KR20200098501A - Liquid crystal composition and liquid crystal display device - Google Patents

Abstract

The problem to be solved by the present invention is to provide a liquid crystal composition having a negative dielectric anisotropy (Δε), a high T _NI , a large Δn, and a small γ ₁ , and using this, the response speed is fast, and has a high VHR. , To provide a VA-type, FFS-type, or IPS-type liquid crystal display device with no or very few display defects, and also to provide a PSA device using a polymerizable compound. 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 device

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

BACKGROUND Liquid crystal display elements have been used in various household electrical equipment, measuring equipment, automobile panels, word processors, electronic notebooks, printers, computers, televisions, starting with watches and calculators. Typical liquid crystal display systems are TN (twisted nematic) type, STN (super twisted nematic) type, DS (dynamic light scattering) type, GH (guest/host) type, IPS (in-plane) Switching) type, OCB (optical compensation birefringence) type, ECB (voltage controlled birefringence) type, VA (vertical alignment) type, CSH (color super homeotropic) type, or FLC (ferroelectric liquid crystal). In addition, static driving, multiplex driving, a simple matrix method, and an active matrix (AM) method driven by a TFT (thin film transistor) or TFD (thin film diode) may be mentioned as a driving method. In these display systems, the IPS type, the ECB type, the VA type, the CSH type, or the like has a characteristic of using a liquid crystal composition in which Δε (dielectric anisotropy) exhibits a negative value. Among these, the VA type display system by AM driving is particularly used for display elements requiring a wide viewing angle with high-speed response, such as a television or a monitor.

As a liquid crystal composition in which Δε is negative, a liquid crystal composition using liquid crystal compounds (A) to (E) (refer to Patent Document 1) and the like having a 2,3-difluorophenylene skeleton as described below is disclosed.

However, neither liquid crystal composition has been made to achieve both the response speed and reliability required for a particularly large-sized liquid crystal display element.

Further, in Patent Document 2, it is disclosed to improve the response speed of a homeotropic liquid crystal cell by using a liquid crystal material having a large index (FoM) represented by the following equation, but it cannot be said that it can be sufficiently satisfied.

From the above, in a liquid crystal composition requiring high-speed response and high reliability, such as a liquid crystal television, the rotational viscosity (γ ₁ ) is small while appropriately adjusting the nematic phase-isotropic liquid phase transition temperature (T _NI ) and refractive index anisotropy (Δn). , The elastic constant (K ₃₃ ) is large, γ ₁ /K ₃₃ is small, and the voltage retention VHR is high.

Japanese Patent Publication No. 2016-216747 Japanese Patent Publication No. 2006-301643

The problem to be solved by the present invention is to provide a liquid crystal composition having a negative dielectric anisotropy (Δε), appropriately adjusting T _NI and Δn, and having a small γ ₁ , and using this, has a fast response speed and a high VHR. It is to provide a VA type, FFS type, or IPS type liquid crystal display device with no or very few display defects.

As a result of intensive examination by the present inventors, it was found that the above-described problem could be solved by a liquid crystal composition containing a compound having a specific chemical structure, and the present invention was completed.

Moreover, by using a polymerizable compound together with the said liquid crystal composition, it discovered that the said subject can be solved, and came to complete the present invention.

The liquid crystal composition of the present invention provides a liquid crystal composition having a negative dielectric anisotropy (Δε), a high T _NI , a large Δn, and a small γ ₁ , and uses this to provide a liquid crystal composition having a fast response speed and a high VHR. A VA type, FFS type, or IPS type liquid crystal display device with no or very few defects can be provided.

The liquid crystal composition of the present invention is 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, and a trifluoromethoxy group,

Y ⁱ¹ and Y ⁱ² each independently represent -O-, -CF ₂ -, -CO-, -CX ⁱ³ X ⁱ⁴ -, wherein at least one of Y ⁱ¹ and Y ⁱ² represents -O-, and X ⁱ³ , X ⁱ⁴ each independently represents the same meaning as X ⁱ¹ ,

L ⁱ¹ , L ⁱ² , L ⁱ³ , L ⁱ⁴ and L ⁱ⁵ are each independently 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 a general Equation (L ⁱ -1)

(In the formula, R ⁱ¹ is 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 alkenyloxy group having 2 to 15 carbon atoms. Indicate,

A ⁱ¹ is

(a) 1,4-cyclohexylene group (one -CH ₂ -present in this group or two or more non-adjacent -CH ₂ -s may be substituted with -O- or -S-.)

(b) 1,4-phenylene group (one -CH= present in this group or two or more non-adjacent -CH=s may be substituted with -N=, and one hydrogen atom present in this group is It may be substituted with a fluorine atom.)

(c) 1,4-cyclohexenylene group, naphthalene-2,6-diyl group, 1,2,3,4-tetrahydronaphthalene-2,6-diyl group, decahydronaphthalene-2,6-diyl group (The hydrogen atom present in these groups may be substituted with a fluorine atom, and one-present in the naphthalene-2,6-diyl group or the 1,2,3,4-tetrahydronaphthalene-2,6-diyl group CH= or two or more non-adjacent -CH= may be substituted with -N=.)

Represents a group selected from the group consisting of,

Z ⁱ¹ is -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 a single bond,

n ⁱ¹ represents 1 or 2, when n ⁱ¹ represents 2 and a plurality of A ⁱ¹ and Z ⁱ¹ exist, they may be the same or different.)

Represents a group represented by,

W ⁱ¹ is the general formula (W ⁱ¹ -1), (W ⁱ¹ -2) or (W ⁱ¹ -3)

(In the formula, * represents the bonding point to L ⁱ² or Y ⁱ² , * represents the bonding point to the carbon atom adjacent to the carbon atom to which L ⁱ⁵ is bonded, and L ⁱ⁶ , L ⁱ⁷ and L ⁱ⁸ are each independently , It represents the same meaning as L ⁱ¹ .),

W ⁱ² is a single bond or -CL ⁱ⁹ L ⁱ¹⁰ -

(L ⁱ⁹ and L ⁱ¹⁰ each independently represent the same meaning as L ⁱ¹ .)

Represents,

One of L ⁱ¹ , L ⁱ² , L ⁱ³ , L ⁱ⁴ , L ⁱ⁵ , L ⁱ⁶ , L ⁱ⁷ , L ⁱ⁸ , L ⁱ⁹ and L ⁱ¹⁰ -CH ₂ -or two or more non-adjacent -CH _2- May be substituted by -C≡C-, -O-, -COO-, -OCO-, or -CO-, and a hydrogen atom present in the alkyl group or alkenyl group may be substituted with a fluorine atom.)

The dielectric anisotropy (Δε) represented by is a liquid crystal composition containing a negative compound and a polymerizable compound, and a liquid crystal display device using this.

As the lower limit, the content of the compound of the general formula (i) in the liquid crystal composition of the present invention is preferably 0.1% by mass, preferably 0.2% by mass, preferably 0.3% by mass, and preferably 0.5% by mass. And, it is preferably 1% by mass, preferably 2% by mass, preferably 3% by mass, preferably 4% by mass, more preferably 20% by mass as an upper limit, and 15% by mass. It is more preferable, it is more preferable that it is 13 mass %, it is more preferable that it is 10 mass %, As a range of content, it is preferable that it is 0.1-25 mass %, It is more preferable that it is 0.1-20 mass %, and 0.1 It is more preferable that it is -15 mass %, and it is especially preferable that it is 1-15 mass %. Hereinafter, the mass% is described as %.

When T _NI is important, the content is preferably reduced, and γ ₁ /K ₃₃ is improved, and when the response speed is important, the content is preferably increased.

In the general formula (i), at least one of X ⁱ¹ and X ⁱ² is preferably a fluorine atom, and both are preferably fluorine atoms.

As for Y ⁱ¹ and Y ⁱ² , a compound in which one is -O- and the other is -CH ₂ -and a compound in which both are -O- are preferable, and a compound in which both are -O- is preferable.

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, and in order to decrease γ ₁ , the number of carbon atoms is 1 to 8 It is preferably an alkyl group or an alkenyl group having 2 to 8 carbon atoms, and 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 linear. In order to increase |Δε|, it is preferable that it is a C1-C8 alkoxy group or a C2-C8 alkenyloxy group, and it is a C1-C5 alkoxy group or a C2-C5 alkoxy group. It is particularly preferred that it is an alkenyloxy group. In order to increase the miscibility with other liquid crystal components, it is preferable that L ⁱ¹ and L ⁱ² are different, the alkoxy group or alkenyloxy group is preferably any one of L ⁱ¹ and L ⁱ² , and the alkoxy group is L ⁱ¹ . desirable. The hydrogen atom present in L ⁱ¹ and L ⁱ² may be substituted with a fluorine atom, but it is preferably not substituted with a fluorine atom.

In addition, L ⁱ¹ and L ⁱ² are

It is preferable to represent.

In order to lower γ ₁ , R ⁱ¹ is preferably an alkyl group having 1 to 8 carbon atoms or an alkenyl group having 2 to 8 carbon atoms, and an alkyl group having 1 to 5 carbon atoms or an egg having 2 to 5 carbon atoms It is particularly preferred that it is a kenyl group. Moreover, it is preferable that it is linear. In order to increase |Δε|, it is preferable that it is a C1-C8 alkoxy group or a C2-C8 alkenyloxy group, and it is a C1-C5 alkoxy group or a C2-C5 alkoxy group. It is particularly preferred that it is an alkenyloxy group. When a plurality of R ⁱ¹ is present, in order to increase the miscibility with other liquid crystal components, R ⁱ¹ is preferably different from each other, an alkoxy group or alkenyloxy group is preferably any one of R ⁱ¹ having a plurality of R ⁱ¹ , and alkoxy It is particularly preferred that the group or alkenyloxy group is R ⁱ¹ in L ⁱ¹ . Although the hydrogen atom present in R ⁱ¹ may be substituted with a fluorine atom, it is preferably not substituted with a fluorine atom.

A ⁱ¹ is

It is preferable to represent a group selected from Specifically, A ¹ is a trans-1,4-cyclohexylene group, unsubstituted 1,4-phenylene group, 2-fluoro-1,4-phenylene group, or 3-fluoro in order to lower γ ₁ It is preferable that it is a -1,4-phenylene group, and it is especially preferable that it is a trans-1,4-cyclohexylene group. In order to improve the miscibility with other liquid crystal components, it is preferably a trans-1,4-cyclohexylene group, a 2-fluoro-1,4-phenylene group, or a 3-fluoro-1,4-phenylene group. . In order to raise T _ni , an unsubstituted 1,4-phenylene group, an unsubstituted 1,4-cyclohexylene group, a 1,4-cyclohexenylene group, or an unsubstituted naphthalene-2,6-diyl group It is desirable. In order to exhibit a negatively large Δε, it is preferably a 2-fluoro-1,4-phenylene group, a 3-fluoro-1,4-phenylene group, or a 2,3-difluoro-1,4-phenylene group. Do. In order to achieve compatible compatibility with other liquid crystal components while exhibiting negatively large Δε, the total number of fluorine atoms present in A ⁱ¹ is preferably 1 to 4, and particularly preferably 1 to 3.

In order to decrease γ ₁ , Z ⁱ¹ is preferably a single bond, -CH ₂ CH ₂ -, -CH ₂ O-, or -OCH ₂ -, and more preferably a single bond or -CH ₂ CH ₂ -. In order to raise T _ni , it is preferably a single bond, -COO-, -OCO-, -CH=CH-, or -C≡C-, and a single bond, -CH=CH- or -C≡C- More preferable. In order to improve the miscibility with other liquid crystal components, it is preferably a single bond, -CH ₂ CH ₂ -, -CH ₂ O- or -OCH ₂ -. In order to improve the long-term reliability in the case of a liquid crystal display element, it is preferably a single bond.

When n ⁱ¹ represents 2, it is preferable that any one or more of a plurality of Z ^i1s represent a single bond. It is preferable that n ⁱ¹ is ₁ when γ ₁ is important. When T _ni is important, it is preferably 2.

W ⁱ¹ is preferably a general formula (W ⁱ¹ -1) or (W ⁱ¹ -3).

W ⁱ² is preferably a single bond.

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, an alkenyloxy group having 2 to 15 carbon atoms, and In order to decrease γ ₁ , it is preferably an alkyl group having 1 to 8 carbon atoms or an alkenyl group having 2 to 8 carbon atoms, and an alkyl group having 1 to 5 carbon atoms or an alkenyl group having 2 to 5 carbon atoms It is particularly preferred. Moreover, it is preferable that it is linear.

It is preferable that at least one of L ⁱ¹ , L ⁱ² and L ⁱ³ is a hydrogen atom, and it is preferable that L ⁱ¹ or L ⁱ³ is a hydrogen atom. It is preferable that 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, L ⁱ³ is an alkyl group having 1 to 8 carbon atoms, and L ⁱ¹ is a hydrogen atom, It is preferable that 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.

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, and preferably a hydrogen atom.

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, and a hydrogen atom is preferred.

L ⁱ⁸ is preferably 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, an alkenyloxy group having 2 to 15 carbon atoms, and , A hydrogen atom is preferred.

It is preferable that L ⁱ⁹ and L ⁱ¹⁰ represent a hydrogen atom.

In addition, in the compound represented by general formula (i), it does not become a structure in which heteroatoms are directly bonded to each other.

Among the compounds represented by general formula (i), each compound represented by the following general formulas (i-1) to (i-48) is preferable. Among them, particularly preferred compounds are general formulas (i-1), (i-2), (i-3), (i-4), (i-5), (i-6), and (i-7) , (i-8), (i-9), (i-10), (i-11) and (i-12) are compounds represented by general formulas (i-1), (i-2), It is a compound represented by (i-3) and (i-4), is a compound represented by general formulas (i-1) and (i-3), and is a compound represented by general formula (i-1).

(In the formula, R ⁱ¹ and R ⁱ² represent the same meaning as R ⁱ¹ in General Formula (i).)

(In the formula, R ⁱ¹ and R ⁱ² represent the same meaning as R ⁱ¹ in General Formula (i).)

(In the formula, R ⁱ¹ and R ⁱ² represent the same meaning as R ⁱ¹ in General Formula (i).)

(In the formula, R ⁱ¹ and R ⁱ² represent the same meaning as R ⁱ¹ in General Formula (i).)

In addition to the compound represented by the general formula (i), the liquid crystal composition of the present invention has general formulas (N-01), (N-02), (N-03), (N-04) and (N-05) It is preferable to contain one type or two or more types of compounds selected from the compound group represented by. These compounds correspond to compounds with genetically negative anisotropy. In these compounds, the sign of Δε is negative, and the absolute value is greater than 2. In addition, Δε of a compound is a value extrapolated from a measured value of dielectric anisotropy of a composition in which the compound is added to a substantially dielectrically neutral composition at 25°C.

In the formula, R ²¹ and R ²² are each independently 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, and Represents an alkenyloxy group, and one or two or more non-adjacent -CH ₂ -in the group are each independently -CH=CH-, -C≡C-, -O-, -CO-, -COO- or May be substituted by -OCO-, and Z ¹ is each independently 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, and still more preferably an alkyl group having 1 to 4 carbon atoms. However, 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, and A number of 1 to 4 alkoxy groups are more preferable.

R ²¹ and R ²² may be an alkenyl group, and are preferably selected from groups represented by any one of formulas (R1) to (R5) (black spots in each formula represent a carbon atom in a ring structure), and Although the formula (R1) or (R2) is preferable, the content of the compound in which R ²¹ and R ²² are alkenyl groups is preferably as small as possible, and it is often preferable not to contain it.

Z ¹ is each independently 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-, a single bond, -CH ₂ CH ₂ -, -OCH ₂ -, -CH ₂ O- is preferred, and a single bond or -CH ₂ O- Is more preferable.

When m is 1, it is preferable that Z ¹ is a single bond.

When m is 2, Z ¹ is preferably -CH ₂ CH ₂ -, -CH ₂ O-.

The fluorine atom of the compound represented by the general formulas (N-01), (N-02), (N-03), (N-04) and (N-05) may be substituted with a chlorine atom which is the same halogen group. However, the content of the compound substituted with a chlorine atom is preferably as small as possible and preferably not contained.

The hydrogen atom present on the ring of the compound represented by general formulas (N-01), (N-02), (N-03), (N-04) and (N-05) is also a fluorine atom or chlorine It may be substituted with an atom. However, the content of the compound substituted with a chlorine atom is preferably as small as possible and preferably not contained.

Compounds represented by general formulas (N-01), (N-02), (N-03), (N-04) and (N-05) are compounds whose absolute value is greater than 3 when Δε is negative. It is desirable. Specifically, it is preferable that R ²² represents an alkoxy group having 1 to 8 carbon atoms or an alkenyloxy group having 2 to 8 carbon atoms.

As a compound represented by a general formula (N-01), a general formula (N-01-1), a general formula (N-01-2), a general formula (N-01-3), and a 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.) One or two types of compounds selected from the compound group represented by It is preferable to contain more.

It is preferable that the liquid crystal composition of this invention 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, or in other words, when it is important to obtain a liquid crystal display device without display defects, a compound represented by the general formula (N-01-3) It is preferable not to include.

As a compound represented by general formula (N-02), general formula (N-02-1), general formula (N-02-2), and general formula (N-02-3)

(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.) One or two types of compounds selected from the compound group represented by It is preferable to contain more.

It is preferable that the liquid crystal composition of this invention contains a compound represented by general formula (i) and a compound represented by general formula (N-02-1).

It is preferable that the liquid crystal composition of this invention contains a compound represented by general formula (i) and a compound represented by general formula (N-02-3).

The liquid crystal composition of the present invention includes 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 general formula (N- It is particularly preferable to contain the compound represented by 02-1) at the same time.

The liquid crystal composition of the present invention includes 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 general formula (N- It is particularly preferable to contain the compound represented by 02-3) at the same time.

As a compound represented by the general formula (N-03), 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.) It is preferable to contain one type or two or more types of compounds represented by.

In the liquid crystal composition of the present invention, it is preferable to combine 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 includes 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 general formula (N- It is particularly preferable to contain the compound represented by 03-1) at the same time.

As a compound represented by the general formula (N-04), 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.) It is preferable to contain one type or two or more types of compounds represented by.

The liquid crystal composition of the present invention includes 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 general formula (N- It is particularly preferable to contain the compound represented by 04-1) at the same time.

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

With respect to the total amount of the liquid crystal composition of the present invention, the lower limit of the preferred content of the compound represented by the general formula (N-01) is 0%, 1%, 5%, 10%, 20%, 30% Is, 40%, 50%, 55%, 60%, 65%, 70%, 75%, 80%. The upper limit of the preferred 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 lower limit of the preferred content of the compound represented by the general formula (N-02) is 0%, 1%, 5%, 10%, 20%, 30% Is, 40%, 50%, 55%, 60%, 65%, 70%, 75%, 80%. The upper limit of the preferred 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 lower limit of the preferred content of the compound represented by the general formula (N-03) is 0%, 1%, 5%, 10%, 20%, and 30%. Is, 40%, 50%, 55%, 60%, 65%, 70%, 75%, 80%. The upper limit of the preferred 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 lower limit of the preferred content of the compound represented by the general formula (N-04) is 0%, 1%, 5%, 10%, 20%, and 30%. Is, 40%, 50%, 55%, 60%, 65%, 70%, 75%, 80%. The upper limit of the preferred 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 lower limit of the preferred content of the compound represented by the formula (N-05) is 0%, 2%, 5%, 8%, 10%, 13%. , 15%, 17%, and 20%. The upper limit of the preferable content is 30%, 28%, 25%, 23%, 20%, 18%, 15%, and 13%.

The liquid crystal composition of the present invention contains 0.1% to 15% of the compound represented by the general formula (i), contains 1% to 20% of the compound represented by the general formula (N-01-1), and contains the general formula ( It is particularly preferable to contain 1% to 30% of the compound represented by N-01-4), and to contain 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 type or two or more types of compounds represented by the general formula (N-06).

(In the formula, R ²¹ and R ²² represent the same meaning as described above.)

The compound represented by the general formula (N-06) is effective when it is desired to adjust various physical properties, but can be used to obtain large refractive index anisotropy (Δn), high T _NI , and large Δε.

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

The liquid crystal composition of the present invention is a general formula (NU-01) to a 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 are each independently, the number of carbon atoms from 1 to 8 alkyl group, C1-C8 alkoxy group, C2-C8 alkenyl group, or C2-C8 alkenyloxy group, and one or two or more non-adjacent -CH in the said group ₂ -may each independently be substituted by -CH=CH-, -C≡C-, -O-, -CO-, -COO-, or -OCO-.) It contains 1 type or 2 or more types of compounds.

More specifically, 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 are an alkyl group having 1 to 5 carbon atoms or It is preferably 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 a compound having such an alkenyl group Silver is preferably 10% or more, preferably 20% or more, preferably 25% or more, preferably 30% or more, preferably 40% or more, and 45% or more with respect to the total amount of the liquid crystal composition of the present invention. This is preferable, and 50% or more is preferable. When high VHR is important, the compound having an alkenyl group is preferably 40% or less, preferably 35% or less, and 30% or less.

In order to achieve both high speed and high reliability, it is preferable to use only the general formula (NU-01) as a compound having an alkenyl group, in which case R ^NU11 is an alkyl group having 2 to 4 carbon atoms, and R ^NU12 is a carbon atom number. It is particularly preferable that it is a 2-3 alkenyl group.

In order to achieve both high speed and high reliability, it is preferable to use general formula (NU-01) and general formula (NU-05) as a compound having an alkenyl group, and in this case, R ^NU11 has 2 to 4 carbon atoms. alkyl group, R ^NU12 is due to the alkenyl carbon atoms and particularly preferably 2 to 3, R ^NU51 is an alkenyl group, R ^NU52 carbon atoms 2-3 is preferably an alkyl group having carbon atom number of 2-3.

In order to achieve 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 compounds having an alkenyl group, in which case R ^NU11 is an alkyl group of carbon atoms 2 to 4, R ^NU12 is due particularly preferred alkenyl carbon atoms, 2 to 3, and, R ^NU51 and R ^NU41 is an alkenyl group, R ^NU52 and R ^NU42 carbon atoms 2-3 is It is preferably an alkyl group having 2 to 3 carbon atoms.

It is preferable that the liquid crystal composition of the present invention contains a compound represented by the general formula (NU-01) and the general formula (NU-02).

It is preferable that the liquid crystal composition of the present invention contains a compound represented by the general formula (NU-01) and the general formula (NU-03).

It is preferable that the liquid crystal composition of the present invention contains a compound represented by the general formula (NU-04) and the general formula (NU-05).

It is preferable that the liquid crystal composition of this invention contains a compound represented by general formula (NU-05) and general formula (NU-06).

It is preferable that the liquid crystal composition of this invention contains a compound represented by general formula (NU-01) and general formula (NU-05).

It is preferable that the liquid crystal composition of the present invention contains a compound represented by the general formula (NU-01) and the general formula (NU-06).

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

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

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, and 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, and 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 polymerizable compounds.

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

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

(In the formula, R ¹¹ , R ¹² , R ¹³ , R ¹⁴ and R ¹⁵ each independently represent either an alkyl group having 1 to 5 carbon atoms, a fluorine atom or a hydrogen atom, and m ^r5 , m ^r7 , n ^r5 and n ^r7 each independently represent 0, 1, or 2, but when m ^r5 , m ^r7 , n ^r5 and/or n ^r7 represent 0, they represent a single bond.)

Represents a polymerizable group represented by, S ¹¹ , S ¹² and S ¹³ each independently represent a single bond or an alkylene group having 1 to 15 carbon atoms, and one of -CH ₂ -in the alkylene group or adjacent Two or more -CH ₂ -which are not present may be substituted with -O-, -OCO-, or -COO-, and when plural P ¹³ and S ¹³ are present, they may be the same or different, respectively.)

A liquid crystal composition containing a polymerizable compound represented by General Formula (RM) is suitable when producing a PSA-type or PSVA-type liquid crystal display device. It is also suitable when manufacturing an NPS type liquid crystal display element. Moreover, it is suitable also when creating 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 a moderately fast polymerization rate, a target pretilt angle can be provided in a short ultraviolet irradiation time. . In addition, it is possible to reduce the residual amount of the polymerizable compound after polymerization. Thereby, the production efficiency of manufacturing a PSA-type or PSVA-type liquid crystal display device can be improved. In addition, there is an effect that display failure (for example, a problem such as seizure) due to a change in the pretilt angle does not occur or is extremely small. In addition, the display defect in this specification refers to a display failure due to a change in the pretilt angle over time, a display failure due to the residual amount of an unreacted polymerizable compound, and a display failure due to a decrease in the voltage retention rate. have.

In the general formula (RM), R ¹⁰¹ , R ¹⁰² , R ¹⁰³ , R ¹⁰⁴ , R ¹⁰⁵ , R ¹⁰⁶ , R ¹⁰⁷ and R ¹⁰⁸ are each independently P ¹³ -S ¹³ -, which may be substituted with a fluorine atom. Represents any one of an alkyl group having 1 to 18 carbon atoms, an alkoxy group having 1 to 18 carbon atoms that may be substituted with 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 to 16 , More preferably 1 to 10, still more preferably 1 to 8, still more preferably 1 to 6, and still more preferably 1 to 3. Further, the alkyl group and the alkoxy group may be linear or branched, but linear is particularly preferable.

In the general formula (RM), R ¹⁰¹ , R ¹⁰² , R ¹⁰³ , R ¹⁰⁴ , R ¹⁰⁵ , R ¹⁰⁶ , R ¹⁰⁷ and R ¹⁰⁸ are P ¹³ -S ¹³ -, the number of carbon atoms which may be substituted with a fluorine atom 1 It is preferable to represent any one of an alkoxy group of to 3, a fluorine atom, or a hydrogen atom, more preferably P ¹³ -S ¹³ -, an alkoxy group having 1 to 3 carbon atoms, a fluorine atom, or a hydrogen atom. Do. This alkoxy group preferably has 1 or more and 3 or less carbon atoms, more preferably 1 or more and 2 or less, and particularly preferably 1.

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

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

It is preferable that at least one of P ¹¹ and P ¹² is a formula (Re-1), more preferably an acrylic group or a methacrylic group, more preferably a methacrylic group, and that P ¹¹ and P ¹² are a methacrylic group. It is particularly preferred.

In the general formula (RM), S ¹¹ , S ¹² and S ¹³ are each independently preferably 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 UV irradiation is sufficiently small, and display defects due to changes in the pretilt angle are less likely to occur, and a PSA type or PSVA type liquid crystal display device The display defect of does not occur, or becomes extremely small. When S ¹¹ , S ¹² and S ¹³ have 1 to 3 carbon atoms, they are suitable for an NPS-type liquid crystal display device.

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% by mass, preferably 0.02% by mass, preferably 0.03% by mass, and 0.04% by mass. Preferably, 0.05 mass% is preferred, 0.06 mass% is preferred, 0.07 mass% is preferred, 0.08 mass% is preferred, 0.09 mass% is preferred, 0.1 mass% is preferred, 0.12 mass% is preferred. And, 0.15 mass% is preferable, 0.17 mass% is preferable, 0.2 mass% is preferable, 0.22 mass% is preferable, 0.25 mass% is preferable, 0.27 mass% is preferable, 0.3 mass% is preferable. , 0.32 mass% is preferred, 0.35 mass% is preferred, 0.37 mass% is preferred, 0.4 mass% is preferred, 0.42 mass% is preferred, 0.45 mass% is preferred, 0.5 mass% is preferred, 0.55 mass% is preferable. 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% by mass, preferably 4.5% by mass, preferably 4% by mass, and 3.5% by mass. Preferably, 3% by mass is preferable, 2.5% by mass is preferable, 2% by mass is preferable, 1.5% by mass is preferable, 1% by mass is preferable, 0.95% by mass is preferable, and 0.9% by mass is preferable And, 0.85 mass% is preferable, 0.8 mass% is preferable, 0.75 mass% is preferable, 0.7 mass% is preferable, 0.65 mass% is preferable, 0.6 mass% is preferable, and 0.55 mass% is preferable. , 0.5% by mass is preferable, 0.45% by mass is preferable, and 0.4% by mass is preferable.

More specifically, in order to obtain a sufficient pretilt angle or a low residual amount of the polymerizable compound or a high voltage retention (VHR), the content is preferably 0.2 to 0.6% by mass, but when the suppression of precipitation at low temperatures is important, The content is preferably 0.01 to 0.4% by mass. In the case of obtaining a particularly fast response speed, it is also preferable to increase the content to 2% by mass.

Moreover, when it contains a plurality of polymerizable compounds represented by 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 particularly preferable to adjust the polymerizable compound represented by the general formula (RM) in the range of 0.1 to 0.6% by mass.

As the polymerizable compound represented by the general formula (RM) according to the present invention, specifically, compounds represented by the general formulas (RM-1) to (RM-10) are preferred, and the PSA type liquid crystal display device using these is , The residual amount of the polymerizable compound is small, has a sufficient pretilt angle, and there is no problem of poor orientation or display due to a change in pretilt, or very little.

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

The liquid crystal composition of the present invention may contain one or two or more compounds having a terphenyl structure or a tetraphenyl structure, and a dielectric anisotropy Δε greater than +2, that is, a compound having a positive dielectric anisotropy. In addition, Δε of a compound is a value extrapolated from a measured value of dielectric anisotropy of a composition in which the compound is added to a substantially dielectrically neutral composition at 25°C. The compounds are used in combination according to desired properties, such as, for example, solubility at low temperature, transition temperature, electrical reliability, refractive index anisotropy, and the like. In particular, the reactivity of the polymerizable compound in the liquid crystal composition containing the polymerizable compound Can accelerate.

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

In addition to the above-described compounds, the liquid crystal composition of the present invention may contain an ordinary nematic liquid crystal, smecting liquid crystal, cholesteric liquid crystal, antioxidant, ultraviolet absorber, light stabilizer, or infrared absorber.

As an antioxidant, 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 is each independently an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, and 2 to 10 carbon atoms of an alkenyl group, or represent an alkenyloxy of 2 to 10 carbon atoms, a group exists, one of the -CH ₂ - or non-neighboring two or more -CH ₂ - are each independently substituted by -O- or -S- Alternatively, one or two or more hydrogen atoms present in the group may each independently be substituted with 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, and It is more preferable that it is an alkyl group of 3-7 atoms or an alkenyl group of 2-7 carbon atoms.

In the general formula (H-4), M ^H4 is an alkylene group having 1 to 15 carbon atoms (one or two or more -CH ₂ -in the alkylene group is -O-,-so that oxygen atoms are not directly adjacent to each other, It may be substituted with CO-, -COO-, -OCO-), -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-, provided A bond, a 1,4-phenylene group (an arbitrary hydrogen atom in the 1,4-phenylene group may be substituted by a fluorine atom) or a trans-1,4-cyclohexylene group, having 1 to 14 carbon atoms It is preferably an alkylene group of, and considering the volatility, the number of carbon atoms is preferably a large number, but considering the viscosity, the number of carbon atoms is preferably not too large, so 2 to 12 carbon atoms are more preferable, and carbon 3-10 atoms are more preferable, 4-10 carbon atoms are more preferable, 5-10 carbon atoms are more preferable, and 6-10 carbon atoms are still more preferable.

In General Formulas (H-1) to (H-4), one of 1,4-phenylene groups or two or more non-adjacent -CH= may be substituted by -N=. Moreover, the hydrogen atoms in the 1,4-phenylene group may each independently be substituted with a fluorine atom or a chlorine atom.

In general formula (H-2) and general formula (H-4), one of 1,4-cyclohexylene group or two or more non-adjacent -CH ₂ -is substituted by -O- or -S- You may have it. Moreover, the hydrogen atoms in the 1,4-cyclohexylene group may each independently be substituted with a fluorine atom or a chlorine atom.

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

When an antioxidant is contained in the liquid crystal composition of this invention, 10 mass ppm or more is preferable, 20 mass ppm or more is preferable, and 50 mass ppm or more is preferable. The upper limit when the antioxidant is contained is 10000 ppm by mass, preferably 1000 ppm by mass, preferably 500 ppm by mass, and preferably 100 ppm by mass.

The liquid crystal composition of the present invention has a nematic phase-isotropic liquid phase transition temperature (T _NI ) of 60°C to 120°C, more preferably 70°C to 100°C, and particularly preferably 70°C to 85°C. In addition, in the present invention, T _NI is expressed as high at 60°C or higher.

For liquid crystal television applications, T _NI is preferably 70 to 80°C. For mobile applications, T _NI is preferably 80 to 90°C. For outdoor display applications such as PID (Public Information Display), T _NI is It is preferably 90 to 110°C.

The liquid crystal composition of the present invention has a refractive index anisotropy (Δn) at 20° C. of 0.08 to 0.14, more preferably 0.09 to 0.13, and particularly preferably 0.09 to 0.12. In more detail, when it corresponds to a thin cell gap, it is preferable to be 0.10 to 0.13, and when it corresponds to a thick cell gap, it is preferable that it is 0.08 to 0.10. In addition, in the present invention, 0.09 or more is expressed as having a large Δn.

The liquid crystal composition of the present invention has a rotational viscosity (γ ₁ ) at 20°C of 50 to 160 mPa·s, preferably 55 to 160 mPa·s, preferably 60 to 160 mPa·s, and 80 to 150 mPa·s. It is preferable that it is s, it is preferable that it is 90-140 mPa*s, it is preferable that it is 90-130 mPa*s, and it is preferable that it is 100-130 mPa*s.

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

Of the compounds constituting the liquid crystal composition of the present invention, the upper limit of the total content of the compound having an alkenyl group is preferably 10%, preferably 8%, preferably 6%, and preferably 5%. And, it is preferably 4%, preferably 3%, preferably 2%, preferably 1%, preferably 0%, and the range of the total content of the compound having an alkenyl group, It is preferably 0 to 10%, preferably 0 to 8%, preferably 0 to 5%, preferably 0 to 4%, preferably 0 to 3%, and 0 to 2% It is desirable. However, the compound represented by the general formula (NU-01) is excluded.

The liquid crystal composition of the present invention contains the compound of the general formula (i), which is an essential component, and furthermore, the general formula (N-01), the general formula (N-02), the general formula (N-03), and the general formula (N -04), containing one or two or more compounds selected from the compound group represented by the general formula (N-05) and the general formula (N-06), and the general formula (NU-01) to (NU- It is preferable to contain one or two or more compounds selected from the compound group represented by 06), and the upper limit of the total content thereof is 100% by mass, 99% by mass, 98% by mass, 97% by mass, and 96 Mass%, 95 mass%, 94 mass%, 93 mass%, 92 mass%, 91 mass%, 90 mass%, 89 mass%, 88 mass%, 87 mass%, 86 mass%, 85 mass%, 84 mass% It is preferable that the lower limit of the total content thereof is 78 mass%, 80 mass%, 81 mass%, 83 mass%, 85 mass%, 86 mass%, 87 mass%, 88 mass%, 89 mass%, It is preferable that they are 90 mass%, 91 mass%, 92 mass%, 93 mass%, 94 mass%, 95 mass%, 96 mass%, 97 mass%, 98 mass%, and 99 mass%.

The liquid crystal display device using the liquid crystal composition of the present invention is particularly useful for a liquid crystal display device for active matrix driving, such as VA, FFS, IPS, PSA, PSVA, PS-IPS or PS-FFS, NPS, PI-less, etc. It can be suitably used for a liquid crystal display element.

The liquid crystal display device according to the present invention includes a first substrate and a second substrate disposed oppositely, a common electrode disposed on the first substrate or the second substrate, and the first substrate or the second substrate. It is preferable to have a pixel electrode provided on the second substrate and having a thin film transistor, and a liquid crystal layer containing a liquid crystal composition provided between the first substrate and the second substrate. If necessary, an alignment film for controlling the alignment direction of liquid crystal molecules may be provided on the side of the first substrate and/or the second substrate facing at least one of the substrates so as to contact the liquid crystal layer. As the alignment film, in addition to the driving mode of the liquid crystal display element, a vertical alignment film or a horizontal alignment film can be appropriately selected, and a known alignment film such as a rubbing alignment film (eg, polyimide) or a photo-alignment film (decomposition polyimide, etc.) You can use Further, 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.

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

The color filter can be created by, for example, a pigment dispersion method, a printing method, an electrodeposition method, or a dyeing method. When a method for preparing a color filter by a pigment dispersion method is described as an example, a curable colored composition for a color filter is applied onto the transparent substrate, subjected to patterning, and cured by heating or irradiation with light. By performing this step for each of the three colors red, green, and blue, a pixel portion for a color filter can be created. In addition, a pixel electrode in which an active element such as a TFT, a thin film diode, or a metal insulator metal resistive element is provided may be provided on the substrate.

It is preferable that the first substrate and the second substrate face each other so that the common electrode or the pixel electrode layer is inside.

The distance between the first substrate and the second substrate may be adjusted through a spacer. In this case, it is preferable to adjust so that the thickness of the light dimming layer obtained may become 1-100 micrometers. It is more preferably 1.5 to 10 μm, and when using a polarizing plate, 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. Moreover, when there are two polarizing plates, it can also adjust so that a viewing angle and contrast may become favorable by adjusting the polarization axis of each polarizing plate. Further, a retardation film for widening the viewing angle may also be used. Examples of the spacer include glass particles, plastic particles, alumina particles, and photoresist materials. Thereafter, a sealing agent such as an epoxy-based thermally strengthening composition is screen-printed on the substrate in a form in which a liquid crystal injection port is formed, and the substrates are attached to each other and heated to thermally cure the sealing agent.

As a method of sandwiching the liquid crystal composition between two substrates, an ordinary 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 of polymerizing the polymerizable compound contained in the liquid crystal composition of the present invention, in order to obtain good alignment performance of the liquid crystal, polymerization is preferably carried out at an appropriate polymerization rate, and thus active energy rays such as ultraviolet rays or electron beams are used alone or in combination or The method of polymerization by sequentially irradiating is preferable. When using ultraviolet rays, a polarized light source may be used or a non-polarized light source may be used. Further, when polymerization is carried out in a state where the liquid crystal composition is sandwiched between two substrates, at least the substrate on the side of the irradiation surface must have adequate transparency with respect to the active energy rays. In addition, a means of polymerizing only a specific portion using a mask during light irradiation, changing the orientation state of the unpolymerized portion by changing conditions such as electric field, magnetic field, or temperature, and performing polymerization by irradiating active energy rays You may use it. In particular, during UV exposure, it is preferable to perform UV exposure while applying an alternating electric field to the liquid crystal composition. The AC electric field to be applied is preferably an AC having a frequency of 10 Hz to 10 kHz, more preferably 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 device can be controlled by the applied voltage. In a PSVA-type liquid crystal display element, it is preferable to control the pretilt angle from 80 degrees to 89.9 degrees from a viewpoint of orientation stability and contrast.

The temperature at the time of irradiation with active energy rays such as ultraviolet rays or electron beams used when polymerizing the polymerizable compound contained in the liquid crystal composition of the present invention is not particularly limited. For example, when applying the liquid crystal composition of the present invention to a liquid crystal display device provided with a substrate having an alignment film, it is preferable that the liquid crystal composition is within a temperature range in which the liquid crystal state is maintained. It is preferable to polymerize at a temperature close to room temperature, that is, typically 15 to 35°C.

On the other hand, for example, in the case of applying the liquid crystal composition of the present invention to a liquid crystal display device (PI-less type liquid crystal display device) provided with a substrate without an alignment layer, a liquid crystal display device provided with a substrate having the alignment layer described above It may be a temperature range wider than the temperature range at the time of irradiation applied to.

As the lamp that generates ultraviolet rays, a metal halide lamp, a high pressure mercury lamp, an ultra high pressure mercury lamp, or the like can be used. Further, as the wavelength of the ultraviolet rays to be irradiated, it is preferable to irradiate ultraviolet rays in a wavelength region other than the absorption wavelength region of the liquid crystal composition, and if necessary, it is preferable to cut and use ultraviolet rays. The intensity of the ultraviolet rays to be irradiated is preferably 0.1 mW/cm ² to 100 W/cm ² , and more preferably ² mW/cm ² to 50 W/cm ² . The amount of energy of ultraviolet irradiation is suitably may be adjusted, it is ^{10mJ / cm 2 ~ 500J / cm} 2 are preferred, 100mJ / cm ² ~ more preferably 200J / cm ^2. When irradiating ultraviolet rays, the intensity may be changed. Although the time to irradiate ultraviolet rays is appropriately selected depending on the intensity of the ultraviolet rays to be irradiated, 10 seconds to 3600 seconds are preferable, and 10 seconds to 600 seconds are more preferable.

Example

Hereinafter, the present invention will be described in more detail with reference to examples, 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 Examples, the following abbreviations are used for the description of the compound.

Each property value was measured according to the method described in the Electronic Information Technology Industry Association standard JEITA ED-2521B revised March 2009, issued by the Electronic Information Technology Industry Association, unless otherwise specified.

(chain)

-n -C _n H _2n+1 Straight-chain alkyl group having n

n- C _n H _2n+1 -a straight-chain alkyl group having n carbon atoms

-On -OC _n H _2n+1 Straight-chain alkoxy group having n

nO- C _n H _2n+1 O- Straight-chain alkoxy group having n carbon atoms

-V -CH=CH ₂

V- CH ₂ =CH-

-V1 -CH=CH-CH ₃

1V- CH ₃ -CH=CH-

-F -F

-OCF3 -OCF ₃

(coupler)

-CF2O- -CF ₂ -O-

-OCF2- -O-CF _2-

-10- -CH ₂ -O-

-O1- -O-CH _2-

-2- -CH ₂ -CH ₂ -

-COO- -COO-

-OCO- -OCO-

-Single bond

(Ring structure)

In Examples, the measured properties are as follows.

T _NI : Nematic phase-isotropic liquid phase transition temperature (℃)

T _→N : Solid phase-nematic phase transition temperature (℃)

Δn: refractive index anisotropy at 20°C

Δε: dielectric anisotropy at 20°C

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: Voltage retention rate at 1V, 60Hz, 60℃ (%)

(Preparation and evaluation results of liquid crystal composition)

The liquid crystal compositions of Example 1 and Comparative Example 1 were prepared, and the physical property values were measured. In addition, the component ratio was designed so that T _NI , Δn and Δε of the physical property values became the same. The component ratios of these liquid crystal compositions and their physical property values are shown in Table 1.

[Table 1]

Similarly, Examples 2-4 and Comparative Examples 2-4 were prepared, and the effect of this invention was confirmed.

[Table 2]

[Table 3]

[Table 4]

As described above, in the liquid crystal composition of the present invention, the dielectric anisotropy (Δε) was negative, T _NI was high, Δn was large, γ ₁ was small, K ₃₃ was large, and γ ₁ /K ₃₃ was small.

It was found that in Comparative Examples 1 and 2, which are liquid crystal compositions except for the compound represented by the general formula (i), with the compositions of Examples 1 and 2 almost matching the values of Δn and Δε, γ ₁ is greatly deteriorated. For this reason, when the liquid crystal display elements of VA type and FFS type were produced using the compositions of these Examples 1 and 2, it was confirmed that the response time was short and had a high VHR. In that case, it was also confirmed that there was no display defect. On the other hand, for the composition of the comparative example, similarly, VA-type and FFS-type liquid crystal display elements were produced and the response time was measured, and the response time was worse than that of the composition of the example.

Further, from the results of the compositions of Examples 3 and 4 in which T _NI was high and Δε increased, it was found that although T _NI and Δε were improved, an increase in γ1 could be suppressed.

In Example 3, in Comparative Example 3, the value of Δε decreased, and thus it was not suitable for low voltage driving. Further, in the comparison between Example 4 and Comparative Example 4, it was found that γ1 was improved by about 8% in the liquid crystal composition of the present invention.

To 99.5% by mass of the liquid crystal composition of Example 1, polymerization in which 0.5% by mass of a polymerizable compound represented by the formula (RM-2) (wherein R ^M1 and R ^M2 represents a methyl group) was added. A liquid crystal composition containing a sexual compound was prepared, and a PSA type liquid crystal display device was produced.

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

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

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

Claims (9)

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, and a trifluoromethoxy group,
Y ⁱ¹ and Y ⁱ² each independently represent -O-, -CF ₂ -, -CO-, -CX ⁱ³ X ⁱ⁴ -, wherein at least one of Y ⁱ¹ and Y ⁱ² represents -O-, and X ⁱ³ , X ⁱ⁴ each independently represents the same meaning as X ⁱ¹ ,
L ⁱ¹ , L ⁱ² , L ⁱ³ , L ⁱ⁴ and L ⁱ⁵ are each independently 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 a general Equation (L ⁱ -1)

(In the formula, R ⁱ¹ is 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 alkenyloxy group having 2 to 15 carbon atoms. Indicate,
A ⁱ¹ is
(a) 1,4-cyclohexylene group (one -CH ₂ -present in this group or two or more non-adjacent -CH ₂ -s may be substituted with -O- or -S-.)
(b) 1,4-phenylene group (one -CH= present in this group or two or more non-adjacent -CH=s may be substituted with -N=, and one hydrogen atom present in this group is It may be substituted with a fluorine atom.)
(c) 1,4-cyclohexenylene group, naphthalene-2,6-diyl group, 1,2,3,4-tetrahydronaphthalene-2,6-diyl group, decahydronaphthalene-2,6-diyl group (The hydrogen atom present in these groups may be substituted with a fluorine atom, and one-present in the naphthalene-2,6-diyl group or the 1,2,3,4-tetrahydronaphthalene-2,6-diyl group CH= or two or more non-adjacent -CH= may be substituted with -N=.)
Represents a group selected from the group consisting of,
Z ⁱ¹ is -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 a single bond,
n ⁱ¹ represents 1 or 2, when n ⁱ¹ represents 2 and a plurality of A ⁱ¹ and Z ⁱ¹ exist, they may be the same or different.)
Represents a group represented by,
W ⁱ¹ is the general formula (W ⁱ¹ -1), (W ⁱ¹ -2) or (W ⁱ¹ -3)

(In the formula, * represents the bonding point to L ⁱ² or Y ⁱ² , * represents the bonding point to the carbon atom adjacent to the carbon atom to which L ⁱ⁵ is bonded, and L ⁱ⁶ , L ⁱ⁷ and L ⁱ⁸ are each independently , It represents the same meaning as L ⁱ¹ .),
W ⁱ² is a single bond or -CL ⁱ⁹ L ⁱ¹⁰ -
(L ⁱ⁹ and L ⁱ¹⁰ each independently represent the same meaning as L ⁱ¹ .)
Represents,
One of L ⁱ¹ , L ⁱ² , L ⁱ³ , L ⁱ⁴ , L ⁱ⁵ , L ⁱ⁶ , L ⁱ⁷ , L ⁱ⁸ , L ⁱ⁹ and L ⁱ¹⁰ -CH ₂ -or two or more non-adjacent -CH _2- May be substituted by -C≡C-, -O-, -COO-, -OCO-, or -CO-, and a hydrogen atom present in the alkyl group or alkenyl group may be substituted with a fluorine atom.)
Liquid crystal composition containing 1 type or 2 or more types of compounds represented by. The method according to claim 1,
General formula (N-01), general formula (N-02), general formula (N-03), general formula (N-04) and general formula (N-05)

(In the formula, R ²¹ and R ²² are each independently 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 2 to 8 carbon atoms. Represents an alkenyloxy group of, and one or two or more non-adjacent -CH ₂ -of the groups are each independently -CH=CH-, -C≡C-, -O-, -CO-, -COO- or May be substituted by -OCO-, and Z ¹ is each independently 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) selected from the group of compounds represented by A liquid crystal composition containing 1 type or 2 or more types of compounds. The method according to claim 1 or 2,
General Formula (NU-01)~General Formula (NU-06)

(In the formula, 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 are each independently, the number of carbon atoms from 1 to Represents an alkyl group of 8, an alkoxy group of 1 to 8 carbon atoms, an alkenyl group of 2 to 8 carbon atoms, or an alkenyloxy group of 2 to 8 carbon atoms, and one of the groups or two or more non-adjacent -CHs ₂ -may each independently be substituted by -CH=CH-, -C≡C-, -O-, -CO-, -COO-, or -OCO-.) Liquid crystal composition containing 1 type or 2 or more types. The method of claim 3,
The liquid crystal composition, 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 method according to any one of claims 3 or 4,
The compound represented by general formula (i), the compound selected from the compound group represented by general formula (N-01)-general formula (N-05), and general formula (NU-01)-general formula (NU-06 The liquid crystal composition, wherein the total content of the compound selected from the compound group represented by) is 95% by mass to 100% by mass. The method according to any one of claims 1 to 5,
General formula (RM)

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

(In the formula, R ¹¹ , R ¹² , R ¹³ , R ¹⁴ and R ¹⁵ each independently represent either an alkyl group having 1 to 5 carbon atoms, a fluorine atom or a hydrogen atom, and m ^r5 , m ^r7 , n ^r5 and n ^r7 each independently represent 0, 1, or 2, but when m ^r5 , m ^r7 , n ^r5 and/or n ^r7 represent 0, they represent a single bond.)
Represents a polymerizable group represented by, S ¹¹ , S ¹² and S ¹³ each independently represent a single bond or an alkylene group having 1 to 15 carbon atoms, and one of the alkylene groups -CH ₂ -or adjacent Two or more -CH ₂ -which are not present may be substituted with -O-, -OCO-, or -COO-, and when plural P ¹³ and S ¹³ are present, they may be the same or different, respectively.)
A liquid crystal composition containing one or two or more polymerizable compounds represented by. A liquid crystal display device using the liquid crystal composition according to any one of claims 1 to 6. A liquid crystal display device for active matrix driving using the liquid crystal composition according to any one of claims 1 to 6. A liquid crystal display device of VA type, IPS type, FFS type, PSA type, or PSVA type using the liquid crystal composition according to any one of claims 1 to 6.