TW201912769A - Application of liquid crystal composition, liquid crystal display element and liquid crystal composition in liquid crystal display element - Google Patents

Abstract

This liquid crystal composition contains a polymerizable compound represented by formula (1) as a first additive, and has a negative dielectric constant anisotropy. In formula (1): R15, R16, and R17 each independently represent hydrogen, -Sp11-P11, -Sp12-P12, or the like; a11 and a12 each independently represent 0, 1, 2, 3, or 4, and the sum of a11 and a12 is 1-8; ring A11 and ring A12 each independently represent an alicyclic hydrocarbon having 3-18 carbon atoms, an aromatic hydrocarbon having 6-18 carbon atoms, or the like; Z11 and Z12 each independently represent a single bond or an alkylene having 1-10 carbon atoms; b11 and b12 each independently represent 0, 1, 2, or 3; Sp11 and Sp12 each independently represent a single bond or the like; and P11 and P12 each independently represent a polymerizable group.

Description

Liquid crystal composition, liquid crystal display element and application of liquid crystal composition in liquid crystal display element

The present invention relates to a liquid crystal composition, a liquid crystal display element containing the composition, and the like. In particular, there is a polymerizable compound (or its polymer) containing a nitrogen atom in a bonding group, and by the action of the compound, it has a high voltage retention rate and does not use existing polyimide or the like The alignment film can also achieve vertical alignment of liquid crystal molecules, and a liquid crystal composition with negative dielectric anisotropy, and a liquid crystal display element.

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

The liquid crystal display element contains a liquid crystal composition having a nematic phase. This composition has appropriate characteristics. By improving the characteristics of the composition, an AM device having good characteristics can be obtained. The relationship between the characteristics of the two is summarized in Table 1 below. The characteristics of the composition will be further described based on a commercially available AM device. The temperature range of the nematic phase is related to the temperature range in which the element can be used. The preferred upper limit temperature of the nematic phase is approximately 70 ° C or higher, and the preferred lower limit temperature of the nematic phase is approximately -10 ° C or lower. The viscosity of the composition is related to the response time of the device. In order to display a moving image with a component, the response time is preferably short. The ideal response time is less than 1 millisecond. Therefore, it is preferable that the viscosity of the composition is small. Furthermore, the viscosity at low temperature is preferably small.

[Table 1]

The optical anisotropy of the composition is related to the contrast of the device. Depending on the mode of the device, a large optical anisotropy or a small optical anisotropy, that is, an appropriate optical anisotropy is required. The product (Δn × d) of the optical anisotropy (Δn) of the composition and the cell gap (d) of the device is designed to maximize the contrast. The appropriate value of the product depends on the type of operation mode. In the VA mode element, the value is in the range of about 0.30 μm to about 0.40 μm, and in the IPS mode or FFS mode, the value is in the range of about 0.20 μm to about 0.30 μm. In these cases, the element having a small cell gap is preferably a composition having a large optical anisotropy. The large dielectric anisotropy of the composition contributes to the low threshold voltage of the device, small power consumption, and large contrast. Therefore, it is preferably a large dielectric anisotropy. The large specific resistance of the composition contributes to a large voltage retention rate and a large contrast ratio of the device. Therefore, in the initial stage, it is preferable to have a composition having a large specific resistance not only at room temperature but also at a temperature close to the upper limit temperature of the nematic phase. Moreover, it is preferable to have a composition having a large specific resistance not only at room temperature but also at a temperature close to the upper limit temperature of the nematic phase after long-term use. The stability of the composition to ultraviolet rays and heat is related to the life of the device. When the stability is high, the life of the device is long. Such characteristics are preferred for AM components used in liquid crystal projectors, liquid crystal televisions, and the like.

In a polymer sustained alignment (PSA) type liquid crystal display element, a liquid crystal composition containing a polymer is used. First, the composition to which a small amount of polymerizable compound is added is injected into the device. Next, while applying a voltage between the substrates of the element, the composition was irradiated with ultraviolet rays. The polymerizable compound is polymerized to form a polymer network structure in the composition. In this composition, the alignment of the liquid crystal molecules can be controlled by the polymer, so the response time of the element is shortened and the afterimage of the image is improved. Such an effect of a polymer can be expected in an element having modes such as TN, ECB, OCB, IPS, VA, FFS, and FPA.

In general liquid crystal display devices, the vertical alignment of liquid crystal molecules is achieved by polyimide alignment films. On the other hand, in a liquid crystal display element that does not have an alignment film, a liquid crystal composition containing a polymer and a polar compound is used. First, a composition added with a small amount of a polymerizable compound and a small amount of a polar compound is injected into the device. Here, polar compounds are adsorbed on the substrate surface and arranged. According to this arrangement, the liquid crystal molecules are aligned. Next, while applying a voltage between the substrates of the element, the composition was irradiated with ultraviolet rays. Here, the polymerizable compound polymerizes and stabilizes the alignment of the liquid crystal molecules. In this composition, the alignment of the liquid crystal molecules can be controlled by the polymer and the polar compound, so the response time of the element is shortened and the afterimage of the image is improved. Furthermore, in an element that does not have an alignment film, a step of forming an alignment film is not necessary. Since there is no alignment film, the resistance of the device will not be reduced due to the interaction between the alignment film and the composition. In an element having modes such as TN, ECB, OCB, IPS, VA, FFS, and FPA, such an effect using a combination of a polymer and a polar compound can be expected.

In an AM element having a TN mode, a composition having positive dielectric anisotropy is used. In an AM element having a VA mode, a composition having negative dielectric anisotropy is used. In an AM element having an IPS mode or an FFS mode, a composition having positive or negative dielectric anisotropy is used. In a polymer-stabilized alignment type AM device, a composition having positive or negative dielectric anisotropy is used. An example of a liquid crystal composition having negative dielectric anisotropy is disclosed in Patent Document 1 below. This method proposes a method of obtaining a PSA type liquid crystal display element without a polyimide alignment film using a liquid crystal composition containing a polymerizable compound having a polar group and having negative dielectric anisotropy. In the method of Patent Document 1, the liquid crystal compound is vertically aligned using a polymerizable compound having a polar group. The vertical alignment of the liquid crystal compound is caused by the polar compound adsorbed on the substrate. In this method, since the polar compound has one polymerizable group, it is difficult to improve the mechanical strength as a polymer, and as a result, the electrical characteristics may decrease. Therefore, the properties of the polymer used in combination with a polymerizable compound having no polar group but having two or more polymerizable groups may be improved. In this case, there is also a problem that the use of a polymerizable compound having two or more polymerizable groups cannot sufficiently satisfy electrical characteristics. [Prior Art Literature] [Patent Literature]

[Patent Document 1] International Publication Manual No. 2017/104154

[Problem to be solved by the invention] One problem to be solved by the present invention is to use a liquid crystal composition containing a polymerizable compound (or a polymer thereof) containing a nitrogen atom in a bonding group and having negative dielectric anisotropy to Provide a liquid crystal display element having good electrical characteristics. In addition, another subject is to provide a liquid crystal composition for obtaining a liquid crystal display element having good electrical characteristics. Furthermore, another object is to provide a liquid crystal display element that does not require a conventional alignment film formed of polyimide or the like or a forming step thereof. [Means to solve the problem]

The present invention uses a liquid crystal composition containing at least one polymerizable compound selected from the group of compounds represented by formula (1) as a first additive and having negative dielectric anisotropy.

[Chem 1]

In formula (1), R ¹⁵ , R ¹⁶ and R ^{17 are} independently hydrogen, halogen, -Sp ¹¹ -P ¹¹ , -Sp ¹² -P ¹² or an alkyl group having 1 to 15 carbon atoms. In the alkyl group, at least One -CH ₂ -may be substituted by -O- or -S-, at least one-(CH ₂ ) ₂ -may be substituted by -CH = CH- or -C≡C-, in these groups, at least one hydrogen may be substituted by Halogen, -Sp ¹¹ -P ¹¹ or -Sp ¹² -P ¹² substitution; a ¹¹ and a ^{12 are} independently 0, 1, 2, 3, or 4, the sum of a ¹¹ and a ¹² is 1-8; Ring A ¹¹ and ring A ^{12 are} independently a divalent group derived from an alicyclic hydrocarbon having 3 to 18 carbon atoms, an aromatic hydrocarbon having 6 to 18 carbon atoms, or a heteroaromatic hydrocarbon having 3 to 18 carbon atoms. In the divalent group, at least one hydrogen may be substituted by halogen, alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, alkenyl having 1 to 12 carbons, or alkenyl having 1 to 12 carbons. In these monovalent hydrocarbon groups, at least one hydrogen may be substituted by halogen; Z ¹¹ and Z ^{12 are} independently a single bond or an alkylene group having 1 to 10 carbon atoms. In the alkylene group, at least one -CH ₂ -Can be substituted by -O-, -CO-, -COO-, or -OCO-, at least one-(CH ₂ ) ₂ -Can be substituted by -CH = CH-, -C (CH ₃ ) = CH-, -CH _{= C (CH 3) -,} - C (CH 3) = C (CH 3) - Substituted or -CH≡CH-, the plurality divalent group, at least one hydrogen may be substituted by halogen; b ¹¹ and b ¹² are independently 0,1,2, or 3, the sum of b ¹¹ and b ¹² is 1 to 6; Sp ¹¹ and Sp ^{12 are} independently a single bond or an alkylene group having 1 to 10 carbon atoms, in which at least one -CH ₂ -may be passed through -O-, -CO-, -COO-,- OCO- or -OCOO- substitution, at least one-(CH ₂ ) ₂ -may be substituted by -CH = CH- or -C≡C-, in these groups, at least one hydrogen may be substituted by halogen; P ¹¹ and P ^{12 is} independently a group represented by the following formula (1a), formula (1b), formula (1c), formula (1d) or formula (1e);

[Chem 2]

In formula (1a), formula (1b), formula (1c), formula (1d) and formula (1e), M ¹¹ and M ^{12 are} independently hydrogen, halogen, alkyl group having 1 to 5 carbon atoms, or at least one C 1 to 5 alkyl groups substituted with hydrogen by halogen; R ¹² , R ¹³ , R ¹⁴ and R ^{18 are} independently hydrogen, or linear, branched or cyclic alkyl groups having 1 to 15 carbon atoms, In the alkyl group, at least one -CH ₂ -may be substituted with -O- or -S-, and at least one-(CH ₂ ) ₂ -may be substituted with -CH = CH- or -C≡C-. At least one hydrogen can be replaced by halogen. The present invention uses a liquid crystal display element containing the liquid crystal composition. The present invention uses a polymer-stabilized alignment type liquid crystal display element, which contains the liquid crystal composition, and the polymerizable compound in the liquid crystal composition is polymerized. The present invention uses a liquid crystal display element without an alignment film, which contains the liquid crystal composition, and the polymerizable compound in the liquid crystal composition is polymerized. The present invention uses the use of a liquid crystal composition used in a liquid crystal display element. The present invention uses the use of a liquid crystal composition used in a polymer-stabilized alignment type liquid crystal display element. The present invention uses the use of a liquid crystal composition used in a liquid crystal display element without an alignment film. [Effect of invention]

By using the liquid crystal composition of the present invention containing a polymerizable compound (or polymer thereof) containing a nitrogen atom in a bonding group, a liquid crystal display element having good electrical characteristics can be manufactured. In addition, since the alignment film forming step is not required, a liquid crystal display element with reduced manufacturing cost can be obtained. Furthermore, a liquid crystal composition having a negative dielectric anisotropy with good compatibility with a polymerizable compound containing a nitrogen atom in a bonding group can be obtained.

How to use the terms in this manual is as follows. Sometimes the terms "liquid crystal composition" and "liquid crystal display element" are simply referred to as "composition" and "element", respectively. "Liquid crystal display element" is a general term for liquid crystal display panel and liquid crystal display module. "Liquid crystal compound" is a compound having a nematic phase and a smectic phase equivalent liquid crystal phase, and although not having a liquid crystal phase, for the purpose of adjusting the temperature range, viscosity, dielectric anisotropy and other characteristics of the nematic phase The general term for compounds mixed in the composition. The liquid crystalline compound has a six-membered ring such as 1,4-cyclohexyl or 1,4-phenylene, and its molecular structure is rod-like. The "polymerizable compound" is a compound added for the purpose of forming a polymer in the composition.

The liquid crystal composition is prepared by mixing multiple liquid crystal compounds. Additives such as optically active compounds, antioxidants, ultraviolet absorbers, dyes, defoamers, polymerizable compounds, polymerization initiators, polymerization inhibitors, and polar compounds are added to the liquid crystal composition as necessary. The liquid crystal compound or additives are mixed in a known order. Even when it is convenient to add an additive, the ratio (content) of the liquid crystalline compound is also expressed as a weight percentage (weight%) based on the weight of the liquid crystal composition containing no additive. The ratio (addition amount) of the additive is expressed in parts by weight based on the weight of the liquid crystal composition containing no additive (for example, the total weight of the first component and the second component is 100 parts by weight). Sometimes parts per million by weight (ppm) are also used. The ratio of the polymerization initiator and the polymerization inhibitor is exceptionally expressed based on the weight of the polymerizable compound.

Sometimes the "upper limit temperature of the nematic phase" is simply referred to as the "upper limit temperature". Sometimes the "lower limit temperature of the nematic phase" is simply referred to as the "lower limit temperature". "High specific resistance" means that in the initial stage, the composition has a large specific resistance not only at room temperature but also at a temperature close to the upper limit temperature, and after long-term use, not only at room temperature but also close to It also has a large specific resistance at the upper limit temperature. "High voltage retention rate" means that the device has a large voltage retention rate not only at room temperature but also at a temperature close to the upper limit temperature in the initial stage, and after long-term use, not only at room temperature but also at It also has a large voltage retention rate at a temperature close to the upper limit temperature. In the composition or element, the characteristics may be studied before and after the time-dependent change test (including accelerated deterioration test). The expression "improving dielectric anisotropy" refers to a composition whose positive dielectric anisotropy is positive, which means that its value increases positively, and to a composition whose dielectric anisotropy is negative, it means its value is negative Increase to the ground.

The compound represented by formula (1) is sometimes simply referred to as "compound (1)". At least one compound selected from the group of compounds represented by formula (1) is sometimes simply referred to as "compound (1)". "Compound (1)" means a compound represented by formula (1), a mixture of two compounds, or a mixture of three or more compounds. The same applies to compounds represented by other formulas. The expression "at least one" A "" means that the number of "A" is arbitrary. The expression "at least one 'A' can be replaced by 'B'" means that when the number of 'A' is one, the position of 'A' is arbitrary, and when the number of 'A' is more than two, their position You can also choose unlimitedly. The rule also applies to the expression "at least one 'A' is replaced by 'B'".

In the chemical formula of the compound of each component, for example, the symbol of the terminal group R ³ is used for various compounds. In these compounds, the two groups represented by any two R ³ may be the same or different. For example, the R of the compound (2-1) ^is ethyl and R of the compound (2-2) is ethyl ^3. In some cases, R ³ of compound (2-1) is ethyl, and R ³ of compound (2-2) is propyl. This rule also applies to other end group symbols. In formula (2), when b is 2, there are two rings C. In this compound, the two rings represented by the two rings C may be the same or different. When b is greater than 2, the rule also applies to any two rings C. The rule also applies to other signs. This rule also applies to the case of two -Sp ⁴ -P ² in compound (5-27).

Surrounded by hexagons ^{A 11, A 12, A 13} , A 14, A 21, B 21, C, D, E, F, G, J, K, P and other symbols are the ring A ^11, ring A ¹² , Ring A ¹³ , ring A ¹⁴ , ring A ²¹ , ring B ²¹ , ring C, ring D, ring E, ring F, ring G, ring J, ring K, ring P and other rings corresponding to each other and represent a six-membered ring , Condensation ring and other rings. The diagonal line across the hexagon indicates that any hydrogen on the ring may be substituted with a group such as -Sp ³ -P ¹ . Subscripts such as 'j' indicate the number of substituted groups. When the subscript 'j' is 0, there is no such substitution. When the subscript 'j' is 2 or more, there are multiple -Sp ³ -P ¹ on the ring J. The multiple groups represented by -Sp ³ -P ¹ may be the same or different.

2-Fluoro-1,4-phenylene refers to the following two divalent groups. In the chemical formula, fluorine can be left (L) or right (R). This rule also applies to asymmetric divalent groups such as tetrahydropyran-2,5-diyl that are generated by removing two hydrogens from the ring. This rule also applies to divalent bonding groups such as carbonyloxy (-COO- or -OCO-).

[Chemical 3]

In this specification, expressions such as "at least one -CH ₂ -may be substituted by -O-" are used. In this case, -CH ₂ -CH ₂ -CH ₂ -can be converted to -O-CH ₂ -O- by substituting -O ₂ -with non-adjacent -CH _2- . However, adjacent -CH ₂ -will not be substituted with -O-. This is because -OO-CH _2- (peroxide) is generated by this substitution. That is, the expression refers to both "one -CH ₂ -may be substituted with -O-" and "at least two non-adjacent -CH ₂ -may be substituted with -O-". This rule applies not only to the substitution of -O-, but also to the substitution of -CH = CH- or -COO- and other divalent groups. In formula (1), R ¹⁵ is an alkyl group having 1 to 15 carbons and the like. The carbon number of this alkyl group may increase by such substitution. At this time, the maximum carbon number is 30. This rule applies not only to monovalent groups such as R ¹⁵ but also to divalent groups such as alkylene.

The alkyl group of the liquid crystal compound is linear or branched, and does not contain a cyclic alkyl group. Straight chain alkyl is better than branched alkyl. These cases are also the same for terminal groups such as alkoxy groups and alkenyl groups. The three-dimensional configuration associated with 1,4-cyclohexyl is generally superior to the cis configuration. Halogen refers to fluorine, chlorine, bromine, and iodine. The preferred halogen is fluorine or chlorine. Further, the preferred halogen is fluorine.

The present invention is as follows.

Item 1. A liquid crystal composition containing at least one polymerizable compound selected from the group of compounds represented by formula (1) as a first additive and having negative dielectric anisotropy.

[Chem 4]

In formula (1), R ¹⁵ , R ¹⁶ and R ^{17 are} independently hydrogen, halogen, -Sp ¹¹ -P ¹¹ , -Sp ¹² -P ¹² or an alkyl group having 1 to 15 carbon atoms. In the alkyl group, at least One -CH ₂ -may be substituted by -O- or -S-, at least one-(CH ₂ ) ₂ -may be substituted by -CH = CH- or -C≡C-, in these groups, at least one hydrogen may be substituted by Halogen, -Sp ¹¹ -P ¹¹ or -Sp ¹² -P ¹² substitution; a ¹¹ and a ^{12 are} independently 0, 1, 2, 3, or 4, the sum of a ¹¹ and a ¹² is 1-8; Ring A ¹¹ and ring A ^{12 are} independently a divalent group derived from an alicyclic hydrocarbon having 3 to 18 carbon atoms, an aromatic hydrocarbon having 6 to 18 carbon atoms, or a heteroaromatic hydrocarbon having 3 to 18 carbon atoms. In the divalent group, at least one hydrogen may be substituted by halogen, alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, alkenyl having 1 to 12 carbons, or alkenyl having 1 to 12 carbons. In these monovalent hydrocarbon groups, at least one hydrogen may be substituted by halogen; Z ¹¹ and Z ^{12 are} independently a single bond or an alkylene group having 1 to 10 carbon atoms. In the alkylene group, at least one -CH ₂ -Can be substituted by -O-, -CO-, -COO-, or -OCO-, at least one-(CH ₂ ) ₂ -Can be substituted by -CH = CH-, -C (CH ₃ ) = CH-, -CH _{= C (CH 3) -,} - C (CH 3) = C (CH 3) - Substituted or -CH≡CH-, the plurality divalent group, at least one hydrogen may be substituted by halogen; b ¹¹ and b ¹² are independently 0,1,2, or 3, the sum of b ¹¹ and b ¹² is 1 to 6; Sp ¹¹ and Sp ^{12 are} independently a single bond or an alkylene group having 1 to 10 carbon atoms, in which at least one -CH ₂ -may be passed through -O-, -CO-, -COO-,- OCO- or -OCOO- substitution, at least one-(CH ₂ ) ₂ -may be substituted by -CH = CH- or -C≡C-, in these groups, at least one hydrogen may be substituted by halogen; P ¹¹ and P ^{12 is} independently a group represented by the following formula (1a), formula (1b), formula (1c), formula (1d) or formula (1e);

[Chemical 5]

In formula (1a), formula (1b), formula (1c), formula (1d) and formula (1e), M ¹¹ and M ^{12 are} independently hydrogen, halogen, alkyl group having 1 to 5 carbon atoms, or at least one C 1 to 5 alkyl groups substituted with hydrogen by halogen; R ¹² , R ¹³ , R ¹⁴ and R ^{18 are} independently hydrogen, or linear, branched or cyclic alkyl groups having 1 to 15 carbon atoms, In the alkyl group, at least one -CH ₂ -may be substituted with -O- or -S-, and at least one-(CH ₂ ) ₂ -may be substituted with -CH = CH- or -C≡C-. At least one hydrogen can be replaced by halogen.

Item 2. The liquid crystal composition according to Item 1, wherein the first additive is represented by any one of Formula (1-1) to Formula (1-3).

[化 6]

In formula (1-1) to formula (1-3), R ¹⁷ is hydrogen, halogen, -Sp ¹¹ -P ¹¹ , -Sp ¹² -P ¹² or an alkyl group having 1 to 15 carbon atoms. At least one -CH ₂ -may be substituted by -O- or -S-, at least one-(CH ₂ ) ₂ -may be substituted by -CH = CH- or -C≡C-, in these groups, at least one hydrogen may Substituted by halogen, -Sp ¹¹ -P ¹¹ or -Sp ¹² -P ¹² ; ring A ¹¹ , ring A ¹² , ring A ^{1 3} and ring A ^{1 4 are} independently alicyclic hydrocarbons having 3 to 18 carbon atoms, A divalent group derived from an aromatic hydrocarbon having 6 to 18 carbon atoms or a heteroaromatic hydrocarbon having 3 to 18 carbon atoms. Among these divalent groups, at least one hydrogen may be substituted by halogen or an alkyl group having 1 to 12 carbon atoms. , An alkoxy group having 1 to 12 carbon atoms, an alkenyl group having 1 to 12 carbon atoms, or an alkenyloxy group having 1 to 12 carbon atoms. In these monovalent hydrocarbon groups, at least one hydrogen may be substituted with halogen; Z ¹¹ , Z ¹² , Z ¹³ and Z ^{14 are} independently a single bond or an alkylene group having 1 to 10 carbon atoms, in which at least one -CH ₂ -may be passed through -O-, -CO-, -COO- , Or -OCO- substitution, at least one-(CH ₂ ) ₂ -can be replaced by -CH = CH-, -C (CH ₃ ) = CH-, -CH = C (CH ₃ )-, -C (CH ₃ ) = C (CH ₃₎ -, a substituted or -CH≡CH-, the plurality of bivalent groups, At least one hydrogen may be substituted by halogen; Sp ¹¹ and Sp ¹² independently a single bond or a C 1-10 alkylene group, which alkylene, at least one -CH ₂ - may be -O -, - CO- , -COO-, -OCO-, or -OCOO-, at least one-(CH ₂ ) ₂ -may be substituted by -CH = CH- or -C≡C-, in these groups, at least one hydrogen may be halogen Substitution; P ¹¹ and P ^{12 are} independently a group represented by the following formula (1a), formula (1b), formula (1c), formula (1d) or formula (1e);

[化 7]

In formula (1a), formula (1b), formula (1c), formula (1d) and formula (1e), M ¹¹ and M ^{12 are} independently hydrogen, halogen, alkyl group having 1 to 5 carbon atoms, or at least one C 1 to 5 alkyl groups substituted with hydrogen by halogen; R ¹² , R ¹³ , R ¹⁴ and R ^{18 are} independently hydrogen, or linear, branched or cyclic alkyl groups having 1 to 15 carbon atoms, In the alkyl group, at least one -CH ₂ -may be substituted with -O- or -S-, and at least one-(CH ₂ ) ₂ -may be substituted with -CH = CH- or -C≡C-. At least one hydrogen can be replaced by halogen.

Item 3. The liquid crystal composition according to Item 1 or Item 2, wherein the ratio of the first additive is in the range of 0.01 parts by weight to 10 parts by weight based on the weight of the liquid crystal composition.

Item 4. The liquid crystal composition according to any one of Item 1 to Item 3, which contains at least one compound selected from the group of compounds represented by formula (2) as the first component.

[Chem 8]

In formula (2), R ³ and R ^{4 are} independently C 1-12 alkyl, C 1-12 alkoxy, C 2-12 alkenyl, or C 2-12 alkenyl Yloxy; ring C and ring E are independently 1,4-cyclohexyl, 1,4-cyclohexenyl, 1,4-phenylene, at least one hydrogen substituted with fluorine or chlorine 1,4 -Phenylene, or tetrahydropyran-2,5-diyl; ring D is 2,3-difluoro-1,4-phenylene, 2-chloro-3-fluoro-1,4-benzene Group, 2,3-difluoro-5-methyl-1,4-phenylene, 3,4,5-trifluoronaphthalene-2,6-diyl, or 7,8-difluorochroman- 2,6-diyl; Z ² and Z ^{3 are} independently a single bond,-(CH ₂ ) _2- , -CH ₂ O-, -OCH _2- , -COO-, or -OCO-; b is 1, 2, or 3, c is 0 or 1, and the sum of b and c is 3 or less.

Item 5. The liquid crystal composition according to Item 4, which contains at least one compound selected from the group of compounds represented by Formula (2-1) to Formula (2-22) as the first component.

[化 9]

[化 10]

In formula (2-1) to formula (2-22), R ³ and R ^{4 are} independently an alkyl group having 1 to 12 carbons, an alkoxy group having 1 to 12 carbons, and an alkenyl group having 2 to 12 carbons , Or an alkenyloxy group having 2 to 12 carbon atoms.

Item 6. The liquid crystal composition according to Item 4 or Item 5, wherein the proportion of the first component is in the range of 10% by weight to 90% by weight based on the weight of the liquid crystal composition.

Item 7. The liquid crystal composition according to any one of Item 1 to Item 6, which contains at least one compound selected from the group of compounds represented by formula (3) as the second component.

[化 11]

In formula (3), R ⁵ and R ^{6 are} independently C 1-12 alkyl, C 1-12 alkoxy, C 2-12 alkenyl, and at least one hydrogen is substituted by fluorine or chlorine Alkyl having 1 to 12 carbons, or alkenyl having 2 to 12 carbons in which at least one hydrogen is substituted with fluorine or chlorine; ring F and ring G are independently 1,4-cyclohexyl, 1,4-extend Phenyl, 2-fluoro-1,4-phenylene, or 2,5-difluoro-1,4-phenylene; Z ⁴ is a single bond,-(CH ₂ ) _2- , -CH ₂ O- , -OCH _2- , -COO-, or -OCO-; d is 1, 2, or 3.

Item 8. The liquid crystal composition according to Item 7, which contains at least one compound selected from the group of compounds represented by Formula (3-1) to Formula (3-13) as the second component.

[Chem 12]

In formula (3-1) to formula (3-13), R ⁵ and R ^{6 are} independently C 1-12 alkyl, C 1-12 alkoxy, C 2-12 alkenyl , At least one hydrogen-substituted alkyl group having 1 to 12 carbon atoms with fluorine or chlorine, or at least one hydrogen-substituted alkenyl group having 2 to 12 carbon atoms with fluorine or chlorine.

Item 9. The liquid crystal composition according to Item 7 or Item 8, wherein the proportion of the second component is in the range of 10% by weight to 90% by weight based on the weight of the liquid crystal composition.

Item 10. The liquid crystal composition according to any one of Item 1 to Item 9, which contains at least one polymerizable compound having a polar group selected from the group of compounds represented by formula (4) as the second addition Thing.

[Chem 13]

In formula (4), R ²¹ is hydrogen, halogen, C 1-12 alkyl, C 1-12 alkoxy, C 2-12 alkenyl, at least one hydrogen substituted by fluorine or chlorine An alkyl group having 1 to 12 carbons, or an alkenyl group having 2 to 12 carbons in which at least one hydrogen is substituted with fluorine or chlorine; R ²² is -OH, -NH ₂ , -OR ²⁰ , -N (R ²⁰ ) ₂ , Or a group represented by -Si (R ²⁰ ) ₃ , where R ²⁰ is hydrogen or an alkyl group having 1 to 5 carbon atoms, in which at least one -CH ₂ -may be substituted by -O-, at least one -(CH ₂ ) ₂ -may be substituted by -CH = CH-, in these groups, at least one hydrogen may be substituted by fluorine; Ring A ²¹ and Ring B ^{21 are} independently 1,4-cyclohexyl, 1,4 -Cyclohexenyl, 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, pyridine-2,5-diyl, Fen-2,7-diyl, phenanthrene-2,7-diyl, anthracene-2,6-diyl, perhydrocyclopenta [a] phenanthrene-3,17-diyl, or 2,3,4 , 7,8,9,10,11,12,13,14,15,16,17-tetradecane And [a] phenanthrene-3,17-diyl, in these rings, at least one hydrogen can be through fluorine, chlorine, C 1-12 alkyl, C 1-12 alkoxy, or at least one hydrogen Substituted by fluorine or chlorine, C1-C12 alkyl; Z ²¹ is a single bond,-(CH ₂ ) _2- , -CH = CH-, -C≡C-, -COO-, -OCO-, -CF ₂ O-, -OCF _2- , -CH ₂ O-, -OCH _2- , or -CF = CF-; Sp ²¹ and Sp ^{22 are} independently a single bond or an alkylene group having 1 to 7 carbon atoms, In the alkylene group, at least one -CH ₂ -may be substituted with -O-, -COO-, or -OCO-, and at least one-(CH ₂ ) ₂ -may be substituted with -CH = CH-. , At least one hydrogen may be substituted by fluorine; a ²¹ is 0, 1, 2, 3, or 4.

Item 11. The liquid crystal composition according to Item 10, wherein the second additive is at least one polymerizable compound selected from the group of compounds represented by Formula (4-1) to Formula (4-9) .

[化 14]

In formula (4-1) to formula (4-9), R ²¹ is hydrogen, halogen, alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, alkenyl having 2 to 12 carbons, At least one hydrogen is substituted with fluorine or chlorine and a C 1-12 alkyl group, or at least one hydrogen is substituted with fluorine or chlorine and a C 2 to 12 alkenyl group; Z ²¹ is a single bond,-(CH ₂ ) _2- , -CH = CH-, -C≡C-, -COO-, -OCO-, -CF ₂ O-, -OCF _2- , -CH ₂ O-, -OCH _2- , or -CF = CF-; Sp ²¹ and Sp ^{22 are} independently a single bond or an alkylene group having 1 to 7 carbon atoms, in which at least one -CH ₂ -may be substituted by -O-, -COO-, or -OCO-, at least One-(CH ₂ ) ₂ -may be substituted by -CH = CH-, in these groups, at least one hydrogen may be substituted by fluorine; L ¹ , L ² , L ³ , L ⁴ , L ⁵ , L ⁶ , L ⁷ , L ⁸ , L ⁹ , L ¹⁰ , L ¹¹ , and L ^{12 are} independently hydrogen, fluorine, methyl, or ethyl.

Item 12. The liquid crystal composition according to Item 10 or Item 11, wherein the ratio of the second additive is in the range of 0.05 parts by weight to 10 parts by weight based on the weight of the liquid crystal composition.

Item 13. The liquid crystal composition according to any one of Item 1 to Item 12, which contains at least one polymerizable compound selected from the group of compounds represented by formula (5) as a third additive.

[化 15]

In formula (5), ring J and ring P are independently cyclohexyl, cyclohexenyl, phenyl, 1-naphthyl, 2-naphthyl, tetrahydropyran-2-yl, 1,3-dioxan Alkan-2-yl, pyrimidin-2-yl, or pyrid-2-yl, in these rings, at least one hydrogen can be through fluorine, chlorine, C 1-12 alkyl, C 1-12 alkoxy Group, or at least one hydrogen is substituted by fluorine or chlorine, a C 1-12 alkyl group; ring K is 1,4-cyclohexyl, 1,4-cyclohexenyl, 1,4-phenylene , Naphthalene-1,2-diyl, naphthalene-1,3-diyl, naphthalene-1,4-diyl, naphthalene-1,5-diyl, naphthalene-1,6-diyl, naphthalene-1, 7-diyl, naphthalene-1,8-diyl, naphthalene-2,3-diyl, naphthalene-2,6-diyl, naphthalene-2,7-diyl, tetrahydropyran-2,5- Diyl, 1,3-dioxane-2,5-diyl, pyrimidine-2,5-diyl, or pyridine-2,5-diyl, in these rings, at least one hydrogen can be fluorine, chlorine , A C 1-12 alkyl group, a C 1-12 alkoxy group, or a C 1-12 alkyl group substituted by fluorine or chlorine for at least one hydrogen; Z ⁵ and Z ^{6 are} independently single bonds Or an alkylene group having 1 to 10 carbon atoms, in which at least one -CH ₂ -may be substituted with -O-, -CO-, -COO-, or -OCO-, and at least one -(CH ₂ ) ₂ -Can be passed -CH = CH-, -C (CH ₃ ) = CH-, -CH = C (CH ₃ )-, or -C (CH ₃ ) = C (CH ₃ )- Substitution, in these groups, at least one hydrogen may be substituted by fluorine or chlorine; P ¹ , P ² , and P ^{3 are} independently polymerizable groups; Sp ³ , Sp ⁴ , and Sp ^{5 are} independently single bonds or carbon numbers 1 to 10 alkylene groups, in which at least one -CH ₂ -may be substituted with -O-, -COO-, -OCO-, or -OCOO-, and at least one-(CH ₂ ) _2- May be substituted by -CH = CH- or -C≡C-, in these groups, at least one hydrogen may be substituted by fluorine or chlorine; q is 0, 1, or 2; j, k, and p are independently 0, 1, 2, 3, or 4, and the sum of j, k, and p is 1 or more.

Item 14. The liquid crystal composition according to Item 13, wherein in the formula (5), P ¹ , P ² , and P ^{3 are} independently selected from the group consisting of formula (P-1) to formula (P-5) The polymerizable group in the group represented by the group.

[Chem 16]

In formula (P-1) to formula (P-5), M ¹ , M ² , and M ^{3 are} independently hydrogen, fluorine, an alkyl group having 1 to 5 carbon atoms, or at least one hydrogen is substituted with fluorine or chlorine C1-C5 alkyl.

Item 15. The liquid crystal composition according to Item 13 or Item 14, wherein the third additive is at least one selected from the group of compounds represented by Formula (5-1) to Formula (5-28) Polymerizable compound.

[化 17]

[Chemical 18]

[Chem 19]

In formula (5-1) to formula (5-28), P ¹ , P ² , and P ^{3 are} independently selected from the group of groups represented by formula (P-1) to formula (P-3) The polymerizable group of here, M ¹ , M ² , and M ^{3 are} independently hydrogen, fluorine, an alkyl group having 1 to 5 carbon atoms, or an alkyl group having 1 to 5 carbon atoms in which at least one hydrogen is substituted with fluorine or chlorine base;

[化 20]

Sp ³ , Sp ⁴ , and Sp ^{5 are} independently a single bond or an alkylene group having 1 to 10 carbon atoms, in which at least one -CH ₂ -may be passed through -O-, -COO-, -OCO- , Or -OCOO-, and at least one-(CH ₂ ) ₂ -may be substituted by -CH = CH- or -C≡C-, in these groups, at least one hydrogen may be substituted by fluorine or chlorine.

Item 16. The liquid crystal composition according to any one of Item 13 to Item 15, wherein the ratio of the third additive is in the range of 0.03 parts by weight to 10 parts by weight based on the weight of the liquid crystal composition.

Item 17. A liquid crystal display element containing the liquid crystal composition according to any one of Item 1 to Item 16.

Item 18. The liquid crystal display element of item 17, wherein the operation mode of the liquid crystal display element is IPS mode, VA mode, FFS mode, or FPA mode, and the driving method of the liquid crystal display element is an active matrix method.

Item 19. A polymer-stable alignment type liquid crystal display element containing the liquid crystal composition according to any one of Item 1 to Item 16, and the polymerizable compound in the liquid crystal composition is polymerized.

Item 20. A liquid crystal display element without an alignment film, which contains the liquid crystal composition according to any one of Item 1 to Item 16, and the polymerizable compound in the liquid crystal composition is polymerized.

Item 21. Use of a liquid crystal composition, which is the liquid crystal composition according to any one of Item 1 to Item 16, which is used in a liquid crystal display element.

Item 22. Use of a liquid crystal composition, which is the liquid crystal composition according to any one of Items 1 to 16, which is used in a polymer-stabilized alignment type liquid crystal display element.

Item 23. Use of a liquid crystal composition, which is the liquid crystal composition according to any one of Item 1 to Item 16, which is used in a liquid crystal display element having no alignment film.

The present invention also includes the following items. (A) A method of manufacturing a liquid crystal display element, by arranging the liquid crystal composition between two substrates and irradiating light with a voltage applied to the composition to make the polarities contained in the composition The radical polymerizable compound is polymerized to produce the liquid crystal display element. (B) For the liquid crystal composition, the upper limit temperature of the nematic phase is 70 ° C or higher, the optical anisotropy (measured at 25 ° C) at a wavelength of 589 nm is 0.08 or higher, and each dielectric at a frequency of 1 kHz The anisotropy (measured at 25 ° C) is -2 or less.

The present invention also includes the following items. (C) The composition, although the compounds (5) to (7) described in Japanese Patent Laid-Open No. 2006-199941 are liquid crystal compounds with positive dielectric anisotropy, the composition contains At least one compound selected from the group of these compounds. (D) The composition containing at least two of the polymerizable compounds having polar groups (4). (E) The composition further contains a polymerizable compound different from the polymerizable compound (4) having a polar group. (F) The composition containing one of additives such as optically active compounds, antioxidants, ultraviolet absorbers, pigments, defoamers, polymerizable compounds, polymerization initiators, polymerization inhibitors, polar compounds, etc. Two, or at least three. (G) An AM device containing the above composition. (H) An element containing the composition and having a mode of TN, ECB, OCB, IPS, FFS, VA, or FPA. (I) A transmission type element containing the composition. (J) Use of the composition as a composition having a nematic phase. (K) Use as an optically active composition by adding an optically active compound to the composition.

The composition of the present invention will be described in the following order. First, the structure of the composition will be described. Second, the main characteristics of the component compounds and the main effects of the compounds on the composition will be described. Third, the combination of the components in the composition, the preferred ratio of the components, and their basis will be described. Fourth, the preferred forms of the component compounds will be described. Fifth, the preferred component compounds are shown. Sixth, the additives that can be added to the composition will be described. Seventh, the method of synthesizing the component compounds will be described. Finally, the use of the composition will be described.

First, the structure of the composition will be described. The composition of the present invention is classified into composition A and composition B. In addition to the liquid crystal compound selected from the compound (2) and the compound (3), the composition A may further contain other liquid crystal compounds, additives and the like. The "other liquid crystal compound" is a liquid crystal compound different from the compound (2) and the compound (3). Such compounds are mixed in the composition for the purpose of further adjusting the characteristics. The additives are optically active compounds, antioxidants, ultraviolet absorbers, pigments, defoamers, polymerizable compounds, polymerization initiators, polymerization inhibitors, polar compounds, and the like.

The composition B contains substantially only the liquid crystal compound selected from the compound (2) and the compound (3). "Substantially" means that although composition B may contain additives, it does not contain other liquid crystal compounds. Compared with composition A, the number of components of composition B is small. From the viewpoint of cost reduction, composition B is superior to composition A. From the viewpoint that the characteristics can be further adjusted by mixing other liquid crystal compounds, composition A is superior to composition B.

Second, the main characteristics of the component compounds and the main effects of the compounds on the characteristics of the composition will be described. Based on the effects of the present invention, the main characteristics of the component compounds are summarized in Table 2. In the symbols in Table 2, L means large or high, M means medium, and S means small or low. Symbols L, M, and S are classifications based on qualitative comparisons between component compounds, and symbol 0 means that the value is zero or close to zero.

[Table 2]

When the component compounds are mixed in the composition, the main effects of the component compounds on the characteristics of the composition are as follows. The compound (1) is adsorbed on the surface of the substrate by the action of the nitrogen atom existing in the bonding group of the molecular structure, and the group extending from the nitrogen atom is compatible with the liquid crystal molecule. In order to obtain the desired effect, the compound (1) must have high compatibility with the liquid crystal compound. It is considered that the group extending from the nitrogen atom in the compound (1) has the same structure as the liquid crystal compound and can improve compatibility, so it is most suitable for this purpose. Compound (1) provides a polymer by polymerization. This polymer stabilizes the alignment of liquid crystal molecules, thus shortening the response time of the element and improving the afterimage of the image. Compound (2) increases dielectric anisotropy and lowers the lower limit temperature. Compound (3) reduces viscosity. Compound (4) controls the alignment of liquid crystal molecules by interacting with the substrate of the device in a non-covalent bonding manner. In addition, the polymer is provided by polymerization to stabilize the alignment of liquid crystal molecules. Furthermore, since it has a mesogen portion composed of at least one ring, high compatibility with a liquid crystal compound can be expected. Compound (5) provides a polymer by polymerization. Since this polymer stabilizes the alignment of liquid crystal molecules, the response time of the device is shortened, and the afterimage of the image is improved. From the viewpoint of alignment of liquid crystal molecules, the polymer of the compound (4) has an interaction with the surface of the substrate, so it is presumed to be more effective than the polymer of the compound (5).

Third, the combination of the components in the composition, the preferred ratio of the components, and their basis will be described. The preferred combination of the components in the composition is compound (1) + compound (2) + compound (3) + compound (4), or compound (1) + compound (2) + compound (3) + compound (4) + Compound (5).

It is considered that the compound (1) as the first additive is easily adsorbed on the electrode substrate side due to the polarity of the nitrogen atom, and the polar impurities in the liquid crystal composition are also easily introduced into the polymer. It is added to the composition for the purpose of electrical characteristics. The preferable ratio of the compound (1) is about 0.01 parts by weight or more, and in order to prevent display defects of the device, the preferable ratio of the compound (1) is about 10 parts by weight or less. A further preferred ratio is in the range of about 0.05 parts by weight to about 5 parts by weight. The compound (4) as the second additive is added to the composition for the purpose of controlling the vertical alignment of the liquid crystal molecules. In order to align the liquid crystal molecules vertically, the preferred ratio of the compound (4) is about 0.05 parts by weight or more, and in order to prevent display defects of the device, the preferred ratio of the compound (4) is about 10 parts by weight or less. A further preferred ratio is in the range of about 0.1 parts by weight to about 5 parts by weight. A particularly preferred ratio is in the range of 0.3 parts by weight to 5 parts by weight.

In order to improve the dielectric anisotropy, the preferred ratio of the compound (2) as the first component is about 10% by weight or more. %the following. A further preferred ratio is in the range of about 20% by weight to about 85% by weight. A particularly good ratio is in the range of about 30% by weight to about 85% by weight.

In order to increase the upper limit temperature or lower the lower limit temperature, the preferred ratio of the compound (3) as the second component is about 10% by weight or more, and in order to improve the dielectric anisotropy, the compound (3) as the second component is preferred The ratio is about 90% by weight or less. A further preferred ratio is in the range of about 15% by weight to about 75% by weight. A particularly good ratio is in the range of about 15% by weight to about 60% by weight.

The compound (5) as the third additive is added to the composition for the purpose of adapting the composition to a polymer-stable alignment type element. In order to improve the long-term reliability of the device, the preferable ratio of the compound (5) is about 0.03 parts by weight or more, and in order to prevent display defects of the device, the preferable ratio of the compound (5) is about 10 parts by weight or less. A further preferred ratio is in the range of about 0.1 parts by weight to about 2 parts by weight. A particularly preferred ratio is in the range of about 0.2 parts by weight to about 1.0 part by weight.

Fourth, the preferred forms of the component compounds will be described. The structure of the compound (1) is represented by the formula (1). In the formula (1), the polymerizable groups P ¹¹ and P ¹² , the bonding groups Sp ¹¹ and Sp ¹² , the rings A ¹¹ and A ¹² , and the group R ¹⁵ to Preferred examples of R ¹⁷ and bonding groups Z ¹¹ and Z ¹² are as follows. This example also applies to the subordinate compounds of compound (1). The compound (1) can arbitrarily adjust the physical properties by appropriately combining the types of these groups. Since there is no big difference in the physical properties of the compounds, the compound (1) may contain more isotopes of ² H (deuterium), ¹³ C, etc. than natural abundances.

[化 21]

In formula (1), P ¹¹ and P ^{12 are} independently a polymerizable group. Examples of the polymerizable group are acryloxy (the following formula (1a)), oxetanyl (the following formula (1b)), vinyloxy (the following formula (1c)), maleyl Imine (the following formula (1d)) or itaconic acid ester (the following formula (1e)). The wavy line from formula (1a) to formula (1e) indicates the bonded part.

[化 22]

Here, in Formula (1a) to Formula (1e), M ¹¹ and M ^{12 are} independently hydrogen, halogen, a C 1-5 alkyl group, or a C 1-5 alkyl group having at least one hydrogen substituted with a halogen R ¹² , R ¹³ , R ¹⁴ and R ^{18 are} independently hydrogen, or a linear, branched or cyclic alkyl group having 1 to 15 carbon atoms, in which at least one -CH ₂ -may be Substituted by -O- or -S-, at least one-(CH ₂ ) ₂ -may be substituted by -CH = CH- or -C≡C-, and in these groups, at least one hydrogen may be substituted by halogen.

In formula (1), Sp ¹¹ and Sp ^{12 are} independently a single bond or an alkylene group having 1 to 10 carbon atoms. In this alkylene group, at least one -CH ₂ -may be passed through -O-, -CO-,- COO- or -OCO- substitution, at least one-(CH ₂ ) ₂ -may be substituted by -CH = CH- or -C≡C-, in these divalent groups, at least one hydrogen may be halogen or carbon number 1 to 3 alkyl substitution.

Sp ¹¹ or the preferred embodiment Sp ¹² single _{bond, -CH 2 -, - CH 2} O -, - OCH 2 -, - COO -, - OCO -, - (CH 2) 2 -, - CH = CH- , -C≡C-, -CH ₂ CH ₂ O-, -OCH ₂ CH _2- , -CH = CH-O-, -O-CH = CH-, -C≡CO-, -OC≡C-, -(CH ₂ ) ₃ -,-(CH ₂ ) ₃ -O-, -O- (CH ₂ ) ₃ -,-(CH ₂ ) ₄ -,-(CH ₂ ) ₄ O-, or -O (CH ₂ ) _4- . Further preferred examples include a single _{bond, -CH 2 -, - CH 2} O -, - OCH 2 -, - COO -, - OCO -, - CH = CH -, - C≡C -, - CH 2 CH 2 O -, -OCH ₂ CH _2- , -CH = CH-O-, or -O-CH = CH-. Particularly preferred examples are single bonds, -CH _2- , -CH = CH-, -CH = CH-O-, -O-CH = CH-, -CH ₂ CH ₂ O-, or -OCH ₂ CH _2- . The best example is a single key. The stereo configuration of the double bond of -CH = CH- may be a cis configuration or a trans configuration. The trans configuration is better than the cis configuration.

In formula (1), R ¹⁵ , R ¹⁶ and R ^{17 are} independently hydrogen, halogen, -Sp ¹¹ -P ¹¹ , -Sp ¹² -P ¹² , or an alkyl group having 1 to 15 carbon atoms. At least one -CH ₂ -may be substituted by -O- or -S-, at least one-(CH ₂ ) ₂ -may be substituted by -CH = CH- or -C≡C-, in these groups, at least one hydrogen may Substituted by halogen, -Sp ¹¹ -P ¹¹ or -Sp ¹² -P ¹² .

In formula (1), a ¹¹ and a ^{12 are} independently 0, 1, 2, 3, or 4. -Sp ¹¹ -P ¹¹ or -Sp ¹² -P ¹² is a monovalent group participating in polymerization. The total number of -Sp ¹¹ -P ¹¹ and -Sp ¹² -P ¹² (that is, a ¹¹ + a ¹² ) is 1 to 8. Preferred examples are 1 to 6, and further preferred examples are 1 to 3. The best example is 1 or 2.

In formula (1), ring A ¹¹ and ring A ^{12 are} independently an alicyclic hydrocarbon having 3 to 18 carbon atoms, an aromatic hydrocarbon having 6 to 18 carbon atoms, or a heteroaromatic having 3 to 18 carbon atoms The divalent radical derived from the removal of two hydrogens by a hydrocarbon. Among these divalent groups, at least one hydrogen may be halogen, alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, alkenyl having 1 to 12 carbons, or alkenyl having 1 to 12 carbons. Substituted by an oxy group, in these monovalent hydrocarbon groups, at least one hydrogen may be substituted by halogen. Furthermore, in ring A ¹¹ , a ¹¹ hydrogens are substituted by -Sp ¹¹ -P ¹¹ , and in ring A ¹² , a ¹² hydrogens are substituted by -Sp ¹² -P ¹² .

Examples of alicyclic hydrocarbons are cyclopropane, cyclobutane, cyclohexane, cycloheptane, cyclooctane and the like represented by C _n H _2n . Other examples are decalin. Examples of aromatic hydrocarbons are benzene, naphthalene, anthracene, phenanthrene, stilbene, indan, indene, tetralin and the like. Examples of heteroaromatic hydrocarbons are pyridine, pyrimidine, furan, pyran, thiophene, benzofuran and the like. These hydrocarbons may be substituted with monovalent groups such as fluorine, chlorine, and alkyl groups. Preferred examples of ring A ¹¹ or ring A ¹² are benzene, fluorobenzene, naphthalene, stilbene, or phenanthrene. A further preferred example is benzene or cyclohexane.

In formula (1), Z ¹¹ and Z ^{12 are} independently a single bond or an alkylene group having 1 to 10 carbon atoms. In this alkylene group, at least one -CH ₂ -may be substituted by -O-, -CO-,- COO- or -OCO- substituted, at least one-(CH ₂ ) ₂ -can be replaced by -CH = CH-, -C (CH ₃ ) = CH-, -CH = C (CH ₃ )-, -C (CH ₃ ) = C (CH ₃ )-, or -CH≡CH- substitution, in these divalent groups, at least one hydrogen may be substituted by halogen.

Preferred examples of Z ¹¹ and Z ¹² are single bonds, alkylene having 1 to 4 carbon atoms, -COO-, -OCO-, -CH ₂ O-, -OCH _2- , -CF ₂ O-, -OCF _2- , -CH = CH-, -CH = CH-COO-, -OCO-CH = CH-, -C (CH ₃ ) = CH-COO-, -OCO-CH = C (CH ₃ )-,- CH = C (CH ₃ ) -COO-, -OCO- (CH ₃ ) C = CH-, -C (CH ₃ ) = C (CH ₃ ) -COO-, -OCO-C (CH ₃ ) = C ( CH ₃ )-, -CO-CH = CH-, -CH = CH-CO-, -C (CH ₃ ) = C (CH ₃ )-, -CH = CH-CH ₂ O-, -OCH ₂ -CH = CH-, -CH = CH-OCH _2- , -CH ₂ O-CH = CH-, or -CH≡CH-. Further preferred examples are single bonds, ethylidene, -COO-, -OCO-, -CH = CH-, -CH = CH-COO-, -OCO-CH = CH-, or -CH≡CH-. The best example is a single key.

In formula (1), b ¹¹ and b ^{12 are} independently 0, 1, 2, or 3. When b ^{1 2} is 0, the compound has b ¹¹ rings represented by A ¹¹ . In this case, the preferred ring A ¹¹ is a divalent group derived by removing two hydrogens from rings such as naphthalene, anthracene, phenanthrene, and benzene. When b ¹¹ and b ¹² are 1, the compound has ring A ¹¹ and ring A ¹² . In this case, the preferred ring A ¹¹ or ring A ¹² is a divalent group derived from benzene, benzene substituted with a substituent such as fluorine, or methyl. When b ¹¹ is 1 and b ¹² is 2, the compound has three rings of ring A ¹¹ , ring A ¹² and ring A ¹² . Preferred ring A ¹¹ or ring A ¹² is a divalent group derived from benzene, benzene substituted with a substituent such as fluorine. The total of b ¹¹ and b ¹² is 1 to 6. The preferred examples are 1 to 4, and the further preferred examples are 2 to 4.

Preferred examples of the compound (1) are compounds represented by the following formula (1-1), formula (1-2) and formula (1-3). [化 23]

In formula (1-1), formula (1-2) and formula (1-3), P ¹¹ and P ^{12 are} independently the polymerizable groups represented by the above formula (1a) to formula (1e). R ¹⁷ is hydrogen, halogen, -Sp ¹¹ -P ¹¹ , -Sp ¹² -P ¹² or an alkyl group having 1 to 15 carbon atoms, in which at least one -CH ₂ -may be passed through -O- or -S- Substitution, at least one-(CH ₂ ) ₂ -may be substituted by -CH = CH- or -C≡C-, in these groups, at least one hydrogen may be substituted by halogen, -Sp ¹¹ -P ¹¹ or -Sp ¹² -P ¹² replaced. Ring A ¹¹ , Ring A ¹² , Ring A ^{1 3} and Ring A ^{1 4 are} independently an alicyclic hydrocarbon having 3 to 18 carbon atoms, an aromatic hydrocarbon having 6 to 18 carbon atoms, or a heterocycle having 3 to 18 carbon atoms A divalent group derived from an aromatic hydrocarbon. Among these divalent groups, at least one hydrogen may be halogen, alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, and olefin having 1 to 12 carbons. Group, or an alkenyloxy group having 1 to 12 carbons, in these monovalent hydrocarbon groups, at least one hydrogen may be substituted with halogen. Z ¹¹ , Z ¹² , Z ¹³ and Z ^{14 are} independently a single bond or an alkylene group having 1 to 10 carbon atoms. In this alkylene group, at least one -CH ₂ -may be passed through -O-, -CO-,- COO- or -OCO- substitution, at least one-(CH ₂ ) ₂ -can be substituted by -CH = CH-, -C (CH ₃ ) = CH-, -CH = C (CH ₃ )-, -C (CH _{3) = C (CH 3)} -, a substituted or -CH≡CH-, the plurality of bivalent groups, at least one hydrogen may be substituted by halogen. Sp ¹¹ and Sp ^{12 are} independently a single bond or an alkylene group having 1 to 10 carbon atoms, in which at least one -CH ₂ -may be passed through -O-, -CO-, -COO-, -OCO- , Or -OCOO- substitution, at least one-(CH ₂ ) ₂ -may be substituted by -CH = CH- or -C≡C-, in these groups, at least one hydrogen may be substituted by halogen.

A further preferable example of the compound (1) is a compound represented by the following formula (1-4).

[化 24]

In formula (1-4), P ¹¹ and P ^{12 are} independently the groups represented by the above formula (1a), formula (1b), formula (1c), formula (1d) or formula (1e). Ring A ¹¹ and ring A ^{12 are} independently 1,4-phenylene groups, and at least one hydrogen on these rings may be substituted with halogen. Sp ¹¹ and Sp ^{12 are} independently a single bond or an alkylene group having 1 to 10 carbon atoms, in which at least one -CH ₂ -may be passed through -O-, -CO-, -COO-, -OCO- , Or -OCOO- substitution, at least one-(CH ₂ ) ₂ -may be substituted by -CH = CH- or -C≡C-, in these groups, at least one hydrogen may be substituted by halogen.

In Formula (2) and Formula (3), R ³ and R ^{4 are} independently C 1-12 alkyl, C 1-12 alkoxy, C 2-12 alkenyl, or C 2 2 to 12 alkenyloxy groups. In order to improve stability, it is preferable that R ³ or R ⁴ is an alkyl group having 1 to 12 carbon atoms, and in order to improve dielectric anisotropy, it is preferable that R ³ or R ⁴ is an alkoxy group having 1 to 12 carbon atoms. R ⁵ and R ^{6 are} independently an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, an alkenyl group having 2 to 12 carbon atoms, and 1 to 12 carbon atoms having at least one hydrogen substituted with fluorine or chlorine Alkyl group, or an alkenyl group having 2 to 12 carbon atoms in which at least one hydrogen is substituted with fluorine or chlorine. In order to reduce the viscosity, it is preferable that R ⁵ or R ⁶ is an alkenyl group having 2 to 12 carbon atoms. In order to improve stability, it is preferable that R ⁵ or R ⁶ is an alkyl group having 1 to 12 carbon atoms. The alkyl group of the liquid crystal compound is linear or branched, and does not contain a cyclic alkyl group. Straight chain alkyl is better than branched alkyl. These cases are also the same for terminal groups such as alkoxy groups and alkenyl groups.

Preferred alkyl groups are methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, or octyl. In order to reduce viscosity, further preferred alkyl groups are ethyl, propyl, butyl, pentyl, or heptyl.

Preferred alkoxy groups are methoxy, ethoxy, propoxy, butoxy, pentyloxy, hexyloxy, or heptyloxy. In order to reduce the viscosity, the preferred alkoxy group is methoxy or ethoxy.

Preferred alkenyl groups 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. In order to reduce the viscosity, the preferred alkenyl group is vinyl, 1-propenyl, 3-butenyl, or 3-pentenyl. The preferred stereo configuration of -CH = CH- in these alkenyl groups depends on the position of the double bond. For reasons such as lowering viscosity, among alkenyl groups such as 1-propenyl, 1-butenyl, 1-pentenyl, 1-hexenyl, 3-pentenyl, 3-hexenyl, etc. are preferred Trans configuration. Among alkenyl groups such as 2-butenyl, 2-pentenyl, 2-hexenyl, etc., a cis configuration is preferred.

Preferred alkenyloxy groups are vinyloxy, allyloxy, 3-butenyloxy, 3-pentenyloxy, or 4-pentenyloxy. In order to reduce the viscosity, the preferred alkenyloxy group is allyloxy or 3-butenyloxy.

Preferred examples of alkyl groups in which at least one hydrogen is substituted by fluorine or chlorine are fluoromethyl, 2-fluoroethyl, 3-fluoropropyl, 4-fluorobutyl, 5-fluoropentyl, 6-fluorohexyl, 7 -Fluoroheptyl, or 8-fluorooctyl. In order to increase the dielectric anisotropy, further preferred examples are 2-fluoroethyl, 3-fluoropropyl, 4-fluorobutyl, or 5-fluoropentyl.

Preferred examples of alkenyl in which at least one hydrogen is substituted 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. In order to reduce the viscosity, further preferred examples are 2,2-difluorovinyl or 4,4-difluoro-3-butenyl.

Ring C and Ring E are independently 1,4-cyclohexyl, 1,4-cyclohexenyl, 1,4-phenylene, 1,4-phenylene with at least one hydrogen substituted by fluorine or chlorine , Or tetrahydropyran-2,5-diyl. Preferred examples of "1,4-phenylene substituted with at least one hydrogen by fluorine or chlorine" are 2-fluoro-1,4-phenylene, 2,3-difluoro-1,4-phenylene, Or 2-chloro-3-fluoro-1,4-phenylene. In order to reduce the viscosity, the preferred ring C or ring E is 1,4-cyclohexyl. To improve the dielectric anisotropy, the preferred ring C or ring E is tetrahydropyran-2,5-diyl. In order to increase the optical anisotropy, the preferred ring C or ring E is 1,4-phenylene. In order to increase the upper limit temperature, the stereo configuration related to 1,4-cyclohexyl is that the trans configuration is superior to the cis configuration. In the chemical formula of tetrahydropyran-2,5-diyl, oxygen may be toward the left (L) or toward the right (R), preferably oxygen toward the left (L).

[化 25]

Ring D is 2,3-difluoro-1,4-phenylene, 2-chloro-3-fluoro-1,4-phenylene, 2,3-difluoro-5-methyl-1,4- Phenylphenyl, 3,4,5-trifluoronaphthalene-2,6-diyl, or 7,8-difluorochroman-2,6-diyl. In order to reduce the viscosity, the preferred ring D is 2,3-difluoro-1,4-phenylene, and in order to reduce the optical anisotropy, the preferred ring D is 2-chloro-3-fluoro-1,4- Phenylene, in order to improve the dielectric anisotropy, the preferred ring D is 7,8-difluorochroman-2,6-diyl.

Ring F and Ring G are independently 1,4-cyclohexyl, 1,4-phenylene, 2-fluoro-1,4-phenylene, or 2,5-difluoro-1,4-phenylene base. To reduce the viscosity or to increase the upper limit temperature, the preferred ring F or ring G is 1,4-cyclohexyl, and to reduce the lower limit temperature, the preferred ring F or ring G is 1,4-cyclophenyl. In order to increase the upper limit temperature, the stereo configuration related to 1,4-cyclohexyl is that the trans configuration is superior to the cis configuration.

Z ² and Z ^{3 are} independently a single bond,-(CH ₂ ) _2- , -CH ₂ O-, -OCH _2- , -COO-, or -OCO-. In order to reduce the viscosity, the preferred Z ² or Z ³ is a single bond. In order to reduce the lower limit temperature, the preferred Z ² or Z ³ is-(CH ₂ ) _2- . In order to increase the dielectric anisotropy, the preferred Z ² or Z ³ is -CH ₂ O- or -OCH _2- . Z ⁴ is a single bond,-(CH ₂ ) _2- , -CH ₂ O-, -OCH _2- , -COO-, or -OCO-. In order to reduce the viscosity, the preferred Z ⁴ is a single bond. In order to reduce the lower limit temperature, the preferred Z ⁴ is-(CH ₂ ) _2- . In order to increase the upper limit temperature, the preferred Z ⁴ is -COO- or -OCO- .

b is 1, 2, or 3, c is 0 or 1, and the sum of b and c is 3 or less. In order to reduce the viscosity, the preferred b is 1, and in order to increase the upper limit temperature, the preferred b is 2 or 3. In order to reduce the viscosity, the preferred c is 0, and in order to reduce the lower limit temperature, the preferred c is 1. d is 1, 2, or 3. In order to reduce the viscosity, the preferred d is 1, and in order to increase the upper limit temperature, the preferred d is 2 or 3.

In formula (4), R ²² is a polar group. Since the compound (4) is added to the composition, it is preferably stable. When compound (4) is added to the composition, it is preferable that the compound does not reduce the voltage retention of the device. The compound (4) preferably has low volatility. The preferred molar mass is above 130 g / mol. A better molar mass is in the range of 150 g / mol to 500 g / mol.

R ²¹ is hydrogen, halogen, alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, alkenyl having 2 to 12 carbons, and carbon 1 to 12 having at least one hydrogen substituted with fluorine or chlorine An alkyl group, or an alkenyl group having 2 to 12 carbons in which at least one hydrogen is substituted with fluorine or chlorine. Preferred R ²¹ is an alkyl group having 1 to 12 carbons.

Ring A ²¹ and Ring B ^{21 are} independently 1,4-cyclohexyl, 1,4-cyclohexenyl, 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, pyridine-2,5-diyl, stilbene-2,7-diyl, phenanthrene-2,7-diyl, anthracene-2,6-diyl, perhydrogen Cyclopenta [a] phenanthrene-3,17-diyl, or 2,3,4,7,8,9,10,11,12,13,14,15,16,17-tetrahydrocyclopenta [a] Phenanthrene-3,17-diyl, in these rings, at least one hydrogen can be hydrogen, fluorine, chlorine, C 1-12 alkyl, C 1-12 alkoxy, or at least one hydrogen Fluorine or chlorine substituted alkyl groups with 1 to 12 carbons. Preferred ring A ²¹ or ring B ²¹ is 1,4-cyclohexyl, 1,4-phenylene, or 2-fluoro-1,4-phenylene.

Z ²¹ is a single bond,-(CH ₂ ) _2- , -CH = CH-, -C≡C-, -COO-, -OCO-, -CF ₂ O-, -OCF _2- , -CH ₂ O- , -OCH _2- , or -CF = CF-. Preferably Z ²¹ is a single bond,-(CH ₂ ) _2- , -CH ₂ O-, -OCH _2- , -COO-, or -OCO-. Furthermore, the preferred Z ²¹ is a single bond.

Sp ²¹ and Sp ^{22 are} independently a single bond or an alkylene group having 1 to 7 carbon atoms, in which at least one -CH ₂ -may be substituted by -O-, -COO-, or -OCO-, at least One-(CH ₂ ) ₂ -may be substituted by -CH = CH-, and in these groups, at least one hydrogen may be substituted by fluorine. Preferably, Sp ²¹ or Sp ²² is a single bond.

a ²¹ is 0, 1, 2, 3, or 4. Preferably a ²¹ is 0, 1, or 2.

In formula (4-1) to formula (4-9), L ¹ , L ² , L ³ , L ⁴ , L ⁵ , L ⁶ , L ⁷ , L ⁸ , L ⁹ , L ¹⁰ , L ¹¹ , and L ^{12 is} independently hydrogen, fluorine, methyl, or ethyl. Preferably, L ¹ to L ¹² are hydrogen, fluorine, or methyl. Furthermore, L ¹ to L ¹² are preferably hydrogen or fluorine.

In formula (5), P ¹ , P ² , and P ^{3 are} independently polymerizable groups. Preferably, P ¹ , P ² , or P ³ is a polymerizable group selected from the group represented by formula (P-1) to formula (P-5). More preferably, P ¹ , P ² , or P ³ is a group represented by formula (P-1), formula (P-2), or formula (P-3). Particularly preferred P ¹ , P ² , or P ³ are groups represented by formula (P-1) or formula (P-2). The most preferred P ¹ , P ² , or P ³ is the base represented by the formula (P-1). The preferred group represented by formula (P-1) is -OCO-CH = CH ₂ or -OCO-C (CH ₃ ) = CH ₂ . The wavy line from formula (P-1) to formula (P-5) indicates the bonded part.

[化 26]

In formula (P-1) to formula (P-5), M ¹ , M ² , and M ^{3 are} independently hydrogen, fluorine, an alkyl group having 1 to 5 carbon atoms, or at least one hydrogen is substituted with fluorine or chlorine C1-C5 alkyl. In order to improve the reactivity, M ¹ , M ² , or M ³ is preferably hydrogen or methyl. Furthermore, among M ¹ , M ² , or M ³ , M ¹ is hydrogen or methyl, and M ² or M ³ is hydrogen.

Sp ³ , Sp ⁴ , and Sp ^{5 are} independently a single bond or an alkylene group having 1 to 10 carbon atoms, in which at least one -CH ₂ -may be passed through -O-, -COO-, -OCO- , Or -OCOO-, and at least one-(CH ₂ ) ₂ -may be substituted by -CH = CH- or -C≡C-, in these groups, at least one hydrogen may be substituted by fluorine or chlorine. Preferred Sp ³ , Sp ⁴ , or Sp ⁵ are single bonds,-(CH ₂ ) _2- , -CH ₂ O-, -OCH _2- , -COO-, -OCO-, -CO-CH = CH- , Or -CH = CH-CO-. Furthermore, Sp ³ , Sp ⁴ , or Sp ⁵ is a single bond.

Ring J and Ring P are independently cyclohexyl, cyclohexenyl, phenyl, 1-naphthyl, 2-naphthyl, tetrahydropyran-2-yl, 1,3-dioxan-2-yl, Pyrimidin-2-yl, or pyridin-2-yl, in these rings, at least one hydrogen can be through fluorine, chlorine, C 1-12 alkyl, C 1-12 alkoxy, or at least one hydrogen It is substituted with a C 1-12 alkyl group substituted with fluorine or chlorine. Preferred ring J or ring P is phenyl. Ring K is 1,4-cyclohexyl, 1,4-cyclohexenyl, 1,4-phenylene, naphthalene-1,2-diyl, naphthalene-1,3-diyl, naphthalene-1 , 4-diyl, naphthalene-1,5-diyl, naphthalene-1,6-diyl, naphthalene-1,7-diyl, naphthalene-1,8-diyl, naphthalene-2,3-diyl , Naphthalene-2,6-diyl, naphthalene-2,7-diyl, tetrahydropyran-2,5-diyl, 1,3-dioxane-2,5-diyl, pyrimidine-2, 5-diyl, or pyridine-2,5-diyl, in these rings, at least one hydrogen may be through fluorine, chlorine, alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, or at least One hydrogen is substituted with fluorine or chlorine substituted C1-C12 alkyl. Preferred ring K is 1,4-phenylene or 2-fluoro-1,4-phenylene.

Z ⁵ and Z ^{6 are} independently a single bond or an alkylene group having 1 to 10 carbon atoms. In this alkylene group, at least one -CH ₂ -may be passed through -O-, -CO-, -COO-, or -OCO -Substitute, and at least one-(CH ₂ ) ₂ -can be replaced by -CH = CH-, -C (CH ₃ ) = CH-, -CH = C (CH ₃ )-, or -C (CH ₃ ) = C (CH ₃ ) -Substitution, in these groups, at least one hydrogen may be substituted by fluorine or chlorine. Preferably Z ⁵ or Z ⁶ is a single bond,-(CH ₂ ) _2- , -CH ₂ O-, -OCH _2- , -COO-, or -OCO-. Furthermore, the preferred Z ⁵ or Z ⁶ is a single bond.

q is 0, 1, or 2. The preferred q is 0 or 1. j, k, and p are independently 0, 1, 2, 3, or 4, and the sum of j, k, and p is 1 or more. Preferably, j, k, or p is 1 or 2.

Fifth, the preferred component compounds are shown. Preferred compound (1) is the compound (1-1) to compound (1-3) described in item 2. Further preferred compound (1) is compound No. 1 to compound No. 54. Particularly preferred compounds (1) are Compound No. 1, Compound No. 2, Compound No. 4 to Compound No. 11, Compound No. 13 to Compound No. 20, Compound No. 22 to Compound No. 29, Compound No. .31 to Compound No. 38, Compound No. 40 to Compound No. 47, Compound No. 49 to Compound No. 54.

[化 27]

[Chem 28]

Among these compounds, it is more preferable that at least one of the first additives is Compound No. 1.

Preferred compound (2) is compound (2-1) to compound (2-22) described in item 5. Among these compounds, it is preferred that at least one of the first components is compound (2-1), compound (2-3), compound (2-4), compound (2-6), compound (2-8), Or compound (2-10). And it is preferred that at least two of the first components are compound (2-1) and compound (2-6), compound (2-1) and compound (2-10), compound (2-3) and compound (2 -6), compound (2-3) and compound (2-10), compound (2-4) and compound (2-6), or a combination of compound (2-4) and compound (2-8).

Preferred compound (3) is the compound (3-1) to compound (3-13) described in item 8. Among these compounds, it is preferred that at least one of the second components is compound (3-1), compound (3-3), compound (3-5), compound (3-6), compound (3-8), Or compound (3-9). And it is preferable that at least two of the second components are compound (3-1) and compound (3-3), compound (3-1) and compound (3-5), or compound (3-1) and compound ( 3-6) combination.

Preferred compound (4) is compound (4-1) to compound (4-9) described in item 11. Further preferred compound (4) is compound (4-10) to compound (4-19).

[化 29]

Preferred compound (5) is compound (5-1) to compound (5-28) described in item 15. Among these compounds, it is preferred that at least one of the third additives is compound (5-1), compound (5-2), compound (5-24), compound (5-25), compound (5-26) , Compound (5-27) or compound (5-28). And preferably at least two of the third additives are compound (5-1) and compound (5-2), compound (5-1) and compound (5-18), compound (5-2) and compound ( 5-24), compound (5-2) and compound (5-25), compound (5-2) and compound (5-26), compound (5-25) and compound (5-26), or compound ( 5-18) and the combination of compound (5-24). Further preferred compound (5) is compound (RM-1) to compound (RM-8).

[化 30]

Sixth, additives other than the first additive, the second additive, and the third additive that can be added to the composition will be described. Such additives are optically active compounds, antioxidants, ultraviolet absorbers, pigments, defoamers, polymerizable compounds, polymerization initiators, polymerization inhibitors, polar compounds, and the like. For the purpose of causing a helical structure of liquid crystal molecules to impart a torsion angle, an optically active compound is added to the composition. Examples of such compounds are compound (Op-1) to compound (Op-5). The preferable ratio of the optically active compound is about 5% by weight or less. A further preferred ratio is in the range of about 0.01% by weight to about 2% by weight.

[化 31]

Anti-oxidants are added in order to prevent a decrease in the specific resistance caused by heating in the atmosphere, or to maintain a large voltage retention rate not only at room temperature but also at a temperature close to the upper limit temperature after using the device for a long time. In the composition. Preferred examples of the antioxidant are compounds (G) where n is an integer of 1 to 9, and the like.

[化 32]

In the compound (G), preferable n is 1, 3, 5, 7, or 9. Furthermore, the optimal n is 7. Since the compound (G) having n of 7 has low volatility, it is effective for maintaining a large voltage retention rate not only at room temperature but also at a temperature close to the upper limit temperature after using the device for a long time. In order to obtain the above effect, the preferable ratio of the antioxidant is about 50 ppm or more, and the preferable ratio of the antioxidant is about 600 ppm or less in order not to lower the upper limit temperature or not to increase the lower limit temperature. A further preferred ratio is in the range of about 100 ppm to about 300 ppm.

Preferred examples of the ultraviolet absorber are benzophenone derivatives, benzoate derivatives, triazole derivatives and the like. In addition, light stabilizers such as amines having steric hindrance are also preferred. In order to obtain the above effect, the preferred ratio of these absorbents or stabilizers is about 50 ppm or more. Below ppm. A further preferred ratio is in the range of about 100 ppm to about 10000 ppm.

In order to make the composition suitable for the guest host (GH) mode element, dichroic dyes such as azo pigments and anthraquinone pigments are added to the composition. The preferable ratio of the pigment is in the range of about 0.01% by weight to about 10% by weight. To prevent foaming, antifoaming agents such as dimethyl silicone oil and methyl phenyl silicone oil are added to the composition. In order to obtain the above-mentioned effect, the preferable ratio of the defoaming agent is about 1 ppm or more, and in order to prevent display defects, the preferable ratio of the defoaming agent is about 1000 ppm or less. A further preferred ratio is in the range of about 1 ppm to about 500 ppm.

In order to adapt the composition to a polymer stable alignment (PSA) type element, a polymerizable compound is used. Compound (1), compound (4) and compound (5) are suitable for this purpose. Compound (1), compound (4), and compound (5) and other polymerizable compounds different from compound (1), compound (4), and compound (5) may also be added to the composition. Preferred examples of other polymerizable compounds are acrylates, methacrylates, vinyl compounds, vinyloxy compounds, allyl ethers, epoxy compounds (oxirane, oxetane), vinyl ketone And other compounds. A further preferred example is acrylate or methacrylate. Based on the total weight of the polymerizable compound, the preferable ratio of the compound (1), the compound (4), and the compound (5) is about 10% by weight or more. A further preferable ratio is about 50% by weight or more. A particularly good ratio is about 80% by weight or more. The proportion of Tejia is also 100% by weight. By changing the types of compound (1), compound (4) and compound (5), or by combining other polymerizable compounds with compound (1), compound (4) and compound (5) in an appropriate ratio, Adjust the reactivity of the polymerizable compound or the pretilt angle of the liquid crystal molecules. By optimizing the pretilt angle, a short response time of the device can be achieved. Since the alignment of the liquid crystal molecules is stabilized, large contrast or long life can be achieved.

Polymerizable compounds such as compound (1), compound (4), and compound (5) are polymerized by ultraviolet irradiation. The polymerization may be carried out in the presence of a suitable initiator such as a photopolymerization initiator. Appropriate conditions for polymerization, suitable types of initiators, and suitable amounts are known to those of ordinary skill in the art and are described in the literature. For example, as a photopolymerization initiator, Omnirad 651 (registered trademark; IGM Resins), Omnirad 184 (registered trademark; IGM Resins), or Austrian Omnirad 1173 (registered trademark; IGM Resins) is suitable for free radical polymerization. Based on the total weight of the polymerizable compound, the preferred ratio of the photopolymerization initiator is in the range of about 0.1% by weight to about 5% by weight. A further preferred ratio is in the range of about 1% by weight to about 3% by weight.

When storing polymerizable compounds such as compound (1), compound (4), and compound (5), a polymerization inhibitor may be added in order to prevent polymerization. The polymerizable compound is usually added to the composition without removing the polymerization inhibitor. Examples of polymerization inhibitors are hydroquinone derivatives such as hydroquinone, methylhydroquinone, 4-tributylbutylcatechol, 4-methoxyphenol, phenothiazine, and the like.

Seventh, the method of synthesizing the component compounds will be described. These compounds can be synthesized by known methods. Exemplify the synthesis method. The method for synthesizing the compound (1) is described in the section of Examples. Compound (2-1) was synthesized by the method described in Japanese Patent Laid-Open No. 2-503441. Compound (3-5) was synthesized by the method described in Japanese Patent Laid-Open No. 57-165328. Compound (4) was synthesized by the method described in International Publication No. 2016/129490. Compound (5-18) was synthesized by the method described in Japanese Patent Laid-Open No. 7-101900. A part of compound (G) is commercially available. The compound of formula (G) where n is 1 is available from Sigma-Aldrich Corporation. The compound (G) in which n is 7 is synthesized by the method described in the specification of US Patent No. 3660505.

Compounds not described in the synthesis method can be synthesized by the methods described in the following book: "Organic Syntheses" (John Wiley & Sons, Inc.), "Organic Reactions (Organic Reactions ”(John Wiley & Sons, Inc.),“ Comprehensive Organic Synthesis ”(Pergamon Press),“ New Experimental Chemistry Lectures ”( Maruzen) etc. The composition is prepared from the compound obtained in the above-described manner using a known method. For example, the component compounds are mixed and then dissolved by heating.

Finally, the use of the composition will be described. Most compositions have a lower limit temperature of about -10 ° C or lower, an upper limit temperature of about 70 ° C or higher, and optical anisotropy in the range of about 0.07 to about 0.20. The composition having an optical anisotropy in the range of about 0.08 to about 0.25 can be prepared by controlling the ratio of component compounds or by mixing other liquid crystal compounds. Furthermore, a composition having optical anisotropy in the range of about 0.10 to about 0.30 can also be prepared. The device containing this composition has a large voltage retention rate. This composition is suitable for AM devices. This composition is particularly suitable for transmission-type AM devices. This composition can be used as a composition having a nematic phase, 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 devices and PM devices having modes such as PC, TN, STN, ECB, OCB, IPS, FFS, VA, and FPA. Especially good for AM components with TN mode, OCB mode, IPS mode or FFS mode. In the AM device having the IPS mode or FFS mode, when no voltage is applied, the alignment of the liquid crystal molecules may be parallel to the glass substrate, or may be vertical. The elements may be reflective, transmissive, or semi-transmissive. It is preferably used for a transmission type element. It can also be used in amorphous silicon-TFT devices or polysilicon-TFT devices. It can also be used in a nematic curvilinear aligned phase (NCAP) type device produced by microencapsulating the composition or a polymer dispersed (polymer dispersed) formed by forming a three-dimensional network polymer in the composition , PD) type components.

An example of a method of manufacturing a conventional polymer-stabilized alignment element is as follows. Assembling an element having two substrates, the two substrates are called an array substrate and a color filter substrate. The substrate has an alignment film. At least one piece of the substrate has an electrode layer. The liquid crystal compound is mixed to prepare a liquid crystal composition. A polymerizable compound is added to this composition. Add additives as needed. The composition is injected into the device. Light irradiation is performed with a voltage applied to this element. It is preferably ultraviolet light. The polymerizable compound is polymerized by light irradiation. By this polymerization, a polymer-containing composition is produced. Polymer stabilized alignment elements are manufactured in this order.

In this sequence, when a voltage is applied, liquid crystal molecules are aligned by the action of an electric field. According to this alignment, the molecules of the polymerizable compound are also aligned. Since the polymerizable compound is polymerized by ultraviolet rays in this state, a polymer that maintains the alignment is generated. By the effect of the polymer, the response time of the device is shortened. Since the afterimage of the image is a malfunction of the liquid crystal molecules, the afterimage is also improved by the effect of the polymer. Furthermore, the polymerizable compound in the composition may be polymerized in advance, and the composition may be disposed between the substrates of the liquid crystal display element.

In the case of using the compound (1), that is, a polymerizable compound containing a nitrogen atom in the bonding group, the substrate of the device does not require an alignment film. An element without an alignment film is manufactured according to the order described in the paragraphs before two paragraphs except that a substrate without an alignment film is used.

In this sequence, the compound (1) is adsorbed on the substrate surface by the action of the nitrogen atom present in the bonding group of the molecular structure, and the group extending from the nitrogen atom is compatible with the liquid crystal molecule. Compound (4) controls the vertical alignment of liquid crystal molecules by interacting with the substrate of the device in a non-covalent bonding manner. According to this arrangement, the liquid crystal molecules are aligned. When a voltage is applied, the alignment of liquid crystal molecules is further promoted. In addition, the polymer is provided by polymerization to stabilize the alignment of liquid crystal molecules. Furthermore, since it has a mesogen portion composed of at least one ring, it is compatible with a liquid crystal compound. Compound (5) provides a polymer by polymerization. This polymer stabilizes the alignment of liquid crystal molecules. In this state, the polymerizable compound is polymerized by ultraviolet rays, so that a polymer that maintains the alignment is generated. By the effect of this polymer, the alignment of liquid crystal molecules is additionally stabilized, and the response time of the device is shortened. Since the afterimage of the image is a malfunction of the liquid crystal molecules, the afterimage is also improved by the effect of the polymer. [Example]

The present invention will be further described in detail by examples. The invention is not limited by these embodiments. The invention also includes a mixture of composition M1 and composition M2. The present invention also includes a mixture obtained by mixing at least two of the compositions of the examples. The synthesized compounds were identified by nuclear magnetic resonance (NMR) analysis and other methods. The characteristics of the compound, composition and device are measured by the following method.

NMR analysis: DRX-500 manufactured by Bruker BioSpin was used for the measurement. ^In the measurement of ¹ H-NMR, the sample was dissolved in a deuterated solvent such as CDCl _3, and the measurement was performed under the conditions of room temperature, 500 MHz, and the number of accumulations 16 times. Use tetramethylsilane as an internal standard. ^In the measurement of ¹⁹ F-NMR, CFCl _{3 was} used as an internal standard, and the total number of times was 24. In the description of NMR spectroscopy, s refers to singlet, d refers to doublet, t refers to triplet, q refers to quartet, and quin refers to quintet (Quintet), sex refers to sixt (sextet), m refers to multiplet (multiplet), br refers to broad peak (broad).

Gas chromatography analysis: A GC-14B gas chromatograph manufactured by Shimadzu Corporation was used for the measurement. The carrier gas is helium (2 mL / min). The sample gasification chamber was set to 280 ° C, and the detector (flame ionization detector (FID)) was set to 300 ° C. For the separation of the component compounds, the capillary column DB-1 (length 30 m, inner diameter 0.32 mm, film thickness 0.25 μm) manufactured by Agilent Technologies Inc. was used; the fixed liquid phase was dimethyl polysilicon Oxane; non-polar). After the column was kept at 200 ° C for 2 minutes, the temperature was raised to 280 ° C at a rate of 5 ° C / min. After preparing the sample as an acetone solution (0.1% by weight), 1 μL of it was injected into the sample gasification chamber. The record meter is the C-R5A chromatograph module (Chromatopac) manufactured by Shimadzu Corporation or its equivalent. The obtained gas chromatogram shows the retention time and area of the peak corresponding to the component compounds.

The solvent used to dilute the sample can be chloroform, hexane, etc. In order to separate the component compounds, the following capillary columns can be used. HP-1 (length 30 m, inner diameter 0.32 mm, film thickness 0.25 μm) manufactured by Agilent Technologies Inc., Rtx-1 (length 30 m, inner) manufactured by Restek Corporation Diameter 0.32 mm, film thickness 0.25 μm), BP-1 (length 30 m, inner diameter 0.32 mm, film thickness 0.25 μm) manufactured by SGE International Pty. Ltd. 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 can be used.

The ratio of the liquid crystal compound contained in the composition can be calculated by the following method. Gas chromatography (FID) was used to analyze the mixture of liquid crystal compounds. The area ratio of peaks in the gas chromatogram corresponds to the ratio of liquid crystal compounds. When using the capillary column described above, the correction coefficient of various liquid crystal compounds can be regarded as 1. Therefore, the ratio (wt%) of the liquid crystal compound can be calculated from the area ratio of the peak.

Measurement sample: When measuring the characteristics of the composition and components, the composition is used directly as a sample. When measuring the characteristics of the compound, a sample for measurement was prepared by mixing the compound (15% by weight) in the mother liquid crystal (85% by weight). Based on the value obtained by the measurement, the characteristic value of the compound is calculated by extrapolation. (Extrapolated value) = {(measured value of the sample)-0.85 × (measured value of the mother liquid crystal)} / 0.15. When the smectic phase (or crystal) is precipitated at 25 ° C at this ratio, the ratio of the compound to the mother liquid crystal is 10% by weight: 90% by weight, 5% by weight: 95% by weight, 1% by weight: 99% % Order changed. Using this extrapolation method, the values of the upper limit temperature, optical anisotropy, viscosity, and dielectric anisotropy related to the compound are obtained.

Use the following mother liquid crystal. The proportion of component compounds is expressed in% by weight.

[化 33]

Measurement method: The characteristics are measured by the following method. Most of these methods are the methods described in the JEITA standard (JEITA · ED-2521B) reviewed and formulated by the Japan Electronics and Information Technology Industries Association (referred to as JEITA) or modified from them Methods. No thin film transistor (TFT) was installed in the TN device used in the measurement.

(1) Transition temperature (℃): Scanning calorimeter Diamond DSC system manufactured by PerkinElmer or high-sensitivity differential scanning manufactured by SSI Nanotechnology is used for the measurement Calorimeter X-DSC7000. The temperature of the sample is raised and lowered at a rate of 3 ° C / min. The transition temperature is determined by extrapolating the starting point of the endothermic peak or exothermic peak generated by the phase change of the sample. The melting point of the compound and the polymerization initiation temperature are also measured using this device. Sometimes the temperature at which the compound transforms from a solid to a smectic phase and a nematic equal liquid crystal phase is simply referred to as "the lower limit temperature of the liquid crystal phase." Sometimes the temperature at which a compound changes from a liquid crystal phase to a liquid is simply called "transparent point." The crystal is expressed as C. When distinguishing the types of crystals, they are expressed as C ₁ and C ₂ , respectively. The smectic phase is represented as S, and the nematic phase is represented as N. In the smectic phase, when the smectic A phase, smectic B phase, smectic C phase, or smectic F phase is distinguished, they are expressed as S _A , S _B , S _C , or S _{F, respectively} . The liquid (isotropic) is represented as I. The transition temperature is expressed as "C 50.0 N 100.0 I", for example. It means that the transition temperature from crystallization to nematic phase is 50.0 ° C, and the transition temperature from nematic phase to liquid is 100.0 ° C.

(2) The upper limit temperature of the nematic phase (NI; ° C): Place the sample on a hot plate equipped with a melting point measuring device of a polarizing microscope and heat at a rate of 1 ° C / min. The temperature when a part of the sample changes from a nematic phase to an isotropic liquid is measured. Sometimes the upper limit temperature of the nematic phase is simply referred to as the "upper limit temperature".

(3) lower limit temperature (T _C; ℃) nematic phase: A sample having a nematic phase into glass vials, at 0 ℃, -10 ℃, -20 ℃ , -30 ℃, and -40 ℃ After storing in the freezer for 10 days, observe the liquid crystal phase. For example, when the sample is in the state of a nematic phase at -20 ° C and changes to a crystal or a smectic phase at -30 ° C, T _{C is} described as <-20 ° C. Sometimes the lower limit temperature of the nematic phase is simply referred to as "lower limit temperature".

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

(5) Viscosity (rotational viscosity; γ1; measured at 25 ° C; mPa · s): based on M. Imai et al. “Molecular Crystals and Liquid Crystals” No. 259 The method described in page 37 (1995) was used for the measurement. A sample was injected into a VA element with a distance (cell gap) of two glass substrates of 20 μm. To this element, a voltage is applied stepwise in a range of 39 volts to 50 volts in units of 1 volt. After no voltage was applied for 0.2 seconds, it was applied repeatedly with only one rectangular wave (rectangular pulse; 0.2 second) and no voltage applied (2 seconds). The peak current and peak time of the transient current generated by the application are measured. Based on these measured values and the equation (8) on page 40 of the paper by M. Imai et al., The value of rotational viscosity is obtained. The dielectric anisotropy required for this calculation is measured by the method described in Measurement (7).

(6) Optical anisotropy (refractive index anisotropy; Δn; measured at 25 ° C): Measured using an Abbe refractometer with a polarizing plate mounted on the eyepiece using light with a wavelength of 589 nm. After rubbing the surface of the main prism in one direction, the sample is dropped on the main prism. The refractive index n∥ is measured when the direction of polarized light is parallel to the direction of rubbing. The refractive index n⊥ is measured when the direction of polarized light is perpendicular to the direction of rubbing. The optical anisotropy value is calculated according to the formula of Δn = n∥-n⊥.

(7) Dielectric anisotropy (Δε; measured at 25 ° C): The value of dielectric anisotropy is calculated according to the formula of Δε = ε∥-ε⊥. The dielectric constants (ε∥ and ε⊥) are determined as follows. 1) Determination of dielectric constant (ε∥): Coat octadecyltriethoxysilane (0.16 mL) in ethanol (20 mL) on a sufficiently 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 with a gap (cell gap) of two glass substrates of 4 μm, and the device was sealed with an adhesive hardened by ultraviolet rays. A sine wave (0.5 V, 1 kHz) was applied to the device, and the dielectric constant (ε∥) in the long axis direction of the liquid crystal molecule was measured after 2 seconds. 2) Measurement of dielectric constant (ε⊥): Apply polyimide solution on a glass substrate that has been sufficiently cleaned. After calcining the glass substrate, the obtained alignment film was subjected to rubbing treatment. A sample was injected into a TN device with a distance (cell gap) of 9 μm and a twist angle of 80 degrees between two glass substrates. A sine wave (0.5 V, 1 kHz) was applied to the device, and the dielectric constant (ε⊥) in the short-axis direction of the liquid crystal molecule was measured after 2 seconds.

(8) Threshold voltage (Vth; measured at 25 ° C; V): LCD5100 type luminance meter manufactured by Otsuka Electronics Co., Ltd. was used for the measurement. The light source is a halogen lamp. A sample is placed in a normally black mode VA device with a gap (cell gap) of 4 μm between two glass substrates and an anti-parallel rubbing direction, using an adhesive hardened by ultraviolet light. The element is sealed. The voltage applied to this element (60 Hz, rectangular wave) is in units of 0.02 V, and increases from 0 V to 20 V in steps. At this time, the element is irradiated with light from the vertical direction, and the amount of light transmitted through the element is measured. A voltage-transmittance curve is prepared in which the transmittance is 100% when the light amount reaches the maximum, and the transmittance is 0% when the light amount is the smallest. The threshold voltage is represented by the voltage when the transmittance reaches 10%.

(9) Voltage retention rate (%): Put the sample in the element without the alignment film, and use the black light F40T10 / BL (peak wavelength 369 nm) manufactured by EYE GRAPHICS Co., Ltd., By irradiating ultraviolet rays, the polymerizable compound is polymerized. The device was charged with a pulse voltage (1 V, 60 microseconds) at 60 ° C. Using a high-speed voltmeter, the attenuated voltage was measured during 1.67 seconds, and the area A between the voltage curve and the horizontal axis per unit period was obtained. Area B is the area without attenuation. The voltage retention rate is expressed by the percentage of area A relative to area B.

(10) Response time (τ; measured at 25 ° C; ms): LCD5100 type luminance meter manufactured by Otsuka Electronics Co., Ltd. was used for the measurement. The light source is a halogen lamp. The low-pass filter is set to 5 kHz. A sample was placed in a VA device with a distance (cell gap) of two glass substrates of 3.5 μm and no alignment film. The component is sealed with an adhesive hardened by ultraviolet light. A voltage of 30 V was applied to the device, and 78 mW / cm ² (405 nm) of ultraviolet light was irradiated for 449 seconds (35 J). For the irradiation of ultraviolet rays, a multi-metal lamp M04-L41 for ultraviolet curing manufactured by EYE GRAPHICS Co., Ltd. was used. A rectangular wave (120 Hz) is applied to this element. At this time, the element is irradiated with light from the vertical direction, and the amount of light transmitted through the element is measured. When the light amount reaches the maximum, the transmittance is regarded as 100%, and when the light amount is the smallest, the transmittance is regarded as 0%. The maximum voltage of the rectangular wave is set so that the transmittance becomes 90%. The minimum voltage of the rectangular wave is set to 2.5 V with a transmittance of 0%. Response time is represented by the time (rise time; rise time; millisecond) required for the transmission rate to change from 10% to 90%.

(11) Elastic constant (K11: splay elastic constant, K33: bend elastic constant; measured at 25 ° C; pN): Toyo Technica Co., Ltd. was used in the measurement EC-1 type elastic constant measuring device manufactured. The sample was injected into a vertical alignment element with a distance (cell gap) of 20 μm between the two glass substrates. A charge of 20 volts to 0 volts was applied to the device, and the electrostatic capacitance and applied voltage were measured. Use the formula (2.98) and formula (2.101) on page 75 of the "Liquid Crystal Device Manual" (Nikkei Industry News Corporation) to fit the measured capacitance (C) to the value of the applied voltage (V). 2.100) to obtain the value of the elastic constant.

(12) Specific resistance (ρ; measured at 25 ° C; Ωcm): Place 1.0 mL of sample in a container equipped with electrodes. A DC voltage (10 V) was applied to the container, and the DC current after 10 seconds was measured. The specific resistance is calculated according to the following formula. (Specific resistance) = {(voltage) × (capacitance of the container)} / {(DC current) × (dielectric constant of vacuum)}.

(13) Pre-tilt angle (degrees): A spectroscopic ellipsometer M-2000U (manufactured by J. A. Woollam Co., Inc.) was used for the measurement of the pre-tilt angle.

(14) Alignment stability (liquid crystal alignment axis stability): Evaluation of changes in the liquid crystal alignment axis on the electrode side of the liquid crystal display element. Measure the alignment angle f (before) of the liquid crystal on the electrode side before applying stress, then apply a rectangular wave of 4.5 V and 60 Hz to the device for 20 minutes, buffer for 1 second, and measure the electrode side again after 1 second and 5 minutes The liquid crystal alignment angle f (after). From these values, the change in liquid crystal alignment angle Δf (deg.) After 1 second and 5 minutes is calculated using the following formula. Δf (deg.) = F (after)-f (before) These measurements are based on J. Hilfiker, B. Johs, C. Herzinger ), "Fin Solid Films" by JF Elman, E. Montbach, D. Bryant and PJ Bos 455-456 (2004) 596-600 for reference. It can be said that the smaller the Δf, the smaller the change rate of the liquid crystal alignment axis, and the better the stability of the liquid crystal alignment axis.

Synthesis Example The synthesis method of compound (No. 1) will be described by the following method.

[Synthesis Example 1] Synthesis of Compound (No. 1)

[化 34]

Step 1 Take compound (Q-1) (3.94 g, 19.58 mmol), triethylamine (4.36 g, 43.1 mmol), and dichloromethane (100 ml) in a container, stir and add methacrylic acid dropwise Chlorine (4.09 g, 39.16 mmol). After stirring at room temperature for 1 hour, the mixture was filtered and concentrated. The obtained residue was purified by silica gel chromatography (toluene) to obtain compound (No. 1) (2.2 g). In addition, the compound (Q-1) is publicly known, and if it is a person having ordinary knowledge in the technical field, it can be easily obtained.

The NMR analysis value of the obtained compound (No. 1) is as follows. ¹ H-NMR (CDCl ₃ ; δppm): 7.03 (d, 8H), 6.33 (s, 2H), 5.74 (s, 2H), 5.69 (s, 1H), 2.06 (s, 6H). Compound No.1 The physical properties are as follows. Transition temperature: C ₁ 91.0 C ₂ 99.2 I

Examples of the composition are shown below. The component compounds are represented by symbols based on the definitions in Table 3 below. In Table 3, the stereo configuration related to 1,4-cyclohexyl is the trans configuration. The number in parentheses after the symbol indicates the chemical formula to which the compound belongs. The symbol (-) refers to other liquid crystal compounds. The ratio (percentage) of the liquid crystal compound is a weight percentage (% by weight) based on the weight of the liquid crystal composition without additives. Finally, summarize the characteristic values of the composition.

[table 3]

Examples of the element 1. Raw material A composition in which a polymerizable compound (1) containing a nitrogen atom in a bonding group and a polymerizable compound (4) having a polar group is added to an element that does not have an alignment film. After ultraviolet irradiation, the vertical alignment of the liquid crystal molecules in the device was evaluated, and the electrical characteristics were also evaluated. First, the raw materials will be described. The raw materials are from the composition (M1) to the composition (M22), the polymerizable compound (1) containing a nitrogen atom in the bonding group, the polymerizable compound (4) having a polar group, and the polymerizable compound (RM-1) to polymerization Sex compounds (RM-8), and listed in sequence.

[Composition M1] 3-HB (2F, 3F) -O2 (2-1) 10% 5-HB (2F, 3F) -O2 (2-1) 7% 2-BB (2F, 3F) -O2 ( 2-4) 7% 3-BB (2F, 3F) -O2 (2-4) 7% 3-B (2F, 3F) B (2F, 3F) -O2 (2-5) 3% 2-HHB ( 2F, 3F) -O2 (2-6) 5% 3-HHB (2F, 3F) -O2 (2-6) 10% 2-HBB (2F, 3F) -O2 (2-10) 8% 3-HBB (2F, 3F) -O2 (2-10) 10% 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) 4% 2-BB (F) B-3 (3-8) 4% NI = 73.2 ℃; Tc <-20 ℃; Δn = 0.113; Δε = -4.0; Vth = 2.18 V; η = 22.6 mPa · s.

[Composition M2] 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 (2-4) 7% 2-HHB (2F, 3F) -O2 (2-6) 7% 3-HHB (2F, 3F) -O2 (2-6) 7% 3-HH2B (2F, 3F) -O2 (2-7) 7% 5-HH2B (2F, 3F) -O2 (2-7) 4% 2-HBB (2F, 3F)- O2 (2-10) 5% 3-HBB (2F, 3F) -O2 (2-10) 5% 4-HBB (2F, 3F) -O2 (2-10) 6% 2-HH-3 (3- 1) 12% 1-BB-5 (3-3) 12% 3-HHB-1 (3-5) 4% 3-HHB-O1 (3-5) 3% 3-HBB-2 (3-6) 3% NI = 82.8 ℃; Tc <-30 ℃; Δn = 0.118; Δε = -4.4; Vth = 2.13 V; η = 22.5 mPa · s .

[Composition M3] 3-HB (2F, 3F) -O2 (2-1) 7% 5-HB (2F, 3F) -O2 (2-1) 7% 3-BB (2F, 3F) -O2 ( 2-4) 8% 3-HHB (2F, 3F) -O2 (2-6) 5% 5-HHB (2F, 3F) -O2 (2-6) 4% 3-HH1OB (2F, 3F) -O2 (2-8) 4% 2-BB (2F, 3F) B-3 (2-9) 5% 2-HBB (2F, 3F) -O2 (2-10) 3% 3-HBB (2F, 3F) -O2 (2-10) 8% 4-HBB (2F, 3F) -O2 (2-10) 5% 5-HBB (2F, 3F) -O2 (2-10) 8% 3-HH-V (3 -1) 27% 3-HH-V1 (3-1) 6% V-HHB-1 (3-5) 3% NI = 78.1 ℃; Tc <-30 ℃; Δn = 0.107; Δ = -3.2; Vth = 2.02 V; η = 15.9 mPa · s.

[Composition M4] 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% 2-HBB (2F, 3F) -O2 (2-10) 6% 3-HBB (2F, 3F) -O2 (2-10) 8% 4-HBB (2F, 3F) -O2 (2-10) 7% 5-HBB (2F, 3F) -O2 (2-10) 7% 3-HDhB (2F, 3F)- O2 (2-16) 5% 3-HH-4 (3-1) 14% V-HHB-1 (3-5) 10% 3-HBB-2 (3-6) 7% NI = 88.5 ℃; Tc ＜ -30 ℃; Δn = 0.108; Δε = -3.8; Vth = 2.25 V; η = 24.6 mPa · s.

[Composition M5] 3-HB (2F, 3F) -O2 (2-1) 7% 3-HB (2F, 3F) -O4 (2-1) 8% 3-H2B (2F, 3F) -O2 ( 2-2) 8% 3-BB (2F, 3F) -O2 (2-4) 10% 2-HHB (2F, 3F) -O2 (2-6) 4% 3-HHB (2F, 3F) -O2 (2-6) 7% 3-HHB (2F, 3F) -1 (2-6) 6% 2-HBB (2F, 3F) -O2 (2-10) 6% 3-HBB (2F, 3F)- O2 (2-10) 6% 4-HBB (2F, 3F) -O2 (2-10) 5% 5-HBB (2F, 3F) -O2 (2-10) 4% 3-HEB (2F, 3F) B (2F, 3F) -O2 (2-11) 3% 3-H1OCro (7F, 8F) -5 (2-14) 3% 3-HDhB (2F, 3F) -O2 (2-16) 5% 3 -HH-O1 (3-1) 5% 1-BB-5 (3-3) 4% V-HHB-1 (3-5) 4% 5-HB (F) BH-3 (3-12) 5% NI = 81.1 ℃; Tc <- 30 ℃; Δn = 0.119; Δε = -4.5; Vth = 1.69 V; η = 31.4 mPa · s.

[Composition M6] 3-HB (2F, 3F) -O4 (2-1) 15% 3-HBB (2F, 3F) -O2 (2-10) 8% 4-HBB (2F, 3F) -O2 ( 2-10) 5% 5-HBB (2F, 3F) -O2 (2-10) 7% 3-dhBB (2F, 3F) -O2 (2-17) 5% 3-chB (2F, 3F) -O2 (2-18) 7% 2-HchB (2F, 3F) -O2 (2-19) 8% 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 = 98.8 ℃; Tc <-30 ℃; Δn = 0.111; Δε = -3.2; Vth = 2.47 V; η = 23.9 mPa · s.

[Composition M7] 3-H2B (2F, 3F) -O2 (2-2) 18% 5-H2B (2F, 3F) -O2 (2-2) 17% 3-HHB (2F, 3CL) -O2 ( 2-12) 5% 3-HBB (2F, 3CL) -O2 (2-13) 8% 5-HBB (2F, 3CL) -O2 (2-13) 7% 3-HDhB (2F, 3F) -O2 (2-16) 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) 4% 3-HHEBH-3 (3-11) 4% NI = 77.5 ℃; Tc <-30 ℃; Δn = 0.084; Δε = -2.6; Vth = 2.43 V; η = 22.8 mPa · s.

[Composition M8] 3-HB (2F, 3F) -O2 (2-1) 8% 3-H2B (2F, 3F) -O2 (2-2) 10% 3-BB (2F, 3F) -O2 ( 2-4) 10% 2O-BB (2F, 3F) -O2 (2-4) 3% 2-HHB (2F, 3F) -O2 (2-6) 4% 3-HHB (2F, 3F) -O2 (2-6) 7% 2-HHB (2F, 3F) -1 (2-6) 5% 2-BB (2F, 3F) B-3 (2-9) 6% 2-BB (2F, 3F) B-4 (2-9) 6% 2-HBB (2F, 3F) -O2 (2-10) 4% 3-HBB (2F, 3F) -O2 (2-10) 7% 3-HH1OCro (7F, 8F) -5 (2-15) 4% 3-HDhB (2F, 3F) -O2 (2-16) 6% 3-dhBB (2F, 3F) -O2 (2-17) 4% 3-HH-V (3-1) 11% 1-BB-5 (3-3) 5% NI = 70.6 ℃; Tc <-20 ℃; Δn = 0.129; Δε = -4.3; Vth = 1.69 V; η = 27.0 mPa · s.

[Composition M9] 3-HB (2F, 3F) -O4 (2-1) 14% 3-H1OB (2F, 3F) -O2 (2-3) 3% 3-BB (2F, 3F) -O2 ( 2-4) 10% 2-HHB (2F, 3F) -O2 (2-6) 7% 3-HHB (2F, 3F) -O2 (2-6) 7% 3-HH1OB (2F, 3F) -O2 (2-8) 6% 2-HBB (2F, 3F) -O2 (2-10) 4% 3-HBB (2F, 3F) -O2 (2-10) 6% 4-HBB (2F, 3F)- O2 (2-10) 4% 3-HH-V (3-1) 14% 1-BB-3 (3-3) 3% 3-HHB-1 (3-5) 4% 3-HHB-O1 ( 3-5) 4% V-HBB-2 (3-6) 4% 1-BB (F) B-2V (3-8) 6% 5-HBBH-1O1 (-) 4% NI = 93.0 ℃; Tc <-30 ℃; Δn = 0.123; Δε = -4.0; Vth = 2.27 V; η = 29.6 mPa · s.

[Composition M10] 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 (2-4) 10% 2-HHB (2F, 3F) -O2 (2-6) 7% 3-HHB (2F, 3F) -O2 (2-6) 7% 5-HHB (2F, 3F) -O2 (2-6) 7% 2-HBB (2F, 3F) -O2 (2-10) 4% 3-HBB (2F, 3F)- O2 (2-10) 7% 5-HBB (2F, 3F) -O2 (2-10) 6% 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) 4% 3-B (F) BB-2 (3-7) 4% NI = 87.6 ℃; Tc <-30 ℃; Δn = 0.126; Δε = -4.5; Vth = 2.21 V; η = 25.3 mPa · s.

[Composition 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 (2-4) 7% 2-HHB (2F, 3F) -O2 (2-6) 6% 3-HHB (2F, 3F) -O2 (2-6) 10% 5-HHB (2F, 3F) -O2 (2-6) 8% 2-HBB (2F, 3F) -O2 (2-10) 5% 3-HBB (2F, 3F)- O2 (2-10) 7% 5-HBB (2F, 3F) -O2 (2-10) 5% 2-HH-3 (3-1) 12% 1-BB-3 (3-3) 6% 3 -HHB-1 (3-5) 3% 3-HHB-O1 (3-5) 4% 3-HBB-2 (3-6) 6% 3-B (F) BB-2 (3-7) 3% NI = 93.0 ℃; Tc <-20 ℃; Δn = 0.124; Δε = -4.5; Vth = 2.22 V; η = 25.0 mPa · s.

[Composition M12] 3-HB (2F, 3F) -O2 (2-1) 7% 5-HB (2F, 3F) -O2 (2-1) 7% 3-BB (2F, 3F) -O2 ( 2-4) 8% 3-HHB (2F, 3F) -O2 (2-6) 4% 5-HHB (2F, 3F) -O2 (2-6) 5% 3-HH1OB (2F, 3F) -O2 (2-8) 5% 2-BB (2F, 3F) B-3 (2-9) 4% 2-HBB (2F, 3F) -O2 (2-10) 3% 3-HBB (2F, 3F) -O2 (2-10) 8% 4-HBB (2F, 3F) -O2 (2-10) 5% 5-HBB (2F, 3F) -O2 (2-10) 8% 3-HH-V (3 -1) 33% V-HHB-1 (3-5) 3% NI = 76.4 ℃; Tc <-30 ℃; Δn = 0.104; Δε = -3.2; Vth = 2.06 V; η = 15.6 mPa · s.

[Composition M13] 2-H1OB (2F, 3F) -O2 (2-3) 6% 3-H1OB (2F, 3F) -O2 (2-3) 4% 3-BB (2F, 3F) -O2 ( 2-4) 3% 2-HH1OB (2F, 3F) -O2 (2-8) 14% 2-HBB (2F, 3F) -O2 (2-10) 7% 3-HBB (2F, 3F) -O2 (2-10) 11% 5-HBB (2F, 3F) -O2 (2-10) 9% 2-HH-3 (3-1) 5% 3-HH-VFF (3-1) 30% 1- BB-3 (3-3) 5% 3-HHB-1 (3-5) 3% 3-HBB-2 (3-6) 3% NI = 78.3 ℃; Tc <-20 ℃; Δn = 0.103; Δε = -3.2; Vth = 2.17 V; η = 17.7 mPa · s.

[Composition M14] 3-HB (2F, 3F) -O2 (2-1) 5% 5-HB (2F, 3F) -O2 (2-1) 7% 3-BB (2F, 3F) -O2 ( 2-4) 8% 3-HHB (2F, 3F) -O2 (2-6) 5% 5-HHB (2F, 3F) -O2 (2-6) 4% 3-HH1OB (2F, 3F) -O2 (2-8) 5% 2-BB (2F, 3F) B-3 (2-9) 4% 2-HBB (2F, 3F) -O2 (2-10) 3% 3-HBB (2F, 3F) -O2 (2-10) 9% 4-HBB (2F, 3F) -O2 (2-10) 4% 5-HBB (2F, 3F) -O2 (2-10) 8% 3-HH-V (3 -1) 27% 3-HH-V1 (3-1) 6% V-HHB-1 (3-5) 5% NI = 81.2 ℃; Tc <-20 ℃; Δn = 0.107; Δ = -3.2; Vth = 2.11 V; η = 15.5 mPa · s.

[Composition M15] 3-H2B (2F, 3F) -O2 (2-2) 7% 3-HHB (2F, 3F) -O2 (2-6) 8% 3-HH1OB (2F, 3F) -O2 ( 2-8) 5% 2-BB (2F, 3F) B-3 (2-9) 7% 2-BB (2F, 3F) B-4 (2-9) 7% 3-HDhB (2F, 3F) -O2 (2-16) 3% 5-HDhB (2F, 3F) -O2 (2-16) 4% 2-HchB (2F, 3F) -O2 (2-19) 8% 4-HH-V (3 -1) 15% 3-HH-V1 (3-1) 6% 1-HH-2V1 (3-1) 6% 3-HH-2V1 (3-1) 4% 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 = 88.7 ℃; Tc <-30 ℃; Δn = 0.115; Δε = -1.9; Vth = 2.82 V; η = 17.3 mPa · s.

[Composition M16] V2-H2B (2F, 3F) -O2 (2-2) 8% V2-H1OB (2F, 3F) -O4 (2-3) 4% 3-BB (2F, 3F) -O2 ( 2-4) 7% 2-HHB (2F, 3F) -O2 (2-6) 7% 3-HHB (2F, 3F) -O2 (2-6) 7% 3-HH2B (2F, 3F) -O2 (2-7) 7% 5-HH2B (2F, 3F) -O2 (2-7) 4% V-HH2B (2F, 3F) -O2 (2-7) 6% V2-HBB (2F, 3F)- O2 (2-10) 5% V-HBB (2F, 3F) -O2 (2-10) 5% V-HBB (2F, 3F) -O4 (2-10) 6% 2-HH-3 (3- 1) 12% 1-BB-5 (3-3) 12% 3-HHB-1 (3-5) 4% 3-HHB-O1 (3- 5) 3% 3-HBB-2 (3-6) 3% NI = 89.9 ℃; Tc <-20 ℃; Δn = 0.122; Δε = -4.2; Vth = 2.16 V; η = 23.4 mPa · s.

[Composition M17] 3-HB (2F, 3F) -O2 (2-1) 3% V-HB (2F, 3F) -O2 (2-1) 3% V2-HB (2F, 3F) -O2 ( 2-1) 5% 5-H2B (2F, 3F) -O2 (2-2) 5% V2-BB (2F, 3F) -O2 (2-4) 3% 1V2-BB (2F, 3F) -O2 (2-4) 3% 3-HHB (2F, 3F) -O2 (2-6) 6% V-HHB (2F, 3F) -O2 (2-6) 6% V-HHB (2F, 3F)- O4 (2-6) 5% V2-HHB (2F, 3F) -O2 (2-6) 4% V2-BB (2F, 3F) B-1 (2-9) 4% V2-HBB (2F, 3F ) -O2 (2-10) 5% V-HBB (2F, 3F) -O2 (2-10) 4% V-HBB (2F, 3F) -O4 (2-10) 5% V-HHB (2F, 3CL) -O2 (2-12) 3% 3-HH-V (3-1) 27% 3-HH-V1 (3-1) 6% V-HHB-1 (3-5) 3% NI = 77.1 ℃; Tc <-20 ℃; Δn = 0.101 ; Δε = -3.0; Vth = 2.04 V; η = 13.9 mPa · s.

[Composition M18] V-HB (2F, 3F) -O2 (2-1) 10% V2-HB (2F, 3F) -O2 (2-1) 10% 2-H1OB (2F, 3F) -O2 ( 2-3) 3% 3-H1OB (2F, 3F) -O2 (2-3) 3% 2O-BB (2F, 3F) -O2 (2-4) 3% V2-BB (2F, 3F) -O2 (2-4) 8% V2-HHB (2F, 3F) -O2 (2-6) 5% 2-HBB (2F, 3F) -O2 (2-10) 3% 3-HBB (2F, 3F)- O2 (2-10) 3% V-HBB (2F, 3F) -O2 (2-10) 6% V-HBB (2F, 3F) -O4 (2-10) 8% V-HHB (2F, 3CL) -O2 (2-12) 7% 3-HH-4 (3-1) 14% V-HHB-1 (3-5) 10% 3-HBB-2 (3-6) 7% NI = 75.9 ℃; Tc <-20 ℃; Δn = 0.114; Δε = -3.9; Vth = 2.20 V; η = 24.7 mPa · s.

[Composition M19] 3-HB (2F, 3F) -O2 (2-1) 12% 2-HH1OB (2F, 3F) -O2 (2-8) 10% 3-HH1OB (2F, 3F) -O2 ( 2-8) 9% 2O-B (2F) B (2F, 3F) -O2 (2-22) 4% 2O-B (2F) B (2F, 3F) -O4 (2-22) 5% 2- HH-3 (3-1) 25% 3-HH-4 (3-1) 6% 1-BB-3 (3-3) 4% 3-HHB-1 (3-5) 9% 3-HBB- 2 (3-6) 7% 5-B (F) BB-2 (3-7) 9% NI = 74.2 ℃; Tc <-20 ℃; Δn = 0.103; Δε = -2.5; Vth = 2.36 V; η = 18.4 mPa · s.

[Composition M20] 3-H1OB (2F, 3F) -O2 (2-3) 10% V-HHB (2F, 3F) -O2 (2-6) 5% 2-HH1OB (2F, 3F) -O2 ( 2-8) 4% 3-HBB (2F, 3F) -O2 (2-10) 5% V-HBB (2F, 3F) -O2 (2-10) 9% 2O-B (2F) B (2F, 3F) -O2 (2-22) 5% 2O-B (2F) B (2F, 3F) -O4 (2-22) 5% 2-HH-3 (3-1) 22% 3-HH-4 ( 3-1) 5% 3-HH-5 (3-1) 3% 3-HB-O2 (3-2) 10% 3-HHB-1 (3-5) 8% 3-HHB-3 (3- 5) 4% 5-B (F) BB-2 (3-7) 5% NI = 74.9 ℃; Tc ＜ -20 ℃; Δn = 0.102; Δε = -2.8; Vth = 2.30 V; η = 19.2 mPa · s.

[Composition M21] 3-HB (2F, 3F) -O2 (2-1) 12% 5-HB (2F, 3F) -O2 (2-1) 8% 3-HH2B (2F, 3F) -O2 ( 2-7) 9% 3-HDhB (2F, 3F) -O2 (2-16) 9% 3-dhBB (2F, 3F) -O2 (2-17) 7% 2O-B (2F) B (2F, 3F) -O2 (2-22) 5% 3-HH-V (3-1) 29% 2-HH-3 (3-1) 2% V-HHB-1 (3-5) 5% V-HBB -2 (3-6) 14% NI = 76.5 ℃; Tc <-20 ℃; Δn = 0.098; Δε = -3.0; Vth = 2.15 V; η = 16.2 mPa · s.

[Composition M22] 2-HHB (2F, 3F) -O2 (2-6) 3% 3-HHB (2F, 3F) -O2 (2-6) 6% V-HHB (2F, 3F) -O1 ( 2-6) 4% V-HHB (2F, 3F) -O2 (2-6) 10% 3-HH2B (2F, 3F) -O2 (2-7) 9% 2O-B (2F) B (2F, 3F) -O2 (2-22) 7% 2O-B (2F) B (2F, 3F) -O4 (2-22) 7% 3-HH-V (3-1) 20% 2-HH-3 ( 3-1) 10% 3-HH-4 (3-1) 6% 3-HB-O2 (3-2) 7% 1-BB-3 (3-3) 4% 5-B (F) BB- 2 (3-7) 7% NI = 75.3 ℃; Tc <-20 ℃; Δn = 0.102; Δε = -2.6; Vth = 2.41 V; η = 17.5 mPa · s.

The polymerizable compound containing a nitrogen atom in the bonding group uses compound (No. 1) as the first additive.

Any one of the following polymerizable compounds having polar groups (4-10) to (4-19) was used as the second additive.

[化 35]

Any one of the following polymerizable compounds (RM-1) to (RM-8) was used as the third additive.

[化 36]

2. Vertical alignment of liquid crystal molecules and voltage retention Example 1 In 100 parts by weight of composition M1, a polymerizable compound (No. 1) containing a nitrogen atom in a bonding group was added at a ratio of 0.2 parts by weight, and The polymerizable compound (4-10) having a polar group is added in a proportion of 3 parts by weight. The mixture was injected into a device with a gap (cell gap) of two glass substrates (cell gap) of 4.0 μm and no alignment film on a hot stage at 100 ° C. For this element, a black lamp F40T10 / BL (peak wavelength 369 nm) manufactured by EYE GRAPHICS Co., Ltd. was used, and 10 J / cm ² of ultraviolet light (irradiance at a wavelength of 365 nm was irradiated from the normal direction to the element 3 mW / cm ² .UIT-150 and UVD-S365 manufactured by Niu Mei Electric Co., Ltd. were used to measure the illuminance and the irradiation amount) to polymerize the polymerizable compound. This element was installed in a polarizing microscope with a polarizer and an analyzer arranged orthogonally, and the element was irradiated with light from below to observe the presence or absence of light leakage. When the liquid crystal molecules are sufficiently aligned and light does not pass through the device, the vertical alignment is judged to be "good". When light passing through the device is observed, it indicates "defect". The vertical alignment of the liquid crystal molecules of this device is good, and the voltage retention rate is 96%.

Comparative Example 1 In 100 parts by weight of composition M1, instead of a polymerizable compound containing a nitrogen atom in the bonding group (No. 1), a polymerizable compound containing no nitrogen atom in the bonding group was added at a ratio of 0.2 parts by weight ( RM-1), and the polymerizable compound (4-10) having a polar group is added at a ratio of 3 parts by weight, except that the composition is injected and irradiated with ultraviolet rays in the same manner as in Example 1. The vertical alignment of the liquid crystal molecules of this device is good, but the voltage retention rate is 55%.

Comparative Example 2 An element was produced by the same method as Comparative Example 1 except that the amount of ultraviolet radiation was 15 J / cm ² . The vertical alignment of the liquid crystal molecules of this device is good, but the voltage retention rate is 83%.

3. Compatibility of the polymerizable compound containing a nitrogen atom in the bonding group The mixture of the liquid crystal composition obtained in the example and the polymerizable compound containing a nitrogen atom in the bonding group, and the comparative example The stability of the mixture of the liquid crystal composition and the polymerizable compound at room temperature was evaluated. After mixing, it changes to an isotropic liquid at 100 ° C and is left to cool to 25 ° C. After a half day at room temperature, the presence or absence of precipitation was confirmed. As a result, no precipitation was confirmed in the mixtures of Example 1 and Comparative Examples 1 to 2, and the compatibility of any compound was good.

It can be seen from the above examples and comparative examples that if a polymerizable compound containing a nitrogen atom in the bonding group is used, the vertical alignment and compatibility will not be affected, and even if the amount of ultraviolet radiation is small, an increased voltage can be obtained The retention rate results. Regarding this result, it is considered that the polymerizable compound containing a nitrogen atom in the bonding group has high reactivity, stabilizes the vertical alignment of the liquid crystal molecules, and also ensures the electrical characteristics as a vertical alignment film. For other liquid crystal compositions (for example, composition (M2) to composition (M22)), and other polymerizable compounds containing nitrogen atoms in the bonding group (for example, compound (No. 2) to compound (No. 54) ). In the case of other polymerizable compounds having a polar group, the same effect can be expected.

From the above results, it can be seen that the polymer formed from the polymerizable compound containing a nitrogen atom in the bonding group and the polymerizable compound having a polar group plays an important role in the uniform vertical alignment of the liquid crystal molecules and the performance of good electrical characteristics , Compatibility with the liquid crystal composition is also good. In addition, if the liquid crystal composition of the present invention is used, it can also be expected to obtain a liquid crystal having characteristics such as a wide temperature range of the usable device, a short response time, a high voltage retention rate, a low threshold voltage, a large contrast, and a long life Display element. Furthermore, it can also be expected to obtain a liquid crystal display device having a liquid crystal composition having a high maximum temperature of the nematic phase, a low minimum temperature of the nematic phase, a low viscosity, an appropriate optical anisotropy, and a negative medium Among characteristics such as high electrical anisotropy, large specific resistance, high stability to ultraviolet rays, and high stability to heat, at least one characteristic is sufficiently satisfied. [Industry availability]

The liquid crystal composition of the present invention can control the alignment and electrical characteristics of liquid crystal molecules in devices that do not have existing alignment films such as polyimide. The liquid crystal display element containing the composition has the characteristics of short response time, large voltage retention, low threshold voltage, large contrast, long life, etc., so it can be used in liquid crystal projectors, liquid crystal televisions and the like.

no

Claims (23)

A liquid crystal composition containing at least one polymerizable compound selected from the group of compounds represented by formula (1) as a first additive and having negative dielectric anisotropy, In formula (1), R ¹⁵ , R ¹⁶ and R ^{17 are} independently hydrogen, halogen, -Sp ¹¹ -P ¹¹ , -Sp ¹² -P ¹² or an alkyl group having 1 to 15 carbon atoms. At least one -CH ₂ -may be substituted by -O- or -S-, at least one-(CH ₂ ) ₂ -may be substituted by -CH = CH- or -C≡C-, in these groups, at least one hydrogen may Substituted by halogen, -Sp ¹¹ -P ¹¹ or -Sp ¹² -P ¹² ; a ¹¹ and a ^{12 are} independently 0, 1, 2, 3, or 4, the total of a ¹¹ and a ¹² is 1-8; ring A ¹¹ and ring A ^{12 are} independently a divalent group derived from an alicyclic hydrocarbon having 3 to 18 carbon atoms, an aromatic hydrocarbon having 6 to 18 carbon atoms, or a heteroaromatic hydrocarbon having 3 to 18 carbon atoms. Among these divalent groups, at least one hydrogen can be substituted by halogen, alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, alkenyl having 1 to 12 carbons, or alkenyl having 1 to 12 carbons. Oxygen substitution, in these monovalent hydrocarbon groups, at least one hydrogen may be substituted with halogen; Z ¹¹ and Z ^{12 are} independently a single bond or an alkylene group having 1 to 10 carbon atoms, and at least one of the alkylene groups- CH ₂ -may be substituted by -O-, -CO-, -COO-, or -OCO-, at least one-(CH ₂ ) ₂ -may be substituted by -CH = CH-, -C (CH ₃ ) = CH-, -CH = C (CH ₃ )-, -C (CH ₃ ) = C (CH ₃ )-, or -CH≡CH- substitution, in these divalent groups, at least one hydrogen may be substituted by halogen; b ¹¹ and b ^{12 are} independently 0, 1, 2, or 3, b ¹¹ and b ¹² The total amount is 1 to 6; Sp ¹¹ and Sp ^{12 are} independently a single bond or an alkylene group having 1 to 10 carbon atoms. In the alkylene group, at least one -CH ₂ -may be passed through -O-, -CO-, -COO-, -OCO-, or -OCOO-, at least one-(CH ₂ ) ₂ -may be substituted by -CH = CH- or -C≡C-, in these groups, at least one hydrogen may be substituted by halogen ; P ¹¹ and P ^{12 are} independently the groups represented by the following formula (1a), formula (1b), formula (1c), formula (1d) or formula (1e); In formula (1a), formula (1b), formula (1c), formula (1d) and formula (1e), M ¹¹ and M ^{12 are} independently hydrogen, halogen, alkyl group having 1 to 5 carbon atoms, or at least one C 1-5 alkyl substituted with hydrogen by halogen; R ¹² , R ¹³ , R ¹⁴ and R ^{18 are} independently hydrogen, or linear, branched or cyclic alkyl having 1 to 15 carbons, In the alkyl group, at least one -CH ₂ -may be substituted with -O- or -S-, and at least one-(CH ₂ ) ₂ -may be substituted with -CH = CH- or -C≡C-. In at least one hydrogen may be substituted by halogen. The liquid crystal composition according to item 1 of the patent application scope, wherein the first additive is represented by any one of formula (1-1) to formula (1-3), In formula (1-1) to formula (1-3), R ¹⁷ is hydrogen, halogen, -Sp ¹¹ -P ¹¹ , -Sp ¹² -P ¹² or an alkyl group having 1 to 15 carbon atoms. , At least one -CH ₂ -may be substituted by -O- or -S-, at least one-(CH ₂ ) ₂ -may be substituted by -CH = CH- or -C≡C-, in these groups, at least one hydrogen May be substituted by halogen, -Sp ¹¹ -P ¹¹ or -Sp ¹² -P ¹² ; Ring A ¹¹ , Ring A ¹² , Ring A ^{1 3} and Ring A ^{1 4 are} independently alicyclic hydrocarbons having 3 to 18 carbon atoms , A divalent group derived from an aromatic hydrocarbon having 6 to 18 carbon atoms, or a heteroaromatic hydrocarbon having 3 to 18 carbon atoms, among these divalent groups, at least one hydrogen may be Group, an alkoxy group having 1 to 12 carbon atoms, an alkenyl group having 1 to 12 carbon atoms, or an alkenyloxy group having 1 to 12 carbon atoms, in these monovalent hydrocarbon groups, at least one hydrogen may be substituted with halogen; Z ¹¹ , Z ¹² , Z ¹³ and Z ^{14 are} independently a single bond or an alkylene group having 1 to 10 carbon atoms, in which at least one -CH ₂ -may be passed through -O-, -CO-,- COO- or -OCO- substitution, at least one-(CH ₂ ) ₂ -can be substituted by -CH = CH-, -C (CH ₃ ) = CH-, -CH = C (CH ₃ )-, -C (CH _{3) = C (CH 3)} -, a substituted or -CH≡CH-, the plurality divalent group , At least one hydrogen may be substituted by halogen; Sp ¹¹ and Sp ¹² are independently a single bond or alkylene group having 1 to 10 carbons, said alkylene, at least one -CH ₂ - may be -O -, - CO-, -COO-, -OCO-, or -OCOO- substitution, at least one-(CH ₂ ) ₂ -may be substituted by -CH = CH- or -C≡C-, in these groups, at least one hydrogen may Substitution by halogen; P ¹¹ and P ^{12 are} independently a group represented by the following formula (1a), formula (1b), formula (1c), formula (1d) or formula (1e); In formula (1a), formula (1b), formula (1c), formula (1d) and formula (1e), M ¹¹ and M ^{12 are} independently hydrogen, halogen, alkyl group having 1 to 5 carbon atoms, or at least one C 1 to 5 alkyl groups substituted with hydrogen by halogen; R ¹² , R ¹³ , R ¹⁴ and R ^{18 are} independently hydrogen, or linear, branched or cyclic alkyl groups having 1 to 15 carbon atoms, In the alkyl group, at least one -CH ₂ -may be substituted with -O- or -S-, and at least one-(CH ₂ ) ₂ -may be substituted with -CH = CH- or -C≡C-. In at least one hydrogen may be substituted by halogen. The liquid crystal composition according to Item 1 or Item 2 of the patent application range, wherein the ratio of the first additive is in the range of 0.01 parts by weight to 10 parts by weight based on the weight of the liquid crystal composition. The liquid crystal composition according to item 1 of the patent application scope, which contains at least one compound selected from the group of compounds represented by formula (2) as the first component, In formula (2), R ³ and R ^{4 are} independently C 1-12 alkyl, C 1-12 alkoxy, C 2-12 alkenyl, or C 2-12 alkenyl Yloxy; ring C and ring E are independently 1,4-cyclohexyl, 1,4-cyclohexenyl, 1,4-phenylene, at least one hydrogen substituted with fluorine or chlorine 1,4 -Phenylene, or tetrahydropyran-2,5-diyl; ring D is 2,3-difluoro-1,4-phenylene, 2-chloro-3-fluoro-1,4-benzene Group, 2,3-difluoro-5-methyl-1,4-phenylene, 3,4,5-trifluoronaphthalene-2,6-diyl, or 7,8-difluorochroman- 2,6-diyl; Z ² and Z ^{3 are} independently a single bond,-(CH ₂ ) _2- , -CH ₂ O-, -OCH _2- , -COO-, or -OCO-; b is 1, 2, or 3, c is 0 or 1, and the sum of b and c is 3 or less. The liquid crystal composition according to item 4 of the patent application scope, which contains at least one compound selected from the group of compounds represented by formula (2-1) to formula (2-22) as the first component, In formula (2-1) to formula (2-22), R ³ and R ^{4 are} independently an alkyl group having 1 to 12 carbons, an alkoxy group having 1 to 12 carbons, and an alkenyl group having 2 to 12 carbons , Or an alkenyloxy group having 2 to 12 carbon atoms. The liquid crystal composition according to item 4 or 5 of the patent application range, wherein the proportion of the first component is in the range of 10% by weight to 90% by weight based on the weight of the liquid crystal composition. The liquid crystal composition according to item 1 of the patent application scope, which contains at least one compound selected from the group of compounds represented by formula (3) as the second component, In formula (3), R ⁵ and R ^{6 are} independently C 1-12 alkyl, C 1-12 alkoxy, C 2-12 alkenyl, and at least one hydrogen is substituted by fluorine or chlorine Alkyl having 1 to 12 carbons, or alkenyl having 2 to 12 carbons in which at least one hydrogen is substituted with fluorine or chlorine; ring F and ring G are independently 1,4-cyclohexyl, 1,4-extend Phenyl, 2-fluoro-1,4-phenylene, or 2,5-difluoro-1,4-phenylene; Z ⁴ is a single bond,-(CH ₂ ) _2- , -CH ₂ O- , -OCH _2- , -COO-, or -OCO-; d is 1, 2, or 3. The liquid crystal composition according to item 7 of the patent application scope, which contains at least one compound selected from the group of compounds represented by formula (3-1) to formula (3-13) as the second component, In formula (3-1) to formula (3-13), R ⁵ and R ^{6 are} independently C 1-12 alkyl, C 1-12 alkoxy, C 2-12 alkenyl , At least one hydrogen-substituted alkyl group having 1 to 12 carbon atoms with fluorine or chlorine, or at least one hydrogen-substituted alkenyl group having 2 to 12 carbon atoms with fluorine or chlorine. The liquid crystal composition according to item 7 or 8 of the patent application range, wherein the proportion of the second component is in the range of 10% by weight to 90% by weight based on the weight of the liquid crystal composition. The liquid crystal composition according to item 1 of the patent application scope, which contains at least one polymerizable compound having a polar group selected from the group of compounds represented by formula (4) as a second additive, In formula (4), R ²¹ is hydrogen, halogen, C 1-12 alkyl, C 1-12 alkoxy, C 2-12 alkenyl, at least one hydrogen substituted by fluorine or chlorine An alkyl group having 1 to 12 carbons, or an alkenyl group having 2 to 12 carbons in which at least one hydrogen is substituted with fluorine or chlorine; R ²² is -OH, -NH ₂ , -OR ²⁰ , -N (R ²⁰ ) ₂ , Or a group represented by -Si (R ²⁰ ) ₃ , where R ²⁰ is hydrogen or an alkyl group having 1 to 5 carbon atoms, in which at least one -CH ₂ -may be substituted with -O-, at least One-(CH ₂ ) ₂ -may be substituted by -CH = CH-, in these groups, at least one hydrogen may be substituted by fluorine; Ring A ²¹ and Ring B ^{21 are} independently 1,4-cyclohexyl, 1, 4-cyclohexenyl, 1,4-phenylene, naphthalene-1,2-diyl, naphthalene-1,3-diyl, naphthalene-1,4-diyl, naphthalene-1,5-di Group, 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, pyridine-2,5-diyl , Stilbene-2,7-diyl, phenanthrene-2,7-diyl, anthracene-2,6-diyl, perhydrocyclopenta [a] phenanthrene-3,17-diyl, or 2,3, 4,7,8,9,10,11,12,13,14,15,16,17-tetradecane Penta [a] phenanthrene-3,17-diyl, in these rings, at least one hydrogen can be through fluorine, chlorine, C 1-12 alkyl, C 1-12 alkoxy, or at least one Hydrogen is substituted by fluorine or chlorine substituted C1-C12 alkyl; Z ²¹ is a single bond,-(CH ₂ ) _2- , -CH = CH-, -C≡C-, -COO-, -OCO- , -CF ₂ O-, -OCF _2- , -CH ₂ O-, -OCH _2- , or -CF = CF-; Sp ²¹ and Sp ^{22 are} independently a single bond or an alkylene group having 1 to 7 carbon atoms In the alkylene group, at least one -CH ₂ -may be substituted with -O-, -COO-, or -OCO-, and at least one-(CH ₂ ) ₂ -may be substituted with -CH = CH-, these In the group, at least one hydrogen may be substituted with fluorine; a ²¹ is 0, 1, 2, 3, or 4. The liquid crystal composition according to item 10 of the patent application range, wherein the second additive is at least one polymerizable member selected from the group of compounds represented by formula (4-1) to formula (4-9) Compound, In formula (4-1) to formula (4-9), R ²¹ is hydrogen, halogen, alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, alkenyl having 2 to 12 carbons, At least one hydrogen is substituted with fluorine or chlorine and a C 1-12 alkyl group, or at least one hydrogen is substituted with fluorine or chlorine and a C 2 to 12 alkenyl group; Z ²¹ is a single bond,-(CH ₂ ) _2- , -CH = CH-, -C≡C-, -COO-, -OCO-, -CF ₂ O-, -OCF _2- , -CH ₂ O-, -OCH _2- , or -CF = CF-; Sp ²¹ and Sp ^{22 are} independently a single bond or an alkylene group having 1 to 7 carbon atoms, in which at least one -CH ₂ -may be substituted with -O-, -COO-, or -OCO-, At least one-(CH ₂ ) ₂ -may be substituted by -CH = CH-, in these groups, at least one hydrogen may be substituted by fluorine; L ¹ , L ² , L ³ , L ⁴ , L ⁵ , L ⁶ , L ⁷ , L ⁸ , L ⁹ , L ¹⁰ , L ¹¹ , and L ^{12 are} independently hydrogen, fluorine, methyl, or ethyl. The liquid crystal composition according to Item 10 or Item 11 of the patent application range, wherein the ratio of the second additive is in the range of 0.05 parts by weight to 10 parts by weight based on the weight of the liquid crystal composition. The liquid crystal composition according to item 1 of the patent application scope, which contains at least one polymerizable compound selected from the group of compounds represented by formula (5) as a third additive, In formula (5), ring J and ring P are independently cyclohexyl, cyclohexenyl, phenyl, 1-naphthyl, 2-naphthyl, tetrahydropyran-2-yl, 1,3-dioxan Alkan-2-yl, pyrimidin-2-yl, or pyrid-2-yl, in these rings, at least one hydrogen can be through fluorine, chlorine, C 1-12 alkyl, C 1-12 alkoxy Group, or at least one hydrogen is substituted by fluorine or chlorine, a C 1-12 alkyl group; ring K is 1,4-cyclohexyl, 1,4-cyclohexenyl, 1,4-phenylene , Naphthalene-1,2-diyl, naphthalene-1,3-diyl, naphthalene-1,4-diyl, naphthalene-1,5-diyl, naphthalene-1,6-diyl, naphthalene-1, 7-diyl, naphthalene-1,8-diyl, naphthalene-2,3-diyl, naphthalene-2,6-diyl, naphthalene-2,7-diyl, tetrahydropyran-2,5- Diyl, 1,3-dioxane-2,5-diyl, pyrimidine-2,5-diyl, or pyridine-2,5-diyl, in these rings, at least one hydrogen can be fluorine, chlorine , A C 1-12 alkyl group, a C 1-12 alkoxy group, or a C 1-12 alkyl group substituted by fluorine or chlorine for at least one hydrogen; Z ⁵ and Z ^{6 are} independently single bonds Or an alkylene group having 1 to 10 carbon atoms, in which at least one -CH ₂ -may be substituted with -O-, -CO-, -COO-, or -OCO-, and at least A-(CH ₂ ) ₂ -can be -CH = CH-, -C (CH ₃ ) = CH-, -CH = C (CH ₃ )-, or -C (CH ₃ ) = C (CH ₃ )- Substitution, in these groups, at least one hydrogen may be substituted by fluorine or chlorine; P ¹ , P ² , and P ^{3 are} independently polymerizable groups; Sp ³ , Sp ⁴ , and Sp ^{5 are} independently single bonds or carbon numbers 1 to 10 alkylene groups, in which at least one -CH ₂ -may be substituted with -O-, -COO-, -OCO-, or -OCOO-, and at least one-(CH ₂ ) ₂ -May be substituted by -CH = CH- or -C≡C-, in these groups, at least one hydrogen may be substituted by fluorine or chlorine; q is 0, 1, or 2; j, k, and p are independently 0 , 1, 2, 3, or 4, and the sum of j, k, and p is 1 or more. The liquid crystal composition according to item 13 of the patent application range, wherein in the formula (5), P ¹ , P ² , and P ^{3 are} independently selected from the formula (P-1) to the formula (P-5) The polymerizable group in the group of groups represented, In formula (P-1) to formula (P-5), M ¹ , M ² , and M ^{3 are} independently hydrogen, fluorine, an alkyl group having 1 to 5 carbon atoms, or at least one hydrogen is substituted with fluorine or chlorine C1-C5 alkyl. The liquid crystal composition according to item 13 of the patent application range, wherein the third additive is at least one polymerizable member selected from the group of compounds represented by formula (5-1) to formula (5-28) Compound, In formula (5-1) to formula (5-28), P ¹ , P ² , and P ^{3 are} independently selected from the group of groups represented by formula (P-1) to formula (P-3) The polymerizable group of here, M ¹ , M ² , and M ^{3 are} independently hydrogen, fluorine, an alkyl group having 1 to 5 carbon atoms, or an alkyl group having 1 to 5 carbon atoms in which at least one hydrogen is substituted with fluorine or chlorine base; Sp ³ , Sp ⁴ , and Sp ^{5 are} independently a single bond or an alkylene group having 1 to 10 carbon atoms, in which at least one -CH ₂ -may be passed through -O-, -COO-, -OCO -, Or -OCOO-, and at least one-(CH ₂ ) ₂ -may be substituted by -CH = CH- or -C≡C-, and in these groups, at least one hydrogen may be substituted by fluorine or chlorine. The liquid crystal composition according to any one of claims 13 to 15, wherein the ratio of the third additive is in the range of 0.03 parts by weight to 10 parts by weight based on the weight of the liquid crystal composition. A liquid crystal display element containing the liquid crystal composition according to any one of the patent application items 1 to 16. The liquid crystal display element as described in item 17 of the patent application range, wherein the operation mode of the liquid crystal display element is a coplanar switching mode, a vertical alignment mode, a fringe field switching mode, or an electric field induced light reaction alignment mode, and a driving method of the liquid crystal display element Active matrix method. A polymer-stabilized alignment type liquid crystal display element, which contains the liquid crystal composition according to any one of claims 1 to 16, and the polymerizable compound in the liquid crystal composition is polymerized. A liquid crystal display element without an alignment film, which contains the liquid crystal composition according to any one of claims 1 to 16, and the polymerizable compound in the liquid crystal composition is polymerized. Use of a liquid crystal composition, which is the liquid crystal composition according to any one of claims 1 to 16, which is used in a liquid crystal display element. The use of a liquid crystal composition, which is the liquid crystal composition according to any one of the patent application items 1 to 16, which is used in a polymer stabilized alignment type liquid crystal display element. Use of a liquid crystal composition, which is the liquid crystal composition as described in any one of the patent application items 1 to 16, which is used in a liquid crystal display element without an alignment film.