JP7348592B2 - Liquid crystal composition and liquid crystal display element - Google Patents

Description

The present invention relates to a liquid crystal composition, a liquid crystal display element containing this composition, and the like. In particular, the present invention relates to a liquid crystal composition having negative dielectric anisotropy, and a liquid crystal display element containing this 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 element.

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

A liquid crystal display element contains a liquid crystal composition having a nematic phase. This composition has suitable properties. By improving the properties of this composition, an AM element with good properties can be obtained. The relationships among these properties are summarized in Table 1 below. The properties of the composition will be further explained based on commercially available AM devices. The temperature range of the nematic phase is related to the usable temperature range of the device. The preferable upper limit temperature of the nematic phase is about 70°C or higher, and the preferable 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. A short response time is preferable for displaying moving images on the device. A shorter response time, even 1 millisecond, is desirable. Therefore, a low viscosity in the composition is preferred. Small viscosities at low temperatures are even more preferred. The elastic constant of the composition is related to the contrast of the device. In order to increase the contrast in the device, a large elastic constant in the composition is more preferred.

The optical anisotropy of a composition is related to the contrast ratio of the device. Depending on the mode of the device, large optical anisotropy or small optical anisotropy, ie, appropriate 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 ranges from about 0.30 μm to about 0.40 μm for devices in VA mode, and from about 0.20 μm to about 0.30 μm for devices in IPS or FFS mode. In these cases, compositions with large optical anisotropy are preferred for devices with small cell gaps. The large dielectric anisotropy in the composition contributes to low threshold voltage, low power consumption and high contrast ratio in the device. Therefore, a large dielectric constant anisotropy is preferred. A large resistivity in the composition contributes to a large voltage holding ratio and a large contrast ratio in the device. Therefore, compositions that have a large specific resistance in the initial stage are preferred. Compositions that have a high resistivity after long-term use are preferred. The stability of the composition against ultraviolet light and heat is related to the lifetime of the device. When this stability is high, the lifetime of the device is long. Such characteristics are preferable for AM elements used in liquid crystal monitors, liquid crystal televisions, and the like.

In general-purpose liquid crystal display elements, vertical alignment of liquid crystal molecules is achieved by a specific polyimide alignment film. In a polymer sustained alignment (PSA) type liquid crystal display element, a polymer is combined with an alignment film. First, a composition to which a small amount of a polymerizable compound is added is injected into the device. Next, the composition is irradiated with ultraviolet light while applying a voltage between the substrates of this device. The polymerizable compound polymerizes to form a polymer network in the composition. In this composition, the orientation of liquid crystal molecules can be controlled by the polymer, so the response time of the device is shortened and image sticking is improved. Such effects of the polymer can be expected in devices having modes such as TN, ECB, OCB, IPS, VA, FFS, and FPA.

A composition having positive dielectric constant anisotropy is used in an AM element having a TN mode. A composition having negative dielectric anisotropy is used in an AM element having VA mode. A composition having positive or negative dielectric constant anisotropy is used in an AM element having an IPS mode or an FFS mode. A composition having positive or negative dielectric constant anisotropy is used in a polymer-supported alignment type AM element. (Patent Documents 1 and 2)

International Publication No. 2012/086504 International Publication No. 2013/178333

The objects of the present invention are a high upper limit temperature of the nematic phase, a low lower limit temperature of the nematic phase, small viscosity, appropriate optical anisotropy, large negative dielectric anisotropy, large specific resistance, high stability against ultraviolet rays, It is an object of the present invention to provide a liquid crystal composition that satisfies at least one of the following properties, such as high stability against and a large elastic constant. Another challenge is to provide liquid crystal compositions that have an appropriate balance between at least two of these properties. Another object is to provide a liquid crystal display element containing such a composition. Another challenge is to provide AM devices with characteristics such as short response time, high voltage holding ratio, low threshold voltage, high contrast ratio, and long lifetime.

式（２）において、環Ａおよび環Ｃは、シクロヘキシル、シクロヘキセニル、フェニル、１－ナフチル、２－ナフチル、テトラヒドロピラン－２－イル、１，３－ジオキサン－２－イル、ピリミジン－２－イル、またはピリジン－２－イルであり、これらの環において、少なくとも１つの水素は、フッ素、塩素、炭素数１から１２のアルキル、炭素数１から１２のアルコキシ、または少なくとも１つの水素がフッ素または塩素で置き換えられた炭素数１から１２のアルキルで置き換えられてもよく；環Ｂは、１，４－シクロヘキシレン、１，４－シクロヘキセニレン、１，４－フェニレン、ナフタレン－１，２－ジイル、ナフタレン－１，３－ジイル、ナフタレン－１，４－ジイル、ナフタレン－１，５－ジイル、ナフタレン－１，６－ジイル、ナフタレン－１，７－ジイル、ナフタレン－１，８－ジイル、ナフタレン－２，３－ジイル、ナフタレン－２，６－ジイル、ナフタレン－２，７－ジイル、テトラヒドロピラン－２，５－ジイル、１，３－ジオキサン－２，５－ジイル、ピリミジン－２，５－ジイル、またはピリジン－２，５－ジイルであり、これらの環において、少なくとも１つの水素は、フッ素、塩素、炭素数１から１２のアルキル、炭素数１から１２のアルコキシ、または少なくとも１つの水素がフッ素または塩素で置き換えられた炭素数１から１２のアルキルで置き換えられてもよく；Ｚ^１およびＺ^２は、単結合または炭素数１から１０のアルキレンであり、このアルキレンにおいて、少なくとも１つの－ＣＨ_２－は、－Ｏ－、－ＣＯ－、－ＣＯＯ－、または－ＯＣＯ－で置き換えられてもよく、少なくとも１つの－ＣＨ_２－ＣＨ_２－は、－ＣＨ＝ＣＨ－、－Ｃ（ＣＨ_３）＝ＣＨ－、－ＣＨ＝Ｃ（ＣＨ_３）－、または－Ｃ（ＣＨ_３）＝Ｃ（ＣＨ_３）－で置き換えられてもよく、これらの基において、少なくとも１つの水素は、フッ素または塩素で置き換えられてもよく；Ｐ^１、Ｐ^２、およびＰ^３は重合性基であり；Ｓｐ^１、Ｓｐ^２、およびＳｐ^３は、単結合または炭素数１から１０のアルキレンであり、このアルキレンにおいて、少なくとも１つの－ＣＨ_２－は、－Ｏ－、－ＣＯＯ－、－ＯＣＯ－、または－ＯＣＯＯ－で置き換えられてもよく、少なくとも１つの－ＣＨ_２－ＣＨ_２－は、－ＣＨ＝ＣＨ－または－Ｃ≡Ｃ－で置き換えられてもよく、これらの基において、少なくとも１つの水素は、フッ素または塩素で置き換えられてもよく；ａは、０、１、または２であり；ｂ、ｃ、およびｄは、０、１、２、３、または４であり；そしてｂ、ｃ、およびｄの和は、１以上である。 The present invention contains at least one compound selected from a compound represented by formula (1) as a first component and a polymerizable compound represented by formula (2) as a first additive, and a nematic phase. and a liquid crystal composition having negative dielectric anisotropy, and a liquid crystal display element containing this composition.

In formula (2), ring A and ring C are cyclohexyl, cyclohexenyl, phenyl, 1-naphthyl, 2-naphthyl, tetrahydropyran-2-yl, 1,3-dioxan-2-yl, pyrimidin-2-yl , or pyridin-2-yl, in which 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 fluorine or chlorine. Ring B may be substituted with alkyl having 1 to 12 carbon atoms; Ring B 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 which at least one hydrogen is fluorine, chlorine, alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, or at least one hydrogen is It may be substituted with a C1-C12 alkyl substituted with fluorine or chlorine; Z ¹ and Z ² are a single bond or a C1-C10 alkylene, and in this alkylene, at least one -CH ₂ - may be replaced with -O-, -CO-, -COO-, or -OCO-, and at least one -CH ₂ -CH ₂ - may be replaced with -CH=CH-, -C(CH ₃ )=CH-, -CH=C(CH ₃ )-, or -C(CH ₃ )=C(CH ₃ )-, in which at least one hydrogen is 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 - may be replaced with -O-, -COO-, -OCO-, or -OCOO-, and at least one -CH ₂ -CH ₂ - may be replaced with -CH=CH- or -C≡C-, in which at least one hydrogen may be replaced by fluorine or chlorine; a is 0, 1, or 2; b, c, and d is 0, 1, 2, 3, or 4; and the sum of b, c, and d is 1 or more.

The advantages of the present invention are a high upper limit temperature of the nematic phase, a lower lower limit temperature of the nematic phase, a small viscosity, an appropriate optical anisotropy, a large negative dielectric anisotropy, a large specific resistance, a high stability against light, and a It is an object of the present invention to provide a liquid crystal composition that satisfies at least one of the following properties, such as high stability against and a large elastic constant. Another advantage is to provide liquid crystal compositions that have a suitable balance between at least two of these properties. Another advantage is to provide liquid crystal display elements containing such compositions. Another advantage is to provide an AM device with characteristics such as short response time, large voltage holding ratio, low threshold voltage, large contrast ratio, and long lifetime.

The terms used in this 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 general term for liquid crystal display panels and liquid crystal display modules. "Liquid crystal compound" refers to a compound that has a liquid crystal phase such as a nematic phase or a smectic phase, and a compound that does not have a liquid crystal phase but is used for the purpose of adjusting the properties of the nematic phase such as temperature range, viscosity, and dielectric anisotropy. A general term for compounds mixed into a composition. This compound has a six-membered ring such as 1,4-cyclohexylene or 1,4-phenylene, and its molecules (liquid crystal molecules) are rod-like. A "polymerizable compound" is a compound added for the purpose of producing a polymer in a composition. Liquid crystalline compounds having alkenyl are not classified as polymerizable compounds in that sense.

A liquid crystal composition is prepared by mixing multiple liquid crystal compounds. Additives such as optically active compounds and polymerizable compounds are added to this liquid crystal composition as necessary. Even when additives are added, the proportion of the liquid crystal compound is expressed as a mass percentage (mass %) based on the mass of the liquid crystal composition that does not contain additives. The proportion of the additive is expressed as a mass percentage (% by mass) based on the mass of the liquid crystal composition that does not contain the additive. That is, the proportions of the liquid crystal compound and additives are calculated based on the total mass of the liquid crystal compound. Mass parts per million (ppm) may be used. The proportions of polymerization initiators and polymerization inhibitors are exceptionally expressed based on the weight of the polymerizable compound.

"Upper limit temperature of nematic phase" may be abbreviated as "upper limit temperature." The "lower limit temperature of nematic phase" may be abbreviated as "lower limit temperature." The expression "increase the dielectric anisotropy" means that for a composition with a positive dielectric anisotropy, the value increases positively, and for a composition with a negative dielectric anisotropy. When it is a thing, it means that its value increases negatively. "High voltage holding rate" means that the device has a large voltage holding rate not only at room temperature but also at temperatures close to the upper limit temperature in the initial stage, and after long-term use, it has a large voltage holding rate not only at room temperature but also at temperatures close to the upper limit temperature. It means having a retention rate. Characteristics of compositions and devices are sometimes investigated through aging tests.

上記の化合物（１ｚ）を例にして説明する。式（１ｚ）において、六角形で囲んだαおよびβの記号はそれぞれ環αおよび環βに対応し、六員環、縮合環のような環を表す。添え字‘ｘ’が２のとき、２つの環αが存在する。２つの環αが表す２つの基は、同一であってもよく、または異なってもよい。このルールは、添え字‘ｘ’が２より大きいとき、任意の２つの環αに適用される。このルールは、結合基Ｚのような、他の記号にも適用される。環βの一辺を横切る斜線は、環β上の任意の水素が置換基（－Ｓｐ－Ｐ）で置き換えられてもよいことを表す。添え字‘ｙ’は置き換えられた置換基の数を示す。添え字‘ｙ’が０のとき、そのような置き換えはない。添え字‘ｙ’が２以上のとき、環β上には複数の置換基（－Ｓｐ－Ｐ）が存在する。この場合にも、「同一であってもよく、または異なってもよい」のルールが適用される。なお、このルールは、Ｒａの記号を複数の化合物に用いた場合にも適用される。

This will be explained using the above compound (1z) as an example. In formula (1z), the symbols α and β enclosed in a hexagon correspond to ring α and ring β, respectively, and represent a ring such as a six-membered ring or a fused ring. When the subscript 'x' is 2, there are two rings α. The two groups represented by the two rings α may be the same or different. This rule applies to any two rings α when the subscript 'x' is greater than 2. This rule also applies to other symbols, such as the linking group Z. A diagonal line across one side of ring β indicates that any hydrogen on ring β may be replaced with a substituent (-Sp-P). The subscript 'y' indicates the number of substituents replaced. When the subscript 'y' is 0, there is no such replacement. When the subscript 'y' is 2 or more, a plurality of substituents (-Sp-P) are present on the ring β. In this case as well, the rule "may be the same or different" is applied. Note that this rule is also applied when the symbol Ra is used for multiple compounds.

In formula (1z), for example, the expression "Ra and Rb are alkyl, alkoxy, or alkenyl" means that Ra and Rb are independently selected from the group of alkyl, alkoxy, and alkenyl. do. 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 compounds represented by formula (1z) may be abbreviated as "compound (1z)." "Compound (1z)" means one compound, a mixture of two compounds, or a mixture of three or more compounds represented by formula (1z). The same applies to compounds represented by other formulas. The expression "at least one compound selected from the compounds represented by formula (1z) and formula (2z)" means at least one compound selected from the group of compound (1z) and compound (2z) .

The expression "at least one 'A'" means that the number of 'A's is arbitrary. The expression "at least one 'A' may be replaced by 'B'" means that when the number of 'A's is one, the position of 'A' is arbitrary, and the number of 'A's is two. If there are more than one, their positions can be selected without restriction. The expression "at least one -CH ₂ - may be replaced by -O-" is sometimes 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, an adjacent -CH ₂ - is never replaced with -O-. This is because -OO-CH ₂ - (peroxide) is produced in this substitution.

For example, in Ra and Rb of formula (1z), alkyl is linear or branched and does not include cyclic alkyl. Straight chain alkyl is preferred over branched alkyl. The same applies to terminal groups such as alkoxy and alkenyl.

テトラヒドロピラン－２，５－ジイルのような二価基においても同様である。カルボニルオキシのような結合基（－ＣＯＯ－または－ＯＣＯ－）も同様である。 Regarding the configuration of 1,4-cyclohexylene, trans is preferable to cis in order to increase the upper limit temperature. Since 2-fluoro-1,4-phenylene is left-right asymmetric, there are left-handed (L) and right-handed (R) orientations.

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

The present invention includes the following items.

式（２）において、環Ａおよび環Ｃは、シクロヘキシル、シクロヘキセニル、フェニル、１－ナフチル、２－ナフチル、テトラヒドロピラン－２－イル、１，３－ジオキサン－２－イル、ピリミジン－２－イル、またはピリジン－２－イルであり、これらの環において、少なくとも１つの水素は、フッ素、塩素、炭素数１から１２のアルキル、炭素数１から１２のアルコキシ、または少なくとも１つの水素がフッ素または塩素で置き換えられた炭素数１から１２のアルキルで置き換えられてもよく；環Ｂは、１，４－シクロヘキシレン、１，４－シクロヘキセニレン、１，４－フェニレン、ナフタレン－１，２－ジイル、ナフタレン－１，３－ジイル、ナフタレン－１，４－ジイル、ナフタレン－１，５－ジイル、ナフタレン－１，６－ジイル、ナフタレン－１，７－ジイル、ナフタレン－１，８－ジイル、ナフタレン－２，３－ジイル、ナフタレン－２，６－ジイル、ナフタレン－２，７－ジイル、テトラヒドロピラン－２，５－ジイル、１，３－ジオキサン－２，５－ジイル、ピリミジン－２，５－ジイル、またはピリジン－２，５－ジイルであり、これらの環において、少なくとも１つの水素は、フッ素、塩素、炭素数１から１２のアルキル、炭素数１から１２のアルコキシ、または少なくとも１つの水素がフッ素または塩素で置き換えられた炭素数１から１２のアルキルで置き換えられてもよく；Ｚ^１およびＺ^２は、単結合または炭素数１から１０のアルキレンであり、このアルキレンにおいて、少なくとも１つの－ＣＨ_２－は、－Ｏ－、－ＣＯ－、－ＣＯＯ－、または－ＯＣＯ－で置き換えられてもよく、少なくとも１つの－ＣＨ_２－ＣＨ_２－は、－ＣＨ＝ＣＨ－、－Ｃ（ＣＨ_３）＝ＣＨ－、－ＣＨ＝Ｃ（ＣＨ_３）－、または－Ｃ（ＣＨ_３）＝Ｃ（ＣＨ_３）－で置き換えられてもよく、これらの基において、少なくとも１つの水素は、フッ素または塩素で置き換えられてもよく；Ｐ^１、Ｐ^２、およびＰ^３は重合性基であり；Ｓｐ^１、Ｓｐ^２、およびＳｐ^３は、単結合または炭素数１から１０のアルキレンであり、このアルキレンにおいて、少なくとも１つの－ＣＨ_２－は、－Ｏ－、－ＣＯＯ－、－ＯＣＯ－、または－ＯＣＯＯ－で置き換えられてもよく、少なくとも１つの－ＣＨ_２－ＣＨ_２－は、－ＣＨ＝ＣＨ－または－Ｃ≡Ｃ－で置き換えられてもよく、これらの基において、少なくとも１つの水素は、フッ素または塩素で置き換えられてもよく；ａは、０、１、または２であり；ｂ、ｃ、およびｄは、０、１、２、３、または４であり；そしてｂ、ｃ、およびｄの和は、１以上である。 Item 1. It contains at least one compound selected from a compound represented by formula (1) as a first component and a polymerizable compound represented by formula (2) as a first additive, and has a nematic phase and a negative dielectric A liquid crystal composition having index anisotropy.

In formula (2), ring A and ring C are cyclohexyl, cyclohexenyl, phenyl, 1-naphthyl, 2-naphthyl, tetrahydropyran-2-yl, 1,3-dioxan-2-yl, pyrimidin-2-yl , or pyridin-2-yl, in which 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 fluorine or chlorine. Ring B may be substituted with alkyl having 1 to 12 carbon atoms; Ring B 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 which at least one hydrogen is fluorine, chlorine, alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, or at least one hydrogen is It may be substituted with a C1-C12 alkyl substituted with fluorine or chlorine; Z ¹ and Z ² are a single bond or a C1-C10 alkylene, and in this alkylene, at least one -CH ₂ - may be replaced with -O-, -CO-, -COO-, or -OCO-, and at least one -CH ₂ -CH ₂ - may be replaced with -CH=CH-, -C(CH ₃ )=CH-, -CH=C(CH ₃ )-, or -C(CH ₃ )=C(CH ₃ )-, in which at least one hydrogen is 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 - may be replaced with -O-, -COO-, -OCO-, or -OCOO-, and at least one -CH ₂ -CH ₂ - may be replaced with -CH=CH- or -C≡C-, in which at least one hydrogen may be replaced by fluorine or chlorine; a is 0, 1, or 2; b, c, and d is 0, 1, 2, 3, or 4; and the sum of b, c, and d is 1 or more.

式（Ｐ－１）から式（Ｐ－５）において、Ｍ^１、Ｍ^２、およびＭ^３は、水素、フッ素、炭素数１から５のアルキル、または少なくとも１つの水素がフッ素または塩素で置き換えられた炭素数１から５のアルキルである。 Item 2. Item 1. The liquid crystal according to item 1, wherein in formula (2), P ¹ , P ² and P ³ are groups selected from polymerizable groups represented by formulas (P-1) to (P-5). Composition.

In 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 is replaced with fluorine or chlorine. is an alkyl group having 1 to 5 carbon atoms.

式（２－１）から式（２－２９）において、Ｓｐ^１、Ｓｐ^２、およびＳｐ^３は、単結合、または炭素数１から１０のアルキレンであり、このアルキレンにおいて、少なくとも１つの－ＣＨ_２－は、－Ｏ－、－ＣＯＯ－、－ＯＣＯ－、または－ＯＣＯＯ－で置き換えられてもよく、少なくとも１つの－ＣＨ_２－ＣＨ_２－は、－ＣＨ＝ＣＨ－または－Ｃ≡Ｃ－で置き換えられてもよく、これらの基において、少なくとも１つの水素は、フッ素または塩素で置き換えられてもよい。Ｐ^４、Ｐ^５、およびＰ^６は、式（Ｐ－１）から式（Ｐ－３）で表される基から選択された重合性基であり；

式（Ｐ－１）から式（Ｐ－３）において、Ｍ^１、Ｍ^２、およびＭ^３は、水素、フッ素、炭素数１から５のアルキル、または少なくとも１つの水素がフッ素または塩素で置き換えられた炭素数１から５のアルキルである。 Item 3. 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 (2-29) as a first additive.

In formulas (2-1) to (2-29), 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 - may be replaced with -O-, -COO-, -OCO-, or -OCOO-, and at least one -CH ₂ -CH ₂ - is -CH=CH- or -C≡C- In these groups, at least one hydrogen may be replaced by fluorine or chlorine. P ⁴ , P ⁵ , and P ⁶ are polymerizable groups selected from the groups represented by formulas (P-1) to (P-3);

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

Item 4. According to any one of Items 1 to 3, the proportion of the first component is in the range of 3% by mass to 30% by mass, and the proportion of the first additive is in the range of 0.03% by mass to 10% by mass. liquid crystal composition.

式（３）において、Ｒ^１およびＲ^２は、水素、炭素数１から１２のアルキル、炭素数１から１２のアルコキシ、炭素数２から１２のアルケニル、炭素数２から１２のアルケニルオキシ、または少なくとも１つの水素がフッ素または塩素で置き換えられた炭素数１から１２のアルキルであり；環Ｄおよび環Ｆは、１，４－シクロヘキシレン、１，４－シクロヘキセニレン、テトラヒドロピラン－２，５－ジイル、１，４－フェニレン、少なくとも１つの水素がフッ素または塩素で置き換えられた１，４－フェニレン、ナフタレン－２，６－ジイル、少なくとも１つの水素がフッ素または塩素で置き換えられたナフタレン－２，６－ジイル、クロマン－２，６－ジイル、または少なくとも１つの水素がフッ素または塩素で置き換えられたクロマン－２，６－ジイルであり；環Ｅは、２，３－ジフルオロ－１，４－フェニレン、２－クロロ－３－フルオロ－１，４－フェニレン、２，３－ジフルオロ－５－メチル－１，４－フェニレン、３，４，５－トリフルオロナフタレン－２，６－ジイル、７，８－ジフルオロクロマン－２，６－ジイル、３，４，５，６－テトラフルオロフルオレン－２，７－ジイル、４，６－ジフルオロジベンゾフラン－３，７－ジイル、４，６－ジフルオロジベンゾチオフェン－３，７－ジイル、または１，１，６，７－テトラフルオロインダン－２，５－ジイルであり；Ｚ^３およびＺ^４は、単結合、エチレン、ビニレン、カルボニルオキシ、またはメチレンオキシであり；ｅは、０、１、２、または３であり；ｆは、０または１であり；ｅとｆとの和は３以下である。 Item 5. Item 5. The liquid crystal composition according to any one of Items 1 to 4, which contains at least one compound selected from compounds represented by formula (3) as a second component.

In formula (3), R ¹ and R ² are hydrogen, alkyl having 1 to 12 carbon atoms, alkoxy having 1 to 12 carbon atoms, alkenyl having 2 to 12 carbon atoms, alkenyloxy having 2 to 12 carbon atoms, or at least is an alkyl having 1 to 12 carbon atoms in which one hydrogen is replaced with fluorine or chlorine; Ring D and Ring F are 1,4-cyclohexylene, 1,4-cyclohexenylene, tetrahydropyran-2,5- diyl, 1,4-phenylene, 1,4-phenylene with at least one hydrogen replaced by fluorine or chlorine, naphthalene-2,6-diyl, naphthalene-2 with at least one hydrogen replaced with fluorine or chlorine, 6-diyl, chroman-2,6-diyl, or chroman-2,6-diyl in which at least one hydrogen is replaced with fluorine or chlorine; Ring E 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-difluorodibenzothiophene-3 ,7-diyl, or 1,1,6,7-tetrafluoroindan-2,5-diyl; Z ³ and Z ⁴ are a single bond, ethylene, vinylene, carbonyloxy, or methyleneoxy; e is 0, 1, 2, or 3; f is 0 or 1; and the sum of e and f is 3 or less.

式（３－１）から式（３－３５）において、Ｒ^１およびＲ^２は、水素、炭素数１から１２のアルキル、炭素数１から１２のアルコキシ、炭素数２から１２のアルケニル、炭素数２から１２のアルケニルオキシ、または少なくとも１つの水素がフッ素または塩素で置き換えられた炭素数１から１２のアルキルである。 Item 6. Item 5. The liquid crystal composition according to any one of Items 1 to 5, which contains at least one compound selected from compounds represented by formulas (3-1) to (3-35) as the second component.

In formulas (3-1) to (3-35), R ¹ and R ² are hydrogen, alkyl having 1 to 12 carbon atoms, alkoxy having 1 to 12 carbon atoms, alkenyl having 2 to 12 carbon atoms, and 2 to 12 alkenyloxy, or C1 to C12 alkyl in which at least one hydrogen is replaced with fluorine or chlorine.

Section 7. Item 7. The liquid crystal composition according to Item 5 or 6, wherein the proportion of the second component is in the range of 10% by mass to 80% by mass.

式（４）において、Ｒ^３およびＲ^４は、炭素数１から１２のアルキル、炭素数１から１２のアルコキシ、炭素数２から１２のアルケニル、少なくとも１つの水素がフッ素または塩素で置き換えられた炭素数１から１２のアルキル、または少なくとも１つの水素がフッ素または塩素で置き換えられた炭素数２から１２のアルケニルであり；環Ｇおよび環Ｉは、１，４－シクロヘキシレン、１，４－フェニレン、２－フルオロ－１，４－フェニレン、または２，５－ジフルオロ－１，４－フェニレンであり；Ｚ^５は、単結合、エチレン、ビニレン、メチレンオキシ、またはカルボニルオキシであり；ｇは、１、２、または３であり；ｇが１であるとき、環Ｇは１，４－シクロヘキシレンである。 Section 8. 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 third component.

In formula (4), R ³ and R ⁴ are alkyl having 1 to 12 carbon atoms, alkoxy having 1 to 12 carbon atoms, alkenyl having 2 to 12 carbon atoms, and carbon in which at least one hydrogen is replaced with fluorine or chlorine. Alkyl having 1 to 12 carbon atoms, or alkenyl having 2 to 12 carbon atoms in which at least one hydrogen is replaced with fluorine or chlorine; Ring G and Ring I 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; g is 1; 2, or 3; when g is 1, ring G is 1,4-cyclohexylene.

式（４－１）から式（４－１２）において、Ｒ^３およびＲ^４は、炭素数１から１２のアルキル、炭素数１から１２のアルコキシ、炭素数２から１２のアルケニル、少なくとも１つの水素がフッ素または塩素で置き換えられた炭素数１から１２のアルキル、または少なくとも１つの水素がフッ素または塩素で置き換えられた炭素数２から１２のアルケニルである。 Item 9. Item 9. The liquid crystal composition according to any one of Items 1 to 8, which contains at least one compound selected from compounds represented by formulas (4-1) to (4-12) as a third component.

In formulas (4-1) to (4-12), R ³ and R ⁴ are alkyl having 1 to 12 carbon atoms, alkoxy having 1 to 12 carbon atoms, alkenyl having 2 to 12 carbon atoms, and at least one hydrogen is an alkyl having 1 to 12 carbon atoms in which is replaced with fluorine or chlorine, or alkenyl having 2 to 12 carbon atoms in which at least one hydrogen is replaced with fluorine or chlorine.

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

Item 11. Item 11. The liquid crystal composition according to any one of Items 1 to 10, which does not contain a compound having a cyclic alkyl.

Item 12. According to any one of claims 1 to 11, the additive does not contain an additive having a partial structure represented by formula (A-1) and an additive having a partial structure represented by formula (A-2). liquid crystal composition.

Item 13. The liquid crystal composition according to any one of claims 1 to 12, used in a polymer-supported alignment type liquid crystal display element.

Section 14. Item 13. A liquid crystal display element comprising the liquid crystal composition according to any one of Items 1 to 12.

Item 15. 15. The liquid crystal display element according to item 14, wherein the operation mode of the liquid crystal display element is IPS mode, VA mode, FFS mode, or FPA mode, and the driving method of the liquid crystal display element is an active matrix method.

Section 16. 13. A polymer-supported alignment type liquid crystal display element containing the liquid crystal composition according to any one of Items 1 to 12, in which a polymerizable compound in the liquid crystal composition is polymerized.

Section 17. Use of the liquid crystal composition according to any one of Items 1 to 12 in a liquid crystal display element.

Section 18. Use of the liquid crystal composition according to any one of Items 1 to 12 in a polymer-supported alignment type liquid crystal display element.

The present invention also includes the following sections. (a) one compound selected from additives such as optically active compounds, antioxidants, ultraviolet absorbers, quenchers, dyes, antifoaming agents, polymerizable compounds, polymerization initiators, and polymerization inhibitors; A composition as described above containing a compound, or three or more compounds. (b) An AM element containing the above composition. (c) The above composition further containing a polymerizable compound, and a polymer supported alignment (PSA) type AM element containing this composition. (d) A polymer supported alignment (PSA) type AM element containing the above composition and in which a polymerizable compound in the composition is polymerized. (e) A device containing the above composition and having a mode of PC, TN, STN, ECB, OCB, IPS, VA, FFS, or FPA. (f) A transmission type element containing the above composition. (g) Use of the above compositions as compositions having a nematic phase. (h) Use of an optically active composition obtained by adding an optically active compound to the above composition.

The composition of the present invention will be explained in the following order. First, the structure of the component compounds in the composition will be explained. Second, the main properties of the component compounds and the main effects that these compounds have on the compositions and devices will be explained. Third, the combinations of component compounds in the composition, their preferred ratios, and their basis will be explained. Fourth, preferred forms of the component compounds will be explained. Fifth, preferred component compounds are shown. Sixth, additives that may be added to the composition will be explained. Seventh, the method of synthesizing the component compounds will be explained. Finally, the uses of the composition will be explained.

First, the structure of the component compounds in the composition will be explained. This composition contains multiple liquid crystal compounds. The composition may also contain additives. Additives include optically active compounds, antioxidants, ultraviolet absorbers, quenchers, dyes, antifoaming agents, polymerizable compounds, polymerization initiators, polymerization inhibitors, polar compounds, and the like. This composition is classified into composition A and composition B from the viewpoint of the liquid crystal compound. Composition A may further contain other liquid crystal compounds, additives, etc. in addition to the liquid crystal compound selected from compound (1), compound (3), and compound (4). "Other liquid crystal compounds" are liquid crystal compounds different from compound (1), compound (3), and compound (4). Such compounds are mixed into the composition for the purpose of further adjusting its properties.

Composition B consists essentially only of liquid crystalline compounds selected from compound (1), compound (3), and compound (4). The term "substantially" means that Composition B may contain additives but does not contain other liquid crystal compounds. Composition B has fewer component compounds than Composition A. Composition B is preferable to composition A from the viewpoint of lowering costs. Composition A is more preferable than composition B from the viewpoint that the properties can be further adjusted by mixing other liquid crystal compounds.

Second, the main properties of the component compounds and the main effects that these compounds have on the compositions and devices will be explained. The main properties of the component compounds are summarized in Table 2 based on the effects of the present invention. In the symbols in Table 2, L means large or high, M means medium, and S means small or low. The symbols L, M, and S are classifications based on qualitative comparisons between component compounds, with 0 (zero) meaning less than S.

The main effects that the component compounds have on the properties of the composition are as follows. Compound (1) lowers the viscosity. Since compound (2) is polymerizable, it gives a polymer by polymerization. This polymer stabilizes the alignment of liquid crystal molecules, thereby shortening the response time of the device and improving image sticking. Compound (3) increases dielectric anisotropy. Compound (4) increases the upper limit temperature or lowers the viscosity.

Third, the combination of component compounds in the composition, their preferred ratios, and their basis will be explained. Preferred combinations of component compounds in the composition are compound (1) + compound (2), compound (1) + compound (2) + compound (3), compound (1) + compound (2) + compound (4), Or compound (1) + compound (2) + compound (3) + compound (4). A more preferred combination is compound (1) + compound (2) + compound (3) + compound (4).

A preferable proportion of compound (1) is about 3% by mass or more in order to lower the viscosity, and about 30% by mass or less in order to lower the minimum temperature. More preferred proportions range from about 3% to about 25% by weight. Particularly preferred proportions range from about 3% to about 20% by weight.

Compound (2) is added to the composition for the purpose of making it compatible with polymer-supported alignment type elements. A preferable proportion of compound (2) is about 0.03% by mass or more in order to orient the liquid crystal molecules, and about 10% by mass or less in order to prevent display defects of the device. A more preferred proportion ranges from about 0.1% to about 2% by weight. Particularly preferred proportions range from about 0.2% to about 1% by weight.

A preferable proportion of compound (3) is about 10% by mass or more in order to increase the dielectric anisotropy, and about 80% by mass or less in order to lower the minimum temperature. More preferred proportions range from about 15% to about 75% by weight. Particularly preferred proportions range from about 20% to about 70% by weight.

A preferred proportion of compound (4) is about 10% by mass or more in order to increase the upper limit temperature or lower the viscosity, and is about 80% by mass or less in order to lower the lower limit temperature. More preferred proportions range from about 15% to about 65% by weight. Particularly preferred proportions range from about 20% to about 60% by weight.

Fourth, preferred forms of the component compounds will be explained. In formula (3) and formula (4), R ¹ and R ² are hydrogen, alkyl having 1 to 12 carbon atoms, alkoxy having 1 to 12 carbon atoms, alkenyl having 2 to 12 carbon atoms, and alkenyl having 2 to 12 carbon atoms. or C1-C12 alkyl in which at least one hydrogen is replaced with fluorine or chlorine. Preferred R ¹ or R ² is alkyl having 1 to 12 carbon atoms to increase stability, and alkoxy having 1 to 12 carbon atoms to increase dielectric anisotropy. R ³ and R ⁴ are alkyl having 1 to 12 carbon atoms, alkoxy having 1 to 12 carbon atoms, alkenyl having 2 to 12 carbon atoms, alkyl having 1 to 12 carbon atoms in which at least one hydrogen is replaced with fluorine or chlorine; , or a C2-C12 alkenyl in which at least one hydrogen is replaced with fluorine or chlorine. Preferred R ³ or R ⁴ is alkenyl having 2 to 12 carbon atoms to reduce viscosity, and alkyl having 1 to 12 carbon atoms to increase stability.

Preferred alkyls are methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, or octyl. More preferred alkyls are methyl, ethyl, propyl, butyl, or pentyl to reduce viscosity.

Preferred alkoxy is methoxy, ethoxy, propoxy, butoxy, pentyloxy, hexyloxy or heptyloxy. More preferred alkoxy is methoxy or ethoxy to reduce viscosity.

Preferred alkenyls are vinyl, 1-propenyl, 2-propenyl, 1-butenyl, 2-butenyl, 3-butenyl, 1-pentenyl, 2-pentenyl, 3-pentenyl, 4-pentenyl, 1-hexenyl, 2-hexenyl, 3-hexenyl, 4-hexenyl, or 5-hexenyl. More preferred alkenyls are vinyl, 1-propenyl, 3-butenyl, or 3-pentenyl to reduce viscosity. The preferred configuration of -CH=CH- in these alkenyls depends on the position of the double bond. In alkenyls such as 1-propenyl, 1-butenyl, 1-pentenyl, 1-hexenyl, 3-pentenyl, and 3-hexenyl, trans is preferred in order to lower the viscosity. Cis is preferred in alkenyl such as 2-butenyl, 2-pentenyl, and 2-hexenyl.

Preferred alkenyloxy is vinyloxy, allyloxy, 3-butenyloxy, 3-pentenyloxy, or 4-pentenyloxy. More preferred alkenyloxy to reduce viscosity is allyloxy or 3-butenyloxy.

Preferred examples of alkyl in which at least one hydrogen is replaced by 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 in order to increase the dielectric anisotropy.

Preferred examples of alkenyl in which at least one hydrogen is replaced by 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. Further preferred examples are 2,2-difluorovinyl or 4,4-difluoro-3-butenyl to reduce viscosity.

または

であり、好ましくは

である。 Ring D and Ring F are 1,4-cyclohexylene, 1,4-cyclohexenylene, tetrahydropyran-2,5-diyl, 1,4-phenylene, 1 in which at least one hydrogen is replaced with fluorine or chlorine. ,4-phenylene, naphthalene-2,6-diyl, naphthalene-2,6-diyl with at least one hydrogen replaced by fluorine or chlorine, chroman-2,6-diyl, or at least one hydrogen with fluorine or chlorine chroman-2,6-diyl substituted with Preferred examples of "1,4-phenylene in which at least one hydrogen is replaced with fluorine or chlorine" are 2-fluoro-1,4-phenylene, 2,3-difluoro-1,4-phenylene or 2-chloro- It is 3-fluoro-1,4-phenylene. Preferred ring D or ring F is 1,4-cyclohexylene in order to lower the viscosity or increase the upper limit temperature, 1,4-phenylene in order to increase the optical anisotropy, and preferable ring It is 1,4-phenylene in which at least one hydrogen has been replaced with fluorine or chlorine to increase the orientation. Tetrahydropyran-2,5-diyl is

or

and preferably

It is.

好ましい環Ｅは、粘度を下げるために２，３－ジフルオロ－１，４－フェニレンであり、光学異方性を下げるために２－クロロ－３－フルオロ－１，４－フェニレンであり、誘電率異方性を上げるために７，８－ジフルオロクロマン－２，６－ジイルである。 Ring E 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 (FLF4), 4,6- Difluorodibenzofuran-3,7-diyl (DBFF2), 4,6-difluorodibenzothiophene-3,7-diyl (DBTF2), or 1,1,6,7-tetrafluoroindan-2,5-diyl (InF4) It is.

Preferred ring E is 2,3-difluoro-1,4-phenylene to lower the viscosity, 2-chloro-3-fluoro-1,4-phenylene to lower the optical anisotropy, and the dielectric constant 7,8-difluorochroman-2,6-diyl is used to increase anisotropy.

Ring G and Ring I are 1,4-cyclohexylene, 1,4-phenylene, 2-fluoro-1,4-phenylene, or 2,5-difluoro-1,4-phenylene. Preferred ring G or ring I is 1,4-cyclohexylene in order to lower the viscosity or increase the upper limit temperature, and 1,4-phenylene in order to increase the optical anisotropy.

Z ³ and Z ⁴ are a single bond, ethylene, vinylene, carbonyloxy, or methyleneoxy. Preferably Z ³ or Z ⁴ is a single bond to lower the viscosity, and methyleneoxy to increase the dielectric anisotropy. Z ⁵ is a single bond, ethylene, vinylene, methyleneoxy, or carbonyloxy. Preferred Z ⁵ is a single bond to reduce viscosity.

Divalent groups such as methyleneoxy are asymmetric. In methyleneoxy, -CH ₂ O- is more preferred than -OCH ₂ -. In carbonyloxy, -COO- is more preferred than -OCO-.

e is 0, 1, 2, or 3, f is 0 or 1, and the sum of e and f is 3 or less. Preferably e is 1 in order to lower the viscosity, and 2 or 3 in order to increase the upper limit temperature. Preferably f is 0 in order to lower the viscosity and 1 in order to increase the upper limit temperature. g is 1, 2, or 3, and when g is 1, ring G is 1,4-cyclohexylene. Preferably g is 1 in order to lower the viscosity, and 2 or 3 in order to increase the upper limit temperature.

In formula (2), P ¹ , P ² and P ³ are polymerizable groups. 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 formula (P-1) is -OCO-CH=CH ₂ or -OCO-C(CH ₃ )=CH ₂ . The wavy lines in formulas (P-1) to (P-5) indicate binding sites.

In 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 is replaced with fluorine or chlorine. is an alkyl group having 1 to 5 carbon atoms. Preferred M ¹ , M ² or M ³ is hydrogen or methyl to increase reactivity. More preferred M ¹ is hydrogen or methyl, and even more preferred M ² or M ³ is hydrogen.

In formulas (2-1) to (2-29), 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). More preferred formula (P-1) is -OCO-CH=CH ₂ or -OCO-C(CH ₃ )=CH ₂ . The wavy lines in formulas (P-1) to (P-3) indicate bonding sites.

In formula (2), 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 replaced with -CH═CH- or -C≡C-, and in these groups , at least one hydrogen may be replaced 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 preferred Sp ¹ , Sp ² or Sp ³ is a single bond.

Ring A and Ring C are cyclohexyl, cyclohexenyl, phenyl, 1-naphthyl, 2-naphthyl, tetrahydropyran-2-yl, 1,3-dioxan-2-yl, pyrimidin-2-yl, or pyridin-2- 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 a carbon number in which at least one hydrogen is replaced with fluorine or chlorine. Optionally substituted with 1 to 12 alkyl. Preferred ring A or ring C is phenyl. Ring B 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, and in these rings, At least one hydrogen is replaced with fluorine, chlorine, C1-12 alkyl, C1-12 alkoxy, or C1-12 alkyl in which at least one hydrogen is replaced with fluorine or chlorine. Good too. Preferred ring B is 1,4-phenylene or 2-fluoro-1,4-phenylene.

Z ¹ and Z ² are a single bond or an alkylene having 1 to 10 carbon atoms, and in this alkylene, at least one -CH ₂ - is -O-, -CO-, -COO-, or -OCO-. Optionally, 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 replaced by fluorine or chlorine. Preferably Z ¹ or Z ² is a single bond, -CH ₂ CH ₂ -, -CH ₂ O-, -OCH ₂ -, -COO-, or -OCO-. More preferred Z ¹ or Z ² is a single bond.

a is 0, 1, or 2. Preferably a is 0 or 1. b, c, and d are 0, 1, 2, 3, or 4, and the sum of b, c, and d is 1 or more. Preferably b, c, or d is 1 or 2.

Fifth, preferred component compounds are shown. Preferred compounds (2) are compounds (2-1) to (2-29) described in item 3. In these compounds, at least one of the first additives is compound (2-1), compound (2-2), compound (2-24), compound (2-25), compound (2-26), or Compound (2-27) is preferred. At least two of the first additives are compound (2-1) and compound (2-2), compound (2-1) and compound (2-24), compound (2-1) and compound (2-25) , compound (2-1) and compound (2-26), compound (2-2) and compound (2-24), compound (2-2) and compound (2-25), compound (2-2) and A combination of compound (2-26), compound (2-25) and compound (2-26) is preferred.

Preferred compounds (3) are compounds (3-1) to (3-35) described in Item 6. In these compounds, at least one of the second components is compound (3-1), compound (3-3), compound (3-6), compound (3-7), compound (3-8), compound ( 3-9), compound (3-10), compound (3-13), compound (3-14), compound (3-16), or compound (3-18). At least two of the third components are compound (3-1) and compound (3-8), compound (3-1) and compound (3-14), compound (3-3) and compound (3-8), Compound (3-3) and compound (3-10), compound (3-3) and compound (3-14), compound (3-6) and compound (3-8), compound (3-6) and compound (3-10), compound (3-6) and compound (3-14), compound (3-6) and compound (3-18), or a combination of compound (3-10) and compound (3-14) It is preferable that

Preferred compounds (4) are compounds (4-1) to (4-12) described in Item 9. In these compounds, at least one of the third components is compound (4-1), compound (4-2), compound (4-4), compound (4-5), compound (4-6), compound ( 4-7), compound (4-8), compound (4-10) or compound (4-12). It is preferable that at least two of the third components are a combination of compound (4-1) and compound (4-4), or compound (4-1) and compound (4-5).

Sixth, additives that may be added to the composition will be explained. Such additives include optically active compounds, antioxidants, ultraviolet absorbers, quenchers, dyes, antifoaming agents, 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 a helical structure of liquid crystal molecules and giving a twist angle. Examples of such compounds are compounds (5-1) to (5-5). The preferred proportion of optically active compound is about 5% by weight or less. More preferred proportions range from about 0.01% to about 2% by weight.

Antioxidants are added to the composition in order to prevent the specific resistance from decreasing due to heating in the atmosphere, or to maintain a high voltage holding rate not only at room temperature but also at temperatures close to the upper limit temperature after the device has been used for a long time. added to things. Preferred examples of the antioxidant include compounds (6-1) to (6-3).

Since compound (6-2) has low volatility, it is effective in maintaining a high voltage holding rate not only at room temperature but also at temperatures close to the upper limit temperature after the device has been used for a long time. The preferred proportion of the antioxidant is about 50 ppm or more to obtain the effect, and about 600 ppm or less so as not to lower the upper limit temperature or increase the lower limit temperature. More preferred proportions range from about 100 ppm to about 300 ppm.

Preferred examples of the ultraviolet absorber include benzophenone derivatives, benzoate derivatives, and triazole derivatives. Light stabilizers such as sterically hindered amines are also preferred. Preferred examples of the light stabilizer include compounds (7-1) to (7-16). The preferable proportion of these absorbers and stabilizers is about 50 ppm or more in order to obtain the effect, and about 10,000 ppm or less so as not to lower the upper limit temperature or increase the lower limit temperature. More preferred proportions range from about 100 ppm to about 10,000 ppm.

A quencher is a compound that prevents decomposition of a liquid crystal compound by receiving light energy absorbed by the liquid crystal compound and converting it into thermal energy. Preferred examples of the quencher include compounds (8-1) to (8-7). The preferred ratio of these quenchers is about 50 ppm or more to obtain the effect, and about 20,000 ppm or less to lower the minimum temperature. More preferred proportions range from about 100 ppm to about 10,000 ppm.

Dichroic dyes such as azo dyes, anthraquinone dyes, etc. are added to the composition in order to make it compatible with a guest host (GH) mode device. Preferred proportions of dye range from about 0.01% to about 10% by weight. Antifoaming agents such as dimethyl silicone oil, methylphenyl silicone oil are added to the composition to prevent foaming. The preferred proportion of the antifoaming agent is about 1 ppm or more to obtain its effect, and about 1000 ppm or less to prevent display defects. More preferred proportions range from about 1 ppm to about 500 ppm.

Polymerizable compounds are used to make them compatible with polymer supported alignment (PSA) type devices. Compound (2) is suitable for this purpose. A polymerizable compound different from compound (2) may be added to the composition together with compound (2). Preferred examples of such polymerizable compounds are compounds such as acrylates, methacrylates, vinyl compounds, vinyloxy compounds, propenyl ethers, epoxy compounds (oxirane, oxetane), and vinyl ketones. Further preferred examples are acrylate or methacrylate derivatives. A preferable proportion of compound (2) is 10% by mass or more based on the total mass of the polymerizable compound. A more preferable ratio is 50% by mass or more. A particularly preferable ratio is 80% by mass or more. The most preferred proportion is 100% by weight.

A polymerizable compound such as compound (2) is polymerized by ultraviolet irradiation. Polymerization may be carried out in the presence of a suitable initiator such as a photoinitiator. Suitable conditions for polymerization, as well as suitable types and amounts of initiators, are known to those skilled in the art and are described in the literature. For example, the photoinitiators Irgacure 651 (registered trademark; BASF), Irgacure 184 (registered trademark; BASF) or Darocur 1173 (registered trademark; BASF) are suitable for radical polymerization. A preferred proportion of photoinitiator ranges from about 0.1% to about 5% by weight, based on the weight of the polymerizable compound. More preferred proportions range from about 1% to about 3% by weight.

When storing a polymerizable compound such as compound (2), a polymerization inhibitor may be added to prevent polymerization. The polymerizable compound is usually added to the composition without removing the polymerization inhibitor. Examples of polymerization inhibitors are hydroquinone, hydroquinone derivatives such as methylhydroquinone, 4-t-butylcatechol, 4-methoxyphenol, phenothiazine, and the like.

Seventh, the method of synthesizing the component compounds will be explained. These compounds can be synthesized by known methods. The synthesis method will be illustrated. Compound (1) is synthesized by the method described in JP-A-5-140003. Compound (2-18) is synthesized by the method described in JP-A-7-101900. Compound (3-8) is synthesized by the method described in Japanese Patent Publication No. 2-503441. Compound (4-4) is synthesized by the method described in JP-A-59-176221. Antioxidants are commercially available. Compound (6-1) is available from Aldrich (Sigma-Aldrich Corporation). Compound (6-2) and the like are synthesized by the method described in US Pat. No. 3,660,505.

Compounds for which the synthesis method was not described are provided by Organic Syntheses, John Wiley & Sons, Inc., Organic Reactions, John Wiley & Sons, Inc., and Comprehensive Organic Synthesis ( It can be synthesized by methods described in books such as Comprehensive Organic Synthesis (Pergamon Press) and New Experimental Chemistry Course (Maruzen). Compositions are prepared from the compounds thus obtained by known methods. For example, the component compounds may be mixed and dissolved together by heating.

Finally, the uses of the composition will be explained. This composition primarily has a lower temperature limit of about -10°C or less, an upper temperature limit of about 70°C or more, and an optical anisotropy in the range of about 0.07 to about 0.20. A composition having an optical anisotropy in the range of about 0.08 to about 0.25 may be prepared by controlling the proportions of the component compounds or by mixing other liquid crystalline compounds. Furthermore, a composition having an optical anisotropy in the range of about 0.10 to about 0.30 may be prepared by trial and error. A device containing this composition has a high voltage holding ratio. This composition is suitable for AM devices. This composition is particularly suitable for transmission type AM devices. This composition can be used as a composition having a nematic phase, or as an optically active composition by adding an optically active compound.

This composition can be used in AM devices. Furthermore, it can also be used for PM elements. This composition can be used for AM devices and PM devices having modes such as PC, TN, STN, ECB, OCB, IPS, FFS, VA, and FPA. Particular preference is given to use in AM elements with TN, OCB, IPS or FFS modes. In an AM element having an IPS mode or an FFS mode, when no voltage is applied, the alignment of liquid crystal molecules may be parallel to or perpendicular to the glass substrate. These elements may be reflective, transmissive, or semi-transmissive. Use in transmission type elements is preferred. Use in amorphous silicon-TFT elements or polycrystalline silicon-TFT elements is also possible. It can also be used in NCAP (nematic curvilinear aligned phase) type devices fabricated by microencapsulating this composition, and PD (polymer dispersed) type devices fabricated in which three-dimensional network polymers are formed in the composition.

An example of a method for manufacturing a polymer-supported alignment type device is as follows. An element having two substrates called an array substrate and a color filter substrate is assembled. This substrate has an alignment film. At least one of the substrates has an electrode layer. A liquid crystal composition is prepared by mixing liquid crystal compounds. A polymerizable compound is added to this composition. Additional additives may be added as necessary. This composition is injected into the device. Light is irradiated with a voltage applied to this element. Ultraviolet light is preferred. The polymerizable compound is polymerized by light irradiation. This polymerization produces a composition containing the polymer. A polymer-supported alignment type element is manufactured by such a procedure.

In this procedure, when a voltage is applied, liquid crystal molecules are aligned by the action of an alignment film and an electric field. The molecules of the polymerizable compound are also oriented according to this orientation. In this state, the polymerizable compound is polymerized by ultraviolet rays, so that a polymer that maintains this orientation is produced. The effect of this polymer shortens the response time of the device. Since image sticking is caused by malfunction of liquid crystal molecules, the effect of this polymer also improves image sticking. Note that it would also be possible to polymerize the polymerizable compound in the composition in advance and place this composition between the substrates of the liquid crystal display element.

The present invention will be explained in more detail by way of examples. The invention is not limited by these examples. The invention includes a mixture of the composition of Example 1 and the composition of Example 2. The present invention also includes mixtures of at least two of the compositions of the examples. The synthesized compounds were identified by methods such as NMR analysis. The properties of the compounds, compositions, and devices were measured by the methods described below.

NMR analysis: DRX-500 manufactured by Bruker Biospin was used for measurement. In ^{the 1} H-NMR measurement, the sample was dissolved in a deuterated solvent such as CDCl ₃ , and the measurement was performed at room temperature, at 500 MHz, and with 16 integrations. Tetramethylsilane was used as an internal standard. ¹⁹ F-NMR measurements were carried out using CFCl ₃ as an internal standard and with 24 integrations. In the description of nuclear magnetic resonance spectra, s means singlet, d means doublet, t means triplet, q means quartet, quin means quintet, sex means sextet, m means multiplet, and br means broad.

Gas chromatography analysis: A GC-14B gas chromatograph manufactured by Shimadzu Corporation was used for measurement. The carrier gas is helium (2 mL/min). The sample vaporization chamber was set at 280°C, and the detector (FID) was set at 300°C. A capillary column DB-1 manufactured by Agilent Technologies Inc. (length 30 m, inner diameter 0.32 mm, film thickness 0.25 μm; stationary liquid phase is dimethylpolysiloxane; nonpolar) was used to separate the component compounds. This column was held at 200°C for 2 minutes and then raised to 280°C at a rate of 5°C/min. After preparing the sample as an acetone solution (0.1% by mass), 1 μL of the solution was injected into the sample vaporization chamber. The recorder was a C-R5A Chromatopac manufactured by Shimadzu Corporation or an equivalent product. The resulting gas chromatogram showed the retention times and peak areas of the peaks corresponding to the component compounds.

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

The proportion of the liquid crystal compound contained in the composition may be calculated by the following method. A mixture of liquid crystalline compounds is analyzed by gas chromatography (FID). The area ratio of the peaks in the gas chromatogram corresponds to the ratio (mass ratio) of the liquid crystal compound. When the capillary column described above is used, the correction coefficient of each liquid crystal compound may be regarded as 1. Therefore, the proportion (mass %) of the liquid crystal compound can be calculated from the area ratio of the peaks.

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

The following mother liquid crystal was used. The proportions of component compounds are expressed in mass %.

Measurement method: Characteristics were measured using the following method. Many of these are methods described in the JEITA standard (JEITA ED-2521B), which is deliberated and established by the Japan Electronics and Information Technology Industries Association (hereinafter referred to as JEITA), or modified from this. It was a method. A thin film transistor (TFT) was not attached to the TN element used in the measurement.

(1) Upper limit temperature of nematic phase (NI; °C): A sample was placed on a hot plate of a melting point measuring device equipped with a polarizing microscope and heated at a rate of 1 °C/min. The temperature at which a portion of the sample changed from a nematic phase to an isotropic liquid was measured. The upper limit temperature of the nematic phase is sometimes abbreviated as "upper limit temperature."

(2) Lower limit temperature of nematic phase (TC; ° _C ): Place a sample having a nematic phase in a glass bottle and place it in a freezer at 0 °C, -10 °C, -20 °C, -30 °C, and -40 °C for 10 days. After storage, the liquid crystal phase was observed. For example, when a sample remained in a nematic phase at -20°C and changed to a crystalline or smectic phase at -30°C, T _C was written as <-20°C. The lower limit temperature of the nematic phase is sometimes abbreviated as "lower limit temperature."

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

(4) Viscosity (rotational viscosity; γ1; measured at 25° C.; mPa·s): A rotational viscosity measurement system LCM-2 model manufactured by Toyo Technica Co., Ltd. was used for the measurement. A sample was injected into a VA element in which the distance between two glass substrates (cell gap) was 10 μm. 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, values of rotational viscosity were obtained. The dielectric anisotropy was measured by the method described in Measurement (6).

(5) Optical anisotropy (refractive index anisotropy; Δn; measured at 25° C.): Measurement was performed using light with a wavelength of 589 nm using an Abbe refractometer with a polarizing plate attached to the eyepiece. After rubbing the surface of the main prism in one direction, the sample was dropped onto 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 Δn=n∥−n⊥.

(6) Dielectric anisotropy (Δε; measured at 25° C.): The value of dielectric anisotropy was calculated from the formula Δε=ε∥−ε⊥. The dielectric constants (ε∥ and ε⊥) were measured as follows.
1) Measurement of dielectric constant (ε∥): A solution of octadecyltriethoxysilane (0.16 mL) in ethanol (20 mL) was applied to a well-washed glass substrate. After rotating the glass substrate with a spinner, it was heated at 150° C. for 1 hour. A sample was placed in a VA element with a cell gap of 4 μm between two glass substrates, and the element was sealed with an adhesive that cures with ultraviolet light. 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⊥): A polyimide solution was applied to a well-cleaned glass substrate. After firing this glass substrate, the obtained alignment film was subjected to a rubbing treatment. A sample was placed in a TN element in which the distance between two glass substrates (cell gap) was 9 μm and the twist angle was 80 degrees. 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 measurement. The light source was a halogen lamp. A sample was placed in a normally black mode VA element in which the cell gap between two glass substrates was 4 μm and the rubbing direction was antiparallel, and an adhesive that was cured by ultraviolet light was applied to the element. It was sealed using. The voltage (60 Hz, rectangular wave) applied to this element was increased in steps of 0.02 V from 0 V to 20 V. At this time, the element was irradiated with light from the perpendicular direction, and the amount of light transmitted through the element was measured. A voltage-transmittance curve was created in which the transmittance is 100% when the amount of light is maximum and the transmittance is 0% when this amount of light is the minimum. The threshold voltage was expressed as the voltage when the transmittance reached 10%.

(8) Voltage holding ratio (VHR-1; measured at 25°C; %): The TN element used in the measurement had a polyimide alignment film, and the distance between the two glass substrates (cell gap) was 5 μm. . After the sample was placed in the device, it was sealed with an adhesive that cures under ultraviolet light. This TN element was charged by applying a pulse voltage (5 V, 60 microseconds). The attenuating voltage was measured for 16.7 milliseconds using a high-speed voltmeter, and the area A between the voltage curve and the horizontal axis in a unit period was determined. Area B was the area when no attenuation occurred. The voltage holding rate was expressed as a percentage of area A to area B.

(9) Voltage holding rate (VHR-2; measured at 80°C; %): The voltage holding rate was measured using the same procedure as above, except that the measurement was performed at 80°C instead of 25°C. The obtained value was expressed in VHR-2.

(10) Voltage holding rate (VHR-3; measured at 25°C; %): After irradiation with ultraviolet rays, voltage holding rate was measured to evaluate stability against ultraviolet rays. The TN device used in the measurements had a polyimide alignment film and a cell gap of 5 μm. A sample was injected into this element, and light was irradiated for 20 minutes. The light source was an ultra-high pressure mercury lamp USH-500D (manufactured by Ushio Inc.), and the distance between the element and the light source was 20 cm. The VHR-3 measurement measured a voltage that decayed over 16.7 milliseconds. Compositions with large VHR-3 have greater stability to ultraviolet light. VHR-3 is preferably 90% or more, more preferably 95% or more.

(11) Voltage holding rate (VHR-4; measured at 25°C; %): After heating the TN element injected with the sample in a thermostat at 80°C for 500 hours, the voltage holding rate was measured and the stability against heat was measured. was evaluated. The VHR-4 measurement measured a voltage that decayed over 16.7 milliseconds. Compositions with large VHR-4 have greater thermal stability.

(12) Response time (τ; measured at 25°C; ms): An LCD5100 type luminance meter manufactured by Otsuka Electronics Co., Ltd. was used for measurement. The light source was a halogen lamp. The low-pass filter was set at 5kHz.
1) Composition that does not contain a polymerizable compound: A sample is placed in a normally black mode VA element in which the distance between two glass substrates (cell gap) is 4 μm and the rubbing direction is antiparallel. Ta. The device was sealed using an adhesive that cures with ultraviolet light. A rectangular wave (60 Hz, 10 V, 0.5 seconds) was applied to this element. At this time, the element was irradiated with light from the perpendicular direction, and the amount of light transmitted through the element was measured. The transmittance was considered to be 100% when this amount of light was at its maximum, and the transmittance was considered to be 0% when this amount of light was at its minimum. The response time was expressed as the time required for the transmittance to change from 90% to 10% (fall time; milliseconds).

2) Composition containing a polymerizable compound: A sample was applied to a normally black mode PVA element in which the distance between two glass substrates (cell gap) was 3.2 μm and the rubbing direction was antiparallel. I put it in. The device was sealed using an adhesive that cures with ultraviolet light. This element was irradiated with ultraviolet rays of 60 mW/cm ² for 500 seconds while applying a voltage of 15 V. For ultraviolet irradiation, an EXECURE4000-D mercury xenon lamp manufactured by HOYA CANDEO OPTRONICS Co., Ltd. was used. A rectangular wave (60 Hz, 10 V, 0.5 seconds) was applied to this element. At this time, the element was irradiated with light from the perpendicular direction, and the amount of light transmitted through the element was measured. The transmittance was considered to be 100% when this amount of light was at its maximum, and the transmittance was considered to be 0% when this amount of light was at its minimum. The response time was expressed as the time required for the transmittance to change from 90% to 10% (fall time; milliseconds).

(13) Elastic constant (K11: splay elastic constant, K33: bend elastic constant; measured at 25°C; pN): For measurement, use an EC-1 elastic constant measuring instrument manufactured by Toyo Technica Co., Ltd. Using. A sample was placed in a vertically aligned cell in which the distance between two glass substrates (cell gap) was 20 μm. A charge of 20 volts to 0 volts was applied to this cell, and the capacitance and applied voltage were measured. Fitting the measured capacitance (C) and applied voltage (V) using equations (2.98) and (2.101) in "Liquid Crystal Device Handbook" (Nikkan Kogyo Shimbun), page 75. Then, the value of the elastic constant was obtained from equation (2.100).

(14) Specific resistance (ρ; measured at 25°C; Ωcm): 1.0 mL of the sample was poured into a container equipped with an electrode. A DC voltage (10V) was applied to this container, and the DC current was measured 10 seconds later. The specific resistance was calculated from the following formula. (Specific resistance) = {(voltage) x (capacitance of container)}/{(DC current) x (vacuum permittivity)}.

Examples of compositions are shown below. Component compounds were represented by symbols based on the definitions in Table 3 below. In Table 3, the configuration for 1,4-cyclohexylene is trans. The number in parentheses after the symbol corresponds to the compound number. The symbol (-) means other liquid crystal compounds. The ratio (percentage) of the liquid crystal compound is the mass percentage (mass %) based on the mass of the liquid crystal composition. Finally, the characteristic values of the composition were summarized.

ＮＩ＝７７．６℃；Ｔｃ＜－２０℃；Δｎ＝０．０９７；Δε＝－３．２；γ１＝１１０．６ｍＰａ・ｓ；τ＝６．６ｍｓ. [Comparative example 1]
5-BB-1 (-) 14%
3-H1OB (2F, 3F)-O2 (3-3) 8%
3-HHB(2F,3F)-O2 (3-8) 11%
2-HH1OB(2F,3F)-O2 (3-10) 6%
3-HH1OB(2F,3F)-O2 (3-10) 20%
3-HB(2F)B(2F,3F)-O2 (3-18) 4%
3-HH-2 (4-1) 25%
3-HHB-1 (4-4) 8%
3-BB-1 (-) 4%
Compound (2-1-1) was added to this composition at a rate of 0.3% by mass.

NI=77.6℃; Tc<-20℃;Δn=0.097;Δε=-3.2;γ1=110.6mPa・s; τ=6.6ms.

ＮＩ＝７３．７℃；Ｔｃ＜－２０℃；Δｎ＝０．０９７；Δε＝－３．１；γ１＝９３．０ｍＰａ・ｓ；τ＝５．９ｍｓ． [Example 1]
2-BB-1 (1) 14%
3-H1OB (2F, 3F)-O2 (3-3) 8%
3-HHB(2F,3F)-O2 (3-8) 11%
2-HH1OB(2F,3F)-O2 (3-10) 6%
3-HH1OB(2F,3F)-O2 (3-10) 20%
3-HB(2F)B(2F,3F)-O2 (3-18) 4%
3-HH-2 (4-1) 25%
3-HHB-1 (4-4) 8%
3-BB-1 (-) 4%
Compound (2-1-1) was added to this composition at a rate of 0.3% by mass.

NI=73.7°C; Tc<-20°C;Δn=0.097;Δε=-3.1; γ1=93.0 mPa·s; τ=5.9ms.

ＮＩ＝７２．９℃；Ｔｃ＜－２０℃；Δｎ＝０．１００；Δε＝－２．４；γ１＝９１．４ｍＰａ・ｓ；Ｋ３３＝１１．９ｐＮ；τ＝５．８ｍｓ． [Example 2]
2-BB-1 (1) 10%
3-HB(2F,3F)-O2 (3-1) 10%
2-HH1OB(2F,3F)-O2 (3-10) 14%
3-HH1OB(2F,3F)-O2 (3-10) 16%
3-HH-2 (4-1) 28%
3-HBB-2 (4-5) 19%
3-BB-1 (-) 3%
Compound (2-25-1) was added to this composition at a rate of 0.3% by mass.

NI=72.9°C; Tc<-20°C;Δn=0.100;Δε=-2.4; γ1=91.4 mPa·s; K33=11.9 pN; τ=5.8 ms.

ＮＩ＝７７．７℃；Ｔｃ＜－２０℃；Δｎ＝０．１１１；Δε＝－２．３；γ１＝９２．５ｍＰａ・ｓ；τ＝５．９ｍｓ. [Example 3]
2-BB-1 (1) 8%
2-H1OB (2F, 3F)-O2 (3-3) 3%
3-H1OB (2F, 3F)-O2 (3-3) 3%
V2-BB(2F,3F)-O2 (3-6) 5%
2-HHB(2F,3F)-O2 (3-8) 3%
3-HHB(2F,3F)-O2 (3-8) 4%
5-HHB(2F,3F)-O2 (3-8) 3%
V-HHB(2F,3F)-O1 (3-8) 3%
V-HHB(2F,3F)-O2 (3-8) 3%
V-HHB(2F,3F)-O4 (3-8) 2%
3-HH2B(2F,3F)-O2 (3-9) 4%
5-HH2B(2F,3F)-O2 (3-9) 4%
2-HBB (2F, 3F)-O2 (3-14) 3%
3-HBB(2F,3F)-O2 (3-14) 3%
3-H1OCro (7F, 8F)-5 (3-26) 3%
3-HH-V (4-1) 7%
3-HH-2 (4-1) 15%
V-HHB-1 (4-4) 4%
V2-HHB-1 (4-4) 4%
5-B(F)BB-2 (4-7) 3%
3-BB-1 (-) 3%
5-BB-1 (-) 3%
1V2-BB-1 (-) 3%
1O1-HBBH-5 (-) 4%
Compound (2-1-1) was added to this composition at a rate of 0.4% by mass.

NI=77.7℃; Tc<-20℃;Δn=0.111;Δε=-2.3;γ1=92.5mPa・s; τ=5.9ms.

ＮＩ＝７４．０℃；Ｔｃ＜－２０℃；Δｎ＝０．１１７；Δε＝－２．５；γ１＝９１．４ｍＰａ・ｓ；τ＝５．８ｍｓ． [Example 4]
2-BB-1 (1) 3%
V-HB(2F,3F)-O2 (3-1) 3%
V-chB(2F,3F)-O2 (3-5) 3%
2-BB (2F, 3F)-O2 (3-6) 3%
3-BB(2F,3F)-O2 (3-6) 3%
2O-BB (2F, 3F)-O2 (3-6) 3%
2O-B(2F)B(2F,3F)-O2 (3-7) 3%
V-HH1OB(2F,3F)-O2 (3-10) 3%
3-HchB(2F,3F)-O2 (3-12) 5%
5-HchB(2F,3F)-O2 (3-12) 5%
V2-HchB(2F,3F)-O2 (3-12) 4%
3-dhBB(2F,3F)-O2 (3-16) 5%
2-B2BB(2F,3F)-O2 (3-22) 3%
2-BB2B (2F, 3F)-3 (3-23) 3%
3-HH1OCro(7F,8F)-5 (3-27) 3%
3-HH-V (4-1) 10%
3-HH-V1 (4-1) 3%
3-HH-2 (4-1) 10%
5-HH-V (4-1) 3%
1V2-HH-2V1 (4-1) 3%
3-HHB-3 (4-4) 3%
V2-BB2B-1 (4-8) 3%
3-HHEBH-3 (4-10) 3%
3-BB-1 (-) 4%
V2-BB-1 (-) 6%
Compound (2-26-1) was added to this composition at a rate of 0.3% by mass.

NI=74.0°C; Tc<-20°C;Δn=0.117;Δε=-2.5; γ1=91.4 mPa·s; τ=5.8 ms.

ＮＩ＝８５．２℃；Ｔｃ＜－２０℃；Δｎ＝０．１１８；Δε＝－２．５；γ１＝９２．８ｍＰａ・ｓ；τ＝５．９ｍｓ． [Example 5]
2-BB-1 (1) 8%
5-HB(2F,3F)-O2 (3-1) 5%
3-DhB(2F,3F)-O2 (3-4) 5%
3-chB(2F,3F)-O2 (3-5) 5%
V-HHB(2F,3F)-O2 (3-8) 3%
V-HHB(2F,3F)-O4 (3-8) 3%
V-HH1OB(2F,3F)-O2 (3-10) 5%
3-HDhB(2F,3F)-O2 (3-13) 3%
4-HBB(2F,3F)-O2 (3-14) 3%
5-HBB(2F,3F)-O2 (3-14) 3%
3-BB(2F)B(2F,3F)-O2 (3-20) 3%
5-BB(2F)B(2F,3F)-O2 (3-20) 3%
V-HH2BB(2F,3F)-O2 (3-24) 3%
V-HH-V (4-1) 8%
V-HH-V1 (4-1) 8%
3-HH-V (4-1) 8%
1V2-HH-3 (4-1) 4%
3-HB-O2 (4-2) 3%
V-HHB-1 (4-4) 3%
3-HBB-2 (4-5) 3%
V-HBB-2 (4-5) 3%
3-HB(F)HH-2 (4-9) 3%
5-HB(F)BH-2 (4-11) 5%
Compound (2-24-1) was added to this composition at a rate of 0.2% by mass.

NI=85.2°C; Tc<-20°C;Δn=0.118;Δε=-2.5; γ1=92.8 mPa·s; τ=5.9ms.

ＮＩ＝８３．６℃；Ｔｃ＜－２０℃；Δｎ＝０．１１８；Δε＝－１．８；γ１＝９１．７ｍＰａ・ｓ；τ＝５．８ｍｓ． [Example 6]
2-BB-1 (1) 7%
3-H2B(2F,3F)-O2 (3-2) 5%
5-H2B(2F,3F)-O2 (3-2) 5%
3-HH1OB(2F,3F)-O2 (3-10) 8%
3-HHB(2F,3Cl)-O2 (3-11) 3%
5-HHB(2F,3Cl)-O2 (3-11) 3%
3-HchB(2F,3F)-O2 (3-12) 3%
5-HchB(2F,3F)-O2 (3-12) 3%
V-HBB (2F, 3F)-O2 (3-14) 3%
3-HBB(2F,3Cl)-O2 (3-15) 4%
5-HBB(2F,3Cl)-O2 (3-15) 3%
3-HH-V1 (4-1) 8%
3-HH-2 (4-1) 20%
5-HB-3 (4-2) 4%
3-HHB-1 (4-4) 3%
V-HBB-3 (4-5) 3%
1-BB(F)B-2V (4-6) 3%
2-BB(F)B-2V (4-6) 3%
3-BB(F)B-2V (4-6) 3%
V2-BB-1 (-) 3%
1V2-BB-1 (-) 3%
Compound (2-25-1) was added to this composition at a rate of 0.15% by mass.

NI=83.6°C; Tc<-20°C;Δn=0.118;Δε=-1.8; γ1=91.7 mPa·s; τ=5.8 ms.

ＮＩ＝７８．５℃；Ｔｃ＜－２０℃；Δｎ＝０．１０７；Δε＝－２．４；γ１＝９０．０ｍＰａ・ｓ；τ＝５．７ｍｓ． [Example 7]
2-BB-1 (1) 3%
3-HB(2F,3F)-O2 (3-1) 5%
5-HB(2F,3F)-O2 (3-1) 5%
3-BB(2F,3F)-O2 (3-6) 10%
3-HHB(2F,3F)-O2 (3-8) 5%
V-HHB(2F,3F)-O2 (3-8) 3%
3-HH2B(2F,3F)-O2 (3-9) 8%
2-HBB (2F, 3F)-O2 (3-14) 3%
3-HBB(2F,3F)-O2 (3-14) 6%
4-HBB(2F,3F)-O2 (3-14) 3%
2-BB (2F, 3F) B-3 (3-19) 3%
2-BB (2F, 3F) B-4 (3-19) 3%
3-HH-V (4-1) 31%
3-HH-VFF (4-1) 4%
3-HHEH-3 (4-3) 4%
5-HBB(F)B-2 (4-12) 2%
5-HBB(F)B-3 (4-12) 2%
Compound (2-1-1) was added to this composition at a rate of 0.4% by mass.

NI=78.5°C; Tc<-20°C;Δn=0.107;Δε=-2.4; γ1=90.0 mPa·s; τ=5.7ms.

ＮＩ＝７３．０℃；Ｔｃ＜－２０℃；Δｎ＝０．１０７；Δε＝－２．９；γ１＝９１．９ｍＰａ・ｓ；τ＝５．８ｍｓ． [Example 8]
2-BB-1 (1) 4%
2-H1OB (2F, 3F)-O2 (3-3) 6%
2-HH1OB(2F,3F)-O2 (3-10) 13%
3-HB (2F, 3F) B-O2 (3-17) 8%
3-HB(2F)B(2F,3F)-O2 (3-18) 4%
3-BB(F)B(2F,3F)-O2 (3-21) 3%
2-B2BB(2F,3F)-O2 (3-22) 3%
3-H2BBB(2F,3F)-O2 (3-25) 3%
5-HFLF4-3 (3-28) 3%
V-HH-V (4-1) 14%
V-HH-V1 (4-1) 5%
3-HH-2 (4-1) 6%
3-HH-4 (4-1) 3%
2-HH-5 (4-1) 3%
3-HB-O2 (4-2) 3%
5-HB-O2 (4-2) 3%
7-HB-1 (4-2) 4%
3-HHB-O1 (4-4) 3%
5-B(F)BB-3 (4-7) 3%
3-HHEBH-3 (4-10) 3%
V2-BB-1 (-) 3%
Compound (2-26-1) was added to this composition at a rate of 0.35% by mass.

NI=73.0°C; Tc<-20°C;Δn=0.107;Δε=-2.9; γ1=91.9 mPa·s; τ=5.8 ms.

ＮＩ＝７８．０℃；Ｔｃ＜－２０℃；Δｎ＝０．１０４；Δε＝－２．８；γ１＝９２．１ｍＰａ・ｓ；τ＝５．８ｍｓ． [Example 9]
2-BB-1 (1) 6%
V-HB(2F,3F)-O2 (3-1) 3%
3-HB(2F,3F)-O2 (3-1) 3%
2-H1OB (2F, 3F)-O2 (3-3) 5%
3-H1OB (2F, 3F)-O2 (3-3) 5%
3-BB(2F,3F)-O2 (3-6) 5%
5-BB(2F,3F)-O2 (3-6) 5%
3-HHB(2F,3F)-O2 (3-8) 4%
3-HH1OB(2F,3F)-O2 (3-10) 12%
V-HH-V (4-1) 2%
V-HH-V1 (4-1) 2%
3-HH-2 (4-1) 10%
3-HH-O1 (4-1) 4%
5-HH-O1 (4-1) 4%
3-HHEH-3 (4-3) 3%
3-HHEH-5 (4-3) 3%
3-HHB-O1 (4-4) 3%
2-BB(F)B-3 (4-6) 3%
2-BB(F)B-5 (4-6) 3%
3-HHEBH-3 (4-10) 3%
3-HHEBH-4 (4-10) 3%
3-HHEBH-5 (4-10) 3%
V2-BB-1 (-) 3%
1V2-BB-1 (-) 3%
Compound (2-25-1) was added to this composition at a rate of 0.2% by mass.

NI=78.0°C; Tc<-20°C;Δn=0.104;Δε=-2.8; γ1=92.1 mPa·s; τ=5.8 ms.

ＮＩ＝７４．０℃；Ｔｃ＜－２０℃；Δｎ＝０．１００；Δε＝－３．３；γ１＝１０７．９ｍＰａ・ｓ． [Example 10]
2-BB-1 (1) 6.5%
3-HB(2F,3F)-O2 (3-1) 15.5%
5-HB(2F,3F)-O2 (3-1) 11%
2O-B(2F)B(2F,3F)-O2 (3-7) 2%
2-HHB(2F,3F)-O2 (3-8) 4%
3-HHB(2F,3F)-O2 (3-8) 12%
2-HBB (2F, 3F)-O2 (3-14) 3%
3-HBB(2F,3F)-O2 (3-14) 8%
4-HBB(2F,3F)-O2 (3-14) 5%
3-HH-2 (4-1) 15%
3-HH-4 (4-1) 6%
3-HHB-1 (4-4) 10%
3-HBB-2 (4-5) 2%
Compound (2-26-1) was added to this composition at a rate of 0.3% by mass.

NI=74.0°C; Tc<-20°C;Δn=0.100;Δε=-3.3; γ1=107.9 mPa·s.

ＮＩ＝７３．５℃；Ｔｃ＜－２０℃；Δｎ＝０．１００；Δε＝－３．１；γ１＝１０３．７ｍＰａ・ｓ． [Example 11]
2-BB-1 (1) 7%
3-HB(2F,3F)-O2 (3-1) 15.5%
5-HB(2F,3F)-O2 (3-1) 11%
2O-B(2F)B(2F,3F)-O2 (3-7) 2%
2-HHB(2F,3F)-O2 (3-8) 5%
3-HHB(2F,3F)-O2 (3-8) 11%
2-HBB (2F, 3F)-O2 (3-14) 3%
3-HBB(2F,3F)-O2 (3-14) 8%
4-HBB(2F,3F)-O2 (3-14) 5%
3-HH-2 (4-1) 15%
3-HH-4 (4-1) 5.5%
3-HHB-1 (4-4) 10%
3-HBB-2 (4-5) 2%
Compound (2-26-1) was added to this composition at a rate of 0.3% by mass.

NI=73.5°C; Tc<-20°C;Δn=0.100;Δε=-3.1; γ1=103.7 mPa·s.

ＮＩ＝７５．１℃；Ｔｃ＜－２０℃；Δｎ＝０．０９９；Δε＝－３．１；γ１＝９９．４ｍＰａ・ｓ． [Example 12]
2-BB-1 (1) 6.5%
3-HB(2F,3F)-O2 (3-1) 15%
5-HB(2F,3F)-O2 (3-1) 14%
2-HHB(2F,3F)-O2 (3-8) 5%
3-HHB(2F,3F)-O2 (3-8) 8.5%
2-HBB (2F, 3F)-O2 (3-14) 2%
3-HBB(2F,3F)-O2 (3-14) 10%
5-HBB(2F,3F)-O2 (3-14) 4%
3-HH-2 (4-1) 15%
3-HH-4 (4-1) 5%
3-HHB-1 (4-4) 12%
3-HBB-2 (4-5) 3%
Compound (2-26-1) was added to this composition at a rate of 0.3% by mass.

NI=75.1°C; Tc<-20°C;Δn=0.099;Δε=-3.1; γ1=99.4 mPa·s.

ＮＩ＝７４．８℃；Ｔｃ＜－２０℃；Δｎ＝０．１００；Δε＝－３．２；γ１＝１０４．９ｍＰａ・ｓ． [Example 13]
2-BB-1 (1) 7.5%
3-HB(2F,3F)-O2 (3-1) 15%
5-HB(2F,3F)-O2 (3-1) 11%
2-HHB(2F,3F)-O2 (3-8) 5%
3-HHB(2F,3F)-O2 (3-8) 9.5%
3-HBB(2F,3F)-O2 (3-14) 9%
4-HBB (2F, 3F)-O2 (3-14) 8%
3-HB(2F)B(2F,3F)-O2 (3-18) 2%
3-HH-2 (4-1) 15%
3-HH-4 (4-1) 7%
3-HHB-1 (4-4) 9%
3-HBB-2 (4-5) 2%
Compound (2-26-1) was added to this composition at a rate of 0.3% by mass.

NI=74.8°C; Tc<-20°C;Δn=0.100;Δε=-3.2; γ1=104.9 mPa·s.

ＮＩ＝７４．１℃；Ｔｃ＜－２０℃；Δｎ＝０．０９９；Δε＝－３．１；γ１＝１０７．０ｍＰａ・ｓ． [Example 14]
2-BB-1 (1) 7%
3-HB(2F,3F)-O2 (3-1) 15.5%
5-HB(2F,3F)-O2 (3-1) 11%
2-HHB(2F,3F)-O2 (3-8) 6%
3-HHB(2F,3F)-O2 (3-8) 9%
2-HBB (2F, 3F)-O2 (3-14) 2%
3-HBB(2F,3F)-O2 (3-14) 10%
4-HBB (2F, 3F)-O2 (3-14) 7%
3-HH-2 (4-1) 15%
3-HH-4 (4-1) 7.5%
3-HHB-1 (4-4) 8%
3-HBB-2 (4-5) 2%
Compound (2-26-1) was added to this composition at a rate of 0.3% by mass.

NI=74.1°C; Tc<-20°C;Δn=0.099;Δε=-3.1; γ1=107.0 mPa·s.

ＮＩ＝７４．９℃；Ｔｃ＜－２０℃；Δｎ＝０．１００；Δε＝－３．３；γ１＝１１４．０ｍＰａ・ｓ． [Example 15]
2-BB-1 (1) 6.5%
3-HB(2F,3F)-O2 (3-1) 15.5%
5-HB(2F,3F)-O2 (3-1) 13%
2-HHB(2F,3F)-O2 (3-8) 4%
3-HHB(2F,3F)-O2 (3-8) 12%
2-HBB (2F, 3F)-O2 (3-14) 4%
3-HBB(2F,3F)-O2 (3-14) 8%
4-HBB(2F,3F)-O2 (3-14) 5%
3-HH-2 (4-1) 15%
3-HH-4 (4-1) 5%
3-HHB-1 (4-4) 10%
3-HBB-2 (4-5) 2%
Compound (2-26-1) was added to this composition at a rate of 0.3% by mass.

NI=74.9°C; Tc<-20°C;Δn=0.100;Δε=-3.3; γ1=114.0 mPa·s.

ＮＩ＝７４．６℃；Ｔｃ＜－２０℃；Δｎ＝０．０９９；Δε＝－３．１；γ１＝９６．１ｍＰａ・ｓ． [Example 16]
2-BB-1 (1) 9%
3-HB(2F,3F)-O2 (3-1) 14%
2O-B(2F)B(2F,3F)-O2 (3-7) 5%
3-HHB(2F,3F)-O1 (3-8) 5%
2-HHB(2F,3F)-O2 (3-8) 8%
3-HHB(2F,3F)-O2 (3-8) 8%
5-HHB(2F,3F)-O2 (3-8) 2.5%
2-HBB (2F, 3F)-O2 (3-14) 4%
3-HBB(2F,3F)-O2 (3-14) 9%
4-HBB(2F,3F)-O2 (3-14) 3%
3-HH-2 (4-1) 18%
3-HH-4 (4-1) 10.5%
3-HHB-1 (4-4) 4%
Compound (2-26-1) was added to this composition at a rate of 0.3% by mass.

NI=74.6°C; Tc<-20°C;Δn=0.099;Δε=-3.1; γ1=96.1 mPa·s.

ＮＩ＝７４．５℃；Ｔｃ＜－２０℃；Δｎ＝０．１００；Δε＝－３．４；γ１＝１００．１ｍＰａ・ｓ． [Example 17]
2-BB-1 (1) 11.5%
2-H1OB (2F, 3F)-O2 (3-3) 5.5%
3-H1OB (2F, 3F)-O2 (3-3) 10%
2-HHB(2F,3F)-O2 (3-8) 4%
3-HHB(2F,3F)-O2 (3-8) 12%
3-HH1OB(2F,3F)-O2 (3-10) 16%
3-HB(2F)B(2F,3F)-O2 (3-18) 4%
3-HH-2 (4-1) 22%
3-HH-4 (4-1) 2.5%
3-HBB-2 (4-5) 12.5%
Compound (2-26-1) was added to this composition at a rate of 0.3% by mass.

NI=74.5°C; Tc<-20°C;Δn=0.100;Δε=-3.4; γ1=100.1 mPa·s.

ＮＩ＝７２．９℃；Ｔｃ＜－２０℃；Δｎ＝０．１０２；Δε＝－３．１． [Example 18]
2-BB-1 (1) 10.5%
3-HB(2F,3F)-O2 (3-1) 14%
2O-B(2F)B(2F,3F)-O2 (3-7) 3%
2-HHB(2F,3F)-O2 (3-8) 7%
3-HHB(2F,3F)-O1 (3-8) 3%
3-HHB(2F,3F)-O2 (3-8) 10.5%
5-HHB(2F,3F)-O2 (3-8) 2%
2-HBB (2F, 3F)-O2 (3-14) 3%
3-HBB(2F,3F)-O2 (3-14) 12%
5-HBB(2F,3F)-O2 (3-14) 4%
3-HH-2 (4-1) 20%
3-HH-4 (4-1) 9%
3-HBB-2 (4-5) 2%
Compound (2-26-1) was added to this composition at a rate of 0.3% by mass.

NI=72.9°C; Tc<-20°C;Δn=0.102; Δε=-3.1.

ＮＩ＝７３．２℃；Ｔｃ＜－２０℃；Δｎ＝０．１０６；Δε＝－３．２． [Example 19]
2-BB-1 (1) 11%
3-HB(2F,3F)-O2 (3-1) 13%
2O-B(2F)B(2F,3F)-O2 (3-7) 4.5%
2-HHB(2F,3F)-O2 (3-8) 8%
3-HHB(2F,3F)-O1 (3-8) 2%
3-HHB(2F,3F)-O2 (3-8) 13%
2-HBB (2F, 3F)-O2 (3-14) 4%
3-HBB(2F,3F)-O2 (3-14) 10.5%
4-HBB(2F,3F)-O2 (3-14) 2%
5-HBB(2F,3F)-O2 (3-14) 2%
3-HH-2 (4-1) 18%
3-HH-4 (4-1) 9%
3-HBB-2 (4-5) 3%
Compound (2-26-1) was added to this composition at a rate of 0.35% by mass.

NI=73.2°C; Tc<-20°C;Δn=0.106; Δε=-3.2.

ＮＩ＝７４．２℃；Ｔｃ＜－２０℃；Δｎ＝０．１０６；Δε＝－３．０． [Example 20]
2-BB-1 (1) 11%
3-HB(2F,3F)-O2 (3-1) 13%
2O-B(2F)B(2F,3F)-O2 (3-7) 4%
2-HHB(2F,3F)-O2 (3-8) 8%
3-HHB(2F,3F)-O2 (3-8) 12.5%
2-HBB (2F, 3F)-O2 (3-14) 4%
3-HBB(2F,3F)-O2 (3-14) 10.5%
4-HBB(2F,3F)-O2 (3-14) 2%
5-HBB(2F,3F)-O2 (3-14) 2%
3-HH-2 (4-1) 18%
3-HH-4 (4-1) 9%
3-HHB-1 (4-4) 2%
3-HBB-2 (4-5) 4%
Compound (2-26-1) was added to this composition at a rate of 0.35% by mass.

NI=74.2°C; Tc<-20°C;Δn=0.106; Δε=-3.0.

ＮＩ＝７４．２℃；Ｔｃ＜－２０℃；Δｎ＝０．１０６；Δε＝－３．０． [Example 21]
2-BB-1 (1) 11%
3-HB(2F,3F)-O2 (3-1) 13%
2O-B(2F)B(2F,3F)-O2 (3-7) 4%
2-HHB(2F,3F)-O2 (3-8) 8%
3-HHB(2F,3F)-O2 (3-8) 12.5%
2-HBB (2F, 3F)-O2 (3-14) 4%
3-HBB(2F,3F)-O2 (3-14) 10.5%
4-HBB(2F,3F)-O2 (3-14) 2%
5-HBB(2F,3F)-O2 (3-14) 2%
3-HH-2 (4-1) 18%
3-HH-4 (4-1) 9%
3-HHB-1 (4-4) 2%
3-HBB-2 (4-5) 4%
Compound (2-26-1) was added to this composition at a rate of 0.33% by mass.

NI=74.2°C; Tc<-20°C;Δn=0.106; Δε=-3.0.

ＮＩ＝７４．２℃；Ｔｃ＜－２０℃；Δｎ＝０．１０６；Δε＝－３．０． [Example 22]
2-BB-1 (1) 11%
3-HB(2F,3F)-O2 (3-1) 13%
2O-B(2F)B(2F,3F)-O2 (3-7) 4%
2-HHB(2F,3F)-O2 (3-8) 8%
3-HHB(2F,3F)-O2 (3-8) 12.5%
2-HBB (2F, 3F)-O2 (3-14) 4%
3-HBB(2F,3F)-O2 (3-14) 10.5%
4-HBB(2F,3F)-O2 (3-14) 2%
5-HBB(2F,3F)-O2 (3-14) 2%
3-HH-2 (4-1) 18%
3-HH-4 (4-1) 9%
3-HHB-1 (4-4) 2%
3-HBB-2 (4-5) 4%
Compound (2-26-1) was added to this composition at a rate of 0.3% by mass.

NI=74.2°C; Tc<-20°C;Δn=0.106; Δε=-3.0.

ＮＩ＝７７．６℃；Ｔｃ＜－２０℃；Δｎ＝０．１００；Δε＝－２．８． [Example 23]
2-BB-1 (1) 11.5%
3-HB(2F,3F)-O2 (3-1) 14%
2O-B(2F)B(2F,3F)-O2 (3-7) 1.5%
2-HHB(2F,3F)-O2 (3-8) 8%
3-HHB(2F,3F)-O2 (3-8) 13%
5-HHB(2F,3F)-O2 (3-8) 4%
2-HBB (2F, 3F)-O2 (3-14) 4%
3-HBB(2F,3F)-O2 (3-14) 10%
3-HH-2 (4-1) 18%
3-HH-4 (4-1) 7.5%
3-HHB-1 (4-4) 8.5%
Compound (2-26-1) was added to this composition at a rate of 0.35% by mass.

NI=77.6°C; Tc<-20°C;Δn=0.100; Δε=-2.8.

ＮＩ＝７６．３℃；Ｔｃ＜－２０℃；Δｎ＝０．１０１；Δε＝－２．９． [Example 24]
2-BB-1 (1) 11%
3-HB(2F,3F)-O2 (3-1) 13.5%
2O-B(2F)B(2F,3F)-O2 (3-7) 3%
2-HHB(2F,3F)-O2 (3-8) 8%
3-HHB(2F,3F)-O2 (3-8) 13.5%
5-HHB(2F,3F)-O2 (3-8) 3%
2-HBB(2F,3F)-O2 (3-14) 4.5%
3-HBB(2F,3F)-O2 (3-14) 9%
3-HH-2 (4-1) 19%
3-HH-4 (4-1) 7%
3-HHB-1 (4-4) 8.5%
Compound (2-26-1) was added to this composition at a rate of 0.35% by mass.

NI=76.3°C; Tc<-20°C;Δn=0.101; Δε=-2.9.

ＮＩ＝７６．０℃；Δｎ＝０．１０９；Δε＝－３．０；γ１＝８７．０ｍＰａ・ｓ． [Example 25]
2-BB-1 (1) 2%
2O-B(2F)B(2F,3F)-O2 (3-7) 5%
2O-B(2F)B(2F,3F)-O4 (3-7) 7%
2-HHB(2F,3F)-O2 (3-8) 2%
3-HHB(2F,3F)-O2 (3-8) 7%
V-HBB (2F, 3F)-O2 (3-14) 8%
3-HBB(2F,3F)-O2 (3-14) 9%
4-HBB (2F, 3F)-O2 (3-14) 4%
3-HB(2F)B(2F,3F)-O2 (3-18) 9%
3-HH-V (4-1) 19%
3-HH-2 (4-1) 20%
3-HH-4 (4-1) 2%
3-HHB-1 (4-4) 2%
3-BB-1 (-) 4%
Compound (2-25-1) was added to this composition at a rate of 0.3% by mass.

NI=76.0°C; Δn=0.109; Δε=-3.0; γ1=87.0 mPa·s.

ＮＩ＝７５．３℃；Ｔｃ＜－２０℃；Δｎ＝０．１０４；Δε＝－３．０；γ１＝１０３．０ｍＰａ・ｓ． [Example 26]
2-BB-1 (1) 4%
3-HB(2F,3F)-O2 (3-1) 14%
2-HHB(2F,3F)-O2 (3-8) 7%
3-HHB(2F,3F)-O1 (3-8) 6%
3-HHB(2F,3F)-O2 (3-8) 8%
2-HBB (2F, 3F)-O2 (3-14) 2%
3-HBB(2F,3F)-O2 (3-14) 8%
4-HBB(2F,3F)-O2 (3-14) 5%
3-HB(2F)B(2F,3F)-O2 (3-18) 7%
3-HH-2 (4-1) 19%
3-HH-4 (4-1) 6%
3-HH-5 (4-1) 3.5%
3-HHB-1 (4-4) 2.5%
3-BB-1 (-) 4%
5-BB-1 (-) 4%
Compound (2-25-1) was added to this composition at a rate of 0.36% by mass.

NI=75.3°C; Tc<-20°C;Δn=0.104;Δε=-3.0; γ1=103.0 mPa·s.

ＮＩ＝７４．８℃；Ｔｃ＜－２０℃；Δｎ＝０．１０３；Δε＝－２．６；γ１＝９４．０ｍＰａ・ｓ． [Example 27]
2-BB-1 (1) 4.5%
3-HB(2F,3F)-O2 (3-1) 14%
2-HHB(2F,3F)-O2 (3-8) 6%
3-HHB(2F,3F)-O1 (3-8) 5%
3-HHB(2F,3F)-O2 (3-8) 8%
2-HBB (2F, 3F)-O2 (3-14) 2%
3-HBB(2F,3F)-O2 (3-14) 8%
4-HBB(2F,3F)-O2 (3-14) 5.5%
3-HB(2F)B(2F,3F)-O2 (3-18) 4%
3-HH-2 (4-1) 19%
3-HH-4 (4-1) 6%
3-HH-5 (4-1) 4%
3-HHB-1 (4-4) 3%
3-HBB-2 (4-5) 3%
3-BB-1 (-) 4%
5-BB-1 (-) 4%
Compound (2-25-1) was added to this composition at a rate of 0.36% by mass.

NI=74.8°C; Tc<-20°C;Δn=0.103;Δε=-2.6; γ1=94.0 mPa·s.

The response time (τ) of the composition of Comparative Example 1 was 6.6 ms. On the other hand, the response time (τ) of the composition of Example 1 was 5.9 ms. Thus, the composition of Example 1 had a shorter response time compared to the composition of Comparative Example. Therefore, it is concluded that the liquid crystal composition of the present invention has excellent properties.

The liquid crystal composition of the present invention has a high upper temperature limit, a low lower temperature limit, a small viscosity, a large optical anisotropy, a large negative dielectric anisotropy, a large specific resistance, high stability against ultraviolet rays, high stability against heat, etc. satisfies at least one of the characteristics, or has an appropriate balance with respect to at least two of the characteristics. The liquid crystal display element containing this composition has characteristics such as short response time, high voltage holding rate, low threshold voltage, large contrast ratio, and long life, so it can be used for liquid crystal monitors, liquid crystal televisions, etc. .

Claims (18)

It contains at least one compound selected from a compound represented by formula (1) as a first component and a polymerizable compound represented by formula (2) as a first additive, and has a nematic phase and a negative dielectric A liquid crystal composition having index anisotropy.

In formula (2), ring A and ring C are cyclohexyl, cyclohexenyl, phenyl, 1-naphthyl, 2-naphthyl, tetrahydropyran-2-yl, 1,3-dioxan-2-yl, pyrimidin-2-yl , or pyridin-2-yl, in which 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 fluorine or chlorine. Ring B may be substituted with alkyl having 1 to 12 carbon atoms; Ring B 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 which at least one hydrogen is fluorine, chlorine, alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, or at least one hydrogen is It may be substituted with a C1-C12 alkyl substituted with fluorine or chlorine; Z ¹ and Z ² are a single bond or a C1-C10 alkylene, and in this alkylene, at least one -CH ₂ - may be replaced with -O-, -CO-, -COO-, or -OCO-, and at least one -CH ₂ -CH ₂ - may be replaced with -CH=CH-, -C(CH ₃ )=CH-, -CH=C(CH ₃ )-, or -C(CH ₃ )=C(CH ₃ )-, in which at least one hydrogen is 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 - may be replaced with -O-, -COO-, -OCO-, or -OCOO-, and at least one -CH ₂ -CH ₂ - may be replaced with -CH=CH- or -C≡C-, in which at least one hydrogen may be replaced by fluorine or chlorine; a is 0, 1, or 2; b, c, and d is 0, 1, 2, 3, or 4; and the sum of b, c, and d is 1 or more. 2. The compound according to claim 1, wherein in formula (2), P ¹ , P ² and P ³ are groups selected from polymerizable groups represented by formulas (P-1) to (P-5). liquid crystal composition.

In 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 is replaced with fluorine or chlorine. is an alkyl group having 1 to 5 carbon atoms. The liquid crystal composition according to claim 1 or 2, containing at least one compound selected from compounds represented by formulas (2-1) to (2-29) as the first additive.

In formulas (2-1) to (2-29), 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 - may be replaced with -O-, -COO-, -OCO-, or -OCOO-, and at least one -CH ₂ -CH ₂ - is -CH=CH- or -C≡C- In these groups, at least one hydrogen may be replaced by fluorine or chlorine. P ⁴ , P ⁵ , and P ⁶ are polymerizable groups selected from the groups represented by formulas (P-1) to (P-3);

In formulas (P-1) to (P-3), M ¹ , M ² , and M ³ are hydrogen, fluorine, alkyl having 1 to 5 carbon atoms, or at least one hydrogen is replaced with fluorine or chlorine. is an alkyl group having 1 to 5 carbon atoms. 4. According to any one of claims 1 to 3, the proportion of the first component is in the range of 3% to 30% by weight, and the proportion of the first additive is in the range of 0.03% to 10% by weight. The liquid crystal composition described. The liquid crystal composition according to any one of claims 1 to 4, containing at least one compound selected from compounds represented by formula (3) as a second component.

In formula (3), R ¹ and R ² are hydrogen, alkyl having 1 to 12 carbon atoms, alkoxy having 1 to 12 carbon atoms, alkenyl having 2 to 12 carbon atoms, alkenyloxy having 2 to 12 carbon atoms, or at least is an alkyl having 1 to 12 carbon atoms in which one hydrogen is replaced with fluorine or chlorine; Ring D and Ring F are 1,4-cyclohexylene, 1,4-cyclohexenylene, tetrahydropyran-2,5- diyl, 1,4-phenylene, 1,4-phenylene with at least one hydrogen replaced by fluorine or chlorine, naphthalene-2,6-diyl, naphthalene-2 with at least one hydrogen replaced with fluorine or chlorine, 6-diyl, chroman-2,6-diyl, or chroman-2,6-diyl in which at least one hydrogen is replaced with fluorine or chlorine; Ring E 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-difluorodibenzothiophene-3 ,7-diyl, or 1,1,6,7-tetrafluoroindan-2,5-diyl; Z ³ and Z ⁴ are a single bond, ethylene, vinylene, carbonyloxy, or methyleneoxy; e is 0, 1, 2, or 3; f is 0 or 1; and the sum of e and f is 3 or less. The liquid crystal composition according to any one of claims 1 to 5, containing at least one compound selected from compounds represented by formulas (3-1) to (3-35) as a second component. .

In formulas (3-1) to (3-35), R ¹ and R ² are hydrogen, alkyl having 1 to 12 carbon atoms, alkoxy having 1 to 12 carbon atoms, alkenyl having 2 to 12 carbon atoms, and 2 to 12 alkenyloxy, or C1 to C12 alkyl in which at least one hydrogen is replaced with fluorine or chlorine. The liquid crystal composition according to claim 5 or 6, wherein the proportion of the second component is in the range of 10% by mass to 80% by mass. The liquid crystal composition according to any one of claims 1 to 7, containing at least one compound selected from compounds represented by formula (4) as a third component.

In formula (4), R ³ and R ⁴ are alkyl having 1 to 12 carbon atoms, alkoxy having 1 to 12 carbon atoms, alkenyl having 2 to 12 carbon atoms, and carbon in which at least one hydrogen is replaced with fluorine or chlorine. Alkyl having 1 to 12 carbon atoms, or alkenyl having 2 to 12 carbon atoms in which at least one hydrogen is replaced with fluorine or chlorine; Ring G and Ring I 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; g is 1; 2, or 3; when g is 1, ring G is 1,4-cyclohexylene. The liquid crystal composition according to any one of claims 1 to 8, containing at least one compound selected from compounds represented by formulas (4-1) to (4-12) as a third component. .

In formulas (4-1) to (4-12), R ³ and R ⁴ are alkyl having 1 to 12 carbon atoms, alkoxy having 1 to 12 carbon atoms, alkenyl having 2 to 12 carbon atoms, and at least one hydrogen is an alkyl having 1 to 12 carbon atoms in which is replaced with fluorine or chlorine, or alkenyl having 2 to 12 carbon atoms in which at least one hydrogen is replaced with fluorine or chlorine. The liquid crystal composition according to claim 8 or 9, wherein the proportion of the third component is in the range of 10% by mass to 80% by mass. The liquid crystal composition according to any one of claims 1 to 10, which does not contain a compound having a cyclic alkyl. According to any one of claims 1 to 11, the additive does not contain an additive having a partial structure represented by formula (A-1) and an additive having a partial structure represented by formula (A-2). liquid crystal composition.

The liquid crystal composition according to any one of claims 1 to 12, used in a polymer-supported alignment type liquid crystal display element. A liquid crystal display element comprising the liquid crystal composition according to any one of claims 1 to 12. 15. The liquid crystal display element according to claim 14, wherein the operation mode of the liquid crystal display element is IPS mode, VA mode, FFS mode, or FPA mode, and the driving method of the liquid crystal display element is an active matrix method. A polymer-supported alignment type liquid crystal display element containing the liquid crystal composition according to any one of claims 1 to 12, in which a polymerizable compound in the liquid crystal composition is polymerized. Use of the liquid crystal composition according to any one of claims 1 to 12 in a liquid crystal display element. Use of the liquid crystal composition according to any one of claims 1 to 12 in a polymer supported alignment type liquid crystal display element.