JP7395940B2 - Liquid crystal composition and liquid crystal display element - Google Patents

Description

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

Liquid crystal display elements using liquid crystal compositions having a negative dielectric anisotropy Δε are widely used in PSA and PSVA type liquid crystal TVs and liquid crystal monitors, and patents have been developed for liquid crystal compositions suitable for these devices. Various polymerizable compounds and liquid crystal compositions containing the same are disclosed in Document 1, Patent Document 2, Patent Document 3, Patent Document 4, and Patent Document 5.

However, the characteristics of liquid crystal compositions containing polymerizable compounds that have been commonly used so far are insufficient for high-definition liquid crystal TVs such as 4K and 8K. Specifically, 4K and 8K liquid crystal display elements require high-definition pixels, and a considerable amount of UV light is blocked by increasing the area of wiring and light shielding parts. For this reason, in the UV irradiation step in manufacturing PSA type and PSVA type liquid crystal display elements, the polymerizable compound is not sufficiently polymerized and a large amount of the polymerizable compound remains. As a result, tilt formation was insufficient, resulting in poor response speed and afterimage due to poor orientation.Also, the remaining polymerizable compound gradually polymerized during driving, causing a change in tilt, resulting in a display defect called image sticking (IS). has been done.

Based on the above, PSA or PSVA type liquid crystal display elements such as high-definition liquid crystal televisions and liquid crystal monitors are required to have extremely high characteristics that set them apart from conventional technologies. There is a need for liquid crystal compositions that can be stably produced using light.

JP2016-216747 Patent No. 4803320 Patent No. 6008065 Patent No. 6233550 Patent No. 5743132

The problem to be solved by the present invention is to provide a liquid crystal composition containing a polymerizable compound that can simultaneously achieve a fast polymerization rate, appropriate tilt formation, high tilt stability, and high voltage holding ratio (VHR), and to provide a liquid crystal composition that can achieve image sticking (IS) using the same. It is an object of the present invention to provide a polymerizable compound suitable for the preparation of a PSA type or PSVA type liquid crystal display element in which the phenomenon (2) is sufficiently suppressed or does not occur, and the liquid crystal composition containing the polymerizable compound.

As a result of intensive studies, the present inventors have found that the above problems can be solved by a liquid crystal composition containing two or more kinds of polymerizable compounds having a specific chemical structure, and have completed the present invention.

The liquid crystal composition of the present invention can simultaneously achieve a fast polymerization rate, appropriate tilt formation, high tilt stability, and high voltage holding ratio VHR, and can sufficiently suppress or cause image sticking (IS). It is possible to provide a high-definition PSA type or PSVA type liquid crystal display element that exhibits excellent display quality.

First, the polymerizable compound-containing liquid crystal composition of the present invention will be explained. In the following description, "total amount" means "total mass", and the unit of content of each compound "%" means "mass %".

The liquid crystal composition of the present invention contains general formula (i) as the first component.

(In the formula, A ⁱ¹ and A ⁱ² are each independently,
(a) 1,4-cyclohexylene group (one -CH ₂ - or two or more non-adjacent -CH ₂ -s present in this group may be replaced with -O-)
(b) 1,4-phenylene group (one -CH= or two or more non-adjacent -CH= present in this group may be replaced with -N=) and (c) naphthalenediyl group, 1,2,3,4-tetrahydronaphthalenediyl group or decahydronaphthalenediyl group (one -CH= or Two or more non-adjacent -CH= may be replaced with -N=.)
The above group (a), group (b) and group (c) each independently represent an alkyl group having 1 to 8 carbon atoms, or an alkyl group having 1 to 8 carbon atoms. May be substituted with an alkoxy group, halogen, cyano group, nitro group or P ⁱ³ -S ⁱ³ -,
P ⁱ¹ , P ⁱ² and P ⁱ³ are each independently represented by formula (R-1) to formula (R-15)

represents a polymerizable group represented by, P ⁱ¹ and P ⁱ² each represent a different thing,
S ⁱ³ represents a single bond or an alkylene group having 1 to 5 carbon atoms, and one -CH ₂ - or two or more non-adjacent -CH ₂ -s in the alkylene group are -O-, May be substituted with -OCO- or -COO-,
n ⁱ¹ represents 1 or 2,
When there are multiple A ^i2s , they may be the same or different. ) Contains a polymerizable compound represented by
As the second component, general formula (RM-22) or general formula (RM-23)

(In the formula, P ⁵ , P ⁶ , P ⁷ and P ⁸ are each independently represented by formula (R-1) to formula (R-15)

S ⁵ , S ⁶ , S ⁷ and S ⁸ each independently represent a single bond or an alkylene group having 1 to 5 carbon atoms, and one of the alkylene groups -CH ₂ - or two or more non-adjacent -CH ₂ - may be substituted with -O-, -OCO- or -COO-, and A ¹ to A ⁸ are each independently a carbon atom. Represents an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, a fluorine atom or a hydrogen atom, and B ¹ to B ¹² are each independently an alkyl group having 1 to 5 carbon atoms, an alkyl group having 1 to 5 carbon atoms, and ~5 alkoxy group, fluorine atom or hydrogen atom. ) Contains a polymerizable compound represented by:

The liquid crystal composition of the present invention is suitable for producing a PSA type or PSVA type liquid crystal display element, and also suitable for producing an NPS type liquid crystal display element. It is also suitable for producing a PI-less type liquid crystal display element, which is characterized by not having an alignment film.
(Polymerizable compound)
The liquid crystal composition of the present invention contains one or more polymerizable compounds represented by the above general formula (i).

According to the present invention, the polymerizable compound represented by the general formula (i) has excellent solubility in the liquid crystal composition and has little precipitation, and the polymerization rate of the polymerizable compound is sufficiently fast and the polymerization reaction proceeds sufficiently. , it is possible to obtain a polymerizable compound-containing liquid crystal composition with a small amount of unreacted polymerizable compound remaining after polymerization.

In the polymerizable compound represented by the above general formula (i), A ⁱ¹ and A ⁱ² are each independently,
(a) 1,4-cyclohexylene group (one -CH ₂ - or two or more non-adjacent -CH ₂ -s present in this group may be replaced with -O-)
(b) 1,4-phenylene group (one -CH= or two or more non-adjacent -CH= present in this group may be replaced with -N=) and
(c) naphthalenediyl group, 1,2,3,4-tetrahydronaphthalenediyl group or decahydronaphthalenediyl group (one - present in the naphthalenediyl group or 1,2,3,4-tetrahydronaphthalenediyl group) CH= or two or more non-adjacent -CH= may be replaced with -N=.

Here, the naphthalenediyl group that A ⁱ¹ and A ⁱ² can take is one of the two positions selected from the 1st to 8th positions, when there is a plurality of P ⁱ¹ , P ⁱ² , or A ⁱ² , a bond with A ⁱ² On the other hand, it is a group that binds to a structural site (hereinafter referred to as a specific structural site) represented by the following formula in the above general formula (i).

(In the above formula, ★ combines with A ⁱ² , and ★★ combines with A ⁱ¹ .)
Examples of the naphthalene diyl group include naphthalene-1,2-diyl group, naphthalene-1,3-diyl group, naphthalene-1,4-diyl group, naphthalene-1,5-diyl group, and naphthalene-1,6-diyl group. group, naphthalene-1,7-diyl group, naphthalene-1,8-diyl group, naphthalene-2,3-diyl group, naphthalene-2,6-diyl group, naphthalene-2,7-diyl group, etc. .

In addition, the 1,2,3,4-tetrahydronaphthalenediyl group that A ⁱ¹ and A ⁱ² can take is one where P ⁱ¹ , P ⁱ² , or A ⁱ² is present at a plurality of two positions selected from the 1st to 8th positions. When present, it is a group that binds to A ⁱ² and, on the other hand, to the above-mentioned specific structural site in general formula (i). Examples of the 1,2,3,4-tetrahydronaphthalene diyl group include 1,2,3,4-tetrahydronaphthalene-2,6-diyl group and 1,2,3,4-tetrahydronaphthalene-1,4-diyl group. group, 1,2,3,4-tetrahydronaphthalene-1,5-diyl group, and the like. In addition, the decahydronaphthalenediyl group that A ⁱ¹ and A ⁱ² can take is A ⁱ² when there is a plurality of P ⁱ¹ , P ⁱ² , or A ⁱ² at one of the two positions selected from the 1st to 10th positions. It is a group that binds to the above-mentioned specific structural site in general formula (i) on the other hand. Examples of the decahydronaphthalenediyl group include decahydronaphthalene-2,6-diyl group.

The above groups (a), (b) and (c) each independently represent an alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, a halogen, a cyano group, a nitro group. Alternatively, it may be substituted with P ⁱ³ -S ⁱ³ -.

Among these, it is preferable that A ⁱ¹ and A ⁱ² each independently represent one of the following structures.

(In the formula, R ⁱ² and R ⁱ³ each independently represent an alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, a fluorine atom, or P ⁱ³ -S ⁱ³ -.)
The above A ⁱ¹ and A ⁱ² each independently represent a 1,4-phenylene group, 2-methyl-1,4-phenylene group, 3-methyl-1,4-phenylene group, 2-methoxy-1,4- More preferably a phenylene group, 3-methoxy-1,4-phenylene group, 2-fluoro-1,4-phenylene group, 3-fluoro-1,4-phenylene group or naphthalene-2,6-diyl group. , 1,4-phenylene group, 2-fluoro-1,4-phenylene group or 3-fluoro-1,4-phenylene group, and particularly preferably 1,4-phenylene group.

In the above general formula (i), the number of rings represented by A ⁱ¹ is one. On the other hand, the number of rings represented by A ⁱ² in the above general formula (i) is one or two depending on the number of n ⁱ¹ . It is presumed that the polymerizable compound represented by the above general formula (i) has such a structure, thereby improving its solubility in the liquid crystal composition and, as a result, becoming less likely to precipitate. When there are two A ^i2s , the two A ^i2s may be the same group or different groups.

In the above general formula (i), P ⁱ¹ , P ⁱ² and P ⁱ³ each independently represent a group selected from the following formulas (R-1) to (R-15), as described above.

Here, P ⁱ¹ and P ⁱ² represent different things. Further, it is preferable that at least one of P ⁱ¹ and P ⁱ² is selected from formula (R-1), and the other is selected from formulas (R-2) to (R-15). In this way, by setting at least one of P ⁱ¹ and P ⁱ² to be an acryloxy group and the other being a non-acryloxy group, the polymerization rate is improved and display defects due to changes in the pretilt angle after UV irradiation are avoided. It can be made difficult. Furthermore, it is more preferable that at least one of P ⁱ¹ and P ⁱ² is the formula (R-1), and the other is the formula (R-2) or (R-3). It is particularly preferred that P ⁱ¹ is formula (R-1) and P ⁱ² is formula (R-2).

P ⁱ³ is preferably a formula (R-1) or a formula (R-2), more preferably a formula (R-1).

In the above general formula (i), S ⁱ³ represents a single bond or an alkylene group having 1 to 5 carbon atoms. One -CH ₂ - or two or more non-adjacent -CH ₂ -s in the alkylene group may be substituted with -O-, -OCO- or -COO-. Among these, S ⁱ³ is preferably a single bond or an alkylene group having 1 to 5 carbon atoms, and particularly preferably a single bond. When S ⁱ³ is a single bond, the amount of the polymerizable compound remaining after irradiation with ultraviolet rays is sufficiently small, and display defects due to changes in the pretilt angle are less likely to occur.

In the above general formula (i), n ⁱ¹ represents 1 or 2, but it is particularly preferable that n ⁱ¹ is 1 because the solubility in the liquid crystal composition becomes better.

The polymerizable compound-containing liquid crystal composition of the present invention contains, as a first component, one or more polymerizable compounds represented by the general formula (i), specifically, the following formula (i- The liquid crystal composition of the present invention contains one or more polymerizable compounds selected from 1) to (i-22), and the lower limit of the content of the first component in the liquid crystal composition of the present invention is 0.01% by mass. preferably 0.02% by mass, 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, 0.08% by mass is preferred, 0.09% by mass is preferred, 0.1% by mass is preferred, 0.12% by mass is preferred, 0.15% by mass is preferred, 0.17% by mass is preferred, 0. 2% by mass is preferred, 0.22% by mass is preferred, 0.25% by mass is preferred, 0.27% by mass is preferred, 0.3% by mass is preferred, 0.32% by mass is preferred, 0.35% by mass %, preferably 0.37% by weight, preferably 0.4% by weight, preferably 0.42% by weight, preferably 0.45% by weight, preferably 0.5% by weight, 0.55% by weight preferable.

Further, the upper limit of the content of the first component in the liquid crystal composition of the present invention is preferably 5% by mass, preferably 4.5% by mass, preferably 4% by mass, preferably 3.5% by mass, and 3% by mass. % is preferable, 2.5% by weight is preferable, 2% by weight is preferable, 1.5% by weight is preferable, 1% by weight is preferable, 0.95% by weight is preferable, 0.9% by weight is preferable, 0. 85% by mass is preferred, 0.8% by mass is preferred, 0.75% by mass is preferred, 0.7% by mass is preferred, 0.65% by mass is preferred, 0.6% by mass is preferred, 0.55% by mass %, preferably 0.5% by weight, preferably 0.45% by weight, and preferably 0.4% by weight.

More specifically, in order to obtain a small residual amount of the polymerizable compound or a high voltage holding rate (VHR), the content of the first component in the liquid crystal composition of the present invention is from 0.2% by mass to 1.5% by mass. It is preferably within the range of %. Further, when placing importance on suppressing precipitation of the polymerizable compound at low temperatures, the content of the first component in the liquid crystal composition of the present invention is preferably within the range of 0.01% by mass to 1.0% by mass. Furthermore, when the liquid crystal composition of the present invention contains a plurality of polymerizable compounds represented by general formula (i), the content of each is within the range of 0.01% by mass to 0.6% by mass. It is preferable. Therefore, in order to solve all of these problems, it is particularly desirable to adjust the first component in the liquid crystal composition of the present invention to a range of 0.1% by mass to 1.0% by mass.

Specifically, as the polymerizable compound represented by the above general formula (i), it is preferable to use one or more polymerizable compounds selected from formulas (i-1) to (i-22). .

Among the compounds represented by formulas (i-1) to (i-22) above, formulas (i-1), (i-3), and (i -6), (i-10), (i-11), (i-14), (i-17), and (i-20), one or more polymerizable compounds may be used. More preferred. Furthermore, in addition to the above-mentioned viewpoints, formulas (i-1), (i-3), (i-6), It is preferable to use one or more polymerizable compounds selected from (i-11) and (i-14), including formula (i-1), formula (i-3), and formula (i-6). It is more preferable to use a compound represented by formula (i-1), it is even more preferable to use a compound represented by formula (i-6), and it is more preferable to use a compound represented by formula (i-1). It is particularly preferable.

In addition to the polymerizable compound represented by the above general formula (i), the liquid crystal composition of the present invention includes a second component selected from the above general formula (RM-22) or general formula (RM-23). Contains one or more polymerizable compounds.

As the second component, the polymerizable compound represented by the general formula (RM-22) can be used as the general formula (RM-2221) to (RM-2229), the general formula (RM-221) to (RM-225), and the general formula Synthetic compounds represented by formulas (RM-22M1) to (RM-22M9) are preferable.

(wherein P ⁵ and P ⁶ are each independently represented by formula (R-1) to formula (R-15)

S ⁵ and S ⁶ each independently represent a single bond or an alkylene group having 1 to 5 carbon atoms, and one -CH ₂ - or Two or more non-adjacent -CH ₂ - groups may be substituted with -O-, -OCO- or -COO-. )
The synthetic compounds represented by the above general formulas (RM-2221) to (RM-2229), general formulas (RM-221) to (RM-225), and general formulas (RM-22M1) to (RM-22M9) Among them, P ⁵ and P ⁶ are each independently preferably a group selected from formula (R-1) to formula (R-3), and preferably a group selected from formula (R-1) or formula (R-2). Preferred groups are Furthermore, S ⁵ and S ⁶ are preferably single bonds.

As the second component, the polymerizable compound represented by the general formula (RM-23) is preferably a polymerizable compound represented by the general formulas (RM-2331) to (RM-2355).

(wherein P ⁷ and P ⁸ are each independently represented by formula (R-1) to formula (R-15)

S ⁷ and S ⁸ each independently represent a single bond or an alkylene group having 1 to 5 carbon atoms, and one -CH ₂ - or Two or more non-adjacent -CH ₂ - groups may be substituted with -O-, -OCO- or -COO-. )
In the above synthetic compounds represented by general formulas (RM-2331) to (RM-2355), P ⁷ and P ⁸ are each independently represented by formulas (R-1) to (R-3). Groups selected from formula (R-1) or formula (R-2) are preferred. Furthermore, S ⁷ and S ⁸ are preferably single bonds.

The polymerizable compound-containing liquid crystal composition of the present invention contains, as a second component, one or more polymerizable compounds selected from general formula (RM-22) or general formula (RM-23). The above general formulas (RM-2221) to (RM-2229), general formulas (RM-221) to (RM-225), general formulas (RM-22M1) to (RM-22M9), and general formulas (RM-22M9), -2331) to (RM-2355), the content of the second component is 0.20% by mass as a lower limit, and 0.20% by mass as a lower limit. It is preferably 22% by weight, preferably 0.23% by weight, preferably 0.24% by weight, and even more preferably 0.26% by weight. Further, the upper limit value is 0.50% by mass, preferably 0.45% by mass, preferably 0.40% by mass, preferably 0.35% by mass, and 0.50% by mass, preferably 0.45% by mass, preferably 0.35% by mass, and 0.50% by mass, preferably 0.45% by mass, 0.40% by mass, preferably 0.35% by mass, and 0.50% by mass, preferably 0.45% by mass. It is preferably 30% by mass, and more preferably 0.28% by mass.

The lower limit of the total content of the first component and the second component in the liquid crystal composition of the present invention is 0.21% by mass, preferably 0.24% by mass, and 0.26% by mass. %, preferably 0.28% by weight, preferably 0.30% by weight, and preferably 0.40% by weight. Further, the upper limit value is 0.60% by mass, preferably 0.50% by mass, preferably 0.48% by mass, preferably 0.45% by mass, and 0.60% by mass, preferably 0.48% by mass, preferably 0.45% by mass, and 0.50% by mass, preferably 0.48% by mass, and preferably 0.45% by mass. It is preferably 42% by weight, preferably 0.40% by weight, preferably 0.35% by weight, and even more preferably 0.30% by weight. The liquid crystal composition of the present invention uses a first component and a second component together as polymerizable compounds, but if the content of the second component is small, the alignment regulating power of the liquid crystal composition is weak or weakens over time. On the other hand, if the content of the second component is too large, problems such as a large amount remaining after curing, a long curing time, and a decrease in the reliability of the liquid crystal occur. Therefore, the contents of the first component and the second component are set in consideration of these balances.

The liquid crystal composition of the present invention comprises a compound selected from the group of compounds represented by the following general formulas (N-01), (N-02), (N-03), (N-04) and (N-05). It is preferable to contain one or more types of. These compounds correspond to compounds having dielectrically negative anisotropy. These compounds have a negative sign of Δε and an absolute value of greater than 2. Note that Δε of the compound is a value extrapolated from the measured value of the dielectric anisotropy of a composition obtained by adding the compound to a dielectrically substantially neutral composition at 25°C.

The liquid crystal composition of the present invention contains one or two compounds selected from the group of compounds represented by the following general formulas (N-01), (N-02), (N-03) and (N-04). It is preferable to contain the above amount.

In general formulas (N-01) to (N-05), R ²¹ and R ²² each independently represent an alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, or a carbon atom number Represents an alkenyl group having 2 to 8 carbon atoms, an alkenyloxy group having 2 to 8 carbon atoms, and one or more non-adjacent -CH ₂ - groups in the group are each independently -CH=CH-, -C≡C-, -O-, -CO-, -COO- or -OCO- may be substituted, and Z ¹ is each independently a single bond, -CH ₂ CH ₂ -, -OCH ₂ -, -CH ₂ O-, -COO-, -OCO-, -OCF ₂ -, -CF ₂ O-, -CH=CH-, -CF=CF- or -C≡C-, and m is , each independently represents 1 or 2.

In general formulas (N-01) to (N-05), R ²¹ is preferably an alkyl group having 1 to 8 carbon atoms, more preferably an alkyl group having 1 to 5 carbon atoms, and R 21 is preferably an alkyl group having 1 to 8 carbon atoms. More preferred are 1 to 4 alkyl groups. However, when Z ¹ represents something other than a single bond, R ²¹ is preferably an alkyl group having 1 to 3 carbon atoms.

In general formulas (N-01) to (N-05), R ²² is preferably an alkyl group having 1 to 8 carbon atoms or an alkoxy group having 1 to 8 carbon atoms; An alkyl group or an alkoxy group having 1 to 4 carbon atoms is more preferred, and an alkoxy group having 1 to 4 carbon atoms is even more preferred.

In general formulas (N-01) to (N-05), when R ²¹ and R ²² are alkenyl groups, formulas (R1) to (R5)

(The black dots in each formula represent carbon atoms in the ring structure.) It is preferable to select from the groups represented by any of the following, and formula (R1) or formula (R2) is more preferable. However, the content of the compound in which R ²¹ and R ²² are alkenyl groups is preferably as small as possible, and preferably not contained.

In general formula (N-04), Z ¹ is each independently a single bond, -CH ₂ CH ₂ -, -OCH ₂ -, -CH ₂ O-, -COO-, -OCO-, -OCF ₂ -, -CF ₂ O-, -CH=CH-, -CF=CF- or -C≡C-, but a single bond, -CH ₂ CH ₂ -, -OCH ₂ -, -CH ₂ O- Preferably, a single bond or -CH ₂ O- is more preferable.

When m is 1, Z ¹ is preferably a single bond.

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

The fluorine atoms of the compounds represented by general formulas (N-01), (N-02), (N-03), (N-04) and (N-05) are replaced with chlorine atoms, which belong to the same halogen group. It's okay if it's done. However, the content of the compound substituted with a chlorine atom is preferably as small as possible, and preferably not contained.

The hydrogen atoms present on the rings of the compounds represented by general formulas (N-01), (N-02), (N-03), (N-04) and (N-05) are fluorine atoms or chlorine atoms. Although it may be substituted with an atom, a chlorine atom is not preferred.

Compounds represented by general formulas (N-01), (N-02), (N-03), (N-04) and (N-05) have a negative Δε and an absolute value greater than 3. Preferably, it is a compound. Specifically, R ²² preferably represents an alkoxy group having 1 to 8 carbon atoms or an alkenyloxy group having 2 to 8 carbon atoms, and an alkoxy group having 1 to 4 carbon atoms is particularly preferable.

The liquid crystal composition of the present invention includes general formula (N-01-1), general formula (N-01-2), general formula (N-01-3) as a compound represented by general formula (N-01). ) and general formula (N-01-4)

(In the formula, R ²¹ represents the same meaning as above, and R ²³ each independently represents an alkoxy group having 1 to 4 carbon atoms.) It is preferable to contain two or more types.

The liquid crystal composition of the present invention comprises a polymerizable compound as a first component, a polymerizable compound as a second component, and compounds represented by general formulas (N-01-1) to (N-01-4). It is preferable to contain one or more compounds selected from the group.

The liquid crystal composition of the present invention comprises a polymerizable compound as a first component, a polymerizable compound as a second component, a compound represented by general formula (N-01-1), and a compound represented by general formula (N-01-4). It is preferable to contain a compound represented by:

The liquid crystal composition of the present invention comprises a polymerizable compound as a first component, a polymerizable compound as a second component, a compound represented by general formula (N-01-3), and a compound represented by general formula (N-01-4). It is preferable to contain a compound represented by:

The liquid crystal composition of the present invention includes general formula (N-02-1), general formula (N-02-2), and general formula (N-02- 3)

(In the formula, R ²¹ represents the same meaning as above, and R ²³ each independently represents an alkoxy group having 1 to 4 carbon atoms.) It is preferable to contain two or more types.

The liquid crystal composition of the present invention preferably contains a polymerizable compound as a first component, a polymerizable compound as a second component, and a compound represented by general formula (N-02-1).

The liquid crystal composition of the present invention comprises a polymerizable compound as a first component, a polymerizable compound as a second component, a compound represented by general formula (N-02-1), and a compound represented by general formula (N-02-3). It is preferable to contain a compound represented by:

The liquid crystal composition of the present invention comprises a polymerizable compound as a first component, a polymerizable compound as a second component, a compound represented by general formula (N-02-1), and a compound represented by general formula (N-01-4). It is preferable to contain a compound represented by:

In the liquid crystal composition of the present invention, as a compound represented by general formula (N-03), general formula (N-03-1)

(In the formula, R ²¹ represents the same meaning as described above, and R ²³ represents an alkoxy group having 1 to 4 carbon atoms.) It is preferable to contain one or more types of compounds represented by the following.

The liquid crystal composition of the present invention preferably contains a polymerizable compound as a first component, a polymerizable compound as a second component, and a compound represented by general formula (N-03-1).

The liquid crystal composition of the present invention comprises a polymerizable compound as a first component, a polymerizable compound as a second component, a compound represented by general formula (N-03-1), and a compound represented by general formula (N-01-4). It is preferable to contain a compound represented by:

The liquid crystal composition of the present invention comprises a polymerizable compound as a first component, a polymerizable compound as a second component, a compound represented by general formula (N-03-1), and a compound represented by general formula (N-02-1). It is preferable to contain a compound represented by and general formula (N-01-1).

The liquid crystal composition of the present invention comprises a polymerizable compound as a first component, a polymerizable compound as a second component, a compound represented by general formula (N-03-1), and a compound represented by general formula (N-01-3). It is preferable to contain a compound represented by the formula (N-01-4) and a compound represented by the general formula (N-01-4).

In the liquid crystal composition of the present invention, as a compound represented by general formula (N-04), general formula (N-04-1)

(In the formula, R ²¹ represents the same meaning as described above, and R ²³ represents an alkoxy group having 1 to 4 carbon atoms.) It is preferable to contain one or more types of compounds represented by the following.

The liquid crystal composition of the present invention preferably contains a polymerizable compound as a first component, a polymerizable compound as a second component, and a compound represented by general formula (N-04-1) at the same time.

The liquid crystal composition of the present invention comprises a polymerizable compound as a first component, a polymerizable compound as a second component, a compound represented by general formula (N-04-1), and a compound represented by general formula (N-01-4). It is particularly preferable to simultaneously contain a compound represented by:

The liquid crystal composition of the present invention comprises a polymerizable compound as a first component, a polymerizable compound as a second component, a compound represented by general formula (N-04-1), and a compound represented by general formula (N-01-3). It is particularly preferable to simultaneously contain the compound represented by the formula (N-01-4) and the compound represented by the general formula (N-01-4).

The liquid crystal composition of the present invention comprises a polymerizable compound as a first component, a polymerizable compound as a second component, a compound represented by general formula (N-04-1), and a compound represented by general formula (N-01-4). It is particularly preferable to simultaneously contain the compound represented by the formula (N-03-1) and the compound represented by the general formula (N-03-1).

The liquid crystal composition of the present invention comprises a polymerizable compound as a first component, a polymerizable compound as a second component, a compound represented by general formula (N-04-1), and a compound represented by general formula (N-02-1). It is particularly preferable to simultaneously contain the compound represented by the formula (N-03-1) and the compound represented by the general formula (N-03-1).

The liquid crystal composition of the present invention comprises a polymerizable compound as a first component, a polymerizable compound as a second component, a compound represented by general formula (N-04-1), and a compound represented by general formula (N-01-4). It is particularly preferable to contain the compound represented by the formula (N-02-1) and the compound represented by the general formula (N-03-1) at the same time.

The liquid crystal composition of the present invention includes a compound selected from the group of compounds represented by formulas (N-05-1) to (N-05-3) as the compound represented by general formula (N-05). May be included.

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

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

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

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

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

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

(In the formula, R ²¹ and R ²² have the same meanings as above.)
The compound represented by the general formula (N-06) is effective when adjusting various physical properties, but it should not be used to obtain large refractive index anisotropy (Δn), high T _NI , and large Δε. I can do it.

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

The liquid crystal composition of the present invention has a general formula (NU-01) to a general formula (NU-08).

(In the formula, R ^NU11 , R ^NU12 , R ^NU21 , R ^NU22 , R ^NU31 , R ^NU32 , R ^NU41 , R ^NU42 , R ^NU51 , R ^NU52 , R ^NU61 , R ^NU62 , R ^NU71 , R ^NU72 , R ^NU81 and R ^NU82 each independently 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. , one or two or more non-adjacent -CH ₂ -s in the group are each independently -CH=CH-, -C≡C-, -O-, -CO-, -COO- or -OCO Contains one or more compounds selected from the group of compounds represented by - (optionally substituted with -).
More specifically, R ^NU11 , R ^NU12 , R ^NU21 , R ^NU22 , R ^NU31 , R ^NU32 , R ^NU41 , R ^NU42 , R ^NU51 , R ^NU52 , R ^NU61 , R ^NU62 , R ^NU71 , R ^NU72 , R ^{NU 81} and R ^NU82 is preferably an alkyl group having 1 to 5 carbon atoms or an alkoxy group having 1 to 5 carbon atoms, and more preferably an alkyl group having 1 to 5 carbon atoms. When the response speed is important, at least one of R ^NU11 , R ^NU21 , R ^NU41 and R ^NU51 is preferably an alkenyl group having 2 to 3 carbon atoms, and is represented by the above formula (R2). Preferred are alkenyl groups.

The compound having an alkenyl group is preferably 30% or less, preferably 25% or less, preferably 20% or less, preferably 15% or less, preferably 10% or less, based on the total amount of the liquid crystal composition of the present invention. % or less is preferable. When high VHR is important, the content of the compound having an alkenyl group is preferably 10% or less, preferably 5% or less, preferably 1% or less, and preferably not contained.

More specifically, R ^NU11 , R ^NU21 , R ^NU31 , R ^NU41 , R ^NU51 , R ^NU61 , R ^NU71 , and R ^NU81 are particularly preferably alkyl groups having 1 to 5 carbon atoms, and R ^NU12 , R ^NU22 , R ^NU32 , R ^NU42 , R ^NU52 , R ^NU62 , R ^NU72 and R ^NU82 are particularly preferably an alkyl group having 1 to 5 carbon atoms or an alkoxy group having 1 to 5 carbon atoms.

The liquid crystal composition of the present invention preferably contains a compound represented by the general formula (NU-01) and a compound represented by the general formula (NU-02).

The liquid crystal composition of the present invention preferably contains a compound represented by the general formula (NU-01) and a compound represented by the general formula (NU-03).

The liquid crystal composition of the present invention preferably contains a compound represented by the general formula (NU-03) and a compound represented by the general formula (NU-04).

The liquid crystal composition of the present invention preferably contains a compound represented by the general formula (NU-03) and a compound represented by the general formula (NU-05).

The liquid crystal composition of the present invention preferably contains a compound represented by the general formula (NU-01) and a compound represented by the general formula (NU-06).

The liquid crystal composition of the present invention preferably contains a compound represented by the general formula (NU-01) and a compound represented by the general formula (NU-07).

The liquid crystal composition of the present invention preferably contains a compound represented by the general formula (NU-01) and a compound represented by the general formula (NU-08).

The liquid crystal composition of the present invention contains a compound represented by general formula (NU-01), a compound represented by general formula (NU-02), and a compound represented by general formula (NU-04). is even more preferable.

It is further preferable that the liquid crystal composition of the present invention contains a compound represented by the general formula (NU-01). Here, in the general formula (NU-01), R ^NU51 is particularly preferably an alkyl group having 1 to 5 carbon atoms, and R ^NU52 is particularly preferably an alkyl group having 1 to 5 carbon atoms.

It is further preferable that the liquid crystal composition of the present invention contains a compound represented by the general formula (NU-01) and a compound represented by the general formula (NU-05). Here, in the general formula (NU-01), R ^NU51 is particularly preferably an alkyl group having 1 to 5 carbon atoms, and R ^NU52 is particularly preferably an alkyl group having 1 to 5 carbon atoms.

The liquid crystal composition of the present invention contains a compound represented by general formula (NU-01), a compound represented by general formula (NU-02), and a compound represented by general formula (NU-05). is even more preferable. Here, in the general formula (NU-01), R ^NU51 is particularly preferably an alkyl group having 1 to 5 carbon atoms, and R ^NU52 is particularly preferably an alkyl group having 1 to 5 carbon atoms.

The liquid crystal composition of the present invention comprises a compound represented by the general formula (NU-01), a compound represented by the general formula (NU-02), a compound represented by the general formula (NU-03), and a compound represented by the general formula (NU-03). It is more preferable to contain a compound represented by NU-05).

The content of the compound represented by general formula (NU-01) is preferably 1 to 60% by mass, more preferably 10 to 50% by mass, and even more preferably 15 to 40% by mass. preferable.

The content of the compound represented by general formula (NU-02) is preferably 1 to 40% by mass, more preferably 5 to 25% by mass, and even more preferably 5 to 25% by mass. preferable.

The content of the compound represented by general formula (NU-03) is preferably 1 to 20% by mass, more preferably 1 to 15% by mass, and even more preferably 1 to 10% by mass. It is preferably 1 to 10% by mass, and more preferably 1 to 10% by mass.

The content of the compound represented by general formula (NU-04) is preferably 1 to 30% by mass, more preferably 3 to 20% by mass, and even more preferably 3 to 10% by mass. preferable.

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

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

The content of the compound represented by general formula (NU-07) is preferably 1 to 30% by mass, more preferably 3 to 20% by mass, and even more preferably 3 to 10% by mass. preferable.

The content of the compound represented by general formula (NU-08) is preferably 1 to 30% by mass, more preferably 3 to 20% by mass, and even more preferably 3 to 10% by mass. preferable.

The liquid crystal composition of the present invention can contain one or more compounds having positive dielectric anisotropy described in paragraphs 0236 to 0509 of Patent Document 4 (Patent No. 6233550). More preferably, a compound has a terphenyl structure or a tetraphenyl structure and has a dielectric anisotropy Δε larger than +2. Note that Δε of the compound is a value extrapolated from the measured value of the dielectric anisotropy of a composition obtained by adding the compound to a dielectrically substantially neutral composition at 25°C. These compounds are used in combination depending on the desired performance, such as low-temperature solubility, transition temperature, electrical reliability, refractive index anisotropy, etc. In particular, liquid crystals containing polymerizable compounds are used. The reactivity of the polymerizable compound in the composition can be accelerated.

The lower limit of the preferable content of the compound having a terphenyl structure or a tetraphenyl structure and having a dielectric anisotropy Δε larger than +2 is 0.1% based on the total amount of the liquid crystal composition of the present invention. , 0.5%, 1%, 1.5%, 2%, 2.5%, 3%, 4%, 5%, 10% be. Preferable upper limit values of the content are, for example, 20%, 15%, 10%, 9%, and 8% in one embodiment of the present invention, based on the total amount of the liquid crystal composition of the present invention. , 7%, 6%, 5%, 4%, and 3%.

The liquid crystal composition of the present invention contains one or two compounds having substantially neutral dielectric anisotropy (Δε of −2 to +2) described in paragraphs 0624 to 0642 of Patent Document 4 (Patent No. 6233550). or more.

The liquid crystal composition of the present invention may contain ordinary nematic liquid crystal, smectic liquid crystal, cholesteric liquid crystal, antioxidant, ultraviolet absorber, light stabilizer, infrared absorber, etc. in addition to the above-mentioned compounds.

Examples of antioxidants include hindered phenols represented by general formulas (H-1) to (H-4).

In general formulas (H-1) to (H-3), R ^H1 is each independently an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, or 2 carbon atoms. represents an alkenyl group having 10 or an alkenyloxy group having 2 to 10 carbon atoms, where one -CH ₂ - or two or more non-adjacent -CH ₂ -s present in the group are each independently - It may be substituted with O- or -S-, and one or more hydrogen atoms present in the group may be each independently substituted with a fluorine atom or a chlorine atom. More specifically, it may be an alkyl group having 2 to 7 carbon atoms, an alkoxy group having 2 to 7 carbon atoms, an alkenyl group having 2 to 7 carbon atoms, or an alkenyloxy group having 2 to 7 carbon atoms. Preferably, an alkyl group having 3 to 7 carbon atoms or an alkenyl group having 2 to 7 carbon atoms is more preferable.

In the general formula (H-4), M ^H4 is an alkylene group having 1 to 15 carbon atoms (one or more -CH ₂ - in the alkylene group is such that an oxygen atom is not directly adjacent to - may be substituted with O-, -CO-, -COO-, -OCO-), -OCH ₂ -, -CH ₂ O-, -COO-, -OCO-, -CF ₂ O-, - OCF ₂ -, -CF ₂ CF ₂ -, -CH=CH-COO-, -CH=CH-OCO-, -COO-CH=CH-, -OCO-CH=CH-, -CH=CH-, - C≡C-, single bond, 1,4-phenylene group (any hydrogen atom in the 1,4-phenylene group may be substituted with a fluorine atom) or trans-1,4-cyclohexylene group As shown, it is preferably an alkylene group having 1 to 14 carbon atoms, and considering volatility, the number of carbon atoms is preferably large, but considering viscosity, it is preferable that the number of carbon atoms is not too large. The number of carbon atoms is more preferably 2 to 12, further preferably 3 to 10, still more preferably 4 to 10, even more preferably 5 to 10, and even more preferably 6 to 10.

In general formulas (H-1) to (H-4), one or two or more non-adjacent -CH= in the 1,4-phenylene group may be substituted with -N=. Further, each hydrogen atom in the 1,4-phenylene group may be independently substituted with a fluorine atom or a chlorine atom.

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

More specific examples include formulas (H-11) to (H-15).

When the liquid crystal composition of the present invention contains an antioxidant, the lower limit thereof is preferably 10 mass ppm, preferably 20 mass ppm, preferably 50 mass ppm, and the upper limit is 10000 mass ppm, but 1000 mass ppm. is preferable, 500 mass ppm is preferable, and 100 mass ppm is preferable.

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. In the present invention, a temperature of 60°C or higher is expressed as having a high _TNI .

For LCD TV applications, the T _NI is preferably 70 to 80°C, for mobile applications, the T _NI is preferably 80 to 90°C, and for outdoor display applications such as PID (Public Information Display), the T _NI is 90 to 80°C. 110°C is preferred.

The liquid crystal composition of the present invention has a refractive index anisotropy (Δn) of 0.08 to 0.14 at 20°C, more preferably 0.09 to 0.13, and more preferably 0.09 to 0.12. Particularly preferred. More specifically, it is preferably from 0.10 to 0.13 when dealing with a thin cell gap, and preferably from 0.08 to 0.10 when dealing with a thick cell gap. Note that the liquid crystal composition of the present invention particularly preferably has a refractive index anisotropy (Δn) of 0.098 to 0.118 at 20°C.

The liquid crystal composition of the present invention has a rotational viscosity (γ ₁ ) at 20° C. of 50 to 160 mPa·s, preferably 55 to 160 mPa·s, preferably 60 to 160 mPa·s, and 80 to 160 mPa·s. to 150 mPa·s, preferably from 90 to 140 mPa·s, preferably from 90 to 130 mPa·s, and preferably from 90 to 115 mPa·s.

The liquid crystal composition of the present invention has a dielectric anisotropy (Δε) of -1.7 to -4.0 at 20°C, preferably -1.7 to -3.5, and -1.8 to -4.0. -3.5 is more preferred, and -1.9 to -3.3 is more preferred.

The liquid crystal composition of the present invention contains a polymerizable compound as a first component and a polymerizable compound as a second component, and further contains a general formula (N-01), a general formula (N-02), and a general formula (N-03). ), general formula (N-04), general formula (N-05), and if necessary, contains one or more compounds selected from the compound group represented by general formula (N-06), and further It is preferable to contain one or more compounds selected from the group of compounds represented by general formulas (NU-01) to (NU-08), and the upper limit of the total content of these compounds is 100% by mass. , 99% by mass, 98% by mass, 97% by mass, 96% by mass, 95% by mass, 94% by mass, 93% by mass, 92% by mass, 91% by mass, 90% by mass, 89% by mass, 88% by mass, 87 It is preferable that they are mass%, 86 mass%, 85 mass%, and 84 mass%, and the lower limit of the total of these contents is 78 mass%, 80 mass%, 81 mass%, 83 mass%, and 85 mass%. , 86% by mass, 87% by mass, 88% by mass, 89% by mass, 90% by mass, 91% by mass, 92% by mass, 93% by mass, 94% by mass, 95% by mass, 96% by mass, 97% by mass, 98 It is preferable that they are mass %, 99 mass %, and 100 mass %.

The liquid crystal composition of the present invention contains a polymerizable compound as a first component and a polymerizable compound as a second component, and further contains a general formula (N-01), a general formula (N-02), and a general formula (N-03). ) and the compound group represented by the general formula (N-04), and further contains one or more compounds selected from the compound group represented by the general formulas (NU-01) to (NU-08). It is particularly preferable to contain one or more selected compounds, and the upper limit of the total content is 100% by mass, 99% by mass, 98% by mass, 97% by mass, 96% by mass, 95% by mass. %, 94% by mass, 93% by mass, 92% by mass, 91% by mass, 90% by mass, 89% by mass, 88% by mass, 87% by mass, 86% by mass, 85% by mass, 84% by mass. , the lower limit of the total of these contents is 78% by mass, 80% by mass, 81% by mass, 83% by mass, 85% by mass, 86% by mass, 87% by mass, 88% by mass, 89% by mass, 90% by mass %, 91% by mass, 92% by mass, 93% by mass, 94% by mass, 95% by mass, 96% by mass, 97% by mass, 98% by mass, 99% by mass, and 100% by mass.

The liquid crystal composition of the present invention can provide a sufficiently high polymerization rate and a sufficiently large pretilt angle. In addition, the liquid crystal display element using the liquid crystal composition of the present invention has a small amount of residual polymerizable compound in the liquid crystal display element after polymerization, and is suitable for high-definition PSA type or PSVA type liquid crystal display elements such as 4K and 8K. Display defects such as IS (Image Sticking) do not occur or can be significantly suppressed. From the above, the production efficiency of high-definition PSA type or PSVA type liquid crystal display elements such as 4K or 8K can be significantly improved, and the industrial value is very high.

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

The liquid crystal display element of the present invention includes a first substrate and a second substrate arranged opposite to each other, a common electrode provided on the first substrate or the second substrate, and a common electrode provided on the first substrate or the second substrate. It is preferable to have a pixel electrode provided on the second substrate and having a thin film transistor, and a liquid crystal layer containing a liquid crystal composition provided between the first substrate and the second substrate. If necessary, an alignment film for controlling the alignment direction of liquid crystal molecules may be provided on the opposite 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. The alignment film can be selected as appropriate, such as a vertical alignment film or a horizontal alignment film, depending on the driving mode of the liquid crystal display element, and may be a rubbing alignment film (for example, polyimide) or a photo alignment film (degradable polyimide, etc.). A known alignment film 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 element of the present invention may be made of a flexible transparent material such as glass or plastic, and one may 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) onto a transparent substrate such as a glass plate.

The color filter can be created by, for example, a pigment dispersion method, a printing method, an electrodeposition method, a dyeing method, or the like. To explain a method for producing a color filter using a pigment dispersion method as an example, a curable coloring composition for a color filter is applied onto the transparent substrate, subjected to a patterning treatment, and then cured by heating or light irradiation. By performing this step for each of the three colors red, green, and blue, pixel portions for color filters can be created. In addition, a pixel electrode provided with an active element such as a TFT, a thin film diode, a metal insulator metal resistivity element, etc. may be provided on the substrate.

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

The distance between the first substrate and the second substrate may be adjusted using a spacer. At this time, it is preferable to adjust the thickness of the resulting light control layer to 1 to 100 μm. It is more preferably from 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 that the contrast is maximized. Further, when there are two polarizing plates, the polarization axis of each polarizing plate can be adjusted so that the viewing angle and contrato are good. Furthermore, a retardation film can also be used to widen the viewing angle. Examples of the spacer include glass particles, plastic particles, alumina particles, photoresist materials, and the like. Thereafter, a sealant such as an epoxy-based thermosetting composition is screen printed on the substrate in a form provided with a liquid crystal injection port, the substrates are bonded together, and the sealant is thermally cured by heating.

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

As a method for polymerizing the polymerizable compound contained in the liquid crystal composition of the present invention, in order to obtain good alignment performance of the liquid crystal, it is desirable to perform polymerization at a moderate polymerization rate. A method of polymerizing by irradiating energy rays singly or in combination or sequentially is preferred. When using ultraviolet light, a polarized light source or a non-polarized light source may be used. Further, when polymerization is carried out with the liquid crystal composition sandwiched between two substrates, at least the substrate on the irradiation surface side must be provided with appropriate transparency to active energy rays. In addition, after polymerizing only a specific part using a mask during light irradiation, by changing conditions such as electric field, magnetic field, or temperature, the orientation state of the unpolymerized part is changed, and active energy rays are further irradiated. Alternatively, a method of polymerization may be used. In particular, when exposing to ultraviolet light, it is preferable to expose the liquid crystal composition to ultraviolet light while applying a direct current electric field or an alternating current electric field. The applied alternating current electric field is preferably an alternating current with a frequency of 1 Hz to 10 kHz, more preferably a frequency of 60 Hz to 10 kHz, and the voltage is selected depending on the desired pretilt angle of the liquid crystal display element. That is, the pretilt angle of the liquid crystal display element can be controlled by the applied voltage. In a PSA type or PSVA type liquid crystal display element, it is preferable to control the pretilt angle from 80 degrees to 89.9 degrees from the viewpoint of alignment stability and contrast. Furthermore, it is more preferable to control the pretilt angle to be as large as 80 degrees to 89 degrees to provide an appropriate tilt. In a PSA type or PSVA type liquid crystal display element, image sticking (IS) occurs if a polymerizable compound remains as it is without polymerizing after the element is manufactured. The amount of the remaining polymerizable compound is preferably 150 ppm or less, preferably 140 ppm or less, preferably 130 ppm or less, preferably 120 ppm or less, preferably 110 ppm or less, particularly preferably 100 ppm or less.

The temperature at the time of irradiation with active energy rays such as ultraviolet rays or electron beams used when polymerizing the polymerizable compound contained in the liquid crystal composition of the present invention is not particularly limited. For example, when applying the liquid crystal composition of the present invention to a liquid crystal display element equipped with a substrate having an alignment film, the temperature is preferably within a temperature 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.

As the lamp for generating ultraviolet light, a metal halide lamp, a high-pressure mercury lamp, an ultra-high-pressure mercury lamp, etc. can be used, and ultra-high-pressure UV lamps manufactured by USHIO and fluorescent ultraviolet lamps manufactured by TOSHIBA are preferred. Further, as for the wavelength of the 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 it is preferable to cut off the ultraviolet rays when used. The intensity of the irradiated ultraviolet rays is preferably 0.1 mW/cm ² to 100 W/cm ² , more preferably 2 mW/cm ² to 50 W/cm ² . The energy amount of the ultraviolet rays to be irradiated can be adjusted as appropriate, but is preferably from 10 mJ/cm ² to 500 J/cm 2 , and more preferably from 100 mJ/ ^{cm 2 to} 200 J/cm ² .

EXAMPLES The present invention will be explained in more detail with reference to Examples below, but the present invention is not limited to these Examples. Moreover, "%" in the compositions of the following examples and comparative examples means "mass %". In the Examples, the following abbreviations are used to describe compounds.

Unless otherwise specified, each physical property value was measured based on the method described in the Electronics and Information Technology Industries Association Standard JEITA ED-2521B, revised in March 2009, published by the Electronics and Information Technology Industries Association.

(side chain)
-n -C _n H _2n+1 Straight-chain alkyl group with n carbon atoms n- C _n H _2n+1 - Straight-chain alkyl group with n carbon atoms -On -OC _n H _2n+1 Straight-chain alkoxy with n carbon atoms Group nO- C _n H _2n+1 O- Straight chain alkoxy group with n carbon atoms -V -CH=CH ₂
V- CH ₂ =CH-
-V1 -CH=CH-CH ₃
1V- CH ₃ -CH=CH-
-F -F
-OCF3 _-OCF3
(linking group)
-1O- -CH ₂ -O-
-O1- -O-CH ₂ -
-2- -CH ₂ -CH ₂ -
-COO- -COO-
-OCO- -OCO-
- Single bond (ring structure)

The properties measured in the examples are as follows.

Tni: Nematic phase-isotropic liquid phase transition temperature (℃)
Δn: Refractive index anisotropy at 20°C Δε: Dielectric constant anisotropy at 20°C γ ₁ : Rotational viscosity at 20°C (mPa・s)
RM: Amount of monomer remaining in the liquid crystal display element after 60 minutes of irradiation with UV light of 313 nm and illuminance of 3 mW/ ^cm2 (ppm)
Tilt: Pretilt angle (°) of the liquid crystal display element after ² minutes of irradiation with 313 nm UV light at an illuminance of 3 mW/cm2
IS: A value obtained by multiplying by 100 the amount of change in pretilt angle after preparing a liquid crystal display element after 60 minutes of UV light irradiation with an illumination intensity of 3mW/ ^cm2 at 313nm and maintaining the driving state for a certain period of time.VHR: Illuminance at 313nm Voltage retention rate (%) when preparing a liquid crystal display element after 60 minutes of irradiation with 3 mW/cm ² UV light and measuring at 1 V, 60 Hz, 60°C
(Synthesis of polymerizable compound)
(Synthesis of RM-13)
A reaction vessel equipped with a stirrer, a condenser, and a thermometer was charged with 47 g (240 mmol) of 4-(tetrahydro-2H-pyran-2-yloxy)phenol, 37 g (288 mmol) of diisopropylethylamine, and 650 ml of methylene chloride. Keep the reaction vessel below 5℃ in a cold bath. 25 g (276 mmol) of acryloyl chloride was slowly added dropwise under a nitrogen gas atmosphere. After the dropwise addition was completed, the reaction vessel was returned to room temperature and reacted for 5 hours. 280 ml of methylene chloride was added to the reaction solution, and the mixture was washed with an aqueous hydrochloric acid solution, followed by water, and further washed with saturated brine, and the organic layer was dried over anhydrous sodium sulfate. After distilling off the solvent, purification was performed using an alumina column of twice the amount (weight ratio) to obtain 59 g of the compound shown in (1).

Next, 59 g of the compound represented by formula (1), 300 ml of tetrahydrofuran, 1 ml of concentrated hydrochloric acid, and 5 ml of methanol were charged into a reaction vessel equipped with a stirrer, a cooler, and a thermometer, and reacted at room temperature for 12 hours. 630 ml of ethyl acetate was added to the reaction solution, washed with water, further washed with saturated brine, and the organic layer was dried over anhydrous sodium sulfate. After distilling off the solvent, purification was performed using a 10 times (by weight) silica column to obtain 34 g of the compound shown in (2).

8. Into a reaction vessel equipped with a stirrer, a condenser, and a thermometer, 125 g (723 mmol) of 4-bromophenol, 116 g (903 mmol) of t-butyl acrylate, 150 g (1.1 mol) of potassium carbonate, and palladium acetate. 11 g (36 mmol) and 1230 ml of N-methyl-2-pyrrolidone were charged and reacted at 125° C. for 5 hours. 1390 ml of ethyl acetate was added to the reaction solution, washed with an aqueous hydrochloric acid solution, and further washed with saturated brine, and the organic layer was dried over anhydrous sodium sulfate. After distilling off the solvent, purification was carried out using a silica column with twice the amount (weight ratio), and 106 g of the compound shown in (3) was obtained by recrystallization with methylene chloride/hexane.

106 g (482 mmol) of the compound represented by formula (3), 75 g (579 mmol) of diisopropylethylamine, and 1410 ml of methylene chloride were placed in a reaction vessel equipped with a stirrer, a cooler, and a thermometer, and the mixture was heated to 5°C or lower in an ice-cooled bath. Keep the reaction vessel warm. 58 g (555 mmol) of methacryloyl chloride was slowly added dropwise under a nitrogen gas atmosphere. After the dropwise addition was completed, the reaction vessel was returned to room temperature and reacted for 5 hours. 600 ml of methylene chloride was added to the reaction solution, and the mixture was washed with an aqueous hydrochloric acid solution, followed by water, and further washed with saturated brine, and the organic layer was dried over anhydrous sodium sulfate. After distilling off the solvent, purification was carried out using a silica column with twice the amount (weight ratio) to obtain 132 g of the compound shown in (4).

132 g (458 mmol) of the compound represented by formula (4), 330 ml of formic acid, and 330 ml of methylene chloride were placed in a reaction vessel equipped with a stirrer, a cooler, and a thermometer, and reacted at 40° C. for 8 hours. Water was added to the reaction solution to precipitate a solid, which was collected by filtration and dried to obtain 92 g of the compound shown in (5).

In a reaction vessel equipped with a stirrer, a condenser, and a thermometer, 5 g (30 mmol) of the compound represented by formula (2), 7 g (30 mmol) of the compound represented by formula (5), and 480 mg (3.9 mmol) of dimethylaminopyridine were added. ) and 48 ml of methylene chloride, and keep the reaction vessel below 5°C in an ice-cooled bath. 4.9 g (39 mmol) of diisopropylcarbodiimide was slowly added dropwise under a nitrogen gas atmosphere. After the dropwise addition was completed, the reaction vessel was returned to room temperature and reacted for 5 hours. After filtering the reaction solution, 23 ml of methylene chloride was added to the filtrate, washed with an aqueous hydrochloric acid solution, and further washed with saturated brine, and the organic layer was dried over anhydrous sodium sulfate. After evaporating the solvent, purification was performed using a 10-fold (weight ratio) silica column, and recrystallization from methylene chloride/hexane yielded 6.1 g of the target compound represented by formula (RM-13).

¹ H-NMR (solvent: deuterated chloroform): δ: 2.08 (s, 3H), 5.79 (d, 1H), 6.03 (dd, 1H), 6.29-6.37 (m, 2H), 6.57-6.64 (m, 2H), 7.17-7.22 (m, 6H), 7.63 (d, 2H), 7.86 (d, 1H)
Infrared absorption spectrum (IR) (KBr): 1760-1700, 1640, 1600 cm ^-1 Melting point: 140°C
(Synthesis of RM-14)
A reaction vessel equipped with a stirrer, a condenser, and a thermometer was charged with 100 g (515 mmol) of 4-(tetrahydro-2H-pyran-2-yloxy)phenol, 80 g (618 mmol) of diisopropylethylamine, and 1380 ml of methylene chloride, and placed on ice. Keep the reaction vessel below 5℃ in a cold bath. 62 g (592 mmol) of methacryloyl chloride was slowly added dropwise under a nitrogen gas atmosphere. After the dropwise addition was completed, the reaction vessel was returned to room temperature and reacted for 5 hours. 590 ml of methylene chloride was added to the reaction solution, and the mixture was washed with an aqueous hydrochloric acid solution, followed by water, and further washed with saturated brine, and the organic layer was dried over anhydrous sodium sulfate. After distilling off the solvent, purification was performed using an alumina column with twice the amount (weight ratio), and recrystallization with methylene chloride/methanol gave 116 g of the compound shown in (6).

Next, 116 g of the compound represented by formula (6), 600 ml of tetrahydrofuran, 2 ml of concentrated hydrochloric acid, and 10 ml of methanol were charged into a reaction vessel equipped with a stirrer, a cooler, and a thermometer, and reacted at room temperature for 12 hours. 1260 ml of ethyl acetate was added to the reaction solution, washed with water, further washed with saturated brine, and the organic layer was dried over anhydrous sodium sulfate. After distilling off the solvent, purification was carried out using a silica column with twice the amount (weight ratio), and 71 g of the compound shown in (7) was obtained by recrystallization with methylene chloride/hexane.

106 g (482 mmol) of the compound represented by formula (3), 75 g (579 mmol) of diisopropylethylamine, and 1410 ml of methylene chloride were placed in a reaction vessel equipped with a stirrer, a cooler, and a thermometer, and the mixture was heated to 5°C or lower in an ice-cooled bath. Keep the reaction vessel warm. 50 g (555 mmol) of acryloyl chloride was slowly added dropwise under a nitrogen gas atmosphere. After the dropwise addition was completed, the reaction vessel was returned to room temperature and reacted for 5 hours. 600 ml of methylene chloride was added to the reaction solution, and the mixture was washed with an aqueous hydrochloric acid solution, followed by water, and further washed with saturated brine, and the organic layer was dried over anhydrous sodium sulfate. After distilling off the solvent, purification was carried out using a silica column with twice the amount (weight ratio) to obtain 132 g of the compound shown in (8).

132 g (482 mmol) of the compound represented by formula (4), 330 ml of formic acid, and 330 ml of methylene chloride were placed in a reaction vessel equipped with a stirrer, a cooler, and a thermometer, and reacted at 40° C. for 8 hours. Water was added to the reaction solution to precipitate a solid, which was collected by filtration and dried to obtain 97 g of the compound shown in (9).

In a reaction vessel equipped with a stirrer, a condenser, and a thermometer, 8.1 g (45 mmol) of the compound represented by formula (7), 9.4 g (43 mmol) of the compound represented by formula (9), and 720 mg (720 mg) of dimethylaminopyridine were added. 5.9 mmol) and 72 ml of methylene chloride, and kept the reaction vessel below 5°C in an ice-cooled bath. 7.5 g (59 mmol) of diisopropylcarbodiimide was slowly added dropwise under a nitrogen gas atmosphere. After the dropwise addition was completed, the reaction vessel was returned to room temperature and reacted for 5 hours. After filtering the reaction solution, 34 ml of methylene chloride was added to the filtrate, washed with an aqueous hydrochloric acid solution, and further washed with saturated brine, and the organic layer was dried over anhydrous sodium sulfate. After distilling off the solvent, purification was carried out using a 10-fold (weight ratio) silica column, and recrystallization from methylene chloride/methanol yielded 6.5 g of the target compound represented by formula (RM-14).

¹ H-NMR (solvent: deuterated chloroform): δ: 2.07 (s, 3H), 5.76-7.77 (m, 1H), 6.05 (dd, 1H), 6.30-6. 37 (m, 2H), 6.57-6.66 (m, 2H), 7.15-7.23 (m, 6H), 7.61-7.63 (m, 2H), 7.86 ( d, 1H)
Infrared absorption spectrum (IR) (KBr): 1750-1700, 1640 cm ^-1 Melting point: 144°C
(Preparation and evaluation results of liquid crystal composition)
Liquid crystal compositions (LC-5) were prepared from liquid crystal compositions (LC-1) and their physical properties were measured. The component ratios and physical property values of these liquid crystal compositions are shown in Table 1.

Example (E-01) in which these liquid crystal compositions were mixed with polymerizable compounds represented by the following formulas (RM-11) to (RM-17) and formulas (RM-21) to (RM-23). ) to (E-06) and comparative examples (C-01) to (C-02) were prepared, and the results of evaluating RM, Tilt, IS, and VHR were as shown in the table below.

In Examples 1 (E-01) to 6 (E-20), RM is a sufficiently small value, Tilt is an appropriate value, IS is a small value, and VHR is a sufficiently high value. I confirmed that there is. From the above, it was confirmed that these Examples solved the problems of the present invention.

On the other hand, it was confirmed that Comparative Example 1 (C-01) containing only the polymerizable compound of the second component of the present invention had a large RM, and the reliability of the liquid crystal display element decreased. Furthermore, although the liquid crystal composition of Comparative Example 2 (C-02) contains the polymerizable compound as the second component of the present invention, it uses a polymerizable compound that has a different structure from the first component of the present invention. The result was that the VHR was low. From the above, it was confirmed that these comparative examples cannot solve the problems of the present invention.

Furthermore, Examples 7 (E-07) to 14 (E-14) were prepared and evaluated, and the results were as shown in the table below.

In Example 7 (E-07) to Example 14 (E-14), RM is a sufficiently small value, Tilt is an appropriate value, IS is a small value, and VHR is a sufficiently high value. I confirmed that there is. From the above, it was confirmed that these Examples solved the problems of the present invention.

Furthermore, Example 15 (E-15) to Example 20 (E-20) were prepared and evaluated, and the results were as shown in the table below.

In Example 15 (E-15) to Example 20 (E-20), RM is a sufficiently small value, Tilt is an appropriate value, IS is a small value, and VHR is a sufficiently high value. I confirmed that there is. From the above, it was confirmed that these Examples solved the problems of the present invention.

Claims (9)

As the first component, general formula (i)

(In the formula, A ⁱ¹ and A ⁱ² are each independently,
(a) 1,4-cyclohexylene group (one -CH ₂ - or two or more non-adjacent -CH ₂ -s present in this group may be replaced with -O-)
(b) 1,4-phenylene group (one -CH= or two or more non-adjacent -CH= present in this group may be replaced with -N=) and (c) naphthalenediyl group, 1,2,3,4-tetrahydronaphthalenediyl group or decahydronaphthalenediyl group (one -CH= or Two or more non-adjacent -CH= may be replaced with -N=.)
The above group (a), group (b) and group (c) each independently represent an alkyl group having 1 to 8 carbon atoms, or an alkyl group having 1 to 8 carbon atoms. May be substituted with an alkoxy group, halogen, cyano group, nitro group or P ⁱ³ -S ⁱ³ -,
P ⁱ¹ , P ⁱ² and P ⁱ³ are each independently represented by formula (R-1) to formula (R-15)

represents a polymerizable group represented by, at least one of P ⁱ¹ and P ⁱ² is selected from formula (R-1), the other is selected from formulas (R-2) to (R-15),
S ⁱ³ represents a single bond or an alkylene group having 1 to 5 carbon atoms, and one -CH ₂ - or two or more non-adjacent -CH ₂ -s in the alkylene group are -O-, May be substituted with -OCO- or -COO-,
n ⁱ¹ represents 1 or 2,
When there are multiple A ^i2s , they may be the same or different. ) Contains a polymerizable compound represented by
As the second component, general formula (RM-22) or general formula (RM-23)

(In the formula, P ⁵ , P ⁶ , P ⁷ and P ⁸ are each independently represented by formula (R-1) to formula (R-15)

S ⁵ , S ⁶ , S ⁷ and S ⁸ each independently represent a single bond or an alkylene group having 1 to 5 carbon atoms, and one of the alkylene groups -CH ₂ - or two or more non-adjacent -CH ₂ - may be substituted with -O-, -OCO- or -COO-, and A ¹ to A ⁸ are each independently a carbon atom. Represents an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, a fluorine atom or a hydrogen atom, and B ¹ to B ¹² are each independently an alkyl group having 1 to 5 carbon atoms, an alkyl group having 1 to 5 carbon atoms, and ~5 alkoxy group, fluorine atom or hydrogen atom. ) A liquid crystal composition containing a polymerizable compound represented by: Furthermore, general formula (N-01), general formula (N-02), general formula (N-03), general formula (N-04) and general formula (N-05)

(In the formula, R ²¹ and R ²² are each independently an alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, an alkenyl group having 2 to 8 carbon atoms, or an alkenyl group having 2 to 8 carbon atoms. represents an alkenyloxy group of 8, and one or two or more non-adjacent -CH ₂ - in the group are each independently -CH=CH-, -C≡C-, -O-, -CO -, -COO- or -OCO-, and Z ¹ is each independently a single bond, -CH ₂ CH ₂ -, -OCH ₂ -, -CH ₂ O-, -COO- , -OCO-, -OCF ₂ -, -CF ₂ O-, -CH=CH-, -CF=CF- or -C≡C-, and m each independently represents 1 or 2. ) The liquid crystal composition according to claim 1, containing one or more compounds selected from the group of compounds represented by the following. Furthermore, general formula (NU-01) to general formula (NU-08)

(In the formula, R ^NU11 , R ^NU12 , R ^NU21 , R ^NU22 , R ^NU31 , R ^NU32 , R ^NU41 , R ^NU42 , R ^NU51 , R ^NU52 , R ^NU61 , R ^NU62 , R ^NU71 , R ^NU72 , R ^NU81 and R ^NU82 each independently 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. , one or two or more non-adjacent -CH ₂ -s in the group are each independently -CH=CH-, -C≡C-, -O-, -CO-, -COO- or -OCO The liquid crystal composition according to claim 2, which contains one or more compounds selected from the group of compounds represented by -. The first component, the second component, a compound selected from the group of compounds represented by the general formula (N-01) to the general formula (N-05), a compound selected from the group of compounds represented by the general formula (NU-01) to the general formula (NU-08), 4. The liquid crystal composition according to claim 3, wherein the total content of the compounds selected from the represented compound group is from 80% by mass to 100% by mass. The first component, the second component, one or more compounds selected from the group of compounds represented by the general formula (N-01) to the general formula (N-05), and the general formula (NU-01) to the general formula (NU -08) One or more compounds selected from the group of compounds represented by -08), an optionally contained antioxidant, an optionally contained ultraviolet absorber, an optionally contained light stabilizer, and an optionally contained antioxidant. 4. The liquid crystal composition according to claim 3, comprising an infrared absorbing agent. A liquid crystal display element using the liquid crystal composition according to any one of claims 1 to 5. A liquid crystal display element for active matrix driving using the liquid crystal composition according to any one of claims 1 to 5. A PSA type or PSVA type liquid crystal display element using the liquid crystal composition according to any one of claims 1 to 5. General formula (i)

(In the formula, A ⁱ¹ and A ⁱ² are each independently,
(a) 1,4-cyclohexylene group (one -CH ₂ - or two or more non-adjacent -CH ₂ -s present in this group may be replaced with -O-)
(b) 1,4-phenylene group (one -CH= or two or more non-adjacent -CH= present in this group may be replaced with -N=) and (c) naphthalenediyl group, 1,2,3,4-tetrahydronaphthalenediyl group or decahydronaphthalenediyl group (one -CH= or Two or more non-adjacent -CH= may be replaced with -N=.)
The above group (a), group (b) and group (c) each independently represent an alkyl group having 1 to 8 carbon atoms, or an alkyl group having 1 to 8 carbon atoms. May be substituted with an alkoxy group, halogen, cyano group, nitro group or P ⁱ³ -S ⁱ³ -,
P ⁱ¹ , P ⁱ² and P ⁱ³ are each independently represented by formula (R-1) to formula (R-15)

represents a polymerizable group represented by, at least one of P ⁱ¹ and P ⁱ² is selected from formula (R-1), the other is selected from formulas (R-2) to (R-15),
S ⁱ³ represents a single bond or an alkylene group having 1 to 5 carbon atoms, and one -CH ₂ - or two or more non-adjacent -CH ₂ -s in the alkylene group are -O-, May be substituted with -OCO- or -COO-,
n ⁱ¹ represents 1 or 2,
When there are multiple A ^i2s , they may be the same or different. ) is a polymerizable compound represented by