KR20200001474A - Liquid crystal composition and liquid crystal display device - Google Patents

Abstract

The purpose of the present invention is to provide a liquid crystal composition which satisfies at least one properties or has an appropriate balance with respect to at least two properties among properties including a high upper limit temperature, a low lower limit temperature, a small viscosity, an appropriate optical anisotropy, a large negative dielectric anisotropy, a large resistivity, high stability to light and high stability to heat; and an active matrix (AM) element including the composition. In order to achieve the purpose, the present invention provides a liquid crystal composition which comprises a specific compound having a small viscosity and a negative dielectric anisotropy as a first component and a specific compound having a large negative dielectric anisotropy as a second component, and may comprise a specific compound having a high upper limit temperature or a small viscosity as a third component, a specific compound having a large negative dielectric anisotropy as a fourth component, or a specific compound having a polymerizable group as an additive.

Description

Liquid crystal composition and a liquid crystal display element {LIQUID CRYSTAL COMPOSITION AND LIQUID CRYSTAL DISPLAY DEVICE}

This invention relates to a liquid crystal composition, the liquid crystal display element containing this composition, etc. In particular, it relates to a liquid crystal composition having a negative dielectric anisotropy, and a liquid crystal display element containing the composition and having modes such as IPS, VA, FFS, and FPA. The present invention also relates to a polymer-supported alignment type liquid crystal display device.

In the liquid crystal display device, the classification based on the operation mode of the liquid crystal molecules is divided into phase change (PC), twisted nematic (TN), super twisted nematic (STN), electrically controlled birefringence (ECB), optically compensated bend (OCB), and IPS. (in-plane switching), vertical alignment (VA), fringe field switching (FFS), and field-induced photo-reactive alignment (FPA). The classification based on the driving method of an element is a passive matrix (PM) and an active matrix (AM). PM is classified into static, multiplex, etc., and AM is classified into a thin film transistor (TFT), a metal insulator metal (MIM), and the like. The classification of TFTs is amorphous silicon and polycrystal silicon. The latter is classified into high temperature type and low temperature type by the manufacturing process. The classification based on the light source is a reflection type using natural light, a transmission type using a backlight, and a semi-transmissive type using both natural light and a backlight.

The liquid crystal display element contains a liquid crystal composition having a nematic phase. This composition has appropriate properties. By improving the characteristic of this composition, the AM element which has a favorable characteristic can be obtained. The relevance in these properties is summarized in Table 1 below. The properties of the composition will be further described based on commercially available AM devices. The temperature range of the nematic phase is related to the temperature range in which the device can be used. The preferred upper limit temperature of the nematic phase is about 70 ° C. or higher, and the preferred lower limit temperature of the nematic phase is about −10 ° C. or lower. The viscosity of the composition is related to the response time of the device. Short response times are desirable for displaying moving images with the device. Shorter response times are preferred even at 1 millisecond. Therefore, small viscosities in the composition are preferred. Small viscosities at low temperatures are more preferred.

TABLE 1 Properties of composition and properties of AM device

Optical anisotropy of the composition is related to the contrast ratio of the device. Depending on the mode of the device, large optical anisotropy or small optical anisotropy, i.e., suitable optical anisotropy is required. The product (Δn × d) of the optical anisotropy (Δn) of the composition and the cell gap (d) of the device is designed to maximize the contrast ratio. The appropriate value of the product depends on the type of operating mode. This value is in the range of about 0.30 µm to about 0.40 µm in the VA mode element, and in the range of about 0.20 µm to about 0.30 µm in the IPS mode or FFS mode element. In these cases, the composition which has big optical anisotropy is preferable for the element of a small cell gap. Large dielectric anisotropy in the composition contributes to low threshold voltage, small power consumption and large contrast ratio in the device. Therefore, large dielectric anisotropy is desirable. The large specific resistance in the composition contributes to the large voltage retention and the large contrast ratio in the device. Therefore, a composition having a large specific resistance in the initial stage is preferable. After using for a long time, a composition having a large specific resistance is preferable. The stability of the composition against light or heat is related to the lifetime of the device. When this stability is high, the lifetime of the device is long. Such a characteristic is suitable for the AM element used for a liquid crystal monitor, a liquid crystal TV, etc.

In the general-purpose liquid crystal display device, vertical alignment of liquid crystal molecules is achieved by a specific polyimide alignment film. In a polymer sustained alignment (PSA) type liquid crystal display device, a polymer is combined with an alignment film. First, a composition to which a small amount of the polymerizable compound is added is injected into the device. Next, an ultraviolet-ray is irradiated to a composition, applying a voltage between the board | substrates of this element. The polymerizable compound is polymerized to produce the mesh structure of the polymer in the composition. In this composition, since it becomes possible to control the orientation of liquid crystal molecules by a polymer, the response time of an element is shortened and the baking of an image improves. Such effects of polymers can be expected for devices having modes such as TN, ECB, OCB, IPS, VA, FFS, and FPA.

In an AM device having a TN mode, a composition having positive dielectric anisotropy is used. In an AM device having a VA mode, a composition having negative dielectric anisotropy is used. In an AM device having the IPS mode or the FFS mode, a composition having positive or negative dielectric anisotropy is used. In a polymer sustained alignment (PSA) type AM device, a composition having positive or negative dielectric anisotropy is used.

Japanese Laid-Open Patent Publication No. 57-114532 International Publication No. 2007-77872

The problem of the present invention is that the characteristics of the high upper limit temperature of the nematic phase, low lower temperature of the nematic phase, small viscosity, suitable optical anisotropy, negatively large dielectric anisotropy, large specific resistance, high stability to light, high stability to heat It is providing the liquid crystal composition which satisfy | fills at least one. Another object is to provide a liquid crystal composition having a suitable balance between at least two of these properties. Another object is to provide a liquid crystal display element containing such a composition. Another object is to provide an AM device having characteristics such as short response time, large voltage holding ratio, low threshold voltage, large contrast ratio, and long lifetime.

This invention contains at least 1 compound selected from the compound represented by Formula (1) as a 1st component, and at least 1 compound selected from the compound represented by Formula (2) as a 2nd component, and contains a nematic phase and a negative It relates to a liquid crystal composition having a dielectric anisotropy of and a liquid crystal display element containing the composition.

In formula (1) and formula (2), R <^1> and R <^2> is C1-C12 alkyl or C2-C12 alkenyl; R ³ is alkenyl having 2 to 12 carbon atoms or alkenyloxy having 2 to 12 carbon atoms; R ⁴ is hydrogen, alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, alkenyl having 2 to 12 carbons, or alkenyloxy having 2 to 12 carbons; Ring A and Ring C are 1,4-cyclohexylene, 1,4-cyclohexenylene, tetrahydropyran-2,5-diyl, 1,4-phenylene, at least one hydrogen is fluorine or chlorine Substituted 1,4-phenylene, naphthalene-2,6-diyl, naphthalene-2,6-diyl, chroman-2,6-diyl, or at least one hydrogen at least one of which is substituted with fluorine or chlorine Is chroman-2,6-diyl substituted with fluorine or chlorine; Ring B is 2,3-difluoro-1,4-phenylene, 2-chloro-3-fluoro-1,4-phenylene, 2,3-difluoro-5-methyl-1,4 -Phenylene, 3,4,5-trifluoronaphthalene-2,6-diyl, 7,8-difluorochroman-2,6-diyl, 3,4,5,6-tetrafluorofluorene -2,7-diyl, 4,6-difluorodibenzofuran-3,7-diyl, 4,6-difluorodibenzothiophen-3,7-diyl, or 1,1,6,7-tetra Fluoroindan-2,5-diyl; Z ¹ to Z ⁴ are a single bond, ethylene, vinylene, carbonyloxy, or methyleneoxy; a is 0, 1, 2, or 3, b is 0 or 1, and the sum of a and b is 3 or less. Provided that when a is 1 and b is 1, when ring A is 1,4-cyclohexylene, ring C is not 1,4-phenylene or ring C is 1,4-cyclohexylene In this case, ring A is not 1,4-phenylene.

Advantages of the present invention include, among other characteristics, high upper temperature of the nematic phase, low lower temperature of the nematic phase, small viscosity, adequate optical anisotropy, negatively large dielectric anisotropy, large specific resistance, high stability against light, and high stability to heat. It is providing the liquid crystal composition which satisfy | fills at least one. Another advantage is to provide a liquid crystal composition having a suitable balance between at least two of these properties. Another advantage is to provide a liquid crystal display element containing such a composition. Another advantage is to provide an AM device with characteristics such as short response time, large voltage retention, low threshold voltage, large contrast ratio and long lifetime.

Usage of the terms in the present specification are as follows. The terms "liquid crystal composition" and "liquid crystal display element" may be abbreviated as "composition" and "element", respectively. "Liquid crystal display element" is a generic term for a liquid crystal display panel and a liquid crystal display module. The "liquid crystalline compound" does not have a compound having a liquid crystal phase such as a nematic phase, a smectic phase, and a liquid crystal phase, but is used in the composition for the purpose of adjusting characteristics such as temperature range, viscosity, and dielectric anisotropy of the nematic phase. Generic term for the compound to be mixed. This compound has 6-membered rings, such as 1, 4- cyclohexylene and 1, 4- phenylene, for example, and the molecule | numerator (liquid crystal molecule) is rod-like. A "polymerizable compound" is a compound added for the purpose of producing a polymer in the composition. The liquid crystalline compound having alkenyl is not classified as a polymerizable compound in this sense.

The liquid crystal composition is prepared by mixing a plurality of liquid crystal compounds. Additives, such as an optically active compound and a polymeric compound, are added to this liquid crystal composition as needed. The ratio of a liquid crystalline compound is represented by the mass percentage (mass%) based on the mass of the liquid crystal composition which does not contain an additive, even when an additive is added. The ratio of an additive is represented by the mass percentage (mass%) based on the mass of the liquid crystal composition which does not contain an additive. That is, the ratio of a liquid crystalline compound and an additive is computed based on the total mass of a liquid crystalline compound. The proportion of the polymerization initiator and the polymerization inhibitor is exceptionally expressed based on the mass of the polymerizable compound.

"Upper limit temperature of a nematic phase" may be abbreviated as "upper limit temperature". The "lower limit temperature of a nematic phase" may be abbreviated as "lower limit temperature". The expression "increasing dielectric anisotropy" means that the value increases positive when the composition has a positive dielectric anisotropy, and that the value increases negative when the composition has a negative dielectric anisotropy. "Large voltage retention" means that the device has a large voltage retention not only at room temperature but also near the upper limit temperature in the initial stage, and has a large voltage retention not only at room temperature but also close to the upper limit temperature after long time use. it means. The characteristic of a composition and an element may be examined by the time-dependent change test.

The compound (1z) described above will be described as an example. In Formula (1z), the symbol of (alpha) and (beta) enclosed by a hexagon corresponds to the ring (alpha) and the ring (beta), respectively, and shows the same ring as a six-membered ring and a condensed ring. When the subscript 'x' is 2, there are two rings α. Two groups represented by two rings α may be the same or different. This rule is applied to any two rings α when the subscript 'x' is greater than two. This rule also applies to other symbols, such as the combiner Z. The diagonal line across one side of the ring β indicates that any hydrogen on the ring β may be substituted with a substituent (-Sp-P). The subscript 'y' indicates the number of substituted substituents. When the subscript 'y' is zero, there is no such substitution. When the subscript 'y' is 2 or more, a plurality of substituents (-Sp-P) are present on the ring β. Also in this case, the rules "may be the same or may be different" apply. And this rule is applied also when the symbol of Ra is used for a some compound.

In the formula (1z), for example, the expression "Ra and Rb are alkyl, alkoxy, or alkenyl" indicates that Ra and Rb are independently selected from the group of alkyl, alkoxy, and alkenyl. it means. That is, the group represented by Ra and the group represented by Rb may be the same or different.

At least one compound selected from the compound represented by formula (1z) may be abbreviated as "compound (1z)". "Compound (1z)" means one compound represented by Formula (1z), a mixture of two compounds, or a mixture of three or more compounds. The same applies to the compound represented by another formula. The expression "at least one compound selected from the compound represented by formula (1z) and formula (2z)" means at least one compound selected from the group of compound (1z) and compound (2z).

The expression of "at least one" A "means that the number of" A "is arbitrary. The expression "at least one 'A' may be substituted with 'B'" indicates that when the number of 'A' is 1, the position of 'A' is arbitrary, and when the number of 'A' is two or more, These positions can be selected without limitation. The expression "at least one -CH ₂ -may be substituted with -O-" may be used. In this case, -CH ₂ -CH ₂ -CH ₂ -may be converted to -O-CH ₂ -O- by replacing non-adjacent -CH ₂ -with -O-. However, adjacent -CH ₂ -is not substituted with -O-. This is because -OO-CH _2- (peroxide) is produced by this substitution.

For example, in Ra and Rb of formula (1z), alkyl is linear or branched, and does not contain cyclic alkyl. Linear alkyl is more preferable than branched alkyl. The same applies to terminal groups such as alkoxy and alkenyl.

As for the three-dimensional arrangement regarding 1, 4- cyclohexylene, trans is more preferable than cis in order to raise an upper limit temperature. Since 2-fluoro-1,4-phenylene is asymmetrical left and right, there are leftward (L) and rightward (R).

The same applies to divalent groups such as tetrahydropyran-2,5-diyl. The same is true for a bonding group (-COO- or -OCO-) such as carbonyloxy.

The present invention is as follows.

Item 1. At least one compound selected from the compound represented by the formula (1) as the first component, and at least one compound selected from the compound represented by the formula (2) as the second component, and negative (-) A liquid crystal composition having a dielectric anisotropy of.

In formula (1) and formula (2), R <^1> and R <^2> is C1-C12 alkyl or C2-C12 alkenyl; R ³ is alkenyl having 2 to 12 carbon atoms or alkenyloxy having 2 to 12 carbon atoms; R ⁴ is hydrogen, alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, alkenyl having 2 to 12 carbons, or alkenyloxy having 2 to 12 carbons; Ring A and Ring C are 1,4-cyclohexylene, 1,4-cyclohexenylene, tetrahydropyran-2,5-diyl, 1,4-phenylene, at least one hydrogen is fluorine or chlorine Substituted 1,4-phenylene, naphthalene-2,6-diyl, naphthalene-2,6-diyl, chroman-2,6-diyl, or at least one hydrogen at least one of which is substituted with fluorine or chlorine Is chroman-2,6-diyl substituted with fluorine or chlorine; Ring B is 2,3-difluoro-1,4-phenylene, 2-chloro-3-fluoro-1,4-phenylene, 2,3-difluoro-5-methyl-1,4 -Phenylene, 3,4,5-trifluoronaphthalene-2,6-diyl, 7,8-difluorochroman-2,6-diyl, 3,4,5,6-tetrafluorofluorene -2,7-diyl, 4,6-difluorodibenzofuran-3,7-diyl, 4,6-difluorodibenzothiophen-3,7-diyl, or 1,1,6,7-tetra Fluoroindan-2,5-diyl; Z ¹ to Z ⁴ are a single bond, ethylene, vinylene, carbonyloxy, or methyleneoxy; a is 0, 1, 2, or 3, b is 0 or 1, and the sum of a and b is 3 or less. Provided that when a is 1 and b is 1, when ring A is 1,4-cyclohexylene, ring C is not 1,4-phenylene or ring C is 1,4-cyclohexylene In this case, ring A is not 1,4-phenylene.

Item 2. The liquid crystal composition according to item 1, containing at least one compound selected from compounds represented by formulas (1-1) to (1-12) as the first component.

Item 3. The liquid crystal composition according to item 1 or 2, which contains at least one compound selected from compounds represented by formulas (2-1) to (2-35) as a second component.

In formulas (2-1) to (2-35), R ³ is alkenyl having 2 to 12 carbon atoms or alkenyloxy having 2 to 12 carbon atoms; R ⁴ is hydrogen, alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, alkenyl having 2 to 12 carbons, or alkenyloxy having 2 to 12 carbons.

Item 4. The liquid crystal composition according to any one of Items 1 to 3, wherein the ratio of the first component is in the range of 5% by mass to 40% by mass, and the ratio of the second component is in the range of 5% by mass to 80% by mass.

Item 5. The liquid crystal composition according to any one of Items 1 to 4, containing at least one compound selected from compounds represented by formula (3) as a third component.

In formula (3), R <^5> and R <^6> is C1-C12 alkyl, C1-C12 alkoxy, C2-C12 alkenyl, or C2 in which at least 1 hydrogen was substituted by fluorine or chlorine. Alkenyl of -12; Ring D and ring E are 1,4-cyclohexylene, 1,4-phenylene, 2-fluoro-1,4-phenylene, or 2,5-difluoro-1,4-phenylene ; Z ⁵ is a single bond, ethylene, vinylene, methyleneoxy, or carbonyloxy; c is 1, 2, or 3.

Item 6. The liquid crystal composition according to any one of Items 1 to 5, containing at least one compound selected from compounds represented by Formulas (3-1) to (3-13) as a third component.

In formulas (3-1) to (3-13), R ⁵ and R ⁶ are alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, alkenyl having 2 to 12 carbons, or at least one hydrogen. Is alkenyl having 2 to 12 carbon atoms substituted with fluorine or chlorine.

Item 7. The liquid crystal composition according to item 5 or 6, wherein the proportion of the third component is in the range of 5% by mass to 80% by mass.

Item 8. The liquid crystal composition according to any one of Items 1 to 7, which contains at least one compound selected from compounds represented by formula (4) as a fourth component.

In formula (4), R <^7> and R <^8> is hydrogen, C1-C12 alkyl, or C1-C12 alkoxy; Ring F and ring I are 1,4-cyclohexylene, 1,4-cyclohexenylene, tetrahydropyran-2,5-diyl, 1,4-phenylene, at least one hydrogen is fluorine or chlorine Substituted 1,4-phenylene, naphthalene-2,6-diyl, naphthalene-2,6-diyl, chroman-2,6-diyl, or at least one hydrogen at least one of which is substituted with fluorine or chlorine Is chroman-2,6-diyl substituted with fluorine or chlorine; Ring G is 2,3-difluoro-1,4-phenylene, 2-chloro-3-fluoro-1,4-phenylene, 2,3-difluoro-5-methyl-1,4 -Phenylene, 3,4,5-trifluoronaphthalene-2,6-diyl, 7,8-difluorochroman-2,6-diyl, 3,4,5,6-tetrafluorofluorene -2,7-diyl, 4,6-difluorodibenzofuran-3,7-diyl, 4,6-difluorodibenzothiophen-3,7-diyl, or 1,1,6,7-tetra Fluoroindan-2,5-diyl; Z ⁶ and Z ⁷ are a single bond, ethylene, vinylene, carbonyloxy, or methyleneoxy; d is 0, 1, 2, or 3, e is 0 or 1, and the sum of d and e is 3 or less. Provided that when d is 1 and e is 1, ring F is 1,4-cyclohexylene, ring I is not 1,4-phenylene or ring I is 1,4-cyclohexylene In this case, ring F is not 1,4-phenylene.

Item 9. The liquid crystal composition according to any one of items 1 to 8, containing at least one compound selected from compounds represented by formulas (4-1) to (4-35) as a fourth component.

In formulas (4-1) to (4-35), R ⁷ and R ⁸ are hydrogen, alkyl having 1 to 12 carbons or alkoxy having 1 to 12 carbons.

Item 10. The liquid crystal composition according to item 8 or 9, wherein the proportion of the fourth component is in the range of 5% by mass to 80% by mass.

Item 11. The liquid crystal composition according to any one of Items 1 to 10, containing at least one compound selected from the polymerizable compounds represented by the formula (5) as the first additive.

In formula (5), ring J and ring L are cyclohexyl, cyclohexenyl, phenyl, 1-naphthyl, 2-naphthyl, tetrahydropyran-2-yl, 1,3-dioxane-2- 1, pyrimidin-2-yl, or pyridin-2-yl, and in these rings, at least one hydrogen is fluorine, chlorine, alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, or at least one Hydrogen may be substituted with alkyl having 1 to 12 carbons substituted with fluorine or chlorine; Ring K is 1,4-cyclohexylene, 1,4-cyclohexenylene, 1,4-phenylene, naphthalene-1,2-diyl, naphthalene-1,3-diyl, naphthalene-1,4- Diyl, naphthalene-1,5-diyl, naphthalene-1,6-diyl, naphthalene-1,7-diyl, naphthalene-1,8-diyl, naphthalene-2,3-diyl, naphthalene-2,6-diyl, Naphthalene-2,7-diyl, tetrahydropyran-2,5-diyl, 1,3-dioxane-2,5-diyl, pyrimidine-2,5-diyl, or pyridine-2,5-diyl, In these rings, at least one hydrogen is substituted with fluorine, chlorine, alkyl having 1 to 12 carbon atoms, alkoxy having 1 to 12 carbon atoms, or alkyl having 1 to 12 carbon atoms in which at least one hydrogen is replaced with fluorine or chlorine. May; Z ⁸ and Z ⁹ are a single bond or alkylene having 1 to 10 carbon atoms, and in this alkylene, at least one -CH ₂ -is -O-, -CO-, -COO-, or -OCO- And at least one -CH ₂ -CH ₂ -is -CH = CH-, -C (CH ₃ ) = CH-, -CH = C (CH ₃ )-, or -C (CH _3). ) = C (CH ₃ )-, and in these groups, at least one hydrogen may be substituted with fluorine or chlorine; P ¹ , P ² , and P ³ are polymerizable groups; Sp ¹ , Sp ² , and Sp ³ are single bonds or alkylene having 1 to 10 carbon atoms, and in this alkylene, at least one -CH ₂ -is -O-, -COO-, -OCO-, Or -OCOO- and at least one -CH ₂ -CH ₂ -may be substituted with -CH = CH- or -C≡C-, and in these groups, at least one hydrogen is fluorine Or chlorine; f is 0, 1, or 2; g, h, and j are 0, 1, 2, 3, or 4; And the sum of g, h and j is 1 or more.

Item 12. The liquid crystal composition according to item 11, wherein P ¹ , P ² , and P ³ are selected from polymerizable groups represented by formulas (P-1) to (P-5).

In formulas (P-1) to (P-5), M ¹ , M ² , and M ³ are hydrogen, fluorine, alkyl having 1 to 5 carbons, or at least one hydrogen substituted with fluorine or chlorine. Alkyl having 1 to 5 carbon atoms.

Item 13. The liquid crystal composition according to any one of items 1 to 12, containing at least one compound selected from polymerizable compounds represented by formulas (5-1) to (5-29) as the first additive.

In Formulas (5-1) to (5-29), P ⁴ , P ⁵ , and P ⁶ are groups selected from polymerizable groups represented by Formulas (P-1) to (P-3), M ¹ , M ² , and M ³ are hydrogen, fluorine, alkyl having 1 to 5 carbons, or alkyl having 1 to 5 carbons in which at least one hydrogen is replaced with fluorine or chlorine;

Sp ¹ , Sp ² , and Sp ³ are single bonds or alkylene having 1 to 10 carbon atoms, and in this alkylene, at least one -CH ₂ -is -O-, -COO-, -OCO-, Or -OCOO- and at least one -CH ₂ -CH ₂ -may be substituted with -CH = CH- or -C≡C-, and in these groups, at least one hydrogen is fluorine Or chlorine.

Item 14. The liquid crystal composition according to any one of Items 11 to 13, wherein a ratio of the first additive is in a range of 0.03% by mass to 10% by mass.

Item 15. A liquid crystal display device containing the liquid crystal composition according to any one of items 1 to 14.

Item 16. The liquid crystal display element according to item 15, wherein the operation mode of the liquid crystal display element is an IPS mode, a VA mode, an FFS mode, or an FPA mode, and the drive method of the liquid crystal display element is an active matrix system.

Item 17. The polymer-supported alignment type liquid crystal display device containing the liquid crystal composition according to any one of items 11 to 14, wherein the polymerizable compound in the liquid crystal composition is polymerized.

Item 18. Use of liquid crystal composition according to any one of items 1 to 14 in a liquid crystal display device.

Item 19. Use of a liquid crystal composition according to any one of items 11 to 14 in a polymer-supported alignment type liquid crystal display device.

The present invention also includes the following terms.

(a) one compound, two compounds, or three selected from additives such as optically active compounds, antioxidants, ultraviolet absorbers, quenchers, pigments, antifoams, polymerizable compounds, polymerization initiators, polymerization inhibitors The above-mentioned composition containing the above compound.

(b) AM element containing said composition.

(c) Said composition which further contains a polymeric compound, and polymeric support orientation (PSA) type AM element containing this composition.

(d) A polymer-supported orientation (PSA) type AM device containing the composition described above, wherein the polymerizable compound in the composition is polymerized.

(e) A device containing the composition described above and having a mode of PC, TN, STN, ECB, OCB, IPS, VA, FFS, or FPA.

(f) A transmissive element containing the composition described above.

(g) Use of said composition as a composition which has a nematic phase.

(h) Use of an optically active composition obtained by adding an optically active compound to the above-mentioned composition.

The composition of this invention is demonstrated in the following order.

First, the composition of the composition will be described. Second, the main properties of the component compounds and the main effects of these compounds on the composition or the device are described. Third, the combination, preferred ratios, and basis thereof of the component compounds in the composition will be described. Fourth, a preferred form of the component compound will be described. Fifth, preferred component compounds are shown. Sixth, the additive which may be added to a composition is demonstrated. Seventh, the synthesis method of the component compounds will be described. Finally, the use of the composition is described.

First, the composition of the composition will be described. This composition contains several liquid crystalline compounds. This composition may contain an additive. The additives are optically active compounds, antioxidants, ultraviolet absorbers, quenchers, pigments, antifoaming agents, polymerizable compounds, polymerization initiators, polymerization inhibitors, polar compounds and the like. This composition is classified into composition A and composition B from a viewpoint of a liquid crystalline compound. Composition A may further contain other liquid crystalline compounds, additives, etc. in addition to the liquid crystalline compounds selected from compound (1), compound (2), compound (3), and compound (4). "Other liquid crystal compounds" are liquid crystal compounds different from compound (1), compound (2), compound (3), and compound (4). Such a compound is mixed with a composition for the purpose of further adjusting a characteristic.

Composition B consists essentially of liquid crystal compounds selected from compound (1), compound (2), compound (3) and compound (4). "Substantially" means that although composition B may contain an additive, it does not contain another liquid crystalline compound. Composition B has fewer components than composition A. From the viewpoint of lowering the cost, the composition B is preferable to the composition A. The composition A is more preferable than the composition B from a viewpoint which can further adjust a characteristic by mixing another liquid crystalline compound.

Second, the main properties of the component compounds and the main effects of these compounds on the composition or the device are described. The main characteristics of the component compounds are summarized in Table 2 based on the effects of the present invention. In the symbol of Table 2, L means big or high, M means medium, and S means small or low. The symbols L, M, and S are classifications based on a qualitative comparison between the component compounds, and 0 (zero) means smaller than S.

[Table 2] Characteristics of Liquid Crystal Compound

The main effects of the component compounds are as follows. Compound (1) increases the dielectric anisotropy, increases the optical anisotropy, and lowers the viscosity. Compound (2) increases the dielectric anisotropy. Compound (3) lowers a viscosity or raises an upper limit temperature. Compound (4) increases the dielectric anisotropy and lowers the lower limit temperature. Since compound (5) is polymerizable, a polymer is provided by polymerization. Since this polymer stabilizes the orientation of liquid crystal molecules, the response time of an element is shortened and the baking of an image is improved.

Third, the combination, preferred ratios, and basis thereof of the component compounds in the composition will be described. Preferred combinations of the component compounds in the composition include compound (1) + compound (2), compound (1) + compound (2) + compound (3), compound (1) + compound (2) + compound (4), Compound (1) + Compound (2) + Compound (5), Compound (1) + Compound (2) + Compound (3) + Compound (4), Compound (1) + Compound (2) + Compound (3) + Compound (5), Compound (1) + Compound (2) + Compound (4) + Compound (5), or Compound (1) + Compound (2) + Compound (3) + Compound (4) + Compound (5) to be. A more preferable combination is compound (1) + compound (2) + compound (3) or compound (1) + compound (2) + compound (3) + compound (4).

The preferable ratio of compound (1) is about 5 mass% or more in order to lower a viscosity, increasing dielectric constant anisotropy, and about 40 mass% or less in order to reduce a minimum temperature. A more preferable ratio is the range of about 10 mass%-about 35 mass%. An especially preferable ratio is the range of about 10 mass%-about 30 mass%.

The preferable ratio of compound (2) is about 5 mass% or more in order to improve dielectric constant anisotropy, and is about 80 mass% or less in order to lower | hang minimum temperature. A more preferable ratio is the range of about 10 mass%-about 75 mass%. An especially preferable ratio is the range of about 20 mass%-about 70 mass%.

A preferred ratio of the compound (3) is about 5% by mass or more for increasing the maximum temperature or decreasing the viscosity, and about 80% by mass or less for increasing the dielectric anisotropy. A more preferable ratio is the range of about 15 mass%-about 75 mass%. An especially preferable ratio is the range of about 30 mass%-about 70 mass%.

The preferred ratio of the compound (4) is about 5% by mass or more for increasing the dielectric anisotropy, and about 80% by mass or less for decreasing the viscosity. A more preferable ratio is the range of about 10 mass%-about 75 mass%. An especially preferable ratio is the range of about 20 mass%-about 70 mass%.

Compound (5) is added to a composition for the purpose of making it suitable for a polymer support orientation element. The preferable ratio of compound (5) is about 0.03 mass% or more in order to orientate a liquid crystal molecule, and is about 10 mass% or less in order to prevent the display fault of an element. A more preferable ratio is the range of about 0.1 mass%-about 2 mass%. An especially preferable ratio is the range of about 0.2 mass%-about 1.0 mass%.

Fourth, a preferred form of the component compound will be described. In formula (1), formula (2), formula (3), and formula (4), R <^1> and R <^2> is C1-C12 alkyl or C2-C12 alkenyl. Preferable R <^1> or R <^2> is C1-C12 alkyl in order to improve stability. R <^3> is C2-C12 alkenyl or C2-C12 alkenyloxy. R ⁴ is hydrogen, alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, alkenyl having 2 to 12 carbons, or alkenyloxy having 2 to 12 carbons. Preferred R ⁴ is alkyl having 1 to 12 carbons for increasing stability, and alkoxy having 1 to 12 carbons for increasing dielectric anisotropy. R <^5> and R <^6> is C1-C12 alkyl, C1-C12 alkoxy, C2-C12 alkenyl, or C2-C12 alkenyl in which at least 1 hydrogen was substituted by fluorine or chlorine. Preferable R <^5> or R <^6> is C2-C12 alkenyl in order to lower | hang a viscosity, and in order to improve stability, it is C1-C12 alkyl. R <^7> and R <^8> is hydrogen, C1-C12 alkyl, or C1-C12 alkoxy.

Preferred alkyl is methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl or octyl. More preferred alkyl is methyl, ethyl, propyl, butyl, or pentyl to lower the viscosity.

Preferred alkoxy is methoxy, ethoxy, propoxy, butoxy, pentyloxy, hexyloxy or heptyloxy. In order to lower a viscosity, more preferable alkoxy is methoxy or ethoxy.

Preferred alkenyls are vinyl, 1-propenyl, 2-propenyl, 1-butenyl, 2-butenyl, 3-butenyl, 1-pentenyl, 2-pentenyl, 3-pentenyl, 4-phene Tenyl, 1-hexenyl, 2-hexenyl, 3-hexenyl, 4-hexenyl, or 5-hexenyl. More preferred alkenyl is vinyl, 1-propenyl, 3-butenyl, or 3-pentenyl to lower the viscosity. Preferred steric configuration of -CH = CH- in this alkenyl depends on the position of the double bond. For alkenyl such as 1-propenyl, 1-butenyl, 1-pentenyl, 1-hexenyl, 3-pentenyl, and 3-hexenyl, for the purpose of lowering the viscosity, trans is preferable. For alkenyl such as 2-butenyl, 2-pentenyl, 2-hexenyl, cis is preferred.

Preferred alkenyloxy is vinyloxy, allyloxy, 3-butenyloxy, 3-pentenyloxy, or 4-pentenyloxy. In order to lower | hang a viscosity, more preferable alkenyloxy is allyloxy or 3-butenyloxy.

Preferred examples of alkyl in which at least one hydrogen is substituted with fluorine or chlorine are fluoromethyl, 2-fluoroethyl, 3-fluoropropyl, 4-fluorobutyl, 5-fluoropentyl, 6-fluorohexyl , 7-fluoroheptyl, or 8-fluorooctyl. More preferred examples are 2-fluoroethyl, 3-fluoropropyl, 4-fluorobutyl, or 5-fluoropentyl for increasing the dielectric anisotropy.

Preferred examples of alkenyl in which at least one hydrogen is substituted with fluorine or chlorine are 2,2-difluorovinyl, 3,3-difluoro-2-propenyl, 4,4-difluoro-3- Butenyl, 5,5-difluoro-4-pentenyl, or 6,6-difluoro-5-hexenyl. More preferred examples are 2,2-difluorovinyl or 4,4-difluoro-3-butenyl in order to lower the viscosity.

Ring A, Ring C, Ring F, and Ring I are 1,4-cyclohexylene, 1,4-cyclohexenylene, tetrahydropyran-2,5-diyl, 1,4-phenylene, at least 1 1,4-phenylene, naphthalene-2,6-diyl in which two hydrogens are replaced with fluorine or chlorine, naphthalene-2,6-diyl, chroman-2,6- in which at least one hydrogen is replaced by fluorine or chlorine Diyl or chromman-2,6-diyl in which at least one hydrogen is replaced with fluorine or chlorine. Preferable examples of “1,4-phenylene in which at least one hydrogen is substituted with fluorine or chlorine” include 2-fluoro-1,4-phenylene and 2,3-difluoro-1,4-phenylene. Or 2-chloro-3-fluoro-1,4-phenylene. Preferred ring A, ring C, ring F, or ring I is 1,4-cyclohexylene for decreasing the viscosity, tetrahydropyran-2,5-diyl for increasing the dielectric anisotropy, and 1 for increasing the optical anisotropy. , 4-phenylene. Tetrahydropyran-2,5-diyl is,

or

, Preferably

to be.

Ring B and Ring G are 2,3-difluoro-1,4-phenylene, 2-chloro-3-fluoro-1,4-phenylene, 2,3-difluoro-5-methyl- 1,4-phenylene, 3,4,5-trifluoronaphthalene-2,6-diyl, 7,8-difluorochroman-2,6-diyl, 3,4,5,6-tetrafluoro Rofluorene-2,7-diyl (FLF4), 4,6-difluorodibenzofuran-3,7-diyl (DBFF2), 4,6-difluorodibenzothiophen-3,7-diyl (DBTF2 ), Or 1,1,6,7-tetrafluoroindan-2,5-diyl (InF4).

Preferred ring B or ring G is 2,3-difluoro-1,4-phenylene for decreasing the viscosity, 2-chloro-3-fluoro-1,4-phenylene for decreasing the optical anisotropy, 7,8-difluorochroman-2,6-diyl to increase the dielectric anisotropy.

Ring D and Ring E are 1,4-cyclohexylene, 1,4-phenylene, 2-fluoro-1,4-phenylene, or 2,5-difluoro-1,4-phenylene . Preferred ring D or ring E is 1,4-cyclohexylene for decreasing the viscosity or for increasing the maximum temperature, and 1,4-phenylene for decreasing the minimum temperature.

Z ^{1 to} Z ⁴ are a single bond, ethylene, vinylene, carbonyloxy, or methyleneoxy. Preferred Z ^{1 to} Z ⁴ are single bonds for decreasing the viscosity, ethylene for decreasing the minimum temperature, and methyleneoxy for increasing the dielectric anisotropy. Z ⁵ is a single bond, ethylene, vinylene, methyleneoxy, or carbonyloxy. Preferred Z ⁵ is a single bond in order to lower the viscosity. Z ⁶ and Z ⁷ are a single bond, ethylene, vinylene, carbonyloxy, or methyleneoxy. Preferred Z ⁶ or Z ⁷ is a single bond for decreasing the viscosity, ethylene for decreasing the minimum temperature, and methyleneoxy for increasing the dielectric anisotropy.

Bivalent groups, such as methyleneoxy, are asymmetrical left and right. In methyleneoxy, -CH ₂ O- is more preferable than -OCH _2- . For carbonyloxy, -COO- is more preferred than -OCO-.

a is 0, 1, 2, or 3, b is 0 or 1, and the sum of a and b is 3 or less. Preferred a is 1 for decreasing the viscosity, and 2 or 3 for increasing the maximum temperature. Preferred b is 0 for decreasing the viscosity, and 1 for decreasing the minimum temperature. c is 1, 2, or 3. Preferred c is 1 for decreasing a viscosity, and 2 or 3 for increasing an upper limit temperature. d is 0, 1, 2, or 3, e is 0 or 1, and the sum of d and e is 3 or less. Preferred d is 1 for decreasing the viscosity, and 2 or 3 for increasing the maximum temperature. Preferred e is 0 for decreasing the viscosity, and 1 for decreasing the minimum temperature.

In the formula (2), when a is 1 and b is 1, when ring A is 1,4-cyclohexylene, ring C is not 1,4-phenylene or ring C is 1,4 In the case of -cyclohexylene, ring A is not 1,4-phenylene.

In Formula (4), when d is 1 and e is 1, when ring F is 1, 4- cyclohexylene, ring I is not 1, 4- phenylene, or ring I is 1,4 In the case of -cyclohexylene, ring F is not 1,4-phenylene.

In the formula ^{(5), P 1, P} 2, and P ³ is a polymerizable group. Preferred P ¹ , P ² , or P ³ is a group selected from polymerizable groups represented by formulas (P-1) to (P-5). More preferable P ¹ , P ² or P ³ is formula (P-1) or formula (P-2). A particularly preferred group (P-1) is a-CH = CH ₂ or -OCO _{-OCO-C (CH 3) =} CH 2. The broken line of Formula (P-1)-Formula (P-5) represents the site | part to couple.

In formulas (P-1) to (P-5), M ¹ , M ² , and M ³ are hydrogen, fluorine, alkyl having 1 to 5 carbons, or at least one hydrogen substituted with fluorine or chlorine. Alkyl having 1 to 5 carbon atoms. Preferred M ¹ , M ² , or M ³ is hydrogen or methyl in order to increase the reactivity. More preferred M ¹ is methyl and more preferred M ² or M ³ is hydrogen.

In Formulas (5-1) to (5-29), P ⁴ , P ⁵ , and P ⁶ are groups represented by Formulas (P-1) to (P-3). Preferred P ⁴ , P ⁵ , or P ⁶ is formula (P-1) or formula (P-2). Further preferred formula (P-1) is -OCO-CH = CH ₂ or -OCO-C (CH ₃ ) = CH ₂ . The broken line of Formula (P-1)-Formula (P-3) represents the site | part to couple.

In the formula ^{(5), Sp 1, Sp} 2, Sp ^3, and is a single bond or an alkylene group of 1 to 10 carbon atoms, in the alkylene group, at least one -CH ₂ - is -O-, - COO—, —OCO—, or —OCOO— may be substituted, and at least one —CH ₂ —CH ₂ — may be substituted with —CH═CH— or —C≡C—, and in these groups, At least one hydrogen may be substituted with fluorine or chlorine. Preferred Sp ¹ , Sp ² , or Sp ³ is a single bond, -CH ₂ CH _2- , -CH ₂ O-, -OCH _2- , -COO-, -OCO-, -CO-CH = CH-, or -CH = CH-CO-. More preferable Sp ¹ , Sp ² or Sp ³ is a single bond.

Ring J and ring L are cyclohexyl, cyclohexenyl, phenyl, 1-naphthyl, 2-naphthyl, tetrahydropyran-2-yl, 1,3-dioxan-2-yl, pyrimidin-2- Mono or pyridin-2-yl, and in these rings, at least one hydrogen is fluorine, chlorine, alkyl having 1 to 12 carbon atoms, alkoxy having 1 to 12 carbon atoms, or at least one hydrogen is replaced with fluorine or chlorine. Or an alkyl having 1 to 12 carbon atoms. Preferred ring J or ring L is phenyl. Ring K is 1,4-cyclohexylene, 1,4-cyclohexenylene, 1,4-phenylene, naphthalene-1,2-diyl, naphthalene-1,3-diyl, naphthalene-1,4- Diyl, naphthalene-1,5-diyl, naphthalene-1,6-diyl, naphthalene-1,7-diyl, naphthalene-1,8-diyl, naphthalene-2,3-diyl, naphthalene-2,6-diyl, Naphthalene-2,7-diyl, tetrahydropyran-2,5-diyl, 1,3-dioxane-2,5-diyl, pyrimidine-2,5-diyl, or pyridine-2,5-diyl, In these rings, at least one hydrogen is substituted with fluorine, chlorine, alkyl having 1 to 12 carbon atoms, alkoxy having 1 to 12 carbon atoms, or alkyl having 1 to 12 carbon atoms in which at least one hydrogen is replaced with fluorine or chlorine. It may be. Preferred ring K is 1,4-phenylene or 2-fluoro-1,4-phenylene.

Z ⁸ and Z ⁹ are a single bond or alkylene having 1 to 10 carbon atoms, and in this alkylene, at least one -CH ₂ -is -O-, -CO-, -COO-, or -OCO- And at least one -CH ₂ -CH ₂ -is -CH = CH-, -C (CH ₃ ) = CH-, -CH = C (CH ₃ )-, or -C (CH _3). ) = C (CH ₃ )-, and in these groups, at least one hydrogen may be substituted with fluorine or chlorine. Preferred Z ⁷ or Z ⁸ is a single bond, -CH ₂ CH _2- , -CH ₂ O-, -OCH _2- , -COO-, or -OCO-. More preferable Z ⁸ or Z ⁹ is a single bond.

f is 0, 1, or 2. Preferred f is 0 or 1. g, h, and j are 0, 1, 2, 3, or 4, and the sum of g, h, and j is 1 or more. Preferred g, h, or j is 1 or 2.

Fifth, preferred component compounds are shown. Preferred compound (1) is compound (1-1) to compound (1-12) described in item 2. In these compounds, compound (1-2), compound (1-4), compound (1-6), compound (1-8), compound (1-10), or compound (1-12) are preferable. .

Preferred compound (2) is compound (2-1) to compound (2-35) described in item 3. In these compounds, at least one of the second components is compound (2-1), compound (2-3), compound (2-6), compound (2-8), compound (2-10), compound ( 2-14) or compound (2-16). At least two of the second components include compound (2-1) and compound (2-8), compound (2-1) and compound (2-14), compound (2-3) and compound (2-8), Compound (2-3) and Compound (2-14), Compound (2-3) and Compound (2-16), Compound (2-6) and Compound (2-8), Compound (2-6) and Compound It is preferable that it is (2-10) or a combination of compound (2-6) and compound (2-14).

Preferred compound (3) is compound (3-1) to compound (3-13) described in item 6. In these compounds, at least 1 of a 3rd component is a compound (3-1), a compound (3-3), a compound (3-5), a compound (3-6), a compound (3-8), or a compound It is preferable that it is (3-9). At least two of the third components are compound (3-1) and compound (3-3), compound (3-1) and compound (3-5), or compound (3-1) and compound (3-6). It is preferable that it is a combination of.

Preferred compound (4) is compound (4-1) to compound (4-35) described in item 9. In these compounds, at least one of the fourth components is compound (4-1), compound (4-3), compound (4-6), compound (4-8), compound (4-10), compound ( 4-14) or compound (4-16). At least two of the fourth components include compound (4-1) and compound (4-8), compound (4-1) and compound (4-14), compound (4-3) and compound (4-8), Compound (4-3) and Compound (4-14), Compound (4-3) and Compound (4-16), Compound (4-6) and Compound (4-8), Compound (4-6) and Compound (4-10) or a combination of Compound (4-6) and Compound (4-14).

Preferred compound (5) is compound (5-1) to compound (5-29) described in item 13. In these compounds, at least 1 of an additive is compound (5-1), compound (5-2), compound (5-24), compound (5-25), compound (5-26), or compound (5). -27) is preferred. At least two of the additives are compound (5-1) and compound (5-2), compound (5-1) and compound (5-18), compound (5-2) and compound (5-24), compound ( 5-2) and compound (5-25), compound (5-2) and compound (5-26), compound (5-25) and compound (5-26), or compound (5-18) and compound ( Preferably a combination of 5-24).

Sixth, the additive which may be added to a composition is demonstrated. Such additives are optically active compounds, antioxidants, ultraviolet absorbers, quenchers, pigments, antifoams, polymerizable compounds, polymerization initiators, polymerization inhibitors, polar compounds and the like. An optically active compound is added to the composition for the purpose of inducing the helical structure of the liquid crystal molecules to impart a twist angle. Examples of such a compound include compound (6-1) to compound (6-5). The preferable ratio of an optically active compound is about 5 mass% or less. A more preferable ratio is the range of about 0.01 mass%-about 2 mass%.

Compounds (7-1) to (7-) in order to prevent a decrease in specific resistance due to heating in the atmosphere or to maintain a large voltage retention not only at room temperature but also at a temperature close to an upper limit temperature after using the device for a long time. You may add antioxidant like 3) to a composition further.

Since compound (7-2) has low volatility, it is effective for maintaining a large voltage retention not only at room temperature but also at a temperature close to an upper limit temperature after using the device for a long time. The preferable ratio of antioxidant is about 50 ppm or more in order to acquire the effect, and is about 600 ppm or less so that an upper limit temperature may not be lowered or a lower limit temperature may not be raised. A further preferred ratio is in the range of about 100 ppm to about 300 ppm.

Preferable examples of the ultraviolet absorber are benzophenone derivatives, benzoate derivatives, triazole derivatives and the like. Light stabilizers such as sterically hindered amines are also preferred. Preferred examples of the stabilizer include compound (8-1) to compound (8-16). The preferable ratio in these absorbents and stabilizers is about 50 ppm or more in order to acquire the effect, and is about 10000 ppm or less so that an upper limit temperature may not be lowered or a lower limit temperature may not be raised. A more preferred ratio is in the range of about 100 ppm to about 10000 ppm.

The quencher is a compound that prevents decomposition of the liquid crystal compound by receiving the light energy absorbed by the liquid crystal compound and converting it into thermal energy. Preferable examples of the matting agent are compounds (9-1) to (9-7) and the like. Preferable ratios in these quencher are about 50 ppm or more in order to acquire the effect, and are about 20000 ppm or less in order not to raise a minimum temperature. A more preferred ratio is in the range of about 100 ppm to about 10000 ppm.

In order to make it suitable for the device of a GH (guest host) mode, dichroic dye, such as an azo dye, an anthraquinone pigment, etc., is added to a composition. The preferable ratio of a pigment is the range of about 0.01 mass%-about 10 mass%. In order to prevent foaming, antifoaming agents such as dimethylsilicone oil and methylphenylsilicone oil are added to the composition. A preferred ratio of the antifoaming agent is about 1 ppm or more for obtaining the effect, and about 1000 ppm or less for preventing display defects. A further preferred ratio is in the range of about 1 ppm to about 500 ppm.

A polymeric compound can be used in order to be suitable for a polymer support orientation (PSA) type device. Compound (5) is suitable for this purpose. You may add a polymeric compound different from compound (5) to a composition with compound (5). Preferable examples of such a polymerizable compound are compounds such as acrylate, methacrylate, vinyl compound, vinyloxy compound, propenyl ether, epoxy compound (oxirane, oxetane), vinyl ketone and the like. More preferred examples are derivatives of acrylates or methacrylates. The preferable ratio of compound (5) is 10 mass% or more based on the total mass of a polymeric compound. A more preferable ratio is 50 mass% or more. An especially preferable ratio is 80 mass% or more. The most preferable ratio is 100 mass%.

Polymerizable compounds like compound (5) polymerize by ultraviolet irradiation. You may superpose | polymerize in presence of appropriate initiators, such as a photoinitiator. Suitable conditions for the polymerization, suitable types of initiators, and suitable amounts are known to those skilled in the art and are described in the literature. For example, the photoinitiator Irgacure651® (BASF), Irgacure184 (BASF), or Darocur1173® (BASF) are suitable for radical polymerization. The preferable ratio of a photoinitiator is the range of about 0.1 mass%-about 5 mass% based on the total mass of a polymeric compound. A more preferable ratio is the range of about 1 mass%-about 3 mass%.

When storing a polymeric compound like compound (5), you may add a polymerization inhibitor in order to prevent superposition | polymerization. The polymerizable compound is usually added to the composition without removing the polymerization inhibitor. Examples of the polymerization inhibitor are hydroquinone, hydroquinone derivatives such as methylhydroquinone, 4-tert-butylcatechol, 4-methoxyphenol, phenothiazine and the like.

Seventh, the synthesis method of the component compounds will be described. These compounds can be synthesized by a known method. Synthesis method is illustrated. Compound (1-6) is synthesize | combined by the method of Unexamined-Japanese-Patent No. 57-114532. Compound (2-1) is synthesize | combined by the method of Unexamined-Japanese-Patent No. 2000-53602. Compound (3-5) is synthesize | combined by the method of Unexamined-Japanese-Patent No. 57-165328. Compound (4-1) is synthesize | combined by the method of Unexamined-Japanese-Patent No. 2-503441. Compound (5-18) is synthesized by the method described in JP-A-7-101900. Antioxidants are commercially available. Compound (7-1) can be obtained from Aldrich (Sigma-Aldrich Corporation). Compound (7-2) and the like are synthesized by the method described in US Patent 3660505.

Compounds which do not describe the synthesis method are Organic Syntheses, John Wiley & Sons, Inc., Organic Reactions, John Wiley & Sons, Inc., Comprehensive Organic Synthesis ( Comprehensive Organic Synthesis, Pergamon Press), a new experimental chemical lecture (Maruzen), etc. can be synthesize | combined by the method as described in books. A composition is prepared by a well-known method from the compound obtained in this way. For example, the component compounds are mixed and dissolved in each other by heating.

Finally, the use of the composition is described. This composition mainly has the lower limit temperature of about -10 degrees C or less, the upper limit temperature of about 70 degreeC or more, and the optical anisotropy of the range of about 0.07 to about 0.20. You may prepare the composition which has the optical anisotropy of the range of about 0.08 to about 0.25 by controlling the ratio of a component compound, or mixing another liquid crystalline compound. By trial and error, you may prepare the composition which has the optical anisotropy of the range of about 0.10 to about 0.30. The element containing this composition has a large voltage retention. This composition is suitable for AM devices. This composition is particularly suitable for transmissive AM devices. This composition can be used as an optically active composition by using as a composition which has a nematic phase, and adding an optically active compound.

This composition can be used as an AM device. It can also be used as a PM element. This composition can be used for AM elements and PM elements having modes such as PC, TN, STN, ECB, OCB, IPS, FFS, VA, and FPA. Particular preference is given to use with AM devices having TN, OCB, IPS mode or FFS mode. In the AM element having the IPS mode or the FFS mode, when the voltage is not applied, the arrangement of the liquid crystal molecules may be parallel to the glass substrate or perpendicular to the glass substrate. These elements may be reflective, transmissive, or transflective. Use as a transmissive element is preferred. Use as an amorphous silicon-TFT device or a polycrystalline silicon-TFT device is also possible. The composition can also be used for NCAP (nematic curvilinear aligned phase) devices produced by microencapsulating the composition or PD (polymer dispersed) devices in which a three-dimensional mesh-like polymer is formed in the composition.

EXAMPLE

The present invention will be described in more detail by way of examples. The present invention is not limited by these examples. The present invention includes a mixture of the composition of Example 1 and the composition of Example 2. This invention also contains the mixture which mixed at least 2 of the composition of an Example. The synthesized compound was identified by methods such as NMR analysis. The characteristic of a compound, a composition, and an element was measured by the following method.

NMR analysis: In the measurement, DRX-500 manufactured by Bruker Biospin was used. ^In the measurement of ¹ H-NMR, the sample was dissolved in a deuterated solvent such as CDCl ₃ , and the measurement was carried out under conditions of 500 MHz and 16 times of integration times at room temperature. Tetramethylsilane was used as internal standard. ^{In 19} F-NMR measurement, CFCl ₃ was used as an internal standard, and the integration was performed 24 times. In the description of the nuclear magnetic resonance spectrum, s is a singlelet, d is a doublet, t is a triplet, q is a quartet, quin is a quintet, and sex is a sext (sextet), m means multiplet, br means broad.

Gas chromatographic analysis: The GC-14B type gas chromatograph manufactured by Shimadzu Corporation was used for the measurement. Carrier gas is helium (2 mL / min). The sample vaporization chamber was set to 280 degreeC, and the detector (FID) was set to 300 degreeC. At the time of separation of the component compounds, Capillary Column DB-1 manufactured by Agilent Technologies Inc. (30 m in length, 0.32 mm in inner diameter, 0.25 µm thick; dimethylpolysiloxane in fixed liquid phase; nonpolar) Was used. This column was hold | maintained at 200 degreeC for 2 minutes, and it heated up to 280 degreeC at the ratio of 5 degreeC / min. The sample was prepared in an acetone solution (0.1 mass%), and 1 microliter of this was injected into the sample vaporization chamber. The recorder is C-R5A Chromatopac manufactured by Shimadzu Corporation, or an equivalent thereof. The obtained gas chromatogram shows the retention time of the peak corresponding to a component compound, and the area of a peak.

Chloroform, hexane, etc. can also be used as a solvent for diluting a sample. In order to separate the component compounds, the following capillary columns may be used. HP-1 manufactured by Agilent Technologies Inc. (30 m long, 0.32 mm inner diameter, 0.25 µm thick), Rtx-1 manufactured by Restek Corporation (30 m long, 0.32 mm inner diameter, 0.25 µm thick), SGE International Pty. BP-1 (length 30m, inner diameter 0.32mm, film thickness 0.25㎛) manufactured by Ltd. The capillary column CBP1-M50-025 (length 50m, inner diameter 0.25mm, film thickness 0.25micrometer) manufactured by Shimadzu Corporation may be used for the purpose of preventing the superposition of a compound peak.

The ratio of the liquid crystalline compound contained in a composition can also be computed by the following method. The mixture of liquid crystalline compounds is analyzed by gas chromatography (FID). The area ratio of the peaks in the gas chromatogram corresponds to the proportion of the liquid crystalline compound. When the capillary column mentioned above is used, the correction coefficient of each liquid crystalline compound may be regarded as one. Therefore, the ratio (mass%) of a liquid crystalline compound can be calculated from the area ratio of the peak.

Measurement sample: When measuring the characteristic of a composition or an element, the composition was used as a sample as it was. When measuring the characteristic of a compound, the sample for a measurement was prepared by mixing this compound (15 mass%) with a mother liquid crystal (85 mass%). The characteristic value of the compound was computed by the extrapolation method from the value obtained by the measurement. (Extrapolation value) = {(measured value of sample) -0.85 × (measured value of mother liquid crystal)} / 0.15. When the smectic phase (or crystal) precipitates at 25 ° C in this ratio, the ratio of the compound and the mother liquid crystal is 10% by mass: 90% by mass, 5% by mass: 95% by mass, 1% by mass: 99% by mass. In order. By this extrapolation, the upper limit temperature, optical anisotropy, viscosity, and dielectric anisotropy of the compound were determined.

The following mother liquid crystal was used. The ratio of a component compound is shown by the mass%.

Measurement method: The measurement of the characteristic was performed by the following method. Most of these methods are methods described in the JEITA standard (JEITA / ED-2521B), which is deliberated by the Japan Electronics and Information Technology Industries Association (JITA), or a method thereof. The thin film transistor (TFT) was not attached to the TN element used for the measurement.

(1) Upper limit temperature (NI; degreeC) of a nematic phase: The sample was put into the hot plate of the melting-point measuring apparatus provided with the polarizing microscope, and it heated at the speed of 1 degree-C / min. The temperature when a part of the sample changed from the nematic phase to the isotropic liquid was measured. The upper limit temperature of a nematic phase may be abbreviated as "upper limit temperature."

(2) Lower limit temperature of nematic phase (T _C ; ° C): A sample having a nematic phase is placed in a glass bottle, and a freezer of 0 ° C, -10 ° C, -20 ° C, -30 ° C, and -40 ° C. After storing for 10 days, the liquid crystal phase was observed. For example, when the sample remained nematic at -20 ° C and changed to crystal or smectic at -30 ° _C , T _C was described as <-20 ° C. The lower limit temperature of a nematic phase may be abbreviated as "lower limit temperature."

(3) Viscosity (bulk viscosity; η; measured at 20 ° C .; mPa · s): An E-type rotational viscometer manufactured by Tokyo Instruments Co., Ltd. was used for the measurement.

(4) Viscosity (rotational viscosity; γ1; measurement at 25 ° C; mPa · s): In the measurement, a rotational viscosity measurement system LCM-2 type manufactured by Toyo Technica Corp. was used. The sample was inject | poured into the VA element whose spacing (cell gap) of two glass substrates is 10 micrometers. A rectangular wave (55 V, 1 ms) was applied to this element. The peak current and peak time of the transient current generated by this application were measured. Using these measured values and dielectric anisotropy, the value of rotational viscosity was obtained. The dielectric anisotropy was measured by the method described in the measurement (6).

(5) Optical anisotropy (refractive index anisotropy; Δn; measured at 25 ° C): The measurement was performed by using an Abbe refractometer having a polarizing plate attached to the eyepiece using light having a wavelength of 589 nm. After rubbing the surface of the main prism in one direction, the sample was dropped into the main prism. The refractive index (n) was measured when the direction of polarization was parallel to the direction of rubbing. The refractive index (n⊥) was measured when the direction of polarization was perpendicular to the direction of rubbing. The value of optical anisotropy was calculated from the formula of (DELTA) n = n |

(6) Dielectric constant anisotropy (Δε; measured at 25 ° C): The value of dielectric constant anisotropy was calculated from the formula of Δε = ε∥-ε⊥. Permittivity (ε∥ and ε⊥) was measured as follows.

1) Measurement of dielectric constant (ε): An ethanol (20 mL) solution of octadecyl triethoxysilane (0.16 mL) was applied to a glass substrate that was well cleaned. After rotating a glass substrate with a spinner, it heated at 150 degreeC for 1 hour. The sample was put into the VA element whose interval (cell gap) of two glass substrates is 4 micrometers, and it sealed with the adhesive agent which hardens with an ultraviolet-ray. A sine wave (0.5 V, 1 kHz) was applied to this element, and after 2 seconds, the dielectric constant (ε∥) in the long axis direction of the liquid crystal molecules was measured.

2) Measurement of dielectric constant (ε⊥): The polyimide solution was apply | coated to the glass substrate wash | cleaned favorably. After baking this glass substrate, the rubbing process was performed to the obtained orientation film. The sample was put in the TN element of 9 micrometers of gaps (cell gap) of two glass substrates, and twist angle of 80 degree | times. A sine wave (0.5 V, 1 kHz) was applied to this element, and after 2 seconds, the dielectric constant (ε⊥) in the minor axis direction of the liquid crystal molecules was measured.

(7) Threshold voltage (Vth; measured at 25 ° C; V): An LCD5100 type luminance meter manufactured by Otsuka Electronics Co., Ltd. was used for the measurement. The light source was a halogen lamp. Samples are placed in a VA device in a normally black mode in which the spacing (cell gap) of two glass substrates is 4 μm and the rubbing direction is antiparallel, and the sample is sealed using an adhesive that cures the device with ultraviolet rays. did. The voltage (60 Hz, square wave) applied to this element was increased in steps of 0.02V from 0V to 20V. At this time, light was irradiated to the device from the vertical direction, and the amount of light transmitted through the device was measured. When this light amount became maximum, the transmittance | permeability curve which created 100% of transmittance and 0% transmittance was created when this light amount was minimum. The threshold voltage is represented by the voltage when the transmittance reaches 10%.

(8) Voltage retention (VHR-1; measured at 25 ° C;%): The TN element used for the measurement had a polyimide alignment film, and the interval (cell gap) of two glass substrates was 5 µm. This element was sealed with the adhesive which hardens with ultraviolet-ray after putting a sample. The TN element was charged by applying a pulse voltage (60 microseconds at 5V). The voltage to decay was measured for 16.7 milliseconds by a high speed voltmeter, and the area A between the voltage curve and the horizontal axis in a unit period was obtained. Area B is the area when no attenuation. The voltage retention is expressed as a percentage of area A to area B.

(9) Voltage retention (VHR-2; measured at 80 ° C;%): The voltage retention was measured in the same procedure as described above except that it was measured at 80 ° C instead of 25 ° C. The obtained value is represented by VHR-2.

(10) Voltage retention (VHR-3; measured at 25 ° C;%): After irradiating ultraviolet rays, the voltage retention was measured, and stability to ultraviolet rays was evaluated. The TN element used for the measurement had a polyimide aligning film, and the cell gap was 5 micrometers. The sample was inject | poured into this element, and light was irradiated for 20 minutes. The light source was an ultrahigh pressure mercury lamp USH-500D (manufactured by Ushio Electric Co., Ltd.), and the distance between the element and the light source was 20 cm. In the measurement of VHR-3, the voltage decaying for 16.7 milliseconds was measured. Compositions with large VHR-3 have great stability against ultraviolet radiation. VHR-3 is preferably at least 90%, more preferably at least 95%.

(11) Voltage retention (VHR-4; measured at 25 ° C;%): After heating the TN element into which the sample was injected in a thermostat at 80 ° C for 500 hours, voltage retention was measured to evaluate the stability to heat. In the measurement of VHR-4, the voltage decaying for 16.7 milliseconds was measured. Compositions with large VHR-4 have great stability against heat.

(12) Response time (τ; measured at 25 ° C; ms): An LCD5100 luminance meter manufactured by Otsuka Electronics Co., Ltd. was used for the measurement. The light source was a halogen lamp. The low-pass filter was set at 5kHz. The sample was put into the VA element of the normally black mode whose spacing (cell gap) of two glass substrates is 4 micrometers, and a rubbing direction is anti-parallel. This element was sealed using the adhesive agent which hardens with an ultraviolet-ray. Rectangular waves (60 Hz, 10 V, 0.5 seconds) were applied to this device. At this time, light was irradiated to the device from the vertical direction, and the amount of light transmitted through the device was measured. The maximum amount of light was considered to be 100% transmittance, and the minimum amount of light was considered to be 0% transmittance. The response time is expressed as the time required to change from 90% of transmittance to 10% (fall time; milliseconds).

(13) Specific resistance (ρ; measured at 25 ° C; Ωcm): 1.0 mL of the sample was injected into a container equipped with an electrode. DC voltage (10V) was applied to this container, and DC current after 10 second was measured. The specific resistance was calculated from the following formula.

(Specific resistance) = {(voltage) x (capacitance of the vessel)} / {(direct current) x (dielectric constant of vacuum)}.

(14) Line Image Sticking Parameter (LISP;%): An afterimage was generated by applying electrical stress to the liquid crystal display element. The luminance of the area with residual afterimages and the luminance of the remaining areas were measured. The rate at which the luminance has decreased due to the afterimage is calculated, and the size of the afterimage is represented by this ratio.

14a) Measurement of luminance: An image of the device was imaged using an imaging color luminance meter (manufactured by Radiant Zemax, PM-1433F-0). The brightness of each area of the device was calculated by analyzing the image using software (Prometric 9.1, manufactured by Radiant Imaging). The light source used the LED backlight of 3500 cd / m <^2> of average brightness.

14b) Setting the stress voltage: The sample was placed in an FFS element (16 cells of 4 cells in length x 4 cells in width) having a cell gap of 3.5 占 퐉 and a matrix structure, and the device was sealed using an adhesive that cured with ultraviolet rays. . The polarizing plate was arrange | positioned in the upper surface and lower surface of this element so that a polarization axis might orthogonally cross. Light was irradiated to this element, and the voltage (rectangle wave, 60 Hz) was applied. The voltage was gradually increased every 0.1 V in the range of 0 V to 7.5 V, and the luminance of the transmitted light at each voltage was measured. The voltage at the maximum luminance was abbreviated as V255. When the luminance became 21.6% of V255 (that is, 127 gradations), the voltage was abbreviated as V127.

14c) Conditions of stress: V255 (rectangle wave, 30 Hz) and 0.5 V (rectangular wave, 30 Hz) were applied to the device at 60 ° C. and 23 hours, and a checker pattern was displayed. Next, V127 (rectangle wave, 0.25 Hz) was applied, and luminance was measured on the conditions of 4000 milliseconds of exposure time.

14d) Calculation of an afterimage: Of the 16 cells, four cells (two vertical cells × two horizontal cells) were calculated and used in the center. These four cells were divided into 25 areas (5 cells in height × 5 cells in width). The average luminance of four areas (two vertical cells × two horizontal cells) in four corners is abbreviated as luminance A. FIG. The area | region except the area | region of four corners from 25 area | regions is a cross type. In the four areas excluding the intersecting area in the center from the cross-shaped area, the minimum value of luminance was abbreviated as luminance B. An afterimage was computed from the following formula.

(Afterimage) = (luminance A-luminance B) / luminance A * 100.

(15) Spreadability: The spreadability of the additive was evaluated qualitatively by applying a voltage to the device and measuring the brightness. The luminance was measured in the same manner as in the above item 14a. The voltage V127 was set in the same manner as in the above item 14b. However, VA devices were used instead of FFS devices. Luminance was measured as follows. First, a DC voltage (2V) was applied to the device for 2 minutes. Next, V127 (square wave, 0.05 Hz) was applied, and luminance was measured on the conditions of 4000 milliseconds of exposure time. The spreadability was evaluated from this result.

Examples of the composition are shown below. A component compound is represented by a symbol based on the definition of following Table 3. In Table 3, the steric configuration regarding 1,4-cyclohexylene is trans. The number in parentheses after the symbol corresponds to the number of the compound. The sign of (-) means another liquid crystalline compound. The ratio (percentage) of the liquid crystal compound is a mass percentage (mass%) based on the mass of the liquid crystal composition. Finally, the characteristic values of the composition are shown collectively.

TABLE 3

Comparative Example 1

NI = 89.3 ° C .; Tc <0 ° C .; eta = 23.0 mPa · s; Δn = 0.110; Δε = -3.5; Vth = 2.14V; γ 1 = 138.9 mPa · s.

Example 1

NI = 85.9 ° C .; Tc <-20 ° C; eta = 18.1 mPa · s; Δn = 0.109; Δε = -3.6; Vth = 2.05V; γ 1 = 125 mPa · s.

Example 2

NI = 85.9 ° C .; Tc <-20 ° C; η = 16.4 mPa · s; Δn = 0.107; Δε = -3.5; Vth = 2.04V; γ 1 = 113.3 mPa · s.

Example 3

NI = 82.2 ° C .; Tc <-20 ° C; eta = 15.2 mPa · s; Δn = 0.107; Δε = -3.4; Vth = 2.03V; γ 1 = 105 mPa · s.

Example 4

NI = 83.1 ° C .; Tc <-20 ° C; η = 16.3 mPa · s; Δn = 0.11; Δε = -3.3; Vth = 2.02V; γ 1 = 112.6 mPa · s.

Example 5

NI = 81.1 ° C .; Tc <-20 ° C; η = 15.9 mPa · s; Δn = 0.109; Δε = -3.2; Vth = 2.01V; γ 1 = 109.8 mPa · s.

Example 6

NI = 83.3 ° C .; Tc <-20 ° C; eta = 12.6 mPa · s; Δn = 0.11; Δε = -3.1; Vth = 2.00V; γ 1 = 87 mPa · s.

Example 7

NI = 80.3 ° C .; Tc <-20 ° C; η = 11.1 mPa · s; Δn = 0.11; Δε = -3.2; Vth = 2.01V; γ1 = 76.7 mPas.

Example 8

NI = 83.7 ° C .; Tc <-20 ° C; eta = 13.7 mPa · s; Δn = 0.111; Δε = -3.1; Vth = 2.01V; γ 1 = 94.6 mPa · s.

Example 9

NI = 81.3 ° C .; Tc <-20 ° C; η = 11.7 mPa · s; Δn = 0.111; Δε = -3.0; Vth = 2.00V; γ 1 = 80.8 mPa · s.

Example 10

NI = 88.4 ° C .; Tc <-20 ° C; eta = 14.8 mPa · s; Δn = 0.109; Δε = -3.1; Vth = 2.01V; γ 1 = 102.2 mPa · s.

Example 11

NI = 83.4 ° C .; Tc <-20 ° C; η = 10.8 mPa · s; Δn = 0.109; Δε = -3.1; Vth = 2.00V; γ 1 = 74.6 mPa · s.

Example 12

NI = 81.9 ° C .; Tc <-20 ° C; eta = 14.5 mPa · s; Δn = 0.112; Δε = -3.5; Vth = 2.04V; γ 1 = 100.1 mPa · s.

Example 13

NI = 88.7 ° C .; Tc <-20 ° C; η = 16.7 mPa · s; Δn = 0.11; Δε = -3.5; Vth = 2.03V; γ 1 = 115.3 mPa · s.

Example 14

NI = 82.4 ° C .; Tc <-20 ° C; eta = 17.1 mPa · s; Δn = 0.109; Δε = -3.2; Vth = 2.02V; γ 1 = 118.1 mPa · s.

Example 15

NI = 86.8 ° C .; Tc <-20 ° C; η = 17.9 mPa · s; Δn = 0.109; Δε = -3.3; Vth = 2.02V; γ 1 = 123.6 mPa · s.

Example 16

NI = 82.3 ° C .; Tc <-20 ° C; η = 12.8 mPa · s; Δn = 0.109; Δε = -3.1; Vth = 2.01V; γ1 = 88.4 mPa · s.

The minimum temperature of the composition nematic phase of the comparative example 1 was 0 degreeC, and the viscosity was 23.0 mPa * s. On the other hand, the minimum temperature of the composition nematic phase of Example 1 was -20 degreeC, and the viscosity was 18.1 mPa * s. Thus, the composition of an Example has a low minimum temperature of a nematic phase compared with the composition of a comparative example, and has a small viscosity. Therefore, it can be concluded that the liquid crystal composition of the present invention has excellent characteristics.

The liquid crystal composition of this invention can be used for a liquid crystal monitor, a liquid crystal TV, etc.

Claims (19)

At least one compound selected from the compound represented by the following formula (1) as the first component, and at least one compound selected from the compound represented by the following formula (2) as the second component, and the negative (-) Liquid crystal composition having dielectric anisotropy:

In the formulas (1) and (2), R ¹ and R ² are alkyl having 1 to 12 carbons or alkenyl having 2 to 12 carbons; R ³ is alkenyl having 2 to 12 carbon atoms or alkenyloxy having 2 to 12 carbon atoms; R ⁴ is hydrogen, alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, alkenyl having 2 to 12 carbons or alkenyloxy having 2 to 12 carbons; Ring A and Ring C are 1,4-cyclohexylene, 1,4-cyclohexenylene, tetrahydropyran-2,5-diyl, 1,4-phenylene, at least one hydrogen is fluorine or chlorine Substituted 1,4-phenylene, naphthalene-2,6-diyl, naphthalene-2,6-diyl, chroman-2,6-diyl, or at least one hydrogen at least one of which is substituted with fluorine or chlorine Is chroman-2,6-diyl substituted with fluorine or chlorine; Ring B is 2,3-difluoro-1,4-phenylene, 2-chloro-3-fluoro-1,4-phenylene, 2,3-difluoro-5-methyl-1,4 -Phenylene, 3,4,5-trifluoronaphthalene-2,6-diyl, 7,8-difluorochroman-2,6-diyl, 3,4,5,6-tetrafluorofluorene -2,7-diyl, 4,6-difluorodibenzofuran-3,7-diyl, 4,6-difluorodibenzothiophen-3,7-diyl, or 1,1,6,7-tetra Fluoroindan-2,5-diyl; Z ^{1 to} Z ⁴ are a single bond, ethylene, vinylene, carbonyloxy or methyleneoxy; a is 0, 1, 2 or 3, b is 0 or 1, and the sum of a and b is 3 or less, provided that when a is 1 and b is 1, ring A is 1,4-cyclohex In the case of silane, ring C is not 1,4-phenylene, or in the case where ring C is 1,4-cyclohexylene, ring A is not 1,4-phenylene. The method of claim 1,
A liquid crystal composition containing at least one compound selected from the compounds represented by the following formulas (1-1) to (1-12) as the first component:

. The method according to claim 1 or 2,
A liquid crystal composition containing at least one compound selected from the compounds represented by the following formulas (2-1) to (2-35) as a second component:

In the formulas (2-1) to (2-35), R ³ is alkenyl having 2 to 12 carbon atoms or alkenyloxy having 2 to 12 carbon atoms; R ⁴ is hydrogen, alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, alkenyl having 2 to 12 carbons or alkenyloxy having 2 to 12 carbons. The method according to any one of claims 1 to 3,
The liquid crystal composition whose ratio of a 1st component is the range of 5 mass%-40 mass%, and the ratio of a 2nd component is a range of 5 mass%-80 mass%. The method according to any one of claims 1 to 4,
Liquid crystal composition containing at least 1 compound chosen from the compound represented by following formula (3) as a 3rd component:

In said Formula (3), R <^5> and R <^6> is C1-C12 alkyl, C1-C12 alkoxy, C2-C12 alkenyl, or carbon number in which at least 1 hydrogen was substituted by fluorine or chlorine. 2 to 12 alkenyl; Ring D and ring E are 1,4-cyclohexylene, 1,4-phenylene, 2-fluoro-1,4-phenylene or 2,5-difluoro-1,4-phenylene; Z ⁵ is a single bond, ethylene, vinylene, methyleneoxy or carbonyloxy; c is 1, 2 or 3. The method according to any one of claims 1 to 5,
Liquid crystal composition containing at least 1 compound chosen from the compound represented by following formula (3-1)-formula (3-13) as a 3rd component:

In said Formula (3-1)-Formula (3-13), R <^5> and R <^6> is C1-C12 alkyl, C1-C12 alkoxy, C2-C12 alkenyl, or at least 1 Hydrogen is alkenyl of 2 to 12 carbon atoms substituted with fluorine or chlorine; The method according to claim 5 or 6,
Liquid crystal composition whose ratio of a 3rd component is 5 mass%-80 mass%. The method according to any one of claims 1 to 7,
Liquid crystal composition containing at least 1 compound chosen from the compound represented by following formula (4) as a 4th component:

In the formula (4), R ⁷ and R ⁸ are hydrogen, alkyl having 1 to 12 carbons or alkoxy having 1 to 12 carbons; Ring F and ring I are 1,4-cyclohexylene, 1,4-cyclohexenylene, tetrahydropyran-2,5-diyl, 1,4-phenylene, at least one hydrogen is fluorine or chlorine Substituted 1,4-phenylene, naphthalene-2,6-diyl, naphthalene-2,6-diyl, chroman-2,6-diyl, or at least one hydrogen at least one of which is substituted with fluorine or chlorine Is chroman-2,6-diyl substituted with fluorine or chlorine; Ring G is 2,3-difluoro-1,4-phenylene, 2-chloro-3-fluoro-1,4-phenylene, 2,3-difluoro-5-methyl-1,4 -Phenylene, 3,4,5-trifluoronaphthalene-2,6-diyl, 7,8-difluorochroman-2,6-diyl, 3,4,5,6-tetrafluorofluorene -2,7-diyl, 4,6-difluorodibenzofuran-3,7-diyl, 4,6-difluorodibenzothiophen-3,7-diyl, or 1,1,6,7-tetra Fluoroindan-2,5-diyl; Z ⁶ and Z ⁷ are single bond, ethylene, vinylene, carbonyloxy or methyleneoxy; d is 0, 1, 2 or 3, e is 0 or 1, and the sum of d and e is 3 or less, provided that when d is 1 and e is 1, ring F is 1,4-cyclohex In the case of silane, ring I is not 1,4-phenylene, or in the case where ring I is 1,4-cyclohexylene, ring F is not 1,4-phenylene. The method according to any one of claims 1 to 8,
A liquid crystal composition containing at least one compound selected from the compounds represented by the following formulas (4-1) to (4-35) as the fourth component:

In the formulas (4-1) to (4-35), R ⁷ and R ⁸ are hydrogen, alkyl having 1 to 12 carbons or alkoxy having 1 to 12 carbons. The method according to claim 8 or 9,
Liquid crystal composition whose ratio of a 4th component is the range of 5 mass%-80 mass%. The method according to any one of claims 1 to 10,
Liquid crystal composition containing at least 1 compound chosen from the polymeric compound represented by following formula (5) as a 1st additive:

In the formula (5), ring J and ring L are cyclohexyl, cyclohexenyl, phenyl, 1-naphthyl, 2-naphthyl, tetrahydropyran-2-yl, 1,3-dioxane-2- 1, pyrimidin-2-yl or pyridin-2-yl, and in these rings, at least one hydrogen is fluorine, chlorine, alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, or at least one hydrogen. May be substituted with alkyl having 1 to 12 carbons substituted with fluorine or chlorine; Ring K is 1,4-cyclohexylene, 1,4-cyclohexenylene, 1,4-phenylene, naphthalene-1,2-diyl, naphthalene-1,3-diyl, naphthalene-1,4- Diyl, naphthalene-1,5-diyl, naphthalene-1,6-diyl, naphthalene-1,7-diyl, naphthalene-1,8-diyl, naphthalene-2,3-diyl, naphthalene-2,6-diyl, Naphthalene-2,7-diyl, tetrahydropyran-2,5-diyl, 1,3-dioxane-2,5-diyl, pyrimidine-2,5-diyl, or pyridine-2,5-diyl, In these rings, at least one hydrogen is substituted with fluorine, chlorine, alkyl having 1 to 12 carbon atoms, alkoxy having 1 to 12 carbon atoms, or alkyl having 1 to 12 carbon atoms in which at least one hydrogen is replaced with fluorine or chlorine. May; Z ⁸ and Z ⁹ are a single bond or alkylene having 1 to 10 carbon atoms, in which at least one -CH ₂ -is substituted with -O-, -CO-, -COO- or -OCO-. At least one -CH ₂ -CH ₂ -may be -CH = CH-, -C (CH ₃ ) = CH-, -CH = C (CH ₃ )-or -C (CH ₃ ) = C (CH ₃ )-, and in these groups, at least one hydrogen may be substituted with fluorine or chlorine; P ¹ , P ² and P ³ are polymerizable groups; Sp ¹ , Sp ² and Sp ³ are single bonds or alkylene having 1 to 10 carbon atoms, in which at least one -CH ₂ -is -O-, -COO-, -OCO- or -OCOO- Or at least one -CH ₂ -CH ₂ -may be substituted with -CH = CH- or -C≡C-, and in these groups, at least one hydrogen may be substituted with fluorine or chlorine. There is; f is 0, 1 or 2; g, h and j are 0, 1, 2, 3 or 4; And the sum of g, h and j is 1 or more. The method of claim 11,
In said Formula (5), P <^1> , P <^2> and P <^3> are group chosen from the polymeric group represented by following formula (P-1)-formula (P-5):

In the formulas (P-1) to (P-5), M ¹ , M ^2, and M ³ are hydrogen, fluorine, alkyl having 1 to 5 carbon atoms, or at least one hydrogen substituted with fluorine or chlorine. Alkyl having 1 to 5 carbon atoms. The method according to any one of claims 1 to 12,
Liquid crystal composition containing at least 1 compound chosen from the polymeric compound represented by following formula (5-1)-formula (5-29) as a 1st additive:

In the formulas (5-1) to (5-29), P ⁴ , P ⁵ and P ⁶ are groups selected from polymerizable groups represented by the following formulas (P-1) to (P-3), M ¹ , M ² and M ³ are hydrogen, fluorine, alkyl having 1 to 5 carbons, or alkyl having 1 to 5 carbons in which at least one hydrogen is replaced with fluorine or chlorine;

Sp ¹ , Sp ² and Sp ³ are single bonds or alkylene having 1 to 10 carbon atoms, in which at least one -CH ₂ -is -O-, -COO-, -OCO- or -OCOO- Or at least one -CH ₂ -CH ₂ -may be substituted with -CH = CH- or -C≡C-, and in these groups, at least one hydrogen may be substituted with fluorine or chlorine. has exist. The method according to any one of claims 11 to 13,
Liquid crystal composition whose ratio of a 1st additive is a range of 0.03 mass%-10 mass%. The liquid crystal display element containing the liquid crystal composition of any one of Claims 1-14. The method of claim 15,
The operation mode of a liquid crystal display element is IPS mode, VA mode, FFS mode, or FPA mode, The liquid crystal display element whose drive system of a liquid crystal display element is an active matrix system. The polymer support orientation liquid crystal display element which contains the liquid crystal composition of any one of Claims 11-14, and is polymerizing the polymerizable compound in this liquid crystal composition. Use of the liquid crystal composition according to any one of claims 1 to 14 in a liquid crystal display element. Use of the liquid crystal composition according to any one of claims 11 to 14 in a polymer-supported alignment type liquid crystal display device.