CN105733609A

CN105733609A - Liquid crystal composition and liquid crystal display element using same

Info

Publication number: CN105733609A
Application number: CN201610086243.0A
Authority: CN
Inventors: 岩下芳典; 根岸真
Original assignee: Dainippon Ink and Chemicals Co Ltd
Current assignee: DIC Corp
Priority date: 2013-03-26
Filing date: 2013-03-26
Publication date: 2016-07-06

Abstract

The invention aims at providing a liquid crystal composition and a liquid crystal display element using the same, wherein the liquid crystal composition is suitable for the liquid crystal display element which cannot enable the dielectric constant anisotropy, the viscosity, the nematic-phase upper limit temperature, the low-temperature nematic-phase stability and gamma 1 which serve as various characteristics of the liquid crystal display element and the screen burning characteristic of the display element to become poor, cannot easily generate a dripping trace during manufacturing and achieves the stable liquid crystal material ejecting quantity in an ODF process.The invention further provides the liquid crystal composition which contains one or more than two compounds shown in a formula (I) (please see the formula in the description), contains one or more than two compounds shown in a formula (II) (please see the formula in the description) and has the negative dielectric constant anisotropy and provides the liquid crystal display element using the liquid crystal composition which contains one or more than two compounds shown in the formula (I) (please see the formula in the description), contains one or more than two compounds shown in the formula (II) (please see the formula in the description) and has the negative dielectric constant anisotropy.

Description

Liquid-crystal composition and use its liquid crystal display cells

The application is original application, the applying date is on March 26th, 2013, and application number is 201380003438.9, and denomination of invention is the divisional application of the Chinese patent application of " liquid-crystal composition and use its liquid crystal display cells ".

Technical field

The present application relates to a kind of liquid-crystal composition useful as the member of formation of liquid crystal indicator etc. and liquid crystal display cells.

Background technology

Liquid crystal display cells, from clock and watch, computer, develops into and uses in meter device, automobile panel, word processor, electronic notebook, printer, computer, TV, clock and watch, advertising display panel etc..As liquid crystal display mode, its representational liquid crystal display mode has TN (twisted-nematic) type, STN (super twisted nematic) type, employs VA (vertical orientated) type of TFT (thin film transistor (TFT)), IPS (plane conversion) type etc..The liquid-crystal composition used in these liquid crystal display cells requires moisture, the empty extraneous factor such as air and heat, light stable, it addition, show liquid crystalline phase in temperature range wide as far as possible centered by room temperature, low viscosity and driving voltage is low.Further, in order to for each display element arrange the suitableeest dielectric constant anisotropy (Δ ε) or and make refractive anisotrop (Δ n) etc. for just when, liquid-crystal composition is made up of to tens of kinds of compounds several.

Using Δ ε in vertical orientated escope is negative liquid-crystal composition, is widely used in liquid crystal TV etc..On the other hand, in all type of drive, require low voltage drive, high-speed responsive, wide operating temperature range.Namely, it is desirable to Δ ε is just and absolute value is big, viscosity (η) nematic phase little, high-isotropic liquid phase transition temperature (T_ni).Further, since the setting of Δ n and the long-pending i.e. Δ n × d of cell gap (d), it is therefore desirable to according to cell gap, the Δ n of liquid-crystal composition is regulated to suitable scope.In addition, when liquid crystal display cells being applied to TV etc. owing to paying attention to high-speed responsive, therefore it is required that γ₁Little liquid-crystal composition.

In the past, in order to constitute γ₁Little liquid-crystal composition, it is common to use there is the compound (with reference to patent documentation 1) of dialkyl group bis cyclohexane skeleton.But, although bis cyclohexane based compound is for γ₁Reducing effect high, but this tendency of compound that generally vapour pressure is high and long alkyl chains is short is especially notable.It addition, also have T_niAlso low tendency, therefore practical situation is: alkyl bicyclic hexane based compound many uses side chain lengths adds up to the compound of carbon number more than 7, and the compound short about side chain lengths is not studied fully.

On the other hand, the purposes of liquid crystal display cells expands, thus big change also occur in its using method, manufacture method, in order to tackle these changes, it is desirable to by the characteristic optimization beyond basic physical properties value known in the past.That is, using the liquid crystal display cells of liquid-crystal composition to widely use VA (vertical orientated) type, IPS (plane conversion) type etc., using thus being also that the display element of the ultra-large type size of more than 50 types is practical by its size.Maximization along with substrate size, liquid-crystal composition to the method for implanting of substrate also from before vacuum impregnation develop into injection (ODF:OneDropFill) method of dripping, this injection method that drips has become the main flow (with reference to patent documentation 2) of method for implanting, and when being dropped on substrate by liquid-crystal composition, drop impression causes the problem that display quality reduces substantially to change.Further, the tilt angle of the liquid crystal material in liquid crystal display cells produces and for the purpose of high-speed responsive, developing PS liquid crystal display cells (polymerstabilized, polymer stabilising), PSA liquid crystal display cells (polymersustainedalignment, polymer maintain orientation) (with reference to patent documentation 3), this problem has become bigger problem.That is, these display elements have the feature that interpolation monomer in liquid-crystal composition, make the monomer cure in compositions.For active matrix liquid-crystal composition, owing to maintaining the necessity of high voltage holding ratio, therefore specifying the compound that can use, the compound in compound with ester bond is limited use.The monomer used in PSA liquid crystal display cells is mainly acrylic ester, is generally in compound to have the compound of ester bond, and this compound is generally not used as active matrix liquid-crystal compounds (with reference to patent documentation 3).Such foreign body can cause the generation of drop impression, thus the yield rate because showing bad caused liquid crystal display cells has been deteriorated into problem.It addition, when adding the additive such as antioxidant, light absorber in liquid-crystal composition also, yield rate is deteriorated becomes problem.

Here, drop impression is defined as: when showing black, and the vestige of the liquid-crystal composition that drips appears the phenomenon of white.

In order to suppress drop impression, disclose following method: in liquid crystal layer, formed polymeric layer by the polymerization of the polymerizable compound that is blended in liquid-crystal composition, thus suppressing the drop impression (patent documentation 4) produced because of the relation with tropism control film.But, in the method, the problem that there is the display burn-in caused by the polymerizable compound being added in liquid crystal, its effect of suppression for drop impression is also insufficient, it is necessary to develops a kind of fundamental characteristics being maintained as liquid crystal display cells and is difficult to produce the liquid crystal display cells of burn-in, drop impression.

Prior art literature

Patent documentation 1: Japanese Unexamined Patent Application Publication 2008-505235 publication

Patent documentation 2: Japanese Unexamined Patent Publication 6-235925 publication

Patent documentation 3: Japanese Unexamined Patent Publication 2002-357830 publication

Patent documentation 4: Japanese Unexamined Patent Publication 2006-58755 publication

Summary of the invention

The problem that invention to solve

The problem that the invention solves the problems that is in that provide a kind of liquid-crystal composition and use its liquid crystal display cells, and described liquid-crystal composition is suitable in the nematic phase stability that will not make under dielectric constant anisotropy, viscosity, nematic phase ceiling temperature, low temperature, γ₁It is deteriorated Deng as the various characteristics of liquid crystal display cells and the burn-in characteristic of display element, it is difficult to produce drop impression when manufacturing, it is achieved the liquid crystal display cells of liquid crystal material spray volume stable in ODF operation.

The method of solution problem

The present inventor etc. are in order to solve above-mentioned problem, have studied for making liquid crystal display cells by legal system of dripping and the composition of the various liquid-crystal compositions of Yan Shi, and find: by using specific liquid-crystal compounds with specific mixed proportion, the drop impression in liquid crystal display cells can be suppressed to produce, this completes the present application.

The present application provides the one dielectric constant anisotropy containing the compound represented by formula (I), formula (II) to be negative liquid-crystal composition and the liquid crystal display cells using this liquid-crystal composition.

It is negative liquid-crystal composition and the liquid crystal display cells using this liquid-crystal composition that the present application provides one to contain the dielectric constant anisotropy selecting a kind or compound of more than two kinds from the compound represented by formula (I) and formula (II) respectively.

[changing 1]

(in formula, R¹For the alkoxyl of the alkyl of carbon number 1 to 8 or carbon number 2 to 8, R²For the thiazolinyl of carbon number 2 to 8, R³And R⁴It is each independently the thiazolinyl of carbon number 2 to 8.)

The effect of invention

The feature that the liquid crystal display cells of the present invention is few owing to having high-speed responsive generation excellent, burn-in, and there is the feature that its generation manufacturing the drop impression caused is few, therefore useful in the display element such as liquid crystal TV, display.

Accompanying drawing explanation

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

Fig. 2 is the plane graph amplified in the region surrounded by II line of the electrode layer 3 comprising thin film transistor (TFT) formed in this Fig. 1 on substrate.

Fig. 3 is the profile cut off by the liquid crystal display cells shown in Fig. 1 on III-III line direction in fig. 2.

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

Detailed description of the invention

As it has been described above, the technique that drop impression produces it be not immediately clear, but, and the probability height that the impurity in liquid-crystal compounds is relevant to the interaction of alignment films, chromatography phenomenon etc..Impurity in liquid-crystal compounds is deeply by the impact of the manufacturing process of compound, even if only the carbon number of side chain is different, the manufacture method of compound is also not necessarily the same.That is, liquid-crystal compounds is owing to manufacturing by accurate manufacturing process, and therefore its cost is high in synthetic, is strongly required to improve manufacture efficiency.Therefore, in order to use somewhat cheap raw material, even if the method that the carbon number only one difference of side chain is also undertaken manufacturing by the raw material of entirely different kind there is also the situation that efficiency is high.Therefore, the manufacturing process of liquid crystal substance is difference for every kind of substance sometimes, even if technique is identical, the different situation of raw material is also great majority, and its result is: most be mixed into different impurity in each substance.But, for drop impression, even if there being the probability that the impurity of denier also produces, it is only therefore limited by the refining generation suppressing drop impression of substance.

On the other hand, about the manufacture method of conventional liquid crystal substance, have, after manufacturing process is established, every kind of substance is defined as certain tendency.Even if analytical technology be developed present, to fully understand that being mixed into which type of impurity is also not easy, but require to be combined the design of thing under the premise being mixed into the impurity that every kind of substance is determined.The impurity of liquid crystal substance and the relation of drop impression have been studied by present inventors etc., and result is understood by rule of thumb: even if comprising the impurity being also difficult to produce drop impression in the composition and easily producing the impurity of drop impression.Therefore, in order to suppress the generation of drop impression, use specific compound critically important with specific mixed proportion, particularly understand the existence being difficult to produce the compositions of drop impression.Preferred implementation described below is to find from above-mentioned viewpoint.

In the liquid-crystal composition of the present application, total containing ratio of the compound group represented by formula (I), it is preferably 15 mass % as lower limit, it is more preferably 20 mass %, more preferably 25 mass %, it is preferably 45 mass % as higher limit, it is more preferably 40 mass %, more preferably 37 mass %, more specifically, when paying attention to answer speed, preferably comprise 20～45 mass %, more preferably 25～45 mass % are contained, when more paying attention to driving voltage, preferably comprise 15～37 mass %, more preferably 15～25 mass % are contained.

Compound represented by formula (I) selects preferably from the compound group represented by the formula (I-1) recorded below～formula (I-5), more preferably select from the compound group represented by formula (I-1), formula (I-3) and formula (I-5), it is preferred that select from the compound group represented by formula (I-1) and formula (I-5), it is particularly preferred to the compound represented by selecting type (I-1).

[changing 2]

In the liquid-crystal composition of the present application, total containing ratio of the compound group represented by formula (II), it is preferably 3 mass % as lower limit, it is more preferably 4 mass %, more preferably 5 mass %, it is preferably 25 mass %, more preferably 20 mass %, more preferably 15 mass % as higher limit.

Compound represented by formula (II) selects preferably from the compound group represented by the formula (II-1) recorded below～formula (II-3), more preferably the compound represented by formula (II-1) and formula (II-2).

[changing 3]

The liquid-crystal composition of the present application can contain the compound selected from the compound group represented by formula (III) shown below further.

[changing 4]

(in formula, R⁵And R⁶Represent the alkene oxygen base of the alkyl of carbon number 1～8, the thiazolinyl of carbon number 2～8, the alkoxyl of carbon number 1～8 or carbon number 2～8, A independently of one another¹Representing Isosorbide-5-Nitrae-cyclohexylidene, Isosorbide-5-Nitrae-phenylene or Pentamethylene oxide .-2,5-bis-base, at A¹When representing Isosorbide-5-Nitrae-phenylene, the hydrogen atom of more than 1 in this Isosorbide-5-Nitrae-phenylene can be replaced by fluorine atoms.)

In the compound represented by formula (III), R⁵And R⁶Represent the alkene oxygen base of the alkyl of carbon number 1～8, the thiazolinyl of carbon number 2～8, the alkoxyl of carbon number 1～8 or carbon number 2～8, R independently of one another⁵It is preferably the alkyl of carbon number 1～8 or the thiazolinyl of carbon number 2～8, more preferably the alkyl of carbon number 1～8, the more preferably alkyl of carbon number 2～5, R⁶It is preferably the alkoxyl of the alkyl of carbon number 1～8, carbon number 1～8, more preferably the alkoxyl of carbon number 1～8, the more preferably alkoxyl of carbon number 2～5.

In the compound represented by formula (III), A¹Represent Isosorbide-5-Nitrae-cyclohexylidene, Isosorbide-5-Nitrae-phenylene or Pentamethylene oxide .-2,5-bis-base, but preferably represent Isosorbide-5-Nitrae-cyclohexylidene or Isosorbide-5-Nitrae-phenylene, at A¹When representing Isosorbide-5-Nitrae-phenylene, it is preferable that the hydrogen atom of more than 2 is replaced by fluorine atoms, and more preferably 1 hydrogen atom is replaced by fluorine atoms, more preferably without replacing.

When the compound represented by liquid-crystal composition selection formula (III) of the present application, its containing ratio is preferably 5～30 mass %, more preferably 7～25 mass %, more preferably 10～20 mass %.

In the compound represented by formula (III), at A¹When representing Isosorbide-5-Nitrae-cyclohexylidene, the formula (IIIa) recorded below represent,

[changing 5]

(R in formula^5aAnd R^6aRepresent respectively and the R in formula (III)⁵And R⁶The identical meaning)

In this compound group, compound represented by preferred formula (IIIa-1)～formula (IIIa-8), more preferably the compound represented by formula (IIIa-1)～formula (IIIa-4), it is preferred that the compound represented by formula (IIIa-1) and formula (IIIa-4).

[changing 6]

Compound represented by formula (IIIa) preferably comprises 1～30 mass %, more preferably contains 1～25 mass %, it is preferred that containing 1～20 mass %.

When using the compound represented by 4 kinds of formula above (IIIa), preferred compositions uses formula (IIIa-1) to the compound represented by formula (IIIa-4), formula (IIIa-1) is preferably more than the 50 mass % in the compound represented by formula (IIIa) to the content of the compound represented by formula (IIIa-4), it is more preferably more than 70 mass %, more preferably more than 80 mass %, it is particularly preferred to be more than 90 mass %.

When using the compound represented by 3 kinds of formulas (IIIa), preferred compositions uses the compound represented by formula (IIIa-1), formula (IIIa-2) and formula (IIIa-4), the content of the compound represented by formula (IIIa-1), formula (IIIa-2) and formula (IIIa-4) is preferably more than the 50 mass % in the compound represented by formula (IIIa), it is more preferably more than 70 mass %, more preferably more than 80 mass %, it is particularly preferred to be more than 90 mass %.

When using the compound represented by 2 kinds of formulas (IIIa), preferred compositions uses the compound represented by formula (IIIa-1) and formula (IIIa-4), the content of the compound represented by formula (IIIa-1) and formula (IIIa-4) is preferably more than the 50 mass % in the compound represented by formula (IIIa), it is more preferably more than 70 mass %, more preferably more than 80 mass %, it is particularly preferred to be more than 90 mass %.

In the compound represented by formula (III), at A¹When representing Isosorbide-5-Nitrae-phenylene, the formula (IIIb) recorded below represent,

[changing 7]

(R in formula^5bAnd R^6bRepresent respectively and the R in formula (III)⁵And R⁶The identical meaning)

In this compound group, select preferably from the compound group represented by formula (IIIb-1)～formula (IIIb-8), more preferably the compound represented by formula (IIIb-1)～formula (IIIb-4), it is preferred that the compound represented by formula (IIIb-1) and formula (IIIb-3), it is particularly preferred to the compound represented by formula (IIIb-1).

[changing 8]

Compound represented by formula (IIIb) preferably comprises 3～30 mass %, more preferably contains 5～15 mass %, it is preferred that containing 7～12 mass %.

When using the compound represented by 4 kinds of formula above (IIIb), preferred compositions uses the compound represented by formula (IIIb-1)～formula (IIIb-4), the content of the compound represented by formula (IIIb-1)～formula (IIIb-4) is preferably more than the 50 mass % in the compound represented by formula (IIIb), it is more preferably more than 70 mass %, more preferably more than 80 mass %, it is particularly preferred to be more than 90 mass %.

When using the compound represented by 3 kinds of formulas (IIIb), preferred compositions uses the compound represented by formula (IIIb-1)～formula (IIIb-3), the content of the compound represented by formula (IIIb-1)～formula (IIIb-3) is preferably more than the 50 mass % in the compound represented by formula (IIIb), it is more preferably more than 70 mass %, more preferably more than 80 mass %, it is particularly preferred to be more than 90 mass %.

When using the compound represented by 2 kinds of formulas (IIIb), preferred compositions uses the compound represented by formula (IIIb-1) and formula (IIIb-3), the content of the compound represented by formula (IIIb-1) and formula (IIIb-3) is preferably more than the 50 mass % in the compound represented by formula (IIIb), it is more preferably more than 70 mass %, more preferably more than 80 mass %, it is particularly preferred to be more than 90 mass %.

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

[changing 9]

(R in formula⁷And R⁸Represent the alkene oxygen base of the alkyl of carbon number 1～8, the thiazolinyl of carbon number 2～8, the alkoxyl of carbon number 1～8 or carbon number 2～8, A independently of one another²Representing Isosorbide-5-Nitrae-cyclohexylidene, Isosorbide-5-Nitrae-phenylene or Pentamethylene oxide .-2,5-bis-base, at A²When representing Isosorbide-5-Nitrae-phenylene, the hydrogen atom of more than 1 in this Isosorbide-5-Nitrae-phenylene can be replaced by fluorine atoms.)

In the compound represented by formula (IV), R⁷And R⁸Represent the alkene oxygen base of the alkyl of carbon number 1～8, the thiazolinyl of carbon number 2～8, the alkoxyl of carbon number 1～8 or carbon number 2～8, R independently of one another⁷It is preferably the alkyl of carbon number 1～8 or the thiazolinyl of carbon number 2～8, more preferably the alkyl of carbon number 1～8, the more preferably alkyl of carbon number 2～5, it is particularly preferred to for the alkyl of carbon number 2 or 3, R⁸It is preferably the alkoxyl of the alkyl of carbon number 1～8, carbon number 1～8, it is more preferably the alkoxyl of carbon number 1～8, the more preferably alkoxyl of carbon number 2～5, it is particularly preferred to for the alkoxyl of carbon number 2 or 3, it is most preferred that for the alkoxyl of carbon number 2.

In the compound represented by formula (IV), A²Represent Isosorbide-5-Nitrae-cyclohexylidene, Isosorbide-5-Nitrae-phenylene or Pentamethylene oxide .-2,5-bis-base, it is preferable that represent Isosorbide-5-Nitrae-cyclohexylidene or Isosorbide-5-Nitrae-phenylene, at A²When representing Isosorbide-5-Nitrae-phenylene, it is preferable that the hydrogen atom of more than 2 is replaced by fluorine atoms, and more preferably 1 hydrogen atom is replaced by fluorine atoms, more preferably without replacing.

In the compound represented by formula (IV), at A²When representing Isosorbide-5-Nitrae-cyclohexylidene, it is possible to contain the compound selected in the compound group represented by formula (IVa) recorded from below further.

[changing 10]

(R in formula^7aAnd R^8aRepresent respectively and the R in formula (IV)⁷And R⁸The identical meaning.)

In the liquid-crystal composition of the present application, total containing ratio of the compound group represented by formula (IVa), it is preferably 3 mass % as lower limit, it is more preferably 5 mass %, more preferably 10 mass %, it is preferably 30 mass % as higher limit, it is more preferably 25 mass %, more preferably 20 mass %, more specifically, when wanting the refractive anisotrop value improving liquid-crystal composition, it is preferable that containing 3～15 mass %, when wanting to reduce refractive anisotrop value, it is preferable that containing 15～30 mass %.

Compound represented by the formula (IVa-1) that compound represented by formula (IVa) is preferably recorded below～formula (IVa-6), more preferably the compound represented by formula (IVa-1)～formula (IVa-4), it is preferred that the compound represented by formula (IVa-1)～formula (IVa-3), the particularly preferably compound represented by formula (IVa-1) and formula (IVa-3), it is most preferred that the compound represented by formula (IVa-1).

[changing 11]

It addition, the liquid-crystal composition in the present application requires high to row-isotropic phase transition temperature (T_ni) when, it is preferable that from the compound group represented by formula (IVa-5) and formula (IVa-6), select at least one.

When using the compound represented by 4 kinds of formula above (IVa), preferred compositions uses the compound represented by formula (IVa-1)～formula (IVa-4), the content of the compound represented by formula (IVa-1)～formula (IVa-4) is preferably more than the 50 mass % in the compound represented by formula (IVa), it is more preferably more than 70 mass %, more preferably more than 80 mass %, it is particularly preferred to be more than 90 mass %.

When using the compound represented by 3 kinds of formulas (IVa) at the same time, preferred compositions uses the compound represented by formula (IVa-1)～formula (IVa-3), the content of the compound represented by formula (IVa-1)～formula (IVa-3) is preferably more than the 50 mass % in the compound represented by formula (IVa), it is more preferably more than 70 mass %, more preferably more than 80 mass %.

When using the compound represented by 2 kinds of formulas (IVa) at the same time, preferred compositions uses the compound represented by formula (IVa-1) and (IVa-3), the content of the compound represented by formula (IVa-1) and formula (IVa-3) is preferably more than the 50 mass % in the compound represented by formula (IVa), it is more preferably more than 70 mass %, more preferably more than 80 mass %, it is particularly preferred to be more than 90 mass %.

In the compound represented by formula (IV), at A²When representing Isosorbide-5-Nitrae-phenylene, it is possible to contain the compound selected from the compound group represented by formula (IVb) further.

[changing 12]

(R in formula^7bAnd R^8bRepresent respectively and the R in formula (IV)⁷And R⁸The identical meaning.)

In the liquid-crystal composition of the present application, total containing ratio of the compound group represented by formula (IVb), it is preferably 5 mass % as lower limit, it is more preferably 8 mass %, more preferably 10 mass %, it is preferably 35 mass % as higher limit, it is more preferably 30 mass %, more preferably 25 mass %, more specifically, when wanting the refractive anisotrop value reducing liquid-crystal composition, it is preferable that containing 5～15 mass %, when wanting to improve refractive anisotrop value, it is preferable that containing 15～35 mass %.

The compound represented by formula (IVb-1)～(IVb-4) that compound represented by formula (IVb) is preferably recorded below, the more preferably compound represented by formula (IVb-1) or formula (IVb-2).

[changing 13]

When using the compound represented by two or more formula (IVb), preferred compositions uses the compound represented by formula (IVb-1) and formula (IVb-2), the content of the compound represented by formula (IVb-1) and formula (IVb-2) is preferably more than the 50 mass % in the compound represented by formula (IVb), it is more preferably more than 70 mass %, more preferably more than 80 mass %, it is particularly preferred to be more than 90 mass %.

The liquid-crystal composition of the present application can contain the compound selected from the compound group represented by logical formula V shown below further.

[changing 14]

(in formula, R^aAnd R^bRepresent the alkene oxygen base of the alkyl of carbon number 1～8, the thiazolinyl of carbon number 2～8, the alkoxyl of carbon number 1～8 or carbon number 2～8 independently of one another, the hydrogen atom of more than 1 in this alkyl, thiazolinyl, alkoxyl and/or alkene oxygen base can be replaced by fluorine atoms, methylene in this alkyl, thiazolinyl, alkoxyl and/or alkene oxygen base when oxygen atom discontinuous in conjunction with can be replaced by oxygen atom, when carbonyl discontinuous in conjunction with can by carbonyl substituted

A³Representing Isosorbide-5-Nitrae-cyclohexylidene, Isosorbide-5-Nitrae-phenylene or Pentamethylene oxide .-2,5-bis-base, at A³When representing Isosorbide-5-Nitrae-phenylene, the hydrogen atom of more than 1 in this Isosorbide-5-Nitrae-phenylene can be replaced by fluorine atoms,

Z¹Represent singly-bound ,-OCH₂-、-OCF₂-、-CH₂O-or-CF₂O-,

N represents 0 or 1,

X¹～X⁶Represent hydrogen atom or fluorine atom, X independently of one another¹～X⁶In at least 1 represent fluorine atom.)

Logical compound represented by formula V, the concrete compound represented by formula (V-1)～(V-16) preferably recorded below, more preferably formula (V-1), formula (V-3)～formula (V-9) and formula (V-12)～formula (V-15), it is preferred that 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), it is most preferred that formula (V-5).

[changing 15]

(in formula, R^aAnd R^bRepresent and the R in logical formula V^aAnd R^bThe identical meaning.)

In the liquid-crystal composition of the present application, total containing ratio of logical compound group represented by formula V, it is preferably 3 mass % as lower limit, it is more preferably 5 mass %, more preferably 8 mass %, it is preferably 35 mass % as higher limit, it is more preferably 30 mass %, more preferably 25 mass %, more specifically, when wanting the refractive anisotrop value reducing liquid-crystal composition, it is preferable that containing 5～15 mass %, when wanting to improve refractive anisotrop value, it is preferable that containing 15～35 mass %.

When selecting the compound represented by logical formula V, the most preferably compound represented by selecting type (V-5), the content of the compound represented by formula (V-5) is preferably more than the 50 mass % in logical compound represented by formula V, it is more preferably more than 70 mass %, more preferably more than 80 mass %, it is particularly preferred to be more than 90 mass %.

R in logical formula V^aAnd R^bRepresent the alkene oxygen base of the alkyl of carbon number 1～8, the thiazolinyl of carbon number 2～8, the alkoxyl of carbon number 1～8 or carbon number 2～8 independently of one another, preferably represent the alkyl of carbon number 1～8 or the thiazolinyl of carbon number 2～8, more preferably the alkyl of carbon number 2～5 or the thiazolinyl of carbon number 2～5 are represented, it is preferred that represent the alkyl of carbon number 2～5, it is preferably straight chain, at R^aAnd R^bWhen being alkyl, it is preferable that respective carbon number is different simultaneously.

It is described in further detail, it is preferable that R^aRepresent propyl group R^bRepresent compound or the R of ethyl^aRepresent butyl R^bRepresent the compound of ethyl.

The liquid-crystal composition of the present application also can contain the compound selected from formula (VI-a) to the compound group represented by formula (VI-e) further.

[changing 16]

(in formula, R⁹¹To R^9aRepresent the thiazolinyl of the alkyl of carbon number 1 to 10, the alkoxyl of carbon number 1 to 10 or carbon number 2 to 10 independently of one another, but R in the compound represented by formula (VI-a)⁹¹Represent alkyl or the alkoxyl of carbon number 2 to 8, the R of carbon number 1 to 8⁹²Represent compound and the R of the thiazolinyl of carbon number 2 to 8⁹¹And R⁹²Independently of one another except the compound of the thiazolinyl of expression carbon number 2 to 8.)

When containing from formula (VI-a) to the compound group represented by formula (VI-e) compound selected, preferably comprise a kind～10 kinds, particularly preferably contain a kind～8 kinds, particularly preferably contain a kind～5 kinds, it is also preferred that containing compound of more than two kinds, it is also preferred that containing a kind of compound, content in this case is preferably 3～20 mass %, it is more preferably 4～15 mass %, more preferably 5～9 mass %.

Preferred R⁹¹To R^9aRepresent the alkoxyl of the alkyl of carbon number 1 to 10, the thiazolinyl of carbon number 2 to 10 or carbon number 2 to 10 independently of one another, more preferably the alkoxyl of the alkyl of carbon number 1 to 5, the thiazolinyl of carbon number 2 to 5 or carbon number 2 to 5 is represented, when representing thiazolinyl, the structure represented by formula (i)～formula (iv) preferably recorded below

[changing 17]

(in formula, the right-hand member at ring structure combines.)

When the liquid-crystal composition of the present application contains reactive monomer, it is preferable that formula (ii) and the structure represented by formula (iv), the more preferably structure represented by formula (ii).

It addition, R⁹¹And R⁹²Can be the same or different, but preferably represent different substituent groups.

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

[changing 18]

[changing 19]

[changing 20]

[changing 21]

[changing 22]

[changing 23]

In these compounds, it is preferable that the compound represented by formula (VI-a1)～formula (VI-a5), formula (VI-b2), formula (VI-b6), formula (VI-c2), formula (VI-c4), formula (VI-c5), formula (VI-d1)～formula (VI-d4) and formula (VI-e2).

nullLiquid-crystal composition in the present application selects a kind from the compound group represented by formula (VI-a3)～formula (VI-a5)、When 2 kinds or 3 kinds parts as other composition，Its total content is preferably 15～40 mass %，It is more preferably 18～35 mass %，More preferably 20～33 mass %，Further specifically，When the compound represented by selecting type (VI-a3)，Its content is preferably 5～30 mass %，It is more preferably 10～25 mass %，More preferably 13～20 mass %，When the compound represented by selecting type (VI-a4)，Its content is preferably 1～15 mass %，It is more preferably 2～12 mass %，More preferably 3～9 mass %，When the compound represented by selecting type (VI-a5)，Its content is preferably 3～15 mass %，It is more preferably 5～10 mass %，More preferably 7～9 mass %.

When the liquid-crystal composition of the present application selects 2 kinds of parts as other compositions from the compound group represented by formula (VI-a3)～formula (VI-a5), preferably select formula (VI-a3) and formula (VI-a4), when selecting a kind, more preferably selecting type (VI-a3).

Compound represented by compound represented by formula (VI) and formula (I) and formula (II) dielectric constant anisotropy substantially 0 in be common, but total containing ratio of the compound represented by formula (I), formula (II) and formula (VI) is preferably 25～65 mass %, it is more preferably 30～60 mass %, more preferably 35～55 mass %.

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

The liquid-crystal composition of the present invention is using the compound represented by formula (I), formula (II) as essential component, it is possible to contain the compound represented by formula (III), formula (IV), logical formula V and formula (VI-a)～formula (VI-e) further.The formula (I) contained in liquid-crystal composition, formula (II), formula (III), formula (IV), the total content of the compound represented by logical formula V and formula (VI-a)～formula (VI-e), it is preferably 60 mass % as lower limit, it is preferably 65 mass %, it is preferably 70 mass %, it is preferably 75 mass %, it is preferably 80 mass %, it is preferably 85 mass %, it is preferably 90 mass %, it is preferably 92 mass %, it is preferably 95 mass %, it is preferably 98 mass %, it is preferably 99 mass %, it is preferably 100 mass % as higher limit, it is preferably 99.5 mass %.

More specifically, the total content of the compound represented by formula (I), formula (II) and formula (III) is preferably 40～75 mass %, more preferably 45～70 mass %, more preferably 50～65 mass %.

The total content of the compound represented by formula (I), formula (II) and formula (IV) is preferably 55～95 mass %, more preferably 60～90 mass %, more preferably 65～85 mass %.

The total content of the compound represented by formula (I), formula (II) and logical formula V is preferably 40～70 mass %, more preferably 45～65 mass %, more preferably 50～60 mass %.

The total content of the compound represented by formula (I), formula (II) and formula (VI) is preferably 35～65 mass %, more preferably 40～60 mass %, more preferably 45～55 mass %.

The total content of the compound represented by formula (I), formula (II), formula (III) and formula (IV) is preferably 75～99 mass %, it is more preferably 80～97 mass %, more preferably 85～97 mass %.

The total content of the compound represented by formula (I), formula (II), formula (III) and logical formula V is preferably 55～85 mass %, it is more preferably 60～80 mass %, more preferably 65～75 mass %.

The total content of the compound represented by formula (I), formula (II), formula (III) and formula (VI) is preferably 45～75 mass %, it is more preferably 50～70 mass %, more preferably 55～65 mass %.

The total content of the compound represented by formula (I), formula (II), formula (IV) and logical formula V is preferably 70～99 mass %, it is more preferably 75～95 mass %, more preferably 80～90 mass %.

When paying attention to reliability and the long-time stability of liquid-crystal composition, preferably making the content with the compound of carbonyl is below 5 mass % relative to the gross mass of above-mentioned composition, it is more preferably below 3 mass %, more preferably below 1 mass %, it is most preferred that be substantially free of.

When paying attention to irradiating, by UV, the stability obtained, preferably making the content having carried out the compound that chlorine atom replaces is below 15 mass % relative to the gross mass of above-mentioned composition, it is more preferably below 10 mass %, more preferably below 5 mass %, it is most preferred that be substantially free of.

Preferably making intramolecular ring structure is all that the content of compound of 6 rings is many, preferably to make intramolecular ring structure be all the content of compound of 6 rings is more than 80 mass % relative to the gross mass of above-mentioned composition, it is more preferably more than 90 mass %, more preferably more than 95 mass %, it is most preferred that be all substantially only that the compound of 6 rings is to constitute liquid-crystal composition by intramolecular ring structure.

In order to suppress the deterioration caused by the oxidation of liquid-crystal composition, preferably make that there is cyclohexadienylidene few as the content of the compound of ring structure, preferably making the content with the compound of cyclohexadienylidene is below 10 mass % relative to the gross mass of above-mentioned composition, it is more preferably below 5 mass %, it is preferred that be substantially free of.

Paying attention to improvement and the T of viscosity_niImprovement when, preferably make that there is the 2-methylbenzene-1 that hydrogen atom can be optionally substituted by halogen in molecule, the content of the compound of 4-bis-base is few, preferably make above-mentioned there is in molecule 2-methylbenzene-1, the content of the compound of 4-bis-base is below 10 mass % relative to the gross mass of above-mentioned composition, it is more preferably below 5 mass %, it is preferred that be substantially free of.

The compound contained in the compositions of first embodiment of the present invention has thiazolinyl as side chain, above-mentioned thiazolinyl and hexamethylene in conjunction with time, the carbon number of this thiazolinyl is preferably 2～5, above-mentioned thiazolinyl and benzene in conjunction with time, the carbon number of this thiazolinyl is preferably 4～5, it is preferable that the unsaturated bond of above-mentioned thiazolinyl and benzene not directly in conjunction with.

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

The value of the refractive anisotrop Δ n of the liquid-crystal composition of the present invention is 0.08 to 0.13 at 25 DEG C, more preferably 0.09 to 0.12.It is described in further detail, when tackling thin cell gap, it is preferred to 0.10 to 0.12, when the cell gap that reply is thick, it is preferred to 0.08 to 0.10.

Rotary viscosity (the γ of the liquid-crystal composition of the present invention₁) it is preferably less than 150, more preferably less than 130, it is particularly preferred to be less than 120.

In the liquid-crystal composition of the present invention, it is preferable that the Z as rotary viscosity with the function of refractive anisotrop shows particular value.

[several 1]

Z=γ₁/(Δn)²

(in formula, γ₁Representing rotary viscosity, Δ n represents refractive anisotrop.)

Z is preferably less than 13000, more preferably less than 12000, it is particularly preferred to be less than 11000.

The liquid-crystal composition of the present invention is when for active matrix display element, it is necessary to have 10¹²Resistivity more than (Ω m), it is preferred to 10¹³More than (Ω m), more preferably 10¹⁴More than (Ω m).

The liquid-crystal composition of the present invention is except above-claimed cpd, common nematic liquid crystal, smectic liquid crystal, cholesteryl liquid crystal, antioxidant, UV absorbent, polymerizable monomer etc. can also be contained according to purposes, when requiring the chemical stability of liquid-crystal composition, preferably in not having chlorine atom in its molecule, when requiring liquid-crystal composition to the stability of the light such as ultraviolet, it is preferable that do not have in its molecule with naphthalene nucleus etc. be representative conjugate length length and there is the condensed ring etc. of absworption peak at ultraviolet region.

As polymerizable monomer, it is preferable that two functional monomers represented by formula (VII).

[changing 24]

(in formula, X⁷And X⁸Represent hydrogen atom or methyl, Sp independently of one another¹And Sp²Represent singly-bound, the alkylidene of carbon number 1～8 or-O-(CH independently of one another₂)_s-(in formula, s represents the integer of 2 to 7, and oxygen atom is combined on 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 Y²Represent fluorine atom or hydrogen atom independently of one another.) ,-C ≡ C-or singly-bound,

B represents Isosorbide-5-Nitrae-phenylene, anti-form-1,4-cyclohexylidene or singly-bound, and in the whole Isosorbide-5-Nitrae-phenylenes in formula, arbitrary hydrogen atom can be replaced by fluorine atoms.)

Preferred X⁷And X⁸Any one in the diacrylate derivative that all represents hydrogen atom, the dimethylacrylate derivant being respectively provided with methyl, it is also preferred that a side represents that hydrogen atom the opposing party represents the compound of methyl.About the polymerization speed of these compounds, diacrylate derivative is the fastest, and dimethylacrylate derivant is slow, and asymmetric compound is in the middle of them, it is possible to use preferred mode according to its purposes.In PSA display element, it is particularly preferred to dimethylacrylate derivant.

Sp¹And Sp²Represent singly-bound, the alkylidene of carbon number 1～8 or-O-(CH independently of one another₂)_s-, but in PSA display element, it is preferable that at least one party is singly-bound, it is preferable that all represent that the compound of singly-bound or a side are alkylidene or the-O-(CH that singly-bound the opposing party represents carbon number 1～8₂)_s-mode.In such a situation it is preferred to the alkyl of 1～4, s preferably 1～4.

Z²Preferably-OCH₂-、-CH₂O-、-COO-、-OCO-、-CF₂O-、-OCF₂-、-CH₂CH₂-、-CF₂CF₂-or singly-bound, more preferably-COO-,-OCO-or singly-bound, it is particularly preferred to singly-bound.

B represents 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 preferable that Isosorbide-5-Nitrae-phenylene or singly-bound.When B represents the ring structure beyond singly-bound, Z²It is also preferred that the linking group beyond singly-bound, when B is singly-bound, Z²It is preferably singly-bound.

From the viewpoint of these, in formula (VII), Sp¹And Sp²Between the structure specifically preferably recorded below of ring structure.

In formula (VII), B represents singly-bound, ring structure are formed by two rings, preferably represent that below formula (VIIa-1) is to formula (VIIa-5), more preferably expression (VIIa-1) is to formula (VIIa-3), it is particularly preferred to expression (VIIa-1).

[changing 25]

(in formula, two ends and Sp¹Or Sp²In conjunction with.)

Comprising the polymerizable compound of these skeletons, the orientation restraint after polymerization is most suitable for PSA type liquid crystal display cells, can obtain good state of orientation, therefore shows uneven suppressed or does not produce completely.

By upper, as polymerizable monomer, it is particularly preferred to formula (VII-1)～formula (VII-4), wherein most preferably formula (VII-2).

[changing 26]

(in formula, Sp²Represent the alkylidene of carbon number 2 to 5.)

The liquid-crystal composition of the present invention adds monomer, even if being also carried out polymerization in the non-existent situation of polymerization initiator but it also may contain polymerization initiator to promote polymerization.As polymerization initiator, benzoin ethers, benzophenone, acetophenones, benzil ketals class, acylphosphine oxide class etc. can be enumerated.It addition, in order to improve storage stability, it is possible to add stabilizer.As operable stabilizer, for instance hydroquinones, hydroquinone monoalkyl ethers, tert-butyl catechol class, pyrogallol class, phenylmercaptan. class, nitro compound class, beta-naphthylamine class, betanaphthol class, nitroso compound etc. can be enumerated.

The liquid-crystal composition containing polymerizable compound of the present invention is useful in liquid crystal display cells, in driven with active matrix liquid crystal display cells particularly useful, it is possible to for PSA pattern, PSVA pattern, VA pattern, IPS pattern or ecb mode liquid crystal display cells.

The polymerizable compound that can be used for by ultraviolet radiation makes it contained containing the liquid-crystal composition of polymerizable compound of the present invention is polymerized thus giving liquid crystal aligning energy, utilizes the birefringence of liquid-crystal composition to control the liquid crystal display cells through light quantity of light.As liquid crystal display cells, in AM-LCD (active matrix liquid crystal display device), TN (twisted nematic liquid crystal display element), STN-LCD (Supertwist Nematic Liquid Crystal Display element), OCB-LCD and IPS-LCD (plane switching liquid crystal display element) useful, in AM-LCD particularly useful, it is possible to for the liquid crystal display cells of transmission-type or reflection-type.

Additionally, content with reference to liquid crystal display cells described later and Fig. 1～4,2 plate bases 2,8 of the liquid crystal cells that liquid crystal display cells uses can use glass or plastics so to have the transparent material of flexibility, can also be the opaque materials such as silicon on the other hand.There is the transparency carrier 2,8 of transparency electrode (layer) 6,14, for instance the transparency carriers such as glass plate 2,8 can obtain by being sputtered at by indium tin oxide (ITO).

Make above-mentioned be formed transparency electrode (layer), TFT substrate 2,8 with transparency electrode (layer) 6,14 be inner side mode relative.At this moment, it is possible to adjusted the interval (with reference to Fig. 1～4) of substrate by sept (not shown).At this moment, it is preferable that the thickness of the light modulation layer obtained is adjusted to 1～100 μm.More preferably 1.5 to 10 μm, when using polarization plates, it is preferable that the refractive anisotrop Δ n's and element thickness d of adjustment liquid crystal is long-pending, makes contrast maximum.It addition, when there being two panels polarization plates 1,9, it is also possible to adjust the polarization axle of each polarization plates and by visual angle, setting contrast for well (with reference to Fig. 1～4).Further, it is possible to use for expanding the phase retardation film at visual angle.As sept, for instance glass particle, plastic pellet, aluminium oxide particles, photo-induced corrosion resistant material etc. can be enumerated.Afterwards, to be provided with the form of liquid crystal injecting port by sealant silk screen printings such as epoxy heat-curable compositions on the substrate, this substrate is fitted each other, heating and make sealant heat cure.

The method that the liquid-crystal composition receiving space housing liquid-crystal composition formed as described above by making 2 plate bases relatively fit is imported the liquid-crystal composition containing polymerizable monomer, common vacuum impregnation or ODF method etc. can be used, although not producing drop impression in vacuum impregnation, but there is the problem injecting vestige residual, in the present application, it is possible to the more appropriately display element for using ODF method to manufacture.

As the method making polymerizable compound be polymerized, owing to wishing the polymerization speed of appropriateness to obtain the good orientation characteristic of liquid crystal, it is thus preferred to by single or and with or method that in turn irradiation ultraviolet radiation or electric wire isoreactivity energy-ray carry out being polymerized.Under using ultraviolet situation, it is possible to use polarized light source, it is possible to use unpolarized light source.It addition, when carrying out when being clamped between 2 plate bases by the liquid-crystal composition containing polymerizable compound being polymerized, it is necessary to make the substrate of at least shadow surface side have the suitable transparency relative to active energy beam.Further, it is possible to use following method: use when light irradiates mask only make specifically partially polymerized after, change the conditions such as electric field, magnetic field or temperature, so that the state of orientation of non-polymeric part changes, irradiate active energy beam further and be polymerized.Particularly when carrying out ultraviolet exposure, it is preferable that the liquid crystal combination beyond the region of objective existence containing polymerizable compound is executed AC field while carrying out ultraviolet exposure.The AC field executed outward is preferably the exchange of frequency 10Hz to 10kHz, more preferably frequency 60Hz to 10kHz, and voltage depends on the desired tilt angle of liquid crystal display cells and selects.That is, it is possible to controlled the tilt angle of liquid crystal display cells by the voltage executed outward.In the liquid crystal display cells of MVA pattern, from the viewpoint of orientation stability and contrast, it is preferable that control to be 80 degree to 89.9 degree by tilt angle.

Temperature during irradiation is preferably in the temperature range of the mesomorphic state of the liquid-crystal composition keeping the present invention.Namely temperature preferably near room temperature is typically polymerized at the temperature of 15～35 DEG C.As producing ultraviolet lamp, it is possible to use metal halide lamp, high-pressure mercury-vapor lamp, extra-high-pressure mercury vapour lamp etc..It addition, as the ultraviolet wavelength irradiated, it is preferable that irradiate not at the ultraviolet of the wavelength region in the absorbing wavelength region of liquid-crystal composition, it is preferable that as required ultraviolet blocking-up and use.The ultraviolet intensity irradiated is preferably 0.1mW/cm²～100W/cm², more preferably 2mW/cm²～50W/cm².The ultraviolet energy irradiated can suitably adjust, but is preferably 10mJ/cm²To 500J/cm², more preferably 100mJ/cm²To 200J/cm².During irradiation ultraviolet radiation, thus it is possible to vary intensity.The time of irradiation ultraviolet radiation suitably selects according to the uitraviolet intensity irradiated, but is preferably 10 seconds to 3600 seconds, more preferably 10 seconds to 600 seconds.

Second invention of the present invention is the liquid crystal display cells of the liquid-crystal composition using the present invention.Fig. 1 is the figure of the composition schematically showing liquid crystal display cells.It addition, in FIG, for convenient explanation, each element is separately recorded.Fig. 2 be by this Fig. 1 is formed on substrate the electrode layer 3 comprising thin film transistor (TFT) (or also referred to as tft layer 3.) the region surrounded by II line amplify plane graph.Fig. 3 is the profile cut off by the liquid crystal display cells shown in Fig. 1 on the III-III line direction in this Fig. 2.Fig. 4 is the figure amplified by the thin film transistor (TFT) in the IV region in this Fig. 3.The liquid crystal display cells of the present invention is described referring to Fig. 1～4.

The composition of the liquid crystal display cells 10 of the present invention has the feature that it is have the transparency electrode (layer) 6 being made up of transparent conductive material (or also referred to as common electrode 6.) first substrate 8, comprise and be formed with the pixel electrode being made up of transparent conductive material and control the second substrate 2 of tft layer 3 of thin film transistor (TFT) of the pixel electrodes that each pixel has and the liquid-crystal composition (or liquid crystal layer 5) being clamped between above-mentioned first substrate 8 and second substrate 2, and the orientation that the liquid crystal molecule in this liquid-crystal composition is when without applied voltage is substantially vertical liquid crystal display cells relative to aforesaid substrate 2,8, and employ the liquid-crystal composition of the invention described above as this liquid-crystal composition.It addition, as shown in figures 1 and 3, above-mentioned second substrate 2 and above-mentioned first substrate 8 can be clamped between a pair polarization plates 1,9.Further, in FIG, between above-mentioned first substrate 8 and common electrode 6, it is provided with color filter 7.Additionally further, it is possible to form a pair alignment films 4 on transparency electrode (layer) 6,14 surface in the way of adjoining with the liquid crystal layer 5 of the present invention and directly to abut with the liquid-crystal composition being constituted this liquid crystal layer 5.

That is, the composition of the liquid crystal display cells 10 of the present invention is: the second polarization plates 1, second substrate 2, the electrode layer (or also referred to as tft layer) 3 comprising thin film transistor (TFT), alignment films 4, the layer 5 comprising liquid-crystal composition, alignment films 4, common electrode 6, color filter 7, first substrate 8 and the first polarization plates 9 are stacked gradually.

Additionally, as shown in Figure 2, about the electrode layer 3 comprising thin film transistor (TFT) formed on second substrate 2 surface, intersect with the data wiring 24 for supplying display signal for supplying the gate wirings 25 of scanning signal, and in the region surrounded by above-mentioned many gate wirings 25 and many single data distribution 24, pixel electrode 21 is formed as rectangular.As the switch element to pixel electrode 21 supply display signal, near above-mentioned gate wirings 25 and the cross one another cross part of above-mentioned data wiring 24, the thin film transistor (TFT) comprising source electrode 26, drain electrode 23 and gate electrode 27 is arranged with pixel electrodes 21 with being connected.Further, in the region surrounded by above-mentioned many gate wirings 25 and many single data distribution 24, it is provided with the storage capacitor 22 preserving the display signal supplied by data wiring 24.

In the present invention, it is possible to being suitably used for as described in Fig. 2～4, thin film transistor (TFT) is the liquid crystal display cells of reciprocal cross stack-type, and gate wirings 25, data wiring 24 etc. are preferably metal film, it is particularly preferred to use the situation of aluminum wiring.Further, gate wirings and data wiring are overlapping across gate insulating film.

It addition, from the view point of prevent the leakage of light, this color filter 7 forms black matrix (not shown) preferably in the part corresponding to thin film transistor (TFT) and storage capacitor 22.

The suitable mode of structure of thin film transistor (TFT) about the liquid crystal display cells of the present invention, for instance as shown in Figure 3 and Figure 4, have: form the gate electrode 11 on substrate 2 surface；The gate insulator 13 arranged in the way of covering this gate electrode 11 and covering the substantially entire surface of aforesaid substrate 2；The semiconductor layer 17 on above-mentioned gate insulator 13 surface is formed in the way of relative with above-mentioned gate electrode 11；The protecting film 18 arranged in the way of covering the part on above-mentioned semiconductor layer 17 surface；By the side end covering above-mentioned protective layer 18 and above-mentioned semiconductor layer 17 and the drain electrode 15 arranged in the way of the above-mentioned gate insulator 13 on aforesaid substrate 2 surface contacts with formation；To cover said protection film 18 and another side end of above-mentioned semiconductor layer 17 and the source electrode 19a, the 19b that arrange in the way of the above-mentioned gate insulator 13 on aforesaid substrate 2 surface contacts with formation；The transparency electrode 14 arranged in the way of covering above-mentioned source electrode 19a, 19b and covering the substantially entire surface of above-mentioned gate insulator 13 along above-mentioned gate insulator 13；And the protective layer 101 (not shown in figure 3) arranged in the way of the part covering above-mentioned transparency electrode 14 and above-mentioned source electrode 19a, 19b.

It addition, as shown in Figures 3 and 4, gate electrode 11 surface can form anodic oxidation coating 12 according to reasons such as the section differences eliminated with gate electrode.Further, under the purpose reducing the width of Schottky barrier (Schottkybarrier), height, it is possible to ohmic contact layer 16 is set between semiconductor layer 17 and drain electrode 15.

In the process of liquid crystal display cells fabricated as described above, the impact of the liquid crystal material producing deeply to be injected of drop impression, but due to the composition of liquid crystal display cells, its impact also cannot be avoided.The color filter 7 particularly formed in liquid crystal display cells or thin film transistor (TFT) etc., as shown in Figure 3, for only the generation of drop impression being impacted with the combination of the liquid-crystal compounds with specified chemical structure across the component of thin alignment films 4, transparency electrode 6,14 etc., the chemical constitution of the pigment therefore used due to such as color filter or the chemical constitution of color filter resin with liquid-crystal composition.

Particularly when the thin film transistor (TFT) of the liquid crystal display cells as the present invention uses reciprocal cross stack-type as above, as shown in figs. 2 to 4, drain electrode 15 is formed in the way of covering grid electrode 11, therefore has the tendency that the area of drain electrode 15 increases.Usual drain electrode is formed by metal materials such as copper, aluminum, chromium, titanium, molybdenum, tantalums, and common mode is for implementing Passivation Treatment.But, for instance as shown in Figure 3 and Figure 4, owing to protecting film 18 is generally relatively thin, alignment films 4 is also thin, and the probability not intercepting ionic substance is high, therefore cannot avoid being produced by the caused drop impression that interacts of metal material with liquid-crystal composition.

But in comprising the liquid crystal display cells of liquid-crystal composition of the present invention, from the viewpoint of the delicate balance between the surface free energy of the liquid-crystal composition of the component of such as liquid crystal display cells and the present invention or energy of adsorption etc., it is believed that the problem producing drop impression also is able to reduce.

The liquid crystal display cells using the liquid-crystal composition of the present invention is taken into account high-speed responsive and shown the useful element of bad suppression, in driven with active matrix liquid crystal display cells particularly useful, it is possible to suitable in VA pattern, PSVA pattern, PSA pattern, IPS pattern or ecb mode use.

Embodiment

Hereinafter enumerate embodiment the present invention is described in further detail, but the invention is not restricted to these embodiments.It addition, " % " in the compositions of below example and comparative example refers to " quality % ".

In embodiment, the characteristic of mensuration is as described below.

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

Refractive anisotrop during Δ n:25 DEG C

Dielectric constant anisotropy during Δ ε: 25 DEG C

Viscosity (mPa s) when η: 20 DEG C

γ₁: the rotary viscosity (mPa s) when 25 DEG C

VHR: the voltage retention (%) when 60 DEG C when frequency 60Hz, applied voltage 1V

Burn-in:

The burn-in evaluation of liquid crystal display cells, is after making the fixed pattern of regulation show 1000 hours in viewing area, carries out following 4 Phase Evaluation by estimating the ghost level of fixed pattern when whole picture is uniformly shown.

◎ is without ghost

Zero ghost is almost little, for admissible level

There is ghost in △, for not admissible level

× there is ghost, very severe

Drop impression:

The evaluation of the drop impression of liquid crystal indicator, is when showing black for whole, carries out following 4 Phase Evaluation by the drop impression estimated appearing white.

◎ is without ghost

Zero ghost is almost little, for admissible level

There is ghost in △, for not admissible level

× there is ghost, very severe

Technological adaptability:

About Technological adaptability, in ODF technique, the operation using the every 1 time 50pL liquid crystal that drips of constant volume measurement pump is carried out 100000 times, then the change of the amount of liquid crystal dripped for every 100 times of " 0～100 time, 101～200 times, 201～300 times ... 99901～100000 times " is carried out following 4 Phase Evaluations.

◎ changes minimum (can stably manufacture liquid crystal display cells)

Zero change is almost little, for admissible level

There is change in △, for not admissible level (causing that yield rate is deteriorated owing to producing speckle)

× there is change, very severe (produces liquid crystal leakage, bubbles of vacuum)

Dissolubility under low temperature:

Dissolubility evaluation under low temperature, it is after modulating liquid crystal composite, weighing 1g liquid-crystal composition in the sample bottle of 2mL, place it in temperature and control in formula test flume, variations in temperature is given continuously then according to 1 circulation "-20 DEG C (keeping 1 hour) → (0.1 DEG C/per minute) → 0 DEG C (keeping 1 hour) → intensification (0.1 DEG C/per minute) → 20 DEG C (keeping 1 hour) → cooling (-0.1 DEG C/per minute) → 0 DEG C (keeping 1 hour) → cooling (-0.1 DEG C/per minute) that heats up →-20 DEG C ", generation by visual observations precipitate from liquid-crystal composition, carry out following 4 Phase Evaluation.

◎ does not observe precipitate in more than 600 hours.

Within more than 0 300 hours, do not observe precipitate.

△ observed precipitate within 150 hours.

Precipitate is observed within × 75 hours.

It addition, about the record of compound in embodiment, use following simple mark.

(side chain)

(ring structure)

[changing 27]

(embodiment 1)

Modulation has the liquid-crystal composition (embodiment 1) of composition shown below, measures its physics value.The results are shown in following table.

Use the liquid-crystal composition of embodiment 1, make VA liquid crystal display cells.This liquid crystal display cells has the thin film transistor (TFT) of reciprocal cross stack-type as active component.The injection of liquid-crystal composition is undertaken by the method for dripping, and carries out the deliquescent evaluation under burn-in, drop impression, Technological adaptability and low temperature.

It addition, the record that mark is the simple mark of above-claimed cpd on the left of content.

[changing 28]

Embodiment 1

[table 1]

T_NI/℃	75.3
		Δn	0.110
n_o	1.486
		Δε	-3.0
ε_⊥	6.6
		η/mPa·s	17.1
γ₁/mPa·s	106
		γ₁/Δn²	8.8
Initial voltage conservation rate/%	99.8
		Voltage retention/% after 150 DEG C of 1h	99.3
Burn-in is evaluated	◎
		Drop impression is evaluated	◎
Technological adaptability is evaluated	◎
		Dissolubility evaluation under low temperature	◎

Known: the liquid-crystal composition of embodiment 1 has the liquid crystal phase temperature range of 75.3 DEG C as the practicality of TV liquid-crystal composition, has the absolute value of big dielectric constant anisotropy, has low viscosity and the suitableeest Δ n.Using the liquid-crystal composition that embodiment 1 is recorded to make VA liquid crystal display cells, by said method, the dissolubility under burn-in, drop impression, Technological adaptability and low temperature is evaluated, result shows extremely excellent evaluation result.

(comparative example 1)

Modulation is without the compound represented by formula (II), according to the liquid-crystal composition shown below (comparative example 1) that the mode with the liquid crystal phase temperature range equal with the compositions of embodiment 1, equal refractive anisotrop value and equal dielectric constant anisotropy value designs, measure its physics value.The results are shown in following table.

Use the liquid-crystal composition of comparative example 1, make VA liquid crystal display cells similarly to Example 1, the deliquescent evaluation result carried out under burn-in, drop impression, Technological adaptability and low temperature is shown in identical table.

It addition, the mark on the left of content is the record of the simple mark of above-claimed cpd similarly to Example 1.

[changing 29]

Comparative example 1

[table 2]

T_NI/℃	75.3
		Δn	0.110
n_o	1.485
		Δε	-3.1
ε_⊥	6.7
		η/mPa·s	16.9
γ₁/mPa·s	111
		γ₁/Δn²	9.2
Initial voltage conservation rate/%	99.3
		Voltage retention/% after 150 DEG C of 1h	98.5
Burn-in is evaluated	○
		Drop impression is evaluated	×
Technological adaptability is evaluated	○
		Dissolubility evaluation under low temperature	△

Liquid-crystal composition (comparative example 1) without the compound represented by formula (II) is compared with the liquid-crystal composition (embodiment 1) containing the compound represented by 11% mass formula (II), although having equal liquid crystal phase temperature range, equal refractive anisotrop value and equal dielectric constant anisotropy value, but display viscosities il rises.About γ 1, the value 111mPa s of comparative example 1 shows value higher compared with the value 106mPa s of embodiment 1, to represent the parameter γ 1/ Δ n of the actual effect answer speed of liquid crystal display cells and display²Value compare also for difference result.The initial stage VHR of comparative example 1 is 99.3%, and at 150 DEG C, high temperature places the VHR after 1 hour is 98.5%, is in a ratio of poor result with embodiment 1.Technological adaptability is evaluated, and result is changed to not admissible level compared with embodiment 1.Evaluating the dissolubility under low temperature, result observes precipitation earlier compared with embodiment 1.

(comparative example 2)

Modulation is without the compound represented by formula (I), according to the liquid-crystal composition shown below (comparative example 2) that the mode with the liquid crystal phase temperature range equal with the compositions of embodiment 1, equal refractive anisotrop value and equal dielectric constant anisotropy value designs, measure its physics value.The results are shown in following table.

Use the liquid-crystal composition of comparative example 2, make VA liquid crystal display cells similarly to Example 1, the deliquescent evaluation result carried out under burn-in, drop impression, Technological adaptability and low temperature is shown in identical table.

[table 3]

Comparative example 2

V-Cy-Cy-V	11.0%
		3-Cy-Cy-2	18.0%
3-Cy-Cy-4	4.5%
		3-Cy-Ph-Ph-2	3.0%
3-Cy-Ph5-O2	13.0%
		5-Cy-Ph5-O2	5.0%
3-Cy-Cy-Ph5-O2	12.0%
		4-Cy-Cy-Ph5-O2	6.5%
2-Cy-Ph-Ph5-O2	6.0%
		3-Cy-Ph-Ph5-O2	7.0%
3-Ph-Ph5-Ph-2	7.0%
		4-Ph-Ph5-Ph-2	7.0%
T_NI/℃	75.6
		Δn	0.110
n_o	1.486
		Δε	-3.0
ε_⊥	6.6
		η/mPa·s	20.1
γ₁/mPa·s	132
		γ₁/Δn²	10.9
Initial voltage conservation rate/%	99.3
		Voltage retention/% after 150 DEG C of 1h	98.6
Burn-in is evaluated	△
		Drop impression is evaluated	△
Technological adaptability is evaluated	×
		Dissolubility evaluation under low temperature	×

Liquid-crystal composition (comparative example 2) without the compound represented by formula (I) is compared with the liquid-crystal composition (embodiment 1) containing the compound represented by 28% mass formula (I), although having equal liquid crystal phase temperature range, equal refractive anisotrop value and equal dielectric constant anisotropy value, but display viscosities il rises.About γ 1, the value 132mPa s of comparative example 2 shows value higher compared with the value 106mPa s of embodiment 1, to represent the parameter γ 1/ Δ n of the actual effect answer speed of liquid crystal display cells and display²Value compare also for difference result.The initial stage VHR of comparative example 2 is 99.3%, and at 150 DEG C, high temperature places the VHR after 1 hour is 98.6%, is in a ratio of poor result with embodiment 1.Technological adaptability is evaluated, and result is changed to not admissible level compared with embodiment 1.Evaluating the dissolubility under low temperature, result observes precipitation earlier compared with embodiment 1.

(embodiment 2)

The liquid-crystal composition (embodiment 2) with composition shown below that modulation designs according to the mode with the liquid crystal phase temperature range equal with the compositions of embodiment 1, equal refractive anisotrop value and equal dielectric constant anisotropy value, measures its physics value.The results are shown in following table.

Use the liquid-crystal composition of embodiment 2, make VA liquid crystal display cells similarly to Example 1, the deliquescent evaluation result carried out under burn-in, drop impression, Technological adaptability and low temperature is shown in identical table.

[table 4]

Embodiment 2

3-Cy-Cy-V	20.0%
		3-Cy-Cy-V1	10.0%
V-Cy-Cy-V	11.0%
		3-Cy-Ph5-O2	12.0%
5-Cy-Ph5-O2	4.5%
		3-Cy-Cy-Ph5-O2	10.0%
4-Cy-Cy-Ph5-O2	3.0%
		2-Cy-Ph-Ph5-O2	7.5%
3-Cy-Ph-Ph5-O2	10.0%
		3-Ph-Ph5-Ph-2	6.0%
4-Ph-Ph5-Ph-2	6.0%
		T_NI/℃	75.4
Δn	0.110
		n_o	1.485
Δε	-3.0
		ε_⊥	6.6
η/mPa·s	16.7
		γ₁/mPa·s	105
γ₁/Δn²	8.7
		Initial voltage conservation rate/%	99.9
Voltage retention/% after 150 DEG C of 1h	99.3
		Burn-in is evaluated	◎
Drop impression is evaluated	◎
		Technological adaptability is evaluated	○
Dissolubility evaluation under low temperature	◎

Known: the liquid-crystal composition of embodiment 2 has the liquid crystal phase temperature range practical as TV liquid-crystal composition, has the absolute value of big dielectric constant anisotropy, has low viscosity and the suitableeest Δ n.Use the liquid-crystal composition that embodiment 2 is recorded to make VA liquid crystal display cells, by said method, the dissolubility under burn-in, drop impression, Technological adaptability and low temperature is evaluated, the evaluation result that result display is excellent.

(comparative example 3)

Modulation is without the compound represented by formula (II), according to the liquid-crystal composition shown below (comparative example 3) that the mode with the liquid crystal phase temperature range equal with the compositions of embodiment 2, equal refractive anisotrop value and equal dielectric constant anisotropy value designs, measure its physics value.The results are shown in following table.

Use the liquid-crystal composition of comparative example 3, make VA liquid crystal display cells similarly to Example 2, the deliquescent evaluation result carried out under burn-in, drop impression, Technological adaptability and low temperature is shown in identical table.

[table 5]

Comparative example 3

3-Cy-Cy-V	18.0%
		3-Cy-Cy-V1	10.0%
3-Cy-Cy-2	12.0%
		3-Cy-Ph5-O2	11.0%
5-Cy-Ph5-O2	7.0%
		3-Cy-Cy-Ph5-O2	11.5%
2-Cy-Ph-Ph5-O2	6.5%
		3-Cy-Ph-Ph5-O2	10.0%
3-Ph-Ph5-Ph-2	7.0%
		4-Ph-Ph5-Ph-2	7.0%
T_NI/℃	75.7
		Δn	0.110
n_o	1.484
		Δε	-3.0
ε_⊥	6.5
		η/mPa·s	16.8
γ₁/mPa·s	114
		γ₁/Δn²	9.4
Initial voltage conservation rate/%	99.4
		Voltage retention/% after 150 DEG C of 1h	98.7
Burn-in is evaluated	△
		Drop impression is evaluated	△
Technological adaptability is evaluated	△
		Dissolubility evaluation under low temperature	○

Liquid-crystal composition (comparative example 3) without the compound represented by formula (II) is compared with the liquid-crystal composition (embodiment 2) containing the compound represented by 11% mass formula (II), although having equal liquid crystal phase temperature range, equal refractive anisotrop value and equal dielectric constant anisotropy value, but display viscosities il rises.About γ 1, the value 114mPa s of comparative example 3 shows value higher compared with the value 105mPa s of embodiment 2, to represent the parameter γ 1/ Δ n of the actual effect answer speed of liquid crystal display cells and display²Value compare also for difference result.The initial stage VHR of comparative example 3 is 99.4%, and at 150 DEG C, high temperature places the VHR after 1 hour is 98.7%, is in a ratio of poor result with embodiment 2.Technological adaptability is evaluated, and result is changed to not admissible level compared with embodiment 2.Evaluating the dissolubility under low temperature, result observes precipitation earlier compared with embodiment 2.

(embodiment 3 and embodiment 4)

The liquid-crystal composition (embodiment 3 and embodiment 4) with composition shown below that modulation designs according to the mode with the liquid crystal phase temperature range equal with the compositions of embodiment 1, equal refractive anisotrop value and equal dielectric constant anisotropy value, measures its physics value.The results are shown in following table.

Use the liquid-crystal composition of embodiment 3 and embodiment 4, make VA liquid crystal display cells similarly to Example 1, the deliquescent evaluation result carried out under burn-in, drop impression, Technological adaptability and low temperature is shown in identical table.

[table 6]

Known: the liquid-crystal composition of embodiment 3 has the liquid crystal phase temperature range practical as TV liquid-crystal composition, has the absolute value of big dielectric constant anisotropy, has low viscosity and the suitableeest Δ n.Use the liquid-crystal composition that embodiment 3 is recorded to make VA liquid crystal display cells, by said method, the dissolubility under burn-in, drop impression, Technological adaptability and low temperature is evaluated, the evaluation result that result display is excellent.

Known: the liquid-crystal composition of embodiment 4 has the liquid crystal phase temperature range practical as TV liquid-crystal composition, has the absolute value of big dielectric constant anisotropy, has low viscosity and the suitableeest Δ n.Use the liquid-crystal composition that embodiment 4 is recorded to make VA liquid crystal display cells, by said method, the dissolubility under burn-in, drop impression, Technological adaptability and low temperature is evaluated, the evaluation result that result display is excellent.

(embodiment 5 and embodiment 6)

The liquid-crystal composition (embodiment 5 and embodiment 6) with composition shown below that modulation designs according to the mode with the liquid crystal phase temperature range equal with the compositions of embodiment 1, equal refractive anisotrop value and equal dielectric constant anisotropy value, measures its physics value.The results are shown in following table.

Use the liquid-crystal composition of embodiment 5 and embodiment 6, make VA liquid crystal display cells similarly to Example 1, the deliquescent evaluation result carried out under burn-in, drop impression, Technological adaptability and low temperature is shown in identical table.

[table 7]

Known: the liquid-crystal composition of embodiment 5 has the liquid crystal phase temperature range practical as TV liquid-crystal composition, has the absolute value of big dielectric constant anisotropy, has low viscosity and the suitableeest Δ n.Use the liquid-crystal composition that embodiment 5 is recorded to make VA liquid crystal display cells, by said method, the dissolubility under burn-in, drop impression, Technological adaptability and low temperature is evaluated, the evaluation result that result display is excellent.

Known: the liquid-crystal composition of embodiment 6 has the liquid crystal phase temperature range practical as TV liquid-crystal composition, has the absolute value of big dielectric constant anisotropy, has low viscosity and the suitableeest Δ n.Use the liquid-crystal composition that embodiment 6 is recorded to make VA liquid crystal display cells, by said method, the dissolubility under burn-in, drop impression, Technological adaptability and low temperature is evaluated, the evaluation result that result display is excellent.

(embodiment 7)

The liquid-crystal composition (embodiment 7) with composition shown below that modulation designs according to the mode with the liquid crystal phase temperature range equal with the compositions of embodiment 1, equal refractive anisotrop value and equal dielectric constant anisotropy value, measures its physics value.The results are shown in following table.

Use the liquid-crystal composition of embodiment 7, make VA liquid crystal display cells similarly to Example 1, the deliquescent evaluation result carried out under burn-in, drop impression, Technological adaptability and low temperature is shown in identical table.

[table 8]

Embodiment 7

3-Cy-Cy-V	29.0%
		V-Cy-Cy-V1	11.0%
3-Cy-Ph5-O2	12.0%
		5-Cy-Ph5-O2	5.0%
3-Cy-Cy-Ph5-O2	12.0%
		4-Cy-Cy-Ph5-O2	3.0%
2-Cy-Ph-Ph5-O2	7.0%
		3-Cy-Ph-Ph5-O2	8.0%
3-Ph-Ph5-Ph-2	6.0%
		4-Ph-Ph5-Ph-2	7.0%
T_NI/℃	75.4
		Δn	0.110
n_o	1.485
		Δε	-3.0
ε_⊥	6.6
		η/mPa·s	17.2
γ₁/mPa·s	108
		γ₁/Δn²	8.9
Initial voltage conservation rate/%	99.6
		Voltage retention/% after 150 DEG C of 1h	99.4
Burn-in is evaluated	◎
		Drop impression is evaluated	○
Technological adaptability is evaluated	◎
		Dissolubility evaluation under low temperature	○

Known: the liquid-crystal composition of embodiment 7 has the liquid crystal phase temperature range practical as TV liquid-crystal composition, has the absolute value of big dielectric constant anisotropy, has low viscosity and the suitableeest Δ n.Use the liquid-crystal composition that embodiment 7 is recorded to make VA liquid crystal display cells, by said method, the dissolubility under burn-in, drop impression, Technological adaptability and low temperature is evaluated, the evaluation result that result display is excellent.

(comparative example 4)

Modulation is without the compound represented by formula (I), according to the liquid-crystal composition shown below (comparative example 4) that the mode with the liquid crystal phase temperature range equal with the compositions of embodiment 7, equal refractive anisotrop value and equal dielectric constant anisotropy value designs, measure its physics value.The results are shown in following table.

Use the liquid-crystal composition of comparative example 4, make VA liquid crystal display cells similarly to Example 7, the deliquescent evaluation result carried out under burn-in, drop impression, Technological adaptability and low temperature is shown in identical table.

[table 9]

Comparative example 4

V-Cy-Cy-V1	11.0%
		3-Cy-Cy-2	18.0%
3-Cy-Cy-4	4.5%
		3-Cy-Ph-Ph-2	6.0%
3-Cy-Ph5-O2	12.0%
		5-Cy-Ph5-O2	9.5%
3-Cy-Cy-Ph5-O2	12.0%
		4-Cy-Cy-Ph5-O2	4.0%
2-Cy-Ph-Ph5-O2	5.0%
		3-Cy-Ph-Ph5-O2	6.0%
3-Ph-Ph5-Ph-2	6.0%
		4-Ph-Ph5-Ph-2	6.0%
T_NI/℃	75.4
		Δn	0.110
n_o	1.486
		Δε	-3.0
ε_⊥	6.4
		η/mPa·s	19.7
γ₁/mPa·s	132
		γ₁/Δn²	10.9
Initial voltage conservation rate/%	99.3
		Voltage retention/% after 150 DEG C of 1h	98.6
Burn-in is evaluated	△
		Drop impression is evaluated	△
Technological adaptability is evaluated	×
		Dissolubility evaluation under low temperature	×

Liquid-crystal composition (comparative example 4) without the compound represented by formula (I) is compared with the liquid-crystal composition (embodiment 7) containing the compound represented by 29% mass formula (I), although having equal liquid crystal phase temperature range, equal refractive anisotrop value and equal dielectric constant anisotropy value, but display viscosities il rises.About γ 1, the value 132mPa s of comparative example 4 shows value higher compared with the value 108mPa s of embodiment 7, to represent the parameter γ 1/ Δ n of the actual effect answer speed of liquid crystal display cells and display²Value compare also for difference result.The initial stage VHR of comparative example 4 is 99.3%, and at 150 DEG C, high temperature places the VHR after 1 hour is 98.6%, is in a ratio of poor result with embodiment 7.Technological adaptability is evaluated, and result is changed to not admissible level compared with embodiment 7.Evaluating the dissolubility under low temperature, result observes precipitation earlier compared with embodiment 7.

(embodiment 8 and embodiment 9)

The liquid-crystal composition (embodiment 8 and embodiment 9) with composition shown below that modulation designs according to the mode with the liquid crystal phase temperature range equal with the compositions of embodiment 7, equal refractive anisotrop value and equal dielectric constant anisotropy value, measures its physics value.The results are shown in following table.

Use the liquid-crystal composition of embodiment 8 and embodiment 9, make VA liquid crystal display cells similarly to Example 1, the deliquescent evaluation result carried out under burn-in, drop impression, Technological adaptability and low temperature is shown in identical table.

[table 10]

Known: the liquid-crystal composition of embodiment 8 has the liquid crystal phase temperature range practical as TV liquid-crystal composition, has the absolute value of big dielectric constant anisotropy, has low viscosity and the suitableeest Δ n.Use the liquid-crystal composition that embodiment 8 is recorded to make VA liquid crystal display cells, by said method, the dissolubility under burn-in, drop impression, Technological adaptability and low temperature is evaluated, the evaluation result that result display is excellent.

Known: the liquid-crystal composition of embodiment 9 has the liquid crystal phase temperature range practical as TV liquid-crystal composition, has the absolute value of big dielectric constant anisotropy, has low viscosity and the suitableeest Δ n.Use the liquid-crystal composition that embodiment 9 is recorded to make VA liquid crystal display cells, by said method, the dissolubility under burn-in, drop impression, Technological adaptability and low temperature is evaluated, the evaluation result that result display is excellent.

(embodiment 10 and embodiment 11)

The liquid-crystal composition (embodiment 10 and embodiment 11) with composition shown below that modulation designs according to the mode with the liquid crystal phase temperature range equal with the compositions of embodiment 7, equal refractive anisotrop value and equal dielectric constant anisotropy value, measures its physics value.The results are shown in following table.

Use the liquid-crystal composition of embodiment 10 and embodiment 11, make VA liquid crystal display cells similarly to Example 1, the deliquescent evaluation result carried out under burn-in, drop impression, Technological adaptability and low temperature is shown in identical table.

[table 11]

Known: the liquid-crystal composition of embodiment 10 has the liquid crystal phase temperature range practical as TV liquid-crystal composition, has the absolute value of big dielectric constant anisotropy, has low viscosity and the suitableeest Δ n.Use the liquid-crystal composition that embodiment 10 is recorded to make VA liquid crystal display cells, by said method, the dissolubility under burn-in, drop impression, Technological adaptability and low temperature is evaluated, the evaluation result that result display is excellent.

Known: the liquid-crystal composition of embodiment 11 has the liquid crystal phase temperature range practical as TV liquid-crystal composition, has the absolute value of big dielectric constant anisotropy, has low viscosity and the suitableeest Δ n.Use the liquid-crystal composition that embodiment 11 is recorded to make VA liquid crystal display cells, by said method, the dissolubility under burn-in, drop impression, Technological adaptability and low temperature is evaluated, the evaluation result that result display is excellent.

(embodiment 12)

The liquid-crystal composition (embodiment 12) with composition shown below that modulation designs according to the mode with the liquid crystal phase temperature range equal with the compositions of embodiment 7, equal refractive anisotrop value and equal dielectric constant anisotropy value, measures its physics value.The results are shown in following table.

Use the liquid-crystal composition of embodiment 12, make VA liquid crystal display cells similarly to Example 1, the deliquescent evaluation result carried out under burn-in, drop impression, Technological adaptability and low temperature is shown in identical table.

[table 12]

Embodiment 12

3-Cy-Cy-V	23.5%
		3-Cy-Cy-V1	10.0%
V-Cy-Cy-V1	10.0%
		1-Ph-Ph-2V1	5.5%
3-Cy-Ph-Ph-2	1.5%
		3-Cy-Ph5-O2	5.0%
3-Ph-Ph5-O2	9.0%
		3-Cy-Cy-Ph5-O2	12.0%
4-Cy-Cy-Ph5-O2	2.5%
		2-Cy-Ph-Ph5-O2	10.0%
3-Cy-Ph-Ph5-O2	11.0%
		T_NI/℃	75.7
Δn	0.110
		n_o	1.486
Δε	-3.0
		ε_⊥	6.4
η/mPa·s	15.3
		γ₁/mPa·s	100
γ₁/Δn²	8.3
		Initial voltage conservation rate/%	99.8
Voltage retention/% after 150 DEG C of 1h	99.1
		Burn-in is evaluated	◎
Drop impression is evaluated	◎
		Technological adaptability is evaluated	○

Known: the liquid-crystal composition of embodiment 12 has the liquid crystal phase temperature range practical as TV liquid-crystal composition, has the absolute value of big dielectric constant anisotropy, has low viscosity and the suitableeest Δ n.Use the liquid-crystal composition that embodiment 12 is recorded to make VA liquid crystal display cells, by said method, the dissolubility under burn-in, drop impression, Technological adaptability and low temperature is evaluated, the evaluation result that result display is excellent.

Symbol description

1 second polarization plates

2 second substrates

3 tft layers or comprise the electrode layer of thin film transistor (TFT)

4 alignment films

5 liquid crystal layers

6 pixel electrodes (common electrode)

7 color filters

8 first substrates

9 first polarization plates

10 liquid crystal display cells

11 gate electrodes

12 anodic oxidation coating

13 gate insulators

14 transparency electrodes (layer)

15 drain electrodes

16 ohmic contact layers

17 semiconductor layers

18 protecting film

19a, 19b source electrode

21 pixel electrodes

22 storage capacitors

23 drain electrodes

24 data wirings

25 gate wirings

26 source electrodes

27 gate electrodes

101 protective layers

Claims

1. a liquid-crystal composition, its dielectric constant anisotropy is negative, it is characterised in that containing the compound represented by a kind or two or more formula (I) and containing the compound represented by a kind or two or more formula (II),

R in formula¹For the alkoxyl of the alkyl of carbon number 1 to 8 or carbon number 2 to 8, R²For the thiazolinyl of carbon number 2 to 8,

In formula, R³And R⁴It is each independently the thiazolinyl of carbon number 2 to 8.

2. liquid-crystal composition according to claim 1, contains a kind or two or more compound selected from the compound group represented by formula (III) further,

In formula, R⁵And R⁶Represent the alkene oxygen base of the alkyl of carbon number 1～8, the thiazolinyl of carbon number 2～8, the alkoxyl of carbon number 1～8 or carbon number 2～8, A independently of one another¹Representing Isosorbide-5-Nitrae-cyclohexylidene, Isosorbide-5-Nitrae-phenylene or Pentamethylene oxide .-2,5-bis-base, at A¹When representing Isosorbide-5-Nitrae-phenylene, the hydrogen atom of more than 1 in this Isosorbide-5-Nitrae-phenylene can be replaced by fluorine atoms.

3. liquid-crystal composition according to claim 1, contains a kind or two or more compound selected from the compound group represented by formula (IV) further,

R in formula⁷And R⁸Represent the alkene oxygen base of the alkyl of carbon number 1～8, the thiazolinyl of carbon number 2～8, the alkoxyl of carbon number 1～8 or carbon number 2～8, A independently of one another²Representing Isosorbide-5-Nitrae-cyclohexylidene, Isosorbide-5-Nitrae-phenylene or Pentamethylene oxide .-2,5-bis-base, at A²When representing Isosorbide-5-Nitrae-phenylene, the hydrogen atom of more than 1 in this Isosorbide-5-Nitrae-phenylene can be replaced by fluorine atoms.

4. liquid-crystal composition according to claim 1, contains a kind or two or more compound selected from the compound group represented by logical formula V further,

In formula, R^aAnd R^bRepresent the alkene oxygen base of the alkyl of carbon number 1～8, the thiazolinyl of carbon number 2～8, the alkoxyl of carbon number 1～8 or carbon number 2～8 independently of one another, the hydrogen atom of more than 1 in this alkyl, thiazolinyl, alkoxyl and/or alkene oxygen base can be replaced by fluorine atoms, methylene in this alkyl, thiazolinyl, alkoxyl and/or alkene oxygen base when oxygen atom discontinuous in conjunction with can be replaced by oxygen atom, when carbonyl discontinuous in conjunction with can by carbonyl substituted

Z¹Represent singly-bound ,-OCH₂-、-OCF₂-、-CH₂O-or-CF₂O-,

N represents 0 or 1,

X¹～X⁶Represent hydrogen atom or fluorine atom, X independently of one another¹～X⁶In at least 1 represent fluorine atom.

5. liquid-crystal composition according to claim 1, it is characterised in that the compound represented by formula (I) select from the compound represented by following formula (I-1)～formula (I-5) a kind or two or more,

Compound represented by formula (II) select from the compound represented by following formula (II-1)～formula (II-3) a kind or two or more,

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

7. the liquid crystal display cells of the liquid-crystal composition used described in claim 1.

8. the liquid crystal display cells of the liquid-crystal composition used described in claim 6.

9. the liquid crystal display of the liquid crystal display cells used described in claim 7 or 8.