TWI710623B - Liquid crystal composition and its use, liquid crystal display element - Google Patents

Abstract

The present invention provides a liquid crystal composition capable of achieving vertical alignment of liquid crystal molecules through the action of a polymer, and a liquid crystal display element containing the composition. The present invention is a nematic liquid crystal composition containing a compound having a polymerizable group and a polar group in the branched structure of the molecular terminal as the first additive and having negative dielectric anisotropy. The composition may also contain A specific liquid crystal compound with a large negative dielectric anisotropy is used as the first component, a specific liquid crystal compound having a high upper limit temperature or a small viscosity is contained as a second component, and a polymerizable compound is contained as a second additive, and The present invention is a liquid crystal display element containing the composition.

Description

Liquid crystal composition and its use, 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, it relates to a compound (or a polymer thereof) containing a polymerizable group and a polar group in the branch structure at the molecular end, and the vertical alignment of the liquid crystal molecule can be achieved by the action of the compound. The dielectric anisotropy is Negative liquid crystal composition, and liquid crystal display element.

In liquid crystal display elements, the classification based on the operation mode of liquid crystal molecules is phase change (PC), twisted nematic (TN), super twisted nematic (STN), and electrically 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) and other modes. The classification based on the driving method of the element is a passive matrix (PM) and an active matrix (AM). PM is classified into static, multiplexed, etc., AM is classified into thin film transistor (TFT), metal insulator metal (MIM), etc. TFTs are classified into amorphous silicon and polycrystal silicon. The latter is classified as high temperature according to the manufacturing steps Type and low temperature type. The light source is classified into a reflective type using natural light, a transmissive type using backlight, and a semi-transmissive type using both natural light and backlight.

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

The optical anisotropy of the composition is related to the contrast ratio of the element. Depending on the mode of the element, a large optical anisotropy or a small optical anisotropy, that is, an appropriate optical anisotropy is required. The optical anisotropy (△n) of the composition and the single element The product (Δn×d) of the cell gap (d) is designed to maximize the contrast ratio. The appropriate product value depends on the type of operation mode. In the VA mode device, the value is in the range of about 0.30 μm to about 0.40 μm, and in the IPS mode or FFS mode device, the value is in the range of about 0.20 μm to about 0.30 μm. In these cases, for an element with a small cell gap, a composition having large optical anisotropy is preferable. The large dielectric anisotropy of the composition contributes to the low threshold voltage of the device, small power consumption, and large contrast ratio. Therefore, a large dielectric anisotropy is preferable. The large specific resistance of the composition contributes to the large voltage holding ratio and large contrast ratio of the element. Therefore, it is preferably 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 in the initial stage. It is preferably 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 better for AM devices 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, a composition containing a small amount of polymerizable compound is injected into the device. Next, while applying a voltage between the substrates of the element, ultraviolet rays are irradiated to the composition. The polymerizable compound is polymerized to form a polymer network structure in the composition. In this composition, the polymer can be used to control the alignment of liquid crystal molecules, so the response time of the element is shortened, and the afterimage of the image is improved. Such effects of polymers can be expected in devices 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 without an alignment film, a liquid crystal composition containing a polymer and a polar compound is used. First, a composition containing a small amount of polymerizable compound and a small amount of polar compound is injected into the device. Here, the polar compounds are adsorbed on the surface of the substrate and arranged. According to this arrangement, the liquid crystal molecules are aligned. Next, while applying a voltage between the substrates of the element, ultraviolet rays are irradiated to the composition. Here, the polymerizable compound is polymerized and stabilizes the alignment of liquid crystal molecules. In this composition, polymers and polar compounds can be used to control the alignment of liquid crystal molecules, so the response time of the device is shortened, and the afterimage of the image is improved. Furthermore, an element without an alignment film does not require a step of forming an alignment film. Since there is no alignment film, the resistance of the device does not decrease due to the interaction between the alignment film and the composition. Such an effect of the combination of a polymer and a polar compound can be expected in devices having modes such as TN, ECB, OCB, IPS, VA, FFS, and FPA.

The AM device having the TN mode uses a composition having positive dielectric anisotropy. The AM device having the VA mode uses a composition having negative dielectric anisotropy. The AM device having the IPS mode or the FFS mode uses a composition having positive or negative dielectric anisotropy. A polymer stabilized alignment type AM device uses a composition having positive or negative dielectric anisotropy. Examples of a liquid crystal composition using a liquid crystal compound having negative dielectric anisotropy and a polymerizable compound having a polar group are disclosed in Patent Documents 1 to 2 below. Patent Document 1 discloses a polymer having a polymerizable group at the side of the compound and a polar group at the end. Synthetic self-aligning additives. Patent Document 2 discloses a polymerizable self-aligning additive having a polymerizable group and a polar group at both ends of the compound. The compounds described in Patent Document 1 and Patent Document 2 are different from the compounds used in the present invention.

[Prior Art Literature]

[Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open No. 2015-168826

[Patent Document 2] International Publication No. 2016/015803 Brochure

The problem to be solved by the present invention is to provide a liquid crystal composition which uses a compound (or a polymer thereof) having a polymerizable group and a polar group in the branched structure of the molecular terminal to control the liquid crystal of a liquid crystal display element without an alignment film Molecular alignment, and polymerizable polar compounds show good compatibility.

The present invention utilizes a liquid crystal composition containing a compound having a polymerizable group and a polar group in a branched structure at the molecular end and has a negative dielectric anisotropy to control the alignment of liquid crystal molecules of a liquid crystal display element without an alignment film.

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

In the formula (1-1), R ¹ is an alkyl group having 1 to 15 carbons. In the R ¹ , at least one -CH ₂ -may be substituted with -O- or -S-, and at least one -CH ₂ CH ₂ -May be substituted by -CH=CH- or -C≡C-, at least one hydrogen may be substituted by halogen; ring A ¹ and ring A ^{2 are} independently 1,4-cyclohexylene or 1,4-cyclohexene Base, 1,4-phenylene, naphthalene-2,6-diyl, decahydronaphthalene-2,6-diyl, 1,2,3,4-tetrahydronaphthalene-2,6-diyl, tetrahydronaphthalene-2,6-diyl Hydropyran-2,5-diyl, 1,3-dioxane-2,5-diyl, pyrimidine-2,5-diyl, pyridine-2,5-diyl, pyridine-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-tetradecahydrocyclopenta[a]phenanthrene-3,17-diyl, in these rings, at least one hydrogen can be fluorine, chlorine, carbon Alkyl having 1 to 12, alkenyl having 2 to 12, alkoxy having 1 to 11, or alkenyl having 2 to 11, in these groups, at least one hydrogen may be substituted by Fluorine or chlorine substitution; a is 0, 1, 2, 3, or 4; Z ¹ is a single bond or an alkylene having 1 to 6 carbon atoms. In the Z ¹ , at least one -CH ₂ -may be controlled by -O -, -CO-, -COO-, -OCO-, or -OCOO- substitution, at least one -CH ₂ CH ₂ -can be substituted by -CH=CH- or -C≡C-, at least one hydrogen in Z ¹ can be substituted by fluorine or chlorine; Sp ¹ is a single bond or a C 1-10 alkylene group, which Sp ^1, at least one -CH ₂ - may be -O -, - CO -, - COO -, - OCO -, or -OCOO- substitution, at least one -CH ₂ CH ₂ -can be replaced by -CH=CH- or -C≡C-, at least one hydrogen in Sp ¹ can be replaced by halogen, and at least one hydrogen in Sp ¹ is selected Substitution from a group in the group represented by formula (1a);

In formula (1a), Sp ¹² is a single bond or an alkylene group having 1 to 10 carbon atoms, and in the Sp ¹² , at least one -CH ₂ -can pass through -O-, -CO-, -COO-, -OCO -Or -OCOO- substitution, at least one -CH ₂ CH ₂ -can be substituted by -CH=CH- or -C≡C-, at least one hydrogen in Sp ¹² can be substituted by halogen; M ¹¹ and M ^{12 are} independently Hydrogen, halogen, alkyl having 1 to 5 carbons, or alkyl having 1 to 5 carbons in which at least one hydrogen is substituted by halogen; R ¹² is an alkyl having 1 to 15 carbons, and at least one of R ¹² -CH ₂ -may be substituted by -O- or -S-, at least one -CH ₂ CH ₂ -may be substituted by -CH=CH- or -C≡C-, at least one hydrogen may be substituted by halogen; formula (1- In 1), P ¹¹ is a group selected from the groups represented by formula (1e) and formula (1f);

In formula (1e) and formula (1f), Sp ¹³ is a single bond or an alkylene having 1 to 10 carbon atoms, and in the Sp ¹³ , at least one -CH ₂ -can be controlled by -O-, -NH-,- CO-, -COO-, -OCO-, or -OCOO- substituted, at least one -CH ₂ CH ₂ -can be substituted by -CH=CH- or -C≡C-, at least one hydrogen in Sp ¹³ can be substituted by halogen ; M ¹³ and M ^{14 are} independently hydrogen, halogen, alkyl with 1 to 5 carbons, or alkyl with 1 to 5 carbons in which at least one hydrogen is substituted by halogen; R ¹³ is selected from formula (1g), formula (1h), and the group in the group represented by formula (1i);

In formula (1g), formula (1h), and formula (1i), Sp ¹⁴ and Sp ^{15 are} independently a single bond or an alkylene group having 1 to 10 carbon atoms, and in the alkylene group, at least one -CH ₂ -Can be substituted by -O-, -NH-, -CO-, -COO-, -OCO-, or -OCOO-, at least one -CH ₂ CH ₂ -can be -CH=CH- or -C≡C- Substitution, at least one hydrogen can be replaced by halogen; In formula (1g) and formula (1i), S ¹ is >CH- or >N-, S ² is >C< or >Si<; X ¹ is -OH,- NH ₂ , -OR ¹⁵ , -N(R ¹⁵ ) ₂ , -COOH, -SH, -B(OH) ₂ , or -Si(R ¹⁵ ) ₃ ; -OR ¹⁵ , -N(R ¹⁵ ) ₂ , and In -Si(R ¹⁵ ) ₃ , R ¹⁵ is hydrogen or an alkyl group having 1 to 10 carbons. In said R ¹⁵ , at least one -CH ₂ -may be substituted by -O-, and at least one -CH ₂ CH _2- It may be substituted by -CH=CH-, and at least one hydrogen in R ¹⁵ may be substituted by halogen.

The present invention includes the following items.

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

In the formula (1-1), R ¹ is an alkyl group having 1 to 15 carbons. In the R ¹ , at least one -CH ₂ -may be substituted by -O- or -S-, and at least one -CH ₂ CH ₂ -May be substituted by -CH=CH- or -C≡C-, at least one hydrogen may be substituted by halogen; ring A ¹ and ring A ^{2 are} independently 1,4-cyclohexylene or 1,4-cyclohexene Base, 1,4-phenylene, naphthalene-2,6-diyl, decahydronaphthalene-2,6-diyl, 1,2,3,4-tetrahydronaphthalene-2,6-diyl, tetrahydronaphthalene-2,6-diyl Hydropyran-2,5-diyl, 1,3-dioxane-2,5-diyl, pyrimidine-2,5-diyl, pyridine-2,5-diyl, pyridine-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-tetradecahydrocyclopenta[a]phenanthrene-3,17-diyl, in these rings, at least one hydrogen can be fluorine, chlorine, carbon Alkyl having 1 to 12, alkenyl having 2 to 12, alkoxy having 1 to 11, or alkenyl having 2 to 11, in these groups, at least one hydrogen may be substituted by Fluorine or chlorine substitution; a is 0, 1, 2, 3, or 4; Z ¹ is a single bond or an alkylene having 1 to 6 carbon atoms. In the Z ¹ , at least one -CH ₂ -may be controlled by -O -, -CO-, -COO-, -OCO-, or -OCOO- substitution, at least one -CH ₂ CH ₂ -can be substituted by -CH=CH- or -C≡C-, at least one hydrogen in Z ¹ can be substituted by fluorine or chlorine; Sp ¹ is a single bond or a C 1-10 alkylene group, which Sp ^1, at least one -CH ₂ - may be -O -, - CO -, - COO -, - OCO -, or -OCOO- substitution, at least one -CH ₂ CH ₂ -can be replaced by -CH=CH- or -C≡C-, at least one hydrogen in Sp ¹ can be replaced by halogen, and at least one hydrogen in Sp ¹ is selected Substitution from a group in the group represented by formula (1a);

In formula (1a), Sp ¹² is a single bond or an alkylene group having 1 to 10 carbon atoms, and in the Sp ¹² , at least one -CH ₂ -can pass through -O-, -CO-, -COO-, -OCO -Or -OCOO- substitution, at least one -CH ₂ CH ₂ -can be substituted by -CH=CH- or -C≡C-, at least one hydrogen in Sp ¹² can be substituted by halogen; M ¹¹ and M ^{12 are} independently Hydrogen, halogen, alkyl having 1 to 5 carbons, or alkyl having 1 to 5 carbons in which at least one hydrogen is substituted by halogen; R ¹² is an alkyl having 1 to 15 carbons, and at least one of R ¹² -CH ₂ -may be substituted by -O- or -S-, at least one -CH ₂ CH ₂ -may be substituted by -CH=CH- or -C≡C-, at least one hydrogen may be substituted by halogen; formula (1- In 1), P ¹¹ is a group selected from the groups represented by formula (1e) and formula (1f);

In formula (1e) and formula (1f), Sp ¹³ is a single bond or an alkylene having 1 to 10 carbon atoms, and in the Sp ¹³ , at least one -CH ₂ -can be controlled by -O-, -NH-,- CO-, -COO-, -OCO-, or -OCOO- substituted, at least one -CH ₂ CH ₂ -can be substituted by -CH=CH- or -C≡C-, at least one hydrogen in Sp ¹³ can be substituted by halogen ; M ¹³ and M ^{14 are} independently hydrogen, halogen, alkyl with 1 to 5 carbons, or alkyl with 1 to 5 carbons in which at least one hydrogen is substituted by halogen; R ¹³ is selected from formula (1g), formula (1h), and the group in the group represented by formula (1i);

In formula (1g), formula (1h), and formula (1i), Sp ¹⁴ and Sp ^{15 are} independently a single bond or an alkylene group having 1 to 10 carbon atoms, and in the alkylene group, at least one -CH ₂ -Can be substituted by -O-, -NH-, -CO-, -COO-, -OCO-, or -OCOO-, at least one -CH ₂ CH ₂ -can be -CH=CH- or -C≡C- Substitution, at least one hydrogen can be replaced by halogen; in formula (1g) and formula (1i), S ¹ is >CH- or >N-, S ² is >C< or >Si<; X ¹ is -OH,- NH ₂ , -OR ¹⁵ , -N(R ¹⁵ ) ₂ , -COOH, -SH, -B(OH) ₂ , or -Si(R ¹⁵ ) ₃ ; -OR ¹⁵ , -N(R ¹⁵ ) ₂ , and In -Si(R ¹⁵ ) ₃ , R ¹⁵ is hydrogen or an alkyl group having 1 to 10 carbons. In said R ¹⁵ , at least one -CH ₂ -may be substituted by -O-, and at least one -CH ₂ CH _2- It may be substituted by -CH=CH-, and at least one hydrogen in R ¹⁵ may be substituted by halogen.

Item 2. The liquid crystal composition according to Item 1, wherein the first additive is at least one polymerizable compound selected from the group of compounds represented by formula (1-2) to formula (1-3),

In formula (1-2) and formula (1-3), R ¹ is an alkyl group having 1 to 12 carbons. In the alkyl group, at least one -CH ₂ -may be substituted by -O-, and at least one -CH ₂ CH ₂ -may be substituted by -CH=CH- or -C≡C-, in these groups, at least one hydrogen may be substituted by fluorine; ring A ¹ and ring A ^{2 are} independently 1,4-cyclohexylene , 1,4-cyclohexenylene, 1,4-phenylene, naphthalene-2,6-diyl, tetrahydropyran-2,5-diyl, 1,3-dioxane-2, 5-diyl, phenanthrene-2,7-diyl, phenanthrene-2,7-diyl, perhydrocyclopenta[a]phenanthrene-3,17-diyl, or 2,3,4,7,8 ,9,10,11,12,13,14,15,16,17-tetradecahydrocyclopenta[a]phenanthrene-3,17-diyl, in these rings, at least one hydrogen can be fluorine, carbon Alkyl having 1 to 8, alkenyl having 2 to 8, alkoxy having 1 to 7, or alkenyl having 2 to 7, in these groups, at least one hydrogen may be substituted by fluoro substituents; a is 0, 1,. 4; Z is a single bond or ^an alkylene group having a carbon number of 1-6, Z is a ^1, at least one -CH ₂ - may be -O-, -CO-, -COO-, -OCO-, or -OCOO- substituted, at least one -CH ₂ CH ₂ -may be substituted with -CH=CH- or -C≡C-, in these groups, at least one hydrogen Can be substituted by fluorine or chlorine; l is 0, 1, 2, 3, 4, 5, or 6, and at least one -CH ₂ -of the alkylene group can be substituted by -O-, -CO-, -COO-, -OCO- or -OCOO- substitution, at least one -CH ₂ CH ₂ -may be substituted by -CH=CH- or -C≡C-, in these groups, at least one hydrogen may be substituted by fluorine; Sp ¹² is A single bond or an alkylene having 1 to 5 carbon atoms, in which at least one -CH ₂ -may be substituted by -O-, -CO-, -COO-, -OCO-, or -OCOO-, At least one -CH ₂ CH ₂ -may be substituted by -CH=CH- or -C≡C-, in these groups, at least one hydrogen may be substituted by fluorine; M ¹¹ and M ^{12 are} independently hydrogen, fluorine, methyl Group, ethyl group, or trifluoromethyl group; R ¹² is hydrogen or an alkyl group having 1 to 5 carbons. In the alkyl group, at least one -CH ₂ -may be substituted by -O- or -S-, 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; Sp ¹³ is a single bond or an alkylene having 1 to 5 carbon atoms In the alkylene group, at least one -CH ₂ -can be substituted by -O-, -CO-, or -COO-, and at least one -CH ₂ CH ₂ -can be -CH=CH- or -C≡ C-substitution, in these groups, at least one hydrogen can be replaced by fluorine; M ¹³ and M ^{14 are} independently hydrogen, fluorine, methyl, ethyl, or trifluoromethyl; Sp ¹⁴ is a single bond or carbon number 1 to 5 alkylene groups, In the alkylene, at least one -CH ₂ -may be substituted by -O-, -CO-, or -COO-, and at least one -CH ₂ CH ₂ -may be -CH=CH- or -C≡C- Substitution, in these groups, at least one hydrogen may be substituted by fluorine; X ¹ is -OH or -N(R ¹⁵ ) ₂ ; in -N(R ¹⁵ ) ₂ , R ¹⁵ is hydrogen or a carbon number of 1 to 5 In the alkyl group, at least one -CH ₂ -may be substituted by -O-, at least one -CH ₂ CH ₂ -may be substituted by -CH=CH-, in these groups, at least one hydrogen may be substituted by Fluorine substitution.

Item 3. The liquid crystal composition according to Item 1, wherein the first additive is at least one polymerizable compound selected from the group of compounds represented by formula (1-4) to formula (1-60),

In formulas (1-4) to (1-60), R ¹ is an alkyl group having 1 to 10 carbons; Z ¹ , Z ¹² , and Z ^{13 are} independently a single bond, -CH ₂ CH ₂ -, or -(CH ₂ ) ₄ -; Sp ¹² , Sp ¹³ , and Sp ^{14 are} independently a single bond or an alkylene group having 1 to 5 carbon atoms, in which at least one -CH ₂ -may be -O -Substitution; 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; l is 0, 1, 2, 3, 4, 5, or 6.

Item 4. The liquid crystal composition according to any one of items 1 to 3, wherein the ratio of the first additive is 10% by weight or less based on the weight of the liquid crystal composition.

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

In formula (2), R ³ and R ^{4 are} independently an alkyl group having 1 to 12 carbons, an alkoxy group having 1 to 12 carbons, an alkenyl group having 2 to 12 carbons, or an alkene having 2 to 12 carbons. Oxy; ring C and ring E are independently 1,4-cyclohexylene, 1,4-cyclohexenylene, 1,4-phenylene, 1,4-in which at least one hydrogen is substituted by fluorine or chlorine Phenylene, or tetrahydropyran-2,5-diyl; ring D is 2,3-difluoro-1,4-phenylene, 2-chloro-3-fluoro-1,4-phenylene , 2,3-Difluoro-5-methyl-1,4-phenylene, 3,4,5-trifluoronaphthalene-2,6-diyl, or 7,8-difluorochroman-2 ,6-diyl; Z ² and Z ^{3 are} independently a single bond, -CH ₂ CH 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 6. The liquid crystal composition according to any one of items 1 to 5, 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 formulas (2-1) to (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 carbons.

Item 7. The liquid crystal composition according to Item 5 or 6, wherein the ratio 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 8. The liquid crystal composition according to any one of items 1 to 7, which contains at least one compound selected from the group of compounds represented by formula (3) as a second component,

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

Item 9. The liquid crystal composition according to any one of items 1 to 8, 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 formulas (3-1) to (3-13), R ⁵ and R ^{6 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. , Alkyl groups having 1 to 12 carbons in which at least one hydrogen is replaced by fluorine or chlorine, or alkenyl groups having 2 to 12 carbons in which at least one hydrogen is replaced by fluorine or chlorine.

Item 10. The liquid crystal composition according to any one of Item 8 or Item 9, wherein the ratio 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 11. The liquid crystal composition according to any one of items 1 to 10, which contains at least one polymerizable compound selected from the group of compounds represented by formula (4) as a second additive,

In formula (4), ring J and ring P are independently cyclohexyl, cyclohexenyl, phenyl, 1-naphthyl, 2-naphthyl, tetrahydropyran-2-yl, 1,3-dioxyl Alk-2-yl, pyrimidin-2-yl, or pyridin-2-yl, in these rings, at least one hydrogen can be fluorine, chlorine, alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons Group, or at least one hydrogen is substituted by fluorine or chlorine substituted alkyl group with carbon number of 1 to 12; ring K is 1,4-cyclohexylene, 1,4-cyclohexenylene, 1,4-phenylene Base, 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 fluorine, Chlorine, an alkyl group having 1 to 12 carbons, an alkoxy group having 1 to 12 carbons, or at least one hydrogen is substituted with an alkyl group having 1 to 12 carbons substituted by fluorine or chlorine; Z ⁵ and Z ^{6 are} independently A single bond or an alkylene having 1 to 10 carbon atoms, in the Z ⁵ and Z ⁶ , at least one -CH ₂ -may be substituted with -O-, -CO-, -COO- or -OCO-, and at least one -CH ₂ CH ₂ -can be replaced by -CH=CH-, -C(CH ₃ )=CH-, -CH=C(CH ₃ )-, or -C(CH ₃ )=C(CH ₃ )-, At least one hydrogen may be replaced by fluorine or chlorine; P ¹ , P ² , and P ³ are polymerizable groups; Sp ³ , Sp ⁴ , and Sp ^{5 are} independently single bonds or alkylene groups with 1 to 10 carbon atoms, so Among the Sp ³ , Sp ⁴ , and Sp ⁵ , at least one -CH ₂ -may be substituted by -O-, -COO-, -OCO-, or -OCOO-, and at least one -CH ₂ CH ₂ -may be- CH=CH- or -C≡C- substituted, at least one hydrogen can be replaced 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 12. The liquid crystal composition according to Item 11, wherein in formula (4), P ¹ , P ² , and P ^{3 are} independently selected from the group consisting of formula (P-1) to formula (P-5) The polymeric group in the group of groups,

In formulas (P-1) to (P-5), M ¹ , M ² , and M ^{3 are} independently hydrogen, fluorine, an alkyl group having 1 to 5 carbons, or at least one hydrogen substituted by fluorine or chlorine An alkyl group having 1 to 5 carbon atoms.

Item 13. The liquid crystal composition according to any one of items 1 to 12, wherein the second additive is selected from the group of compounds represented by formula (4-1) to formula (4-29) At least one polymerizable compound,

In formula (4-1) to formula (4-29), P ¹ , P ² , and P ^{3 are} independently selected from the group of groups represented by formula (P-1) to formula (P-3) In the polymerizable group, here, M ¹ , M ² , and M ^{3 are} independently hydrogen, fluorine, an alkyl group having 1 to 5 carbons, or an alkyl group having 1 to 5 carbons in which at least one hydrogen is replaced by fluorine or chlorine alkyl;

Sp ³ , Sp ⁴ , and Sp ^{5 are} independently a single bond or an alkylene group having 1 to 10 carbon atoms. Among the Sp ³ , Sp ⁴ , and Sp ⁵ , at least one -CH ₂ -may be through -O-, -COO-, -OCO-, or -OCOO- substituted, and at least one -CH ₂ CH ₂ -may be substituted with -CH=CH- or -C≡C-, and at least one hydrogen may be substituted with fluorine or chlorine.

Item 14. The liquid crystal composition according to any one of Items 11 to 13, wherein the ratio of the second additive is in the range of 0.03% by weight to 10% by weight based on the weight of the liquid crystal composition.

Item 15. The liquid crystal composition according to any one of items 1 to 14, which contains at least one polymerizable compound selected from the group of compounds represented by formula (5) as a third additive,

In formula (5), R ⁵⁰ 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 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 by fluorine or chlorine; R ⁵¹ is -OH, -NH ₂ , -OR ⁵³ , -N(R ⁵³ ) ₂ , Or a group represented by -Si(R ⁵³ ) ₃ , where R ⁵³ is hydrogen or an alkyl group having 1 to 5 carbons, 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 ⁵⁰ and ring B ^{50 are} independently 1,4-cyclohexylene, 1,4-cyclohexenylene, 1,4-phenylene, naphthalene-1,2-diyl, naphthalene-1,3-diyl, naphthalene-1,4-diyl, naphthalene-1,5 -Diyl, naphthalene-1,6-diyl, naphthalene-1,7-diyl, naphthalene-1,8-diyl, naphthalene-2,3-diyl, naphthalene-2,6-diyl, naphthalene -2,7-diyl, tetrahydropyran-2,5-diyl, 1,3-dioxane-2,5-diyl, pyrimidine-2,5-diyl, pyridine-2,5- Diyl, phenanthrene-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-tetradecahydrocyclopenta[a]phenanthrene-3,17-diyl, among these rings, at least One hydrogen may be replaced by fluorine, chlorine, an alkyl group having 1 to 12 carbons, an alkoxy group having 1 to 12 carbons, or an alkyl group having 1 to 12 carbons in which at least one hydrogen is substituted by fluorine or chlorine; Z ⁵⁰ It 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 ⁵¹ and Sp ^{52 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 controlled by -O- , -COO-, or -OCO- substitution, at least one -CH ₂ CH ₂ -can be substituted by -CH=CH-, in these groups, at least one hydrogen can be substituted by fluorine; a ⁵⁰ is 0, 1, 2 , 3, or 4.

Item 16. The liquid crystal composition according to Item 15, wherein the ratio of the third additive is in the range of 0.3% by weight to 10% by weight based on the weight of the liquid crystal composition.

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

Item 18. The liquid crystal display element according to 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 mode of the liquid crystal display element is an active matrix mode.

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

Item 20. A liquid crystal display element without an alignment film, comprising the liquid crystal composition according to any one of Items 1 to 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 Items 1 to 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 stable alignment type liquid crystal display device.

Item 23. 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 liquid crystal display device that does not have an alignment film.

By using the liquid crystal composition containing a polymerizable polar compound having a polar group of the present invention, the step of forming an alignment film is not required, and therefore, a liquid crystal display element with reduced manufacturing cost can be obtained. Furthermore, a liquid crystal composition having good compatibility with the polymerizable polar compound and having negative dielectric anisotropy can be obtained.

The usage of the terms in this specification is as follows. The terms "liquid crystal composition" and "liquid crystal display element" are sometimes abbreviated as "composition" and "device", respectively. "Liquid crystal display element" is the general term for liquid crystal display panels and liquid crystal display modules. A "liquid crystal compound" is a compound having a liquid crystal phase such as a nematic phase and a smectic phase, and although it does not have a liquid crystal phase, it is for the purpose of adjusting the temperature range, viscosity, and dielectric anisotropy of the nematic phase. The general term for the compounds mixed in the composition. The compound has a six-membered ring such as 1,4-cyclohexylene 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 a plurality of liquid crystal compounds. Additives such as optically active compounds, antioxidants, ultraviolet absorbers, pigments, defoamers, polymerizable compounds, polymerization initiators, polymerization inhibitors, and polar compounds are added to the liquid crystal composition as necessary. Liquid crystal compounds or additives are mixed in this order. Even when an additive is added, the ratio (content) of the liquid crystal compound is represented by the weight percentage (% by weight) based on the weight of the liquid crystal composition containing no additive. The ratio (addition amount) of the additives is represented by the weight percentage (weight %) based on the weight of the liquid crystal composition containing no additives. 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.

The "upper limit temperature of the nematic phase" is sometimes simply referred to as the "upper limit temperature". The "lower limit temperature of the nematic phase" is sometimes referred to simply as the "lower limit temperature". "High specific resistance" means that the composition has a large specific resistance 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 close to It also has a large specific resistance at the upper limit temperature. "High voltage holding rate" means that the device has a large voltage holding 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 holding rate at a temperature close to the upper limit temperature. In a composition or element, characteristics may be studied before and after a time-dependent change test (including an accelerated deterioration test). The expression "increasing dielectric anisotropy" refers to a positive increase in the value of a composition with positive dielectric anisotropy, and a negative value in the case of a composition with negative dielectric anisotropy Increase to the ground.

The compound represented by formula (2) may be abbreviated as "compound (2)". At least one compound selected from the group of compounds represented by formula (2) may be simply referred to as "compound (2)". "Compound (2)" refers to one compound, a mixture of two compounds, or a mixture of three or more compounds represented by formula (2). The same is true for 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 positions Can also choose unlimitedly. This rule also applies to the expression "at least one ‘A’ is replaced by a ‘B’". In addition, in this specification, the compound represented by formula (1-1) and the compounds represented by formula (1-2) to formula (1-60) as its subordinate formula may be collectively referred to as Compound (1).

In the chemical formula of the component compound, the symbol of the terminal group R ¹ is used for various compounds. In these compounds, two groups represented by any two R ¹ may be the same or different. For example, there is a case where R ¹ of compound (1-1) is ethyl, and R ¹ of compound (1-2) is ethyl. There are also cases where R ¹ of compound (1-1) is ethyl, and R ¹ of compound (1-2) is propyl. This rule also applies to the markings of other end groups. In formula (1-1), when a is 2, two rings A exist. In this compound, the two rings represented by the two rings A may be the same or different. When a is greater than 2, this rule also applies to any two rings A. This rule also applies to other marks. This rule also applies to situations such as two -Sp ⁴ -P ² in compound (4-27).

Symbols such as A, C, D, E surrounded by hexagons respectively correspond to rings such as ring A, ring C, ring D, and ring E, and indicate rings such as six-membered rings and condensed rings. The oblique line crossing the hexagon indicates that any hydrogen on the ring can be replaced by 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 plural 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 leftward (L) or rightward (R). This rule also applies to asymmetric divalent groups such as tetrahydropyran-2,5-diyl which are formed by removing two hydrogens from the ring. This rule also applies to divalent bonding groups such as carbonyloxy (-COO- or -OCO-).

Expressions such as "at least one -CH ₂ -may be substituted by -O-" are used in this specification. In this case, -CH ₂ -CH ₂ -CH ₂ -can be converted to -O-CH ₂ -O- by replacing non-adjacent -CH ₂ -with -O-. However, the adjacent -CH ₂ -will not be substituted by -O-. This is because -OO-CH _2- (peroxide) is generated in the substitution. That is, the expression means both "one -CH ₂ -can be substituted by -O-" and "at least two non-adjacent -CH ₂ -can be substituted by -O-". This rule applies not only to the case of substitution with -O-, but also to the case of substitution with a divalent group such as -CH=CH- or -COO-. In the formula (1), R ¹ is an alkyl group having 1 to 25 carbon atoms or the like. The carbon number of the alkyl group may increase by such substitution. At this time, the maximum carbon number is 30. This rule applies not only to such R ¹ is a monovalent radical, is also applicable to a divalent alkyl extending like.

The alkyl group of the liquid crystal compound is linear or branched, and does not include a cyclic alkyl group. Straight-chain alkyl is better than branched alkyl. The same applies to terminal groups such as alkoxy and alkenyl. The three-dimensional configuration related to 1,4-cyclohexylene is usually the trans configuration better than the cis configuration. Halogen refers to fluorine, chlorine, bromine, and iodine. The preferred halogen is fluorine or chlorine. A particularly preferred halogen is fluorine.

The present invention also includes the following items. (a) A method for manufacturing a liquid crystal display element, which comprises disposing the liquid crystal composition between two substrates, and irradiating light with a voltage applied to the composition, so that the in-molecule contained in the composition End points A compound having a polymerizable group and a polar group in the branch structure is polymerized to produce the liquid crystal display element. (b) The liquid crystal composition, wherein the upper limit temperature of the nematic phase is 70°C or higher, the optical anisotropy (measured at 25°C) at a wavelength of 589nm is 0.08 or higher, and the dielectric anisotropy at a frequency of 1kHz (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 selected At least one compound from the group of these compounds. (d) The composition containing at least two compounds (1-1) having a polymerizable group and a polar group in the branched structure at the molecular terminal. (e) The composition further contains a polar compound different from the compound (1-1) having a polymerizable group and a polar group in the branched structure of the molecule terminal. (f) The composition, which contains one, two, or at least three optically active compounds, antioxidants, ultraviolet absorbers, pigments, defoamers, polymerizable compounds, polymerization initiators, polymerization inhibitors, and polar compounds And other additives. (g) An AM device containing the composition. (h) A device containing the composition and having a TN mode, ECB mode, OCB mode, IPS mode, FFS mode, VA mode, or FPA mode. (i) A transmissive element containing the composition. (j) Use 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 composition of the composition will be explained. Second, the main characteristics of the component compounds and the compound The main effects of the composition on the composition will be explained. Thirdly, the combination of the components in the composition, the preferable ratio of the components, and the basis will be described. Fourth, the preferred form of the component compounds will be described. Fifth, the preferred component compounds are shown. Sixth, additives that can be added to the composition will be described. Seventh, the synthesis method of the component compounds will be described. Finally, the use of the composition will be explained.

First, the composition of the composition will be explained. 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 essentially contains only the liquid crystal compound selected from the compound (2) and the compound (3). "Substantially" means that although the composition 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, the composition A is superior to the 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 explained. Based on the effects of the present invention, the main characteristics of the component compounds are summarized in Table 2. In the notation in Table 2, L means large or high, M Means moderate, S means small or low. The symbols L, M, and S are classifications based on the qualitative comparison between component compounds, and the symbol 0 means that the value is zero or close to zero.

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 polar group and controls the alignment of the liquid crystal molecules. In order to obtain the desired effect, the compound (1) must have high compatibility with the liquid crystal compound. It can be considered that compound (1) has a six-membered ring such as 1,4-cyclohexylene or 1,4-phenylene and has a rod-shaped molecular structure, and has a branched structure at one end of the molecular structure. It improves compatibility and is therefore most suitable for this purpose. The compound (1) forms a polymer by polymerization. Since the polymer stabilizes the alignment of liquid crystal molecules, the response time of the device is shortened, and the afterimage of the image is improved. The compound (2) increases the dielectric anisotropy and lowers the minimum temperature. Compound (3) reduces viscosity. Compound (4) forms a polymer by polymerization. Since the 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 the alignment of liquid crystal molecules, the polymer of compound (1) has Therefore, it is inferred that it is more effective than the polymer of compound (4). The compound (5) has a polar group and a polymerizable group in a linear form at the end of the molecular structure, and controls and promotes the alignment of liquid crystal molecules in the same manner as the compound (1).

Thirdly, the combination of the components in the composition, the preferable ratio of the components, and the basis will be described. A preferable combination of the components in the composition is compound (1) + compound (2) + compound (3), or compound (1) + compound (2) + compound (3) + compound (4). Compound (5) can also be further combined in these combinations.

The compound (1) is added to the composition for the purpose of controlling the alignment of liquid crystal molecules. In order to align the liquid crystal molecules, the preferable ratio of the compound (1) is about 0.05% by weight or more, and in order to prevent poor display of the device, the preferable ratio of the compound (1) is about 10% by weight or less. A particularly preferable ratio is in the range of about 0.1% by weight to about 7% by weight. A particularly preferable ratio is in the range of about 0.5% by weight to about 5% by weight.

In order to increase the dielectric anisotropy, the preferred proportion of the compound (2) is about 10% by weight or more, and in order to reduce the minimum temperature, the preferred proportion of the compound (2) is about 90% by weight or less. A particularly preferable ratio is in the range of about 20% by weight to about 85% by weight. A particularly preferable 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 proportion of compound (3) is about 10% by weight or more, and in order to increase the dielectric anisotropy, the preferred proportion of compound (3) is about 90% by weight or less. A particularly preferable ratio is in the range of about 15% by weight to about 75% by weight. A particularly preferable ratio is in the range of about 15% by weight to about 60% by weight.

The compound (4) is added to the composition for the purpose of being suitable for a polymer stable alignment type element. In order to improve the long-term reliability of the device, the preferred ratio of the compound (4) is about 0.03% by weight or more. To prevent poor display of the device, the preferred ratio of the compound (4) is about 10% by weight or less. A particularly preferable ratio is in the range of about 0.1% by weight to about 2% by weight. A particularly preferred ratio is in the range of about 0.2% by weight to about 1.0% by weight.

The compound (5) is added to the composition for the purpose of controlling and promoting the alignment of liquid crystal molecules. In order to align the liquid crystal molecules, the preferred ratio of the compound (5) is about 0.05% by weight or more, and in order to prevent poor display of the device, the preferred ratio of the compound (5) is about 10% by weight or less. A particularly preferable ratio is in the range of about 0.1% by weight to about 7% by weight. A particularly preferable ratio is in the range of about 0.3% by weight to about 5% by weight.

Fourth, the preferred form of the component compounds will be described. In formula (1-1), X ¹ in formula (1f), formula (1g), formula (1h), and formula (1i) is a polar group. Since the compound (1-1) is added to the composition, it is preferably stable. When the compound (1-1) is added to the composition, it is preferable that the compound does not reduce the voltage holding ratio of the device. The compound (1-1) preferably has low volatility. The preferred molar mass is 130 g/mol or more. A particularly preferred molar mass is in the range of 150 g/mol to 800 g/mol. The preferred compound (1-1) has acryloxy group (-OCO-CH=CH ₂ ), methacryloxy group (-OCO-(CH ₃ )C=CH ₂ ), acrylic acid α-hydroxyalkyl Polymeric groups such as esters.

In formula (1f), formula (1g), formula (1h), and formula (1i), X ¹ is -OH, -NH ₂ , -OR ¹⁵ , -N(R ¹⁵ ) ₂ , -COOH, -SH, A group represented by -B(OH) ₂ or -Si(R ¹⁵ ) ₃ , where R ¹⁵ is hydrogen or an alkyl group having 1 to 5 carbon atoms, in which at least one -CH ₂ -may be Substituting -O-, at least one -CH ₂ CH ₂ -may be substituted with -CH=CH-, and in these groups, at least one hydrogen may be substituted with fluorine. From the viewpoint of high solubility in the liquid crystal composition, X ^{1 is} particularly preferably -OH or -NH ₂ . -OH is superior to -O-, -CO-, or -COO- because of its high anchoring force. Particularly preferred is a group having multiple heteroatoms (nitrogen, oxygen). The compound having such a polar group is effective even at a low concentration.

In the formula (1-1), R ¹ is an alkyl group having 1 to 15 carbons. In the R ¹ , at least one -CH ₂ -may be substituted with -O- or -S-, and at least one -CH ₂ CH ₂ -May be substituted by -CH=CH- or -C≡C-, at least one hydrogen may be substituted by halogen.

Ring A ¹ and Ring A ^{2 are} independently 1,4-cyclohexylene, 1,4-cyclohexenylene, 1,4-phenylene, naphthalene-2,6-diyl, decalin-2 ,6-Diyl, 1,2,3,4-tetrahydronaphthalene-2,6-diyl, tetrahydropyran-2,5-diyl, 1,3-dioxane-2,5-di Base, pyrimidine-2,5-diyl, pyridine-2,5-diyl, pyridine-2,7-diyl, phenanthrene-2,7-diyl, anthracene-2,6-diyl, perhydro ring Pentano[a]phenanthrene-3,17-diyl, or 2,3,4,7,8,9,10,11,12,13,14,15,16,17-tetradecahydrocyclopenta[ a] Phenanthrene-3,17-diyl, in these rings, at least one hydrogen may be fluorine, chlorine, alkyl having 1 to 12 carbons, alkenyl having 2 to 12 carbons, or alkane having 1 to 11 carbons. An oxy group or an alkenyloxy group having a carbon number of 2 to 11 is substituted. In these groups, at least one hydrogen may be substituted with fluorine or chlorine. Preferred ring A ¹ or ring A ² is 1,4-cyclohexylene, 1,4-phenylene, 2-fluoro-1,4-phenylene, naphthalene-2,6-diyl, or 3 -Ethyl-1,4-phenylene.

In the formula (1-1), Z ¹ is a single bond or an alkylene group having 1 to 6 carbons, and in the Z ¹ at least one -CH ₂ -can pass through -O-, -CO-, -COO-, -OCO- or -OCOO- substitution, at least one -CH ₂ CH ₂ -can be replaced by -CH=CH- or -C≡C-, at least one hydrogen can be replaced by fluorine or chlorine. Preferably Z ¹ is a single bond, -CH ₂ CH ₂ -, -CH ₂ O-, -OCH ₂ -, -COO-, or -OCO-. Z ¹ is particularly preferably a single bond.

In formula (1-1), a is 0, 1, 2, 3, or 4. Preferably a is 0, 1, 2, or 3. More preferably, a is 0, 1, or 2. Particularly preferred a is 1 or 2.

In the formula (1-1), Sp ¹ is a single bond or an alkylene group having 1 to 10 carbons, and in the Sp ¹ at least one -CH ₂ -can pass through -O-, -CO-, -COO-, -OCO- or -OCOO- substitution, at least one -CH ₂ CH ₂ -can be substituted by -CH=CH- or -C≡C-, at least one hydrogen can be substituted by halogen, in these groups, at least one hydrogen Substituted by a group selected from the group represented by the formula (1a);

In the formula (1a), Sp ¹² is a single bond or an alkylene group having 1 to 10 carbon atoms, and in the Sp ¹² , at least one -CH ₂ -can pass through -O-, -CO-, -COO-, -OCO -Or -OCOO- substitution, at least one -CH ₂ CH ₂ -can be substituted by -CH=CH- or -C≡C-, at least one hydrogen can be substituted by halogen. Preferred Sp ¹² is a single bond, an alkylene group having 1 to 5 carbon atoms, or an alkylene group having 1 to 5 carbon atoms substituted by -CH ₂ --O-. Particularly preferred Sp ¹² is a single bond, an alkylene group having 1 to 3 carbon atoms, or an alkylene group having 1 to 3 carbon atoms substituted with -CH ₂ --O-.

M ¹¹ and M ^{12 are} independently hydrogen, halogen, alkyl having 1 to 5 carbons, or alkyl having 1 to 5 carbons in which at least one hydrogen is substituted with halogen. In order to improve the reactivity, preferred M ¹¹ or M ¹² is hydrogen or methyl. More preferably, M ¹¹ or M ¹² is hydrogen.

R ¹² is an alkyl group having 1 to 15 carbons. In the R ¹² , at least one -CH ₂ -may be substituted by -O- or -S-, and at least one -CH ₂ CH ₂ -may be substituted by -CH=CH- Or -C≡C- substitution, at least one hydrogen may be substituted by halogen. Preferably, R ¹² is hydrogen, or an alkylene group having 1 to 5 carbons, or a -CH ₂ -alkylene group having 1 to 5 carbons substituted by -O-. Particularly preferred R ¹² is hydrogen, or an alkylene group having 1 to 3 carbons, or an alkylene group having 1 to 3 carbons substituted by -CH ₂ -with -O-. Particularly preferred R ¹² is hydrogen or methyl. In the case where R ¹² is -CH ₂ -OH, the effect of the presence of two hydroxyl groups in the molecule makes it possible to expect vertical alignment added at a low concentration.

In formula (1-1), preferred Sp ¹ is an alkylene group having 1 to 5 carbons, or an alkylene group having 1 to 5 carbons substituted by -CH ₂ --O-. Particularly preferred Sp ¹ is an alkylene group having 1 to 3 carbons, or a -CH ₂ -alkylene group having 1 to 3 carbons substituted by -O-. In these groups, at least one hydrogen may be The polymerizable group represented by (1a) is substituted.

P ¹¹ is a group selected from the groups represented by formula (1e) and formula (1f),

In formula (1e), R ¹³ is a group selected from the groups represented by formula (1g), formula (1h), and formula (1i).

In formula (1e) and formula (1f), Sp ¹³ is a single bond or an alkylene group having 1 to 10 carbon atoms, and in the Sp ¹³ , at least one -CH ₂ -can be controlled by -O-, -NH-,- CO-, -COO-, -OCO-, or -OCOO- substituted, at least one -CH ₂ CH ₂ -may be substituted with -CH=CH- or -C≡C-, in these groups, at least one hydrogen may Replaced by halogen. Preferably, Sp ¹³ is an alkylene group having 1 to 7 carbon atoms, or an alkylene group having 1 to 5 carbon atoms substituted by -CH ₂ --O-. Particularly preferred Sp ¹³ is an alkylene group having 1 to 5 carbon atoms, or an alkylene group having 1 to 5 carbon atoms substituted by -CH ₂ -with -O-. Particularly preferred Sp ¹³ is -CH ₂ -.

In the formula (1e), M ¹³ and M ^{14 are} independently hydrogen, halogen, an alkyl group having 1 to 5 carbons, or an alkyl group having 1 to 5 carbons in which at least one hydrogen is substituted by halogen. In order to improve the reactivity, it is more Preferably M ¹³ or M ¹⁴ is hydrogen or methyl. Particularly preferred M ¹³ or M ¹⁴ is hydrogen.

In formula (1e), R ¹³ is a group selected from the group of polar groups represented by formula (1g), formula (1h), and formula (1i), preferably R ¹³ is formula (1g) or The polar group represented by formula (1h). Particularly preferred R ¹³ is a polar group represented by formula (1g).

In formula (1g), formula (1h), and formula (1i), Sp ¹⁴ and Sp ^{15 are} independently a single bond or an alkylene group having 1 to 10 carbon atoms, and at least one of Sp ¹⁴ and Sp ¹⁵ is- CH ₂ -can be substituted by -O-, -NH-, -CO-, -COO-, -OCO-, or -OCOO-, at least one -CH ₂ CH ₂ -can be -CH=CH- or -C≡ C-substituted, in these groups, at least one hydrogen may be substituted by halogen. Preferred Sp ¹⁴ Sp ¹⁵ carbon atoms or alkylene of 1 to 7, or a -CH ₂ - replaced by -O- alkylene group having a carbon number of 1 to 5. Particularly preferred Sp ¹⁴ or Sp ¹⁵ is an alkylene group having 1 to 5 carbon atoms, or a -CH ₂ -alkylene group having 1 to 5 carbon atoms substituted by -O-. Particularly preferred Sp ¹⁴ or Sp ¹⁵ is -CH ₂ -.

In formula (1h) and formula (1i), S ¹ is >CH- or >N-, and S ² is >C< or >Si<. The preferred S ¹ is >CH-, and the preferred S ² is >C<.

In formula (1f), formula (1g), and formula (1i), X ¹ is -OH, -NH ₂ , -OR ⁵ , -N(R ¹⁵ ) ₂ , -COOH, -SH, -B(OH) ₂ , or -Si(R ¹⁵ ) ₃ , where R ¹⁵ is hydrogen or an alkyl group having 1 to 10 carbons. In the alkyl group, at least one -CH ₂ -may be substituted by -O-, and at least one- CH ₂ -CH ₂ -may be substituted by -CH=CH-, and in these groups, at least one hydrogen may be substituted by fluorine or chlorine. Preferably X ¹ is -OH, -NH ₂ , or -N(R ¹⁵ ) ₂ , where R ¹⁵ is hydrogen or an alkyl group having 1 to 10 carbons, and at least one of -CH ₂ in R ¹⁵ -May be substituted by -O-, at least one -CH ₂ CH ₂ -may be substituted by -CH=CH-, at least one hydrogen may be substituted by halogen. Preferably X ¹ is an alkyl group having 1 to 5 carbons or an alkoxy group having 1 to 4 carbons. Particularly preferred X ¹ is -OH, -NH ₂ , or -N(R ¹⁵ ) ₂ . Particularly preferred X ¹ is -OH.

In formulas (1-4) to (1-60), R ¹ is an alkyl group having 1 to 10 carbons; Z ¹ , Z ¹² , and Z ^{13 are} independently a single bond, -CH ₂ CH ₂ -, or -(CH ₂ ) ₄ -; Sp ¹² , Sp ¹³ , and Sp ^{14 are} independently a single bond or an alkylene group having 1 to 5 carbon atoms, in which at least one -CH ₂ -may be -O -Substitution; 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.

In formula (2) and formula (3), R ³ and R ^{4 are} independently an alkyl group having 1 to 12 carbons, an alkoxy group having 1 to 12 carbons, an alkenyl group having 2 to 12 carbons, or a carbon number 2 to 12 alkenyloxy. In order to improve the stability, preferably R ³ or R ⁴ is an alkyl group having 1 to 12 carbons. In order to increase the dielectric anisotropy, preferably R ³ or R ⁴ is an alkoxy group having 1 to 12 carbons. R ⁵ and R ^{6 are} independently an alkyl group having 1 to 12 carbons, an alkoxy group having 1 to 12 carbons, an alkenyl group having 2 to 12 carbons, or a carbon number of 1 to 12 in which at least one hydrogen is substituted by fluorine or chlorine The alkyl group or the alkenyl group having 2 to 12 carbons in which at least one hydrogen is replaced by fluorine or chlorine. In order to reduce the viscosity, preferably R ⁵ or R ⁶ is an alkenyl group having 2 to 12 carbons, and in order to improve stability, preferably R ⁵ or R ⁶ is an alkyl group having 1 to 12 carbons. 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. The same applies to terminal groups such as alkoxy and alkenyl.

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

Preferred alkoxy groups are methoxy, ethoxy, propoxy, butoxy, pentoxy, hexyloxy, or heptoxy. In order to reduce the viscosity, particularly preferred alkoxy groups are 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, particularly preferred alkenyl groups are vinyl, 1-propenyl, 3-butenyl, or 3-pentenyl. The preferred configuration of -CH=CH- in these alkenyl groups depends on the position of the double bond. In order to reduce viscosity and other reasons, preferred among alkenyl groups such as 1-propenyl, 1-butenyl, 1-pentenyl, 1-hexenyl, 3-pentenyl, and 3-hexenyl Trans configuration. Among alkenyl groups such as 2-butenyl, 2-pentenyl, and 2-hexenyl, the cis configuration is preferred. Among these alkenyl groups, linear alkenyl groups are preferred to branched alkenyl groups.

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

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

Preferred examples of alkenyl groups in which at least one hydrogen is replaced by fluorine or chlorine are 2,2-difluorovinyl, 3,3-difluoro-2-propenyl, 4,4-difluoro-3-butenyl , 5,5-difluoro-4-pentenyl, or 6,6-difluoro-5-hexenyl. In order to reduce the viscosity, particularly preferred examples are 2,2-difluorovinyl or 4,4-difluoro-3-butenyl.

Ring C and Ring E are independently 1,4-cyclohexylene, 1,4-cyclohexenylene, 1,4-phenylene, 1,4-phenylene in which at least one hydrogen is substituted by fluorine or chlorine , Or tetrahydropyran-2,5-diyl. Preferred examples of "1,4-phenylene in which at least one hydrogen is substituted by fluorine or chlorine" are 2-fluoro-1,4-phenylene and 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-cyclohexylene. In order to increase 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 maximum temperature, the three-dimensional configuration related to 1,4-cyclohexylene is the trans configuration better than the cis configuration. Tetrahydropyran-2,5-diyl is

or

, Preferably

Ring D is 2,3-difluoro-1,4-phenylene, 2-chloro-3-fluoro-1,4-phenylene, 2,3-difluoro-5-methyl-1,4- Phenylene, 3,4,5-trifluoronaphthalene-2,6-diyl, or 7,8-difluorochroman-2,6-diyl. In order to reduce the viscosity, the preferred ring D is 2,3-difluoro-1,4-phenylene. In order to reduce the optical anisotropy, the preferred ring D is 2-chloro-3-fluoro-1,4- 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-cyclohexylene, 1,4-phenylene, 2-fluoro -1,4-phenylene, or 2,5-difluoro-1,4-phenylene. In order to reduce the viscosity or to increase the upper limit temperature, the preferred ring F or ring G is 1,4-cyclohexylene, and in order to reduce the lower limit temperature, the preferred ring F or ring G is 1,4-phenylene. In order to increase the maximum temperature, the three-dimensional configuration related to 1,4-cyclohexylene is the trans configuration better than the cis configuration.

Z ² and Z ^{3 are} independently a single bond, -CH ₂ CH 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 CH 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 CH 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 CH ₂ -, and 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 minimum temperature, the preferred c is 1. d is 1, 2, or 3. In order to reduce the viscosity, the preferable d is 1, and in order to increase the upper limit temperature, the preferable d is 2 or 3.

In formula (4), 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 of groups 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 preferable P ¹ , P ² , or P ³ is a group represented by 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 lines of formula (P-1) to formula (P-5) indicate the bonding position.

In formulas (P-1) to (P-5), M ¹ , M ² , and M ^{3 are} independently hydrogen, fluorine, an alkyl group having 1 to 5 carbons, or at least one hydrogen substituted by fluorine or chlorine An alkyl group having 1 to 5 carbon atoms. In order to improve the reactivity, preferred M ¹ , M ² or M ³ are hydrogen or methyl. More preferably, M ¹ is hydrogen or methyl, and more preferably M ² or M ³ is hydrogen.

Sp ³ , Sp ⁴ , and Sp ^{3 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 controlled by -O-, -COO-, -OCO -Or -OCOO- substituted, and at least one -CH ₂ CH ₂ -may be substituted with -CH=CH- or -C≡C-, in these groups, at least one hydrogen may be substituted with fluorine or chlorine. Preferably Sp ³ , Sp ⁴ , or Sp ⁵ is a single bond, -CH ₂ -CH ₂ -, -CH ₂ O-, -OCH ₂ -, -COO-, -OCO-, -CO-CH=CH- , Or -CH=CH-CO-. More preferably, 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, Pyrimidine-2-yl or pyridin-2-yl, in these rings, at least one hydrogen may be fluorine, chlorine, alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, or at least one hydrogen It is substituted by a fluorine or chlorine substituted alkyl group having 1 to 12 carbons. The preferred ring J or ring P is phenyl. Ring K is 1,4-cyclohexylene, 1,4-cyclohexenylene, 1,4-phenylene, naphthalene-1,2-diyl, naphthalene-1,3-diyl, naphthalene-1,4-diyl, naphthalene-1,5 -Diyl, naphthalene-1,6-diyl, naphthalene-1,7-diyl, naphthalene-1,8-diyl, naphthalene-2,3-diyl, naphthalene-2,6-diyl, naphthalene -2,7-diyl, tetrahydropyran-2,5-diyl, 1,3-dioxane-2,5-diyl, pyrimidine-2,5-diyl, or pyridine-2,5 -A diyl group, in these rings, at least one hydrogen may be substituted by fluorine, chlorine, an alkyl group having 1 to 12 carbons, an alkoxy group having 1 to 12 carbons, or at least one hydrogen having a carbon number of 1 substituted by fluorine or chlorine To 12 alkyl substitution. 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 the alkylene group, at least one -CH ₂ -may be -O- _, -CO- _, -COO- _, or- OCO- substitution, and at least one -CH ₂ CH 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 with fluorine or chlorine. Preferably Z ⁵ or Z ⁶ is a single bond, -CH ₂ CH ₂ -, -CH ₂ O-, -OCH ₂ -, -COO-, or -OCO-. Preferably, Z ⁵ or Z ⁶ is a single bond.

q is 0, 1, or 2. Preferably 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 (1-1) is the compound (1-2) and the compound (1-3) described in Item 2. Particularly desirable compound (1-1) is the compound (1-4) to the compound (1-60) described in Item 3. Among these compounds, preferably at least one of the first additives is compound (1-4), compound (1-5), compound (1-6), compound (1-12), compound (1-20) , Compound (1-22), compound (1-23), compound (1-24), compound (1-25), compound (1-42), Compound (1-43), Compound (1-44). Preferably, at least two of the first additives are compound (1-4) and compound (1-5), or a combination of compound (1-5) and compound (1-6).

Preferred compound (2) includes compound (2-1) to compound (2-22) described in Item 6. Among these compounds, at least one of the first components is preferably compound (2-1), compound (2-3), compound (2-4), compound (2-6), compound (2-8), Or compound (2-10). Preferably 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) includes compound (3-1) to compound (3-13) described in Item 9. Among these compounds, at least one of the second components is preferably compound (3-1), compound (3-3), compound (3-5), compound (3-6), compound (3-8), Or compound (3-9). Preferably 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) includes compound (4-1) to compound (4-29) described in Item 13. Among these compounds, preferably at least one of the second additives is compound (4-1), compound (4-2), compound (4-24), compound (4-25), compound (4-26) , Compound (4-27) or Compound (4-29). Preferably at least two of the second additives are compound (4-1) and compound (4-2), compound (4-1) and compound (4-18), compound (4-2) and compound (4 -24), compound (4-2) And compound (4-25), compound (4-2) and compound (4-26), compound (4-25) and compound (4-26), or compound (4-18) and compound (4-24) The combination.

Examples of preferable compound (5) are compound (5-1) to compound (5-10). The preferable ratio of the compound (5) is in the range of about 0.3% by weight to about 10% by weight.

Sixth, for additives other than the first additive that can be added to the composition Be explained. Such additives include 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 (6-1) to compound (6-5). A preferable ratio of the optically active compound is about 5 wt% or less. A particularly preferable ratio is in the range of about 0.01% by weight to about 2% by weight.

In order to prevent the decrease in 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 element for a long time, the antioxidant Add to the composition. Preferred examples of antioxidants are compound (7) in which n is an integer from 1 to 9, and the like.

In compound (7), preferred n is 1, 3, 5, 7, or 9. A particularly good n is 7. The compound (7) with n of 7 has low volatility and is therefore effective for maintaining a large voltage holding ratio 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 effect, the preferable ratio of the antioxidant is about 50 ppm or more. In order not to lower the upper limit temperature or to increase the lower limit temperature, the preferable ratio of the antioxidant is about 600 ppm or less. A particularly preferred ratio is in the range of about 100 ppm to about 300 ppm.

Preferred examples of ultraviolet absorbers are benzophenone derivatives, benzoate derivatives, triazole derivatives, and the like. Furthermore, light stabilizers such as amines with steric hindrance are also preferable. In order to obtain the effect, the preferred ratio of these absorbents or stabilizers is about 50 ppm or more. In order not to lower the upper limit temperature or increase the lower limit temperature, the preferred ratio of these absorbents or stabilizers is about Below 10000ppm. A particularly preferred ratio is in the range of about 100 ppm to about 10000 ppm.

In order to be suitable for components in the guest host (GH) mode, the Dichroic dyes such as azo dyes and anthraquinone dyes are added to the composition. The preferred 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 effect, the preferred ratio of the defoaming agent is about 1 ppm or more, and in order to prevent display failure, the preferred ratio of the defoaming agent is about 1000 ppm or less. A particularly preferred ratio is in the range of about 1 ppm to about 500 ppm.

In order to be suitable for polymer stable alignment (PSA) type elements, polymerizable compounds are used. Compound (1) and compound (4) are suitable for this purpose. The compound (5) can be added to the composition together with the compound (1) and the compound (4). Furthermore, another polymerizable compound different from the compound (1), the compound (4), and the compound (5) may be added to the composition together with the compound (1) and the compound (4). Preferred examples of other polymerizable compounds are acrylates, methacrylates, vinyl compounds, vinyloxy compounds, propenyl ethers, epoxy compounds (oxetane, oxetane), vinyl Ketones and other compounds. A particularly preferred example is acrylate or methacrylate. Based on the total weight of the polymerizable compound, the preferred ratio of the compound (1), the compound (4), and the compound (5) is about 10% by weight or more. A particularly preferable ratio is about 50% by weight or more. A more preferable ratio is about 80% by weight or more. A particularly preferred ratio 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, The reactivity of the polymerizable compound or the pretilt angle of the liquid crystal molecules can be adjusted. By optimizing the pretilt angle, a short response time of the device can be achieved. The alignment of the liquid crystal molecules is stabilized due to This can achieve a large contrast ratio or a long life.

Polymerizable compounds such as compound (1), compound (4), and compound (5) are polymerized by ultraviolet irradiation. It is also possible to perform polymerization in the presence of an appropriate initiator such as a photopolymerization initiator. The appropriate conditions for polymerization, the appropriate type of initiator, and the appropriate amount are known to those skilled in the art and are described in the literature. For example, as a photopolymerization initiator, Irgacure 651 (registered trademark; BASF), Irgacure 184 (registered trademark; BASF), or Darocur 1173 ( Registered trademark; BASF) 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 particularly preferable 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), in order to prevent polymerization, a polymerization inhibitor may be added. The polymerizable compound is usually added to the composition without removing the polymerization inhibitor. Examples of polymerization inhibitors are hydroquinone, hydroquinone derivatives such as methylhydroquinone, 4-tert-butylcatechol, 4-methoxyphenol, phenothiazine, and the like.

Seventh, the synthesis method of the component compounds will be described. These compounds can be synthesized by known methods. Illustrate the synthesis method. The synthesis method of compound (1) is described in the section of Examples. Compound (2-1) was synthesized by the method described in JP 2-503441 A. Compound (3-5) was synthesized by the method described in Japanese Patent Laid-Open No. 57-165328. Compound (5) was synthesized by the method described in the manual of International Publication No. 2016/015803. Compound The compound (4-18) was synthesized by the method described in Japanese Patent Laid-Open No. 7-101900. A part of compound (7) is commercially available. The compound of formula (7) where n is 1 can be obtained from Sigma-Aldrich Corporation. Compound (7) in which n is 7 is synthesized by the method described in the specification of U.S. Patent No. 3660505.

Compounds without a description of the synthesis method can be synthesized by the method 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 Lecture'' (Maruzen )Wait. The composition is prepared from the compound obtained in the manner described above using a known method. For example, the component compounds are mixed and then heated to dissolve each other.

Finally, the use of the composition will be explained. Most of the compositions have a lower limit temperature of about -10°C or lower, an upper limit temperature of about 70°C or higher, and an optical anisotropy in the range of about 0.07 to about 0.20. It is also possible to prepare a composition having an optical anisotropy in the range of about 0.08 to about 0.25 by controlling the ratio of component compounds or by mixing other liquid crystal compounds. Furthermore, it is also possible to prepare a composition having an optical anisotropy in the range of about 0.10 to about 0.30 through trial and error. The device containing this composition has a large voltage holding ratio. This composition is suitable for AM devices. The composition is particularly suitable for transmission type AM devices. The composition can be used as a composition having a nematic phase, and can be used as an optically active group by adding an optically active compound Into things.

This composition can be used for AM devices. It can also be used for PM devices. The composition can be used for AM devices and PM devices with PC, TN, STN, ECB, OCB, IPS, FFS, VA, FPA and other modes. It is particularly preferred for AM devices with TN mode, OCB mode, IPS mode or FFS mode. In an AM device with an IPS mode or an 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. These elements can be reflective, transmissive, or semi-transmissive. It is preferably used for transmissive elements. It can also be used for amorphous silicon-TFT devices or polysilicon-TFT devices. It can also be used for nematic curvilinear aligned phase (NCAP) type devices produced by microencapsulating the composition, or for polymer dispersed, polymer dispersed, in which three-dimensional network polymers are formed in the composition. PD) type element.

An example of a method of manufacturing a conventional polymer stable alignment type element is as follows. Assemble an element including two substrates, which are called an array substrate and a color filter substrate. The substrate has an alignment film. At least one of the substrates has an electrode layer. The liquid crystal compounds are mixed to prepare a liquid crystal composition. A polymerizable compound is added to this composition. If necessary, additives can be further added. The composition is injected into the device. Light irradiation is performed in a state where a voltage is applied to the element. Preferably it is ultraviolet light. The polymerizable compound is polymerized by light irradiation. This polymerization produces a polymer-containing composition. The polymer stabilized alignment type components are manufactured in this order.

In this sequence, when a voltage is applied, the liquid crystal molecules are Alignment. 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 produced. With the effect of the polymer, the response time of the device is shortened. Since the afterimage of the image is the poor operation of the liquid crystal molecules, the afterimage is also improved by the effect of the polymer. In addition, the polymerizable compound in the composition may be polymerized in advance, and the composition may be arranged between the substrates of the liquid crystal display element.

In the case of using compound (1), that is, a compound having a polymerizable group and a polar group in the branch structure at the molecular end, an alignment film is not required on the substrate of the element. The device without the alignment film is manufactured in accordance with the procedure described in the paragraph two paragraphs before, except that the substrate without the alignment film is used.

In this sequence, the compound (1) is arranged on the substrate due to the interaction of the polar group with the surface of the substrate. According to this arrangement, the liquid crystal molecules are aligned. When voltage is applied, the alignment of liquid crystal molecules is further promoted. Since the polymerizable group is polymerized by ultraviolet rays in this state, a polymer that maintains the alignment is produced. Due to the effect of the polymer, the alignment of the liquid crystal molecules is additionally stabilized, and the response time of the device is shortened. Since the afterimage of the image is the poor operation 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 through examples. The present invention is not limited by these embodiments. The present invention 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 compound is based on nuclear magnetic resonance (nuclear magnetic resonance, NMR) analysis and other methods to identify. The characteristics of the compound, composition, and device were measured by the following methods.

NMR analysis: DRX-500 manufactured by Bruker BioSpin was used in the measurement. ^{In the 1} H-NMR measurement, the sample is dissolved in a deuterated solvent such as CDCl ₃ and the measurement is performed under the conditions of room temperature, 500 MHz, and 16 cumulative times. Use tetramethylsilane as the internal standard. ^{In the 19} F-NMR measurement, CFCl _{3 was} used as an internal standard, and the measurement was carried out at 24 times of accumulation. 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 sextet, m refers to multiplet, and br refers to broad.

Gas chromatographic analysis: GC-14B gas chromatograph manufactured by Shimadzu Corporation was used in the measurement. The carrier gas is helium (2mL/min). The sample vaporization chamber was set to 280°C, and the detector (flame ionization detector (FID)) was set to 300°C. When separating the component compounds, use the capillary column DB-1 manufactured by Agilent Technologies Inc. (length 30m, inner diameter 0.32mm, film thickness 0.25μm; the fixed liquid phase is dimethyl polysiloxane Alkane; non-polar). After the column was kept at 200°C for 2 minutes, the temperature was increased to 280°C at a rate of 5°C/min. After preparing the sample into an acetone solution (0.1% by weight), 1 μL of it was injected into the sample vaporization chamber. The recorder is a C-R5A Chromatopac manufactured by Shimadzu Corporation or its equivalent. The resulting gas chromatogram shows the peak retention time and peak surface area corresponding to the component compounds. product.

The solvent used to dilute the sample can be chloroform, hexane, etc. In order to separate the component compounds, the following capillary column can be used. HP-1 (length 30m, inner diameter 0.32mm, film thickness 0.25μm) manufactured by Agilent Technologies, Rtx-1 (length 30m, inner diameter 0.32mm, film thickness 0.25μm) manufactured by Restek Corporation ), BP-1 (length 30m, inner diameter 0.32mm, film thickness 0.25μm) manufactured by SGE International Pty. Ltd. in Australia. 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 method described below. Gas chromatography (FID) was used to analyze the mixture of liquid crystal compounds. The peak area ratio in the gas chromatogram corresponds to the ratio of liquid crystal compounds. When using the capillary column described above, the correction factor of various liquid crystal compounds can be regarded as 1. Therefore, the ratio (weight %) 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 the device, the composition is directly used as the 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 property value of the compound is calculated by extrapolation. (Extrapolated value)={(Measured value of sample)-0.85×(Measured value of mother liquid crystal)}/0.15. At this ratio, when the smectic phase (or crystal) is precipitated at 25°C, the ratio of the compound to the mother liquid crystal is 10wt%: 90wt%, 5wt%: 95wt%, 1wt%: 99wt Change the order of the amount %. This extrapolation method is used to obtain the maximum temperature, optical anisotropy, viscosity, and dielectric anisotropy values related to the compound.

The following mother liquid crystals are used. The ratio of component compounds is expressed in% by weight.

Measurement method: Use the following method to measure the characteristics. Most of these methods are the methods described in the JEITA standard (JEITA.ED-2521B) reviewed and established by the Japan Electronics and Information Technology Industries Association (JEITA) or modified method. In the TN device used for the measurement, no thin film transistor (TFT) was installed.

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

(2) Lower limit temperature of nematic phase (T _C ;°C): Put the sample with nematic phase into a glass bottle at 0°C, -10°C, -20°C, -30°C, and -40°C After storage in the refrigerator for 10 days, the liquid crystal phase was observed. For example, when the sample is in a nematic state at -20°C and changes to a crystalline or smectic phase at -30°C, T _{C is} described as <-20°C. The lower limit temperature of the nematic phase is sometimes referred to simply as the "lower limit temperature".

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

(4) Viscosity (rotational viscosity; γ1; measured at 25°C; mPa·s): According to M. Imai et al. "Molecular Crystals and Liquid Crystals" No. 259 The measurement was performed by the method described on page 37 (1995). A sample was injected into a VA device with a distance (cell gap) of 20 μm between two glass substrates. The voltage was applied stepwise in units of 1 volt in the range of 39 volts to 50 volts to the device. After the voltage was not applied for 0.2 seconds, it was repeatedly applied with only one rectangular wave (rectangular pulse; 0.2 second) and no voltage (2 seconds) applied. The peak current and peak time of the transient current generated by the application are measured. The value of rotational viscosity is obtained based on these measured values and the calculation formula (8) on page 40 of the paper by M. Imai et al. The dielectric anisotropy required for this calculation is measured by the method described in Measurement (6).

(5) Optical anisotropy (refractive index anisotropy; Δn; measured at 25°C): Using light with a wavelength of 589 nm, it was measured with an Abbe refractometer with a polarizing plate attached to an eyepiece. After rubbing the surface of the main shaft in one direction, Drop the sample onto the main stalk. 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 value of optical anisotropy is calculated according to the formula of △n=n∥-n⊥.

(6) Dielectric anisotropy (△ε; measured at 25°C): The value of dielectric anisotropy is calculated according to the formula of △ε=ε∥-ε⊥. The dielectric constant (ε∥ and ε⊥) is measured in the following manner.

1) Measurement of dielectric constant (ε∥): a solution of octadecyltriethoxysilane (0.16mL) in ethanol (20mL) is coated on a fully washed glass substrate. After rotating the glass substrate with a spinner, it was heated at 150°C for 1 hour. A sample was placed in a VA device with a distance (cell gap) of 4 μm between two glass substrates, and the device was sealed with an adhesive cured by ultraviolet rays. A sine wave (0.5 V, 1 kHz) was applied to the device, and after 2 seconds, the dielectric constant (ε∥) in the long axis direction of the liquid crystal molecules was measured.

2) Measurement of dielectric constant (ε⊥): Coat a polyimide solution on a sufficiently washed glass substrate. After firing the glass substrate, rubbing treatment is performed on the resulting alignment film. A sample was injected into a TN device with a gap (cell gap) of 9 μm between two glass substrates and a twist angle of 80 degrees. A sine wave (0.5V, 1kHz) was applied to the device, and after 2 seconds, the dielectric constant (ε⊥) in the minor axis direction of the liquid crystal molecules was measured.

(7) Threshold voltage (Vth; measured at 25°C; V): LCD5100 luminance meter manufactured by Otsuka Electronics Co., Ltd. was used in the measurement. The light source is a halogen lamp. Place a sample in a VA device in a normally black mode (normally black mode) with a distance of 4 μm between two glass substrates (cell gap) and an anti-parallel rubbing direction, and use an adhesive cured by ultraviolet light to make the device seal. For this component The applied voltage (60 Hz, rectangular wave) is 0.02V as the unit, and it is gradually increased from 0V to 20V. At this time, the element was irradiated with light from the vertical direction, and the amount of light passing through the element was measured. A voltage-transmittance curve is made that has a transmittance of 100% when the amount of light reaches its maximum and a transmittance of 0% when the amount of light reaches its minimum. The threshold voltage is expressed by the voltage when the transmittance reaches 10%.

(8) Voltage holding ratio (VHR-1; measured at 25°C; %): The TN device used in the measurement has a polyimide alignment film, and the interval (cell gap) between two glass substrates is 5 μm. After the device is injected with a sample, it is sealed with an adhesive that is cured by ultraviolet light. A pulse voltage (5V, 60 microseconds) was applied to the TN device to charge it. Using a high-speed voltmeter, the attenuated voltage was measured during 16.7 milliseconds, and the area A between the voltage curve and the horizontal axis in a unit period was obtained. Area B is the area without attenuation. The voltage retention rate is expressed by the percentage of area A to area B.

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

(10) Voltage retention rate (VHR-3; measured at 25°C; %): After irradiating ultraviolet rays, the voltage retention rate is measured to evaluate the stability to ultraviolet rays. The TN device used for the measurement has a polyimide alignment film, and the cell gap is 5 μm. The sample was injected into the element, and light was irradiated for 20 minutes. The light source is an ultra-high pressure mercury lamp USH-500D (manufactured by USHIO Motor), and the distance between the element and the light source is 20cm. In the measurement of VHR-3, the attenuated voltage was measured during 16.7 milliseconds. have The composition of large VHR-3 has great stability to ultraviolet rays. VHR-3 is preferably 90% or more, and more preferably 95% or more.

(11) Voltage retention rate (VHR-4; measured at 25°C; %): After heating the sample-infused TN element in a constant temperature bath at 80°C for 500 hours, measure the voltage retention rate to evaluate the resistance to heat stability. In the measurement of VHR-4, the attenuated voltage was measured during 16.7 milliseconds. A composition with a large VHR-4 has a large stability to heat.

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

(13) Elastic constant (K11: splay elastic constant, K33: Bend elastic constant; measured at 25°C; pN): An EC-1 elastic constant tester manufactured by TOYO Corporation Co., Ltd. was used in the measurement. A sample was injected into a vertical alignment element with a distance between two glass substrates (cell gap) of 20 μm. A charge of 20V to 0V was applied to the device, and the capacitance and applied voltage were measured. Fitting (fitting) the measured capacitance (C) and applied voltage (V) using the formula (2.98) and formula (2.101) on page 75 of "Liquid Crystal Device Handbook" (Nikkan Kogyo Shimbun), According to formula (2.100), the value of elastic constant is obtained.

(14) Specific resistance (ρ; measured at 25°C; Ωcm): Put 1.0 mL of the sample in a container equipped with electrodes. A DC voltage (10V) 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 container)}/{(DC current)×(dielectric constant of vacuum)}.

(15) Pretilt angle (degrees): A spectroscopic ellipsometer M-2000U (manufactured by J.A. Woollam Co., Inc.) was used for the measurement of the pretilt angle.

(16) Alignment stability (liquid crystal alignment axis stability): The change of the liquid crystal alignment axis on the electrode side of the liquid crystal display element was evaluated. Measure the alignment angle Φ (before) of the liquid crystal on the electrode side before stress is applied, then apply a rectangular wave of 4.5V, 60Hz to the device for 20 minutes, buffer for 1 second, and measure the liquid crystal on the electrode side again after 1 second and 5 minutes later Alignment angle Φ(after). From these values, the following formula was used to calculate the change ΔΦ (deg.) of the liquid crystal alignment angle after 1 second and 5 minutes later.

△Φ(deg.)=Φ(after)-Φ(before) (Equation 2)

These measurements are based on J. Hilfiker, B. Johs, C. Herzinger, JF Elman (JFElman), E. Momba E. Montbach, D. Bryant, and PJ Bos's "Thin Solid Films" 455-456 (2004) 596-600 are used as reference . It can be said that the smaller the ΔΦ, the smaller the rate of change of the liquid crystal alignment axis, and the better the stability of the liquid crystal alignment axis.

Synthesis example 1

The compound (1-23-1) was synthesized by the following method.

Step 1

The compound (T-1) (40.0 g), triethyl phosphinyl acetate (40.7 g) and toluene (800 ml) were put into the reactor and cooled to 0°C. Add B slowly to it Sodium alkoxide (20% ethanol solution) (61.8 g), return to room temperature and stir for 12 hours. After the insoluble matter was separated by filtration, the reaction mixture was poured into water, and the aqueous layer was extracted with toluene. The mixed organic layer was washed with water and dried with anhydrous magnesium sulfate. This solution was concentrated under reduced pressure, and the residue was purified by silica gel chromatography (volume ratio, toluene:heptane=4:1) to obtain compound (T-2) (42.0 g; 83%).

Step 2

Put compound (T-2) (42.0g), toluene (400ml), and isopropanol (400ml) into the reactor, and stir at room temperature for 24 hours under a hydrogen environment with Pd/C (0.7g) . The reaction mixture was poured into water, and the water layer was extracted with toluene. The mixed organic layer was washed with salt water, and dried with anhydrous magnesium sulfate. The solution was concentrated under reduced pressure, and the residue was purified by silica gel chromatography (volume ratio, toluene:heptane=4:1) to obtain compound (T-3) (40.1 g; 95%).

Step 3

The compound (T-3) (40.1 g) and tetrahydrofuran (THF) (400 ml) were put into the reactor and cooled to -60°C. Lithium diisopropylamide (LDA) (1.13M; THF solution; 142 ml) was slowly added dropwise and stirred for 1 hour. Methyl chloroformate (11.0 ml) was slowly added dropwise thereto, returned to room temperature and stirred for 5 hours. After the insoluble matter was separated by filtration, the reaction mixture was poured into water, and the aqueous layer was extracted with toluene. The mixed organic layer was washed with water and dried with anhydrous magnesium sulfate. Concentrate the solution under reduced pressure After shrinking, the residue was purified by silica gel chromatography (volume ratio, toluene:heptane=4:1) to obtain compound (T-4) (30.5 g; 65%).

Step 4

Lithium aluminum hydride (1.7g) and THF (300ml) were put into the reactor and cooled in an ice bath. A solution of compound (T-4) (30.5 g) in THF (600 ml) was slowly added, returned to room temperature and stirred for 3 hours. The reaction mixture was poured into water, and the aqueous layer was extracted with ethyl acetate. The mixed organic layer was washed with salt water, and dried with anhydrous magnesium sulfate. The solution was concentrated under reduced pressure, and the residue was purified by silica gel chromatography (volume ratio, toluene:ethyl acetate=1:1). Further, purification was performed by recrystallization from heptane to obtain compound (T-5) (20.1 g, 80%).

Step 5

The compound (T-5) (20.1 g), triethylamine (10.3 ml) and THF (200 ml) were put into the reactor and cooled to 0°C. Methacrylic chloride (6.0 ml) was slowly added dropwise thereto, returned to room temperature and stirred for 4 hours. After the insoluble matter was separated by filtration, the reaction mixture was poured into water, and the aqueous layer was extracted with ethyl acetate. The mixed organic layer was washed with water and dried with anhydrous magnesium sulfate. The solution was concentrated under reduced pressure, and the residue was purified by silica gel chromatography (volume ratio, toluene:ethyl acetate=9:1) to obtain compound (1-23-1) (7.7 g; 32%).

The NMR analysis value of the obtained compound (1-23-1) is as follows.

¹ H-NMR: Chemical shift δ (ppm; CDCl ₃ ): 6.11 (s, 1H), 5.58 (s, 1H), 4.29-4.26 (m, 1H), 4.14-4.11 (m, 1H), 3.60-3.57 (m,1H), 3.50-3.47(m,1H), 1.98-1.95(m,5H), 1.78-1.67(m,8H), 1.32-1.11(m,12H), 0.99-0.81(m,13H)

The physical properties of compound (1-23-1) are as follows.

Transition temperature: C 65.0 I.

[Synthesis Example 2]

Synthesis of compound (1-4-1)

Step 1

Combine paraformaldehyde (30.0g), 1,4-diazabicyclo[2.2.2]octane (1,4-diazabicyclo[2.2.2]octane, DABCO) (56.0g), and water (600ml ) Put it into the reactor and stir for 15 minutes at room temperature. A THF (1200 ml) solution of compound (T-6) (50.0 g) was added dropwise thereto, and the mixture was stirred at room temperature for 72 hours. The reaction mixture was poured into water, and the aqueous layer was extracted with ethyl acetate. The mixed organic layer was washed with water and dried with anhydrous magnesium sulfate. This solution was concentrated under reduced pressure, and the residue was purified by silica gel chromatography (volume ratio, toluene:ethyl acetate=4:1) to obtain compound (T-7) (43.2 g; 65%).

Step 2

The compound (T-7) (42.2 g) was used as a raw material, and imidazole (26.3 g) and dichloromethane (800 ml) were put into the reactor and cooled to 0°C. A solution of tert-Butyl diphenyl chlorosilane (TBDPSCl) (106.4 g) in dichloromethane (100 ml) was slowly added dropwise thereto, returned to room temperature and stirred for 12 hours. The reaction mixture was poured into water, and the aqueous layer was extracted with dichloromethane. The mixed organic layer was washed with water and dried with anhydrous magnesium sulfate. The solution was concentrated under reduced pressure, and the residue was purified by silica gel chromatography (volume ratio, heptane:ethyl acetate=10:1) to obtain compound (T-8) (107.0 g; 90%).

Step 3

The compound (T-8) (107.0 g), THF (800 ml), methanol (200 ml), and water (100 ml) were put into the reactor and cooled to 0°C. Add hydrogen to it Lithium monohydrate (24.3 g), returned to room temperature and stirred for 12 hours. The reaction mixture was poured into water, 6N hydrochloric acid (100 ml) was slowly added to make it acidic, and then the aqueous layer was extracted with ethyl acetate. The mixed organic layer was washed with water and dried with anhydrous magnesium sulfate. The solution was concentrated under reduced pressure and purified by recrystallization from heptane to obtain compound (T-9) (47.4 g; 48%).

Step 4

Compound (1-23-1) (7.7g), compound (T-9) (8.0g), N,N-dimethyl-4-aminopyridine (DMAP) ) (1.0g) and dichloromethane (200ml) were put into the reactor and cooled to 0°C. A solution of N,N'-dicyclohexylcarbodiimide (N,N'-dicyclohexylcarbodiimide, DCC) (4.8g) in dichloromethane (60ml) was slowly added dropwise, returned to room temperature and stirred for 12 hours . After the insoluble matter was separated by filtration, the reaction mixture was poured into water, and the aqueous layer was extracted with dichloromethane. The mixed organic layer was washed with water and dried with anhydrous magnesium sulfate. The solution was concentrated under reduced pressure, and the residue was purified by silica gel chromatography (volume ratio, heptane:ethyl acetate=19:1) to obtain compound (T-10) (9.8 g; 70%).

Step 5

The compound (T-10) (9.8 g) and THF (100 ml) were put into the reactor and cooled to 0°C. Tetra-n-butyl ammonium fluoride (TBAF) (1.00M; THF solution; 16.5 ml) was slowly added thereto, returned to room temperature and stirred for 1 hour. The reaction mixture was poured into water, and the aqueous layer was extracted with ethyl acetate. Wash the mixed organic layer with salt water, And use anhydrous magnesium sulfate for drying. The solution was concentrated under reduced pressure, and the residue was purified by silica gel chromatography (volume ratio, toluene:ethyl acetate=9:1). Further purification was performed by recrystallization from heptane to obtain compound (1-4-1) (3.1 g; 47%).

The NMR analysis value of the obtained compound (1-4-1) is as follows.

¹ H-NMR: Chemical shift δ(ppm; CDCl ₃ ): 6.25(s,1H), 6.10(s,1H), 5.85(s,1H), 5.57(s,1H), 4.33(d,J=4.5 Hz, 2H), 4.27-4.16 (m, 2H), 4.13-4.08 (m, 2H), 2.31 (s, 1H), 2.26-2.22 (m, 1H), 1.94 (s, 3H), 1.81-1.61 ( m,8H), 1.32-1.08(m,12H), 1.00-0.79(m,13H).

The physical properties of compound (1-4-1) are as follows.

Transition temperature: C 49.6 I.

[Synthesis Example 3]

Synthesis of compound (1-4-2)

Step 1

Put compound (T-11) (15.0g), N,N-dimethyl-4-aminopyridine (DMAP) (9.33g), Michler's acid (9.54g) and methylene chloride (250ml) into In the reactor, cool to 0°C. N,N'-Dicyclohexylcarbodiimide (DCC) (15.7 g) was slowly added thereto, returned to room temperature and stirred for 12 hours. After the insoluble matter was separated by filtration, the reaction mixture was poured into water, and the aqueous layer was extracted with dichloromethane. The mixed organic layer was washed with water and dried with anhydrous magnesium sulfate. The solution was concentrated under reduced pressure. The residue and ethanol (250 ml) were put into the reactor and stirred at 70°C. After the insoluble matter was separated by filtration, the reaction mixture was poured into brine, and the aqueous layer was extracted with ethyl acetate. Dry the mixed organic layers with anhydrous magnesium sulfate. The solution was concentrated under reduced pressure, and the residue was purified by silica gel chromatography (volume ratio, heptane:toluene=1:1) to obtain compound (T-12) (10.2 g; 55%).

Step 2

Lithium aluminum hydride (0.6 g) and THF (100 ml) were put into the reactor and cooled in an ice bath. A solution of compound (T-12) (10.2 g) in THF (100 ml) was slowly added, returned to room temperature and stirred for 3 hours. After the insoluble matter was separated by filtration, the reaction mixture was poured into water, and the aqueous layer was extracted with ethyl acetate. The mixed organic layer was washed with salt water, and dried with anhydrous magnesium sulfate. The solution was concentrated under reduced pressure, and the residue was purified by silica gel chromatography (volume ratio, toluene:ethyl acetate=1:1) to obtain compound (T-13) (7.35 g; 81%).

Step 3

Put compound (T-13) (7.35g), triethylamine (3.75ml), N,N-dimethyl-4-aminopyridine (DMAP) (0.27g), methylene chloride (200ml) into Into the reactor, cool to 0°C. Triisopropylsilyl chloride (TIPSCl) (5.05ml) was slowly added dropwise, returned to room temperature and stirred for 24 hours. After the insoluble matter was separated by filtration, the reaction mixture was poured into water, and the aqueous layer was extracted with ethyl acetate. The mixed organic layer was washed with salt water, and dried with anhydrous magnesium sulfate. This solution was concentrated under reduced pressure, and the residue was purified by silica gel chromatography (volume ratio, toluene:ethyl acetate=19:1) to obtain compound (T-14) (6.50 g; 60%).

Step 4

The compound (T-14) (6.50 g), triethylamine (3.77 ml), and THF (200 ml) were put into the reactor and cooled to 0°C. Methacrylic chloride (2.00 ml) was slowly added dropwise thereto, returned to room temperature and stirred for 4 hours. After the insoluble matter was separated by filtration, the reaction mixture was poured into water, and the aqueous layer was extracted with toluene. The mixed organic layer was washed with water and dried with anhydrous magnesium sulfate. The solution was concentrated under reduced pressure, and the residue was purified by silica gel chromatography (volume ratio, toluene:heptane=1:1) to obtain compound (T-15) (4.70 g; 63%).

Step 5

The compound (T-15) (4.70 g) and THF (100 ml) were put into the reactor and cooled to 0°C. TBAF (1.00M; THF solution; 10.3 ml) was slowly added thereto, returned to room temperature and stirred for 1 hour. The reaction mixture was poured into water, and the aqueous layer was extracted with ethyl acetate. Use salt water to mix the organic layer It is washed and dried with anhydrous magnesium sulfate. The solution was concentrated under reduced pressure, and the residue was purified by silica gel chromatography (volume ratio, toluene:ethyl acetate=9:1) to obtain compound (T-16) (1.50 g; 45%).

Step 6

Using compound (T-16) (1.50 g) as a raw material, the compound (T-17) (1.51 g; 55%) was obtained by the same method as in the fourth step of Synthesis Example 2.

Step 7

Using compound (T-17) (1.51 g) as a raw material, the compound (1-4-2) (0.45 g; 45%) was obtained by the same method as in the fifth step of Synthesis Example 2.

The NMR analysis value of the obtained compound (1-4-2) is as follows.

¹ H-NMR: Chemical shift δ(ppm; CDCl ₃ ): 6.25(s,1H), 6.09(s,1H), 5.82(d,J=1.1Hz,1H), 5.55(s,1H), 5.22- 5.17(m,1H), 4.32-4.26(m,3H), 4.17-4.12(m,3H), 2.50(s,1H), 2.03-1.89(m,5H), 1.83-1.58(m,9H), 1.41-1.08 (m, 11H), 0.96-0.78 (m, 13H). The physical properties of compound (1-4-2) are as follows.

Transition temperature: C 61.2 I.

[Synthesis Example 4]

Synthesis of compound (1-23-2)

Step 1

Put compound (T-18) (20.0g) and THF (200ml) into the reactor, cool to -70°C, slowly add lithium diisopropylamine (LDA) (1.10M; THF solution; 68.0ml) dropwise , And stir for 1 hour. Methyl chloroformate (7.00 g) was slowly added thereto, returned to room temperature and stirred for 4 hours. After the insoluble matter was separated by filtration, the reaction mixture was poured into water, and the aqueous layer was extracted with toluene. The mixed organic layer was washed with water and dried with anhydrous magnesium sulfate. This solution was concentrated under reduced pressure, and the residue was purified by silica gel chromatography (volume ratio, toluene:heptane=9:1) to obtain compound (T-19) (19.4 g; 82%).

Step 2

Put lithium aluminum hydride (1.93 g) and THF (200 ml) into the reactor, and cool to 0°C. A THF (100 ml) solution of compound (T-19) (19.4 g) was slowly added thereto, returned to room temperature and stirred for 3 hours. After the insoluble matter was separated by filtration, the reaction mixture was poured into water, and the aqueous layer was extracted with ethyl acetate. The mixed organic layer was washed with water and dried with anhydrous magnesium sulfate. The solution was concentrated under reduced pressure, and the residue was purified by silica gel chromatography (volume ratio, toluene:ethyl acetate=1:1) to obtain compound (T-20) (6.0 g; 38%).

Step 3

The compound (T-20) (6.0 g), triethylamine (3.2 ml), and THF (100 ml) were put into the reactor and cooled to 0°C. Methacrylic chloride (1.8 ml) was slowly added thereto, returned to room temperature and stirred for 5 hours. After the insoluble matter was separated by filtration, the reaction mixture was poured into water, and the aqueous layer was extracted with ethyl acetate. The mixed organic layer was washed with water and dried with anhydrous magnesium sulfate. The solution was concentrated under reduced pressure, and the residue was purified by silica gel chromatography (volume ratio, toluene:ethyl acetate=9:1) to obtain compound (1-23-2) (2.5 g; 34%).

The NMR analysis value of the obtained compound (1-23-2) is as follows.

¹ H-NMR: Chemical shift δ(ppm; CDCl ₃ ): 6.10(s,1H), 5.57(d,J=1.1Hz,1H), 4.38(dd,J=11.4Hz,J=4.3Hz,1H) , 4.23(dd,J=11.3Hz,J=6.7Hz,1H), 3.71-3.68(m,1H), 3.63-3.60(m,1H), 1.97(s,1H), 1.94(s,3H), 1.82-1.62(m,9H), 1.41-1.18(m,7H), 1.14-0.79(m,16H).

The physical properties of compound (1-23-2) are as follows.

Transition temperature: C 68.4 S _A 89.3 I

[Synthesis Example 5]

Synthesis of compound (1-4-3)

Step 1

Put compound (T-7), 3,4-dihydro-2H-pyran (23.3g), pyridinium p-Toluenesulfonate (Pyridinium p-Toluenesulfonate, PPTS) (5.80g) into the reactor and add Stir at 50°C for 10 hours. After the insoluble matter was separated by filtration, the reaction mixture was poured into water, and the aqueous layer was extracted with dichloromethane. The mixed organic layer was washed with water and dried with anhydrous magnesium sulfate. The solution was concentrated under reduced pressure, and the residue was purified by silica gel chromatography (volume ratio, heptane:ethyl acetate=2:1) to obtain compound (T-21) (39.5 g; 80%).

Step 2

The compound (T-21) (39.5 g), THF (400 ml), and water (400 ml) were put into the reactor and cooled to 0°C. Lithium hydroxide monohydrate (15.4 g) was added thereto, returned to room temperature and stirred for 12 hours. The reaction mixture was poured into water, 6N hydrochloric acid (60 ml) was slowly added to make it acidic, and then the aqueous layer was extracted with ethyl acetate. The mixed organic layer was washed with water and dried with anhydrous magnesium sulfate. The solution was concentrated under reduced pressure to obtain compound (T-22) (32.6 g; 95%).

Step 3

The compound (1-23-2) (2.0 g), the compound (T-22) (1.18 g), DMAP (0.32 g), and dichloromethane (100 ml) were put into the reactor and cooled to 0°C. A solution of DCC (1.30 g) in dichloromethane (60 ml) was slowly added dropwise thereto, returned to room temperature and stirred for 12 hours. After the insoluble matter was separated by filtration, the reaction mixture was poured into water, and the aqueous layer was extracted with dichloromethane. The mixed organic layer was washed with water and dried with anhydrous magnesium sulfate. The solution was concentrated under reduced pressure, and the residue was purified by silica gel chromatography (volume ratio, toluene:ethyl acetate=19:1) to obtain compound (T-23) (2.37 g; 82%).

Step 4

The compound (T-23) (2.37g), pyridine p-toluenesulfonate (PPTS) (0.54g), THF (50ml) and methanol (50ml) were put into the reactor and stirred at 50°C for 5 hours. After the insoluble matter was separated by filtration, the reaction mixture was poured into water, and the aqueous layer was extracted with ethyl acetate. The mixed organic layer was washed with water and dried with anhydrous magnesium sulfate. The solution was concentrated under reduced pressure, and the residue was purified by silica gel chromatography (volume ratio, toluene:ethyl acetate=9:1) to obtain compound (1-4-3) (1.50 g; 75%).

The NMR analysis value of the obtained compound (1-4-3) is as follows.

¹ H-NMR: Chemical shift δ (ppm; CDCl ₃ ): 6.24 (s, 1H), 6.09 (s, 1H), 5.84 (s, 1H), 5.57 (s, 1H), 4.33-4.27 (m, 4H) ), 4.20-4.16(m,2H), 2.34-2.31(m,1H), 1.97-1.90(m,4H), 1.82-1.67(m,8H), 1.43-1.39(m,1H), 1.31-1.18 (m, 6H), 1.15-0.75 (m, 16H).

The physical properties of compound (1-4-3) are as follows.

Transition temperature: C 66.5 I

[Synthesis Example 6]

Synthesis of compound (1-24-1)

Step 1

Compound (T-24) (30.0g), ethanol (14.4ml), potassium phosphate (53.6g), copper iodide (1.60g), ethyl acetate (32.8g) and dimethyl sulfide (dimethyl sulfoxide, DMSO) (500ml) was put into the reactor and stirred at 80°C for 6 hours. After the insoluble matter was separated by filtration, the reaction mixture was poured into water, and the aqueous layer was extracted with toluene. The mixed organic layer was washed with water and dried with anhydrous magnesium sulfate. This solution was concentrated under reduced pressure, and the residue was purified by silica gel chromatography (volume ratio, toluene:heptane=4:1) to obtain compound (T-25) (19.5 g; 73%).

Step 2

Using the compound (T-25) (19.5 g) as a raw material, the compound (T-26) (16.2 g; 70%) was obtained by the same method as in the first step of Synthesis Example 4.

Step 3

Using the compound (T-26) (16.2 g) as a raw material, the compound (T-27) (6.0 g; 45%) was obtained by the same method as in the second step of Synthesis Example 4.

Step 4

Using compound (T-27) (6.0 g) as a raw material, the compound (1-24-1) (2.3 g; 31%) was obtained by the same method as in the third step of Synthesis Example 4.

The NMR analysis value of the obtained compound (1-24-1) is as follows.

¹ H-NMR: Chemical shift δ (ppm; CDCl ₃ ): 7.18-7.17 (m, 4H), 6.09 (s, 1H), 5.57 (s, 1H), 4.47-4.38 (m, 2H), 3.91-3.85 (m,2H), 3.19-3.14(m,1H), 2.44(tt,J=12.2Hz,J=3.0Hz,1H), 1.93-1.86(m,8H), 1.48-1.38(m,2H), 1.34-1.19(m,9H), 1.07-0.99(m,2H), 0.89(t,J=6.8Hz,3H).

The physical properties of compound (1-24-1) are as follows.

Transition temperature: C 36.1 I.

[Synthesis Example 7]

Synthesis of compound (1-5-2)

Step 1

Using the compound (1-24-1) (2.0 g) as a raw material, the compound (T-28) (2.2 g; 76%) was obtained by the same method as in the third step of Synthesis Example 5.

Step 2

Using compound (T-28) (2.2 g) as a raw material, the compound (1-5-2) (1.3 g; 70%) was obtained by the same method as in the fourth step of Synthesis Example 5.

The NMR analysis value of the obtained compound (1-5-2) is as follows.

¹ H-NMR: Chemical shift δ(ppm; CDCl ₃ ): 7.17-7.16(m,4H), 6.21(s,1H), 6.07(s,1H), 5.81(d,J=1.0Hz,1H), 5.55(s,1H), 4.46-4.39(m,4H), 4.27(d,J=6.2Hz,2H), 3.42-3.37(m,1H), 2.44(tt,J=12.2Hz,J=3.1Hz ,1H), 2.22-2.21(m,1H), 1.95(s,3H), 1.87-1.85(m,4H), 1.46-1.38(m,2H), 1.34-1.19(m,9H), 1.07-0.99 (m,2H), 0.89(t,J=7.0Hz,3H).

The physical properties of compound (1-5-2) are as follows.

Transition temperature: C 52.3 I.

[Synthesis Example 8]

Synthesis of compound (1-25-2)

Step 1

The compound (T-29) (30.0 g), triethyl phosphinyl acetate (33.0 g) and toluene (500 ml) were put into the reactor and cooled to 0°C. Sodium ethoxide (20% ethanol solution) (50.1 g) was slowly added dropwise thereto, returned to room temperature and stirred for 6 hours. After the insoluble matter was separated by filtration, the reaction mixture was poured into water, and the aqueous layer was extracted with toluene. The mixed organic layer was washed with water and dried with anhydrous magnesium sulfate. The solution was concentrated under reduced pressure, and the residue was purified by silica gel chromatography (volume ratio, toluene:heptane=4:1) to obtain compound (T-30) (32.8 g; 85%).

Step 2

Put compound (T-30) (32.8g), toluene (300ml), isopropanol (Iso Propyl Alcohol, IPA) (300ml) and Pd/C (0.55g) into the reactor, Stir for 12 hours under hydrogen atmosphere. After the insoluble matter was separated by filtration, the reaction mixture was poured into water, and the aqueous layer was extracted with toluene. The mixed organic layer was washed with water and dried with anhydrous magnesium sulfate. The solution was concentrated under reduced pressure, and the residue was purified by silica gel chromatography (volume ratio, toluene:heptane=4:1). Further purification was carried out by recrystallization from heptane to obtain compound (T-31) (16.8 g; 51%).

Step 3

Using the compound (T-31) (16.8 g) as a raw material, the compound (T-32) (14.1 g; 71%) was obtained by the same method as in the first step of Synthesis Example 4.

Step 4

Using compound (T-32) (14.1 g) as a raw material, the compound (T-33) (6.0 g; 52%) was obtained by the same method as in the second step of Synthesis Example 4.

Step 5

Using compound (T-33) (6.0 g) as a raw material, compound (1-25-2) (2.3 g; 32%) was obtained by the same method as in the third step of Synthesis Example 4.

The NMR analysis value of the obtained compound (1-25-2) is as follows.

¹ H-NMR: Chemical shift δ (ppm; CDCl ₃ ): 7.14-7.10 (m, 4H), 6.12 (s, 1H), 5.59 (s, 1H), 4.43-4.40 (m, 1H), 4.28-4.25 (m,1H), 3.75-3.64(m,2H), 2.55(t,J=7.6Hz,2H), 2.47-2.42(m,1H), 2.14(s,1H), 1.96-1.91(m,7H) ), 1.74-1.69(m,1H), 1.62-1.22(m,11H), 0.88(t,J=6.8Hz,3H).

The physical properties of compound (1-25-2) are as follows.

Transition temperature: C<-50.0 I.

[Synthesis Example 9]

Synthesis of compound (1-6-1)

Step 1

Using compound (1-25-1) (2.0 g) as a raw material, compound (T-34) (1.9 g; 68%) was obtained by the same method as in the third step of Synthesis Example 5.

Step 2

Using compound (T-34) (1.9 g) as a raw material, the compound (1-6-1) (1.2 g; 75%) was obtained by the same method as in the fourth step of Synthesis Example 5.

The NMR analysis value of the obtained compound (1-6-1) is as follows.

¹ H-NMR: Chemical shift δ (ppm; CDCl ₃ ): 7.13-7.10 (m, 4H), 6.27 (s, 1H), 6.11 (s, 1H), 5.86 (s, 1H), 5.58 (s, 1H) ), 4.40-4.32(m,4H), 4.25-4.20(m,2H), 2.56(t,J=7.6Hz,2H), 2.45(tt,J=12.1Hz,J=2.9Hz,1H), 2.35 -2.32(m,1H), 2.04-1.91(m,7H), 1.62-1.26(m,12H), 0.88(t,J=6.8Hz,3H).

The physical properties of compound (1-6-1) are as follows.

Transition temperature: C 35.8 I.

[Synthesis Example 10]

Synthesis of compound (1-23-3)

Step 1

Put 2-(1,3-dioxan-2-yl)ethyltriphenylphosphonium bromide (103.7g) and THF (500ml) into the reactor, cool to -30°C, and add tertiary butyl Potassium alkoxide (25.4g) and stirred for 1 hour. A THF (300 ml) solution of compound (T-35) (50.0 g) was slowly added dropwise thereto, returned to room temperature and stirred for 6 hours. Insoluble matter After filtration and separation, the reaction mixture was poured into water, and the aqueous layer was extracted with toluene. The mixed organic layer was washed with water and dried with anhydrous magnesium sulfate. The solution was concentrated under reduced pressure, and the residue was purified by silica gel chromatography (volume ratio, toluene:heptane=1:1) to obtain compound (T-36) (63.0 g; 92%).

Step 2

The compound (T-36) (63.0 g), toluene (500 ml), IPA (500 ml) and Pd/C (0.55 g) were put into the reactor and stirred for 16 hours under a hydrogen atmosphere. After the insoluble matter was separated by filtration, the reaction mixture was poured into water, and the aqueous layer was extracted with toluene. The mixed organic layer was washed with water and dried with anhydrous magnesium sulfate. The solution was concentrated under reduced pressure, and the residue was purified by silica gel chromatography (volume ratio, toluene:heptane=1:1) to obtain compound (T-37) (60.1 g; 95%).

Step 3

The compound (T-37) (60.1 g), formic acid (75.8 g), and toluene (1000 ml) were put in the reactor and stirred at 100°C for 6 hours. After the insoluble matter was separated by filtration, it was neutralized with an aqueous sodium hydrogen carbonate solution, and the aqueous layer was extracted with toluene. The mixed organic layer was washed with water and dried with anhydrous magnesium sulfate. The solution was concentrated under reduced pressure, and the residue was purified by silica gel chromatography with toluene to obtain compound (T-38) (45.0 g; 89%).

Step 4

Compound (T-38) (45.0g), potassium peroxymonosulfate (OXONE) (108.3 g) Put Dimethyl Formamide (DMF) (1000ml) into the reactor and stir at room temperature for 8 hours. After the insoluble matter was separated by filtration, the reaction mixture was poured into water, and the aqueous layer was extracted with ethyl acetate. The mixed organic layer was washed with water and dried with anhydrous magnesium sulfate. The solution was concentrated under reduced pressure to obtain compound (T-39) (28.5 g; 60%).

Step 5

The compound (T-39) (28.5 g), sulfuric acid (0.5 ml), and methanol (500 ml) were put into the reactor and stirred at 60°C for 5 hours. After filtering the insoluble matter, it was concentrated, and the residue was purified by silica gel chromatography with toluene to obtain compound (T-40) (22.3 g; 75%).

Step 6

Using the compound (T-40) (22.3 g) as a raw material, the compound (T-41) (18.3 g; 70%) was obtained by the same method as in the first step of Synthesis Example 4.

Step 7

Using the compound (T-41) (18.3 g) as a raw material, the compound (T-42) (5.9 g; 38%) was obtained by the same method as in the second step of Synthesis Example 4.

Step 8

Using the compound (T-42) (5.9 g) as a raw material, the compound (1-23-3) (2.4 g; 34%) was obtained by the same method as in the third step of Synthesis Example 4.

The NMR analysis value of the obtained compound (1-23-3) is as follows.

¹ H-NMR: Chemical shift δ (ppm; CDCl ₃ ): 6.11 (s, 1H), 5.81 (s, 1H), 4.31-4.28 (m, 1H), 4.17-4.14 (m, 1H), 3.63-3.58 (m,1H), 3.54-3.49(m,1H), 1.98-1.95(m,4H), 1.84-1.69(m,9H), 1.41-1.18(m,10H), 1.15-1.06(m,4H) , 1.02-0.80 (m, 13H).

The physical properties of compound (1-23-3) are as follows.

Transition temperature: C 33.6 S _A 101 I.

[Synthesis Example 11]

Synthesis of compound (1-4-4)

Step 1

Using the compound (1-23-3) (2.0 g) as a raw material, the compound (T-43) (2.1 g; 74%) was obtained by the same method as in the third step of Synthesis Example 5.

Step 2

Using compound (T-43) (2.1 g) as a raw material, the compound (1-4-4) (1.3 g; 72%) was obtained by the same method as in the fourth step of Synthesis Example 5.

The NMR analysis value of the obtained compound (1-4-4) is as follows.

¹ H-NMR: Chemical shift δ (ppm; CDCl ₃ ): 6.25 (s, 1H), 6.10 (s, 1H), 5.85 (d, J = 1.1 Hz, 1H), 5.57 (s, 1H), 4.33 ( d,J=6.5Hz,2H), 4.24-4.11(m,4H), 2.28(t,J=6.6Hz,1H), 2.09-2.03(m,1H), 1.94(s,3H), 1.75-1.67 (m,8H), 1.44-1.39(m,2H), 1.32-1.18(m,8H), 1.15-1.06(m,4H), 1.02-0.79(m,13H).

The physical properties of compound (1-4-4) are as follows.

Transition temperature: C 71.4 I.

[Synthesis Example 12]

Synthesis of compound (1-42-1)

Step 1

The compound (T-20) (2.0 g), the compound (T-22) (2.63 g), DMAP (0.78 g), and dichloromethane (100 ml) were put into the reactor and cooled to 0°C. A dichloromethane (60 ml) solution of DCC (2.92 g) was slowly added dropwise thereto, returned to room temperature and stirred for 12 hours. After the insoluble matter was separated by filtration, the reaction mixture was poured into water, and the aqueous layer was extracted with dichloromethane. The mixed organic layer was washed with water and dried with anhydrous magnesium sulfate. Put the solution in It was concentrated under reduced pressure, and the residue was purified by silica gel chromatography (volume ratio, toluene:ethyl acetate=9:1) to obtain compound (T-44) (2.83 g; 68%).

Step 2

The compound (T-44) (2.83 g), pyridine p-toluenesulfonate (PPTS) (1.09 g), THF (50 ml) and methanol (50 ml) were put into the reactor, and stirred at 50°C for 8 hours. After the insoluble matter was separated by filtration, the reaction mixture was poured into water, and the aqueous layer was extracted with ethyl acetate. The mixed organic layer was washed with water and dried with anhydrous magnesium sulfate. The solution was concentrated under reduced pressure, and the residue was purified by silica gel chromatography (volume ratio, toluene:ethyl acetate=1:1) to obtain compound (1-42-1) (1.47 g; 70%).

The NMR analysis value of the obtained compound (1-42-1) is as follows.

¹ H-NMR: Chemical shift δ (ppm; CDCl ₃ ): 6.24 (s, 2H), 5.82 (s, 2H), 4.35-4.31 (m, 6H), 4.22-4.19 (m, 2H), 2.36 (s ,2H), 1.97-1.91(s,1H), 1.82-1.63(m,8H), 1.43-1.18(m,7H), 1.15-0.79(m,16H).

The physical properties of compound (1-42-1) are as follows.

Transition temperature: C 102 I.

[Synthesis Example 13]

Synthesis of compound (1-43-1)

Step 1

Using the compound (T-27) (2.0 g) as a raw material, the compound (T-45) (2.7 g; 64%) was obtained by the same method as the first step of Synthesis Example 12.

Step 2

Using the compound (T-45) (2.7 g) as a raw material, the compound (1-43-1) (1.3 g; 65%) was obtained by the same method as in the second step of Synthesis Example 12.

The NMR analysis value of the obtained compound (1-43-1) is as follows.

¹ H-NMR: Chemical shift δ(ppm; CDCl ₃ ): 7.20-7.16(m,4H), 6.26(s,2H), 5.83(d,J=0.8Hz,2H), 4.46(d,J=6.6 Hz,4H), 4.28(d,J=6.3Hz,4H), 3.44-3.39(m,1H), 2.44(tt,J=12.2Hz,J=3.1Hz,1H), 2.16-2.13(m,2H ), 1.87-1.85(m,4H), 1.46-1.19(m,11H), 1.07-0.99(m,2H), 0.89(t,J=6.8Hz,3H).

The physical properties of compound (1-43-1) are as follows.

Transition temperature: C 65.8 I.

[Synthesis Example 14]

Synthesis of compound (1-44-1)

Step 1

Using the compound (T-33) (2.0 g) as a raw material, the compound (T-46) (2.5 g; 59%) was obtained by the same method as in the first step of Synthesis Example 12.

Step 2

Using the compound (T-46) (2.7 g) as a raw material, the compound (1-44-1) (1.1 g; 60%) was obtained by the same method as in the second step of Synthesis Example 12.

The NMR analysis value of the obtained compound (1-44-1) is as follows.

¹ H-NMR: Chemical shift δ(ppm; CDCl ₃ ): 7.14-7.10(m,4H), 6.27(s,2H), 5.87(d,J=1.1Hz,2H), 4.39-4.33(m,6H) ), 4.27-4.20(m,2H), 2.57-2.54(m,2H), 2.45(tt,J=12.2Hz,J=3.1Hz,1H), 2.38-2.35(m,2H), 2.05-1.91( m,5H), 1.63-1.26(m,11H), 0.88(t,J=6.8Hz,3H).

The physical properties of compound (1-44-1) are as follows.

Transition temperature: C 65.6 I.

[Synthesis Example 15]

Synthesis of compound (1-42-2)

Step 1

Using the compound (T-42) (2.0 g) as a raw material, the compound (T-47) (2.7 g; 67%) was obtained by the same method as in the first step of Synthesis Example 12.

Step 2

Using compound (T-47) (2.7 g) as a raw material, the compound (1-42-2) (1.3 g; 64%) was obtained by the same method as in the second step of Synthesis Example 12.

The NMR analysis value of the obtained compound (1-42-2) is as follows.

¹ H-NMR: Chemical shift δ (ppm; CDCl ₃ ): 6.25 (s, 2H), 5.85 (d, J = 1.1 Hz, 2H), 4.33 (d, J = 6.3 Hz, 4H), 4.25-4.22 ( m,2H), 4.18-4.14(m,2H), 2.30-2.28(m,2H), 2.11-2.06(m,1H), 1.75-1.67(m,8H), 1.44-1.39(m,2H), 1.32-0.79 (m, 25H).

The physical properties of compound (1-42-2) are as follows.

Transition temperature: C 85.7 S _A 125 I.

[Synthesis Example 16]

Synthesis of compound (1-24-2)

Step 1

The compound (T-24) (50.0 g) and THF (1000 ml) were put into the reactor and cooled to -70°C. Isopropylmagnesium chloride-lithium chloride (1.3M; THF solution; 130.0ml) was slowly added dropwise and stirred for 1 hour. DMF (13.0 ml) was added dropwise thereto, returned to room temperature and stirred for 4 hours. After the insoluble matter was separated by filtration, the reaction mixture was poured into water, and the aqueous layer was extracted with toluene. The mixed organic layer was washed with water and dried with anhydrous magnesium sulfate. This solution was concentrated under reduced pressure, and the residue was purified by silica gel chromatography (volume ratio, toluene:heptane=4:1) to obtain compound (T-48) (34.5 g; 95%).

Step 2

Put methoxymethyl-triphenylphosphonium chloride (54.9g) and THF (1000ml) into the reactor and cool to -30°C. Potassium tert-butoxide (18.0 g) was added and stirred for 1 hour. A THF (50 ml) solution of compound (T-48) (34.5 g) was added dropwise thereto, returned to room temperature and stirred for 5 hours. After the insoluble matter was separated by filtration, the reaction mixture was poured into water, and the aqueous layer was extracted with toluene. The mixed organic layer was washed with water and dried with anhydrous magnesium sulfate. The solution was concentrated under reduced pressure, and the residue was purified by silica gel chromatography (volume ratio, toluene:heptane=1:4) to obtain compound (T-49) (31.7 g; 83%).

Step 3

The compound (T-49) (31.7 g), formic acid (50.9 g), and toluene (1000 ml) were put in the reactor and stirred at 100°C for 6 hours. After the insoluble matter was separated by filtration, the reaction mixture was poured into water, neutralized with sodium bicarbonate water, and the aqueous layer was extracted with toluene. The mixed organic layer was washed with water and dried with anhydrous magnesium sulfate. The solution was concentrated under reduced pressure, and the residue was purified by silica gel chromatography (volume ratio, toluene:heptane=4:1) to obtain compound (T-50) (26.5 g; 88%).

Step 4

The compound (T-50) (26.5 g), triethyl phosphinyl acetate (26.2 g) and toluene (500 ml) were put into the reactor and cooled to 0°C. Sodium ethoxide (20% ethanol solution) (39.7 g) was slowly added dropwise thereto, returned to room temperature and stirred for 6 hours. After the insoluble matter was separated by filtration, the reaction mixture was poured into water, and toluene was used to The aqueous layer is extracted. The mixed organic layer was washed with water and dried with anhydrous magnesium sulfate. The solution was concentrated under reduced pressure, and the residue was purified by silica gel chromatography (volume ratio, toluene:heptane=9:1) to obtain compound (T-51) (30.6 g; 92%).

Step 5

The compound (T-51) (30.6 g), Pd/C (0.55 g), toluene (250 ml), and IPA (250 ml) were put into the reactor and stirred for 12 hours under a hydrogen atmosphere. After the insoluble matter was separated by filtration, the reaction mixture was poured into water, and the aqueous layer was extracted with toluene. The mixed organic layer was washed with water and dried with anhydrous magnesium sulfate. The solution was concentrated under reduced pressure, and the residue was purified by silica gel chromatography (volume ratio, toluene:heptane=9:1) to obtain compound (T-52) (29.2 g; 95%).

Step 6

The compound (T-52) (29.2 g) and THF (250 ml) were put into the reactor and cooled to -70°C. Slowly add lithium diisopropylamine (LDA) (1.1M; THF solution; 92.5 ml) dropwise. After stirring for 1 hour, benzyl chloromethyl ether (16.0 g) was added dropwise thereto, returning to room temperature and stirring for 12 hours. After the insoluble matter was separated by filtration, the reaction mixture was poured into water, and the aqueous layer was extracted with toluene. The mixed organic layer was washed with water and dried with anhydrous magnesium sulfate. The solution was concentrated under reduced pressure, and the residue was purified by silica gel chromatography (volume ratio, toluene:heptane=9:1) to obtain compound (T-53) (31.5 g; 80%).

Step 7

The compound (T-53) (31.5 g), palladium hydroxide (0.28 g), toluene (250 ml), and IPA (250 ml) were put into the reactor and stirred for 12 hours under a hydrogen atmosphere. After the insoluble matter was separated by filtration, the reaction mixture was poured into water, and the aqueous layer was extracted with toluene. The mixed organic layer was washed with water and dried with anhydrous magnesium sulfate. The solution was concentrated under reduced pressure, and the residue was purified by silica gel chromatography (volume ratio, toluene:ethyl acetate=4:1) to obtain compound (T-54) (23.3 g; 92%).

Step 8

Put compound (T-54) (23.3g), 3,4-dihydro-2H-pyran (5.8g), PPTS (pyridinium p-toluenesulfonate) (1.5g), and dichloromethane (500ml) Put into the reactor and stir for 8 hours at room temperature. The reaction mixture was poured into water, and the aqueous layer was extracted with dichloromethane. The mixed organic layer was washed with water and dried with anhydrous magnesium sulfate. The solution was concentrated under reduced pressure, and the residue was purified by silica gel chromatography (volume ratio, toluene:ethyl acetate=9:1) to obtain compound (T-55) (25.4 g; 89%).

Step 9

Lithium Aluminium Hydride (LAH) (1.2 g) and THF (300 ml) were put into the reactor and cooled to 0°C. A THF (100 ml) solution of compound (T-55) (25.4 g) was slowly added dropwise thereto, returned to room temperature and stirred for 3 hours. After the insoluble matter was separated by filtration, the reaction mixture was poured into water, and the aqueous layer was extracted with ethyl acetate. The mixed organic layer was washed with water and dried with anhydrous magnesium sulfate. Concentrate the solution under reduced pressure After shrinking, the residue was purified by silica gel chromatography (volume ratio, toluene:ethyl acetate=4:1) to obtain compound (T-56) (19.2 g; 83%).

Step 10

The compound (T-56) (19.2 g), triethylamine (7.6 ml) and THF (200 ml) were put into the reactor and cooled to 0°C. Methacrylic chloride (5.3 ml) was slowly added thereto, returned to room temperature and stirred for 5 hours. After the insoluble matter was separated by filtration, the reaction mixture was poured into water, and the aqueous layer was extracted with ethyl acetate. The mixed organic layer was washed with water and dried with anhydrous magnesium sulfate. This solution was concentrated under reduced pressure, and the residue was purified by silica gel chromatography (volume ratio, toluene:ethyl acetate=19:1) to obtain compound (T-57) (17.9 g; 80%).

Step 11

The compound (T-57) (17.9 g), pyridine p-toluenesulfonate (PPTS) (4.6 g), THF (200 ml) and methanol (200 ml) were put into the reactor, and stirred at 50°C for 6 hours. After the insoluble matter was separated by filtration, the reaction mixture was poured into water, and the aqueous layer was extracted with ethyl acetate. The mixed organic layer was washed with water and dried with anhydrous magnesium sulfate. The solution was concentrated under reduced pressure, and the residue was purified by silica gel chromatography (volume ratio, toluene:ethyl acetate=9:1) to obtain compound (1-24-2) (12.4 g; 84%).

The NMR analysis value of the obtained compound (1-24-2) is as follows.

¹ H-NMR: Chemical shift δ (ppm; CDCl ₃ ): 7.13-7.09 (m, 4H), 6.10 (s, 1H), 5.57 (s, 1H), 4.33-4.30 (m, 1H), 4.23-4.20 (m, 1H), 3.65-3.62 (m, 1H), 3.58-3.54 (m, 1H), 2.66 (t, J=8.0Hz, 2H), 2.45-2.39 (m, 1H), 1.94-1.81 (m ,8H), 1.74-1.60(m,2H), 1.46-1.19(m,12H), 1.07-0.99(m,2H), 0.89(t,J=6.9Hz,3H).

The physical properties of compound (1-24-2) are as follows.

Transition temperature: C -24.7 I.

[Synthesis Example 17]

Synthesis of compound (1-5-2)

Step 1

Using compound (1-24-2) (2.0 g) as a raw material, compound (T-58) (2.1 g; 74%) was obtained by the same method as in the third step of Synthesis Example 5.

Step 2

Using compound (T-58) (2.1 g) as a raw material, the compound (1-5-2) (1.4 g; 78%) was obtained by the same method as in the fourth step of Synthesis Example 5.

The NMR analysis value of the obtained compound (1-5-2) is as follows.

¹ H-NMR: Chemical shift δ (ppm; CDCl ₃ ): 7.14-7.08 (m, 4H), 6.24 (s, 1H), 6.10 (s, 1H), 5.85 (s, 1H), 5.57 (s, 1H) ), 4.32(d,J=6.1Hz,2H), 4.27-4.18(m,4H), 2.67(t,J=7.4Hz,2H), 2.45-2.40(m,2H), 2.18-2.12(m, 1H), 1.93 (s, 3H), 1.88-1.84 (m, 4H), 1.77-1.72 (m, 2H), 1.46-1.38 (m, 2H), 1.34-1.19 (m, 9H), 1.07-0.99 ( m,2H), 0.89(t,J=6.8Hz,3H).

The physical properties of compound (1-5-2) are as follows.

Transition temperature: C -30.2 S _A -26.3 I.

[Synthesis Example 18]

Synthesis of compound (1-25-2)

Step 1

Put methoxymethyl-triphenylphosphonium chloride (84.2g) and THF (1000ml) into the reactor and cool to -30°C. Potassium tert-butoxide (27.6g) was added and stirred for 1 hour. Compound (T-29) (50.0g) in THF (500ml) was added dropwise Liquid, return to room temperature and stir for 5 hours. After the insoluble matter was separated by filtration, the reaction mixture was poured into water, and the aqueous layer was extracted with toluene. The mixed organic layer was washed with water and dried with anhydrous magnesium sulfate. The solution was concentrated under reduced pressure, and the residue was purified by silica gel chromatography (volume ratio, toluene:heptane=1:4) to obtain compound (T-59) (46.3 g; 83%).

Step 2

The compound (T-59) (46.3 g), p-toluenesulfonic acid (PTSA) (3.2 g), and toluene (1000 ml) were put into the reactor and stirred at 100°C for 12 hours. After the insoluble matter was separated by filtration, the reaction mixture was poured into water, and the aqueous layer was extracted with toluene. The mixed organic layer was washed with water and dried with anhydrous magnesium sulfate. The solution was concentrated under reduced pressure, and the residue was purified by silica gel chromatography (volume ratio, toluene:heptane=1:1) to obtain compound (T-60) (49.2 g; 95%).

Step 3

The compound (T-60) (49.2 g), formic acid (74.4 g), and toluene (1000 ml) were put in the reactor and stirred at room temperature for 8 hours. After the insoluble matter was separated by filtration, the reaction mixture was poured into water and neutralized with sodium bicarbonate water. The aqueous layer was extracted with toluene, the mixed organic layer was washed with water, and dried with anhydrous magnesium sulfate. The solution was concentrated under reduced pressure, and the residue was purified by silica gel chromatography (volume ratio, toluene:heptane=1:1) to obtain compound (T-61) (35.0 g; 84%).

Step 4

Put methoxymethyl-triphenylphosphonium chloride (55.7g) and THF (1000ml) into the reactor and cool to -30°C. Potassium tert-butoxide (18.2 g) was added and stirred for 1 hour. A solution of compound (T-61) (35.0 g) in THF (500 ml) was added dropwise thereto, returned to room temperature and stirred for 5 hours. After the insoluble matter was separated by filtration, the reaction mixture was poured into water, and the aqueous layer was extracted with toluene. The mixed organic layer was washed with water and dried with anhydrous magnesium sulfate. This solution was concentrated under reduced pressure, and the residue was purified by silica gel chromatography (volume ratio, toluene:heptane=1:4) to obtain compound (T-62) (36.5 g; 94%).

Step 5

The compound (T-62) (36.5 g), formic acid (58.6 g), and toluene (1000 ml) were put in the reactor, and stirred at 100°C for 4 hours. After the insoluble matter was separated by filtration, the reaction mixture was poured into water and neutralized with sodium bicarbonate water. The aqueous layer was extracted with toluene, the mixed organic layer was washed with water, and dried with anhydrous magnesium sulfate. The solution was concentrated under reduced pressure, and the residue was purified by silica gel chromatography (volume ratio, toluene:heptane=1:1) to obtain compound (T-63) (33.0 g; 95%).

Step 6

Using the compound (T-63) (33.0 g) as a raw material, the compound (T-64) (38.2 g; 92%) was obtained by the same method as in the fourth step of Synthesis Example 16.

Step 7

Using compound (T-64) (38.2 g) as a raw material, the compound (T-65) (18.7 g; 48%) was obtained by the same method as in the fifth step of Synthesis Example 16.

Step 8

Using compound (T-65) (18.7 g) as a raw material, the compound (T-66) (21.5 g; 85%) was obtained by the same method as in the sixth step of Synthesis Example 16.

Step 9

Using the compound (T-66) (21.5 g) as a raw material, the compound (T-67) (15.6 g; 90%) was obtained by the same method as in the seventh step of Synthesis Example 16.

Step 10

Using compound (T-67) (15.6 g) as a raw material, the compound (T-68) (16.8 g; 88%) was obtained by the same method as in the eighth step of Synthesis Example 16.

Step 11

Using compound (T-68) (16.8 g) as a raw material, the compound (T-69) (13.0 g; 85%) was obtained by the same method as in the ninth step of Synthesis Example 16.

Step 12

Using the compound (T-69) (13.0 g) as a raw material, the compound (T-70) (11.6 g; 77%) was obtained by the same method as in the 10th step of Synthesis Example 16.

Step 13

Using compound (T-70) (11.6 g) as a raw material, compound (1-25-2) (7.8 g; 82%) was obtained by the same method as in the 11th step of Synthesis Example 16.

The NMR analysis value of the obtained compound (1-25-2) is as follows.

¹ H-NMR: Chemical shift δ (ppm; CDCl ₃ ): 7.11-7.08 (m, 4H), 6.11 (s, 1H), 5.57 (s, 1H), 4.31-4.28 (m, 1H), 4.19-4.16 (m,1H), 3.63-3.60(m,1H), 3.55-3.52(m,1H), 1.95(s,3H), 1.89-1.81(m,5H), 1.62-1.56(m,2H), 1.47 -1.28(m,12H), 1.09-1.01(m,2H), 0.88(t,J=6.7Hz,3H).

The physical properties of compound (1-25-2) are as follows.

Transition temperature: C<-50 I.

[Synthesis Example 19]

Synthesis of compound (1-6-2)

Step 1

Using compound (1-25-2) (3.0 g) as a raw material, compound (T-71) (3.2 g; 75%) was obtained by the same method as in the third step of Synthesis Example 5.

Step 2

Using compound (T-71) (3.2 g) as a raw material, the compound (1-6-2) (1.9 g; 70%) was obtained by the same method as in the fourth step of Synthesis Example 5.

The NMR analysis value of the obtained compound (1-6-2) is as follows.

¹ H-NMR: Chemical shift δ (ppm; CDCl ₃ ): 7.12-7.08 (m, 4H), 6.26 (s, 1H), 6.11 (s, 1H), 5.86 (s, 1H), 5.58 (s, 1H) ), 4.34(d,J=6.5Hz,2H), 4.26-4.14(m,4H), 2.55(t,J=7.8Hz,2H), 2.45-2.40(m,1H), 2.34(s,1H) , 2.13-2.08(m,1H), 1.95(s,3H), 1.90-1.84(m,4H), 1.63-1.56(m,2H), 1.48-1.39(m,4H), 1.35-1.27(m, 7H), 1.09-1.01 (m, 2H), 0.88 (t, J=6.8Hz, 3H).

The physical properties of compound (1-6-2) are as follows.

Transition temperature: C 35.9 I.

[Synthesis Example 20]

Synthesis of compound (1-28-1)

Step 1

Using the compound (T-72) (50.0 g) as a raw material, the compound (T-73) (31.8 g; 70%) was obtained by the same method as in the first step of Synthesis Example 6.

Step 2

Using the compound (T-73) (31.8 g) as a raw material, the compound (T-74) (26.2 g; 72%) was obtained by the same method as in the second step of Synthesis Example 6.

Step 3

Using the compound (T-74) (26.2 g) as a raw material, the compound (T-75) (10.1 g; 46%) was obtained by the same method as in the third step of Synthesis Example 6.

Step 4

Using compound (T-75) (10.1g) as a raw material, by combining with the synthesis example 6 In the same manner as in the fourth step, compound (1-28-1) (3.8 g; 32%) was obtained.

The NMR analysis value of the obtained compound (1-28-1) is as follows.

¹ H-NMR: Chemical shift δ (ppm; CDCl ₃ ): 7.18-7.16 (m, 4H), 6.09 (s, 1H), 5.57 (s, 1H), 4.47-4.38 (m, 2H), 3.91-3.83 (m, 2H), 3.20-3.14 (m, 1H), 2.45-2.40 (m, 1H), 1.97-1.72 (m, 12H), 1.42-0.82 (m, 22H).

The physical properties of compound (1-28-1) are as follows.

Transition temperature: C 46.3 I.

[Synthesis Example 21]

Synthesis of compound (1-9-1)

Step 1

Using the compound (1-28-1) (3.0 g) as a raw material, the compound (T-76) (3.1 g; 75%) was obtained by the same method as in the third step of Synthesis Example 5.

Step 2

Using compound (T-76) (3.1 g) as a raw material, the compound (1-9-1) (1.9 g; 71%) was obtained by the same method as in the fourth step of Synthesis Example 5.

The NMR analysis value of the obtained compound (1-9-1) is as follows.

¹ H-NMR: Chemical shift δ (ppm; CDCl ₃ ): 7.17 (s, 4H), 6.21 (s, 1H), 6.07 (s, 1H), 5.80 (s, 1H), 5.56 (s, 1H), 4.46-4.39(m,4H), 4.27(d,J=6.6Hz,2H), 3.42-3.37(m,1H), 2.45-2.39(m,1H), 2.12(t,J=6.6Hz,1H) , 1.91-1.72(m,11H), 1.46-0.95(m,16H), 0.89-0.82(m,5H).

The physical properties of compound (1-9-1) are as follows.

Transition temperature: C 80.0 I.

[Synthesis Example 22]

Synthesis of compound (1-23-4)

Step 1

The compound (T-77) (50.0 g), triethyl phosphinyl acetate (48.3 g) and toluene (500 ml) were put into the reactor and cooled to 0°C. Sodium ethoxide (20% ethanol solution) (73.3 g) was slowly added dropwise thereto, returned to room temperature and stirred for 6 hours. After the insoluble matter was separated by filtration, the reaction mixture was poured into water, and toluene was used to The aqueous layer is extracted. The mixed organic layer was washed with water and dried with anhydrous magnesium sulfate. This solution was concentrated under reduced pressure, and the residue was purified by silica gel chromatography (volume ratio, toluene:heptane=9:1) to obtain compound (T-78) (60.7 g; 97%).

Step 2

The compound (T-78) (60.7 g), Pd/C (0.51 g), toluene (500 ml), and IPA (50 ml) were put into the reactor and stirred for 12 hours under a hydrogen atmosphere. After the insoluble matter was separated by filtration, the reaction mixture was poured into water, and the aqueous layer was extracted with toluene. The mixed organic layer was washed with water and dried with anhydrous magnesium sulfate. This solution was concentrated under reduced pressure, and the residue was purified by silica gel chromatography (volume ratio, toluene:heptane=9:1), and then purified by recrystallization from a solvent mixture (solmix) to obtain Compound (T-79) (33.6 g; 55%).

Step 3

Using compound (T-79) (33.6 g) as a raw material, compound (T-80) (38.8 g; 86%) was obtained by the same method as in the sixth step of Synthesis Example 16.

Step 4

Using the compound (T-80) (38.8 g) as a raw material, the compound (T-81) (29.8 g; 95%) was obtained by the same method as in the seventh step of Synthesis Example 16.

Step 5

Using the compound (T-81) (29.8 g) as a raw material, the compound (T-82) (34.6 g; 95%) was obtained by the same method as in the eighth step of Synthesis Example 16.

Step 6

Using the compound (T-82) (34.6 g) as a raw material, the compound (T-83) (30.5 g; 97%) was obtained by the same method as in the ninth step of Synthesis Example 16.

Step 7

Using the compound (T-83) (30.5 g) as a raw material, the compound (T-84) (26.6 g; 75%) was obtained by the same method as in the 10th step of Synthesis Example 16.

Step 8

Using compound (T-84) (26.6 g) as a raw material, the compound (1-23-4) (18.3 g; 83%) was obtained by the same method as in the 11th step of Synthesis Example 16.

The NMR analysis value of the obtained compound (1-23-4) is as follows.

¹ H-NMR: Chemical shift δ (ppm; CDCl ₃ ): 6.10 (s, 1H), 5.57 (s, 1H), 4.40-4.37 (m, 1H), 4.24-4.20 (m, 1H), 3.69-3.61 (m,2H), 1.9-1.94(m,4H), 1.78-1.58(m,9H), 1.43-1.37(m,1H), 1.32-1.02(m,17H), 0.90-0.79(m,9H) .

The physical properties of compound (1-23-4) are as follows.

Transition temperature: C 54.5 S _A 81.0 I.

[Synthesis Example 23]

Synthesis of compound (1-4-5)

Step 1

Using compound (1-23-4) (3.0 g) as a raw material, compound (T-85) (3.3 g; 78%) was obtained by the same method as in the third step of Synthesis Example 5.

Step 2

Using compound (T-85) (3.3 g) as a raw material, the compound (1-4-5) (2.1 g; 75%) was obtained by the same method as in the fourth step of Synthesis Example 5.

The NMR analysis value of the obtained compound (1-4-5) is as follows.

¹ H-NMR: Chemical shift δ (ppm; CDCl ₃ ): 6.24 (s, 1H), 6.09 (s, 1H), 5.84 (s, 1H), 5.56 (s, 1H), 4.33-4.28 (m, 4H) ), 4.20-4.16(m,2H), 2.28(t,J=6.6Hz,1H), 1.97-1.91(m,4H), 1.79-1.69(m,8H), 1.47-1.41(m,1H), 1.32-1.07(m,17H), 0.90-0.82(m,9H).

The physical properties of compound (1-4-5) are as follows.

Transition temperature: C 64.0 I.

The examples of the composition are shown below. The component compounds are represented by symbols based on the definition in Table 3 below. In Table 3, the three-dimensional configuration related to 1,4-cyclohexylene 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 crystalline compound is the weight percentage (% by weight) based on the weight of the liquid crystal composition containing no additives. Finally, the characteristic values of the composition are summarized.

Table 3 Representation method of compounds using symbols

R-(A ₁ )-Z ₁ -． . . . . Z _n -(A _n )-R'

Examples of components

1. Raw materials

A composition in which a compound having a polymerizable group and a polar group in the branched structure of the molecular terminal is added to the element without the alignment film is injected. After irradiating ultraviolet rays, the vertical alignment of the liquid crystal molecules in the device was studied. First, the raw materials will be described. The raw materials are the composition (M1) to the composition (M18), the compound (PC-1) to the compound (PC-28), and the polymerizable compound (RM-1 ) To polymerizable compounds (RM-8), listed in order.

[Composition M1]

NI=73.2℃; Tc<-20℃; △n=0.113; △ε=-4.0; Vth=2.18V; η=22.6mPa. s.

[Composition M2]

NI=82.8℃; Tc<-30℃; △n=0.118; △ε=-4.4; Vth=2.13V; η=22.5mPa. s.

[Composition M3]

NI=78.1℃; Tc<-30℃; △n=0.107; △ε=-3.2; Vth=2.02V; η=15.9mPa. s.

[Composition M4]

NI=88.5℃; Tc<-30℃; △n=0.108; △ε=-3.8; Vth=2.25V; η=24.6mPa. s;

[Composition M5]

NI=81.1℃; Tc<-30℃; △n=0.119; △ε=-4.5; Vth=1.69V; η=31.4mPa. s.

[Composition M6]

NI=98.8℃; Tc<-30℃; △n=0.111; △ε=-3.2; Vth=2.47V; η=23.9mPa. s.

[Composition M7]

NI=77.5℃; Tc<-30℃; △n=0.084; △ε=-2.6; Vth=2.43V; η=22.8mPa. s.

[Composition M8]

NI=70.6℃; Tc<-20℃; △n=0.129; △ε=-4.3; Vth=1.69V; η=27.0mPa. s.

[Composition M9]

NI=93.0℃; Tc<-30℃; △n=0.123; △ε=-4.0; Vth=2.27V; η=29.6mPa. s.

[Composition M10]

NI=87.6℃; Tc<-30℃; △n=0.126; △ε=-4.5; Vth=2.21V; η=25.3 mPa. s.

[Composition M11]

NI=93.0℃; Tc<-20℃; △n=0.124; △ε=-4.5; Vth=2.22V; η=25.0mPa. s.

[Composition M12]

3-HB(2F,3F)-O2 (2-1) 7%

NI=76.4℃; Tc<-30℃; △n=0.104; △ε=-3.2; Vth=2.06V; η=15.6mPa. s.

[Composition M13]

NI=78.3℃; Tc<-20℃; △n=0.103; △ε=-3.2; Vth=2.17V; η=17.7mPa. s.

[Composition M14]

NI=81.2℃; Tc<-20℃; △n=0.107; △ε=-3.2; Vth=2.11V; η=15.5mPa. s.

[Composition M15]

NI=88.7℃; Tc<-30℃; △n=0.115; △ε=-1.9; Vth=2.82V; η=17.3mPa. s.

[Composition M16]

NI=89.9℃; Tc<-20℃; △n=0.122; △ε=-4.2; Vth=2.16V; η=23.4mPa. s.

[Composition M17]

NI=77.1℃; Tc<-20℃; △n=0.101; △ε=-3.0; Vth=2.04V; η=13.9mPa. s.

[Composition M18]

NI=75.9℃; Tc<-20℃; △n=0.114; △ε=-3.9; Vth=2.20V; η=24.7mPa. s.

[Composition M19]

NI=74.2℃; Tc<-20℃; △n=0.103; △ε=-2.5; Vth=2.36V; η=18.4mPa. s.

[Composition M20]

NI=74.9℃; Tc<-20℃; △n=0.102; △ε=-2.8; Vth=2.30V; η=19.2mPa. s.

[Composition M21]

NI=76.5℃; Tc<-20℃; △n=0.098; △ε=-3.0; Vth=2.15V; η=16.2mPa. s.

[Composition M22]

NI=75.3℃; Tc<-20℃; △n=0.102; △ε=-2.6; Vth=2.41V; η=17.5mPa. s.

The following compounds (PC-1) to (PC-28) having a polymerizable group and a polar group in the branched structure of the molecular terminal were used as the first additive.

Change the following polymerizable compound (RM-1) to polymerizable compound (RM-8) Used as a second additive.

2. Vertical alignment of liquid crystal molecules

Example 1

A compound (PC-1) having a polymerizable group and a polar group in the branched structure of the molecular terminal was added to the composition (M1) at a ratio of 5% by weight. The mixture was injected on a hot stage at 100° C. into an element with a distance (cell gap) of 4.0 μm between two glass substrates and no alignment film. By using the ultra-high pressure mercury lamp USH-250-BY (manufactured by Ushio Motor) to irradiate the device with ultraviolet rays (28J), the compound having a polymerizable group and a polar group (PC-1 ) Perform polymerization. This element was placed in a polarizing microscope in which a polarizer and an analyzer were arranged in parallel, and light was irradiated to the element from below to observe whether there was light leakage. When the liquid crystal molecules are fully aligned and light does not pass through the device, the vertical alignment is judged to be "good". When the light passing through the element is observed, it is indicated as "bad".

Example 2 to Example 55 and Comparative Example 1 to Comparative Example 2

A mixture of the composition and a compound having a polymerizable group and a polar group in the branch structure at the molecular terminal is used to produce an element without an alignment film. In the same manner as in Example 1, the presence or absence of light leakage was observed. The results are summarized in Table 4 and Table 5. In Example 18, the polymerizable compound (RM-1) was also added in a ratio of 0.5% by weight. In Comparative Example 1, for comparison, the following polar compound (A-1) described in Patent Document 5 was selected. Since this compound does not have a branched structure at the molecular end, it is different from the compound (1-1).

As can be seen from Tables 4 and 5, in Examples 1 to 55, although the type of the composition or the first additive and the concentration of the polar compound were changed, no light leakage was observed. This result shows that even if there is no alignment film in the device, the vertical alignment is good, and the liquid crystal molecules are aligned stably. In Example 18 and Example 40, a polymerizable compound (RM-1) was further added as a second additive, but the same structure was obtained. fruit. On the other hand, in Comparative Example 1 and Comparative Example 2, light leakage was observed. This result indicates that the vertical alignment is not good.

3. Compatibility of polar compounds

The stability at room temperature of the mixture of the liquid crystal composition and the first additive obtained in the example was evaluated. After mixing, it was isotropic at 100°C and left to cool to 25°C. The presence or absence of precipitation was confirmed after half a day at room temperature. As a result, precipitation was not confirmed in the mixture of Example 1 to Example 55, and the compatibility of the first additive was good. On the other hand, precipitation was confirmed in the mixture of Comparative Example 1 to Comparative Example 2, and the compatibility of the polar compound was poor.

From the above results, it can be seen that a polymer produced from a compound having a polymerizable group and a polar group in the branched structure of the molecular terminal plays an important role in the vertical alignment of liquid crystal molecules, and also improves the compatibility with the liquid crystal composition. This tendency is the same even when the compounds shown in Synthesis Example 1 to Synthesis Example 23 other than the compound (PC-1) to the compound (PC-28) shown in Table 4 and Table 5 are used. Therefore, if the liquid crystal composition of the present invention is used, it is possible to obtain an AM device having characteristics such as a short response time, a large voltage retention rate, a low threshold voltage, a large contrast ratio, and a long life. Furthermore, a liquid crystal display element having a liquid crystal composition having a high upper limit temperature of the nematic phase, a low lower limit temperature of the nematic phase, low viscosity, appropriate optical anisotropy, and negative dielectric properties can be obtained. Among the characteristics of high anisotropy, high specific resistance, high stability to ultraviolet light, and high stability to heat, at least one characteristic is satisfied.

[Industrial availability]

The liquid crystal composition of the present invention can be controlled in a device without an alignment film The alignment of liquid crystal molecules can be used in LCD projectors, LCD monitors, LCD TVs, etc.

Claims (23)

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

In the formula (1-1), R ¹ is an alkyl group having 1 to 15 carbons. In the R ¹ , at least one -CH ₂ -may be substituted with -O- or -S-, and at least one -CH ₂ CH ₂ -May be substituted by -CH=CH- or -C≡C-, at least one hydrogen may be substituted by halogen; ring A ¹ and ring A ^{2 are} independently 1,4-cyclohexylene or 1,4-cyclohexene Base, 1,4-phenylene, naphthalene-2,6-diyl, decahydronaphthalene-2,6-diyl, 1,2,3,4-tetrahydronaphthalene-2,6-diyl, tetrahydronaphthalene-2,6-diyl Hydropyran-2,5-diyl, 1,3-dioxane-2,5-diyl, pyrimidine-2,5-diyl, pyridine-2,5-diyl, pyridine-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-tetradecahydrocyclopenta[a]phenanthrene-3,17-diyl, in these rings, at least one hydrogen can be fluorine, chlorine, carbon Alkyl having 1 to 12, alkenyl having 2 to 12, alkoxy having 1 to 11, or alkenyl having 2 to 11, in these groups, at least one hydrogen may be substituted by fluoro or chloro substituent; a is 0, 1,. 4; Z is a single bond or ^an alkylene group having a carbon number of 1-6, Z is a ^1, at least one -CH ₂ - may be -O -, -CO-, -COO-, -OCO-, or -OCOO- substitution, at least one -CH ₂ CH ₂ -can be substituted by -CH=CH- or -C≡C-, at least one hydrogen in Z ¹ can be substituted by fluorine or chlorine; Sp ¹ is a single bond or a C 1-10 alkylene group, which Sp ^1, at least one -CH ₂ - may be -O -, - CO -, - COO -, - OCO -Or -OCOO- substituted, at least one -CH ₂ CH ₂ -can be substituted by -CH=CH- or -C≡C-, at least one hydrogen in Sp ¹ can be replaced by halogen, and at least one hydrogen in Sp ¹ can be replaced by Substitution by a group selected from the group represented by the formula (1a);

In formula (1a), Sp ¹² is a single bond or an alkylene group having 1 to 10 carbon atoms, and in the Sp ¹² , at least one -CH ₂ -can pass through -O-, -CO-, -COO-, -OCO -Or -OCOO- substitution, at least one -CH ₂ CH ₂ -can be substituted by -CH=CH- or -C≡C-, at least one hydrogen in Sp ¹² can be substituted by halogen; M ¹¹ and M ^{12 are} independently Hydrogen, halogen, alkyl having 1 to 5 carbons, or alkyl having 1 to 5 carbons in which at least one hydrogen is substituted by halogen; R ¹² is an alkyl having 1 to 15 carbons, and at least one of R ¹² -CH ₂ -may be substituted by -O- or -S-, at least one -CH ₂ CH ₂ -may be substituted by -CH=CH- or -C≡C-, at least one hydrogen may be substituted by halogen; formula (1- In 1), P ¹¹ is a group selected from the groups represented by formula (1e) and formula (1f);

In formula (1e) and formula (1f), Sp ¹³ is a single bond or an alkylene having 1 to 10 carbon atoms, and in the Sp ¹³ , at least one -CH ₂ -can be controlled by -O-, -NH-,- CO-, -COO-, -OCO-, or -OCOO- substituted, at least one -CH ₂ CH ₂ -can be substituted by -CH=CH- or -C≡C-, at least one hydrogen in Sp ¹³ can be substituted by halogen ; M ¹³ and M ^{14 are} independently hydrogen, halogen, alkyl with 1 to 5 carbons, or alkyl with 1 to 5 carbons in which at least one hydrogen is substituted by halogen; R ¹³ is selected from formula (1g), formula (1h), and the group in the group represented by formula (1i);

In formula (1g), formula (1h), and formula (1i), Sp ¹⁴ and Sp ^{15 are} independently a single bond or an alkylene group having 1 to 10 carbon atoms, and in the alkylene group, at least one -CH ₂ -Can be substituted by -O-, -NH-, -CO-, -COO-, -OCO-, or -OCOO-, at least one -CH ₂ CH ₂ -can be -CH=CH- or -C≡C- Substitution, at least one hydrogen can be replaced by halogen; In formula (1g) and formula (1i), S ¹ is >CH- or >N-, S ² is >C< or >Si<; X ¹ is -OH,- NH ₂ , -OR ¹⁵ , -N(R ¹⁵ ) ₂ , -COOH, -SH, -B(OH) ₂ , or -Si(R ¹⁵ ) ₃ ; -OR ¹⁵ , -N(R ¹⁵ ) ₂ , and In -Si(R ¹⁵ ) ₃ , R ¹⁵ is hydrogen or an alkyl group having 1 to 10 carbons. In said R ¹⁵ , at least one -CH ₂ -may be substituted by -O-, and at least one -CH ₂ CH _2- It may be substituted by -CH=CH-, and at least one hydrogen in R ¹⁵ may be substituted by halogen. The liquid crystal composition according to claim 1, wherein the first additive is at least one polymerizable compound selected from the group of compounds represented by formula (1-2) to formula (1-3),

In formula (1-2) and formula (1-3), R ¹ is an alkyl group having 1 to 12 carbons. In the alkyl group, at least one -CH ₂ -may be substituted by -O-, and at least one -CH ₂ CH ₂ -may be substituted by -CH=CH- or -C≡C-, in these groups, at least one hydrogen may be substituted by fluorine; ring A ¹ and ring A ^{2 are} independently 1,4-cyclohexylene , 1,4-cyclohexenylene, 1,4-phenylene, naphthalene-2,6-diyl, tetrahydropyran-2,5-diyl, 1,3-dioxane-2, 5-diyl, phenanthrene-2,7-diyl, phenanthrene-2,7-diyl, perhydrocyclopenta[a]phenanthrene-3,17-diyl, or 2,3,4,7,8 ,9,10,11,12,13,14,15,16,17-tetradecahydrocyclopenta[a]phenanthrene-3,17-diyl, in these rings, at least one hydrogen can be fluorine, carbon Alkyl having 1 to 8, alkenyl having 2 to 8, alkoxy having 1 to 7, or alkenyl having 2 to 7, in these groups, at least one hydrogen may be substituted by fluoro substituents; a is 0, 1,. 4; Z is a single bond or ^an alkylene group having a carbon number of 1-6, Z is a ^1, at least one -CH ₂ - may be -O-, -CO-, -COO-, -OCO-, or -OCOO- substituted, at least one -CH ₂ CH ₂ -may be substituted with -CH=CH- or -C≡C-, in these groups, at least one hydrogen Can be substituted by fluorine or chlorine; l is 0, 1, 2, 3, 4, 5, or 6, and at least one -CH ₂ -of the alkylene group can be substituted by -O-, -CO-, -COO-, -OCO- or -OCOO- substitution, at least one -CH ₂ CH ₂ -may be substituted by -CH=CH- or -C≡C-, in these groups, at least one hydrogen may be substituted by fluorine; Sp ¹² is A single bond or an alkylene having 1 to 5 carbon atoms, in which at least one -CH ₂ -may be substituted by -O-, -CO-, -COO-, -OCO-, or -OCOO-, At least one -CH ₂ CH ₂ -may be substituted by -CH=CH- or -C≡C-, in these groups, at least one hydrogen may be substituted by fluorine; M ¹¹ and M ^{12 are} independently hydrogen, fluorine, methyl Group, ethyl group, or trifluoromethyl group; R ¹² is hydrogen or an alkyl group having 1 to 5 carbons. In the alkyl group, at least one -CH ₂ -may be substituted by -O- or -S-, 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; Sp ¹³ is a single bond or an alkylene having 1 to 5 carbon atoms In the alkylene group, at least one -CH ₂ -can be substituted by -O-, -CO-, or -COO-, and at least one -CH ₂ CH ₂ -can be -CH=CH- or -C≡ C-substitution, in these groups, at least one hydrogen can be replaced by fluorine; M ¹³ and M ^{14 are} independently hydrogen, fluorine, methyl, ethyl, or trifluoromethyl; Sp ¹⁴ is a single bond or carbon number 1 to 5 alkylene groups, In the alkylene, at least one -CH ₂ -may be substituted by -O-, -CO-, or -COO-, and at least one -CH ₂ CH ₂ -may be -CH=CH- or -C≡C- Substitution, in these groups, at least one hydrogen may be replaced by fluorine; X ¹ is -OH or -N(R ¹⁵ ) ₂ ; in -N(R ¹⁵ ) ₂ , R ¹⁵ is hydrogen or a carbon number of 1 to 5 In the alkyl group, at least one -CH ₂ -may be substituted by -O-, at least one -CH ₂ CH ₂ -may be substituted by -CH=CH-, in these groups, at least one hydrogen may be substituted by Fluorine substitution. The liquid crystal composition according to claim 1, wherein the first additive is at least one polymerizable compound selected from the group of compounds represented by formula (1-4) to formula (1-60),

In formulas (1-4) to (1-60), R ¹ is an alkyl group having 1 to 10 carbons; Z ¹ , Z ¹² , and Z ^{13 are} independently a single bond, -CH ₂ CH ₂ -, or -(CH ₂ ) ₄ -; Sp ¹² , Sp ¹³ , and Sp ^{14 are} independently a single bond or an alkylene group having 1 to 5 carbon atoms, in which at least one -CH ₂ -may be -O -Substitution; 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; l is 0, 1, 2, 3, 4, 5, or 6. The liquid crystal composition according to any one of items 1 to 3 of the scope of patent application, wherein the ratio of the first additive is 10% by weight or less based on the weight of the liquid crystal composition. The liquid crystal composition according to any one of items 1 to 3 in the scope of the patent application, 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 an alkyl group having 1 to 12 carbons, an alkoxy group having 1 to 12 carbons, an alkenyl group having 2 to 12 carbons, or an alkene having 2 to 12 carbons. Oxy; ring C and ring E are independently 1,4-cyclohexylene, 1,4-cyclohexenylene, 1,4-phenylene, 1,4-in which at least one hydrogen is substituted by fluorine or chlorine Phenylene, or tetrahydropyran-2,5-diyl; ring D is 2,3-difluoro-1,4-phenylene, 2-chloro-3-fluoro-1,4-phenylene , 2,3-Difluoro-5-methyl-1,4-phenylene, 3,4,5-trifluoronaphthalene-2,6-diyl, or 7,8-difluorochroman-2 ,6-diyl; Z ² and Z ^{3 are} independently a single bond, -CH ₂ CH 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 any one of items 1 to 3 of the scope of patent application, which contains at least one selected from the group of compounds represented by formula (2-1) to formula (2-22) Compound as the first component,

In formulas (2-1) to (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 carbons. The liquid crystal composition according to claim 5, wherein the ratio 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 any one of items 1 to 3 in the scope of the patent application, which contains at least one compound selected from the group of compounds represented by formula (3) as a second component,

In formula (3), R ⁵ and R ^{6 are} independently an alkyl group having 1 to 12 carbons, an alkoxy group having 1 to 12 carbons, an alkenyl group having 2 to 12 carbons, and at least one hydrogen is substituted by fluorine or chlorine The alkyl group having 1 to 12 carbons, or the alkenyl group having 2 to 12 carbons in which at least one hydrogen is replaced by fluorine or chlorine; ring F and ring G are independently 1,4-cyclohexylene, 1,4-alkylene Phenyl, 2-fluoro-1,4-phenylene, or 2,5-difluoro-1,4-phenylene; Z ⁴ is a single bond, -CH ₂ CH ₂ -, -CH ₂ O-, -OCH ₂ -, -COO-, or -OCO-; d is 1, 2, or 3. The liquid crystal composition according to any one of items 1 to 3 of the scope of patent application, which contains at least one selected from the group of compounds represented by formula (3-1) to formula (3-13) Compound as the second component,

In formulas (3-1) to (3-13), R ⁵ and R ^{6 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. , Alkyl groups having 1 to 12 carbons in which at least one hydrogen is replaced by fluorine or chlorine, or alkenyl groups having 2 to 12 carbons in which at least one hydrogen is replaced by fluorine or chlorine. The liquid crystal composition as described in item 8 of the scope of patent application, wherein the ratio 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 any one of items 1 to 3 of the scope of patent application, which contains at least one polymerizable compound selected from the group of compounds represented by formula (4) as a second additive,

In formula (4), ring J and ring P are independently cyclohexyl, cyclohexenyl, phenyl, 1-naphthyl, 2-naphthyl, tetrahydropyran-2-yl, 1,3-dioxyl Alk-2-yl, pyrimidin-2-yl, or pyridin-2-yl, in these rings, at least one hydrogen can be fluorine, chlorine, alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons Group, or at least one hydrogen is substituted by fluorine or chlorine substituted alkyl group with carbon number of 1 to 12; ring K is 1,4-cyclohexylene, 1,4-cyclohexenylene, 1,4-phenylene Base, 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 fluorine, Chlorine, an alkyl group having 1 to 12 carbons, an alkoxy group having 1 to 12 carbons, or at least one hydrogen is substituted with an alkyl group having 1 to 12 carbons substituted by fluorine or chlorine; Z ⁵ and Z ^{6 are} independently A single bond or an alkylene having 1 to 10 carbon atoms, in the Z ⁵ and Z ⁶ , at least one -CH ₂ -may be substituted with -O-, -CO-, -COO- or -OCO-, and at least one -CH ₂ CH ₂ -can be replaced by -CH=CH-, -C(CH ₃ )=CH-, -CH=C(CH ₃ )-, or -C(CH ₃ )=C(CH ₃ )-, At least one hydrogen may be replaced by fluorine or chlorine; P ¹ , P ² , and P ³ are polymerizable groups; Sp ³ , Sp ⁴ , and Sp ^{5 are} independently single bonds or alkylene groups with 1 to 10 carbon atoms, so Among the Sp ³ , Sp ⁴ , and Sp ⁵ , at least one -CH ₂ -may be substituted by -O-, -COO-, -OCO-, or -OCOO-, and at least one -CH ₂ CH ₂ -may be- CH=CH- or -C≡C- substituted, at least one hydrogen can be replaced 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 claim 11, wherein in formula (4), P ¹ , P ² , and P ^{3 are} independently represented by formula (P-1) to formula (P-5) The polymerizable group in the group of groups,

In formulas (P-1) to (P-5), M ¹ , M ² , and M ^{3 are} independently hydrogen, fluorine, an alkyl group having 1 to 5 carbons, or at least one hydrogen substituted by fluorine or chlorine An alkyl group having 1 to 5 carbon atoms. The liquid crystal composition according to claim 11, wherein the second additive is at least one polymerizable compound selected from the group of compounds represented by formula (4-1) to formula (4-29),

In formula (4-1) to formula (4-29), P ¹ , P ² , and P ^{3 are} independently selected from the group of groups represented by formula (P-1) to formula (P-3) In the polymerizable group, here, M ¹ , M ² , and M ^{3 are} independently hydrogen, fluorine, an alkyl group having 1 to 5 carbons, or an alkyl group having 1 to 5 carbons in which at least one hydrogen is replaced by fluorine or chlorine alkyl;

Sp ³ , Sp ⁴ , and Sp ^{5 are} independently a single bond or an alkylene group having 1 to 10 carbon atoms. Among the Sp ³ , Sp ⁴ , and Sp ⁵ , at least one -CH ₂ -may be through -O-, -COO-, -OCO-, or -OCOO- substituted, and at least one -CH ₂ CH ₂ -may be substituted with -CH=CH- or -C≡C-, and at least one hydrogen may be substituted with fluorine or chlorine. The liquid crystal composition according to claim 11, wherein the ratio of the second additive is in the range of 0.03% by weight to 10% by weight based on the weight of the liquid crystal composition. The liquid crystal composition according to any one of items 1 to 3 of the scope of patent application, which contains at least one polymerizable compound selected from the group of compounds represented by formula (5) as a third additive,

In formula (5), R ⁵⁰ 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 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 by fluorine or chlorine; R ⁵¹ is -OH, -NH ₂ , -OR ⁵³ , -N(R ⁵³ ) ₂ , Or a group represented by -Si(R ⁵³ ) ₃ , where R ⁵³ is hydrogen or an alkyl group having 1 to 5 carbons, 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 ⁵⁰ and ring B ^{50 are} independently 1,4-cyclohexylene, 1,4-cyclohexenylene, 1,4-phenylene, naphthalene-1,2-diyl, naphthalene-1,3-diyl, naphthalene-1,4-diyl, naphthalene-1,5 -Diyl, naphthalene-1,6-diyl, naphthalene-1,7-diyl, naphthalene-1,8-diyl, naphthalene-2,3-diyl, naphthalene-2,6-diyl, naphthalene -2,7-diyl, tetrahydropyran-2,5-diyl, 1,3-dioxane-2,5-diyl, pyrimidine-2,5-diyl, pyridine-2,5- Diyl, phenanthrene-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-tetradecahydrocyclopenta[a]phenanthrene-3,17-diyl, among these rings, at least One hydrogen may be replaced by fluorine, chlorine, an alkyl group having 1 to 12 carbons, an alkoxy group having 1 to 12 carbons, or an alkyl group having 1 to 12 carbons in which at least one hydrogen is substituted by fluorine or chlorine; Z ⁵⁰ It 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 ⁵¹ and Sp ^{52 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 controlled by -O- , -COO-, or -OCO- substitution, at least one -CH ₂ CH ₂ -can be substituted by -CH=CH-, in these groups, at least one hydrogen can be substituted by fluorine; a ⁵⁰ is 0, 1, 2 , 3, or 4. The liquid crystal composition according to claim 15 of the patent application, wherein the ratio of the third additive is in the range of 0.3% by weight to 10% by weight based on the weight of the liquid crystal composition. A liquid crystal display element, which contains items such as items 1 to The liquid crystal composition according to any one of Item 16. The liquid crystal display element described in item 17 of the scope of patent application, wherein the operation mode of the liquid crystal display element is in-plane switching mode, vertical alignment mode, fringe field switching mode, or electric field induced light response alignment mode, and the driving mode of the liquid crystal display element It is an active matrix method. A polymer stable alignment type liquid crystal display element, which contains the liquid crystal composition according to any one of items 1 to 16 in the scope of patent application, 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 items 1 to 16 in the scope of the patent application, and the polymerizable compound in the liquid crystal composition is polymerized. A use of a liquid crystal composition, the liquid crystal composition being the liquid crystal composition according to any one of items 1 to 16 in the scope of patent application, which is used in a liquid crystal display element. A use of a liquid crystal composition, the liquid crystal composition being the liquid crystal composition according to any one of items 1 to 16 in the scope of patent application, which is used in a polymer stable alignment type liquid crystal display element. A use of a liquid crystal composition, the liquid crystal composition being the liquid crystal composition according to any one of items 1 to 16 in the scope of the patent application, which is used in a liquid crystal display element without an alignment film.