CN105733607B - Liquid-crystal composition and use its liquid crystal display element and liquid crystal display - Google Patents

Liquid-crystal composition and use its liquid crystal display element and liquid crystal display Download PDF

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CN105733607B
CN105733607B CN201610183588.8A CN201610183588A CN105733607B CN 105733607 B CN105733607 B CN 105733607B CN 201610183588 A CN201610183588 A CN 201610183588A CN 105733607 B CN105733607 B CN 105733607B
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alkyl
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CN105733607A (en
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岩下芳典
根岸真
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DIC Corp
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Dainippon Ink and Chemicals Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K19/00—Liquid crystal materials
    • C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
    • C09K19/06—Non-steroidal liquid crystal compounds
    • C09K19/08—Non-steroidal liquid crystal compounds containing at least two non-condensed rings
    • C09K19/30—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing saturated or unsaturated non-aromatic rings, e.g. cyclohexane rings
    • C09K19/3001—Cyclohexane rings
    • C09K19/3003—Compounds containing at least two rings in which the different rings are directly linked (covalent bond)
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K19/00—Liquid crystal materials
    • C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
    • C09K19/42—Mixtures of liquid crystal compounds covered by two or more of the preceding groups C09K19/06 - C09K19/40
    • C09K19/44—Mixtures of liquid crystal compounds covered by two or more of the preceding groups C09K19/06 - C09K19/40 containing compounds with benzene rings directly linked
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K19/00—Liquid crystal materials
    • C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
    • C09K19/06—Non-steroidal liquid crystal compounds
    • C09K19/08—Non-steroidal liquid crystal compounds containing at least two non-condensed rings
    • C09K19/30—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing saturated or unsaturated non-aromatic rings, e.g. cyclohexane rings
    • C09K19/3001—Cyclohexane rings
    • C09K19/3003—Compounds containing at least two rings in which the different rings are directly linked (covalent bond)
    • C09K2019/3004—Cy-Cy

Abstract

The problem to be solved by the present invention is that providing a kind of liquid-crystal composition and using its liquid crystal display element and liquid crystal display, the liquid-crystal composition contains the compound represented by formula (I 1) and the compound containing a kind or represented by two or more logical formula (II) and containing the compound represented by general formula (IIIb), the dielectric constant anisotropy of the liquid-crystal composition is negative, in formula (II), R1Indicate the alkyl of carbon atom number 2~5 or the alkoxy of carbon atom number 1~4, R in formula (IIIb)3bAnd R4bEach independently represent the alkenyloxy group of the alkyl of carbon atom number 1~8, the alkenyl of carbon atom number 2~8, the alkoxy of carbon atom number 1~8 or carbon atom number 2~8.

Description

Liquid-crystal composition and use its liquid crystal display element and liquid crystal display
The application be original application the applying date be on March 26th, 2013, application No. is 201380003468.X, denominations of invention For《Liquid-crystal composition and use its liquid crystal display element》Chinese patent application divisional application.
Technical field
The present application is related to a kind of liquid-crystal composition and liquid that the member of formation as liquid crystal display device etc. is useful Crystal display element.
Background technology
Liquid crystal display element is developed to since clock and watch, calculator at meter device, automobile panel, word It is used in reason device, electronic notebook, printer, computer, TV, clock and watch, advertising display panel etc..As liquid crystal display mode, Its representative liquid crystal display mode has TN (twisted-nematic) type, STN (super twisted nematic) type, has used TFT (film crystals Pipe) VA (vertical orientation) type, IPS (plane conversion) type etc..The liquid-crystal composition used in these liquid crystal display elements is wanted It asks and the extraneous factors such as moisture, empty air and heat, light is stablized, in addition, being shown within the scope of temperature as wide as possible centered on by room temperature Liquid crystalline phase, low sticky and driving voltage are low.Further, in order to for each display element be arranged most suitable dielectric constant respectively to Anisotropic (Δ ε) or (Δ n) etc. is most just when liquid-crystal composition is by several to tens of kinds of compounds with refractive anisotrop is made It constitutes.
The liquid-crystal composition that Δ ε is negative is used in vertical orientation escope, is widely used in liquid crystal TV etc..Another party Face requires low voltage drive, high-speed responsive, wide operating temperature range in all type of drive.I.e., it is desirable that Δ ε is just and absolutely To being worth, big, viscosity (η) is small, high nematic phase-isotropic liquid phase transition temperature (Tni).In addition, due to Δ n and cell gap (d) setting of product, that is, Δ n × d, it is therefore desirable to which the Δ n of liquid-crystal composition is adjusted to by range appropriate according to cell gap. In addition to this, in the case where liquid crystal display element is applied to TV etc. due to paying attention to high-speed responsive, therefore it is required that γ1It is small Liquid-crystal composition.
In the past, in order to constitute γ1Small liquid-crystal composition, usually using the compound with dialkyl group bis cyclohexane skeleton (referring to patent document 1).However, although bis cyclohexane based compound is for γ1Reducing effect it is high, but usually vapour pressure it is high and The long alkyl chains short compound tendency is especially notable.In addition, also TniAlso low tendency, therefore actual conditions are：Alkyl Bis cyclohexane based compound mostly adds up to the compound of 7 or more carbon atom number, the change short about side chain lengths using side chain lengths Object is closed not studied adequately.
On the other hand, the purposes of liquid crystal display element expands, to which changing greatly also occur in its application method, manufacturing method, In order to cope with these variations, it is desirable that by the characteristic optimization other than former known basic physical properties value.That is, using liquid-crystal composition Liquid crystal display element VA (vertical orientation) type, IPS (plane conversion) type etc. is widely used, to by its size also be 50 types with On ultra-large type size display element it is practical and use.With the enlargement of substrate size, liquid-crystal composition is to substrate Method for implanting also develops to the injection (ODF that drips from pervious vacuum impregnation：One Drop Fill) method, the injection method that drips The mainstream (with reference to patent document 2) of method for implanting is had become, drop impression causes display quality when liquid-crystal composition is dropped on substrate The problem of reduction, is obviously changed.Further, it is generated and high-speed responsive with the pre-tilt angle of the liquid crystal material in liquid crystal display element For the purpose of, develop PS liquid crystal display elements (polymer stabilized, polymer stabilising), PSA liquid crystal display elements (polymer sustained alignment, polymer maintain to be orientated) (with reference to patent document 3), the problem is at bigger Problem.That is, these display elements have following feature：Monomer is added into liquid-crystal composition, makes the monomer cure in composition. For active matrix liquid-crystal composition, due to maintaining the necessity of high voltage holding ratio, the specified change that can be used Object is closed, the compound with ester bond is used by limitation in compound.The monomer used in PSA liquid crystal display elements is mainly third Olefin(e) acid ester system, usually the compound with ester bond in compound, this compound are usually not used as active matrix liquid-crystalization Close object (with reference to patent document 3).Such foreign matter can cause the generation of drop impression, to the liquid crystal display caused by display is bad The yield rate of element is deteriorated into problem.In addition, when adding the additives such as antioxidant, light absorber into liquid-crystal composition It is that yield rate, which is deteriorated, becomes problem.
Here, drop impression is defined as：In the case where showing black, the trace for the liquid-crystal composition that drips appears showing for white As.
In order to inhibit drop impression, following method is disclosed：Pass through the poly- of the polymerizable compound of mixing in a liquid crystal composition It closes and forms polymeric layer in the liquid crystal layer, to inhibit the drop impression (patent document generated by the relationship with tropism control film 4).However, in the method, there are problems that showing burn-in caused by adding the polymerizable compound in liquid crystal, for Its effect of the inhibition of drop impression is also insufficient, needs to develop a kind of fundamental characteristics being maintained as liquid crystal display element and is difficult to generate The liquid crystal display element of burn-in, drop impression.
Existing technical literature
Patent document 1：Japanese Unexamined Patent Application Publication 2008-505235 bulletins
Patent document 2：Japanese Unexamined Patent Publication 6-235925 bulletins
Patent document 3：Japanese Unexamined Patent Publication 2002-357830 bulletins
Patent document 4：Japanese Unexamined Patent Publication 2006-58755 bulletins
Invention content
Problems to be solved by the invention
The problem to be solved by the present invention is that a kind of liquid-crystal composition is provided and uses its liquid crystal display element, it is described Liquid-crystal composition is suitable for that the nematic phase under dielectric constant anisotropy, viscosity, nematic phase ceiling temperature, low temperature will not be made to stablize Property, γ1Burn-in characteristic Deng various characteristics and display element as liquid crystal display element is deteriorated, it is difficult to generate when manufacturing Drop impression realizes the liquid crystal display element for the liquid crystal material spray volume stablized in ODF processes.
Solution to the problem
The inventors of the present invention in order to solve the above problems, have studied for making liquid crystal display element by dropping method most The composition of suitable various liquid-crystal compositions, and find：It, can by using specific liquid-crystal compounds with specific mixed proportion The drop impression in liquid crystal display element is inhibited to generate, this completes the present application.
The present application provides one kind containing the compound represented by formula (I-1) and contains a kind or two or more general formula (II) dielectric constant anisotropy of the compound represented by is the liquid-crystal composition born and the liquid using the liquid-crystal composition Crystal display element.
[changing 1]
(in formula, R1Indicate the alkyl of carbon atom number 2~5 or the alkoxy of carbon atom number 1~4.)
The effect of invention
The liquid crystal display element of the present invention generates few feature due to excellent with high-speed responsive, burn-in, and has Drop impression caused by it is manufactured generates few feature, therefore useful in the display elements such as liquid crystal TV, display.
Description of the drawings
Fig. 1 is the figure for the composition for schematically showing liquid crystal display element.
Fig. 2 is by the region of the electrode layer 3 comprising thin film transistor (TFT) being formed in the Fig. 1 on substrate being surrounded by II lines The plan view of amplification.
Fig. 3 is the sectional view for cutting off liquid crystal display element shown in FIG. 1 on III-III lines direction in fig. 2.
Fig. 4 is the figure for amplifying the thin film transistor (TFT) in the regions IV in Fig. 3.
Specific implementation mode
As described above, the technique that drop impression generates it is not immediately clear, the impurity still and in liquid-crystal compounds and alignment films The relevant possibility such as interaction, chromatography phenomenon it is high.Impurity in liquid-crystal compounds is deeply by the manufacturing process of compound It influences, even if the carbon atom number of only side chain is different, the manufacturing method of compound is also not necessarily the same.That is, liquid-crystal compounds due to It is manufactured by accurate manufacturing process, therefore its cost is high in synthetic, is strongly required to improve manufacture efficiency.Cause This, in order to use slightly cheap raw material, by the raw material of entirely different type the carbon atom number only one difference of side chain There is also efficient situations for the method manufactured.Therefore, the manufacturing process of liquid crystal substance is sometimes for each substance Difference, even if technique is identical, the different situation of raw material is also most of, as a result：Majority has been mixed into difference in each substance Impurity.But for drop impression, there is the possibility generated the impurity of denier, therefore only pass through the refined of substance It is limited to inhibit the generation of drop impression.
On the other hand, the manufacturing method about common liquid crystal substance has true to each substance after manufacturing process establishment It is set to certain tendency.Even if being developed in analytical technology present, fully to understand which type of has been mixed into is miscellaneous Matter is also not easy, but requires the design that object is combined under the premise of being mixed into the impurity determined for each substance.This Shen Please inventor etc. the impurity of liquid crystal substance and the relationship of drop impression are studied, as a result understand by rule of thumb：Even if in group Close in object includes also to be difficult to the impurity for generating drop impression and the impurity for easy ting produce drop impression.Therefore, in order to inhibit the generation of drop impression, It is critically important using specific compound with specific mixed proportion, especially understand depositing for the composition for being difficult to generate drop impression .Recorded preferred embodiment is found from the above perspective below.
In the liquid-crystal composition of the present application, as the compound represented by first composition, that is, formula (I-1) in liquid crystal Containing ratio in composition is preferably 3 mass % as lower limiting value, preferably 5 mass %, preferably 7 mass %, as the upper limit Value is preferably 30 mass %, preferably 25 mass %, preferably 23 mass %.More specifically, in the feelings for paying attention to answer speed Under condition, 15~30 mass %, further preferably 20~30 mass % are preferably comprised, it is excellent in the case where more paying attention to driving voltage Choosing contains 3~20 mass %, further preferably 5~15 mass %.
As the containing ratio of the compound represented by logical formula (II), 10~40 mass % are preferably comprised, further preferably 15 ~35 mass %, further preferably 10~23 mass %.
The chemical combination represented by formula (II-1)~formula (II-8) that compound represented by logical formula (II) is preferably recorded from below It selects at least one kind of in object group, is more preferably selected from the compound group represented by formula (II-1)~formula (II-5) and formula (II-7) It selects, is further preferably selected from the compound group represented by formula (II-1) and formula (II-3)~formula (II-5), particularly preferably It is selected from the compound group represented by formula (II-1), formula (II-3) and formula (II-4), most preferably selecting type (II-1) institute table The compound shown.
[changing 2]
In addition, the liquid-crystal composition in the present application requires high nematic-isotropic phase transition temperature (Tni) feelings Under condition, preferably selected from the compound group represented by formula (II-5)~formula (II-8) it is at least one kind of, more preferably from formula (II-5) with And it is selected in the compound group represented by formula (II-7), the compound represented by further preferred selecting type (II-5).
In the case of compound in the liquid-crystal composition of the present application represented by selecting type (II-1), contain Rate is preferably 5~30 mass %, more preferably 7~28 mass %, further preferably 10~25 mass %, and particularly preferably 10 ~23 mass %.
The liquid-crystal composition of the present application can be containing a kind or 2 kinds from formula (I-2) as shown below and (I-3) The compound selected in represented compound group.
[changing 3]
In the case of compound represented by selecting type (I-2) and formula (I-3), it is represented to preferably select formula (I-2) Compound.
In the case of compound represented by selecting type (I-2) and formula (I-3), total containing ratio of these compounds is excellent It is selected as 3~20 mass %, more preferably 4~15 mass %, further preferably 5~12 mass %.
The liquid-crystal composition of the present application can further contain the chemical combination represented by the logical formula (III) as shown below The compound selected in object group.
[changing 4]
(R in formula3And R4It is former to each independently represent the alkyl of carbon atom number 1~8, the alkenyl of carbon atom number 2~8, carbon The alkoxy of subnumber 1~8 or the alkenyloxy group of carbon atom number 2~8,1 in the alkyl, alkenyl, alkoxy and/or alkenyloxy group Above hydrogen atom can be replaced by fluorine atoms, and the methylene in the alkyl, alkenyl, alkoxy and/or alkenyloxy group is in oxygen atom It can be replaced by oxygen atom in the case of discontinuous combination, can be replaced by carbonyl in the case where carbonyl discontinuously combines, A1 1 or 4 cyclohexylidene, Isosorbide-5-Nitrae-phenylene or oxinane -2,5- diyl are indicated, in A1In the case of indicating Isosorbide-5-Nitrae-phenylene, 1 or more hydrogen atom in the 1,4- phenylenes can be replaced by fluorine atoms.)
In compound represented by logical formula (III), R3And R4Each independently represent carbon atom number 1~8 alkyl, The alkenyloxy group of the alkenyl of carbon atom number 2~8, the alkoxy of carbon atom number 1~8 or carbon atom number 2~8, R3Preferably carbon is former The alkyl of subnumber 1~8 or the alkenyl of carbon atom number 2~8, the more preferably alkyl of carbon atom number 1~8, further preferably The alkyl of carbon atom number 2~5, R4Preferably the alkyl of carbon atom number 1~8, carbon atom number 1~8 alkoxy, more preferably carbon The alkoxy of atomicity 1~8, the further preferably alkoxy of carbon atom number 2~5.
In compound represented by logical formula (III), A1Indicate 1,4- cyclohexylidenes, 1,4- phenylenes or tetrahydrochysene pyrrole It mutters -2,5- diyls, preferably 1 or 4 cyclohexylidene or Isosorbide-5-Nitrae-phenylene, in A1Indicate Isosorbide-5-Nitrae-phenylene in the case of, this 1, 1 or more hydrogen atom in 4- phenylenes can be replaced by fluorine atoms, and preferably 3 hydrogen atoms below are replaced by fluorine atoms, More preferable 2 hydrogen atoms below are replaced by fluorine atoms, and further preferred 1 hydrogen atom is replaced by fluorine atoms, particularly preferably It is unsubstituted.
In compound represented by logical formula (III), in A1In the case of indicating 1 or 4 cyclohexylidene, by what is recorded below General formula (IIIa) expression,
[changing 5]
(R in formula3aAnd R4aIt indicates respectively and the R in logical formula (III)3And R4The identical meaning.)
In the compound group, preferably selected from the compound group represented by formula (IIIa-1)~formula (IIIa-8), more Compound represented by preferred formula (IIIa-1)~formula (IIIa-4), further preferred formula (IIIa-1), formula (IIIa-3) and Compound represented by formula (IIIa-4), the compound represented by particularly preferred formula (IIIa-1) and formula (IIIa-4).
[changing 6]
Compound represented by general formula (IIIa) preferably comprises 3~30 mass %, further preferably 3~28 mass %, into One step preferably comprises 3~25 mass %, particularly preferably contains 3~23 mass %, most preferably 3~20 mass %.
In the case where using the compound represented by 4 kinds of formula above (IIIa), formula (IIIa-1) is preferably applied in combination To the compound represented by formula (IIIa-4), the content of the compound represented by formula (IIIa-1) to formula (IIIa-4) is preferably logical 50 mass % or more in compound represented by formula (IIIa), more preferably 70 mass % or more, further preferably 80 matter Measure % or more, particularly preferably 90 mass % or more.
In the case where using the compound represented by 3 kinds of general formulas (IIIa), formula (IIIa-1), formula is preferably applied in combination (IIIa-2) and the compound represented by formula (IIIa-4), formula (IIIa-1), formula (IIIa-2) and formula (IIIa-4) institute table The content for the compound shown is preferably the 50 mass % or more in the compound represented by general formula (IIIa), more preferably 70 matter Measure % or more, further preferably 80 mass % or more, particularly preferably 90 mass % or more.
Using compound represented by 2 kinds of general formulas (IIIa), be preferably applied in combination formula (IIIa-1) and The content of compound represented by compound represented by formula (IIIa-4), formula (IIIa-1) and formula (IIIa-4) is preferably logical 50 mass % or more in compound represented by formula (IIIa), more preferably 70 mass % or more, further preferably 80 matter Measure % or more, particularly preferably 90 mass % or more.
In compound represented by logical formula (III), in A1It is logical by what is recorded below in the case of indicating Isosorbide-5-Nitrae-phenylene Formula (IIIb) expression,
[changing 7]
(R in formula3bAnd R4bIt indicates respectively and the R in logical formula (III)3And R4The identical meaning)
In the compound group, the compound represented by preferred formula (IIIb-1)~formula (IIIb-8), more preferable formula (IIIb-1) compound represented by~formula (IIIb-4), represented by further preferred formula (IIIb-1) and formula (IIIb-3) Compound, the compound represented by particularly preferred formula (IIIb-1).
[changing 8]
Compound represented by general formula (IIIb) preferably comprises 1~20 mass %, further preferably 2~15 mass %, into One step preferably comprises 3~18 mass %, particularly preferably contains 5~15 mass %.
In the case where using the compound represented by 4 kinds of formula above (IIIb), formula (IIIb-1) is preferably applied in combination The content of compound represented by~formula (IIIb-4), the compound represented by formula (IIIb-1)~formula (IIIb-4) is preferably logical 50 mass % or more in compound represented by formula (IIIb), more preferably 70 mass % or more, further preferably 80 matter Measure % or more, particularly preferably 90 mass % or more.
In the case where using the compound represented by 3 kinds of general formulas (IIIb), formula (IIIb-1)~formula is preferably applied in combination (IIIb-3) content of the compound represented by, the compound represented by formula (IIIb-1)~formula (IIIb-3) is preferably general formula (IIIb) the 50 mass % or more in the compound represented by, more preferably 70 mass % or more, further preferably 80 matter Measure % or more, particularly preferably 90 mass % or more.
Using compound represented by 2 kinds of general formulas (IIIb), be preferably applied in combination formula (IIIb-1) and The content of compound represented by compound represented by formula (IIIb-3), formula (IIIb-1) and formula (IIIb-3) is preferably logical 50 mass % or more in compound represented by formula (IIIb), more preferably 70 mass % or more, further preferably 80 matter Measure % or more, particularly preferably 90 mass % or more.
The liquid-crystal composition of the present application can further contain the chemical combination represented by the logical formula (IV) as shown below The compound selected in object group.
[changing 9]
(R in formula5And R6It is former to each independently represent the alkyl of carbon atom number 1~8, the alkenyl of carbon atom number 2~8, carbon The alkoxy of subnumber 1~8 or the alkenyloxy group of carbon atom number 2~8,1 in the alkyl, alkenyl, alkoxy and/or alkenyloxy group Above hydrogen atom can be replaced by fluorine atoms, and the methylene in the alkyl, alkenyl, alkoxy and/or alkenyloxy group is in oxygen atom It can be replaced by oxygen atom in the case of discontinuous combination, can be replaced by carbonyl in the case where carbonyl discontinuously combines, A2 1 or 4 cyclohexylidene, Isosorbide-5-Nitrae-phenylene or oxinane -2,5- diyl are indicated, in A2In the case of indicating Isosorbide-5-Nitrae-phenylene, 1 or more hydrogen atom in the 1,4- phenylenes can be replaced by fluorine atoms.)
In compound represented by logical formula (IV), R5And R6Each independently represent alkyl, the carbon of carbon atom number 1~8 The alkenyloxy group of the alkenyl of atomicity 2~8, the alkoxy of carbon atom number 1~8 or carbon atom number 2~8, R5Preferably carbon atom The alkyl of number 1~8 or the alkenyl of carbon atom number 2~8, the more preferably alkyl of carbon atom number 1~8, further preferably carbon The alkyl of atomicity 2~5, R6Preferably the alkyl of carbon atom number 1~8, carbon atom number 1~8 alkoxy, more preferably carbon is former The alkoxy of subnumber 1~8, the further preferably alkoxy of carbon atom number 2~5.
In compound represented by logical formula (IV), A2Indicate 1,4- cyclohexylidenes, 1,4- phenylenes or oxinane- 2,5- diyls, preferably 1 or 4 cyclohexylidene or Isosorbide-5-Nitrae-phenylene, in A2In the case of indicating Isosorbide-5-Nitrae-phenylene, the Isosorbide-5-Nitrae-Asia 1 or more hydrogen atom in phenyl can be replaced by fluorine atoms, and preferably 3 hydrogen atoms below are replaced by fluorine atoms, more excellent 2 hydrogen atoms below are selected to be replaced by fluorine atoms, further preferred 1 hydrogen atom is replaced by fluorine atoms, particularly preferably without taking Generation.
In compound represented by logical formula (IV), in A2In the case of indicating 1 or 4 cyclohexylidene, by what is recorded below General formula (IVa) expression,
[changing 10]
(R in formula5aAnd R6aIt indicates respectively and the R in logical formula (IV)5And R6The identical meaning.)
In the compound group, the compound represented by formula (IVa-1)~formula (IVa-6) preferably recorded below is more excellent Select the compound represented by formula (IVa-1)~formula (IVa-4), the change represented by further preferred formula (IVa-1)~formula (IVa-3) Close object, the compound represented by particularly preferred formula (IVa-1) and formula (IVa-3).
[changing 11]
In addition, the liquid-crystal composition in the present application requires high nematic-isotropic phase transition temperature (Tni) feelings Under condition, preferably selected from the compound group represented by formula (IVa-5) and formula (IVa-6) at least one kind of.
In the case where using the compound represented by 4 kinds of formula above (IVa), formula (IVa-1) is preferably applied in combination extremely The content of compound represented by formula (IVa-4), the compound represented by formula (IVa-1) to formula (IVa-4) is preferably general formula (IVa) the 50 mass % or more in the compound represented by, more preferably 70 mass % or more, further preferably 80 mass % More than, particularly preferably 90 mass % or more.
In the case where using the compound represented by 3 kinds of general formulas (IVa), formula (IVa-1) is preferably applied in combination to formula (IVa-3) content of the compound represented by, the compound represented by formula (IVa-1) to formula (IVa-3) is preferably general formula (IVa) 50 mass % or more in represented compound, more preferably 70 mass % or more, further preferably 80 mass % or more, Particularly preferably 90 mass % or more.
In the case where using the compound represented by 2 kinds of general formulas (IVa), formula (IVa-1) and formula is preferably applied in combination (IVa-3) content of the compound represented by the compound represented by, formula (IVa-1) and formula (IVa-3) is preferably general formula (IVa) the 50 mass % or more in the compound represented by, more preferably 70 mass % or more, further preferably 80 mass % More than, particularly preferably 90 mass % or more.
In compound represented by logical formula (IV), in A2It is logical by what is recorded below in the case of indicating Isosorbide-5-Nitrae-phenylene Formula (IVb) expression,
[changing 12]
(R in formula5bAnd R6bIt indicates respectively and the R in logical formula (IV)5And R6The identical meaning)
In the compound group, the compound represented by formula (IVb-1)~(IVb-4) preferably recorded below, more preferably Compound represented by formula (IVb-1) or formula (IVb-2).
[changing 13]
Using compound represented by two or more general formula (IVb), be preferably applied in combination formula (IVb-1) with And the compound represented by formula (IVb-2), the content of the compound represented by formula (IVb-1) and formula (IVb-2) are preferably logical 50 mass % or more in compound represented by formula (IVb), more preferably 70 mass % or more, further preferably 80 matter Measure % or more, particularly preferably 90 mass % or more.
The liquid-crystal composition of the present application can further contain the compound represented by the logical formula (V) as shown below The compound selected in group.
[changing 14]
(R in formula7And R8It is former to each independently represent the alkyl of carbon atom number 1~8, the alkenyl of carbon atom number 2~8, carbon The alkoxy of subnumber 1~8 or the alkenyloxy group of carbon atom number 2~8,1 in the alkyl, alkenyl, alkoxy and/or alkenyloxy group Above hydrogen atom can be replaced by fluorine atoms, and the methylene in the alkyl, alkenyl, alkoxy and/or alkenyloxy group is in oxygen atom It can be replaced by oxygen atom in the case of discontinuous combination, can be replaced by carbonyl in the case where carbonyl discontinuously combines,
A31 or 4 cyclohexylidene, Isosorbide-5-Nitrae-phenylene or oxinane -2,5- diyl are indicated, in A3Indicate 1,4- phenylenes In the case of, 1 or more hydrogen atom in the Isosorbide-5-Nitrae-phenylene can be replaced by fluorine atoms,
Z1Indicate singly-bound ,-CH2CH2-、-OCH2-、-OCF2-、-CH2O- or-CF2O-,
N indicates 0 or 1,
X1~X6Each independently represent hydrogen atom or fluorine atom, X1~X6In at least one indicate fluorine atom.)
Compound represented by logical formula (V), the chemical combination represented by general formula (V-1)~(V-16) specifically preferably recorded below Object, more preferable formula (V-1), formula (V-3)~formula (V-9) and formula (V-12)~formula (V-15), further preferred formula (V-1), formula (V-3), formula (V-5), formula (V-6), formula (V-9), formula (V-12) and formula (V-15), particularly preferred formula (V-1), formula (V-5), formula (V-6), most preferably formula (V-5).
[changing 15]
(in formula, R7And R8It indicates and the R in logical formula (V)7And R8The identical meaning.)
, it is preferable to use compound represented by formula (V-5), formula using the compound represented by formula (V) is led to (V-5) content of the compound represented by is preferably the 50 mass % or more in the compound represented by logical formula (V), more preferably 70 mass % or more, further preferably 80 mass % or more.
R in logical formula (V)7And R8Each independently represent the alkyl of carbon atom number 1~8, the alkene of carbon atom number 2~8 The alkenyloxy group of base, the alkoxy of carbon atom number 1~8 or carbon atom number 2~8, preferably indicate carbon atom number 1~8 alkyl or The alkenyl of person's carbon atom number 2~8 more preferably indicates the alkyl of carbon atom number 2~5 or the alkenyl of carbon atom number 2~5, into one The preferred alkyl for indicating carbon atom number 2~5 of step, preferably straight chain, in R7And R8In the case of being alkyl simultaneously, preferably respectively Carbon atom number it is different.
It is described in further detail, preferably R7Indicate propyl R8Indicate the compound or R of ethyl7Indicate butyl R8Indicate ethyl Compound.
The liquid-crystal composition of the present application can also further contain represented from general formula (VI-a) to general formula (VI-e) Compound group in the compound that selects.
[changing 16]
(in formula, R91~R9aEach independently represent the alkyl of carbon atom number 1 to 10, the alkoxy of carbon atom number 1 to 10 Or the alkenyl of carbon atom number 2 to 10, but R in general formula (VI-a)91Indicate alkyl, the R of carbon atom number 392Indicate carbon atom number 2 Alkenyl compound, R91Indicate alkyl, the R of carbon atom number 392Indicate the compound of 1- acrylic, R91Indicate carbon atom number 2 Alkyl, R92Indicate the compound of 1- acrylic, R91Indicate alkyl, the R of carbon atom number 392Indicate the alkyl of carbon atom number 2~5 Compound and R91Indicate alkyl, the R of carbon atom number 392Except the compound for indicating the alkoxy of carbon atom number 1~4.)
In the case of the compound selected in containing the compound group represented by from general formula (VI-a) to general formula (VI-e), 1 kind~10 kinds are preferably comprised, particularly preferably contains a kind~8 kinds, particularly preferably contains a kind~5 kinds, it is also preferred that containing two or more Compound, further preferably contain a kind of compound, content in this case is preferably 1~20 mass %, further preferably 1 ~15 mass %, particularly preferably 2~10 mass %.
It is preferred that R91To R9aEach independently represent the alkyl of carbon atom number 1 to 10, the alkenyl of carbon atom number 2 to 10 or The alkoxy of carbon atom number 2 to 10 more preferably indicates that the alkyl of carbon atom number 1 to 5, the alkenyl of carbon atom number 2 to 5 or carbon are former The alkoxy of subnumber 2 to 5, in the case where indicating alkenyl, the structure represented by formula (i)~formula (iv) preferably recorded below,
[changing 17]
It (in formula, is combined in the right end of ring structure.)
In the case where the liquid-crystal composition of the present application contains reactive monomer, preferred formula (ii) and formula (iv) institute The structure of expression, the structure represented by more preferable formula (ii).
In addition, R91And R92It can be the same or different, but preferably indicate different substituent groups.
From the aspects of, compound represented by formula (VI-a) to formula (VI-e) it is more specific preferably below the change recorded Close object.
[changing 18]
[changing 19]
[changing 20]
[changing 21]
[changing 22]
[changing 23]
In these compounds, preferred formula (VI-a1), formula (VI-a2), formula (VI-b2), formula (VI-b6), formula (VI-c2), Compound represented by formula (II-c4), formula (VI-c5), formula (VI-d1), formula (VI-d2) and formula (VI-e2).
Compound represented by logical formula (VI) and the compound represented by formula (I-1), (I-2), (I-3) and logical formula (II) It is common in terms of dielectric constant anisotropy substantially 0, but about formula (I-1), (I-2), (I-3) and logical formula (II) The ratio of compound represented by represented compound and logical formula (VI), formula (I-1) preferably in a liquid crystal composition, (I- 2), the compound represented by (I-3) and logical formula (II) in total content of the compound represented by logical formula (VI), formula (I- 1), the content of the compound represented by (I-2), (I-3) and logical formula (II) is 60~85 mass %, more preferably 60~90 matter Measure %, particularly preferably 60~95 mass %.In addition, formula (I-1), (I-2), (I-3) and logical formula (II) and logical formula (VI) Total content preferably comprises 15~70 mass %, further preferably 20~65 mass %, more in the content of composition entirety 25~60 mass %, further preferably 30~55 mass % are preferably comprised, 35~50 mass % are particularly preferably contained.
The 1,4- cyclohexyl of the application is preferably anti-form-1,4- cyclohexyl.
The liquid-crystal composition of the present invention, can using the compound represented by formula (I-1) and logical formula (II) as essential component Further to contain formula (I-2), formula (I-3), logical formula (III), logical formula (IV), logical formula (V) and general formula (VIa)~general formula (VI- E) compound represented by.The formula (I-1) that contains in a liquid crystal composition, formula (I-2), (I-3), logical formula (II), general formula (III), the total content for leading to the compound represented by formula (IV), logical formula (V) and general formula (VI-a)~general formula (VI-e), as Lower limiting value is preferably 60 mass %, preferably 65 mass %, preferably 70 mass %, preferably 75 mass %, preferably 80 matter Measure %, preferably 85 mass %, preferably 90 mass %, preferably 92 mass %, preferably 95 mass %, preferably 98 matter % is measured, preferably 99 mass % are preferably 100 mass % as upper limit value, preferably 99.5 mass %.
More specifically, total content of the compound represented by formula (I-1) and logical formula (II) is preferably 20~50 matter Measure %, more preferably 25~45 mass %, further preferably 28~42 mass %.
Total content of compound represented by formula (I-1) and formula (II-1) is preferably 10~50 mass %, more preferably For 15~45 mass %, further preferably 18~42 mass %.
In the case where selecting to lead to the compound represented by formula (III), formula (I-1), formula (II-1) and logical formula (III) institute Total content of the compound of expression is preferably 10~50 mass %, more preferably 15~45 mass %, and further preferably 18 ~42 mass %.
In the case where selecting to lead to the compound represented by formula (IV), formula (I-1), formula (II-1) and logical formula (IV) institute table The total content for the compound shown is preferably 50~80 mass %, more preferably 45~75 mass %, further preferably 46~ 73 mass %.
In the case where selecting to lead to the compound represented by formula (V), represented by formula (I-1), formula (II-1) and logical formula (V) Total content of compound be preferably 20~65 mass %, more preferably 25~60 mass %, further preferably 30~55 Quality %.
In the case where selecting to lead to the compound represented by formula (III) and logical formula (IV), formula (I-1), is led at formula (II-1) Total content of compound represented by formula (III) and logical formula (IV) is preferably 55~99 mass %, and more preferably 60~95 Quality %, further preferably 65~90 mass %.
In the case where selecting to lead to the compound represented by formula (III) and logical formula (V), formula (I-1), is led at formula (II-1) Total content of compound represented by formula (III) and logical formula (V) is preferably 35~80 mass %, more preferably 40~75 matter Measure %, further preferably 45~70 mass %.
In the case where selecting to lead to the compound represented by formula (IV) and logical formula (V), formula (I-1), formula (II-1), general formula (IV) total content of the compound and represented by logical formula (V) is preferably 50~95 mass %, more preferably 55~90 matter Measure %, further preferably 58~86 mass %.
In the case where selecting to lead to the compound represented by formula (III), logical formula (IV) and logical formula (V), formula (I-1), formula (II-1), the total content for leading to the compound represented by formula (III), logical formula (IV) and logical formula (V) is preferably 65~100 matter Measure %, more preferably 70~100 mass %, further preferably 75~100 mass %.
The liquid-crystal composition of the present application be preferably free of in the molecule have the oxygen atoms such as peroxide (- CO-OO-) structure that The compound of this structure combined.
In the case where paying attention to the reliability and long-time stability of liquid-crystal composition, preferably make the compound with carbonyl Content relative to above-mentioned composition gross mass be 5 mass % hereinafter, more preferably 3 mass % are hereinafter, further preferably 1 Quality % is hereinafter, be most preferably substantially free of.
In the case of the stability for paying attention to obtaining by UV irradiations, preferably make the compound for having carried out chlorine atom substitution Content relative to above-mentioned composition gross mass be 15 mass % hereinafter, more preferably 10 mass % are hereinafter, further preferably 5 Quality % is hereinafter, be most preferably substantially free of.
It is preferred that keeping the content of the compound of all 6 membered rings of the ring structure of intramolecular more, preferably make the ring structure of intramolecular The content of the compound of all 6 membered rings is 80 mass % or more, more preferably 90 matter relative to the gross mass of above-mentioned composition % or more, further preferably 95 mass % or more are measured, most preferably substantially only by all 6 membered rings of the ring structure of intramolecular Compound constitutes liquid-crystal composition.
In order to inhibit to be deteriorated caused by the oxidation by liquid-crystal composition, preferably make have cyclohexadienylidene as ring structure The content of compound is few, and the content of the compound with cyclohexadienylidene is preferably made relative to the gross mass of above-mentioned composition to be 10 Quality % is hereinafter, more preferably 5 mass % are hereinafter, be further preferably substantially free of.
In improvement and the T for paying attention to viscosityniImprovement in the case of, preferably allow in the molecule have hydrogen atom by halogen The content of the compound of 2- methylbenzenes-Isosorbide-5-Nitrae-diyl of element substitution is few, preferably makes above-mentioned in the molecule with 2- methylbenzenes-Isosorbide-5-Nitrae- The content of the compound of diyl relative to above-mentioned composition gross mass be 10 mass % hereinafter, more preferably 5 mass % hereinafter, Further preferably it is substantially free of.
In the case that the compound contained in the composition of the first embodiment of the present invention has alkenyl as side chain, When above-mentioned alkenyl is combined with hexamethylene, the carbon atom number of the alkenyl is preferably 2~5, when above-mentioned alkenyl is combined with benzene, the alkene The carbon atom number of base is preferably 4~5, and the unsaturated bond of preferably above-mentioned alkenyl is not bound directly with benzene.
The value of the dielectric constant anisotropy Δ ε of the liquid-crystal composition of the present application preferably at 25 DEG C for -2.0 to - 6.0, more preferably -2.5 to -5.0, particularly preferably -2.5 to -4.0, are described in further detail, the case where paying attention to answer speed Under, preferably -2.5~-3.4, in the case where paying attention to driving voltage, preferably -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 preferably at 25 DEG C, more Preferably 0.09 to 0.12.It is described in further detail, in the case where coping with thin cell gap, preferably 0.10 to 0.12, it is answering In the case of thick cell gap, preferably 0.08 to 0.10.
Rotary viscosity (the γ of the liquid-crystal composition of the present invention1) it is preferably 150 hereinafter, more preferably 130 hereinafter, especially excellent It is selected as 120 or less.
In the liquid-crystal composition of the present invention, shown preferably as the Z of rotary viscosity and the function of refractive anisotrop Particular value.
[number 1]
(the Δ n) of Z=γ 1/2
(in formula, γ1Indicate that rotary viscosity, Δ n indicate refractive anisotrop.)
Z is preferably 13000 hereinafter, more preferably 12000 hereinafter, particularly preferably 11000 or less.
It is necessary to have 10 for active matrix display element for the liquid-crystal composition of the present invention12(Ω m) with On resistivity, preferably 1013More than (Ω m), more preferably 1014More than (Ω m).
The liquid-crystal composition of the present invention can also contain common nematic liquid other than above compound according to purposes Crystalline substance, smectic liquid crystal, cholesteryl liquid crystal, antioxidant, ultra-violet absorber, polymerizable monomer etc. are requiring liquid-crystal composition In the case of chemical stability, preferably its intramolecular do not have chlorine atom, require liquid-crystal composition to light such as ultraviolet lights In the case of stability, preferably do not have with naphthalene nucleus etc. for the conjugate length length of representative and in ultraviolet region presence in its intramolecular The condensed ring etc. of absorption peak.
As polymerizable monomer, two functional monomers represented by preferred formula (VII).
[changing 24]
(in formula, X7And X8Each independently represent hydrogen atom or methyl, Sp1And Sp2Each independently represent list Key, the alkylidene of carbon atom number 1~8 or-O- (CH2)s(in formula, s indicates that 2 to 7 integer, oxygen atom are incorporated in aromatic rings On.),
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 Y2Each independently represent fluorine atom or hydrogen atom.) ,-C ≡ C- or singly-bound,
B indicates Isosorbide-5-Nitrae-phenylene, anti-form-1,4- cyclohexylidenes or singly-bound, arbitrary in whole Isosorbide-5-Nitrae-phenylenes in formula Hydrogen atom can be replaced by fluorine atoms.)
It is preferred that X7And X8It indicates the diacrylate derivative of hydrogen atom, all have the dimethylacrylate of methyl Any of derivative a, it is also preferred that side indicates that hydrogen atom another party indicates the compound of methyl.About these compounds Polymerization speed, diacrylate derivative is most fast, and dimethylacrylate derivative is slow, asymmetric compound among them, Preferred mode can be used according to its purposes.In PSA display elements, particularly preferred dimethylacrylate derivative.
Sp1And Sp2Each independently represent singly-bound, the alkylidene of carbon atom number 1~8 or-O- (CH2)s, but In PSA display elements, a preferably at least side is singly-bound, preferably indicates that the compound of singly-bound or a side are singly-bound another party's table Show the alkylidene or-O- (CH of carbon atom number 1~82)sMode.In such a situation it is preferred to 1~4 alkyl, s preferably 1 ~4.
Z1It is preferred that-OCH2-、-CH2O-、-COO-、-OCO-、-CF2O-、-OCF2-、-CH2CH2-、-CF2CF2Or singly-bound, More preferably-COO- ,-OCO- or singly-bound, particularly preferred singly-bound.
B indicates 1,4- phenylenes, the anti-form-1 that arbitrary hydrogen atom can be replaced by fluorine atoms, 4- cyclohexylidenes or list Key, preferably Isosorbide-5-Nitrae-phenylene or singly-bound.In the case of the ring structure other than B indicates singly-bound, Z2It is also preferred that other than singly-bound Linking group, in the case where B is singly-bound, Z1Preferably singly-bound.
From the aspects of, in logical formula (VII), Sp1And Sp2Between the specific knot preferably recorded below of ring structure Structure.
In the case that B indicates that singly-bound, ring structure are formed by two rings in logical formula (VII), formula below is preferably indicated (VIIa-1) to formula (VIIa-5), more preferable expression (VIIa-1) to formula (VIIa-3), particularly preferred expression (VIIa-1).
[changing 25]
(in formula, both ends and Sp1Or Sp2In conjunction with.)
The polymerizable compound for including these skeletons, the orientation restraint after polymerization are most suitable for PSA type liquid crystal display element, Good state of orientation can be obtained, therefore show uneven suppressed or do not generate completely.
By upper, as polymerizable monomer, particularly preferred general formula (VII-1)~general formula (VII-4), wherein most preferably general formula (VII-2)。
[changing 26]
(in formula, Sp2Indicate the alkylidene of carbon atom number 2 to 5.)
In the case of adding monomer in the liquid-crystal composition of the present invention, even if in the case where polymerization initiator is not present Also it is polymerize, but polymerization initiator can also be contained in order to promote to polymerize.As polymerization initiator, benzoin ether can be enumerated Class, benzophenone, acetophenones, benzil ketals class, acylphosphine oxide class etc..In addition, in order to improve storage stability, it can To add stabilizer.As the stabilizer that can be used, such as hydroquinones, quinhydrones monoalkyl ethers, tert-butyl o benzene can be enumerated Diphenols, pyrogallol class, benzenethiol class, nitro compound species, beta-naphthylamine class, betanaphthol class, nitroso compound etc..
The liquid-crystal composition containing polymerizable compound of the present invention is useful in liquid crystal display element, is driven in active matrix It employs particularly useful in liquid crystal display element, can be used in PSA patterns, PSVA patterns, VA patterns, IPS patterns or ecb mode Use liquid crystal display element.
The liquid-crystal composition containing polymerizable compound of the present invention can be used for making by ultraviolet light irradiation poly- contained by it The compound polymerization of conjunction property controls the liquid through light quantity of light using the birefringence of liquid-crystal composition to assign liquid crystal aligning energy Crystal display element.As liquid crystal display element, in AM-LCD (active matrix liquid crystal display device), TN (nematic liquid crystal display members Part), STN-LCD (Supertwist Nematic Liquid Crystal Display element), OCB-LCD and IPS-LCD (plane switching liquid crystal display element) In it is useful, it is particularly useful in AM-LCD, can be used for transmission-type or the liquid crystal display element of reflection-type.
In addition, with reference to the content of aftermentioned liquid crystal display element and Fig. 1~4, liquid crystal list used in liquid crystal display element 2 plate bases 2,8 of member can use glass or the plastics transparent material with flexibility in this way, on the other hand can also be silicon Etc. opaque material.Transparent substrate 2,8 with transparent electrode (layer) 6,14, such as can be by by indium tin oxide (ITO) it sputters on the transparent substrates such as glass plate 2,8 and obtains.
Make it is above-mentioned be formed with transparent electrode (layer), TFT substrate 2,8 by transparent electrode (layer) 6,14 be inside in a manner of phase It is right.At this moment, the interval (referring to Fig.1~4) of substrate can be adjusted by spacer (not shown).At this moment, it will preferably obtain The thickness of light modulation layer is adjusted to 1~100 μm.It further preferably 1.5 to 10 μm, using polarization plates, preferably adjusts The product of the refractive anisotrop Δ n and element thickness d of whole liquid crystal keep contrast maximum.In addition, there is two panels polarization plates 1,9 In the case of, it can also adjust the polarization axle of each polarization plates and be good (referring to Fig.1~4) by visual angle, setting contrast.Into one Step can also use the phase difference film for expanding visual angle.As spacer, such as glass particle, plastic pellet, oxygen can be enumerated Change aluminum particulate, photo-induced corrosion resistant material etc..Later, by epoxy heat-curable composition etc. in the form of being provided with liquid crystal injecting port Sealant silk-screen printing on the substrate, which is bonded each other, heats and makes sealant heat cure.
To being received as described above by the liquid-crystal composition for accommodating liquid-crystal composition for making 2 plate bases relatively be bonded and being formed Hold the method that space imports the liquid-crystal composition containing polymerizable monomer, common vacuum impregnation or ODF methods can be used Deng, although not generating drop impression in vacuum impregnation, there is the problem of injection trace residual, in the present application, Ke Yigeng It is suitably used for the display element manufactured using ODF methods.
As the method for making polymerizable compound polymerize, due to the good orientation characteristic of liquid crystal in order to obtain, it is hoped that there will be suitable The polymerization speed of degree, therefore preferably either and ultraviolet light or electric wire isoreactivity energy are used or in turn irradiate by single The method that ray is polymerize.In the case of using ultraviolet, polarized light source can be used, non-polarized light can also be used Source.In addition, the case where being polymerize in the state that the liquid-crystal composition containing polymerizable compound is clamped between 2 plate bases Under, it is necessary to make the substrate of at least irradiation surface side that there is the transparency appropriate relative to active energy beam.Further, it is possible to use such as Lower method：Light only made using mask when irradiating it is specific it is partially polymerized after, change the conditions such as electric field, magnetic field or temperature, to So that the state of orientation of unpolymerized part is changed, further irradiates active energy beam and polymerize.It is especially ultraviolet in progress When line exposing, preferably ultraviolet light exposure is carried out while applying AC field to the liquid crystal combination beyond the region of objective existence containing polymerizable compound Light.The AC field applied outside is preferably the exchange of frequency 10Hz to 10kHz, more preferably frequency 60Hz to 10kHz, and voltage relies on It is selected in the desired pre-tilt angle of liquid crystal display element.That is, liquid crystal display member can be controlled by the voltage applied outside The pre-tilt angle of part.In the liquid crystal display element of MVA patterns, from the viewpoint of orientation stability and contrast, preferably will Pre-tilt angle control is 80 degree to 89.9 degree.
Temperature when irradiation is preferably within the temperature range of keeping the mesomorphic state of the liquid-crystal composition of the present invention.It is preferred that The temperature of near room temperature is typically polymerize at a temperature of 15~35 DEG C.As the lamp for generating ultraviolet light, can use Metal halide lamp, high-pressure mercury-vapor lamp, extra-high-pressure mercury vapour lamp etc..In addition, the wavelength as the ultraviolet light irradiated, preferably irradiates Not in the ultraviolet light of the wavelength region of the absorbing wavelength region of liquid-crystal composition, ultraviolet blocking-up preferably as needed and use. The intensity of the ultraviolet light irradiated is preferably 0.1mW/cm2~100W/cm2, more preferably 2mW/cm2~50W/cm2.It is irradiated The energy of ultraviolet light can suitably adjust, but preferably 10mJ/cm2To 500J/cm2, more preferably 100mJ/cm2To 200J/ cm2.When irradiating ultraviolet light, thus it is possible to vary intensity.The time of irradiation ultraviolet light suitably selects according to the uitraviolet intensity of irradiation, excellent It is selected as 10 seconds to 3600 seconds, more preferably 10 seconds to 600 seconds.
The second invention of the present invention is the liquid crystal display element using the liquid-crystal composition of the present invention.Fig. 1 is schematically Indicate the figure of the composition of liquid crystal display element.In addition, in Fig. 1, each integral part is separated record for convenience of explanation.Figure 2 be (or the also referred to as tft layer 3 of electrode layer 3 comprising thin film transistor (TFT) that will be formed in the Fig. 1 on substrate.) The plan view for the region amplification being surrounded by II lines.Fig. 3 is on III-III lines direction in the Fig. 2 by liquid crystal shown in FIG. 1 Show the sectional view of element cut-out.Fig. 4 is the figure for amplifying the thin film transistor (TFT) in the regions IV in the Fig. 3.Referring to Fig. 1~4 To illustrate the liquid crystal display element of the present invention.
The composition of the liquid crystal display element 10 of the present invention has following feature：It is with being made of transparent conductive material (or the also referred to as common electrode 6 of transparent electrode (layer) 6.) first substrate 8, comprising being formed with by transparent conductive material structure At pixel electrode and control second of the tft layer 3 of the thin film transistor (TFT) of pixel electrodes possessed by each pixel Substrate 2 and the liquid-crystal composition (or liquid crystal layer 5) being clamped between above-mentioned first substrate 8 and second substrate 2, and the liquid Orientation of the liquid crystal molecule in no applied voltage in crystal composite is substantially vertical liquid crystal display relative to aforesaid substrate 2,8 Element, and used the liquid-crystal composition of aforementioned present invention as the liquid-crystal composition.In addition, as shown in figures 1 and 3, on Stating second substrate 2 and above-mentioned first substrate 8 can be clamped between a pair of of polarization plates 1,9.Further, in Fig. 1, above-mentioned Colour filter 7 is equipped between one substrate 8 and common electrode 6.In addition further, it is possible to with the present invention liquid crystal layer 5 adjoining and with It constitutes the mode that the liquid-crystal composition of the liquid crystal layer 5 directly abuts and forms a pair of of alignment films 4 on 6,14 surface of transparent electrode (layer).
That is, the composition of the liquid crystal display element 10 of the present invention is：By the second polarization plates 1, second substrate 2, include film crystalline substance The electrode layer (or also referred to as tft layer) 3 of body pipe, the layer 5 comprising liquid-crystal composition, alignment films 4, is total to alignment films 4 It is stacked gradually with electrode 6, colour filter 7, first substrate 8 and the first polarization plates 9.
In addition, as shown in Fig. 2, about the electrode layer 3 comprising thin film transistor (TFT) for being formed in 2 surface of second substrate, it is used for The gate wirings 25 and the data wiring 24 for supplying display signal for supplying scanning signal intersect, and by above-mentioned more In the region that root gate wirings 25 are surrounded with more single data wirings 24, pixel electrode 21 is formed as rectangular.As electric to pixel The supply of pole 21 shows the switch element of signal, attached in above-mentioned gate wirings 25 and 24 cross one another cross part of above-mentioned data wiring Closely, including the thin film transistor (TFT) of source electrode 26, drain electrode 23 and gate electrode 27 is arranged with being connect with pixel electrodes 21.Into one Step is equipped with and preserves through data wiring 24 in the region surrounded by above-mentioned more gate wirings 25 and more single data wirings 24 The storage 22 of the display signal of supply.
In the present invention, it is folded for reciprocal cross that the thin film transistor (TFT) as recorded in Fig. 2~4 can be suitably used for The liquid crystal display element of (Inverted Staggered) type, gate wirings 25, data wiring 24 etc. are preferably metal film, especially The case where it is preferable to use aluminum wirings.Further, gate wirings and data wiring are overlapped across gate insulating film.
In addition, from the viewpoint of the leakage for preventing light, the colour filter 7 is preferably corresponding to thin film transistor (TFT) and storage electricity The part of container 22 forms black matrix (not shown).
A suitable form for the structure of the thin film transistor (TFT) of liquid crystal display element about the present invention, such as such as Fig. 3 Shown in Fig. 4, have：It is formed in the gate electrode 11 on 2 surface of substrate；To cover the gate electrode 11 and cover the big of aforesaid substrate 2 Cause the gate insulating layer 13 that entire mode is arranged；Above-mentioned gate insulating layer is formed in a manner of opposite with above-mentioned gate electrode 11 The semiconductor layer 17 on 13 surfaces；The protective film 18 being arranged in a manner of covering the part on 17 surface of above-mentioned semiconductor layer；To cover Cover a side end for stating protective layer 18 and above-mentioned semiconductor layer 17 and exhausted with the above-mentioned grid that is formed in 2 surface of aforesaid substrate The drain electrode 15 that the mode that edge layer 13 contacts is arranged；To cover another side of said protection film 18 and above-mentioned semiconductor layer 17 Source electrode 19a, 19b that portion and the mode contacted with the above-mentioned gate insulating layer 13 for being formed in 2 surface of aforesaid substrate are arranged；To cover It covers and states source electrode 19a, 19b and the mode of the substantially entire surface that covers above-mentioned gate insulating layer 13 along above-mentioned gate insulating layer 13 The transparent electrode 14 of setting；And it is set in a manner of the part to cover above-mentioned transparent electrode 14 and above-mentioned source electrode 19a, 19b The protective layer 101 (not shown in figure 3) set.
In addition, as shown in Figures 3 and 4, it can be with shape according to the reasons such as elimination and the segment difference of gate electrode on 11 surface of gate electrode At anodic oxidation coating 12.Further, the width of Schottky barrier (Schottky barrier), the purpose of height are being reduced Under, ohmic contact layer 16 can be set between semiconductor layer 17 and drain electrode 15.
During manufacture liquid crystal display element as described above, the shadow of the deep liquid crystal material injected of generation of drop impression It rings, but due to the composition of liquid crystal display element, influence can not also avoid.The colour filter especially formed in liquid crystal display element Device 7 or thin film transistor (TFT) etc., as shown in figure 3, for liquid-crystal composition only across thin alignment films 4, transparent electrode 6,14 etc. Component, therefore due to the chemical constitution of pigment used in such as colour filter or the chemical constitution of colour filter resin with have The combination of the liquid-crystal compounds of specified chemical structure and the generation of drop impression is impacted.
Especially reciprocal cross stack-type as described above is used in the thin film transistor (TFT) of the liquid crystal display element as the present invention In the case of, as shown in figs. 2 to 4, drain electrode 15 is formed in a manner of covering grid electrode 11, therefore has the area of drain electrode 15 to increase Tendency.Usual drain electrode is formed by metal materials such as copper, aluminium, chromium, titanium, molybdenum, tantalums, and common mode is to implement Passivation Treatment. But such as shown in Figure 3 and Figure 4, since protective film 18 is usually relatively thin, alignment films 4 are also thin, and do not intercept ionic substance can Energy property is high, therefore the drop impression caused by the interaction by metal material and liquid-crystal composition can not be avoided to generate.
But in the liquid crystal display element of the liquid-crystal composition comprising the present invention, from the component of such as liquid crystal display element From the viewpoint of delicate balance between the surface free energy or adsorption energy etc. of the liquid-crystal composition of the present invention, it is believed that production The problem of raw drop impression, can also be reduced.
Liquid crystal display element using the liquid-crystal composition of the present invention is to have taken into account high-speed responsive and the undesirable inhibition of display Useful element, it is particularly useful in driven with active matrix liquid crystal display element, can be adapted for VA patterns, PSVA patterns, PSA patterns, IPS patterns or ecb mode are used.
Embodiment
It enumerates embodiment below the present invention is described in further detail, but the present invention is not limited to these Examples.In addition, below " % " of the composition of embodiment and comparative example refers to " quality % ".
In embodiment, the characteristic of measurement is as described below.
Tni：Nematic phase-isotropic liquid phase transition temperature (DEG C)
Δn：Refractive anisotrop at 25 DEG C
Δε：Dielectric constant anisotropy at 25 DEG C
η：Viscosity (mPas) at 20 DEG C
γ1：Rotary viscosity (mPas) at 25 DEG C
VHR：Voltage retention (%) when 60 DEG C under conditions of frequency 60Hz, applied voltage 1V
Burn-in：
The burn-in of liquid crystal display element is evaluated, be make in display area as defined in after fixed pattern shows 1000 hours, The ghost level of fixed pattern when to entire picture uniformly show by estimating carries out 4 Phase Evaluations below.
◎ is without ghost
Zero ghost is almost seldom, is admissible level
There are ghosts for Δ, are not admissible level
× there are ghost, very severes
Drop impression：
The evaluation of the drop impression of liquid crystal display device is in the case where whole face shows black, by range estimation to appearing white Drop impression carry out 4 Phase Evaluations below.
◎ is without ghost
Zero ghost is almost seldom, is admissible level
There are ghosts for Δ, are not admissible level
× there are ghost, very severes
Technological adaptability：
About Technological adaptability, in ODF techniques, will use constant volume measurement pump the operation of the every 1 time 50pL liquid crystal that drips into Row 100000 times, then to " 0~100 time, 101~200 times, 201~300 times ... 99901~100000 times " every 100 The variation of the secondary amount of liquid crystal to drip carries out following 4 Phase Evaluations.
◎ is changed very little and (can steadily be manufactured liquid crystal display element)
Zero variation is almost seldom, is admissible level
There is variation in Δ, for not admissible horizontal (causing yield rate to be deteriorated due to generating spot)
× there is variation, very severe (generates liquid crystal leakage, bubbles of vacuum)
Dissolubility under low temperature：
Dissolubility evaluation under low temperature, is the weighing 1g liquid crystal combinations in the sample bottle of 2mL after modulating liquid-crystal composition Object places it in temperature control formula test flume, then according to " -20 DEG C of (0.1 DEG C/every of (being kept for 1 hour) → heatings of 1 cycle Minute) → 0 DEG C of (being kept for 1 hour) → heating (0.1 DEG C/per minute) → 20 DEG C of (being kept for 1 hour) → (- 0.1 DEG C/every point of coolings Clock) → 0 DEG C of (being kept for 1 hour) → cooling (- 0.1 DEG C/per minute) → -20 DEG C " temperature change is continuously assigned, pass through visual observations From the generation of the precipitate in liquid-crystal composition, 4 Phase Evaluations below are carried out.
◎ 600 hours or more does not observe precipitate.
Precipitate is not observed within 0 300 hours or more.
Δ observes precipitate within 150 hours.
Precipitate is observed within × 75 hours.
In addition, the record about compound in embodiment, uses following simple mark.
(side chain)
-n -CnH2n+1The straight-chain alkyl of carbon atom number n
-On -OCnH2n+1The straight-chain alkoxy of carbon atom number n
- V-C=CH2Vinyl
- Vn-C=C-CnH2n+11- alkene
(ring structure)
[changing 27]
(embodiment 1)
The liquid-crystal composition with composition shown below is modulated, its physics value is measured.It the results are shown in following table.
Using the liquid-crystal composition of embodiment 1, VA liquid crystal display elements are made.The liquid crystal display element has reciprocal cross stack-type Thin film transistor (TFT) as active component.The injection of liquid-crystal composition is carried out by dropping method, and it is suitable to carry out burn-in, drop impression, technique Deliquescent evaluation under answering property and low temperature.
In addition, the mark on the left of content is the record of the simple mark of above compound.
[changing 28]
Embodiment 1
[table 1]
TN/℃ 75.8
Δn 0.108
no 1.484
Δε -3.0
ε⊥ 6.5
η/mPa·s 16.9
γ1/mPa·s 116
γ1/Δn2 9.9
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 to：The liquid-crystal composition of embodiment 1 has as TV 75.8 DEG C of liquid crystalline phase temperature of liquid-crystal composition practicality Range is spent, the absolute value with big dielectric constant anisotropy has low sticky and most suitable Δ n.Use embodiment 1 The liquid-crystal composition of record makes VA liquid crystal display elements, by the above method to burn-in, drop impression, Technological adaptability and low Dissolubility under temperature is evaluated, and as a result shows extremely excellent evaluation result.
(comparative example 1)
Modulation is without the compound represented by logical formula (II), according to the liquid crystalline phase same with the composition of embodiment 1 The following institute that the mode of temperature range, same refractive anisotrop value and same dielectric constant anisotropy value designs The liquid-crystal composition shown measures its physics value.It the results are shown in following table.
Using the liquid-crystal composition of comparative example 1, make VA liquid crystal display elements similarly to Example 1, will carry out burn-in, Deliquescent evaluation result under drop impression, Technological adaptability and low temperature is shown in identical table.
In addition, the mark on the left of content is the record of the simple mark of above compound similarly to Example 1.
[changing 29]
Comparative example 1
[table 2]
TNI/℃ 75.4
Δn 0.108
no 1.481
Δε -3.0
ε⊥ 6.5
η/mPa·s 18.3
γ1/mPa·s 121
γ1/Δn2 10.4
Initial voltage conservation rate/% 98.8
Voltage retention/% after 150 DEG C of 1h 97.8
Burn-in is evaluated ×
Drop impression is evaluated ×
Technological adaptability is evaluated Δ
Dissolubility evaluation under low temperature Δ
Liquid-crystal composition (comparative example 1) without the compound represented by logical formula (II) with contain 20% logical formula (II) institute table The liquid-crystal composition (embodiment 1) for the compound shown is compared, although with same liquid crystal phase temperature range, same refractive index Anisotropy value and same dielectric constant anisotropy value, but show that viscosities il rises.About γ 1, the value of comparative example 1 121mPas shows the higher value compared with the value 116mPas of embodiment 1, to indicate liquid crystal display element and display Actual effect answer speed 1/ Δ n of parameter γ2Value be compared also be difference as a result, but its gap not counting more.But compare The initial stage VHR of example 1 be 98.9%, and at 150 DEG C high temperature place 1 hour after VHR be 97.8%, compared with Example 1 for The result being significantly deteriorated.Technological adaptability is evaluated, as a result variation is the level that can not allow compared with Example 1. The dissolubility under low temperature is evaluated, as a result observes precipitation earlier compared with Example 1.
(comparative example 2)
Modulation is without the compound represented by formula (I-1), according to the liquid crystalline phase temperature same with the composition of embodiment 1 The mode of degree range, same refractive anisotrop value and same dielectric constant anisotropy value designs as shown below Liquid-crystal composition (comparative example 2), measure its physics value.It the results are shown in following table.
Using the liquid-crystal composition of comparative example 2, make VA liquid crystal display elements similarly to Example 1, will carry out burn-in, Deliquescent evaluation result under drop impression, Technological adaptability and low temperature is shown in identical table.
[table 3]
Comparative example 2
3-Cy-Cy-2 20.0%
5-Cy-Cy-V 21.0%
3-Cy-Ph5-O2 12.0%
5-Cy-Ph5-O2 5.0%
3-Cy-Cy-Ph5-O2 13.0%
2-Cy-Ph-Ph5-O2 9.0%
3-Cy-Ph-Ph5-O2 10.0%
3-Ph-Ph5-Ph-2 10.0%
TNI/℃ 75.9
Δn 0.108
no 1.482
Δε -3.0
ε⊥ 6.4
η/mPa·s 20.1
γ1/mPa·s 141
γ1/Δn2 12.1
Initial voltage conservation rate/% 99.0
Voltage retention/% after 150 DEG C of 1h 98.4
Burn-in is evaluated Δ
Drop impression is evaluated ×
Technological adaptability is evaluated Δ
Dissolubility evaluation under low temperature ×
Liquid-crystal composition (comparative example 2) without the compound represented by formula (I-1) with it is represented containing 19% formula (I-1) The liquid-crystal composition (embodiment 1) of compound compare, although each with same liquid crystal phase temperature range, same refractive index Anisotropy value and same dielectric constant anisotropy value, but show that viscosities il rises.About γ1, the value of comparative example 2 141mPas shows compared with the value 116mPas of embodiment 1 high 20% or more value, with indicate liquid crystal display element and The parameter γ of the actual effect answer speed of display1/Δn2Value be compared the initial stage VHR of comparative example 2 of the result for being also difference and be 99.0%, and the VHR after high temperature is placed 1 hour at 150 DEG C is 98.4%, is compared with Example 1 the result of difference.To technique Adaptability is evaluated, and as a result variation is the level that can not allow compared with Example 1.The dissolubility under low temperature is evaluated, as a result Observe precipitation earlier compared with Example 1.
(embodiment 2 and embodiment 3)
Modulation according to the liquid crystal phase temperature range same with the composition of embodiment 1, same refractive index respectively to different Property value and same dielectric constant anisotropy value mode design with composition as shown below liquid-crystal composition (implement Example 2 and embodiment 3), measure its physics value.It the results are shown in following table.
Using the liquid-crystal composition of embodiment 2 and embodiment 3, VA liquid crystal display elements are made 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]
Known to：The liquid-crystal composition of embodiment 2 has as the TV liquid crystal phase temperature ranges of liquid-crystal composition practicality, tool There is the absolute value of big dielectric constant anisotropy, there is low sticky and most suitable Δ n.The liquid recorded using embodiment 2 Crystal composite makes VA liquid crystal display elements, by the above method to molten under burn-in, drop impression, Technological adaptability and low temperature Solution property is evaluated, and as a result shows excellent evaluation result.
Known to：The liquid-crystal composition of embodiment 3 has as the TV liquid crystal phase temperature ranges of liquid-crystal composition practicality, tool There is the absolute value of big dielectric constant anisotropy, there is low sticky and most suitable Δ n.The liquid recorded using embodiment 3 Crystal composite makes VA liquid crystal display elements, by the above method to molten under burn-in, drop impression, Technological adaptability and low temperature Solution property is evaluated, and as a result shows excellent evaluation result.
(embodiment 4 and embodiment 5)
Modulation according to the liquid crystal phase temperature range same with the composition of embodiment 1, same refractive index respectively to different Property value and same dielectric constant anisotropy value mode design with composition as shown below liquid-crystal composition (implement Example 4 and embodiment 5), measure its physics value.It the results are shown in following table.
Using the liquid-crystal composition of embodiment 4 and embodiment 5, VA liquid crystal display elements are made 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 5]
Known to：The liquid-crystal composition of embodiment 4 has as the TV liquid crystal phase temperature ranges of liquid-crystal composition practicality, tool There is the absolute value of big dielectric constant anisotropy, there is low sticky and most suitable Δ n.The liquid recorded using embodiment 4 Crystal composite makes VA liquid crystal display elements, by the above method to molten under burn-in, drop impression, Technological adaptability and low temperature Solution property is evaluated, and as a result shows excellent evaluation result.
Known to：The liquid-crystal composition of embodiment 5 has as the TV liquid crystal phase temperature ranges of liquid-crystal composition practicality, tool There is the absolute value of big dielectric constant anisotropy, there is low sticky and most suitable Δ n.The liquid recorded using embodiment 5 Crystal composite makes VA liquid crystal display elements, by the above method to molten under burn-in, drop impression, Technological adaptability and low temperature Solution property is evaluated, and as a result shows excellent evaluation result.
(embodiment 6 and embodiment 7)
Modulation according to the liquid crystal phase temperature range same with the composition of embodiment 1, same refractive index respectively to different Property value and same dielectric constant anisotropy value mode design with composition as shown below liquid-crystal composition (implement Example 6 and embodiment 7), measure its physics value.It the results are shown in following table.
Using the liquid-crystal composition of embodiment 6 and embodiment 7, VA liquid crystal display elements are made 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 to：The liquid-crystal composition of embodiment 6 has as the TV liquid crystal phase temperature ranges of liquid-crystal composition practicality, tool There is the absolute value of big dielectric constant anisotropy, there is low sticky and most suitable Δ n.The liquid recorded using embodiment 6 Crystal composite makes VA liquid crystal display elements, by the above method to molten under burn-in, drop impression, Technological adaptability and low temperature Solution property is evaluated, and as a result shows excellent evaluation result.
Known to：The liquid-crystal composition of embodiment 7 has as the TV liquid crystal phase temperature ranges of liquid-crystal composition practicality, tool There is the absolute value of big dielectric constant anisotropy, there is low sticky and most suitable Δ n.The liquid recorded using embodiment 7 Crystal composite makes VA liquid crystal display elements, by the above method to molten under burn-in, drop impression, Technological adaptability and low temperature Solution property is evaluated, and as a result shows excellent evaluation result.
(embodiment 8)
Modulation according to the liquid crystal phase temperature range same with the composition of embodiment 1, same refractive index respectively to different Property value and same dielectric constant anisotropy value mode design with composition as shown below liquid-crystal composition (implement Example 8), measure its physics value.It the results are shown in following table.
Using the liquid-crystal composition of embodiment 8, make VA liquid crystal display elements similarly to Example 1, will carry out burn-in, Deliquescent evaluation result under drop impression, Technological adaptability and low temperature is shown in identical table.
[table 7]
Embodiment 8
3-Cy-Cy-2 20.0%
3-Cy-Cy-V 21.0%
3-Cy-Cy-Ph-1 3.0%
3-Cy-Ph5-O2 5.5%
3-Ph-Ph5-O2 10.0%
3-Cy-Cy-Ph5-O2 13.0%
4-Cy-Cy-Ph5-O2 2.5%
2-Cy-Ph-Ph5-O2 5.0%
3-Cy-Ph-Ph5-O2 10.0%
3-Ph-Ph5-Ph-2 10.0%
TNI/℃ 75.5
Δn 0.108
no 1.486
Δε -3.0
ε⊥ 6.4
η/mPa·s 14.7
γ1/mPa·s 102
γ1/Δn2 8.7
Initial voltage conservation rate/% 99.9
Voltage retention/% after 150 DEG C of 1h 99.2
Burn-in is evaluated ◎
Drop impression is evaluated ◎
Technological adaptability is evaluated ◎
Dissolubility evaluation under low temperature ◎
Known to：The liquid-crystal composition of embodiment 8 has as the TV liquid crystal phase temperature ranges of liquid-crystal composition practicality, tool There is the absolute value of big dielectric constant anisotropy, there is low sticky and most suitable Δ n.The liquid recorded using embodiment 8 Crystal composite makes VA liquid crystal display elements, by the above method to molten under burn-in, drop impression, Technological adaptability and low temperature Solution property is evaluated, and as a result shows excellent evaluation result.
(comparative example 3 and comparative example 4)
Modulation is without the compound represented by logical formula (II) respectively, according to the liquid same with the composition of embodiment 8 The liquid that the mode of crystalline phase temperature range, same refractive anisotrop value and same dielectric constant anisotropy value designs Crystal composite (comparative example 3) and without the compound represented by formula (I-1), according to same with the composition of embodiment 8 Liquid crystal phase temperature range, the mode of same refractive anisotrop value and same dielectric constant anisotropy value designs Liquid-crystal composition (comparative example 4), measure its physics value.It the results are shown in following table.
Using comparative example 3 and the liquid-crystal composition of comparative example 4, VA liquid crystal display elements are made 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]
Liquid-crystal composition (comparative example 3) without the compound represented by logical formula (II) with it is represented containing 20% formula (II) The liquid-crystal composition (embodiment 8) of compound compare, although each with same liquid crystal phase temperature range, same refractive index Anisotropy value and same dielectric constant anisotropy value, but show that viscosities il rises.About γ1, the value of comparative example 3 108mPas shows the higher value compared with the value 102mPas of embodiment 1, to indicate liquid crystal display element and display Actual effect answer speed parameter γ1/Δn2Value be compared also be difference as a result, but its gap it is not big.But compare The initial stage VHR of example 3 be 98.9%, and at 150 DEG C high temperature place 1 hour after VHR be 98.0%, compared with Example 8 for The result being significantly deteriorated.Technological adaptability is evaluated, as a result variation is the level that can not allow compared with Example 8. The dissolubility under low temperature is evaluated, as a result observes precipitation earlier compared with Example 8.
Liquid-crystal composition (comparative example 4) without the compound represented by general formula (I-1) with contain 21% formula (I-1) institute table The liquid-crystal composition (embodiment 8) for the compound shown is compared, although with same liquid crystal phase temperature range, same refractive index Anisotropy value and same dielectric constant anisotropy value, but show that viscosities il rises.About γ1, the value of comparative example 4 129mPas shows compared with the value 102mPas of embodiment 1 high 25% or more value, with indicate liquid crystal display element and The parameter γ of the actual effect answer speed of display1/Δn2Value be compared also be difference result.The initial stage VHR of comparative example 4 is 99.2%, and the VHR after high temperature is placed 1 hour at 150 DEG C is 98.5%, the knot to be significantly deteriorated compared with Example 8 Fruit.Technological adaptability is evaluated, as a result variation is the level that can not allow compared with Example 8.It evaluates molten under low temperature As a result Xie Xing observes precipitation earlier compared with Example 8.
(embodiment 9 and embodiment 10)
Modulation according to the liquid crystal phase temperature range same with the composition of embodiment 8, same refractive index respectively to different Property value and same dielectric constant anisotropy value mode design with composition as shown below liquid-crystal composition (implement Example 9 and embodiment 10), measure its physics value.It the results are shown in following table.
Using the liquid-crystal composition of embodiment 9 and embodiment 10, VA liquid crystal display members are made similarly to Example 8 The deliquescent evaluation result carried out under burn-in, drop impression, Technological adaptability and low temperature is shown in identical table by part.
[table 9]
Known to：The liquid-crystal composition of embodiment 9 has as the TV liquid crystal phase temperature ranges of liquid-crystal composition practicality, tool There is the absolute value of big dielectric constant anisotropy, there is low sticky and most suitable Δ n.The liquid recorded using embodiment 9 Crystal composite makes VA liquid crystal display elements, by the above method to molten under burn-in, drop impression, Technological adaptability and low temperature Solution property is evaluated, and as a result shows excellent evaluation result.
Known to：The liquid-crystal composition of embodiment 10 has as the TV liquid crystal phase temperature ranges of liquid-crystal composition practicality, Absolute value with big dielectric constant anisotropy has low sticky and most suitable Δ n.It is recorded using embodiment 10 Liquid-crystal composition makes VA liquid crystal display elements, by the above method under burn-in, drop impression, Technological adaptability and low temperature Dissolubility is evaluated, and as a result shows excellent evaluation result.
(embodiment 11 and embodiment 12)
Modulation according to the liquid crystal phase temperature range same with the composition of embodiment 8, same refractive index respectively to different Property value and same dielectric constant anisotropy value mode design with composition as shown below liquid-crystal composition (implement Example 11 and embodiment 12), measure its physics value.It the results are shown in following table.
Using the liquid-crystal composition of embodiment 11 and embodiment 12, VA liquid crystal display members are made similarly to Example 8 The deliquescent evaluation result carried out under burn-in, drop impression, Technological adaptability and low temperature is shown in identical table by part.
[table 10]
Known to：The liquid-crystal composition of embodiment 11 has as the TV liquid crystal phase temperature ranges of liquid-crystal composition practicality, Absolute value with big dielectric constant anisotropy has low sticky and most suitable Δ n.It is recorded using embodiment 11 Liquid-crystal composition makes VA liquid crystal display elements, by the above method under burn-in, drop impression, Technological adaptability and low temperature Dissolubility is evaluated, and as a result shows excellent evaluation result.
Known to：The liquid-crystal composition of embodiment 12 has as the TV liquid crystal phase temperature ranges of liquid-crystal composition practicality, Absolute value with big dielectric constant anisotropy has low sticky and most suitable Δ n.It is recorded using embodiment 12 Liquid-crystal composition makes VA liquid crystal display elements, by the above method under burn-in, drop impression, Technological adaptability and low temperature Dissolubility is evaluated, and as a result shows excellent evaluation result.
(embodiment 13 and embodiment 14)
Modulation according to the liquid crystal phase temperature range same with the composition of embodiment 8, same refractive index respectively to different Property value and same dielectric constant anisotropy value mode design with composition as shown below liquid-crystal composition (implement Example 13 and embodiment 14), measure its physics value.It the results are shown in following table.
Using the liquid-crystal composition of embodiment 13 and embodiment 14, VA liquid crystal display members are made similarly to Example 8 The deliquescent evaluation result carried out under burn-in, drop impression, Technological adaptability and low temperature is shown in identical table by part.
[table 11]
Known to：The liquid-crystal composition of embodiment 13 has as the TV liquid crystal phase temperature ranges of liquid-crystal composition practicality, Absolute value with big dielectric constant anisotropy has low sticky and most suitable Δ n.It is recorded using embodiment 13 Liquid-crystal composition makes VA liquid crystal display elements, by the above method under burn-in, drop impression, Technological adaptability and low temperature Dissolubility is evaluated, and as a result shows excellent evaluation result.
Known to：The liquid-crystal composition of embodiment 14 has as the TV liquid crystal phase temperature ranges of liquid-crystal composition practicality, Absolute value with big dielectric constant anisotropy has low sticky and most suitable Δ n.It is recorded using embodiment 14 Liquid-crystal composition makes VA liquid crystal display elements, by the above method under burn-in, drop impression, Technological adaptability and low temperature Dissolubility is evaluated, and as a result shows excellent evaluation result.
Symbol description
1 second polarization plates
2 second substrates
3 tft layers include the electrode layer of thin film transistor (TFT)
4 alignment films
5 liquid crystal layers
6 pixel electrodes (common electrode)
7 colour filters
8 first substrates
9 first polarization plates
10 liquid crystal display elements
11 gate electrodes
12 anodic oxidation coatings
13 gate insulating layers
14 transparent electrodes (layer)
15 drain electrodes
16 ohmic contact layers
17 semiconductor layers
18 protective films
19a, 19b source electrode
21 pixel electrodes
22 storages
23 drain electrodes
24 data wirings
25 gate wirings
26 source electrodes
27 gate electrodes
101 protective layers

Claims (9)

1. a kind of liquid-crystal composition containing the compound represented by formula (I-1) and contains the chemical combination represented by general formula (II-1) 7~28 mass % of object, and contain the compound represented by general formula (IIIb), the compound represented by general formula (IIIa), general formula (IVa) compound represented by compound, general formula (IVb) represented by and the compound represented by general formula (V-5), the liquid crystal The dielectric constant anisotropy of composition be it is negative,
In formula, R3bIndicate the alkyl of carbon atom number 1~8, R4bIndicate the alkoxy of carbon atom number 1~8,
In formula, R3aAnd R4aEach independently represent the alkyl of carbon atom number 1~8, the alkenyl of carbon atom number 2~8, carbon atom number 1~8 alkoxy or the alkenyloxy group of carbon atom number 2~8,1 or more in the alkyl, alkenyl, alkoxy and/or alkenyloxy group Hydrogen atom can be replaced by fluorine atoms, the methylene in the alkyl, alkenyl, alkoxy and/or alkenyloxy group does not connect in oxygen atom It can be replaced by oxygen atom in the case of continuous combination, can be replaced by carbonyl in the case where carbonyl discontinuously combines,
In formula, R5aAnd R6aEach independently represent the alkyl of carbon atom number 1~8, the alkenyl of carbon atom number 2~8, carbon atom number 1~8 alkoxy or the alkenyloxy group of carbon atom number 2~8,1 or more in the alkyl, alkenyl, alkoxy and/or alkenyloxy group Hydrogen atom can be replaced by fluorine atoms, the methylene in the alkyl, alkenyl, alkoxy and/or alkenyloxy group does not connect in oxygen atom It can be replaced by oxygen atom in the case of continuous combination, can be replaced by carbonyl in the case where carbonyl discontinuously combines,
In formula, R5bAnd R6bEach independently represent the alkyl of carbon atom number 1~8, the alkenyl of carbon atom number 2~8, carbon atom number 1~8 alkoxy or the alkenyloxy group of carbon atom number 2~8,1 or more in the alkyl, alkenyl, alkoxy and/or alkenyloxy group Hydrogen atom can be replaced by fluorine atoms, the methylene in the alkyl, alkenyl, alkoxy and/or alkenyloxy group does not connect in oxygen atom It can be replaced by oxygen atom in the case of continuous combination, can be replaced by carbonyl in the case where carbonyl discontinuously combines,
In formula, R7And R8Each independently represent the alkyl of carbon atom number 1~8, the alkenyl of carbon atom number 2~8, carbon atom number 1 ~8 alkoxy or the alkenyloxy group of carbon atom number 2~8,1 or more in the alkyl, alkenyl, alkoxy and/or alkenyloxy group Hydrogen atom can be replaced by fluorine atoms, the methylene in the alkyl, alkenyl, alkoxy and/or alkenyloxy group does not connect in oxygen atom It can be replaced by oxygen atom in the case of continuous combination, can be replaced by carbonyl in the case where carbonyl discontinuously combines.
2. liquid-crystal composition according to claim 1, contain the compound group represented by the formula (I-2) and formula (I-3) 1 kind of middle selection or 2 kinds of compounds,
[changing 3]
3. liquid-crystal composition according to claim 1, the content of the compound represented by formula (I-1) is 10~23 matter Measure %.
4. liquid-crystal composition according to claim 1 further contains the compound represented by logical formula (III),
[changing 4]
R in formula3And R4Each independently represent the alkyl of carbon atom number 1~8, the alkenyl of carbon atom number 2~8, carbon atom number 1 ~8 alkoxy or the alkenyloxy group of carbon atom number 2~8,1 or more in the alkyl, alkenyl, alkoxy and/or alkenyloxy group Hydrogen atom can be replaced by fluorine atoms, the methylene in the alkyl, alkenyl, alkoxy and/or alkenyloxy group does not connect in oxygen atom It can be replaced by oxygen atom in the case of continuous combination, can be replaced by carbonyl in the case where carbonyl discontinuously combines, A1It indicates 1,4- cyclohexylidenes or oxinane -2,5- diyls.
5. liquid-crystal composition according to claim 1 further contains the compound represented by logical formula (IV),
R in formula5And R6Each independently represent the alkyl of carbon atom number 1~8, the alkenyl of carbon atom number 2~8, carbon atom number 1 ~8 alkoxy or the alkenyloxy group of carbon atom number 2~8,1 or more in the alkyl, alkenyl, alkoxy and/or alkenyloxy group Hydrogen atom can be replaced by fluorine atoms, the methylene in the alkyl, alkenyl, alkoxy and/or alkenyloxy group does not connect in oxygen atom It can be replaced by oxygen atom in the case of continuous combination, can be replaced by carbonyl in the case where carbonyl discontinuously combines, A2It indicates 1 or 4 cyclohexylidene, Isosorbide-5-Nitrae-phenylene or oxinane -2,5- diyl, in A2Indicate Isosorbide-5-Nitrae-phenylene in the case of, this 1, 1 or more hydrogen atom in 4- phenylenes can be replaced by fluorine atoms.
6. liquid-crystal composition according to claim 1 further contains the compound represented by logical formula (V),
R in formula7And R8Each independently represent the alkyl of carbon atom number 1~8, the alkenyl of carbon atom number 2~8, carbon atom number 1 ~8 alkoxy or the alkenyloxy group of carbon atom number 2~8,1 or more in the alkyl, alkenyl, alkoxy and/or alkenyloxy group Hydrogen atom can be replaced by fluorine atoms, the methylene in the alkyl, alkenyl, alkoxy and/or alkenyloxy group does not connect in oxygen atom It can be replaced by oxygen atom in the case of continuous combination, can be replaced by carbonyl in the case where carbonyl discontinuously combines,
A31 or 4 cyclohexylidene, Isosorbide-5-Nitrae-phenylene or oxinane -2,5- diyl are indicated, in A3Indicate the feelings of 1,4- phenylenes Under condition, 1 or more hydrogen atom in the Isosorbide-5-Nitrae-phenylene can be replaced by fluorine atoms,
Z1Indicate singly-bound ,-CH2CH2-、-OCH2-、-OCF2-、-CH2O- or-CF2O-,
N indicates 0 or 1,
X1~X6Each independently represent hydrogen atom or fluorine atom, X1~X6In at least one indicate fluorine atom.
7. liquid-crystal composition according to claim 1, contains reactive monomer.
8. a kind of liquid crystal display element using liquid-crystal composition described in claim 1.
9. a kind of liquid crystal display using liquid crystal display element according to any one of claims 8.
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