TWI542671B - Liquid crystal composition, liquid crystal display element, and liquid crystal display - Google Patents

Description

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

The present invention relates to a liquid crystal composition, a liquid crystal display element using the liquid crystal composition, and a liquid crystal display.

The liquid crystal display element is used in various measuring machines, automobile panels, word processors, electronic notebooks, printers, computers, televisions, clocks, advertisement display boards, and the like, including clocks and computers. The liquid crystal display method is represented by a TN (twisted nematic) type, an STN (super twisted nematic) type, a TFT (thin film) type VA (vertical alignment) type, or an IPS (transverse electric field effect) type. The liquid crystal composition used in the liquid crystal display elements is required to be stable with respect to external factors such as moisture, air, heat, light, and the like, and the liquid crystal phase is exhibited in a wide temperature range as wide as the room temperature. It is low in viscosity and low in driving voltage. Further, in order to match the optimum dielectric anisotropy (??) or / and the refractive index anisotropy (?n) as the most appropriate values for the individual display elements, the liquid crystal composition is composed of several kinds. It is composed of dozens of compounds.

In the vertical alignment type display, a liquid crystal composition having a negative value of Δ ε is used, and it is widely used for 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 high nematic phase-isotropic liquid phase transition temperature (T _ni ) is required. Further, depending on the setting of Δn × d of the product of Δn and the liquid crystal cell gap (d), it is necessary to adjust Δn of the liquid crystal composition to an appropriate range in which the liquid crystal cell gap is matched. Further, 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 viscosity (γ ₁ ) is required.

Conventionally, in order to form a liquid crystal composition having a small γ ₁ , a compound having a dialkyl bicyclohexane skeleton is generally used (see Patent Document 1). However, although the bicyclohexane compound has a high effect on the reduction of γ ₁ , it is generally remarkable that the vapor pressure is high and the alkyl chain length is short. Also, there is a tendency that T _ni is also low. Therefore, in actuality, a compound having a side chain length of 7 or more carbon atoms is often used as the alkylbicyclohexane compound, and a compound having a short side chain length is not sufficiently studied.

It is also known as a liquid crystal composition using a dialkylbicyclohexane compound having a short side chain length (see Patent Document 2), but a compound having three ring structures is often used as a dielectric constant. A compound having a negative opposite polarity and a compound having a difluoroethylene skeleton is used as a balance of physical properties as a whole of the composition. However, since the difluoroethylene skeleton used in the composition has a problem of low stability to light, it is desired to develop a liquid crystal composition which does not use a compound such as the above.

On the other hand, in order to expand the use of the liquid crystal display element, it has been observed that the method of use and the method of manufacture are also greatly changed. In order to cope with the change, it is necessary to optimize the characteristics other than the basic physical property values known in the related art. In other words, a liquid crystal display device using a liquid crystal composition has been widely used in a VA (Vertical Alignment) type or an IPS (Transverse Field Effect) type, and the size thereof has also been put into practical use. And for people to use. With the increase in the size of the substrate, the method of injecting the liquid crystal composition into the substrate has also become the mainstream of the injection method from the conventional vacuum injection method to the ODF (One Drop Fill) method (refer to the patent). In Document 3), the problem of dropping the display quality when the liquid crystal composition is dropped on the substrate causes the problem of a drop in display quality to float on the surface. The drop mark here is defined as a phenomenon in which the trace of the liquid crystal composition is whitened and floats when the black color is displayed.

Development of a PS liquid crystal display element (polymer stabilized) and a PSA liquid crystal display element (polymer sustained alignment) for the purpose of controlling the high-speed responsiveness of the pretilt angle of the liquid crystal material in the liquid crystal display device (refer to Patent Document 4), but the aforementioned problems become a greater problem. Usually, these display elements have a feature of adding a monomer to the liquid crystal composition and hardening the monomer in the composition. On the other hand, since the liquid crystal composition for an active matrix has a necessity of maintaining a high voltage holding ratio, a compound having an ester bond is restricted in use, and the types of compounds that can be used are small.

The monomer used for the PSA liquid crystal display element is mainly an acrylate type, and the acrylate type compound generally has an ester bond. As the acrylate compound, a liquid crystal compound for an active matrix is not usually used (see Patent Document 4). When the liquid crystal composition for the active matrix contains a large number of acrylate-based compounds, the occurrence of dripping marks is caused, and the yield of the liquid crystal display element due to display failure is deteriorated. Further, when an additive such as an antioxidant or a light absorber is added to the liquid crystal composition, the yield is also deteriorated.

As a method of suppressing the dropping of the trace, it is revealed that the polymerizable compound mixed in the liquid crystal composition is polymerized to form a polymer layer in the liquid crystal layer, thereby suppressing the dropping of the relationship with the alignment control film. Method (Patent Document 5). However, in this method, there is a problem of imprinting due to the display of a polymerizable compound added to the liquid crystal composition, and the addition of the mark is suppressed. The system effect is insufficient. Therefore, there is a need to develop a liquid crystal display element which maintains the basic characteristics as a liquid crystal display element while making it difficult to generate an imprint or a drop mark.

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. Hei 6-235925

Patent Document 4 Japanese Patent Laid-Open Publication No. 2002-357830

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

An object of the present invention is to provide a dielectric anisotropy (Δε), a viscosity (η), an upper limit temperature (T _ni ) of a nematic phase, a stability (solubility) of a nematic phase at a low temperature, and a rotational viscosity. (γ ₁ ), a liquid crystal composition which is excellent in the imprinting property and which is less likely to cause dripping when the liquid crystal display element is produced, and which can be stably discharged in the ODF step, a liquid crystal display element using the liquid crystal composition, and a liquid crystal display.

In order to solve the above problems, the inventors of the present invention have studied the constitution of various liquid crystal compositions which are most suitable for producing liquid crystal display elements by the dropping method, and found that by using a specific liquid crystal compound at a specific mixing ratio, it is possible to suppress the dropping of liquid crystal display elements. This is accomplished to complete the present invention. That is, the first embodiment of the present invention is the liquid crystal composition of the following (i) to (vii).

(i) a liquid crystal composition comprising a liquid crystal composition having a negative dielectric anisotropy, comprising: a component (B) containing a dielectric property represented by the following formula (1): a compound having a dielectric anisotropy of a dielectric property of greater than -2 and less than +2, and a component (A) containing a compound selected from the following formulas (2) to (5); Two or more kinds of compounds are shown in the compound group, and the dielectric property is negative.

(wherein R ¹ and R ⁴ each independently represent an alkyl group having 1 to 8 carbon atoms, and R ² and R ³ each independently represent an alkyl group having 1 to 8 carbon atoms or 2 to 8 carbon atoms; The alkenyl group, the alkyl group of R ² and R ³ or the methylene group in the alkenyl group may be substituted by an oxygen atom as long as the oxygen atom is not bonded, or may be carbonyl as long as the carbonyl group is not bonded to the bond. Replace.)

(ii) The liquid crystal composition according to (i) above, wherein the component (A) is selected from the group consisting of the following formula (2.1), formula (2.2), formula (3.1), formula (3.2), and formula (4.1). Two or more compounds of the compound group represented by the formula (4.2), the formula (5.1) and the formula (5.2).

(iii) The liquid crystal composition according to the above (i) or (ii), wherein the component (B) comprises a compound represented by the following formula (6.1) or (6.2).

(iv) The liquid crystal composition according to any one of the above (i) to (iii), wherein the component (A) comprises a compound represented by the following formula (7.1) or (7.2).

(v) The liquid crystal composition according to any one of the above (i) to (iv), wherein the component (B) comprises a compound represented by the following formula (8).

(wherein R ⁵ represents an alkyl group having 2 or 5 carbon atoms or an alkoxy group having 1 to 3 carbon atoms.)

The liquid crystal composition according to any one of the above (i) to (v), wherein the component (A) comprises a compound represented by the following formula (9.1) or (9.2).

(vii) The liquid crystal composition according to any one of the above (i) to (vi), wherein the component (A) comprises the compound represented by the following (10.1) or (10.2).

A second embodiment of the present invention is a liquid crystal display device characterized by using the liquid crystal composition of the first embodiment.

A third embodiment of the present invention is a liquid crystal display characterized by using the liquid crystal display element of the second embodiment.

The liquid crystal composition of the present invention has a dielectric anisotropy (Δε), a viscosity (η), an upper limit temperature (T _ni ) of a nematic phase, a stability (solubility) of a nematic phase at a low temperature, and a rotation. Each of the characteristics of the viscosity (γ ₁ ) and the like is good, and can be stably discharged in the ODF step at the time of manufacture of the liquid crystal display element.

Further, the liquid crystal display element using the liquid crystal composition of the present invention has excellent high-speed response and rarely produces an imprint, resulting in less occurrence of dripping marks in the ODF step at the time of manufacture. Therefore, the liquid crystal composition of the present invention is useful for display elements such as liquid crystal TVs and screens.

As mentioned above, the detailed procedure for producing the drop marks is not known at present. However, it is considered that there is a high possibility that the impurity in the liquid crystal compound (liquid crystal composition), the interaction of the alignment film, the chromatographic phenomenon, and the like are related to the generation of the dropping mark. The presence or absence of impurities in the liquid crystal compound greatly affects the manufacturing process of the compound. In general, a method for producing a liquid crystal compound is to carry out a procedure suitable for each compound and a raw material. A compound similar to a known compound, even in the case of producing a compound having a different number of side chains, the procedure is not necessarily similar or identical to the procedure of the known compound. Since liquid crystal compounds are manufactured by a precise manufacturing process, their cost is high in chemical products, and there is a strong demand for improvement in manufacturing efficiency. Therefore, in order to use as cheap a raw material as possible, even when there is only one different similar compound in the number of side chains to be produced, there is a case where it is more efficient to manufacture a completely different kind of raw material instead of a known raw material. Therefore, the manufacturing procedure of the liquid crystal precursor (liquid crystal composition) is different for each original, and the raw materials are often different even if the procedures are the same. As a result, each original is often mixed with different impurities. On the other hand, the addition of traces may also occur due to the extremely small amount of impurities, and there is a limit to relying solely on the purification of the original body to suppress the occurrence of the drip marks.

On the other hand, in the method for producing a general-purpose liquid crystal precursor, after the manufacturing procedure is established, each of the original bodies tends to be fixed. Even after already Nowadays, it is not easy to fully understand what kind of impurities are mixed in, and it is necessary to design a liquid crystal composition on the premise that each of the original bodies is mixed with fixed impurities.

The inventors of the present invention have examined the relationship between the impurities of the liquid crystal precursor and the dropping marks. As a result, it has been empirically found that the impurities contained in the liquid crystal composition have impurities which are less likely to cause dripping marks and impurities which are liable to cause dropping marks. Further, in order to suppress the occurrence of dripping marks, it has been found that it is important to use a liquid crystal composition system containing a specific compound in a specific mixing ratio. That is, the liquid crystal composition of the present invention is a composition which is particularly difficult to cause a drop mark. The preferred embodiments described below are found from the above viewpoints.

The present invention will be specifically described below, but the present invention is not limited thereto.

Unless otherwise specified, "%" means % by mass.

Liquid Crystal Composition

The liquid crystal composition according to the first embodiment of the present invention is a liquid crystal composition having a negative dielectric anisotropy, and contains the component (A) and the component (B).

The component (A) is a component containing two or more kinds of compounds selected from the group consisting of the compounds represented by the following formulas (2) to (5) and having a negative dielectric property. The component having a negative dielectric property here is a component having a dielectric anisotropy of "-2 or less".

Component (B) contains a compound having a dielectric property represented by the following formula (1) and having a dielectric anisotropy of "greater than -2 and less than +2" and having a dielectric property of neutrality. .

The dielectric anisotropy of each component and the dielectric anisotropy of the liquid crystal composition are values measured by a usual method at 25 °C.

(wherein R ¹ and R ⁴ each independently represent an alkyl group having 1 to 8 carbon atoms, and R ² and R ³ each independently represent an alkyl group having 1 to 8 carbon atoms or 2 to 8 carbon atoms; The alkenyl group, the alkyl group of R ² and R ³ or the methylene group in the alkenyl group may be substituted by an oxygen atom as long as the oxygen atom is not bonded, or may be carbonyl as long as the carbonyl group is not bonded to the bond. Replace.)

Ingredient (A)

The alkyl group of R ¹ in the above formula (2) may be linear or branched, but is preferably linear. The number of carbon atoms of the alkyl group of R ¹ is not particularly limited, but the number of carbon atoms is preferably from 1 to 6, more preferably from 2 to 5, and most preferably 2 or 4.

The alkyl group of R ³ in the above formula (3) may be linear or branched, but is preferably linear. The number of carbon atoms of the alkyl group of R ³ is not particularly limited, but the number of carbon atoms is preferably 2 to 6, preferably 2 to 4, and 2 or 3.

The alkyl group of R ² in the above formula (4) may be linear or branched, but is preferably linear. The number of carbon atoms of the alkyl group of R ² is not particularly limited, but the number of carbon atoms is preferably 2 to 6, preferably 2 to 4, and most preferably 3 or 4.

The alkyl group of R ⁴ in the above formula (5) may be linear or branched, but is preferably linear. The alkyl group of R ¹ and R ⁴ is not particularly limited as long as it has 1 to 8 carbon atoms, but the number of carbon atoms is preferably 1 to 6, more preferably 2 to 5, and most preferably 2 or 3.

The component (A) in the liquid crystal composition is selected from the following formula (2.1), formula (2.2), formula (3.1), formula (3.2), formula (4.1), formula (4.2), and formula (5.1). Two or more kinds of compounds of the compound group represented by the formula (5.2) are preferred.

When the compound represented by the formula (2.1) is contained, the content thereof is preferably from 1 to 20%, more preferably from 3 to 18%, and most preferably from 6 to 16% in the liquid crystal composition.

When the compound represented by the formula (2.2) is contained, the content thereof is preferably from 1 to 30%, more preferably from 3 to 25%, and most preferably from 6 to 21% in the liquid crystal composition.

When the compound represented by the formula (3.1) is contained, the content thereof is preferably from 1 to 30%, more preferably from 3 to 25%, and most preferably from 6 to 20% in the liquid crystal composition.

When the compound represented by the formula (3.2) is contained, the content thereof is preferably from 1 to 20%, more preferably from 3 to 16%, and most preferably from 6 to 12% in the liquid crystal composition.

When the compound represented by the formula (4.1) is contained, the content thereof is preferably from 1 to 20%, more preferably from 3 to 16%, and most preferably from 6 to 14% in the liquid crystal composition.

When the compound represented by the formula (4.2) is contained, the content thereof is preferably from 1 to 20%, more preferably from 3 to 15%, and most preferably from 6 to 13% in the liquid crystal composition.

When the compound represented by the formula (5.1) is contained, the content thereof is preferably from 1 to 20%, more preferably from 3 to 16%, and most preferably from 6 to 12% in the liquid crystal composition.

When the compound represented by the formula (5.2) is contained, the content thereof is preferably from 1 to 20%, more preferably from 3 to 18%, and most preferably from 7 to 15% in the liquid crystal composition.

The component (A) may additionally contain a compound represented by the following formula (a1).

When the compound represented by the formula (a1) is contained, the content thereof is preferably from 1 to 20%, more preferably from 3 to 15%, and most preferably from 6 to 10% in the liquid crystal composition.

The component (A) may additionally contain a compound represented by the following formula (a2).

When the compound represented by the formula (a2) is contained, the content thereof is preferably from 1 to 20%, more preferably from 3 to 15%, and most preferably from 5 to 10% in the liquid crystal composition.

The component (A) may additionally contain a compound represented by the following formula (a3).

When the compound represented by the formula (a3) is contained, the content thereof is preferably from 1 to 20%, more preferably from 3 to 15%, most preferably from 4 to 9%, in the liquid crystal composition.

The component (A) may additionally contain a compound of at least one of the compounds represented by the following formula (7.1) and formula (7.2).

When the compound represented by the formula (7.1) is contained, the content thereof is preferably from 1 to 20%, more preferably from 2 to 15%, and most preferably from 3 to 12% in the liquid crystal composition.

When the compound represented by the formula (7.2) is contained, the content thereof is preferably from 1 to 20%, more preferably from 5 to 18%, and most preferably from 10 to 15% in the liquid crystal composition.

The component (A) in the liquid crystal composition may further contain a compound of at least one of the compounds represented by the following formulas (9.1) and (9.2).

When the compound represented by the formula (9.1) is contained, the content thereof is preferably from 1 to 20%, more preferably from 4 to 15%, and most preferably from 7 to 15% in the liquid crystal composition.

When the compound represented by the formula (9.2) is contained, the content thereof is preferably from 1 to 20%, more preferably from 5 to 18%, and most preferably from 10 to 15% in the liquid crystal composition.

The compound represented by the formula (9.1) and the compound represented by the formula (9.2) are preferably contained in the liquid crystal composition together with the compound represented by the formula (2.1) or the compound represented by the formula (2.2).

The component (A) in the liquid crystal composition may further contain a compound of at least one of the compounds represented by the following formulas (10.1) and (10.2).

When the compound represented by the formula (10.1) is contained, the content thereof is preferably from 1 to 20%, more preferably from 4 to 15%, and most preferably from 7 to 14% in the liquid crystal composition.

When the compound represented by the formula (10.2) is contained, the content thereof is preferably from 1 to 20%, more preferably from 3 to 18%, and most preferably from 6 to 16% in the liquid crystal composition.

The compound represented by the formula (10.1) and the compound represented by the formula (10.2) are preferably contained in the liquid crystal composition together with the compound represented by the formula (5.1) or the compound represented by the formula (5.2).

When the liquid crystal composition contains both the compound represented by the formula (10.1) and the compound represented by the formula (10.2), the total content thereof is preferably 5 to 35%, more preferably 10 to 30%, in the liquid crystal composition. Good, 15~25% best.

The component (A) may additionally contain a compound represented by the following formula (a4).

When the compound represented by the formula (a4) is contained, the content thereof is preferably from 1 to 10%, more preferably from 1 to 6%, most preferably from 1 to 4%, in the liquid crystal composition.

The liquid crystal composition includes a compound represented by the formula (1) and one or more compounds selected from the group consisting of compounds represented by the formula (2), the formula (9.1) and the formula (9.2), and is selected from the group consisting of When one or more compounds of the compound group represented by the formula (5), the formula (7.1), the formula (7.2), the formula (10.1), and the formula (10.2), the total content of the compounds is preferably 25 to 90. %, and 35~90% is better, 35~75% is better, 35~65% is better, 38~60% is best.

The liquid crystal composition includes a compound represented by the formula (1) and one or more compounds selected from the group consisting of compounds represented by the formula (2), the formula (9.1) and the formula (9.2), and is selected from the group consisting of When one or more compounds of the compound group represented by the formula (3), the formula (a1), and the formula (a3) are used, the total content of the compounds is preferably 25 to 80%, and preferably 30 to 75%. 35~70% is better, 40~65% is better, 40~60% is best.

The liquid crystal composition includes a compound represented by the formula (1) and one or more compounds selected from the group consisting of compounds represented by the formula (2), the formula (9.1) and the formula (9.2), and is selected from the group consisting of When one or more compounds of the compound group represented by the formula (4) and the formula (a2) are used, the total content of the compounds is preferably from 20 to 70%, and preferably from 25 to 65%, and from 25 to 60%. Good, 25~55% is excellent, 30~50% is best.

The liquid crystal composition includes a compound represented by the formula (1) and one or more compounds selected from the group consisting of compounds represented by the formula (2), the formula (9.1) and the formula (9.2), and is selected from the group consisting of One or more compounds selected from the group consisting of the formula (5), the formula (7.1), the formula (7.2), the formula (10.1), and the formula (10.2) are selected from the group consisting of the formula (3) and the formula (a1). And 1 in the group of compounds shown by formula (a3) When the above compounds are used, the total content of the compounds is preferably 40 to 90%, and 50 to 90% is preferred, 55 to 90% is better, 60 to 90% is particularly preferred, and 65 to 87% is optimal.

The liquid crystal composition includes a compound represented by the formula (1) and one or more compounds selected from the group consisting of compounds represented by the formula (2), the formula (9.1) and the formula (9.2), and is selected from the group consisting of One or more compounds selected from the group consisting of the formula (5), the formula (7.1), the formula (7.2), the formula (10.1), and the formula (10.2), which are selected from the group consisting of the formula (4) and the formula (a2) When one or more compounds of the compound group are shown, the total content of the compounds is preferably 35 to 90%, preferably 35 to 85%, 35 to 80%, and 35 to 75%. 40~70% is the best.

The liquid crystal composition includes a compound represented by the formula (1) and one or more compounds selected from the group consisting of compounds represented by the formula (2), the formula (9.1) and the formula (9.2), and is selected from the group consisting of One or more compounds selected from the group consisting of the formula (3), the formula (a1), and the formula (a3), and one selected from the group consisting of the compounds represented by the formula (4) and the formula (a2) When the above compounds are used, the total content of the compounds is preferably from 30 to 90%, preferably from 30 to 80%, more preferably from 35 to 75%, particularly preferably from 40 to 70%, and most preferably from 45 to 65%.

The liquid crystal composition includes a compound represented by the formula (1) and one or more compounds selected from the group consisting of compounds represented by the formula (2), the formula (9.1) and the formula (9.2), and is selected from the group consisting of One or more compounds selected from the group consisting of the formula (3), the formula (a1), and the formula (a3) are selected from the group consisting of the formula (5), the formula (7.1), the formula (7.2), and the formula (10.1). And one or more compounds selected from the group consisting of the compounds represented by the formula (10.2), and one or more compounds selected from the group consisting of the compounds represented by the formula (4) and the formula (a2), The total content of the compound is preferably 60 to 98%, and 65 to 95% is preferred, 70 to 90% is better, 70 to 87% is particularly preferred, and 70 to 84% is optimal.

In the liquid crystal composition, the compound having two or more fluorine atoms, specifically, the formula (2), the formula (3), the formula (4), the formula (5), the formula (a1), the formula (a2), The ratio of the compound represented by the formula (a3), the formula (7.1), the formula (7.2), the formula (9.1), the formula (9.2), the formula (10.1), the formula (10.2), and the formula (c1) may also be It is 100%, and preferably 60~98%, and 65~95% is better, 70~90% is better, 70~87% is better, and 70~84% is best.

"Ingredients (B)"

The component (B) in the liquid crystal composition may contain only the compound represented by the above formula (1), but it is preferred to further contain at least one of the compounds represented by the following formulas (6.1) to (6.3). .

When the compound represented by the formula (6.1) is contained, the content thereof is preferably from 1 to 20%, more preferably from 3 to 15%, and most preferably from 6 to 10% in the liquid crystal composition.

When the compound represented by the formula (6.2) is contained, the content thereof is preferably from 1 to 20%, more preferably from 3 to 15%, and most preferably from 6 to 10% in the liquid crystal composition.

When the compound represented by the formula (6.3) is contained, the content thereof is preferably from 1 to 20%, more preferably from 3 to 16%, and most preferably from 6 to 10% in the liquid crystal composition.

The component (B) is preferably one or more selected from the group consisting of compounds represented by the following formula (8).

(wherein R ⁵ represents an alkyl group having 2 or 5 carbon atoms or an alkoxy group having 1 to 3 carbon atoms.)

The compound represented by the above formula (8) is specifically a compound represented by the following formulas (8.1) to (8.5).

When the compound represented by the formula (8.1) is contained, the content thereof is preferably from 1 to 35%, more preferably from 5 to 30%, and most preferably from 10 to 25% in the liquid crystal composition.

When the compound represented by the formula (8.2) is contained, the content thereof is preferably from 1 to 20%, more preferably from 3 to 15%, and most preferably from 5 to 10% in the liquid crystal composition.

When the compound represented by the formula (8.3) is contained, the content thereof is preferably from 1 to 20%, more preferably from 1 to 10%, most preferably from 2 to 8%, in the liquid crystal composition.

When the compound represented by the formula (8.4) is contained, the content thereof is preferably from 1 to 20%, more preferably from 1 to 10%, most preferably from 2 to 8%, in the liquid crystal composition.

When the compound represented by the formula (8.5) is contained, the content thereof is preferably from 1 to 20%, more preferably from 2 to 15%, and most preferably from 4 to 10% in the liquid crystal composition.

The component (B) may additionally contain a compound represented by the following formula (b1).

When the compound represented by the formula (b1) is contained, the content thereof is preferably from 1 to 30%, more preferably from 3 to 26%, and most preferably from 5 to 22% in the liquid crystal composition.

The component (B) may additionally contain a compound represented by the following formula (b2).

When the compound represented by the formula (b2) is contained, the content thereof is preferably from 1 to 20%, more preferably from 2 to 15%, and most preferably from 4 to 10% in the liquid crystal composition.

The component (B) may additionally contain a compound represented by the following formula (b3).

When the compound represented by the formula (b3) is contained, the content thereof is preferably from 1 to 20%, more preferably from 5 to 15%, and most preferably from 8 to 12% in the liquid crystal composition.

"mixing ratio of component (A) to component (B)"

In the liquid crystal composition, the content ratio (mixing ratio) of the component (A) having a negative dielectric property and the component (B) having a dielectric property is as long as the liquid crystal composition has a negative dielectric constant. The opposite sex is not particularly limited, but it is preferable to contain the component (A) more than the component (B).

Specifically, in the liquid crystal composition, it is preferable to contain a component (A) having a negative dielectric anisotropy of 50% or more, and preferably 60 to 98%, more preferably 65 to 95%, and 70 to 90%. Particularly good, 70~87% is especially good, 70~84% is the best. Further, the liquid crystal composition preferably contains the component (B) in an amount of 5 to 45%, preferably 10 to 40%, more preferably 15 to 35%.

Dielectric Anisotropy (△ε)

The dielectric anisotropy (??) of the liquid crystal composition of the present invention is preferably -2.0 to -6.0 at 25 °C, more preferably -2.3 to -5.0, and particularly preferably -2.3 to -4.0. In further detail, it is preferable to pay attention to the response speed of -2.3 to -3.4, and it is preferable to use -3.4 to -4.0 when the driving voltage is emphasized.

"Refractive index anisotropy (△n)"

The refractive index anisotropy (?n) of the liquid crystal composition of the present invention is preferably from 0.08 to 0.13 at 25 °C, more preferably from 0.09 to 0.12. Further, it is preferably 0.10 to 0.12 corresponding to a thin liquid crystal cell gap, and preferably 0.08 to 0.10 corresponding to a thick liquid crystal cell gap.

Rotational Viscosity (γ ₁ )

The liquid crystal composition of the present invention has a rotational viscosity (γ ₁ ) of preferably 240 mPa·s or less, more preferably 165 mPa·s or less, more preferably 160 mPa·s or less, and most preferably 155 mPa·s or less.

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

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

Z is preferably 18,000 or less, more preferably 16,000 or less, and particularly preferably 14,000 or less.

Viscosity (η)

The viscosity (η) of the liquid crystal composition of the present invention is preferably 26 mPa·s or less, more preferably 24.5 mPa·s, more preferably 22.5 mPa·s or less, and most preferably 21 mPa·s or less.

The specific resistance of the liquid crystal composition of the present invention, in the case of using the display in the active matrix element, is preferably ¹⁰¹¹ or more (Ω‧m), more preferably 10 ¹² (Ω‧m) or more, particularly preferably 10 ¹³ (Ω‧m) or more, preferably 10 ¹⁴ (Ω‧m) or more.

"Other Ingredients: Ingredient (C)"

The liquid crystal composition of the present invention may also contain the component (C) which does not belong to the component (A) or the component (B). The content of the component (C) in the liquid crystal composition is not particularly limited, but is preferably 20% or less, more preferably 1 to 10%, and particularly preferably 1 to 6%.

A compound having a positive dielectric anisotropy may be contained as the component (C), and for example, a compound represented by the following formula (c1) may be contained.

When the compound represented by the formula (c1) is contained, the content thereof is preferably from 1 to 20%, more preferably from 2 to 10%, most preferably from 3 to 7%, in the liquid crystal composition.

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

As the polymerizable monomer, a bifunctional monomer represented by the formula (VI) is preferred.

(wherein, X ⁷ and X ^{8 are} each independently and represent a hydrogen atom or a methyl group, and Sp ¹ and Sp ^{2 are} each independently and 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 is -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 are} each independently and 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 all of the 1,4-phenylene groups in the formula may be used as an arbitrary hydrogen atom. The fluorine atom is substituted).

Preferably, any of X ⁷ and X ⁸ represents a diacrylate derivative of a hydrogen atom, and a dimethacrylate derivative each having a methyl group, one of which represents a hydrogen atom and the other represents a methyl group. Also preferred. The polymerization rate of the compounds is the fastest, the diacrylate derivative is the fastest, the dimethacrylate derivative is the slowest, the asymmetric compound is in the middle thereof, and the preferred form can be used depending on the use thereof. Among the PSA display elements, a dimethacrylate derivative is particularly preferred.

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

Z ² is -OCH ₂ -, -CH ₂ O-, -COO-, -OCO-, -CF ₂ O-, -OCF ₂ -, -CH ₂ CH ₂ -, -CF ₂ CF ₂ - or a single bond Good, -COO-, -OCO- or single button is better, single button is especially good.

B represents an arbitrary hydrogen atom which may be substituted with a fluorine atom, a 1,4-phenylene group, a trans-1,4-cyclohexylene group or a single bond, but a 1,4-phenylene group or a single bond is preferred. When B represents a ring structure other than a single bond, Z ² represents a linking group other than a single bond is also preferable, when B 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 specifically preferably the structure described below.

In the formula (VI), B represents a single bond, and when a ring structure is formed by two rings, it is preferred that the following formula (VIa-1) to formula (VIa-5) represent a formula (VIa-1) to The formula (VIa-3) is more preferable, and the formula (VIa-1) is the best.

(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 since a good alignment state is obtained, display unevenness can be suppressed or not caused at all.

As described above, the polymerizable monomer is particularly preferred from the formula (VI-1) to the formula (VI-4), and among them, the formula (VI-2) is particularly preferable.

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

When the bifunctional monomer represented by the formula (VI) is used as the polymerizable monomer, the content of the bifunctional monomer in the liquid crystal composition is preferably 2% or less, and preferably 1.5% or less, and 1%. The following is better, preferably below 0.5%, and best below 0.4%. If it is 2% or less, the occurrence of the aforementioned dropping marks can be reduced.

When a monomer is added to the liquid crystal composition of the present invention, the polymerization can be carried out even 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, benzophenones, acetophenones, benzyl 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-butyl catechols, pyrogallols, thiophenols, nitro compounds, and β. - naphthylamines, β-naphthols, nitroso compounds, and the like.

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

The liquid crystal composition containing the polymerizable compound of the present invention can be polymerized by ultraviolet irradiation by the polymerization of the polymerizable compound contained therein to impart liquid crystal alignment ability, and can be used for liquid crystal which can control the amount of light transmitted by the birefringence of the liquid crystal composition. Display component. As a liquid crystal display element, in AM-LCD (Active Matrix Liquid Crystal Display Element), TN (Nematic Liquid Crystal Display Element), STN-LCD (Super Twisted Nematic Liquid Crystal Display Element), OCB-LCD, and IPS-LCD (Landscape Electric field effect liquid crystal display element) It is useful and is particularly useful in AM-LCDs and can be used for transmissive or reflective liquid crystal display elements.

The two substrates of the liquid crystal cells used in the liquid crystal display element may be made of a transparent material such as glass or plastic, or may be an opaque material such as tantalum. The transparent substrate having the transparent electrode layer can be obtained, for example, by sputtering indium tin oxide (ITO) on a transparent substrate such as a glass plate.

The substrates are opposed to each other such that the transparent electrode layer is inside. At this time, the interval of the substrate can be adjusted by the spacer. At this time, it is preferable to adjust the thickness of the obtained light control layer to 1 to 100 μm. More preferably, it is 1.5 to 10 μm, and in the case of using a polarizing plate, it is preferable to adjust the product of the refractive index anisotropy Δn of the liquid crystal and the cell thickness d to maximize the contrast. Further, in the case of having two polarizing plates, the polarization axes of the respective polarizing plates can be adjusted to adjust the viewing angle and contrast. Further, a retardation film for expanding the viewing angle can also be used. Examples of the separator include glass particles, plastic particles, alumina particles, and a photoresist. Then, a sealing agent such as an epoxy-based thermosetting composition is screen-printed on the substrate so that the substrates are bonded to each other and heated to thermally cure the sealant.

A method of sandwiching a liquid crystal composition containing a polymerizable compound between two substrates may be a normal vacuum injection method or an ODF method. However, in the vacuum injection method, although no dropping marks are formed, there is an injection. In the case of the present invention, the display element manufactured by the ODF method can be more suitably used.

As a method of polymerizing a polymerizable compound, an appropriate polymerization rate is desired in order to obtain a good alignment property of a liquid crystal. Specifically, it is preferred to carry out the polymerization by using the active energy ray such as ultraviolet rays or electron beams alone or in combination with a plurality of types of active energy rays. In the case of using ultraviolet rays, a polarized light source or a non-polarized light source may be used. In addition, when the liquid crystal composition containing the polymerizable compound is polymerized in a state of being sandwiched between the two substrates, at least the substrate on the irradiation surface side must have appropriate transparency to the active energy ray. Further, it is also possible to use a method in which, when light is irradiated, a mask is used, and only a specific portion is polymerized, and conditions such as an electric field, a magnetic field, or a temperature are changed, whereby the alignment state of the unpolymerized portion is changed, and the active energy is further irradiated. Lines are aggregated. In particular, in the case of ultraviolet exposure, it is preferred to apply an alternating electric field to the liquid crystal composition containing the polymerizable compound while performing ultraviolet exposure. 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. The voltage can be selected according to the desired pretilt angle of the liquid crystal display element. That is, the pretilt angle of the liquid crystal display element can be controlled according to the applied voltage. In the liquid crystal display element of the MVA mode, it is preferable to control the pretilt angle at 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 composition of the present invention maintains a liquid crystal state. It is preferred to carry out the polymerization at a temperature close to room temperature, that is, typically at a temperature of from 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 preferable to irradiate ultraviolet rays which are not in the wavelength region of the absorption wavelength region of the liquid crystal composition, and it is preferably used by cutting ultraviolet rays as necessary. 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 energy of the irradiated ultraviolet rays can be appropriately adjusted, but is preferably from 10 mJ/cm ² to 500 J/cm ² , more preferably from 100 mJ/cm ² to 200 J/cm ² . The intensity can be changed when ultraviolet rays are irradiated. The time for irradiating the ultraviolet rays can be appropriately selected depending on the intensity of the ultraviolet rays to be irradiated, but is preferably from 10 seconds to 3600 seconds, more preferably from 10 seconds to 600 seconds.

"Liquid Crystal Display Element"

As shown in Fig. 1, the liquid crystal display device of the second embodiment of the present invention has a first substrate including a common electrode including a transparent conductive material, a pixel electrode including a transparent conductive material, and a pixel for controlling each pixel. The second substrate of the thin film transistor of the pixel electrode and the liquid crystal composition sandwiched between the first substrate and the second substrate are preferable. As the liquid crystal composition, the liquid crystal composition of the first embodiment was used. In the liquid crystal composition, the alignment of the liquid crystal molecules when no voltage is applied is slightly perpendicular to the substrate.

As described above, the generation of the dropping marks is greatly affected by the type and combination of the liquid crystal compounds constituting the injected liquid crystal material (liquid crystal composition). Furthermore, the type or combination of the members constituting the display element also affects the generation of the drop marks. In particular, a member in which a color filter or a thin film transistor and a liquid crystal composition are formed separately in a liquid crystal display element, since it is only a thin member such as an alignment film or a transparent electrode, the color filter or thin film transistor There is a possibility that the liquid crystal composition is affected to cause a drop mark.

In particular, in the case where the thin film transistor in the liquid crystal display device is of an inverted staggered type, the tantalum electrode is formed by covering the gate electrode, and thus the area of the thin film transistor tends to increase. The tantalum electrode is formed of a metal material such as copper, aluminum, chromium, titanium, molybdenum or tantalum. In general, the passivation treatment is a usual form. However, since the protective film is generally thin, the alignment film is also thin, and the possibility of not blocking the ionic substance is high, the interaction between the metal material and the liquid crystal composition is dripping when the conventional liquid crystal composition is used. The production of marks will occur frequently.

On the other hand, as shown by the results of the evaluation of the dropping mark in the following examples, the liquid crystal composition of the first embodiment of the present invention is used, and although the detailed mechanism is not explained, it can be sufficiently reduced to become a conventional problem. The addition of traces is produced.

The liquid crystal composition of the first embodiment of the present invention is applied, for example, to a liquid crystal display element in which the thin film transistor shown in Fig. 2 is an inverted staggered type. In this case, it is preferable to use aluminum wiring.

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

In the liquid crystal display of the present invention, the liquid crystal display element of the present invention is applied to a display (display device) by a known method.

Example

The present invention will be further described in detail by the following examples, but the invention is not limited to the examples. In addition, "%" in the composition of the following examples and comparative examples means "% by mass".

In the examples, the measured characteristics are 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 : 25 ° C rotational viscosity (mPa ‧ s)

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

Voltage holding ratio after 1 hour at 150 ° C: After maintaining for 1 hour in an environment of 150 ° C, the voltage holding ratio (%) measured under the same conditions as the initial VHR

[Branding evaluation]

In the evaluation of the imprint of the liquid crystal display device, after the fixed pattern specified in the display region is displayed for 1000 hours, the afterimage level of the fixed pattern when the full screen is uniformly displayed is visually observed in the following four stages.

◎: no afterimage

○: A level that can be tolerated even with a slight residual image

△: Level with residual image and unacceptable

×: There is an afterimage and it is quite bad

[Evaluation of dripping marks]

In the evaluation of the dripping mark of the liquid crystal display device, the white dripping mark which floated on the whole surface was shown, and the following four-stage evaluation was performed visually.

◎: no afterimage

○: A level that can be tolerated even with a slight residual image

△: Level with residual image and unacceptable

×: There is an afterimage and it is quite bad

[Evaluation of program suitability]

Program suitability. In the ODF program, use a constant-capacity pump to add 50pL of liquid crystal per 100 times, and perform 100,000 times, and the following "0~100 times, 101~200 times, 201~300 times, ...99901~100000 times" The change in the amount of liquid crystal added 100 times per drop was evaluated in the following four stages.

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

○: A level that can be tolerated even with some slight changes

△: A level that is variable and unacceptable (the yield is deteriorated due to the generation of spots)

×: There is a change and it is quite bad (liquid crystal leakage or vacuum bubble generation)

[Evaluation of Solubility at Low Temperature]

The solubility evaluation at low temperature was carried out by preparing a liquid crystal composition, and weighing 1 g of the liquid crystal composition in a 2 mL sample bottle, and placing it in a temperature-controlled test tank, and the following "-20 ° C (for 1 hour) → Temperature rise (0.1 ° C / min) → 0 ° C (for 1 hour) → Temperature (0.1 ° C / min) → 20 ° C (for 1 hour) → Cooling (-0.1 ° C / min) → 0 ° C (keep 1 Hour)→cooling (−0.1° C./min)→-20° C. As a single cycle, the temperature change was continuously applied, and the precipitate generated from the liquid crystal composition was visually observed, and the following four-stage evaluation was performed.

◎: No precipitate was observed for 600 hours or more.

○: No precipitate was observed for 300 hours or longer.

△: Precipitates were observed within 150 hours.

×: Precipitates were observed within 75 hours.

[Example 1 and Comparative Example 1]

A liquid crystal composition of the composition shown in Table 1 was prepared, and the physical property value was measured.

Further, the VA liquid crystal display elements shown in Fig. 1 were produced by using the liquid crystal compositions of Example 1 and Comparative Example 1. The liquid crystal display element has an inversely staggered thin film transistor as an active element. The injection of the liquid crystal composition is carried out by a dropping method (ODF method). Further, the obtained display element was subjected to imprinting, dropping, program suitability, and solubility at low temperature by the above method. The results are shown in Table 2.

In Table 1, the compound represented by the chemical formula (b4) of Comparative Example 1 is a compound represented by the structural formula of the following formula (b4).

The liquid crystal composition of Example 1 has a practical liquid crystal phase temperature range of 80.5 ° C as a liquid crystal composition for TV, and has a large absolute value of dielectric anisotropy, and has low rotational viscosity and is most suitable. △n. Moreover, the solubility at low temperatures is also good. Further, the VA liquid crystal display device having the configuration shown in Fig. 1 produced by using the liquid crystal composition of Example 1 showed excellent results in the evaluation of the imprinting, the dropping marks, and the program suitability. The VA liquid crystal display device preferably has an initial voltage holding ratio and a voltage holding ratio after one hour at 150 °C.

[Example 2, Comparative Example 2]

A liquid crystal composition of the composition shown in Table 3 was prepared, and the physical property value was measured.

Moreover, the display elements produced using the liquid crystal compositions of Example 2 and Comparative Example 2 in the same manner as in Example 1 were subjected to imprinting, dropping marks, program suitability, and solubility at low temperatures. The results are shown in Table 4.

The liquid crystal composition of Example 2 has a practical liquid crystal phase temperature range of 87.3 ° C which is a liquid crystal composition for TV, and the refractive index anisotropy and dielectric anisotropy are also good. Moreover, the solubility at low temperatures is also good. Further, the VA liquid crystal display device having the configuration shown in Fig. 1 produced by using the liquid crystal composition of Example 2 showed excellent results in the evaluation of the imprinting, the dropping, and the program suitability. The VA liquid crystal display device preferably has an initial voltage holding ratio and a voltage holding ratio after one hour at 150 °C.

[Examples 3 to 6]

A liquid crystal composition of the composition shown in Table 5 was prepared, and the physical property value was measured.

Further, the display elements produced in the same manner as in Example 1 using the liquid crystal compositions of Examples 3 to 6 were evaluated for imprinting, dropping marks, program suitability, and solubility at low temperatures. The results are shown in Table 6.

The liquid crystal compositions of Examples 3 to 6 have a practical liquid crystal phase temperature range of 78.3 to 81.3 ° C which is a liquid crystal composition for TV, and the refractive index anisotropy and dielectric anisotropy are also good. The liquid crystal compositions of Examples 3, 5, and 6 were extremely excellent in the evaluation of solubility at low temperatures.

The VA liquid crystal display element of Example 3 was extremely excellent in the evaluation of imprinting, dropping marks, and program suitability. The VA liquid crystal display element of Example 4 was extremely excellent in branding evaluation. The VA liquid crystal display element of Example 5 was extremely excellent in evaluation of dropping marks. The VA liquid crystal display element of Example 6 was extremely excellent in the evaluation of the imprint and the evaluation of the dripping.

In the VA liquid crystal display devices of Examples 3 to 6, the initial voltage holding ratio and the voltage holding ratio after one hour at 150 ° C showed excellent results.

[Examples 7 to 10]

Liquid crystal compositions having the compositions shown in Table 7 were prepared, and their physical property values were measured.

Further, the display elements produced in the same manner as in Example 1 using the liquid crystal compositions of Examples 7 to 10 were evaluated for imprinting, dropping marks, program suitability, and solubility at low temperatures. The results are shown in Table 8.

The liquid crystal compositions of Examples 7 to 10 have a practical liquid crystal phase temperature range of 70.3 to 78.4 ° C which is a liquid crystal composition for TV, and the refractive index anisotropy and dielectric anisotropy are also good. The liquid crystal compositions of Examples 7 to 9 were extremely excellent in the evaluation of solubility at low temperatures.

The VA liquid crystal display element of Example 7 was extremely excellent in the evaluation of imprinting, dropping marks, and program suitability. The VA liquid crystal display element of Example 8 was extremely excellent in evaluation of imprinting and evaluation of program suitability. The VA liquid crystal display element of Example 10 was extremely excellent in the evaluation of the imprinting and the evaluation of the dripping.

The VA liquid crystal display devices of Examples 7 to 10 showed excellent results in both the initial voltage holding ratio and the voltage holding ratio after one hour at 150 °C.

[Examples 11 to 14]

A liquid crystal composition of the composition shown in Table 9 was prepared, and the physical property value was measured.

Moreover, the display elements produced using the liquid crystal compositions of Examples 11 to 14 in the same manner as in Example 1 were subjected to imprinting, dropping marks, program suitability, and solubility at low temperatures. The results are shown in Table 10.

The liquid crystal compositions of Examples 11 to 14 have a practical liquid crystal phase temperature range of 70.1 to 78.5 ° C which is a liquid crystal composition for TV, and the refractive index anisotropy and dielectric anisotropy are also good. The liquid crystal compositions of Examples 11 to 14 were extremely excellent in the evaluation of solubility at low temperatures.

The VA liquid crystal display elements of Examples 11 and 12 were extremely excellent in the evaluation of imprinting, dropping marks, and program suitability. The VA liquid crystal display element of Example 13 was extremely excellent in branding evaluation. The VA liquid crystal display element of Example 14 was extremely excellent in the evaluation of the imprinting and the evaluation of the dripping.

The VA liquid crystal display devices of Examples 11 to 14 showed excellent results in both the initial voltage holding ratio and the voltage holding ratio after one hour at 150 °C.

[Examples 15 to 18]

Liquid crystal compositions having the compositions shown in Table 11 were prepared, and their physical property values were measured.

Further, the display elements produced in the same manner as in Example 1 using the liquid crystal compositions of Examples 15 to 18 were subjected to imprinting, dropping marks, program suitability, and solubility at low temperatures. The results are shown in Table 12.

The liquid crystal compositions of Examples 15 to 18 have a practical liquid crystal phase temperature range of 65.3 to 70.8 ° C as a liquid crystal composition for TV, and the refractive index anisotropy and dielectric anisotropy are also good. The liquid crystal compositions of Examples 15, 16, and 18 were extremely excellent in the evaluation of solubility at low temperatures.

The VA liquid crystal display element of Example 15 was extremely excellent in the evaluation of imprinting, dropping marks, and program suitability. The VA liquid crystal display element of Example 16 was extremely excellent in the evaluation of the imprint and the evaluation of the dripping. VA liquid crystal display element of Example 17, evaluation of imprinting and evaluation of program suitability Very excellent. The VA liquid crystal display element of Example 18 was extremely excellent in the evaluation of program suitability.

The VA liquid crystal display devices of Examples 15 to 18 showed excellent results in both the initial voltage holding ratio and the voltage holding ratio after one hour at 150 °C.

[Examples 19 to 22]

Liquid crystal compositions having the compositions shown in Table 13 were prepared, and their physical property values were measured.

Further, the display elements produced by using the liquid crystal compositions of Examples 19 to 22 in the same manner as in Example 1 were subjected to evaluation of imprinting, dropping marks, program suitability, and solubility at low temperatures. The results are shown in Table 14.

The liquid crystal compositions of Examples 19 to 22 have a practical liquid crystal phase temperature range of 74.5 to 80.2 ° C which is a liquid crystal composition for TV, and the refractive index anisotropy and dielectric anisotropy are also good. The liquid crystal compositions of Examples 19 to 22 were extremely excellent in the evaluation of solubility at low temperatures.

The VA liquid crystal display elements of Examples 19 and 20 were extremely excellent in the evaluation of imprinting, dropping marks, and program suitability. The VA liquid crystal display element of Example 21 was extremely excellent in branding evaluation. The VA liquid crystal display element of Example 22 was extremely excellent in the evaluation of the imprint and the evaluation of the dripping.

The VA liquid crystal display devices of Examples 19 to 22 showed excellent results in both the initial voltage holding ratio and the voltage holding ratio after one hour at 150 °C.

[Examples 23 to 26]

Liquid crystal compositions having the compositions shown in Table 15 were prepared, and their physical property values were measured.

Moreover, the display elements produced using the liquid crystal compositions of Examples 23 to 26 in the same manner as in Example 1 were subjected to evaluation of imprinting, dropping marks, program suitability, and solubility at low temperatures. The results are shown in Table 16.

The liquid crystal compositions of Examples 23 to 26 have a practical liquid crystal phase temperature range of 75.2 to 77.8 ° C which is a liquid crystal composition for TV, and the refractive index anisotropy and dielectric anisotropy are also good. The liquid crystal compositions of Examples 23, 25, and 26 were extremely excellent in the evaluation of solubility at low temperatures.

The VA liquid crystal display element of Example 23 was extremely excellent in the evaluation of imprinting, dropping marks, and program suitability. The VA liquid crystal display element of Example 24 was extremely excellent in branding evaluation. The VA liquid crystal display element of Example 25 was extremely excellent in evaluation of dropping marks. The VA liquid crystal display element of Example 26 was extremely excellent in the evaluation of the imprint and the evaluation of the dripping.

The VA liquid crystal display devices of Examples 23 to 26 showed excellent results in both the initial voltage holding ratio and the voltage holding ratio after one hour at 150 °C.

[Examples 27 to 30]

A liquid crystal composition of the composition shown in Table 17 was prepared, and the physical property value was measured.

Further, the display elements produced in the same manner as in Example 1 using the liquid crystal compositions of Examples 27 to 30 were subjected to imprinting, dropping marks, program suitability, and solubility at low temperatures. The results are shown in Table 18.

The liquid crystal compositions of Examples 27 to 30 have a practical liquid crystal phase temperature range of 79.0 to 80.2 ° C which is a liquid crystal composition for TV, and the refractive index anisotropy and dielectric anisotropy are also good. The liquid crystal compositions of Examples 27, 28, and 30 were extremely excellent in the evaluation of solubility at low temperatures.

The VA liquid crystal display element of Example 27 was extremely excellent in the evaluation of imprinting, dropping marks, and program suitability. The VA liquid crystal display element of Example 28 was extremely excellent in the evaluation of the imprint and the evaluation of the dripping. The VA liquid crystal display element of Example 29 was extremely excellent in the evaluation of the imprinting and the evaluation of the suitability of the program. The VA liquid crystal display element of Example 30 was extremely excellent in the evaluation of program suitability.

The VA liquid crystal display devices of Examples 27 to 30 showed excellent results in both the initial voltage holding ratio and the voltage holding ratio after one hour at 150 °C.

[Examples 31 to 34]

Liquid crystal compositions having the compositions shown in Table 19 were prepared, and their physical property values were measured.

Moreover, the display elements produced using the liquid crystal compositions of Examples 31 to 34 in the same manner as in Example 1 were subjected to imprinting, dropping marks, program suitability, and solubility at low temperatures. The results are shown in Table 20.

The liquid crystal compositions of Examples 31 to 34 have a practical liquid crystal phase temperature range of 75.6 to 79.1 ° C as a liquid crystal composition for TV, and the refractive index anisotropy and dielectric anisotropy are also good. The liquid crystal compositions of Examples 31, 33, and 34 were extremely excellent in the evaluation of solubility at low temperatures.

The VA liquid crystal display element of Example 31 was extremely excellent in evaluation of dropping marks and program suitability. VA liquid crystal display element of Example 32 The piece is extremely excellent in the evaluation of the brand. The VA liquid crystal display element of Example 33 was extremely excellent in the evaluation of the imprint and the evaluation of the dripping. The VA liquid crystal display element of Example 34 was extremely excellent in the evaluation of the imprinting and the evaluation of the dripping.

The VA liquid crystal display devices of Examples 31 to 34 showed excellent results in both the initial voltage holding ratio and the voltage holding ratio after one hour at 150 °C.

[Examples 35 to 40]

The liquid crystal composition of the composition shown in Table 21 was prepared, and the physical property value was measured.

Further, the display elements produced in the same manner as in Example 1 using the liquid crystal compositions of Examples 35 to 40 were evaluated for imprinting, dropping marks, program suitability, and solubility at low temperatures. The results are shown in Table 22.

The liquid crystal compositions of Examples 35 to 40 have a practical liquid crystal phase temperature range of 74.6 to 75.4 ° C which is a liquid crystal composition for TV, and the refractive index anisotropy and dielectric anisotropy are also good. The liquid crystal compositions of Examples 35, 37, 38, and 40 were extremely excellent in the evaluation of solubility at low temperatures.

The VA liquid crystal display element of Example 35 was extremely excellent in the evaluation of imprinting, dropping marks, and program suitability. The VA liquid crystal display element of Example 36 was extremely excellent in branding evaluation. The VA liquid crystal display element of Example 37 was extremely excellent in evaluation of dropping marks. The VA liquid crystal display element of Example 38 was extremely excellent in the evaluation of the imprinting and the evaluation of the dripping. The VA liquid crystal display element of Example 39 was extremely excellent in branding evaluation. The VA liquid crystal display element of Example 40 was extremely excellent in evaluation of dropping marks.

The VA liquid crystal display devices of Examples 35 to 40 showed excellent results in both the initial voltage holding ratio and the voltage holding ratio after one hour at 150 °C.

[Examples 41 to 44]

A liquid crystal composition of the composition shown in Table 23 was prepared, and the physical property value was measured.

Further, the display elements produced by using the liquid crystal compositions of Examples 41 to 44 in the same manner as in Example 1 were subjected to imprinting, dropping marks, program suitability, and solubility at low temperatures. The results are shown in Table 24.

The liquid crystal compositions of Examples 41 to 44 have a practical liquid crystal phase temperature range of 72.4 to 80.7 ° C which is a liquid crystal composition for TV, and the refractive index anisotropy and dielectric anisotropy are also good. The liquid crystal compositions of Examples 41 to 43 were extremely excellent in the evaluation of solubility at low temperatures.

The VA liquid crystal display element of Example 41 was extremely excellent in the evaluation of imprinting, dropping marks, and program suitability. The VA liquid crystal display element of Example 42 was extremely excellent in evaluation of dropping marks. The VA liquid crystal display element of Example 43 was extremely excellent in the evaluation of the imprint and the evaluation of the dripping. The VA liquid crystal display element of Example 44 was extremely excellent in branding evaluation.

The VA liquid crystal display devices of Examples 41 to 44 showed excellent results in both the initial voltage holding ratio and the voltage holding ratio after one hour at 150 °C.

[Examples 45 to 50]

A liquid crystal composition of the composition shown in Table 25 was prepared, and the physical property value was measured.

Further, the display elements produced in the same manner as in Example 1 using the liquid crystal compositions of Examples 45 to 50 were evaluated for imprinting, dropping marks, program suitability, and solubility at low temperatures. The results are shown in Table 26.

The liquid crystal compositions of Examples 45 to 50 have a practical liquid crystal phase temperature range of 78.1 to 83.3 ° C which is a liquid crystal composition for TV, and the refractive index anisotropy and dielectric anisotropy are also good. The liquid crystal compositions of Examples 45 to 47, 49, and 50 were extremely excellent in the evaluation of solubility at low temperatures.

The VA liquid crystal display element of Example 45 was extremely excellent in the evaluation of imprinting, dropping marks, and program suitability. The VA liquid crystal display element of Example 46 was extremely excellent in the evaluation of the imprinting and the evaluation of the suitability of the program. The VA liquid crystal display element of Example 48 was extremely excellent in the evaluation of the imprint and the evaluation of the dripping. The VA liquid crystal display element of Example 49 was extremely excellent in evaluation of dropping marks. The VA liquid crystal display element of Example 50 was extremely excellent in the evaluation of the imprinting and the evaluation of the dripping.

The VA liquid crystal display devices of Examples 45 to 50 showed excellent results in both the initial voltage holding ratio and the voltage holding ratio after one hour at 150 °C.

[Examples 51 to 53]

Liquid crystal compositions having the compositions shown in Table 27 were prepared, and their physical property values were measured.

Further, the display elements produced in the same manner as in Example 1 using the liquid crystal compositions of Examples 51 to 53 were evaluated for imprinting, dropping marks, program suitability, and solubility at low temperatures. The results are shown in Table 28.

The liquid crystal compositions of Examples 51 to 53 have a liquid crystal phase temperature range of 80.0 to 81.0 ° C which is practical as a liquid crystal composition for TV, and the refractive index anisotropy and dielectric anisotropy are also good. The liquid crystal compositions of Examples 51 and 53 were extremely excellent in the evaluation of solubility at low temperatures.

The VA liquid crystal display element of Example 51 was extremely excellent in the evaluation of the drop mark and the evaluation of the program suitability. The VA liquid crystal display element of Example 52 was extremely excellent in branding evaluation. The VA liquid crystal display element of Example 53 was extremely excellent in the evaluation of the imprint and the evaluation of the dripping.

The VA liquid crystal display devices of Examples 51 to 53 exhibited excellent results in both the initial voltage holding ratio and the voltage holding ratio after one hour at 150 °C.

[Examples 54 to 57]

A liquid crystal composition of the composition shown in Table 29 was prepared, and the physical property value was measured.

Further, with respect to the display elements produced in the same manner as in Example 1 using the liquid crystal compositions of Examples 54 to 57, the imprinting, the dropping, the program suitability, and the solubility at low temperature were evaluated. The results are shown in Table 30.

The liquid crystal compositions of Examples 54 to 57 have a practical liquid crystal phase temperature range of 75.6 to 79.1 ° C as a liquid crystal composition for TV, and the refractive index anisotropy and dielectric anisotropy are also good. The liquid crystal compositions of Examples 54, 56, and 57 were extremely excellent in the evaluation of solubility at low temperatures.

The VA liquid crystal display element of Example 54 was extremely excellent in the evaluation of the imprinting, the evaluation of the dropping mark, and the evaluation of the suitability of the program. The VA liquid crystal display element of Example 55 was extremely excellent in branding evaluation. The VA liquid crystal display element of Example 56 was extremely excellent in evaluation of dropping marks. The VA liquid crystal display element of Example 57 was extremely excellent in the evaluation of the imprint and the evaluation of the dripping.

The VA liquid crystal display devices of Examples 54 to 57 showed excellent results in both the initial voltage holding ratio and the voltage holding ratio after one hour at 150 °C.

The respective configurations and combinations of the above-described embodiments are examples, and the additions, omissions, substitutions, and other changes may be made without departing from the spirit and scope of the invention. Further, the present invention is not limited to the respective embodiments, and is limited to the scope of the patent application.

[Industrial availability]

The liquid crystal composition of the present invention can be widely applied to the fields of liquid crystal display elements and liquid crystal displays.

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 is a schematic view showing an example of a configuration of a liquid crystal display element according to a second embodiment of the present invention.

Fig. 2 is a cross-sectional view showing an example of a configuration of an inverted staggered thin film transistor.

Claims (11)

A liquid crystal composition comprising a negative dielectric constant anisotropy liquid crystal composition, comprising: a component (B) comprising the following formula (1) and the following formula (8.1); a dielectrically neutral compound, and having a dielectric anisotropy of a dielectricity greater than -2 and less than +2 is a neutral component; a component (A) containing a compound represented by the following formula (2) and the following formula (5), and having a dielectric property of negative; (wherein R ¹ and R ⁴ each independently represent an alkyl group having 1 to 8 carbon atoms); and the following formula (9.1), the following formula (9.2), and the following formula are contained in an amount of 0% by mass or more; 7.1), the following formula (7.2), the following formula (3), the following formula (4), the following formula (6.1), the following formula (6.2), the following formula (8), and the following formula (b3) a compound represented by the formula (1), the formula (8.1), the formula (2), the formula (5), the formula (9.1), the formula (9.2), the formula (7.1), The total content of the compound represented by the formula (7.2), the formula (3), the formula (4), the formula (6.1), the formula (6.2), the formula (8) and the formula (b3) is 80 mass. % or more and 99% by mass or less; (R ² and R ³ each independently represent an alkyl group having 1 to 8 carbon atoms or an alkenyl group having 2 to 8 carbon atoms; an alkyl group of R ² and R ³ or a methylene group in an alkenyl group, as long as oxygen The atom is not bonded to the bond, and may be substituted by an oxygen atom, or may be substituted by a carbonyl group as long as the carbonyl group is not bonded to the bond; (wherein R ⁵ represents an alkyl group having 2 or 5 carbon atoms or an alkoxy group having 1 to 3 carbon atoms; except in the case of the formula (8.1); The liquid crystal composition of claim 1, wherein the negative component (A) comprises a compound selected from the group consisting of compounds represented by the following formula (3) or (4); (wherein R ² and R ³ each independently represent an alkyl group having 1 to 8 carbon atoms or an alkenyl group having 2 to 8 carbon atoms; an alkyl group of R ² and R ³ or a methylene group in an alkenyl group; As long as the oxygen atom is not bonded to the bond, it may be substituted by an oxygen atom, or may be substituted by a carbonyl group as long as the carbonyl group is not bonded. The liquid crystal composition according to claim 1 or 2, wherein the component (A) comprises a compound group selected from the group consisting of the following formula (3.1), formula (3.2), formula (4.1), and formula (4.2). More than 2 kinds of compounds in the group; The liquid crystal composition of claim 1 or 2, wherein the component (B) comprises a compound represented by the following formula (6.1) or (6.2); The liquid crystal composition of claim 1 or 2, wherein the component (A) comprises a compound represented by the following formula (7.1) or (7.2); The liquid crystal composition according to claim 1 or 2, wherein the component (B) comprises a compound represented by the following formula (8); (wherein R ⁵ represents an alkyl group having ⁵ carbon atoms or an alkoxy group having 1 to 3 carbon atoms). The liquid crystal composition according to claim 1 or 2, wherein the component (A) comprises a compound represented by the following formula (9.1) or (9.2); The liquid crystal composition according to claim 1 or 2, wherein the component (A) comprises a compound represented by the following formula (10.1) or (10.2); The liquid crystal composition of claim 1 or 2, wherein the refractive index anisotropy (?n) is from 0.09 to 0.12. A liquid crystal display element characterized by using the liquid crystal composition according to any one of claims 1 to 9. A liquid crystal display characterized by using a liquid crystal display element as in claim 10 of the patent application.