JP2023034229A - liquid crystal display element - Google Patents

Abstract

To provide a liquid crystal display element which has a high contrast ratio.SOLUTION: A liquid crystal display element is provided, including an electrode group formed in one or both of a pair of substrates which are arranged face to face, a plurality of active elements connected to the electrode group, liquid crystal alignment films formed on the surfaces of the pair of substrates which face each other, and a liquid crystal composition which has negative dielectric anisotropy and is held between the pair of substrates, wherein the liquid crystal alignment film is formed from a liquid crystal alignment agent which includes a polymer obtained by polymerizing at least one compound selected as diamine from diamine compounds expressed in formula (1) and a raw material composition which contains a tetracarboxylic acid dianhydride. In formula (1), R1 and R2 represent hydrogen or the like, R1 and R2 together may be replaced or may form methylene, X represents halogen or the like, and n is 0, 1, 2, 3 or 4.SELECTED DRAWING: None

Description

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

In liquid crystal display elements, classification based on the operation mode of liquid crystal molecules is PC (phase change), TN (twisted nematic), STN (super twisted nematic), ECB (electrically controlled birefringence), OCB (optically compensated bend), IPS. (in-plane switching), VA (vertical alignment), FFS (fringe field switching), FPA (field-induced photo-reactive alignment), and the like. Classification based on the drive system 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), and the like. TFT classifications are amorphous silicon and polycrystalline silicon. The latter is classified into a high temperature type and a low temperature type depending on the manufacturing process. Classifications based on light source are reflective, which uses natural light, transmissive, which uses backlight, and transflective, which 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 device with good properties can be obtained. The relationships between these properties are summarized in Table 1 below. The properties of the composition are further described based on commercially available AM devices. The temperature range of the nematic phase is related to the usable temperature range of the device. The preferred upper limit temperature of the nematic phase is about 70°C or higher, and the preferred lower limit temperature of the nematic phase is about -10°C or lower. The viscosity of the composition is related to the response time of the device. A short response time is desirable for displaying moving images on the device. A shorter response time, even 1 millisecond, is desirable. Therefore, low viscosity in the composition is preferred. A low viscosity at low temperature is more preferred.

The optical anisotropy of the composition is related to the contrast ratio of the device. Depending on the mode of the device, a large optical anisotropy or a small optical anisotropy, ie a suitable optical anisotropy is required. The product (Δn×d) of the optical anisotropy (Δn) of the composition and the cell gap (d) of the device is designed to maximize the contrast ratio. Appropriate values for the product depend on the type of operating mode. This value ranges from about 0.30 μm to about 0.40 μm for VA mode devices and from about 0.20 μm to about 0.30 μm for IPS or FFS mode devices. In these cases, a composition with a large optical anisotropy is preferred for devices with a small cell gap. A large dielectric anisotropy in the composition contributes to a low threshold voltage, a small power consumption and a large contrast ratio in the device. Therefore, a large dielectric 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 with high resistivity in the initial stage are preferred. Compositions that have a high resistivity after prolonged use are preferred. The stability of the composition to 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 a general-purpose liquid crystal display device, vertical alignment of liquid crystal molecules is achieved by a specific polyimide alignment film. In a polymer supported alignment (PSA) type liquid crystal display device, a polymer is combined with an alignment film. First, a composition to which a small amount of polymerizable compound is added is injected into the device. The composition is then irradiated with ultraviolet light while a voltage is applied across the substrates of the device. The polymerizable compound polymerizes to produce a polymer network in the composition. In this composition, the orientation of the liquid crystal molecules can be controlled by the polymer, thereby shortening the response time of the device and improving image sticking. Such effects of polymers can be expected in devices with modes such as TN, ECB, OCB, IPS, VA, FFS and FPA.

A composition having a positive dielectric anisotropy is used in an AM device having a TN mode. A composition having a negative dielectric anisotropy is used in an AM device having a VA mode. A composition having positive or negative dielectric anisotropy is used in an AM device having an IPS mode or FFS mode. Compositions having positive or negative dielectric anisotropy are used in polymer sustained alignment (PSA) type AM devices. An example of a liquid crystal composition having negative dielectric anisotropy is disclosed in Patent Document 1 below.

In order to provide these liquid crystal display elements with uniform display characteristics, it is necessary to control the alignment of the liquid crystal molecules. The liquid crystal alignment film plays such a role. The liquid crystal alignment film is one of the important factors that affect the display quality of the liquid crystal display element, and the role of the liquid crystal alignment film is becoming more important year by year as the quality of the display element is improved.

At present, a solution (varnish) obtained by dissolving a polyamic acid, a soluble polyimide or a polyamic acid ester in an organic solvent is mainly used for forming a liquid crystal alignment film. In order to form a liquid crystal alignment film with these varnishes, the varnish is applied to a substrate, and then the coating film is solidified by heating or the like to form various liquid crystal alignment films. apply.
Specifically, for example, as a method of forming a polyimide film for forming a liquid crystal alignment film on a substrate, a liquid crystal alignment agent containing polyamic acid, which is a polyimide precursor, is applied onto the substrate, and then baked to form a polyimide. A liquid crystal containing an imide group-containing polyamic acid obtained from an imide group-containing diamine, in addition to a method of forming a film or a method of applying a liquid crystal aligning agent containing a solvent-soluble polyimide on a substrate and removing the solvent to form a polyimide film A method of coating an alignment agent on a substrate is known (see Patent Document 2, for example).
In addition, as the alignment treatment method, there is a rubbing method in which the surface of the alignment film is rubbed with a cloth to adjust the direction of the polymer molecules, and a method in which the alignment film is irradiated with linearly polarized ultraviolet rays to photoisomerize or dimerize the polymer molecules. A photo-orientation method is known in which a photochemical change such as anisotropy is caused to impart anisotropy to a film. Of these, the photo-alignment method has higher uniformity of alignment than the rubbing method, and since it is a non-contact alignment treatment method, it does not damage the film and prevents display defects of liquid crystal display elements such as dust generation and static electricity. There is an advantage that the cause of occurrence can be reduced.
As one of the above photo-alignment methods, a decomposition-type photo-alignment method is known. In this decomposition-type photo-alignment method, for example, by irradiating a polyimide film with polarized ultraviolet rays, anisotropic decomposition is caused by utilizing the polarization direction dependence of the ultraviolet absorption of the molecular structure, and the remaining undecomposed This is a method of aligning liquid crystals with polyimide (see, for example, Patent Document 3).

International Publication No. 2012-053323 JP-A-9-185064 JP-A-9-297313

SUMMARY OF THE INVENTION An object of the present invention is to provide a liquid crystal display device having a high contrast ratio. Another object is to provide a liquid crystal display device having a proper balance between at least two properties such as high contrast ratio, short response time, large voltage holding ratio, low threshold voltage and long life. .

式（１）において、Ｒ^１およびＲ^２は、水素、ハロゲン、炭素数１から６のアルキル、炭素数１から６のハロアルキル、または炭素数１から６のアルコキシであり、Ｒ^１とＲ^２は一体となって、置換されてもよいメチレンを形成してもよく；Ｘは、ハロゲン、炭素数１から６のアルキル、炭素数１から６のハロアルキル、または炭素数１から６のアルコキシであり；ｎは、０、１、２、３、または４である。 The present invention comprises: an electrode group formed on one or both of a pair of substrates arranged to face each other; a plurality of active elements connected to the electrode group; A liquid crystal display element comprising the formed liquid crystal alignment film and a liquid crystal composition having a negative dielectric anisotropy sandwiched between the pair of substrates, wherein the liquid crystal alignment film comprises a diamine represented by the formula (1 ) is a liquid crystal alignment film formed from a liquid crystal alignment agent containing a polymer obtained by polymerizing a raw material composition containing at least one compound selected from diamine compounds represented by and tetracarboxylic dianhydrides, It relates to a liquid crystal display element.

In formula (1), R ¹ and R ² are hydrogen, halogen, alkyl having 1 to 6 carbon atoms, haloalkyl having 1 to 6 carbon atoms, or alkoxy having 1 to 6 carbon atoms, and R ¹ and R ² are may be taken together to form optionally substituted methylene; X is halogen, alkyl of 1 to 6 carbons, haloalkyl of 1 to 6 carbons, or alkoxy of 1 to 6 carbons; n is 0, 1, 2, 3, or 4;

An advantage of the present invention is to provide a liquid crystal display device with a high contrast ratio. Another advantage is to provide a liquid crystal display device having a proper balance between at least two properties such as high contrast ratio, short response time, large voltage holding ratio, low threshold voltage and long life. .

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" means a compound having a liquid crystal phase such as a nematic phase or a smectic phase, or a compound having no liquid crystal phase, but for the purpose of adjusting the properties of the nematic phase such as temperature range, viscosity, dielectric It is a general term for compounds mixed in the 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 forming a polymer in the composition. Alkenyl-containing liquid crystalline compounds are not classified as polymerizable in that sense.

A liquid crystal composition is prepared by mixing a plurality of liquid crystalline compounds. Additives such as optically active compounds and polymerizable compounds are added to the liquid crystal composition as necessary. The ratio of the liquid crystalline compound, even when the additive is added, is represented by mass percentage (% by mass) based on the mass of the liquid crystal composition containing no additive. The proportion of the additive is represented by mass percentage (% by mass) based on the mass of the liquid crystal composition containing no additive. That is, the ratio of the liquid crystalline compound and the additive is calculated based on the total mass of the liquid crystalline compound. Mass parts per million (ppm) are sometimes used. Proportions of polymerization initiators and polymerization inhibitors are exceptionally expressed on the basis of the weight of the polymerizable compound.

"The upper limit temperature of the nematic phase" may be abbreviated as "the upper limit temperature". "Lower limit temperature of nematic phase" may be abbreviated as "lower limit temperature". The expression "increase the dielectric anisotropy" means that the value increases positively in the case of a composition with a positive dielectric anisotropy, and in a composition with a negative dielectric anisotropy. When it is a thing, it means that its value increases negatively. "Large voltage holding ratio" means that the element has a large voltage holding ratio at the initial stage not only at room temperature but also at temperatures close to the upper limit temperature, and after long-term use, the voltage is large not only at room temperature but also at temperatures close to the upper limit temperature. It means having a retention rate. Properties of compositions and devices may be examined by aging tests.

"Liquid crystal aligning agent" is a liquid crystal aligning agent capable of imparting anisotropy by irradiating polarized ultraviolet rays when the film is formed on a substrate, and in the present specification, simply "liquid crystal aligning agent". It is also called "liquid crystal aligning agent for photo-alignment". In the present invention, "tetracarboxylic dianhydrides" refer to tetracarboxylic dianhydrides, tetracarboxylic diesters or tetracarboxylic diester dihalides. In the present invention, diamines and dihydrazides are sometimes referred to as "diamines".

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。

The above compound (1z) will be described as an example. In formula (1z), the symbols α and β surrounded by hexagons correspond to ring α and ring β, respectively, and represent rings such as six-membered rings and condensed rings. When the index 'x' is 2, there are two rings α. Two groups represented by two rings α may be the same or different. This rule applies to any two rings α when the index 'x' is greater than two. This rule also applies to other symbols, such as the bonding group Z. A slash 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 substituted substituents. When the index 'y' is 0, there is no such replacement. When the subscript 'y' is 2 or more, there are multiple substituents (-Sp-P) on the ring β. In this case as well, the "can be the same or can be different" rule applies. This rule also applies when the symbol Ra is used for a plurality of 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 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 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' is arbitrary. The expression "at least one 'A' may be replaced with 'B'" means that when the number of 'A' is 1, the position of 'A' is arbitrary, and the number of 'A' is 2 When there are more than one, their positions can be chosen without restriction. The expression "at least one -CH ₂ - may be replaced with -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, adjacent -CH ₂ - is not replaced by -O-. This is because —O—O—CH ₂ — (peroxide) is produced by this replacement.

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。 Alkyl in the liquid crystalline compound is linear or branched and does not include cyclic alkyl. Linear alkyls are preferred over branched alkyls. The same applies to terminal groups such as alkoxy and alkenyl. The configuration of 1,4-cyclohexylene is preferably trans rather than cis in order to increase the maximum temperature. Since 2-fluoro-1,4-phenylene is left-right asymmetric, there is a leftward (L) and a rightward (R).

The same is true for divalent groups such as tetrahydropyran-2,5-diyl. The same is true for linking groups such as carbonyloxy (-COO- or -OCO-).

The present invention includes the following items.

式（１）において、Ｒ^１およびＲ^２は、水素、ハロゲン、炭素数１から６のアルキル、炭素数１から６のハロアルキル、または炭素数１から６のアルコキシであり、Ｒ^１とＲ^２は一体となって、置換されてもよいメチレンを形成してもよく；Ｘは、ハロゲン、炭素数１から６のアルキル、炭素数１から６のハロアルキル、または炭素数１から６のアルコキシであり；ｎは、０、１、２、３、または４である。 Item 1. A group of electrodes formed on one or both of a pair of substrates arranged to face each other, a plurality of active elements connected to the group of electrodes, and a liquid crystal formed on the facing surfaces of each of the pair of substrates. A liquid crystal display element comprising an alignment film and a liquid crystal composition having negative dielectric anisotropy sandwiched between the pair of substrates, wherein the liquid crystal alignment film is represented by formula (1) as a diamine. A liquid crystal aligning film formed from a liquid crystal aligning agent containing a polymer obtained by polymerizing a raw material composition containing at least one compound selected from diamine compounds and tetracarboxylic dianhydrides, a liquid crystal display element.

In formula (1), R ¹ and R ² are hydrogen, halogen, alkyl having 1 to 6 carbon atoms, haloalkyl having 1 to 6 carbon atoms, or alkoxy having 1 to 6 carbon atoms, and R ¹ and R ² are may be taken together to form optionally substituted methylene; X is halogen, alkyl of 1 to 6 carbons, haloalkyl of 1 to 6 carbons, or alkoxy of 1 to 6 carbons; n is 0, 1, 2, 3, or 4;

式（１－１）において、Ｒ^１およびＲ^２は、水素、ハロゲン、炭素数１から６のアルキル、炭素数１から６のハロアルキル、または炭素数１から６のアルコキシであり、Ｒ^１とＲ^２は一体となって、置換されてもよいメチレンを形成してもよく；Ｘは、ハロゲン、炭素数１から６のアルキル、炭素数１から６のハロアルキル、または炭素数１から６のアルコキシであり；ｎは、０、１、２、３、または４である。 Section 2. The liquid crystal alignment film contains a polymer obtained by polymerizing a raw material composition containing at least one compound selected from diamine compounds represented by formula (1-1) as diamines and tetracarboxylic dianhydrides. Item 1. The liquid crystal display element according to Item 1, which is a liquid crystal alignment film formed from a liquid crystal alignment agent.

In formula (1-1), R ¹ and R ² are hydrogen, halogen, alkyl having 1 to 6 carbon atoms, haloalkyl having 1 to 6 carbon atoms, or alkoxy having 1 to 6 carbon atoms, and R ¹ and R ² may be taken together to form optionally substituted methylene; X is halogen, alkyl having 1 to 6 carbon atoms, haloalkyl having 1 to 6 carbon atoms, or alkoxy having 1 to 6 carbon atoms; Yes; n is 0, 1, 2, 3, or 4.

式（１－１）において、Ｒ^１およびＲ^２は、水素、ハロゲン、炭素数１から６のアルキル、炭素数１から６のハロアルキル、または炭素数１から６のアルコキシであり、Ｒ^１とＲ^２は一体となって、置換されてもよいメチレンを形成してもよく；Ｘは、ハロゲン、炭素数１から６のアルキル、炭素数１から６のハロアルキル、または炭素数１から６のアルコキシであり；ｎは、０である。 Item 3. The liquid crystal alignment film contains a polymer obtained by polymerizing a raw material composition containing at least one compound selected from diamine compounds represented by formula (1-1) as diamines and tetracarboxylic dianhydrides. 3. The liquid crystal display element according to item 2, which is a liquid crystal alignment film formed from a liquid crystal alignment agent.

In formula (1-1), R ¹ and R ² are hydrogen, halogen, alkyl having 1 to 6 carbon atoms, haloalkyl having 1 to 6 carbon atoms, or alkoxy having 1 to 6 carbon atoms, and R ¹ and R ² may be taken together to form optionally substituted methylene; X is halogen, alkyl having 1 to 6 carbon atoms, haloalkyl having 1 to 6 carbon atoms, or alkoxy having 1 to 6 carbon atoms; Yes; n is 0.

式（２）において、Ｒ^３およびＲ^４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Ａおよび環Ｃ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Ｂ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^１およびＺ^２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；ａは０、１、２、または３であり、ｂは０または１であり；そしてａとｂとの和は３以下である。 Section 4. 4. The liquid crystal display element according to any one of items 1 to 3, wherein the liquid crystal composition contains, as component A, at least one compound selected from compounds represented by formula (2).

In formula (2), R ³ and R ⁴ 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 C 1-12 alkyl in which one hydrogen is replaced by fluorine or chlorine; ring A and ring C are 1,4-cyclohexylene, 1,4-cyclohexenylene, tetrahydropyran-2,5- diyl, 1,4-phenylene, 1,4-phenylene in which at least one hydrogen is replaced by fluorine or chlorine, naphthalene-2,6-diyl, naphthalene-2 in which at least one hydrogen is replaced by fluorine or chlorine, 6-diyl, chroman-2,6-diyl, or chroman-2,6-diyl in which at least one hydrogen is replaced by fluorine or chlorine; Ring B is 2,3-difluoro-1,4-phenylene , 2-chloro-3-fluoro-1,4-phenylene, 2,3-difluoro-5-methyl-1,4-phenylene, 3,4,5-trifluoronaphthalene-2,6-diyl, 7,8 -difluorochroman-2,6-diyl, 3,4,5,6-tetrafluorofluorene-2,7-diyl, 4,6-difluorodibenzofuran-3,7-diyl, 4,6-difluorodibenzothiophene-3 ,7-diyl, or 1,1,6,7-tetrafluoroindan-2,5-diyl; Z ¹ and Z ² are a single bond, ethylene, vinylene, methyleneoxy, or carbonyloxy; is 0, 1, 2, or 3, b is 0 or 1; and the sum of a and b is 3 or less.

式（２－１）から式（２－３５）において、Ｒ^３およびＲ^４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 5. 5. The liquid crystal composition according to any one of items 1 to 4, wherein the component A contains at least one compound selected from compounds represented by formulas (2-1) to (2-35). Liquid crystal display element.

In formulas (2-1) to (2-35), R ³ and R ⁴ 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 alkyl having 1 to 12 carbon atoms in which at least one hydrogen is replaced with fluorine or chlorine.

Item 6. Item 6. The liquid crystal display element according to item 4 or 5, wherein the proportion of component A is in the range of 5% by mass to 95% by mass.

式（３）において、Ｒ^５およびＲ^６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Ｄおよび環Ｅ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^３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；ｃは、１、２、または３である。 Item 7. 7. The liquid crystal display element according to any one of items 1 to 6, wherein the liquid crystal composition contains, as component B, at least one compound selected from compounds represented by formula (3).

In formula (3), R ⁵ and R ⁶ are alkyl having 1 to 12 carbon atoms, alkoxy having 1 to 12 carbon atoms, alkenyl having 2 to 12 carbon atoms, 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 D and ring E are 1,4-cyclohexylene, 1,4-phenylene, 2-fluoro-1,4-phenylene, or 2,5-difluoro-1,4-phenylene; Z ³ is a single bond, ethylene, vinylene, methyleneoxy, or carbonyloxy; c is 1, 2 or 3.

式（３－１）から式（３－１４）において、Ｒ^５およびＲ^６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 8. 8. The liquid crystal composition according to any one of items 1 to 7, wherein the component B contains at least one compound selected from compounds represented by formulas (3-1) to (3-14). Liquid crystal display element.

In formulas (3-1) to (3-14), R ⁵ and R ⁶ 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 alkyl of 1 to 12 carbon atoms in which is replaced by fluorine or chlorine, or alkenyl of 2 to 12 carbon atoms in which at least one hydrogen is replaced by fluorine or chlorine.

Item 9. Item 9. The liquid crystal display element according to item 7 or 8, wherein the proportion of component B is in the range of 5% by mass to 95% by mass.

式（４）において、環Ｉおよび環Ｋ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Ｊ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^６およびＺ^７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_２ＣＨ_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からＰ^３は、重合性基であり；Ｓｐ^１から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_２ＣＨ_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；ｆは、０、１、または２であり；ｇ、ｈ、およびｉは、０、１、２、３、または４であり；そしてｇ、ｈ、およびｉの和は、１以上である。 Item 10. 10. The liquid crystal display element according to any one of items 1 to 9, wherein the liquid crystal composition contains, as additive X, at least one compound selected from polymerizable compounds represented by formula (4).

In formula (4), ring I and ring K are cyclohexyl, cyclohexenyl, phenyl, 1-naphthyl, 2-naphthyl, tetrahydropyran-2-yl, 1,3-dioxan-2-yl, pyrimidin-2-yl , or pyridin-2-yl, wherein in these rings at least one hydrogen is fluorine, chlorine, alkyl of 1 to 12 carbons, alkoxy of 1 to 12 carbons, or at least one hydrogen is fluorine or chlorine ring J 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 may be substituted with alkyl having 1 to 12 carbon atoms substituted with fluorine or chlorine; Z ⁶ and Z ⁷ are a single bond or alkylene having 1 to 10 carbon atoms, in which at least one —CH _2- may be replaced by -O-, -CO-, -COO- or -OCO- and at least one -CH ₂ CH ₂ - is -CH=CH-, -C(CH ₃ ) =CH-, -CH=C(CH ₃ )-, or -C(CH ₃ )=C(CH ₃ )- in which at least one hydrogen is fluorine or chlorine; P ¹ to P ³ are polymerizable groups; Sp ¹ to Sp ³ are a single bond or alkylene having 1 to 10 carbon atoms, in which at least one —CH ₂ — may be replaced with -O-, -COO-, -OCO-, or -OCOO- and at least one -CH ₂ CH ₂ - is replaced with -CH=CH- or -C≡C- in these groups at least one hydrogen may be replaced by fluorine or chlorine; f is 0, 1, or 2; g, h, and i are 0, 1, 2, 3, or 4; and the sum of g, h, and i is 1 or greater.

式（Ｐ－１）から式（Ｐ－５）において、Ｍ^１から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 11. 11. The liquid crystal display element according to Item 10, wherein P ¹ to P ³ in formula (4) are groups selected from polymerizable groups represented by formulas (P-1) to (P-5).

In formulas (P-1) to (P-5), M ¹ to M ³ are hydrogen, fluorine, alkyl having 1 to 5 carbon atoms, or C 1 in which at least one hydrogen is replaced with fluorine or chlorine is an alkyl of from to 5;

式（４－１）から式（４－２９）において、Ｓｐ^１から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_２ＣＨ_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；Ｐ^４から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から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 12. Any one of items 1 to 11, wherein the liquid crystal composition contains, as additive X, at least one compound selected from polymerizable compounds represented by formulas (4-1) to (4-29). 3. The liquid crystal display element according to .

In formulas (4-1) to (4-29), Sp ¹ to Sp ³ are a single bond or alkylene having 1 to 10 carbon atoms, and in this alkylene, at least one —CH ₂ — is —O may be replaced by -, -COO-, -OCO-, or -OCOO-, at least one -CH ₂ CH ₂ - may be replaced by -CH=CH- or -C≡C-; In these groups, at least one hydrogen may be replaced by fluorine or chlorine; P ⁴ to P ⁶ are selected from groups represented by formulas (P-1) to (P-3) is a polymerizable group;

In formulas (P-1) to (P-3), M ¹ to M ³ are hydrogen, fluorine, alkyl having 1 to 5 carbon atoms, or C 1 in which at least one hydrogen is replaced by fluorine or chlorine is an alkyl of from to 5;

Item 13. 13. The liquid crystal display element according to any one of Items 10 to 12, wherein the proportion of the additive X is in the range of 0.03% by mass to 10% by mass.

Item 14. 14. The liquid crystal display element according to any one of items 1 to 13, wherein the operation mode is IPS mode, VA mode, FFS mode, or FPA mode, and the driving method is an active matrix method.

The liquid crystal display device of the present invention will be described in the following order. First, the configuration of the liquid crystal display element will be described. Secondly, the configuration of the liquid crystal alignment film will be described. Thirdly, a method for manufacturing a liquid crystal alignment film will be described. Fourthly, the configuration of the liquid crystal composition will be described. Fifth, the main properties of the component compounds of the liquid crystal composition and the main effects of these compounds on liquid crystal compositions and devices are described. Sixthly, the combination of the component compounds in the liquid crystal composition, preferred proportions, and grounds thereof will be explained. Seventh, preferred forms of the component compounds of the liquid crystal composition will be described. Eighth, preferable component compounds of the liquid crystal composition are shown. Ninth, additives that may be added to the liquid crystal composition will be described. Tenth, a method for synthesizing the compound will be described. Finally, applications of the liquid crystal composition will be explained.

First, the configuration of the liquid crystal display element will be described. A liquid crystal display element of the present invention comprises: an electrode group formed on one or both of a pair of substrates arranged to face each other; a plurality of active elements connected to the electrode group; and a liquid crystal composition having negative dielectric anisotropy sandwiched between the pair of substrates. The liquid crystal alignment film used in the liquid crystal display element of the present invention comprises a raw material composition containing at least one compound selected from diamine compounds represented by formula (1) as diamines and tetracarboxylic dianhydrides. It is a liquid crystal alignment film formed from a liquid crystal alignment agent containing a polymer formed by polymerization. The liquid crystal display device of the present invention can realize excellent display quality due to its high contrast ratio.

The electrode is not particularly limited as long as it is an electrode formed on one surface of the substrate. Such electrodes include, for example, ITO and metal vapor deposition films. Also, the electrode may be formed on the entire surface of one surface of the substrate, or may be formed in a desired patterned shape, for example. The desired shape of the electrode includes, for example, a comb shape or a zigzag structure. The electrodes may be formed on one substrate of the pair of substrates, or may be formed on both substrates. The form of formation of the electrodes differs depending on the type of liquid crystal display element. In the case of a device, electrodes are arranged on both of the pair of substrates. The liquid crystal alignment layer is formed on the substrate or electrode.

In the case of a homogeneously aligned liquid crystal display element (for example, IPS, FFS, etc.), the configuration includes, from the backlight side, at least a backlight, a first polarizing film, a first substrate, a first liquid crystal alignment film, a liquid crystal layer, It has a second substrate and a second polarizing film, and the polarizing axis of the polarizing film is such that the polarizing axis of the first polarizing film (direction of polarized light absorption) and the polarizing axis of the second polarizing film intersect (preferably perpendicular). At this time, the polarizing axis of the first polarizing film and the liquid crystal orientation direction can be set to be parallel or perpendicular to each other. A liquid crystal display device in which the polarization axis of the first polarizing film and the liquid crystal orientation direction are parallel to each other is called O-mode, and a liquid crystal display device in which they are perpendicular to each other is called E-mode. The liquid crystal alignment film used in the liquid crystal display device of the present invention can be applied to both O-mode and E-mode, and can be selected depending on the purpose.

When the polarization axis of the polarized light irradiated in order to add anisotropy to the liquid crystal alignment agent is aligned parallel to the polarization axis of the polarized light from the polarizing film placed on the backlight side, the light absorption wavelength range of the liquid crystal alignment film increases the transmittance of Therefore, the transmittance of the liquid crystal display element can be further improved.

The liquid crystal layer is formed in such a manner that the liquid crystal composition is sandwiched between the pair of substrates whose surfaces on which the liquid crystal alignment films are formed face each other. In the formation of the liquid crystal layer, spacers such as fine particles and resin sheets can be used as necessary to form an appropriate gap between the pair of substrates.

A vacuum injection method and an ODF (One Drop Fill) method are known as methods of forming a liquid crystal layer.

In the vacuum injection method, a gap (cell gap) is provided so that the surfaces of the liquid crystal alignment films face each other, a liquid crystal injection port is left, a sealant is printed, and the substrates are bonded together. After liquid crystal is injected and filled into the cell gap defined by the substrate surface and the sealing agent using a vacuum differential pressure, the injection port is sealed to manufacture the liquid crystal display element.

In the ODF method, a sealant is printed on the outer circumference of the liquid crystal alignment film surface of one of a pair of substrates, and liquid crystal is dropped on the inner region of the sealant, and then the other substrate is placed so that the liquid crystal alignment film surfaces face each other. glue together. Then, the liquid crystal is spread over the entire surface of the substrate, and then the entire surface of the substrate is irradiated with ultraviolet light to cure the sealant, thereby manufacturing a liquid crystal display element.

In addition to the UV curing type, a heat curing type is also known as a sealant used for laminating substrates. Printing of the sealant can be performed by, for example, a screen printing method.

Secondly, the configuration of the liquid crystal alignment film will be described. The liquid crystal alignment film used in the liquid crystal display element of the present invention comprises a raw material composition containing at least one compound selected from diamine compounds represented by formula (1) as diamines and tetracarboxylic dianhydrides. It is formed from a liquid crystal aligning agent containing a polymer that is polymerized.

<Diamines>
In formula (1), R ¹ and R ² are hydrogen, halogen, alkyl having 1 to 6 carbon atoms, haloalkyl having 1 to 6 carbon atoms, or alkoxy having 1 to 6 carbon atoms, and R ¹ and R ² are Together they may form an optionally substituted methylene. The methylene substituents include halogen such as fluorine and chlorine, alkyl optionally substituted with halogen such as fluorine and chlorine, and alkoxy having 1 to 4 carbon atoms, halogen atoms such as fluorine and chlorine, and Examples include alkyl or aryl optionally substituted with alkoxy having 1 to 4 carbon atoms. X is halogen, alkyl having 1 to 6 carbon atoms, haloalkyl having 1 to 6 carbon atoms, or alkoxy having 1 to 6 carbon atoms. n is 0, 1, 2, 3, or 4; The bonding position of X and the amino group (-NH ₂ ) is any of the substitutable positions of the benzene ring to which the bond is bonded.

Alkyl may be linear, branched or cyclic. Specific examples of alkyl include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, isopentyl, neopentyl, tert-pentyl, 1-methylbutyl, 1-ethylpropyl, hexyl, isohexyl, Examples include 1-methylpentyl, 1-ethylbutyl, cyclopentyl, cyclohexyl and the like.
Halogen includes fluorine, chlorine, bromine, iodine, and the like. A haloalkyl is a group in which at least one hydrogen atom of an alkyl is replaced with a halogen. The number of halogen atoms in haloalkyl is preferably 1 to 5, more preferably 1 to 4, even more preferably 1 to 3. Specific examples of haloalkyl include difluoromethyl, trifluoromethyl, 1,1-difluoroethyl, 2,2-difluoroethyl, 2,2,2-trifluoroethyl, 3-fluoropropyl, chloromethyl, dichloromethyl, trichloromethyl etc. can be mentioned. Alkoxy may be linear, branched or cyclic. Specific examples of alkoxy include methoxy, ethoxy, propyl, isopropyloxy, butyloxy, isobutyloxy, sec-butyloxy, tert-butyloxy, pentyloxy, isopentyloxy, neopentyloxy, tert-pentyloxy, 1-methylbutyloxy. , 1-ethylpropyloxy, hexyloxy, isohexyloxy, 1-methylpentyloxy, 1-ethylbutyloxy, cyclopentyloxy, cyclohexyloxy and the like.

At least one compound (diamine compound (1)) selected from the diamine compounds represented by formula (1) is used as a monomer to form a coating film with a polymer synthesized, and when irradiated with polarized light, the coating film has a high Liquid crystal orientation is imparted. This is presumed to be due to the following mechanism.
That is, it is considered that the diamine compound (1) has a structure in which phenyl esters are bonded to adjacent carbons of cyclopropane, so that photo-fries rearrangement reaction occurs upon irradiation with light. Therefore, when a polymer coating film synthesized using this diamine compound (1) is irradiated with polarized light for photo-alignment, among the randomly oriented polymer chains, the diamine of the polymer main chain that is approximately parallel to the polarization direction A photochemical reaction (photofries rearrangement reaction) occurs selectively in the originating structural unit. As a result, the orientation component due to polymer chains that are generally perpendicular to the polarization direction becomes dominant, resulting in a highly oriented state in a specific direction.
When this oriented film is used as a liquid crystal alignment film of a liquid crystal display element, as a result of the interaction between the surface of the liquid crystal alignment film and the liquid crystal molecules, the liquid crystal molecules are aligned in a direction substantially perpendicular to the polarization direction of the irradiated polarized light. The long axes are aligned and oriented uniformly, and high anisotropy is imparted to the liquid crystal layer.
From the above, the diamine compound (1) is useful as a raw material monomer (diamine monomer) for polymers used in liquid crystal aligning agents. And the liquid crystal aligning film with high liquid crystal aligning property can be formed by using the polymer synthesize|combined using this diamine compound for a liquid crystal aligning agent. By applying this liquid crystal alignment film to a liquid crystal display element, the liquid crystal layer is imparted with a high degree of alignment, making it possible to perform display with high contrast.
In the present specification, the state in which a component oriented in a specific direction among the polymer chains is dominant is expressed as oriented polymer chains, and the polymer chains forming the oriented film are oriented in a specific direction. It is sometimes expressed that anisotropy occurs to be in a state of being oriented to In addition, having polymer chains aligned in a specific direction is sometimes expressed as having high anisotropy.

A preferred example of the diamine compound (1) is the diamine compound (1-1). The polymer synthesized using the diamine compound (1-1) has high linearity because the amino group is located at the para position with respect to the ester, and the liquid crystal alignment film using the polymer has high anisotropy. You can express your sexuality. Among the diamine compounds (1-1), compounds in which n is 0 are useful from the viewpoint of easy availability of raw materials for their production.

Among these diamine compounds, compounds in which two esters on the cyclopropane ring are in the trans configuration are preferred. Such a compound has high linearity and contributes to high anisotropy of the liquid crystal alignment film.

Specific examples of the diamine compound (1) include the compounds shown below.

For example, like the relationship between compound (1-1-2a) and compound (1-1-2b), compounds having the same number and attached with a and b have an enantiomer relationship. In this specification, a mixture of compounds having an enantiomeric relationship with each other is sometimes referred to as a "diamine isomer mixture". Such a diamine isomer mixture can also be used in the raw material composition as the diamine compound (1).

The content of the diamine compound (1) is preferably 40 to 100 mol %, more preferably 50 to 100 mol %, relative to the total amount of diamines used as raw materials. When the polymer used in the present invention is a block polymer, the blending amount of the diamine compound (1) is preferably 10 to 100 mol%, more preferably 20 to 70 mol%, based on the total amount of diamines used as raw materials. preferable.

A plurality of diamine compounds (1) may be used as diamines. Other diamine compounds may be used in addition to the diamine compound (1).

Other diamine compounds can be selected without limitation from known diamine compounds. Here, other diamine compounds include not only diamines but also dihydrazides.
Diamines can be classified into two types according to their structures. That is, when the skeleton connecting two amino groups is viewed as a main chain, there are groups branched from the main chain, that is, diamines having side-chain groups and diamines having no side-chain groups. A diamine having such a side chain group is sometimes referred to as a side chain type diamine, and a diamine having no such side chain group is sometimes referred to as a non-side chain type diamine. This side chain group is a group having the effect of increasing the pretilt angle.
By appropriately using the non-side chain type diamine and the side chain type diamine properly, it is possible to correspond to the pretilt angle required for each.

Side chain type diamines are preferably used in combination to the extent that the properties of the present invention are not impaired. In addition, it is preferable to selectively use the side-chain type diamine and the non-side-chain type diamine for the purpose of improving properties such as vertical alignment with respect to liquid crystal molecules, VHR, and afterimage properties.

Specific examples of other diamine compounds include the compounds shown below.

式（ＤＩ－１１）から式（ＤＩ－１３）、式（ＤＩ－１６）、式（ＤＩ－１７）、式（ＤＩ－２７）において、ｓは１から１２の整数であり、式（ＤＩ－２１）において、ｓは１から１２の整数であり、ｔは１または２であり、式（ＤＩ－２０）において、ｕは１から５の整数である。式（ＤＩ－１１）および式（ＤＩ－１２）において、Ｂｏｃはｔｅｒｔ－ブトキシカルボニル基である。

In formulas (DI-11) to formula (DI-13), formula (DI-16), formula (DI-17), and formula (DI-27), s is an integer of 1 to 12, and formula (DI- 21), s is an integer of 1 to 12, t is 1 or 2, and u is an integer of 1 to 5 in formula (DI-20). In formulas (DI-11) and (DI-12), Boc is a tert-butoxycarbonyl group.

The compound of formula (DI-29) is a compound that undergoes photofries transition. Since the diamine compound (1) exhibits good photoreactivity even with low-energy light irradiation, it is not necessary to use it in combination with other photoreactive diamine compounds. You may

<Tetracarboxylic dianhydrides>
The tetracarboxylic dianhydrides can be selected without limitation from known tetracarboxylic dianhydrides. A tetracarboxylic dianhydride may be derived into a tetracarboxylic acid diester or a tetracarboxylic acid diester dichloride and used in the raw material composition. That is, the term "tetracarboxylic dianhydrides" includes not only tetracarboxylic dianhydrides but also derivatives of tetracarboxylic dianhydrides such as tetracarboxylic diesters and tetracarboxylic diester dihalides. do. Any one of these may be subjected to polymerization, or two or more thereof may be combined for polymerization.
In addition, the tetracarboxylic dianhydride may belong to an aromatic system (including a heteroaromatic ring system) in which a dicarboxylic anhydride is directly bonded to an aromatic ring, or a dicarboxylic anhydride may be directly bonded to an aromatic ring. may belong to aliphatic systems (including heterocyclic ring systems) where is not attached.

Specific examples of tetracarboxylic dianhydrides include the compounds shown below.

式（ＡＮ－２）および式（ＡＮ－８）において、ｖは１から１２の整数である。

In formulas (AN-2) and (AN-8), v is an integer of 1 to 12.

<Polymer>
The polymer is a polymer obtained by polymerizing a raw material composition containing at least one compound selected from diamine compounds represented by formula (1) as diamines and tetracarboxylic dianhydrides, and this polymer is , polyamic acid and derivatives of polyamic acid. The polymer may be composed of multiple polyamic acids or multiple derivatives of polyamic acids, or may be composed of a mixture of polyamic acids and derivatives of polyamic acids. Derivatives of polyamic acids may include polyimides, partial polyimides, polyamic acid esters, polyamic acid-polyamide copolymers and polyamideimides.

式（ＰＡＡ）において、Ｘ^１は４価の有機基を表す。Ｘ^２は２価の有機基を表す。 A polyamic acid is a polymer synthesized by a polymerization reaction of diamines and a tetracarboxylic dianhydride, and has a structural unit represented by formula (PAA).

In formula (PAA), ^X1 represents a tetravalent organic group. ^X2 represents a divalent organic group.

式（ＰＩ）および式（ＰＡＥ）において、Ｘ^１は４価の有機基、Ｘ^２は２価の有機基、Ｚはアルキルを表す。 Derivatives of polyamic acid are compounds in which a part of polyamic acid is replaced with other atoms or atomic groups to modify the properties, and in particular, it is preferred that the solubility in the solvent used for the liquid crystal aligning agent is increased. Specific examples of such polyamic acid derivatives include 1) polyimide obtained by a dehydration ring-closing reaction of all amino groups and carboxyl groups of polyamic acid, 2) partial polyimide obtained by a partial dehydration ring-closure reaction, and 3) polyamic acid. 4) Polyamic acid-polyamide copolymer obtained by replacing part of the acid dianhydride contained in the tetracarboxylic acid dianhydride compound with an organic dicarboxylic acid and reacting and 5) a polyamideimide obtained by dehydrating and ring-closing a part or all of the polyamic acid-polyamide copolymer. Among these derivatives, for example, polyimides include those having a structural unit represented by the formula (PI), and polyamic acid esters include those having a structural unit represented by the formula (PAE). can be mentioned.

In formula (PI) and formula (PAE), ^X1 represents a tetravalent organic group, ^X2 represents a divalent organic group, and Z represents alkyl.

The polyamic acid or polyamic acid derivative may be a block polymer comprising a first polymer chain and a second polymer chain that is structurally different from the first polymer chain. In addition, the block polymer may further contain another polymer chain having a structure different from that of the first polymer chain and the second polymer chain. For example, the block polymer of polyamic acid includes a solution of a specific polyamic acid (PAA1) represented by the formula (PAA) and a solution of polyamic acid (PAA2) having a different combination of polyamic acid (PAA1) and X ¹ and X ² . It can be formed by mixing and heating. The block polymer of polyamic acid thus formed comprises blocks represented by (PAA1) _n1 and blocks represented by (PAA2) _n2 . _n1 and n2 in (PAA1) n1 and (PAA2) _n2 are each independently an integer of 1 or more, preferably each independently an integer of 2 or more. In the block polymer, the polymer chains using the diamine compound (1) in the raw material composition may be any one, two or more, or all polymer chains.
The polyamic acid block polymer may be synthesized by preparing two or more polyamic acids independently and then mixing and heating them. Alternatively, two or more polyamic acids may be synthesized in the same reaction vessel and then heated. may be combined.

When the polyamic acid is a polyimide, the resulting polyamic acid solution is mixed with acid anhydrides such as acetic anhydride, propionic anhydride and trifluoroacetic anhydride as dehydrating agents, and triethylamine, pyridine and collidine as dehydration ring closure catalysts. Polyimide can be obtained by imidization reaction at 20° C. to 150° C. with a tertiary amine such as Polyamic acid is precipitated from the resulting polyamic acid solution using a large amount of poor solvent (alcoholic solvents such as methanol, ethanol, isopropyl alcohol, and glycolic solvents such as ethylene glycol), and the precipitated polyamic acid is dissolved in toluene, A polyimide can also be obtained by an imidation reaction at 20° C. to 150° C. in a solvent such as xylene together with the dehydrating agent and the dehydration ring-closing catalyst.

In the imidization reaction, the ratio of the dehydrating agent to the dehydration ring-closing catalyst is preferably 0.1 to 10 (molar ratio). The total amount of the dehydrating agent and dehydration ring-closing catalyst used is preferably 1.5 to 10 times the molar amount of the tetracarboxylic dianhydride used in the synthesis of the polyamic acid. By adjusting the dehydrating agent, catalyst amount, reaction temperature and reaction time used in this imidization reaction, the degree of imidization can be controlled, thereby obtaining a partial polyimide in which only a portion of the polyamic acid is imidized. be able to. The resulting polyimide can be separated from the solvent used for the reaction and re-dissolved in another solvent to be used as a liquid crystal aligning agent, or can be used as a liquid crystal aligning agent without separating from the solvent. .

A polyamic acid ester is synthesized by reacting a polyamic acid with a hydroxyl group-containing compound, a halide, an epoxy group-containing compound, or the like, or by a tetracarboxylic acid diester or tetracarboxylic acid diester derived from a tetracarboxylic dianhydride. It can be obtained by a synthesis method by reacting a dichloride with a diamine. A tetracarboxylic acid diester derived from a tetracarboxylic acid dianhydride can be obtained, for example, by reacting a tetracarboxylic acid dianhydride with two equivalents of alcohol to open the ring, and a tetracarboxylic acid diester dichloride is a tetracarboxylic acid It can be obtained by reacting a diester with two or more equivalents of a chlorinating agent (for example, thionyl chloride). The polyamic acid ester may have only the amic acid ester structure, or may be a partially esterified product in which the amic acid structure and the amic acid ester structure coexist.

The polyamic acid or polyamic acid derivative using the diamine compound represented by formula (1) as a raw material can be produced in the same manner as known polyamic acids or polyamic acid derivatives used for forming polyimide films.
The total amount of tetracarboxylic dianhydrides charged is preferably 0.9 mol to 1.1 mol per 1 mol of diamines.

The molecular weight of the polyamic acid or polyamic acid derivative is preferably from 5,000 to 500,000, more preferably from 5,000 to 50,000, in terms of polystyrene-equivalent weight-average molecular weight (Mw). These molecular weights can be obtained from measurements by gel permeation chromatography (GPC).

The existence of polyamic acid or polyamic acid derivative can be confirmed by analyzing the solid content obtained by precipitating with a large amount of poor solvent by IR (infrared spectroscopy) and NMR (nuclear magnetic resonance analysis). . In addition, an extract with an organic solvent of a decomposition product of polyamic acid or a derivative of polyamic acid with a strong alkaline aqueous solution such as potassium hydroxide or sodium hydroxide is subjected to gas chromatography (GC), high performance liquid chromatography (HPLC) or gas chromatography. The monomers used can be confirmed by analysis by graphic mass spectrometry (GC-MS).

<Liquid crystal aligning agent>
The liquid crystal aligning agent contains at least one polymer selected from polyamic acid and polyamic acid derivatives. One type or two or more types of polymers may be used. A liquid crystal aligning agent containing only one type of polymer may be referred to as a single-layer liquid crystal aligning agent. A liquid crystal aligning agent containing two or more kinds of polymers may be referred to as a blend type liquid crystal aligning agent. A blend type liquid crystal aligning agent is used particularly when VHR reliability and other electrical characteristics are considered important.

When two-component polymers are used, for example, one polymer is selected to have excellent liquid crystal alignment ability, and the other is selected to have excellent performance in improving the electrical properties of the liquid crystal display device. It is suitable for obtaining a liquid crystal aligning agent having well-balanced liquid crystal aligning properties and electrical properties.
A liquid crystal aligning agent composed of a two-component polymer is known to have a phenomenon in which a polymer with a small surface energy separates into an upper layer and a polymer with a large surface energy separates into a lower layer. By appropriately changing the structure and molecular weight of each polymer and adjusting their surface energy, one polymer can be segregated in the upper layer of the thin film and the other polymer can be segregated in the lower layer of the thin film. That is, by adjusting the surface energy of the polymer, a polymer with excellent liquid crystal alignment ability is segregated in the upper layer of the thin film, and a polymer with excellent electrical property improvement ability of the liquid crystal display element is segregated in the lower layer of the thin film. It is possible to obtain a desired liquid crystal alignment film with a good balance of . By confirming that the surface energy of the liquid crystal alignment film thus formed is the same as or equivalent to the surface energy of the film formed from the polymer intended to be segregated on the upper layer, the desired liquid crystal alignment can be obtained. It can be confirmed that a membrane was obtained.

Examples of a method for causing layer separation include a method in which the molecular weight of the polymer to be segregated in the upper layer is made smaller than that of the polymer to be segregated in the lower layer, and a method in which polyimide is used as the polymer to be segregated in the upper layer.

The diamine compound represented by formula (1) may be used as a raw material monomer for the polymer to be segregated in the upper layer of the thin film, or may be used as a raw material monomer for the polymer to be segregated in the lower layer of the thin film. Although it may be used as a raw material monomer for the polymer, it is preferably used as a raw material monomer for the polymer to be segregated in the upper layer of the thin film.

The liquid crystal aligning agent may further contain a solvent from the viewpoint of coating properties of the liquid crystal aligning agent and adjusting the concentration of polyamic acid or polyamic acid derivative. As the solvent, any solvent capable of dissolving the polymer component can be used without any particular limitation. Depending on the purpose of use, the solvent can be appropriately selected from solvent affinity for polyamic acid or its derivatives and other solvents intended to improve coatability. The solvent may be one kind or a mixed solvent of two or more kinds.

Aprotic polar organic solvents that are affinity for polyamic acid or polyamic acid derivatives include N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, dimethylimidazolidinone, N-methylcaprolactam, N- methylpropionamide, N,N-dimethylacetamide, dimethylsulfoxide, N,N-dimethylformamide, N,N-diethylformamide, diethylacetamide, N,N-dimethylisobutyramide, γ-butyrolactone, γ-valerolactone, and the like. be done. Among these, N-methyl-2-pyrrolidone, dimethylimidazolidinone, γ-butyrolactone, or γ-valerolactone are preferred.

Examples of other solvents for the purpose of improving coating properties include ethylene glycol monoalkyl ethers such as ethylene glycol monobutyl ether and ethylene glycol mono-tert-butyl ether, diethylene glycol monoalkyl ethers such as diethylene glycol monoethyl ether, and diethylene glycol ethylmethyl. Ether, diethylene glycol dialkyl ether such as diethylene glycol diethyl ether, diethylene glycol butyl methyl ether. In addition, propylene glycol monoalkyl ether such as propylene glycol monomethyl ether and 1-butoxy-2-propanol, dipropylene glycol monoalkyl ether such as dipropylene glycol monomethyl ether, ethylene glycol monoalkyl, triethylene glycol monoalkyl ether, phenyl acetate. , and ester compounds such as these acetates. Furthermore, dialkyl malonate such as diethyl malonate, alkyl lactate, diisobutyl ketone, diacetone alcohol, 3-methyl-3-methoxybutyl alcohol, 4-methyl-2-pentanol, 2,6-dimethyl-4-heptanol, tetralin , and isophorone.

Among these, diisobutyl ketone, 4-methyl-2-pentanol, 2,6-dimethyl-4-heptanol, ethylene glycol monobutyl ether, ethylene glycol mono-tert-butyl ether, diethylene glycol monoethyl ether, diethylene glycol ethyl methyl ether, Diethylene glycol diethyl ether, diethylene glycol butyl methyl ether, 1-butoxy-2-propanol, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether or butyl cellosolve acetate are preferred.

The polymer concentration in the liquid crystal aligning agent is not particularly limited, and an optimum value may be selected according to the following various coating methods. Generally, in order to suppress unevenness, pinholes, etc. during application, it is preferably 0.1 to 30% by weight, more preferably 1 to 10% by weight, based on the weight of the liquid crystal aligning agent.

The preferable range of the viscosity of the liquid crystal aligning agent varies depending on the coating method, the concentration of the polyamic acid or the polyamic acid derivative, the type of the polyamic acid or the polyamic acid derivative used, and the type and ratio of the solvent. For example, in the case of application by a printing machine, the viscosity is preferably from 5 to 100 mPa·s, more preferably from 10 to 80 mPa·s. If it is 5 mPa·s or more, a sufficient film thickness can be easily obtained, and if it is 100 mPa·s or less, printing unevenness can be easily suppressed. In the case of application by spin coating, the viscosity is preferably from 5 to 200 mPa·s, more preferably from 10 to 100 mPa·s. When applying using an inkjet coating device, the viscosity is preferably 5 to 50 mPa·s, more preferably 5 to 20 mPa·s. The viscosity of the liquid crystal aligning agent is measured by a rotational viscosity measurement method, for example, using a rotational viscometer (Model TVE-20L manufactured by Toki Sangyo Co., Ltd.) (measurement temperature: 25° C.).

A liquid crystal aligning agent may be comprised only from a polymer component, and may further contain various additives. Various additives can be selected and used according to their respective purposes in order to improve various properties of the alignment film. Examples of additives that can be used in the liquid crystal aligning agent are shown below.

The liquid crystal aligning agent may contain an alkenyl-substituted nadimide compound, a compound having a radically polymerizable unsaturated double bond, an oxazine compound, or an oxazoline compound for the purpose of stabilizing the electrical properties of the liquid crystal display element for a long period of time. For the purpose of stabilizing the electrical properties of the display element for a long period of time, the purpose of improving the hardness of the film, or the purpose of improving the adhesion to the sealant, an epoxy compound may be contained to improve adhesion to the substrate and the sealant. For the purpose of improving, it may contain a silane compound, and for the purpose of stabilizing the electrical properties in the liquid crystal display element for a long time or increasing the strength of the alignment film, a compound having a cyclocarbonate group or a hydroxyalkylamide moiety or a hydroxyl group may contain a compound having

Specific examples of these compounds include 1,3-bis(4,5-dihydro-2-oxazolyl)benzene, N,N,N',N'-tetraglycidyl-4,4'-diaminodiphenylmethane, 3 - glycidoxypropyltrimethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, (3,3′,4,4′-diepoxy)bicyclohexyl, 3-glycidoxypropyltriethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-aminopropyltriethoxysilane and the like.

A liquid crystal aligning agent containing a polymer obtained by polymerizing a raw material composition containing at least one compound selected from diamine compounds represented by formula (1) and tetracarboxylic dianhydrides as diamines is photoaligned. A photo-alignment method can be applied to the alignment treatment in the process of forming the liquid crystal alignment film.

Thirdly, a method for manufacturing a liquid crystal alignment film will be described. The liquid crystal alignment film used in the liquid crystal display device of the present invention can be obtained by a normal method. Specifically, it can be formed using a step of applying a liquid crystal aligning agent to a substrate to form a coating film, and a step of irradiating the coating film with light. A step of applying a liquid crystal aligning agent to a substrate to form a coating film, a step of heating and drying the coating film to form a film of the liquid crystal aligning agent, and irradiating the film of the liquid crystal aligning agent with light to create anisotropy. It is preferable to manufacture by passing through the process of providing and the process of heating and baking the film|membrane of the liquid crystal aligning agent which provided anisotropy. That is, the liquid crystal alignment film of the present invention is preferably irradiated with light to impart anisotropy after the coating process and the heat drying process, and then subjected to the heat baking process. When a liquid crystal aligning agent containing a polyamic acid or a derivative of a polyamic acid is used, the polyamic acid undergoes an imidation reaction by this heating and baking step to form a polyimide. Moreover, it is preferable that the light irradiated for imparting anisotropy is polarized ultraviolet rays.

A coating film can be formed by apply|coating a liquid crystal aligning agent to the board|substrate in a liquid crystal display element similarly to manufacture of the normal liquid crystal aligning film. The substrate may be provided with electrodes such as ITO (Indium TinOxide), IZO (In2O3-ZnO), IGZO (In-Ga-ZnO4) electrodes, color filters, etc. Glass, silicon nitride, acrylic, polycarbonate substrates made of polyimide, etc.;

A spinner method, a printing method, a dipping method, a dropping method, an inkjet method, and the like are generally known as methods for applying a liquid crystal aligning agent to a substrate. These methods are equally applicable in the present invention.

As the heat-drying step, a method of heat-treating in an oven or an infrared furnace, a method of heat-treating on a hot plate, and the like are generally known. The heating and drying step is preferably carried out at a temperature within a range where the solvent can evaporate, and more preferably at a temperature relatively lower than the temperature in the heating and baking step. Specifically, the heat drying temperature is preferably in the range of 30°C to 150°C, more preferably in the range of 50°C to 120°C.

The heating and baking step can be performed under the conditions necessary for the polyamic acid or the polyamic acid derivative to undergo an imidation reaction. For baking the coating film, a method of heat treatment in an oven or an infrared furnace, a method of heat treatment on a hot plate, and the like are generally known. These methods are similarly applicable in the present invention. In general, the temperature is preferably about 90°C to 300°C for 1 minute to 3 hours, more preferably 120°C to 280°C, even more preferably 150°C to 250°C.
When it is important to improve the anisotropy of the film or to improve the afterimage property when the liquid crystal display element is produced, it is preferable to gradually raise the temperature in the heating step, for example, stepwise. It is possible to heat and bake multiple times at different temperatures while increasing the temperature, or heat while changing the temperature from low to high. Also, both heating methods may be combined.

When heating and firing at different temperatures a plurality of times, a plurality of heating devices set to different temperatures may be used, or a single heating device may be used while sequentially changing the temperatures to different temperatures.
When heating and firing at different temperatures multiple times, the initial firing temperature is preferably from 90°C to 180°C, and the final firing temperature is preferably from 185°C to 300°C. For example, heat and bake at 110°C and then heat and bake at 220°C, heat and bake at 110°C and then heat and bake at 230°C, heat and bake at 130°C and then heat and bake at 220°C, and heat and bake at 150°C and then heat and bake at 200°C. It is preferable to heat and bake at 150°C and then heat and bake at 220°C, heat and bake at 150°C and then heat and bake at 230°C, or heat and bake at 170°C and then heat and bake at 200°C. It is also preferable to increase the number of stages and heat and bake while slowly raising the temperature. When heating and baking are performed in two or more stages by changing the heating temperature, the heating time in each heating step is preferably 5 minutes to 30 minutes.

When firing is performed by changing the temperature from low temperature to high temperature, the initial temperature is preferably 90°C to 180°C. The final temperature is preferably 185°C to 300°C, more preferably 190°C to 230°C. The heating time is preferably 5 to 60 minutes, more preferably 20 to 60 minutes. The heating speed can be, for example, 0.5° C./minute to 40° C./minute. The temperature rising speed during temperature rising may not be constant.

In the method for producing a liquid crystal alignment film, a known photo-alignment method can be suitably used as a means for imparting anisotropy to the thin film in order to align the liquid crystal in one direction with respect to the horizontal and / or vertical direction. .

A method for manufacturing a liquid crystal alignment film by a photo-alignment method will be described in detail. The liquid crystal alignment film using the photo-alignment method is applied to the thin film after drying the coating film with linearly polarized light or non-polarized light to impart anisotropy to the thin film, and the film is heated and baked. can be formed by Alternatively, the thin film can be formed by drying the coating film by heating, baking the film by heating, and then irradiating the thin film with linearly polarized light or non-polarized light. From the viewpoint of liquid crystal orientation, the light irradiation step is preferably performed before the heating and baking step.

Furthermore, in order to increase the liquid crystal alignment ability of the liquid crystal alignment film, linearly polarized light or non-polarized light can be irradiated while heating the coating film. Irradiation with light may be performed in the step of drying the coating film by heating, or in the step of baking by heating, or may be performed between the step of drying by heating and the step of baking by heating.
For the heating temperature in the case of irradiating the coating film with light in the step of drying by heating or the step of baking by heating, the above description of the drying by heating or baking by heating can be referred to. The heating temperature in the case of irradiating light between the heat drying step and the heat baking step is preferably in the range of 30°C to 150°C, more preferably in the range of 50°C to 110°C.

As the light, for example, ultraviolet light containing light with a wavelength of 150 to 800 nm or visible light can be used, and ultraviolet light containing light with a wavelength of 200 to 400 nm is preferable. Also, linearly polarized light or non-polarized light can be used. The light is not particularly limited as long as it can impart liquid crystal alignment ability to the thin film, but linearly polarized light is preferable when a strong alignment control force is to be exerted on the liquid crystal.

The liquid crystal alignment film used in the liquid crystal display device of the present invention can exhibit high anisotropy even with low-energy light irradiation. The irradiation amount of linearly polarized light in the light irradiation step is preferably 0.05 to 10 J/cm ² , more preferably 0.1 to 5 J/cm ² . Although the irradiation angle of the linearly polarized light to the film surface is not particularly limited, it is preferably perpendicular to the film surface as much as possible from the viewpoint of shortening the alignment treatment time when it is desired to develop a strong alignment control force on the liquid crystal. Further, the liquid crystal alignment film of the present invention can orient liquid crystals in a direction perpendicular to the polarization direction of linearly polarized light by irradiating it with linearly polarized light.

Light sources used in the process of irradiating linearly polarized light or non-polarized light include super high pressure mercury lamps, high pressure mercury lamps, low pressure mercury lamps, deep UV lamps, halogen lamps, metal halide lamps, high power metal halide lamps, xenon lamps, and mercury. Xenon lamps, excimer lamps, KrF excimer lasers, fluorescent lamps, LED lamps, sodium lamps, microwave-excited electrodeless lamps, etc. can be used without limitation.

The liquid crystal alignment film used in the liquid crystal display element of the present invention can be preferably obtained by a method further including steps other than the steps described above.

The liquid crystal alignment film used in the liquid crystal display element of the present invention does not necessarily require a step of washing the film after baking or light irradiation with a washing liquid, but a washing step can be provided for convenience of other steps. Cleaning methods using a cleaning liquid include brushing, jet spray, steam cleaning, ultrasonic cleaning, and the like. These methods may be performed alone or in combination. Pure water, alcohols such as methyl alcohol, ethyl alcohol, and isopropyl alcohol, aromatic hydrocarbons such as benzene, toluene, and xylene, halogenated hydrocarbons such as methylene chloride, and ketones such as acetone and methyl ethyl ketone can be used as the cleaning liquid. can be used, but is not limited to these. Of course, these washing liquids are sufficiently purified and contain few impurities. Such a cleaning method can also be applied to the cleaning step in the formation of the liquid crystal alignment film.

Annealing treatment with heat or light can be used before and after the heating and baking process, or before and after irradiation with polarized or non-polarized light, in order to enhance the liquid crystal alignment ability. In the annealing treatment, the annealing temperature is 30° C. to 180° C., preferably 50° C. to 150° C., and the time is preferably 1 minute to 2 hours. Annealing light used for the annealing treatment includes a UV lamp, a fluorescent lamp, an LED lamp, and the like. The irradiation amount of light is preferably 0.3 to 10 J/cm ² .

The thickness of the liquid crystal alignment film used in the liquid crystal display device of the present invention is not particularly limited, but is preferably 10 to 300 nm, more preferably 30 to 150 nm. The film thickness of the liquid crystal alignment film can be measured by a known film thickness measuring device such as a profilometer or an ellipsometer.

The liquid crystal alignment film used in the liquid crystal display device of the present invention is characterized by having particularly large anisotropy of alignment. The magnitude of such anisotropy can be evaluated by the method using polarized IR described in JP-A-2005-275364. It can also be evaluated by a method using ellipsometry. Specifically, the retardation value of the liquid crystal alignment film can be measured using a spectroscopic ellipsometer. The retardation value of the film increases in proportion to the degree of orientation of the polymer main chain. In other words, a polymer film with a large retardation value has a large degree of orientation, and when used as a liquid crystal alignment film, it is thought that a liquid crystal alignment film with a larger anisotropy has a large alignment control force with respect to the liquid crystal composition. be done.

Fourthly, the constitution of the composition will be explained. This composition contains a plurality of liquid crystalline compounds. This composition may 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 crystalline compound. Composition (a) may further contain other liquid crystalline compounds, additives, etc., in addition to the liquid crystalline compound selected from compound (2) and compound (3). "Another liquid crystalline compound" is a liquid crystalline compound different from compound (2) and compound (3). Such compounds are incorporated into the composition for the purpose of further adjusting its properties.

Composition (b) consists essentially of a liquid crystalline compound selected from compound (2) and compound (3). "Substantially" means that the composition (b) may contain additives, but does not contain other liquid crystalline compounds. Composition (b) has fewer components than composition (a). Composition (b) is preferable to composition (a) from the viewpoint of cost reduction. The composition (a) is preferable to the composition (b) from the viewpoint that the properties can be further adjusted by mixing other liquid crystalline compounds.

Fifth, the main properties of the constituent compounds of the liquid crystal composition and the main effects of these compounds on the composition and device are described. 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 medium, and S small or low. The symbols L, M, S are classifications based on qualitative comparisons between component compounds, with 0 (zero) meaning less than S.

The main effects of the component compounds are as follows. Compound (2) increases dielectric anisotropy. Compound (3) lowers the viscosity or raises the maximum temperature. Since compound (4) is polymerizable, it gives a polymer by polymerization. This polymer stabilizes the orientation of the liquid crystal molecules, thus shortening the response time of the device and improving image sticking.

Sixthly, the combination of the component compounds in the liquid crystal composition, preferred proportions, and grounds thereof will be explained. Preferred combinations of the component compounds in the composition are compound (2)+compound (3) or compound (2)+compound (3)+compound (4).

A preferable ratio of compound (2) is about 5% by mass or more for increasing the dielectric anisotropy, and about 95% by mass or less for lowering the minimum temperature. A more preferred proportion ranges from about 10% to about 90% by weight. A particularly preferred proportion ranges from about 15% to about 85% by weight.

A preferable ratio of compound (3) is about 5% by mass or more for lowering the viscosity or raising the upper limit temperature, and about 95% by mass or less for lowering the lower limit temperature. A more preferred proportion ranges from about 10% to about 90% by weight. A particularly preferred proportion ranges from about 15% to about 85% by weight.

The compound (4) is added to the composition for the purpose of adapting it to a polymer support alignment type device. A preferable proportion of compound (4) is about 0.03% by mass or more for aligning liquid crystal molecules, and about 10% by mass or less for preventing display defects of the device. A more preferred percentage ranges from about 0.1% to about 2% by weight. A particularly preferred proportion ranges from about 0.2% to about 1.0% by weight.

Seventh, preferred forms of the component compounds of the liquid crystal composition will be described. In formulas (2) and (3), R ³ and R ⁴ are hydrogen, alkyl having 1 to 12 carbon atoms, alkoxy having 1 to 12 carbon atoms, alkenyl having 2 to 12 carbon atoms, alkenyloxy, or alkyl having 1 to 12 carbon atoms in which at least one hydrogen is replaced with fluorine or chlorine. Preferred R ³ or R ⁴ is alkyl having 1 to 12 carbon atoms for increasing stability, alkoxy having 1 to 12 carbon atoms for increasing dielectric anisotropy, or Alkenyl having 2 to 12 carbon atoms for lowering the threshold voltage. R ⁵ and R ⁶ 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 by fluorine or chlorine or C2-C12 alkenyl in which at least one hydrogen is replaced by fluorine or chlorine. Preferred R ⁵ or R ⁶ 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 are methoxy, ethoxy, propoxy, butoxy, pentyloxy, hexyloxy or heptyloxy. More preferred alkoxy is methoxy or ethoxy for reducing 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. Trans is preferred in alkenyls such as 1-propenyl, 1-butenyl, 1-pentenyl, 1-hexenyl, 3-pentenyl, and 3-hexenyl in order to lower the viscosity. Cis is preferred in alkenyls such as 2-butenyl, 2-pentenyl, 2-hexenyl.

Preferred alkenyloxy are vinyloxy, allyloxy, 3-butenyloxy, 3-pentenyloxy or 4-pentenyloxy. A more preferred alkenyloxy for reducing 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 for increasing 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.

Ring A and ring C are 1,4-cyclohexylene, 1,4-cyclohexenylene, tetrahydropyran-2,5-diyl, 1,4-phenylene, and 1 in which at least one hydrogen is replaced by fluorine or chlorine. ,4-phenylene, naphthalene-2,6-diyl, naphthalene-2,6-diyl in which at least one hydrogen is replaced by fluorine or chlorine, chroman-2,6-diyl, or at least one hydrogen is fluorine or chlorine is chroman-2,6-diyl replaced with Preferred examples of "1,4-phenylene in which at least one hydrogen is replaced by fluorine or chlorine" are 2-fluoro-1,4-phenylene, 2,3-difluoro-1,4-phenylene or 2-chloro- 3-fluoro-1,4-phenylene. Preferred ring A or ring C is 1,4-cyclohexylene for lowering the viscosity or raising the upper limit temperature, 1,4-phenylene for lowering the lower limit temperature, and dielectric anisotropy. tetrahydropyran-2,5-diyl or 1,4-phenylene in which at least one hydrogen has been replaced by fluorine or chlorine to increase the

好ましい環Ｂ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、誘電率異方性を上げるために４，６－ジフルオロジベンゾチオフェン－３，７－ジイルである。 Ring B is 2,3-difluoro-1,4-phenylene, 2-chloro-3-fluoro-1,4-phenylene, 2,3-difluoro-5-methyl-1,4-phenylene, 3,4, 5-trifluoronaphthalene-2,6-diyl, 7,8-difluorochroman-2,6-diyl, 3,4,5,6-tetrafluorofluorene-2,7-diyl (FLF4), 4,6- Difluorodibenzofuran-3,7-diyl (DBFF2), 4,6-difluorodibenzothiophene-3,7-diyl (DBTF2), or 1,1,6,7-tetrafluoroindane-2,5-diyl (InF4) is.

Preferred ring B is 2,3-difluoro-1,4-phenylene for lowering viscosity and 4,6-difluorodibenzothiophene-3,7-diyl for increasing dielectric anisotropy.

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

Z ¹ and Z ² are a single bond, ethylene, vinylene, methyleneoxy, or carbonyloxy. Preferred Z ¹ or Z ² is a single bond for lowering the viscosity, ethylene for lowering the minimum temperature, and methyleneoxy for increasing the dielectric anisotropy. ^Z3 is a single bond, ethylene, vinylene, methyleneoxy, or carbonyloxy. Preferred ^Z3 is a single bond to reduce viscosity.

A divalent group such as methyleneoxy is asymmetric. In methyleneoxy, -CH ₂ O- is preferred to -OCH ₂ -. In carbonyloxy, -COO- is preferred to -OCO-.

a is 0, 1, 2, or 3, b is 0 or 1, and the sum of a and b is 3 or less. Preferably, a is 1 for lowering the viscosity, and 2 or 3 for raising the maximum temperature. Preferred b is 0 for lowering the viscosity and 1 for lowering the minimum temperature. c is 1, 2, or 3; Preferred c is 1 for lowering the viscosity or lowering the lower limit temperature, and 2 or 3 for raising the upper limit temperature.

In formula (4), ring I and ring K are cyclohexyl, cyclohexenyl, phenyl, 1-naphthyl, 2-naphthyl, tetrahydropyran-2-yl, 1,3-dioxan-2-yl, pyrimidin-2-yl , or pyridin-2-yl, wherein in these rings at least one hydrogen is fluorine, chlorine, alkyl of 1 to 12 carbons, alkoxy of 1 to 12 carbons, or at least one hydrogen is fluorine or chlorine may be substituted with alkyl having 1 to 12 carbon atoms substituted with . A preferred ring I or ring K is phenyl. Ring J 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 by fluorine, chlorine, alkyl having 1 to 12 carbon atoms, alkoxy having 1 to 12 carbon atoms, or alkyl having 1 to 12 carbon atoms in which at least one hydrogen is replaced by fluorine or chlorine good too. A preferred ring J is 1,4-phenylene or 2-fluoro-1,4-phenylene.

Z ⁶ and Z ⁷ are a single bond or alkylene having 1 to 10 carbon atoms, and in this alkylene, at least one —CH ₂ — is —O—, —CO—, —COO—, or —OCO— 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. Preferred Z ⁶ or Z ⁷ is a single bond, -CH ₂ CH ₂ -, -CH ₂ O-, -OCH ₂ -, -COO- or -OCO-. More preferred ^Z6 or ^Z7 is a single bond.

Sp ¹ to Sp ³ are a single bond or alkylene having 1 to 10 carbon atoms, in which at least one -CH ₂ - is -O-, -COO-, -OCO- or -OCOO- optionally, at least one -CH ₂ CH ₂ - may be replaced with -CH=CH- or -C≡C- in which at least one hydrogen is fluorine or chlorine; may be replaced. Preferred Sp ¹ to Sp ³ are 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 to Sp ³ are single bonds.

f is 0, 1, or 2; Preferred f is 0 or 1. g, h, and i are 0, 1, 2, 3, or 4, and the sum of g, h, and i is 1 or greater. Preferred g, h, or i are 1 or 2.

P ¹ to P ³ are polymerizable groups. Preferred P ¹ to P ³ are polymerizable groups selected from groups represented by formulas (P-1) to (P-5). More preferred P ¹ to P ³ are groups represented by formula (P-1), formula (P-2), or formula (P-3). Particularly preferred P ¹ to P ³ are groups represented by formula (P-1) or formula (P-2). Most preferred P ¹ to P ³ are groups represented by formula (P-1). A preferred group represented by 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 to M ³ are hydrogen, fluorine, alkyl having 1 to 5 carbon atoms, or C 1 in which at least one hydrogen is replaced by fluorine or chlorine is an alkyl of from to 5; Preferred M ¹ to M ³ are hydrogen or methyl to increase reactivity. More preferred M ¹ is hydrogen or methyl, and more preferred M ² or M ³ is hydrogen.

In formulas (4-1) to (4-29), ^P4 to ^P6 are groups represented by formulas (P-1) to (P-3). Preferred P ⁴ to P ⁶ are 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 binding sites.

Eighth, preferable component compounds of the liquid crystal composition are shown. Preferred compounds (2) are compounds (2-1) to (2-35) described in item 5. In these compounds, at least one component A is compound (2-1), compound (2-3), compound (2-6), compound (2-7), compound (2-8), compound (2 -10), compound (2-14), compound (2-16), or compound (2-18). at least two of component A are compound (2-1) and compound (2-8), compound (2-1) and compound (2-14), compound (2-3) and compound (2-8), compound (2-3) and compound (2-14), compound (2-3) and compound (2-16), compound (2-6) and compound (2-8), compound (2-6) and compound ( 2-10), or a combination of compound (2-6) and compound (2-14).

Preferred compounds (3) are compounds (3-1) to (3-14) described in Item 8. In these compounds, at least one component B is compound (3-1), compound (3-3), compound (3-5), compound (3-6), compound (3-8), compound (3 -9), or compound (3-14). at least two of component B are compound (3-1) and compound (3-3), compound (3-1) and compound (3-5), compound (3-1) and compound (3-6), or A combination of compound (3-1) and compound (3-14) is preferred.

Preferred compounds (4) are compounds (4-1) to (4-29) described in item 12. In these compounds, at least one of the additives X is compound (4-1), compound (4-2), compound (4-24), compound (4-25), compound (4-26), or compound (4-27) is preferred. at least two of the additives X are compound (4-1) and compound (4-2), compound (4-1) and compound (4-18), compound (4-2) and compound (4-24), compound (4-2) and compound (4-25), compound (4-2) and compound (4-26), compound (4-25) and compound (4-26), or compound (4-18) and A combination of compounds (4-24) is preferred.

Ninth, additives that may be added to the liquid crystal composition will be described. 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 to give a twist angle. Examples of such compounds are compounds (5-1) to (5-5). A preferred proportion of the optically active compound is about 5 mass % or less. A more preferred proportion ranges from about 0.01% to about 2% by weight.

In order to prevent a decrease in resistivity due to heating in the atmosphere, or to maintain a large voltage holding ratio not only at room temperature but also at temperatures close to the upper limit temperature after using the device for a long time, the compound (6-1 ) to compound (6-3) may further be added to the composition.

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

Preferred examples of UV absorbers are benzophenone derivatives, benzoate derivatives, triazole derivatives and the like. Light stabilizers such as sterically hindered amines are also preferred. Preferred examples of light stabilizers include compounds (7-1) to (7-16). A preferable ratio of these absorbents and stabilizers is about 50 ppm or more to obtain the effect, and about 10000 ppm or less so as not to lower the upper limit temperature or raise the lower limit temperature. More preferred proportions range from about 100 ppm to about 10,000 ppm.

The quenching agent is a compound that receives light energy absorbed by the liquid crystal compound and converts it into heat energy, thereby preventing decomposition of the liquid crystal compound. Preferred examples of the quenching agent include compounds (8-1) to (8-7). A preferable proportion of these quenchers is about 50 ppm or more to obtain the effect, and about 20000 ppm or less so as not to raise the lower limit 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 match the GH (guest host) mode device. Preferred percentages of pigment range from about 0.01% to about 10% by weight. Antifoaming agents such as dimethylsilicone oil, methylphenylsilicone oil, etc. are added to the composition to prevent foaming. A preferable 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 percentages range from about 1 ppm to about 500 ppm.

Polymerizable compounds are used to accommodate polymer-supported alignment (PSA) type devices. Compound (4) is suitable for this purpose. A polymerizable compound different from compound (4) may be added to the composition together with compound (4). Preferred examples of such polymerizable compounds are compounds such as acrylates, methacrylates, vinyl compounds, vinyloxy compounds, propenyl ethers, epoxy compounds (oxiranes, oxetanes), vinyl ketones. Further preferred examples are derivatives of acrylates or methacrylates. A preferred proportion of compound (4) 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 mass.

A polymerizable compound such as compound (4) is polymerized by UV irradiation. Polymerization may be carried out in the presence of a suitable initiator such as a photoinitiator. Suitable conditions for polymerization, suitable types of initiators, and suitable amounts are known to those skilled in the art and 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 total weight of the polymerizable compound. A more preferred percentage is in the range of about 1% to about 3% by weight.

When storing a polymerizable compound such as compound (4), 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.

Tenth, a method for synthesizing the compound will be described. These compounds can be synthesized by known methods. Exemplify synthetic methods. Diamine compound (1) is synthesized by the method described in Japanese Patent No. 6907424. Compound (2-1) is synthesized by the method described in JP-T-2-503441. Compound (3-5) is synthesized by the method described in JP-A-57-165328. Compound (4-18) is synthesized by the method described in JP-A-7-101900. 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 method of synthesis was not listed were classified as Organic Syntheses (John Wiley & Sons, Inc), Organic Reactions (John Wiley & Sons, Inc), Comprehensive Organic Synthesis (John Wiley & Sons, Inc). Synthesis, Pergamon Press) and Shin Jikken Kagaku Koza (Maruzen). Compositions are prepared by known methods from the compounds thus obtained. For example, the component compounds are mixed and dissolved together by heating.

Finally, applications of the liquid crystal composition will be explained. This composition mainly 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. Compositions having 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 large voltage holding ratio. This composition is suitable for AM devices. This composition is particularly suitable for transmissive AM devices. This composition can be used as a composition having a nematic phase, and can be used as an optically active composition by adding an optically active compound.

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

The present invention will be described in more detail by way of examples. The invention is not limited by these examples. The present invention includes a mixture of the composition of Example 1 and the composition of Example 2. The 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. Properties of compounds, compositions, and devices were measured by the methods described below.

NMR analysis: DRX-500 manufactured by Bruker Biospin was used for the 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 with 16 integration times. Tetramethylsilane was used as an internal standard. In ^{the 19} F-NMR measurement, CFCl ₃ was used as an internal standard, and 24 integration times were performed. In the description of the nuclear magnetic resonance spectrum, s means singlet, d doublet, t triplet, q quartet, quin quintet, sex sextet, m multiplet, and br broad.

Gas chromatographic analysis: A GC-14B type gas chromatograph manufactured by Shimadzu Corporation was used for the measurement. Carrier gas is helium (2 mL/min). The sample vaporization chamber was set at 280°C and the detector (FID) 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 for separation of component compounds. The column was held at 200°C for 2 minutes and then heated to 280°C at a rate of 5°C/min. After the sample was prepared in an acetone solution (0.1% by mass), 1 μL of the solution was injected into the sample vaporization chamber. The recorder is C-R5A type Chromatopac manufactured by Shimadzu Corporation or its equivalent. The resulting gas chromatogram showed peak retention times and peak areas corresponding to the component compounds.

Chloroform, hexane, or the like 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). For the purpose of preventing overlapping of compound peaks, a capillary column CBP1-M50-025 (length 50 m, inner diameter 0.25 mm, film thickness 0.25 μm) manufactured by Shimadzu Corporation may be used.

The ratio of the liquid crystalline 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 peak area ratio in the gas chromatogram corresponds to the ratio of the liquid crystalline compound. When using the capillary column described above, the correction factor for each liquid crystalline compound may be considered to be 1. Therefore, the proportion (% by mass) of the liquid crystalline compound can be calculated from the peak area ratio.

Measurement sample: When measuring the properties of the composition or device, the composition was used as a sample as it was. When measuring the properties of the compound, a sample for measurement was prepared by mixing this compound (15% by mass) with mother liquid crystals (85% by mass). The characteristic value of the compound was calculated by extrapolation from the value obtained by the measurement. (Extrapolated value)={(measured value of sample)−0.85×(measured value of mother liquid crystal)}/0.15. When the smectic phase (or crystal) precipitates at 25°C in this ratio, the ratio of the compound 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 in this order. changed. By this extrapolation method, the maximum temperature, optical anisotropy, viscosity, and dielectric anisotropy values for the compound were obtained.

The following mother liquid crystals were used. The proportions of the component compounds are shown in % by mass.

Measurement method: Properties were measured by the following methods. Many of these are methods described in the JEITA standard (JEITA ED-2521B) deliberated and enacted by the Japan Electronics and Information Technology Industries Association (JEITA), or modified methods thereof. Met. A thin film transistor (TFT) was not attached to the TN device used for the measurement.

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

(2) Lower limit temperature of nematic phase (TC; ° _C ): A sample with a nematic phase was placed in a glass bottle and placed 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, the T _C was described 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): For measurement, a rotational viscosity measurement system LCM-2 manufactured by Toyo Technica Co., Ltd. was used. A sample was injected into a VA device in which the interval (cell gap) between two glass substrates was 10 μm. A rectangular wave (55 V, 1 ms) was applied to this device. The peak current and peak time of the transient current generated by this application were measured. Using these measurements and the dielectric anisotropy, rotational viscosity values were obtained. 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 with an Abbe refractometer equipped with a polarizing plate attached to an eyepiece using light with a wavelength of 589 nm. 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 rubbing direction. The refractive index n⊥ was measured when the polarization direction was perpendicular to the rubbing direction. 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⊥. 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-cleaned 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 device in which the interval (cell gap) between two glass substrates was 4 μm, and this device was sealed with an ultraviolet curable adhesive. A sine wave (0.5 V, 1 kHz) was applied to this device, and after 2 seconds the permittivity (ε∥) in the longitudinal direction of the liquid crystal molecules was measured.
2) Measurement of dielectric constant (ε⊥): A well-cleaned glass substrate was coated with a polyimide solution. After baking this glass substrate, the resulting alignment film was subjected to a rubbing treatment. A sample was placed in a TN device in which the distance (cell gap) between the two glass substrates was 9 μm and the twist angle was 80 degrees. A sine wave (0.5 V, 1 kHz) was applied to this device, and after 2 seconds the permittivity (ε⊥) in the minor axis direction of the liquid crystal molecules was measured.

(7) Threshold voltage (Vth; measured at 25° C.; V): A luminance meter LCD5100 manufactured by Otsuka Electronics Co., Ltd. was used for the measurement. The light source was a halogen lamp. A sample is placed in a normally black mode VA element in which the distance (cell gap) between two glass substrates is 4 μm and the rubbing direction is anti-parallel, and an adhesive that cures this element with ultraviolet light is applied. It was sealed using The voltage (60 Hz, rectangular wave) applied to this device was increased stepwise from 0 V to 20 V by 0.02 V. At this time, the device was irradiated with light from a vertical direction, and the amount of light transmitted through the device was measured. A voltage-transmittance curve was prepared in which the transmittance was 100% when the amount of light was maximum and the transmittance was 0% when the amount of light was 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 device used for measurement had a polyimide alignment film, and the distance between the two glass substrates (cell gap) was 5 μm. . The device was sealed with a UV curable adhesive after the sample was placed. This TN device was charged by applying a pulse voltage (5 V for 60 microseconds). The decaying voltage was measured with a high-speed voltmeter for 16.7 milliseconds, and the area A between the voltage curve and the horizontal axis in a unit period was determined. Area B was the area when there was no attenuation. The voltage holding ratio was expressed as a percentage of area A with respect to area B.

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

(10) Voltage holding ratio (VHR-3; measured at 25° C.; %): After irradiation with ultraviolet rays, the voltage holding ratio was measured to evaluate the stability against ultraviolet rays. The TN device used for measurement had a polyimide alignment film and a cell gap of 5 μm. A sample was injected into this device and irradiated with light 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 the voltage decaying over 16.7 milliseconds. A composition with a large VHR-3 has a large UV stability. 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 into which the sample was injected in a constant temperature chamber at 80°C for 500 hours, the voltage holding rate was measured and the stability against heat was measured. evaluated. The VHR-4 measurement measured the voltage decaying over 16.7 milliseconds. Compositions with large VHR-4 have greater thermal stability.

(12) Response time (τ; measured at 25°C; ms): A luminance meter LCD5100 manufactured by Otsuka Electronics Co., Ltd. was used for the measurement. The light source was a halogen lamp. A Low-pass filter was set at 5 kHz. A sample was placed in a normally black mode VA device in which the interval (cell gap) between the two glass substrates was 4 μm and the rubbing direction was antiparallel. The device was sealed with a UV curable adhesive. A rectangular wave (60 Hz, 10 V, 0.5 seconds) was applied to this device. At this time, the device was irradiated with light from a vertical direction, and the amount of light transmitted through the device was measured. It was considered that the transmittance was 100% when the amount of light was maximum, and the transmittance was 0% when the amount of light was minimum. The response time was expressed as the time required for the transmittance to change from 90% to 10% (fall time; milliseconds).

(13) Specific resistance (.rho.; measured at 25.degree. C.; .OMEGA.cm): 1.0 mL of a sample was injected into a container equipped with electrodes. A DC voltage (10 V) was applied to this container, and the DC current was measured after 10 seconds. The specific resistance was calculated from the following formula. (Specific resistance)={(Voltage)×(Electric capacity of container)}/{(DC current)×(Vacuum permittivity)}.

(14) Contrast ratio: The luminance-voltage characteristics (BV characteristics) of the manufactured liquid crystal cell were measured, and the contrast ratio (CR) was obtained using the minimum luminance and the maximum luminance.
CR= _Bmax / _Bmin
In the formula, B _max indicates the maximum brightness in the BV characteristic, and B _min indicates the minimum brightness in the BV characteristic. A larger CR value means that the brightness display is clearer and the contrast is better.

The component compounds of the liquid crystal composition are represented by symbols based on the definitions in Table 3 below. In Table 3, the configuration for 1,4-cyclohexylene is trans. The numbers in parentheses after the symbols correspond to the compound numbers. The symbol (-) means other liquid crystalline 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 are summarized.

1. Liquid Crystal Compositions Liquid crystal compositions used in Examples are shown below.
[Composition Example M1]
3-HB(2F,3F)-O2 (2-1) 10%
5-HB(2F,3F)-O2(2-1) 10%
3-H2B (2F, 3F)-O2 (2-2) 8%
5-H2B (2F, 3F)-O2 (2-2) 8%
3-HDhB(2F,3F)-O2(2-13) 5%
3-HBB(2F,3F)-O2(2-14) 8%
4-HBB(2F,3F)-O2(2-14) 5%
5-HBB(2F,3F)-O2(2-14) 5%
V-HBB (2F, 3F)-O2 (2-14) 5%
V2-HBB(2F,3F)-O2(2-14) 5%
3-HH-4 (3-1) 14%
V-HHB-1 (3-5) 11%
3-HBB-2 (3-6) 6%
NI=89.4° C.; Tc<−30° C.; Δn=0.109; Δε=−3.8; Vth=2.24 V; η=24.6 mPa·s.

[Composition example M2]
3-HB(2F,3F)-O2 (2-1) 10%
V-HB (2F, 3F)-O2 (2-1) 7%
3-BB(2F,3F)-O2 (2-6) 7%
V2-BB(2F, 3F)-O1 (2-6) 7%
2-HHB(2F, 3F)-O2 (2-8) 5%
3-HHB(2F,3F)-O2(2-8) 10%
3-HBB(2F,3F)-O2(2-14) 10%
V-HBB(2F,3F)-O2(2-14) 8%
3-B (2F, 3F) B (2F, 3F)-O2 (2) 3%
2-HH-3 (3-1) 14%
3-HB-O1 (3-2) 5%
3-HHB-1 (3-5) 3%
3-HHB-O1 (3-5) 3%
3-HHB-3 (3-5) 5%
2-BB(F)B-3 (3-8) 3%
NI=72.5° C.; Tc<−20° C.; Δn=0.112; Δε=−3.9; Vth=2.14 V; η=22.8 mPa·s.

[Composition example M3]
3-HB(2F,3F)-O4 (2-1) 6%
3-H2B (2F, 3F)-O2 (2-2) 8%
3-H1OB (2F, 3F)-O2 (2-3) 5%
3-BB(2F,3F)-O2 (2-6) 10%
3-HHB(2F,3F)-O2(2-8) 7%
V-HHB (2F, 3F)-O2 (2-8) 7%
V-HHB (2F, 3F)-O4 (2-8) 7%
3-HBB(2F,3F)-O2(2-14) 6%
V-HBB (2F, 3F)-O2 (2-14) 6%
1V2-HBB (2F, 3F)-O2 (2-14) 5%
3-HH-V (3-1) 11%
1-BB-3 (3-3) 6%
3-HHB-1 (3-5) 4%
3-HHB-O1 (3-5) 4%
3-HBB-2 (3-6) 5%
3-B(F)BB-2 (3-7) 3%
NI=87.7° C.; Tc<−30° C.; Δn=0.129; Δε=−4.4; Vth=2.17 V; η=26.2 mPa·s.

[Composition example M4]
3-HB(2F,3F)-O2 (2-1) 7%
1V2-HB (2F, 3F)-O2 (2-1) 7%
3-BB(2F,3F)-O2 (2-6) 8%
3-HHB(2F,3F)-O2(2-8) 5%
5-HHB(2F,3F)-O2(2-8) 4%
3-HH1OB (2F, 3F)-O2 (2-10) 5%
2-HBB(2F,3F)-O2(2-14) 3%
3-HBB(2F,3F)-O2(2-14) 8%
4-HBB(2F,3F)-O2(2-14) 5%
V-HBB(2F,3F)-O2(2-14) 8%
2-BB (2F, 3F) B-3 (2-19) 4%
3-HH-V (3-1) 27%
3-HH-V1 (3-1) 6%
V-HHB-1 (3-5) 3%
NI=78.2° C.; Tc<−30° C.; Δn=0.109; Δε=−3.3; Vth=2.08 V; η=16.3 mPa·s.

[Composition Example M5]
3-HB(2F,3F)-O4 (2-1) 15%
3-chB(2F,3F)-O2(2-5) 7%
2-HchB(2F,3F)-O2(2-12) 8%
3-HBB(2F,3F)-O2(2-14) 8%
5-HBB(2F,3F)-O2(2-14) 7%
V-HBB (2F, 3F)-O2 (2-14) 5%
3-dhBB(2F,3F)-O2(2-16) 5%
5-HH-V (3-1) 18%
7-HB-1 (3-2) 5%
V-HHB-1 (3-5) 7%
V2-HHB-1 (3-5) 7%
3-HBB(F)B-3 (3-13) 8%
NI=98.5° C.; Tc<−30° C.; Δn=0.112; Δε=−3.2; Vth=2.47 V; η=23.5 mPa·s.

[Composition example M6]
3-H2B (2F, 3F)-O2 (2-2) 18%
5-H2B (2F, 3F)-O2 (2-2) 17%
3-HHB(2F,3CL)-O2(2-11) 5%
3-HBB(2F,3CL)-O2(2-15) 8%
5-HBB(2F,3CL)-O2(2-15) 7%
3-DhHB(2F,3F)-O2 (2) 5%
3-HH-V (3-1) 11%
3-HH-VFF (3-1) 7%
F3-HH-V (3-1) 10%
3-HHEH-3 (3-4) 4%
3-HB(F)HH-2 (3-10) 3%
3-HHEBH-3 (3-11) 5%
NI=78.2° C.; Tc<−30° C.; Δn=0.084; Δε=−2.6; Vth=2.45 V; η=22.5 mPa·s.

[Composition Example M7]
3-H2B (2F, 3F)-O2 (2-2) 7%
V-HHB (2F, 3F)-O2 (2-8) 8%
3-HH1OB (2F, 3F)-O2 (2-10) 5%
2-HchB(2F,3F)-O2(2-12) 8%
3-HDhB(2F,3F)-O2(2-13) 3%
2-BB (2F, 3F) B-3 (2-19) 7%
2-BB (2F, 3F) B-4 (2-19) 7%
3-DhH1OB(2F,3F)-O2 (2) 4%
4-HH-V (3-1) 15%
3-HH-V1 (3-1) 6%
1-HH-2V1 (3-1) 5%
3-HH-2V1 (3-1) 5%
V2-BB-1 (3-3) 5%
1V2-BB-1 (3-3) 5%
3-HHB-1 (3-5) 6%
3-HB(F)BH-3 (3-12) 4%
NI=87.5° C.; Tc<−30° C.; Δn=0.115; Δε=−2.0; Vth=2.82 V; η=17.2 mPa·s.

[Composition example M8]
V-HB (2F, 3F)-O2 (2-1) 8%
3-H2B (2F, 3F)-O2 (2-2) 10%
3-BB(2F,3F)-O2 (2-6) 10%
2O-BB(2F, 3F)-O2 (2-6) 3%
2-HHB(2F,3F)-O2 (2-8) 4%
3-HHB(2F,3F)-O2(2-8) 7%
V-HHB (2F, 3F)-O2 (2-8) 5%
3-HDhB(2F,3F)-O2(2-13) 6%
2-HBB(2F,3F)-O2(2-14) 5%
3-HBB(2F,3F)-O2(2-14) 6%
3-dhBB(2F,3F)-O2(2-16) 4%
2-BB (2F, 3F) B-3 (2-19) 6%
2-BB (2F, 3F) B-4 (2-19) 6%
3-HH1OCro(7F,8F)-5(2-27) 4%
3-HH-V (3-1) 11%
1-BB-5 (3-3) 5%
NI=70.9° C.; Tc<−20° C.; Δn=0.129; Δε=−4.4; Vth=1.74 V; η=27.2 mPa·s.

[Composition example M9]
3-HB(2F,3F)-O2 (2-1) 7%
V-HB (2F, 3F)-O2 (2-1) 8%
3-H2B (2F, 3F)-O2 (2-2) 8%
3-BB(2F,3F)-O2 (2-6) 10%
2-HHB(2F,3F)-O2 (2-8) 4%
3-HHB(2F,3F)-O2(2-8) 7%
V-HHB (2F, 3F)-O2 (2-8) 6%
3-HDhB(2F,3F)-O2(2-13) 6%
2-HBB(2F,3F)-O2(2-14) 5%
3-HBB(2F,3F)-O2(2-14) 6%
V-HBB (2F, 3F)-O2 (2-14) 5%
V2-HBB(2F,3F)-O2(2-14) 4%
3-H1OCro(7F,8F)-5(2-26) 3%
3-HEB (2F, 3F) B (2F, 3F)-O2 (2) 3%
3-HH-O1 (3-1) 5%
1-BB-5 (3-3) 4%
V-HHB-1 (3-5) 4%
5-HBBH-3 (3) 5%
NI=81.5° C.; Tc<−30° C.; Δn=0.122; Δε=−4.7; Vth=1.76 V; η=31.8 mPa·s.

[Composition Example M10]
V-HB (2F, 3F)-O4 (2-1) 14%
V-H1OB (2F, 3F)-O2 (2-3) 3%
3-BB(2F,3F)-O2 (2-6) 10%
3-HHB(2F,3F)-O2(2-8) 7%
V2-HHB (2F, 3F)-O2 (2-8) 7%
V-HH1OB (2F, 3F)-O2 (2-10) 6%
V-HBB (2F, 3F)-O4 (2-14) 9%
1V2-HBB (2F, 3F)-O2 (2-14) 5%
3-HH-V (3-1) 13%
1-BB-3 (3-3) 3%
3-HHB-1 (3-5) 4%
3-HHB-O1 (3-5) 4%
V-HBB-2 (3-6) 5%
1-BB(F)B-2V (3-8) 6%
5-HBBH-1O1 (-) 4%
NI = 93.6°C; Tc <-30°C; Δn = 0.125; Δε = -3.9; Vth = 2.20V;

[Composition Example M11]
3-HB(2F,3F)-O4 (2-1) 6%
3-H2B (2F, 3F)-O2 (2-2) 8%
3-H1OB (2F, 3F)-O2 (2-3) 4%
3-BB(2F,3F)-O2 (2-6) 7%
3-HHB(2F,3F)-O2(2-8) 10%
V-HHB (2F, 3F)-O2 (2-8) 7%
V-HHB (2F, 3F)-O4 (2-8) 7%
3-HBB(2F,3F)-O2(2-14) 6%
V-HBB (2F, 3F)-O2 (2-14) 6%
1V2-HBB (2F, 3F)-O2 (2-14) 5%
2-HH-3 (3-1) 12%
1-BB-3 (3-3) 6%
3-HHB-1 (3-5) 4%
3-HHB-O1 (3-5) 4%
3-HBB-2 (3-6) 5%
3-B(F)BB-2 (3-7) 3%
NI=92.8° C.; Tc<−20° C.; Δn=0.126; Δε=−4.4; Vth=2.19 V; η=26.0 mPa·s.

[Composition example M12]
3-HB(2F,3F)-O2 (2-1) 5%
1V2-HB (2F, 3F)-O2 (2-1) 7%
V2-BB(2F, 3F)-O2 (2-6) 8%
3-HHB(2F,3F)-O2(2-8) 5%
5-HHB(2F,3F)-O2(2-8) 4%
3-HH1OB (2F, 3F)-O2 (2-10) 5%
2-HBB(2F,3F)-O2(2-14) 3%
3-HBB(2F,3F)-O2(2-14) 8%
4-HBB(2F,3F)-O2(2-14) 5%
V-HBB(2F,3F)-O2(2-14) 8%
2-BB (2F, 3F) B-3 (2-19) 4%
3-HH-V (3-1) 27%
3-HH-V1 (3-1) 6%
V-HHB-1 (3-5) 5%
NI=81.7° C.; Tc<−20° C.; Δn=0.110; Δε=−3.2; Vth=2.12 V; η=15.8 mPa·s.

[Composition example M13]
3-HB(2F,3F)-O2 (2-1) 7%
1V2-HB (2F, 3F)-O2 (2-1) 7%
3-BB(2F,3F)-O2 (2-6) 8%
3-HHB(2F,3F)-O2(2-8) 5%
5-HHB(2F,3F)-O2(2-8) 4%
3-HH1OB (2F, 3F)-O2 (2-10) 5%
2-HBB(2F,3F)-O2(2-14) 3%
3-HBB(2F,3F)-O2(2-14) 8%
4-HBB(2F,3F)-O2(2-14) 5%
V-HBB(2F,3F)-O2(2-14) 8%
2-BB (2F, 3F) B-3 (2-19) 4%
3-HH-V (3-1) 33%
V-HHB-1 (3-5) 3%
NI=76.0° C.; Tc<−30° C.; Δn=0.107; Δε=−3.2; Vth=2.08 V; η=16.0 mPa·s.

2. Liquid Crystal Aligning Agent The diamine compound (1), other diamine compounds, tetracarboxylic dianhydrides, solvents, and additives used in the examples are shown below.
<Diamine compound (1)>

<Other diamine compounds>

<Tetracarboxylic dianhydride>

<Solvent>
NMP: N-methyl-2-pyrrolidone BC: Butyl cellosolve (ethylene glycol monobutyl ether)

<Additive>
Ad1: 3-aminopropyltriethoxysilane Ad2: 1,3-bis(4,5-dihydro-2-oxazolyl)benzene

<Varnish Preparation Example 1: Varnish A1>
Diamine isomer mixture 1 (0.883 g) was placed in a 100 mL three-necked flask equipped with a stirring blade and a nitrogen inlet tube, and NMP (10.0 g) was added and stirred. AN-6 (0.617 g) and NMP (2.5 g) were added to this solution and stirred at room temperature for 12 hours. NMP (6.0 g) and BC (5.0 g) are added thereto, and the solution is heated and stirred at 80 ° C. until the weight average molecular weight of the polymer of the solute reaches the target weight average molecular weight, and the weight average of the solute is Varnish A1 was obtained with a molecular weight of approximately 18,000 and a polymer concentration of 6% by weight.

<Varnish Preparation Examples 2 to 14: Varnishes A2 to A14>
Varnishes A2 to A14 having a polymer concentration of 6% by weight were prepared in the same manner as in Preparation Example 1, except that the compounds used as diamines and tetracarboxylic dianhydrides were changed. In the varnishes A12 to A14, the heating and stirring conditions were adjusted so that the weight average molecular weight of the polymer was about 50,000.

<Varnish Preparation Example 15: Varnish A15>
A two-stage polymerization process was performed to synthesize a block polymer of polyamic acid.
(1) Step 1 Add DI-3 (0.408 g), DI-24 (1.011 g), and NMP (20.0 g) to a 200 mL three-necked flask equipped with a stirring blade and a nitrogen inlet tube. Stirred. AN-9 (1.17 g), AN-1 (0.747 g), and NMP (10.0 g) were added to this solution, and stirring was continued at room temperature for 6 hours to obtain a first polyamic acid solution. .
(2) Step 2 Diamine isomer mixture 1 (1.57 g), AN-6 (1.10 g), and NMP (34.0 g) were added to the flask used for the first-stage polymerization. Stirring was continued for hours to obtain a mixed solution of the first polyamic acid and the second polyamic acid. BC (30.0 g) was added to this reaction solution and stirred for 8 hours while heating to 60° C. to obtain a polyamic acid block polymer solution with a polymer concentration of 6% by weight. This polyamic acid block polymer solution is designated as varnish A15.

<Varnish Preparation Example 16: Varnish A16>
A varnish A16 having a polymer concentration of 6% by weight was prepared in the same manner as in Preparation Example 15, except that the compounds used as diamines and tetracarboxylic dianhydrides were changed.

Preparation Examples 1 to 14 and Preparation Examples 15 and 16 are summarized in Tables 4 and 5, respectively.

<Preparation of Liquid Crystal Aligning Agents: Liquid Crystal Aligning Agents 1 to 16 and Comparative Liquid Crystal Aligning Agent 1>
Varnish A1 was diluted with an NMP/BC mixed solution (NMP/BC=7/3 weight ratio) and stirred to give a liquid crystal aligning agent 1 so as to have a concentration of 4% by weight.
Liquid crystal aligning agents 2 to 16 and comparative liquid crystal aligning agent 1 were prepared in the same manner as liquid crystal aligning agent 1, except for the varnish used and the presence or absence of additives. Liquid crystal aligning agents 1 to 16 and comparative liquid crystal aligning agent 1 are summarized in Table 6. In Table 6, the amount of additive added is expressed in parts by weight relative to the weight of the polymer in the varnish.

[Example 1]
The liquid crystal aligning agent 1 was applied to the glass substrate with FFS electrodes and the glass substrate with column spacers by a spinner method. After coating, the substrate is heated at 60° C. for 80 seconds to evaporate the solvent, and then, using Multilight ML-501C/B manufactured by Ushio Inc., the substrate is exposed to ultraviolet light through a polarizing plate from a vertical direction. was irradiated with linearly polarized light of The exposure energy at this time is determined by measuring the amount of light using an ultraviolet integrating light meter UIT-150 (light receiver: UVD-S254) manufactured by Ushio Inc., and exposing so that the amount of light becomes 1.0 J/cm ² at a wavelength of 254 nm. adjusted the time. After that, baking treatment was performed at 220° C. for 30 minutes to form an alignment film having a thickness of about 100 nm. The two substrates thus produced were bonded together with the surfaces on which the liquid crystal alignment films are formed facing each other, and with a gap for injecting the liquid crystal composition between the opposed liquid crystal alignment films. At this time, the polarization directions of the linearly polarized light applied to the respective liquid crystal alignment films were made parallel. A liquid crystal composition (composition example M1) was injected into this cell to prepare a liquid crystal display element having a cell thickness of 5 μm. When the contrast ratio of the manufactured liquid crystal display device was measured, it was 3,900.

[Comparative Example 1]
A liquid crystal display element was produced in the same manner as in Example 1, except that the comparative liquid crystal aligning agent 1 was used instead of the liquid crystal aligning agent 1. When the contrast ratio of the manufactured liquid crystal display device was measured, it was 3,200.

[Examples 2 to 16]
Liquid crystal display elements of Examples 2 to 16 were produced by changing the liquid crystal aligning agent, the liquid crystal composition, and the amount of ultraviolet light exposure, and the contrast ratio was measured. The results are summarized in Table 7.

As shown in Table 7, the contrast ratios of the liquid crystal display elements of Examples 1 to 16 were all higher than the contrast ratio of the liquid crystal display element of Comparative Example 1. Formula (DI-29) used in Comparative Example 1 is a diamine compound that undergoes photofries transition. The liquid crystal alignment film using the diamine compound (1) has better alignment than the conventionally known liquid crystal alignment film using a diamine compound that causes optical Fries transition, and the liquid crystal display device using the same has It was found to have a high contrast ratio.

The liquid crystal display device of the present invention can be used for liquid crystal monitors, liquid crystal televisions and the like.

Claims (14)

A group of electrodes formed on one or both of a pair of substrates arranged to face each other, a plurality of active elements connected to the group of electrodes, and a liquid crystal formed on the facing surfaces of each of the pair of substrates. A liquid crystal display element comprising an alignment film and a liquid crystal composition having negative dielectric anisotropy sandwiched between the pair of substrates, wherein the liquid crystal alignment film is represented by formula (1) as a diamine. A liquid crystal aligning film formed from a liquid crystal aligning agent containing a polymer obtained by polymerizing a raw material composition containing at least one compound selected from diamine compounds and tetracarboxylic dianhydrides, a liquid crystal display element.

In formula (1), R ¹ and R ² are hydrogen, halogen, alkyl having 1 to 6 carbon atoms, haloalkyl having 1 to 6 carbon atoms, or alkoxy having 1 to 6 carbon atoms, and R ¹ and R ² are may be taken together to form optionally substituted methylene; X is halogen, alkyl of 1 to 6 carbons, haloalkyl of 1 to 6 carbons, or alkoxy of 1 to 6 carbons; n is 0, 1, 2, 3, or 4; The liquid crystal alignment film contains a polymer obtained by polymerizing a raw material composition containing at least one compound selected from diamine compounds represented by formula (1-1) as diamines and tetracarboxylic dianhydrides. 2. The liquid crystal display element according to claim 1, which is a liquid crystal alignment film formed from a liquid crystal alignment agent.

In formula (1-1), R ¹ and R ² are hydrogen, halogen, alkyl having 1 to 6 carbon atoms, haloalkyl having 1 to 6 carbon atoms, or alkoxy having 1 to 6 carbon atoms, and R ¹ and R ² may be taken together to form optionally substituted methylene; X is halogen, alkyl having 1 to 6 carbon atoms, haloalkyl having 1 to 6 carbon atoms, or alkoxy having 1 to 6 carbon atoms; Yes; n is 0, 1, 2, 3, or 4. The liquid crystal alignment film contains a polymer obtained by polymerizing a raw material composition containing at least one compound selected from diamine compounds represented by formula (1-1) as diamines and tetracarboxylic dianhydrides. 3. The liquid crystal display element according to claim 2, which is a liquid crystal alignment film formed from a liquid crystal alignment agent.

In formula (1-1), R ¹ and R ² are hydrogen, halogen, alkyl having 1 to 6 carbon atoms, haloalkyl having 1 to 6 carbon atoms, or alkoxy having 1 to 6 carbon atoms, and R ¹ and R ² may be taken together to form optionally substituted methylene; X is halogen, alkyl having 1 to 6 carbon atoms, haloalkyl having 1 to 6 carbon atoms, or alkoxy having 1 to 6 carbon atoms; Yes; n is 0. 4. The liquid crystal display element according to any one of claims 1 to 3, wherein the liquid crystal composition contains, as component A, at least one compound selected from compounds represented by formula (2).

In formula (2), R ³ and R ⁴ 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 C 1-12 alkyl in which one hydrogen is replaced by fluorine or chlorine; ring A and ring C are 1,4-cyclohexylene, 1,4-cyclohexenylene, tetrahydropyran-2,5- diyl, 1,4-phenylene, 1,4-phenylene in which at least one hydrogen is replaced by fluorine or chlorine, naphthalene-2,6-diyl, naphthalene-2 in which at least one hydrogen is replaced by fluorine or chlorine, 6-diyl, chroman-2,6-diyl, or chroman-2,6-diyl in which at least one hydrogen is replaced by fluorine or chlorine; Ring B is 2,3-difluoro-1,4-phenylene , 2-chloro-3-fluoro-1,4-phenylene, 2,3-difluoro-5-methyl-1,4-phenylene, 3,4,5-trifluoronaphthalene-2,6-diyl, 7,8 -difluorochroman-2,6-diyl, 3,4,5,6-tetrafluorofluorene-2,7-diyl, 4,6-difluorodibenzofuran-3,7-diyl, 4,6-difluorodibenzothiophene-3 ,7-diyl, or 1,1,6,7-tetrafluoroindan-2,5-diyl; Z ¹ and Z ² are a single bond, ethylene, vinylene, methyleneoxy, or carbonyloxy; is 0, 1, 2, or 3, b is 0 or 1; and the sum of a and b is 3 or less. 5. The liquid crystal composition according to any one of claims 1 to 4, wherein the component A contains at least one compound selected from compounds represented by formulas (2-1) to (2-35). liquid crystal display element.

In formulas (2-1) to (2-35), R ³ and R ⁴ 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 alkyl having 1 to 12 carbon atoms in which at least one hydrogen is replaced with fluorine or chlorine. 6. The liquid crystal display device according to claim 4, wherein the proportion of component A is in the range of 5% by mass to 95% by mass. 7. The liquid crystal display element according to any one of claims 1 to 6, wherein the liquid crystal composition contains, as component B, at least one compound selected from compounds represented by formula (3).

In formula (3), R ⁵ and R ⁶ are alkyl having 1 to 12 carbon atoms, alkoxy having 1 to 12 carbon atoms, alkenyl having 2 to 12 carbon atoms, 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 D and ring E are 1,4-cyclohexylene, 1,4-phenylene, 2-fluoro-1,4-phenylene, or 2,5-difluoro-1,4-phenylene; Z ³ is a single bond, ethylene, vinylene, methyleneoxy, or carbonyloxy; c is 1, 2 or 3. 8. The liquid crystal composition according to any one of claims 1 to 7, wherein the component B contains at least one compound selected from compounds represented by formulas (3-1) to (3-14). liquid crystal display element.

In formulas (3-1) to (3-14), R ⁵ and R ⁶ 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 alkyl of 1 to 12 carbon atoms in which is replaced by fluorine or chlorine, or alkenyl of 2 to 12 carbon atoms in which at least one hydrogen is replaced by fluorine or chlorine. 9. The liquid crystal display device according to claim 7, wherein the proportion of component B is in the range of 5% by mass to 95% by mass. 10. The liquid crystal display element according to any one of claims 1 to 9, wherein the liquid crystal composition contains, as additive X, at least one compound selected from polymerizable compounds represented by formula (4).

In formula (4), ring I and ring K are cyclohexyl, cyclohexenyl, phenyl, 1-naphthyl, 2-naphthyl, tetrahydropyran-2-yl, 1,3-dioxan-2-yl, pyrimidin-2-yl , or pyridin-2-yl, wherein in these rings at least one hydrogen is fluorine, chlorine, alkyl of 1 to 12 carbons, alkoxy of 1 to 12 carbons, or at least one hydrogen is fluorine or chlorine ring J 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 may be substituted with alkyl having 1 to 12 carbon atoms substituted with fluorine or chlorine; Z ⁶ and Z ⁷ are a single bond or alkylene having 1 to 10 carbon atoms, in which at least one —CH _2- may be replaced by -O-, -CO-, -COO- or -OCO- and at least one -CH ₂ CH ₂ - is -CH=CH-, -C(CH ₃ ) =CH-, -CH=C(CH ₃ )-, or -C(CH ₃ )=C(CH ₃ )- in which at least one hydrogen is fluorine or chlorine; P ¹ to P ³ are polymerizable groups; Sp ¹ to Sp ³ are a single bond or alkylene having 1 to 10 carbon atoms, in which at least one —CH ₂ — may be replaced with -O-, -COO-, -OCO-, or -OCOO- and at least one -CH ₂ CH ₂ - is replaced with -CH=CH- or -C≡C- in these groups at least one hydrogen may be replaced by fluorine or chlorine; f is 0, 1, or 2; g, h, and i are 0, 1, 2, 3, or 4; and the sum of g, h, and i is 1 or greater. 11. The liquid crystal display element according to claim 10, wherein P ¹ to P ³ in formula (4) are groups selected from polymerizable groups represented by formulas (P-1) to (P-5).

In formulas (P-1) to (P-5), M ¹ to M ³ are hydrogen, fluorine, alkyl having 1 to 5 carbon atoms, or C 1 in which at least one hydrogen is replaced with fluorine or chlorine is an alkyl of from to 5; 12. Any one of claims 1 to 11, wherein the liquid crystal composition contains, as additive X, at least one compound selected from polymerizable compounds represented by formulas (4-1) to (4-29). The liquid crystal display device according to the above item.

In formulas (4-1) to (4-29), Sp ¹ to Sp ³ are a single bond or alkylene having 1 to 10 carbon atoms, and in this alkylene, at least one —CH ₂ — is —O may be replaced by -, -COO-, -OCO-, or -OCOO-, at least one -CH ₂ CH ₂ - may be replaced by -CH=CH- or -C≡C-; In these groups, at least one hydrogen may be replaced by fluorine or chlorine; P ⁴ to P ⁶ are selected from groups represented by formulas (P-1) to (P-3) is a polymerizable group;

In formulas (P-1) to (P-3), M ¹ to M ³ are hydrogen, fluorine, alkyl having 1 to 5 carbon atoms, or C 1 in which at least one hydrogen is replaced by fluorine or chlorine is an alkyl of from to 5; 13. The liquid crystal display element according to any one of claims 10 to 12, wherein the proportion of additive X is in the range of 0.03% by mass to 10% by mass. 14. The liquid crystal display element according to any one of claims 1 to 13, wherein the operation mode is IPS mode, VA mode, FFS mode or FPA mode, and the driving system is active matrix system.