TW201527498A - Liquid crystal composition and liquid crystal display element using the same - Google Patents

Abstract

The subject of the present invention is to provide a liquid crystal composition and a liquid crystal display element using the same. The liquid crystal composition provided will not degrade the characteristics of a liquid crystal display element such as dielectric anisotropy, viscosity, upper limit temperature of nemantic phase, nemantic phase stability at low temperature, and [gamma] 1 and so on, and afterimage characteristic of a display element. Dripping trace is hard to generate during the manufacturing, and stable spraying amount of liquid crystal material can be achieved in the one drop filling (ODF) step, which is suitable for the liquid crystal display element. In this invention, a liquid crystal composition with negative dielectric anisotropy is provided, which comprises at least one or more compounds represented by general formula (I), at least one or more compounds represented by general formula (II), and compounds represented by formula (IIIb-1). This invention also provides a liquid crystal display element using the liquid crystal composition.

Description

Liquid crystal composition and liquid crystal display element using same

The present invention relates to a liquid crystal composition and a liquid crystal display element which can be used as constituent members of a liquid crystal display device or the like.

The liquid crystal display element can be used for various measuring machines represented by watches, calculators, automobile panels, word processors, electronic notebooks, printers, computers, televisions, advertisement display boards, and the like. Typical examples of the liquid crystal display method include TN (Twisted Nematic) type, STN (Super Twisted Nematic) type, and TFT (Thin Film Transistor) type (Vertical Alignment). , Vertical alignment type or IPS (In Plane Switching) type. The liquid crystal composition used for the liquid crystal display elements is required to be stable to external factors such as moisture, air, heat, light, and the like, and exhibits a liquid crystal phase in a temperature range as wide as possible centered on the room temperature, and is low in viscosity. And the driving voltage is low. Further, in order to optimize the dielectric anisotropy (Δε) or/and the refractive index anisotropy (Δn) and the like which are optimum for each display element, the liquid crystal composition contains several to several tens of kinds. Compound.

In the vertical alignment type display, a liquid crystal composition having a negative Δ ε is used, and it is widely used in a liquid crystal TV or the like. On the other hand, in all driving methods, low voltage driving, high speed response, and a wide operating temperature range are required. That is, it is required that Δε is positive and the absolute value is large, the viscosity (η) is small, and the nematic phase-isotropic liquid phase transition temperature (T _ni ) is high. Further, it is necessary to adjust the Δn of the liquid crystal composition to an appropriate range in accordance with the cell gap in accordance with the setting of Δn × d which is the product of Δn and the cell gap (d). In addition, when a liquid crystal display element is applied to a television or the like, since high-speed responsiveness is emphasized, a liquid crystal composition having a small γ ₁ is required.

In order to form a liquid crystal composition having a small γ ₁ , a compound having a dialkyl bicyclohexane skeleton has been generally used (see Patent Document 1). However, although the bicyclohexane compound has a large effect of lowering γ ₁ , the tendency is generally high for a compound having a high vapor pressure and a short alkyl chain length. Further, since T _{ni is} also low, the alkyl bicyclohexane compound is often a compound having a side chain length of 7 or more in total, and in practice, a compound having a short side chain length has not been sufficiently obtained. the study.

On the other hand, as the use of liquid crystal display elements continues to expand, significant changes can be seen in terms of their methods of use and manufacturing methods. In order to cope with such changes, it is required to optimize characteristics other than the basic physical property values previously known. Chemical. In other words, a liquid crystal display device using a liquid crystal composition can be widely used in a VA (Vertical Alignment) type or an IPS (In Plane Switching) type, and can have a size of 50 Å or more. The display element of the ultra-large size is put into practical use. With the increase in the size of the substrate, the method of injecting the liquid crystal composition into the substrate has also been changed from the previous vacuum injection method to the one-drop filling (ODF) method (refer to Patent Document 2), and the liquid crystal is composed. The problem of dropping the traces when the material is dropped on the substrate causes the deterioration of the display quality to be superficial. Further, based on the purpose of obtaining high-speed responsiveness by the formation of the pretilt angle of the liquid crystal material in the liquid crystal display element, a PS liquid crystal display element (polymer stabilized) and a PSA liquid crystal display element (polymer sustained alignment, The polymer maintains alignment (see Patent Document 3), and this problem has become a bigger problem. That is, the display elements have a feature that the liquid crystal composition adds a monomer and hardens the monomer in the composition. In terms of the necessity of maintaining a high voltage holding ratio, a compound which can be used for the liquid crystal composition for an active matrix is specified, and the use of a compound having an ester bond in the compound is limited. The monomer used in the PSA liquid crystal display element is mainly an acrylate type, and usually has an ester bond in a compound, and such a compound is generally not used as a liquid crystal compound for an active matrix (refer to a patent) Document 3). Such a foreign matter causes the occurrence of a drop mark, and the deterioration of the yield of the liquid crystal display element due to poor display becomes a problem. Further, when an additive such as an antioxidant or a light absorber is added to the liquid crystal composition, the yield is also deteriorated.

Here, the term "drop" is defined as a phenomenon in which a trace of a liquid crystal composition is dropped in a white form when a black display is performed.

In order to suppress the dropping mark, there is disclosed a method of forming a polymer layer in a liquid crystal layer by polymerizing a polymerizable compound mixed in a liquid crystal composition, thereby suppressing generation of a relationship with an alignment control film. The drop is added to the mark (Patent Document 4). However, in this method, there is a problem of displaying an afterimage due to a polymerizable compound added to the liquid crystal, and the effect of suppressing the dropping of the trace is insufficient, and development of a basic property as a liquid crystal display element is required and it is difficult to develop. A liquid crystal display element that produces an afterimage or a drop.

Patent Document 1: Japanese Patent Laid-Open Publication No. 2008-505235

Patent Document 2: Japanese Patent Laid-Open No. Hei 6-235925

Patent Document 3: Japanese Patent Laid-Open Publication No. 2002-357830

Patent Document 4: Japanese Patent Laid-Open No. 2006-58755

An object of the present invention is to provide a liquid crystal composition which does not impart dielectric anisotropy, viscosity, a nematic phase upper limit temperature, and a nematic phase stability at a low temperature, and a liquid crystal display element using the liquid crystal composition. γ ₁ or the like is a suitable liquid crystal display element for each of the characteristics of the liquid crystal display element and the afterimage characteristics of the display element, which is less likely to cause dripping marks during production, and which realizes a stable discharge amount of the liquid crystal material in the ODF step.

In order to solve the above problems, the present inventors have studied the constitution of various liquid crystal compositions which are most suitable for producing a liquid crystal display element by a dropping method, and found that it is possible to suppress liquid crystal display elements by using a specific liquid crystal compound at a specific mixing ratio. A drop mark is created to complete the invention.

The present invention provides a liquid crystal composition containing a dielectric of a compound represented by the general formula (I), the general formula (II) and the formula (IIIb-1), and a liquid crystal display element using the liquid crystal composition. Anisotropy is negative,

(wherein R ¹¹ represents an alkyl group having 1 to 3 carbon atoms, R ²² represents an alkyl group having 1 to 3 carbon atoms or a hydrogen atom, and R ¹ and R ² each independently represent an alkyl group having 1 to 8 carbon atoms; And an alkenyl group having 2 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms or an alkenyloxy group having 2 to 8 carbon atoms).

The liquid crystal display device of the present invention is characterized in that it has excellent high-speed response and less generation of afterimages, and has a feature that the occurrence of dripping marks due to its manufacture is small, and therefore, it can be used for a liquid crystal TV, a monitor (monitor) And other display elements.

1‧‧‧second polarizer

2‧‧‧second substrate

3‧‧‧Thin-film transistor layer, electrode layer containing thin film transistor

4‧‧‧Alignment film

5‧‧‧Liquid layer

6‧‧‧pixel electrode (common electrode)

7‧‧‧Color filters

8‧‧‧First substrate

9‧‧‧First polarizer

10‧‧‧Liquid display components

11‧‧‧ gate electrode

12‧‧‧Anodic oxide film

13‧‧‧ gate insulation

14‧‧‧Transparent electrode (layer)

15‧‧‧汲electrode

16‧‧‧Ohm contact layer

17‧‧‧Semiconductor layer

18‧‧‧Protective film

19a‧‧‧Source electrode

19b‧‧‧Source electrode

21‧‧‧pixel electrode

22‧‧‧Storage capacitor

23‧‧‧汲electrode

24‧‧‧Data wiring

25‧‧‧ gate wiring

26‧‧‧Source electrode

27‧‧‧ gate electrode

101‧‧‧Protective layer

Fig. 1 is a view schematically showing the configuration of a liquid crystal display element.

Fig. 2 is an enlarged plan view showing a region surrounded by the line II of the electrode layer 3 including the thin film transistor formed on the substrate in Fig. 1.

Fig. 3 is a cross-sectional view showing the liquid crystal display element shown in Fig. 1 taken along the line III-III in Fig. 2.

Fig. 4 is an enlarged view of a thin film transistor of the region IV in Fig. 3.

As mentioned above, the process of creating drop marks is not yet clear. However, it is highly likely that it is related to the interaction of impurities in the liquid crystal compound with the alignment film, the chromatographic phenomenon, and the like. The impurities in the liquid crystal compound have a large influence on the manufacturing process of the compound. For example, even if only the number of carbon atoms in the side chain is different, the manufacturing method of the compound may not be the same. That is, since the liquid crystal compound is manufactured by a precise manufacturing process, the cost thereof is high in the finished product, and the manufacturing efficiency is strongly required to be improved. Therefore, in order to use a raw material which is as inexpensive as possible, even if the number of carbon atoms in the side chain is only one difference, the efficiency of manufacturing from completely different raw materials may be more excellent. Therefore, the manufacturing process of the liquid crystal precursor sometimes differs depending on each original, and even if the processes are the same, the raw materials are different in most cases, and as a result, impurities which are different depending on each original are often mixed. However, even a very small amount of impurities may cause dripping marks, and there is a limit in suppressing the occurrence of dripping marks only by purification of the original body.

On the other hand, a general method for producing a liquid crystal original has a tendency to fixedly determine each original after the manufacturing process is established. That is to say, it is easy to analyze the technology, and it is not easy to completely understand what kind of impurities are mixed in, and it is necessary to extract the design composition before mixing the impurities determined according to each original. The inventors of the present invention have studied the relationship between the impurities of the liquid crystal precursor and the dropping marks, and as a result, it has been empirically confirmed that even if it is contained in the composition, it is difficult to produce impurities which are dripped and impurities which are likely to cause dripping. Therefore, in order to suppress the generation of the dropping marks, it is important to use a specific compound in a specific mixing ratio, and it is particularly clear that there is a composition which is difficult to produce a dropping mark. The preferred embodiments described below are based on the above findings.

In the liquid crystal composition of the present invention, the total content of the compound group represented by the formula (I) is preferably 2% by mass, more preferably 3% by mass, and further preferably 3% by mass. The amount is preferably 5% by mass, more preferably 25% by mass, still more preferably 20% by mass, still more preferably 15% by mass, and more specifically, when the response speed is important, it is preferably contained. 10 to 25% by mass, more preferably 15 to 25% by mass, and more preferably 2 to 20% by mass, more preferably 5 to 15% by mass, in the case where the driving voltage is more important.

The compound represented by the formula (I) is preferably a formula (I-1) to (I-8) described below. Preferably, it is selected from the group of compounds represented by the formula (I-1) to the formula (I-4), the formula (I-6) and the formula (I-8), and further preferably. It is selected from the group of compounds represented by formula (I-1) to formula (I-3), formula (I-6) and formula (I-8), and more preferably from formula (I-1) to formula (I) The compound represented by the formula (I-1) and the formula (I-3) is preferably selected from the group of compounds represented by I-3).

In the liquid crystal composition of the present invention, when one or two or more compounds are selected from the group of compounds represented by the formula (I-1), the formula (I-2) and the formula (I-3), The content thereof is independently from the number of the selected compound species, and is preferably from 3 to 15% by mass, more preferably from 5 to 10% by mass, even more preferably from 7 to 13% by mass.

In the liquid crystal composition of the present invention, the total content of the compound group represented by the formula (II) is preferably 3% by mass, more preferably 4% by mass, still more preferably 5 mass, as the lower limit. %, as the upper limit, is preferably 25% by mass, more preferably 20% by mass, still more preferably 15% by mass.

The compound represented by the formula (II) is preferably a formula (II-1) to a formula (II-8) described below. The compound represented by the formula (II-1) to the formula (II-4) is more preferably selected from the group of the compounds represented by the formula (II-1) and the compound represented by the formula (II-1) and the formula (II-3). More preferably, it is a compound represented by the formula (II-1).

When four or more compounds represented by the formula (II) are used, it is preferred to use a compound represented by the formula (II-1) to the formula (II-4) in combination, and the formula (II-1)-form is used. The content of the compound represented by the formula (II-4) is preferably 50% by mass or more, more preferably 70% by mass or more, still more preferably 80% by mass or more, particularly preferably 80% by mass or more. 90% by mass or more.

When three kinds of compounds represented by the formula (II) are used, it is preferred to use a compound represented by the formula (II-1) to the formula (II-3) in combination, and the formula (II-1) to the formula (II) The content of the compound represented by the formula (3) is preferably 50% by mass or more, more preferably 70% by mass or more, still more preferably 80% by mass or more, and particularly preferably 90% by mass of the compound represented by the formula (II). %the above.

When two compounds represented by the formula (II) are used, it is preferred to use a compound represented by the formula (II-1) and the formula (II-3) in combination, and the formula (II-1) and the formula (II) The content of the compound represented by the formula (3) is preferably 50% by mass or more, more preferably 70% by mass or more, still more preferably 80% by mass or more, and particularly preferably 90% by mass of the compound represented by the formula (II). %the above.

In the liquid crystal composition of the present invention, the content of the compound represented by the formula (IIIb-1) is preferably 5% by mass, more preferably 8% by mass, still more preferably 10% by mass. The upper limit is preferably 25% by mass, more preferably 20% by mass, still more preferably 15% by mass, and more specifically, when the value of the refractive index anisotropy of the liquid crystal composition is to be lowered. Preferably, it is contained in an amount of 10 to 25% by mass, more preferably 15 to 25% by mass, and in the case where the value of the refractive index anisotropy is to be increased, it is preferably 5 to 20% by mass, more preferably contained. 5~15% by mass.

The liquid crystal composition of the present invention may further contain a compound selected from the group consisting of compounds represented by the formula (III) shown below. (wherein R ³ and R ⁴ each independently represent an alkyl group having 1 to 8 carbon atoms, an alkenyl group having 2 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms or a carbon number of 2 to 8; Alkenyloxy, n represents 0 or 1, but does not include a compound wherein R ³ is an alkyl group having ³ carbon atoms, R ⁴ is an alkoxy group having 2 carbon atoms, and n represents 1.

In the compound represented by the formula (III), R ³ and R ⁴ each independently represent an alkyl group having 1 to 8 carbon atoms, an alkenyl group having 2 to 8 carbon atoms, and an alkoxy group having 1 to 8 carbon atoms. Or an alkenyloxy group having 2 to 8 carbon atoms, and R ^{3 is} preferably an alkyl group having 1 to 8 carbon atoms or an alkenyl group having 2 to 8 carbon atoms, more preferably an alkyl group having 1 to 8 carbon atoms. Further, it is preferably an alkyl group having 2 to 5 carbon atoms, and R ^{4 is} preferably an alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, more preferably 1 to 8 carbon atoms. The alkoxy group is more preferably an alkoxy group having 2 to 5 carbon atoms.

In the case of the compound represented by the formula (III), when n represents 0, the formula (IIIa) described below is used. (wherein R ^3a and R ^4a each have the same meaning as R ³ and R ⁴ in the formula (III)), and in the compound group, it is preferably a formula (IIIa-1) to a formula (IIIa-8). ) The compound represented by the formula (IIIa-1) to the formula (IIIa-4) is more preferably a compound represented by the formula (IIIa-1) and the formula (IIIa-4).

The compound represented by the formula (IIIa) preferably contains 3 to 30% by mass, more preferably 3 to 25% by mass, still more preferably 3 to 20% by mass.

When four or more compounds represented by the formula (IIIa) are used, it is preferred to use a compound represented by the formula (IIIa-1) to the formula (IIIa-4) in combination, and the formula (IIIa-1) to the formula The content of the compound represented by the formula (IIIa-4) is preferably 50% by mass or more, more preferably 70% by mass or more, still more preferably 80% by mass or more, particularly preferably 80% by mass or more. 90% by mass or more.

When three compounds represented by the formula (IIIa) are used, it is preferred to use a compound represented by the formula (IIIa-1), the formula (IIIa-2) and the formula (IIIa-4) in combination, and the formula (IIIa) The content of the compound represented by the formula (IIIa-2) and the formula (II1a-4) is preferably 50% by mass or more, and more preferably 70% by mass or more, based on the compound represented by the formula (IIIa). Further, it is preferably 80% by mass or more, and particularly preferably 90% by mass or more.

In the case of using two compounds represented by the formula (IIIa), it is preferred to use a compound represented by the formula (IIIa-1) and the formula (IIIa-4) in combination, the formula (IIIa-1) and the formula (IIIa). -4) The content of the compound represented by the formula (IIIa) is preferably 50% by mass or more, more preferably 70% by mass or more, further preferably 80% by mass or more, and particularly preferably 90% by mass or more.

In the case of the compound represented by the formula (III), when n represents 1, the formula (IIIb) described below is used. (wherein R ^3b and R ^4b each have the same meaning as R ³ and R ⁴ in the formula (III), but excluding R ^3b is represented by an alkyl group having 3 carbon atoms, and R ^4b is represented by 2 carbon atoms; The compound represented by the alkoxy group) is preferably a compound (IIIb-2) to (IIIb-6) described below. The compound represented by the formula (IIIb-2) to the formula (IIIb-4) is more preferably a compound represented by the formula (IIIb-2) or the formula (IIIb-3), and particularly preferably It is a compound represented by the formula (IIIb-3).

Further, in the case where the liquid crystal composition of the present invention is required to have a high nematic phase-isotropic phase transition temperature (T _ni ), it is preferably represented by the formula (IIIb-5) and the formula (IIIb-6). At least one of the compound groups is selected.

With respect to the compound group represented by the formula (IIIb), the liquid crystal skeleton (mesogenic group) is the same as the formula (IIIb-1) which is an essential component in the present invention, and is represented by the combination formula (IIIb-1). When the compound represented by the formula (IIIb) is used in combination of four or more kinds, it is preferred to use the compound of the formula (IIIb-1) in combination with the compound (IIIb-2). The compound represented by the formula (IIIb-4), the content of the compound represented by the formula (IIIb-2) to the formula (IIIb-4) is preferably 50% by mass or more of the compound represented by the formula (IIIb). It is more preferably 70% by mass or more, further preferably 80% by mass or more, and particularly preferably 90% by mass or more.

When a combination of the compound represented by the formula (IIIb-1) and the compound represented by the formula (IIIb) is used in combination, it is preferred to use the compound (IIIb) in combination with the compound represented by the formula (IIIb-1). -2) and the compound represented by the formula (IIIb-3), the content of the compound represented by the formula (IIIb-2) and the formula (IIIb-3) is preferably 50% by weight of the compound represented by the formula (IIIb) % or more is more preferably 70% by mass or more, and still more preferably 80% by mass or more.

When a combination of the compound represented by the formula (IIIb-1) and the compound represented by the formula (IIIb) is used in combination, it is preferred to use the compound (IIIb) in combination with the compound represented by the formula (IIIb-1). And the content of the compound represented by the formula (IIIb-3) is preferably 50% by mass or more, more preferably 70% by mass or more, and further preferably 70% by mass or more. It is 80% by mass or more, and particularly preferably 90% by mass or more.

The liquid crystal composition of the present invention may contain a compound selected from the group consisting of compounds represented by the following formula (IV). (wherein R ⁵ and R ⁶ each independently represent an alkyl group having 1 to 8 carbon atoms, an alkenyl group having 2 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms or a carbon number of 2 to 8; Alkenyloxy).

In the liquid crystal composition of the present invention, the total content of the compound group represented by the formula (IV) is preferably 5% by mass, more preferably 10% by mass, even more preferably 15%, as the lower limit. %, as the upper limit value, is preferably 30% by mass, more preferably 25% by mass, still more preferably 22% by mass, and more specifically, a case where the value of the refractive index anisotropy of the liquid crystal composition is to be lowered. In the case of 5 to 15% by mass, it is preferable to contain 15 to 30% by mass in the case where the value of the refractive index anisotropy is to be increased.

The compound represented by the formula (IV) is preferably the formula (IV-1) to (IV-4) described below. The compound represented by the formula (IV-1) or the formula (IV-2) is more preferred.

When two or more compounds represented by the formula (IV) are used, it is preferred to use a compound represented by the formula (IV-1) and the formula (IV-2) in combination, and a formula (IV-1) and a formula. The content of the compound represented by the formula (IV-2) is preferably 50% by mass or more, more preferably 70% by mass or more, still more preferably 80% by mass or more, and particularly preferably 90% by mass or more.

The liquid crystal composition of the present invention may further contain a compound selected from the group consisting of compounds represented by the following formula (V). (wherein R ⁷ and R ⁸ each independently represent an alkyl group having 1 to 8 carbon atoms, an alkenyl group having 2 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms or a carbon number of 2 to 8; The alkenyloxy group, one or more hydrogen atoms of the alkyl group, the alkenyl group, the alkoxy group and/or the alkenyloxy group may be substituted with a fluorine atom, the alkyl group, the alkenyl group, the alkoxy group and/or the oxyalkylene group. The methylene group in the group may be substituted with an oxygen atom as long as the oxygen atom is discontinuously bonded, and may be substituted into a carbonyl group as long as the carbonyl group is discontinuously bonded, and A ³ represents a 1,4-cyclohexylene group, 1, 4 - a phenyl or tetrahydropyran-2,5-diyl group, in the case where A ³ represents a 1,4-phenylene group, one or more hydrogen atoms in the 1,4-phenylene group may be Substituted as a fluorine atom, Z ¹ represents a single bond, -OCH ₂ -, -OCF ₂ -, -CH ₂ O-, or -CF ₂ O-, n represents 0 or 1, and X ¹ to X ⁶ independently represent a hydrogen atom. Or a fluorine atom, but at least one of X ¹ to X ⁶ represents a fluorine atom).

Specifically, the compound represented by the formula (V) is preferably the formula (V-1) to (V-16) described below. (wherein, R ⁷ and R ⁸ represent a compound represented by the same meaning as R ⁷ and R ⁸ in the formula (V)), more preferably a formula (V-1) or a formula (V-3)-form ( V-9) and formula (V-12)~formula (V-15), further preferably of formula (V-1), formula (V-3), formula (V-5), formula (V-6) , formula (V-9), formula (V-12) and formula (V-15), particularly preferably formula (V-1), formula (V-5), formula (V-6), the best formula (V-5).

In the case of using the compound represented by the general formula (V), it is preferred to use The compound represented by the formula (V-5), the content of the compound represented by the formula (V-5) is preferably 50% by mass or more, more preferably 70% by mass or more, more preferably 70% by mass or more based on the compound represented by the formula (V). It is preferably 80% by mass or more, and particularly preferably 90% by mass or more.

R ⁷ and R ⁸ in the formula (V) each independently represent an alkyl group having 1 to 8 carbon atoms, an alkenyl group having 2 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms or 2 carbon atoms. The alkenyloxy group of ~8 preferably represents an alkyl group having 1 to 8 carbon atoms or an alkenyl group having 2 to 8 carbon atoms, more preferably an alkyl group having 2 to 5 carbon atoms or 2 to 2 carbon atoms. The alkenyl group of 5 is more preferably an alkyl group having 2 to 5 carbon atoms, and is preferably a straight chain. When R ⁷ and R ⁸ are both alkyl groups, it is preferred that the number of carbon atoms is different. .

More specifically, R ⁷ represents a propyl group and R ⁸ represents a compound of an ethyl group, or R ⁷ represents a butyl group and R ⁸ represents a compound of an ethyl group.

Further, the liquid crystal composition of the present invention may further contain a compound selected from the group consisting of compounds represented by the formulae (VI-a) to (VI-e).

(wherein R ⁹¹ to R ^9a each independently represent an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms or an alkenyl group having 2 to 10 carbon atoms, but the formula (VI-a) In the compound represented by the formula, R ⁹¹ represents an alkyl group having 1 to 3 carbon atoms, and R ⁹² represents a compound having 1 to 5 carbon atoms or a hydrogen atom.

Containing a compound group selected from the group consisting of formula (VI-a) to formula (VI-e) In the case of the compound, it is preferably one to ten, more preferably one to eight, and particularly preferably one to five, and more preferably two or more compounds, and more preferably The content of the compound is preferably from 20 to 60% by mass, more preferably from 20 to 50% by mass, even more preferably from 25 to 45% by mass, even more preferably from 30 to 40% by mass.

R ⁹¹ to R ^9a are each independently an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms or an alkoxy group having 2 to 10 carbon atoms, more preferably 1 carbon atom. The alkyl group having 5 to 5, the alkenyl group having 2 to 5 carbon atoms or the alkoxy group having 2 to 5 carbon atoms, in the case of indicating an alkenyl group, is preferably the formula (i) to the following formula ( Iv)

(In the formula, the structure in which the right end is bonded to the ring structure) is preferably a structure represented by the formula (ii) and the formula (iv) when the liquid crystal composition of the present invention contains a reactive monomer. More preferably, it is a structure represented by the formula (ii).

Further, R ⁹¹ and R ⁹² may be the same or different, and preferably represent different substituents.

In these respects, the compound represented by the formula (VI-a) to the formula (VI-e), more specifically, the compound described below is preferred.

Among these, the formula (VI-a1) to the formula (VI-a5), the formula (VI-b2), the formula (VI-b6), the formula (VI-c2), the formula (VI-c4), and the formula are preferred. (VI-c5), a compound represented by the formula (VI-d1) to the formula (VI-d4) and the formula (VI-e2).

Select 1 from the group of compounds represented by formula (VI-a3)~(VI-a5) In the case of two or three kinds of other components of the liquid crystal composition in the invention of the present invention, the total content thereof is preferably 15 to 40% by mass, more preferably 18 to 35% by mass, and still more preferably 20 ～3% by mass, more specifically, in the case of selecting a compound represented by the formula (VI-a3), the content thereof is preferably from 5 to 30% by mass, more preferably from 10 to 25% by mass, still more preferably 13 to 20% by mass, in the case of selecting a compound represented by the formula (VI-a4), the content thereof is preferably from 1 to 15% by mass, more preferably from 2 to 12% by mass, and still more preferably from 3 to 9% by mass. When the compound represented by the formula (VI-a5) is selected, the content thereof is preferably from 3 to 15% by mass, more preferably from 5 to 10% by mass, still more preferably from 7 to 9% by mass.

In the case where two kinds of other components of the liquid crystal composition in the present invention are selected from the group of compounds represented by the formula (VI-a3) to the formula (VI-a5), the selection formula (VI-a3) is preferred. And the formula (VI-a4), when one type is selected, it is more preferable to select the formula (VI-a3).

The compound represented by the formula (VI) is common to the compound represented by the formula (I) in that the dielectric anisotropy is substantially zero, and the total content of the compound represented by the formula (I) and the formula (VI) The rate is preferably from 25 to 60% by mass, more preferably from 30 to 55% by mass, even more preferably from 35 to 50% by mass.

The 1,4-cyclohexyl group in the present application is preferably a trans-1,4-cyclohexyl group.

The liquid crystal composition of the present invention contains, as an essential component, a compound represented by the general formula (I), the general formula (II) and the formula (IIIb-1), and further contains the general formula (III) and the general formula (IV). A compound represented by the formula (V) and the formula (VI-a) to the formula (VI-e). The general formula (I), the general formula (II), the formula (IIIb-1), the general formula (III), the general formula (IV), the general formula (V) and the general formula (VI-) contained in the liquid crystal composition. The total content of the compound represented by the formula (VI-e) is preferably 60% by mass, preferably 65% by mass, preferably 70% by mass, and more preferably 75% by mass. More preferably, it is 80% by mass, more preferably 85% by mass, still more preferably 90% by mass, further preferably 92% by mass, further preferably 95% by mass, particularly preferably 98% by mass, and particularly preferably 99% by mass. The mass%, as the upper limit value, is preferably 100% by mass, and more preferably 99.5% by mass.

More specifically, the total content of the compounds represented by the general formula (I), the general formula (II) and the formula (IIIb-1) is preferably from 20 to 45% by mass, more preferably from 25 to 40% by mass, and further Good is 30~37% by mass.

The total content of the compounds represented by the formula (I), the formula (II), the formula (IIIb-1) and the formula (III) is preferably from 35 to 55% by mass, more preferably from 40 to 50% by mass, further It is preferably 42 to 48% by mass.

The total content of the compounds represented by the formula (I), the formula (II), the formula (IIIb-1) and the formula (IV) is preferably from 40 to 65% by mass, more preferably from 45 to 60% by mass, further It is preferably 47 to 55 mass%.

The total content of the compounds represented by the formula (I), the formula (II), the formula (IIIb-1) and the formula (V) is preferably from 25 to 50% by mass, more preferably from 30 to 45% by mass, further It is preferably 35 to 43% by mass.

The total content of the compounds represented by the formula (I), the formula (II), the formula (IIIb-1) and the formula (VI) is preferably from 55 to 80% by mass, more preferably from 60 to 75% by mass, further It is preferably 63 to 72% by mass.

The total content of the compounds represented by the formula (I), the formula (II), the formula (IIIb-1), the formula (III) and the formula (IV) is preferably from 50 to 75% by mass, more preferably 55. ~70% by mass, further preferably 58 to 65% by mass.

The total content of the compounds represented by the formula (I), the formula (II), the formula (IIIb-1), the formula (III) and the formula (V) is preferably from 35 to 65% by mass, more preferably 40. ~60% by mass, further preferably 45 to 55% by mass.

The total content of the compounds represented by the formula (I), the formula (II), the formula (IIIb-1), the formula (III) and the formula (VI) is preferably 65 to 95% by mass, more preferably 70. ~90% by mass, further preferably 75 to 85% by mass.

General formula (I), general formula (II), formula (IIIb-1), general formula (IV) and general formula (V) The total content of the compounds represented is preferably from 45 to 70% by mass, more preferably from 50 to 65% by mass, still more preferably from 53 to 60% by mass.

The total content of the compounds represented by the formula (I), the formula (II), the formula (IIIb-1), the formula (IV) and the formula (VI) is preferably from 70 to 99% by mass, more preferably 75. ~95% by mass, and more preferably 80 to 90% by mass.

The total content of the compounds represented by the formula (I), the formula (II), the formula (IIIb-1), the formula (V) and the formula (VI) is preferably from 60 to 85% by mass, more preferably 65. ~80% by mass, and more preferably 70 to 75% by mass.

The total content of the compounds represented by the formula (I), the formula (II), the formula (IIIb-1), the formula (III), the formula (IV) and the formula (V) is preferably 55 to 80 by mass. % is more preferably 60 to 75% by mass, further preferably 63 to 70% by mass.

The total content of the compounds represented by the formula (I), the formula (II), the formula (IIIb-1), the formula (III), the formula (IV) and the formula (VI) is preferably 80% by mass or more. More preferably, it is 85 mass% or more, More preferably, it is 90 mass% or more.

The total content of the compounds represented by the general formula (I), the general formula (II), the formula (IIIb-1), the general formula (III), the general formula (V) and the general formula (VI) is preferably 70 to 95 mass. More preferably, it is 75 to 90% by mass, and further preferably 80 to 85% by mass.

The total content of the compounds represented by the formula (I), the formula (II), the formula (IIIb-1), the formula (IV), the formula (V) and the formula (VI) is preferably from 80 to 99 by mass. % is more preferably 85 to 95% by mass, still more preferably 87 to 92% by mass.

The total content of the compounds represented by the general formula (I), the general formula (II), the formula (IIIb-1), the general formula (III), the general formula (IV), the general formula (V) and the general formula (VI) It is preferably 90% by mass or more, more preferably 95% by mass or more, further preferably 97% by mass or more, and more preferably substantially 100% by mass, and more preferably 99.5% by mass or more.

When paying attention to the reliability and long-term stability of the liquid crystal composition, it is preferably The content of the compound having a carbonyl group is 5% by mass or less, more preferably 3% by mass or less, still more preferably 1% by mass or less, and most preferably substantially no content, based on the total mass of the composition. .

When the stability of the ultraviolet (ultraviolet) irradiation is emphasized, the content of the compound substituted with a chlorine atom is preferably 15% by mass or less, more preferably 10%, based on the total mass of the composition. It is preferably 5% by mass or less, more preferably 5% by mass or less, and most preferably substantially not contained.

Preferably, the content of the compound in which the ring structure in the molecule is a six-membered ring is increased, and it is more preferable that the content of the compound having a ring structure of six rings in the molecule is set to 80 mass with respect to the total mass of the above composition. More preferably, it is 90% by mass or more, and more preferably 95% by mass or more, and it is preferable that the liquid crystal composition is substantially composed of only a compound having a ring structure of six rings in the molecule.

In order to suppress deterioration caused by oxidation of the liquid crystal composition, it is preferred to reduce the content of the compound having a cyclohexene group as a ring structure, and it is preferred to compare the content of the compound having a cyclohexenyl group with respect to the total mass of the above composition. It is preferably 10% by mass or less, more preferably 5% by mass or less, and further preferably substantially not contained.

In the case where the improvement of viscosity and the improvement of T _{ni are} emphasized, it is preferred to reduce the content of a compound having a 2-methylbenzene-1,4-diyl group in which a hydrogen atom can be substituted by a halogen, preferably a molecule. The content of the compound having the above 2-methylbenzene-1,4-diyl group is 10% by mass or less, more preferably 5% by mass or less, more preferably substantially 5% by mass based on the total mass of the above-mentioned composition. Does not contain.

In the case where the compound contained in the composition of the first embodiment of the present invention has an alkenyl group as a side chain, in the case where the above alkenyl group is bonded to cyclohexane, the number of carbon atoms of the alkenyl group is preferably 2 ~5, in the case where the above alkenyl group is bonded to benzene, the number of carbon atoms of the alkenyl group is preferably 4 to 5. It is preferred that the unsaturated bond of the above alkenyl group is not directly bonded to benzene.

The value of the dielectric anisotropy Δ ε of the liquid crystal composition in the invention of the present invention is preferably -2.0 to -6.0, more preferably -2.5 to -5.0, still more preferably -2.5 to -4.0 at 25 ° C, if more detailed The description is preferably -2.5 to -3.4 when the response speed is emphasized, and is preferably -3.4 to -4.0 when the driving voltage is emphasized.

The value of the refractive index anisotropy Δn of the liquid crystal composition in the present invention is preferably from 0.08 to 0.13, more preferably from 0.09 to 0.12 at 25 °C. More specifically, it is preferably 0.10 to 0.12 in the case of a thinner cell gap, and preferably 0.08 to 0.10 in the case of a thicker cell gap.

The rotational viscosity (γ ₁ ) of the liquid crystal composition in the present invention is preferably 150 or less, more preferably 130 or less, and still more preferably 120 or less.

In the liquid crystal composition of the present invention, a function Z of rotational viscosity and refractive index anisotropy is preferably a specific value.

(wherein, γ ₁ represents a rotational viscosity, and Δn represents a refractive index anisotropy) Z is preferably 13,000 or less, 12,000 or less, and particularly preferably 11,000 or less.

In the case of being used in an active matrix display device, the liquid crystal composition of the present invention must have a resistivity of 10 ¹² (Ω·m) or more, preferably 10 ¹³ (Ω·m) or more, more preferably 10 ¹⁴ ( Ω.m) or more.

In addition to the above compounds, the liquid crystal composition of the present invention may contain a usual nematic liquid crystal, a smectic liquid crystal, a cholesteric liquid crystal, an antioxidant, an ultraviolet absorber, a polymerizable monomer, etc. depending on the use, and a liquid crystal composition is required. In the case of chemical stability, it is preferred that the molecule does not have a chlorine atom in the molecule. When the liquid crystal composition is required to have stability against light such as ultraviolet rays, it is preferable that the molecule does not have a naphthalene ring or the like. The conjugated length is long and a condensed ring having an absorption peak is present in the ultraviolet region.

The polymerizable monomer is preferably a difunctional monomer represented by the formula (VII).

(wherein, X ⁷ and X ⁸ each independently represent a hydrogen atom or a methyl group, and Sp ¹ and Sp ² each independently represent a single bond, an alkylene group having 1 to 8 carbon atoms or -O-(CH ₂ ) _s -

(wherein s represents an integer from 2 to 7, the oxygen atom is set to be bonded to the aromatic ring), and Z ² represents -OCH ₂ -, -CH ₂ O-, -COO-, -OCO-, -CF ₂ O- , -OCF ₂ -, -CH ₂ CH ₂ -, -CF ₂ CF ₂ -, -CH=CH-COO-, -CH=CH-OCO-, -COO-CH=CH-, -OCO-CH=CH -, -COO-CH ₂ CH ₂ -, -OCO-CH ₂ CH ₂ -, -CH ₂ CH ₂ -COO-, -CH ₂ CH ₂ -OCO-, -COO-CH ₂ -, -OCO-CH ₂ -, -CH ₂ -COO-, -CH ₂ -OCO-, -CY ¹ =CY ² - (wherein Y ¹ and Y ² each independently represent a fluorine atom or a hydrogen atom), -C≡C- or a single bond B represents a 1,4-phenylene group, a trans-1,4-cyclohexylene group or a single bond, and any of the hydrogen atoms in the 1,4-phenylene group in the formula may be substituted with a fluorine atom).

X ⁷ and X ⁸ each represent a diacrylate derivative of a hydrogen atom, and X ⁷ and X ⁸ each represent a dimethacrylate derivative having a methyl group, and one of them is preferably a hydrogen atom. It is also preferred that the compound of the methyl group is present. Regarding the polymerization rate of the compounds, the diacrylate derivative is the fastest, the dimethacrylate derivative is slow, and the asymmetric compound is centered, and a preferred aspect can be used depending on the use thereof. A dimethacrylate derivative is particularly preferred in the PSA display element.

Sp ¹ and Sp ² each independently represent a single bond, an alkylene group having 1 to 8 carbon atoms or -O-(CH ₂ ) _s -, and at least one of the PSA display elements is preferably a single bond, preferably A compound which represents a single bond, or one of which is a single bond, and the other represents an alkylene group having 1 to 8 carbon atoms or -O-(CH ₂ ) _s -. In this case, it is preferably an alkyl group of 1 to 4, and s is preferably 1 to 4.

Z ^{2 is} preferably -OCH ₂ -, -CH ₂ O-, -COO-, -OCO-, -CF ₂ O-, -OCF ₂ -, -CH ₂ CH ₂ -, -CF ₂ CF ₂ - or The key is more preferably -COO-, -OCO- or a single bond, and particularly preferably a single bond.

B represents a 1,4-phenylene group, a trans-1,4-cyclohexylene group or a single bond which may be substituted with a fluorine atom, preferably a 1,4-phenylene group or a single bond. When B represents a ring structure other than a single bond, Z ^{2 is} also preferably a linking group other than a single bond. When B is a single bond, Z ^{2 is} preferably a single bond.

In these terms, in the general formula (VII), the ring structure between Sp ¹ and Sp ² is specifically preferably the structure described below.

In the general formula (VII), when B represents a single bond and the ring structure is formed of two rings, it preferably represents the following formula (VIIa-1) to formula (VIIa-5).

(where the two ends are set to bond with Sp ¹ or Sp ² )

More preferably, it is represented by the formula (VIIa-1) to the formula (VIIa-3), and particularly preferably represents the formula (VIIa-1).

Since the alignment restricting force of the polymerizable compound containing the skeletons after polymerization is most suitable for the PSA type liquid crystal display device, a good alignment state can be obtained, so that display unevenness is suppressed, or display unevenness does not occur at all.

In the above aspect, the polymerizable monomer is preferably a formula (VII-1) to a formula (VII-4), and among them, the formula (VII-2) is most preferable.

(wherein, Sp ² represents an alkylene group having 2 to 5 carbon atoms)

In the case where a monomer is added to the liquid crystal composition of the present invention, the polymerization is carried out in the absence of a polymerization initiator, but a polymerization initiator may be contained in order to promote the polymerization. Examples of the polymerization initiator include benzoin ethers, diphenylketones, acetophenones, benzoin ketals, and fluorenylphosphine oxides. Further, in order to improve storage stability, a stabilizer may be added. Examples of stabilizers that can be used include hydroquinones, hydroquinone monoalkyl ethers, tert-butylcatechols, pyrogallols, thiophenols, and nitro compounds. Classes, β-naphthylamines, β-naphthols, nitroso compounds, and the like.

The liquid crystal composition containing the polymerizable compound of the present invention can be used for a liquid crystal display element, and can be particularly used for a liquid crystal display element for active matrix driving, and can be used in a PSA mode, a PSVA (Polymer Stabilized Vertically Alignment) mode, Liquid crystal display element for VA mode, IPS mode or ECB (Electrically Controlled Birefringence) mode.

The liquid crystal composition containing a polymerizable compound of the present invention is polymerized by ultraviolet irradiation to impart a liquid crystal alignment ability, and can be used to control the light transmittance by utilizing the birefringence of the liquid crystal composition. Liquid crystal display element. As a liquid crystal display element, it can be used for AM-LCD (Active Matrix-Liquid Crystal Display) Liquid crystal display element), TN (twisted nematic liquid crystal display element), STN-LCD (super twisted nematic liquid crystal display element), OCB-LCD and IPS-LCD (coplanar switching liquid crystal display element), especially for AM - LCD, and can be used for a transmissive or reflective liquid crystal display element.

Further, when the liquid crystal display element described below and the contents of FIGS. 1 to 4 are used as a reference, the two substrates 2 and 8 of the liquid crystal cell used for the liquid crystal display element may use glass or a transparent material which is soft like plastic, and the other In terms of opaque materials such as enamel. The transparent substrates 2 and 8 including the transparent electrodes (layers) 6 and 14 can be obtained, for example, by sputtering indium tin oxide (ITO, Indium Tin Oxide) on a transparent substrate such as the glass plates 2 and 8.

The substrates 2 and 8 on which the transparent electrodes (layers) or TFTs are formed are opposed to each other such that the transparent electrodes (layers) 6 and 14 are inside. At this time, the substrate pitch can also be adjusted via a spacer (not shown) (see FIGS. 1 to 4). In this case, it is preferable to adjust so that the thickness of the obtained light control layer becomes 1 to 100 μm. Further, it is preferably 1.5 to 10 μm. When a polarizing plate is used, it is preferable to adjust the product of the refractive index anisotropy Δn of the liquid crystal and the cell thickness d so that the contrast is maximized. Further, when two polarizing plates 1 and 9 are provided, the polarization axes of the respective polarizing plates can be adjusted to adjust the viewing angle or contrast (see FIGS. 1 to 4). Further, a retardation film for increasing the viewing angle can be used. Examples of the separator include glass particles, plastic particles, alumina particles, and photoresist materials. Thereafter, a sealing agent such as an epoxy thermosetting composition is screen-printed on the substrate in the form of a liquid crystal injection port, and the substrates are bonded to each other to heat the sealing agent.

A method of introducing a liquid crystal composition containing a polymerizable monomer into a liquid crystal composition accommodating space in which a liquid crystal composition formed by bonding two substrates to each other in such a manner as described above can be used, and a general vacuum injection method or In the ODF method or the like, the vacuum injection method does not cause a drop mark, but has a problem of remaining after the injection. In the invention of the present invention, the display element manufactured by the ODF method can be used more suitably.

As a method of polymerizing a polymerizable compound, in order to obtain a good alignment of liquid crystals The performance is desirably a moderate polymerization rate, and therefore it is preferred to carry out the polymerization by separately using, using, or sequentially irradiating an active energy ray such as an ultraviolet ray or an electron beam. For the case of using ultraviolet rays, a polarized light source or a non-polarized light source may be used. In the case where the liquid crystal composition containing the polymerizable compound is polymerized between the two substrates, it is necessary to impart appropriate transparency to the active energy ray to the substrate on the irradiation surface side. Further, a method in which only a specific portion is polymerized by using a mask after light irradiation, a condition such as an electric field, a magnetic field, or a temperature is changed, and an alignment state of an unpolymerized portion is changed, and an active energy ray is irradiated. Perform polymerization. In particular, when ultraviolet exposure is performed, it is preferred to perform ultraviolet exposure while applying an alternating electric field to the liquid crystal composition containing the polymerizable compound. The applied alternating electric field is preferably an alternating current having a frequency of 10 Hz to 10 kHz, more preferably a frequency of 60 Hz to 10 kHz, and the voltage can be selected in accordance with a pretilt angle required for the liquid crystal display element. That is, the pretilt angle of the liquid crystal display element can be controlled by the applied voltage. In the liquid crystal display device of the MVA (Multi-Domain Vertical Alignment) mode, it is preferable to control the pretilt angle to 80 to 89.9 degrees from the viewpoint of alignment stability and contrast.

The temperature at the time of irradiation is preferably within a temperature range in which the liquid crystal state of the liquid crystal composition of the present invention can be maintained. It is preferred to carry out the polymerization at a temperature close to room temperature, that is, typically 15 to 35 °C. As the lamp for generating ultraviolet rays, a metal halide lamp, a high pressure mercury lamp, an ultrahigh pressure mercury lamp, or the like can be used. Further, as the wavelength of the ultraviolet ray to be irradiated, it is preferred to irradiate the ultraviolet ray in the wavelength region of the absorption wavelength region of the non-liquid crystal composition, and it is preferable to use it as needed to cut off the ultraviolet ray. The intensity of the ultraviolet ray to be irradiated is preferably from 0.1 mW/cm ² to 100 W/cm ² , more preferably from 2 mW/cm ² to 50 W/cm ² . The ultraviolet energy to be irradiated can be suitably adjusted, preferably from 10 mJ/cm ² to 500 J/cm ² , more preferably from 100 mJ/cm ² to 200 J/cm ² . It can also change the intensity when irradiated with ultraviolet light. The time for irradiating the ultraviolet rays can be appropriately selected depending on the intensity of the ultraviolet rays to be irradiated, and is preferably from 10 seconds to 3600 seconds, more preferably from 10 seconds to 600 seconds.

The second invention of the present invention uses liquid crystal display having the liquid crystal composition of the present invention Show components. Fig. 1 is a view schematically showing the configuration of a liquid crystal display element. In addition, in FIG. 1, for the sake of explanation, it is convenient to separate and separate each component. 2 is a plan view showing an enlarged region of the electrode layer 3 (or also referred to as a thin film transistor layer 3) including the thin film transistor formed on the substrate in FIG. Figure 3 is a cross-sectional view showing the liquid crystal display element shown in Figure 1 taken along the line III-III in Figure 2 . Fig. 4 is an enlarged view of the thin film transistor of the region IV in Fig. 3. Hereinafter, a liquid crystal display element of the present invention will be described with reference to Figs.

The liquid crystal display device 10 of the present invention has a configuration in which the liquid crystal display device includes a first substrate 8 including a transparent electrode (layer) 6 (also referred to as a common electrode 6) made of a transparent conductive material, and includes a pixel electrode formed of a transparent conductive material; a second substrate 2 on which the thin film transistor layer 3 of the thin film transistor for controlling the pixel electrode included in each pixel is formed; and the first substrate 8 and the second substrate 2 are sandwiched between Between the liquid crystal composition (or the liquid crystal layer 5), the alignment of the liquid crystal molecules in the liquid crystal composition is substantially perpendicular to the substrates 2, 8 when no voltage is applied, and the liquid crystal display element has a liquid crystal composition using the above-described present invention. The material is characteristic of the liquid crystal composition. Further, as shown in FIGS. 1 and 3, the second substrate 2 and the first substrate 8 may be sandwiched between the pair of polarizing plates 1 and 9. Further, in FIG. 1, a color filter 7 is provided between the first substrate 8 and the common electrode 6. Further, a pair of alignment films 4 may be formed on the surfaces of the transparent electrodes (layers) 6 and 14 so as to be adjacent to the liquid crystal layer 5 of the present invention and directly in contact with the liquid crystal composition constituting the liquid crystal layer 5.

That is, the liquid crystal display element 10 of the present invention sequentially laminates the second polarizing plate 1, the second substrate 2, the electrode layer (or also referred to as a thin film transistor layer) 3 including the thin film transistor, the alignment film 4, and the liquid crystal. The composition of the layer 5, the alignment film 4, the common electrode 6, the color filter 7, the first substrate 8, and the first polarizing plate 9.

Further, as shown in FIG. 2, the gate wiring 25 for supplying the scanning signal and the data wiring 24 for supplying the display signal formed on the electrode layer 3 including the thin film transistor formed on the surface of the second substrate 2 cross each other, and The plurality of gate wirings 25 and the plurality of data wirings 24 In the region surrounded, the pixel electrodes 21 are formed in a matrix shape. As a switching element that supplies a display signal to the pixel electrode 21, a source electrode 26 and a drain electrode 23 are provided in the vicinity of an intersection of the gate wiring 25 and the data wiring 24, and the pixel electrode 21 is connected to the pixel electrode 21; Thin film transistor of gate electrode 27. Further, a storage capacitor 22 for storing a display signal supplied via the data wiring 24 is provided in a region surrounded by the plurality of gate wirings 25 and the plurality of data wirings 24.

In the present invention, it is particularly preferable that the thin film transistor is an inverted staggered liquid crystal display element as described in FIGS. 2 to 4, and the gate wiring 25 or the data wiring 24 is preferably used. In order to use a metal film, it is particularly preferable to use aluminum wiring. Further, the gate wiring and the data wiring are overlapped via the gate insulating film.

Further, from the viewpoint of preventing light leakage, the color filter 7 preferably forms a black matrix (not shown) in a portion corresponding to the thin film transistor and the storage capacitor 22.

A preferred embodiment of the thin film transistor of the liquid crystal display device of the present invention is as follows. For example, as shown in FIG. 3 and FIG. 4, the gate electrode 11 is formed on the surface of the substrate 2 to cover the gate electrode. a gate insulating layer 13 provided to cover substantially the entire surface of the substrate 2, and a semiconductor layer 17 formed on the surface of the gate insulating layer 13 opposite to the gate electrode 11 to cover the semiconductor layer A protective film 18 provided in a part of the surface of the substrate 17 is provided so as to cover the protective layer 18 and one end portion of the semiconductor layer 17 and is in contact with the gate insulating layer 13 formed on the surface of the substrate 2 The drain electrode 15 and the source electrode 19a, 19b provided to cover the other end portion of the protective film 18 and the semiconductor layer 17 and in contact with the gate insulating layer 13 formed on the surface of the substrate 2 a transparent electrode 14 disposed to cover the source electrode 19a, 19b and emulating the gate insulating layer 13 covering substantially the entire surface of the gate insulating layer 13, and a portion covering the transparent electrode 14 The protective layer 101 is provided above the source electrode 19a, 19b of the embodiment (not shown in FIG. 3).

Moreover, as shown in FIGS. 3 and 4, based on the elimination of the step difference from the gate electrode, etc., An anodized film 12 can also be formed on the surface of the gate electrode 11. Further, in order to reduce the width or height of the Schottky barrier, an ohmic contact layer 16 may be provided between the semiconductor layer 17 and the gate electrode 15.

As described above, in the process of manufacturing a liquid crystal display element, the occurrence of the dropping mark is greatly affected by the liquid crystal material to be injected, and the influence of the liquid crystal display element cannot be avoided. In particular, the color filter 7 or the thin film transistor formed in the liquid crystal display element, as shown in FIG. 3, is a member which is separated from the liquid crystal composition by only the thin alignment film 4 or the transparent electrodes 6, 14 and the like. Therefore, for example, the chemical structure of the pigment used in the color filter or the combination of the chemical structure of the color filter resin and the liquid crystal compound having a specific chemical structure may affect the occurrence of the dropping mark.

In particular, when the reverse-staggered type is used as the thin film transistor of the liquid crystal display element of the present invention, as shown in FIGS. 2 to 4, since the gate electrode 15 is formed to cover the gate electrode 11, there is The tendency of the area of the drain electrode 15 to increase. In general, the gate electrode is usually formed of a metal material such as copper, aluminum, chromium, titanium, molybdenum or tantalum, and is subjected to passivation treatment. However, as shown in, for example, FIGS. 3 and 4, the protective film 18 is generally thin, and the alignment film 4 is also thin, and it is likely that the ionic substance is not blocked, and therefore, the interaction between the metal material and the liquid crystal composition cannot be avoided. Lead to the creation of drops.

However, it is considered that the liquid crystal display element including the liquid crystal composition of the present invention may be, for example, a subtle balance between the surface free energy or the adsorption energy of the liquid crystal display element of the present invention. Reduce the problem of the occurrence of dripping marks.

The liquid crystal display element using the liquid crystal composition of the present invention is useful for simultaneously achieving high-speed response and suppressing display defects, and is particularly useful for active matrix driving liquid crystal display elements, and can be applied to VA mode, PSVA mode, PSA mode, IPS mode or The purpose of the ECB mode.

[Examples]

Hereinafter, the present invention will be described in more detail by way of examples, but the invention is not limited thereto These embodiments. Moreover, "%" in the compositions of the following examples and comparative examples means "% by mass".

In the examples, the properties measured were as follows.

T _ni : nematic phase-isotropic liquid phase transfer temperature (°C)

△n: refractive index anisotropy at 25 ° C

△ ε: dielectric anisotropy at 25 ° C

η: viscosity at 20 ° C (mPa.s)

γ ₁ : rotational viscosity at 25 ° C (mPa.s)

VHR (Voltage Holding Ratio): Voltage holding ratio at 60 ° C at a frequency of 60 Hz and a voltage of 1 V (%)

Afterimage: The afterimage evaluation of the liquid crystal display element was evaluated by displaying the specific fixed pattern for 1000 hours in the display area, and visually evaluating the level of the residual image of the fixed pattern when the entire screen was uniformly displayed by the following four levels.

◎ no residual image

○ Although there is a slight residual image, the level that can be tolerated

△ has residual image and can not be tolerated

× has residual image and is quite serious

Drop mark: The evaluation of the drop mark of the liquid crystal display device was evaluated by visually displaying the white mark on the entire surface by the following four levels.

◎ no residual image

○ Although there is a slight residual image, the level that can be tolerated

△ has residual image and can not be tolerated

× has residual image and is quite serious

Process suitability: Process suitability is in the ODF process, using an isometric metering pump to perform 100,000 operations of adding 50 pL of liquid crystal per drop, with the following four levels for the following "0 to 100 times, 101 to 200 times, 201 to 300 times, ...99901~100000 times" The change in the amount of liquid crystal added per 100 times was evaluated.

◎ Very small change (can stably manufacture liquid crystal display elements)

○Although a slight change but acceptable level

△ There is a change and it is not acceptable (the yield is deteriorated due to the occurrence of marks)

× varies and is quite serious (liquid crystal leakage or vacuum bubbles are generated)

Solubility at low temperature: Solubility evaluation at low temperature After preparing a liquid crystal composition, 1 g of a liquid crystal composition was weighed in a 2 mL sample bottle, placed in a temperature-controlled test tank, and the following operation was set to one. Cycle "-20 ° C (for 1 hour) → temperature increase (0.1 ° C / min) → 0 ° C (for 1 hour) → temperature (0.1 ° C / min) → 20 ° C (for 1 hour) → cooling (-0.1 ° C / per minute) → 0 ° C (for 1 hour) → cooling (-0.1 ° C / min) → -20 ° C" and continue to impart temperature changes, visual observation of the production of precipitates from the liquid crystal composition, the following four Ratings are evaluated.

◎ No precipitate was observed for 600 hours or more.

○ No precipitate was observed for more than 300 hours.

△ The precipitate was observed within 150 hours.

× Precipitate was observed within 75 hours.

Further, in the examples, the following abbreviations are used for the description of the compounds.

(side chain)

-n -C _n H _{2n+1 a} linear alkyl group having n carbon atoms

-On -OC _n H _2n+1 linear alkoxy group having n carbon atoms

-V -C=CH ₂ vinyl

-Vn -C=CC _n H _{2n+1 1} atomic number of carbon atoms (n+1)

(ring structure)

(Example 1)

A liquid crystal composition (Example 1) having the composition shown below was prepared, and the physical property values thereof were measured. The results are shown in the table below.

A VA liquid crystal display element was produced using the liquid crystal composition of Example 1. The liquid crystal display element has an inverted staggered thin film transistor as an active element. The injection of the liquid crystal composition was carried out by a dropping method, and the residual image, the dropping mark, the process suitability, and the solubility at low temperature were evaluated.

Further, the left side mark of the content is a description of the abbreviation of the above compound.

Example 1

It is understood that the liquid crystal composition of Example 1 has a liquid crystal phase temperature range of 75.0 ° C which is practical as a liquid crystal composition for TV, has a large absolute value of dielectric anisotropy, and has low viscosity and optimum Δn. . The VA liquid crystal display element was produced using the liquid crystal composition described in Example 1, and the afterimage, the dropping mark, the process suitability, and the solubility at low temperature were evaluated by the above method, and as a result, the evaluation result was extremely excellent.

(Comparative Example 1)

The preparation of the compound represented by the formula (I) is carried out, and has a liquid crystal phase temperature range equivalent to that of the composition of Example 1, an equivalent refractive index anisotropy value, and an equivalent dielectric anisotropy. The liquid crystal composition (Comparative Example 1) shown below was designed and measured for the physical property value. The results are shown in the table below.

A VA liquid crystal display element was produced in the same manner as in Example 1 using the liquid crystal composition of Comparative Example 1, and the afterimage, the dropping mark, the process suitability, and the solubility at low temperature were evaluated, and the results are shown in the same table. in.

Further, the symbol on the left side of the content is the same as in the first embodiment, and the description of the above compound is abbreviated.

Comparative example 1

As described above, the liquid crystal composition (Comparative Example 1) containing no compound represented by the formula (I) has the same liquid crystal composition (Example 1) containing 10% by mass of the compound represented by the formula (I). The liquid crystal phase temperature range, the equivalent value of the refractive index anisotropy, and the equivalent dielectric anisotropy value, but the viscosity η increases. Regarding γ ₁ , the value of Comparative Example 1 is 118 mPa. s with the value of Example 1 of 106 mPa. Compared with s, a higher value is displayed, and even if the value of γ ₁ /Δn ² which is a parameter indicating the effective response speed of the liquid crystal display element and the display is compared, it is a poor result. The initial VHR of Comparative Example 1 was 99.0%. On the other hand, the VHR after standing at a high temperature of 150 ° C for 1 hour was 98.5%, which was inferior to the result of Example 1. The process suitability was evaluated, and as a result, the level of change was not allowed as compared with Example 1. When the solubility at low temperature was evaluated, precipitation was observed earlier than in Example 1.

(Comparative Example 2 and Comparative Example 3)

The preparation does not contain the compound represented by the formula (II), and has a liquid crystal phase temperature range equivalent to the composition of the embodiment 1, an equivalent refractive index anisotropy value, and an equivalent dielectric anisotropy. The liquid crystal composition (Comparative Example 2) shown below and the compound represented by the formula (IIIb-1) were designed, and the liquid crystal phase temperature range equivalent to that of the composition of Example 1 was The liquid crystal composition (Comparative Example 3) shown below was designed in such a manner that the value of the refractive index anisotropy and the equivalent dielectric anisotropy were the same, and the physical property values were measured. The results are shown in the table below.

Using the liquid crystal compositions of Comparative Example 2 and Comparative Example 3, a VA liquid crystal display device was produced in the same manner as in Example 1, and the residual image, the dropping mark, the process suitability, and the solubility at low temperature were evaluated. Shown in the same table.

As described above, the liquid crystal composition (Comparative Example 2) containing no compound represented by the formula (II) has the same liquid crystal composition (Example 1) as the compound represented by the formula (II): 9% by mass. The liquid crystal phase temperature range, the equivalent value of the refractive index anisotropy, and the equivalent dielectric anisotropy value, but the viscosity η increases. Regarding γ ₁ , the value of Comparative Example 2 is 121 mPa. s with the value of Example 1 of 106 mPa. Compared with s, a higher value is displayed, and even if the value of γ ₁ /Δn ² which is a parameter indicating the effective response speed of the liquid crystal display element and the display is compared, it is a poor result. The initial VHR of Comparative Example 2 was 99.1%. On the other hand, the VHR after standing at a high temperature of 150 ° C for 1 hour was 98.3%, which was inferior to the result of Example 1. The process suitability was evaluated, and as a result, the level of change was not allowed as compared with Example 1. When the solubility at low temperature was evaluated, precipitation was observed earlier than in Example 1.

As described above, the liquid crystal composition (Comparative Example 3) containing no compound represented by the formula (IIIb-1) has a liquid crystal composition containing a compound represented by the formula (IIIb-1) of 13% by mass (Example 1). The equivalent liquid crystal phase temperature range, the same value of the refractive index anisotropy, and the equivalent dielectric anisotropy value, but the viscosity η increases. Regarding γ ₁ , the value of Comparative Example 3 is 111 mPa. s with the value of Example 1 of 106 mPa. Compared with s, a higher value is displayed, and even if the value of γ ₁ /Δn ² which is a parameter indicating the effective response speed of the liquid crystal display element and the display is compared, it is a poor result, but the difference is not necessarily large. However, the initial VHR of Comparative Example 3 was 98.9%. On the other hand, the VHR after leaving at a high temperature of 150 ° C for 1 hour was 97.8%, which was substantially inferior to the result of Example 1. The process suitability was evaluated, and as a result, the level of change was not allowed as compared with Example 1. When the solubility at low temperature was evaluated, precipitation was observed earlier than in Example 1.

(Example 2 and Example 3)

A liquid crystal composition having the composition shown below was prepared in such a manner as to have a liquid crystal phase temperature range equivalent to that of the composition of Example 1, equivalent value of refractive index anisotropy, and equivalent dielectric anisotropy. (Example 2 and Example 3), and the physical property values were measured. The results are shown in the table below.

Using the liquid crystal compositions of Example 2 and Example 3, a VA liquid crystal display device was produced in the same manner as in Example 1, and the residual image, the dropping mark, the process suitability, and the solubility at low temperature were evaluated. Shown in the same table.

It is understood that the liquid crystal composition of the second embodiment has a liquid crystal phase temperature range which is practical as a liquid crystal composition for TV, has a large absolute value of dielectric anisotropy, and has low viscosity and optimum Δn. The VA liquid crystal display device was produced by using the liquid crystal composition described in Example 2, and the residual image, the dropping mark, the process suitability, and the solubility at low temperature were evaluated by the above method, and as a result, excellent evaluation results were obtained.

It is understood that the liquid crystal composition of Example 3 has a liquid crystal phase temperature range which is practical as a liquid crystal composition for TV, has a large absolute value of dielectric anisotropy, and has low viscosity and optimum Δn. The VA liquid crystal display element was produced using the liquid crystal composition described in Example 3, and the afterimage, the dropping mark, the process suitability, and the solubility at low temperature were evaluated by the above method, and as a result, excellent evaluation results were obtained.

(Example 4 and Example 5)

A liquid crystal composition having the composition shown below was prepared in such a manner as to have a liquid crystal phase temperature range equivalent to that of the composition of Example 1, equivalent value of refractive index anisotropy, and equivalent dielectric anisotropy. (Example 4 and Example 5), and the physical property values were measured. The results are shown in the table below.

Using the liquid crystal compositions of Example 4 and Example 5, a VA liquid crystal display element was produced in the same manner as in Example 1, and the residual image, the dropping mark, the process suitability, and the solubility at low temperature were evaluated. Shown in the same table.

It is understood that the liquid crystal composition of Example 4 has a liquid crystal phase temperature range which is practical as a liquid crystal composition for TV, has a large absolute value of dielectric anisotropy, and has low viscosity and optimum Δn. A VA liquid crystal display device was produced using the liquid crystal composition described in Example 4, and The residual image, the drop mark, the process suitability, and the solubility at low temperature were evaluated by the above method, and the results were excellent.

It is understood that the liquid crystal composition of Example 5 has a liquid crystal phase temperature range which is practical as a liquid crystal composition for TV, has a large absolute value of dielectric anisotropy, and has low viscosity and optimum Δn. The VA liquid crystal display element was produced using the liquid crystal composition described in Example 5, and the residual image, the dropping mark, the process suitability, and the solubility at low temperature were evaluated by the above method, and as a result, excellent evaluation results were obtained.

(Example 6)

A liquid crystal composition having the composition shown below was prepared in such a manner as to have a liquid crystal phase temperature range equivalent to that of the composition of Example 1, equivalent value of refractive index anisotropy, and equivalent dielectric anisotropy. (Example 6), and the physical property value was measured. The results are shown in the table below.

Using the liquid crystal composition of Example 6, a VA liquid crystal display element was produced in the same manner as in Example 1, and the residual image, the dropping mark, the process suitability, and the solubility at low temperature were evaluated, and the results were shown in the same table. in.

It is understood that the liquid crystal composition of Example 6 has a liquid crystal phase temperature range which is practical as a liquid crystal composition for TV, has a large absolute value of dielectric anisotropy, and has low viscosity and optimum Δn. The VA liquid crystal display element was produced using the liquid crystal composition described in Example 6, and the residual image, the dropping mark, the process suitability, and the solubility at low temperature were evaluated by the above method, and as a result, excellent evaluation results were obtained.

(Example 7)

Prepared to have the same liquid crystal phase temperature range and equivalent dielectric as the composition of Example 1. A liquid crystal composition having the following composition, which is designed to have a higher refractive index value, that is, a narrower gap in a liquid crystal display, and which is designed to cope with a high-speed response (Example 7), and is determined Its physical value. The results are shown in the table below.

Using the liquid crystal composition of Example 7, a VA liquid crystal display element was produced in the same manner as in Example 1, and the residual image, the dropping mark, the process suitability, and the solubility at low temperature were evaluated, and the results were shown in the same table. in.

It is understood that the liquid crystal composition of Example 7 has a liquid crystal composition for TV. The liquid crystal phase temperature range used has a large absolute value of dielectric anisotropy, and has low viscosity and optimum Δn. The VA liquid crystal display element was produced using the liquid crystal composition described in Example 7, and the residual image, the dropping mark, the process suitability, and the solubility at low temperature were evaluated by the above method, and as a result, excellent evaluation results were obtained.

(Comparative Example 4 and Comparative Example 5)

The preparation does not contain the compound represented by the formula (I), and has a liquid crystal phase temperature range equivalent to the composition of the embodiment 7, an equivalent refractive index anisotropy value, and an equivalent dielectric anisotropy. The liquid crystal composition (Comparative Example 4) shown below and the compound represented by the formula (II) were designed to have the same liquid crystal phase temperature range and equivalent refractive index as the composition of Example 7. The liquid crystal composition (Comparative Example 5) shown below was designed in such a manner that the value of the anisotropy and the value of the dielectric anisotropy were the same, and the physical property value was measured. The results are shown in the table below.

Using the liquid crystal compositions of Comparative Example 4 and Comparative Example 5, a VA liquid crystal display device was produced in the same manner as in Example 7, and the residual image, the dropping mark, the process suitability, and the solubility at low temperature were evaluated. Shown in the same table.

As described above, the liquid crystal composition (Comparative Example 4) containing no compound represented by the formula (I) has the same liquid crystal composition (Example 7) containing 10% by mass of the compound represented by the formula (I). The liquid crystal phase temperature range, the equivalent value of the refractive index anisotropy, and the equivalent dielectric anisotropy value, but the viscosity η increases. Regarding γ ₁ , the value of Comparative Example 4 is 124 mPa. s with the value of Example 7 of 112 mPa. Compared with s, a higher value is displayed, and even if the value of γ ₁ /Δn ² which is a parameter indicating the effective response speed of the liquid crystal display element and the display is compared, it is a poor result. The initial VHR of Comparative Example 4 was 98.7%. On the other hand, the VHR after leaving at 150 ° C for 1 hour was 98.0%, which was inferior to the result of Example 7. The process suitability was evaluated, and as a result, the level of change was not allowed as compared with Example 7. When the solubility at low temperature was evaluated, precipitation was observed earlier than in Example 7.

As described above, the liquid crystal composition (Comparative Example 5) containing no compound represented by the formula (II) has the same liquid crystal composition (Example 7) containing 9.5% by mass of the compound represented by the formula (II). The liquid crystal phase temperature range, the equivalent value of the refractive index anisotropy, and the equivalent dielectric anisotropy value, but the viscosity η increases. Regarding γ ₁ , the value of Comparative Example 5 is 129 mPa. s with the value of Example 7 of 112 mPa. Compared with s, a higher value is displayed, and even if the value of γ ₁ /Δn ² which is a parameter indicating the effective response speed of the liquid crystal display element and the display is compared, it is a poor result. The initial VHR of Comparative Example 5 was 98.6%. On the other hand, the VHR after leaving at 150 ° C for 1 hour was 97.7%, which was inferior to the result of Example 7. The process suitability was evaluated, and as a result, the level of change was not allowed as compared with Example 7. When the solubility at low temperature was evaluated, precipitation was observed earlier than in Example 7.

(Comparative Example 6)

A value which does not contain the compound represented by the formula (IIIb-1) and which has a liquid crystal phase temperature range equivalent to that of the composition of Example 7, an equivalent refractive index anisotropy, and an equivalent dielectric anisotropy The liquid crystal composition (Comparative Example 6) shown below was designed and measured for the physical property value. The results are shown in the table below.

Using the liquid crystal composition of Comparative Example 6, a VA liquid crystal display device was produced in the same manner as in Example 7, and the residual image, the dropping mark, the process suitability, and the solubility at low temperature were evaluated, and the results were shown in the same table. in.

As described above, the liquid crystal composition (Comparative Example 6) containing no compound represented by the formula (IIIb-1) has a liquid crystal composition containing a compound represented by the formula (IIIb-1) of 13% by mass (Example 7). The equivalent liquid crystal phase temperature range, the same value of the refractive index anisotropy, and the equivalent dielectric anisotropy value, but the viscosity η increases. Regarding γ ₁ , the value of Comparative Example 6 is 115 mPa. s with the value of Example 7 of 112 mPa. Compared with s, a higher value is displayed, and even if the value of γ ₁ /Δn ² which is a parameter indicating the effective response speed of the liquid crystal display element and the display is compared, it is a poor result, but the difference is not necessarily large. However, the initial VHR of Comparative Example 6 was 98.7%. On the other hand, the VHR after leaving at a high temperature of 150 ° C for 1 hour was 97.5%, which was substantially inferior to the result of Example 7. The process suitability was evaluated, and as a result, the level of change was not allowed as compared with Example 7. When the solubility at low temperature was evaluated, precipitation was observed earlier than in Example 7.

(Example 8 and Example 9)

A liquid crystal composition having the composition shown below was prepared in such a manner as to have a liquid crystal phase temperature range equivalent to that of the composition of Example 7, an equivalent value of refractive index anisotropy, and an equivalent dielectric anisotropy. (Example 8 and Example 9), and the physical property values were measured. The results are shown in the table below.

Using the liquid crystal compositions of Example 8 and Example 9, a VA liquid crystal display element was produced in the same manner as in Example 7, and the residual image, the dropping mark, the process suitability, and the solubility at low temperature were evaluated. Shown in the same table.

It is understood that the liquid crystal composition of Example 8 has a liquid crystal phase temperature range which is practical as a liquid crystal composition for TV, has a large absolute value of dielectric anisotropy, and has low viscosity and optimum Δn. The VA liquid crystal display element was produced using the liquid crystal composition described in Example 8, and the residual image, the dropping mark, the process suitability, and the solubility at low temperature were evaluated by the above method, and as a result, excellent evaluation results were obtained.

It is understood that the liquid crystal composition of Example 9 has a liquid crystal phase temperature range which is practical as a liquid crystal composition for TV, has a large absolute value of dielectric anisotropy, and has low viscosity and optimum Δn. The VA liquid crystal display device was produced using the liquid crystal composition described in Example 9, and the afterimage, the dropping mark, the process suitability, and the solubility at low temperature were evaluated by the above method, and as a result, excellent evaluation results were obtained.

(Example 10 and Example 11)

A liquid crystal composition having the composition shown below was prepared in such a manner as to have a liquid crystal phase temperature range equivalent to that of the composition of Example 7, an equivalent value of refractive index anisotropy, and an equivalent dielectric anisotropy. (Example 10 and Example 11), and the physical property values were measured. The results are shown in the table below.

Using the liquid crystal compositions of Example 10 and Example 11, a VA liquid crystal display device was produced in the same manner as in Example 7, and the residual image, the dropping mark, the process suitability, and the solubility at low temperature were evaluated. Shown in the same table.

It is understood that the liquid crystal composition of Example 10 has a liquid crystal phase temperature range which is practical as a liquid crystal composition for TV, has a large absolute value of dielectric anisotropy, and has low viscosity and optimum Δn. The VA liquid crystal display element was produced using the liquid crystal composition described in Example 10, and the residual image, the dropping mark, the process suitability, and the solubility at low temperature were evaluated by the above method, and as a result, excellent evaluation results were obtained.

It is understood that the liquid crystal composition of Example 11 has a liquid crystal phase temperature range which is practical as a liquid crystal composition for TV, has a large absolute value of dielectric anisotropy, and has low viscosity and optimum Δn. A VA liquid crystal display device was produced using the liquid crystal composition described in Example 11, and the residual image, the dropping mark, the process suitability, and the solubility at low temperature were evaluated by the above method. Excellent evaluation results.

(Embodiment 12)

A liquid crystal composition having the composition shown below was prepared in such a manner as to have a liquid crystal phase temperature range equivalent to that of the composition of Example 7, an equivalent value of refractive index anisotropy, and an equivalent dielectric anisotropy. (Example 12). And determine its physical property value. The results are shown in the table below.

Using the liquid crystal composition of Example 12, a VA liquid crystal display element was produced in the same manner as in Example 7, and the residual image, the dropping mark, the process suitability, and the solubility at low temperature were evaluated, and the results were shown in the same table. in.

It is understood that the liquid crystal composition of Example 12 has a liquid crystal phase temperature range which is practical as a liquid crystal composition for TV, has a large absolute value of dielectric anisotropy, and has low viscosity and optimum Δn. The VA liquid crystal display element was produced using the liquid crystal composition described in Example 12, and the residual image, the dropping mark, the process suitability, and the solubility at low temperature were evaluated by the above method, and as a result, excellent evaluation results were obtained.

1‧‧‧second polarizer

2‧‧‧second substrate

3‧‧‧Thin-film transistor layer, electrode layer containing thin film transistor

4‧‧‧Alignment film

5‧‧‧Liquid layer

6‧‧‧pixel electrode (common electrode)

7‧‧‧Color filters

8‧‧‧First substrate

9‧‧‧First polarizer

10‧‧‧Liquid display components

Claims (9)

A liquid crystal composition having a negative dielectric anisotropy and containing one or more compounds selected from the group consisting of compounds represented by the formula (I), and containing a compound selected from the group consisting of the formula (II) One or two or more compounds of the compound group represented by the formula, and the compound represented by the formula (IIIb-1), (wherein R ¹¹ represents an alkyl group having 1 to 3 carbon atoms, and R ²² represents an alkyl group having 1 to 3 carbon atoms or a hydrogen atom) (wherein R ¹ and R ² each independently represent an alkyl group having 1 to 8 carbon atoms, an alkenyl group having 2 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms or a carbon number of 2 to 8; Alkenyloxy) The liquid crystal composition of the first aspect of the invention, which further comprises one or more compounds selected from the group consisting of compounds represented by the formula (III). (wherein R ³ and R ⁴ each independently represent an alkyl group having 1 to 8 carbon atoms, an alkenyl group having 2 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms or a carbon number of 2 to 8; Alkenyloxy, n represents 0 or 1, but does not include a compound wherein R ³ is an alkyl group having ³ carbon atoms, R ⁴ is an alkoxy group having 2 carbon atoms, and n represents 1. The liquid crystal composition of the first aspect of the invention, which further comprises one or more compounds selected from the group consisting of compounds represented by the formula (IV). (wherein R ⁵ and R ⁶ each independently represent an alkyl group having 1 to 8 carbon atoms, an alkenyl group having 2 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms or a carbon number of 2 to 8; Alkenyloxy). The liquid crystal composition of the first aspect of the invention is selected from the group consisting of one or more of the compound groups represented by the following formula (I-1), formula (I-2) and formula (I-3). As the compound represented by the formula (I), The liquid crystal composition of claim 1, which comprises the compound represented by the formula (II-1) as a compound represented by the formula (II), The liquid crystal composition of claim 1, which further contains a reactive monomer. A liquid crystal display element using the liquid crystal composition of claim 1 of the patent application. A liquid crystal display element using the liquid crystal composition of claim 6 of the patent application. A liquid crystal display using the liquid crystal display element of claim 7 or 8.