JP7298136B2 - Liquid crystal composition and liquid crystal display element - Google Patents

Description

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

Liquid crystal display elements are used in watches, calculators, various household electric appliances, industrial measuring instruments, automobile panels, mobile phones, smart phones, notebook PCs, tablet PCs, televisions, and the like. Typical liquid crystal display methods are TN (twisted nematic) type, STN (super twisted nematic) type, GH (guest-host) type, IPS (in-plane switching) type, and FFS (fringe field switching) type. , OCB (optically compensated birefringence) type, ECB (voltage controlled birefringence) type, VA (vertical alignment) type, CSH (color super homeotropic) type, FLC (ferroelectric liquid crystal), and the like. Examples of drive systems include static drive, multiplex drive, simple matrix system, and active matrix (AM) system driven by TFTs (thin film transistors), TFDs (thin film diodes), and the like. In these display systems, the IPS type, FFS type, ECB type, VA type, CSH type, etc. use a liquid crystal composition (n-type liquid crystal composition) exhibiting a negative dielectric anisotropy (Δε). It is known to exhibit advantageous properties.

Display systems using n-type liquid crystal compositions are represented by the VA type, the PSA (Polymer Sustained Alignment) type or the PSVA (Polymer Stabilized Vertical Alignment) type in which the alignment is controlled by polymerizing a polymerizable compound in the liquid crystal phase. and a horizontal alignment system represented by IPS type and FFS type. The vertical alignment method is characterized by a wide viewing angle, high transmittance, high contrast, and fast response speed, and is mainly used for large display devices such as TVs and monitors. On the other hand, the horizontal alignment method is used in mobile devices such as smartphones and tablet PCs, and is also used in liquid crystal televisions because of its wide viewing angle, high transmittance, low power consumption, and optimum compatibility with touch panels. is also progressing.

PSA type or PSVA type liquid crystal display devices form a polymer structure in the cell to control the pretilt angle of the liquid crystal molecules, and among the features of the vertical alignment method, particularly high speed response and high contrast are known. ing.

In the manufacture of a PSA or PSVA liquid crystal display element, a liquid crystal composition containing a polymerizable compound is injected between substrates, a voltage is applied to orient the liquid crystal molecules, and then ultraviolet rays are irradiated to irradiate the polymerizable compound. is polymerized to fix the orientation of the liquid crystal molecules. Therefore, in the step of polymerizing the polymerizable compound in the liquid crystal composition, the polymerization rate of the polymerizable compound is very important. When the polymerization rate is high, the residual amount of the polymerizable compound is reduced with a short ultraviolet irradiation time, so that deterioration of the liquid crystal composition due to ultraviolet rays is less likely to occur. In addition, there is also the merit of high productivity that can be manufactured with less energy.

On the other hand, when the polymerization rate of the polymerizable compound is slow, a long UV irradiation time is required in order to reduce the residual amount of the polymerizable compound. As described above, when strong ultraviolet rays are irradiated for a long period of time in the polymerization process, the size of the production apparatus is increased, the production efficiency is lowered, and deterioration of the liquid crystal composition due to the ultraviolet rays is caused. However, if the irradiation time of ultraviolet rays is shortened, the residual amount of the polymerizable compound increases, and the remaining polymerizable compound causes a display defect called burn-in.

For the reasons described above, a liquid crystal composition in which the polymerization speed of a polymerizable compound is improved is desired.

As an approach for improving the polymerization speed of a polymerizable compound, as shown in Examples of Patent Document 1, a compound such as the formula (A) is used, and the absorption wavelength of the liquid crystal material used is shifted to the long wavelength side. Although a method for improving the polymerization rate of a polymerizable compound by stretching the polymerizable compound has been proposed, the reliability represented by changes in the pretilt angle and the voltage holding rate was not sufficient.

Japanese Patent Publication No. 2013-503952

The problem to be solved by the present invention is that the polymerization rate of the polymerizable compound is sufficiently high, and display defects such as image sticking (IS) caused by changes in the pretilt angle do not occur or are extremely small, and the VHR is improved. It is an object of the present invention to provide a liquid crystal composition containing a polymerizable compound suitable for a highly reliable PSA-type or PSVA-type liquid crystal display element, and to provide a liquid crystal display element using the same.

As a result of extensive studies, the present inventors have found that the above problems can be solved by a liquid crystal composition containing a compound having a specific chemical structure and a polymerizable compound, and have completed the present invention.

The liquid crystal composition of the present invention has a negative dielectric anisotropy (Δε), a large refractive anisotropy (Δn), a high nematic phase-isotropic liquid phase transition temperature (T _ni ), and a small rotational viscosity. (γ ₁ ) and the polymerization rate of the polymerizable compound is sufficiently high. Since the liquid crystal display element using the liquid crystal composition of the present invention has a small residual amount of the polymerizable compound, the change in pretilt angle before and after driving is small, the voltage holding ratio (VHR) is high, and display defects such as burn-in occur. Exhibits excellent display quality with no or suppressed

The liquid crystal composition of the present invention has, as a first component, general formula (i)

(wherein R ⁱ¹ and R ⁱ² each independently represent an alkyl group having 1 to 8 carbon atoms, and one or two or more non-adjacent —CH ₂ — in the alkyl group are each independently may be substituted by -CH=CH-, -C≡C-, -O-, -CO-, -COO- or -OCO-, and A ⁱ¹ is a 1,4-cyclohexylene group (this One —CH ₂ — present in the group or two or more —CH ₂ — which are not adjacent may be replaced with —O—.), n ⁱ¹ represents 0, 1 or 2. .) containing one or more compounds represented by the general formula (L)

(wherein R ^L1 and R ^L2 each independently represent an alkyl group having 1 to 8 carbon atoms, and one or two or more non-adjacent —CH ₂ — in the alkyl group are each independently may be substituted by -CH=CH-, -C≡C-, -O-, -CO-, -COO- or -OCO-,
A ^L1 , A ^L2 and A ^L3 are each independently
(a) a 1,4-cyclohexylene group (one —CH ₂ — present in this group or two or more non-adjacent —CH ₂ — may be replaced with —O—),
(b) a 1,4-phenylene group (one -CH= or two or more non-adjacent -CH= present in this group may be replaced with -N=) and (c) naphthalene-2,6-diyl group, 1,2,3,4-tetrahydronaphthalene-2,6-diyl group or decahydronaphthalene-2,6-diyl group (naphthalene-2,6-diyl group or 1,2 , 1 -CH= or two or more non-adjacent -CH= present in the 3,4-tetrahydronaphthalene-2,6-diyl group may be replaced with -N=.)
represents a group selected from the group consisting of, and the above groups (a), (b) and (c) each independently represent an alkyl group (one —CH ₂ — present in this group or adjacent two or more —CH ₂ — that are not adjacent may be replaced by —O—), an alkenyl group (one —CH ₂ — present in this group, or two or more —CH _2- may be replaced with -O-), may be substituted with a cyano group, a fluorine atom or a chlorine atom,
Z ^L1 and Z ^L2 are each independently a single bond, -CH ₂ CH ₂ -, -(CH ₂ ) ₄ -, -OCH ₂ -, -CH ₂ O-, -COO-, -OCO-, -OCF ₂ represents -, -CF ₂ O-, -CH=N-N=CH-, -CH=CH-, -CF=CF- or -C≡C-,
n ^L1 represents 0, 1, 2 or 3,
When there are a plurality of A ^L2 , they may be the same or different, and when there are a plurality of Z ^L2 , they may be the same or different. ), and compounds represented by general formula (N-1d) or (N-1). ) contains one or more compounds represented by the formula (N-1d) and / or general formula (N-1) as a third component

(wherein R ^{3 Nd11} and R ^{3 Nd12} each independently represent an alkyl group having 1 to 8 carbon atoms, and one or two or more non-adjacent —CH ₂ — in the alkyl group are each independently may be substituted by -CH=CH-, -C≡C-, -O-, -CO-, -COO- or -OCO-, and ^nNd11 represents 1, 2 or 3.)

(wherein R ^N11 and R ^N12 each independently represent an alkyl group having 1 to 8 carbon atoms, and one or two or more non-adjacent —CH ₂ — in the alkyl group each independently may be substituted by -CH=CH-, -C≡C-, -O-, -CO-, -COO- or -OCO-, and n ^N11 and n ^N12 are each independently 0, 1 , 2 or 3, wherein n ^N11 +n ^N12 represents 1, 2 or 3, A ^N11 and A ^N12 each independently
(a) a 1,4-cyclohexylene group (one —CH ₂ — present in this group or two or more non-adjacent —CH ₂ — may be replaced with —O—),
(b) a 1,4-phenylene group (one -CH= or two or more non-adjacent -CH= present in this group may be replaced with -N=) and (c) naphthalene-2,6-diyl group, 1,2,3,4-tetrahydronaphthalene-2,6-diyl group or decahydronaphthalene-2,6-diyl group (naphthalene-2,6-diyl group or 1,2 , 1 -CH= or two or more non-adjacent -CH= present in the 3,4-tetrahydronaphthalene-2,6-diyl group may be replaced with -N=.)
represents a group selected from the group consisting of, and the above groups (a), (b) and (c) each independently represent an alkyl group (one —CH ₂ — present in this group or adjacent two or more —CH ₂ — that are not adjacent may be replaced by —O—), an alkenyl group (one —CH ₂ — present in this group, or two or more —CH ₂ — may be replaced with —O—.), may be substituted with a cyano group, a fluorine atom or a chlorine atom, and Z ^N11 and Z ^N12 are each independently a single bond, —CH ₂ CH ₂ -, -(CH ₂ ) ₄ -, -OCH ₂ -, -CH ₂ O-, -COO-, -OCO-, -OCF _{2 -, -CF 2 O-} , -CH=N-N=CH-, -CH=CH-, -CF=CF- or -C≡C-, and when there are a plurality of A ^N11 and/or A ^N12 , they may be the same or different, and Z ^N11 and /or when a plurality of Z ^N12 are present, they may be the same or different, except for compounds represented by general formula (N-1d). ) containing one or more compounds selected from the group of compounds represented by the formula (II) as a fourth component

(wherein R ²⁰¹ , R ²⁰² , R ²⁰³ , R ²⁰⁴ , R ²⁰⁵ , R 206 , R ²⁰⁷ , R ^{208 ,} R ²⁰⁹ and R ²¹⁰ are each independently P ²¹ -S ²¹ -, a fluorine atom, an alkyl group having 1 to 18 carbon atoms which may be substituted, 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 from formula (R-1) to formula (R-7)

(wherein R ¹¹ , R ¹² , R ¹³ , R ¹⁴ and R ¹⁵ each independently represent an alkyl group having 1 to 5 carbon atoms, a fluorine atom or a hydrogen atom, m ^r5 , m ^r7 , ^nr5 and ^nr7 each independently represent 0, 1, or 2.), and ^S21 represents a single bond or an alkylene group having 1 to 15 carbon atoms. , one or more —CH ₂ — in the alkylene group may be replaced with —O—, —OCO— or —COO— such that the oxygen atoms are not directly adjacent, and n ²¹ is 0 , 1 or 2, and A ²¹ is
(a) 1,4-cyclohexylene group (one —CH ₂ — present in this group or two or more non-adjacent —CH ₂ — may be replaced with —O—);
(b) a 1,4-phenylene group (one -CH= or two or more non-adjacent -CH= present in this group may be replaced with -N=) and (c) naphthalene-2,6-diyl group, 1,2,3,4-tetrahydronaphthalene-2,6-diyl group or decahydronaphthalene-2,6-diyl group (naphthalene-2,6-diyl group or 1,2 , 1 -CH= or two or more non-adjacent -CH= present in the 3,4-tetrahydronaphthalene-2,6-diyl group may be replaced with -N=.)
represents a group selected from the group consisting of, and the above groups (a), (b) and (c) are each independently an alkyl group having 1 to 12 carbon atoms, an alkyl group having 1 to 12 carbon atoms, may be substituted with an alkoxy group, halogen, cyano group, nitro group or P ²¹ -S ²¹ - and has at least one or more P ²¹ -S ²¹ - in one molecule of general formula (II) , L ²¹ is a single bond, -OCH ₂ -, -CH ₂ O-, -C ₂ H ₄ -, -OC ₂ H ₄ O-, -COO-, -OCO-, -CH=CR ^a -COO-, -CH=CR ^a -OCO-, -COO-CR ^a =CH-, -OCO-CR ^a =CH-, -(CH ₂ ) _z -COO-, -(CH ₂ ) _z -OCO-, -OCO- (CH ₂ ) _z —, —COO—(CH ₂ ) _z —, —CH═CH—, —CF ₂ O—, —OCF ₂ — or —C≡C— (wherein R ^a is independently represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, wherein z each independently represents an integer of 1 to 4), wherein P ²¹ , S ²¹ , and A ²¹ are present in plurality; If so, they may be the same or different. ) contains a polymerizable compound represented by

In general formula (i), R ⁱ¹ is 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 alkenyloxy group having 2 to 8 carbon atoms. is preferably an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, an alkenyl group having 2 to 5 carbon atoms or an alkenyloxy group having 2 to 5 carbon atoms. An alkyl group having 2 to 5 carbon atoms or an alkenyl group having 2 to 5 carbon atoms is more preferable. R ⁱ² is preferably an alkyl group having 1 to 8 carbon atoms or an alkenyl group having 2 to 8 carbon atoms, preferably an alkyl group having 1 to 5 carbon atoms or an alkenyl group having 2 to 5 carbon atoms; An alkyl group having 1 to 3 carbon atoms or an alkenyl group having 2 to 5 carbon atoms is more preferable, and an alkyl group having 1 carbon atom is particularly preferable. A ⁱ¹ is a 1,4-cyclohexylene group (one —CH ₂ — present in this group or two or more non-adjacent —CH ₂ — may be replaced with —O—). is preferably an unsubstituted 1,4-cyclohexylene group. n ⁱ¹ represents 0, 1 or 2, preferably 1 or 2, particularly preferably 1.

The compounds represented by the general formula (i) are represented by formulas (i-0.1) to (i-0.7), formulas (i-1.1) to formulas (i-1.7) and formulas ( It is preferably a compound selected from the group of compounds represented by formulas (i-2.1) to (i-2.7).

In the group of compounds represented by formulas (i-0.1) to (i-0.7), formula (i-0.3), formula (i-0.5), formula (i-0. 7) is more preferred, and formula (i-0.7) is particularly preferred.

In the group of compounds represented by formulas (i-1.1) to (i-1.7), formula (i-1.3), formula (i-1.6), formula (i-1. Compounds represented by 7) are more preferred, and compounds represented by formula (i-1.3) are particularly preferred.

In the group of compounds represented by formulas (i-2.1) to (i-2.7), formula (i-2.3), formula (i-2.6), formula (i-2. A compound represented by 7) is more preferable, and a compound represented by formula (i-2.3) is particularly preferable.

Preferred lower limits for the content of the compound represented by formula (i) with respect to the total amount of the composition of the present invention are 1%, 2%, 3%, 5%, 7 %. Preferred upper limits of the content are 20%, 15%, 13%, 10% and 9%. Hereinafter, unless otherwise specified, % means % by mass.

One of the compounds represented by formula (i) may be used alone, or two or more of them may be used in combination. By using a combination of two or more of the compounds represented by formula (i), the effects of the present invention can be remarkably obtained. When two or more compounds represented by formula (i) are used, compounds represented by formulas (i-0.1) to (i-0.7) and formulas (i-1.1) to (i- A combination with a compound represented by 1.7) is preferable, and a combination of two kinds of compounds represented by formulas (i-1.1) to (i-1.7) is also preferable.

The liquid crystal composition of the present invention preferably contains one or more compounds represented by formula (L). The compound represented by the general formula (L) corresponds to a dielectrically almost neutral compound (the value of Δε is from −2 to 2). However, compounds represented by general formula (i) are excluded.

The compounds represented by general formula (L) may be used alone, or may be used in combination. Although there is no particular limitation on the types of compounds that can be combined, they are appropriately used in combination according to desired properties such as low-temperature solubility, transition temperature, electrical reliability, and birefringence. The type of compound used is, for example, one type as one embodiment of the present invention. Alternatively, in another embodiment of the present invention, 2 types, 3 types, 4 types, 5 types, 6 types, 7 types, 8 types, 9 types, 10 types Kinds or more.

The compound represented by the general formula (L) is a so-called non-polar compound with Δε near zero. Therefore, the number of polar groups such as halogen atoms in the molecule is preferably 2 or less, preferably 1 or less. It is preferable that it is not substituted when paying attention to viscosity.

The preferred lower limit of the content of the compound represented by the general formula (L) with respect to the total amount of the composition of the present invention is 1%, 10%, 20%, and 30%, 40%, 50%, 55%, 60%, 65%, 70%, 75%, 80%. Preferred upper limits of the content are 95%, 85%, 75%, 65%, 55%, 45%, 35% and 25%.

Compounds represented by general formula (i), general formula (L), general formula (N-1d), general formula (N-1) and general formula (II) with respect to the total amount of the composition of the present invention Preferred lower limits of the content are 50%, 55%, 60%, 65%, 70%, 75%, 80%, 85%, and 90% , 95%, 99%, and 100%. Preferred upper limits of the content are 100%, 95%, 85%, 75% and 65%.

In order to solve the problems of the present invention, it is preferable that the lower limit is high and the upper limit is high.

Both R ^L1 and R ^L2 are preferably alkyl groups when reliability is important, and at least one of them is preferably alkenyl group when viscosity reduction is important.

The halogen atoms present in the molecule are preferably fluorine atoms, and the number thereof is preferably 0, 1, 2 or 3, preferably 0 or 1.

When the ring structure to which R ^L1 and R ^L2 are bonded is a phenyl group (aromatic), R L1 and R L2 are a linear alkyl group having 1 to 5 carbon atoms, a linear C 1 to 4 and an alkenyl group having 4 to 5 carbon atoms are preferable, and when the ring structure to which it is bonded is a saturated ring structure such as cyclohexane, pyran and dioxane, a straight chain having 1 to 5 carbon atoms Alkyl groups, straight-chain alkoxy groups having 1 to 4 carbon atoms and straight-chain alkenyl groups having 2 to 5 carbon atoms are preferred. In order to stabilize the nematic phase, the total number of carbon atoms and, if present, oxygen atoms is preferably 5 or less, and is preferably linear.

The alkenyl group is preferably selected from groups represented by any one of formulas (R1) to (R5). (The black dots in each formula represent carbon atoms in the ring structure.)

^nL1 is preferably 0 when the response speed is emphasized, 2 or 3 is preferable for improving the upper limit temperature of the nematic phase, and 1 is preferable for balancing these. Moreover, in order to satisfy the properties required for a liquid crystal composition, it is preferable to combine compounds having different values.

A ^L1 , A ^L2 and A ^L3 are preferably aromatic when it is desired to increase Δn, preferably aliphatic for improving the response speed, and each independently trans- 1,4-cyclohexylene group, 1,4-phenylene group, 2-fluoro-1,4-phenylene group, 3-fluoro-1,4-phenylene group, 3,5-difluoro-1,4-phenylene group , 1,4-cyclohexenylene group, 1,4-bicyclo[2.2.2]octylene group, piperidine-1,4-diyl group, naphthalene-2,6-diyl group, decahydronaphthalene-2,6 -diyl group or 1,2,3,4-tetrahydronaphthalene-2,6-diyl group, more preferably the following structure,

It more preferably represents a trans-1,4-cyclohexylene group or a 1,4-phenylene group.

Z ^L1 and Z ^L2 are preferably single bonds when the response speed is important.

The compound represented by formula (L) preferably has 0 or 1 halogen atoms in the molecule.

The compound represented by general formula (L) is preferably a compound selected from the group of compounds represented by general formulas (L-1) to (L-7).

The compound represented by general formula (L-1) is the following compound.

(In the formula, R ^L11 and R ^L12 each independently have the same meaning as R ^L1 and R ^L2 in general formula (L).)
R ^L11 and R ^L12 are preferably linear alkyl groups having 1 to 5 carbon atoms, linear alkoxy groups having 1 to 4 carbon atoms and linear alkenyl groups having 2 to 5 carbon atoms. .

The compound represented by general formula (L-1) can be used alone, or two or more compounds can be used in combination. The types of compounds that can be combined are not particularly limited, but they are appropriately combined and used according to the required properties such as low-temperature solubility, transition temperature, electrical reliability, and birefringence. The types of compounds to be used are, for example, one type, two types, three types, four types, and five or more types as one embodiment of the present invention.

Preferred lower limits of the content are 1%, 2%, 3%, 5%, 7% and 10% relative to the total amount of the composition of the present invention. Preferred upper limits of the content are 40%, 35%, 33%, 30% and 25% relative to the total amount of the composition of the present invention.

When the viscosity of the composition of the present invention is kept low and a composition having a high response speed is required, it is preferable that the above lower limit value is high and the upper limit value is high. Furthermore, when a composition of the present invention is required to have a high Tni and good temperature stability, it is preferred that the lower limit is moderate and the upper limit is moderate. Further, when it is desired to increase the dielectric anisotropy in order to keep the driving voltage low, it is preferable that the lower limit value and the upper limit value are low. It is not preferable to increase the upper limit to improve viewing angle characteristics.

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

(In the formula, R ^L12 has the same meaning as R ^L2 in general formula (L-1).)
The compound represented by general formula (L-1-1) is a compound selected from the group of compounds represented by formulas (L-1-1.1) to (L-1-1.3). is preferred, preferably a compound represented by formula (L-1-1.2) or formula (L-1-1.3), especially represented by formula (L-1-1.3) It is preferably a compound that

The preferred lower limit of the content of the compound represented by formula (L-1-1.3) with respect to the total amount of the composition of the present invention is 1%, 2%, 3%, 5%, 7%, 10%. Preferred upper limits of the content are 20%, 15%, 13%, 10%, 8%, 7%, 6%, relative to the total amount of the composition of the present invention. %, 5%, 3%.

The compound represented by general formula (L-1) is preferably a compound selected from the group of compounds represented by general formula (L-1-2).

(In the formula, R ^L12 has the same meaning as R ^L2 in general formula (L-1).)
The lower limit of the preferred content of the compound represented by formula (L-1-2) with respect to the total amount of the composition of the present invention is 1%, 5%, 10%, and 15%. , 17%, 20%, 23%, 25%, 27%, 30%, 35%. Preferred upper limits of the content are 60%, 55%, 50%, 45%, 42%, 40%, and 38% of the total amount of the composition of the present invention. %, 35%, 33%, and 30%.

Furthermore, the compound represented by general formula (L-1-2) is a compound selected from the group of compounds represented by formulas (L-1-2.1) to (L-1-2.4). and preferably compounds represented by formulas (L-1-2.2) to (L-1-2.4). In particular, the compound represented by formula (L-1-2.2) is preferred because it particularly improves the response speed of the composition of the present invention. Further, when obtaining Tni higher than the response speed, it is preferable to use a compound represented by formula (L-1-2.3) or formula (L-1-2.4). The content of the compounds represented by formulas (L-1-2.3) and (L-1-2.4) is not preferably 30% or more in order to improve solubility at low temperature.

Preferred lower limits for the content of the compound represented by formula (L-1-2.2) with respect to the total amount of the composition of the present invention are 10%, 15%, and 18%, 20%, 23%, 25%, 27%, 30%, 33%, 35%, 38%, 40%. Preferred upper limits of the content are 60%, 55%, 50%, 45%, 43%, 40%, and 38% of the total amount of the composition of the present invention. %, 35%, 32%, 30%, 27%, 25%, 22%.

The lower limit of the preferable total content of the compound represented by formula (L-1-1.3) and the compound represented by formula (L-1-2.2) with respect to the total amount of the composition of the present invention The values are 10%, 15%, 20%, 25%, 27%, 30%, 35% and 40%. Preferred upper limits of the content are 60%, 55%, 50%, 45%, 43%, 40%, and 38% of the total amount of the composition of the present invention. %, 35%, 32%, 30%, 27%, 25%, 22%.

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

(In the formula, R ^L13 and R ^L14 each independently represent an alkyl group having 1 to 8 carbon atoms or an alkoxy group having 1 to 8 carbon atoms.)
R ^L13 and R ^L14 are preferably linear alkyl groups having 1 to 5 carbon atoms, linear alkoxy groups having 1 to 4 carbon atoms and linear alkenyl groups having 2 to 5 carbon atoms. .

Preferred lower limits of the content of the compound represented by formula (L-1-3) with respect to the total amount of the composition of the present invention are 1%, 5%, 10%, and 13%. , 15%, 17%, 20%, 23%, 25%, and 30%. Preferred upper limits of the content are 60%, 55%, 50%, 45%, 40%, 37%, and 35% with respect to the total amount of the composition of the present invention. %, 33%, 30%, 27%, 25%, 23%, 20%, 17%, 15%, 13%, 10% %.
Further, the compound represented by general formula (L-1-3) is a compound selected from the group of compounds represented by formulas (L-1-3.1) to (L-1-3.12). is preferably a compound represented by formula (L-1-3.1), formula (L-1-3.3) or formula (L-1-3.4). In particular, the compound represented by formula (L-1-3.1) is preferred because it particularly improves the response speed of the composition of the present invention. Further, when obtaining Tni higher than the response speed, formula (L-1-3.3), formula (L-1-3.4), formula (L-1-3.11) and formula (L- 1-3.12) is preferably used. Sum of compounds represented by formula (L-1-3.3), formula (L-1-3.4), formula (L-1-3.11) and formula (L-1-3.12) The content of is not preferably 20% or more in order to improve the solubility at low temperature.

The preferred lower limit of the content of the compound represented by formula (L-1-3.1) with respect to the total amount of the composition of the present invention is 1%, 2%, 3%, 5%, 7%, 10%, 13%, 15%, 18%, 20%. Preferred upper limits of the content are 20%, 18%, 17%, 15%, 13%, 10%, 8% with respect to the total amount of the composition of the present invention. %, 7%, 6%.

In order to solve the problems of the present invention, formula (L-1-3.1), formula (L-1-3.3), formula (L-1-3.4), formula (L-1- 3.11) and a combination of two or more compounds selected from the group of compounds represented by formula (L-1-3.12). When the response speed is important, it is also preferable to use the compound represented by the formula (L-1-1.3).

The compound represented by general formula (L-2) is the following compound.

(In the formula, R ^L21 and R ^L22 each independently have the same meaning as R ^L1 and R ^L2 in general formula (L).)
R ^L21 is preferably an alkyl group having 1 to 5 carbon atoms or an alkenyl group having 2 to 5 carbon atoms, and R ^L22 is an alkyl group having 1 to 5 carbon atoms, an alkenyl group having 4 to 5 carbon atoms, or a carbon atom Alkoxy groups of numbers 1 to 4 are preferred.

The compound represented by general formula (L-2) can be used alone, or two or more compounds can be used in combination. The types of compounds that can be combined are not particularly limited, but they are appropriately combined and used according to the required properties such as low-temperature solubility, transition temperature, electrical reliability, and birefringence. The types of compounds to be used are, for example, one type, two types, three types, four types, and five or more types as one embodiment of the present invention.

If the solubility at low temperatures is important, setting the content to a large amount is effective, and conversely, if the response speed is important, setting the content to a small amount is effective. Furthermore, in order to improve drip marks and seizure properties, it is preferable to set the range of the content in the middle.

The preferred lower limit of the content of the compound represented by formula (L-2) with respect to the total amount of the liquid crystal composition (or liquid crystal mixture) obtained by the production method according to the present invention is 1%. %, 3%, 5%, 7%, 10%. Preferred upper limits of the content are 20%, 18%, 15%, and 13% with respect to the total amount of the liquid crystal composition (or liquid crystal mixture) obtained by the production method according to the present invention. Yes, 10%, 8%, 7%, 6%, 5%, 3%.

Furthermore, the compound represented by the general formula (L-2) is preferably a compound selected from the group of compounds represented by the formulas (L-2.1) to (L-2.6), and the formula Compounds represented by (L-2.1), formula (L-2.3), formula (L-2.4) and formula (L-2.6) are preferred.

The compound represented by general formula (L-3) is the following compound.

(In the formula, R ^L31 and R ^L32 each independently have the same meaning as R ^L1 and R ^L2 in general formula (L), but R ^L32 does not represent an alkoxy group or an alkenyloxy group. , R ^L31 and R ^L32 are each independently preferably an alkyl group having 1 to 5 carbon atoms or an alkenyl group having 4 to 5 carbon atoms.)
The compound represented by general formula (L-3) can be used alone, or two or more compounds can be used in combination. The types of compounds that can be combined are not particularly limited, but they are appropriately combined and used according to the required properties such as low-temperature solubility, transition temperature, electrical reliability, and birefringence. The types of compounds to be used are, for example, one type, two types, three types, four types, and five or more types as one embodiment of the present invention.

The preferred lower limit of the content of the compound represented by formula (L-3) with respect to the total amount of the liquid crystal composition (or liquid crystal mixture) obtained by the production method according to the present invention is 1%. %, 3%, 5%, 7%, 10%. Preferred upper limits of the content are 20%, 15%, 13%, and 10% with respect to the total amount of the liquid crystal composition (or liquid crystal mixture) obtained by the production method according to the present invention. Yes, 8%, 7%, 6%, 5%, 3%.

When a high birefringence is to be obtained, setting the content to a large amount is highly effective, and conversely, when a high Tni is emphasized, setting the content to a small amount is highly effective. Furthermore, in order to improve drip marks and seizure properties, it is preferable to set the range of the content in the middle.

Furthermore, the compound represented by the general formula (L-3) is preferably a compound selected from the group of compounds represented by the formulas (L-3.1) to (L-3.4), and the formula A compound represented by (L-3.1) or formula (L-3.4) is more preferable.

The compound represented by general formula (L-4) is the following compound.

(In the formula, R ^L41 and R ^L42 each independently have the same meaning as R ^L1 and R ^L2 in general formula (L).)
R ^L41 is preferably an alkyl group having 1 to 5 carbon atoms or an alkenyl group having 2 to 5 carbon atoms, and R ^L42 is an alkyl group having 1 to 5 carbon atoms, an alkenyl group having 4 to 5 carbon atoms, or a carbon atom Alkoxy groups of numbers 1 to 4 are preferred. )
The compound represented by general formula (L-4) can be used alone, or two or more compounds can be used in combination. The types of compounds that can be combined are not particularly limited, but they are appropriately combined and used according to the required properties such as low-temperature solubility, transition temperature, electrical reliability, and birefringence. The types of compounds to be used are, for example, one type, two types, three types, four types, and five or more types as one embodiment of the present invention.

In the composition of the present invention, the content of the compound represented by the general formula (L-4) is determined by solubility at low temperature, transition temperature, electrical reliability, birefringence, process suitability, drip marks, It is necessary to make appropriate adjustments according to required performance such as image sticking and dielectric anisotropy.

Preferred lower limits for the content of the compound represented by formula (L-4) with respect to the total amount of the composition of the present invention are 1%, 2%, 3%, and 5%. , 7%, 10%, 14%, 16%, 20%, 23%, 26%, 30%, 35%, 40% . The upper limit of the preferable content of the compound represented by formula (L-4) with respect to the total amount of the composition of the present invention is 50%, 40%, 35%, and 30%. , 20%, 15%, 10%, 5%.

The compound represented by general formula (L-4) is preferably, for example, compounds represented by formulas (L-4.1) to (L-4.3).

Depending on the required performance such as solubility at low temperature, transition temperature, electrical reliability, birefringence, even if it contains the compound represented by formula (L-4.1), -4.2), it contains both the compound represented by formula (L-4.1) and the compound represented by formula (L-4.2) or may contain all of the compounds represented by formulas (L-4.1) to (L-4.3). The lower limit of the preferable content of the compound represented by formula (L-4.1) or formula (L-4.2) with respect to the total amount of the composition of the present invention is 3%, and 5%. , 7%, 9%, 11%, 12%, 13%, 18%, 21%, and the preferred upper limit is 45, 40% , 35%, 30%, 25%, 23%, 20%, 18%, 15%, 13%, 10%, 8% .

When both the compound represented by formula (L-4.1) and the compound represented by formula (L-4.2) are contained, the amount of both compounds relative to the total amount of the composition of the present invention Preferred lower limits of the content are 15%, 19%, 24%, and 30%, and preferred upper limits are 45, 40%, 35%, and 30%. Yes, 25%, 23%, 20%, 18%, 15%, 13%.

The compound represented by general formula (L-4) is preferably a compound represented by, for example, formulas (L-4.4) to (L-4.6), and formula (L-4.4 ) is preferably a compound represented by

Depending on the required performance such as low-temperature solubility, transition temperature, electrical reliability, and birefringence, even if the compound represented by formula (L-4.4) is contained, formula (L -4.5), it contains both the compound represented by formula (L-4.4) and the compound represented by formula (L-4.5) It's okay to be there.

The lower limit of the preferable content of the compound represented by formula (L-4.4) or formula (L-4.5) with respect to the total amount of the composition of the present invention is 3%, and 5%. Yes, 7%, 9%, 11%, 12%, 13%, 18%, 21%. Preferred upper limits are 45, 40%, 35%, 30%, 25%, 23%, 20%, 18%, 15%, 13 %, 10%, and 8%.

When both the compound represented by formula (L-4.4) and the compound represented by formula (L-4.5) are contained, the total amount of both compounds in the composition of the present invention Preferred lower limits of the content are 15%, 19%, 24%, and 30%, and preferred upper limits are 45, 40%, 35%, and 30%. Yes, 25%, 23%, 20%, 18%, 15%, 13%.

The compound represented by general formula (L-4) is preferably a compound represented by formula (L-4.7) to formula (L-4.10), particularly formula (L-4. Compounds represented by 9) are preferred.

The compound represented by general formula (L-5) is the following compound.

(In the formula, R ^L51 and R ^L52 each independently have the same meaning as R ^L1 and R ^L2 in general formula (L), but R ^L52 does not represent an alkoxy group or an alkenyloxy group. , R ^L51 and R ^L52 are each independently preferably an alkyl group having 1 to 5 carbon atoms or an alkenyl group having 2 to 5 carbon atoms.

The compound represented by general formula (L-5) can be used alone, or two or more compounds can be used in combination. The types of compounds that can be combined are not particularly limited, but they are appropriately combined and used according to the required properties such as low-temperature solubility, transition temperature, electrical reliability, and birefringence. The types of compounds to be used are, for example, one type, two types, three types, four types, and five or more types as one embodiment of the present invention.

In the composition of the present invention, the content of the compound represented by the general formula (L-5) is determined by solubility at low temperature, transition temperature, electrical reliability, birefringence, process suitability, drip marks, It is necessary to make appropriate adjustments according to required performance such as image sticking and dielectric anisotropy.

The preferred lower limit of the content of the compound represented by formula (L-5) with respect to the total amount of the composition of the present invention is 1%, 2%, 3%, and 5%. , 7%, 10%, 14%, 16%, 20%, 23%, 26%, 30%, 35%, 40% . The upper limit of the preferable content of the compound represented by formula (L-5) with respect to the total amount of the composition of the present invention is 50%, 40%, 35%, and 30%. , 20%, 15%, 10%, and 5% The compound represented by the general formula (L-5) is represented by the formula (L-5.1), the formula (L-5.2 ) or the compound represented by the formula (L-5.3), and particularly preferably the compound represented by the formula (L-5.1) or the formula (L-5.2).

Preferred lower limits for the content of these compounds with respect to the total amount of the composition of the present invention are 1%, 2%, 3%, 5% and 7%. The preferred upper limits of the content of these compounds are 20%, 15%, 13%, 10% and 9%.

The compound represented by general formula (L-5) is preferably a compound represented by formula (L-5.4) or formula (L-5.5).

Preferred lower limits for the content of these compounds with respect to the total amount of the composition of the present invention are 1%, 2%, 3%, 5% and 7%. The preferred upper limits of the content of these compounds are 20%, 15%, 13%, 10% and 9%.

The compound represented by general formula (L-6) is the following compound.

(wherein R ^L61 and R ^L62 each independently represent the same meaning as R ^L1 and R ^L2 in general formula (L), and X ^L61 , X ^L62 , X ^L63 and X ^L64 each independently represents a hydrogen atom or a fluorine atom, but two or more of X ^L61 to X ^L64 do not represent a fluorine atom at the same time.)
The compounds represented by general formula (L-6) can be used alone, or two or more compounds can be used in combination. The types of compounds that can be combined are not particularly limited, but they are appropriately combined and used according to the required properties such as low-temperature solubility, transition temperature, electrical reliability, and birefringence. The types of compounds to be used are, for example, one type, two types, three types, four types, and five or more types as one embodiment of the present invention.

The preferred lower limit of the content of the compound represented by formula (L-6) with respect to the total amount of the composition of the present invention is 1%, 2%, 3%, and 5%. , 7%, 10%, 14%, 16%, 20%, 23%, 26%, 30%, 35%, 40% . The upper limit of the preferable content of the compound represented by formula (L-6) with respect to the total amount of the composition of the present invention is 50%, 40%, 35%, and 30%. , 20%, 15%, 10%, 5%. When emphasis is placed on increasing Δn, it is preferable to increase the content, and when emphasis is placed on precipitation at low temperature, it is preferable to decrease the content.

The compounds represented by general formula (L-6) are preferably compounds represented by formulas (L-6.1) to (L-6.6).

Although there is no particular limitation on the types of compounds that can be combined, it is preferable to contain 1 to 3 types, more preferably 1 to 4 types from among these compounds.

Preferred lower limits for the content of these compounds with respect to the total amount of the composition of the present invention are 1%, 2%, 3%, 5% and 7%. The preferred upper limits of the content of these compounds are 20%, 15%, 13%, 10% and 9%.

The compound represented by general formula (L-7) is the following compound.

(Wherein, R ^L71 and R ^L72 each independently represent the same meaning as R ^L1 and R ^L2 in general formula (L), A ^L71 and A ^L72 each independently represent A ^L2 and has the same meaning as A ^L3 , but the hydrogen atoms on A ^L71 and A ^L72 may each independently be substituted with a fluorine atom, and Z ^L71 has the same meaning as Z ^L2 in general formula (L); ^XL71 and ^XL72 each independently represent a fluorine atom or a hydrogen atom, but do not represent a fluorine atom at the same time.)
In the formula, R ^L71 and R ^L72 are each independently preferably an alkyl group having 1 to 5 carbon atoms, an alkenyl group having 2 to 5 carbon atoms or an alkoxy group having 1 to 4 carbon atoms, and A ^L71 and A ^L72 are each independently preferably a 1,4-cyclohexylene group or a 1,4-phenylene group, hydrogen atoms on A ^L71 and A ^L72 may each independently be substituted with a fluorine atom, and Z ^L71 is a single A bond or COO- is preferred, a single bond is preferred, and X ^L71 and X ^L72 are preferably hydrogen atoms.

Although there is no particular limitation on the types of compounds that can be combined, they are combined according to the required properties such as low-temperature solubility, transition temperature, electrical reliability, and birefringence. The types of compounds to be used are, for example, one type, two types, three types, and four types as one embodiment of the present invention.

In the composition of the present invention, the content of the compound represented by the general formula (L-7) is determined by solubility at low temperature, transition temperature, electrical reliability, birefringence, process suitability, drip marks, It is necessary to make appropriate adjustments according to required performance such as image sticking and dielectric anisotropy.

The preferred lower limit of the content of the compound represented by formula (L-7) with respect to the total amount of the composition of the present invention is 1%, 2%, 3%, and 5%. , 7%, 10%, 14%, 16%, and 20%. The upper limit of the preferable content of the compound represented by formula (L-7) with respect to the total amount of the composition of the present invention is 30%, 25%, 23%, and 20%. , 18%, 15%, 10%, and 5%.

It is preferable to increase the content of the compound represented by formula (L-7) when a high T _ni embodiment of the composition of the present invention is desired, and when a low viscosity embodiment is desired. A small amount is preferred.

Furthermore, the compound represented by general formula (L-7) is preferably a compound represented by formula (L-7.11) to formula (L-7.13), and the compound represented by formula (L-7. A compound represented by 11) is preferable.

Further, the compounds represented by general formula (L-7) are the compounds represented by formulas (L-7.21) to (L-7.23). A compound represented by formula (L-7.21) is preferred.

Furthermore, the compound represented by general formula (L-7) is preferably a compound represented by formula (L-7.31) to formula (L-7.34), and the compound represented by formula (L-7. 31) or/and a compound represented by formula (L-7.32).

Furthermore, the compound represented by general formula (L-7) is preferably a compound represented by formula (L-7.41) to formula (L-7.44), and the compound represented by formula (L-7. 41) or/and a compound represented by formula (L-7.42).

Further, the compounds represented by general formula (L-7) are preferably compounds represented by formulas (L-7.51) to (L-7.53).

The liquid crystal composition of the present invention contains, as a third component, one or two or more compounds selected from the group of compounds represented by general formula (N-1d) and/or general formula (N-1) described later. contains.

The compound represented by the general formula (N-1d) corresponds to a dielectrically negative compound (the sign of Δε is negative and its absolute value is greater than 2). Only one kind of the compound represented by the general formula (N-1d) may be used, or two or more kinds thereof may be used.

(wherein R ^{3 Nd11} and R ^{3 Nd12} each independently represent an alkyl group having 1 to 8 carbon atoms, and one or two or more non-adjacent —CH ₂ — in the alkyl group are each independently may be substituted by -CH=CH-, -C≡C-, -O-, -CO-, -COO- or -OCO-, and ^nNd11 represents 1, 2 or 3.)
In general formula (N-1d), R ^Nd11 is 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 a An alkenyloxy group is preferred, an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, an alkenyl group having 2 to 5 carbon atoms or an alkenyloxy group having 2 to 5 carbon atoms is preferred. More preferably an alkyl group having 1 to 5 atoms or an alkenyl group having 2 to 5 carbon atoms, more preferably an alkyl group having 2 to 5 carbon atoms or an alkenyl group having 2 to 3 carbon atoms, Alkenyl groups (propenyl groups) are particularly preferred. A linear alkyl group having 1 to 5 carbon atoms, a linear alkoxy group having 1 to 4 carbon atoms and a linear alkenyl group having 2 to 5 carbon atoms are preferred. In order to stabilize the nematic phase, the total number of carbon atoms and, if present, oxygen atoms is preferably 5 or less, and is preferably linear. Especially preferred is the propyl group. R ^Nd12 is preferably 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 alkenyloxy group having 2 to 8 carbon atoms, and Alkyl groups having 1 to 5 carbon atoms, alkoxy groups having 1 to 5 carbon atoms, alkenyl groups having 2 to 5 carbon atoms or alkenyloxy groups having 2 to 5 carbon atoms are preferred, and alkyl groups having 1 to 5 carbon atoms or An alkenyl group having 2 to 5 carbon atoms is more preferable, an alkyl group having 2 to 5 carbon atoms or an alkenyl group having 2 to 3 carbon atoms is more preferable, and an alkenyl group having 3 carbon atoms (propenyl group) is particularly preferable. . A linear alkyl group having 1 to 5 carbon atoms, a linear alkoxy group having 1 to 4 carbon atoms and a linear alkenyl group having 2 to 5 carbon atoms are preferred. In order to stabilize the nematic phase, the total number of carbon atoms and, if present, oxygen atoms is preferably 5 or less, and is preferably linear. Particular preference is given to methoxy and ethoxy groups.

In general formula (N-1d), n ^Nd11 is preferably 1 or 2, and it is preferable to include both a compound in which n ^Nd11 is 1 and a compound in which n ^Nd11 is 2, and a compound in which n ^Nd11 is 2. It is also preferred to contain only

The compound represented by the general formula (N-1d) is preferably the compound represented by the compound represented by the general formula (N-1-10) and the compound represented by the general formula (N-1-11). .

The compound represented by general formula (N-1-10) is the following compound.

(In the formula, R ^N1101 and R ^N1102 each independently have the same meaning as R ^Nd11 and R ^Nd12 in general formula (N-1d).)
R ^N1101 is preferably an alkyl group having 1 to 5 carbon atoms or an alkenyl group having 2 to 5 carbon atoms, preferably an ethyl group, a propyl group, a butyl group, a vinyl group or a 1-propenyl group. ^RN1102 is preferably an alkyl group having 1 to 5 carbon atoms, an alkenyl group having 4 to 5 carbon atoms or an alkoxy group having 1 to 4 carbon atoms, and preferably an ethoxy group, a propoxy group or a butoxy group.

The compounds represented by general formula (N-1-10) can be used alone, or two or more compounds can be used in combination. The types of compounds that can be combined are not particularly limited, but they are appropriately combined and used according to the required properties such as low-temperature solubility, transition temperature, electrical reliability, and birefringence. The types of compounds to be used are, for example, one type, two types, three types, four types, and five or more types as one embodiment of the present invention.

When emphasizing the improvement of Δε, it is preferable to set the content higher, when emphasizing solubility at low temperatures, setting the content higher is more effective, and when emphasizing _TNI , the content A higher setting is more effective. Furthermore, in order to improve drip marks and seizure properties, it is preferable to set the range of the content in the middle.

The lower limit of the preferable content of the compound represented by formula (N-1-10) with respect to the total amount of the composition of the present invention is 5%, 10%, 13%, 15% , 17%, and 20%. Preferred upper limits of the content are 35%, 30%, 28%, 25%, 23%, 20%, 18%, relative to the total amount of the composition of the present invention. %, 15%, 13%.

Furthermore, the compound represented by general formula (N-1-10) is a compound selected from the group of compounds represented by formulas (N-1-10.1) to (N-1-10.14). Is preferably, more preferably a compound represented by formula (N-1-10.1) to (N-1-10.5), formula (N-1-10.1), or formula A compound represented by (N-1-10.2) is more preferable, and a compound represented by formula (N-1-10.2) is particularly preferable.

The compound represented by general formula (N-1-11) is the following compound.

(In the formula, R ^N1111 and R ^N1112 each independently have the same meaning as R ^Nd11 and R ^Nd12 in general formula (N-1d).)
R ^N1111 is preferably an alkyl group having 1 to 5 carbon atoms or an alkenyl group having 2 to 5 carbon atoms, preferably an ethyl group, a propyl group, a butyl group, a vinyl group or a 1-propenyl group. ^RN1112 is preferably an alkyl group having 1 to 5 carbon atoms, an alkenyl group having 4 to 5 carbon atoms or an alkoxy group having 1 to 4 carbon atoms, and preferably an ethoxy group, a propoxy group or a butoxy group.

The compounds represented by general formula (N-1-11) can be used alone, or two or more compounds can be used in combination. The types of compounds that can be combined are not particularly limited, but they are appropriately combined and used according to the required properties such as low-temperature solubility, transition temperature, electrical reliability, and birefringence. The types of compounds to be used are, for example, one type, two types, three types, four types, and five or more types as one embodiment of the present invention.

When emphasizing the improvement of Δε, it is preferable to set the content higher, when emphasizing solubility at low temperatures, setting the content lower is more effective, and when emphasizing _TNI , the content A higher setting is more effective. Furthermore, in order to improve drip marks and seizure properties, it is preferable to set the range of the content in the middle.

The lower limit of the preferable content of the compound represented by formula (N-1-11) with respect to the total amount of the composition of the present invention is 5%, 10%, 13%, 15% , 17%, and 20%. Preferred upper limits of the content are 35%, 30%, 28%, 25%, 23%, 20%, 18%, relative to the total amount of the composition of the present invention. %, 15%, 13%.

Furthermore, the compound represented by general formula (N-1-11) is a compound selected from the group of compounds represented by formulas (N-1-11.1) to (N-1-11.14). is preferably a compound represented by the formula (N-1-11.1) to (N-1-11.4), and the formula (N-1-11.2) and the formula ( Further preferred are compounds represented by N-1-11.4).

Compounds represented by formula (N-1d) include formula (N-1-10.1), formula (N-1-10.2), formula (N-1-11.2), formula (N -1-11.4) and formula (N-1-11.14), it is preferable to use one or more compounds selected from the group of compounds represented by formula (N-1-11.14).

The compound represented by the general formula (N-1) corresponds to a dielectrically negative compound (the sign of Δε is negative and its absolute value is greater than 2). The compound represented by the general formula (N-1) is preferably a compound having a negative Δε and an absolute value of 3 or more. Further, only one kind of the compound represented by the general formula (N-1) may be used, or two or more kinds thereof may be used.

(wherein R ^N11 and R ^N12 each independently represent an alkyl group having 1 to 8 carbon atoms, and one or two or more non-adjacent —CH ₂ — in the alkyl group each independently may be substituted by -CH=CH-, -C≡C-, -O-, -CO-, -COO- or -OCO-, and n ^N11 and n ^N12 are each independently 0, 1 , 2 or 3, wherein n ^N11 +n ^N12 represents 1, 2 or 3, A ^N11 and A ^N12 each independently
(a) a 1,4-cyclohexylene group (one —CH ₂ — present in this group or two or more non-adjacent —CH ₂ — may be replaced with —O—),
(b) a 1,4-phenylene group (one -CH= or two or more non-adjacent -CH= present in this group may be replaced with -N=) and (c) naphthalene-2,6-diyl group, 1,2,3,4-tetrahydronaphthalene-2,6-diyl group or decahydronaphthalene-2,6-diyl group (naphthalene-2,6-diyl group or 1,2 , 1 -CH= or two or more non-adjacent -CH= present in the 3,4-tetrahydronaphthalene-2,6-diyl group may be replaced with -N=.)
represents a group selected from the group consisting of, and the above groups (a), (b) and (c) each independently represent an alkyl group (one —CH ₂ — present in this group or adjacent two or more —CH ₂ — that are not adjacent may be replaced by —O—), an alkenyl group (one —CH ₂ — present in this group, or two or more —CH ₂ — may be replaced with —O—.), may be substituted with a cyano group, a fluorine atom or a chlorine atom, and Z ^N11 and Z ^N12 are each independently a single bond, —CH ₂ CH ₂ -, -(CH ₂ ) ₄ -, -OCH ₂ -, -CH ₂ O-, -COO-, -OCO-, -OCF _{2 -, -CF 2 O-} , -CH=N-N=CH-, -CH=CH-, -CF=CF- or -C≡C-, and when there are a plurality of A ^N11 and/or A ^N12 , they may be the same or different, and Z ^N11 and /or when a plurality of Z ^N12 are present, they may be the same or different, except for compounds represented by general formula (N-1d). )
In general formula (N-1), R ¹¹ and R ¹² 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 Alkenyloxy groups having 2 to 8 carbon atoms are preferred, alkyl groups having 1 to 5 carbon atoms, alkoxy groups having 1 to 5 carbon atoms, alkenyl groups having 2 to 5 carbon atoms or An alkenyloxy group is preferred, an alkyl group having 1 to 5 carbon atoms or an alkenyl group having 2 to 5 carbon atoms is more preferred, and an alkyl group having 2 to 5 carbon atoms or an alkenyl group having 2 to 3 carbon atoms is further preferred. An alkyl group having 3 carbon atoms or a propenyl group is particularly preferred.

Further, when the ring structure to which it is bonded is a phenyl group (aromatic), a linear alkyl group having 1 to 5 carbon atoms, a linear alkoxy group having 1 to 4 carbon atoms and carbon An alkenyl group having 4 to 5 atoms is preferable, and when the ring structure to which it is bonded is a saturated ring structure such as cyclohexane, pyran and dioxane, a linear alkyl group having 1 to 5 carbon atoms, a linear C 1 -C 4 alkoxy groups and linear C 2 -C 5 alkenyl groups are preferred. In order to stabilize the nematic phase, the total number of carbon atoms and, if present, oxygen atoms is preferably 5 or less, and is preferably linear.

The alkenyl group is preferably selected from groups represented by any one of formulas (R1) to (R5). (The black dots in each formula represent carbon atoms in the ring structure.)

Preferred are alkyl groups having 1 to 5 carbon atoms and alkoxy groups having 1 to 5 carbon atoms, and they are methyl, ethyl, propyl, methoxy, ethoxy and propoxy groups.

A ^N11 and A ^N12 are preferably aromatic when it is required to independently increase Δn, preferably aliphatic in order to improve the response speed, trans-1,4 -cyclohexylene group, 1,4-phenylene group, 2-fluoro-1,4-phenylene group, 3-fluoro-1,4-phenylene group, 3,5-difluoro-1,4-phenylene group, 2, 3-difluoro-1,4-phenylene group, 1,4-cyclohexenylene group, 1,4-bicyclo[2.2.2]octylene group, piperidine-1,4-diyl group, naphthalene-2,6- It preferably represents a diyl group, decahydronaphthalene-2,6-diyl group or 1,2,3,4-tetrahydronaphthalene-2,6-diyl group, more preferably represents the following structure,

A trans-1,4-cyclohexylene group, a 1,4-cyclohexenylene group or a 1,4-phenylene group is preferred, and a trans-1,4-cyclohexylene group or 1,4-phenylene group is more preferred.

Z ^N11 and Z ^N12 preferably each independently represent -CH ₂ O-, -CF ₂ O-, -CH ₂ CH ₂ -, -CF ₂ CF ₂ - or a single bond, and -CH ₂ O-, —CH ₂ CH ₂ — or a single bond is more preferred, and —CH ₂ O— or a single bond is particularly preferred.

^nN11 + ^nN12 is preferably 1 or ² , a combination where ^nN11 is ¹ and ^nN12 is 0, a combination where ^nN11 is 2 and ^nN12 is 0, One combination, where ^nN11 is 2 and ^nN12 is 1, is preferred. However, compounds represented by general formula (N-1d) are excluded. Liquid crystal compounds having a terphenyl skeleton and negative dielectric anisotropy are also excluded.

The lower limit of the preferable content of the compound represented by the general formula (N-1) with respect to the total amount of the composition of the present invention is 1%, 10%, 20%, and 30%. Yes, 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% is.

The preferred lower limit of the total content of the compound represented by the general formula (N-1d) and the compound represented by the general formula (N-1) with respect to the total amount of the composition of the present invention is 1%. Yes, 10%, 20%, 30%, 40%, 50%, 55%, 60%, 65%, 70%, 75% Yes, 80%. The upper limit of the preferred content is 95%, 85%, 75%, 65%, 55%, 45%, 35%, 25%, 20% is.

Specifically, the compound represented by general formula (N-1) is a compound selected from the group of compounds represented by general formulas (N-1-1) to (N-1-18). preferable.

The compound represented by general formula (N-1-1) is the following compound.

(In the formula, R ^N111 represents an alkyl group having 1 to 5 carbon atoms or an alkenyl group having 2 to 5 carbon atoms, and R ^N112 represents an alkyl group having 1 to 5 carbon atoms or an alkoxy group having 1 to 4 carbon atoms. represents a group.)
R ^N111 is preferably an alkyl group having 1 to 5 carbon atoms or an alkenyl group having 2 to 5 carbon atoms, preferably a propyl group, a pentyl group or a vinyl group. R ^N112 is preferably an alkyl group having 1 to 5 carbon atoms, an alkenyl group having 4 to 5 carbon atoms, or an alkoxy group having 1 to 4 carbon atoms, preferably an ethoxy group or a butoxy group.

The compounds represented by general formula (N-1-1) can be used alone, or two or more compounds can be used in combination. The types of compounds that can be combined are not particularly limited, but they are appropriately combined and used according to the required properties such as low-temperature solubility, transition temperature, electrical reliability, and birefringence. The types of compounds to be used are, for example, one type, two types, three types, four types, and five or more types as one embodiment of the present invention.

When emphasizing the improvement of Δε, it is preferable to set the content higher, when emphasizing the solubility at low temperatures, setting the _content a little higher is more effective, It is effective when set to a small value. Furthermore, in order to improve drip marks and seizure properties, it is preferable to set the range of the content in the middle.

The lower limit of the preferable content of the compound represented by formula (N-1-1) with respect to the total amount of the composition of the present invention is 5%, 10%, 13%, 15% , 17%, 20%, 23%, 25%, 27%, 30%, 33%, 35%. Preferred upper limits of the content are 50%, 40%, 38%, 35%, 33%, 30%, and 28% of the total amount of the composition of the present invention. %, 25%, 23%, 20%, 18%, 15%, 13%, 10%, 8%, 7%, 6 %, 5%, 3%.

Furthermore, the compound represented by general formula (N-1-1) is a compound selected from the group of compounds represented by formulas (N-1-1.1) to (N-1-1.23). is preferably a compound represented by formulas (N-1-1.1) to (N-1-1.4), and formulas (N-1-1.1) and formulas (N -1-1.3) is preferred.

The compounds represented by formulas (N-1-1.1) to (N-1-1.22) can be used alone or in combination, but the composition of the present invention The lower limits of the preferred content of these compounds alone or of these compounds with respect to the total amount are 5%, 10%, 13%, 15%, 17%, 20%, and 23%. , 25%, 27%, 30%, 33%, 35%. Preferred upper limits of the content are 50%, 40%, 38%, 35%, 33%, 30%, and 28% of the total amount of the composition of the present invention. %, 25%, 23%, 20%, 18%, 15%, 13%, 10%, 8%, 7%, 6 %, 5%, 3%.

The compound represented by general formula (N-1-2) is the following compound.

(In the formula, R ^N121 represents an alkyl group having 1 to 5 carbon atoms or an alkenyl group having 2 to 5 carbon atoms, and R ^N122 represents an alkyl group having 1 to 5 carbon atoms or an alkoxy group having 1 to 4 carbon atoms. represents a group.)
R ^N121 is preferably an alkyl group having 1 to 5 carbon atoms or an alkenyl group having 2 to 5 carbon atoms, preferably an ethyl group, a propyl group, a butyl group or a pentyl group. R ^N122 is preferably an alkyl group having 1 to 5 carbon atoms, an alkenyl group having 4 to 5 carbon atoms or an alkoxy group having 1 to 4 carbon atoms, and is preferably a methyl group, a propyl group, a methoxy group, an ethoxy group or a propoxy group. preferable.

The compounds represented by general formula (N-1-2) can be used alone, or two or more compounds can be used in combination. The types of compounds that can be combined are not particularly limited, but they are appropriately combined and used according to the required properties such as low-temperature solubility, transition temperature, electrical reliability, and birefringence. The types of compounds to be used are, for example, one type, two types, three types, four types, and five or more types as one embodiment of the present invention.

When emphasizing the improvement of Δε, it is preferable to set the content higher, and when emphasizing the solubility at low temperatures, setting the content _lower is more effective. The effect is high when set to a large amount. Furthermore, in order to improve drip marks and seizure properties, it is preferable to set the range of the content in the middle.

The lower limit of the preferred content of the compound represented by formula (N-1-2) with respect to the total amount of the composition of the present invention is 5%, 7%, 10%, and 13%. , 15%, 17%, 20%, 23%, 25%, 27%, 30%, 33%, 35%, 37% , 40%, and 42%. Preferred upper limits of the content are 50%, 48%, 45%, 43%, 40%, 38%, and 35% of the total amount of the composition of the present invention. %, 33%, 30%, 28%, 25%, 23%, 20%, 18%, 15%, 13%, 10 %, 8%, 7%, 6%, 5%.

Further, the compound represented by general formula (N-1-2) is a compound selected from the group of compounds represented by formulas (N-1-2.1) to (N-1-2.22). Preferably, there are formulas (N-1-2.3) to formulas (N-1-2.7), formulas (N-1-2.10), formulas (N-1-2.11), formulas Compounds represented by (N-1-2.13) and formula (N-1-2.20) are preferable, and when emphasizing improvement of Δε, formula (N-1-2.3) A compound represented by the formula (N-1-2.7) is preferable, and when emphasizing the improvement of _TNI , the formula (N-1-2.10), the formula (N-1-2.11) And it is preferably a compound represented by formula (N-1-2.13), and when emphasis is placed on improving the response speed, it is a compound represented by formula (N-1-2.20) is preferred.

The compounds represented by formulas (N-1-2.1) to (N-1-2.22) can be used alone or in combination, but the composition of the present invention The lower limit of the preferred content of these compounds alone or with respect to the total amount of is 5%, 10%, 13%, 15%, 17%, 20%, 23 %, 25%, 27%, 30%, 33%, 35%. Preferred upper limits of the content are 50%, 40%, 38%, 35%, 33%, 30%, and 28% of the total amount of the composition of the present invention. %, 25%, 23%, 20%, 18%, 15%, 13%, 10%, 8%, 7%, 6 %, 5%, 3%.

The compound represented by general formula (N-1-3) is the following compound.

(In the formula, R ^N131 represents an alkyl group having 1 to 5 carbon atoms or an alkenyl group having 2 to 5 carbon atoms, and R ^N132 represents an alkyl group having 1 to 5 carbon atoms or an alkoxy group having 1 to 4 carbon atoms. represents a group.)
R ^N131 is preferably an alkyl group having 1 to 5 carbon atoms or an alkenyl group having 2 to 5 carbon atoms, preferably an ethyl group, a propyl group or a butyl group. R ^N132 is preferably an alkyl group having 1 to 5 carbon atoms, an alkenyl group having 3 to 5 carbon atoms or an alkoxy group having 1 to 4 carbon atoms, preferably a 1-propenyl group, an ethoxy group, a propoxy group or a butoxy group. .

The compound represented by general formula (N-1-3) can be used alone, or two or more compounds can be used in combination. The types of compounds that can be combined are not particularly limited, but they are appropriately combined and used according to the required properties such as low-temperature solubility, transition temperature, electrical reliability, and birefringence. The types of compounds to be used are, for example, one type, two types, three types, four types, and five or more types as one embodiment of the present invention.

When emphasizing the improvement of Δε, it is preferable to set the content higher, when emphasizing the solubility at low temperatures, setting the _content a little higher is more effective, It is highly effective when set roughly. Furthermore, in order to improve drip marks and seizure properties, it is preferable to set the range of the content in the middle.

The lower limit of the preferable content of the compound represented by formula (N-1-3) with respect to the total amount of the composition of the present invention is 5%, 10%, 13%, 15% , 17%, and 20%. Preferred upper limits of the content are 35%, 30%, 28%, 25%, 23%, 20%, 18%, relative to the total amount of the composition of the present invention. %, 15%, 13%.

Furthermore, the compound represented by general formula (N-1-3) is a compound selected from the group of compounds represented by formulas (N-1-3.1) to (N-1-3.21). is preferably a compound represented by formulas (N-1-3.1) to (N-1-3.7) and formula (N-1-3.21), and formula (N -1-3.1), formula (N-1-3.2), formula (N-1-3.3), formula (N-1-3.4) and formula (N-1-3.6 ) are preferred.

Compounds represented by formula (N-1-3.1) to formula (N-1-3.4), formula (N-1-3.6) and formula (N-1-3.21) are alone can be used in combination, but the combination of formula (N-1-3.1) and formula (N-1-3.2), formula (N-1-3.3 ), formulas (N-1-3.4) and formulas (N-1-3.6). The lower limits of the preferred content of these compounds alone or of these compounds with respect to the total amount of the composition of the present invention are 5%, 10%, 13%, 15%, 17%, 20 %. Preferred upper limits of the content are 35%, 30%, 28%, 25%, 23%, 20%, 18%, relative to the total amount of the composition of the present invention. %, 15%, 13%.

The compound represented by general formula (N-1-4) is the following compound.

(In the formula, R ^N141 represents an alkyl group having 1 to 5 carbon atoms or an alkenyl group having 2 to 5 carbon atoms, and R ^N142 represents an alkyl group having 1 to 5 carbon atoms or an alkoxy group having 1 to 4 carbon atoms. represents a group.)
R ^N141 and R ^N142 are each independently preferably an alkyl group having 1 to 5 carbon atoms, an alkenyl group having 4 to 5 carbon atoms or an alkoxy group having 1 to 4 carbon atoms, methyl group, propyl group, ethoxy or butoxy groups are preferred.

The compounds represented by general formula (N-1-4) can be used alone, or two or more compounds can be used in combination. The types of compounds that can be combined are not particularly limited, but they are appropriately combined and used according to the required properties such as low-temperature solubility, transition temperature, electrical reliability, and birefringence. The types of compounds to be used are, for example, one type, two types, three types, four types, and five or more types as one embodiment of the present invention.

When emphasizing the improvement of Δε, it is preferable to set the content higher, when emphasizing the solubility at low temperatures, setting the _content a little higher is more effective, It is effective when set to a small value. Furthermore, in order to improve drip marks and seizure properties, it is preferable to set the range of the content in the middle.

Preferred lower limits for the content of the compound represented by formula (N-1-4) with respect to the total amount of the composition of the present invention are 3%, 5%, 7%, and 10%. , 13%, 15%, 17%, and 20%. Preferred upper limits of the content are 35%, 30%, 28%, 25%, 23%, 20%, 18%, relative to the total amount of the composition of the present invention. %, 15%, 13%, 11%, 10%, 8%.

Furthermore, the compound represented by general formula (N-1-4) is a compound selected from the group of compounds represented by formulas (N-1-4.1) to (N-1-4.14). is preferably a compound represented by formulas (N-1-4.1) to (N-1-4.4), formula (N-1-4.1), formula (N -1-4.2) and compounds represented by formula (N-1-4.4) are preferred.

The compounds represented by formulas (N-1-4.1) to (N-1-4.14) can be used alone or in combination, but the composition of the present invention The lower limits of the preferable content of these compounds alone or of these compounds with respect to the total amount are 3%, 5%, 7%, 10%, 13%, 15%, and 17%. and 20%. Preferred upper limits of the content are 35%, 30%, 28%, 25%, 23%, 20%, 18%, relative to the total amount of the composition of the present invention. %, 15%, 13%, 11%, 10%, 8%.

The compound represented by general formula (N-1-16) is the following compound.

(In the formula, ^RN1161 represents an alkyl group having 1 to 5 carbon atoms or an alkenyl group having 2 to 5 carbon atoms, and ^RN1162 represents an alkyl group having 1 to 5 carbon atoms or an alkoxy group having 1 to 4 carbon atoms. represents a group.)
^RN1161 is preferably an alkyl group having 1 to 5 carbon atoms or an alkenyl group having 2 to 5 carbon atoms, preferably an ethyl group, a propyl group or a butyl group. R ^N1162 is preferably an alkyl group having 1 to 5 carbon atoms, an alkenyl group having 4 to 5 carbon atoms or an alkoxy group having 1 to 4 carbon atoms, and preferably an ethoxy group, a propoxy group or a butoxy group.

The compound represented by general formula (N-1-16) can be used alone, or two or more compounds can be used in combination. The types of compounds that can be combined are not particularly limited, but they are appropriately combined and used according to the required properties such as low-temperature solubility, transition temperature, electrical reliability, and birefringence. The types of compounds to be used are, for example, one type, two types, three types, four types, and five or more types as one embodiment of the present invention.

When emphasizing the improvement of Δε, it is preferable to set the content higher, when emphasizing the solubility at low temperatures, setting the _content a little higher is more effective, It is highly effective when set roughly. Furthermore, in order to improve drip marks and seizure properties, it is preferable to set the range of the content in the middle.

The lower limit of the preferable content of the compound represented by formula (N-1-16) with respect to the total amount of the composition of the present invention is 5%, 10%, 13%, 15% , 17%, and 20%. Preferred upper limits of the content are 35%, 30%, 28%, 25%, 23%, 20%, 18%, relative to the total amount of the composition of the present invention. %, 15%, 13%.

The compound represented by general formula (N-1-18) is the following compound.

(In the formula, ^RN1181 represents an alkyl group having 1 to 5 carbon atoms or an alkenyl group having 2 to 5 carbon atoms, and ^RN1182 represents an alkyl group having 1 to 5 carbon atoms or an alkoxy group having 1 to 4 carbon atoms. represents a group.)
^RN1181 is preferably an alkyl group having 1 to 5 carbon atoms or an alkenyl group having 2 to 5 carbon atoms, preferably a methyl group, an ethyl group, a propyl group or a butyl group. ^RN1182 is preferably an alkyl group having 1 to 5 carbon atoms, an alkenyl group having 4 to 5 carbon atoms or an alkoxy group having 1 to 4 carbon atoms, and preferably an ethoxy group, a propoxy group or a butoxy group.

The compound represented by general formula (N-1-18) can be used alone, or two or more compounds can be used in combination. The types of compounds that can be combined are not particularly limited, but they are appropriately combined and used according to the required properties such as low-temperature solubility, transition temperature, electrical reliability, and birefringence. The types of compounds to be used are, for example, one type, two types, three types, four types, and five or more types as one embodiment of the present invention.

When emphasizing the improvement of Δε, it is preferable to set the content higher, when emphasizing the solubility at low temperatures, setting the _content a little higher is more effective, It is highly effective when set roughly. Furthermore, in order to improve drip marks and seizure properties, it is preferable to set the range of the content in the middle.

The lower limit of the preferable content of the compound represented by formula (N-1-18) with respect to the total amount of the composition of the present invention is 5%, 10%, 13%, 15% , 17%, and 20%. Preferred upper limits of the content are 35%, 30%, 28%, 25%, 23%, 20%, 18%, relative to the total amount of the composition of the present invention. %, 15%, 13%.

Furthermore, the compound represented by general formula (N-1-18) is a compound selected from the group of compounds represented by formulas (N-1-18.1) to (N-1-18.5). is preferably a compound represented by the formula (N-1-18.1) to (N-1-11.3), the formula (N-1-18.2 and the formula (N- 1-18.3) are preferred.

The liquid crystal composition of the present invention contains a polymerizable compound represented by general formula (II) as a fourth component.

(wherein R ²⁰¹ , R ²⁰² , R ²⁰³ , R ²⁰⁴ , R ²⁰⁵ , R 206 , R ²⁰⁷ , R ^{208 ,} R ²⁰⁹ and R ²¹⁰ are each independently P ²¹ -S ²¹ -, a fluorine atom, an alkyl group having 1 to 18 carbon atoms which may be substituted, 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 from formula (R-1) to formula (R-7)

(wherein R ¹¹ , R ¹² , R ¹³ , R ¹⁴ and R ¹⁵ each independently represent an alkyl group having 1 to 5 carbon atoms, a fluorine atom or a hydrogen atom, m ^r5 , m ^r7 , ^nr5 and ^nr7 each independently represent 0, 1, or 2, but are not directly adjacent to an oxygen atom.), ^S21 represents a single bond or represents an alkylene group having 1 to 15 carbon atoms, and one or more —CH ₂ — in the alkylene group are —O—, —OCO— or —COO— so that oxygen atoms are not directly adjacent to each other. and n ²¹ represents 0, 1 or 2, and A ²¹ is
(a) 1,4-cyclohexylene group (one —CH ₂ — present in this group or two or more non-adjacent —CH ₂ — may be replaced with —O—);
(b) a 1,4-phenylene group (one -CH= or two or more non-adjacent -CH= present in this group may be replaced with -N=) and (c) naphthalene-2,6-diyl group, 1,2,3,4-tetrahydronaphthalene-2,6-diyl group or decahydronaphthalene-2,6-diyl group (naphthalene-2,6-diyl group or 1,2 , 1 -CH= or two or more non-adjacent -CH= present in the 3,4-tetrahydronaphthalene-2,6-diyl group may be replaced with -N=.)
represents a group selected from the group consisting of, and the above groups (a), (b) and (c) are each independently an alkyl group having 1 to 12 carbon atoms, an alkyl group having 1 to 12 carbon atoms, optionally substituted with an alkoxy group, halogen, cyano group, nitro group or P ²¹ -S ²¹ -, having at least one or more P ²¹ -S ²¹ - in one molecule of general formula (II), L ²¹ is a single bond, -OCH ₂ -, -CH ₂ O-, -C ₂ H ₄ -, -OC ₂ H ₄ O-, -COO-, -OCO-, -CH=CR ^a -COO-, - CH=CR ^a -OCO-, -COO-CR ^a =CH-, -OCO-CR ^a =CH-, -(CH ₂ ) _z -COO-, -(CH ₂ ) _z -OCO-, -OCO-( CH ₂ ) _z —, —COO—(CH ₂ ) _z —, —CH═CH—, —CF ₂ O—, —OCF ₂ — or —C≡C— (wherein each R ^a is independently hydrogen represents an atom or an alkyl group having 1 to 3 carbon atoms, wherein z each independently represents an integer of 1 to 4), but there are a plurality of P ²¹ , S ²¹ and A ²¹ case, they may be the same or different. )
In general formula (II), the compound represented by general formula (II) preferably has 1 or 2 or more P ²¹ -S ²¹ - in one molecule, and 4 or less P ²¹ -S ²¹ -. The number of P ²¹ —S ²¹ — present in one molecule of the general formula (II) is preferably 1 or more and 4 or less, more preferably 1 or more and 3 or less, and in the general formula (II) It is particularly preferred that the number of P ²¹ —S ²¹ — in the molecule of the represented compound is 2 or 3. That is, the compound represented by general formula (II) has a ^{structure in which at least two benzene rings and, if necessary, ring A 21 are linked, and the plurality of benzene rings and ring A 21 have} P ²¹ -S ²¹ - Since it has at least one, the compound represented by the general formula (II) exhibits actions and effects as a polymerizable compound.

In the general formula (II), one or more selected from the group consisting of R ²⁰¹ , R ²⁰² , R ²⁰³ , R ²⁰⁴ , R ²⁰⁵ , R ²⁰⁶ , R ²⁰⁷ , R ²⁰⁸ , R ²⁰⁹ and R ²¹⁰ is P ²¹ -S ²¹ -, any one or more of R ²⁰¹ , R ²⁰² , R ²⁰⁴ , R ²⁰⁷ , R ²⁰⁹ or R ²¹⁰ is preferably P ²¹ -S ²¹ - , R ²⁰¹ and R ²¹⁰ are P ²¹ —S ²¹ —.

In general formula (II) above, R ²⁰¹ and R ²¹⁰ are each independently preferably P ²¹ -S ²¹ -, in which case R ²⁰¹ and R ²¹⁰ are the same P ²¹ -S ²¹ - or different P ²¹ -S ²¹ -.

In general formula (II) above, R ²⁰¹ , R ²⁰² , R ²⁰³ , R ²⁰⁴ , R 205 , R ²⁰⁶ , R ²⁰⁷ , ^{R 208 ,} R ²⁰⁹ and R ²¹⁰ are each independently P ²¹ -S ²¹ - , an alkyl group having 1 to 18 carbon atoms which may be substituted with a fluorine atom, an alkoxy group having 1 to 18 carbon atoms which may be substituted with a fluorine atom, a fluorine atom or a hydrogen atom, but this In the case, the number of carbon atoms of the alkyl group and alkoxy group is preferably 1 to 16, more preferably 1 to 10, still more preferably 1 to 8, still more preferably 1 to 6, and further It is more preferably 1 to 4, and particularly preferably 1 to 3. In addition, the alkyl group and alkoxy group may be linear or branched, but are particularly preferably linear.

In general formula (II) above, R ²⁰² , R ²⁰³ , R ²⁰⁴ , R ²⁰⁵ , R ^{206 , R 207 ,} R ²⁰⁸ and R ²⁰⁹ are each independently P ²¹ -S ²¹ -, having 1 to 3 alkyl group, alkoxy group having 1 to 3 carbon atoms, fluorine atom or hydrogen atom, more preferably P ²¹ —S ²¹ —, methyl group, methoxy group, fluorine atom or hydrogen atom , a methyl group, a methoxy group, a fluorine atom or a hydrogen atom.

P ²¹ preferably has the formula (R-1), more preferably an acryl group or a methacryl group, even more preferably a methacryl group.

^S21 is preferably a single bond or an alkylene group having 1 to 3 carbon atoms, more preferably a single bond.

In the above general formula (II), ⁿ²¹ is preferably 0 or 1.

In general formula (II) above, A ²¹ is preferably a 1,4-phenylene group or a naphthalene-2,6-diyl group, more preferably a 1,4-phenylene group.

In general formula (II) above, L ²¹ is a single bond, -OCH ₂ -, -CH ₂ O-, -C ₂ H ₄ -, -COO-, -OCO-, -CH=CH-COO-, - CH=CH-OCO-, -COO-CH=CH-, -OCO-CH=CH-, -C ₂ H ₄ -COO-, -C ₂ H ₄ -OCO-, -OCO-C ₂ H ₄ -, -COO-C ₂ H ₄ -, -CH=CH-, -CF ₂ O-, -OCF ₂ - or -C≡C- is preferred.

The total content of the polymerizable compound represented by the general formula (II) is 0.01 to 5% by mass, and the lower limit of the content is preferably 0.02% by mass, preferably 0.03% by mass, 0.04% by weight is preferred, 0.05% by weight is preferred, 0.06% by weight is preferred, 0.07% by weight is preferred, 0.08% by weight is preferred, 0.09% by weight is preferred, and 0.07% by weight is preferred. 1% by weight is preferred, 0.15% by weight is preferred, 0.2% by weight is preferred, 0.25% by weight is preferred, 0.3% by weight is preferred, 0.35% by weight is preferred, 0.4% by weight %, preferably 0.5% by mass, preferably 0.55% by mass, and the upper limit of the content is preferably 4.5% by mass, preferably 4% by mass, preferably 3.5% by mass, 3% by mass % is preferred, 2.5% by weight is preferred, 2% by weight is preferred, 1.5% by weight is preferred, 1% by weight is preferred, 0.95% by weight is preferred, 0.9% by weight is preferred, 0.5% by weight is preferred. 85% by weight is preferred, 0.8% by weight is preferred, 0.75% by weight is preferred, 0.7% by weight is preferred, 0.65% by weight is preferred, 0.6% by weight is preferred, 0.55% by weight % is preferred.

The compound represented by general formula (II) according to the present invention is preferably a polymerizable compound represented by general formula (IV).

In the above general formula (IV), R ⁷ and R ⁸ each independently represent any one of the above formulas (R-1) to (R-7), and X ¹ to X ⁸ each independently represents a fluorine atom, a hydrogen atom, a trifluoromethyl group, a trifluoromethoxy group, an alkyl group having 1 to 3 carbon atoms or an alkoxy group having 1 to 3 carbon atoms. In general formula (IV) above, R ⁷ and R ⁸ are each independently preferably a methacryl group or an acryl group.

The compound represented by the general formula (IV) is more preferably one or more selected from the group consisting of general formulas (IV-11) to (IV-19), and the general formula (IV-11), general formula (IV-12), general formula (IV-16) and general formula (IV-17) are particularly preferred.

The hydrogen atoms in the 1,4-phenylene groups in the general formula above are further substituted with -F, -CF ₃ , -CH ₃ or any of formulas (R-1) to (R-7). can be

The total content of the polymerizable compound represented by the general formula (IV) is 0.01 to 5% by mass, and the lower limit of the content is preferably 0.02% by mass, more preferably 0.03% by mass. , preferably 0.04% by mass, preferably 0.05% by mass, preferably 0.06% by mass, preferably 0.07% by mass, preferably 0.08% by mass, preferably 0.09% by mass, 0 .1 wt% is preferred, 0.15 wt% is preferred, 0.2 wt% is preferred, 0.25 wt% is preferred, 0.3 wt% is preferred, 0.35 wt% is preferred, 0.4 % by mass is preferred, 0.5% by mass is preferred, 0.55% by mass is preferred, and the upper limit of the content is preferably 4.5% by mass, preferably 4% by mass, preferably 3.5% by mass, 3 % by weight is preferred, 2.5% by weight is preferred, 2% by weight is preferred, 1.5% by weight is preferred, 1% by weight is preferred, 0.95% by weight is preferred, 0.9% by weight is preferred, 0 .85% by weight is preferred, 0.8% by weight is preferred, 0.75% by weight is preferred, 0.7% by weight is preferred, 0.65% by weight is preferred, 0.6% by weight is preferred, 0.55% by weight is preferred % by weight is preferred.

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 is more preferred, and -2.5 to -5.0 is particularly preferred.

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, more preferably 0.09 to 0.12. Especially preferred. More specifically, it is preferably 0.10 to 0.13 for a thin cell gap and 0.08 to 0.10 for a thick cell gap.

The liquid crystal composition of the present invention has a viscosity (η) at 20° C. of 10 to 50 mPa·s, preferably 10 to 45 mPa·s, more preferably 10 to 40 mPa·s, more preferably 10 to 35 mPa·s. ·s, preferably 10 to 30 mPa·s, more preferably 10 to 25 mPa·s, particularly preferably 10 to 22 mPa·s.

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, more preferably 60 to 160 mPa·s. to 150 mPa s, preferably 60 to 140 mPa s, preferably 60 to 130 mPa s, preferably 60 to 125 mPa s, preferably 60 to 120 mPa s is more preferably 60 to 115 mPa·s, more preferably 60 to 110 mPa·s, and particularly preferably 60 to 100 mPa·s.

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, particularly preferably 70°C to 85°C.

Compounds represented by general formula (i), general formula (L), general formula (N-1d), general formula (N-1) and general formula (II) with respect to the total amount of the composition of the present invention The lower limit of the total preferable content is 80%, 85%, 88%, 90%, 92%, 93%, 94%, 95%, 96%, 97%, 98%, 99%, 100%. Preferred upper limits of the content are 100%, 99%, 98% and 95%.

The preferred lower limit of the total content of the compounds represented by the general formula (i) in the neutral compound (compound represented by the general formula (i) and the compound represented by the general formula (L)) is 0 5%, 1%, 3%, 5%, 7%, 9%, 12%, 15%. Preferred upper limits are 20%, 15%, 12%, 10%, 8%, 6% and 5%.

Preferred lower limits for the total content of the compounds represented by general formula (i) and general formula (L) with respect to the total amount of the liquid crystal composition of the present invention are 5%, 10%, and 15%. %, 20%, 25%, 30%. Preferred upper limits of the content are 70%, 60%, 55%, 50%, 45% and 40%.

In the liquid crystal composition of the present invention, as a combination of neutral compounds, compounds represented by general formulas (i), (L-1), (L-4) and/or (L-5) can be combined. preferable.

In the liquid crystal composition of the present invention, the combination of neutral compounds is preferably a combination of compounds represented by general formulas (i), (L-1-3) and (L-2).

In the liquid crystal composition of the present invention, the combination of neutral compounds is preferably a combination of compounds represented by general formulas (i), (L-1-3) and (L-3).

In the liquid crystal composition of the present invention, in order to speed up the polymerization rate of the polymerizable compound, it is possible to combine the compounds represented by general formulas (i) and (L-3.6) or (L-3.7). preferable.

When the response speed is important, it is preferable to contain a compound having an alkenyl group. The upper limit of the preferred total content of alkenyl group-containing compounds with respect to the total amount of the composition of the present invention is 95%, 90%, 85%, 80%, and 75%. Yes, 70%, 65%, 60%, 55%, 50%, 45%, 40%, 35%, 30%, 25% Yes, 20%, 15%, 10%, 5%.

When reliability is emphasized, it is preferable to reduce the amount of the compound having an alkenyl group. The preferred upper limits of the total content of alkenyl group-containing compounds with respect to the total amount of the composition of the present invention are 30%, 25%, 20%, 15%, and 13%. , 10%, 8%, 5%, 3%, 2%, and 1%, preferably not substantially contained.

The liquid crystal composition of the present invention preferably does not contain a compound having a structure in which oxygen atoms are bonded to each other, such as a peracid (--CO--OO--) structure.

When the reliability and long-term stability of the liquid crystal crude product of the present invention are emphasized, the content of the compound having a carbonyl group is preferably 5% or less, preferably 3%, relative to the total mass of the composition. It is more preferably 1% or less, more preferably 1% or less, and most preferably not substantially contained.

When the stability against UV irradiation is emphasized, the content of the compound substituted with chlorine atoms is preferably 15% or less, preferably 10% or less, relative to the total mass of the composition. % or less, more preferably 5% or less, preferably 3% or less, and even more preferably not substantially contained.

It is preferable to increase the content of compounds having all 6-membered ring structures in the molecule, and the content of compounds having all 6-membered ring structures in the molecule is increased to 80% relative to the total mass of the composition. % or more, more preferably 90% or more, even more preferably 95% or more, and substantially all of the ring structures in the molecule are six-membered rings. most preferably.

In order to improve the tilt stability of the composition, it is preferable to increase the content of the compound having an alkyl group and an alkoxy group in the side chain, and the content of the compound having an alkyl group and an alkoxy group in the side chain is It is preferably 85% or more, preferably 87% or more, preferably 90% or more, preferably 93% or more, preferably 95% or more, relative to the total mass of the composition. is preferred, 98% or more is preferred, and substantially 100% is more preferred. Substantially 100% means 100% excluding polymerizable compounds, stabilizers and additionally contaminating impurities.

In order to suppress deterioration of the composition due to oxidation, it is preferable to reduce the content of the compound having a cyclohexenylene group as a ring structure, and the content of the compound having a cyclohexenylene group is added to the total mass of the composition. On the other hand, it is preferably 10% or less, preferably 8% or less, more preferably 5% or less, preferably 3% or less, and further preferably substantially free.

When emphasizing improvement of viscosity and improvement of Tni, it is possible to reduce the content of a compound having a 2-methylbenzene-1,4-diyl group in the molecule, in which a hydrogen atom may be substituted with a halogen. Preferably, the content of the compound having a 2-methylbenzene-1,4-diyl group in the molecule is 10% or less, preferably 8% or less, relative to the total mass of the composition. , more preferably 5% or less, preferably 3% or less, and even more preferably not substantially contained.

In order to solve the problems of the present invention, the compound represented by the general formula (i) which is the first component, the compound represented by the general formula (L) which is the second component and the general formula which is the third component It is necessary to combine the compound represented by (N-1d) and/or general formula (N-1) with the polymerizable compound represented by general formula (II) as the fourth component.

In the present application, "substantially not contained" means not contained except for unintentionally contained substances.

When monomers are added to the composition of the present invention, polymerization proceeds even in the absence of a polymerization initiator, but a polymerization initiator may be contained to promote polymerization. Examples of polymerization initiators include benzoin ethers, benzophenones, acetophenones, benzyl ketals, acylphosphine oxides and the like.

The liquid crystal composition of the present invention may contain formulas (Q-11) to (Q-14) as antioxidants, and the content thereof is preferably adjusted appropriately within the range of 1 ppm to 1000 ppm.

The liquid crystal composition of the present invention can also contain at least one compound represented by general formula (I-2) as a light stabilizer (HALS).

(In the formula, R ^H1 and R ^H2 each independently represent a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, and M represents an alkylene group having 1 to 15 carbon atoms, but present in M one or more —CH ₂ — are —O—, —CH═CH—, —C≡C—, —CO—, —OCO—, —COO—, trans-1,4-cyclohexylene group, 1, It may be substituted with a 4-phenylene group or naphthalene-2,6-diyl group.)
In general formula (I-2), R ^{1 H1} and R ^{1 H2} are particularly preferably hydrogen atoms. When it is an alkyl group, it preferably has 1 to 8 carbon atoms, more preferably 1 to 5 carbon atoms, even more preferably 1 to 3 carbon atoms, and 1 carbon atom. is particularly preferred.

In general formula (I-2), M represents an alkylene group having 1 to 15 carbon atoms, but considering the viscosity imparted to the liquid crystal composition and its own volatility, M is an alkylene group having 2 to 10 carbon atoms. Alkylene having 4 to 8 carbon atoms is preferred, and alkylene having 6 or 8 carbon atoms is even more preferred.

Specific examples include compounds represented by general formulas (I-24), (I-26) and (I-28). R ^H1 and R ^H2 in these formulas are as described above.

More specifically, compounds represented by general formula (I-24H), general formula (I-26H) and general formula (I-28H) include compounds represented by general formula (I-28H). (2,2,6,6-Tetramethyl-4-piperidyl) sebacate is most suitable.

A compound represented by general formula (I-3) is also preferred. Since the compound represented by the general formula (I-3) has a high effective amine concentration, it is a compound that acts more effectively. In addition, light stabilizers with a small molecular weight are often adsorbed to the alignment film in the liquid crystal display element and induce display unevenness, but the compound represented by the general formula (I-3) has a large molecular weight. Therefore, it is possible to prevent display unevenness from being induced.

(In the formula, R ^H3 , R ^H4 and R ^H5 each independently represent a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, n ^H1 and n ^H2 each independently represent 0 to 2. n ^H3 represents 1 or 2. When there are multiple ^RH5 , they may be the same or different.)
In general formula (I-3), R ^H3 , R ^H4 and R ^H5 are particularly preferably hydrogen atoms. When it is an alkyl group, it preferably has 1 to 8 carbon atoms, more preferably 1 to 5 carbon atoms, even more preferably 1 to 3 carbon atoms, and 1 carbon atom. is more preferred.

Specifically, compounds represented by general formulas (I-31), (I-32) and (I-33) are preferred. R ^H3 , R ^H4 and R ^H5 in these formulas are as described above.

More specifically, compounds represented by formula (I-31H), formula (I-31C), formula (I-32H) and formula (I-33H) are preferred.

The liquid crystal composition of the present invention preferably contains 0.01% or more, preferably 0.02% or more, and preferably 0.03% or more of a light stabilizer (HALS) as a lower limit in the composition. It is preferably contained, preferably 0.05% or more, preferably 0.07% or more, preferably 0.1% or more, preferably 0.15% or more, The content is preferably 0.2% or more, preferably 0.25% or more, preferably 0.3% or more, preferably 0.5% or more, and 1% or more. is preferred. In addition, the upper limit is preferably 5% or less, preferably 3% or less, preferably 1% or less, preferably 0.5% or less, and 0.45% or less. preferably 0.4% or less, preferably 0.35% or less, preferably 0.3% or less, preferably 0.25% or less, and 0.3% or less. The content is preferably 2% or less, preferably 0.15% or less, preferably 0.1% or less, preferably 0.07% or less, and 0.05% or less. is preferable, and it is preferable to contain 0.03% or less.

More specifically, the content is preferably 0.01 to 5% by mass, preferably 0.01 to 0.3% by mass, more preferably 0.02 to 0.3% by mass, 0.05 to 0.25% by weight is particularly preferred. More specifically, the content is preferably 0.01 to 0.1% by mass when emphasis is placed on suppressing precipitation at low temperatures.

The composition containing the polymerizable compound of the present invention is imparted with liquid crystal alignment ability by polymerizing the polymerizable compound contained therein by ultraviolet irradiation, and the birefringence of the composition is used to control the amount of transmitted light. used for liquid crystal display elements.

A liquid crystal display device using the composition of the present invention has no or very few display defects such as image sticking (IS), has a high VHR, and is excellent in reliability. It can be applied to the PSVA mode or PSA mode of liquid crystal display elements for commercial applications. Moreover, it can also be applied to a liquid crystal display element characterized by not having an alignment film.

In addition, in the process of manufacturing a liquid crystal display element by the ODF method, it is necessary to drop an optimum liquid crystal injection amount according to the size of the liquid crystal display element. Since it is possible to drop the liquid crystal stably for a long period of time without being affected by rapid pressure changes and shocks in the device, the yield of the liquid crystal display element can be kept high. In particular, it is difficult to control the deviation from the optimum value within a certain range in the compact liquid crystal display element that is frequently used in smartphones, which are becoming popular recently, because the optimum liquid crystal injection amount is small, but the liquid crystal composition of the present invention By using a substance, it is possible to realize a stable liquid crystal material ejection amount even in a small liquid crystal display device.

According to the liquid crystal composition of the present invention, the polymerization rate of the polymerizable compound is sufficiently high, there is no display defect such as IS caused by the change in pretilt angle, or there is very little display defect, the VHR is high, and the reliability is excellent. A liquid crystal display element can be obtained. As described above, the liquid crystal composition of the present invention can remarkably improve the production efficiency of PSA or PSVA liquid crystal display devices, and has a very high industrial utility value.

The liquid crystal composition of the present invention is suitable for producing a PSA-type or PSVA-type liquid crystal display element, and is also suitable for producing an NPS-type liquid crystal display element. It is also suitable for manufacturing a PI-less type liquid crystal display device that does not have an alignment film.

The liquid crystal composition of the present invention is also suitable for a liquid crystal display element having no alignment film, that is, a mode commonly called PI-less. For example, compounds having spontaneous orientation described in Japanese Patent Application No. 2013-552125, Japanese Patent Application No. 2014-517515, Japanese Patent No. 06081361, Japanese Patent Application No. 2015-546888, Japanese Patent Application No. 2017-12710, WO2017041893A, Japanese Patent No. 06070973, WO17/047177, etc. It is preferably used in combination with the liquid crystal composition of the invention.

The liquid crystal composition of the present invention is useful for liquid crystal display elements for active matrix driving, and can be used for liquid crystal display elements such as PSA, PSVA, PS-IPS, PS-FFS and NPS.

A liquid crystal display element of the present invention comprises: a first substrate and a second substrate arranged to face each other; a common electrode provided on the first substrate or the second substrate; It is preferable to have a pixel electrode provided on two substrates 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 opposing surface side of at least one of the first substrate and/or the second substrate so as to be in contact with the liquid crystal layer. As the alignment film, a vertical alignment film, a horizontal alignment film, or the like can be appropriately selected in accordance with the drive mode of the liquid crystal display element. known alignment films can be used. Furthermore, a color filter may be appropriately provided on the first substrate or the second substrate, and a 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 device of the present invention can be made of a flexible transparent material such as glass or plastic, and one of them can be made of 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.

A color filter can be produced by, for example, a pigment dispersion method, a printing method, an electrodeposition method, a dyeing method, or the like. A method for producing a color filter by a pigment dispersion method will be described as an example. A curable coloring composition for a color filter is applied onto the transparent substrate, patterned, and cured by heating or light irradiation. By performing this process for each of the three colors of red, green, and blue, a pixel portion for a color filter can be produced. In addition, a pixel electrode provided with an active element such as a TFT, a thin film diode, a metal insulator metal resistivity element, or the like may be provided on the substrate.

It is preferable that the first substrate and the second substrate are opposed to each other so that the common electrode and the pixel electrode layer are inside.

A space between the first substrate and the second substrate may be adjusted via a spacer. In this case, it is preferable to adjust the thickness of the obtained light control layer to 1 to 100 μm. It is more preferably 1.5 to 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. Moreover, when there are two polarizing plates, the polarizing axis of each polarizing plate can be adjusted to improve the viewing angle and contrast. Furthermore, a retardation film for widening the viewing angle can also be used. Examples of spacers include glass particles, plastic particles, alumina particles, photoresist materials, and the like. After that, a sealing agent such as an epoxy-based thermosetting composition is screen-printed on the substrates provided with a liquid crystal injection port, if necessary, and the substrates are bonded together and heated to thermally cure the sealing agent.

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

As a method for polymerizing the polymerizable compound contained in the liquid crystal composition of the present invention, it is desirable to polymerize at an appropriate polymerization rate in order to obtain good alignment performance of the liquid crystal. A method of polymerizing by irradiating energy rays singly, in combination, or in sequence is preferred. When using ultraviolet rays, a polarized light source may be used, or a non-polarized light source may be used. In the case where the liquid crystal composition is sandwiched between two substrates and the polymerization is carried out, at least the substrate on the irradiation surface side must be given appropriate transparency to the active energy ray. In addition, after polymerizing only a specific portion using a mask during light irradiation, the orientation state of the unpolymerized portion is changed by changing the conditions such as the electric field, magnetic field, or temperature, and then the active energy ray is further irradiated. It is also possible to use a means of polymerizing by In particular, when the liquid crystal composition is exposed to ultraviolet rays, it is preferable to apply the ultraviolet rays while applying a DC electric field or an AC electric field to the liquid crystal composition. The AC electric field to be applied is preferably AC with a frequency of 1 Hz to 10 kHz, more preferably 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. In the PSA type or PSVA type liquid crystal display device, it is preferable to control the pretilt angle from 80 degrees to 89.9 degrees from the viewpoint of alignment stability and contrast.
In a PSA-type or PSVA-type liquid crystal display element, IS occurs if the polymerizable compound remains as it is without being polymerized after the element is manufactured. The amount of the remaining polymerizable compound is preferably 20 ppm or less, more preferably 15 ppm or less, particularly preferably 10 ppm or less, and particularly preferably 0 or less than the detection limit.

There are no particular restrictions on the temperature during irradiation of active energy rays such as ultraviolet rays or electron beams used for polymerizing the polymerizable compound contained in the liquid crystal composition of the present invention. 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, the temperature is preferably within a range in which the liquid crystal state of the liquid crystal composition is maintained. That is, it is preferable to polymerize at 15 to 50°C.

A metal halide lamp, a high-pressure mercury lamp, an ultra-high-pressure mercury lamp, or the like can be used as a lamp for generating ultraviolet rays, and an ultra-high-pressure UV lamp manufactured by USHIO and a fluorescent type ultraviolet lamp manufactured by TOSHIBA are preferable. As for the wavelength of ultraviolet rays to be irradiated, it is preferable to irradiate ultraviolet rays in a wavelength range that is not in the absorption wavelength range of the liquid crystal composition, and if necessary, it is preferable to cut the ultraviolet rays. The intensity of the ultraviolet rays to be irradiated 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 amount of the ultraviolet rays to be irradiated can be appropriately adjusted, but is preferably 10 mJ/cm ² to 500 J/cm 2 , more preferably 100 mJ/ ^{cm 2 to} 200 J/cm ² .

The present invention will be described in more detail with reference to examples below, but the present invention is not limited to these examples. In addition, "%" in the compositions of the following examples and comparative examples means "% by mass".
In addition, the following abbreviations are used for the description of the compounds in the examples.
(ring structure)

The properties measured in the examples are as follows.

Δn: refractive index anisotropy at 293 K Δε: dielectric anisotropy at 293 K T _ni : nematic phase-isotropic liquid phase transition temperature (°C)
γ ₁ : Rotational viscosity at 293K (mPa s)
(Manufacturing method and evaluation method of liquid crystal display element)
First, a polyimide alignment film for inducing vertical alignment was applied to the substrate with ITO, and then the polyimide alignment film was rubbed to obtain a liquid crystal cell including the substrate with ITO. A liquid crystal composition containing a polymerizable compound was injected into the liquid crystal cell using a vacuum injection method with a cell gap of 3.5 μm. JALS2096 manufactured by JSR Corporation was used as a material for forming a vertical alignment film.

Thereafter, the liquid crystal cell into which the liquid crystal composition containing the polymerizable compound was injected was irradiated with ultraviolet light using a high-pressure mercury lamp while a voltage of 10 V was applied at a frequency of 100 Hz. At this time, the illuminance measured under the condition of a center wavelength of 365 nm was adjusted to 100 mW/cm ² , and the UV rays were irradiated with an integrated light amount of 20 J/cm ² . The UV irradiation condition described above was defined as irradiation condition 1. This irradiation condition 1 imparts a pretilt angle to the liquid crystal molecules in the liquid crystal cell.

Next, using a fluorescent UV lamp, the illuminance measured under the condition of a central wavelength of 313 nm was adjusted to 3 mW/cm ² , and ultraviolet light was further irradiated with an integrated light amount of 10 J/cm ² to obtain a liquid crystal display element. . The UV irradiation condition described above was referred to as irradiation condition 2. Irradiation condition 2 reduces the residual amount of the polymerizable compound in the liquid crystal cell that has not reacted under irradiation condition 1 .

After irradiation with ultraviolet rays, display defects (burn-in) were evaluated based on changes in the pretilt angle. First, the pretilt angle of the liquid crystal display element was measured and used as the pretilt angle (initial). This liquid crystal display device was irradiated with a backlight for 24 hours while applying a voltage of 30 V at a frequency of 100 Hz. After that, the pretilt angle was measured and defined as the pretilt angle (after the test). A value obtained by subtracting the pretilt angle (after the test) from the measured pretilt angle (initial) was taken as the pretilt angle change amount (=absolute value of change in pretilt angle) [°]. The pretilt angle was measured using OPTIPRO manufactured by Shintech.

The closer the pretilt angle change amount is to 0[°], the lower the possibility of display failure due to the change in the pretilt angle. more likely.

The residual amount [ppm] of the polymerizable compound in the liquid crystal display element after being irradiated with ultraviolet rays under each of the irradiation conditions 1 and 2 was measured. A method for measuring the residual amount of the polymerizable compound will be described. First, the liquid crystal display element was disassembled to obtain an acetonitrile solution of eluted components including the liquid crystal composition, polymer, and unreacted polymerizable compound. This was analyzed by high performance liquid chromatography to measure the peak area of each component. The amount of the remaining polymerizable compound was determined from the ratio of the peak area of the liquid crystal compound used as an index to the peak area of the unreacted polymerizable compound. The residual amount of the polymerizable compound was determined from this value and the amount of the polymerizable compound initially added. The detection limit for the residual amount of the polymerizable compound was 30 ppm. In the case where the polymerizable compound remains after the ultraviolet irradiation under the irradiation conditions 1 and 2, there is a high possibility that the remaining polymerizable compound will cause display defects.

The voltage holding ratio (VHR) of the liquid crystal display element after being irradiated with ultraviolet rays under the irradiation conditions 1 and 2 was measured under the conditions of a frequency of 60 Hz, a voltage of 1 V, and a temperature of 60°C.
(Preparation of Liquid Crystal Composition and Evaluation Results)
Liquid crystal compositions LC-1 to LC-4 and LC-R1 to LC-R3 were prepared and their physical properties were measured. The composition of the liquid crystal composition and the physical property values thereof are shown in the table below.

(Examples 1 to 4 and Comparative Examples 1 to 2)
A polymerizable compound represented by RM-4 was added as a polymerizable compound to the prepared liquid crystal compositions LC-1 to LC-4 and LC-R1 to LC-R2 at a mixing ratio of 0.3%, A polymerizable compound-containing liquid crystal composition was prepared. Various evaluations were performed, and examples 1 to 4 and comparative examples 1 to 2 were obtained.

In Examples 1 to 4, it was confirmed that the residual amount of the polymerizable compound after UV irradiation was remarkably small, the amount of pretilt angle change was very small, and the VHR was very high. On the other hand, in Comparative Example 1, the residual amount of the polymerizable compound was very large, suggesting that display defects such as IS tend to occur. When the amount of change in pretilt angle was actually evaluated, the result was inferior to that of the example. It was confirmed that Comparative Example 2 had a large pretilt angle change amount and a low VHR.

From the above, it was confirmed that Examples 1 to 4 have solved the problems of the present invention.

A series of evaluations was conducted by replacing the polymerizable compound RM-4 used in Examples 1 to 4 with RM-3. It was confirmed that a liquid crystal display element having a high density was obtained.

A series of evaluations was conducted by substituting the polymerizable compound RM-4 used in Examples 1 to 4 with RM-2. It has been confirmed that the liquid crystal composition is a liquid crystal composition having a high density and that an excellent liquid crystal display device can be obtained.

The polymerizable compound RM-4 used in Examples 1 to 4 was replaced with RM-1, and a series of evaluations was performed. It has been confirmed that the liquid crystal composition is a liquid crystal composition having a high density and that an excellent liquid crystal display device can be obtained.
(Example 5 to Example 10)
Polymerizable compound RM-3 was added to prepared liquid crystal compositions LC-5 to LC-10 to prepare polymerizable compound-containing liquid crystal compositions. Various evaluations were performed, and Examples 5 to 10 were obtained.

In Examples 5 to 10, it was confirmed that the residual amount of the polymerizable compound was remarkably small, the amount of pretilt angle change was small, and the VHR was high.

Comparative Examples 1 to 8 were found to have a large residual amount of the polymerizable compound under the irradiation conditions 1 and 2. In addition, it was confirmed that Comparative Example 8 had a large amount of change in pretilt angle and a low VHR, although the residual amount of the polymerizable compound was small.

From the above, the liquid crystal composition of the present invention has a sufficiently high polymerization rate of the polymerizable compound, does not have display defects such as burn-in due to changes in the pretilt angle, has a high VHR, and is a PSA type with excellent reliability. Or it was confirmed that it is most suitable for a PSVA type liquid crystal display element.

Claims (9)

As the first component, the general formula (i)

(wherein R ⁱ¹ represents 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 alkenyloxy group having 2 to 8 carbon atoms; , R ⁱ² represents an alkyl group having 1 to 8 carbon atoms or an alkenyl group having 2 to 8 carbon atoms, and A ⁱ¹ represents a 1,4-cyclohexylene group (one —CH ₂ - or two or more non-adjacent -CH ₂ - may be replaced with -O-), and n ⁱ¹ represents 0, 1 or 2.) one type of compound represented by Or containing two or more, as a second component, the general formula (L)

(wherein R ^L1 and R ^L2 each independently represent an alkyl group having 1 to 8 carbon atoms, and one or two or more non-adjacent —CH ₂ — in the alkyl group are each independently may be substituted with -CH=CH-, -C≡C-, -O-, -CO-, -COO- or -OCO-, and A ^L1 , A ^L2 and A ^L3 are each independently
(a) a 1,4-cyclohexylene group (one —CH ₂ — present in this group or two or more non-adjacent —CH ₂ — may be replaced with —O—),
(b) a 1,4-phenylene group (one -CH= or two or more non-adjacent -CH= present in this group may be replaced with -N=) and (c) naphthalene-2,6-diyl group, 1,2,3,4-tetrahydronaphthalene-2,6-diyl group or decahydronaphthalene-2,6-diyl group (naphthalene-2,6-diyl group or 1,2 , 1 -CH= or two or more non-adjacent -CH= present in the 3,4-tetrahydronaphthalene-2,6-diyl group may be replaced with -N=.)
represents a group selected from the group consisting of, and the above groups (a), (b) and (c) each independently represent an alkyl group (one —CH ₂ — present in this group or adjacent two or more —CH ₂ — that are not adjacent may be replaced by —O—), an alkenyl group (one —CH ₂ — present in this group, or two or more —CH _2- may be replaced with -O-), may be substituted with a cyano group, a fluorine atom or a chlorine atom, and Z ^L1 and Z ^L2 are each independently a single bond, -CH ₂ CH ₂ -, -(CH ₂ ) ₄ -, -OCH ₂ -, -CH ₂ O-, -COO-, -OCO-, -OCF _{2 -, -CF 2 O-} , -CH=N-N=CH-, -CH=CH-, -CF=CF- or -C≡C-, n ^L1 represents 0, 1, 2 or 3, but when there are a plurality of A ^L2 , they may be the same They may be different, and when a plurality of Z ^L2 are present, they may be the same or different, except for the compounds represented by the general formula (i). ) contains one or more compounds represented by the formula (N-1d) and / or general formula (N-1) as a third component

(wherein R ^{3 Nd11} and R ^{3 Nd12} each independently represent an alkyl group having 1 to 8 carbon atoms, and one or two or more non-adjacent —CH ₂ — in the alkyl group are each independently may be substituted by -CH=CH-, -C≡C-, -O-, -CO-, -COO- or -OCO-, and ^nNd11 represents 1, 2 or 3.)

(wherein R ^N11 and R ^N12 each independently represent an alkyl group having 1 to 8 carbon atoms, and one or two or more non-adjacent —CH ₂ — in the alkyl group each independently may be substituted by -CH=CH-, -C≡C-, -O-, -CO-, -COO- or -OCO-, and n ^N11 and n ^N12 are each independently 0, 1 , 2 or 3, wherein n ^N11 +n ^N12 represents 1, 2 or 3, A ^N11 and A ^N12 each independently
(a) a 1,4-cyclohexylene group (one —CH ₂ — present in this group or two or more non-adjacent —CH ₂ — may be replaced with —O—),
(b) a 1,4-phenylene group (one -CH= or two or more non-adjacent -CH= present in this group may be replaced with -N=) and (c) naphthalene-2,6-diyl group, 1,2,3,4-tetrahydronaphthalene-2,6-diyl group or decahydronaphthalene-2,6-diyl group (naphthalene-2,6-diyl group or 1,2 , 1 -CH= or two or more non-adjacent -CH= present in the 3,4-tetrahydronaphthalene-2,6-diyl group may be replaced with -N=.)
represents a group selected from the group consisting of, and the above groups (a), (b) and (c) each independently represent an alkyl group (one —CH ₂ — present in this group or adjacent two or more —CH ₂ — that are not adjacent may be replaced by —O—), an alkenyl group (one —CH ₂ — present in this group, or two or more —CH ₂ — may be replaced with —O—.), may be substituted with a cyano group, a fluorine atom or a chlorine atom, and Z ^N11 and Z ^N12 are each independently a single bond, —CH ₂ CH ₂ -, -(CH ₂ ) ₄ -, -OCH ₂ -, -CH ₂ O-, -COO-, -OCO-, -OCF _{2 -, -CF 2 O-} , -CH=N-N=CH-, -CH=CH-, -CF=CF- or -C≡C-, and when there are a plurality of A ^N11 and/or A ^N12 , they may be the same or different, and Z ^N11 and / Or when there are multiple ^ZN12 , they may be the same or different. However, compounds represented by general formula (N-1d) are excluded. ) containing one or more compounds selected from the group of compounds represented by the formula (II) as a fourth component

(wherein R ²⁰¹ , R ²⁰² , R ²⁰³ , R ²⁰⁴ , R ²⁰⁵ , R 206 , R ²⁰⁷ , R ^{208 ,} R ²⁰⁹ and R ²¹⁰ are each independently P ²¹ -S ²¹ -, a fluorine atom, an alkyl group having 1 to 18 carbon atoms which may be substituted, 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 from formula (R-1) to formula (R-7)

(wherein R ¹¹ , R ¹² , R ¹³ , R ¹⁴ and R ¹⁵ each independently represent an alkyl group having 1 to 5 carbon atoms, a fluorine atom or a hydrogen atom, m ^r5 , m ^r7 , ^nr5 and ^nr7 each independently represent 0, 1, or 2.), and ^S21 represents a single bond or an alkylene group having 1 to 15 carbon atoms. , one or more —CH ₂ — in the alkylene group may be replaced with —O—, —OCO— or —COO— such that the oxygen atoms are not directly adjacent, and n ²¹ is 0 , 1 or 2, and A ²¹ is
(a) 1,4-cyclohexylene group (one —CH ₂ — present in this group or two or more non-adjacent —CH ₂ — may be replaced with —O—);
(b) a 1,4-phenylene group (one -CH= or two or more non-adjacent -CH= present in this group may be replaced with -N=) and (c) naphthalene-2,6-diyl group, 1,2,3,4-tetrahydronaphthalene-2,6-diyl group or decahydronaphthalene-2,6-diyl group (naphthalene-2,6-diyl group or 1,2 , 1 -CH= or two or more non-adjacent -CH= present in the 3,4-tetrahydronaphthalene-2,6-diyl group may be replaced with -N=.)
represents a group selected from the group consisting of, and the above groups (a), (b) and (c) are each independently an alkyl group having 1 to 12 carbon atoms, an alkyl group having 1 to 12 carbon atoms, may be substituted with an alkoxy group, halogen, cyano group, nitro group or P ²¹ -S ²¹ - and has at least one or more P ²¹ -S ²¹ - in one molecule of general formula (II) , L ²¹ is a single bond, -OCH ₂ -, -CH ₂ O-, -C ₂ H ₄ -, -OC ₂ H ₄ O-, -COO-, -OCO-, -CH=CR ^a -COO-, -CH=CR ^a -OCO-, -COO-CR ^a =CH-, -OCO-CR ^a =CH-, -(CH ₂ ) _z -COO-, -(CH ₂ ) _z -OCO-, -OCO- (CH ₂ ) _z —, —COO—(CH ₂ ) _z —, —CH═CH—, —CF ₂ O—, —OCF ₂ — or —C≡C— (wherein R ^a is independently represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, wherein z each independently represents an integer of 1 to 4), wherein P ²¹ , S ²¹ , and A ²¹ are present in plurality; If so, they may be the same or different. ) A liquid crystal composition containing a polymerizable compound represented by
As the compound represented by the general formula (i), formulas (i-1.1) to (i-1.7)

Contains one or more compounds selected from the group of compounds represented by
As the compound represented by the general formula (L), the general formula (L-2)

(Wherein, R ^L21 and R ^L22 each independently represent the same meaning as R ^L1 and R ^L2 in general formula (L).)
The liquid crystal composition, wherein the total content of the compounds represented by formulas (i-1.1) to (i-1.7) is 3 to 15% by mass with respect to the total amount of the liquid crystal composition. . As compounds represented by general formula (L), general formulas (L-1) , (L-3) to (L-5)

(wherein R ^L11 , R ^L12 , R ^L31 , R ^L32 , R ^L41 , R ^L42 , R ^L51 and R ^L52 each independently represent the same meaning as R ^L1 and R ^L2 in general formula (L) , R ^L31 , R ^L32 and R ^L52 do not represent an alkoxy group or an alkenyloxy group.), further comprising one or more compounds selected from the group represented by thing. As a compound represented by general formula (N-1), general formula (N-1-3)

(In the formula, R ^N131 represents an alkyl group having 1 to 5 carbon atoms or an alkenyl group having 2 to 5 carbon atoms, and R ^N132 represents an alkyl group having 1 to 5 carbon atoms or an alkoxy group having 1 to 4 carbon atoms. 3. The liquid crystal composition according to claim 1, which contains a compound represented by ). As compounds represented by general formula (i), formulas (i-0.1) to formula (i-0.7)

4. The liquid crystal composition according to any one of claims 1 to 3 , containing one or more compounds selected from the group of compounds represented by: As compounds represented by general formula (i), formulas (i-2.1) to formula (i-2.7)

5. The liquid crystal composition according to any one of claims 1 to 4, containing one or more compounds selected from the group of compounds represented by: A liquid crystal display element comprising two substrates and a liquid crystal phase containing the liquid crystal composition according to any one of claims 1 to 5 provided between the two substrates. 7. The liquid crystal display device according to claim 6 , which is for active matrix driving. 8. The liquid crystal display element according to claim 6 , which is of PSA type or PSVA type. 9. The liquid crystal display element according to claim 6 , wherein at least one of said two substrates does not have an alignment film.