CN105838387B

CN105838387B - Liquid-crystal composition, liquid crystal display element and liquid crystal display

Info

Publication number: CN105838387B
Application number: CN201610283993.7A
Authority: CN
Inventors: 栗泽和树; 小川真治; 岩下芳典
Original assignee: Dainippon Ink and Chemicals Co Ltd
Current assignee: Shijiazhuang Chengzhi Yonghua Display Material Co Ltd
Priority date: 2013-03-26
Filing date: 2013-03-26
Publication date: 2019-03-08
Anticipated expiration: 2033-03-26
Also published as: CN105838387A

Abstract

The present invention relates to liquid-crystal composition, liquid crystal display element and liquid crystal displays.A kind of liquid-crystal composition that dielectric constant anisotropy is negative, it is characterized in that, contain the one kind or two or more compound selected from compound group represented by logical formula (I), contain the one kind or two or more compound selected from compound group represented by logical formula (II), contain compound represented by formula (IIIb-1), in formula, R¹¹Indicate the alkyl of carbon atom number 1~3, R²²The alkyl or hydrogen atom for indicating carbon atom number 1~3, in formula, R¹And R²Each independently represent the alkenyloxy group of the alkyl of carbon atom number 1~8, the alkenyl of carbon atom number 2~8, the alkoxy of carbon atom number 1~8 or carbon atom number 2~8.

Description

Liquid-crystal composition, liquid crystal display element and liquid crystal display

It is on March 26th, 2013 that the application, which is the applying date, application No. is 201380046517.8, entitled " liquid crystal Composition and use its liquid crystal display element " Chinese patent application divisional application.

Technical field

The present application is related to the component parts as liquid crystal display device etc. and useful liquid-crystal composition and liquid crystal Show element.

Background technique

Liquid crystal display element is currently used to various sensing equipments, automobile panel, text headed by clock, calculator Processor, electronic notebook, printer, computer, television set, clock, advertising display panel etc..As liquid crystal display mode, generation Table mode has TN (twisted-nematic) type, STN (super twisted nematic) type, the VA (vertical orientation) using TFT (thin film transistor (TFT)) Type, IPS (plane conversion) type etc..Liquid-crystal composition used in these liquid crystal display elements is required to moisture, empty air and heat, light Etc. extraneous factors are stable, furthermore show liquid crystalline phase within the scope of the temperature as wide as possible centered on room temperature, low viscosity and drive Dynamic voltage is low.In turn, liquid-crystal composition is in order to make to combine most suitable dielectric constant anisotropy (Δ ε) for each display element Or/and (Δ n) etc. is most to constitute just when and by several to tens of kinds of compounds to refractive anisotrop.

The liquid-crystal composition being negative in vertically oriented escope using Δ ε is widely used in liquid crystal TV etc..On the other hand, Whole driving methods are required to low voltage drive, high-speed response, wide operating temperature range.I.e., it is desirable that Δ ε is positive and absolute value Greatly, small, the high nematic phase of viscosity (η)-isotropic liquid phase transition temperature (T_ni).Furthermore, it is necessary to by Δ n and cell gap (d) the Δ n of liquid-crystal composition is adjusted to range appropriate according to cell gap by product, that is, Δ n × d setting.And work as liquid Crystal display element is applied to pay attention to high speed responsiveness whens television set etc., therefore it is required that γ₁Small liquid-crystal composition.

In the past, in order to constitute γ₁Small liquid-crystal composition, usually using the compound with dialkyl group bicyclohexane skeleton (referring to patent document 1).However, although bicyclohexane based compound is to reduction γ₁Effect is good, but general vapour pressure is high, alkyl This tendency of the short compound of chain length is especially significant.In addition, there is also T_niAlso low tendency, therefore, actual conditions are alkane Base bicyclohexane based compound is mostly using the compound for adding up to 7 or more carbon atom number of side chain length, not to side chain lengths Short compound is sufficiently studied.

On the other hand, with the purposes for expanding liquid crystal display element, it is anticipated that its application method, manufacturing method also have Big variation, in order to cope with such case, it is necessary to the characteristic other than those previously known basic physics values into Row optimization.That is, with using the liquid crystal display element of liquid-crystal composition that VA (vertical orientation) type, IPS (plane turn is widely used Change) type etc., for its size, the display element of ultra-large type sizes more than also practical and 50 types of use.With substrate size Enlargement, method for implanting from liquid-crystal composition to substrate also by previous vacuum impregnation be changed into dropwise addition injection (ODF:One Drop Fill) mainstream (referring to patent document 2) of the method as method for implanting, liquid-crystal composition is added dropwise to drop impression when substrate The problem of leading to the reduction of display quality, also highlights.In turn, so that the pre-tilt angle of the liquid crystal material in liquid crystal display element Generation realize high speed responsiveness for the purpose of, develop PS liquid crystal display element (polymer stabilized, polymer stabilizing Change), PSA liquid crystal display element (polymer sustained alignment, polymer maintain orientation) is (referring to patent document 3), and the above problem is at bigger problem.Monomer is added in a liquid crystal composition and makes to combine that is, these display elements have The feature of monomer cure in object.Active matrix needs to maintain high voltage retention with liquid-crystal composition, therefore is able to use Compound be specific, and the use of the compound in compound with ester bond is restricted.Make in PSA liquid crystal display element Monomer has ester bond based on acrylic acid series in usual compound, such compound is usually used not as active matrix Liquid-crystal compounds uses (referring to patent document 3).Such foreign matter induces the generation of drop impression, because show it is bad caused by liquid crystal Show that the deterioration of the yield rate of element becomes problem.In addition, adding the additives such as antioxidant, light absorber in a liquid crystal composition When yield rate deterioration also become problem.

Here, the trace that drop impression is defined as that liquid-crystal composition is added dropwise in black display and generates emerges white phenomenon.

In order to inhibit drop impression, following methods are disclosed: using the polymerization for the polymerizable compound being mixed into liquid-crystal composition, Polymeric layer is formed in the liquid crystal layer, to inhibit the drop impression (patent document 4) generated by the relationship with tropism control film.So And this method there are problems that because showing burn-in caused by making an addition to the polymerizable compound in liquid crystal, for inhibiting drop impression Effect it is also insufficient, burn-in, drop impression are difficult to happen while needing to maintain the fundamental characteristics as liquid crystal display element The exploitation of liquid crystal display element.

Existing technical literature

Patent document

Patent document 1: Japanese Unexamined Patent Application Publication 2008-505235 bulletin

Patent document 2: Japanese Unexamined Patent Publication 6-235925 bulletin

Patent document 3: Japanese Unexamined Patent Publication 2002-357830 bulletin

Patent document 4: Japanese Unexamined Patent Publication 2006-58755 bulletin

Summary of the invention

Problems to be solved by the invention

Project to be solved by this invention is, provides a kind of liquid-crystal composition and the liquid crystal display element using it, institute State nematic phase stability that liquid-crystal composition is suitable under dielectric constant anisotropy, viscosity, nematic phase ceiling temperature, low temperature, γ₁When will not deteriorate Deng the burn-in characteristic of every characteristic and display element as liquid crystal display element, be difficult to generate manufacture Drop impression, realize liquid crystal material stable in ODF process discharge rate liquid crystal display element.

Means for solving the problems

In order to solve the above problems, the inventors of the present invention are to the production for being most suitable for the liquid crystal display element by instillation progress The composition of various liquid-crystal compositions is studied, and discovery is by carrying out specific liquid-crystal compounds with specific mixed proportion It uses, the generation of the drop impression in liquid crystal display element is able to suppress, so as to complete the present application.

The present application provides a kind of liquid-crystal composition that dielectric constant anisotropy is negative and has used the liquid crystal combination The liquid crystal display element of object, the liquid-crystal composition contain logical formula (I), lead to chemical combination represented by formula (II) and formula (IIIb-1) Object.

[changing 1]

(in formula, R¹¹Indicate the alkyl of carbon atom number 1~3, R²²Indicate the alkyl or hydrogen atom of carbon atom number 1~3, R¹With R²Each independently represent the alkyl of carbon atom number 1~8, the alkenyl of carbon atom number 2~8, carbon atom number 1~8 alkoxy or The alkenyloxy group of carbon atom number 2~8.)

The effect of invention

Liquid crystal display element of the invention has the feature that high speed responsiveness is excellent, generation burn-in is few, has because of its manufacture The few feature of the generation of caused drop impression, therefore be useful for display elements such as liquid crystal TV, displays.

Detailed description of the invention

Fig. 1 is the figure for schematically showing the composition of liquid crystal display element.

Fig. 2 is that the II line area defined of the electrode layer 3 comprising the thin film transistor (TFT) being formed on substrate in the Fig. 1 passes through Amplified top view.

Fig. 3 is on III-III line direction in Fig. 2 by sectional view made of liquid crystal display element shown in FIG. 1 cutting.

Fig. 4 is the amplified figure of the region IV, that is, thin film transistor (TFT) in Fig. 3.

Specific embodiment

As described above, the process that drop impression generates it is not immediately clear, but, impurity and alignment films in liquid-crystal compounds A possibility that interaction, chromatography phenomenon etc. are related is very high.Although manufacture work of the impurity by compound in liquid-crystal compounds The substantially influence of skill, still, even if only the carbon atom number of side chain is different, the manufacturing method of compound is also not exactly the same.That is, liquid Brilliant compound is manufactured by accurate manufacturing process, and therefore, cost is higher in chemical products, needs manufacture efficiency strongly Raising.Accordingly, there exist in order to use slightly cheap raw material, even if the carbon atom number of side chain differs only by one, also have by complete Efficiency higher situation when raw material not of the same race is manufactured.Therefore, the manufacturing process of liquid crystal substance according to each substance not Same and different, even if technique is identical, raw material is also different in most cases, as a result, each substance has been mixed into not respectively mostly Same impurity.But, even if the impurity of denier, which is also possible to, leads to the generation of drop impression, inhibit only by the purification of substance The generation of drop impression is limited.

On the other hand, there are each substances to have determined that after manufacturing process is established for the manufacturing method of widely used liquid crystal substance Tendency.Even if having the present of development in analytical technology, to have full knowledge that and be mixed into which kind of impurity also not a duck soup, need Each substance is combined the design of object under the premise of being mixed into determining impurity.The impurity to liquid crystal substance such as present inventor It is studied with the relationship of drop impression, as a result, disclose presence by rule of thumb and be difficult to generate drop impression comprising in the composition Impurity and be easy to produce the impurity of drop impression.Therefore, in order to inhibit the generation of drop impression, by specific compound specifically to mix Ratio is carried out using being important, and especially, specifies the presence for being difficult to generate the composition of drop impression.Preferred reality as described below The mode of applying is found based on foregoing viewpoint.

In the liquid-crystal composition of the present application, lead to total containing ratio of compound group represented by formula (I), as lower limit Value, preferably 2 mass %, more preferably 3 mass %, further preferably 5 mass %, as upper limit value, preferably 25 matter % is measured, more specifically more preferably 20 mass %, further preferably 15 mass % when paying attention to response speed, preferably contain There are 10~25 mass %, further preferably 15~25 mass %, when more paying attention to driving voltage, preferably comprise 2~20 mass %, Further preferably 5~15 mass %.

Compound group represented by formula (I-1)~formula (I-8) that compound represented by logical formula (I) is preferably recorded from below Middle selection is more preferably selected from compound group represented by formula (I-1)~formula (I-4), formula (I-6) and formula (I-8), further It is preferred that being selected from compound group represented by formula (I-1)~formula (I-3), formula (I-6) and formula (I-8), particularly preferably from formula (I- 1) it selects in compound group represented by~formula (I-3), is most preferably selected from compound represented by formula (I-1) and formula (I-3) It selects.

[changing 2]

In the liquid-crystal composition of the present application, when the compound group represented by formula (I-1), formula (I-2) and the formula (I-3) It is middle when having selected one kind or two or more compound, containing ratio regardless of the classes of compounds selected quantity, preferably respectively From independently being 3~15 mass %, more preferably 5~10 mass %, further preferably 7~13 mass %.

In the liquid-crystal composition of the present application, lead to total containing ratio of compound group represented by formula (II), as lower limit Value, preferably 3 mass %, more preferably 4 mass %, further preferably 5 mass %, as upper limit value, preferably 25 matter Measure %, more preferably 20 mass %, further preferably 15 mass %.

Chemical combination represented by formula (II-1)~formula (II-8) that compound represented by logical formula (II) is preferably recorded from below It is selected in object group, more preferably compound, further preferably formula (II-1) and formula represented by formula (II-1)~formula (II-4) (II-3) compound represented by the compound represented by, particularly preferably formula (II-1).

[changing 3]

When the compound represented by the logical formula (II) using 4 kinds or more, formula (II-1)~formula (II- is preferably applied in combination 4) compound represented by, represented by the preferably logical formula (II) of the content of compound represented by formula (II-1)~formula (II-4) 50 mass % or more in compound, more preferably 70 mass % or more, further preferably 80 mass % or more, particularly preferably For 90 mass % or more.

When using compound represented by 3 kinds of logical formula (II)s, formula (II-1)~formula (II-3) institute table is preferably applied in combination The compound shown, compound represented by the preferably logical formula (II) of the content of compound represented by formula (II-1)~formula (II-3) In 50 mass % or more, more preferably 70 mass % or more, further preferably 80 mass % or more, particularly preferably 90 matter Measure % or more.

When using compound represented by 2 kinds of logical formula (II)s, formula (II-1) and formula (II-3) institute table is preferably applied in combination Compound represented by the preferably logical formula (II) of the content of compound represented by the compound shown, formula (II-1) and formula (II-3) In 50 mass % or more, more preferably 70 mass % or more, further preferably 80 mass % or more, particularly preferably 90 matter Measure % or more.

In the liquid-crystal composition of the present application, the containing ratio of compound represented by formula (IIIb-1), as lower limit value, Preferably 5 mass %, more preferably 8 mass %, further preferably 10 mass %, as upper limit value, preferably 25 mass %, More preferably 20 mass %, further preferably 15 mass %, more specifically, the refractive index of liquid-crystal composition to be reduced respectively to When the value of the opposite sex, 10~25 mass %, further preferably 15~25 mass % are preferably comprised, refractive anisotrop to be improved When value, 5~20 mass %, further preferably 5~15 mass % are preferably comprised.

The liquid-crystal composition of the present application can be further containing the chemical combination represented by the logical formula (III) as shown below The compound selected in object group.

[changing 4]

R in formula³And R⁴Each independently represent the alkyl of carbon atom number 1~8, the alkenyl of carbon atom number 2~8, carbon atom number 1~8 alkoxy or the alkenyloxy group of carbon atom number 2~8, n indicate 0 or 1, but R³For the alkyl and R of carbon atom number 3⁴For carbon atom The alkoxy and n of number 2 indicate except 1 compound.

In compound represented by logical formula (III), R³And R⁴Alkyl, the carbon for each independently representing carbon atom number 1~8 are former The alkenyloxy group of the alkenyl of subnumber 2~8, the alkoxy of carbon atom number 1~8 or carbon atom number 2~8, R³Preferably carbon atom number 1~ 8 alkyl or the alkenyl of carbon atom number 2~8, the more preferably alkyl of carbon atom number 1~8, further preferably carbon atom number 2 ~5 alkyl, R⁴Preferably the alkyl of carbon atom number 1~8, carbon atom number 1~8 alkoxy, more preferably carbon atom number 1~ 8 alkoxy, the further preferably alkoxy of carbon atom number 2~5.

In compound represented by logical formula (III), when n is indicated with 0, the general formula (IIIa) recorded below is indicated

[changing 5]

(R in formula^3aAnd R^4aIt respectively indicates and the R in logical formula (III)³And R⁴The identical meaning), in the compound group, preferably For compound represented by formula (IIIa-1)~formula (IIIa-8), more preferably represented by formula (IIIa-1)~formula (IIIa-4) Compound represented by compound, further preferably formula (IIIa-1) and formula (IIIa-4).

[changing 6]

Compound represented by general formula (IIIa) preferably comprises 3~30 mass %, further preferably 3~25 mass %, into One step preferably comprises 3~20 mass %.

When the compound represented by the general formula (IIIa) using 4 kinds or more, formula (IIIa-1) is preferably applied in combination to formula (IIIa-4) content of the compound represented by, compound represented by formula (IIIa-1) to formula (IIIa-4) is preferably general formula (IIIa) the 50 mass % or more in the compound represented by, more preferably 70 mass % or more, further preferably 80 matter Measure % or more, particularly preferably 90 mass % or more.

When using compound represented by 3 kinds of general formulas (IIIa), formula (IIIa-1), formula (IIIa-2) is preferably applied in combination With compound represented by formula (IIIa-4), compound represented by formula (IIIa-1), formula (IIIa-2) and formula (IIIa-4) Content is preferably the 50 mass % or more in compound represented by general formula (IIIa), more preferably 70 mass % or more, into one Step is preferably 80 mass % or more, particularly preferably 90 mass % or more.

When using compound represented by 2 kinds of general formulas (IIIa), formula (IIIa-1) and formula (IIIa- is preferably applied in combination 4) content of compound represented by the compound represented by, formula (IIIa-1) and formula (IIIa-4) is preferably general formula (IIIa) institute 50 mass % or more in the compound of expression, more preferably 70 mass % or more, further preferably 80 mass % or more, it is special It You Xuanwei not 90 mass % or more.

In compound represented by logical formula (III), when n indicates 1, the general formula (IIIb) recorded below is indicated

[changing 7]

(R in formula^3bAnd R^4bIt respectively indicates and the R in logical formula (III)³And R⁴The identical meaning, but R^3bFor carbon atom number 3 Alkyl and R^4bExcept compound represented by alkoxy for carbon atom number 2), in the compound group, preferably record below Change represented by compound represented by formula (IIIb-2)~formula (IIIb-6), more preferably formula (IIIb-2)~formula (IIIb-4) Close object, further preferably compound represented by formula (IIIb-2) and formula (IIIb-3), particularly preferably formula (IIIb-3) institute The compound of expression.

[changing 8]

In addition, working as the demanding nematic of the liquid-crystal composition-isotropic phase transition temperature (T of the present application_ni) when, it is excellent Choosing selects at least one kind of from compound group represented by formula (IIIb-5) and formula (IIIb-6).

Compound group represented by general formula (IIIb), liquid crystal skeleton (mesomorphic base) with as required in the present application The formula (IIIb-1) of ingredient is identical, when and with compound and general formula (IIIb) institute table represented by 4 kinds or more of formula (IIIb-1) When the compound shown, preferably with formula (IIIb-1) represented by formula (IIIb-2)~formula (IIIb-4) is applied in combination together with compound The content of represented compound, compound represented by formula (IIIb-2)~formula (IIIb-4) is preferably general formula (IIIb) institute table 50 mass % or more in the compound shown, more preferably 70 mass % or more, further preferably 80 mass % or more, especially Preferably 90 mass % or more.

It is excellent when compound represented by compound represented by 3 kinds of formulas (IIIb-1) and general formula (IIIb) is applied in combination Compound represented by formula (IIIb-2) and formula (IIIb-3) is applied in combination together with compound represented by choosing and formula (IIIb-1), The content of compound represented by formula (IIIb-2) and formula (IIIb-3) is preferably in compound represented by general formula (IIIb) 50 mass % or more, more preferably 70 mass % or more, further preferably 80 mass % or more.

It is excellent when compound represented by compound represented by 2 kinds of formulas (IIIb-1) and general formula (IIIb) is applied in combination Compound represented by formula (IIIb-3), formula (IIIb-3) institute is applied in combination together with compound represented by choosing and formula (IIIb-1) The content of the compound of expression is preferably the 50 mass % or more in compound represented by general formula (IIIb), more preferably 70 matter Measure % or more, further preferably 80 mass % or more, particularly preferably 90 mass % or more.

The liquid-crystal composition of the present application can contain the choosing of the compound group represented by the logical formula (IV) as shown below The compound selected.

[changing 9]

R in formula⁵And R⁶Each independently represent the alkyl of carbon atom number 1~8, the alkenyl of carbon atom number 2~8, carbon atom number 1~8 alkoxy or the alkenyloxy group of carbon atom number 2~8.

In the liquid-crystal composition of the present application, lead to total containing ratio of compound group represented by formula (IV), as lower limit Value, preferably 5 mass %, more preferably 10 mass %, further preferably 15 mass %, as upper limit value, preferably 30 matter Measure %, more preferably 25 mass %, further preferably 22 mass %, more specifically, the refraction of liquid-crystal composition to be reduced When the anisotropic value of rate, 5~15 mass % are preferably comprised, when the value of refractive anisotrop to be improved, preferably comprise 15~ 30 mass %.

Compound represented by formula (IV-1)~(IV-4) that compound represented by logical formula (IV) is preferably recorded below, Compound represented by more preferable formula (IV-1) or formula (IV-2).

[changing 10]

When using compound represented by logical formula (IV) of more than two kinds, formula (IV-1) and formula (IV- is preferably applied in combination 2) represented by the preferably logical formula (IV) of the content of compound represented by the compound represented by, formula (IV-1) and formula (IV-2) 50 mass % or more in compound, more preferably 70 mass % or more, further preferably 80 mass % or more, particularly preferably For 90 mass % or more.

The liquid-crystal composition of the present application can be further containing the compound represented by the logical formula (V) as shown below The compound selected in group.

[changing 11]

R in formula⁷And R⁸Each independently represent the alkyl of carbon atom number 1~8, the alkenyl of carbon atom number 2~8, carbon atom number 1~8 alkoxy or the alkenyloxy group of carbon atom number 2~8,1 or more in the alkyl, alkenyl, alkoxy and/or alkenyloxy group Hydrogen atom can be replaced by fluorine original, as long as the methylene oxygen atom in the alkyl, alkenyl, alkoxy and/or alkenyloxy group is discontinuously tied Conjunction can be replaced by oxygen atom, as long as carbonyl, which discontinuously combines, to be replaced by carbonyl,

A³It indicates 1 or 4 cyclohexylidene, Isosorbide-5-Nitrae-phenylene or oxinane -2,5- diyl, works as A³When indicating Isosorbide-5-Nitrae-phenylene, 1 or more hydrogen atom in the Isosorbide-5-Nitrae-phenylene can be replaced by fluorine atoms,

Z¹Indicate singly-bound ,-OCH₂-、-OCF₂-、-CH₂O- or-CF₂O-,

N indicates 0 or 1,

X¹~X⁶Each independently represent hydrogen atom or fluorine atom, X¹~X⁶In at least one indicate fluorine atom.

General formula (V-1)~(V-15) that compound represented by logical formula (V) is specifically preferably recorded below is represented Compound, more preferably formula (V-1), formula (V-3)~formula (V-9) and formula (V-12)~formula (V-15), further preferably formula (V-1), formula (V-3), formula (V-5), formula (V-6), formula (V-9), formula (V-12) and formula (V-15), particularly preferably formula (V-1), formula (V-5), formula (V-6), most preferably formula (V-5).

[changing 12]

In formula, R⁷And R⁸It indicates and the R in logical formula (V)⁷And R⁸The identical meaning.

, it is preferable to use compound represented by formula (V-5), formula (V-5) institute when using compound represented by logical formula (V) The content of the compound of expression is preferably the 50 mass % or more in compound represented by logical formula (V), more preferably 70 matter Measure % or more, further preferably 80 mass % or more, particularly preferably 90 mass % or more.

R in logical formula (V)⁷And R⁸Each independently represent the alkyl of carbon atom number 1~8, the alkenyl of carbon atom number 2~8, The alkoxy of carbon atom number 1~8 or the alkenyloxy group of carbon atom number 2~8 preferably indicate the alkyl or carbon atom of carbon atom number 1~8 The alkenyl of number 2~8 more preferably indicates the alkyl of carbon atom number 2~5 or the alkenyl of carbon atom number 2~5, further preferably indicates The alkyl of carbon atom number 2~5, preferably straight chain, work as R⁷And R⁸When being alkyl, preferably respective carbon atom number is different.

Further specifically, preferably R⁷Indicate propyl and R⁸Indicate the compound or R of ethyl⁷Indicate butyl and R⁸It indicates The compound of ethyl.

The liquid-crystal composition of the present application can be further containing from general formula (VI-a) to general formula (VI-e) institute table The compound selected in the compound group shown.

[changing 13]

In formula, R⁹¹To R^9aEach independently represent the alkyl of carbon atom number 1 to 10, the alkoxy of carbon atom number 1 to 10 or The alkenyl of carbon atom number 2 to 10, in compound represented by general formula (VI-a), R⁹¹Indicate alkyl, the R of carbon atom number 1~3⁹²Table Except showing the 1- alkene of carbon atom number 1~5 or the compound of hydrogen atom.

When containing the compound selected in compound group represented by from general formula (VI-a) to general formula (VI-e), preferably contain There are a kind~10 kinds, particularly preferably contain a kind~8 kinds, particularly preferably contain a kind~5 kinds, it is also preferred that containing chemical combination of more than two kinds Object, it is also preferred that containing a kind of compound, content in this case is preferably 20~60 mass %, more preferably 20~50 matter Measure %, further preferably 25~45 mass %, particularly preferably 30~40 mass %.

R⁹¹To R^9aThe alkyl of carbon atom number 1 to 10, the alkenyl or carbon of carbon atom number 2 to 10 are preferably indicated each independently The alkoxy of atomicity 2 to 10 more preferably indicates the alkyl of carbon atom number 1 to 5, the alkenyl or carbon atom number of carbon atom number 2 to 5 2 to 5 alkoxy, when indicating alkenyl, structure represented by formula (i)~formula (iv) for preferably recording below works as the application When the liquid-crystal composition of invention contains reactive monomer, preferably structure, more preferably formula represented by formula (ii) and formula (iv) (ii) structure represented by.

[changing 14]

In formula, ring structure is incorporated by right end.

In addition, R⁹¹And R⁹²It can be the same or different, preferably indicate different substituent groups.

From these viewpoints, the more specifically preferably record below of compound represented by formula (VI-a) to formula (VI-e) Compound.

[changing 15]

[changing 16]

[changing 17]

[changing 18]

[changing 19]

[changing 20]

Wherein, preferred formula (VI-a1)~formula (VI-a-5), formula (VI-b2), formula (VI-b6), formula (VI-c2), formula (II- C4), compound represented by formula (VI-c5), formula (VI-d1)~formula (VI-d4) and formula (VI-e2).

When the compound group selection 1 represented by formula (VI-a3)~formula (VI-a5) of the liquid-crystal composition in the present application Kind, a part as other compositions of 2 kinds or 3 kinds when, total content is preferably 15~40 mass %, more preferably 18~35 matter %, further preferably 20~33 mass % are measured, more specifically, when the compound represented by selecting type (VI-a3), Its content is preferably 5~30 mass %, more preferably 10~25 mass %, further preferably 13~20 mass %, works as selection When compound represented by formula (VI-a4), content is preferably 1~15 mass %, more preferably 2~12 mass %, further Preferably 3~9 mass %, when the compound represented by selecting type (VI-a5), content is preferably 3~15 mass %, more excellent It is selected as 5~10 mass %, further preferably 7~9 mass %.

When the compound group selection 2 represented by formula (VI-a3)~formula (VI-a5) of the liquid-crystal composition in the present application When planting a part as other compositions, formula (VI-a3) and formula (VI-a4) are preferably selected, when selecting a kind, is more preferably selected Formula (VI-a3).

Compound represented by compound represented by logical formula (VI) and logical formula (I) dielectric constant anisotropy generally Be on 0 this aspect it is common, the total containing ratio for leading to compound represented by formula (I) and logical formula (VI) is preferably 25~60 mass %, More preferably 30~55 mass %, further preferably 35~50 mass %.

1,4- cyclohexyl in the application is preferably anti-form-1,4- cyclohexyl.

Liquid-crystal composition in the present invention is with compound represented by logical formula (I), logical formula (II) and formula (IIIb-1) must Ingredient is needed, it can be further represented containing logical formula (III), logical formula (IV), logical formula (V) and general formula (VI-a)~general formula (VI-e) Compound.Logical formula (I) contained in liquid-crystal composition, logical formula (II), formula (IIIb-1), logical formula (III), logical formula (IV), Total content of compound represented by logical formula (V) and general formula (VI-a)~general formula (VI-e), as lower limit value, preferably 60 matter Measure %, preferably 65 mass %, preferably 70 mass %, preferably 75 mass %, preferably 80 mass %, preferably 85 matter Measure %, preferably 90 mass %, preferably 92 mass %, preferably 95 mass %, preferably 98 mass %, preferably 99 matter % is measured, as upper limit value, preferably 100 mass %, preferably 99.5 mass %.

More specifically, total content of compound represented by logical formula (I), logical formula (II) and formula (IIIb-1) is preferably 20~45 mass %, more preferably 25~40 mass %, further preferably 30~37 mass %.

Total content of compound represented by logical formula (I), logical formula (II), formula (IIIb-1) and logical formula (III) is preferably 35~55 mass %, more preferably 40~50 mass %, further preferably 42~48 mass %.

Total content of compound represented by logical formula (I), logical formula (II), formula (IIIb-1) and logical formula (IV) is preferably 40 ~65 mass %, more preferably 45~60 mass %, further preferably 47~55 mass %.

Total content of compound represented by logical formula (I), logical formula (II), formula (IIIb-1) and logical formula (V) is preferably 25 ~50 mass %, more preferably 30~45 mass %, further preferably 35~43 mass %.

Total content of compound represented by logical formula (I), logical formula (II), formula (IIIb-1) and logical formula (VI) is preferably 55 ~80 mass %, more preferably 60~75 mass %, further preferably 63~72 mass %.

The total of compound represented by logical formula (I), logical formula (II), formula (IIIb-1), logical formula (III) and logical formula (IV) contains Amount is preferably 50~75 mass %, more preferably 55~70 mass %, further preferably 58~65 mass %.

The total of compound represented by logical formula (I), logical formula (II), formula (IIIb-1), logical formula (III) and logical formula (V) contains Amount is preferably 35~65 mass %, more preferably 40~60 mass %, further preferably 45~55 mass %.

The total of compound represented by logical formula (I), logical formula (II), formula (IIIb-1), logical formula (III) and logical formula (VI) contains Amount is preferably 65~95 mass %, more preferably 70~90 mass %, further preferably 75~85 mass %.

Total content of compound represented by logical formula (I), logical formula (II), formula (IIIb-1), logical formula (IV) and logical formula (V) Preferably 45~70 mass %, more preferably 50~65 mass %, further preferably 53~60 mass %.

The total of compound represented by logical formula (I), logical formula (II), formula (IIIb-1), logical formula (IV) and logical formula (VI) contains Amount is preferably 70~99 mass %, more preferably 75~95 mass %, further preferably 80~90 mass %.

Total content of compound represented by logical formula (I), logical formula (II), formula (IIIb-1), logical formula (V) and logical formula (VI) Preferably 60~85 mass %, more preferably 65~80 mass %, further preferably 70~75 mass %.

Compound represented by logical formula (I), logical formula (II), formula (IIIb-1), logical formula (III), logical formula (IV) and logical formula (V) Total content be preferably 55~80 mass %, more preferably 60~75 mass %, further preferably 63~70 mass %.

Chemical combination represented by logical formula (I), logical formula (II), formula (IIIb-1), logical formula (III), logical formula (IV) and logical formula (VI) Total content of object is preferably 80 mass % or more, more preferably 85 mass % or more, further preferably 90 mass % or more.

Compound represented by logical formula (I), logical formula (II), formula (IIIb-1), logical formula (III), logical formula (V) and logical formula (VI) Total content be preferably 70~95 mass %, more preferably 75~90 mass %, further preferably 80~85 mass %.

Compound represented by logical formula (I), logical formula (II), formula (IIIb-1), logical formula (IV), logical formula (V) and logical formula (VI) Total content be preferably 80~99 mass %, more preferably 85~95 mass %, further preferably 87~92 mass %.

Logical formula (I), logical formula (II), formula (IIIb-1), logical formula (III), logical formula (IV), logical formula (V) and logical formula (VI) institute table Total content of the compound shown is preferably 90 mass % or more, more preferably 95 mass % or more, further preferably 97 matter % or more is measured, is preferably essentially 100 mass %, preferably 99.5 mass % or more.

When paying attention to the reliability and long-time stability of liquid-crystal composition, relative to the gross mass of aforementioned composition, preferably The content of compound with carbonyl is set as 5 mass % hereinafter, being more preferably set as 3 mass % hereinafter, being further preferably set as 1 Quality % is hereinafter, most preferably contain substantially no.

When the stability for paying attention to irradiating UV, relative to the gross mass of aforementioned composition, preferably chlorine atom is replaced Compound content be set as 15 mass % hereinafter, more preferably be set as 10 mass % hereinafter, further preferably be set as 5 mass % with Under, most preferably contain substantially no.

It is preferred that increasing the content of the compound of all hexatomic rings of ring structure of intramolecular, relative to the total of aforementioned composition The content of the compound of all hexatomic rings of the ring structure of intramolecular is preferably set as 80 mass % or more, more preferably set by quality For 90 mass % or more, 95 mass % or more are further preferably set as, most preferably liquid-crystal composition is substantially only by intramolecular The compound of all hexatomic rings of ring structure is constituted.

In order to inhibit liquid-crystal composition because deteriorating caused by oxidation, preferably reducing has cyclohexadienylidene as ring structure The content of compound preferably the content of the compound with cyclohexadienylidene is set relative to the gross mass of aforementioned composition For 10 mass % hereinafter, being more preferably set as 5 mass % hereinafter, further preferably containing substantially no.

When the improvement and T for paying attention to viscosity_niImprovement when, there is preferably reduction intramolecular hydrogen atom can be replaced by halogen atom 2- methylbenzene-Isosorbide-5-Nitrae-diyl compound content will preferably have 2- methylbenzene-Isosorbide-5-Nitrae-diyl compound in previous molecular Content be set as relative to aforementioned composition gross mass be 10 mass % hereinafter, more preferably be set as 5 mass % hereinafter, further It is preferred that containing substantially no.

In the case that the compound contained in the composition of first embodiment of the invention has alkenyl as side chain, When foregoing alkenyl is incorporated into hexamethylene, the carbon atom number of the alkenyl is preferably 2~5, when foregoing alkenyl is incorporated into benzene, the alkene The carbon atom number of base is preferably 4~5, and the unsaturated bond of preferably foregoing alkenyl is not bound directly with benzene.

The value of the dielectric constant anisotropy Δ ε of liquid-crystal composition in the present application is preferably -2.0 at 25 DEG C To -6.0, more preferably -2.5 to -5.0, particularly preferably -2.5 to -4.0, further specifically, when attention response speed When, preferably -2.5~-3.4, when paying attention to driving voltage, preferably -3.4~-4.0.

The value of the refractive anisotrop Δ n of liquid-crystal composition in the present invention at 25 DEG C preferably 0.08 to 0.13, More preferably 0.09 to 0.12.Further specifically, when corresponding to thin cell gap, preferably 0.10 to 0.12, when When corresponding to thick cell gap, preferably 0.08 to 0.10.

Rotary viscosity (the γ of liquid-crystal composition in the present invention₁) be preferably 150 hereinafter, more preferably 130 hereinafter, especially Preferably 120 or less.

In liquid-crystal composition in the present invention, showed preferably as the Z of rotary viscosity and the function of refractive anisotrop To be specifically worth.

[number 1]

1/ Δ n of Z=γ²

(in formula, γ₁Indicate that rotary viscosity, Δ n indicate refractive anisotrop.)

Z is preferably 13000 hereinafter, more preferably 12000 hereinafter, particularly preferably 11000 or less.

When liquid-crystal composition of the invention is used for active matrix display element, it is necessary to have 10¹²Electricity more than (Ω m) Resistance rate, preferably 10¹³(Ω m), more preferably 10¹⁴More than (Ω m).

Other than above compound, depending on the application, liquid-crystal composition of the invention can also contain common nematic liquid Crystalline substance, smectic liquid crystal, cholesteric liquid crystal, antioxidant, ultraviolet absorbing agent, polymerizable monomer etc., when the change for requiring liquid-crystal composition When learning stability, preferably its intramolecular does not have chlorine atom, when requiring stability of the liquid-crystal composition to light such as ultraviolet lights, wishes Hoping its intramolecular without conjugation chain length representated by naphthalene nucleus etc., there are condensed rings of absorption peak etc. in long ultraviolet region.

As polymerizable monomer, two functional monomers represented by preferred formula (VII).

[changing 21]

(in formula, X⁷And X⁸Hydrogen atom or methyl are each independently represented,

Sp¹And Sp²Each independently represent singly-bound, the alkylidene of carbon atom number 1~8 or-O- (CH₂)_s-

(in formula, s indicates that 2 to 7 integer, hydrogen atom are incorporated into aromatic rings.),

Z²Expression-OCH₂-、-CH₂O-、-COO-、-OCO-、-CF₂O-、-OCF₂-、-CH₂CH₂-、-CF₂CF₂,-CH=CH- COO- ,-CH=CH-OCO- ,-COO-CH=CH- ,-OCO-CH=CH- ,-COO-CH₂CH₂-、-OCO-CH₂CH₂-、-CH₂CH₂- COO-、-CH₂CH₂-OCO-、-COO-CH₂-、-OCO-CH₂-、-CH₂-COO-、-CH₂-OCO-、-CY¹=CY²(in formula, Y¹And Y² Each independently represent fluorine atom or hydrogen atom.) ,-C ≡ C- or singly-bound,

B indicates that Isosorbide-5-Nitrae-phenylene, anti-form-1,4- cyclohexylidene or singly-bound, all Isosorbide-5-Nitrae-phenylenes in formula are any Hydrogen atom can be replaced by fluorine atoms.)

It is preferred that X⁷And X⁸Indicate the diacrylate derivative of hydrogen atom, the dimethylacrylate that all has methyl spreads out Any one of biology a, it is also preferred that side indicates that hydrogen atom another party indicates the compound of methyl.The polymerization speed of these compounds Degree are as follows: diacrylate derivative is most fast, dimethylacrylate derivative is slow, asymmetric compound occupy between the two, can By according to its purposes using in a manner of preferred.Particularly preferred dimethylacrylate derivative in PSA display element.

Sp¹And Sp²Each independently represent singly-bound, the alkylidene of carbon atom number 1~8 or-O- (CH₂)_s, PSA display member A preferably at least side is singly-bound in part, preferably indicates that the compound of singly-bound or a side indicate that singly-bound another party indicates carbon atom number 1~8 alkylidene or-O- (CH₂)_sMode.It is at this time preferably 1~4 alkyl, s is preferably 1~4.

Z¹Preferably-OCH₂-、-CH₂O-、-COO-、-OCO-、-CF₂O-、-OCF₂-、-CH₂CH₂-、-CF₂CF₂Or singly-bound, More preferably-COO- ,-OCO- or singly-bound, particularly preferably singly-bound.

B indicates Isosorbide-5-Nitrae-phenylene, the anti-form-1 that arbitrary hydrogen atom can be replaced by fluorine atoms, 4- cyclohexylidene or singly-bound, It is preferred that 1,4- phenylene or singly-bound.When B indicate singly-bound other than ring structure when, Z²Linking group preferably also other than singly-bound, When B is singly-bound, Z¹Preferably singly-bound.

From these viewpoints, lead in formula (VII), Sp¹And Sp²Between ring structure specifically preferably below record Structure.

In logical formula (VII), when B indicates that singly-bound, ring structure are formed by two rings, preferably indicate following formula (VIIa-1) extremely Formula (VIIa-5), more preferable expression (VIIa-1) to formula (VIIa-3), particularly preferred expression (VIIa-1).

[changing 22]

In formula, both ends are incorporated into Sp¹Or Sp²。

Orientation restraining force after polymerizable compound polymerization comprising these skeletons is most suitable to PSA type liquid crystal display element , it can get good state of orientation, therefore, show uneven suppressed or do not occur completely.

In conclusion as polymerizable monomer, particularly preferably general formula (VII-1)~general formula (VII-4), wherein most preferably For general formula (VII-2).

[changing 23]

(in formula, Sp²Indicate the alkylidene of carbon atom number 2 to 5.)

When liquid-crystal composition of the invention adds monomer, polymerization also be will do it when even if there be no polymerization initiator, but It may be to promote polymerization and contain polymerization initiator.As polymerization initiator, benzoin ethers, benzophenone can be enumerated Class, acetophenones, benzil ketals class, acylphosphine oxide class etc..In addition, can also be added steady to improve storage stability Determine agent.As the stabilizer being able to use, can enumerate for example hydroquinones, quinhydrones monoalkyl ethers, tert-butyl catechol class, Pyrogallol class, benzenethiol class, nitro compound species, beta-naphthylamine class, betanaphthol class, nitroso compound etc..

Liquid-crystal composition containing polymerizable compound of the invention be for liquid crystal display element it is useful, particularly with Active matrix drive with liquid crystal display element be it is useful, can be used for PSA mode, PSVA mode, VA mode, IPS mode or Ecb mode liquid crystal display element.

Liquid-crystal composition containing polymerizable compound of the invention irradiates the polymerization so that contained therein by ultraviolet light Property compound polymerization occurs to being endowed liquid crystal aligning ability, for the birefringent transmitted light to light using liquid-crystal composition Measure the liquid crystal display element controlled.As liquid crystal display element, for AM-LCD (active matrix liquid crystal display device), TN (nematic liquid crystal display element), STN-LCD (Supertwist Nematic Liquid Crystal Display element), OCB-LCD and IPS-LCD (plane conversion Liquid crystal display element) be it is useful, be particularly useful for AM-LCD, can be used for the liquid crystal display member of transmission-type or reflection-type Part.

In addition, if with reference to the content of aftermentioned liquid crystal display element and Fig. 1~4, liquid used in liquid crystal display element 2 pieces of substrates 2,8 of brilliant unit can be used glass or have the transparent material of flexibility as plastics, can also be with a side The opaque material such as silicon.Transparent substrate 2,8 with transparent electrode (layer) 6,14 such as can by glass plate 2,8 thoroughly Tin indium oxide (ITO) is sputtered on bright substrate and is obtained.

Make to be previously formed transparent electrode (layer), TFT substrate 2,8 in a manner of 6,14 inside of transparent electrode (layer) phase It is right.At this point, the interval (referring to Fig.1~4) of substrate can also be adjusted by spacer (not shown).At this point, it is preferred that so as to obtaining The light modulation layer obtained is adjusted with a thickness of 1~100 μm of mode.Further preferably 1.5 to 10 μm, when using polarizer, It is preferred that being adjusted in such a way that contrast becomes maximum to the refractive anisotrop Δ n and the product of element thickness d of liquid crystal.This Outside, when there is two pieces of polarizers 1,9, also the polarizing axis of adjustable each polarizer is thus with visual angle, contrast for good side Formula is adjusted (referring to Fig.1~4).In turn, the phase difference film for expanding visual angle can also be used.It, can be with as spacer It enumerates such as glass particle, plastic pellet, aluminium oxide particles, photo-induced corrosion resistant material.Then, by epoxy thermoset composition Equal sealants carry out silk-screen printing in the form of being equipped with liquid crystal injecting port on the substrate, which are bonded each other, heating makes Sealant heat cure.

The liquid-crystal composition of the receiving liquid-crystal composition formed and making 2 pieces of substrates opposite as described above and being bonded is held Common vacuum impregnation or ODF method etc. can be used in the method that space imports the liquid-crystal composition containing polymerizable monomer of receiving, Although vacuum impregnation does not generate drop impression, deposit has the problem of residual after the implantation, and the present application can be more suitably used for The display element manufactured using ODF method.

In order to obtain the good orientation characteristic of liquid crystal, as the method for polymerizeing polymerizable compound, it is hoped that there will be appropriate poly- Close speed, thus preferably by individually or and with or successively irradiation ultraviolet light or electron ray isoreactivity energy-ray gathered The method of conjunction.When using ultraviolet light, polarizing light source both can be used, non-polarized light light source also can be used.In addition, making to contain When thering is the liquid-crystal composition of polymerizable compound to be polymerize with the state being held between 2 pieces of substrates, at least shadow surface one is needed The substrate of side has the transparency appropriate for active energy beam.Further, it is also possible to use following methods: making in irradiation light Only made with mask it is specific it is partially polymerized after, make the orientation shape of unpolymerized part by changing the conditions such as electric field, magnetic field or temperature State changes, and further irradiating active energy beam makes its polymerization.Especially when carrying out ultraviolet exposure, preferably on one side to containing There is the liquid-crystal composition of polymerizable compound to apply AC field and carries out ultraviolet exposure on one side.The AC field of application is preferably The exchange of frequency 10Hz to 10kHz, more preferably frequency 60Hz to 10kHz, voltage is according to the desired pre- of liquid crystal display element Inclination angle is selected.I.e., it is possible to be controlled using pre-tilt angle of the voltage applied to liquid crystal display element.In MVA mode Liquid crystal display element in, from the viewpoint of orientation stability and contrast, preferably by pre-tilt angle control at 80 degree to 89.9 Degree.

Temperature when irradiation is preferably within the temperature range of maintaining the mesomorphic state of liquid-crystal composition of the invention.It is preferred that Close to room temperature temperature, it is i.e. typical for 15~35 DEG C of temperature polymerize.As the lamp for generating ultraviolet light, can be used Metal halide lamp, high-pressure mercury-vapor lamp, extra-high-pressure mercury vapour lamp etc..In addition, the wavelength as the ultraviolet light irradiated, preferably irradiates Wavelength region in the ultraviolet light in the absorbing wavelength domain of liquid-crystal composition, is not preferably as needed filtered ultraviolet light and makes With.The intensity of the ultraviolet light irradiated is preferably 0.1mW/cm²~100W/cm², more preferably 2mW/cm²~50W/cm².It is shone The energy for the ultraviolet light penetrated can be with appropriate adjustment, preferably 10mJ/cm²To 500J/cm², more preferably 100mJ/cm²To 200J/ cm².Intensity can also be changed when irradiating ultraviolet light.The time of irradiation ultraviolet light is suitably selected according to the intensity of the ultraviolet light irradiated It selects, preferably 10 seconds to 3600 seconds, more preferably 10 seconds to 600 seconds.

The second aspect of the present invention is the liquid crystal display element for having used liquid-crystal composition according to the present invention.Fig. 1 is Schematically show the figure of the composition of liquid crystal display element.In addition, for ease of description, each component is separated progress in Fig. 1 It records.Fig. 2 is to be exaggerated (or the also referred to as film of electrode layer 3 including the thin film transistor (TFT) on the substrate that is formed in the Fig. 1 Transistor layer 3.) II line area defined top view.Fig. 3 is that the III-III line direction in the Fig. 2 will be shown in Fig. 1 Liquid crystal display element cutting made of sectional view.Fig. 4 is the region the IV i.e. figure of thin film transistor (TFT) being exaggerated in the Fig. 3.With Under, a pair liquid crystal display element according to the present invention is illustrated referring to Fig.1~4.

The composition of liquid crystal display element 10 according to the present invention is liquid crystal display element with the following characteristics: having the One substrate 8, the second substrate 2 and liquid-crystal composition (or the liquid crystal layer being held between aforementioned first substrate 8 and the second substrate 2 5), the first substrate 8 has (or the also referred to as public electrode of transparent electrode (layer) 6 formed by transparent conductive material 6.), the second substrate 2 include the pixel electrode that is formed by transparent conductive material be formed with and have to each pixel before The tft layer 3 for the thin film transistor (TFT) that pixel electrode is controlled is stated, the liquid crystal molecule in the liquid-crystal composition is not being applied Being oriented to relative to aforesaid base plate 2,8 generally vertically when making alive, uses aforementioned liquid-crystal composition of the invention as the liquid Brilliant composition.In addition, as shown in figures 1 and 3, aforementioned the second substrate 2 and aforementioned first substrate 8 can also be held on a pair of of polarisation Between plate 1,9.In turn, in Fig. 1, colour filter 7 is equipped between aforementioned first substrate 8 and public electrode 6.It further, can be with Saturating in a manner of directly being contacted with liquid crystal layer 5 according to the present invention adjoining and with the liquid-crystal composition for being constituted the liquid crystal layer 5 A pair of of alignment films 4 are formed on 6,14 surface of prescribed electrode (layer).

That is, liquid crystal display element 10 according to the present invention is to be sequentially laminated with the second polarizer 1, the second substrate 2, include The electrode layer (or also referred to as tft layer) 3 of thin film transistor (TFT), alignment films 4, the layer 5 comprising liquid-crystal composition, orientation The composition of film 4, public electrode 6, colour filter 7, first substrate 8 and the first polarizer 9.

In addition, as shown in Fig. 2, being used in the electrode layer 3 of the thin film transistor (TFT) comprising the surface for being formed in the second substrate 2 It supplies the grid wiring 25 of scanning signal and the data wiring 24 for supplying display signal is mutually reported to the leadship after accomplishing a task, and in aforesaid plurality of grid Pole wiring 25 and multiple data are routed in 24 area defined, and pixel electrode 21 is formed as rectangular.As to pixel electrode The switch element of 21 supply display signals, it is attached in the portion of reporting to the leadship after accomplishing a task that aforementioned grid wiring 25 and aforementioned data wiring 24 are mutually reported to the leadship after accomplishing a task Closely, the thin film transistor (TFT) comprising source electrode 26, drain electrode 23 and gate electrode 27 is conjointly equipped with aforementioned pixel electrode 21.Into And be routed in 24 area defined in aforesaid plurality of grid wiring 25 and multiple data, it is equipped with and saves through data wiring 24 And the storage capacitance 22 for the display signal being supplied to.

In the present invention, as documented by Fig. 2~4, the liquid that thin film transistor (TFT) is reverse interleaved type can be appropriately used for Crystal display element, the preferably metal film such as grid wiring 25, data wiring 24, the case where particularly preferably wiring using aluminium.In turn, Grid wiring and data wiring are overlapped across gate insulating film.

In addition, the colour filter 7 is preferably corresponding to thin film transistor (TFT) and storage electricity from the viewpoint of the leakage for preventing light The part for holding 22 forms black matrix (not shown).

One preferred embodiment of the structure of the thin film transistor (TFT) of liquid crystal display element according to the present invention is, such as such as schemes Shown in 3 and Fig. 4, comprising: the gate electrode 11 on 2 surface of substrate is formed in, to cover the gate electrode 11 and cover the big of aforesaid base plate 2 The gate insulation layer 13 for causing the mode of entire surface to be arranged, is formed in aforementioned gate insulation layer 13 in the mode opposite with aforementioned gate electrode 11 Surface semiconductor layer 17, the protective film 18 being arranged in a manner of covering a part on the surface of aforementioned semiconductor layer 17, with Cover a side end of aforementioned protective layer 18 and aforementioned semiconductor layer 17 and exhausted with the aforementioned grid that are formed in 2 surface of aforesaid base plate The drain electrode 15 that the mode that edge layer 13 is in contact is arranged, to cover another side of aforementioned protective film 18 and aforementioned semiconductor layer 17 Source electrode 19a, 19b that end and the mode being in contact with the aforementioned gate insulation layer 13 for being formed in 2 surface of aforesaid base plate are arranged, with Cover aforementioned source electrode 19a, 19b and as aforementioned gate insulation layer 13 covers the mode of the substantially entire surface of aforementioned gate insulation layer 13 It is set in a manner of the transparent electrode 14 of setting, and a part to cover aforementioned transparent electrode 14 and aforementioned source electrode 19a, 19b The protective layer 101 (not shown in Fig. 3) set.

In addition, as shown in Figures 3 and 4, it can also be for the reason for making gate electrode not have level difference etc., in gate electrode 11 Surface forms anodic oxidation coating 12.In turn, it can also partly led for the width of Schottky barrier, the purpose of height is reduced Ohmic contact layer 16 is set between body layer 17 and drain electrode 15.

During manufacturing liquid crystal display element as described above, the generation of drop impression is by the liquid crystal material injected It substantially influences, not can avoid the influence using the composition of liquid crystal display element.As shown in figure 3, being especially formed at liquid Colour filter 7 or thin film transistor (TFT) in crystal display element etc. are only by thin alignment films 4, transparent electrode 6,14 etc. and liquid crystal group The component that object separates is closed, therefore, is tied for example, by the chemical structure of pigment used in colour filter or the chemistry of colour filter resin Structure with specified chemical structure liquid-crystal compounds combination and drop impression is had an impact.

Especially using film of the reverse interleaved type as liquid crystal display element according to the present invention as described above When transistor, as shown in figs. 2 to 4, drain electrode 15 is formed in a manner of covering grid electrode 11, therefore there are the areas of drain electrode 15 The tendency of increase.In general, common mode is, drain electrode is formed by metal materials such as copper, aluminium, chromium, titanium, molybdenum, tantalums and quilt Implement Passivation Treatment.But, such as shown in Figures 3 and 4, usual protective film 18 is thin, alignment films 4 are also thin, can not block from A possibility that sub- property substance, is high, thus, it not can avoid drop impression caused by the interaction because of metal material and liquid-crystal composition Generation.

But, in the liquid crystal display element containing liquid-crystal composition according to the present invention, it is believed that from such as liquid crystal Show the delicate balance between the component of element and the surface free energy of liquid-crystal composition according to the present invention or adsorption energy etc. From the perspective of, it also can reduce leading to the problem of for drop impression.

The liquid crystal display element for having used liquid-crystal composition of the invention is to have taken into account high-speed response and the undesirable suppression of display System useful element, be especially with liquid crystal display element to active matrix drive it is useful, VA mode, PSVA can be suitable for Mode, PSA mode, IPS mode or ecb mode.

Embodiment

It is exemplified below embodiment further progress of the present invention is described in detail, but the present invention is not limited to these Examples.In addition, with Under embodiment and comparative example composition in " % " mean " quality % ".

The characteristic measured in embodiment is as follows.

T_ni: nematic phase-isotropic liquid phase transition temperature (DEG C)

Refractive anisotrop at n:25 DEG C of Δ

Dielectric constant anisotropy at ε: 25 DEG C of Δ

Viscosity (mPas) at η: 20 DEG C

γ₁: the rotary viscosity (mPas) at 25 DEG C

VHR: frequency 60Hz, the voltage retention (%) under conditions of application voltage 1V at 60 DEG C

Burn-in:

Liquid crystal display element burn-in evaluation be, in display area show as defined in fixed pattern after 1000 hours again into When row full frame is uniformly shown, the horizontal of the ghost of fixed pattern is carried out according to 4 grades of evaluations below by estimating.

◎ is without ghost

Zero slightly ghost but be the level that can permit

△ has ghost and the level for that can not allow

× have ghost and be mutually on duty

Drop impression:

The evaluation of the drop impression of liquid crystal display device emerges the drop impression of white according to following when being by estimating to completely black display 4 grades of evaluations carry out.

◎ is without ghost

Zero slightly ghost but be the level that can permit

△ has ghost and the level for that can not allow

× have ghost and be mutually on duty

Technological adaptability:

Technological adaptability is, in ODF technique, 50pL liquid crystal is respectively added dropwise every time using volumetric metering pump is determined, carries out 100000 times, to every in " 0~100 time, 101~200 times, 201~300 times, 99901~100000 times " below The variation of 100 amount of liquid crystal to be dripped is evaluated according to 4 ranks below.

◎ is changed very little and (can steadily be manufactured liquid crystal display element)

Zero varies slightly but is the level that can permit

△ change and for can not allow level (due to spot generation and yields be deteriorated)

× change and be mutually on duty and (liquid crystal leakage, bubbles of vacuum occur)

Dissolubility under low temperature:

Dissolubility evaluation under low temperature is that after modulating liquid-crystal composition, 1g liquid crystal combination is weighed in the sample bottle of 2mL Object continuously applies it in temperature control formula test flume using the following temperature change recycled as 1 that recycles: " -20 DEG C (holding 1 hour) → heat up (0.1 DEG C/per minute) → 0 DEG C (being kept for 1 hour) → heating (0.1 DEG C/per minute) → 20 DEG C of (guarantors Hold 1 hour) → cooling (- 0.1 DEG C/per minute) → 0 DEG C of (being kept for 1 hour) → cooling (- 0.1 DEG C/per minute) → -20 DEG C ", lead to Cross range estimation the precipitate generated from liquid-crystal composition is carried out from, carry out it is below 4 grades evaluation.

Precipitate is not observed within ◎ 600 hours or more.

Precipitate is not observed within 0 300 hours or more.

△ observed precipitate within 150 hours.

Precipitate is observed within × 75 hours.

In addition, the record of compound is write a Chinese character in simplified form using below in embodiment.

Side chain

-n-C_nH_2n+1The straight-chain alkyl of carbon atom number n

-On-OC_nH_2n+1The straight-chain alkoxy of carbon atom number n

- V-C=CH₂Vinyl

- Vn-C=C-C_nH_2n+1The 1- alkene of carbon atom number (n+1)

Ring structure

[changing 24]

Embodiment 1

The liquid-crystal composition (embodiment 1) with following compositions is modulated, its physics value is measured.It the results are shown in following In table.

VA liquid crystal display element is made using the liquid-crystal composition of embodiment 1.The liquid crystal display element has reverse interleaved The thin film transistor (TFT) of type is as active component.The injection of liquid-crystal composition is carried out by instillation, carries out burn-in, drop impression, work Deliquescent evaluation under skill adaptability and low temperature.

In addition, what the mark on the left of content recorded is writing a Chinese character in simplified form for above compound.

[changing 25]

Embodiment 1

[table 1]

T_NI/℃	75.0
		Δn	0.106
n_o	1.486
		Δε	-3.3
ε_⊥	6.7
		η/mPa·s	16.3
γ₁/mPa·s	106
		γ₁/Δn²	9.4
Initial voltage conservation rate/%	99.8
		Voltage retention/% after 150 DEG C of 1h	99.4
Burn-in evaluation	◎
		Drop impression evaluation	◎
Technological adaptability evaluation	◎
		Dissolubility evaluation under low temperature	◎

As it can be seen that the liquid-crystal composition of embodiment 1 has as TV liquid-crystal composition 75.0 DEG C practical of liquid crystalline phase Temperature range, the absolute value with big dielectric constant anisotropy have low sticky and most suitable Δ n.Use embodiment 1 The liquid-crystal composition of record makes VA liquid crystal display element and by preceding method to burn-in, drop impression, Technological adaptability and low temperature Under dissolubility when being evaluated, show extremely excellent evaluation result.

Comparative example 1

Modulation is free of compound represented by logical formula (I), to have the liquid crystal phase temperature same with the composition of embodiment 1 The mode of the value of range, the value of same refractive anisotrop and same dielectric constant anisotropy designs as shown below Liquid-crystal composition (comparative example 1), measure its physics value.It the results are shown in following table.

Make VA liquid crystal display element similarly to Example 1 using the liquid-crystal composition of comparative example 1, will carry out burn-in, The result of deliquescent evaluation under drop impression, Technological adaptability and low temperature is shown in same table.

In addition, what the mark on the left of content recorded similarly to Example 1 is writing a Chinese character in simplified form for aforesaid compound.

[changing 26]

Comparative example 1

[table 2]

T_NI/℃	76.0
		Δn	0.106
n_o	1.485
		Δε	-3.3
ε_⊥	6.7
		η/mPa·s	17.8
γ₁/mPa·s	118
		γ₁/Δn²	10.5
Initial voltage conservation rate/%	99.0
		Voltage retention/% after 150 DEG C of 1h	98.5
Burn-in evaluation	×
		Drop impression evaluation	×
Technological adaptability evaluation	△
		Dissolubility evaluation under low temperature	△

Liquid-crystal composition (comparative example 1) without compound represented by logical formula (I) and the logical formula (I) containing 10% mass The liquid-crystal composition (embodiment 1) of represented compound is compared, although having same liquid crystal phase temperature range, same folding The value of rate anisotropic value and same dielectric constant anisotropy is penetrated, but shows as viscosities il rising.About γ 1, comparative example 1 value, that is, 118mPas shows as higher value compared with value, that is, 106mPas of embodiment 1, using as indicating liquid crystal display The 1/ Δ n of parameter, that is, γ of effective response speed in element and display²Value be compared also as poor result.Compare The initial VHR of example 1 is 99.0%, and the VHR after 150 DEG C of high temperature are placed 1 hour is 98.5%, compared with Example 1 for compared with The result of difference.When evaluating Technological adaptability, compared with Example 1 to change the level that can not allow.To low temperature Under dissolubility when being evaluated, observe precipitation earlier compared with Example 1.

Comparative example 2 and comparative example 3

Modulation is free of compound represented by logical formula (II), to have the liquid crystalline phase temperature same with the composition of embodiment 1 The following institute that the mode of the value of degree range, the value of same refractive anisotrop and same dielectric constant anisotropy designs The liquid-crystal composition (comparative example 2) that shows and without compound represented by formula (IIIb-1), to have the composition with embodiment 1 The side of the value of the value and same dielectric constant anisotropy of same liquid crystal phase temperature range, same refractive anisotrop The liquid-crystal composition (comparative example 3) as shown below of formula design, measures its physics value.It the results are shown in following table.

Using the liquid-crystal composition of comparative example 2 and comparative example 3, VA liquid crystal display element is made similarly to Example 1, it will Burn-in, drop impression, Technological adaptability and the result of the deliquescent evaluation under low temperature is carried out to be shown in same table.

[table 3]

Liquid-crystal composition (comparative example 2) without compound represented by logical formula (II) and the general formula containing 9% mass (II) liquid-crystal composition (embodiment 1) of the compound represented by is compared, although having same liquid crystal phase temperature range, same Refractive anisotrop value and same dielectric constant anisotropy value, but show as viscosities il rising.About γ 1, than Value, that is, 121mPas compared with example 1 shows as higher value compared with value, that is, 106mPas of embodiment 1, using as indicating liquid crystal The 1/ Δ n of parameter, that is, γ of effective response speed in display element and display²Value be compared also as poor result. The initial VHR of comparative example 2 is 99.1%, and the VHR after 150 DEG C of high temperature are placed 1 hour is 98.3%, compared with Example 1 For poor result.When evaluating Technological adaptability, compared with Example 1 to change the level that can not allow.Right When dissolubility under low temperature is evaluated, precipitation is observed earlier compared with Example 1.

Liquid-crystal composition (comparative example 3) without compound represented by formula (IIIb-1) and the formula containing 13% mass (IIIb-1) liquid-crystal composition (embodiment 1) of the compound represented by is compared, with same liquid crystal phase temperature range, on an equal basis Refractive anisotrop value and same dielectric constant anisotropy value, but show as viscosities il rising.About γ 1, than Value, that is, 111mPas compared with example 1 shows as higher value compared with value, that is, 106mPas of embodiment 1, using as indicating liquid crystal The 1/ Δ n of parameter, that is, γ of effective response speed in display element and display²Value be compared also to be poor as a result, But its difference is simultaneously little.Only, the initial VHR of comparative example 1 is 98.9%, and the VHR after 150 DEG C of high temperature are placed 1 hour is 97.8%, the result to be substantially deteriorated compared with Example 1.When evaluating Technological adaptability, compared with Example 1 for Change the level that can not allow.When the dissolubility under to low temperature is evaluated, precipitation is observed earlier compared with Example 1.

Embodiment 2 and embodiment 3

Modulation is to have the liquid crystal phase temperature range same with the composition of embodiment 1, same refractive anisotrop Value and same dielectric constant anisotropy value the liquid-crystal composition (embodiment 2 with following compositions that designs of mode With embodiment 3), measure its physics value.It the results are shown in following table.

Using the liquid-crystal composition of embodiment 2 and embodiment 3, VA liquid crystal display element is made similarly to Example 1, it will Burn-in, drop impression, Technological adaptability and the result of the deliquescent evaluation under low temperature is carried out to be shown in same table.

[table 4]

As it can be seen that the liquid-crystal composition of embodiment 2 has as TV liquid-crystal composition practical liquid crystal phase temperature range, Absolute value with big dielectric constant anisotropy has low sticky and most suitable Δ n.The liquid recorded using embodiment 2 Brilliant composition makes VA liquid crystal display element and by preceding method to the dissolution under burn-in, drop impression, Technological adaptability and low temperature When property is evaluated, the evaluation result that is excellent in.

As it can be seen that the liquid-crystal composition of embodiment 3 has as TV liquid-crystal composition practical liquid crystal phase temperature range, Absolute value with big dielectric constant anisotropy has low sticky and most suitable Δ n.The liquid recorded using embodiment 3 Brilliant composition makes VA liquid crystal display element and by preceding method to the dissolution under burn-in, drop impression, Technological adaptability and low temperature When property is evaluated, the evaluation result that is excellent in.

Embodiment 4 and embodiment 5

Modulation is to have the liquid crystal phase temperature range same with the composition of embodiment 1, same refractive anisotrop Value and same dielectric constant anisotropy value the liquid-crystal composition (embodiment 4 with following compositions that designs of mode With embodiment 5), measure its physics value.It the results are shown in following table.

Using the liquid-crystal composition of embodiment 4 and embodiment 5, VA liquid crystal display element is made similarly to Example 1, it will Burn-in, drop impression, Technological adaptability and the result of the deliquescent evaluation under low temperature is carried out to be shown in same table.

[table 5]

As it can be seen that the liquid-crystal composition of embodiment 4 has as TV liquid-crystal composition practical liquid crystal phase temperature range, Absolute value with big dielectric constant anisotropy has low sticky and most suitable Δ n.The liquid recorded using embodiment 4 Brilliant composition makes VA liquid crystal display element and by preceding method to the dissolution under burn-in, drop impression, Technological adaptability and low temperature When property is evaluated, the evaluation result that is excellent in.

As it can be seen that the liquid-crystal composition of embodiment 5 has as TV liquid-crystal composition practical liquid crystal phase temperature range, Absolute value with big dielectric constant anisotropy has low sticky and most suitable Δ n.The liquid recorded using embodiment 5 Brilliant composition makes VA liquid crystal display element and by preceding method to the dissolution under burn-in, drop impression, Technological adaptability and low temperature When property is evaluated, the evaluation result that is excellent in.

Embodiment 6

Modulation is with the composition with embodiment 1 same liquid crystal phase temperature range, same refractive anisotrop The liquid-crystal composition (embodiment 6) with following compositions that the mode of value and the value of same dielectric constant anisotropy designs, Measure its physics value.It the results are shown in following table.

Using the liquid-crystal composition of embodiment 6, make VA liquid crystal display element similarly to Example 1, will carry out burn-in, The result of deliquescent evaluation under drop impression, Technological adaptability and low temperature is shown in same table.

[table 6]

Embodiment 6

3-Cy-Cy-V1	10.0%
		3-Ph-Ph5-O2	11.0%
3-Cy-Cy-Ph5-O2	13.0%
		3-Cy-Cy-2	15.0%
3-Cy-Cy-4	6.0%
		3-Cy-Cy-5	8.0%
1-Ph-Ph-2V1	3.5%
		3-Cy-Ph-Ph-2	5.0%
3-Cy-Ph5-O2	10.5%
		2-Cy-Ph-Ph5-O2	6.0%
3-Cy-Ph-Ph5-O2	12.0%
		T_NI/℃	75.1
Δn	0.106
		n_o	1.484
Δε	-3.3
		ε_⊥	6.7
η/mPa·s	17.1
		γ₁/mPa·s	113
γ₁/Δn²	10.1
		Initial voltage conservation rate/%	99.8
Voltage retention/% after 150 DEG C of 1h	99.4
		Burn-in evaluation	○
Drop impression evaluation	○
		Technological adaptability evaluation	◎
Dissolubility evaluation under low temperature	○

As it can be seen that the liquid-crystal composition of embodiment 6 has as TV liquid-crystal composition practical liquid crystal phase temperature range, Absolute value with big dielectric constant anisotropy has low sticky and most suitable Δ n.The liquid recorded using embodiment 6 Brilliant composition makes VA liquid crystal display element and by preceding method to the dissolution under burn-in, drop impression, Technological adaptability and low temperature When property is evaluated, the evaluation result that is excellent in.

Embodiment 7

Modulation is to have the liquid crystal phase temperature range same with the composition of embodiment 1 and same dielectric constant respectively to different Property value, with higher refractive index be that its gap is narrower in a liquid crystal display, designs corresponding to the mode of high-speed response Liquid-crystal composition (embodiment 7) with following compositions, measures its physics value.It the results are shown in following table.

Using the liquid-crystal composition of embodiment 7, make VA liquid crystal display element similarly to Example 1, will carry out burn-in, The result of deliquescent evaluation under drop impression, Technological adaptability and low temperature is shown in same table.

[table 7]

Embodiment 7

3-Cy-Cy-V	10.0%
		3-Ph-Ph5-O2	9.5%
3-Cy-Cy-Ph5-O2	13.0%
		3-Cy-Cy-2	18.0%
3-Cy-Cy-4	7.0%
		1-Ph-Ph-2V1	1.5%
3-Cy-Ph-Ph-2	8.0%
		3-Cy-Ph5-O2	11.0%
2-Cy-Ph-Ph5-O2	6.0%
		3-Cy-Ph-Ph5-O2	11.0%
3-Ph-Ph5-Ph-2	5.0%
		T_NI/℃	75.5
Δn	0.112
		n_o	1.487
Δε	-3.3
		ε_⊥	6.7
η/mPa·s	16.7
		γ₁/mPa·s	112
γ₁/Δn²	8.9
		Initial voltage conservation rate/%	99.8
Voltage retention/% after 150 DEG C of 1h	99.3
		Burn-in evaluation	◎
Drop impression evaluation	◎
		Technological adaptability evaluation	◎
Dissolubility evaluation under low temperature	◎

As it can be seen that the liquid-crystal composition of embodiment 7 has as TV liquid-crystal composition practical liquid crystal phase temperature range, Absolute value with big dielectric constant anisotropy has low sticky and most suitable Δ n.The liquid recorded using embodiment 7 Brilliant composition makes VA liquid crystal display element and by preceding method to the dissolution under burn-in, drop impression, Technological adaptability and low temperature When property is evaluated, the evaluation result that is excellent in.

Comparative example 4 and comparative example 5

Modulation is free of compound represented by logical formula (I), to have same liquid crystal phase temperature with the composition of embodiment 7 The mode of the value of range, the value of same refractive anisotrop and same dielectric constant anisotropy designs as shown below Liquid-crystal composition (comparative example 4) and without compound represented by logical formula (II), it is same to have with the composition of embodiment 7 Liquid crystal phase temperature range, the mode of the value of the value of same refractive anisotrop and same dielectric constant anisotropy sets The liquid-crystal composition (comparative example 5) as shown below of meter, measures its physics value.It the results are shown in following table.

Using the liquid-crystal composition of comparative example 4 and comparative example 5, VA liquid crystal display element is made similarly to Example 7, it will Burn-in, drop impression, Technological adaptability and the result of the deliquescent evaluation under low temperature is carried out to be shown in same table.

[table 8]

Liquid-crystal composition (comparative example 4) without compound represented by logical formula (I) and the logical formula (I) containing 10% mass The liquid-crystal composition (embodiment 7) of represented compound is compared, although having same liquid crystal phase temperature range, same folding The value of rate anisotropic value and same dielectric constant anisotropy is penetrated, but shows as viscosities il rising.About γ 1, comparative example 4 value, that is, 124mPas shows as higher value compared with value, that is, 112mPas of embodiment 7, using as indicating liquid crystal display The 1/ Δ n of parameter, that is, γ of effective response speed in element and display²Value be compared also as poor result.Compare The initial VHR of example 4 is 98.7%, and the VHR after 150 DEG C of high temperature are placed 1 hour is 98.0%, compared with Example 7 for compared with The result of difference.When evaluating Technological adaptability, compared with Example 7 to change the level that can not allow.To low temperature Under dissolubility when being evaluated, observe precipitation earlier compared with Example 7.

Liquid-crystal composition (comparative example 5) without compound represented by logical formula (II) and the general formula containing 9.5% mass (II) liquid-crystal composition (embodiment 7) of the compound represented by is compared, although having same liquid crystal phase temperature range, same Refractive anisotrop value and same dielectric constant anisotropy value, but show as viscosities il rising.About γ 1, than Value, that is, 129mPas compared with example 4 shows as higher value compared with value, that is, 112mPas of embodiment 7, using as indicating liquid crystal The 1/ Δ n of parameter, that is, γ of effective response speed in display element and display²Value be compared also as poor result. The initial VHR of comparative example 5 is 98.6%, and the VHR after 150 DEG C of high temperature are placed 1 hour is 97.7%, compared with Example 7 For poor result.When evaluating Technological adaptability, compared with Example 7 to change the level that can not allow.Right When dissolubility under low temperature is evaluated, precipitation is observed earlier compared with Example 7.

Comparative example 6

Modulation is free of compound represented by formula (IIIb-1), to have same liquid crystalline phase with the composition of embodiment 7 The mode of the value of temperature range, the value of same refractive anisotrop and same dielectric constant anisotropy designs following Shown in liquid-crystal composition (comparative example 6), measure its physics value.It the results are shown in following table.

Using the liquid-crystal composition of comparative example 6, make VA liquid crystal display element similarly to Example 7, will carry out burn-in, The result of deliquescent evaluation under drop impression, Technological adaptability and low temperature is shown in same table.

[table 9]

Comparative example 6

3-Cy-Cy-V	10.0%
		3-Ph-Ph5-O2	9.5%
3-Cy-Cy-2	18.0%
		3-Cy-Cy-4	6.5%
1-Ph-Ph-2V1	2.0%
		3-Cy-Ph-Ph-2	8.0%
3-Cy-Ph5-O2	12.0%
		4-Cy-Cy-Ph5-O2	12.0%
2-Cy-Ph-Ph5-O2	6.0%
		3-Cy-Ph-Ph5-O2	11.0%
3-Ph-Ph5-Ph-2	5.0%
		T_NI/℃	75.5
Δn	0.112
		n_o	1.488
Δε	-3.3
		ε_⊥	6.9
η/mPa·s	17.2
		γ₁/mPa·s	115
γ₁/Δn²	9.2
		Initial voltage conservation rate/%	98.7
Voltage retention/% after 150 DEG C of 1h	97.5
		Burn-in evaluation	×
Drop impression evaluation	△
		Technological adaptability evaluation	△
Dissolubility evaluation under low temperature	×

Liquid-crystal composition (comparative example 6) without compound represented by formula (IIIb-1) and the formula containing 13% mass (IIIb-1) liquid-crystal composition (embodiment 7) of the compound represented by is compared, although have same liquid crystal phase temperature range, The value of the value of same refractive anisotrop and same dielectric constant anisotropy, but show as viscosities il rising.About γ 1, value, that is, 115mPas of comparative example 4 shows as higher value compared with value, that is, 112mPas of embodiment 7, using as indicating The 1/ Δ n of parameter, that is, γ of effective response speed in liquid crystal display element and display²Value be compared also to be poor As a result, but its difference and less.Only, the initial VHR of comparative example 6 is 98.7%, and the VHR after 150 DEG C of high temperature are placed 1 hour It is 97.5%, the result to be substantially deteriorated compared with Example 7.When evaluating Technological adaptability, compared with Example 7 To change the level that can not allow.When the dissolubility under to low temperature is evaluated, analysis is observed earlier compared with Example 7 Out.

Embodiment 8 and embodiment 9

Modulation is to have same liquid crystal phase temperature range, same refractive anisotrop with the composition of embodiment 7 Value and same dielectric constant anisotropy value the liquid-crystal composition (embodiment 8 with following compositions that designs of mode With embodiment 9), measure its physics value.It the results are shown in following table.

Using the liquid-crystal composition of embodiment 8 and embodiment 9, VA liquid crystal display element is made similarly to Example 7, it will Burn-in, drop impression, Technological adaptability and the result of the deliquescent evaluation under low temperature is carried out to be shown in same table.

[table 10]

As it can be seen that the liquid-crystal composition of embodiment 8 has as TV liquid-crystal composition practical liquid crystal phase temperature range, Absolute value with big dielectric constant anisotropy has low sticky and most suitable Δ n.The liquid recorded using embodiment 8 Brilliant composition makes VA liquid crystal display element and by preceding method to the dissolution under burn-in, drop impression, Technological adaptability and low temperature When property is evaluated, the evaluation result that is excellent in.

As it can be seen that the liquid-crystal composition of embodiment 9 has as TV liquid-crystal composition practical liquid crystal phase temperature range, Absolute value with big dielectric constant anisotropy has low sticky and most suitable Δ n.The liquid recorded using embodiment 9 Brilliant composition makes VA liquid crystal display element and by preceding method to the dissolution under burn-in, drop impression, Technological adaptability and low temperature When property is evaluated, the evaluation result that is excellent in.

Embodiment 10 and embodiment 11

Modulation is to have same liquid crystal phase temperature range, same refractive anisotrop with the composition of embodiment 7 Value and same dielectric constant anisotropy value the liquid-crystal composition (embodiment 10 with following compositions that designs of mode With embodiment 11), measure its physics value.It the results are shown in following table.

Using the liquid-crystal composition of embodiment 10 and embodiment 11, VA liquid crystal display element is made similarly to Example 7, The result of the deliquescent evaluation carried out under burn-in, drop impression, Technological adaptability and low temperature is shown in same table.

[table 11]

As it can be seen that the liquid-crystal composition of embodiment 10 has as TV liquid-crystal composition practical liquid crystal phase temperature model It encloses, the absolute value with big dielectric constant anisotropy has low sticky and most suitable Δ n.It is recorded using embodiment 10 Liquid-crystal composition, production VA liquid crystal display element simultaneously by preceding method under burn-in, drop impression, Technological adaptability and low temperature When dissolubility is evaluated, the evaluation result that is excellent in.

As it can be seen that the liquid-crystal composition of embodiment 11 has as TV liquid-crystal composition practical liquid crystal phase temperature model It encloses, the absolute value with big dielectric constant anisotropy has low sticky and most suitable Δ n.It is recorded using embodiment 11 Liquid-crystal composition, production VA liquid crystal display element simultaneously by preceding method under burn-in, drop impression, Technological adaptability and low temperature When dissolubility is evaluated, the evaluation result that is excellent in.

Embodiment 12

Modulation is to have same liquid crystal phase temperature range, same refractive anisotrop with the composition of embodiment 7 Value and same dielectric constant anisotropy value the liquid-crystal composition (embodiment with following compositions that designs of mode 12) its physics value, is measured.It the results are shown in following table.

Using the liquid-crystal composition of embodiment 12, VA liquid crystal display element is made similarly to Example 7, will be burnt The result of deliquescent evaluation under screen, drop impression, Technological adaptability and low temperature is shown in same table.

[table 12]

Embodiment 12

3-Cy-Cy-V1	10.0%
		3-Ph-Ph5-O2	11.0%
3-Cy-Cy-Ph5-O2	13.0%
		3-Cy-Cy-2	15.0%
3-Cy-Cy-4	5.0%
		3-Cy-Cy-5	7.0%
1-Ph-Ph-2V1	2.0%
		3-Cy-Ph-Ph-2	5.0%
3-Cy-Ph5-O2	11.0%
		2-Cy-Ph-Ph5-O2	6.0%
3-Cy-Ph-Ph5-O2	10.0%
		3-Ph-Ph5-Ph-2	5.0%
T_NI/℃	75.9
		Δn	0.112
n_o	1.486
		Δε	-3.4
ε_⊥	6.8
		η/mPa·s	17.9
γ₁/mPa·s	121
		γ₁/Δn²	9.6
Initial voltage conservation rate/%	99.9
		Voltage retention/% after 150 DEG C of 1h	99.3
Burn-in evaluation	○
		Drop impression evaluation	◎
Technological adaptability evaluation	○
		Dissolubility evaluation under low temperature	○

As it can be seen that the liquid-crystal composition of embodiment 12 has as TV liquid-crystal composition practical liquid crystal phase temperature model It encloses, the absolute value with big dielectric constant anisotropy has low sticky and most suitable Δ n.It is recorded using embodiment 12 Liquid-crystal composition, production VA liquid crystal display element simultaneously by preceding method under burn-in, drop impression, Technological adaptability and low temperature When dissolubility is evaluated, the evaluation result that is excellent in.

Symbol description

1 second polarizer

2 the second substrates

3 tft layers, the electrode layer comprising thin film transistor (TFT)

4 alignment films

5 liquid crystal layers

6 pixel electrodes (public electrode)

7 colour filters

8 first substrates

9 first polarizers

10 liquid crystal display elements

11 gate electrodes

12 anodic oxidation coatings

13 gate insulation layers

14 transparent electrodes (layer)

15 drain electrodes

16 ohmic contact layers

17 semiconductor layers

18 protective films

19a, 19b source electrode

21 pixel electrodes

22 storage capacitances

23 drain electrodes

The wiring of 24 data

25 grid wirings

26 source electrodes

27 gate electrodes

101 protective layers

Claims

1. a kind of liquid-crystal composition that dielectric constant anisotropy is negative, which is characterized in that

The one kind or two or more compound selected from compound group represented by logical formula (I) containing 2~25 mass %, contains There is the one kind or two or more compound of 3~25 mass % selected from compound group represented by logical formula (II), containing 5~ Compound represented by the formula (IIIb-1) of 25 mass %, compound represented by the formula (VI-a3) containing 15~19 mass %, The one kind or two or more compound selected in compound group represented by slave general formula (IIIa) containing 3~30 mass %, contains There is the compound selected from compound group represented by general formula (V-5), containing represented by formula (VI-c5)~(VI-c8) 1 kind or more of the compound selected in compound group,

In formula, R¹¹Indicate the alkyl of carbon atom number 1~3, R²²Indicate the alkyl or hydrogen atom of carbon atom number 1~3,

In formula, R¹And R²Each independently represent the alkyl of carbon atom number 1~8, the alkenyl of carbon atom number 2~8, carbon atom number 1~ 8 alkoxy or the alkenyloxy group of carbon atom number 2~8,

R in formula^3aAnd R^4aEach independently represent the alkyl of carbon atom number 1~8, the alkenyl of carbon atom number 2~8, carbon atom number 1~ 8 alkoxy or the alkenyloxy group of carbon atom number 2~8,

R in formula⁷And R⁸Each independently represent the alkyl of carbon atom number 1~8, the alkenyl of carbon atom number 2~8, carbon atom number 1~8 Alkoxy or carbon atom number 2~8 alkenyloxy group, 1 or more hydrogen in the alkyl, alkenyl, alkoxy and/or alkenyloxy group is former Son can be replaced by fluorine atoms, as long as the methylene oxygen atom in the alkyl, alkenyl, alkoxy and/or alkenyloxy group discontinuously combines It can be replaced by oxygen atom, as long as carbonyl, which discontinuously combines, to be replaced by carbonyl,

2. liquid-crystal composition according to claim 1, wherein further containing one kind or two or more from logical formula (III) The compound of represented compound group selection,

R in formula³And R⁴Each independently represent the alkyl of carbon atom number 1~8, the alkenyl of carbon atom number 2~8, carbon atom number 1~8 Alkoxy or carbon atom number 2~8 alkenyloxy group, n indicate 0 or 1, R³For the alkyl and R of carbon atom number 3⁴For carbon atom number 2 Alkoxy and n are indicated except 1 compound.

3. liquid-crystal composition according to claim 1, wherein further containing one kind or two or more from logical formula (IV) institute The compound of the compound group selection of expression,

R in formula⁵And R⁶Each independently represent the alkyl of carbon atom number 1~8, the alkenyl of carbon atom number 2~8, carbon atom number 1~8 Alkoxy or carbon atom number 2~8 alkenyloxy group.

4. liquid-crystal composition according to claim 1, wherein represented from following formula (I-1), formula (I-2) and formula (I-3) Compound group selection it is one kind or two or more as compound represented by logical formula (I),

5. liquid-crystal composition according to claim 1, wherein contain compound represented by formula (II-1) as general formula (II) compound represented by,

6. liquid-crystal composition according to claim 1, wherein further contain reactive monomer.

7. a kind of liquid crystal display element, it uses liquid-crystal compositions described in claim 1.

8. a kind of liquid crystal display element, it uses liquid-crystal compositions as claimed in claim 6.

9. a kind of liquid crystal display, it uses the liquid crystal display elements described in claim 7 or 8.