TWI763954B - Liquid crystal composition and liquid crystal display element - Google Patents

Abstract

The problem to be solved by the present invention is to provide a liquid crystal composition with negative dielectric anisotropy (Δε), high T _NI , large Δn, and small γ ₁ , and to provide a VA type with no display defects or very few display defects Or FFS type or IPS type liquid crystal display element, which uses the above-mentioned liquid crystal composition, and has a fast response speed and high VHR. The liquid crystal composition of this invention solves the said subject by the liquid crystal composition containing the compound of general formula (i).

Description

Liquid crystal composition and liquid crystal display element

The present invention relates to a liquid crystal composition and a liquid crystal display element using the same.

Liquid crystal display elements are used in various household electrical appliances including clocks and calculators, measuring equipment, automotive panels, typewriters, electronic notepads, printers, computers, televisions, and the like. Typical examples of liquid crystal display methods include: TN (twisted nematic) type, STN (super twisted nematic) type, DS (dynamic light scattering) type, GH (guest-host) type, and IPS (transverse electric field effect) type , OCB (optically compensated birefringence) type, ECB (electrically controlled birefringence) type, VA (vertical alignment) type, CSH (color super vertical alignment) type, or FLC (ferroelectric liquid crystal) and so on. Further, as the driving method, static driving, multiplexing driving, simple matrix method, and active matrix (AM) method of driving by TFT (Thin Film Transistor), TFD (Thin Film Diode), or the like can also be exemplified. Among these display methods, the IPS type, the ECB type, the VA type, or the CSH type has the characteristic of "using a liquid crystal composition with a negative value of Δε (dielectric anisotropy)". Among them, the VA-type display system using AM drive is used in display elements requiring high-speed response and wide viewing angle, such as televisions and monitors.

As a liquid crystal composition whose Δε is a negative value, liquid crystal compositions using the following liquid crystal compounds (A) to (E) having a 2,3-difluorophenylene skeleton (see Patent Document 1) are disclosed.

However, any liquid crystal composition cannot have the response speed and reliability required especially in large-scale liquid crystal display elements. In addition, in Patent Document 2, it is disclosed that the response speed of the vertical liquid crystal cell is improved by using a liquid crystal material having a large exponent (FoM) represented by the following formula, but it cannot be said to be sufficient.

Therefore, in liquid crystal compositions that require high-speed response and high reliability, such as liquid crystal televisions, it is required to adjust the nematic-isotropic liquid phase transition temperature (T _NI ) and the refractive index anisotropy (Δn) appropriately. The rotational viscosity (γ ₁ ) is small, the elastic constant (K ₃₃ ) is large, the γ ₁ /K ₃₃ is small, and the voltage holding ratio VHR is high.

[Prior Art Literature] [Patent Literature] Patent Document 1: Japanese Patent Laid-Open No. 2016-216747 Patent Document 2: Japanese Patent Laid-Open No. 2006-301643

[The problem to be solved by the invention]

The problem to be solved by the present invention is to provide a liquid crystal composition whose dielectric anisotropy (Δε) is negative, while appropriately adjusting T _NI and Δn, the γ ₁ is also small, and a liquid crystal composition with no display defects or very few display defects is provided. The VA type, FFS type or IPS type liquid crystal display element, which uses the above-mentioned liquid crystal composition, has fast response speed and high VHR. [Technical means to solve the problem]

As a result of intensive research, the present inventors found that the above-mentioned problems can be solved by a liquid crystal composition containing a compound having a specific chemical structure, and completed the present invention.

Furthermore, by using a polymerizable compound together with this liquid crystal composition, the above-mentioned problems can be solved, and the present invention has been completed. [Effect of invention]

The present invention can provide a liquid crystal composition with negative dielectric anisotropy (Δε), high T _NI , large Δn, and small γ ₁ , and the present invention can provide a VA type or FFS with no display defects or very few display defects type or IPS type liquid crystal display element, which uses the above-mentioned liquid crystal composition, has a fast response speed, and has a high VHR.

The liquid crystal composition of the present invention contains a compound represented by the general formula (i) having a negative dielectric anisotropy (Δε); the present invention is a liquid crystal composition further containing a polymerizable compound, and the present invention uses the above-mentioned liquid crystal The composition of the liquid crystal display element.

(In the formula, X ⁱ¹ and X ⁱ² each independently represent a hydrogen atom, a fluorine atom, a chlorine atom, a cyano group, a trifluoromethyl group, and a trifluoromethoxy group, and Y ⁱ¹ and Y ⁱ² each independently represent -O-, - CF ₂ -, -CO-, -CX ⁱ³ X ⁱ⁴ -, but one or more of Y ⁱ¹ and Y ⁱ² represent -O-, X ⁱ³ and X ⁱ⁴ independently represent the same meaning as X ⁱ¹ , L ⁱ¹ , L ⁱ² , L ⁱ³ , L ⁱ⁴ and L ⁱ⁵ each independently represent a hydrogen atom, a bromine atom, an iodine atom, a hydroxyl group, an alkyl group having 1 to 15 carbon atoms, an alkenyl group having 2 to 15 carbon atoms, or the general formula (L ⁱ -1) the base represented,

(In the formula, R ⁱ¹ represents a hydrogen atom, an alkyl group having 1 to 15 carbon atoms, an alkoxy group having 1 to 15 carbon atoms, an alkenyl group having 2 to 15 carbon atoms, or an alkenyl group having 2 to 15 carbon atoms. group, A ⁱ¹ represents a group selected from (a) 1,4-cyclohexylene group (one -CH ₂ - present in this group or two or more -CH ₂ - which are not adjacent to each other may be replaced by -O- or - S-substitution) (b) 1,4-phenylene group (one -CH= present in this group or two or more non-adjacent -CH= may be substituted by -N=, present in this group One hydrogen atom may be substituted by a fluorine atom) (c) 1,4-cyclohexenyl, naphthalene-2,6-diyl, 1,2,3,4-tetrahydronaphthalene-2,6- Diyl, decahydronaphthalene-2,6-diyl (the hydrogen atoms present in these radicals can also be substituted by fluorine atoms, and in naphthalene-2,6-diyl or 1,2,3,4 One of -CH= in tetrahydronaphthalene-2,6-diyl group or two or more non-adjacent -CH= may be substituted by -N=) group in the group, Z ⁱ¹ represents -CH ₂ O-, -OCH ₂ -, -CF ₂ O-, -OCF ₂ -, -COO-, -OCO-, -CH ₂ CH ₂ -, -CF ₂ CF ₂ -, -CH=CH-, -CF =CF-, -C≡C- or single bond, n ⁱ¹ represents 1 or 2, when n ⁱ¹ represents 2 and there are multiple A ⁱ¹ and Z ⁱ¹ , they may be the same or different); W ⁱ¹ represents The basis represented by the general formula (W ⁱ¹ -1), (W ⁱ¹ -2) or (W ⁱ¹ -3),

(In the formula, ・ represents the bonding point with L ⁱ² or Y ⁱ² , * represents the bonding point with the carbon atom adjacent to the carbon atom bonded with L ⁱ⁵ , and L ⁱ⁶ , L ⁱ⁷ and L ⁱ⁸ respectively independently represent Same meaning as L ⁱ¹ ), W ⁱ² represents a single bond or -CL ⁱ⁹ L ⁱ¹⁰ -, (L ⁱ⁹ and L ⁱ¹⁰ independently represent the same meaning as L ⁱ¹ ), L ⁱ¹ , L ⁱ² , L ⁱ³ , L ⁱ⁴ , L One -CH 2 - present in ⁱ⁵ , L ⁱ⁶ , L ⁱ⁷ , L ⁱ⁸ , L ⁱ⁹ , and L ⁱ¹⁰ or _two or more -CH ₂ - that are not adjacent to each other may also be represented by -C≡C-, -O- , -COO-, -OCO- or -CO- substituted, and the hydrogen atom existing in the alkyl or alkenyl group can also be substituted by a fluorine atom).

The lower limit of the content of the compound of the general formula (i) in the liquid crystal composition of the present invention is preferably 0.1 mass %, preferably 0.2 mass %, preferably 0.3 mass %, preferably 0.5 mass % , preferably 1 mass%, preferably 2 mass%, preferably 3 mass%, preferably 4 mass%, as the upper limit, more preferably 20 mass%, more preferably 15 mass%, more preferably 13% by mass, more preferably 10% by mass, and the range of the content is preferably 0.1 to 25% by mass, more preferably 0.1 to 20% by mass, still more preferably 0.1 to 15% by mass, particularly preferably 1 to 10% by mass 15% by mass. Hereinafter, mass % is described as %.

In the case of attaching importance to T _NI , it is better to make the content smaller, and in the case of improving γ ₁ /K ₃₃ and attaching importance to the response speed, it is better to make the content larger.

In general formula (i), it is preferable that at least one of X ⁱ¹ and X ⁱ² is a fluorine atom, and it is preferable that both are a fluorine atom. Y ⁱ¹ and Y ⁱ² are preferably a compound in which one is O- and the other is -CH ₂ -, and a compound in which both are -O-, preferably a compound in which both are -O-.

Preferably, L ⁱ¹ and L ⁱ² each independently represent a hydrogen atom, an alkyl group having 1 to 15 carbon atoms, and an alkenyl group having 2 to 15 carbon atoms. In order to reduce γ ₁ , they are preferably 1 to 8 carbon atoms. The alkyl group or the alkenyl group having 2 to 8 carbon atoms is particularly preferably an alkyl group having 1 to 5 carbon atoms or an alkenyl group having 2 to 5 carbon atoms. Moreover, it is preferable that it is a linear form. In order to increase |Δε|, an alkoxy group having 1 to 8 carbon atoms or an alkenyloxy group having 2 to 8 carbon atoms is preferable, and an alkoxy group having 1 to 5 carbon atoms or an alkoxy group having 1 to 5 carbon atoms is particularly preferable. 2 to 5 of the alkenyloxy. In order to improve the miscibility with other liquid crystal components, it is preferable that L ⁱ¹ and L ⁱ² are different, and either one of L ⁱ¹ and L ⁱ² is preferably an alkoxy group or an alkenyloxy group, and it is particularly preferable that L ⁱ¹ is an alkoxy group base. The hydrogen atoms present in L ⁱ¹ and L ⁱ² may also be substituted by fluorine atoms, preferably not substituted by fluorine atoms.

In addition, L ⁱ¹ and L ⁱ² represent

is better.

In order to reduce γ1, R ⁱ¹ is preferably an alkyl group having ₁ to 8 carbon atoms or an alkenyl group having 2 to 8 carbon atoms, more preferably an alkyl group having 1 to 5 carbon atoms or an alkyl group having 2 to 5 carbon atoms of alkenyl. Moreover, it is preferable that it is a linear form. In order to increase |Δε|, an alkoxy group having 1 to 8 carbon atoms or an alkenyloxy group having 2 to 8 carbon atoms is preferable, and an alkoxy group having 1 to 5 carbon atoms or an alkoxy group having 1 to 5 carbon atoms is particularly preferable. 2 to 5 of the alkenyloxy. In the case where a plurality of R ⁱ¹ are present, in order to improve the miscibility with other liquid crystal components, it is preferable that the R ⁱ¹ are different from each other, and it is preferable that any one of the plurality of R ⁱ¹ is an alkoxy group or an alkenyloxy group. group, preferably R ⁱ¹ in L ⁱ¹ is an alkoxy group or an alkenyloxy group. The hydrogen atoms present in R ⁱ¹ may also be substituted by fluorine atoms, preferably not substituted by fluorine atoms.

A ⁱ¹ preferably represents selected from

base in the middle. Specifically, in order to reduce γ ₁ , A ¹ is preferably trans-1,4-cyclohexylene, unsubstituted 1,4-phenylene, 2-fluoro-1,4-phenylene, or 3-Fluoro-1,4-phenylene, particularly preferably trans-1,4-cyclohexylene. In order to improve the miscibility with other liquid crystal components, trans-1,4-cyclohexylene, 2-fluoro-1,4-phenylene or 3-fluoro-1,4-phenylene is preferable. In order to improve T _NI , unsubstituted 1,4-phenylene, unsubstituted 1,4-cyclohexylene, 1,4-cyclohexenylene, or unsubstituted naphthalene-2 are preferred , 6 - two bases. In order to exhibit a large negative Δε, 2-fluoro-1,4-phenylene, 3-fluoro-1,4-phenylene or 2,3-difluoro-1,4-phenylene is preferable. The total number of fluorine atoms present in A ⁱ¹ is preferably 1 to 4, and particularly preferably 1 to 3, in order to exhibit a large negative Δε and also to have miscibility with other liquid crystal components.

In order to reduce γ ₁ , Z ⁱ¹ is preferably a single bond, -CH ₂ CH ₂ -, -CH ₂ O- or -OCH ₂ -, more preferably a single bond or -CH ₂ CH ₂ -. In order to improve T _NI , a single bond, -COO-, -OCO-, -CH=CH- or -C≡C- is preferable, and a single bond, -CH=CH- or -C≡C- is more preferable. In order to improve the miscibility with other liquid crystal components, a single bond, -CH ₂ CH ₂ -, -CH ₂ O- or -OCH ₂ - is preferable. In order to improve long-term reliability when forming a liquid crystal display element, a single bond is preferable.

When n ⁱ¹ represents 2, it is preferable that any one or more of Z ⁱ¹ present in plural represents a single bond. When γ ₁ is emphasized, n ⁱ¹ is preferably 1. In the case where T _NI is important, 2 is preferable. W ⁱ¹ is preferably the general formula (W ⁱ¹ -1) or (W ⁱ¹ -3). ^Wi2 is preferably a single key.

L ⁱ³ preferably represents a hydrogen atom, an alkyl group having 1 to 15 carbon atoms, an alkoxy group having 1 to 15 carbon atoms, an alkenyl group having 2 to 15 carbon atoms, and an alkenyloxy group having 2 to 15 carbon atoms. In order to reduce γ1, it is preferably an alkyl group having ₁ to 8 carbon atoms or an alkenyl group having 2 to 8 carbon atoms, particularly preferably an alkyl group having 1 to 5 carbon atoms or an alkyl group having 2 to 5 carbon atoms. alkenyl. Moreover, it is preferable that it is a linear form.

Preferably, at least one of L ⁱ¹ , L ⁱ² and L ⁱ³ is a hydrogen atom, and preferably L ⁱ¹ or L ⁱ³ is a hydrogen atom. Preferably, L ⁱ¹ is an alkyl group having 1 to 8 carbon atoms or an alkoxy group having 1 to 8 carbon atoms, L ⁱ² is a hydrogen atom, and L ⁱ³ is an alkyl group having 1 to 8 carbon atoms, preferably L ⁱ¹ is a hydrogen atom, L ⁱ² is an alkyl group having 1 to 8 carbon atoms or an alkoxy group having 1 to 8 carbon atoms, and L ⁱ³ is an alkyl group having 1 to 8 carbon atoms.

Preferably, L ⁱ⁴ and L ⁱ⁵ each independently represent a hydrogen atom, an alkyl group having 1 to 15 carbon atoms, and an alkenyl group having 2 to 15 carbon atoms, preferably a hydrogen atom.

Preferably, L ⁱ⁶ and L ⁱ⁷ each independently represent a hydrogen atom, an alkyl group having 1 to 15 carbon atoms, and an alkenyl group having 2 to 15 carbon atoms, preferably a hydrogen atom.

Preferably, L ⁱ⁸ represents a hydrogen atom, an alkyl group having 1 to 15 carbon atoms, an alkoxy group having 1 to 15 carbon atoms, an alkenyl group having 2 to 15 carbon atoms, and an alkenyl group having 2 to 15 carbon atoms. , preferably a hydrogen atom.

Preferably, L ⁱ⁹ and L ⁱ¹⁰ represent a hydrogen atom.

Furthermore, in the compound represented by the general formula (i), there is no case where the heteroatoms are directly bonded to each other.

Among the compounds represented by the general formula (i), each of the compounds represented by the following general formulae (i-1) to (i-48) is preferable. Among them, the preferred compounds are the general formula (i-1), (i-2), (i-3), (i-4), (i-5), (i-6), (i-7) , (i-8), (i-9), (i-10), (i-11) and (i-12) represent the compounds of general formula (i-1), (i-2), The compounds represented by (i-3) and (i-4) are compounds represented by general formulae (i-1) and (i-3), and are compounds represented by general formula (i-1).

(In the formula, R ⁱ¹ and R ⁱ² have the same meaning as R ⁱ¹ in the general formula (i))

(In the formula, R ⁱ¹ and R ⁱ² have the same meaning as R ⁱ¹ in the general formula (i))

(In the formula, R ⁱ¹ and R ⁱ² have the same meaning as R ⁱ¹ in the general formula (i))

(In the formula, R ⁱ¹ and R ⁱ² have the same meaning as R ⁱ¹ in the general formula (i)) The liquid crystal composition of the present invention preferably contains one or two kinds of compounds other than the compound represented by the general formula (i). The above compounds are selected from the compound group represented by the general formulae (N-01), (N-02), (N-03), (N-04) and (N-05). Compounds such as these correspond to compounds having negative anisotropy with respect to the dielectric. Compounds such as these show that the sign of Δε is negative and the absolute value thereof is larger than 2. In addition, the Δε of the compound is the value extrapolated from the measured value of the dielectric anisotropy of the composition prepared by adding the compound to a composition having a substantially neutral dielectric property at 25°C.

In the formula, R ²¹ and R ²² each independently represent an alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, an alkenyl group having 2 to 8 carbon atoms, or an alkyl group having 2 to 8 carbon atoms. In the alkenyloxy group, one of the groups or two or more of the non-adjacent -CH ₂ - may be independently represented by -CH=CH-, -C≡C-, -O-, -CO-, - COO- or -OCO- is substituted, Z ¹ independently represents a single bond, -CH ₂ CH ₂ -, -OCH ₂ -, -CH ₂ O-, -COO-, -OCO-, -OCF ₂ -, -CF ₂ O-, -CH=CH-, -CF=CF- or -C≡C-, and m each independently represents 1 or 2. R ²¹ is preferably an alkyl group having 1 to 8 carbon atoms, more preferably an alkyl group having 1 to 5 carbon atoms, still more preferably an alkyl group having 1 to 4 carbon atoms. Among them, when Z ¹ represents other than a single bond, R ²¹ is preferably an alkyl group having 1 to 3 carbon atoms. R ²² is preferably an alkyl group having 1 to 8 carbon atoms or an alkoxy group having 1 to 8 carbon atoms, more preferably an alkyl group having 1 to 5 carbon atoms or an alkoxy group having 1 to 4 carbon atoms, Still more preferred is an alkoxy group having 1 to 4 carbon atoms. R ²¹ and R ²² can also be alkenyl groups, preferably selected from the group represented by any one of formula (R1) to formula (R5) (the black point in each formula represents a carbon atom in the ring structure), more It is preferably the formula (R1) or the formula (R2), but the content of the compound in which R ²¹ and R ²² are alkenyl groups is preferably as small as possible, and in many cases, it is better not to contain them.

Z ¹ independently represents a single bond, -CH ₂ CH ₂ -, -OCH ₂ -, -CH ₂ O-, -COO-, -OCO-, -OCF ₂ -, -CF ₂ O-, -CH=CH -, -CF=CF- or -C≡C-, preferably a single bond, -CH ₂ CH ₂ -, -OCH ₂ -, -CH ₂ O-, more preferably a single bond or -CH ₂ O-. When m is 1, Z ¹ is preferably a single bond. When m is 2, Z ¹ is preferably -CH ₂ CH ₂ - or -CH ₂ O-.

The fluorine atom of the compounds represented by the general formulae (N-01), (N-02), (N-03), (N-04) and (N-05) may also be substituted by a chlorine atom which is also a halogen group. Among them, it is preferable that the content of the compound substituted by chlorine atom is as small as possible, and it is preferable not to contain it.

The hydrogen atoms present in the rings of the compounds represented by the general formulae (N-01), (N-02), (N-03), (N-04) and (N-05) can also be further replaced by fluorine atoms or fluorine atoms. Chlorine atom substitution. Among them, it is preferable that the content of the compound substituted by chlorine atom is as small as possible, and it is preferable not to contain it.

The compounds represented by the general formulae (N-01), (N-02), (N-03), (N-04) and (N-05) are preferably compounds whose Δε is negative and whose absolute value is greater than 3 . Specifically, R ²² preferably represents an alkoxy group having 1 to 8 carbon atoms or an alkenyloxy group having 2 to 8 carbon atoms.

The compound represented by the general formula (N-01) preferably contains one or two or more kinds selected from the group consisting of the general formula (N-01-1), the general formula (N-01-2), the general formula (N-01 -3) and a compound in the compound group represented by the general formula (N-01-4),

(In the formula, R ²¹ represents the same meaning as described above, and R ²³ each independently represents an alkoxy group having 1 to 4 carbon atoms). The liquid crystal composition of the present invention preferably contains a compound represented by general formula (i), and a compound represented by general formula (N-01-1) and general formula (N-01-4). When high VHR is required, that is, when high reliability is required, and further, when it is important to obtain a liquid crystal display element with no display failure, it is preferable not to contain the general formula (N The compound represented by -01-3). The compound represented by the general formula (N-02) preferably contains one or two or more kinds selected from the group consisting of the general formula (N-02-1), the general formula (N-02-2), and the general formula (N- 02-3) the compounds in the compound group represented,

(In the formula, R ²¹ represents the same meaning as described above, and R ²³ each independently represents an alkoxy group having 1 to 4 carbon atoms). The liquid crystal composition of the present invention preferably contains the compound represented by the general formula (i) and the compound represented by the general formula (N-02-1). The liquid crystal composition of the present invention preferably contains the compound represented by the general formula (i) and the compound represented by the general formula (N-02-3). The liquid crystal composition of the present invention preferably contains a compound represented by the general formula (i), a compound represented by the general formula (N-01-1), a compound represented by the general formula (N-01-4), and The compound represented by the general formula (N-02-1). The liquid crystal composition of the present invention preferably contains a compound represented by the general formula (i), a compound represented by the general formula (N-01-1), a compound represented by the general formula (N-01-4), and The compound represented by the general formula (N-02-3). The compound represented by the general formula (N-03) preferably contains one or more compounds represented by the general formula (N-03-1),

(In the formula, R ²¹ represents the same meaning as described above, and R ²³ represents an alkoxy group having 1 to 4 carbon atoms).

The liquid crystal composition of the present invention is preferably a combination of the compound represented by the general formula (i) and the compound represented by the general formula (N-03-1). The liquid crystal composition of the present invention preferably contains a compound represented by the general formula (i), a compound represented by the general formula (N-01-1), a compound represented by the general formula (N-01-4), and The compound represented by the general formula (N-03-1).

The compound represented by the general formula (N-04) preferably contains one or more compounds represented by the general formula (N-04-1),

(In the formula, R ²¹ represents the same meaning as described above, and R ²³ represents an alkoxy group having 1 to 4 carbon atoms).

The liquid crystal composition of the present invention preferably contains a compound represented by the general formula (i), a compound represented by the general formula (N-01-1), a compound represented by the general formula (N-01-4), and The compound represented by the general formula (N-04-1).

The compound represented by general formula (N-05) is preferably a compound selected from the group of compounds represented by formula (N-05-1) to formula (N-05-3).

With respect to the total amount of the liquid crystal composition of the present invention, the preferable lower limit of the content of the compound represented by the general formula (N-01) is 0%, 1%, 5%, 10%, 20%, 30%, 40%, 50%, 55%, 60%, 65%, 70%, 75%, 80%. The preferable upper limit of the content is 95%, 85%, 75%, 65%, 55%, 45%, 35%, 25%, 20%, 15%, and 10%.

With respect to the total amount of the liquid crystal composition of the present invention, the preferable lower limit of the content of the compound represented by the general formula (N-02) is 0%, 1%, 5%, 10%, 20%, 30%, 40%, 50%, 55%, 60%, 65%, 70%, 75%, 80%. The preferable upper limit of the content is 95%, 85%, 75%, 65%, 55%, 45%, 35%, 25%, 20%, 15%, and 10%.

With respect to the total amount of the liquid crystal composition of the present invention, the preferable lower limit of the content of the compound represented by the general formula (N-03) is 0%, 1%, 5%, 10%, 20%, 30%, 40%, 50%, 55%, 60%, 65%, 70%, 75%, 80%. The preferable upper limit of the content is 95%, 85%, 75%, 65%, 55%, 45%, 35%, 25%, 20%, 15%, and 10%.

With respect to the total amount of the liquid crystal composition of the present invention, the preferable lower limit of the content of the compound represented by the general formula (N-04) is 0%, 1%, 5%, 10%, 20%, 30%, 40%, 50%, 55%, 60%, 65%, 70%, 75%, 80%. The preferable upper limit of the content is 95%, 85%, 75%, 65%, 55%, 45%, 35%, 25%, 20%, 15%, and 10%.

With respect to the total amount of the liquid crystal composition of the present invention, the preferable lower limit of the content of the compound represented by the formula (N-05) is 0%, 2%, 5%, 8%, 10%, and 13%, 15%, 17%, 20%. The preferable upper limit values of the content are 30%, 28%, 25%, 23%, 20%, 18%, 15%, and 13%.

The liquid crystal composition of the present invention preferably contains 0.1% to 15% of the compound represented by the general formula (i), 1% to 20% of the compound represented by the general formula (N-01-1), and 1% To 30% of the compound represented by the general formula (N-01-4), containing 1% to 20% of the compound represented by the general formula (N-04-1).

The liquid crystal composition of the present invention may further contain one or more compounds represented by the general formula (N-06).

(In the formula, R ²¹ and R ²² have the same meaning as described above) The compound represented by the general formula (N-06) is effective when various physical properties are to be adjusted, and in order to obtain a large refractive index anisotropy (Δn) ), high T _NI , and large Δε can be used.

With respect to the total amount of the liquid crystal composition of the present invention, the preferable lower limit of the content of the compound represented by the formula (N-06) is 0%, 2%, 5%, 8%, 10%, and 13%, 15%, 17%, 20%. The preferable upper limit of the content is 30%, 28%, 25%, 23%, 20%, 18%, 15%, 13%, 10%, 5%.

The liquid crystal composition of the present invention contains one or more compounds selected from the compound group represented by the general formula (NU-01) to the general formula (NU-06),

(wherein, R ^NU11 , R ^NU12 , R ^NU21 , R ^NU22 , R ^NU31 , R ^NU32 , R ^NU41 , R ^NU42 , R ^NU51 , R ^NU52 , R ^NU61 and R ^NU62 independently represent one of the carbon atoms of 1 to 8 An alkyl group, an alkoxy group having 1 to 8 carbon atoms, an alkenyl group having 2 to 8 carbon atoms, or an alkenyloxy group having 2 to 8 carbon atoms, one of these groups or two or more non-adjacent ones— CH ₂ - may be independently replaced by -CH=CH-, -C≡C-, -O-, -CO-, -COO- or -OCO-). In more detail, R NU11 , R ^NU12 , R ^NU21 , R ^NU22 , R ^NU31 , R ^NU32 , R ^NU41 , R ^NU42 , R ^NU51 , R ^NU52 , R ^NU61 and R ^NU62 preferably ^have 1 to 5 carbon atoms An alkyl group, an alkoxy group having 1 to 5 carbon atoms, or an alkenyl group having 2 to 3 carbon atoms, more preferably an alkyl group having 1 to 5 carbon atoms or an alkenyl group having 2 to 3 carbon atoms. When the response speed is important, at least one of R ^NU11 , R ^NU21 , R ^NU31 , R ^NU41 , R ^NU51 and R ^NU61 is preferably an alkenyl group having 2 to 3 carbon atoms, and the compound having such an alkenyl group is relatively The total amount of the liquid crystal composition of the present invention is preferably 10% or more, preferably 20% or more, preferably 25% or more, preferably 30% or more, preferably 40% or more, preferably 45% % or more, preferably 50% or more. When a high VHR is important, the compound having an alkenyl group is preferably 40% or less, preferably 35% or less, more preferably 30% or less. In order to have both high speed and high reliability, it is preferable to use only general formula (NU-01) as the compound having an alkenyl group. In this case, R ^NU11 is an alkyl group having 2 to 4 carbon atoms, R ^NU12 is an alkenyl group having 2 to 3 carbon atoms. In order to have both high speed and high reliability, it is preferable to use the general formula (NU-01) and the general formula (NU-05) as the compound having an alkenyl group, and in this case, it is particularly preferable that R ^NU11 has 2 carbon atoms R NU12 is an alkyl group having 2 to 3 carbon atoms, preferably R ^NU51 is an alkyl group ^{having 2 to 3 carbon atoms, and R NU52 is} an alkyl group having 2 to 3 carbon atoms. In order to have both high speed and high reliability, it is preferable to use general formula (NU-01), general formula (NU-05), and general formula (NU-04) as the compound having an alkenyl group, and in this case, it is particularly preferable R ^NU11 is an alkyl group having 2 to 4 carbon atoms, R ^NU12 is an alkenyl group having 2 to 3 carbon atoms, preferably R ^NU51 and R ^NU41 are an alkenyl group having 2 to 3 carbon atoms, R ^NU52 and R ^NU42 is an alkyl group having 2 to 3 carbon atoms.

The liquid crystal composition of the present invention preferably contains a compound represented by the general formula (NU-01) and the general formula (NU-02). The liquid crystal composition of the present invention preferably contains a compound represented by the general formula (NU-01) and the general formula (NU-03). The liquid crystal composition of the present invention preferably contains a compound represented by the general formula (NU-04) and the general formula (NU-05). The liquid crystal composition of the present invention preferably contains a compound represented by the general formula (NU-05) and the general formula (NU-06). It is preferable that the liquid crystal composition of this invention contains the compound represented by general formula (NU-01) and general formula (NU-05). The liquid crystal composition of the present invention preferably contains a compound represented by the general formula (NU-01) and the general formula (NU-06). The liquid crystal composition of the present invention preferably contains a compound represented by the general formula (NU-01), the general formula (NU-05), and the general formula (NU-06).

5-60 mass % is preferable, as for content of the compound represented by general formula (NU-01), 10-50 mass % is more preferable, and 25-45 mass % is still more preferable.

The content of the compound represented by the general formula (NU-02) is preferably 3 to 30% by mass, more preferably 5 to 25% by mass, still more preferably 5 to 20% by mass.

The content of the compound represented by the general formula (NU-03) is preferably 0 to 20% by mass, more preferably 0 to 15% by mass, and still more preferably 0 to 10% by mass.

The content of the compound represented by the general formula (NU-04) is preferably 3 to 30% by mass, more preferably 3 to 20% by mass, still more preferably 3 to 10% by mass.

The content of the compound represented by the general formula (NU-05) is preferably 0 to 30% by mass, more preferably 1 to 20% by mass, and still more preferably 3 to 20% by mass.

The content of the compound represented by the general formula (NU-06) is preferably 1 to 30% by mass, more preferably 3 to 20% by mass, and still more preferably 3 to 10% by mass.

The liquid crystal composition of the present invention may contain one or two or more types of polymerizable compounds.

The liquid crystal composition of the present invention may contain one or more of the polymerizable compounds represented by the general formula (RM) as the polymerizable compound.

(In the formula, R ¹⁰¹ , R ¹⁰² , R ¹⁰³ , R ¹⁰⁴ , R ¹⁰⁵ , R ¹⁰⁶ , R ¹⁰⁷ and R ¹⁰⁸ each independently represent the number of carbon atoms which may be substituted by P ¹³ -S ¹³ - and fluorine atoms from 1 to Any of the alkyl group of 18, the alkoxy group of 1 to 18 carbon atoms which may be substituted by a fluorine atom, a fluorine atom or a hydrogen atom, P ¹¹ , P ¹² and P ¹³ are each independently represented by the formula (Re-1 ) to the polymerizable group represented by the formula (Re-9),

(In the formula, R ¹¹ , R ¹² , R ¹³ , R ¹⁴ and R ¹⁵ each independently represent any one of an alkyl group having 1 to 5 carbon atoms, a fluorine atom or a hydrogen atom, m ^r5 , m ^r7 , and n ^r5 and n ^r7 independently represent 0, 1, or 2, and when m ^r5 , m ^r7 , n ^r5 and/or n ^r7 represent 0, represent a single bond), S ¹¹ , S ¹² and S ¹³ independently Represents a single bond or an alkylene group having 1 to 15 carbon atoms, and one -CH ₂ - or two or more non-adjacent -CH ₂ - in the alkylene group may also be represented by -O-, -OCO- or - COO-substitution, when there are a plurality of P ¹³ and S ¹³ , they may be the same or different respectively). The liquid crystal composition containing the polymerizable compound represented by the general formula (RM) is suitable for the production of PSA type or PSVA type liquid crystal display elements. It is also suitable for the production of NPS type liquid crystal display elements. Moreover, it is suitable also when producing the PI-less type liquid crystal display element characterized by not having an alignment film.

Since the liquid crystal composition containing the compound represented by the general formula (i) and the polymerizable compound represented by the general formula (RM) has an appropriately fast polymerization rate, the desired pretilt angle can be imparted with a short ultraviolet irradiation time. Furthermore, the residual amount of the polymerizable compound after polymerization can be reduced. Thereby, the production efficiency of manufacturing a PSA type or PSVA type liquid crystal display element can be improved. In addition, there is no display failure caused by a change in the pretilt angle (for example, defects such as afterimages), or the display failure caused by a change in the pretilt angle is extremely small. In addition, the display failure in this specification refers to the display failure caused by the change of the pretilt angle with time, the display failure caused by the residual amount of the unreacted polymerizable compound, and the display failure caused by the decrease of the voltage holding ratio.

In the above general formula (RM), R ¹⁰¹ , R ¹⁰² , R ¹⁰³ , R ¹⁰⁴ , R ¹⁰⁵ , R ¹⁰⁶ , R ¹⁰⁷ and R ¹⁰⁸ each independently represent those that may be substituted by P ¹³ -S ¹³ - and fluorine atoms. Any of an alkyl group having 1 to 18 carbon atoms, an alkoxy group having 1 to 18 carbon atoms that may be substituted by a fluorine atom, a fluorine atom or a hydrogen atom, in the case of an alkyl group and an alkoxy group The preferable number of carbon atoms is 1-16, more preferably 1-10, still more preferably 1-8, still more preferably 1-6, still more preferably 1-3. In addition, the above-mentioned alkyl group and alkoxy group may be linear or branched, and linear is particularly preferable.

In the above general formula (RM), R ¹⁰¹ , R ¹⁰² , R ¹⁰³ , R ¹⁰⁴ , R ¹⁰⁵ , R ¹⁰⁶ , R ¹⁰⁷ and R ¹⁰⁸ represent the number of carbon atoms which may be substituted by P ¹³ -S ¹³ - and fluorine atoms Any one of 1 to 3 alkoxy groups, fluorine atoms or hydrogen atoms is preferable, and represents any one of P ¹³ -S ¹³ -, an alkoxy group having 1 to 3 carbon atoms, a fluorine atom or a hydrogen atom whichever is better. The number of carbon atoms in the alkoxy group is preferably 1 or more and 3 or less, more preferably 1 or more and 2 or less, and particularly preferably 1.

Moreover, P ¹¹ , P ¹² and P ¹³ may all be the same polymerizable group (formula (Re-1) to (Re-9)), or may be different polymerizable groups.

In the above-mentioned general formula (RM), it is preferable that P ¹¹ , P ¹² and P ¹³ each independently represent the formula (Re-1), the formula (Re-2), the formula (Re-3), and the formula (Re-4). ), formula (Re-5) or formula (Re-7), more preferably formula (Re-1), formula (Re-2), formula (Re-3) or formula (Re-4), more preferably The formula (Re-1) is more preferably an acrylic group or a methacryl group.

Preferably at least one of P ¹¹ and P ¹² is the formula (Re-1), more preferably acryl group or methacryloyl group, particularly preferably methacryloyl group, especially preferably P ¹¹ and P ¹² For the methacryloyl group.

In the above general formula (RM), S ¹¹ , S ¹² and S ¹³ are preferably each independently a single bond or an alkylene group having 1 to 5 carbon atoms, and particularly preferably a single bond. When S ¹¹ , S ¹² and S ¹³ are single bonds, the residual amount of the polymerizable compound after ultraviolet irradiation is very small, and the display failure caused by the change of the pretilt angle becomes difficult to occur. PSA type or PSVA type liquid crystal Display failure of the display element does not occur, or becomes very rare. When S ¹¹ , S ¹² and S ¹³ have 1 to 3 carbon atoms, they are suitable for NPS type liquid crystal display elements.

The lower limit of the content of the polymerizable compound represented by the general formula (RM) in the liquid crystal composition of the present invention is preferably 0.01 mass %, preferably 0.02 mass %, preferably 0.03 mass %, preferably 0.04 mass % mass %, preferably 0.05 mass %, preferably 0.06 mass %, preferably 0.07 mass %, preferably 0.08 mass %, preferably 0.09 mass %, preferably 0.1 mass %, preferably 0.12 mass % %, preferably 0.15 mass%, preferably 0.17 mass%, preferably 0.2 mass%, preferably 0.22 mass%, preferably 0.25 mass%, preferably 0.27 mass%, preferably 0.3 mass% , preferably 0.32 mass%, preferably 0.35 mass%, preferably 0.37 mass%, preferably 0.4 mass%, preferably 0.42 mass%, preferably 0.45 mass%, preferably 0.5 mass%, Preferably it is 0.55 mass %. The upper limit of the content of the polymerizable compound represented by the general formula (RM) in the liquid crystal composition of the present invention is preferably 5 mass %, preferably 4.5 mass %, preferably 4 mass %, preferably 3.5 mass % mass %, preferably 3 mass %, preferably 2.5 mass %, preferably 2 mass %, preferably 1.5 mass %, preferably 1 mass %, preferably 0.95 mass %, preferably 0.9 mass % %, preferably 0.85 mass%, preferably 0.8 mass%, preferably 0.75 mass%, preferably 0.7 mass%, preferably 0.65 mass%, preferably 0.6 mass%, preferably 0.55 mass% , preferably 0.5 mass %, preferably 0.45 mass %, preferably 0.4 mass %.

In more detail, in order to obtain a sufficient pretilt angle or a small residual amount of polymerizable compounds or a high voltage holding ratio (VHR), the content is preferably 0.2 to 0.6 mass %, and emphasis is placed on suppressing precipitation at low temperatures. In this case, the content thereof is preferably 0.01 to 0.4% by mass. In particular, when a fast response speed is obtained, it is preferable to increase the content to 2% by mass. Moreover, when it contains the polymerizable compound represented by a some general formula (RM), it is preferable that each content is 0.01-0.4 mass %. Therefore, in order to solve all these problems, it is especially preferable to adjust the polymerizable compound represented by general formula (RM) in the range of 0.1-0.6 mass %.

As the polymerizable compound represented by the general formula (RM) of the present invention, specifically, the compounds represented by the general formulae (RM-1) to (RM-10) are preferably used, and PSA-type liquid crystal displays such as these are used. The residual amount of the polymerizable compound of the device is small, the pretilt angle is sufficient, and there are no defects such as poor alignment or poor display caused by changes in the pretilt angle, or there are very few defects.

In the formula, R ^M1 and R ^M2 each independently represent any one of an alkyl group having 1 to 5 carbon atoms, a fluorine atom or a hydrogen atom, more preferably an alkyl group having 1 carbon atom or a hydrogen atom.

The liquid crystal composition of the present invention is a compound having a triphenyl structure or a tetraphenyl structure and a dielectric anisotropy Δε greater than +2, that is, it may contain one or more compounds having a positive dielectric anisotropy. In addition, the Δε of the compound is the value extrapolated from the measured value of the dielectric anisotropy of the composition prepared by adding the compound to a composition having a substantially neutral dielectric property at 25°C. The compound can be used in combination according to desired properties such as solubility at low temperature, transition temperature, electrical reliability, refractive index anisotropy, etc. In particular, the polymerizable compound in the liquid crystal composition containing the polymerizable compound can be used in combination. accelerated reactivity.

The lower limit of the preferable content of the compound having a triphenyl structure or a tetraphenyl structure and a dielectric anisotropy Δε greater than +2 relative to the total amount of the liquid crystal composition of the present invention is 0.1%, 0.5%, and 1%, 1.5%, 2%, 2.5%, 3%, 4%, 5%, 10%. The upper limit of the preferred content is relative to the total amount of the liquid crystal composition of the present invention, for example, in one aspect of the present invention, it is 20%, 15%, 10%, 9%, 8%, 7% %, 6%, 5%, 4%, 3%.

The liquid crystal composition of the present invention may contain, in addition to the above-mentioned compounds, common nematic liquid crystals, smectic liquid crystals, cholesteric liquid crystals, antioxidants, ultraviolet absorbers, light stabilizers, or infrared absorbers.

As an antioxidant, hindered phenol (hindered phenol) represented by general formula (H-1) - general formula (H-4) is mentioned.

In general formula (H-1) to general formula (H-3), R ^H1 each independently represents an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, and an alkoxy group having 2 to 10 carbon atoms. The alkenyl group or the alkenyloxy group with 2 to 10 carbon atoms, one -CH ₂ - or two or more non-adjacent -CH ₂ - existing in the group may be independently replaced by -O- or -S. -Substitution, and one or two or more hydrogen atoms present in the group may be independently substituted by a fluorine atom or a chlorine atom. More specifically, it is preferably an alkyl group having 2 to 7 carbon atoms, an alkoxy group having 2 to 7 carbon atoms, an alkenyl group having 2 to 7 carbon atoms, or an alkenyloxy group having 2 to 7 carbon atoms, More preferably, it is an alkyl group having 3 to 7 carbon atoms or an alkenyl group having 2 to 7 carbon atoms.

In the general formula (H-4), M ^H4 represents an alkylene group having 1 to 15 carbon atoms (one or two or more of -CH ₂ - in the alkylene group may be - O-, -CO-, -COO-, -OCO- substituted), -OCH ₂ -, -CH ₂ O-, -COO-, -OCO-, -CF ₂ O-, -OCF ₂ -, -CF ₂ CF ₂ -, -CH=CH-COO-, -CH=CH-OCO-, -COO-CH=CH-, -OCO-CH=CH-, -CH=CH-, -C≡C-, single bond , 1,4-phenylene (any hydrogen atom in 1,4-phenylene may be substituted by fluorine atom) or trans-1,4-cyclohexylene, preferably with 1 to 14 carbon atoms For the alkylene group, if considering volatility, the number of carbon atoms is preferably larger, if considering the viscosity, the number of carbon atoms is preferably not too large, so the number of carbon atoms is preferably 2 to 12, more preferably It is 3 to 10 carbon atoms, more preferably 4 to 10 carbon atoms, more preferably 5 to 10 carbon atoms, more preferably 6 to 10 carbon atoms.

In general formula (H-1) to general formula (H-4), one of the 1,4-phenylene groups or two or more -CH= that are not adjacent to each other may be substituted by -N=. In addition, the hydrogen atoms in the 1,4-phenylene group may be independently substituted with a fluorine atom or a chlorine atom.

In general formula (H-2) and general formula (H-4), one or two or more -CH ₂ - which are not adjacent to the 1,4-cyclohexylene group in the general formula (H-4) may also be replaced by -O- or -S- replace. In addition, the hydrogen atoms in the 1,4-cyclohexylene group may be independently substituted with a fluorine atom or a chlorine atom.

More specifically, Formula (H-11) to Formula (H-15) are mentioned, for example.

When the liquid crystal composition of the present invention contains an antioxidant, it is preferably 10 mass ppm or more, preferably 20 mass ppm or more, and more preferably 50 mass ppm or more. In the case of containing an antioxidant, the upper limit is 10000 mass ppm, preferably 1000 mass ppm, preferably 500 mass ppm, more preferably 100 mass ppm.

The liquid crystal composition of the present invention has a nematic-isotropic liquid phase transition temperature (T _NI ) of 60°C to 120°C, more preferably 70°C to 100°C, particularly preferably 70°C to 85°C. In addition, in this invention, 60 degreeC or more is shown as _TNI high. In the case of LCD TV application, the T _NI is preferably 70 to 80°C. In the case of portable use, the T _NI is preferably 80 to 90°C. In the case of PID (Public Information Display) and other outdoor display applications, T _NI is preferably 90 to 110°C.

The refractive index anisotropy (Δn) of the liquid crystal composition of the present invention at 20° C. is 0.08 to 0.14, more preferably 0.09 to 0.13, still more preferably 0.09 to 0.12. If further detailed, it is preferably 0.10 to 0.13 when corresponding to a thin cell gap, and preferably 0.08 to 0.10 when corresponding to a thick cell gap. In addition, in this invention, 0.09 or more is shown as Δn being large.

The rotational viscosity (γ ₁ ) of the liquid crystal composition of the present invention at 20°C is 50 to 160 mPa･s, preferably 55 to 160 mPa･s, preferably 60 to 160 mPa･s, preferably 80 to 150 mPa･s , preferably 90 to 140 mPa･s, preferably 90 to 130 mPa･s, preferably 100 to 130 mPa･s.

The dielectric anisotropy (Δε) of the liquid crystal composition of the present invention at 20°C is -2.0 to -8.0, preferably -2.0 to -6.0, more preferably -2.0 to -5.0, more preferably -2.5 to - 4.0, preferably -2.5 to -3.5.

The total upper limit of the content of the compound having an alkenyl group in the compound constituting the liquid crystal composition of the present invention is preferably 10%, preferably 8%, preferably 6%, preferably 5%, preferably 4% %, preferably 3%, preferably 2%, preferably 1%, preferably 0%, the total range of the content of the compound having an alkenyl group is preferably 0-10%, preferably 0-8 %, preferably 0 to 5%, preferably 0 to 4%, preferably 0 to 3%, preferably 0 to 2%. However, the compound represented by general formula (NU-01) is not included.

The liquid crystal composition of the present invention is preferably a compound of the general formula (i) containing essential components, and further contains one or two or more compounds selected from the group consisting of the general formula (N-01), the general formula (N-02), the general formula ( The compounds in the compound group represented by general formula (N-04), general formula (N-05) and general formula (N-06) further contain one or more compounds selected from general formula ( For the compounds in the compound group represented by NU-01) to (NU-06), the total upper limit of the equivalent content is preferably 100% by mass, 99% by mass, 98% by mass, 97% by mass, 96% by mass mass %, 95 mass %, 94 mass %, 93 mass %, 92 mass %, 91 mass %, 90 mass %, 89 mass %, 88 mass %, 87 mass %, 86 mass % % by mass, 85% by mass, 84% by mass, and the total lower limit of the equivalent content is preferably 78% by mass, 80% by mass, 81% by mass, 83% by mass, 85% by mass, and 86% by mass %, 87% by mass, 88% by mass, 89% by mass, 90% by mass, 91% by mass, 92% by mass, 93% by mass, 94% by mass, 95% by mass, 96% by mass %, 97 mass %, 98 mass %, and 99 mass %.

The liquid crystal display element using the liquid crystal composition of the present invention is particularly useful for active matrix driving liquid crystal display elements, and can be suitably used for VA, FFS, IPS, PSA, PSVA, PS-IPS or PS-FFS, NPS, PI-less and other liquid crystal display components.

The liquid crystal display element of the present invention preferably has "a first substrate and a second substrate arranged to face each other", "a common electrode provided on the first substrate or the second substrate", and "a common electrode provided on the first substrate or the second substrate" 2 substrates having pixel electrodes of thin film transistors" and "a liquid crystal layer provided between the first substrate and the second substrate and containing a liquid crystal composition". Optionally, an alignment film for controlling the alignment direction of liquid crystal molecules may be provided on the opposite surface side of at least one of the first substrate and/or the second substrate by contacting the liquid crystal layer. As the alignment film, a vertical alignment film or a horizontal alignment film can be appropriately selected according to the driving mode of the liquid crystal display element. ) and other well-known alignment films. Furthermore, the color filter may be appropriately provided on the first substrate or the second substrate, and the color filter may be provided on the pixel electrode or the common electrode.

The two substrates of the liquid crystal cell used in the liquid crystal display element of the present invention can be made of glass or a transparent material with flexibility like plastic, and one of them can also be an opaque material such as silicon. A transparent substrate having a transparent electrode layer can be obtained by sputtering indium tin oxide (ITO) on a transparent substrate such as a glass plate, for example.

The color filter can be produced by, for example, a pigment dispersion method, a printing method, an electrodeposition method, or a dyeing method. Taking a method of producing a color filter by a pigment dispersion method as an example, the curable coloring composition for a color filter is coated on the transparent substrate, subjected to patterning treatment, and then heated or illuminated of hardening. By performing this step for each of the three colors of red, green, and blue, a pixel portion for a color filter can be formed. In addition, pixel electrodes provided with active elements such as TFTs, thin film diodes, metal-insulator-metal resistive elements, etc. can also be arranged on the substrate.

Preferably, the first substrate and the second substrate face each other so that the common electrode or the pixel electrode layer is on the inside.

The interval between the first substrate and the second substrate can also be adjusted through a spacer. In this case, it is preferable to adjust the thickness of the obtained light-adjusting layer to be 1 to 100 μm. More preferably, it is 1.5-10 μm, and when a polarizing plate is used, it is preferable to adjust the product of the refractive index anisotropy Δn of the liquid crystal and the cell thickness d so as to maximize the contrast ratio. In addition, when there are two polarizing plates, the polarization axis of each polarizing plate can also be adjusted so that the viewing angle or the contrast is good. Furthermore, a retardation film for expanding the viewing angle can also be used. As a spacer, a glass particle, a plastic particle, an alumina particle, a photoresist material, etc. are mentioned, for example. Then, a sealant such as an epoxy-based thermosetting composition is screen-printed on the substrate in a shape provided with a liquid crystal injection port, the substrates are bonded to each other, and the sealant is thermally cured by heating.

As a method of sandwiching the liquid crystal composition between two substrates, a general vacuum injection method, an ODF method, or the like can be used.

In order to form the alignment state of the liquid crystal display element of the present invention, it can be produced by using a liquid crystal composition containing a polymerizable compound in the liquid crystal composition, and polymerizing the polymerizable compound in the liquid crystal composition. .

As a method for polymerizing the polymerizable compound contained in the liquid crystal composition of the present invention, the following method is preferable. In order to obtain good alignment performance of the liquid crystal, it is preferable to polymerize at a moderate polymerization rate. They are used in combination or sequentially irradiated with active energy rays such as ultraviolet rays or electron rays to polymerize. When using ultraviolet light, a polarized light source can be used, and a non-polarized light source can also be used. Furthermore, when the polymerization is performed in a state where the liquid crystal composition is sandwiched between two substrates, at least the substrate on the irradiated surface side must have appropriate transparency with respect to the active energy rays. In addition, the following means can also be used: after using a mask to polymerize only a specific part during irradiation, changing the conditions such as electric field, magnetic field or temperature, thereby changing the alignment state of the unpolymerized part, and further irradiating active energy rays to polymerize it . In particular, when UV exposure is performed, it is preferable to apply an AC electric field to the liquid crystal composition and simultaneously perform UV exposure. The applied AC electric field is preferably AC at a frequency of 10 Hz to 10 kHz, more preferably at a frequency of 60 Hz to 10 kHz, and the voltage is selected depending on the desired pretilt angle of the liquid crystal display element. That is, the pretilt angle of the liquid crystal display element can be controlled by the applied voltage. For a PSVA type liquid crystal display element, from the viewpoint of alignment stability and contrast, it is preferable to control the pretilt angle to 80 degrees to 89.9 degrees.

The temperature at the time of irradiation with active energy rays such as ultraviolet rays or electron rays used when polymerizing the polymerizable compound contained in the liquid crystal composition of the present invention is not particularly limited. For example, when the liquid crystal composition of the present invention is applied to a liquid crystal display element having a substrate having an alignment film, it is preferably within a temperature range in which the liquid crystal composition maintains a liquid crystal state. A temperature close to room temperature is preferred, that is, the polymerization is typically carried out at 15-35°C.

On the other hand, for example, when the liquid crystal composition of the present invention is applied to a liquid crystal display element (PI-less type liquid crystal display element) having a substrate without an alignment film, its temperature range can be compared with The temperature range at the time of irradiation of the liquid crystal display element of the substrate of the alignment film is wide.

As the lamp for generating ultraviolet rays, a metal halide lamp, a high-pressure mercury lamp, an ultra-high pressure mercury lamp, or the like can be used. Moreover, as the wavelength of the ultraviolet rays to be irradiated, it is preferable to irradiate the ultraviolet rays in the wavelength range which is not the absorption wavelength range of the liquid crystal composition, and if necessary, it is preferable to filter the ultraviolet rays and use them. The intensity of the irradiated ultraviolet rays is preferably 0.1 mW/cm ² to 100 W/cm ² , more preferably 2 mW/cm ² to 50 W/cm ² . The energy of the irradiated ultraviolet rays can be adjusted appropriately, preferably 10 mJ/cm ² to 500 J/cm ² , more preferably 100 mJ/cm ² to 200 J/cm ² . The intensity can also be changed when UV rays are irradiated. The time of irradiating the ultraviolet rays can be appropriately selected according to the intensity of the irradiated ultraviolet rays, preferably 10 seconds to 3600 seconds, more preferably 10 seconds to 600 seconds. [Example]

The following examples are given to further describe the present invention in detail, but the present invention is not limited to these examples. In addition, "%" in the composition of the following Examples and Comparative Examples means "mass %". In the description of the compounds in the examples, the following codes are used.

The physical properties are measured based on the methods described in JEITA ED-2521B (Revised in March 2009, issued by the Electronic Information Technology Industry Association) stipulated by the Electronic Information Technology Industry Association unless otherwise specified.

(Side chain) -n -C _n H _2n+1 Linear alkyl group of carbon number n n- C _n H _2n+1 - Linear alkyl group of carbon number n -On -OC _n H _{2n+ A} linear alkoxy group with n carbon number nO- C _n H _2n+1 O- Linear alkoxy group with carbon number n -V -CH=CH ₂ V- CH ₂ =CH- -V1 - CH=CH-CH ₃ 1V- CH ₃ -CH=CH- -F -F -OCF3 -OCF ₃ (bonding group) -CF2O- -CF ₂ -O- -OCF2- -O-CF ₂ - -1O- -CH ₂ -O- -O1- -O-CH ₂ - -2- -CH ₂ -CH ₂ - -COO- -COO- -OCO- -OCO- - Single bond (ring structure)

In the examples, the properties measured are as follows.

T _NI : Nematic phase-isotropic liquid phase transition temperature (°C) T _{→ N} : Solid phase-nematic phase transition temperature (°C) Δn : Refractive index anisotropy at 20°C Δε : Between 20°C Electrical anisotropy γ ₁ : Rotational viscosity at 20°C (mPa･s) K ₁₁ : Elastic constant K ₁₁ (pN) at 20° C K ₃₃ : Elastic constant K ₃₃ (pN) at 20° C VHR : 1V , Voltage holding ratio (%) at 60 Hz and 60° C. (Results of preparation and evaluation of liquid crystal compositions) The liquid crystal compositions of Example 1 and Comparative Example 1 were prepared, and their physical properties were measured. In addition, the composition ratio is designed so that T _NI , Δn and Δε in the physical property values become the same. The composition ratios of the liquid crystal compositions and their physical properties are shown in Table 1.

[Table 1]

Examples 2 to 4 and Comparative Examples 2 to 4 were prepared in the same manner, and the effects of the present invention were confirmed.

[Table 2]

[table 3]

[Table 4]

As described above, the liquid crystal composition of the present invention has a negative dielectric anisotropy (Δε), a higher T _NI , a larger Δn, a smaller γ ₁ , a larger K ₃₃ , and a smaller γ ₁ /K ₃₃ .

It can be seen that the values of Δn and Δε are almost the same as those of the compositions of Examples 1 and 2, but the liquid crystal compositions that do not contain the compound represented by the general formula (i), that is, Comparative Examples 1 and 2, have large γ1 and deteriorate. Therefore, it was confirmed that when VA type and FFS type liquid crystal display elements were produced using the compositions of these Examples 1 and 2, the response time was short and the VHR was high. At this time, it was also confirmed that there was no display defect. On the other hand, about the composition of the comparative example, VA type and FFS type liquid crystal display elements were produced similarly, and the response time was measured, and the response time was worse than the composition of an Example.

Furthermore, from the results of the compositions of Examples 3 and 4 in which T _NI was high and Δε was large, it was found that even if T _NI and Δε were improved, the increase in γ1 was suppressed.

In Example 3, the value of Δε was reduced, and it became unsuitable for low-voltage driving. In addition, in the comparison between Example 4 and Comparative Example 4, it was found that in the liquid crystal composition of the present invention, γ1 was improved by about 8%.

The following liquid crystal composition containing a polymerizable compound was prepared, and a PSA type liquid crystal display element was produced. (RM-2) represented by a polymerizable compound (wherein, in the formula, R ^M1 and R ^M2 represent a methyl group) ".

Furthermore, in the production of the PSA type liquid crystal display element, ultraviolet rays having peaks at 313 nm and 365 nm were irradiated. The measurement conditions of the response speed were as follows: Von was 5 V, Voff was 0.5 V, the measurement temperature was 20° C., and DMS703 from AUTRONIC-MELCHERS was used as the measurement device.

It was confirmed that _TNI was high, Δn was large, γ ₁ was small, K ₃₃ was large, γ ₁ was small, and high-speed response was possible.

As described above, it was found that the present invention has excellent effects.

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Claims (9)

A liquid crystal composition containing one or more compounds represented by the general formula (i),

(in the formula, X ⁱ¹ and X ⁱ² each independently represent a hydrogen atom, a fluorine atom, a chlorine atom, a cyano group, a trifluoromethyl group, a trifluoromethoxy group, and Y ⁱ¹ and Y ⁱ² each independently represent -O-, - CO-, -CX ⁱ³ X ⁱ⁴ -, but one or more of Y ⁱ¹ and Y ⁱ² represents -O-, and X ⁱ³ represents a hydrogen atom, a chlorine atom, a cyano group, a trifluoromethyl group, or a trifluoromethoxy group, X ⁱ⁴ represents a hydrogen atom, a fluorine atom, a chlorine atom, a cyano group, a trifluoromethyl group, or a trifluoromethoxy group, and L ⁱ¹ , L ⁱ² , L ⁱ³ , L ⁱ⁴ and L ⁱ⁵ each independently represent a hydrogen atom and a bromine atom , an iodine atom, a hydroxyl group, an alkyl group having 1 to 15 carbon atoms, an alkenyl group having 2 to 15 carbon atoms, or a group represented by the general formula (L ⁱ -1),

(wherein, R ⁱ¹ represents a hydrogen atom, an alkyl group having 1 to 15 carbon atoms, an alkoxy group having 1 to 15 carbon atoms, an alkenyl group having 2 to 15 carbon atoms, or an alkenyl group having 2 to 15 carbon atoms group, A ⁱ¹ represents a group selected from (a) 1,4-cyclohexylene group (one -CH ₂ - or two or more non-adjacent -CH ₂ - present in this group may also be -O- or - S-substituted) (b) 1,4-phenylene (one -CH= present in this group or two or more non-adjacent -CH= can also be substituted by -N=, present in this group One hydrogen atom can also be replaced by a fluorine atom) (c) 1,4-cyclohexenyl, naphthalene-2,6-diyl, 1,2,3,4-tetrahydronaphthalene-2,6- Diyl, decahydronaphthalene-2,6-diyl (the hydrogen atoms present in these radicals can also be replaced by fluorine atoms, and, in naphthalene-2,6-diyl or 1,2,3,4 -One of -CH= in tetrahydronaphthalene-2,6-diyl group or the group of two or more -CH= that are not adjacent to each other can also be substituted by -N=), Z ⁱ¹ represents -CH ₂ O-, -OCH ₂ -, -CF ₂ O-, -OCF ₂ -, -COO-, -OCO-, -CH ₂ CH ₂ -, -CF ₂ CF ₂ -, -CH=CH-, -CF =CF-, -C≡C- or single bond, n ⁱ¹ represents 1 or 2, when n ⁱ¹ represents 2, and when there are multiple A ⁱ¹ and Z ⁱ¹ , they can be the same or different); W ⁱ¹ represents the base represented by the general formula (W ⁱ¹ -1), (W ⁱ¹ -2) or (W ⁱ¹ -3),

(In the formula, ‧ represents a bond point with L ⁱ² or Y ⁱ² , * represents a bond point with a carbon atom adjacent to the carbon atom bonded with L ⁱ⁵ , and L ⁱ⁶ , L ⁱ⁷ and L ⁱ⁸ each independently represent Same meaning as L ⁱ¹ ), W ⁱ² represents a single bond or -CL ⁱ⁹ L ⁱ¹⁰ -, (L ⁱ⁹ and L ⁱ¹⁰ independently represent the same meaning as L ⁱ¹ ), L ⁱ¹ , L ⁱ² , L ⁱ³ , L ⁱ⁴ , L One -CH ₂ - existing in ⁱ⁵ , L ⁱ⁶ , L ⁱ⁷ , L ⁱ⁸ , L ⁱ⁹ and L ⁱ¹⁰ or two or more non-adjacent -CH ₂ - may also be represented by -C≡C-, -O- , -COO-, -OCO- or -CO- substituted, and the hydrogen atom present in the alkyl or alkenyl group may also be substituted by a fluorine atom). The liquid crystal composition according to claim 1, which contains one or more kinds selected from the group consisting of general formula (N-01), general formula (N-02), general formula (N-03), general formula (N- 04), and the compounds in the compound group represented by the general formula (N-05),

(in the formula, R ²¹ and R ²² each independently represent an alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, an alkenyl group having 2 to 8 carbon atoms, or an alkyl group having 2 to 8 carbon atoms. The alkenyloxy group of 8, one of the groups or not adjacent two or more -CH ₂ - may be independently represented by -CH=CH-, -C≡C-, -O-, -CO-, -COO- or -OCO- substituted, Z ¹ independently represents a single bond, -CH ₂ CH ₂ -, -OCH ₂ -, -CH ₂ O-, -COO-, -OCO-, -OCF ₂ -, - CF ₂ O-, -CH=CH-, -CF=CF- or -C≡C-, m respectively independently represents 1 or 2). The liquid crystal composition according to claim 1 or 2, which contains one or more compounds selected from the group of compounds represented by the general formula (NU-01) to the general formula (NU-06),

(wherein, R ^NU11 , R ^NU12 , R ^NU21 , R ^NU22 , R ^NU31 , R ^NU32 , R ^NU41 , R ^NU42 , R ^NU51 , R ^NU52 , R ^NU61 and R ^NU62 independently represent one of the carbon atoms of 1 to 8 An alkyl group, an alkoxy group having 1 to 8 carbon atoms, an alkenyl group having 2 to 8 carbon atoms, or an alkenyloxy group having 2 to 8 carbon atoms, one of these groups or two or more non-adjacent ones— CH ₂ - can also be independently substituted by -CH=CH-, -C≡C-, -O-, -CO-, -COO- or -OCO-). The liquid crystal composition according to claim 3, wherein the compound represented by the general formula (NU-01) has an alkenyl group, and the total content thereof is 0% by mass to 50% by mass. The liquid crystal composition according to claim 3, wherein the compound represented by the general formula (i), the compound selected from the group of compounds represented by the general formula (N-01) to the general formula (N-05), and The total content of the compounds selected from the compound group represented by the general formula (NU-01) to the general formula (NU-06) is 95% by mass to 100% by mass. The liquid crystal composition according to claim 1 or 2, which contains one or more polymerizable compounds represented by the general formula (RM),

(wherein, R ¹⁰¹ , R ¹⁰² , R ¹⁰³ , R ¹⁰⁴ , R ¹⁰⁵ , R ¹⁰⁶ , R ¹⁰⁷ and R ¹⁰⁸ each independently represent the ^number of carbon atoms ¹ to Any of the alkyl group of 18, the alkoxy group of 1 to 18 carbon atoms which may be substituted by a fluorine atom, a fluorine atom or a hydrogen atom, P ¹¹ , P ¹² and P ¹³ are each independently represented by the formula (Re-1 ) to the polymerizable group represented by the formula (Re-9),

(in the formula, R ¹¹ , R ¹² , R ¹³ , R ¹⁴ and R ¹⁵ each independently represent any one of an alkyl group having 1 to 5 carbon atoms, a fluorine atom or a hydrogen atom, m ^r5 , m ^r7 , n ^r5 and n ^r7 independently represent 0, 1, or 2, and when m ^r5 , m ^r7 , n ^r5 and/or n ^r7 represent 0, represent a single bond), S ¹¹ , S ¹² and S ¹³ independently Represents a single bond or an alkylene group with 1 to 15 carbon atoms, one -CH ₂ - or two or more non-adjacent -CH ₂ - in the alkylene group may also be -O-, -OCO- or - COO-substitution, when there are multiple P ¹³ and S ¹³ , may be the same or different respectively). A liquid crystal display element using the liquid crystal composition according to any one of claims 1 to 6. A liquid crystal display element for active matrix driving, which uses the liquid crystal composition according to any one of claims 1 to 6. A VA type, IPS type, FFS type, PSA type or PSVA type liquid crystal display element using the liquid crystal composition according to any one of claims 1 to 6.