CN108473873A

CN108473873A - Liquid-crystal composition and liquid crystal display element

Info

Publication number: CN108473873A
Application number: CN201780006882.4A
Authority: CN
Inventors: 斋藤将之; 荻田和寛; 近藤史尚
Original assignee: JNC Corp; Chisso Petrochemical Corp
Current assignee: JNC Corp; JNC Petrochemical Corp
Priority date: 2016-04-18
Filing date: 2017-01-30
Publication date: 2018-08-31
Also published as: JP6860008B2; TW201807175A; JPWO2017183248A1; WO2017183248A1; KR20180132602A

Abstract

The present invention provides the liquid-crystal composition that a kind of effect using polymer may achieve the vertical orientation of liquid crystal molecule；And the liquid crystal display element containing the composition.The present invention is a kind of nematic liquid-crystal composition for containing and being selected from least one of the group of polar compound represented by formula (1) compound as the first additive and having negative dielectric anisotropy；And the liquid crystal display element containing the composition.In formula (1), ring A and ring C independently are cyclohexyl, phenyl etc.；Ring B is 1,4 cyclohexylidenes, 1,4 phenylenes etc.；Z¹And Z²For singly-bound etc.；Sp¹、Sp²And Sp³It independently is the alkylidene etc. of singly-bound, carbon number 1 to 10；P¹、P²And P³It independently is polymerism base；A is 0 to 3, and b, c and d are independently 0 to 4, and the sum of b, c and d are 2 or more.

Description

Liquid-crystal composition and liquid crystal display element

Technical field

It is the liquid-crystal composition born, the liquid crystal display member containing the composition the present invention relates to a kind of dielectric anisotropy Part etc..More particularly to it is a kind of containing the polar compound (or its polymer) with polymerism base and using the compound Effect may achieve the liquid-crystal composition and liquid crystal display element of the vertical orientation of liquid crystal molecule.

Background technology

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

Liquid crystal display element contains with nematic liquid-crystal composition.The composition has characteristic appropriate.Pass through The characteristic of the composition is improved, the AM elements with superperformance are can get.Association in these characteristic is summarized in down It states in table 1.The characteristic of composition is further illustrated based on commercially available AM elements.Nematic temperature range and element Workable temperature range is associated.Nematic preferred upper limit temperature is about 70 DEG C or more, and nematic preferred lower limit Temperature is about -10 DEG C or less.The viscosity of composition is associated with the response time of element.In order to show dynamic image with element, Preferably the response time is short.Preferably it is shorter than 1 millisecond of response time.It is therefore preferable that the viscosity for composition is small.And then preferably It is small for the viscosity under low temperature.

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

The optical anisotropy of composition is with the contrast of element than associated.According to the pattern of element, and need big Optical anisotropy or small optical anisotropy, i.e., optical anisotropy appropriate.Optical anisotropy (the Δ n) of composition It is designed to that contrast ratio is made to be maximum with the product (Δ n × d) of the cell gap (d) of element.The value of product appropriate depends on fortune The type of operation mode.In the element of VA patterns, the range that described value is about 0.30 μm to about 0.40 μm, IPS patterns or FFS mode Element in, range that described value is about 0.20 μm to about 0.30 μm.It is excellent for the element small to cell gap in the case of these It is selected as with big optically anisotropic composition.The big dielectric anisotropy of composition contributes to the low threshold in element electric Pressure, small consumption electric power and big contrast ratio.It is therefore preferable that being big dielectric anisotropy.The big specific resistance of composition Contribute to the big voltage retention of element and big contrast ratio.It is therefore preferable that for the ratio electricity for having big in the starting stage The composition of resistance.Preferably still there is the composition of big specific resistance after prolonged use.Composition to ultraviolet light or heat Stability is associated with the service life of element.When the stability is high, the long lifespan of element.Such characteristic is to being used for crystal projection For the AM elements of instrument, LCD TV etc. preferably.

In general liquid crystal display element, the vertical orientation of liquid crystal molecule can be reached using specific alignment film of polyimide At.Polymer stabilizing is orientated in the liquid crystal display element of (polymer sustained alignment, PSA) type, makes polymer It is combined with alignment films.First, the composition added with a small amount of polymerizable compound is injected into element.Then, on one side Apply voltage between the substrate of the element, ultraviolet light is irradiated to composition on one side.Polymerizable compound polymerize and The reticular structure of polymer is generated in composition.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 it can be expected that polymer such effect.

On the other hand, do not have in the liquid crystal display element of alignment films using containing polymer and without polymerism base The liquid-crystal composition (patent document 1 to patent document 5) of polar compound.First, will be added with a small amount of polymerizable compound and The composition of a small amount of polar compound is injected into element.Herein, polar compound is adsorbed in substrate surface and is arranged.Liquid Brilliant molecule is orientated according to the arrangement.Then, apply voltage between the substrate of the element on one side, composition is shone on one side Penetrate ultraviolet light.Herein, polymerizable compound is polymerize, and the orientation of liquid crystal molecule is made to stabilize.It, can profit in the composition The orientation of liquid crystal molecule is controlled with polymer and polar compound, therefore the response time of element shortens, the image retention of image obtains Improve.In turn, the step of alignment films need not be formed in the element without alignment films.Since there is no alignment films, therefore utilize The resistance of the interaction of alignment films and composition, element will not reduce.With TN, ECB, OCB, IPS, VA, FFS, FPA etc Pattern element in it can be expected that the combination using polymer and polar compound such effect.

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

Existing technical literature

Patent document

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

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

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

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

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

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

Invention content

Problem to be solved by the invention

One object of the present invention be provide it is a kind of containing the polar compound (or its polymer) with polymerism base Liquid-crystal composition, herein, polar compound have the high compatibility with liquid crystal compounds.Another object is to provide a kind of profit It may achieve the liquid-crystal composition of the vertical orientation of liquid crystal molecule with the effect of the polymer generated from the polar compound.It is another Purpose is to provide a kind of liquid-crystal composition, meet nematic ceiling temperature is high, nematic lower limit temperature is low, viscosity is small, Appropriate, the negative dielectric anisotropy of optical anisotropy is big, specific resistance is big, stability high to the stability of ultraviolet light, to heat At least one of characteristic of height etc.Another object be provide it is a kind of have between at least two of these characteristics it is appropriate flat The liquid-crystal composition of weighing apparatus.Another object is to provide a kind of liquid crystal display element containing such composition.A further object is to provide It is a kind of have the response time is short, voltage retention is big, starting voltage is low, contrast than the characteristics such as big, long lifespan AM elements.

Technical means to solve problem

Containing at least one of the group of polar compound being selected from represented by formula (1) compound the present invention relates to a kind of As the first additive and with the liquid-crystal composition of negative dielectric anisotropy, and the liquid crystal containing the composition Show element.

In formula (1), ring A and ring C independently are cyclohexyl, cyclohexenyl group, phenyl, 1- naphthalenes, 2- naphthalenes, oxinane- 2- bases, 1,3- dioxane -2- bases, pyrimidine -2-base or pyridine -2- bases, in these rings, at least one hydrogen can be through fluorine, chlorine, carbon number 1 To the carbon number 1 that 12 alkyl, the alkoxy of carbon number 1 to 12, the alkenyl of carbon number 2 to 12, at least one hydrogen replace through fluorine or chlorine to The alkenyl for the carbon number 2 to 12 that 12 alkyl or at least one hydrogen replace through fluorine or chlorine replaces；Ring B be 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- diyls, 1,3- dioxanes -2,5- diyl, pyrimidine -2,5- diyl or pyridine -2,5- diyl, in 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, the alkenyl of carbon number 2 to 12, at least one hydrogen through fluorine or The alkenyl for the carbon number 2 to 12 that the alkyl or at least one hydrogen of the carbon number 1 to 12 of chlorine substitution replace through fluorine or chlorine replaces；Z¹And Z² It independently is the alkylidene of singly-bound or carbon number 1 to 10, in the alkylidene, at least one-CH₂It can be through-O- ,-CO- ,-COO- Or-OCO- substitutions, and at least one-CH₂CH₂It can be through-CH=CH- ,-C (CH₃)=CH- ,-CH=C (CH₃)-or-C (CH₃) =C (CH₃)-replace, in these bases, at least one hydrogen can replace through fluorine or chlorine；A is 0,1,2 or 3；B, c and d independently be 0, 1,2,3 or 4, and the sum of b, c and d are 2 or more；Sp¹、Sp²And Sp³It independently is the alkylidene of singly-bound or carbon number 1 to 10, institute It states in alkylidene, at least one-CH₂It can replace through-O- ,-COO- ,-OCO- or-OCOO-, and at least one-CH₂CH₂It can Replace through-CH=CH- or-C ≡ C-, in these bases, at least one hydrogen can replace through fluorine or chlorine；P¹、P²And P³It independently is formula (P-A) the polymerism base represented by,

In formula (P-A), Sp⁴For singly-bound or the alkylidene of carbon number 1 to 7, in the alkylidene, at least one-CH₂Can through- O- ,-COO- or-OCO- substitutions, at least one-CH₂CH₂It can replace through-CH=CH-, in these bases, at least one hydrogen can be through fluorine Substitution；R¹For-OH ,-OR⁰、-NH₂、-NHR⁰Or-N (R⁰)₂Represented base, herein, R⁰For hydrogen or the alkyl of carbon number 1 to 12；M⁴ And M⁵It independently is the alkyl for the carbon number 1 to 5 that hydrogen, fluorine, the alkyl of carbon number 1 to 5 or at least one hydrogen replace through fluorine or chlorine.

The effect of invention

An advantage of the invention be provide it is a kind of containing the polar compound (or its polymer) with polymerism base Liquid-crystal composition, herein, polar compound have the high compatibility with liquid crystal compounds.Another advantage is to provide a kind of profit It may achieve the liquid-crystal composition of the vertical orientation of liquid crystal molecule with the effect of the polymer generated from the polar compound.It is another Advantage is to provide a kind of liquid-crystal composition, meet nematic ceiling temperature is high, nematic lower limit temperature is low, viscosity is small, Appropriate, the negative dielectric anisotropy of optical anisotropy is big, specific resistance is big, stability high to the stability of ultraviolet light, to heat At least one of characteristic of height etc.Another advantage be provide it is a kind of have between at least two of these characteristics it is appropriate flat The liquid-crystal composition of weighing apparatus.Another advantage is to provide a kind of liquid crystal display element containing such composition.Another advantage is to provide It is a kind of have the response time is short, voltage retention is big, starting voltage is low, contrast than the characteristics such as big, long lifespan AM elements.

Specific implementation mode

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

Liquid-crystal composition is prepared by mixing plurality of liquid crystals compound.It is regarded in the liquid-crystal composition Addition optically active compound, antioxidant, ultra-violet absorber, pigment, antifoaming agent, polymerizable compound, polymerization is needed to draw Send out the additive of agent, polymerization inhibitor, polar compound etc.Even if added with additive, liquid crystal liquid crystal property chemical combination The ratio (content) of object be also by the weight percent (weight %) of the weight based on the liquid-crystal composition not comprising additive come It indicates.The ratio (additive amount) of additive is by the weight percent of the weight based on the liquid-crystal composition not comprising additive (weight %) is indicated.Sometimes parts per million by weight (ppm) is used.The ratio of polymerization initiator and polymerization inhibitor is exceptionally It is indicated based on the weight of polymerizable compound.

Sometimes " nematic ceiling temperature " is referred to as " ceiling temperature ".Sometimes referred to as by " nematic lower limit temperature " For " lower limit temperature "." specific resistance is big " refers to composition has big specific resistance in the starting stage, moreover, being used in long-time Still there is big specific resistance afterwards." voltage retention is big " be finger element in the starting stage not only at room temperature, but also close Also there is big voltage retention at a temperature of ceiling temperature, moreover, after prolonged use not only at room temperature, Er Qie Close to also having big voltage retention at a temperature of ceiling temperature.In composition or element, tested sometimes in ongoing change (including activated deterioration test) is front and back to study characteristic.The dielectric anisotropy that is expressed in of " improving dielectric anisotropy " is positive group Refer to that its value positively increases when closing object, refers to that its value negatively increases when dielectric anisotropy is negative composition.

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

" at least one-CH₂Can replace through-O- " etc be expressed in the specification and use.In the case of described ,- CH₂-CH₂-CH₂Not adjacent-CH can be passed through₂Warp-O- replaces and is converted to-O-CH₂-O-.However, adjacent-CH₂It will not Replace through-O-.This is because generation-O-O-CH in the substitution₂(peroxide).That is, the statement refers to "-a CH₂- Can replace through-O- " and " at least two-CH not abutted₂Both can replace through-O- ".The rule is applicable not only to replace For-O- the case where, the case where being also applied for being substituted by the bilvalent radical of-CH=CH- or-COO- etc.

In the chemical formula of component cpd, by terminal groups R²Mark be used for multiple compounds.In these compounds, arbitrarily Two R²Two represented bases can be identical, or also can be different.For example, there is the R of compound (1-1)²For ethyl, and chemical combination The R of object (1-2)²For ethyl the case where.Also there is the R of compound (1-1)²For ethyl, and the R of compound (1-2)²For the feelings of propyl Condition.The rule is also applied for the mark of other terminal groups etc..In formula (1), when subscript ' a ' is 2, there are two ring B.It is described In compound, two bases represented by two ring B can be identical, or also can be different.The rule is also applied for subscript ' a ' and is more than Any two ring B when 2.The rule is also applied for other marks.

The marks such as A, B, C, D surrounded with hexagon are correspondings with the rings such as ring A, ring B, ring C, ring D respectively, expression hexatomic ring, The rings such as condensed ring.The crosscutting oblique line in one side of the hexagon is indicated that the arbitrary hydrogen on ring can be through-Sp¹-P¹Equal bases substitution.‘c’ Etc. subscripts indicate the quantity of base being substituted.When subscript ' c ' is 0, such substitution is not present.When subscript ' c ' is 2 or more, There are multiple-Sp on ring A¹-P¹。-Sp¹-P¹Represented multiple bases can be identical, or also can be different." ring A and ring C are independent Ground is since subject is multiple, therefore to use " independently " in the statement of X, Y or Z ".When subject is " ring A ", since subject is Odd number, therefore do not use " independently ".When " ring A " in multiple formulas in use, the rule of " can be identical, or also can be different " is applicable in In " ring A ".It is also the same for other bases.

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

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

The present invention is following items etc..

A kind of 1. liquid-crystal compositions of item, contain at least one in the group selected from the polar compound represented by formula (1) Kind compound has negative dielectric anisotropy as the first additive,

Liquid-crystal composition of the item 2. according to item 1, wherein in the formula (1) according to item 1, ring A and ring C are independently For cyclohexyl, phenyl, 1- naphthalenes or 2- naphthalenes, in these rings, at least one hydrogen can be through fluorine, chlorine, the alkyl of carbon number 1 to 12, carbon The alkyl for the carbon number 1 to 12 that the alkoxy of number 1 to 12, the alkenyl of carbon number 2 to 12, at least one hydrogen replace through fluorine or chlorine or The alkenyl for the carbon number 2 to 12 that at least one hydrogen replaces through fluorine or chlorine replaces；Ring B is 1,4- cyclohexylidenes, 1,4- phenylenes, naphthalene- 1,2- diyl or naphthalene -2,6- diyl, in these rings, at least one hydrogen can be through fluorine, chlorine, the alkyl of carbon number 1 to 12, carbon number 1 to 12 Alkoxy, the alkyl of carbon number 1 to 12 that replaces through fluorine or chlorine of the alkenyl of carbon number 2 to 12, at least one hydrogen or at least one The alkenyl for the carbon number 2 to 12 that hydrogen replaces through fluorine or chlorine replaces；A is 0 or 1.

Liquid-crystal composition of the item 3. according to item 1 or item 2, wherein the first additive is selected from formula (1-1) to formula (1- 13) at least one of group of polar compound represented by compound,

In formula (1-1) to formula (1-13), R¹For-OH ,-OR⁰、-NH₂、-NHR⁰Or-N (R⁰)₂Represented base, herein, R⁰ For hydrogen or the alkyl of carbon number 1 to 12；R²For hydrogen, fluorine, chlorine, the alkyl of carbon number 1 to 12, the alkoxy of carbon number 1 to 12, carbon number 2 to What the alkyl or at least one hydrogen for the carbon number 1 to 12 that 12 alkenyl, at least one hydrogen replace through fluorine or chlorine replaced through fluorine or chlorine The alkenyl of carbon number 2 to 12；Z¹And Z²It independently is the alkylidene of singly-bound or carbon number 1 to 10, in the alkylidene, at least one- CH₂It can replace through-O- ,-CO- ,-COO- or-OCO-, and at least one-CH₂CH₂It can be through-CH=CH- ,-C (CH₃)= CH- ,-CH=C (CH₃)-or-C (CH₃)=C (CH₃)-replace, in these bases, at least one hydrogen can replace through fluorine or chlorine；Sp¹And Sp³It independently is the alkylidene of singly-bound or carbon number 1 to 10, in the alkylidene, at least one-CH₂Can through-O- ,-COO- ,- OCO- or-OCOO- substitutions, and at least one-CH₂CH₂It can replace through-CH=CH- or-C ≡ C-, in these bases, at least one A hydrogen can replace through fluorine or chlorine；Sp⁴For singly-bound or the alkylidene of carbon number 1 to 7, in the alkylidene, at least one-CH₂Can through- O- ,-COO- or-OCO- substitutions, at least one-CH₂CH₂It can replace through-CH=CH-, in these bases, at least one hydrogen can be through fluorine Substitution；L¹、L²、L³、L⁴、L⁵And L⁶It independently is hydrogen, fluorine, methyl or ethyl.

Liquid-crystal composition of the item 4. according to any one of item 1 to item 3, wherein the weight based on liquid-crystal composition, the The ratio of one additive is the range of 0.05 weight % to 10 weight %.

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

In formula (2), R³And R⁴It independently is the alkene of the alkyl of carbon number 1 to 12, the alkoxy of carbon number 1 to 12, carbon number 2 to 12 The alkenyloxy group of base or carbon number 2 to 12；Ring D and ring F independently be 1,4- cyclohexylidenes, 1,4- cyclohexadienylidenes, 1,4- phenylenes, The 1,4- phenylenes or oxinane -2,5- diyls that at least one hydrogen replaces through fluorine or chlorine；Ring E is the bis- fluoro- Asias 1,4- benzene of 2,3- The fluoro- 1,4- phenylenes of the chloro- 3- of base, 2-, bis- fluoro- 5- methyl-1s of 2,3-, 4- phenylenes, tri- fluoronaphthalene -2,6- diyls of 3,4,5- or 7, 8- difluoro chromogen alkane -2,6- diyls (7,8-difluorochroman-2,6-diyl)；Z³And Z⁴Independently be singly-bound ,- CH₂CH₂-、-CH₂O-、-OCH₂,-COO- or-OCO-；F is 1,2 or 3, and g is 0 or 1, and the sum of f and g are 3 or less.

Liquid-crystal composition of the item 6. according to any one of item 1 to item 5, contains selected from formula (2-1) to formula (2-22) At least one of represented group of compound compound as first composition,

In formula (2-1) to formula (2-22), R³And R⁴It independently is the alkyl of carbon number 1 to 12, the alkoxy of carbon number 1 to 12, carbon The alkenyl of number 2 to 12 or the alkenyloxy group of carbon number 2 to 12.

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

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

In formula (3), R⁵And R⁶It independently is the alkene of the alkyl of carbon number 1 to 12, the alkoxy of carbon number 1 to 12, carbon number 2 to 12 The carbon number 2 that the alkyl or at least one hydrogen for the carbon number 1 to 12 that base, at least one hydrogen replace through fluorine or chlorine replace through fluorine or chlorine To 12 alkenyl；Ring G and ring I independently is 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-；H is 1,2 or 3.

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

In formula (3-1) to formula (3-13), R⁵And R⁶It independently is the alkyl of carbon number 1 to 12, the alkoxy of carbon number 1 to 12, carbon The alkyl or at least one hydrogen for the carbon number 1 to 12 that the alkenyl of number 2 to 12, at least one hydrogen replace through fluorine or chlorine are through fluorine or chlorine The alkenyl of substituted carbon number 2 to 12.

Liquid-crystal composition of the item 10. according to item 8 or item 9, wherein the weight based on liquid-crystal composition, second composition Ratio be 10 weight % to 70 weight % range.

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

In formula (4), ring J and ring P independently are cyclohexyl, cyclohexenyl group, phenyl, 1- naphthalenes, 2- naphthalenes, oxinane- 2- bases, 1,3- dioxane -2- bases, pyrimidine -2-base or pyridine -2- bases, in these rings, at least one hydrogen can be through fluorine, chlorine, carbon number 1 To 12 alkyl, carbon number 1 to 12 alkoxy or the alkyl of carbon number 1 to 12 that replaces through fluorine or chlorine of at least one hydrogen replace； Ring K is 1,4- cyclohexylidenes, 1,4- cyclohexadienylidenes, 1,4- phenylenes, naphthalene -1,2- diyls, naphthalene -1,3- diyls, naphthalene -1,4- two Base, naphthalene -1,5- diyls, naphthalene -1,6- diyls, naphthalene -1,7- diyls, naphthalene -1,8- diyls, naphthalene -2,3- diyls, naphthalene -2,6- diyls, Naphthalene -2,7- diyls, oxinane -2,5- diyls, 1,3- dioxane -2,5- diyls, pyrimidine -2,5- diyls or pyridine -2,5- two Base, in these rings, at least one hydrogen can be through fluorine, chlorine, the alkyl of carbon number 1 to 12, the alkoxy of carbon number 1 to 12 or at least one The alkyl for the carbon number 1 to 12 that a hydrogen replaces through fluorine or chlorine replaces；Z⁶And Z⁷It independently is the alkylidene of singly-bound or carbon number 1 to 10, institute It states in alkylidene, at least one-CH₂It can replace through-O- ,-CO- ,-COO- or-OCO-, and at least one-CH₂CH₂It can Through-CH=CH- ,-C (CH₃)=CH- ,-CH=C (CH₃)-or-C (CH₃)=C (CH₃)-replace, in these bases, at least one hydrogen It can replace through fluorine or chlorine；P⁴、P⁵And P⁶For the polymerism base different from the polymerism base represented by the formula (P-A) according to 1； Sp⁵、Sp⁶And Sp⁷It independently is the alkylidene of singly-bound or carbon number 1 to 10, in the alkylidene, at least one-CH₂Can through- O- ,-COO- ,-OCO- or-OCOO- substitutions, and at least one-CH₂CH₂It can replace through-CH=CH- or-C ≡ C-, these bases In, at least one hydrogen can replace through fluorine or chlorine；Q is 0,1 or 2；J, k and p independently is 0,1,2,3 or 4, and the sum of j, k and p It is 1 or more.

Liquid-crystal composition of the item 12. according to item 11, wherein in formula (4), P⁴、P⁵And P⁶It independently is and is selected from formula (P- 1) to the base in the group of the polymerism base represented by formula (P-5),

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

Liquid-crystal composition of the item 13. according to item 11 or item 12, wherein the second additive is selected from formula (4-1) to formula At least one of the group of polymerizable compound represented by (4-28) compound,

In formula (4-1) to formula (4-28), P⁴、P⁵And P⁶It independently is the polymerization being selected from represented by formula (P-1) to formula (P-3) Base in the group of property base,

Herein, M¹、M²And M³Hydrogen, fluorine, the alkyl of carbon number 1 to 5 or at least one hydrogen independently is through fluorine or chlorine to replace Carbon number 1 to 5 alkyl；Sp⁵、Sp⁶And Sp⁷It independently is the alkylidene of singly-bound or carbon number 1 to 10, in the alkylidene, at least One-CH₂It can replace through-O- ,-COO- ,-OCO- or-OCOO-, and at least one-CH₂CH₂It can be through-CH=CH- or-C ≡ C- replace, and in these bases, at least one hydrogen can replace through fluorine or chlorine.

Liquid-crystal composition of the item 14. according to any one of item 11 to item 13, wherein the weight based on liquid-crystal composition Amount, the ratio of the second additive are the range of 0.03 weight % to 10 weight %.

15. a kind of liquid crystal display elements of item, containing the liquid-crystal composition described in any one of with good grounds item 1 to item 14.

16. liquid crystal display element according to item 15, wherein the operating mode of liquid crystal display element be IPS patterns, VA patterns, FFS mode or FPA patterns, and the type of drive of liquid crystal display element is active matrix mode.

17. a kind of liquid crystal display elements of polymer stabilizing orientating type of item, containing with good grounds item 1 to any one of item 10 institute The liquid-crystal composition stated, and the first additive contained in the liquid-crystal composition is polymerize.

18. a kind of liquid crystal display elements of polymer stabilizing orientating type of item, containing any one of with good grounds item 11 to item 14 The liquid-crystal composition, and the first additive contained in the liquid-crystal composition and the second additive are polymerize.

19. a kind of liquid crystal display elements without alignment films of item, described in any one of with good grounds item 1 to item 10 Liquid-crystal composition, and the first additive contained in the liquid-crystal composition is polymerize.

20. a kind of liquid crystal display elements without alignment films of item, containing the liquid described in any one of with good grounds 11 to 14 Crystal composite, and the first additive contained in the liquid-crystal composition and the second additive are polymerize.

A kind of purposes of 21. liquid-crystal compositions according to any one of item 1 to item 14 of item is used for liquid crystal display member In part.

A kind of purposes of 22. liquid-crystal compositions according to any one of item 1 to item 14 of item, is used for polymer stabilizing In the liquid crystal display element of orientating type.

A kind of purposes of 23. liquid-crystal compositions according to any one of item 1 to item 14 of item is used to not have orientation In the liquid crystal display element of film.

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

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

The composition of the present invention is illustrated in the following order.First, the composition of composition is illustrated.Second, The main effect that key property and the compound to component cpd are brought to the characteristic of composition illustrates.The Three, the combination of the ingredient in composition, the preferred proportion of ingredient and its basis are illustrated.4th, to component cpd Preferred configuration illustrate.5th, preferred component cpd is shown.6th, it pair can make an addition to the additive in composition It illustrates.7th, the synthetic method of component cpd is illustrated.Finally, the purposes of composition is illustrated.

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

Composition B substantially only includes the liquid crystal compounds in compound (2) and compound (3)." substantial " Though additive can be contained by referring to composition B, other liquid crystal compounds are free of.Compared with composition A, the ingredient of composition B Quantity it is few.In terms of reducing costs, composition B is better than composition A.It can be by mixing other liquid crystal compounds For viewpoint further to adjust characteristic, composition A is better than composition B.

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

The characteristic of 2. liquid crystal compounds of table

Characteristic	Compound (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
			Specific resistance	L	L

1) negative dielectric anisotropy

When component cpd is mixed in composition, main effect that component cpd is brought to the characteristic of composition It is as described below.Compound (1) is adsorbed in substrate surface using the effect of polar group, and controls the orientation of liquid crystal molecule.For The desired effect of acquisition, compound (1) must have the high compatibility with liquid crystal compounds.Compound (1) has The hexatomic ring of 1 or 4 cyclohexylidene or Isosorbide-5-Nitrae-phenylene etc since its molecular structure is rodlike, therefore is most suitable for the purpose.Change It closes object (1) and polymer is formed by polymerization.The polymer shortens element due to making the orientation of liquid crystal molecule stabilize Response time, and improve the image retention of image.Compound (2) improves dielectric anisotropy, and reduces lower limit temperature.Compound (3) viscosity is reduced, ceiling temperature is improved or reduces lower limit temperature.Compound (4) is for being further adapted to polymer stabilizing The purpose of the element of orientating type and make an addition in composition.Compound (4) forms polymer by polymerization.The polymer by In making the orientation of liquid crystal molecule stabilize, therefore shorten the response time of element, and improves the image retention of image.With regard to liquid crystal molecule For the viewpoint of orientation, the polymer of compound (1) is inferred compared to chemical combination due to the interaction with substrate surface The polymer of object (4) and more effective fruit.

Third illustrates the combination of the ingredient in composition, the preferred proportion of ingredient and its basis.In composition Ingredient preferably be combined as compound (1)+compound (2)+compound (3) or compound (1)+compound (2)+compound (3)+compound (4).

Compound (1) is made an addition in composition for the purpose of the orientation of control liquid crystal molecule.In order to make liquid crystal point Son is orientated, and compound (1) is preferably in a proportion of about 0.05 weight % or more, and the display of element is bad in order to prevent, chemical combination Object (1) is preferably in a proportion of about 10 weight % or less.And then about 0.1 weight % is preferably in a proportion of to the range of about 7 weight %.It is special It is not preferably in a proportion of about 0.5 weight % to the range of about 5 weight %.

In order to improve dielectric anisotropy, compound (2) is preferably in a proportion of about 10 weight % or more, in order to reduce lower limit Temperature, compound (2) are preferably in a proportion of about 90 weight % or less.And then about 20 weight % are preferably in a proportion of to about 85 weight % Range.Particularly preferred ratio is ranges 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 about 70 weight % or less.And then it is preferably in a proportion of about The range of 15 weight % to about 65 weight %.Particularly preferred ratio is ranges of the about 20 weight % to about 60 weight %.

In order to make the long-term reliability of element improve, compound (4) is preferably in a proportion of about 0.03 weight % or more, in order to Prevent the display of element bad, compound (4) is preferably in a proportion of about 10 weight % or less.And then it is preferably in a proportion of about 0.1 weight Measure the range of % to about 2 weight %.Particularly preferred ratio is ranges of the about 0.2 weight % to about 1.0 weight %.

4th, the preferred configuration of component cpd is illustrated.In formula (P-A), R¹For-OH ,-OR⁰、-NH₂、-NHR⁰ Or-N (R⁰)₂Represented base, herein, R⁰For hydrogen or the alkyl of carbon number 1 to 12.Polar group has and glass substrate or metal oxygen The interaction of the non-covalently bonded on the surface of compound film.For the viewpoint of high solubility in a liquid crystal composition, R¹ Particularly preferably-OH or-NH₂.- OH is better than-O- ,-CO- or-COO- because having high anchor force.Particularly preferably have The base of multiple hetero atoms (nitrogen, oxygen).Even if the compound with such polar group is low concentration, also effectively.Compound (1) is preferred For to ultraviolet light or thermostabilization.When compound (1) to be added in composition, the preferably described compound will not reduce element Voltage retention.Compound (1) preferably has low volatility.Preferred molal weight is 130g/mol or more.In turn The range that preferred molal weight is 150g/mol to 500g/mol.

In formula (1), ring A and ring C independently are cyclohexyl, cyclohexenyl group, phenyl, 1- naphthalenes, 2- naphthalenes, oxinane- 2- bases, 1,3- dioxane -2- bases, pyrimidine -2-base or pyridine -2- bases, in these rings, at least one hydrogen can be through fluorine, chlorine, carbon number 1 To the carbon number 1 that 12 alkyl, the alkoxy of carbon number 1 to 12, the alkenyl of carbon number 2 to 12, at least one hydrogen replace through fluorine or chlorine to The alkenyl for the carbon number 2 to 12 that 12 alkyl or at least one hydrogen replace through fluorine or chlorine replaces.Preferred ring A or ring C is hexamethylene Base or phenyl.Ring B be 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- diyls, 1,3- dioxane -2,5- diyls, pyrimidine -2,5- diyls or pyridine - 2,5- diyls, in these rings, at least one hydrogen can be through fluorine, chlorine, the alkyl of carbon number 1 to 12, the alkoxy of carbon number 1 to 12, carbon number 2 Replace to the alkyl of 12 carbon number 1 to 12 of alkenyl, at least one hydrogen through fluorine or chlorine substitution or at least one hydrogen through fluorine or chlorine Carbon number 2 to 12 alkenyl substitution.Preferred ring B is 1,4- phenylenes or the fluoro- 1,4- phenylenes of 2-.

Z¹And Z²It independently is the alkylidene of singly-bound or carbon number 1 to 10, in the alkylidene, at least one-CH₂Can through- O- ,-CO- ,-COO- or-OCO- substitutions, and at least one-CH₂CH₂It can be through-CH=CH- ,-C (CH₃)=CH- ,-CH=C (CH₃)-or-C (CH₃)=C (CH₃)-replace, in these bases, at least one hydrogen can replace through fluorine or chlorine.Preferred Z¹Or Z²For list Key ,-CH₂CH₂-、-CH₂O-、-OCH₂,-COO- or-OCO-.And then preferred Z¹Or Z²For singly-bound.

A is 0,1,2 or 3.Preferred a is 0,1 or 2.B, c and d independently is 0,1,2,3 or 4, and the sum of b, c and d are 2 or more.

Sp¹、Sp²And Sp³It independently is the alkylidene of singly-bound or carbon number 1 to 10, in the alkylidene, at least one-CH₂- It can replace through-O- ,-COO- ,-OCO- or-OCOO-, and at least one-CH₂CH₂It can replace through-CH=CH- or-C ≡ C-, In these bases, at least one hydrogen can replace through fluorine or chlorine.Preferred Sp¹Or Sp²For singly-bound and at least one-CH₂Warp-O- substitutions Carbon number 1 to 10 alkylidene.Sp⁴For singly-bound or the alkylidene of carbon number 1 to 7, in the alkylidene, at least one-CH₂It can Replace through-O- ,-COO- or-OCO-, at least one-CH₂CH₂It can replace through-CH=CH-, in these bases, at least one hydrogen can It is fluorine-substituted.

P¹、P²And P³It independently is the polymerism base represented by formula (P-A).

M⁴And M⁵Independently be carbon number 1 that hydrogen, fluorine, the alkyl of carbon number 1 to 5 or at least one hydrogen replace through fluorine or chlorine to 5 alkyl.In order to improve reactivity, preferred M⁴Or M⁵For hydrogen or methyl.And then preferred M⁴Or M⁵For hydrogen.

In formula (1-1) to formula (1-13), R²For hydrogen, fluorine, chlorine, the alkyl of carbon number 1 to 12, the alkoxy of carbon number 1 to 12, carbon The alkyl or at least one hydrogen for the carbon number 1 to 12 that the alkenyl of number 2 to 12, at least one hydrogen replace through fluorine or chlorine are through fluorine or chlorine The alkenyl of substituted carbon number 2 to 12.Preferred R²For the alkyl of carbon number 1 to 12.

L¹、L²、L³、L⁴、L⁵And L⁶It independently is hydrogen, fluorine, methyl or ethyl.Preferred L¹To L⁶For hydrogen, fluorine or methyl.Into And preferred L¹To L⁶For hydrogen or fluorine.

In formula (2) and formula (3), R³And R⁴Independently be the alkyl of carbon number 1 to 12, the alkoxy of carbon number 1 to 12, carbon number 2 to 12 alkenyl or the alkenyloxy group of carbon number 2 to 12.In order to improve the stability to ultraviolet light or heat, preferred R³Or R⁴For carbon number 1 to 12 alkyl, in order to improve dielectric anisotropy, preferred R³Or R⁴For the alkoxy of carbon number 1 to 12.R⁵And R⁶It independently is carbon The carbon number 1 that the alkyl of 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 of the carbon number 2 to 12 replaced to 12 alkyl or at least one hydrogen through fluorine or chlorine.In order to reduce viscosity, preferred R⁵ Or R⁶For the alkenyl of carbon number 2 to 12, in order to improve the stability to ultraviolet light or heat, preferred R⁵Or R⁶For the alkane of carbon number 1 to 12 Base.

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

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

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

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

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

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

Ring D and ring F independently is 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-, bis- fluoro- 1,4- phenylenes of 2,3- or the fluoro- 1,4- phenylenes of the chloro- 3- of 2-.In order to reduce Viscosity, preferred ring D or ring F are 1 or 4 cyclohexylidene, and in order to improve dielectric anisotropy, preferred ring D or ring F are tetrahydrochysene pyrrole It mutters -2,5- diyls, in order to improve optical anisotropy, preferred ring D or ring F are Isosorbide-5-Nitrae-phenylene.Oxinane -2,5- diyls For

Or

Preferably

Ring E is bis- fluoro- 1,4- phenylenes of 2,3-, the fluoro- 1,4- phenylenes of the chloro- 3- of 2-, bis- fluoro- 5- methyl-1s of 2,3-, and 4- is sub- Phenyl, tri- fluoronaphthalene -2,6- diyls of 3,4,5- or 7,8- difluoro chromogen alkane -2,6- diyls.In order to reduce viscosity, preferred ring E is 2,3- bis- fluoro- Isosorbide-5-Nitrae-phenylenes, in order to reduce optical anisotropy, preferred ring E is the fluoro- Isosorbide-5-Nitrae-phenylenes of the chloro- 3- of 2-, in order to Dielectric anisotropy is improved, preferred ring E is 7,8- difluoro chromogen alkane -2,6- diyls.

Ring G and ring I independently is the fluoro- 1,4- phenylenes of 1,4- cyclohexylidenes, 1,4- phenylenes, 2- or 2,5- bis- fluoro- 1, 4- phenylenes.In order to reduce viscosity or in order to improve ceiling temperature, preferred ring G or ring I for 1 or 4 cyclohexylidene, in order to reduce Lower limit temperature, preferred ring G or ring I are Isosorbide-5-Nitrae-phenylene.

Z³And Z⁴It independently is singly-bound ,-CH₂CH₂-、-CH₂O-、-OCH₂,-COO- or-OCO-.It is excellent in order to reduce viscosity The Z of choosing³Or Z⁴For singly-bound, in order to reduce lower limit temperature, preferred Z³Or Z⁴For-CH₂CH₂, in order to improve dielectric anisotropy, Preferred Z³Or Z⁴For-CH₂O- or-OCH₂-。Z⁵For singly-bound ,-CH₂CH₂-、-CH₂O-、-OCH₂,-COO- or-OCO-.In order to drop Low viscosity, preferred Z⁵For singly-bound, in order to reduce lower limit temperature, preferred Z⁵For-CH₂CH₂, excellent in order to improve ceiling temperature The Z of choosing⁵For-COO- or-OCO-.

F is 1,2 or 3, and g is 0 or 1, and the sum of f and g are 3 or less.In order to reduce viscosity, preferred f is 1, in order to carry High ceiling temperature, preferred f are 2 or 3.In order to reduce viscosity, preferred g is 0, and in order to reduce lower limit temperature, preferred g is 1. H is 1,2 or 3.In order to reduce viscosity, preferred h is 1, and in order to improve ceiling temperature, preferred h is 2 or 3.

In formula (4), P⁴、P⁵And P⁶It independently is different from the polymerism base represented by the formula (P-A) according to item 1 Polymerism base.The polymerism base does not have-OH ,-OR⁰、-NH₂、-NHR⁰Or-N (R⁰)₂Etc polar group.Herein, R⁰For hydrogen Or the alkyl of carbon number 1 to 12.Preferred P⁴、P⁵Or P⁶To be selected from the group of the polymerism base represented by formula (P-1) to formula (P-5) In base.And then preferred P⁴、P⁵Or P⁶For the base represented by formula (P-1), formula (P-2) or formula (P-3).Particularly preferred P⁴、P⁵ Or P⁶For the base represented by formula (P-1) or formula (P-2).Most preferred P⁴、P⁵Or P⁶For the base represented by formula (P-1).Formula (P-1) Represented preferred base is acryloxy (- OCO-CH=CH₂) or methacryloxy (- OCO-C (CH₃) C=CH₂)。 Formula (P-1) indicates the position of bond to the wave of formula (P-5).

In formula (P-1) to formula (P-5), M¹、M²And M³It independently is hydrogen, fluorine, the alkyl of carbon number 1 to 5 or at least one The alkyl for the carbon number 1 to 5 that hydrogen replaces through fluorine or chlorine.In order to improve reactivity, preferred M¹、M²Or M³For hydrogen or methyl.And then it is excellent The M of choosing¹For hydrogen or methyl, and preferred M in turn²Or M³For hydrogen.

Sp⁵、Sp⁶And Sp⁷It independently is the alkylidene of singly-bound or carbon number 1 to 10, in the alkylidene, at least one-CH₂- It can replace through-O- ,-COO- ,-OCO- or-OCOO-, and at least one-CH₂CH₂It can replace through-CH=CH- or-C ≡ C-, In these bases, at least one hydrogen can replace through fluorine or chlorine.Preferred Sp⁵、Sp⁶Or Sp⁷For singly-bound ,-CH₂CH₂-、-CH₂O-、- OCH₂,-COO- ,-OCO- ,-CO-CH=CH- or-CH=CH-CO-.And then preferred Sp⁵、Sp⁶Or Sp⁷For singly-bound.

Ring J and ring P independently is cyclohexyl, cyclohexenyl group, phenyl, 1- naphthalenes, 2- naphthalenes, oxinane -2- bases, 1,3- Dioxane -2- bases, pyrimidine -2-base or pyridine -2- bases, in these rings, alkane that at least one hydrogen can be through fluorine, chlorine, carbon number 1 to 12 The alkyl for the carbon number 1 to 12 that base, the alkoxy of carbon number 1 to 12 or at least one hydrogen replace through fluorine or chlorine replaces.Preferred ring J or ring P is phenyl.Ring K is 1,4- cyclohexylidenes, 1,4- cyclohexadienylidenes, 1,4- phenylenes, naphthalene -1,2- diyls, naphthalene -1,3- Diyl, naphthalene -1,4- diyls, naphthalene -1,5- diyls, naphthalene -1,6- diyls, naphthalene -1,7- diyls, naphthalene -1,8- diyls, naphthalene -2,3- diyls, Naphthalene -2,6- diyls, naphthalene -2,7- diyls, oxinane -2,5- diyls, 1,3- dioxane -2,5- diyls, pyrimidine -2,5- diyls or Pyridine -2,5- diyl, in these rings, at least one hydrogen can through fluorine, chlorine, the alkyl of carbon number 1 to 12, carbon number 1 to 12 alkoxy, Or the alkyl of carbon number 1 to 12 of at least one hydrogen through fluorine or chlorine substitution replaces.Preferred ring K is that 1,4- phenylenes or 2- are fluoro- 1,4- phenylenes.

Z⁶And Z⁷It independently is the alkylidene of singly-bound or carbon number 1 to 10, in the alkylidene, at least one-CH₂Can through- O- ,-CO- ,-COO- or-OCO- substitutions, and at least one-CH₂CH₂It can be through-CH=CH- ,-C (CH₃)=CH- ,-CH=C (CH₃)-or-C (CH₃)=C (CH₃)-replace, in these bases, at least one hydrogen can replace through fluorine or chlorine.Preferred Z⁶Or Z⁷For list Key ,-CH₂CH₂-、-CH₂O-、-OCH₂,-COO- or-OCO-.And then preferred Z⁶Or Z⁷For singly-bound.

Q is 0,1 or 2.Preferred q is 0 or 1.J, k and p independently is 0,1,2,3 or 4, and the sum of j, k and p be 1 with On.Preferred j, k or p are 1 or 2.

5th, preferred component cpd is shown.Preferred compound (1) is the compound (1-1) described in item 3 to chemical combination Object (1-13).In these compounds, preferably at least one of the first additive is compound (1-1), compound (1-3), changes Close object (1-5), compound (1-6), compound (1-7), compound (1-9), compound (1-10) or compound (1-11).It is preferred that It is compound (1-1) and compound (1-5), compound (1-3) and compound (1-5) or change for at least two of the first additive Close the combination of object (1-10) and compound (1-11).

Preferred compound (2) is the compound (2-1) described in item 6 to compound (2-22).In these compounds, preferably At least one for first composition is compound (2-1), compound (2-3), compound (2-4), compound (2-6), compound (2-8) or compound (2-10).Preferably at least two of first composition are compound (2-1) and compound (2-6), compound (2-1) and compound (2-10), compound (2-3) and compound (2-6), compound (2-3) and compound (2-10), compound The combination of (2-4) and compound (2-6) or compound (2-4) and compound (2-8).

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

Preferred compound (4) is the compound (4-1) described in item 13 to compound (4-28).It is excellent in these compounds Be selected as the second additive at least one be compound (4-1), compound (4-2), compound (4-24), compound (4-25), Compound (4-26) or compound (4-27).Preferably at least two of the second additive are compound (4-1) and compound (4- 2), compound (4-1) and compound (4-18), compound (4-2) and compound (4-24), compound (4-2) and compound (4- 25), compound (4-2) and compound (4-26), compound (4-25) and compound (4-26) or compound (4-18) and chemical combination The combination of object (4-24).

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

In order to prevent by the reduction of the specific resistance caused by the heating in air, or in order to be used for a long time by element Afterwards, not only at room temperature, big voltage retention but also at a temperature of close to ceiling temperature is also maintained, and by antioxidant It makes an addition in composition.The preference of antioxidant is the compound (6) of integer etc. that n is 1 to 9.

In compound (6), preferred n is 1,3,5,7 or 9.And then preferred n is 7.The compound (6) that n is 7 is due to waving Hair property is small, therefore for after by element long-time use, not only at room temperature, but also at a temperature of close to ceiling temperature It maintains for big voltage retention effectively.In order to obtain the effect, antioxidant is preferably in a proportion of about 50ppm or more, In order not to reducing ceiling temperature, or in order not to improve lower limit temperature, antioxidant is preferably in a proportion of about 600ppm or less.Into And about 100ppm is preferably in a proportion of to the range of about 300ppm.

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

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

In order to be suitable for the element that polymer stabilizing is orientated (PSA) type, and use polymerizable compound.Compound (1) and Compound (4) is suitable for the purpose.Also can by compound (1) and compound (4) and with compound (1) and compound (4) Different polymerizable compounds make an addition in composition together.The preference of such polymerizable compound is acrylate, methyl Acrylate, vinyl compound, ethyleneoxy compounds, propenyl ether, epoxide (oxirane, oxa- ring fourth Alkane), the compounds such as vinyl ketone.And then preference is acrylate or methacrylate.Based on the total of polymerizable compound Weight, compound (1) and compound (4) are preferably in a proportion of about 10 weight % or more.And then it is preferably in a proportion of about 50 weight % More than.Particularly preferred ratio is about 80 weight % or more.Particularly preferred ratio is also 100 weight %.By changing compound (1) And the type of compound (4), or by making other polymerizable compounds and compound (1) and compound (4) with ratio appropriate Combination can adjust the reactivity of polymerizable compound or the pre-tilt angle of liquid crystal molecule.By optimizing pre-tilt angle, it may achieve member The short response time of part.The orientation of liquid crystal molecule stabilizes, therefore may achieve big contrast ratio or long-life.

The polymerizable compound is irradiated by ultraviolet light and polymerize.It also can be in the initiator appropriate such as Photoepolymerizationinitiater initiater In the presence of polymerize.The appropriate type and appropriate amount of felicity condition, initiator for being polymerize have been this field skill Known to art personnel, and it is described in the literature.Such as gorgeous good solid (Irgacure) 651 (registered trademark as Photoepolymerizationinitiater initiater； BASF (BASF)), gorgeous good solid (Irgacure) 184 (registered trademark；BASF) or (registrations of Da Luoka (Darocur) 1173 Trade mark；BASF) it is suitable for free radical polymerization.Total weight based on polymerizable compound, the preferred proportion of Photoepolymerizationinitiater initiater It is ranges of the about 0.1 weight % to about 5 weight %.And then about 1 weight % is preferably in a proportion of to the range of about 3 weight %.

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

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

7th, the synthetic method of component cpd is illustrated.These compounds can be synthesized using known method. Illustrate synthetic method.The synthetic method of compound (1) is recorded in the item of embodiment.Compound (2-1) is special using Japan Method described in sharp special table level 2-503441 bulletins synthesizes.Compound (3-5) is to utilize Japanese Patent Laid-Open No. Sho 57- Method described in No. 165328 bulletins synthesizes.Compound (4-18) is to utilize Japanese Patent Laid-Open 7-101900 bulletins Described in method synthesize.A part for compound (6) is commercially available.The compound that the n of formula (6) is 1 can be from Sigma's Order Ritchie company (Sigma-Aldrich Corporation) obtains.The compound (6) etc. that n is 7 is to utilize United States Patent (USP) Method described in No. 3660505 specifications synthesizes.

The compound for not recording synthetic method can be using synthesizing at the method described in book below：《Organic synthesis》 (Organic Syntheses, John Wei Li fathers and sons publishing company (John Wiley＆Sons, Inc.)),《Organic reaction》 (Organic Reactions, John Wei Li fathers and sons publishing company),《Comprehensive organic synthesis》(Comprehensive Organic Synthesis, Pei Geman publishing company (Pergamon Press)),《New experimental chemistry lecture》(ball is kind) etc..Composition is profit With well known method, prepared by the compound obtained in this way.For example, component cpd is mixed, then by adding Heat and so that it is mutually dissolved.

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

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

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

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

In the case where the polar compound with polymerism base of compound (1) etc is used as polymerizable compound, Alignment films are not needed on the substrate of element.Element without alignment films is according to the sequence described in the first two paragraph by not having There is the substrate manufacture of alignment films.

In the sequence, compound (1) occurs to be arranged on substrate due to interaction because of polar group with substrate surface. According to the arrangement, liquid crystal molecule is orientated.When applying voltage, further promote the orientation of liquid crystal molecule.Due to polymerization Property base be to be polymerize in this condition using ultraviolet light, therefore generate the polymer for maintaining the orientation.Gathered using described The effect of object is closed, the orientation of liquid crystal molecule additionally stabilizes, and the response time of element shortens.Since the image retention of image is liquid crystal The running of molecule is bad, therefore utilizes the effect of the polymer, and image retention is also improved simultaneously.

[embodiment]

The present invention is further described in detail according to embodiment.The present invention is not restricted by the embodiments.This hair The bright mixture for including composition (M1) and composition (M2).The present invention also includes to be mixed at least two of the composition of embodiment Mixture made of conjunction.Synthesized compound is to utilize nuclear magnetic resonance (nuclear magnetic resonance, NMR) point The methods of analysis is identified.The characteristic of compound, composition and element is measured using following methods.

NMR is analyzed：The DRX-500 manufactured using this guest (Bruker BioSpin) company of Brooker Baier when measurement.¹H- In the measurement of NMR, sample is made to be dissolved in CDCl₃In equal deuterated solvents, at room temperature with 500MHz, the item that cumulative number is 16 times Part is measured.Using tetramethylsilane as internal standard.¹⁹In the measurement of F-NMR, CFCl is used₃As internal standard, with Cumulative number 24 times carries out.In the explanation of NMR spectrum, s refers to unimodal (singlet), and d refers to doublet (doublet), t refers to triplet (triplet), and q refers to quartet (quartet), and quin refers to quintet (quintet), Sex refers to sextet (sextet), and m refers to multiplet (multiplet), and br refers to broad peak (broad).

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

(specific resistance)={ (voltage) × (capacitance of container) }/{ (DC current) × (dielectric constant of vacuum) }

(formula 1)

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

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

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

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

[synthesis example 1]

The synthesis of compound (1-7)

First, the synthesis of compound (T-4) is illustrated.

1st step

By polyformaldehyde (paraformaldehyde) (60.0g), 1,4- diazabicyclos [2.2.2] octane (DABCO (1, 4-diazabicyclo[2.2.2]octane)；56.0g) and water (200ml) is put into reactor, is stirred at room temperature 15 points Clock.Tetrahydrofuran (Tetrahydrofuran, THF) (400ml) solution of compound (T-1) (50.0g) is added dropwise, at room temperature Stirring 72 hours.Reaction mixture is injected into water, water layer is extracted using ethyl acetate.Using water to generating together Organic layer cleaned, be dried using anhydrous magnesium sulfate.The solution is concentrated under reduced pressure, utilizes silica gel color Spectrometry (volumetric ratio, toluene：Ethyl acetate=2：1) residue is purified and obtains compound (T-2) (44.1g；68%).

Second step

Compound (T-2) (44.1g), imidazoles (25.0g) and dichloromethane (400ml) are put into reactor, it is cooling To 0 DEG C.Tert-butyl chloro-silicane (TBSCl is added dropwise；Dichloromethane solution (200ml) 53g), is warming up to room temperature one on one side It stirs 4 hours on side.Reaction mixture is injected into water, water layer is extracted using dichloromethane.Using water to producing together Raw organic layer is cleaned, and is dried using anhydrous magnesium sulfate.The solution is concentrated under reduced pressure, utilizes silica gel Chromatography (volumetric ratio, heptane：Ethyl acetate=9：1) residue is purified and obtains compound (T-3) (69.6g；84%).

Third step

Compound (T-3) (69.6g), THF (600ml), methanol (150ml) and water (100ml) are put into reactor, It is cooled to 0 DEG C.Addition lithium hydroxide monohydrate (23.9g) thereto restores to room temperature and stirs 12 hours.Reaction is mixed It closes object to be injected into water, is slowly added 6N hydrochloric acid (20ml) after being formed as acidity, water layer is extracted using ethyl acetate. The organic layer generated together is cleaned using water, is dried using anhydrous magnesium sulfate.Under reduced pressure to the solution into Row concentration, obtains compound (T-4) (21.6g；35%).

Then, the method for synthesis compound (1-7) is illustrated.

4th step

Compound (T-5) is synthesized according to well-established law.By compound (T-5) (7.5g), tetrakis triphenylphosphine palladium (1.3g), bromine Change tetrabutylammonium (TBAB (Tetrabutylammonium Bromide)；1.5g), the bromo- 3,5- diformazans of potassium carbonate (6.4g), 1- Oxygroup benzene (5g), toluene (200ml), 2- propyl alcohol (isopropyl alcohol, IPA)；80ml), pure water (20ml) is put into anti- It answers in device, is stirred at 90 DEG C.Reaction mixture is injected into water, water layer is extracted using toluene.Utilize water The organic layer generated together is cleaned, is dried using anhydrous magnesium sulfate.The solution is concentrated under reduced pressure, Utilize silica gel chromatography (volumetric ratio, toluene：Ethyl acetate=9：1) residue is purified, and then by from heptane and toluene Mixed solvent (volumetric ratio, 1：1) recrystallization is purified and obtains compound (T-6) (7.18g；85%).

5th step

Compound (T-6) (7.18g), dichloromethane (200ml) are put into reactor, are cooled to -50 DEG C.It is added dropwise three Boron bromide (2.1ml).It is stirred while being warming up to room temperature 5 hours.Reaction mixture is injected into water, dichloromethane is utilized Water layer is extracted.The organic layer generated together is cleaned using water, is dried using anhydrous magnesium sulfate.It is depressurizing Under the solution is concentrated, utilize silica gel chromatography (volumetric ratio, toluene：Ethyl acetate=1：1) residue is purified And obtain compound (T-7) (5.3g；80%).

6th step

By compound (T-7) (5.3g), ethylene carbonate (3.0g), potassium carbonate (6.5g) and dimethylformamide (Dimethyl Formamide, DMF) (200ml) is put into reactor, is stirred at 100 DEG C.By reaction mixture It is injected into water, water layer is extracted using ethyl acetate.The organic layer generated together is cleaned using water, utilizes nothing Water magnesium sulfate is dried.The solution is concentrated under reduced pressure, utilizes silica gel chromatography (volumetric ratio, toluene：Acetic acid second Ester=1：1) residue is purified and obtains compound (T-8) (5.5g；83%).

7th step

By compound (T-8) (5.3g), compound (T-4) (5.9g), N, N- dimethyl -4-aminopyridine (DMAP (N, N- dimethyl-4-aminopyridine)；1.52g) and dichloromethane (150ml) is put into reactor, is cooled to 0 DEG C.Drop Add N, N'- dicyclohexylcarbodiimides (DCC (N, N'-dicyclohexyl carbodiimide)；Dichloromethane 7.7g) (50ml) solution.It is stirred while being warming up to room temperature 5 hours.Reaction mixture is injected into water, dichloromethane pair is utilized Water layer extracts.The organic layer generated together is cleaned using water, is dried using anhydrous magnesium sulfate.Under reduced pressure The solution is concentrated, silica gel chromatography (volumetric ratio, toluene are utilized：Heptane=1：1) residue is purified and is obtained Compound (T-9) (8.3g；81%).

8th step

Compound (T-9) (8.3g), THF (100ml) are put into reactor, are cooled to 0 DEG C.The fluorination tetrabutyl is added dropwise Ammonium (TBAF (Tetrabutylammonium Fluoride)；2.9g), it is stirred while being warming up to room temperature 3 hours.It will reaction Mixture is injected into water, is extracted to water layer using ethyl acetate.The organic layer generated together is cleaned using water, It is dried using anhydrous magnesium sulfate.The solution is concentrated under reduced pressure, utilizes silica gel chromatography (volumetric ratio, toluene： Ethyl acetate=1：1) residue is purified, and then compound (1-7) is obtained by being purified from the recrystallization of heptane (4.5g；75%).

Compound (1-7)¹H-NMR(ppm；CDCl₃):δ7.48-7.46(m,2H),7.27-7.26(m,2H),6.75 (d, J=2.3Hz, 2H), 6.47-6.46 (m, 1H), 6.30 (s, 2H), 5.86 (d, J=1.1Hz, 2H), 4.54 (t, J= 4.4Hz, 4H), 4.33 (s, 4H), 4.27-4.25 (m, 4H), 2.52-2.47 (m, 1H), 2.34 (s, 2H), 1.90 (t, J= 14Hz, 4H), 1.51-1.44 (m, 2H), 1.35-1.20 (m, 9H), 1.09-1.02 (m, 2H), 0.90 (t, J=6.9Hz, 3H)

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

Table 3 uses the expression method of the compound of mark

R-(A₁)-Z₁-·····-Z_n-(A_n)-R’

The embodiment of element

1. raw material

Composition of the injection added with polar compound into the element without alignment films.After irradiating ultraviolet light, grind Study carefully the vertical orientation of the liquid crystal molecule in the element.Raw material is illustrated first.Raw material is from composition (M1) to combination Object (M18), polar compound (PC-1) to polar compound (PC-5), polymerizable compound (RM-1) to polymerizable compound (RM-9) suitable for selection in.Composition is as described below.

[composition (M1)]

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

[composition (M2)]

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

[composition (M3)]

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

[composition (M4)]

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

[composition (M5)]

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

[composition (M6)]

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

[composition (M7)]

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

[composition (M8)]

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

[composition (M9)]

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

[composition (M10)]

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

[composition (M11)]

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

[composition (M12)]

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

[composition (M13)]

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

[composition (M14)]

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

[composition (M15)]

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

[composition (M16)]

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

[composition (M17)]

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

[composition (M18)]

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

First additive is polar compound (PC-1) to polar compound (PC-5).

Second additive is polymerizable compound (RM-1) to polymerizable compound (RM-9).

2. the vertical orientation of liquid crystal molecule

Embodiment 1

Polar compound (PC-1) is made an addition to the ratio of 5 weight % in composition (M1).On 100 DEG C of hot microscope carrier During the interval (cell gap) that the mixture is injected into two panels glass substrate is 4.0 μm and the element without alignment films. Ultraviolet light (28J) is irradiated to the element by using extra-high-pressure mercury vapour lamp USH-250-BY (oxtail (Ushio) motor manufacturing), To make polar compound (PC-1) be polymerize.The element configuration is shown in polarization element and the polarisation of analyzer orthogonal configuration Micro mirror, from lower section, to element irradiation light, to observe, whether there is or not light leakages.When light does not penetrate element, it is judged as that vertical orientation is " good It is good ".It is fully orientated this is because being inferred as liquid crystal molecule.When observing the light through element, it is expressed as " bad ".

Embodiment 2 is to embodiment 18 and comparative example 1

Do not had to make using the polar compound with polymerism base is made an addition to the mixture prepared in composition There is the element of alignment films.To observe, whether there is or not light leakages in the same manner as in Example 1.Result is summarized in table 4.Embodiment 18 In, polymerizable compound (RM-1) is also added with the ratio of 0.5 weight %.In comparative example 1, in order to be compared, select following Polar compound (PC-11).This is because the compound does not have polymerism base, thus it is different from compound (1).

The vertical orientation of 4. liquid crystal molecule of table

According to table 4 it is found that in embodiment 1 to embodiment 18, though the type of composition or polar compound is changed, not Observe light leakage.The result indicates that even if, No yield point film in the component, vertical orientation is also good, liquid crystal molecule steadily into Row is orientated.In embodiment 18, and then it is added to polymerizable compound (RM-1), but obtains same result.On the other hand, compare Light leakage is observed in example 1.The result expression vertical orientation is simultaneously non-good.Therefore, it is known that by the polarity with polymerism base The polymer that object generates is closed to play an important role to the vertical orientation of liquid crystal molecule.

Industrial availability

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

Claims

1. a kind of liquid-crystal composition, contain at least one of the group of polar compound represented by the formula (1) chemical combination Object has negative dielectric anisotropy as the first additive,

In formula (1), ring A and ring C independently be cyclohexyl, cyclohexenyl group, phenyl, 1- naphthalenes, 2- naphthalenes, oxinane -2- bases, 1,3- dioxane -2- bases, pyrimidine -2-base or pyridine -2- bases, in these rings, at least one hydrogen can be through fluorine, chlorine, carbon number 1 to 12 The alkane for the carbon number 1 to 12 that alkyl, the alkoxy of carbon number 1 to 12, the alkenyl of carbon number 2 to 12, at least one hydrogen replace through fluorine or chlorine The alkenyl for the carbon number 2 to 12 that base or at least one hydrogen replace through fluorine or chlorine replaces；Ring B is 1,4- cyclohexylidenes, the Asias 1,4- ring Hexenyl, 1,4- phenylenes, naphthalene -1,2- diyls, naphthalene -1,3- diyls, naphthalene -1,4- diyls, naphthalene -1,5- diyls, naphthalene -1,6- two Base, 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, in these rings, at least one hydrogen can be through Fluorine, chlorine, the alkyl of carbon number 1 to 12, the alkoxy of carbon number 1 to 12, the alkenyl of carbon number 2 to 12, at least one hydrogen take through fluorine or chlorine The alkenyl for the carbon number 2 to 12 that the alkyl of the carbon number 1 to 12 in generation or at least one hydrogen replace through fluorine or chlorine replaces；Z¹And Z²It is independent Ground is the alkylidene of singly-bound or carbon number 1 to 10, in the alkylidene, at least one-CH₂Can through-O- ,-CO- ,-COO- or- OCO- replaces, and at least one-CH₂CH₂It can be through-CH=CH- ,-C (CH₃)=CH- ,-CH=C (CH₃)-or-C (CH₃)=C (CH₃)-replace, in these bases, at least one hydrogen can replace through fluorine or chlorine；A is 0,1,2 or 3；B, c and d independently be 0,1,2, 3 or 4, and the sum of b, c and d are 2 or more；Sp¹、Sp²And Sp³It independently is the alkylidene of singly-bound or carbon number 1 to 10, the Asia In alkyl, at least one-CH₂It can replace through-O- ,-COO- ,-OCO- or-OCOO-, and at least one-CH₂CH₂Can through- CH=CH- or-C ≡ C- replace, and in these bases, at least one hydrogen can replace through fluorine or chlorine；P¹、P²And P³It independently is formula (P-A) Represented polymerism base,

In formula (P-A), Sp⁴For singly-bound or the alkylidene of carbon number 1 to 7, in the alkylidene, at least one-CH₂Can through-O- ,- COO- or-OCO- substitutions, at least one-CH₂CH₂It can replace through-CH=CH-, in these bases, at least one hydrogen can take through fluorine Generation；R¹For-OH ,-OR⁰、-NH₂、-NHR⁰Or-N (R⁰)₂Represented base, herein, R⁰For hydrogen or the alkyl of carbon number 1 to 12；M⁴And M⁵It independently is the alkyl for the carbon number 1 to 5 that hydrogen, fluorine, the alkyl of carbon number 1 to 5 or at least one hydrogen replace through fluorine or chlorine.

2. liquid-crystal composition according to claim 1, wherein in formula (1) according to claim 1, ring A and ring C It independently is cyclohexyl, phenyl, 1- naphthalenes or 2- naphthalenes, in these rings, alkane that at least one hydrogen can be through fluorine, chlorine, carbon number 1 to 12 The alkyl for the carbon number 1 to 12 that base, the alkoxy of carbon number 1 to 12, the alkenyl of carbon number 2 to 12, at least one hydrogen replace through fluorine or chlorine, Or the alkenyl of carbon number 2 to 12 of at least one hydrogen through fluorine or chlorine substitution replaces；Ring B be 1,4- cyclohexylidenes, 1,4- phenylenes, Naphthalene -1,2- diyl or naphthalene -2,6- diyl, in these rings, at least one hydrogen can through fluorine, chlorine, the alkyl of carbon number 1 to 12, carbon number 1 to The alkyl or at least one for the carbon number 1 to 12 that 12 alkoxy, 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 a hydrogen replaces through fluorine or chlorine replaces；A is 0 or 1.

3. liquid-crystal composition according to claim 1 or 2, wherein the first additive is selected from formula (1-1) to formula (1-13) At least one of represented group of polar compound compound,

In formula (1-1) to formula (1-13), R¹For-OH ,-OR⁰、-NH₂、-NHR⁰Or-N (R⁰)₂Represented base, herein, R⁰For hydrogen or The alkyl of carbon number 1 to 12；R²For hydrogen, the alkene of fluorine, chlorine, the alkyl of carbon number 1 to 12, the alkoxy of carbon number 1 to 12, carbon number 2 to 12 The carbon number 2 that the alkyl or at least one hydrogen for the carbon number 1 to 12 that base, at least one hydrogen replace through fluorine or chlorine replace through fluorine or chlorine To 12 alkenyl；Z¹And Z²It independently is the alkylidene of singly-bound or carbon number 1 to 10, in the alkylidene, at least one-CH₂It can Replace through-O- ,-CO- ,-COO- or-OCO-, and at least one-CH₂CH₂It can be through-CH=CH- ,-C (CH₃)=CH- ,-CH =C (CH₃)-or-C (CH₃)=C (CH₃)-replace, in these bases, at least one hydrogen can replace through fluorine or chlorine；Sp¹And Sp³It is independent Ground is the alkylidene of singly-bound or carbon number 1 to 10, in the alkylidene, at least one-CH₂Can through-O- ,-COO- ,-OCO- or- OCOO- replaces, and at least one-CH₂CH₂It can replace through-CH=CH- or-C ≡ C-, in these bases, at least one hydrogen can be through Fluorine or chlorine substitution；Sp⁴For singly-bound or the alkylidene of carbon number 1 to 7, in the alkylidene, at least one-CH₂It can be through-O- ,-COO- Or-OCO- substitutions, at least one-CH₂CH₂It can replace through-CH=CH-, in these bases, at least one hydrogen can be fluorine-substituted；L¹、 L²、L³、L⁴、L⁵And L⁶It independently is hydrogen, fluorine, methyl or ethyl.

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 the range of 0.05 weight % to 10 weight %.

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

In formula (2), R³And R⁴Independently be the alkyl of carbon number 1 to 12, the alkoxy of carbon number 1 to 12, carbon number 2 to 12 alkenyl or The alkenyloxy group of carbon number 2 to 12；Ring D and ring F independently is 1,4- cyclohexylidenes, 1,4- cyclohexadienylidenes, 1,4- phenylenes, at least The 1,4- phenylenes or oxinane -2,5- diyls that one hydrogen replaces through fluorine or chlorine；Ring E be bis- fluoro- 1,4- phenylenes of 2,3-, The fluoro- 1,4- phenylenes of the chloro- 3- of 2-, bis- fluoro- 5- methyl-1s of 2,3-, 4- phenylenes, tri- fluoronaphthalene -2,6- diyls of 3,4,5- or 7,8- bis- Fluorine chromogen alkane -2,6- diyls；Z³And Z⁴It independently is singly-bound ,-CH₂CH₂-、-CH₂O-、-OCH₂,-COO- or-OCO-；F is 1,2 Or 3, g is 0 or 1, and the sum of f and g are 3 or less.

6. liquid-crystal composition according to any one of claim 1 to 5 contains selected from formula (2-1) to formula (2-22) institute At least one of group of compound of expression compound as first composition,

In formula (2-1) to formula (2-22), R³And R⁴It independently is the alkyl of carbon number 1 to 12, the alkoxy of carbon number 1 to 12, carbon number 2 To 12 alkenyl or the alkenyloxy group of carbon number 2 to 12.

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

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

In formula (3), R⁵And R⁶It independently is the alkyl of carbon number 1 to 12, the alkoxy of carbon number 1 to 12, the alkenyl of carbon number 2 to 12, extremely The carbon number 2 to 12 that the alkyl or at least one hydrogen for the carbon number 1 to 12 that few hydrogen replaces through fluorine or chlorine replace through fluorine or chlorine Alkenyl；Ring G and ring I independently is the fluoro- 1,4- phenylenes of 1,4- cyclohexylidenes, 1,4- phenylenes, 2- or bis- fluoro- 1,4- of 2,5- are sub- Phenyl；Z⁵For singly-bound ,-CH₂CH₂-、-CH₂O-、-OCH₂,-COO- or-OCO-；H is 1,2 or 3.

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

In formula (3-1) to formula (3-13), R⁵And R⁶It independently is the alkyl of carbon number 1 to 12, the alkoxy of carbon number 1 to 12, carbon number 2 Replace to the alkyl of 12 carbon number 1 to 12 of alkenyl, at least one hydrogen through fluorine or chlorine substitution or at least one hydrogen through fluorine or chlorine Carbon number 2 to 12 alkenyl.

10. liquid-crystal composition according to claim 8 or claim 9, wherein the weight based on liquid-crystal composition, second composition Ratio is the range of 10 weight % to 70 weight %.

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

In formula (4), ring J and ring P independently be cyclohexyl, cyclohexenyl group, phenyl, 1- naphthalenes, 2- naphthalenes, oxinane -2- bases, 1,3- dioxane -2- bases, pyrimidine -2-base or pyridine -2- bases, in these rings, at least one hydrogen can be through fluorine, chlorine, carbon number 1 to 12 The alkyl for the carbon number 1 to 12 that alkyl, the alkoxy of carbon number 1 to 12 or at least one hydrogen replace through fluorine or chlorine replaces；Ring K is 1,4- cyclohexylidenes, 1,4- cyclohexadienylidenes, 1,4- phenylenes, naphthalene -1,2- diyls, naphthalene -1,3- diyls, naphthalene -1,4- diyls, Naphthalene -1,5- diyls, naphthalene -1,6- diyls, naphthalene -1,7- diyls, naphthalene -1,8- diyls, naphthalene -2,3- diyls, naphthalene -2,6- diyls, naphthalene -2, 7- diyls, oxinane -2,5- diyl, 1,3- dioxanes -2,5- diyl, pyrimidine -2,5- diyl or pyridine -2,5- diyl, this In a little rings, at least one hydrogen can be passed through through fluorine, chlorine, the alkyl of carbon number 1 to 12, the alkoxy of carbon number 1 to 12 or at least one hydrogen The alkyl substitution of fluorine or the carbon number 1 to 12 of chlorine substitution；Z⁶And Z⁷It independently is the alkylidene of singly-bound or carbon number 1 to 10, the alkylene In base, at least one-CH₂It can replace through-O- ,-CO- ,-COO- or-OCO-, and at least one-CH₂CH₂It can be through-CH= CH-、-C(CH₃)=CH- ,-CH=C (CH₃)-or-C (CH₃)=C (CH₃)-replace, in these bases, at least one hydrogen can be through fluorine Or chlorine substitution；P⁴、P⁵And P⁶For the polymerism different from the polymerism base represented by formula according to claim 1 (P-A) Base；Sp⁵、Sp⁶And Sp⁷It independently is the alkylidene of singly-bound or carbon number 1 to 10, in the alkylidene, at least one-CH₂Can through- O- ,-COO- ,-OCO- or-OCOO- substitutions, and at least one-CH₂CH₂It can replace through-CH=CH- or-C ≡ C-, these bases In, at least one hydrogen can replace through fluorine or chlorine；Q is 0,1 or 2；J, k and p independently is 0,1,2,3 or 4, and the sum of j, k and p It is 1 or more.

12. liquid-crystal composition according to claim 11, wherein in formula (4), P⁴、P⁵And P⁶It independently is and is selected from formula (P- 1) to the base in the group of the polymerism base represented by formula (P-5),

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

13. liquid-crystal composition according to claim 11 or 12, wherein the second additive is selected from formula (4-1) to formula (4- 28) at least one of group of polymerizable compound represented by compound,

In formula (4-1) to formula (4-28), P⁴、P⁵And P⁶It independently is the polymerism base being selected from represented by formula (P-1) to formula (P-3) Group in base,

Herein, M¹、M²And M³It independently is the carbon that hydrogen, fluorine, the alkyl of carbon number 1 to 5 or at least one hydrogen replace through fluorine or chlorine The alkyl of number 1 to 5；Sp⁵、Sp⁶And Sp⁷It independently is the alkylidene of singly-bound or carbon number 1 to 10, in the alkylidene, at least one A-CH₂It can replace through-O- ,-COO- ,-OCO- or-OCOO-, and at least one-CH₂CH₂It can be through-CH=CH- or-C ≡ C- replaces, and in these bases, at least one hydrogen can replace through fluorine or chlorine.

14. the liquid-crystal composition according to any one of claim 11 to 13, wherein the weight based on liquid-crystal composition, The ratio of second additive is the range of 0.03 weight % to 10 weight %.

15. a kind of liquid crystal display element, which is characterized in that it is containing the liquid crystal described in any one of with good grounds claim 1 to 14 Composition.

16. liquid crystal display element according to claim 15, wherein the operating mode of liquid crystal display element is in-plane switching Pattern, vertical alignment mode, fringe field switching mode or electric field induction light reaction alignment mode, and the driving of liquid crystal display element Mode is active matrix mode.

17. a kind of liquid crystal display element of polymer stabilizing orientating type, which is characterized in that it contains with good grounds claims 1 to 10 Any one of described in liquid-crystal composition, and the first additive contained in the liquid-crystal composition is polymerize.

18. a kind of liquid crystal display element of polymer stabilizing orientating type, which is characterized in that it contains with good grounds claim 11 to 14 Any one of described in liquid-crystal composition, and the first additive contained in the liquid-crystal composition and the second additive carry out Polymerization.

19. a kind of liquid crystal display element without alignment films, contains liquid according to any one of claim 1 to 10 Crystal composite, and the first additive contained in the liquid-crystal composition is polymerize.

20. a kind of liquid crystal display element without alignment films, described in any one of with good grounds claim 11 to 14 Liquid-crystal composition, and the first additive contained in the liquid-crystal composition and the second additive are polymerize.

21. a kind of liquid-crystal composition according to any one of claim 1 to 14 is used in liquid crystal display element.

22. a kind of liquid-crystal composition according to any one of claim 1 to 14 is used for polymer stabilizing orientating type In liquid crystal display element.

23. a kind of liquid-crystal composition according to any one of claim 1 to 14 is used for the liquid crystal without alignment films In display element.