CN111712557A - Liquid crystal composition and liquid crystal display element - Google Patents

Abstract

The present invention provides a liquid crystal composition and an AM device comprising the composition. The liquid crystal composition has high upper limit temperature, low lower limit temperature, low viscosity, appropriate optical anisotropy, large dielectric anisotropy, and specific resistance. Among the properties such as large, high stability, and large elastic constant, at least one of the properties is satisfied, or there is an appropriate balance with respect to at least two properties. A liquid crystal composition containing a specific compound having a polymerizable group as a first additive, and may also contain a specific compound having a large negative dielectric anisotropy as a first component, and a second component having a high upper limit A specific compound having a low temperature or viscosity, or a specific compound having a polymerizable group as a second additive.

Description

Liquid crystal composition and liquid crystal display element

technical field

The present invention relates to a liquid crystal composition, a liquid crystal display element containing the composition, and the like. In particular, it relates to a liquid crystal composition with negative dielectric anisotropy, and a liquid crystal composition containing the composition and having in-plane switching (IPS), vertical alignment (VA), fringe field switching (Fringe Field switching) , FFS), electric field-induced photo-reactive alignment (field-induced photo-reactive alignment, FPA) and other modes of liquid crystal display elements. The present invention also relates to a polymer-stabilized alignment type liquid crystal display element.

Background technique

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

The liquid crystal display element contains a liquid crystal composition having a nematic phase. The composition has suitable properties. By improving the properties of the composition, an AM device having good properties can be obtained. The associations among these properties are summarized in Table 1 below. The properties of the composition will be further described based on a commercially available AM device. The temperature range of the nematic phase correlates to the temperature range over which the element can be used. The preferable upper limit temperature of the nematic phase is about 70°C or higher, and the preferable lower limit temperature of the nematic phase is about -10°C or lower. The viscosity of the composition correlates to the response time of the element. In order to display a moving image with an element, it is preferable that the response time is short. The ideal is a response time of less than 1 millisecond. Therefore, the viscosity of the composition is preferably small. Furthermore, it is preferable that the viscosity at low temperature is small. The elastic constant of the composition correlates to the contrast of the element. In the element, in order to improve the contrast ratio, it is more preferable that the elastic constant of the composition be large.

Table 1. Properties of compositions and properties of AM devices

The optical anisotropy of the composition correlates to the contrast ratio of the element. Depending on the mode of the element, the optical anisotropy needs to be large or the optical anisotropy is small, that is, the optical anisotropy is appropriate. The product (Δn×d) of the optical anisotropy (Δn) of the composition and the cell gap (d) of the element is designed to maximize the contrast ratio. The appropriate value of the product depends on the type of operation mode. In the element of the VA mode, the value is in the range of about 0.30 μm to about 0.40 μm, and in the element of the IPS mode or the FFS mode, the value is in the range of about 0.20 μm to about 0.30 μm. In these cases, a composition having a large optical anisotropy is preferable for an element with a small cell gap. The large dielectric anisotropy of the composition contributes to the low threshold voltage, low power consumption and high contrast ratio of the device. Therefore, it is preferable that the dielectric anisotropy is large. A high specific resistance of the composition contributes to a high voltage holding ratio and a high contrast ratio of the element. Therefore, a composition having a large specific resistance in the initial stage is preferable. A composition having a large specific resistance after long-term use is preferred. The stability of the composition to UV light or heat correlates with the lifetime of the element. When the stability is high, the life of the element is long. Such characteristics are preferable for AM elements used for liquid crystal monitors, liquid crystal televisions, and the like.

In general-purpose liquid crystal display elements, the vertical alignment of liquid crystal molecules can be realized by a specific polyimide alignment film. In a polymer sustained alignment (PSA) type liquid crystal display element, a polymer and an alignment film are combined. First, a composition to which a small amount of a polymerizable compound is added is injected into the element. Next, a voltage is applied between the substrates facing the element, and ultraviolet rays are irradiated on the composition. The polymerizable compound is polymerized to form a polymer network structure in the composition. In the composition, the alignment of the liquid crystal molecules can be controlled by using the polymer, so that the response time of the element is shortened, and the afterimage of the image is improved. Such effects of polymers can be expected in elements having modes such as TN, ECB, OCB, IPS, VA, FFS, and FPA.

On the other hand, in the liquid crystal display element which does not have an alignment film, the liquid crystal composition containing a polymer and a polar compound is used. First, a composition to which a small amount of a polymerizable compound and a small amount of a polar compound are added is injected into the element. Here, the polar compound is adsorbed on the substrate surface of the element and arranged. According to the arrangement, the liquid crystal molecules are aligned. Next, the composition is irradiated with ultraviolet rays while applying a voltage between the substrates of the element. Here, the polymerizable compound is polymerized to stabilize the alignment of the liquid crystal molecules. In the composition, the alignment of the liquid crystal molecules can be controlled by the polymer and the polar compound, so that the response time of the element is shortened, and the afterimage of the image is improved. Furthermore, in the element which does not have an alignment film, the process of forming an alignment film is unnecessary. Since there is no alignment film, the resistance of the element does not decrease due to the interaction between the alignment film and the composition. Such effects brought about by the combination of the polymer and the polar compound can be expected in elements having modes such as TN, ECB, OCB, IPS, VA, FFS, and FPA.

A composition having a positive dielectric anisotropy is used in an AM element having a TN mode. A composition having a negative dielectric anisotropy is used in an AM element having a VA mode. Compositions having positive or negative dielectric anisotropy are used in AM elements having IPS mode, FFS mode, or FPA mode. Compositions with positive or negative dielectric anisotropy are used in polymer-stabilized oriented elements. A composition having positive or negative dielectric anisotropy is used in an element without an alignment film.

prior art literature

Patent Literature

Patent Document 1: International Publication No. 2015-004954

Patent Document 2: Japanese Patent Laid-Open No. 2003-307720

Patent Document 3: Japanese Patent Laid-Open No. 2004-131704

Patent Document 4: Specification of European Patent Application Publication No. 1889894

SUMMARY OF THE INVENTION

The problem to be solved by the invention

An object of the present invention is to provide a liquid crystal composition which satisfies the requirements of high upper limit temperature of nematic phase, low minimum temperature of nematic phase, low viscosity, suitable optical anisotropy, large negative dielectric anisotropy, and specific resistance. At least one of characteristics such as large, high stability to ultraviolet rays, high stability to heat, and large elastic constant. Another subject is to provide a liquid crystal composition having an appropriate balance between at least two of these properties. Another subject is to provide a liquid crystal display element containing such a composition. Another subject is to provide an AM element having characteristics such as a short response time, a large voltage holding ratio, a low threshold voltage, a large contrast ratio, and a long life.

Existing polymerizable compounds cannot provide a liquid crystal composition that satisfies high stability to ultraviolet rays.

technical solutions to problems

The present invention relates to a liquid crystal composition containing at least one compound selected from the polymerizable compounds represented by formula (1) as a first additive, and a liquid crystal display element containing the composition, and Has a nematic phase.

In formula (1), ring A ¹ and ring A ³ are cyclohexyl, cyclohexenyl, phenyl, 1-naphthyl, 2-naphthyl, tetrahydropyran-2-yl, 1,3-dioxyl Alkyl-2-yl, pyrimidin-2-yl or pyridin-2-yl, in these rings, at least one hydrogen can be replaced by fluorine, chlorine, alkyl with 1 to 12 carbons, alkoxy with 1 to 12 carbons, Or at least one hydrogen is substituted by an alkyl group having 1 to 12 carbon atoms substituted by fluorine or chlorine; Ring A ² is 1,4-cyclohexylene, 1,4-cyclohexenylene, 1,4-phenylene, Naphthalene-1,2-diyl, Naphthalene-1,3-diyl, Naphthalene-1,4-diyl, Naphthalene-1,5-diyl, Naphthalene-1,6-diyl, Naphthalene-1,7 -diyl, naphthalene-1,8-diyl, naphthalene-2,3-diyl, naphthalene-2,6-diyl, naphthalene-2,7-diyl, tetrahydropyran-2,5-diyl base, 1,3-dioxane-2,5-diyl, pyrimidine-2,5-diyl or pyridine-2,5-diyl, in these rings, at least one hydrogen can be replaced by fluorine, chlorine, carbon number An alkyl group of 1 to 12, an alkoxy group of 1 to 12 carbon atoms, or an alkyl group of 1 to 12 carbon atoms in which at least one hydrogen is substituted by fluorine or chlorine; P ¹ , P ² and P ³ are polymerizable groups, and at least one of P ¹ , P ² and P ³ is a polymerizable group represented by formula (P-1);

Z ¹ and Z ² are a single bond or an alkylene group having 1 to 10 carbon atoms, and in the alkylene group, at least one -CH ₂ - may be substituted by -O-, -CO-, -COO- or -OCO- , at least one -CH ₂ -CH ₂ - can be via -CH=CH-, -C(CH ₃ )=CH-, -CH=C(CH ₃ )- or -C(CH ₃ )=C(CH ₃ ) -Substituted, among these groups, at least one hydrogen can be substituted by fluorine or chlorine; Sp ¹ , Sp ² and Sp ³ are single bonds or alkylene groups with 1 to 10 carbon atoms, and in the alkylene groups, at least one -CH ₂ - can be substituted by -O-, -COO-, -OCO- or -OCOO-, at least one -CH ₂ -CH ₂ - can be substituted by -CH=CH- or -C≡C-, among these groups, at least One hydrogen may be substituted by fluorine or chlorine; a is 0, 1 or 2; b, c and d are 0, 1, 2, 3 or 4, and the sum of b, c and d is 1 or more;

In formula (P-1), M ¹ is an alkyl group having 1 to 5 carbon atoms; n is an integer of 1 to 5.

effect of invention

The advantages of the present invention are to provide a liquid crystal composition which satisfies the requirements of high upper limit temperature of nematic phase, low lower limit temperature of nematic phase, low viscosity, suitable optical anisotropy, large negative dielectric anisotropy, and specific resistance. At least one of characteristics such as large, high stability to ultraviolet rays, high stability to heat, and large elastic constant. Another advantage is to provide a liquid crystal composition with a suitable balance between at least two of these properties. Another advantage is to provide a liquid crystal display element containing such a composition. Still another advantage is to provide an AM element with characteristics such as short response time, high voltage holding ratio, low threshold voltage, high contrast ratio, and long life.

Detailed ways

The usage method of the term in the said specification is as follows. The terms of "liquid crystal composition" and "liquid crystal display element" may be abbreviated as "composition" and "element", respectively. A "liquid crystal display element" is a general term for a liquid crystal display panel and a liquid crystal display module. "Liquid crystal compound" is a compound having a liquid crystal phase such as a nematic phase and a smectic phase, and a compound that does not have a liquid crystal phase but is used to adjust the temperature range, viscosity, and dielectric anisotropy of the nematic phase. Generic term for compounds mixed in a composition for the purpose. The compound has, for example, a six-membered ring such as 1,4-cyclohexylene or 1,4-phenylene, and its molecule (liquid crystal molecule) is rodlike. The "polymerizable compound" is a compound added for the purpose of forming a polymer in the composition. The liquid crystal compound having an alkenyl group is not classified as a polymerizable compound in its meaning.

The liquid crystal composition is prepared by mixing a plurality of liquid crystal compounds. Additives such as an optically active compound or a polymerizable compound are optionally added to the liquid crystal composition. Even when an additive is added, the ratio of the liquid crystal compound is represented by the mass percentage (mass %) based on the mass of the liquid crystal composition not containing the additive. The ratio of the additive is represented by the mass percentage (mass %) based on the mass of the liquid crystal composition not containing the additive. That is, the ratio of the liquid crystal compound or the additive is calculated based on the total mass of the liquid crystal compound. Parts per million by mass (ppm) are sometimes used. The ratio of the polymerization initiator and the polymerization inhibitor is expressed based on the mass of the polymerizable compound exceptionally.

The "upper limit temperature of the nematic phase" is sometimes simply referred to as the "upper limit temperature". The "lower limit temperature of the nematic phase" is sometimes simply referred to as the "lower limit temperature". The expression "improving the dielectric anisotropy" means that the value of the composition with a positive dielectric anisotropy increases positively, and when the composition has a negative dielectric anisotropy, it means that the value is negative. increase to the ground. "Large voltage retention ratio" means that the element has a large voltage retention ratio not only at room temperature but also at a temperature close to the upper limit temperature in the initial stage, and not only at room temperature but also at a temperature close to the upper limit temperature after long-term use It has a large voltage holding ratio even at the temperature of the upper limit temperature. The properties of a composition or element are sometimes studied by time-varying tests.

The compound (1z) will be described as an example. In formula (1z), the symbols α and β enclosed by a hexagon correspond to ring α and ring β, respectively, and represent rings such as a six-membered ring and a condensed ring. When the subscript 'x' is 2, there are two rings α. The two groups represented by the two rings α may be the same or different. The rules apply to any two rings α where the subscript 'x' is greater than 2. The rules also apply to other notations such as the bonding group Z. A diagonal line crossing one side of ring β indicates that any hydrogen on ring β may be substituted with a substituent (-Sp-P). The subscript 'y' denotes the number of substituted substituents. When the subscript 'y' is 0, there is no such substitution. When the subscript 'y' is 2 or more, a plurality of substituents (-Sp-P) are present on the ring β. The rule "may be the same, or it may be different" also applies in this case. Again, the rules also apply when the notation for Ra is used in a variety of compounds.

In formula (1z), for example, the expression "Ra and Rb are alkyl, alkoxy or alkenyl" means that Ra and Rb are independently selected from the group of alkyl, alkoxy and alkenyl. That is, the group represented by Ra and the group represented by Rb may be the same or different.

At least one compound selected from the compounds represented by the formula (1z) may be abbreviated as "compound (1z)" in some cases. "Compound (1z)" refers to one compound represented by formula (1z), a mixture of two compounds, or a mixture of three or more compounds. The same applies to compounds represented by other formulae. The expression "at least one compound selected from the compounds represented by formula (1z) and formula (2z)" means at least one compound selected from the group of compound (1z) and compound (2z).

The expression "at least one 'A'" means that the number of 'A's is arbitrary. The expression "at least one 'A' may be substituted by 'B'" means that when the number of 'A' is one, the position of 'A' is arbitrary, and when the number of 'A' is two or more, their positions There are also unlimited options. The expression "at least one _-CH2- may be substituted with -O-" is sometimes used. In that case, _-CH2 - _CH2 -CH2- can be converted to -O- _CH2 - _O- by substituting a non-adjacent _-CH2- with -O-. However, the adjacent _-CH2- is not substituted with -O-. This is because -OO-CH ₂ - (peroxide) is formed in the substitution.

The alkyl group of the liquid crystal compound is linear or branched, and does not contain a cyclic alkyl group. Straight chain alkyl groups are preferred over branched alkyl groups. The same applies to terminal groups such as an alkoxy group and an alkenyl group. To increase the upper temperature limit, the steric configuration associated with 1,4-cyclohexylene is the trans configuration over the cis configuration. Since 2-fluoro-1,4-phenylene is left-right asymmetric, there are leftward (L) and rightward (R) directions.

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

The present invention is the following items and the like.

Item 1. A liquid crystal composition comprising at least one compound selected from the polymerizable compounds represented by formula (1) as a first additive, and having a nematic phase.

In formula (1), ring A ¹ and ring A ³ are cyclohexyl, cyclohexenyl, phenyl, 1-naphthyl, 2-naphthyl, tetrahydropyran-2-yl, 1,3-dioxyl Alkyl-2-yl, pyrimidin-2-yl or pyridin-2-yl, in these rings, at least one hydrogen can be replaced by fluorine, chlorine, alkyl with 1 to 12 carbons, alkoxy with 1 to 12 carbons, Or at least one hydrogen is substituted by an alkyl group having 1 to 12 carbon atoms substituted by fluorine or chlorine; Ring A ² is 1,4-cyclohexylene, 1,4-cyclohexenylene, 1,4-phenylene, Naphthalene-1,2-diyl, Naphthalene-1,3-diyl, Naphthalene-1,4-diyl, Naphthalene-1,5-diyl, Naphthalene-1,6-diyl, Naphthalene-1,7 -diyl, naphthalene-1,8-diyl, naphthalene-2,3-diyl, naphthalene-2,6-diyl, naphthalene-2,7-diyl, tetrahydropyran-2,5-diyl base, 1,3-dioxane-2,5-diyl, pyrimidine-2,5-diyl or pyridine-2,5-diyl, in these rings, at least one hydrogen can be replaced by fluorine, chlorine, carbon number An alkyl group of 1 to 12, an alkoxy group of 1 to 12 carbon atoms, or an alkyl group of 1 to 12 carbon atoms in which at least one hydrogen is substituted by fluorine or chlorine; P ¹ , P ² and P ³ are polymerizable groups, and at least one of P ¹ , P ² and P ³ is a polymerizable group represented by formula (P-1);

Z ¹ and Z ² are a single bond or an alkylene group having 1 to 10 carbon atoms, and in the alkylene group, at least one -CH ₂ - may be substituted by -O-, -CO-, -COO- or -OCO- , at least one -CH ₂ -CH ₂ - can be via -CH=CH-, -C(CH ₃ )=CH-, -CH=C(CH ₃ )- or -C(CH ₃ )=C(CH ₃ ) -Substituted, among these groups, at least one hydrogen can be substituted by fluorine or chlorine; Sp ¹ , Sp ² and Sp ³ are single bonds or alkylene groups with 1 to 10 carbon atoms, and in the alkylene groups, at least one -CH ₂ - can be substituted by -O-, -COO-, -OCO- or -OCOO-, at least one -CH ₂ -CH ₂ - can be substituted by -CH=CH- or -C≡C-, among these groups, at least One hydrogen may be substituted by fluorine or chlorine; a is 0, 1 or 2; b, c and d are 0, 1, 2, 3 or 4, and the sum of b, c and d is 1 or more;

In formula (P-1), M ¹ is an alkyl group having 1 to 5 carbon atoms; n is an integer of 1 to 5.

Item 2. The liquid crystal composition according to Item 1, wherein in the formula (1), P ¹ , P ² and P ³ are polymerizable groups selected from the group consisting of the polymerizable groups represented by the formula (P-1) to the formula (P-6). group in , and at least one of P ¹ , P ² and P ³ is a polymerizable group represented by formula (P-1).

In formula (P-1) to formula (P-6), M ¹ is an alkyl group having 1 to 5 carbon atoms; M ² , M ³ and M ⁴ are hydrogen, fluorine, an alkyl group having 1 to 5 carbon atoms, or an alkyl group having 1 to 5 carbons in which at least one hydrogen is substituted by fluorine or chlorine; n is an integer of 1 to 5.

Item 3. The liquid crystal composition according to Item 1 or Item 2, comprising at least one compound selected from the group consisting of compounds represented by formula (1-1) to formula (1-30) as a first additive.

In formula (1-1) to formula (1-30), R ¹ is hydrogen, alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, alkenyl having 2 to 12 carbons, carbon number Alkenyloxy group of 2 to 12, or alkyl group of carbon number 1 to 12 in which at least one hydrogen is substituted by fluorine or chlorine; P ⁵ , P ⁶ and P ⁷ are selected from formula (P-1) to formula (P- 4) a group in the polymerizable group represented, and at least one of P ⁵ , P ⁶ and P ⁷ is a polymerizable group represented by formula (P-1);

Here, M ¹ is an alkyl group having 1 to 5 carbon atoms; M ² , M ³ and M ⁴ are hydrogen, fluorine, an alkyl group having 1 to 5 carbon atoms, or a carbon number 1 wherein at least one hydrogen is substituted by fluorine or chlorine. to 5 alkyl groups; n is an integer from 1 to 5; Sp ¹ , Sp ² and Sp ³ are single bonds or alkylene groups with carbon numbers from 1 to 10, in the alkylene groups, at least one -CH ₂ - can be Substituted by -O-, -COO-, -OCO- or -OCOO-, at least one -CH ₂ -CH ₂ - can be substituted by -CH=CH- or -C≡C-, in these groups, at least one hydrogen can be Substituted by fluorine or chlorine.

Item 4. The liquid crystal composition according to any one of Items 1 to 3, wherein the ratio of the first additive is in the range of 0.03% by mass to 10% by mass.

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

In formula (2), R ¹ and R ² are hydrogen, alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, alkenyl having 2 to 12 carbons, alkenyl having 2 to 12 carbons Oxy group, or an alkyl group having 1 to 12 carbon atoms in which at least one hydrogen is substituted by fluorine or chlorine; Ring D and Ring F are 1,4-cyclohexylene, 1,4-cyclohexenylene, tetrahydropyran -2,5-diyl, 1,4-phenylene, 1,4-phenylene with at least one hydrogen substituted with fluorine or chlorine, naphthalene-2,6-diyl, at least one hydrogen with fluorine or chlorine substituted naphthalene-2,6-diyl, chroman-2,6-diyl, or chroman-2,6-diyl in which at least one hydrogen is substituted by fluorine or chlorine; ring E is 2,3-diyl Fluoro-1,4-phenylene, 2-chloro-3-fluoro-1,4-phenylene, 2,3-difluoro-5-methyl-1,4-phenylene, 3,4, 5-Trifluoronaphthalene-2,6-diyl, 7,8-difluorochroman-2,6-diyl, 3,4,5,6-tetrafluorofluorene-2,7-diyl, 4 ,6-difluorodibenzofuran-3,7-diyl, 4,6-difluorodibenzothiophene-3,7-diyl or 1,1,6,7-tetrafluoroindan-2, 5-diyl; Z ³ and Z ⁴ are single bond, ethylene, methyleneoxy or carbonyloxy; e is 0, 1, 2 or 3, f is 0 or 1; and the sum of e and f 3 or less.

Item 6. The liquid crystal composition according to any one of Items 1 to 5, comprising at least one compound selected from the group of compounds represented by formula (2-1) to formula (2-35) as first ingredient.

In formula (2-1) to formula (2-35), R ¹ and R ² are hydrogen, alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, alkenyl having 2 to 12 carbons , an alkenyloxy group having 2 to 12 carbons, or an alkyl group having 1 to 12 carbons in which at least one hydrogen is substituted with fluorine or chlorine.

Item 7. The liquid crystal composition according to Item 5 or Item 6, wherein the ratio of the first component is in the range of 10% by mass to 90% by mass.

Item 8. The liquid crystal composition according to any one of Items 1 to 7, comprising at least one compound selected from the group consisting of compounds represented by formula (3) as a second component.

In formula (3), R ³ and R ⁴ are an alkyl group having 1 to 12 carbons, an alkoxy group having 1 to 12 carbons, an alkenyl group having 2 to 12 carbons, a carbon having at least one hydrogen substituted with fluorine or chlorine Alkyl of 1 to 12, or alkenyl of 2 to 12 carbons in which at least one hydrogen is substituted by fluorine or chlorine; Ring G and Ring I are 1,4-cyclohexylene, 1,4-phenylene, 2 -Fluoro-1,4-phenylene or 2,5-difluoro-1,4-phenylene; Z ⁵ is a single bond, ethylene or carbonyloxy; g is 1, 2 or 3.

Item 9. The liquid crystal composition according to any one of Items 1 to 8, comprising at least one compound selected from the group consisting of compounds represented by formula (3-1) to formula (3-13) as a second component .

In formula (3-1) to formula (3-13), R ³ and R ⁴ are alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, alkenyl having 2 to 12 carbons, at least An alkyl group having 1 to 12 carbons in which one hydrogen is substituted with fluorine or chlorine, or an alkenyl group having 2 to 12 carbons in which at least one hydrogen is substituted with fluorine or chlorine.

Item 10. The liquid crystal composition according to Item 8 or Item 9, wherein the ratio of the second component is in the range of 10% by mass to 90% by mass.

Item 11. The liquid crystal composition according to any one of Items 1 to 10, comprising at least one compound selected from the group consisting of polymerizable compounds represented by formula (4) as a second additive.

In formula (4), ring I and ring K are cyclohexyl, cyclohexenyl, phenyl, 1-naphthyl, 2-naphthyl, tetrahydropyran-2-yl, 1,3-dioxane- 2-yl, pyrimidin-2-yl or pyridin-2-yl, in these rings, at least one hydrogen can be fluorine, chlorine, alkyl with 1 to 12 carbons, alkoxy with 1 to 12 carbons, or at least One hydrogen is substituted by fluorine or chlorine substituted alkyl group with carbon number from 1 to 12; ring J is 1,4-cyclohexylene, 1,4-cyclohexenylene, 1,4-phenylene, naphthalene-1 ,2-diyl, naphthalene-1,3-diyl, naphthalene-1,4-diyl, naphthalene-1,5-diyl, naphthalene-1,6-diyl, naphthalene-1,7-diyl , naphthalene-1,8-diyl, naphthalene-2,3-diyl, naphthalene-2,6-diyl, naphthalene-2,7-diyl, tetrahydropyran-2,5-diyl, 1 ,3-dioxane-2,5-diyl, pyrimidine-2,5-diyl or pyridine-2,5-diyl, in these rings, at least one hydrogen can be replaced by fluorine, chlorine, carbon number from 1 to 12 The alkyl group, the alkoxy group of carbon number 1 to 12, or the alkyl group of carbon number 1 to 12 substituted by fluorine or chlorine at least one hydrogen is substituted; Z ⁶ and Z ⁷ are single bond or carbon number 1 to 10 In the alkylene group, at least one -CH ₂ - can be substituted by -O-, -CO-, -COO- or -OCO-, and at least one -CH ₂ -CH ₂ - can be substituted by -CH=CH -, -C(CH ₃ )=CH-, -CH=C(CH ₃ )- or -C(CH ₃ )=C(CH ₃ )- substituted, in these groups, at least one hydrogen may be substituted by fluorine or chlorine ; P ⁹ , P ¹⁰ and P ¹¹ are groups selected from the polymerizable groups represented by formula (P-7) to formula (P-11);

Sp ⁵ , Sp ⁶ and Sp ⁷ are a single bond or an alkylene group having 1 to 10 carbon atoms, and in the alkylene group, at least one -CH ₂ - may be via -O-, -COO-, -OCO- or - OCOO-substituted, at least one -CH ₂ -CH ₂ - can be substituted by -CH=CH- or -C≡C-, in these groups, at least one hydrogen can be substituted by fluorine or chlorine; h is 0, 1 or 2; i, j and k are 0, 1, 2, 3 or 4, and the sum of i, j and k is 1 or more;

In formula (P-7) to formula (P-11), M ⁵ , M ⁶ and M ⁷ are hydrogen, fluorine, an alkyl group having 1 to 5 carbon atoms, or a carbon number 1 wherein at least one hydrogen is substituted by fluorine or chlorine to 5 alkyl groups.

Item 12. The liquid crystal composition according to any one of Item 1 to Item 11, comprising at least one compound selected from the group consisting of compounds represented by formula (4-1) to formula (4-29) as a second addition thing.

In formula (4-1) to formula (4-29), P ¹² , P ¹³ and P ¹⁴ are polymerizable groups selected from the groups represented by formula (P-7) to formula (P-9);

Here, M ⁵ , M ⁶ and M ⁷ are hydrogen, fluorine, an alkyl group having 1 to 5 carbon atoms, or an alkyl group having 1 to 5 carbon atoms in which at least one hydrogen is substituted with fluorine or chlorine; Sp ⁵ , Sp ⁶ and Sp ⁷ is a single bond or an alkylene group having 1 to 10 carbon atoms, in the alkylene group, at least one -CH ₂ - may be substituted by -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.

Item 13. The liquid crystal composition according to Item 11 or Item 12, wherein the ratio of the second additive is in the range of 0.03% by mass to 10% by mass.

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 IPS mode, VA mode, FFS mode or FPA mode, and the driving method of the liquid crystal display element is an active matrix method.

Item 16. A polymer-stabilized alignment type liquid crystal display element comprising the liquid crystal composition according to any one of Items 1 to 13, or a polymerizable compound in the liquid crystal composition that is polymerized.

Item 17. Use of a liquid crystal composition, which is the liquid crystal composition according to any one of Items 1 to 13, in a liquid crystal display element.

Item 18. Use of a liquid crystal composition, which is the liquid crystal composition according to any one of Items 1 to 13, in a polymer-stabilized alignment type liquid crystal display element.

The present invention also includes the following items. (a) The composition further comprising at least additives such as optically active compounds, antioxidants, ultraviolet absorbers, pigments, antifoaming agents, polymerizable compounds, polymerization initiators, polymerization inhibitors, polar compounds, and the like One as a third addition. (b) An AM device comprising the composition. (c) A polymer stabilized orientation (PSA) type AM device comprising the composition. (d) A polymer-stabilized orientation (PSA) type AM device comprising the composition in which the polymerizable compound is polymerized. (e) An element comprising the composition and having a mode of PC, TN, STN, ECB, OCB, IPS, VA, FFS or FPA. (f) A transmissive element comprising the composition. (g) Use of the composition as a composition having a nematic phase. (h) Use of an optically active composition obtained by adding an optically active compound to the composition.

The composition of the present invention will be described in the following order. First, the constitution of the composition will be described. Second, the main characteristics of the component compounds and the main effects that the compounds bring to the composition or the device are explained. Third, the combination of the component compounds in the composition, the preferred ratio, and the basis thereof will be described. Fourth, the preferable form of a component compound is demonstrated. Fifth, preferred constituent compounds are shown. Sixth, additives that can be added to the composition will be described. Seventh, the synthesis method of the component compounds will be described. Finally, the use of the composition will be explained.

First, the constitution of the composition will be described. The composition contains various liquid crystal compounds. The composition may also contain additives. The additives are optically active compounds, antioxidants, ultraviolet absorbers, matting agents, pigments, defoaming agents, polymerizable compounds, polymerization initiators, polymerization inhibitors, polar compounds, and the like. The compositions are classified into composition A and composition B from the viewpoint of the liquid crystal compound. In addition to the liquid crystal compound selected from the compound (2) and the compound (3), the composition A may further contain other liquid crystal compounds, additives, and the like. The "other liquid crystal compound" is a liquid crystal compound different from the compound (2) and the compound (3). Such a compound is mixed in the composition for the purpose of further adjusting the properties.

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

Second, the main characteristics of the component compounds and the main effects that the compounds bring to the composition or the device are explained. Based on the effects of the present invention, the main characteristics of the component compounds are summarized in Table 2. In the notation in Table 2, L means large or high, M means medium, and S means small or low. Notations L, M, S are classifications based on qualitative comparisons between constituent compounds, and notation 0 (zero) means less than S (small).

Table 2. Properties of the compounds

characteristic Compound (2) Compound (3) upper limit temperature S～L S～L Viscosity M～L S～M optical anisotropy M～L S～L Dielectric Anisotropy M～L¹⁾ 0 specific resistance L L

1) The dielectric anisotropy is negative, and the sign indicates the magnitude of the absolute value.

The main effects of the component compounds on the properties of the composition are as follows. The compound (1) and the compound (4) provide a polymer by polymerizing, which shortens the response time of the element and improves the afterimage of the image. Compound (2) increases the dielectric anisotropy and lowers the minimum temperature. Compound (3) lowers the viscosity, or raises the upper limit temperature.

Third, the combination of the components in the composition, the preferred ratio of the component compound, and the basis thereof will be described. Preferred combinations of ingredients in the composition are compound (1)+compound (2), compound (1)+compound (2)+compound (3) or compound (1)+compound (2)+compound (3)+ Compound (4). A more preferable combination is compound (1)+compound (2)+compound (3).

The polymerizable compound such as compound (1) is added to the composition for the purpose of being suitable for a polymer-stabilized oriented element. In order to shorten the response time, the preferable ratio of the polymerizable compound is about 0.03 mass % or more, and the preferable ratio of the polymerizable compound is about 10 mass % or less in order to prevent the display failure of the element. A more preferable ratio is in the range of about 0.1 mass % to about 0.8 mass %. A particularly preferable ratio is in the range of about 0.3 mass % to about 0.5 mass %.

In order to increase the dielectric anisotropy, the preferable ratio of the compound (2) is about 10 mass % or more, and the preferable ratio of the compound (2) is about 90 mass % or less in order to lower the minimum temperature. A more preferable ratio is in the range of about 20% by mass to about 80% by mass. A particularly preferable ratio is in the range of about 30% by mass to about 70% by mass.

The preferable ratio of compound (3) is about 10 mass % or more for raising the upper limit temperature or for reducing viscosity, and about 90 mass % or less for improving dielectric anisotropy. A more preferable ratio is in the range of about 20% by mass to about 80% by mass. A particularly preferable ratio is in the range of about 30% by mass to about 70% by mass.

A polymerizable compound such as compound (4) is added to the composition for the purpose of being suitable for a polymer-stabilized oriented element. In order to shorten the response time, the preferable ratio of the polymerizable compound is about 0.03 mass % or more, and the preferable ratio of the polymerizable compound is about 10 mass % or less in order to prevent the display failure of the element. A more preferable ratio is in the range of about 0.1 mass % to about 0.8 mass %. A particularly preferable ratio is in the range of about 0.3 mass % to about 0.5 mass %.

Fourth, the preferable form of a component compound is demonstrated. First, two kinds of liquid crystal compounds are summarized and described, and then, two kinds of additives are described.

(a) Liquid crystal compound

In formula (2) and formula (3), R ¹ and R ² are alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, alkenyl having 2 to 12 carbons, and 2 to 12 carbons alkenyloxy, or an alkyl group having 1 to 12 carbons in which at least one hydrogen is substituted by fluorine or chlorine. In order to improve stability, preferably R ¹ or R ² is an alkyl group having 1 to 12 carbon atoms, and in order to improve dielectric anisotropy, preferably R ¹ or R ² is an alkoxy group having 1 to 12 carbon atoms. R ³ and R ⁴ are alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, alkenyl having 2 to 12 carbons, alkane having 1 to 12 carbons in which at least one hydrogen is substituted by fluorine or chlorine group, or an alkenyl group having 2 to 12 carbons in which at least one hydrogen is substituted with fluorine or chlorine. In order to reduce viscosity, preferable R ³ or R ⁴ is an alkenyl group having 2 to 12 carbon atoms, and in order to improve stability, preferable R ³ or R ⁴ is an alkyl group having 1 to 12 carbon atoms.

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

Preferred alkoxy groups are methoxy, ethoxy, propoxy, butoxy, pentyloxy, hexyloxy or heptyloxy. Further preferred alkoxy groups are methoxy groups or ethoxy groups in order to lower the viscosity.

Preferred alkenyl groups are vinyl, 1-propenyl, 2-propenyl, 1-butenyl, 2-butenyl, 3-butenyl, 1-pentenyl, 2-pentenyl, 3- Pentenyl, 4-pentenyl, 1-hexenyl, 2-hexenyl, 3-hexenyl, 4-hexenyl or 5-hexenyl. Further preferred alkenyl groups are vinyl, 1-propenyl, 3-butenyl or 3-pentenyl in order to reduce viscosity. The preferred stereoconfiguration of -CH=CH- in these alkenyl groups depends on the position of the double bond. In terms of viscosity reduction, etc., among alkenyl groups such as 1-propenyl, 1-butenyl, 1-pentenyl, 1-hexenyl, 3-pentenyl, and 3-hexenyl The trans configuration is preferred. Among alkenyl groups such as 2-butenyl, 2-pentenyl, and 2-hexenyl, the cis configuration is preferred.

Preferred alkenyloxy groups are vinyloxy, allyloxy, 3-butenyloxy, 3-pentenyloxy or 4-pentenyloxy. Further preferred alkenyloxy groups are allyloxy groups or 3-butenyloxy groups in order to lower the viscosity.

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

Preferred examples of alkenyl groups in which at least one hydrogen is substituted with fluorine or chlorine are 2,2-difluorovinyl, 3,3-difluoro-2-propenyl, 4,4-difluoro-3-butenyl, 5,5-difluoro-4-pentenyl or 6,6-difluoro-5-hexenyl. In order to lower the viscosity, more preferable examples are 2,2-difluorovinyl or 4,4-difluoro-3-butenyl.

Ring D and Ring F are 1,4-cyclohexylene, 1,4-cyclohexenylene, tetrahydropyran-2,5-diyl, 1,4-phenylene, at least one hydrogen through fluorine or Chlorine-substituted 1,4-phenylene, naphthalene-2,6-diyl, naphthalene-2,6-diyl with at least one hydrogen substituted with fluorine or chlorine, chroman-2,6-diyl, or Chromane-2,6-diyl with at least one hydrogen replaced by fluorine or chlorine. In order to reduce viscosity or to increase the upper limit temperature, preferable ring D or ring F is 1,4-cyclohexylene, and in order to increase optical anisotropy, preferable ring D or ring F is 1,4-phenylene.

Ring E is 2,3-difluoro-1,4-phenylene, 2-chloro-3-fluoro-1,4-phenylene, 2,3-difluoro-5-methyl-1,4- Phenylene, 3,4,5-trifluoronaphthalene-2,6-diyl, 7,8-difluorochroman-2,6-diyl, 3,4,5,6-tetrafluorofluorene- 2,7-diyl (FLF4), 4,6-difluorodibenzofuran-3,7-diyl (DBFF2), 4,6-difluorodibenzothiophene-3,7-diyl (DBTF2 ) or 1,1,6,7-tetrafluoroindan-2,5-diyl (InF4). In order to increase the dielectric anisotropy, the preferred ring E is 2,3-difluoro-1,4-phenylene.

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

Z ³ and Z ⁴ are a single bond, ethylene, methyleneoxy or carbonyloxy. In order to reduce the viscosity, the preferred Z ³ or Z ⁴ is a single bond, in order to reduce the minimum temperature, the preferred Z ³ or Z ⁴ is ethylene, and in order to improve the dielectric anisotropy, the preferred Z ³ or Z ⁴ is methylene base oxygen. Z ⁵ is a single bond, ethylene or carbonyloxy. ^In order to reduce viscosity, the preferred Z5 is a single bond.

A divalent group such as a methyleneoxy group is left-right asymmetric. In methyleneoxy, -CH ₂ O- is better than -OCH ₂ -. Among carbonyloxy groups, -COO- is better than -OCO-.

e is 0, 1, 2 or 3, f is 0 or 1; and the sum of e and f is 3 or less. In order to lower the viscosity, e is preferably 1, and in order to increase the upper limit temperature, e is preferably 2. In order to lower the viscosity, f is preferably 0, and in order to lower the minimum temperature, f is preferably 1. g is 1, 2 or 3. In order to lower the viscosity, g is preferably 1, and in order to increase the upper limit temperature, g is preferably 2.

(b) Additives

In formula (1) and formula (4), ring A ¹ and ring A ³ are cyclohexyl, cyclohexenyl, phenyl, 1-naphthyl, 2-naphthyl, tetrahydropyran-2-yl, 1 ,3-dioxan-2-yl, pyrimidin-2-yl or pyridin-2-yl, in these rings, at least one hydrogen can be changed to fluorine, chlorine, alkyl with 1 to 12 carbons, 1 to 12 carbons alkoxy, or at least one hydrogen is substituted by fluorine or chlorine substituted alkyl with 1 to 12 carbons. Preferred ring A ¹ and ring A ³ are phenyl groups. Ring A ² is 1,4-cyclohexylene, 1,4-cyclohexenylene, 1,4-phenylene, naphthalene-1,2-diyl, naphthalene-1,3-diyl, naphthalene- 1,4-diyl, naphthalene-1,5-diyl, naphthalene-1,6-diyl, naphthalene-1,7-diyl, naphthalene-1,8-diyl, naphthalene-2,3-diyl base, naphthalene-2,6-diyl, naphthalene-2,7-diyl, tetrahydropyran-2,5-diyl, 1,3-dioxane-2,5-diyl, pyrimidine-2 ,5-diyl or pyridine-2,5-diyl, in these rings, at least one hydrogen can be replaced by fluorine, chlorine, alkyl with 1 to 12 carbons, alkoxy with 1 to 12 carbons, or at least one Hydrogen is substituted with an alkyl group having 1 to 12 carbons substituted with fluorine or chlorine. Preferred ring A ² is 1,4-phenylene or 2-fluoro-1,4-phenylene.

Ring I and Ring K are cyclohexyl, cyclohexenyl, phenyl, 1-naphthyl, 2-naphthyl, tetrahydropyran-2-yl, 1,3-dioxan-2-yl, pyrimidine- 2-yl or pyridin-2-yl, in these rings, at least one hydrogen can be through fluorine, chlorine, alkyl with 1 to 12 carbons, alkoxy with 1 to 12 carbons, or at least one hydrogen through fluorine or chlorine Substituted alkyl group having 1 to 12 carbon atoms. Preferred ring I or ring K is phenyl. Ring J is 1,4-cyclohexylene, 1,4-cyclohexenylene, 1,4-phenylene, naphthalene-1,2-diyl, naphthalene-1,3-diyl, naphthalene-1 ,4-diyl, naphthalene-1,5-diyl, naphthalene-1,6-diyl, naphthalene-1,7-diyl, naphthalene-1,8-diyl, naphthalene-2,3-diyl , naphthalene-2,6-diyl, naphthalene-2,7-diyl, tetrahydropyran-2,5-diyl, 1,3-dioxane-2,5-diyl, pyrimidine-2, 5-diyl or pyridine-2,5-diyl, in these rings, at least one hydrogen can be replaced by fluorine, chlorine, alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, or at least one hydrogen Substituted with alkyl having 1 to 12 carbons substituted with fluorine or chlorine. Preferred ring J is 1,4-phenylene or 2-fluoro-1,4-phenylene.

P ¹ , P ² and P ³ are polymerizable groups, and at least one of P ¹ , P ² and P ³ is a polymerizable group represented by formula (P-1). Preferable P ¹ , P ² or P ³ is a group selected from the polymerizable groups represented by formula (P-1) to formula (P-6).

The wavy lines in the formula (P-1) to the formula (P-6) indicate the bonding site.

In formula (P-1) to formula (P-6), M ¹ is an alkyl group having 1 to 5 carbon atoms. In order to improve reactivity, the preferred M ¹ is methyl. M ² , M ³ and M ⁴ are hydrogen, fluorine, an alkyl group having 1 to 5 carbons, or an alkyl group having 1 to 5 carbons in which at least one hydrogen is substituted with fluorine or chlorine. In order to increase reactivity, preferred M ² , M ³ or M ⁴ is hydrogen or methyl. Further preferred M ² is hydrogen or methyl, and further preferred M ³ or M ⁴ is hydrogen. n is an integer of 1 to 5. Preferably n is 1.

P ⁹ , P ¹⁰ and P ¹¹ are groups selected from polymerizable groups represented by formula (P-7) to formula (P-11). The wavy lines of the formula (P-7) to the formula (P-11) indicate the bonding site.

In formula (P-7) to formula (P-11), M ⁵ , M ⁶ and M ⁷ are hydrogen, fluorine, an alkyl group having 1 to 5 carbon atoms, or a carbon number 1 wherein at least one hydrogen is substituted by fluorine or chlorine to 5 alkyl groups. In order to increase reactivity, preferred ^M5 , ^M6 or ^M7 is hydrogen or methyl. Further preferred M ⁵ is hydrogen or methyl, and further preferred M ⁶ or M ⁷ is hydrogen.

Z ¹ , Z ² , Z ⁶ and Z ⁷ are a single bond or an alkylene group having 1 to 10 carbon atoms, and in the alkylene group, at least one -CH ₂ - may be via -O-, -CO-, -COO - or -OCO- substituted, at least one -CH ₂ -CH ₂ - may be via -CH=CH-, -C(CH ₃ )=CH-, -CH=C(CH ₃ )- or -C(CH ₃ ) =C( _CH3 )-substituted, in these groups, at least one hydrogen may be substituted with fluorine or chlorine. Preferred Z ¹ , Z ² , Z ⁶ or Z ⁷ are a single bond, -CH ₂ -CH ₂ -, -CH ₂ O-, -OCH ₂ -, -COO- or -OCO-. Further preferred Z ¹ , Z ² , Z ⁶ or Z ⁷ is a single bond.

Sp ¹ , Sp ² , Sp ³ , Sp ⁵ , Sp ⁶ and Sp ⁷ are single bonds or alkylene groups having 1 to 10 carbon atoms, and in the alkylene groups, at least one -CH ₂ - may be through -O-, -COO-, -OCO- or -OCOO- substituted, at least one -CH ₂ -CH ₂ - can be substituted by -CH=CH- or -C≡C-, in these groups, at least one hydrogen can be substituted by fluorine or chlorine . Preferred Sp ¹ , Sp ² , Sp ³ , Sp ⁵ , Sp ⁶ or Sp ⁷ are single bonds, -CH ₂ -CH ₂ -, -CH ₂ O-, -OCH ₂ -, -COO-, -OCO-, -CO-CH=CH- or -CH=CH-CO-. More preferably, Sp ¹ , Sp ² , Sp ³ , Sp ⁵ , Sp ⁶ or Sp ⁷ are single bonds.

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

Fifth, preferred constituent compounds are shown. Preferred compounds (1) are the compounds (1-1) to (1-29) described in item 3. Among these compounds, preferably at least one of the first additives is compound (1-1), compound (1-2), compound (1-24), compound (1-25), compound (1-26), Compound (1-27) or Compound (1-29). Preferably, at least two of the first additives are compound (1-1) and compound (1-2), compound (1-1) and compound (1-18), compound (1-2) and compound (1- 24), compound (1-2) and compound (1-25), compound (1-2) and compound (1-26), compound (1-25) and compound (1-26) or compound (1-18) ) and a combination of compounds (1-24).

Preferred compounds (2) are the compounds (2-1) to (2-35) described in item 6. Among these compounds, at least one of the first components is preferably compound (2-1), compound (2-3), compound (2-6), compound (2-8), compound (2-10), compound (2-13), compound (2-14) or compound (2-18). Preferably, at least two of the first components are compound (2-1) and compound (2-8), compound (2-1) and compound (2-14), compound (2-3) and compound (2-8) ), compound (2-3) and compound (2-10), compound (2-3) and compound (2-14), compound (2-6) and compound (2-8), compound (2-6) and compound (2-10), compound (2-6) and compound (2-18) or a combination of compound (2-10) and compound (2-14).

Preferred compounds (3) are the compounds (3-1) to (3-13) described in Item 9. Among these compounds, at least one of the second components is preferably compound (3-1), compound (3-3), compound (3-5), compound (3-6), compound (3-7) or compound (3-9). Preferably, at least two of the second components are compound (3-1) and compound (3-3), compound (3-1) and compound (3-5), or compound (3-1) and compound (3-6) )The combination.

Preferred compounds (4) are the compounds (4-1) to (4-29) described in Item 12. Among these compounds, preferably at least one of the second additives is compound (4-1), compound (4-2), compound (4-24), compound (4-25), compound (4-26) or Compound (4-27). Preferably, at least two of the second additives are compound (4-1) and compound (4-2), compound (4-1) and compound (4-18), compound (4-2) and compound (4- 24), compound (4-2) and compound (4-25), compound (4-2) and compound (4-26), compound (4-25) and compound (4-26) or compound (4-18) ) and a combination of compounds (4-24).

Sixth, additives that can be added to the composition will be described. Such additives are optically active compounds, antioxidants, ultraviolet absorbers, matting agents, pigments, antifoaming agents, polymerizable compounds, polymerization initiators, polymerization inhibitors, polar compounds, and the like. The optically active compound is added to the composition for the purpose of imparting a torsion angle by inducing a helical structure of liquid crystal molecules. Examples of such compounds are compound (5-1) to compound (5-5). The preferable ratio of an optically active compound is about 5 mass % or less. A more preferable ratio is in the range of about 0.01% by mass to about 2% by mass.

Antioxidants are added to the combination in order to prevent a decrease in specific resistance caused by heating in the atmosphere or to maintain a large voltage holding ratio not only at room temperature but also at temperatures close to the upper limit temperature after using the element for a long time. thing. Preferable examples of the antioxidant are compound (6-1) to compound (6-3) and the like.

Since the compound (6-2) has low volatility, it is effective for maintaining a large voltage holding ratio not only at room temperature but also at a temperature close to the upper limit temperature after the device is used for a long time. In order to obtain the above-mentioned effects, the preferable ratio of the antioxidant is about 50 ppm or more, and the preferable ratio of the antioxidant is about 600 ppm or less in order not to lower the upper limit temperature or not to raise the lower limit temperature. A further preferred ratio is in the range of about 100 ppm to about 300 ppm.

Preferable examples of the ultraviolet absorber are benzophenone derivatives, benzoate derivatives, triazole derivatives and the like. In addition, light stabilizers such as sterically hindered amines are also preferred. Preferable examples of the light stabilizer are compound (7-1) to compound (7-16) and the like. In order to obtain the effect, the preferable ratio of these absorbents or stabilizers is about 50 ppm or more, and in order not to lower the upper limit temperature or not to raise the lower limit temperature, the preferable ratio of these absorbents or stabilizers is about 10000 ppm or less. A further preferred ratio is in the range of about 100 ppm to about 10,000 ppm.

The matting agent is a compound that prevents decomposition of the liquid crystal compound by receiving light energy absorbed by the liquid crystal compound and converting it into thermal energy. Preferable examples of the matting agent are compound (8-1) to compound (8-7) and the like. In order to obtain the said effect, the preferable ratio of these matting agents is about 50 ppm or more, and in order to lower the minimum temperature, the preferable ratio of these matting agents is about 20000 ppm or less. A further preferred ratio is in the range of about 100 ppm to about 10,000 ppm.

Dichroic dyes such as azo-based dyes, anthraquinone-based dyes, and the like are added to the composition in order to be suitable for a guest host (GH) mode device. The preferable ratio of a pigment|dye is the range of about 0.01 mass % to about 10 mass %. In order to prevent foaming, antifoaming agents such as dimethyl silicone oil and methyl phenyl silicone oil are added to the composition. In order to obtain the above-mentioned effects, the preferred ratio of the antifoaming agent is about 1 ppm or more, and the preferred ratio of the antifoaming agent is about 1000 ppm or less in order to prevent poor display. A further preferred ratio is in the range of about 1 ppm to about 500 ppm.

In order to be suitable for polymer stabilized orientation (PSA) type elements, polymeric compounds are used. Compound (1) or compound (4) are suitable for this purpose. Compound (1) or compound (4), and a polymerizable compound different from these compounds may be added to the composition together. Preferable examples of other polymerizable compounds are acrylates, methacrylates, vinyl compounds, vinyloxy compounds, propenyl ethers, epoxy compounds (oxiranes, oxetanes), vinyl ketones and other compounds. Further preferable examples are acrylates and methacrylates.

Adjustment can be achieved by changing the type of compound (1) or compound (4), or by combining a polymerizable compound different from compound (1) or compound (4) with compound (1) or compound (4) in an appropriate ratio. The reactivity of the polymerizable compound or the pretilt angle of the liquid crystal molecules. By optimizing the pretilt angle, a short response time of the element can be achieved. The alignment of the liquid crystal molecules is stabilized, so that a large contrast ratio or a long lifetime can be achieved.

A polymerizable compound such as compound (1) or compound (4) is polymerized by ultraviolet irradiation. The polymerization can also be carried out in the presence of an appropriate polymerization initiator such as a photopolymerization initiator. Appropriate conditions for carrying out the polymerization, appropriate types and amounts of initiators are known to those of ordinary skill in the art to which this invention pertains, and are described in the literature. For example, as a photopolymerization initiator, Irgacure 651 (registered trademark; BASF), Irgacure 184 (registered trademark; BASF), or Darocur 1173 (registered trademark) ; BASF (BASF)) is suitable for free radical polymerization. A preferable ratio of the photopolymerization initiator is in the range of about 0.1% by mass to about 5% by mass based on the mass of the polymerizable compound. A more preferable ratio is in the range of about 1% by mass to about 3% by mass.

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

Polar compounds are organic compounds having polarity. Here, compounds having ionic bonds are not included. Atoms such as oxygen, sulfur, and nitrogen are electrically negative and tend to have partial negative charges. Carbon and hydrogen are neutral or have a tendency to have a partial positive charge. Polarity arises from the unequal distribution of partial charges among atoms of different species in a compound. For example, the polar compound has at least one of partial structures such as -OH, -COOH, -SH, -NH ₂ , >NH, and >N-.

Seventh, the synthesis method of the component compounds will be described. These compounds can be synthesized by known methods. Synthetic methods are exemplified. The synthesis example of compound (1) is described in the section of Example. Compound (2-1) was synthesized by the method described in Japanese Patent Laid-Open No. 2000-053602. Compound (3-1) was synthesized by the method described in Japanese Patent Laid-Open No. Sho 59-176221. Compound (4-19) was synthesized by the method described in Japanese Patent Laid-Open No. 7-101900. Antioxidants are commercially available. Compound (6-1) can be obtained from Sigma-Aldrich Corporation. Compound (6-2) and the like were synthesized by the method described in the specification of US Pat. No. 3,660,505.

Compounds whose synthesis methods are not described can be synthesized by the methods described in the following books: "Organic Syntheses" (John Wiley & Sons, Inc.), "Organic Reactions" (John Wiley & Sons, Inc.), Comprehensive Organic Synthesis (Pergamon Press), Lectures on New Experimental Chemistry (Maruzen), etc. Compositions are prepared from the compounds obtained in the manner described using existing methods. For example, the component compounds are mixed and then heated to dissolve each other.

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

The composition can be used in AM devices. Furthermore, it can also be used for PM elements. The composition can be used for AM elements and PM elements having modes such as PC, TN, STN, ECB, OCB, IPS, FFS, VA, FPA, etc. It is particularly preferred for AM elements having TN mode, OCB mode, IPS mode or FFS mode. In an AM element having an IPS mode or an FFS mode, when no voltage is applied, the alignment of the liquid crystal molecules may be parallel to the glass substrate, or may be perpendicular. These elements can be reflective, transmissive or transflective. It is preferably used for transmission type elements. Can also be used for amorphous silicon-TFT elements or polysilicon-TFT elements. It can also be used for a nematic curvilinear aligned phase (NCAP) type element prepared by microencapsulating the composition, or a polymer dispersed (PD) in which a three-dimensional network polymer is formed in the composition. type components.

An example of the method of manufacturing a polymer-stabilized orientation type element is as follows. Assemble components with two substrates called array substrate and color filter substrate. The substrate has an alignment film. At least one of the substrates has an electrode layer. The liquid crystal compound is mixed to prepare a liquid crystal composition. A polymerizable compound is added to the composition. Additives can be further added as needed. The composition is injected into the element. Light irradiation is performed in a state where a voltage is applied to the element. Ultraviolet rays are preferred. The polymerizable compound is polymerized by light irradiation. The polymer-containing composition is produced by the polymerization. The polymer stabilized oriented elements are fabricated in the sequence described above.

In the above procedure, when a voltage is applied, the liquid crystal molecules are aligned by the action of the alignment film and the electric field. According to the orientation, the molecules of the polymerizable compound are also oriented. Since the polymerizable compound is polymerized by ultraviolet rays in the above state, a polymer maintaining the above-mentioned orientation is produced. Through the effect of the polymer, the response time of the element is shortened. Since the afterimage of the image is caused by the malfunction of the liquid crystal molecules, the afterimage is also simultaneously improved by the effect of the polymer. Furthermore, the polymerizable compound in the composition may be polymerized in advance, and the composition may be disposed between the substrates of the liquid crystal display element.

Example

The present invention will be further described in detail through examples. The present invention is not limited by these examples. The present invention comprises a mixture of the composition of Example 1 and the composition of Example 2. The present invention also includes mixtures obtained by mixing at least two of the compositions of the examples. The synthesized compounds were identified by methods such as nuclear magnetic resonance (NMR) analysis. The properties of compounds, compositions, and elements were measured by the methods described below.

NMR analysis: DRX-500 manufactured by Bruker BioSpin was used for the measurement. In the measurement of ¹ H-NMR, the sample is dissolved in a deuterated solvent such as CDCl ₃ , and the measurement is performed at room temperature under the conditions of 500 MHz and 16 cumulative times. Tetramethylsilane was used as an internal standard. In the measurement of ¹⁹ F-NMR, CFCl ₃ was used as an internal standard, and the cumulative number of times was 24. In the description of NMR spectra, s means singlet, d means doublet, t means triplet, q means quartet, and quin means fivefold Peak (quintet), sex means sextet (sextet), m means multiplet (multiplet), br means broad peak (broad).

Gas chromatographic analysis: A GC-14B gas chromatograph manufactured by Shimadzu Corporation was used for the measurement. The carrier gas was helium (2 mL/min). The sample vaporization chamber was set to 280°C, and the detector (flameionization detector (FID)) was set to 300°C. For the separation of component compounds, a capillary column DB-1 (length 30 m, inner diameter 0.32 mm, film thickness 0.25 μm) manufactured by Agilent Technologies Inc. was used; the stationary liquid phase was dimethylpolysiloxane ; no polarity). After the column was held at 200°C for 2 minutes, the temperature was raised to 280°C at a rate of 5°C/min. After the sample was prepared as an acetone solution (0.1 mass %), 1 μL of the solution was injected into the sample vaporization chamber. The recorder is a C-R5A type chromatograph package (Chromatopac) manufactured by Shimadzu Corporation or its equivalent. The obtained gas chromatogram showed the retention time of the peak and the area of the peak corresponding to the component compounds.

As a solvent for diluting the sample, chloroform, hexane, or the like can be used. In order to separate the component compounds, the following capillary columns can be used. HP-1 manufactured by Agilent Technologies Inc. (length 30 m, inner diameter 0.32 mm, film thickness 0.25 μm), Rtx-1 manufactured by Restek Corporation (length 30 m, inner diameter 0.32 mm, film thickness 0.25 μm), BP-1 (length 30 m, inner diameter 0.32 mm, film thickness 0.25 μm) manufactured by SGE International Pty. Ltd, Australia. For the purpose of preventing overlapping of compound peaks, a capillary column CBP1-M50-025 (length 50 m, inner diameter 0.25 mm, film thickness 0.25 μm) manufactured by Shimadzu Corporation was used.

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

Measurement sample: When measuring the properties of the composition and the element, the composition was directly used as a sample. When the properties of the compound were measured, a sample for measurement was prepared by mixing the compound (15% by mass) with the mother liquid crystal (85% by mass). From the value obtained by the measurement, the characteristic value of the compound was calculated by an extrapolation method. (Extrapolated value)={(Measured value of sample)−0.85×(Measured value of mother liquid crystal)}/0.15. When the smectic phase (or crystal) is precipitated at 25°C under the above ratio, the ratio of the compound to the mother liquid crystal is 10 mass %: 90 mass %, 5 mass %: 95 mass %, 1 mass %: 99 mass % The order of mass % was changed. The values of the upper limit temperature, optical anisotropy, viscosity, and dielectric anisotropy related to the compound were obtained by the above-mentioned extrapolation method.

The following mother liquid crystals were used. The ratio of the component compounds is represented by mass %.

Measurement method: The measurement of the characteristic was carried out by the following method. Most of these methods are methods described in the JEITA standard (JEITA·ED-2521B) reviewed and formulated by the Japan Electronics and Information Technology Industries Association (hereinafter referred to as JEITA) or modified ones. method. In the TN element used for the measurement, a thin film transistor (TFT) was not mounted.

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

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

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

(4) Viscosity (rotational viscosity; γ1; measured at 25° C.; mPa·s): The rotational viscosity measurement system LCM-2 type of Toyo Technica Co., Ltd. was used for the measurement. A sample was injected into a VA element in which the distance (cell gap) between two glass substrates was 10 μm. A rectangular wave (55V, 1 ms) was applied to the element. The peak current and peak time of the transient current produced by the application were measured. Using these measured values and dielectric anisotropy, the value of rotational viscosity was obtained. The dielectric anisotropy was measured by the method described in Measurement (6).

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

(6) Dielectric anisotropy (Δε; measured at 25° C.): The value of the dielectric anisotropy was calculated according to the formula of Δε=ε∥−ε⊥. The dielectric constants (ε∥ and ε⊥) were measured as follows.

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

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

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

(8) Voltage holding ratio (VHR-1; measured at 25° C.; %): The TN element used for the measurement had a polyimide alignment film, and the distance (cell gap) between the two glass substrates was 5 μm. After placing the sample, the element was sealed with an adhesive cured by UV light. The TN element was charged by applying a pulse voltage (5V, 60 microseconds). Using a high-speed voltmeter, the decayed voltage was measured for 16.7 milliseconds, and the area A between the voltage curve and the horizontal axis in a unit cycle was obtained. Area B is the area without attenuation. Voltage retention is expressed as the percentage of area A relative to area B.

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

(10) Voltage holding ratio (VHR-3; measured at 25° C.; %): After irradiation with ultraviolet rays, the voltage holding ratio was measured to evaluate the stability to ultraviolet rays. The TN element used for the measurement has a polyimide alignment film, and the cell gap is 5 μm. A sample was injected into the element, and light was irradiated for 30 minutes. The light source is an ultra-high pressure mercury lamp USH-500D (manufactured by USHIO Motor), and the distance between the element and the light source is 20cm. In the measurement of VHR-3, the decayed voltage was measured during 166.7 milliseconds. Compositions with large VHR-3 have large UV stability. VHR-3 is preferably 90% or more, more preferably 95% or more.

(11) Voltage holding ratio (VHR-4; measured at 25° C.; %): After heating the TN element injected with the sample in a constant temperature bath at 80° C. for 500 hours, the voltage holding ratio was measured to evaluate the resistance to heat. stability. In the measurement of VHR-4, the decayed voltage was measured during 16.7 milliseconds. Compositions with large VHR-4 have large thermal stability.

(12) Response time (τ; measured at 25° C.; ms): LCD5200 type luminance meter manufactured by Otsuka Electronics Co., Ltd. was used for the measurement. The light source is a halogen lamp. The low-pass filter (Low-pass filter) is set to 500Hz.

A sample was placed in a normally blackmode PSA element with a gap (cell gap) between two glass substrates of 3.2 μm. The element was irradiated with ultraviolet rays of 76 mW/cm ² while applying a voltage of 15 V, and the pretilt angle was set to 0.9°±0.2°. For ultraviolet irradiation, a metal halide lamp (US4-X0401FKTN) manufactured by Eye Graphics Co., Ltd. was used. Then, without applying a voltage, ultraviolet rays of 3.8 mW/cm ² were irradiated for 60 minutes. When irradiating ultraviolet rays, a black light (F40T10) manufactured by Eye Graphics Co., Ltd. was used. A rectangular wave (30 Hz, 7.5 V, 1 second) was applied to the element. At this time, the element was irradiated with light from the vertical direction, and the amount of light transmitted through the element was measured. The transmittance was regarded as 100% when the light amount was the maximum, and the transmittance was regarded as 0% when the light amount was the minimum. The response time is represented by the time (fall time; fall time; milliseconds) required for the transmittance to change from 90% to 10%.

(13) Elastic constant (K11: splay elastic constant, K33: bending (bend) elastic constant; measured at 25°C; pN): a product manufactured by Toyo Technica Co., Ltd. was used for the measurement EC-1 type elastic constant tester. A sample was placed in a vertical alignment cell whose interval (cell gap) between two glass substrates was 20 μm. A charge of 20 volts to 0 volts was applied to the cell, and the electrostatic capacitance and the applied voltage were measured. Using equations (2.98) and (2.101) on page 75 of the "Handbook of Liquid Crystal Devices" (Nikkan Kogyo Shimbun), the measured electrostatic capacitance (C) was fitted to the value of the applied voltage (V), and the equation (2.100) to obtain the value of the elastic constant.

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

[Synthesis Example 1]

Synthesis of polymerizable compound (1-2-1)

first step

In a nitrogen atmosphere, compound (T-1) (3 g, 14.69 mmol) (3 g, 14.69 mmol) and dichloromethane (300 ml) synthesized by a conventional method were put into a reactor, and cooled to 0°C. To this were added compound (T-2) (5.63 g, 48.48 mmol), 1-(3-dimethylaminopropyl)carbodiimide (9.29 g, 48.48 mmol) synthesized by a conventional method, and Triethylamine (9.01 ml, 64.64 mmol) and warmed to room temperature. The reaction mixture was poured into water, and the aqueous layer was extracted with ethyl acetate. The combined organic layers were washed with water and dried over anhydrous magnesium sulfate. The solution was concentrated under reduced pressure, and the residue was purified by silica gel column chromatography (dichloromethane/ethyl acetate=19/1, volume ratio) and recrystallization to obtain compound (1-2-1) ) (4.13 g, 70% yield).

¹ H-NMR (ppm; CDCl ₃ ): δ 7.81-7.76 (m, 3H), 7.60 (d, J=8.3 Hz, 1H), 7.45 (t, J=8.4 Hz, 1H), 7.30 (d, J=8.4Hz, 1H), 6.54(s, 1H), 6.48(s, 1H), 6.15(s, 1H), 6.08(s, 1H), 4.21(s, 4H), 3.36(s, 6H).

Transition temperature: C 105.3I.

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

Table 3. Representation of compounds using symbols

R-(A ₁ )-Z ₁ -·····-Z _n -(A _n )-R'

[Composition example 1]

NI=78.4℃; Tc<-20℃; Δn=0.105; Δε=-2.7; Vth=2.43V; η=16.2mPa·s.

[Example 1]

The polymerizable compound (1-2-1) was added to the composition of Composition Example 1 in a ratio of 0.3% by mass.

The voltage holding ratio was measured by the method described in the measurement method (10).

NI=78.4℃; VHR-3=90.8%.

[Comparative Example 1]

The polymerizable compound A was added to the composition of Composition Example 1 at a ratio of 0.3% by mass.

The voltage holding ratio was measured by the method described in the measurement method (10).

NI=78.4℃; VHR-3=81.0%.

Comparison of Features

The composition of Example 1 contained the polymerizable compound (1-2-1) in a ratio of 0.3% by mass. The VHR-3 of the composition was 90.8%. In Comparative Example 1, a polymerizable compound A having a similar structure was used instead of the polymerizable compound (1-2-1). As a result, the VHR-3 of the composition was 81.0%. As mentioned above, the composition of Example 1 has a larger VHR-3 than the composition of Comparative Example 1. Thus, it can be concluded that the liquid crystal composition of the present invention has excellent properties.

Other composition examples are shown below.

[Composition example 2]

NI=73.2℃; Tc<-20℃; Δn=0.113; Δε=-4.0; Vth=2.18V; η=22.6mPa·s.

[Composition example 3]

NI=82.8℃; Tc<-30℃; Δn=0.118; Δε=-4.4; Vth=2.13V; η=22.5mPa·s.

[Composition example 4]

NI=78.1℃; Tc<-30℃; Δn=0.107; Δε=-3.2; Vth=2.02V; η=15.9mPa·s.

[Composition example 5]

NI=88.5℃; Tc<-30℃; Δn=0.108; Δε=-3.8; Vth=2.25V; η=24.6mPa·s.

[Composition example 6]

NI=81.1℃; Tc<-30℃; Δn=0.119; Δε=-4.5; Vth=1.69V; η=31.4mPa·s.

[Composition example 7]

NI=98.8℃; Tc<-30℃; Δn=0.111; Δε=-3.2; Vth=2.47V; η=23.9mPa·s.

[Composition example 8]

NI=77.5℃; Tc<-30℃; Δn=0.084; Δε=-2.6; Vth=2.43V; η=22.8mPa·s.

[Composition example 9]

NI=70.6℃; Tc<-20℃; Δn=0.129; Δε=-4.3; Vth=1.69V; η=27.0mPa·s.

[Composition example 10]

NI=93.0℃; Tc<-30℃; Δn=0.123; Δε=-4.0; Vth=2.27V; η=29.6mPa·s.

[Composition example 11]

NI=87.6℃; Tc<-30℃; Δn=0.126; Δε=-4.5; Vth=2.21V; η=25.3mPa·s.

[Composition example 12]

NI=93.0℃; Tc<-20℃; Δn=0.124; Δε=-4.5; Vth=2.22V; η=25.0mPa·s.

[Composition example 13]

NI=76.4℃; Tc<-30℃; Δn=0.104; Δε=-3.2; Vth=2.06V; η=15.6mPa·s.

[Composition example 14]

NI=78.3℃; Tc<-20℃; Δn=0.103; Δε=-3.2; Vth=2.17V; η=17.7mPa·s.

[Composition example 15]

NI=81.2℃; Tc<-20℃; Δn=0.107; Δε=-3.2; Vth=2.11V; η=15.5mPa·s.

[Composition example 16]

NI=88.7℃; Tc<-30℃; Δn=0.115; Δε=-1.9; Vth=2.82V; η=17.3mPa·s.

[Composition Example 17]

NI=89.9℃; Tc<-20℃; Δn=0.122; Δε=-4.2; Vth=2.16V; η=23.4mPa·s.

[Composition example 18]

NI=77.1℃; Tc<-20℃; Δn=0.101; Δε=-3.0; Vth=2.04V; η=13.9mPa·s.

[Composition Example 19]

NI=75.9℃; Tc<-20℃; Δn=0.114; Δε=-3.9; Vth=2.20V; η=24.7mPa·s.

[Composition example 20]

NI=75.9℃; Δn=0.101; Δε=-2.7.

[Composition example 21]

NI=78.4℃; Tc<-30℃; Δn=0.105; Δε=-2.7; Vth=2.43V; η=16.2mPa·s.

[Composition example 22]

NI=76.0℃; Tc<-20℃; Δn=0.097; Δε=-3.0; Vth=2.20V.

[Composition example 23]

NI=75.3℃; Δn=0.109; Δε=-3.1; Vth=2.29V.

[Composition example 24]

NI=73.5℃; Tc<-20℃; Δn=0.100; Δε=-2.6.

[Composition example 25]

NI=74.8℃; Tc<-20℃; Δn=0.099; Δε=-3.2.

[Composition example 26]

NI=71.1℃; Tc<-20℃; Δn=0.105; Δε=-2.7.

[Composition example 27]

NI=74.5℃; Tc<-20℃; Δn=0.109; Δε=-3.1; Vth=2.37V.

[Example 2 to Example 27]

The following polymerizable compounds (1-1-1) to polymerizable compounds (1-26-2) were added to the compositions of Composition Examples 2 to 27. The composition example and the combination of the polymerizable compound are shown in Table 4.

Table 4. Example 2 to Example 27

Industrial Availability

The liquid crystal composition of the present invention has high upper limit temperature, low lower limit temperature, low viscosity, suitable optical anisotropy, large negative dielectric anisotropy, large specific resistance, high stability to ultraviolet rays, and high stability to heat. , a large elastic constant, etc., at least one of the properties is satisfied, or there is an appropriate balance with respect to at least two properties. The liquid crystal display element containing the composition has the characteristics of short response time, high voltage holding ratio, low threshold voltage, high contrast ratio, long life and the like, so it can be used in liquid crystal monitors, liquid crystal televisions and the like.

Claims (18)

1. A liquid crystal composition containing at least one compound selected from polymerizable compounds represented by the formula (1) as a first additive and having a nematic phase;

in the formula (1), ring A¹And ring A³Cyclohexyl, cyclohexenyl, phenyl, 1-naphthyl, 2-naphthyl, tetrahydropyran-2-yl, 1, 3-dioxan-2-yl, pyrimidin-2-yl or pyridin-2-yl, in which ring at least one hydrogen may be substituted by fluorine, chlorine, an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, or an alkyl group having 1 to 12 carbon atoms in which at least one hydrogen is substituted by fluorine or chlorine; ring A²Is 1, 4-cyclohexylene, 1, 4-cyclohexenylene, 1, 4-phenylene, naphthalene-1, 2-diyl, naphthalene-1, 3-diyl, naphthalene-1, 4-diyl, naphthalene-1, 5-diyl, naphthalene-1, 6-diyl, naphthalene-1, 7-diyl, naphthalene-1, 8-diyl, naphthalene-2, 3-diyl, naphthalene-2, 6-diyl, naphthalene-2, 7-diyl, tetrahydropyran-2, 5-diyl, 1, 3-dioxane-2, 5-diyl, pyrimidine-2, 5-diyl or pyridine-2, 5-diyl, in which at least one hydrogen is substituted by fluorine, chlorine, an alkyl group having a carbon number of 1 to 12, an alkoxy group having a carbon number of 1 to 12, a carboxyl group, a salt thereof, and a pharmaceutically acceptable carrier, Or at least one hydrogen is substituted by a fluorine or chlorine substituted alkyl group of carbon number 1 to 12; p¹、P²And P³Is a polymerizable group, and P¹、P²And P³At least one is a polymerizable group represented by the formula (P-1);

Z¹and Z²Is a single bond or an alkylene group having 1 to 10 carbon atoms, in which at least one-CH group₂-may be substituted by-O-, -CO-, -COO-or-OCO-, at least one-CH₂-CH₂-may be via-CH ═ CH-, -C (CH)₃)＝CH-、-CH＝C(CH₃) -or-C (CH)₃)＝C(CH₃) -substitution, of which at least one hydrogen may be substituted by fluorine or chlorine; sp¹、Sp²And Sp³Is a single bond or an alkylene group having 1 to 10 carbon atoms, in which at least one-CH group₂At least one-CH which may be substituted by-O-, -COO-, -OCO-or-OCOO-)₂-CH₂-may be substituted by-CH-or-C ≡ C-, at least one of these groups being hydrogen-substituted byFluoro or chloro; a is 0, 1 or 2; b. c and d are 0, 1,2, 3 or 4, and the sum of b, c and d is 1 or more;

in the formula (P-1), M¹An alkyl group having 1 to 5 carbon atoms; n is an integer of 1 to 5.

2. The liquid crystal composition according to claim 1, wherein in formula (1), P is¹、P²And P³Is a group selected from the polymerizable groups represented by the formulae (P-1) to (P-6), and P¹、P²And P³At least one is a polymerizable group represented by the formula (P-1);

in the formulae (P-1) to (P-6), M¹An alkyl group having 1 to 5 carbon atoms; m²、M³And M⁴Hydrogen, fluorine, an alkyl group having 1 to 5 carbon atoms, or an alkyl group having 1 to 5 carbon atoms in which at least one hydrogen is substituted with fluorine or chlorine; n is an integer of 1 to 5.

3. The liquid crystal composition according to claim 1 or 2, comprising at least one compound selected from the group consisting of compounds represented by formulae (1-1) to (1-30) as a first additive;

in the formulae (1-1) to (1-30), R¹Is hydrogen, alkyl group having 1 to 12 carbon atoms, alkoxy group having 1 to 12 carbon atoms, alkenyl group having 2 to 12 carbon atoms, alkenyloxy group having 2 to 12 carbon atoms, or alkyl group having 1 to 12 carbon atoms in which at least one hydrogen is substituted with fluorine or chlorine; p⁵、P⁶And P⁷Is a group selected from the polymerizable groups represented by the formulae (P-1) to (P-4), and P⁵、P⁶And P⁷At least one is a polymerizable group represented by the formula (P-1);

here, M¹An alkyl group having 1 to 5 carbon atoms; m²、M³And M⁴Hydrogen, fluorine, an alkyl group having 1 to 5 carbon atoms, or an alkyl group having 1 to 5 carbon atoms in which at least one hydrogen is substituted with fluorine or chlorine; n is an integer of 1 to 5; sp¹、Sp²And Sp³Is a single bond or an alkylene group having 1 to 10 carbon atoms, in which at least one-CH group₂At least one-CH which may be substituted by-O-, -COO-, -OCO-or-OCOO-)₂-CH₂-may be substituted by-CH ═ CH-or-C ≡ C-, at least one of these groups being substituted by fluorine or chlorine.

4. The liquid crystal composition according to any one of claims 1 to 3, wherein the proportion of the first additive is in the range of 0.03 to 10% by mass.

5. The liquid crystal composition according to any one of claims 1 to 4, comprising at least one compound selected from the compounds represented by formula (2) as a first component;

in the formula (2), R¹And R²Is hydrogen, alkyl group having 1 to 12 carbon atoms, alkoxy group having 1 to 12 carbon atoms, alkenyl group having 2 to 12 carbon atoms, alkenyloxy group having 2 to 12 carbon atoms, or alkyl group having 1 to 12 carbon atoms in which at least one hydrogen is substituted with fluorine or chlorine; ring D and ring F are 1, 4-ylideneCyclohexyl, 1, 4-cyclohexenylene, tetrahydropyran-2, 5-diyl, 1, 4-phenylene in which at least one hydrogen is substituted by fluorine or chlorine, naphthalene-2, 6-diyl in which at least one hydrogen is substituted by fluorine or chlorine, chromane-2, 6-diyl, or chromane-2, 6-diyl in which at least one hydrogen is substituted by fluorine or chlorine; ring E is 2, 3-difluoro-1, 4-phenylene, 2-chloro-3-fluoro-1, 4-phenylene, 2, 3-difluoro-5-methyl-1, 4-phenylene, 3,4, 5-trifluoronaphthalene-2, 6-diyl, 7, 8-difluorochromane-2, 6-diyl, 3,4,5, 6-tetrafluorofluorene-2, 7-diyl, 4, 6-difluorodibenzofuran-3, 7-diyl, 4, 6-difluorodibenzothiophene-3, 7-diyl, or 1,1,6, 7-tetrafluoroindan-2, 5-diyl; z³And Z⁴Is a single bond, ethylene, methyleneoxy or carbonyloxy; e is 0, 1,2 or 3, f is 0 or 1; and the sum of e and f is 3 or less.

6. The liquid crystal composition according to any one of claims 1 to 5, containing at least one compound selected from the group of compounds represented by formulae (2-1) to (2-35) as a first component;

in the formulae (2-1) to (2-35), R¹And R²Is hydrogen, alkyl group having 1 to 12 carbon atoms, alkoxy group having 1 to 12 carbon atoms, alkenyl group having 2 to 12 carbon atoms, alkenyloxy group having 2 to 12 carbon atoms, or alkyl group having 1 to 12 carbon atoms in which at least one hydrogen is substituted with fluorine or chlorine.

7. The liquid crystal composition according to claim 5 or 6, wherein the proportion of the first component is in the range of 10 to 90 mass%.

8. The liquid crystal composition according to any one of claims 1 to 7, comprising at least one compound selected from the group consisting of compounds represented by formula (3) as a second component;

in the formula (3), R³And R⁴Is 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 alkyl group having 1 to 12 carbon atoms wherein at least one hydrogen is substituted with fluorine or chlorine, or an alkenyl group having 2 to 12 carbon atoms wherein at least one hydrogen is substituted with fluorine or chlorine; ring G and ring I are 1, 4-cyclohexylene, 1, 4-phenylene, 2-fluoro-1, 4-phenylene or 2, 5-difluoro-1, 4-phenylene; z⁵Is a single bond, ethylene or carbonyloxy; g is 1,2 or 3.

9. The liquid crystal composition according to any one of claims 1 to 8, comprising at least one compound selected from the group consisting of compounds represented by formulae (3-1) to (3-13) as a second component;

in formulae (3-1) to (3-13), R³And R⁴Is 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 alkyl group having 1 to 12 carbon atoms wherein at least one hydrogen is substituted with fluorine or chlorine, or an alkenyl group having 2 to 12 carbon atoms wherein at least one hydrogen is substituted with fluorine or chlorine.

10. The liquid crystal composition according to claim 8 or 9, wherein the proportion of the second component is in the range of 10 to 90 mass%.

11. The liquid crystal composition according to any one of claims 1 to 10, comprising at least one compound selected from polymerizable compounds represented by formula (4) as a second additive;

in the formula (4), ring I and ring K are cyclohexyl, cyclohexenyl, phenyl, 1-naphthyl, 2-naphthyl, tetrahydropyran-2-yl, 1, 3-dioxan-2-yl, pyrimidin-2-yl or pyridin-2-yl, and in these rings, at least one hydrogen may be substituted with fluorine, chlorine, an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, or an alkyl group having 1 to 12 carbon atoms in which at least one hydrogen is substituted with fluorine or chlorine; ring J is 1, 4-cyclohexylene, 1, 4-cyclohexenylene, 1, 4-phenylene, naphthalene-1, 2-diyl, naphthalene-1, 3-diyl, naphthalene-1, 4-diyl, naphthalene-1, 5-diyl, naphthalene-1, 6-diyl, naphthalene-1, 7-diyl, naphthalene-1, 8-diyl, naphthalene-2, 3-diyl, naphthalene-2, 6-diyl, naphthalene-2, 7-diyl, tetrahydropyran-2, 5-diyl, 1, 3-dioxane-2, 5-diyl, pyrimidine-2, 5-diyl or pyridine-2, 5-diyl, in which at least one hydrogen atom is substituted with fluorine, chlorine, an alkyl group having a carbon number of 1 to 12, an alkoxy group having a carbon number of 1 to 12, Or at least one hydrogen is substituted by a fluorine or chlorine substituted alkyl group of carbon number 1 to 12; z⁶And Z⁷Is a single bond or an alkylene group having 1 to 10 carbon atoms, in which at least one-CH group₂-may be substituted by-O-, -CO-, -COO-or-OCO-, at least one-CH₂-CH₂-may be via-CH ═ CH-, -C (CH)₃)＝CH-、-CH＝C(CH₃) -or-C (CH)₃)＝C(CH₃) -substitution, of which at least one hydrogen may be substituted by fluorine or chlorine; p⁹、P¹⁰And P¹¹Is a group selected from the polymerizable groups represented by the formulae (P-7) to (P-11);

Sp⁵、Sp⁶and Sp⁷Is a single bond or an alkylene group having 1 to 10 carbon atoms, in which at least one-CH group₂May be substituted by-O-, -COO-, -OCO-or-OCOO-At least one-CH₂-CH₂-may be substituted by-CH ═ CH-or-C ≡ C-, at least one of these groups being substituted by fluorine or chlorine; h is 0, 1 or 2; i. j and k are 0, 1,2, 3 or 4, and the sum of i, j and k is 1 or more;

in formulae (P-7) to (P-11), M⁵、M⁶And M⁷Hydrogen, fluorine, an alkyl group having 1 to 5 carbon atoms, or an alkyl group having 1 to 5 carbon atoms in which at least one hydrogen is substituted with fluorine or chlorine.

12. The liquid crystal composition according to any one of claims 1 to 11, containing at least one compound selected from the group consisting of compounds represented by formulae (4-1) to (4-29) as a second additive;

in formulae (4-1) to (4-29), P¹²、P¹³And P¹⁴Is a polymerizable group selected from the group represented by the formulae (P-7) to (P-9);

here, M⁵、M⁶And M⁷Hydrogen, fluorine, an alkyl group having 1 to 5 carbon atoms, or an alkyl group having 1 to 5 carbon atoms in which at least one hydrogen is substituted with fluorine or chlorine; sp⁵、Sp⁶And Sp⁷Is a single bond or an alkylene group having 1 to 10 carbon atoms, in which at least one-CH group₂At least one-CH which may be substituted by-O-, -COO-, -OCO-or-OCOO-)₂-CH₂-may be substituted by-CH ═ CH-or-C ≡ C-, in which at least one hydrogenMay be substituted by fluorine or chlorine.

13. The liquid crystal composition according to claim 11 or 12, wherein the proportion of the second additive is in the range of 0.03 to 10% by mass.

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

15. The liquid crystal display element according to claim 14, wherein an operation mode of the liquid crystal display element is an in-plane switching mode, a vertical alignment mode, a fringe field switching mode, or an electric field induced photoreaction alignment mode, and a driving mode of the liquid crystal display element is an active matrix mode.

16. A polymer-stabilized alignment type liquid crystal display element comprising the liquid crystal composition according to any one of claims 1 to 13, or a polymerizable compound in the liquid crystal composition, and polymerized.

17. Use of a liquid crystal composition according to any one of claims 1 to 13 in a liquid crystal display element.

18. Use of a liquid crystal composition according to any one of claims 1 to 13 in a liquid crystal display element of polymer stabilized alignment type.