥-ε ⊥ formula Anisotropic value.Dielectric constant (ε ∥ and ε ⊥) is determined as follows.

1) measure of dielectric constant (ε ∥)：Eight decyl triethoxysilanes are coated with the glass substrate through fully cleaning Ethanol (20mL) solution of (0.16mL).Made using circulator after glass substrate rotation, heated 1 hour at 150 DEG C.At 2 The interval (cell gap) of glass substrate utilizes the bonding agent hardened with ultraviolet to be put into sample in 4 μm of VA elements By the component seal.Sine wave (0.5V, 1kHz) is applied to the element, on the long axis direction that liquid crystal molecule is determined after 2 seconds Dielectric constant (ε ∥).

2) measure of dielectric constant (ε ⊥)：Polyimide solution is coated with the glass substrate through fully cleaning.Will be described After glass substrate calcining, the alignment films to gained carry out friction treatment.Be 9 μm at the interval (cell gap) of 2 sheet glass substrates, Torsion angle is injects sample in 80 degree of TN elements.Sine wave (0.5V, 1kHz) is applied to the element, liquid crystal is determined after 2 seconds The dielectric constant (ε ⊥) of the short-axis direction of molecule.

(7) starting voltage (Vth；Determined at 25 DEG C；V)：Manufactured during measure using great Zhong electronics limited company LCD5100 type luminance meters.Light source is Halogen lamp LED.At the interval (cell gap) of 2 sheet glass substrates be 4 μm and frictional direction is anti- Sample is put into the parallel VA elements for normally showing black pattern (normally black mode), uses and is carried out firmly with ultraviolet The bonding agent of change is by the component seal.The voltage (60Hz, square wave) applied to the element is from 0V in units of 0.02V Periodically increase to 20V.Now, the light quantity through element is determined to element irradiation light from vertical direction.It is formed in the light Transmitance is 100% when amount reaches maximum, and voltage-transmittance curve that transmitance is 0% when the light quantity is minimum.Threshold Voltage is voltage when reaching 10% with transmitance to represent.

(8) voltage retention (VHR-1；Determined at 25 DEG C；%)：TN elements for measure have orientation of polyimide Film, moreover, the interval (cell gap) of 2 sheet glass substrates is 5 μm.The element is utilized hard with ultraviolet after injection sample The bonding agent of change is sealed.Apply pulse voltage (5V, 60 microseconds) to the TN elements to charge.Existed using high speed potentiometer The voltage of decay is determined in a period of 16.7 milliseconds, the area A between the voltage curve of unit period and transverse axis is obtained.Area B Area when not decaying for voltage.Voltage retention is by area A is represented relative to the percentage of area B.

(9) voltage retention (VHR-2；Determined at 80 DEG C；%)：In addition to replacing 25 DEG C and being determined at 80 DEG C, With sequential determination voltage retention same as described above.The value of gained is represented by VHR-2.

(10) voltage retention (VHR-3；Determined at 25 DEG C；%)：After irradiation ultraviolet radiation, voltage retention is determined, is commented Stability of the valency to ultraviolet.TN elements for measure have alignment film of polyimide, moreover, cell gap is 5 μm.Described Sample, irradiation light 20 minutes are injected in element.Light source is extra-high-pressure mercury vapour lamp USH-500D (oxtail (Ushio) motor manufacturing), Element and light source at intervals of 20cm.In VHR-3 measure, decayed voltage is determined during 16.7 milliseconds.With big VHR-3 composition has big stability to ultraviolet.VHR-3 is preferably more than 90%, and especially preferably more than 95%.

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

(12) response time (τ；Determined at 25 DEG C；ms)：Manufactured during measure using great Zhong electronics limited company LCD5100 type luminance meters.Light source is Halogen lamp LED.Low pass filter (Low-pass filter) is set as 5kHz.In 2 sheet glass The interval (cell gap) of substrate for 3.5 μm and is put into sample in the VA elements without alignment films.Use is carried out with ultraviolet The bonding agent of hardening is by the component seal.To the element while applying 30V voltage, while irradiation 78mW/cm² The ultraviolet 449 seconds (35J) of (405nm).Rugged (EYE GRAPHICS) limited company of rock is used in ultraviolet irradiation What is manufactured is UV-cured with many metalized lamp M04-L41.Square wave (120Hz) is applied to the element.Now, from vertical direction pair Element irradiation light, determines the light quantity through element.It is considered as transmitance 100% when the light quantity reaches maximum, in the light quantity It is considered as transmitance 0% during for minimum.The maximum voltage of square wave is set in the way of transmitance turns into 90%.Square wave Minimum voltage be set to transmitance turn into 0% 2.5V.Response time be as transmitance from needed for 10% is changed to 90% (rise time time wanted；rise time；Millisecond) represent.

(13) elastic constant (K11：Splay (spray) elastic constant, K33：Bend (bend) elastic constant；At 25 DEG C Determine；pN)：The EC-1 type elastic constants manufactured during measure using Dongyang technology (TOYO Corporation) limited company Analyzer.Sample is injected in 20 μm of vertical orientated element is in the interval (cell gap) of 2 sheet glass substrates.To the element The electric charge of 20 volts to 0 volt of application, determines electrostatic capacitance and applies voltage.Use《Liquid-crystal apparatus handbook》(daily magazine industry Newspaper office) formula (2.98) in page 75, formula (2.101) is to the electrostatic capacitance (C) that is determined and applies the value of voltage (V) and intends Close (fitting), the value of elastic constant is obtained according to formula (2.100).

(14) ratio resistance (ρ；Determined at 25 DEG C；Ωcm)：Sample 1.0mL is put into the container for possess electrode.To institute State container and apply DC voltage (10V), the DC current after determining 10 seconds.Ratio resistance is calculated by following formula.(ratio resistance)= { (voltage) × (electrical capacity 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 measure of pre-tilt angle Limit company (J.A.Woollam Co., Inc.) manufactures).

(16) orientation stability (liquid crystal aligning axle stability)：Evaluate the liquid crystal aligning axle of the electrode side of liquid crystal display cells Change.The liquid crystal aligning angle φ (before) for applying the electrode side before stress is determined, then, square wave is applied to element After 4.5V, 60Hz 20 minutes, buffer 1 second, determine the liquid crystal aligning angle φ of electrode side again after 1 second and after 5 minutes (after).The changes delta φ of the liquid crystal aligning angle after 1 second and after 5 minutes is calculated by these values and using following formula (deg.)。

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

With J. Xi Er Ficks, B. Jansens, the conspicuous Singhs of C., J.F. Chinese mugwort Germanias, E. covers special Bach, D. Bryants, with P.J. Bo Si (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 is to be surveyed with reference to carry out these It is fixed.It may be said that the rate of change of the smaller liquid crystal aligning axles of Δ φ is smaller, the stability of liquid crystal aligning axle is better.

The embodiment of following presentation composition.Component cpd is represented based on the definition of Table 3 below with mark.In table 3, The spatial configuration related to 1,4- cyclohexylidenes is anti-configuration.Number table in the parantheses after the compound through 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 liquid-crystal composition.Finally conclude the characteristic value of composition.

Table 3. uses the list notation of the compound of mark

R-(A₁)-Z₁-·····-Z_n-(A_n)-R′

The embodiment of element

1. raw material

Make without alignment films element, come study liquid crystal molecule vertical orientated, polymerizable compound conversion ratio, And the response time.Raw material is illustrated first.Raw material is liquid-crystal composition (M1) to liquid-crystal composition (M15), polymerism Compound (RM-1) to polymerizable compound (RM-8), polar compound (PC-1) is sequentially listed to polar compound (PC-33).

[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=81.5 DEG C；Tc<-30℃；Δ n=0.119；Δ ε=- 4.5；Vth=1.70V；η=31.8mPas.

[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=88.3 DEG C；Tc<-30℃；Δ n=0.115；Δ ε=- 2.0；Vth=2.80V；η=17.8mPas.

Following polymerizable compound (RM-1) to polymerizable compound (RM-8) is used as the first additive.

Following polar compound (PC-1) to polar compound (PC-33) is used as the second additive.

2. liquid crystal molecule is vertical orientated

Test number 1

By polymerizable compound (RM-1) with 0.5 weight % ratio and by polar compound (PC-1) with 5 weight %'s Ratio is made an addition in composition (M1).The mixture is injected into the interval of 2 sheet glass substrates on 100 DEG C of hot microscope carrier (cell gap) is 4.0 μm and not had in the element of alignment films.By using extra-high-pressure mercury vapour lamp USH-250-BY (oxtails (Ushio) motor manufacturing) to the element irradiation ultraviolet radiation (28J), polymerize polymerizable compound.By the element configuration In polarization element and the parellel arranged petrographic microscope of analyzer, light leak is whether there is to observe to element irradiation light from lower section.In liquid Brilliant molecule is fully orientated, light not by element when, judge vertical orientated for " good ".When observing the light through element, table It is shown as " bad ".

Test number 2 is to test number 33

Make not having using the mixture for combining composition, polymerizable compound and polar compound and take To the element of film.To whether there is light leak with the identical method of test number 1 to observe.Result is summarized in table 4.

The liquid crystal molecule of table 4. it is vertical orientated

3. the conversion ratio of polymerizable compound

Polar compound is made an addition in composition together with polymerizable compound.The polymerizable compound is because of polymerization It is consumed to form polymer.The conversion ratio of this reaction is preferably big.Because：For the viewpoint of the image retention of image, The residual (amount of unreacted polymerizable compound) of polymerizable compound is preferably few.Making polymer stabilizing orientating type During element, for by the optimized purpose of the pre-tilt angle of liquid crystal molecule, generally with two stage irradiation ultraviolet radiations.In next experiment In, after the ultraviolet of irradiation first stage, determine the residual of polymerizable compound and calculate conversion ratio.In order to be compared, The following polymerizable compound (RM-9) of selection.The compound is because of the definition of mark from except compound (1).

It is polymerize as follows.Do not have to be made in the method described in the paragraph of " liquid crystal molecule vertical orientated " There is the element of alignment films.To the element while applying 30V voltage, while irradiation 78mW/cm²The ultraviolet 359 of (405nm) Second (28J).The UV-cured with many of rugged (EYE GRAPHICS) the limited company manufacture of rock is used in ultraviolet irradiation Metalized lamp M04-L41.Then, using high performance liquid chromatography (High Performance Liquid Chromatography, HPLC) determine the residual of polymerizable compound and calculate conversion ratio.Result is summarized in table 5.Test number 1 is to test number 8 conversion ratio is 34% to 44% scope.In comparative example 1, by the polymerizable compound (RM-1) used in test number 1 Replace with polymerizable compound (RM-9) and polymerize.Conversion ratio is 16% in the case of described.According to the comparison, it can draw Conclusion：The composition of the present invention is also excellent for the viewpoint of conversion ratio.

The conversion ratio of the polymerizable compound of table 5.

4. the response time

As described in table 6, by what is combined various compositions, polymerizable compound and polar compound and prepare Mixture is injected into the element without alignment films.According to described item (12), polymerism is made by irradiation ultraviolet radiation After compound polymerization, the response time of element is determined.In order to be compared, by being not added with polymerizable compound and polar compound Composition (M5) or composition (M9) under state make element, and determines the response time in the same way.Can by table 6 Know, in test number 1 into test number 33, the response time is 5.2 milliseconds to 10.4 milliseconds of scope.On the other hand, 1 is compared It is respectively 21.8 milliseconds and 21.7 milliseconds with the response time for being compared 2.That is, polymerizable compound and polar compound are being not added with When, the response time is about 2 times.Therefore, it could be assumed that：The polymer and polar compounds derived by polymerizable compound (1) The combination of thing (4) or polar compound (5) is effective in terms of the response time is shortened.

The response time of table 6.

In liquid crystal display cells, the preferably response time is short.The response time of embodiment shown in table 6 be 5.2 milliseconds extremely 10.4 milliseconds of scope, it is short compared with comparative example.It may be said that result is：Due to using comprising polymerizable compound and polar compound Liquid-crystal composition, although the species of each composition is different, the element without alignment films reaches the short response time.Because Even if No yield point film, liquid crystal molecule is also stably orientated, this is the feature of the invention that should be illustrated.

[industrial applicability]

The liquid-crystal composition of the present invention can control the orientation of liquid crystal molecule in the element without alignment films.Described group Compound high ceiling temperature, low lower limit temperature, small viscosity, appropriate optical anisotropy, negative big dielectric it is each to Different in nature, big ratio resistance, the high stability to ultraviolet, in the characteristics such as the high stability of heat, meeting at least one characteristic, or Person has appropriate balance at least two characteristics.When liquid crystal display cells containing the composition have short response Between, big voltage retention, low starting voltage, the characteristic such as big contrast ratio, long-life, therefore available for liquid crystal projection apparatus, liquid Brilliant TV etc..

Claims

1. a kind of liquid-crystal composition, it contains selected from least one of the group of compound represented by formula (1) polymerism Compound contains at least one polar compound as the second additive as the first additive, and with negative dielectric it is each to The opposite sex,

In formula (1), ring A and ring C independently be cyclohexyl, cyclohexenyl group, phenyl, 1- naphthyls, 2- naphthyls, oxinane -2- bases, In 1,3- dioxane -2- bases, pyrimidine -2-base or pyridine -2- bases, these rings, at least one hydrogen can be through fluorine, chlorine, carbon number 1 to 12 The alkyl of carbon number 1 to 12 that replaces through fluorine or chlorine of alkyl, the alkoxy of carbon number 1 to 12 or at least one hydrogen replace；Ring B 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 through fluorine, chlorine, the alkyl of carbon number 1 to 12, the alkoxy of carbon number 1 to 12 or at least one hydrogen through fluorine Or the alkyl substitution of the carbon number 1 to 12 of chlorine substitution；Z¹And Z²It independently is the alkylidene of singly-bound or carbon number 1 to 10, the alkylidene In, at least one-CH₂- can replace through-O- ,-CO- ,-COO- or-OCO-, moreover, at least one-CH₂-CH₂- can be through-CH= CH-、-C(CH₃)=CH- ,-CH=C (CH₃)-or-C (CH₃)=C (CH₃In)-substitution, these bases, at least one hydrogen can be through fluorine Or chlorine substitution；P¹、P²And P³For polymerism base；Sp¹、Sp²And Sp³The alkylidene of singly-bound or carbon number 1 to 10 independently is, it is described In alkylidene, at least one-CH₂- can replace through-O- ,-COO- ,-OCO- or-OCOO-, moreover, at least one-CH₂-CH₂- It can replace through-CH=CH- or-C ≡ C-, in these bases, at least one hydrogen can replace through fluorine or chlorine；A is 0,1 or 2；B, c and d It independently is 0,1,2,3 or 4；Wherein, when ring A and ring C is phenyl, a is 1 or 2, and when a is 1, Sp¹And Sp³For list Key.

2. liquid-crystal composition according to claim 1, wherein, in formula (1), P¹、P²And P³It independently is selected from formula (P-1) Polymerism base into the group of the base represented by formula (P-5),

Formula (P-1) is into formula (P-5), M¹、M²And M³Hydrogen, fluorine, the alkyl of carbon number 1 to 5 or at least one hydrogen independently are through fluorine Or the alkyl of the carbon number 1 to 5 of chlorine substitution.

3. liquid-crystal composition according to claim 1 or 2, wherein, the first additive is selected from formula (1-1) to formula (1-12) At least one of represented group of compound polymerizable compound,

Formula (1-1) is into formula (1-12), P¹、P²And P³It independently is the group selected from the base represented by formula (P-1) to formula (P-3) In polymerism base, herein, M¹、M²And M³Hydrogen, fluorine, the alkyl of carbon number 1 to 5 or at least one hydrogen independently are through fluorine or chlorine The alkyl of substituted carbon number 1 to 5；

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

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 additive is 0.03 weight % to 10 weight % scope.

5. liquid-crystal composition according to any one of claim 1 to 4, it contains selected from the compound represented by formula (2) At least one of group compound as first composition,

In formula (2), R¹And R²Independently be the alkyl of carbon number 1 to 12, the alkoxy of carbon number 1 to 12, the alkenyl of carbon number 2 to 12 or The alkenyloxy group of carbon number 2 to 12；Ring D and ring F independently are 1,4- cyclohexylidenes, 1,4- cyclohexadienylidenes, 1,4- phenylenes, at least 1,4- phenylenes or oxinane -2,5- diyls that one hydrogen replaces through fluorine or chlorine；Ring E be the fluoro- 1,4- phenylenes of 2,3- bis-, The fluoro- 1,4- phenylenes of the chloro- 3- of 2-, the fluoro- 5- methyl isophthalic acids of 2,3- bis-, 4- phenylenes, the fluoronaphthalene -2,6- diyls of 3,4,5- tri- or 7,8- Difluoro chroman -2,6- diyls；Z³And Z⁴It independently is singly-bound ,-CH₂CH₂-、-CH₂O-、-OCH₂- ,-COO- or-OCO-；E be 1, 2 or 3, f be 0 or 1, moreover, e and f's and for less than 3.

6. liquid-crystal composition according to any one of claim 1 to 5, it contains selected from formula (2-1) to formula (2-21) institute At least one of group of compound of expression compound as first composition,

Formula (2-1) is into formula (2-21), R¹And R²It independently is the alkyl, the alkoxy of carbon number 1 to 12, carbon number 2 of carbon number 1 to 12 Alkenyl or the alkenyloxy group of carbon number 2 to 12 to 12.

7. the liquid-crystal composition according to claim 5 or 6, wherein, the weight based on liquid-crystal composition, the ratio of first composition Example is 10 weight % to 90 weight % scope.

8. liquid-crystal composition according to any one of claim 1 to 7, it contains selected from the compound represented by formula (3) At least one of group compound as second composition,

In formula (3), 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 alkene for 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 Base；Ring G and ring I independently are the fluoro- 1,4- phenylenes of 1,4- cyclohexylidenes, 1,4- phenylenes, 2- or the fluoro- 1,4- of 2,5- bis- are sub- Phenyl；Z⁵For singly-bound ,-CH₂CH₂-、-CH₂O-、-OCH₂- ,-COO- or-OCO-；G is 1,2 or 3.

9. liquid-crystal composition according to any one of claim 1 to 8, it contains selected from formula (3-1) to formula (3-13) institute At least one of group of compound of expression compound as second composition,

Formula (3-1) is into formula (3-13), R³And R⁴It independently is the alkyl, the alkoxy of carbon number 1 to 12, carbon number 2 of carbon number 1 to 12 What the alkyl or at least one hydrogen for the carbon number 1 to 12 that alkenyl, at least one hydrogen to 12 replace through fluorine or chlorine replaced through fluorine or chlorine The alkenyl of carbon number 2 to 12.

10. liquid-crystal composition according to claim 8 or claim 9, wherein, the weight based on liquid-crystal composition, second composition Ratio is 10 weight % to 90 weight % scope.

11. liquid-crystal composition according to any one of claim 1 to 10, wherein, the second additive is containing with choosing From the polar compound of the heteroatomic polar group in nitrogen, oxygen, sulphur and phosphorus.

12. the liquid-crystal composition according to any one of claim 1 to 11, it contains represented selected from formula (4) and formula (5) At least one of the group of compound polar compound as the second additive,

MES-R⁶ (4)

(R⁵)_h-R⁶ (5)

In formula (4), MES is the mesomorphic base with least one ring；In formula (5), R⁵For the alkyl of carbon number 4 to 20, the alkyl In, at least one-CH₂- can be taken through the cycloalkylidene of-CH=CH- ,-CF=CH- ,-CH=CF- ,-C ≡ C- or carbon number 3 to 8 In generation, these bases, at least one hydrogen can replace through fluorine or chlorine；In formula (4) and formula (5), R⁶For the oxygen atom with OH structures, SH The polar group of at least one of the sulphur atom and one-level of structure, the nitrogen-atoms of two grades or tertiary amine group；H is 1 or 2.

13. the liquid-crystal composition according to any one of claim 1 to 12, it contains selected from the change represented by formula (4-1) At least one of group of compound compound as the second additive,

In formula (4-1), ring J and ring K independently are 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, during these bases can be condensed ring, these bases, at least one hydrogen can Replace through base T, herein, base T is-OH ,-(CH₂)_j- OH, halogen ,-CN ,-NO₂,-NCO ,-NCS ,-OCN ,-SCN ,-C (=O) N (R⁰)₂,-C (=O) R⁰、-N(R⁰)₂、-(CH₂)_j-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 In 25 alkyl carbonyl oxy or the alkoxy carbonyloxy group of carbon number 2 to 25, 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, j is 1,2,3 or 4；Z⁶For-O- ,-S- ,-CO- ,-CO-O- ,-OCO- ,-O-CO- O-、-OCH₂-、-CH₂O-、-SCH₂-、-CH₂S-、-CF₂O-、-OCF₂-、-CF₂S-、-SCF₂-、-(CH₂)_j-、-CF₂CH₂-、- CH₂CF₂-、-(CF₂)_j- ,-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, j is 1,2,3 or 4；R⁶For the alkyl of carbon number 1 to 25, in the alkyl, At least one-CH₂- can be through-NR⁰-, the cycloalkylidene of-O- ,-S- ,-CO- ,-COO- ,-OCO- ,-OCOO- or carbon number 3 to 8 takes Generation, herein, R⁰For hydrogen or the alkyl of carbon number 1 to 12, at least one tertiary carbon (>CH-) can through nitrogen (>N-) replace, moreover, at least One hydrogen can replace through fluorine or chlorine, wherein, R⁶Oxygen atom with OH structures, the sulphur atom of SH structures or one-level, two grades or At least one of nitrogen-atoms of tertiary amine group；R⁷For hydrogen, halogen, carbon number 1 to 25 alkyl, in the alkyl, at least one Individual-CH₂- can be through-NR⁰-, the cycloalkylidene substitution of-O- ,-S- ,-CO- ,-CO-O- ,-O-CO- ,-O-CO-O- or carbon number 3 to 8, Moreover, at least one tertiary carbon (>CH-) can through nitrogen (>N-) replace, 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；I is 0,1,2,3,4 or 5.

14. the liquid-crystal composition according to any one of claim 1 to 12, it contains selected from the change represented by formula (5-1) At least one of group of compound polar compound as the second additive,

R⁵-R⁶ (5-1)

In formula (5-1), R⁵For the alkyl of carbon number 4 to 20, in the alkyl, at least one-CH₂- can be through-CH=CH- ,-CF= In CH- ,-CH=CF-, the cycloalkylidene substitution of-C ≡ C- or carbon number 3 to 8, these bases, at least one hydrogen can take through fluorine or chlorine Generation；R⁶For the alkyl of carbon number 1 to 25, in the alkyl, at least one-CH₂- can be through-NR⁰-、-O-、-S-、-CO-、-COO-、- The cycloalkylidene substitution of OCO- ,-OCOO- or carbon number 3 to 8, herein, R⁰For hydrogen or the alkyl of carbon number 1 to 12, at least one three Level carbon (>CH-) can through nitrogen (>N-) replace, moreover, at least one hydrogen can also replace through fluorine or chlorine, wherein, R⁶With OH structures At least one of oxygen atom, the sulphur atom of SH structures or one-level, the nitrogen-atoms of two grades or tertiary amine group.

15. the liquid-crystal composition according to any one of claim 12 to 14, wherein, formula according to claim 12 (4) and in formula (5), R⁶For the base represented by formula (A1) to any one of formula (A4),

Formula (A1) is into formula (A4), Sp⁴、Sp⁶And Sp⁷Independently be singly-bound or base (- Sp "-X " -), herein, Sp " be carbon number 1 to In 20 alkylidene, the alkylidene, at least one-CH₂- can be through-O- ,-S- ,-NH- ,-N (R⁰)-、-CO-、-CO-O-、-O- CO、-O-CO-O-、-S-CO-、-CO-S-、-N(R⁰)-CO-O-、-O-CO-N(R⁰)-、-N(R⁰)-CO-N(R⁰)-,-CH=CH-, Or-C ≡ C- substitutions, in these bases, at least one hydrogen can replace through fluorine, chlorine or-CN, moreover, X " be-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, this Place, R⁰For hydrogen or the alkyl of carbon number 1 to 12, Y²And Y³It independently is hydrogen, fluorine, chlorine or-CN；Sp⁵For>CH-、>CR¹¹-、>N- or >C<；X¹For-OH ,-OR¹¹、-COOH、-NH₂、-NHR¹¹、-N(R¹¹)₂、-SH、-SR¹¹、

Herein, R⁰For hydrogen or the alkyl of carbon number 1 to 12；X²For-O- ,-CO- ,-NH- ,-NR¹¹- ,-S- or singly-bound；Z⁷For carbon number 1 In alkylidene, the ester ring type base of carbon number 5 or 6 or combinations thereof to 15, these bases, at least one hydrogen can through-OH ,- OR¹¹、-COOH、-NH₂、-NHR¹¹、-N(R¹¹)₂, fluorine or chlorine substitution；R¹¹For the alkyl of carbon number 1 to 15, in the alkyl, at least One-CH₂- 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 L is the aromatic series base of carbon number 6 to 25 or the ester ring type base of carbon number 3 to 25, and these bases can be condensed ring, In these bases, 1 to 3 hydrogen can be through R^LSubstitution；R^LFor-OH ,-(CH₂)_j- OH, fluorine, chlorine ,-CN ,-NO₂、-NCO、-NCS、- OCN ,-SCN ,-C (=O) N (R⁰)₂,-C (=O) R⁰、-N(R⁰)₂、-(CH₂)_j-N(R⁰)₂、-SH、-SR⁰, carbon number 6 to 20 virtue Base, the heteroaryl of carbon number 6 to 20, 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 In the alkoxy carbonyloxy group of the alkoxy carbonyl of number 2 to 25, the alkyl carbonyl oxy of carbon number 2 to 25 or carbon number 2 to 25, these bases, At least one hydrogen can replace through fluorine or chlorine, herein, R⁰For hydrogen or the alkyl of carbon number 1 to 12, j is 1,2,3 or 4；K be 0,1,2, Or 3；M is 2,3,4 or 5.

16. liquid-crystal composition according to claim 13, wherein, the second additive is selected from formula (4-1-1) to formula (4-1- 4) at least one of group of compound represented by compound,

In formula (4-1-1) and formula (4-1-4), ring J and ring K independently be Isosorbide-5-Nitrae-cyclohexylidene, Isosorbide-5-Nitrae-phenylene, the fluoro- Isosorbide-5-Nitraes of 2-- The fluoro- 1,3- phenylenes of phenylene, 2-, 2- ethyl -1,4- phenylenes, 2,6- diethyl -1,4- phenylenes, 2- Trifluoromethyl-1s, The fluoro- 1,4- phenylenes of 4- phenylenes, 2,3- bis-, the fluoro- 1,4- phenylenes of 2,5- bis-, the fluoro- 1,4- phenylenes of 2,6- bis- or 2,3,5, The fluoro- 1,4- phenylenes of 6- tetra-；Ring L is cyclohexyl or phenyl；Z⁶For singly-bound, ethylidene or carbonyloxy group；Z⁷For singly-bound, carbon number 1 to In 15 alkylidene, the ester ring type base of carbon number 5 or 6 or combinations thereof, these bases, at least one hydrogen can be through-OH ,-OR¹¹、- COOH、-NH₂、-NHR¹¹、-NR¹¹ ₂Or halogen substitution, R¹¹For the alkyl of carbon number 1 to 15, in these bases, at least one-CH₂- can Replace through-C ≡ C- ,-CH=CH- ,-COO- ,-OCO- ,-CO- ,-O- or-NH-；Sp⁴For singly-bound, ethylidene, propylidene or Methylene epoxide, Sp⁷For singly-bound or the alkylidene of carbon number 1 to 5, in the alkylidene ,-CH₂- can replace through-O- or-NH-；R⁷ For the alkyl or fluorine of carbon number 1 to 8；I is 0,1,2,3,4 or 5；X¹For-OH ,-COOH ,-SH ,-OCH₃Or-NH₂；X²For singly-bound Or-O-.

17. liquid-crystal composition according to claim 14, wherein, the second additive is selected from formula (5-1-1) to formula (5-1- 29) at least one of group of compound represented by compound,

R⁵-OH (5-1-1)

R⁵-COOH (5-1-9)

R⁵-NH₂ (5-1-11)

Formula (5-1-1) is into formula (5-1-29), R⁵For the alkyl of carbon number 4 to 20, in the alkyl, at least one-CH₂- can through- In CH=CH- ,-CF=CH- ,-CH=CF-, the cycloalkylidene substitution of-C ≡ C- or carbon number 3 to 8, these bases, at least one hydrogen It can replace through fluorine or chlorine.

18. the liquid-crystal composition according to any one of claim 1 to 17, wherein, the weight based on liquid-crystal composition, the The ratio of two additives is less than 10 weight %.

19. a kind of liquid crystal display cells, it is containing the liquid-crystal composition any one of with good grounds claim 1 to 18.

20. liquid crystal display cells according to claim 19, wherein, the operating mode of liquid crystal display cells is coplanar switching Pattern, vertical alignment mode, fringe field switching mode or electric field induction light reaction alignment mode, and the drive of liquid crystal display cells Flowing mode is active matrix mode.

21. a kind of liquid crystal display cells of polymer stabilizing orientating type, it is containing any one of with good grounds claim 1 to 18 Liquid-crystal composition, and polymerizable compound in the liquid-crystal composition polymerize.

22. a kind of liquid crystal display cells without alignment films, it is containing the liquid any one of with good grounds claim 1 to 18 Polymerizable compound in crystal composite, and the liquid-crystal composition is polymerize.

23. a kind of purposes of liquid-crystal composition, the liquid-crystal composition is the liquid according to any one of claim 1 to 18 Crystal composite, it is used in liquid crystal display cells.

24. a kind of purposes of liquid-crystal composition, the liquid-crystal composition is the liquid according to any one of claim 1 to 18 Crystal composite, it is used in the liquid crystal display cells of polymer stabilizing orientating type.

25. a kind of purposes of liquid-crystal composition, the liquid-crystal composition is the liquid according to any one of claim 1 to 18 Crystal composite, it is used in the liquid crystal display cells without alignment films.