KR101943931B1 - Liquid crystal composition and liquid crystal display element - Google Patents

Abstract

In properties such as high upper temperature limit of mematic phase, low lower limit temperature on nematic phase, small viscosity, suitable optical anisotropy, negative dielectric anisotropy, high specific resistance, high stability against ultraviolet rays, and high stability against heat, A liquid crystal composition which satisfies at least one characteristic or has an appropriate balance for at least two characteristics is provided. A short response time, a large voltage holding ratio, a low threshold voltage, a large contrast ratio, a long lifetime, and the like. A liquid crystal composition containing, as a first additive, a compound contributing to high stability to heat or ultraviolet rays, having a negative dielectric anisotropy, and having a nematic phase, A specific compound having a high upper limit temperature or a small viscosity as a second component, and a specific compound having a polymerizable group as a second additive.

Description

TECHNICAL FIELD [0001] The present invention relates to a liquid crystal composition and a liquid crystal display device,

The present invention relates to a liquid crystal composition, a liquid crystal display element containing the composition, and the like. In particular, the present invention relates to a liquid crystal composition having a negative dielectric anisotropy, and a liquid crystal display element containing the composition and having modes such as IPS, VA, FFS, and FPA. To a polymer supporting alignment type liquid crystal display device.

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

The liquid crystal display element contains a liquid crystal composition having a nematic phase. This organism has appropriate characteristics. By improving the characteristics of this composition, an AM device having good characteristics can be obtained. The relationships in the two characteristics are summarized in Table 1 below. The properties of the composition are further described based on commercially available AM devices. The temperature range of the nematic phase is related to the temperature range in which the device can be used. The preferred upper limit temperature on the nematic phase is at least about 70 캜, and the preferred lower limit temperature at the nematic phase is about -10 캜 or lower. The viscosity of the composition is related to the response time of the device. A short response time is desirable to display moving images with the device. A short response time is desirable even at 1 ms. Thus, a small viscosity in the composition is preferred. Small viscosity at low temperature is more preferred.

[Table 1] Composition and characteristics in AM device

The optical anisotropy of the composition is related to the contrast ratio of the device. Depending on the mode of the device, a large optical anisotropy or a small optical anisotropy, i.e. a proper optical anisotropy, is required. The product (? N x d) of the optical anisotropy (? N) of the composition and the cell gap (d) of the device is designed to maximize the contrast ratio. The value of the appropriate product depends on the type of operation mode. This value is in the range of about 0.30 mu m to about 0.40 mu m for the VA mode device and about 0.20 mu m to about 0.30 mu m for the IPS mode or FFS mode device. In such a case, a composition having a large optical anisotropy is preferable for a device having a small cell gap. The large dielectric anisotropy in the composition contributes to a low threshold voltage in the device, low power consumption and a large contrast ratio. Therefore, a large dielectric anisotropy is preferable. The large resistivity in the composition contributes to a large voltage holding ratio and a large contrast ratio in the device. Therefore, a composition having a large resistivity at an early stage as well as at a room temperature is preferable. After long use, a composition having a large specific resistance at room temperature as well as at high temperature is preferable. The stability of the composition against ultraviolet light and heat is related to the lifetime of the device. When the stability is high, the lifetime of the device is long. Such characteristics are preferable for an AM device used for a liquid crystal projector, a liquid crystal TV, and the like.

In a polymer sustained alignment (PSA) type liquid crystal display device, a liquid crystal composition containing a polymer is used. First, a composition to which a small amount of a polymerizable compound is added is injected into the device. Next, the composition is irradiated with ultraviolet rays while a voltage is applied between the substrates of the device. The polymerizable compound is polymerized to produce the mesh structure of the polymer in the composition. In this composition, since the orientation of the liquid crystal molecules can be controlled by the polymer, the response time of the device is shortened and the burning of the image is improved. This effect of the polymer can be expected for devices with modes such as TN, ECB, OCB, IPS, VA, FFS and FPA.

In the AM device having the TN mode, a composition having positive (+) dielectric anisotropy is used. In an AM device having a VA mode, a composition having negative dielectric anisotropy is used. In an AM element having an IPS mode or an FFS mode, a composition having a positive or negative dielectric constant anisotropy is used. In a polymer sustained alignment (PSA) type AM device, a composition having a positive or negative dielectric constant anisotropy is used. A compound having a negative dielectric anisotropy is disclosed in Patent Document 1 below.

International Publication 2012-053323

It is an object of the present invention to provide a method of manufacturing a semiconductor device having a high upper limit temperature in a nematic phase, a low lower limit temperature on a nematic phase, a small viscosity, a proper optical anisotropy, a large negative dielectric anisotropy, a high specific resistance, a high stability against ultraviolet rays, The liquid crystal composition satisfying at least one characteristic. Another object is a liquid crystal composition having an appropriate balance between at least two characteristics. Another object is a liquid crystal display element containing such a composition. Another object is an AM device having characteristics such as a short response time, a large voltage holding ratio, a low threshold voltage, a large contrast ratio, and a long lifetime.

The present invention provides, as a first additive, a liquid crystal composition containing at least one compound selected from the group of compounds represented by formula (1), having a negative dielectric anisotropy, and having a nematic phase, Liquid crystal display device.

In Formula (1), R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , and R ⁸ are independently hydrogen or alkyl having 1 to 4 carbon atoms; Ring A and Ring B are independently selected from the group consisting of cyclohexylene, cyclohexenylene, decahydronaphthalenediyl, dihydropyranediyl, tetrahydropyranediyl, dioxanediyl, phenylene, naphthalenediyl, pyrimidinediyl, Wherein at least one hydrogen in the ring is fluorine, chlorine, alkyl of 1 to 5 carbon atoms, alkoxy of 1 to 5 carbon atoms, or alkyl of 1 to 5 carbon atoms in which at least one hydrogen is substituted by fluorine or chlorine Lt; / RTI > Z ¹ , Z ² , and Z ³ are independently a single bond or alkylene having 1 to 10 carbon atoms, and at least one -CH ₂ - in the alkylene is -O-, -S-, -CO- , -COO-, -OCO-, or -SiH ₂ -, and at least one -CH ₂ -CH ₂ - may be substituted with -CH = CH- or -C≡C-, , At least one hydrogen may be substituted with fluorine or chlorine; a and b are independently 1 or 2; c is 0, 1 or 2, and ring A when c is 0 is selected from the group consisting of cyclohexenylene, decahydronaphthalenediyl, dihydropyranediyl, tetrahydropyranediyl, dioxanediyl, naphthalenediyl, pyrimidine At least one hydrogen in the ring is selected from the group consisting of fluorine, chlorine, alkyl of 1 to 5 carbon atoms, alkoxy of 1 to 5 carbon atoms, or alkyl of 1 to 5 carbon atoms in which at least one hydrogen is substituted with fluorine or chlorine Lt; / RTI > alkyl.

An advantage of the present invention is that it has properties such as a high upper limit temperature of a nematic phase, a lower lower limit temperature on a nematic phase, a lower viscosity, an appropriate optical anisotropy, a larger negative dielectric anisotropy, a higher specific resistance, a higher stability against ultraviolet rays, And is a liquid crystal composition that satisfies at least one characteristic. Another advantage is a liquid crystal composition having an appropriate balance between at least two properties. Another advantage is a liquid crystal display element containing such a composition. Another advantage is an AM device having characteristics such as a short response time, a large voltage holding ratio, a low threshold voltage, a large contrast ratio, and a long lifetime.

The usage of the terms in this specification is as follows. Liquid crystal composition " and " liquid crystal display element " are abbreviated as " composition " &Quot; Liquid crystal display element " is a general term for a liquid crystal display panel and a liquid crystal display module. The term "liquid crystalline compound" refers to a compound having no liquid crystal phase such as a nematic phase, a smectic phase, or the like and a liquid crystal phase in which the composition has no nematic phase, viscosity and dielectric anisotropy It is a general term for compounds to be mixed. This 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 producing a polymer in a composition.

The liquid crystal composition is prepared by mixing a plurality of liquid crystal compounds. The proportion (content) of the liquid crystalline compound is expressed as a weight percentage (% by weight) based on the weight of the liquid crystal composition. To this composition, additives such as an optically active compound, an antioxidant, an ultraviolet absorber, a dye, a defoamer, a polymerizable compound, a polymerization initiator and a polymerization inhibitor are added as needed. The proportion of the additive (addition amount) is represented by the weight percentage (% by weight) based on the weight of the liquid crystal composition, similarly to the proportion of the liquid crystalline compound. Percent by weight (ppm) may be used. The proportion of the polymerization initiator and the polymerization inhibitor is exceptionally expressed based on the weight of the polymerizable compound.

Quot; the upper limit temperature of the nematic phase " is abbreviated as the " upper limit temperature ".Quot; lower limit temperature of the nematic phase " may be abbreviated as " lower limit temperature ". "High resistivity" means that the composition has a high resistivity at an initial stage not only at room temperature but also near the upper limit temperature of the nematic phase, and has a large specific resistance even at a temperature close to the upper limit temperature of the nematic phase as well as at room temperature after prolonged use It means to have. "The voltage holding ratio is high" means that the device has a large voltage holding ratio at an initial stage not only at room temperature but also at a temperature close to the upper limit temperature of a nematic phase, and has a large voltage holding ratio at a temperature close to the upper limit temperature Retention rate. The expression " enhancing the dielectric anisotropy " means that when the composition has a positive dielectric anisotropy, the value increases in positive, and when the composition has negative dielectric anisotropy, the value increases negatively.

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 (3) may be abbreviated as " compound (3) " &Quot; Compound (3) " means one compound represented by formula (3), a mixture of two compounds, or a mixture of three or more compounds. The same applies to the 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' may be replaced with 'B' may be replaced with a case where the number of 'A' is one, the position of 'A' is arbitrary, and the number of 'A' , These positions can be selected without limitation. This rule also applies to the expression "at least one 'A' is replaced with" B ".

In the formulas of the constituent compounds, the symbols of the terminal group R ⁹ are used for a plurality of compounds. In these compounds, two groups represented by any two R ⁹ may be the same or different. For example, there is a case where R ⁹ in the compound (2-1) is ethyl and R ⁹ in the compound (2-2) is ethyl. And R ⁹ is the compound (2-1) ethyl, also in the case of R ⁹ is propyl compound (2-2). This rule is also applied to symbols such as other end groups. In the formula (2), when d is 2, two rings C exist. In this compound, the two rings represented by two rings C may be the same or different. This rule applies to any two rings C when d is greater than two. This rule also applies to symbols such as Z ⁶ , circle F, and the like. This rule also applies to the case of two -Sp ² -P ⁵ in the compound (4-27).

The symbols A, B, and C surrounded by hexagons correspond to six-membered ring or condensed ring such as ring A, ring B, ring C, and the like. In the compound (1) or the compound (4), the diagonal line crossing the hexagon indicates that any cyclic hydrogen may be substituted with a group such as -Sp ¹ -P ¹ . and subscripts such as h represent the number of substituted groups. When the subscript is 0, there is no such substitution. When h is 2 or more, there are a plurality of -Sp ¹ -P ¹ on ring I. The plurality of groups represented by -Sp ¹ -P ¹ may be the same or different.

Alkyl is straight-chain or branched and does not include cyclic alkyl. Straight chain alkyl is preferred over branched alkyl. The above also applies to terminal groups such as alkoxy, alkenyl and the like. The steric arrangement for 1,4-cyclohexylene is preferably trans rather than sheath in order to increase the upper limit temperature. 2-fluoro-1,4-phenylene means the following two divalent groups. In the formula, fluorine may be leftward (L) or rightward (R). This rule also applies to asymmetric bivalent groups produced by removing two hydrogens from the ring, such as tetrahydropyran-2,5-diyl. This rule applies also to linking groups such as carbonyloxy (-COO- and -OCO-).

The present invention is as follows.

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

In Formula (1), R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , and R ⁸ are independently hydrogen or alkyl having 1 to 4 carbon atoms; Ring A and Ring B are independently selected from the group consisting of cyclohexylene, cyclohexenylene, decahydronaphthalenediyl, dihydropyranediyl, tetrahydropyranediyl, dioxanediyl, phenylene, naphthalenediyl, pyrimidinediyl, Wherein at least one hydrogen in the ring is fluorine, chlorine, alkyl of 1 to 5 carbon atoms, alkoxy of 1 to 5 carbon atoms, or alkyl of 1 to 5 carbon atoms in which at least one hydrogen is substituted by fluorine or chlorine Lt; / RTI > Z ¹ , Z ² , and Z ³ are independently a single bond or alkylene having 1 to 10 carbon atoms, and at least one -CH ₂ - in the alkylene is -O-, -S-, -CO- , -COO-, -OCO-, or -SiH ₂ -, and at least one -CH ₂ -CH ₂ - may be substituted with -CH = CH- or -C≡C-, , At least one hydrogen may be substituted with fluorine or chlorine; a and b are independently 1 or 2; c is 0, 1 or 2, and ring A when c is 0 is selected from the group consisting of cyclohexenylene, decahydronaphthalenediyl, dihydropyranediyl, tetrahydropyranediyl, dioxanediyl, naphthalenediyl, pyrimidine At least one hydrogen in the ring is selected from the group consisting of fluorine, chlorine, alkyl of 1 to 5 carbon atoms, alkoxy of 1 to 5 carbon atoms, or alkyl of 1 to 5 carbon atoms in which at least one hydrogen is substituted with fluorine or chlorine Lt; / RTI > alkyl.

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

R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , and R ⁸ independently represent hydrogen or an alkyl group having 1 to 4 carbon atoms / RTI >

Item 3. The liquid crystal composition according to Item 1 or 2, wherein the proportion of the first additive is in the range of 0.005 wt% to 1 wt% based on the weight of the liquid crystal composition.

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

In formula (2), R ⁹ and R ¹⁰ are independently selected from the group consisting of alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, alkenyl having 2 to 12 carbons, alkenyloxy having 2 to 12 carbons, Are hydrogen of 1 to 12 carbon atoms substituted with fluorine or chlorine; 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 replaced by fluorine or chlorine , Or tetrahydropyran-2,5-diyl; Ring D is 2,3-difluoro-1,4-phenylene, 2-chloro-3-fluoro-1,4-phenylene, 2,3- -Phenylene, 3,4,5-trifluoronaphthalene-2,6-diyl, or 7,8-difluorochroman-2,6-diyl; Z ⁴ and Z ⁵ are, independently, a single bond, ethylene, methyleneoxy, or carbonyloxy; d is 1, 2, or 3; e is 0 or 1; The sum of d and e is 3 or less.

Item 5. The liquid crystal composition according to any one of Items 1 to 4, which contains, as the first component, at least one compound selected from the group of compounds represented by Formulas (2-1) to (2-21).

In formulas (2-1) to (2-21), R ⁹ and R ¹⁰ independently represent alkyl having 1 to 12 carbon atoms, alkoxy having 1 to 12 carbon atoms, alkenyl having 2 to 12 carbon atoms, Alkenyloxy having 1 to 12 carbon atoms, or alkyl having 1 to 12 carbon atoms in which at least one hydrogen is substituted with fluorine or chlorine.

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

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

In formula (3), R ¹¹ and R ¹² independently represent alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, alkenyl having 2 to 12 carbons, carbon number in which at least one hydrogen is substituted with fluorine or chlorine Alkyl having 1 to 12 carbon atoms, or alkenyl having 2 to 12 carbon atoms in which at least one hydrogen is substituted with fluorine; The rings F and the ring G are independently selected from the group consisting of 1,4-cyclohexylene, 1,4-phenylene, 2-fluoro-1,4-phenylene, or 2,5-difluoro- It is wen; Z ⁶ is a single bond, ethylene or carbonyloxy; f is 1, 2, or 3;

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

In formulas (3-1) to (3-13), R ¹¹ and R ¹² independently represent alkyl having 1 to 12 carbon atoms, alkoxy having 1 to 12 carbon atoms, alkenyl having 2 to 12 carbon atoms, Alkyl having 1 to 12 carbon atoms in which hydrogen is substituted with fluorine or chlorine, or alkenyl having 2 to 12 carbon atoms in which at least one hydrogen is substituted with fluorine.

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

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

In formula (4), Ring I and Ring K are independently selected from the group consisting of cyclohexyl, cyclohexenyl, phenyl, 1-naphthyl, 2-naphthyl, tetrahydropyran- Wherein at least one hydrogen in said ring is selected from the group consisting of fluorine, chlorine, alkyl of 1 to 12 carbon atoms, alkoxy of 1 to 12 carbon atoms, or at least one of hydrogen, One hydrogen may be substituted with alkyl having 1 to 12 carbon atoms substituted with fluorine or chlorine; The ring J is preferably selected from the group consisting of 1,4-cyclohexylene, 1,4-cyclohexenylene, 1,4-phenylene, naphthalene-1,2-diyl, naphthalene- Naphthalene-1,6-diyl, naphthalene-1,7-diyl, naphthalene-1,8-diyl, naphthalene-2,3-diyl, naphthalene- Naphthalene-2,7-diyl, tetrahydropyran-2,5-diyl, 1,3-dioxane-2,5-diyl, pyrimidine-2,5-diyl or pyridine- In these rings, at least one hydrogen is substituted with fluorine, chlorine, alkyl having 1 to 12 carbon atoms, alkoxy having 1 to 12 carbon atoms, or alkyl having 1 to 12 carbon atoms in which at least one hydrogen is substituted with fluorine or chlorine It may be; Z ⁷ and Z ⁸ are independently a single bond or an alkylene having 1 to 10 carbon atoms, and in the alkylene, at least one -CH ₂ - represents -O-, -CO-, -COO-, or - O-, at least one -CH ₂ -CH ₂ - may be replaced by -CH═CH-, -C (CH ₃ ) ═CH-, -CH═C (CH ₃ ) -, or -C CH ₃ ) = C (CH ₃ ) -, in which at least one hydrogen may be substituted with fluorine or chlorine; P ¹ , P ² , and P ³ are independently a polymerizable group; Sp ¹ , Sp ² , and Sp ³ are each independently a single bond or alkylene having 1 to 10 carbon atoms, and at least one -CH ₂ - in the alkylene is -O-, -COO-, OCO-, or -OCOO-, and at least one -CH ₂ -CH ₂ - may be substituted with -CH═CH- or -C≡C-, and in these groups, at least one hydrogen May be substituted with fluorine or chlorine; g is 0, 1, or 2; h, i, and j are independently 0, 1, 2, 3, or 4; The sum of h, i, and j is 1 or more.

Item 11. A compound according to item 10, wherein in the formula (4), P ¹ , P ² , and P ³ are independently a polymerizable group selected from the group of groups represented by formulas (P-1) to (P-5) Liquid crystal composition.

In the formulas (P-1) to (P-5), M ¹ , M ² and M ³ are independently hydrogen, fluorine, alkyl of 1 to 5 carbon atoms, or at least one hydrogen atom is fluorine or chlorine Substituted alkyl having 1 to 5 carbon atoms.

Item 12: A liquid crystal display device according to any one of Items 1 to 11, which contains, as a second additive, at least one polymerizable compound selected from the group of compounds represented by the formulas (4-1) to (4-27) Composition.

In the formulas (4-1) to (4-27), P ⁴ , P ⁵ and P ⁶ are independently selected from groups of groups represented by formulas (P-1) to (P-3) A polymerizable group;

In the formulas (P-1) to (P-3), M ¹ , M ² and M ³ are independently hydrogen, fluorine, alkyl of 1 to 5 carbon atoms, or at least one hydrogen atom is fluorine or chlorine Substituted alkyl having 1 to 5 carbon atoms; In the formulas (4-1) to (4-27), Sp ¹ , Sp ² , and Sp ³ are independently a single bond or alkylene having 1 to 10 carbon atoms, -CH ₂ - may be substituted with -O-, -COO-, -OCO-, or -OCOO-, and at least one -CH ₂ -CH ₂ - may be replaced by -CH = CH- or -C≡C -, and in these groups, at least one hydrogen may be substituted with fluorine or chlorine.

Item 13. The liquid crystal composition according to any one of items 10 to 12, wherein the proportion of the second additive is in the range of 0.03 wt% to 10 wt% based on the weight of the liquid crystal composition.

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

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

Item 16. A polymer-supported alignment type liquid crystal display element comprising the liquid crystal composition according to any one of Items 10 to 13, wherein the polymerizable compound in the liquid crystal composition is polymerized.

Item 17. The use of the liquid crystal composition according to any one of Items 1 to 13 in a liquid crystal display element.

Item 18. The use of the liquid crystal composition according to any one of Items 10 to 13 in a polymer-supported alignment type liquid crystal display device.

The present invention also includes the following items. (a) at least one compound selected from the group consisting of an optically active compound, an antioxidant, an ultraviolet absorber, a dye, an antifoaming agent, a polymerizable compound, a polymerization initiator, The composition as described above. (b) an AM device containing the composition as described above. (c) a polymer support orientation (PSA) type AM device containing the above composition further containing a polymerizable compound. (d) a Polymer Supporting Oriented (PSA) type AM device containing the above composition and polymerizing the polymerizable compound in the composition. (e) a device containing the above composition and having modes of PC, TN, STN, ECB, OCB, IPS, VA, FFS or FPA. (f) a transmissive element containing the composition described above. (g) Use of the composition as a composition having a nematic phase. (h) Use as an optically active composition by adding an optically active compound to the composition.

The composition of the present invention is described in the following order. First, the composition of the composition will be described. Secondly, the main characteristics of the constituent compounds and the principal effects of the compounds on the composition are described. Third, the combination of components in the composition, the preferred proportions of the components and their rationale are explained. Fourth, the preferred form of the component compound is described. Fifth, represents the preferred constituent compounds. Sixth, the additives that may be added to the composition are described. Seventh, the synthesis method of the component compounds will be described. Finally, the use of the composition is described.

First, the composition of the constituent compounds in the composition is described. The composition of the present invention is classified into Composition A and Composition B. The composition A may further contain other liquid crystal compounds, additives, etc. in addition to the liquid crystal compounds selected from the compounds (2) and (3). The "other liquid crystal compound" is a liquid crystal compound which is different from the compound (2) and the compound (3). Such compounds are incorporated into the composition for the purpose of further tailoring the properties. The additives include optically active compounds, antioxidants, ultraviolet absorbers, pigments, antifoaming agents, polymerizable compounds, polymerization initiators, polymerization inhibitors and the like.

Composition B consists solely of liquid-crystalline compounds selected from compounds (2) and (3). &Quot; Substantially " means that the composition may contain additives but does not contain other liquid crystalline compounds. An example of the composition B is a composition containing the compound (1), the compound (2), and the compound (3) as essential components. Composition B has a smaller number of components as compared to Composition A. From the viewpoint of lowering the cost, the composition B is preferable to the composition A. The composition A is preferable to the composition B from the viewpoint of further adjusting the characteristics by mixing other liquid crystal compounds.

Secondly, the main properties of the constituent compounds and the major effects of the compounds on the properties of the compositions are described. The main properties of the component compounds are summarized in Table 2 based on the effects of the present invention. In the symbols in Table 2, L means larger or higher, M means medium, and S means smaller or lower. The symbols L, M and S are classified based on a qualitative comparison between the constituent compounds, and 0 (zero) means that the value is zero or close to zero.

[Table 2] Properties of Compound

The main effects of the component compound on the properties of the composition when the component compound is mixed into the composition are as follows. The first additive compound (1) contributes to high stability against heat or ultraviolet rays. The first additive does not affect the properties such as the upper limit temperature, the optical anisotropy, and the dielectric anisotropy because the added amount is extremely small. The first component, compound (2), increases the dielectric anisotropy and lowers the lower temperature limit. The compound (3) as the second component lowers the viscosity or raises the upper limit temperature. The second additive, the polymerizable compound (4), provides a polymer by polymerization, which shortens the response time of the device and improves the burning of the image.

Third, the combination of components in the composition, the preferred proportions of the component compounds and their rationale are described. The preferred combination of components in the composition is a combination of a first additive plus a first component, a first additive + a first component + a second component, a first additive + a first component + a second additive, or a first additive + Second component + second additive. A more preferable combination is the first additive + the first component + the second component or the first additive + the first component + the second component + the second additive.

A preferable proportion of the first additive is about 0.005% by weight or more for enhancing stability against ultraviolet rays or heat, and about 1% by weight or less for lowering the lower limit temperature. A more preferred range is from about 0.01% to about 0.5% by weight. A particularly preferred range is from about 0.03% to about 0.3% by weight.

The preferred proportion of the first component is at least about 10% by weight for increasing the dielectric anisotropy and about 90% by weight or less for lowering the lower limit temperature. A more preferred range is from about 20% to about 80% by weight. A particularly preferred ratio is in the range of about 30 wt% to about 70 wt%.

A preferred proportion of the second component is at least about 10% by weight to increase the upper temperature limit, or to lower the viscosity, and up to about 90% by weight to increase the dielectric anisotropy. A more preferred range is from about 20% to about 80% by weight. A particularly preferred ratio is in the range of about 30 wt% to about 70 wt%.

The second additive (polymerizable compound) is added to the composition for the purpose of being suitable for a polymer supported orientation type device. A preferable proportion of this additive is about 0.03% by weight or more for aligning the liquid crystal molecules, and is about 10% by weight or less to prevent defective display of the device. A more preferred ratio is in the range of about 0.1 wt% to about 2 wt%. A particularly preferred ratio is in the range of about 0.2 wt% to about 1.0 wt%.

Fourth, the preferred form of the component compound is described. In Formula (1), R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , and R ⁸ are independently hydrogen or alkyl having 1 to 4 carbon atoms. Preferred R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , or R ⁸ is hydrogen or methyl. More preferred R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , or R ⁸ is methyl.

Ring A and Ring B are independently selected from the group consisting of cyclohexylene, cyclohexenylene, decahydronaphthalenediyl, dihydropyranediyl, tetrahydropyranediyl, dioxanediyl, phenylene, naphthalenediyl, pyrimidinediyl, Wherein at least one hydrogen in the ring is fluorine, chlorine, alkyl of 1 to 5 carbon atoms, alkoxy of 1 to 5 carbon atoms, or alkyl of 1 to 5 carbon atoms in which at least one hydrogen is substituted by fluorine or chlorine . Preferred Ring A or Ring B is 1,4-cyclohexylene, 1,4-cyclohexenylene, decahydronaphthalene-2,6-diyl, 3,4-dihydro-2H- Dihydro-2H-pyran-2,5-diyl, 3,6-dihydro-2H-pyran-2,5-diyl, tetrahydropyran- 1,2-phenylene, 1,3-phenylene, 1,4-phenylene, naphthalene-1,3-diyl, naphthalene-1,4-diyl, naphthalene- Naphthalene-2,6-diyl, naphthalene-2,7-diyl, naphthalene-1,8-diyl, naphthalene-2,3-diyl, Diyl, or pyridine-2,5-diyl. In these rings, at least one hydrogen is selected from the group consisting of fluorine, chlorine, alkyl of 1 to 5 carbon atoms, alkoxy of 1 to 5 carbon atoms, Or an alkyl having 1 to 5 carbon atoms in which at least one hydrogen is substituted with fluorine or chlorine. More preferred Ring A or Ring B is 1,4-phenylene, 2-fluoro-1,4-phenylene, naphthalene-1,4-diyl, or naphthalene-2,6-diyl.

a and b are independently 1 or 2; Preferred a or b is 1. c is 0, 1 or 2, and ring A when c is 0 is selected from the group consisting of cyclohexenylene, decahydronaphthalenediyl, dihydropyranediyl, tetrahydropyranediyl, dioxanediyl, naphthalenediyl, pyrimidine At least one hydrogen in the ring is selected from the group consisting of fluorine, chlorine, alkyl of 1 to 5 carbon atoms, alkoxy of 1 to 5 carbon atoms, or alkyl of 1 to 5 carbon atoms in which at least one hydrogen is substituted with fluorine or chlorine Lt; / RTI > alkyl. The preferred c is 0 or 1.

Z ¹ , Z ² , and Z ³ are independently a single bond or alkylene having 1 to 10 carbon atoms, and at least one -CH ₂ - in the alkylene is -O-, -S-, -CO- , -COO-, -OCO-, or -SiH ₂ -, and at least one -CH ₂ -CH ₂ - may be substituted with -CH = CH- or -C≡C-, In the group, at least one hydrogen may be substituted with fluorine or chlorine. Preferably, Z ¹ , Z ² , or Z ³ is a single bond or an alkylene having 1 to 10 carbon atoms. In this alkylene, at least one -CH ₂ - may be substituted with -O-, Hydrogen may be substituted with fluorine. A more preferred example is a single bond.

In the formulas (2) and (3), R ⁹ and R ¹⁰ independently represent alkyl having 1 to 12 carbon atoms, alkoxy having 1 to 12 carbon atoms, alkenyl having 2 to 12 carbon atoms, Oxy, or alkyl having 1 to 12 carbon atoms in which at least one hydrogen is substituted with fluorine or chlorine. Preferable R ⁹ or R ¹⁰ is alkyl having 1 to 12 carbon atoms for enhancing stability and alkoxy having 1 to 12 carbon atoms for increasing dielectric anisotropy. R ¹¹ and R ¹² are independently selected from the group consisting of alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, alkenyl having 2 to 12 carbons, alkyl having 1 to 12 carbons in which at least one hydrogen is substituted with fluorine or chlorine, Is an alkenyl having 2 to 12 carbon atoms in which at least one hydrogen is substituted with fluorine. Preferable R ¹¹ or R ¹² is alkenyl having 2 to 12 carbon atoms in order to lower the viscosity, and is alkyl having 1 to 12 carbon atoms in order to improve stability.

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

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

Preferred alkoxy is methoxy, ethoxy, propoxy, butoxy, pentyloxy, hexyloxy, or heptyloxy. To lower the viscosity, the more preferred alkoxy is methoxy or ethoxy.

Preferred alkenyl are vinyl, 1-propenyl, 2-propenyl, 1-butenyl, 2-butenyl, 3-butenyl, 1-pentenyl, Decenyl, 1-hexenyl, 2-hexenyl, 3-hexenyl, 4-hexenyl, or 5-hexenyl. More preferred alkenyls are vinyl, 1-propenyl, 3-butenyl, or 3-pentenyl for lowering the viscosity. The preferred configuration of -CH = CH- in these alkeny depends on the position of the double bond. For lowering the viscosity or for other purposes, trans is preferred for alkenyl such as 1-propenyl, 1-butenyl, 1-pentenyl, 1-hexenyl, 3-pentenyl and 3-hexenyl. In the case of alkenyl such as 2-butenyl, 2-pentenyl and 2-hexenyl, cis is preferable. In these alkenyls, straight-chain alkenyl is preferred over branching.

Preferred alkenyloxy is vinyloxy, allyloxy, 3-butenyloxy, 3-pentenyloxy, or 4-pentenyloxy. To lower the viscosity, the more preferred alkenyloxy is allyloxy or 3-butenyloxy.

Preferred examples of the alkenyl in which at least one hydrogen is substituted with fluorine are 2,2-difluorovinyl, 3,3-difluoro-2-propenyl, 4,4-difluoro- , 5,5-difluoro-4-pentenyl, or 6,6-difluoro-5-hexenyl. A more preferred example is 2,2-difluorovinyl or 4,4-difluoro-3-butenyl for lowering the viscosity.

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 replaced by fluorine or chlorine , Or tetrahydropyran-2,5-diyl. Preferred examples of " 1,4-phenylene in which at least one hydrogen is substituted with fluorine or chlorine " include 2-fluoro-1,4-phenylene, 2,3-difluoro- Or 2-chloro-3-fluoro-1,4-phenylene. A preferred ring C or ring E is 1,4-cyclohexylene for lowering the viscosity, tetrahydropyran-2,5-diyl for increasing the dielectric anisotropy and 1,4-phenylene for increasing the optical anisotropy. The steric arrangement for 1,4-cyclohexylene is preferably trans rather than sheath in order to increase the upper limit temperature. Tetrahydropyran-2,5-

Ring D is 2,3-difluoro-1,4-phenylene, 2-chloro-3-fluoro-1,4-phenylene, 2,3- -Phenylene, 3,4,5-trifluoronaphthalene-2,6-diyl, or 7,8-difluorochroman-2,6-diyl. A preferred ring D is 2,3-difluoro-1,4-phenylene to lower viscosity, 2-chloro-3-fluoro-1,4-phenylene to lower optical anisotropy, 7,8-difluorochroman-2,6-diyl to enhance it.

The rings F and the ring G are independently selected from the group consisting of 1,4-cyclohexylene, 1,4-phenylene, 2-fluoro-1,4-phenylene, or 2,5-difluoro- It's Len. A preferred ring F or ring G is 1,4-cyclohexylene for lowering the viscosity or for increasing the upper temperature limit, and 1,4-phenylene for lowering the lower limit temperature.

Z ⁴ and Z ⁵ are, independently, a single bond, ethylene, methyleneoxy, or carbonyloxy. Preferred Z ⁴ or Z ⁵ is a single bond to lower the viscosity, ethylene to lower the lower limit temperature, and methyleneoxy to increase the dielectric anisotropy. Z ⁶ is a single bond, ethylene or carbonyloxy. A preferred Z ⁶ is a single bond to lower the viscosity.

d is 1, 2 or 3; The preferred d is 1 to lower the viscosity and 2 or 3 to increase the upper temperature limit. e is 0 or 1. The preferred e is 0 to lower the viscosity and 1 to lower the lower temperature. f is 1, 2, or 3; The preferred f is 1 to lower the viscosity and 2 or 3 to increase the upper temperature limit.

In the formula (4), P ¹ , P ² , and P ³ are independently a polymerizable group. Preferable P ¹ , P ² , or P ³ is a polymerizable group selected from the group of groups represented by formulas (P-1) to (P-5). More preferably, P ¹ , P ² , or P ³ is a group (P-1) or a group (P-2). Particularly preferred group (P-1) is -OCO-CH = CH ₂ or -OCO-C (CH ₃ ) = CH ₂ . The dashed lines of the groups (P-1) to (P-5) represent bonding sites.

In the groups (P-1) to (P-5), M ¹ , M ² and M ³ are independently hydrogen, fluorine, alkyl of 1 to 5 carbon atoms, or at least one hydrogen atom is fluorine or chlorine Substituted alkyl having 1 to 5 carbon atoms. Preferred M ¹ , M ² , or M ³ is hydrogen or methyl to increase reactivity. More preferred M &^lt; ¹ > is methyl, more preferably M < ^{2 >} or M < ³ > is hydrogen.

In the formulas (4-1) to (4-27), P ⁴ , P ⁵ and P ⁶ are independently a group represented by formulas (P-1) to (P-3). Preferred P ⁴ , P ⁵ , or P ⁶ is a group (P-1) or a group (P-2). A more preferable group (P-1) is -OCO-CH = CH ₂ or -OCO-C (CH ₃ ) = CH ₂ . The dashed lines of the groups (P-1) to (P-3) represent the bonding sites.

In the formula (4), Sp ¹ , Sp ² , and Sp ³ are independently a single bond or alkylene having 1 to 10 carbon atoms, and at least one -CH ₂ - in the alkylene is -O- , -COO-, -OCO-, or -OCOO-, and at least one -CH ₂ -CH ₂ - may be substituted with -CH = CH- or -C≡C-, , Wherein at least one hydrogen may be substituted with fluorine or chlorine. Preferred Sp ¹ , Sp ² or Sp ³ is a single bond, -CH ₂ CH ₂ -, -CH ₂ O-, -OCH ₂ -, -COO-, -OCO-, -CO-CH═CH- or -CH = CH-CO-. More preferred Sp ¹ , Sp ² , or Sp ³ is a single bond.

Ring I and ring K are independently selected from the group consisting of cyclohexyl, cyclohexenyl, phenyl, 1-naphthyl, 2- naphthyl, tetrahydropyran-2-yl, 2-yl or pyridin-2-yl, wherein at least one hydrogen is fluorine, chlorine, alkyl of 1 to 12 carbon atoms, alkoxy of 1 to 12 carbon atoms, or at least one hydrogen is fluorine or chlorine May be substituted with alkyl having 1 to 12 carbon atoms. A preferred ring I or ring K is phenyl. The ring J is preferably selected from the group consisting of 1,4-cyclohexylene, 1,4-cyclohexenylene, 1,4-phenylene, naphthalene-1,2-diyl, naphthalene- Naphthalene-1,6-diyl, naphthalene-1,7-diyl, naphthalene-1,8-diyl, naphthalene-2,3-diyl, naphthalene- Naphthalene-2,7-diyl, tetrahydropyran-2,5-diyl, 1,3-dioxane-2,5-diyl, pyrimidine-2,5-diyl or pyridine- In these rings, at least one hydrogen is substituted with fluorine, chlorine, alkyl having 1 to 12 carbon atoms, alkoxy having 1 to 12 carbon atoms, or alkyl having 1 to 12 carbon atoms in which at least one hydrogen is substituted with fluorine or chlorine It is possible. A preferred ring J is 1,4-phenylene or 2-fluoro-1,4-phenylene.

Z ⁷ and Z ⁸ are independently a single bond or an alkylene having 1 to 10 carbon atoms, and in the alkylene, at least one -CH ₂ - represents -O-, -CO-, -COO-, or - O-, at least one -CH ₂ -CH ₂ - may be replaced by -CH═CH-, -C (CH ₃ ) ═CH-, -CH═C (CH ₃ ) -, or -C CH ₃ ) = C (CH ₃ ) -, and in these groups, at least one hydrogen may be substituted with fluorine or chlorine. Preferred Z ⁷ or Z ⁸ is a single bond, -CH ₂ CH ₂ -, -CH ₂ O-, -OCH ₂ -, -COO-, or -OCO-. More preferably, Z ⁷ or Z ⁸ is a single bond.

g is 0, 1, or 2; Preferably, g is 0 or 1. h, i, and j are independently 0, 1, 2, 3, or 4, and the sum of h, i, and j is one or more. Preferred h, i, or j is 1 or 2.

Fifth, represents the preferred constituent compounds. Preferred compounds (1) are the compounds (1-1) to (1-5) described in the item 2. In these compounds, at least one of the first additives is preferably a compound (1-1), a compound (1-3), or a compound (1-4). It is preferable that at least two of the first additives are a combination of the compound (1-1) and the compound (1-3) or the compound (1-3) and the compound (1-4).

Preferred compounds (2) are the compounds (2-1) to (2-21) described in the item 5. In these compounds, at least one of the first components is a compound (2-1), a compound (2-4), a compound (2-5), a compound (2-7) (2-15). At least two of the first components are selected from compounds (2-1) and (2-7), compounds (2-1) and (2-15), compounds (2-4) It is preferable that the compound is a combination of the compound (2-4) and the compound (2-15) or the compound (2-5) and the compound (2-10).

Preferred compounds (3) are the compounds (3-1) to (3-13) described in the item 8. In these compounds, at least one of the second components is a compound (3-1), a compound (3-3), a compound (3-5), a compound (3-6) (3-8). Wherein at least two of the second components are selected from compounds (3-1) and (3-3), compounds (3-1) and (3-5), or compounds (3-1) Is preferable.

Preferred compounds (4) are the compounds (4-1) to (4-27) described in the item 12. In these compounds, at least one of the second additives is a compound (4-1), a compound (4-2), a compound (4-24), a compound (4-25) (4-27). At least two of the second additives are selected from compounds (4-1) and (4-2), compounds (4-1) and (4-18), compounds (4-2) and (4-24) The compound (4-2) and the compound (4-25), the compound (4-2) and the compound (4-26), the compound (4-25) and the compound (4-26) Is preferably a combination of the compounds (4-24). In the groups (P-1) to (P-3), preferable M ¹ , M ² , or M ³ is hydrogen or methyl. Preferred Sp ¹ , Sp ² or Sp ³ is a single bond, -CH ₂ CH ₂ -, -CH ₂ O-, -OCH ₂ -, -COO-, -OCO-, -CO-CH═CH- or -CH = CH-CO-.

Sixth, the additives that may be added to the composition are described. Such additives include optically active compounds, antioxidants, ultraviolet absorbers, pigments, antifoaming agents, polymerizable compounds, polymerization initiators, polymerization inhibitors and the like. An optically active compound is added to the composition for the purpose of inducing the helical structure of the liquid crystal to give a twist angle. Examples of such compounds are compounds (5-1) to (5-5). The preferred proportion of optically active compound is about 5% by weight or less. A more preferred range is from about 0.01% to about 2% by weight.

Antioxidants are added to the composition in order to prevent degradation of the resistivity due to heating in the atmosphere or to maintain a high voltage holding ratio at room temperature as well as at the upper limit temperature after long use of the device. Preferable examples of the antioxidant include a compound (6) wherein n is an integer of 1 to 9, and the like.

In the compound (6), n is preferably 1, 3, 5, 7, or 9. More preferred n is 7. The compound (6) wherein n is 7 is effective to maintain a large voltage holding ratio at a temperature close to the upper limit temperature as well as at room temperature after using the device for a long time because the volatility is small. A preferable proportion of the antioxidant is about 50 ppm or more for obtaining the effect, and is not more than about 600 ppm so as not to lower the upper limit temperature or increase the lower limit temperature. A more preferred ratio is in the range of about 100 ppm to about 300 ppm.

Preferable examples of the ultraviolet absorber include benzophenone derivatives, benzoate derivatives, triazole derivatives and the like. Light stabilizers such as amines with steric hindrance are also desirable. A preferable ratio in these absorbents and stabilizers is about 50 ppm or more for obtaining the effect, and is not more than about 10,000 ppm so as not to lower the upper limit temperature or increase the lower limit temperature. A more preferred range is from about 100 ppm to about 10000 ppm.

In order to adapt to a device in the GH (guest host) mode, a dichroic dye such as an azo dye, an anthraquinone dye or the like is added to the composition. A preferred ratio of the pigments is in the range of about 0.01 wt% to about 10 wt%. In order to prevent foaming, antifoaming agents such as dimethyl silicone oil, methylphenyl silicone oil and the like are added to the composition. A preferable proportion of defoaming agent is about 1 ppm or more for obtaining the effect and about 1000 ppm or less for preventing defective display. A more preferred ratio is in the range of about 1 ppm to about 500 ppm.

Polymeric compounds are used to adapt to polymeric backing (PSA) type devices. Compound (4) is suitable for this purpose. A polymerizable compound different from the compound (4) may be added to the composition together with the compound (4). Preferable examples of such a polymerizable compound are compounds such as acrylate, methacrylate, vinyl compound, vinyloxy compound, propenyl ether, epoxy compound (oxirane, oxetane), vinyl ketone and the like. A more preferred example is a derivative of acrylate or methacrylate. A preferable proportion of the compound (4) is 10% by weight or more based on the total weight of the polymerizable compound. A more preferable ratio is 50% by weight or more. A particularly preferable ratio is 80% by weight or more. The most preferred ratio is 100% by weight.

The polymerizable compound such as the compound (4) is polymerized by ultraviolet irradiation. And may be polymerized in the presence of a suitable initiator such as a photopolymerization initiator. Suitable conditions for the polymerization, the appropriate type of initiator, and the appropriate amount are well known to those skilled in the art and are described in the literature. For example, photo-initiators Irgacure 651 (registered trademark; BASF), Irgacure 184 (registered trademark BASF), or Darocur 1173 (registered trademark BASF) are suitable for radical polymerization. A preferable proportion of the photopolymerization initiator ranges from about 0.1 wt% to about 5 wt% based on the total weight of the polymerizable compound. A more preferred range is from about 1% to about 3% by weight.

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

Seventh, the synthesis method of the component compounds will be described. These compounds can be synthesized by a known method. The synthesis method is exemplified. Compound (2-1) is synthesized by the method described in Japanese Patent Application Laid-Open No. 2000-053602. Compound (3-1) is synthesized by the method described in Japanese Patent Laid-Open No. 59-176221. The compound (3-13) is synthesized by the method described in JP-A-2-237949. The compound (4-18) is synthesized by the method described in JP-A-7-101900. Compounds of formula (6) wherein n is 1 are available from Sigma-Aldrich Corporation. Compound (6) having n = 7 is synthesized by the method described in USP 3660505. The compound (1-3) is synthesized by the following method.

Step 1:

A mixture of 2,2,6,6-tetramethyl-4-piperidinol (15.00 g, 95.39 mmol) and NaH (60%, 3.80 g, 95.01 mmol) was heated to reflux in THF for 2 hours. The reaction mixture was cooled to -10 ° C or lower, and a THF solution of 1,1'-biphenyl-4,4'-dicarbonyldichloride (12.00 g, 43.00 mmol) was slowly added dropwise while maintaining the temperature at -10 ° C. The reaction mixture was stirred at room temperature for 1 hour, quenched with water and extracted with MTBE (methyl-tert-butyl ether). Silica gel was added to the combined organic layer, the mixture was filtered, and the solvent was distilled off to obtain bis (2,2,6,6-tetramethylpiperidin4-yl) -1,1'-biphenyl- (6 g, yield: 26.7%).

_{^{1 H-NMR (CDCl 3;}} δppm): 8.12 (dd, 4H), 7.69 (dd, 4H), 5.48 (tt, 2H), 2.08 (dd, 4H), 1.57 (br, 2H), 1.36-1.31 ( m, 16H), 1.21 (s, 12H).

Compounds that do not disclose the synthetic methods are commercially available from Organic Syntheses, John Wiley & Sons, Inc., Organic Reactions, John Wiley & Sons, Inc., Compensation Organic Synthesis, Comprehensive Organic Synthesis, Pergamon Press), and New Experimental Chemistry Lecture (Maruzen). The composition is prepared from the thus obtained compound by a known method. For example, the constituent compounds are mixed and dissolved with each other by heating.

Finally, the use of the composition is described. The composition mainly has a lower limit temperature of about -10 占 폚 or lower, an upper limit temperature of about 70 占 폚 or higher, and an optical anisotropy ranging from about 0.07 to about 0.20. An element containing this composition has a large voltage holding ratio. This composition is suitable for AM devices. This composition is particularly suitable for transmissive AM devices. By controlling the proportions of the component compounds, or by mixing other liquid crystalline compounds, it is also possible to prepare compositions having optical anisotropy in the range of about 0.08 to about 0.25, and compositions having optical anisotropy in the range of about 0.10 to about 0.30 have. This composition can be used as a composition having a nematic phase or as an optically active composition by adding an optically active compound.

This composition can be used as an AM device. It can also be used as a PM device. This composition can be used for AM devices and PM devices having modes such as PC, TN, STN, ECB, OCB, IPS, FFS, VA, and FPA. Use in an AM device having TN, OCB, IPS mode or FFS mode is particularly preferred. In the AM element having the IPS mode or the FFS mode, when the voltage is zero, the arrangement of the liquid crystal molecules may be parallel to the glass substrate or may be vertical. These elements may be reflective, transmissive or transflective. It is preferable to use it as a transmission type device. It can be used as an amorphous silicon TFT device or a polycrystalline silicon TFT device. A nematic curvilinear aligned phase (NCAP) device manufactured by microencapsulating the composition, or a PD (polymer dispersed) device in which a three-dimensional network polymer is formed in the composition.

Example

The present invention will be described in more detail by way of examples. The present invention is not limited by these embodiments. The present invention includes a mixture of the composition of Example 1 and the composition of Example 2. The present invention also includes a mixture of at least two of the compositions of the Examples. The synthesized compound was confirmed by a method such as NMR analysis. The properties of the compound and the composition were measured by the following methods.

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

Gas Chromatographic Analysis: GC-14 type B gas chromatograph manufactured by Shimadzu Corporation was used for measurement. The carrier gas is helium (2 mL / min). The sample vaporization chamber was set at 280 占 폚 and the detector (FID) at 300 占 폚. For the separation of the constituent compounds, a capillary column DB-1 (length 30 m, inner diameter 0.32 mm, film thickness 0.25 占 퐉; dimethylpolysiloxane; non-polar) was prepared by Agilent Technologies Inc., Were used. The column was maintained at 200 ° C for 2 minutes and then heated to 280 ° C at a rate of 5 ° C / minute. The sample was prepared with an acetone solution (0.1 wt%), and 1 μL of the sample was injected into the sample gasifying chamber. The recorder is C-R5A type Chromatopac manufactured by Shimadzu Corporation, or its equivalent. The obtained gas chromatogram shows the retention time of the peak corresponding to the component compound and the area of the peak.

As a solvent for diluting the sample, chloroform, hexane and the like may be used. To separate the constituent compounds, the following capillary column may be used. HP-1 (length 30 m, inner diameter 0.32 mm, film thickness 0.25 μm) manufactured by Agilent Technologies Inc., Rtx-1 (length 30 m, inner diameter 0.32 mm, film thickness 0.25 μm) manufactured by Restek Corporation, SGE International Pty. BP-1 (length 30 m, inner diameter 0.32 mm, film thickness 0.25 mu m) A capillary column CBP1-M50-025 (length 50 m, inner diameter 0.25 mm, film thickness 0.25 m) manufactured by Shimadzu Corporation may be used for the purpose of preventing superposition of compound peaks.

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

Measurement sample: When the characteristics of the composition or device were measured, the composition was used as a sample. In the measurement of the characteristics of the compound, a sample for measurement was prepared by mixing this compound (15% by weight) with the parent liquid crystal (85% by weight). From the values obtained by the measurement, the characteristic values of the compounds were calculated by extrapolation. (Extrapolated value) = {(measured value of sample) -0.85 (measured value of liquid crystal)} / 0.15. When the smectic phase (or crystal) precipitates at 25 ° C at this ratio, the ratio of the compound and the parent liquid crystal is 10 wt%: 90 wt%, 5 wt%: 95 wt%, 1 wt%: 99 wt% Change. The values of the upper limit temperature, optical anisotropy, viscosity, and dielectric anisotropy of the compound were determined by this extrapolation method.

The following mother liquid crystals were used. The proportion of the component compound is expressed as% by weight.

Measurement method: Properties were measured in the following manner. Most of these are methods described in the JEITA standard (JEITA ED-2521B), which is deliberated by the Japan Electronics and Information Technology Industries Association (JEITA). A thin film transistor (TFT) was not mounted on the TN device used for the measurement.

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

(2) Nematic phase lower limit temperature (T _C ; ° C): A sample having a nematic phase is placed in a glass bottle and cooled in a freezer at 0 ° C, -10 ° C, -20 ° C, -30 ° C, After 10 days of storage, the liquid crystal phase was observed. For example, when the sample is a nematic phase at -20 캜, and when it is changed to a crystalline or smectic phase at -30 캜, T _C is expressed as < -20 캜. The lower limit temperature of the nematic phase may be abbreviated as &quot; lower limit temperature &quot;.

(3) Viscosity (bulk viscosity;?; Measured at 20 占 폚, mPa 占 퐏): E-type rotational viscometer manufactured by Tokyo Instruments Co., Ltd. was used for measurement.

(4) Viscosity (rotational viscosity;? 1; measured at 25 占 폚, mPa 占 퐏): The measurement was carried out according to the method described in M. Imai et al., Molecular Crystals and Liquid Crystals, Vol. 259, 37 (1995). A sample was placed in a VA device in which the interval (cell gap) between the two glass substrates was 20 占 퐉. This device was applied stepwise every 1 volt in the range of 39 volts to 50 volts. After 0.2 seconds of unattended operation, application was repeated under conditions of only one rectangular wave (rectangular pulse; 0.2 seconds) and unattended (2 seconds). The peak current (peak current) and the peak time (peak time) of the transient current generated by this application were measured. From these measurements and from M. Imai et al., Page 40, equation (8), the values of rotational viscosity were obtained. The dielectric anisotropy required for this calculation was measured according to the following measurement (6).

(5) Optical anisotropy (refractive index anisotropy;? N; measured at 25 占 폚): The measurement was performed using an Abbe refractometer equipped with a polarizing plate on an eyepiece using light having a wavelength of 589 nm. After rubbing the surface of the primary prism in one direction, the sample was dropped onto the primary prism. The refractive index (n ∥) was measured when the direction of polarization parallel to the direction of rubbing. The refractive index (n?) Was measured when the direction of polarization was perpendicular to the direction of rubbing. The value of optical anisotropy was calculated from the formula of Δn = n ∥ -n⊥.

6, the dielectric anisotropy (Δε; measured at 25 ℃): The value of dielectric anisotropy is calculated according to the equation of Δε = ε ∥ -ε⊥. The dielectric constant (ε ∥ and ε⊥) were measured as follows.

1) Measurement of dielectric constant ( ?? ): A well-cleaned glass substrate was coated with an ethanol (20 mL) solution of octadecyltriethoxysilane (0.16 mL). The glass substrate was rotated by a spinner, and then heated at 150 DEG C for 1 hour. A sample was placed in a VA device having a gap (cell gap) between two glass substrates of 4 mu m, and the device was sealed with an adhesive cured with 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 longitudinal direction of the liquid crystal molecule was measured.

2) Measurement of dielectric constant (??): A polyimide solution was applied to a glass substrate which had been washed well. After the glass substrate was baked, the resulting alignment film was rubbed. A sample was placed in a TN device in which the interval (cell gap) between the two glass substrates was 9 mu m and the twist angle was 80 DEG. A sine wave (0.5 V, 1 kHz) was applied to the device, and after 2 seconds, the dielectric constant (??) In the direction of the short axis of the liquid crystal molecule was measured.

(7) Threshold voltage (Vth; measured at 25 캜; V): An LCD 5100-type luminance meter manufactured by Otsuka Electronics Co., Ltd. was used for the measurement. The light source was a halogen lamp. A sample was placed in a VA device in a normally black mode in which the interval (cell gap) between the two glass substrates was 4 占 퐉 and the rubbing direction was antiparallel, and the device was sealed using an adhesive cured with ultraviolet rays did. The voltage applied to the device (60 Hz, rectangular wave) was gradually increased from 0 V to 20 V by 0.02 V stepwise. At this time, light was irradiated from the vertical direction to the device, and the amount of light transmitted through the device was measured. A transmittance of 100% was obtained when the light quantity reached its maximum, and a voltage-transmittance curve with a transmittance of 0% when the light quantity was minimum was prepared. The threshold voltage is expressed by the voltage when the transmittance becomes 10%.

(8) Voltage maintenance rate (VHR-9; measured at 25 캜;%): The TN device used for the measurement had a polyimide alignment film and the gap (cell gap) between the two glass substrates was 5 탆. The device was sealed with an adhesive that was cured with ultraviolet light after loading the sample. The TN device was charged by applying a pulse voltage (60 microseconds at 1 V). The attenuation voltage was measured with a high-speed voltmeter for 166.7 ms, and the area A between the voltage curve and the horizontal axis in the unit period was obtained. Area B is the area when not attenuated. The voltage holding ratio is expressed as a percentage of the area A with respect to the area B.

(9) Voltage maintenance ratio (VHR-10; measured at 60 占 폚;%): The voltage holding ratio was measured in the same manner as described above except that the temperature was measured at 60 占 폚 instead of 25 占 폚. The obtained value is indicated by VHR-10.

(10) Voltage maintenance rate (VHR-11; measured at 60 占 폚;%): The voltage maintenance rate was measured after irradiating ultraviolet rays, and the stability against ultraviolet rays was evaluated. The TN device used for the measurement had a polyimide alignment film and the cell gap was 5 m. A sample was injected into the device and irradiated with ultraviolet rays of 5 mW / cm ² for 167 minutes. The light source was a black light, F40T10 / BL (peak wavelength 369 nm) manufactured by Eye Graphics Co., Ltd., and the distance between the element and the light source was 5 mm. In the measurement of VHR-11, the attenuation voltage was measured for 166.7 ms. A composition having a large VHR-11 has a great stability against ultraviolet rays.

(11) Voltage maintenance rate (VHR-12; measured at 60 캜;%): The TN device into which the sample was injected was heated for 20 hours in a thermostatic chamber at 120 캜, and the voltage retention was measured. In the measurement of VHR-12, the voltage attenuating for 166.7 ms was measured. Compositions with large VHR-12 have great stability to heat.

(12) Response time (τ; measured at 25 ° C., ms): An LCD 5100 type luminance meter manufactured by Otsuka Electronics Co., Ltd. was used for the measurement. The light source was a halogen lamp. The low-pass filter was set at 5 kHz. A sample was placed in a VA device in a normally black mode in which the interval (cell gap) between the two glass substrates was 4 占 퐉 and the rubbing direction was antiparallel. The device was sealed using an ultraviolet curable adhesive. A rectangular wave (60 Hz, 10 V, 0.5 second) was applied to the device. At this time, light was irradiated from the vertical direction to the device, and the amount of light transmitted through the device was measured. When the amount of light is maximized, the transmittance is 100%, and when the amount of light is minimum, the transmittance is regarded as 0%. The response time is expressed as a fall time (ms) required to change the transmittance from 90% to 10%.

(13) Resistivity (ρ; measured at 25 ° C; Ωcm): A 1.0 mL sample was injected into a container equipped with electrodes. A direct current voltage (10 V) was applied to the vessel, and the direct current after 10 seconds was measured. The resistivity was calculated by the following equation. (Electric resistance) = {(voltage) x (electric capacity of the container)} / {(direct current) x (permittivity of vacuum)}.

The compounds in the examples are represented by symbols based on the definitions in Table 3 below. In Table 3, the steric configuration for 1,4-cyclohexylene is trans. The number in parentheses after the symbol corresponds to the number of the compound. (-) means other liquid crystalline compounds. The proportion (percentage) of the liquid crystalline compound is the weight percentage (% by weight) based on the weight of the liquid crystal composition. Finally, the property values of the composition are summarized and described.

[Table 3]

[Example 1]

2-H1OB (2F, 3F) -O2 (2-4) 3%

3-HIOB (2F, 3F) -O2 (2-4) 10%

1V2-BB (2F, 3F) -O2 (2-5) 10%

V-HHB (2F, 3F) -O1 (2-7) 12%

V-HHB (2F, 3F) -O2 (2-7) 12%

3-HH1OB (2F, 3F) -O2 (2-10) 6%

2-BB (2F, 3F) B-3 (2-11) 6%

3-HH-V (3-1) 25%

3-HH-V1 (3-1) 6%

4-HH-V1 (3-1) 3%

V-HHB-1 (3-5) 3%

V2-HHB-1 (3-5) 4%

The composition having the negative dielectric anisotropy was prepared, and its properties were measured. NI = 80.1 DEG C; Tc < -20 C; ? N = 0.103; ? = -3.9; Vth = 2.09 V; ? = 20.7 mPa 占 퐏; VHR-11 = 36.3%.

Compound (1-1) was added to this composition in a ratio of 0.05% by weight, and VHR-11 was measured. VHR-11 = 67.1%.

[Example 2]

3-HIOB (2F, 3F) -O2 (2-4) 8%

V2-BB (2F, 3F) -O1 (2-5) 4%

V2-BB (2F, 3F) -O2 (2-5) 9%

1V2-BB (2F, 3F) -O4 (2-5) 6%

V-HHB (2F, 3F) -O2 (2-7) 10%

V-HHB (2F, 3F) -O4 (2-7) 3%

1V2-HHB (2F, 3F) -O2 (2-7) 4%

3-HH1OB (2F, 3F) -O2 (2-10) 12%

3-HH-V (3-1) 26%

1-HH-2V1 (3-1) 3%

3-HH-2V1 (3-1) 3%

5-HB-O2 (3-2) 3%

3-HHB-O1 (3-5) 5%

V-HHB-1 (3-5) 4%

The composition having the negative dielectric anisotropy was prepared, and its properties were measured. NI = 77.0 DEG C; Tc < -20 C; ? N = 0.099; ? = -3.4; Vth = 2.22 V;侶 = 18.6 mPa 揃 s; VHR-11 = 34.7%.

Compound (1-3) was added to this composition in a ratio of 0.1% by weight, and VHR-11 was measured. VHR-11 = 64.5%.

[Example 3]

3-HIOB (2F, 3F) -O2 (2-4) 8%

3-BB (2F, 3F) -O2 (2-5) 8%

2O-BB (2F, 3F) -O2 (2-5) 5%

2-HH1OB (2F, 3F) -O2 (2-10) 8%

3-HH1OB (2F, 3F) -O2 (2-10) 7%

2-BB (2F, 3F) B-3 (2-11) 8%

3-HDhB (2F, 3F) -O2 (2-13) 10%

3-HH-V (3-1) 24%

3-HH-V1 (3-1) 10%

V2-HHB-1 (3-5) 9%

101-HBBH-4 (-) 3%

The composition having the negative dielectric anisotropy was prepared, and its properties were measured. NI = 83.7 DEG C; Tc < -20 C; [Delta] n = 0.107; ?? = -3.7; Vth = 2.21 V;侶 = 22.9 mPa 揃 s; VHR-11 = 37.9%.

Compound (1-2) was added to this composition in a ratio of 0.05% by weight, and VHR-11 was measured. VHR-11 = 69.5%.

[Example 4]

3-H2B (2F, 3F) -O2 (2-3) 15%

5-H2B (2F, 3F) -O2 (2-3) 12%

3-HHB (2F, 3F) -O2 (2-7) 8%

5-HHB (2F, 3F) -O2 (2-7) 6%

2-HHB (2F, 3F) -1 (2-7) 5%

3-HBB (2F, 3F) -O2 (2-15) 10%

4-HBB (2F, 3F) -O2 (2-15) 6%

1V2-HBB (2F, 3F) -O2 (2-15) 4%

2-HH-3 (3-1) 20%

3-HH-4 (3-1) 10%

V2-BB (F) B-1 (3-8) 4%

The composition having the negative dielectric anisotropy was prepared, and its properties were measured. NI = 80.0 DEG C; Tc < -20 C; ? N = 0.096; ? = -3.4; Vth = 2.19 V; ? = 19.0 mPa 占 퐏.

Compound (1-3) was added to this composition in a ratio of 0.1% by weight, and VHR-11 was measured. VHR-11 = 90.4%.

[Example 5]

V2-BB (2F, 3F) -O2 (2-5) 12%

1V2-BB (2F, 3F) -O2 (2-5) 5%

1V2-BB (2F, 3F) -O4 (2-5) 3%

V-HHB (2F, 3F) -O1 (2-7) 5%

V-HHB (2F, 3F) -O2 (2-7) 12%

V-HHB (2F, 3F) -O4 (2-7) 5%

3-HDhB (2F, 3F) -O2 (2-13) 5%

3-dHBB (2F, 3F) -O2 (2-16) 4%

3-HH-V (3-1) 32%

1-BB-3 (3-3) 5%

3-HHEH-3 (3-4) 3%

V-HHB-1 (3-5) 3%

1-BB (F) B-2V (3-8) 3%

3-HHEBH-4 (3-9) 3%

The composition having the negative dielectric anisotropy was prepared, and its properties were measured. NI = 78.6 DEG C; Tc < -20 C; [Delta] n = 0.107; ? = -2.7; Vth = 2.36 V;侶 = 18.8 mPa 揃 s.

Compound (1-4) was added to this composition in a proportion of 0.05% by weight, and VHR-11 was measured. VHR-11 = 89.6%.

[Example 6]

V2-BB (2F, 3F) -O2 (2-5) 12%

1V2-BB (2F, 3F) -O2 (2-5) 6%

1V2-BB (2F, 3F) -O4 (2-5) 3%

V-HHB (2F, 3F) -O1 (2-7) 6%

V-HHB (2F, 3F) -O2 (2-7) 7%

V-HHB (2F, 3F) -O4 (2-7) 5%

1V2-HHB (2F, 3F) -O4 (2-7) 5%

3-DhHlOB (2F, 3F) -O2 (2-14) 5%

3-dHBB (2F, 3F) -O2 (2-16) 5%

3-HH-V (3-1) 26%

3-HH-VFF (3-1) 3%

V2-HB-1 (3-2) 6%

V-HHB-1 (3-5) 5%

2-BB (F) B-5 (3-8) 3%

5-HBB (F) B-3 (3-13) 3%

The composition having the negative dielectric anisotropy was prepared, and its properties were measured. NI = 79.0 DEG C; Tc < -20 C; ? N = 0.112; ? = -2.9; Vth = 2.35 V;侶 = 19.8 mPa 揃 s.

Compound (1-5) was added to this composition in a ratio of 0.05% by weight, and VHR-11 was measured. VHR-11 = 79.7%.

[Example 7]

3-HIOB (2F, 3F) -O2 (2-4) 10%

1V2-BB (2F, 3F) -O2 (2-5) 10%

V-HHB (2F, 3F) -O1 (2-7) 11%

V-HHB (2F, 3F) -O2 (2-7) 12%

3-HH1OB (2F, 3F) -O2 (2-10) 9%

2-BB (2F, 3F) B-3 (2-11) 7%

3-HH-V (3-1) 26%

3-HH-V1 (3-1) 6%

1-HH-2 V1 (3-1) 3%

3-HHB-3 (3-5) 3%

V-HHB-1 (3-5) 3%

The composition having the negative dielectric anisotropy was prepared, and its properties were measured. NI = 81.6 DEG C; Tc < -20 C; ? N = 0.103; ?? = -3.7; Vth = 2.15 V; ? = 20.9 mPa 占 퐏.

Compound (1-4) was added to this composition in a ratio of 0.06% by weight, and VHR-11 was measured. VHR-11 = 66.8%.

[Example 8]

3-HB (2F, 3F) -O2 (2-1) 8%

3-HIOB (2F, 3F) -O2 (2-4) 8%

3-BB (2F, 3F) -O2 (2-5) 5%

2-HH1OB (2F, 3F) -O2 (2-10) 8%

3-HH1OB (2F, 3F) -O2 (2-10) 7%

3-HDhB (2F, 3F) -O2 (2-13) 10%

3-HH-V (3-1) 25%

3-HH-V1 (3-1) 10%

V2-HHB-1 (3-5) 11%

2-BB (F) B-3 (3-8) 8%

The composition having the negative dielectric anisotropy was prepared, and its properties were measured. NI = 79.4 DEG C; Tc < -20 C; ? N = 0.100; ? = -3.5; Vth = 2.20 V; ? = 19.5 mPa 占 퐏.

Compound (1-3) was added to this composition in a ratio of 0.1% by weight, and VHR-11 was measured. VHR-11 = 68.9%.

[Example 9]

V2-HB (2F, 3F) -O2 (2-1) 5%

3-H2B (2F, 3F) -O2 (2-3) 9%

3-HHB (2F, 3F) -O2 (2-7) 12%

2-HH1OB (2F, 3F) -O2 (2-10) 7%

3-HH1OB (2F, 3F) -O2 (2-10) 12%

3-HDhB (2F, 3F) -O2 (2-13) 3%

2-HH-3 (3-1) 27%

1-BB-3 (3-3) 13%

3-HHB-1 (3-5) 3%

3-B (F) BB-2 (3-7) 3%

3-HB (F) HH-5 (3-10) 3%

3-HB (F) BH-3 (3-12) 3%

The composition having the negative dielectric anisotropy was prepared, and its properties were measured. NI = 78.9 DEG C; Tc < -20 C; ? N = 0.098; ? = -2.9; Vth = 2.34 V;侶 = 18.2 mPa 揃 s.

Compound (1-1) was added to this composition in a ratio of 0.05% by weight, and VHR-11 was measured. VHR-11 = 81.3%.

[Example 10]

5-H2B (2F, 3F) -O2 (2-3) 9%

5-BB (2F, 3F) -O4 (2-5) 5%

5-HHB (2F, 3F) -O2 (2-7) 3%

V-HHB (2F, 3F) -O2 (2-7) 6%

3-HH2B (2F, 3F) -O2 (2-9) 3%

3-HH1OB (2F, 3F) -O2 (2-10) 13%

2-BB (2F, 3F) B-3 (2-11) 3%

2-HHB (2F, 3CL) -O2 (2-18) 3%

4-HHB (2F, 3CL) -O2 (2-18) 3%

2-HH-3 (3-1) 22%

3-HH-V (3-1) 5%

V2-BB-1 (3-3) 3%

1-BB-3 (3-3) 13%

3-HB (F) HH-5 (3-10) 3%

5-HBBH-3 (3-11) 3%

3-HB (F) BH-3 (3-12) 3%

The composition having the negative dielectric anisotropy was prepared, and its properties were measured. NI = 78.9 DEG C; Tc < -20 C; ? N = 0.103; ? = -2.6; Vth = 2.49 V; ? = 17.6 mPa 占 퐏.

Compound (1-3) was added to this composition in a ratio of 0.1% by weight, and VHR-11 was measured. VHR-11 = 80.0%.

[Example 11]

3-H2B (2F, 3F) -O2 (2-3) 20%

5-H2B (2F, 3F) -O2 (2-3) 12%

3-HHB (2F, 3F) -O2 (2-7) 8%

5-HHB (2F, 3F) -O2 (2-7) 6%

3-HDhB (2F, 3F) -O2 (2-13) 5%

3-HBB (2F, 3F) -O2 (2-15) 10%

4-HBB (2F, 3F) -O2 (2-15) 6%

2-HH-3 (3-1) 16%

3-HH-4 (3-1) 13%

1V-HBB-2 (3-6) 4%

The composition having the negative dielectric anisotropy was prepared, and its properties were measured. NI = 76.2 DEG C; Tc < -20 C; [Delta] n = 0.089; ? = -3.6; Vth = 2.12 V;侶 = 19.8 mPa 揃 s.

Compound (1-3) was added to this composition in a ratio of 0.05% by weight, and VHR-11 was measured. VHR-11 = 87.1%.

[Example 12]

3-HB (2F, 3F) -O2 (2-1) 5%

V-HB (2F, 3F) -O4 (2-1) 4%

5-BB (2F, 3F) -O2 (2-5) 6%

3-B (2F, 3F) B (2F, 3F) -O2 2-6 3%

V-HHB (2F, 3F) -O2 (2-7) 10%

3-HH1OB (2F, 3F) -O2 (2-10) 10%

2-BB (2F, 3F) B-3 (2-11) 5%

4-HBB (2F, 3F) -O2 (2-15) 5%

V-HBB (2F, 3F) -O2 (2-15) 7%

3-HBB (2F, 3CL) -O2 (2-19) 3%

3-HH-O1 (3-1) 3%

3-HH-V (3-1) 26%

3-HB-O2 (3-2) 3%

V-HHB-1 (3-5) 7%

3-BB (F) B-5 (3-8) 3%

The composition having the negative dielectric anisotropy was prepared, and its properties were measured. NI = 80.6 DEG C; Tc < -20 C; ? N = 0.114; ?? = -3.2; Vth = 2.27 V; ? = 24.0 mPa 占 퐏.

Compound (1-4) was added to this composition in a ratio of 0.06% by weight, and VHR-11 was measured. VHR-11 = 82.9%.

[Example 13]

3-chB (2F, 3F) -O2 (2-2) 6%

3-BB (2F, 3F) -O4 (2-5) 6%

V2-BB (2F, 3F) -O2 (2-5) 6%

3-HHB (2F, 3F) -O2 (2-7) 5%

V-HHB (2F, 3F) -O1 (2-7) 6%

V-HHB (2F, 3F) -O2 (2-7) 9%

2-HCHB (2F, 3F) -O2 (2-8) 3%

3-DhHB (2F, 3F) -O2 (2-12) 5%

3-HEB (2F, 3F) B (2F, 3F) -O2 (2-17) 3%

3-H, OCRO (7F, 8F) -5 (2-20) 3%

3-HH, OCRO (7F, 8F) -5 (2-21) 3%

3-HH-V (3-1) 23%

4-HH-V (3-1) 3%

5-HH-V (3-1) 6%

7-HB-1 (3-2) 3%

V-HHB-1 (3-5) 4%

V-HBB-2 (3-6) 3%

2-BB (F) B-3 (3-8) 3%

The composition having the negative dielectric anisotropy was prepared, and its properties were measured. NI = 70.9 DEG C; Tc < -20 C; ? N = 0.092; ?? = -3.2; Vth = 2.16 V; ? = 22.9 mPa 占 퐏.

Compound (1-5) was added to this composition in a ratio of 0.05% by weight, and VHR-11 was measured. VHR-11 = 84.3%.

[Example 14]

5-H2B (2F, 3F) -O2 (2-3) 9%

5-BB (2F, 3F) -O4 (2-5) 5%

5-HHB (2F, 3F) -O2 (2-7) 3%

V-HHB (2F, 3F) -O2 (2-7) 6%

3-HH2B (2F, 3F) -O2 (2-9) 3%

3-HH1OB (2F, 3F) -O2 (2-10) 13%

2-BB (2F, 3F) B-3 (2-11) 3%

2-HHB (2F, 3CL) -O2 (2-18) 3%

4-HHB (2F, 3CL) -O2 (2-18) 3%

2-HH-3 (3-1) 22%

3-HH-V (3-1) 5%

V2-BB-1 (3-3) 3%

1-BB-5 (3-3) 13%

3-HBB-2 (3-6) 3%

3-HB (F) HH-5 (3-10) 3%

3-HB (F) BH-3 (3-12) 3%

The composition having the negative dielectric anisotropy was prepared, and its properties were measured. NI = 76.1 DEG C; Tc < -20 C; ? N = 0.103; ? = -2.6; Vth = 2.47 V;侶 = 16.8 mPa 揃 s.

Compound (1-1) was added to this composition in a ratio of 0.05% by weight, and VHR-11 was measured. VHR-11 = 82.3%.

[Example 15]

3-BB (2F, 3F) -O4 (2-5) 6%

V2-BB (2F, 3F) -O2 (2-5) 12%

3-HHB (2F, 3F) -O2 (2-7) 5%

V-HHB (2F, 3F) -O1 (2-7) 6%

V2-HHB (2F, 3F) -O2 (2-7) 12%

3-DhHB (2F, 3F) -O2 (2-12) 5%

3-HEB (2F, 3F) B (2F, 3F) -O2 (2-17) 3%

3-H, OCRO (7F, 8F) -5 (2-20) 3%

3-HH, OCRO (7F, 8F) -5 (2-21) 3%

3-HH-V (3-1) 23%

4-HH-V (3-1) 3%

5-HH-V (3-1) 6%

7-HB-1 (3-2) 3%

V-HHB-1 (3-5) 4%

V-HBB-2 (3-6) 3%

2-BB (F) B-3 (3-8) 3%

The composition having the negative dielectric anisotropy was prepared, and its properties were measured. NI = 76.1 DEG C; Tc < -20 C; ? N = 0.099; ? = -3.0; Vth = 2.25 V; ? = 22.7 mPa 占 퐏.

Compound (1-4) was added to this composition in a ratio of 0.03% by weight, and VHR-11 was measured. VHR-11 = 81.4%.

[Example 16]

3-H2B (2F, 3F) -O2 (2-3) 20%

5-H2B (2F, 3F) -O2 (2-3) 12%

3-HHB (2F, 3F) -O2 (2-7) 8%

5-HHB (2F, 3F) -O2 (2-7) 6%

3-HDhB (2F, 3F) -O2 (2-13) 5%

3-HBB (2F, 3F) -O2 (2-15) 10%

4-HBB (2F, 3F) -O2 (2-15) 6%

2-HH-3 (3-1) 16%

3-HH-4 (3-1) 13%

1V-HBB-2 (3-6) 4%

The composition having the negative dielectric anisotropy was prepared, and its properties were measured. NI = 76.2 DEG C; Tc < -20 C; [Delta] n = 0.089; ? = -3.6; Vth = 2.12 V;侶 = 19.8 mPa 揃 s.

Compound (1-2) was added to this composition in a ratio of 0.03% by weight, and VHR-11 was measured. VHR-11 = 86.2%.

[Example 17]

3-BB (2F, 3F) -O4 (2-5) 6%

V2-BB (2F, 3F) -O2 (2-5) 12%

3-HHB (2F, 3F) -O2 (2-7) 8%

V-HHB (2F, 3F) -O1 (2-7) 6%

V2-HHB (2F, 3F) -O2 (2-7) 12%

3-DhHB (2F, 3F) -O2 (2-12) 5%

3-HEB (2F, 3F) B (2F, 3F) -O2 (2-17) 3%

3-H, OCRO (7F, 8F) -5 (2-20) 3%

3-HH-V (3-1) 23%

4-HH-V (3-1) 3%

5-HH-V (3-1) 6%

7-HB-1 (3-2) 3%

V-HHB-1 (3-5) 4%

V-HBB-2 (3-6) 3%

2-BB (F) B-3 (3-8) 3%

The composition having the negative dielectric anisotropy was prepared, and its properties were measured. NI = 77.1 DEG C; Tc < -20 C; ? N = 0.100; ? = -2.9; Vth = 2.30 V;侶 = 21.2 mPa 揃 s.

Compound (1-5) was added to this composition in a ratio of 0.03% by weight, and VHR-11 was measured. VHR-11 = 82.5%.

[Example 18]

3-HB (2F, 3F) -O2 (2-1) 6%

3-BB (2F, 3F) -O4 (2-5) 6%

V2-BB (2F, 3F) -O2 (2-5) 12%

3-HHB (2F, 3F) -O2 (2-7) 8%

V-HHB (2F, 3F) -O1 (2-7) 6%

V2-HHB (2F, 3F) -O2 (2-7) 12%

3-HDhB (2F, 3F) -O2 (2-13) 5%

3-HH-V (3-1) 23%

4-HH-V (3-1) 3%

5-HH-V (3-1) 6%

7-HB-1 (3-2) 3%

V-HHB-1 (3-5) 4%

V-HBB-2 (3-6) 3%

2-BB (F) B-3 (3-8) 3%

The composition having the negative dielectric anisotropy was prepared, and its properties were measured. NI = 72.3 DEG C; Tc < -20 C; ? N = 0.098; ? = -2.8; Vth = 2.28 V; ? = 17.8 mPa 占 퐏.

Compound (1-3) was added to this composition in a ratio of 0.1% by weight, and VHR-11 was measured. VHR-11 = 85.8%.

In Examples 1 to 3, the effects of addition of the first additive were compared. The voltage holding ratio (VHR-11) was measured by the method described in the aforementioned measuring method (10). First, a composition without adding the first additive was injected into the TN device. The device was irradiated with ultraviolet rays of 5 mW / cm &lt; ² &gt; for 167 minutes, and then the voltage maintenance ratio was measured. Next, the composition to which the first additive was added was injected into the TN device, irradiated with ultraviolet rays, and then the voltage holding ratio was measured. The effect of the first additive was evaluated by comparing these measured values. The results are summarized in Table 4. In Examples 1 to 3, the voltage holding ratio (VHR-11) of the composition to which the first additive was not added was about 36%. VHR-11 could be controlled at about 67% by adding the first additive to the composition. In Examples 4 to 18, VHR-11 ranges from 66.8% to 90.4%, and a high voltage maintenance ratio can be maintained. Therefore, it can be concluded that the liquid crystal composition of the present invention has excellent properties.

[Table 4] Effect by addition of the first additive

[Industrial applicability]

The liquid crystal composition of the present invention is characterized in that at least one member selected from the group consisting of at least one member selected from the group consisting of a high upper limit temperature, a lower lower limit temperature, a lower viscosity, a proper optical anisotropy, a negative large anisotropy, a large specific resistance, a high stability against ultraviolet rays, Characteristic, or have an appropriate balance for at least two characteristics. A liquid crystal display element containing this composition has properties such as short response time, large voltage holding ratio, low threshold voltage, large contrast ratio, and long life, and thus can be used for a liquid crystal projector, a liquid crystal TV, and the like.

Claims (20)

The first additive contains at least one compound selected from the group of compounds represented by the following formula (1), and at least one compound selected from the group of compounds represented by the following formula (2) A liquid crystal composition having a negative dielectric anisotropy and a nematic phase, wherein the ratio of the first additive is in the range of 0.005 wt% to 1 wt% based on the weight of the liquid crystal composition, Wherein the ratio of the first component is in the range of 10 wt% to 90 wt%

R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ⁸ are independently hydrogen or alkyl having 1 to 4 carbon atoms; Ring A and Ring B are independently selected from the group consisting of cyclohexylene, cyclohexenylene, decahydronaphthalenediyl, dihydropyranediyl, tetrahydropyranediyl, dioxanediyl, phenylene, naphthalenediyl, pyrimidinediyl, Wherein at least one hydrogen in the ring is fluorine, chlorine, alkyl of 1 to 5 carbon atoms, alkoxy of 1 to 5 carbon atoms, or alkyl of 1 to 5 carbon atoms in which at least one hydrogen is substituted by fluorine or chlorine Lt; / RTI &gt; Z ¹ , Z ² , and Z ³ are independently a single bond or alkylene having 1 to 10 carbon atoms, and at least one -CH ₂ - in the alkylene is -O-, -S-, -CO- , -COO-, -OCO-, or -SiH ₂ -, and at least one -CH ₂ -CH ₂ - may be substituted with -CH = CH- or -C≡C-, , At least one hydrogen may be substituted with fluorine or chlorine; a and b are independently 1 or 2; c is 0, 1 or 2, and ring A when c is 0 is selected from the group consisting of cyclohexenylene, decahydronaphthalenediyl, dihydropyranediyl, tetrahydropyranediyl, dioxanediyl, naphthalenediyl, pyrimidine At least one hydrogen in the ring is selected from the group consisting of fluorine, chlorine, alkyl of 1 to 5 carbon atoms, alkoxy of 1 to 5 carbon atoms, or alkyl of 1 to 5 carbon atoms in which at least one hydrogen is substituted with fluorine or chlorine Lt; / RTI &gt; alkyl,
In the formula (2), R ⁹ and R ¹⁰ independently represent an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, an alkenyl group having 2 to 12 carbon atoms, an alkenyloxy group having 2 to 12 carbon atoms, One hydrogen is alkyl of 1 to 12 carbon atoms substituted with fluorine or chlorine; 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 replaced by fluorine or chlorine , Or tetrahydropyran-2,5-diyl; Ring D is 2,3-difluoro-1,4-phenylene, 2-chloro-3-fluoro-1,4-phenylene, 2,3- -Phenylene, 3,4,5-trifluoronaphthalene-2,6-diyl, or 7,8-difluorochroman-2,6-diyl; Z ⁴ and Z ⁵ are, independently, a single bond, ethylene, methyleneoxy, or carbonyloxy; d is 1, 2, or 3; e is 0 or 1; And the sum of d and e is 3 or less. The method according to claim 1,
A liquid crystal composition comprising as a first additive at least one compound selected from the group of compounds represented by the following formulas (1-1) to (1-5):

R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ⁸ independently represent hydrogen or an alkyl group having 1 to 4 carbon atoms Lt; / RTI &gt; 3. The method according to claim 1 or 2,
A liquid crystal composition comprising, as a first component, at least one compound selected from the group of compounds represented by the following formulas (2-1) to (2-21)

In the formulas (2-1) to (2-21), R ⁹ and R ¹⁰ are independently selected from the group consisting of alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, alkenyl having 2 to 12 carbons, Alkenyloxy having 1 to 12 carbon atoms, or alkyl having 1 to 12 carbon atoms in which at least one hydrogen is substituted with fluorine or chlorine. 3. The method according to claim 1 or 2,
A liquid crystal composition comprising, as a second component, at least one compound selected from the group of compounds represented by the following formula (3):

In the formula (3), R ¹¹ and R ¹² are independently selected from the group consisting of alkyl having 1 to 12 carbon atoms, alkoxy having 1 to 12 carbon atoms, alkenyl having 2 to 12 carbon atoms, Alkyl having 1 to 12 carbon atoms, or alkenyl having 2 to 12 carbon atoms in which at least one hydrogen is substituted with fluorine; The rings F and the ring G are independently selected from the group consisting of 1,4-cyclohexylene, 1,4-phenylene, 2-fluoro-1,4-phenylene, or 2,5-difluoro- It is wen; Z ⁶ is a single bond, ethylene or carbonyloxy; f is 1, 2, or 3; 3. The method according to claim 1 or 2,
A liquid crystal composition comprising as a second component at least one compound selected from the group of compounds represented by the following formulas (3-1) to (3-13)

In the formulas (3-1) to (3-13), R ¹¹ and R ¹² independently represent alkyl having 1 to 12 carbon atoms, alkoxy having 1 to 12 carbon atoms, alkenyl having 2 to 12 carbon atoms, Alkyl of 1 to 12 carbon atoms in which hydrogen is replaced by fluorine or chlorine, or alkenyl of 2 to 12 carbon atoms in which at least one hydrogen is substituted by fluorine. 5. The method of claim 4,
Wherein the proportion of the second component is in the range of 10% by weight to 90% by weight, based on the weight of the liquid crystal composition. 3. The method according to claim 1 or 2,
A liquid crystal composition comprising, as a second additive, at least one polymerizable compound selected from the group of compounds represented by the following formula (4)

In the above formula (4), Ring I and Ring K are independently selected from the group consisting of cyclohexyl, cyclohexenyl, phenyl, 1-naphthyl, 2-naphthyl, tetrahydropyran- Yl, pyrimidin-2-yl, or pyridin-2-yl, wherein at least one hydrogen is fluorine, chlorine, alkyl of 1 to 12 carbon atoms, alkoxy of 1 to 12 carbon atoms, At least one hydrogen may be substituted with alkyl having 1 to 12 carbon atoms substituted with fluorine or chlorine; The ring J is preferably selected from the group consisting of 1,4-cyclohexylene, 1,4-cyclohexenylene, 1,4-phenylene, naphthalene-1,2-diyl, naphthalene- Naphthalene-1,6-diyl, naphthalene-1,7-diyl, naphthalene-1,8-diyl, naphthalene-2,3-diyl, naphthalene- Naphthalene-2,7-diyl, tetrahydropyran-2,5-diyl, 1,3-dioxane-2,5-diyl, pyrimidine-2,5-diyl or pyridine- In these rings, at least one hydrogen is substituted with fluorine, chlorine, alkyl having 1 to 12 carbon atoms, alkoxy having 1 to 12 carbon atoms, or alkyl having 1 to 12 carbon atoms in which at least one hydrogen is substituted with fluorine or chlorine It may be; Z ⁷ and Z ⁸ are independently a single bond or an alkylene having 1 to 10 carbon atoms, and in the alkylene, at least one -CH ₂ - represents -O-, -CO-, -COO-, or - O-, at least one -CH ₂ -CH ₂ - may be replaced by -CH═CH-, -C (CH ₃ ) ═CH-, -CH═C (CH ₃ ) -, or -C CH ₃ ) = C (CH ₃ ) -, in which at least one hydrogen may be substituted with fluorine or chlorine; P ¹ , P ² and P ³ are independently a polymerizable group; Sp ¹ , Sp ² and Sp ³ are independently a single bond or an alkylene having 1 to 10 carbon atoms, and at least one -CH ₂ - in the alkylene is -O-, -COO-, -OCO -, or -OCOO-, and at least one -CH ₂ -CH ₂ - may be replaced by -CH═CH- or -C≡C-, and in these groups, at least one hydrogen is , Fluorine or chlorine; g is 0, 1, or 2; h, i, and j are independently 0, 1, 2, 3, or 4; The sum of h, i and j is 1 or more. 8. The method of claim 7,
Wherein P ¹ , P ² and P ³ are independently a polymerizable group selected from the group of groups represented by the following formulas (P-1) to (P-5) in the formula (4)

In the formulas (P-1) to (P-5), M ¹ , M ² and M ³ are independently hydrogen, fluorine, alkyl of 1 to 5 carbon atoms, or at least one hydrogen atom is fluorine or chlorine Substituted alkyl having 1 to 5 carbon atoms. 3. The method according to claim 1 or 2,
A liquid crystal composition comprising, as a second additive, at least one polymerizable compound selected from the group of compounds represented by the following formulas (4-1) to (4-27)

In the formulas (4-1) to (4-27), P ⁴ , P ⁵ and P ⁶ are independently a group of groups represented by the following formulas (P-1) to (P-3) &Lt; / RTI &gt;

In the formulas (P-1) to (P-3), M ¹ , M ² and M ³ are independently hydrogen, fluorine, alkyl of 1 to 5 carbon atoms, Alkyl having 1 to 5 carbon atoms; In the formula (4-1) ~ Formula (4-27), Sp ^1, Sp ^2, Sp ^3, and are, each independently, a single bond or an alkylene group of 1 to 10 carbon atoms, in the alkylene group, at least one -CH ₂ - may be substituted with -O-, -COO-, -OCO-, or -OCOO-, and at least one -CH ₂ -CH ₂ - may be replaced by -CH = CH- or -C≡ C-, and in these groups, at least one hydrogen may be substituted with fluorine or chlorine. 8. The method of claim 7,
Wherein the proportion of the second additive is in the range of 0.03 wt% to 10 wt% based on the weight of the liquid crystal composition. A liquid crystal display element comprising the liquid crystal composition according to claim 1 or 2. 12. The method of claim 11,
A liquid crystal display element in which the operation mode of the liquid crystal display element is the IPS mode, the VA mode, the FFS mode, or the FPA mode, and the liquid crystal display element is driven by the active matrix system. A polymer-supported alignment type liquid crystal display element comprising the liquid crystal composition according to claim 7, wherein the polymerizable compound in the liquid crystal composition is polymerized. 3. The method according to claim 1 or 2,
A liquid crystal composition for use as a liquid crystal display element. 8. The method of claim 7,
A liquid crystal composition for use as a polymer supported alignment type liquid crystal display device. delete delete delete delete delete