TW201416423A - Liquid crystal composition and liquid crystal display element using thereof - Google Patents

Abstract

An object of the present invention is to provide a liquid crystal composition and a liquid crystal display element using the liquid crystal composition, wherein the liquid crystal composition does not worsen various properties such as a dielectric anisotropy, a viscosity, a nematic-phase upper-limit temperature, γ 1, etc. as liquid crystal display element and the burn-in property of display element, hardly causes the occurrence of dropping marks during production, and is suitable for a liquid crystal display element for realizing a stable delivery quantity of a liquid crystal material during ODF process, which is characterized by comprising the liquid crystal display the compound represented by the formula (I) and comprising 15% or more of the compound represented by the general formula (II).

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 are used as constituent members of a liquid crystal display device or the like.

The liquid crystal display is used in various measuring machines, such as watches and electronic computers, automobile panels, word processors, electronic notebooks, printing machines, computers, televisions, watches, advertising billboards, and the like. The liquid crystal display method is represented by TN (twisted nematic) type, STN (super twisted nematic) type, VA (vertical alignment) type using TFT thin film transistor, and IPS (in). Plane switching, lateral electric field drive type, etc. The liquid crystal composition used for the liquid crystal display elements is required to have an external factor for moisture, air, heat, light, etc., and to exhibit a liquid crystal phase as far as possible at a wide temperature range centered on a room temperature, low viscosity, and drive. The voltage is low. Further, in order to optimize the dielectric anisotropy (Δε) or the refractive index anisotropy (Δn) for each display element, the liquid crystal composition is preferably several to several tens The composition of the compound.

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

Conventionally, in order to form a liquid crystal composition having a small γ ₁ , a compound having a dialkylbicyclohexane skeleton is generally used (see Patent Document 1). However, the dicyclohexane-based compound has a particularly high effect of lowering γ ₁ and a compound having a high vapor chain length and a short alkyl chain length, which is particularly remarkable. In addition, since T _ni is also low, the alkyl dicyclohexane compound is often a compound having a side chain length of 7 or more in total, and is practically not sufficient for a compound having a short side chain. Explore.

A liquid crystal composition using a dialkyl dicyclohexane compound having a short side chain (see Patent Document 2) is known, and a compound having a tricyclic structure is often used as a compound having a negative dielectric constant, and difluorocarbon is used. A compound of the vinyl skeleton to achieve a balance of physical properties as a whole. However, the difluoroethylene skeleton used in the composition has a problem of low stability to light, and development of a liquid crystal composition which does not use such a compound is desired.

On the other hand, since the use of the liquid crystal display element is increasing, the method of use and the manufacturing method thereof can be greatly changed. In order to cope with this, it is necessary to optimize characteristics other than the basic physical property values. In other words, a liquid crystal display device using a liquid crystal composition has been widely used such as a VA (Vertical Alignment) type or an IPS (Transverse Electric Field Drive) type, and a display element having an ultra-large size of 50 Å or more has been 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 been changed from the conventional vacuum injection method to the ODF (One Drop Fill) method (see Patent Document 3), and the following problems have arisen: The dropping of the liquid crystal composition onto the substrate causes a drop in display quality. low. Further, in order to make the pretilt angle of the liquid crystal material in the liquid crystal display element high-speed responsiveness, a PS liquid crystal display element (polymer stabilized) and a PSA liquid crystal display element (polymer sustained alignment) have been developed. Maintaining the alignment) (refer to Patent Document 4), but this problem becomes a bigger problem. That is, the display elements of the present invention are characterized in that a monomer is added to the liquid crystal composition to harden the monomer in the composition. The liquid crystal composition for the active matrix is required to be specific because of its necessity to maintain a high voltage holding ratio, and the use of a compound having an ester bond in the compound is limited. The monomer used for the PSA liquid crystal display device is mainly an acrylate type, and generally has an ester bond in the compound, and such a compound is not generally used as a liquid crystal composition for an active matrix (see Patent Document 4). Such a foreign matter attracts the generation of dripping marks, and the deterioration of the product yield of the liquid crystal display element due to the defect is a problem. Further, when an additive such as an antioxidant or a light absorbing agent is added to the liquid crystal composition, there is a problem that the yield of the product is deteriorated.

Here, the so-called dripping trace is defined as a phenomenon in which the trace of the liquid crystal composition drops in a black display state.

In order to suppress the dripping trace, a method has been disclosed in which a polymer layer is formed in a liquid crystal layer by polymerization of a polymerizable compound mixed in a liquid crystal composition, whereby the relationship with the alignment suppressing film is suppressed to suppress the generated drop. Method of the trace (Patent Document 5). However, in this method, there is a problem of the imprint of the display of the polymerizable compound added to the liquid crystal, and the effect of suppressing the dripping trace is not sufficient, and it is desired to develop a liquid crystal display element which can be maintained as a liquid crystal display. The basic characteristics of the components, and it is not easy to produce marks and drops.

Prior technical literature Patent literature

Patent Document 1 Japanese Patent Publication No. 2008-505235

Patent Document 2 Japanese Patent Laid-Open Publication No. 2012-136623

Patent Document 3 Japanese Patent Laid-Open No. 6-235925

Patent Document 4 Japanese Patent Laid-Open Publication No. 2002-357839

Patent Document 5 Japanese Patent Laid-Open Publication No. 2006-58755

[Summary of the Invention]

The problem to be solved by the present invention is to provide a liquid crystal composition and a liquid crystal display element using the liquid crystal composition which does not cause a dielectric constant anisotropy, a viscosity, a nematic phase upper limit temperature, and a low temperature nematic phase Stability, γ _{1 ,} etc., as the characteristics of the liquid crystal display element and the imprinting characteristics of the display element are deteriorated, and dripping marks are less likely to occur during manufacture, and the liquid crystal composition suitable for the liquid crystal display element can be realized by the discharge amount of the stable liquid crystal material in the ODF step. Things.

In order to solve the above-mentioned problems, the present inventors have studied the structure of various liquid crystal compositions which are optimally produced by the liquid crystal display element of the dropping method, and found that the liquid crystal display element can be suppressed by using a specific liquid crystal compound at a specific mixing ratio. The present invention is completed by the generation of traces in the middle.

The present invention provides a liquid crystal composition, and a liquid crystal display element using the same, which has a negative dielectric anisotropy and is characterized by containing a compound represented by the formula (1) And containing 15% by mass or more of the compound represented by the formula (II) (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 2 to 8 carbon atoms; The alkenyloxy group, one or more hydrogen atoms of the alkyl group, the alkenyl group, the alkoxy group or the alkenyloxy group may be substituted by a fluorine atom, and the alkyl group, the alkenyl group, the alkoxy group or the alkenyloxy group may be used. The methylene group may be substituted by an oxygen atom as long as the oxygen atom is not bonded, and may be substituted by a carbonyl group as long as the carbonyl group is not bonded.

The liquid crystal display device of the present invention is characterized in that it has excellent high-speed response and low generation of imprinting, and has a feature that the number of dripping marks caused by the manufacture thereof is small, and thus it is used for a display element such as a liquid crystal TV or a screen.

[Formation for implementing the invention]

As described above, the process of producing the traces is not known, but it is highly likely to be related to the interaction between the impurities in the liquid crystal compound and the alignment film, the chromatographic phenomenon, and the like. The impurities in the liquid crystal compound are greatly affected by the manufacturing process of the compound, and the method of producing the compound, for example, is not necessarily the same even if the number of carbon atoms in the side chain is different. That is, since the liquid crystal compound is manufactured by a precise process, the cost thereof is high in the finished product, and it is highly desirable to improve the manufacturing efficiency. Therefore, in order to use even a little bit of raw material, for example even one side The number of carbon atoms in the chain is different, and it is also preferable to manufacture all of the raw materials. Therefore, the manufacturing process of the liquid crystal precursor is different for each of the original bodies. For example, even if the processes are the same, most of the raw materials are different, and as a result, different impurities are often mixed in the respective original bodies. However, even a very small amount of impurities may have a possibility of dropping marks, and only the purification of the original body has a limit for suppressing the generation of dripping marks.

On the other hand, in the manufacturing method of a general-purpose liquid crystal original, when the manufacturing process is established, each of the original bodies tends to be fixed. Even if the analytical technique is more developed, it is difficult to fully understand what kind of impurities are mixed in, and it is necessary to design the composition under the premise that the impurities mixed in the respective original bodies are fixed. As a result of examining the relationship between the impurities of the liquid crystal precursor and the dropping of the traces, the present inventors have empirically understood that the inclusions in the composition have impurities which are less likely to cause dripping marks and impurities which are likely to occur. Therefore, in order to suppress the generation of dripping marks, it is important to use a specific composition in a specific ratio, and in particular, the presence of impurities which are less likely to cause dripping marks. The preferred embodiments described below are those obtained from the above points of view.

The liquid crystal composition of the present invention contains the compound represented by the formula (I) as the first component, preferably 10 to 40%, more preferably 10 to 35%, more preferably 15 to 35%, and even more preferably It is better to contain 15~30%, and 15~25% is more excellent. More specifically, when it is important to respond to the response speed, it is better to have 20~30%, and 20~25% is better. When the reliability of the driving voltage or the voltage holding ratio is important, it is preferably 15% to 20%.

The compound represented by the formula (II) as the second component contains 15% or more, more preferably 15 to 25%, more preferably 15 to 20%. In the formula (II), R ¹ represents 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 an oxyalkylene having 2 to 8 carbon atoms. The base is preferably an alkyl group having 1 to 8 carbon atoms or an alkenyl group having 2 to 8 carbon atoms, and more preferably an alkyl group having 1 to 8 carbon atoms, and more preferably 3 carbon atoms. More preferably, it is an alkyl group of ~5, and more preferably an alkyl group having 3 or 5 carbon atoms.

In the formula (11), R ² represents 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 an oxyalkylene having 2 to 8 carbon atoms. The alkyl group is preferably an alkyl group having 1 to 8 carbon atoms or an alkoxy group having 1 to 8 carbon atoms, and an alkyl group having 3 to 5 carbon atoms or an alkoxy group having 2 to 4 carbon atoms is More preferably, it is more preferably an alkyl group having 3 or 5 carbon atoms or an alkoxy group having 2 or 4 carbon atoms, and still more preferably an alkoxy group having 2 or 4 carbon atoms.

When the improvement of the response speed of the display element is emphasized, the alkenyl group is preferred, and when the reliability of the voltage holding ratio or the like is emphasized, the alkyl group is preferred. When R ¹ and R ² represent an alkenyl group, the following structure is preferred.

(where, the system is bonded to the right end of the ring structure.)

R ¹ represents an alkyl group having 3 to 5 carbon atoms, and R ² represents a content of a compound of the formula (II) having an alkoxy group having 2 to 4 carbon atoms, preferably a compound represented by the formula (II). More than 50%, more than 70% is better, and more than 80% is better.

The compound represented by the formula (II) is specifically preferably a compound represented by the following formula (II-1) to formula (II-8), more preferably a formula (II-1)-form ( The compound represented by the formula (II-4) is more preferably a compound represented by the formula (II-1) and the formula (II-3), and particularly preferably a compound represented by the formula (II-1).

The compound represented by the formula (II) contains 15% or more, and preferably contains 15% or more of the compound represented by the formula (II-1).

The liquid crystal composition of the present invention preferably contains a compound represented by the formula (III) as a third component.

(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; Any one or more of the hydrogen atoms of the alkyl group, the alkenyl group, the alkoxy group or the alkenyloxy group may be substituted by a fluorine atom; the alkyl group, the alkenyl group, the alkoxy group or the alkenyloxy group; The methylene group may be substituted with an oxygen atom as long as the oxygen atom is not bonded to the bond, and the carbonyl group may be substituted as long as the carbonyl group is not bonded.

When the compound represented by the formula (III) is contained, it is preferably 5 to 35%, preferably 10 to 30%, more preferably 15 to 20%.

In the formula (III), R ³ preferably represents 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 to 8 carbon atoms. The alkenyloxy group 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, particularly preferably a carbon atom. A number of 3 to 5 alkyl groups. In the formula (III), R ⁴ preferably represents 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 to 8 carbon atoms. The alkenyloxy group is preferably an alkyl group having 1 to 8 carbon atoms or an alkoxy group having 1 to 8 carbon atoms, more preferably an alkyl group having 1 to 5 carbon atoms or 1 to 1 carbon atom. Further, the alkoxy group of 4 is more preferably an alkoxy group having 1 to 4 carbon atoms, and particularly preferably an alkoxy group having 2 or 3 carbon atoms.

When the improvement of the response speed of the display element is emphasized, the alkenyl group is preferred, and when the reliability of the voltage holding ratio or the like is emphasized, the alkyl group is preferred. When R ³ and R ⁴ represent an alkenyl group, the following structure is preferred.

(where, the system is bonded to the right end of the ring structure.)

The compound represented by the formula (III) is specifically preferably a compound represented by the following formula (III-1) to formula (III-6), more preferably a formula (III-1)-form ( The compound represented by III-4) is more preferably a compound represented by the formula (III-1) to the formula (III-3).

The liquid crystal composition of the present invention preferably contains a compound represented by the formula (IV) as the fourth component.

(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 2 to 8 carbon atoms; Any one or more of the hydrogen atoms of the alkyl group, the alkenyl group, the alkoxy group or the alkenyloxy group may be substituted by a fluorine atom; the alkyl group, the alkenyl group, the alkoxy group or the alkenyloxy group; The methylene group may be substituted with an oxygen atom as long as the oxygen atom is not bonded to the bond, and the carbonyl group may be substituted as long as the carbonyl group is not bonded.

When the compound represented by the formula (IV) is contained, it is preferably 5 to 30%, more preferably 10 to 25%, even more preferably 10 to 20%.

In the formula (IV), R ⁵ preferably represents 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 to 8 carbon atoms. The alkenyloxy group 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, more preferably carbon. The alkyl group having 2 to 5 atomic atoms is particularly preferably an alkyl group having 2 or 3 carbon atoms.

In the formula (IV), R ⁶ preferably represents 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 to 8 carbon atoms. The alkenyloxy group is preferably an alkyl group having 1 to 8 carbon atoms or an alkoxy group having 1 to 8 carbon atoms, more preferably an alkyl group having 1 to 5 carbon atoms or 1 to 1 carbon atom. Further, the alkoxy group of 4 is more preferably an alkoxy group having 1 to 4 carbon atoms, particularly preferably an alkoxy group having 2 or 3 carbon atoms, and most preferably an alkoxy group having 2 carbon atoms.

When the improvement of the response speed of the display element is emphasized, the alkenyl group is preferred, and when the reliability of the voltage holding ratio or the like is emphasized, the alkyl group is preferred. When R ⁵ and R ⁶ represent an alkenyl group, the following structure is preferred.

(where, the system is bonded to the right end of the ring structure.)

The compound represented by the formula (IV) is specifically preferably a compound represented by the following formula (IV-1) to formula (IV-4), more preferably a formula (IV-1) or a formula (IV). The compound represented by IV-2).

The liquid crystal composition of the present invention preferably contains a compound represented by the formula (V) as the fifth component.

(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 2 to 8 carbon atoms; Any one or more of the hydrogen atoms of the alkyl group, the alkenyl group, the alkoxy group or the alkenyloxy group may be substituted by a fluorine atom; the alkyl group, the alkenyl group, the alkoxy group or the alkenyloxy group; The methylene group may be substituted by an oxygen atom as long as the oxygen atom is not bonded, and may be substituted by a carbonyl group as long as the carbonyl group is not bonded; A represents a 1,4-cyclohexene-extension hexyl group, a 1,4-phenylene group or a tetrahydrofuran. -2.5-diyl, and when A represents 1,4-phenylene, one or more hydrogen atoms in the 1,4-phenylene group may be substituted by 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; X ¹ to X ⁶ each independently represent a hydrogen atom or a fluorine atom, but at least one of X ¹ to X ⁶ Represents a fluorine atom.)

When the compound represented by the formula (V) is contained, it is preferably 3 to 20%, more preferably 5 to 15%, and more preferably, the compound represented by the formula (V), the formula (IV-1) and the formula. The proportion of the compound represented by (IV-2) is preferably 50% or more, more preferably 75% or more, and still more preferably 90% or more.

In the formula (V), 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 The alkenyloxy group having 2 to 8 carbon atoms is preferably an alkyl group having 1 to 8 carbon atoms or an alkenyl group having 2 to 8 carbon atoms, preferably an alkyl group having 1 to 8 carbon atoms. More preferably, it is an alkyl group having 2 to 5 carbon atoms, particularly preferably an alkyl group having 3 to 5 carbon atoms, and the number of carbon atoms of R ⁷ and R ⁸ is also preferably the same.

When the improvement of the response speed of the display element is emphasized, the alkenyl group is preferred, and when the reliability of the voltage holding ratio or the like is emphasized, the alkyl group is preferred. When R ⁷ and R ⁸ represent an alkenyl group, the following structure is preferred.

(where, the system is bonded to the right end of the ring structure.)

In the general formula (V), X ¹ to X ⁶ preferably each independently represent a hydrogen atom or a fluorine atom, and preferably 1 to 5 are fluorine atoms, more preferably 1 to 4 are fluorine atoms. More preferably, one to three are fluorine atoms, and more preferably one to two are fluorine atoms, and most preferably two are fluorine atoms.

In this case, when the number of fluorine atoms is one, it is preferred that either of X ³ to X ⁶ is fluorine, more preferably X ³ or X ⁴ is a fluorine atom; and when two fluorine atoms are used, it is preferably Any of X ³ to X ⁶ is a fluorine atom, more preferably X ³ and X ⁴ or X ⁵ and X ⁶ are fluorine atoms, and more preferably X ³ and X ⁴ are fluorine atoms; when the fluorine atom is 3 More preferably, at least X ³ and X ⁴ or at least X ⁵ and X ⁶ are fluorine atoms, and more preferably at least X ³ and X ⁴ are fluorine atoms.

In the formula (V), A preferably represents a 1,4-cyclohexene-extension hexyl group, a 1,4-phenylene group or a tetrahydrofuran-2.5-diyl group, and a display element produced using the liquid crystal composition And when the liquid crystal display emphasizes the response speed, it preferably represents 1,4-phenylene or tetrahydrofuran-2.5-diyl, more preferably 1,4-phenyl; when the driving voltage is emphasized, it indicates 1,4 - phenyl or tetrahydrofuran-2.5-diyl is preferred, more preferably tetrahydrofuran-2.5-diyl; when the operating temperature range is emphasized, that is, it must be in the high operating temperature range, More preferably, it is a cyclohexyl group or a tetrahydrofuran-2.5-diyl group, more preferably a 1,4-cyclohexylene ring-extension group; when it represents a 1,4-phenylene group, one or more hydrogen atoms in the benzene ring It may also be substituted by fluorine, and it is preferably unsubstituted, substituted by 1 or substituted by 2, preferably 2-hydroxybenzene when substituted, and 2,3-difluorobenzene when substituted by 2.

In the formula (V), Z ¹ preferably represents a single bond, -OCH ₂ -, -OCF ₂ -, -CH ₂ O-, or CF ₂ O-, but to represent a single bond, -OCF ₂ - or CF ₂ O- is better, and more preferably represents a single bond.

In the general formula (V), n preferably represents 0 or 1, but it is preferable to express 0 when the response speed is emphasized, and 1 is preferable when the operating temperature range is emphasized, that is, when it is necessary to be in the high operating temperature range. .

The compound represented by the formula (V) is specifically preferably a compound represented by the following formula (V-1) to formula (V-14), more preferably a formula (V-1) or a formula ((). V-3)~(V-9) and (V-12)~(V-15), and more preferably (V-1), (V-3), (V-5) , formula (V-6), formula (V-9), formula (V-12), formula (V-13) and formula (V-15), particularly preferred formula (V-1), formula (V- 5), formula (V-6), and the most preferred formula (V-5).

In the formula (V), 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 atom. The number of 2 to 8 alkenyloxy groups 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 a carbon number. The alkenyl group of 2 to 5 is more preferably an alkyl group having 2 to 5 carbon atoms. When both R ⁷ and R ⁸ are alkyl groups, it is preferred that the number of carbon atoms is different.

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

The liquid crystal composition of the present invention can be used in a wide range of nematic phase-isotropic liquid phase transition temperature (T _NI ), preferably 60 to 120 ° C, and 70 to 100 ° C is more preferable, 70 ~ 90 ° C is especially good.

The liquid crystal composition of the present invention must contain a compound of the formula (I) and the formula (II), and preferably a compound represented by the formulae (III) to (V). The content in this case is preferably as described below.

When the compound represented by the formula (I), the formula (II) and the formula (III) is contained, the total content of the compounds is preferably from 25 to 80%, more preferably from 30 to 75%, more preferably from 35 to 70%. Good, 35~65% is especially good, 38~60% is the best.

When the compound represented by the formula (I), the formula (II) and the formula (IV) is contained, the total content of the compounds is preferably 30 to 90%, more preferably 35 to 85%, more preferably 40 to 80%. Good, 45~75% is especially good, 50~70% is the best.

When the compound represented by the formula (I), the formula (II) and the formula (V) is contained, the total content of the compounds is preferably 25 to 70%, more preferably 25 to 65%, more preferably 25 to 60%. Good, 25~55% is especially good, 30~50% is the best.

When the compound represented by the formula (I), the formula (II), (III) and (IV) is contained, the total content of the compounds is preferably 45 to 95%, more preferably 50 to 95%, and 55 to 55. 95% is better, 60~90% is especially good, and 65~85% is the best.

When the compound represented by the formula (I), the formula (II), (III) and (V) is contained, the total content of the compounds is preferably 35 to 90%, more preferably 35 to 85%, and more preferably 35 to 85%. 80% is better, 35~75% is especially good, and 40~70% is the best.

When the compound represented by the formula (I), the formula (II), (IV) and (V) is contained, the total content of the compounds is preferably 35 to 95%, more preferably 40 to 95%, and 45 to 45. 90% is better, 50~85% is especially good, and 55~75% is the best.

When the compound represented by the formula (I) and all the formulae (II) to (V) is contained, the total content of the compounds is preferably 60 to 98%, more preferably 65 to 98%, and more preferably 70 to 98%. Better, 73~98% is especially good, 80~95% is the best.

Among the compounds constituting the liquid crystal composition of the present invention, the compound having a fluorine atom number of 2 or more, specifically, the formula (II), (III), (IV) and the formula (V) containing two or more fluorine atoms The proportion of the compound represented is preferably 40-80%, 45-75% is better, 50-70% is better, and more specifically, when the response speed is emphasized, 50%-60% is Preferably, 60~70% is preferred when the drive voltage is emphasized.

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

(wherein R ⁹¹ and R ⁹² 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, in the formula (VII-) In a), a compound in which R ⁹¹ represents an alkyl group having 3 carbon atoms and R ⁹² represents an alkyl group having 2 carbon atoms is removed.

When a compound selected from the group consisting of the compounds represented by the general formulae (VII-a) to (VII-d) is contained, it is preferably one to ten, more preferably one to eight, and particularly preferred. In the case of one to five kinds, it may contain two or more kinds of compounds. In this case, the content is preferably 5 to 40%, more preferably 5 to 35%, and most preferably 7 to 30%.

R ⁹¹ and R ⁹² preferably each independently represent an alkyl group having 1 to 10 carbon atoms or an alkenyl group having 2 to 10 carbon atoms, more preferably an alkyl group having 1 to 5 carbon atoms or 2 carbon atoms. The alkenyl group to 5, when an alkenyl group is represented, is preferably the following structure.

(In the formula, it is bonded to the right end of the ring structure.) It is particularly preferable to the following structure.

(where, the system is bonded to the right end of the ring structure.)

Further, R ⁹¹ and R ⁹² may be the same or different, and it is preferred to represent a different substituent.

From the viewpoints of the above, the compound represented by the formula (VII-a) to the formula (VII-e), more specifically, the compound described below is preferred.

Among these, (VII-a1), (VII-a2), (VII-a16), (VII-a-18), (VII-b2), (VII-b6), (VII-c2), (VII-c4), (VII-c5), (VII-d1) to (VII-d4) or (VII-e2) are preferred.

The compound of the formula (VII) and the compound of the formula (I) are common to a dielectric anisotropy of up to 0, and the ratio of the compound of the formula (I) to the compound of the formula (VII) is Within the total content of (I) and the formula (VII), the formula (I) is preferably from 40 to 85%, more preferably from 45 to 80%, particularly preferably from 50 to 75%. Further, the total content of the formula (I) and the formula (VII) is preferably from 10 to 70%, more preferably from 15 to 65%, even more preferably from 20% to the entire content of the composition. 60%, more preferably 25 to 55%, and particularly preferably 30 to 50%.

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

The dielectric anisotropy of the liquid crystal composition of the present invention is preferably -2.0 to -6.0 at 25 ° C, more preferably -2.5 to -5.0, and particularly preferably -2.5 to -4.0, more specifically In other words, when the response speed is emphasized, it is preferably -2.5 to -3.4, and when the drive voltage is emphasized, it is preferably -3.4 to -4.0.

The refractive index anisotropy 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. In more detail, 0.10~0.12 is preferred when the interstitial space is required, and 0.08~0.10 is preferred when the interstitial space is required.

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 particularly preferably 120 or less.

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

(wherein γ ₁ represents rotational viscosity, and Δn represents refractive index anisotropy.)

Z is preferably 13,000 or less, more preferably 12,000 or less, and particularly preferably 11,000 or less.

The liquid crystal composition of the present invention, when used in an active matrix display device, must be 10 ¹² (Ω.m) The above specific resistance is preferably 10 ¹³ (Ω.m) or more, more preferably 10 ¹⁴ (Ω. m) above.

The liquid crystal composition of the present invention may contain, in addition to the above-mentioned compounds, a general nematic liquid crystal, a matrix liquid crystal, a cholesteric liquid crystal, an antioxidant, an ultraviolet absorber, a polymerizable monomer, and the like.

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

(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 of 2 to 7, the oxygen atom is 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-cycloalkylene group or a single bond, all of which are 1,4-phenylene groups, and any hydrogen atom may be fluorine. Atomic substitution.)

X ⁷ and X ^{8 are} preferably a diacrylate derivative in which either a hydrogen atom or a dimethacrylate derivative having a methyl group, one of which represents a hydrogen atom and the other represents a hydrogen atom. Methyl compounds are also preferred. The polymerization rate of these compounds is the fastest in diacrylate derivatives, the slowest in dimethacrylate derivatives, and the asymmetric compounds are in the middle, which may be better used depending on the application. The PSA display element is particularly preferred as a dimethacrylate derivative.

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. Further, the compound which represents a single bond or one of the single bonds represents the form of an alkylene group having 1 to 8 carbon atoms or -O-(CH ₂ ) _s -. In this case, an alkyl group of 1 to 4 is preferred, and s is preferably 1 to 4.

Z ² , preferably -OCH ₂ -, -CH ₂ O-, -COO-, -OCO-, -CF ₂ O-, -OCF ₂ -, -CH ₂ CH ₂ -, -CF ₂ CF ₂ - or A single button, more preferably -COO-, -OCO- or a single button, particularly preferably a single button.

B represents an arbitrary hydrogen atom which may be substituted with a fluorine atom, a 1,4-phenylene group, a trans-1,4-cycloalkylene group or a single bond, and a 1,4-phenylene group or a single bond is preferred. When C represents a ring structure other than a single bond, Z ² may be a linking group other than a single bond, and when C is a single bond, Z ² is preferably a single bond.

From the viewpoints of the above, in the general formula (VI), the ring structure between Sp ¹ and Sp ² is preferably a structure as described below.

In the formula (VI), when C represents a single bond and the ring structure forms two rings, it preferably represents the following formula (VIa-1) to formula (VIa-5), and more preferably represents the formula (VIa-1). ) to the formula (VIa-3), particularly preferably the formula (VIa-1).

(wherein, both ends are bonded to Sp ¹ or Sp ² .)

The polymerizable compound containing these skeletons is most suitable for a PSA type liquid crystal display element after polymerization, and a good alignment state can be obtained, so that display unevenness can be suppressed or not caused.

From the above, the polymerizable monomer is particularly preferred from the formula (VI-1) to the formula (VI-4), and the formula (VI-2) is most preferred.

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

When a monomer is added to the liquid crystal composition of the present invention, polymerization can be carried out even in the absence of a polymerization initiator, but a polymerization initiator may be contained in order to promote polymerization. The polymerization initiator may, for example, be a benzoin ether, a diphenyl ketone, an acetophenone, a benzil ketal or a mercaptophosphine oxide. Moreover, in order to improve the preservation stability, a stabilizer may also be added. Examples of the stabilizer that can be used include hydroquinones, hydroquinone monoalkyl ethers, tertiary butyl catechols, pyrogallols, thiophenols, nitro compounds, and β-naphthalene. Amines, β-naphthols, nitroso compounds, and the like.

The liquid crystal composition containing a polymerizable compound of the present invention is used for a liquid crystal display element, particularly for a liquid crystal display element for active matrix driving, and can be used for a liquid crystal display element for PSA mode, PSVA mode, VA mode, IPS mode or ECB mode. .

The liquid crystal composition containing a polymerizable compound of the present invention is used in a polymerizable compound contained therein, and is polymerized by irradiation of ultraviolet rays to impart alignment ability to liquid crystal, and light is controlled by birefringence of the liquid crystal composition. The light transmittance of the liquid crystal display element. As a liquid crystal display element, in AM-LCD (active matrix type liquid crystal display element), TN (nematic liquid crystal display element), STN-LCD (super twisted nematic liquid crystal display element), OCB-LCD, and IPS-LCD ( A lateral electric field-driven liquid crystal display element is useful, and is particularly useful for an AM-LCD, and can be used for a transmissive or reflective liquid crystal display element.

For the two substrates of the liquid crystal cell of the liquid crystal display element, a flexible transparent material such as glass or plastic can be used, and an opaque material such as tantalum can also be used. A transparent substrate having a transparent electrode can be obtained, for example, by sputtering indium tin oxide (ITO) on a transparent substrate such as a glass plate.

The substrate is opposed to each other such that the transparent electrode layer is inside. At this time, the interval of the substrate can also be adjusted through the spacer. In this case, it is preferred to adjust the thickness of the obtained light control layer to be 1 to 100 μm. It is more preferable that 1.5 to 10 μm is used. 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 in such a manner that the contrast is maximized. Moreover, when there are two polarizing plates, the polarizing axes of the polarizing plates can also be adjusted to adjust the viewing angle or contrast to be good. Further, a retardation film for widening the viewing angle can also be used. Examples of the spacer include glass particles, plastic particles, alumina particles, and photoresist materials. Thereafter, a sealant such as an epoxy thermosetting composition is screen-printed on the substrate in the shape of a designed liquid crystal injection port, and the substrates are bonded to each other, and the heat sealant is thermally cured.

A method of sandwiching a liquid crystal composition containing a polymerizable compound between two substrates can be carried out by vacuum using a usual vacuum injection method or ODF method. Although the injection method does not cause dripping marks, there is a problem of residual after the injection. In the present invention, a display element manufactured by ODF is preferably used.

In order to obtain a good alignment performance of a liquid crystal and to obtain a moderate polymerization rate in order to obtain a good alignment property of a liquid crystal, it is preferred to polymerize by using an active energy ray such as ultraviolet rays or electron beams in a single use or in combination. method. When ultraviolet rays are used, a polarized light source or a non-polarized light source can be used. In addition, when polymerization is carried out in a state in which a liquid crystal composition containing a polymerizable compound is sandwiched between two substrates, it is necessary to at least irradiate the surface side of the laminate to have appropriate transparency to the active energy ray. Further, it is also possible to use a means for irradiating only a specific portion after light irradiation, and changing the alignment state of the unpolymerized portion by changing conditions such as an electric field, a magnetic field, or a temperature, and then irradiating the active energy ray to cause the active energy ray to be irradiated. polymerization. In particular, when exposed to ultraviolet light, it is preferred to perform ultraviolet exposure under an alternating electric field applied to a liquid crystal composition containing a polymerizable compound. The applied alternating electric field is preferably an alternating current having a frequency of 10 Hz to 10 kHz, and a frequency of 60 Hz to 10 kHz is preferred, and the voltage can be selected depending on the desired pretilt angle of 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 MVA mode liquid crystal display element, the pretilt angle is preferably controlled from 80 degrees 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, a temperature of typically 15 to 35 °C. For the generation of ultraviolet lamps, metal halide lamps, high pressure mercury lamps, ultra high pressure mercury lamps, and the like can be used. Further, it is preferable that the wavelength of the ultraviolet ray to be irradiated is to illuminate the ultraviolet ray having a wavelength range of the absorption wavelength range of the non-liquid crystal composition, and it is possible to cut off the ultraviolet ray if necessary. The intensity of the ultraviolet ray to be irradiated is preferably from 0.1 mW/cm ² to 100 mW/cm ^{2 and more} preferably from 2 mW/cm ² to 50 mW/cm ² . The energy of the ultraviolet ray to be irradiated can be appropriately adjusted, and is preferably 10 mJ/cm ² to 500 mJ/cm ^{2 and more} preferably 100 mJ/cm ² to 200 mJ/cm ² . The intensity can also be changed when ultraviolet rays are irradiated. The time at which the ultraviolet ray is irradiated may be appropriately selected depending on the intensity of the ultraviolet ray to be irradiated, and preferably 10 seconds to 3600 seconds, more preferably 10 seconds to 600 seconds.

The liquid crystal display device of the present invention is a liquid crystal display device having a first electrode having a common electrode made of a transparent conductive material and controlled by a transparent conductive material. a second substrate of the thin film transistor of the pixel electrode and the pixel electrode included in each pixel, and a liquid crystal composition sandwiched between the first substrate and the second substrate, wherein liquid crystal molecules in the liquid crystal composition are not applied The alignment at the time of voltage is slightly perpendicular to the substrate, and the liquid crystal composition is the liquid crystal composition of the present invention described above.

The generation of the drop marks is greatly affected by the liquid crystal material to be injected, and the influence of the composition of the display elements is unavoidable. In particular, since a color filter, a thin film transistor, or the like formed in a liquid crystal display element has no member other than a thin alignment film, a transparent electrode, or the like, and the liquid crystal composition is separated, the combination also has a drop mark. The impact of the production.

In particular, when the thin film transistor is of an inverted staggered type, the tantalum electrode is formed so as to cover the gate electrode, so that the area thereof tends to increase.汲 The electrode is formed of a metal material such as copper, aluminum, chromium, titanium, molybdenum or tantalum, and is generally subjected to a passivation treatment in a usual form. However, the protective film is generally thin, the alignment film is thin, and the possibility of not blocking the ionic substance is high, so that the occurrence of dripping marks caused by the interaction of the metal material and the liquid crystal composition cannot be avoided.

In the present invention, it is preferable to use the thin film transistor shown in Fig. 2 as an inverted staggered liquid crystal display element, which is preferable when aluminum wiring is used.

The liquid crystal display element using the liquid crystal composition of the present invention is useful for both high-speed response and suppression of display poorness, and particularly for liquid crystal display elements for active matrix driving, and can be used in VA mode, PSVA mode, PSA mode, IPS mode or ECB mode.

[Examples]

The invention is further illustrated in the following examples, but the invention is not limited to the examples. Further, "%" in the compositions of the following examples and comparative examples means "% by mass".

In the examples, the properties measured are as described below.

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 (mPa.s) at 25 ° C

VHR: 60°C voltage holding ratio at 60°C and 1V applied voltage (%)

Branding: the imprinting evaluation of the liquid crystal display element, which is displayed in the display area After 1000 hours of the fixed pattern, the afterimage level of the fixed pattern at the time of full-screen uniform display was visually evaluated according to the following four-stage evaluation.

◎ no afterimage

○ Only some minor afterimages are acceptable levels

△ There are residual images as unacceptable levels

× has afterimage, very poor

Dropping trace: Evaluation of the dripping trace of the liquid crystal display device, and visually showing the white dripping traces in the black state by the following four stages of evaluation.

◎ no traces of dripping

○ Only some traces of traces are acceptable levels

△ There are traces of dripping that are unacceptable

× There are traces of dripping, very poor

Process suitability: Process suitability, in the ODF process, using a fixed-volume metering pump, 100000 times each time the liquid crystal drops 50L, according to the following four stages of evaluation of the following "0 ~ 100 times, 101 ~ 200 times, 201 ~ 300 times, ...99901~100000 times, the change in the amount of liquid crystal dropped every 100 times.

◎The change is extremely small (the liquid crystal display element can be stably produced)

○ Only slightly changed to an allowable level

△ There is a change that is unacceptable (the yield is deteriorated due to the occurrence of spots)

×Changed, very poor (generating leaky liquid crystal or vacuum bubble)

Solubility at low temperature: Solubility evaluation at low temperature, after modulating the liquid crystal composition, weigh 1 g of the liquid crystal composition into a 2 mL sample vial, place it in a temperature-controlled test cell, and continue to give 1 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) → temperature drop (-0.1 ° C / per The change in temperature of the liquid crystal composition was observed by visual observation of the temperature change of -20 ° C. The evaluation was carried out in the following four stages.

◎ No precipitates were observed for more than 600 hours

○No precipitates were observed for more than 300 hours

△ observed precipitates within 150 hours

× precipitates were observed within 75 hours

Further, the description of the compounds in the examples is as follows.

(side chain)

-n -C _n H _2n+1 linear alkyl group having n carbon atoms

-On -OC _n H _2n+1 linear alkoxy group with n number of carbon atoms

-V -C=CH ₂ vinyl

(ring structure)

(Example 1)

A liquid crystal composition having the composition shown below was prepared, and the physical property value thereof was measured. The results are shown in the table below.

Using the liquid crystal composition of Example 1, a VA liquid crystal display element shown in Fig. 1 was produced. The liquid crystal display element has an inversely staggered thin film transistor as an active element. The injection of the liquid crystal composition was carried out by a dropping method, and the imprinting, the dropping trace, the process suitability, and the solubility at low temperature were evaluated.

Further, the symbol on the left side of the content describes the abbreviation of the above compound.

The liquid crystal composition of Example 1 has a liquid crystal layer temperature range of 76.5 ° C which is practical as a liquid crystal composition for TV, and has a large absolute value of dielectric anisotropy, and has low viscosity and optimum Δn. Using the liquid crystal composition described in Example 1, the VA liquid crystal display device shown in FIG. 1 was produced, and the results of the imprinting, the dropping trace, the process suitability, and the solubility at low temperature were evaluated by the above-described methods, and the display was extremely excellent. Evaluation results.

(Examples 2 and 3)

A liquid crystal composition having the composition shown below was prepared, and the physical property value thereof was measured. The results are shown in the table below.

Using the liquid crystal compositions of Examples 2 and 3, a VA liquid crystal display device was produced in the same manner as in Example 1, and the results of evaluation of the imprinting, the dropping trace, the process suitability, and the solubility at low temperature are shown in the same table.

The liquid crystal compositions of Examples 2 and 3 have a liquid crystal layer temperature range which is practical as a liquid crystal composition for TV, and have a large absolute value of dielectric anisotropy, and have low viscosity and optimum Δn. Using the liquid crystal compositions described in Examples 2 and 3, the VA liquid crystal display device shown in Fig. 1 was produced, and the results of the imprinting, the dropping trace, the process suitability, and the solubility at low temperature were evaluated by the above-described methods, and the display was excellent. Evaluation results.

(Comparative Example 1)

The liquid crystal composition shown below was prepared without the compound represented by the formula (I), and the properties thereof were measured. The results are shown in the table below.

Further, the symbol on the left side of the content is the abbreviation of the above compound in the same manner as in the first embodiment.

The liquid crystal composition (Comparative Example 1) containing no compound represented by the formula (I) showed an increase in viscosity η as compared with the liquid crystal composition (Examples 1 to 3) containing the compound represented by the formula (I). Regarding γ ₁ , the value of Comparative Example 1 is 154 mPa. s, showing a value of 157 mPa compared to Example 2. The value of s is a poor result if the value of γ ₁ /Δn ² of the parameter indicating the effective response speed in the liquid crystal display element and the display is compared. In the first comparative example, the VHR was 98.7%. On the other hand, the VHR after standing at a high temperature of 150 ° C for 1 hour was 97.6%. The results of the process suitability evaluation were inferior to those of Examples 1 to 3. As a result of evaluating the solubility at a low temperature, an earlier precipitation was observed as compared with Examples 1 to 3.

(Comparative Example 2)

The liquid crystal composition shown below was prepared by containing only 12% of the compound represented by the formula (II), and the properties thereof were measured. The results are shown in the table below.

A liquid crystal composition containing only 12% of the compound represented by the general formula (II) (Comparative Example 2) and a liquid crystal composition containing 15% or more of the compound represented by the general formula (II) (Examples 1 to 3) In comparison, the viscosity η is increased. In Comparative Example 2, the initial VHR was 99.0%. On the other hand, the VHR after leaving at a high temperature of 150 ° C for 1 hour was 98.2%. The results of the process suitability evaluation were inferior to those of Examples 1 to 3. As a result of evaluating the solubility at a low temperature, an earlier precipitation was observed as compared with Examples 1 to 3.

(Examples 4 and 5)

A liquid crystal composition having the composition shown below was prepared, and the physical property value thereof was measured. The results are shown in the table below.

Using the liquid crystal compositions of Examples 4 and 5, a VA liquid crystal display device was produced in the same manner as in Example 1, and the results of evaluation of the imprinting, the dropping trace, the process suitability, and the solubility at low temperature are shown in the same table.

The liquid crystal compositions of Examples 4 and 5 have a liquid crystal layer temperature range which is practical as a liquid crystal composition for TV, and have a large absolute value of dielectric anisotropy, and have low viscosity and optimum Δn. Using the liquid crystal compositions described in Examples 4 and 5, the VA liquid crystal display device shown in Fig. 1 was produced, and the results of the imprinting, the dropping trace, the process suitability, and the solubility at low temperature were evaluated by the above methods, and the display was excellent. Evaluation results.

(Examples 6 and 7)

A liquid crystal composition having the composition shown below was prepared, and the physical property value thereof was measured. The results are shown in the table below.

Using the liquid crystal compositions of Examples 6 and 7, a VA liquid crystal display device was produced in the same manner as in Example 1, and the results of evaluation of the imprinting, the dropping trace, the process suitability, and the solubility at low temperature are shown in the same table.

The liquid crystal compositions of Examples 6 and 7 have a liquid crystal layer temperature range which is practical as a liquid crystal composition for TV, and have a large absolute value of dielectric anisotropy, and have low viscosity and optimum Δn. Using the liquid crystal compositions described in Examples 6 and 7, the VA liquid crystal display device shown in Fig. 1 was produced, and the above-described method was used to perform imprinting, dropping marks, and processes. The results of evaluation of solubility in solubility and low temperature showed excellent evaluation results.

(Examples 8 and 9)

A liquid crystal composition having the composition shown below was prepared, and the physical property value thereof was measured. The results are shown in the table below.

Using the liquid crystal compositions of Examples 8 and 9, a VA liquid crystal display device was produced in the same manner as in Example 1, and the results of evaluation of the imprinting, the dropping trace, the process suitability, and the solubility at low temperature are shown in the same table.

The liquid crystal compositions of Examples 8 and 9 have a liquid crystal layer temperature range which is practical as a liquid crystal composition for TV, and have a large absolute value of dielectric anisotropy, and have low viscosity and optimum Δn. Use embodiment In the liquid crystal composition described in 8 and 9, the VA liquid crystal display device shown in Fig. 1 was produced, and the results of the imprinting, the dropping trace, the process suitability, and the solubility at low temperature were evaluated by the above-described methods, and excellent evaluation results were obtained. .

(Examples 10 and 11)

A liquid crystal composition having the composition shown below was prepared, and the physical property value thereof was measured. The results are shown in the table below.

Using the liquid crystal compositions of Examples 10 and 11, a VA liquid crystal display device was produced in the same manner as in Example 1, and the results of evaluation of the imprinting, the dropping trace, the process suitability, and the solubility at low temperature are shown in the same table.

The liquid crystal compositions of Examples 10 and 11 have a liquid crystal layer temperature range which is practical as a liquid crystal composition for TV, and have a large absolute value of dielectric anisotropy, and have low viscosity and optimum Δn. Using the liquid crystal compositions described in Examples 10 and 11, the VA liquid crystal display device shown in Fig. 1 was produced, and the results of the imprinting, the dropping trace, the process suitability, and the solubility at low temperature were evaluated by the above-described methods, and the display was excellent. Evaluation results.

(Examples 12 and 13)

A liquid crystal composition having the composition shown below was prepared, and the physical property value thereof was measured. The results are shown in the table below.

Using the liquid crystal compositions of Examples 12 and 13, a VA liquid crystal display device was produced in the same manner as in Example 1, and the results of evaluation of the imprinting, the dropping trace, the process suitability, and the solubility at low temperature are shown in the same table.

The liquid crystal compositions of Examples 12 and 13 have a liquid crystal layer temperature range which is practical as a liquid crystal composition for TV, and have a large absolute value of dielectric anisotropy, and have low viscosity and optimum Δn. Using the liquid crystal compositions described in Examples 12 and 13, the VA liquid crystal display device shown in Fig. 1 was produced, and the results of the imprinting, the dropping trace, the process suitability, and the solubility at low temperature were evaluated by the above-described methods, and the results were excellent. Evaluation results.

(Example 14)

A liquid crystal composition having the composition shown below was prepared, and the physical property value thereof was measured. The results are shown in the table below.

Using the liquid crystal composition of Example 14, a VA liquid crystal display element was produced in the same manner as in Example 1, and the results of evaluation of the imprinting, the dropping trace, the process suitability, and the solubility at low temperature are shown in the same table.

The liquid crystal composition of Example 14 has a liquid crystal layer temperature range which is practical as a liquid crystal composition for TV, and has a large absolute value of dielectric anisotropy, and has low viscosity and optimum Δn. Using the liquid crystal composition described in Example 14, the VA liquid crystal display device shown in Fig. 1 was produced, and the results of the imprinting, the dropping trace, the process suitability, and the solubility at low temperature were evaluated by the above-described methods, and the evaluation was excellent. result.

(Comparative Examples 3 and 4)

The liquid crystal composition (Comparative Example 3) which does not contain the compound represented by the formula (I) exhibits viscosity η and rotational viscosity as compared with the liquid crystal composition (Examples 12 to 14) containing the compound represented by the formula (I). The rise of γ ₁ . In Comparative Example 3, the initial VHR was 98.9%. On the other hand, the VHR after standing at a high temperature of 150 ° C for 1 hour was 97.9%. As a result of the evaluation of the process suitability, it was a level that could not be allowed to change as compared with Examples 12 to 14. As a result of evaluating the solubility at low temperature, an earlier precipitation was observed as compared with Examples 12 to 14.

A liquid crystal composition containing only 9% of the compound represented by the formula (I1) (Comparative Example 4) and a liquid crystal composition containing 15% or more of the compound represented by the formula (II) (Examples 12 to 14) In comparison, the viscosity η and the rotational viscosity γ ₁ are increased. In Comparative Example 4, the initial VHR was 99.1%. On the other hand, the VHR after leaving at a high temperature of 150 ° C for 1 hour was 98.0%. As a result of the evaluation of the process suitability, it was a level that could not be allowed to change as compared with Examples 12 to 14. As a result of evaluating the solubility at low temperature, an earlier precipitation was observed as compared with Examples 12 to 14.

(Examples 15 and 16)

A liquid crystal composition having the composition shown below was prepared, and the physical property value thereof was measured. The results are shown in the table below.

Using the liquid crystal compositions of Examples 15 and 16, a VA liquid crystal display device was produced in the same manner as in Example 1, and the results of evaluation of the imprinting, the dropping trace, the process suitability, and the solubility at low temperature are shown in the same table.

The liquid crystal compositions of Examples 15 and 16 have a liquid crystal layer temperature range which is practical as a liquid crystal composition for TV, and have a large absolute value of dielectric anisotropy, and have low viscosity and optimum Δn. Using the liquid crystal compositions described in Examples 15 and 16, the VA liquid crystal display device shown in Fig. 1 was produced, and the results of the imprinting, the dropping trace, the process suitability, and the solubility at low temperature were evaluated by the above methods, and the display was excellent. Evaluation results.

(Examples 17 and 18)

A liquid crystal composition having the composition shown below was prepared, and the physical property value thereof was measured. The results are shown in the table below.

Using the liquid crystal compositions of Examples 17 and 18, a VA liquid crystal display device was produced in the same manner as in Example 1, and the results of evaluation of the imprinting, the dropping trace, the process suitability, and the solubility at low temperature are shown in the same table.

The liquid crystal compositions of Examples 17 and 18 have a liquid crystal layer temperature range which is practical as a liquid crystal composition for TV, and have a large absolute value of dielectric anisotropy, and have low viscosity and optimum Δn. Using the liquid crystal compositions described in Examples 17 and 18, the VA liquid crystal display device shown in Fig. 1 was produced, and the results of the imprinting, the dropping trace, the process suitability, and the solubility at low temperature were evaluated by the above-described methods, and the display was excellent. Evaluation results.

(Examples 19 and 20)

A liquid crystal composition having the composition shown below was prepared, and the physical property value thereof was measured. The results are shown in the table below.

Using the liquid crystal compositions of Examples 19 and 20, a VA liquid crystal display device was produced in the same manner as in Example 1, and the results of evaluation of the imprinting, the dropping trace, the process suitability, and the solubility at low temperature are shown in the same table.

The liquid crystal compositions of Examples 19 and 20 have a liquid crystal layer temperature range which is practical as a liquid crystal composition for TV, and have a large absolute value of dielectric anisotropy, and have low viscosity and optimum Δn. Using the liquid crystal compositions described in Examples 19 and 20, the VA liquid crystal display device shown in Fig. 1 was produced, and the above-described method was used to imprint and drip traces. The results of the evaluation of the process suitability and the solubility at low temperatures showed excellent evaluation results.

(Examples 21 and 22)

A liquid crystal composition having the composition shown below was prepared, and the physical property value thereof was measured. The results are shown in the table below.

Using the liquid crystal compositions of Examples 21 and 22, a VA liquid crystal display device was produced in the same manner as in Example 1, and the results of evaluation of the imprinting, the dropping trace, the process suitability, and the solubility at low temperature are shown in the same table.

The liquid crystal compositions of Examples 21 and 22 have a liquid crystal layer temperature range which is practical as a liquid crystal composition for TV, and have a large absolute value of dielectric anisotropy, and have low viscosity and optimum Δn. Use implementation In the liquid crystal compositions described in Examples 21 and 22, the VA liquid crystal display device shown in Fig. 1 was produced, and the results of the imprinting, the dropping trace, the process suitability, and the solubility at low temperature were evaluated by the above methods, and the evaluation was excellent. result.

(Examples 23 and 24)

A liquid crystal composition having the composition shown below was prepared, and the physical property value thereof was measured. The results are shown in the table below.

Using the liquid crystal compositions of Examples 23 and 24, a VA liquid crystal display device was produced in the same manner as in Example 1, and the results of evaluation of the imprinting, the dropping trace, the process suitability, and the solubility at low temperature are shown in the same table.

The liquid crystal compositions of Examples 23 and 24 have a liquid crystal layer temperature range which is practical as a liquid crystal composition for TV, and have a large absolute value of dielectric anisotropy, and have low viscosity and optimum Δn. Using the liquid crystal compositions described in Examples 23 and 24, the VA liquid crystal display device shown in Fig. 1 was produced, and the results of the imprinting, the dropping trace, the process suitability, and the solubility at low temperature were evaluated by the above-described methods, and the display was excellent. Evaluation results.

1‧‧‧Polar plate

2‧‧‧Substrate

3‧‧‧Transparent electrode or transparent electrode with active components

4‧‧‧Alignment film

5‧‧‧LCD

11‧‧‧ gate electrode

12‧‧‧Anodic oxide film

13‧‧‧Brake insulation

14‧‧‧Transparent electrode

15‧‧‧汲 electrode

16‧‧‧Ohm contact layer

17‧‧‧Semiconductor layer

18‧‧‧Protective film

19a‧‧‧Source electrode 1

19b‧‧‧Source electrode 2

100‧‧‧Substrate

101‧‧‧Protective layer

Fig. 1 shows an example of the structure of a liquid crystal display element of the present invention.

Fig. 2 shows an example of the structure of an inverted staggered thin film transistor.

Claims (14)

A liquid crystal composition having a negative dielectric anisotropy characterized by containing a compound represented by formula (1) And containing 15% by mass or more of the compound represented by the formula (II) (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 2 to 8 carbon atoms; Any one or more of the hydrogen atoms of the alkyl group, the alkenyl group, the alkoxy group or the alkenyloxy group may be substituted by a fluorine atom; the alkyl group, the alkenyl group, the alkoxy group or the alkenyloxy group; The methylene group may be substituted by an oxygen atom as long as the oxygen atom is not bonded, and may be substituted by a carbonyl group as long as the carbonyl group is not bonded. The liquid crystal composition of claim 1, which contains 10 to 35 mass% of the compound represented by the formula (I). The liquid crystal composition of claim 1, which contains 25 to 40% by mass of the compound represented by the formula (II). The liquid crystal composition according to any one of claims 1 to 3, which contains at least two or more compounds represented by the formula (II). The liquid crystal composition of the first aspect of the invention, wherein R ¹ in the formula (II) represents an alkyl group having 3 to 5 carbon atoms or an alkenyl group having 2 to 5 carbon atoms, and R ² represents a carbon number. 2 to 4 alkoxy groups or alkenyl groups having 3 to 5 carbon atoms. The liquid crystal composition of claim 1, which contains 15% by mass or more of the compound represented by the formula (II-1) The liquid crystal composition of claim 1, which comprises the compound 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; Any one or more of the hydrogen atoms of the alkyl group, the alkenyl group, the alkoxy group or the alkenyloxy group may be substituted by a fluorine atom; the alkyl group, the alkenyl group, the alkoxy group or the alkenyloxy group; The methylene group may be substituted by an oxygen atom as long as the oxygen atom is not bonded, and may be substituted by a carbonyl group as long as the carbonyl group is not bonded. The liquid crystal composition of claim 1, which comprises the compound 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 2 to 8 carbon atoms; Any one or more of the hydrogen atoms of the alkyl group, the alkenyl group, the alkoxy group or the alkenyloxy group may be substituted by a fluorine atom; the alkyl group, the alkenyl group, the alkoxy group or the alkenyloxy group; The methylene group may be substituted by an oxygen atom as long as the oxygen atom is not bonded, and may be substituted by a carbonyl group as long as the carbonyl group is not bonded. The liquid crystal composition of claim 1, which comprises the compound represented by the 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 2 to 8 carbon atoms; Any one or more of the hydrogen atoms of the alkyl group, the alkenyl group, the alkoxy group or the alkenyloxy group may be substituted by a fluorine atom; the alkyl group, the alkenyl group, the alkoxy group or the alkenyloxy group; The methylene group may be substituted by an oxygen atom as long as the oxygen atom is not bonded, and may be substituted by a carbonyl group as long as the carbonyl group is not bonded; A represents a 1,4-cyclohexene-extension hexyl group, a 1,4-phenylene group or a tetrahydrofuran. -2.5-diyl, and when A represents 1,4-phenylene, one or more hydrogen atoms in the 1,4-phenylene group may be substituted by 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; X ¹ to X ⁶ each independently represent a hydrogen atom or a fluorine atom, but at least one of X ¹ to X ⁶ Refers to the fluorine atom). A liquid crystal composition containing 15 to 30% by mass of a compound represented by the formula (I) of the first aspect of the patent application, containing 15 to 25% by mass of the formula (II- 1) The compound represented by 10 to 20% by mass of the compound represented by the formula (III) of claim 7 of the patent application, containing 10 to 25% by mass of the patent application The compound represented by the formula (IV) in the eighth aspect, and contains 0 to 20% by mass of the compound represented by the formula (V) of the ninth application of the patent application. The liquid crystal composition of claim 1, which contains a reactive monomer. A liquid crystal display element using the liquid crystal composition of the first aspect of the patent application. A liquid crystal display element using the liquid crystal composition of claim 11 of the patent application. A liquid crystal display using a liquid crystal display element as disclosed in claim 12 or 13.