JP2021088619A - Liquid crystal composition and liquid crystal display element - Google Patents

Abstract

To provide a liquid crystal composition and a liquid crystal display element containing a polymerizable compound for manufacturing a PSA type or PSVA type liquid crystal display element, wherein the polymerizable compound has a sufficiently high polymerization rate, and a liquid crystal display element using the liquid crystal composition has no or extremely little display failures by changes in a pretilt angle but has a sufficient pretilt angle and is excellent in a response performance.SOLUTION: A liquid crystal composition and a liquid crystal display element contain a polymerizable compound represented by a general formula (i) as a first component. In the formula (i), R101 to R104 each independently represent -O-(CH2)m1-CH3 or the like, where m1 represents 0, 1, 2 or 3; Li1 represents a single bond, -C2H4, C3H6, or the like; Ai1 represents 1,4-cyclohexylene group or the like; ni1 represents 0 or 1; Pi1, Pi2 and Pi3 each independently represent a polymerizable group having a specific structure; and Spi1, Spi2 and Spi3 each independently represent a single bond or an alkylene group having 1 to 5 carbon atoms.SELECTED DRAWING: None

Description

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

The PSA (Polymer Sustained Position) type liquid crystal display element has a structure in which a polymer structure is formed in a cell in order to control the pretilt angle of liquid crystal molecules, and is practical as a liquid crystal display element due to its high-speed response and high contrast. It has been transformed.

In the production of a PSA type liquid crystal display element, a polymerizable composition containing a liquid crystal compound and a polymerizable compound is injected between substrates, and a voltage is applied to orient the liquid crystal molecules to polymerize the polymerizable compound to polymerize the liquid crystal molecules. It is done by fixing the orientation of. It is known that the cause of the burn-in, which is a display defect of the PSA type liquid crystal display element, is due to impurities and a change in the orientation of the liquid crystal molecules (change in the pretilt angle).

The seizure caused by the change in the pretilt angle of the liquid crystal molecules is that the structure of the polymer changes when the same pattern is continuously displayed for a long time when the display element is configured, and as a result, the pretilt angle changes. Is. Therefore, a polymerizable compound that forms a polymer having a rigid structure in which the polymer structure does not change is required.

Conventionally, in order to prevent seizure by improving the rigidity of a polymer, Patent Document 1 uses a polymerizable compound having a biphenyl structure as a ring structure to form a display element, and Patent Document 2 has a ring structure. Disclosed as a display element using a polymerizable compound having a terphenyl structure.

As shown in Examples of Patent Document 1 and Patent Document 2, by using the following compound (A) having a biphenyl skeleton and compound (B) having a terphenyl skeleton, Attempts have been made to improve seizure caused by changes in the pretilt angle.

In recent years, in the production of liquid crystal elements, a liquid crystal composition having an appropriately high polymerization rate has been required for the purpose of improving production efficiency. However, the liquid crystal composition containing the compound (A) and the compound (B) as the main polymerizable compound has not been sufficiently polymerized, and therefore has been required to be improved.

WO2010 / 084823 Japanese Unexamined Patent Publication No. 2012-241125 Japanese Patent No. 6233550

The problem to be solved by the present invention is that the polymerization rate of the polymerizable compound is sufficiently high, and the device using the polymerizable compound has no or extremely few display defects due to a change in the pretilt angle, and has a sufficient pretilt angle. Further, it is an object of the present invention to provide a liquid crystal composition containing a polymerizable compound for producing a PSA type or PSVA type liquid crystal display element having excellent response performance, and to provide a liquid crystal display element using the same.

As a result of diligent studies by the present inventors, it has been found that the above-mentioned problems can be solved by a liquid crystal composition containing a polymerizable compound having a specific chemical structure, and the present invention has been completed.

That is, an object of the present invention is to provide a liquid crystal composition containing a polymerizable compound represented by the general formula (i) as a first component.

A further object of the present invention is to provide a liquid crystal display element using the liquid crystal composition.

The liquid crystal composition of the present invention has a low modulus (η) and a small rotational viscosity (γ1) without lowering the modulus anisotropy (Δn) and the nematic phase-isotropic liquid phase transition temperature (Tni). A liquid crystal composition having a large elastic constant (K33), a sufficiently high polymerization rate of the polymerizable compound, and no precipitation of the polymerizable compound. The liquid crystal display element using the liquid crystal composition of the present invention has a sufficient pretilt angle, a small residual amount of the polymerizable compound, a high voltage retention rate (VHR), a high-speed response, and a misalignment or seizure. It shows excellent display quality with no or suppressed display defects.

In the liquid crystal composition of the present invention, the pretilt angle and the residual amount of the polymerizable compound can be controlled by using a specific polymerizable compound, and the production efficiency can be easily improved by optimizing and reducing the energy cost for production. .. Therefore, the liquid crystal composition of the present invention and the liquid crystal display element using the same are very useful.

The liquid crystal composition of the present invention contains one or more polymerizable compounds represented by the general formula (i).

(During the ceremony,
R ^{101 to} R ¹⁰⁴ are independently of hydrogen atom, fluorine atom, -O- (CH ₂ ) _m1- CH ₃ , -CH ₂ F, -CHF ₂ , -CF ₃ or -Sp ⁱ³ -P ⁱ³ . Representing any, m1 represents 0, 1, 2 or 3, and at least one or more groups of ^{R 101 to} R ¹⁰⁴ _{are -O- (CH 2} ) _m1- CH ₃ , -CH ₂ F,-. Represents CHF ₂ or -CF ₃
L ⁱ¹ represents a single _{bond, -C 2 H 4 -, -} C 3 H 6 -, - C 4 H 8 -, - OCH 2 -, - CH 2 O -, - CO -, - COO -, - OCO- , -OCOOCH _2- , -CH ₂ OCOO-, -OCH ₂ CH ₂ O-, -CH = CRa-COO-, -CH = CRa-OCO-, -COO-CRa = CH-, -OCO-CRa = CH -, -COO-CRa = CH-COO-, -COO-CRa = CH-OCO-, -OCO-CRa = CH-COO-, -OCO-CRa = CH-OCO-, -CH _{2 OCO-, -COOCH 2 -, - OCOCH 2 -,} - C 2 H 4 OCO -, - C 2 H 4 COO -, - COOC 2 H 4 -, - OCOC 2 H 4 -, - CH = CH -, - CF = CF-, -CF = CH-, -CH = CF-, -CF ₂ O-, -OCF _2- , -CF ₂ CH _2- , -CH ₂ CF _2- , -CF ₂ CF _2- or -C ≡ C-, (In the formula, Ra independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms).
A ⁱ¹ is
(A) 1,4-cyclohexylene group, (this is present in the group one -CH ₂ - - or nonadjacent two or more -CH ₂ may be replaced by -O-.)
(B) From the group consisting of 1,4-phenylene groups (one -CH = existing in this group or two or more -CH = not adjacent to each other may be replaced with -N =). Representing the group to be selected, the group (a) and the group (b) may be substituted with ^{an alkyl group having 1 to 8 carbon atoms or Pi3-} S ^i3-.
n ⁱ¹ represents 0 or 1 and represents
^{Pi 1} , ^{Pi 2} and ^{Pi 3} each independently represent a polymerizable group selected from formulas (R-1) to (R-15).

Sp ⁱ¹ , Sp ⁱ² and Sp ⁱ³ 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 alkylene groups in the alkylene group. of -CH ₂ -, as the oxygen atoms are not directly adjacent, -O -, - OCO- or -COO- in may be substituted. )
The liquid crystal composition containing the polymerizable compound represented by the general formula (i) has an appropriately high polymerization rate, and can impart a desired pretilt angle in a short ultraviolet irradiation time. Further, when the polymerization rate is moderately high, the residual amount of the polymerizable compound can be reduced. Therefore, the production efficiency of manufacturing the PSA type liquid crystal display element can be improved. In addition, there is an effect that display defects (for example, defects such as burn-in) due to a change in the pre-tilt angle do not occur or are extremely small. The display defects in the present specification include display defects due to changes in the pretilt angle after polymerization over time, display defects due to the residual amount of unreacted polymerizable compound, and display defects due to a decrease in voltage retention rate. I am considering it.

In the polymerizable compound represented by the general formula (i), R ^{101 to} R ¹⁰⁴ are independently hydrogen atom, fluorine atom, -O- (CH ₂ ) _m1- CH ₃ , -CH ₂ F, respectively. It _{represents either −CHF 2} , −CF ₃ or −Sp ⁱ³ −P ⁱ³ , and m1 represents 0, 1, 2 or 3. Here, ^{at least one or more groups of R 101 to} R ¹⁰⁴ have m1 of 0, 1, 2 or 3, -O- (CH ₂ ) _m1 -CH ₃ , -CH ₂ F, -CHF ₂ , Or -CF ₃ , but at least one or more groups of ^{R 101 to} R ¹⁰⁴ are preferably groups represented by _{-O- (CH 2} ) _m1- CH _{3 in} ^{which m1 is 0 or 1, and R 101.} preferably at least one or more groups is m1 = 0 that is -OCH ₃ out of to R ^104, it is preferable one group out of R 101 ^{to R 104} is -OCH _3. Thus, at least one or more groups of ^{R 101 to} R ¹⁰⁴ _{represent -O (CH 2} ) _m1 -CH ₃ , -CH ₂ F, -CHF ₂ , or -CF ₃ , but other Rs. ^{The 101 to} R ¹⁰⁴ groups represent a hydrogen atom, a fluorine atom or −Sp ⁱ³ −P ^i3, and are preferably a hydrogen atom or a fluorine atom.

In the polymerizable compound represented by the general formula ^{(i), L i1} is a single _{bond, -C 2 H 4 -, -} C 3 H 6 -, - C 4 H 8 -, - OCH 2 -, - CH ₂ O-, -CO-, -COO-, -OCO-, -OCOOCH _2- , -CH ₂ OCOO-, -OCH ₂ CH ₂ O-, -CH = CRa-COO-, -CH = CRa-OCO- , -COO-CRa = CH-, -OCO-CRa = CH-, -COO-CRa = CH-COO-, -COO-CRa = CH-OCO-, -OCO-CRa = CH-COO-, -OCO- _{CRa = CH-OCO -, -} CH 2 OCO -, - COOCH 2 -, - OCOCH 2 -, - C 2 H 4 OCO -, - C 2 H 4 COO -, - COOC 2 H 4 -, - OCOC 2 H _{4 -, - CH = CH -} , - CF = CF -, - CF = CH -, - CH = CF -, - CF 2 O -, - OCF 2 -, - CF 2 CH 2 -, - CH 2 CF 2 -, -CF ₂ CF _2- or -C ≡ C-, (in the formula, Ra independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms), where ^{Li 1} is a single bond. _{-C 2 H 4 -, - OCH} 2 -, - CH 2 O -, - CO -, - COO -, - OCO -, - CH = CHCOO -, - CH = CH-OCO -, - COO-CH = CH -, - preferably OCO-CH = CH- or -COO-CH = is ^{CH-COO-, L i1} is a single _{bond, -C 2 H 4 -, -} OCH 2 -, - CH 2 O -, - CO -, - preferably COO- or ^{-OCO-, L i1} represents a single bond, -OCH ₂ - is preferably or _-CH 2 O-in ^which, it is preferred that ^{L i1} is a single bond.

In the polymerizable compound represented by the general formula (i), A ⁱ¹ is (a) a 1,4-cyclohexylene group (one -CH _2- or two non-adjacent groups present in this group). The above −CH ₂₋ may be replaced with −O−) or (b) 1,4-phenylene group (one −CH = or two or more non-adjacent groups present in this group). -CH = represents a group selected from the group consisting of -N =), and the groups (a) and (b) are alkyl groups having 1 to 8 carbon atoms or ^Pi3. Although it may be substituted with ^{−S i3 −, A i1} is preferably a 1,4-cyclohexylene group or a 1,4-phenylene group, and A ⁱ¹ is preferably a 1,4-phenylene group.

In the polymerizable compound represented by the general formula (i), ^{ni1 represents 0 or 1, and ni1} is preferably 0 because the solubility in the liquid crystal composition becomes better.

In the polymerizable compound represented by the general formula (i), ^{Pi 1} , ^{Pi 2} and ^{Pi 3} are independently selected from the following formulas (R-1) to (R-15) as described above. Represents a group to be polymerized.

It is preferable that P ⁱ¹ and P ⁱ² are independently selected from the formulas (R-1) to (R-6), and the formulas (R-1) to (R-3) and the formula (R-3) are selected. It is preferably selected from the formula (R-1) to the formula (R-3), and is preferably selected from the formula (R-1) or the formula (R-2). Is preferable. P ⁱ¹ and ^{P i2} may be the same be a group different groups respectively ^{but, P i1} and ^{P i2} is preferably represent the same ^group, both ^{P i1} and ^{P i2} formula (R- It is preferable to represent 1) or the formula (R-2), and it is preferable that ^{both Pi1} and ^Pi2 represent the formula (R-2).

^Pi3 is preferably selected from formulas (R-1) to (R-6), and is preferably selected from formulas (R-1) to formulas (R-3) and formulas (R-6). Is preferable, and it is preferable to select from the formulas (R-1) to (R-3), and it is preferable to select from the formula (R-1) or the formula (R-2).

In the polymerizable compound represented by the general formula ^{(i), Sp i1, Sp} i2 and ^{Sp i3} are each independently a single bond or an alkylene group having 1 to 5 carbon atoms, in the alkylene radical one -CH ₂ - or nonadjacent two or more -CH ₂ -, as the oxygen atoms are not directly adjacent, -O -, - OCO- or -COO- in may be substituted. Sp ^{i1, Sp i2} and ^{Sp i3} are each independently is preferably selected from a single bond or an alkylene group having 1 to 3 carbon atoms, either ^{Sp i1} or ^{Sp i2} represents a single bond, The other is preferably selected from alkylene groups having 1 to 3 carbon atoms, ^{and both Sp i1} and Sp ⁱ² are preferably single bonds. When Sp ⁱ¹ , Sp ⁱ² and Sp ⁱ³ are single bonds, the residual amount of the polymerizable compound after irradiation with ultraviolet rays is sufficiently small, and display defects due to changes in the pretilt angle are less likely to occur.

The polymerizable compound-containing liquid crystal composition of the present invention contains one or more polymerizable compounds represented by the general formula (i) as the first component, specifically, the formula (i-) described below. 1) It contains one or more polymerizable compounds selected from (i-25), but 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 is preferable, 0.03% by mass is preferable, 0.04% by mass is preferable, 0.05% by mass is preferable, 0.06% by mass is preferable, and 0.07% by mass is preferable. 0.08% by mass is preferable, 0.09% by mass is preferable, 0.1% by mass is preferable, 0.12% by mass is preferable, 0.15% by mass is preferable, 0.17% by mass is preferable, and 0. 2% by mass is preferable, 0.22% by mass is preferable, 0.25% by mass is preferable, 0.27% by mass is preferable, 0.3% by mass is preferable, 0.32% by mass is preferable, and 0.35% by mass is preferable. % Is preferable, 0.37% by mass is preferable, 0.4% by mass is preferable, 0.42% by mass is preferable, 0.45% by mass is preferable, 0.5% by mass is preferable, and 0.55% by mass is preferable. preferable.

The upper limit of the content of the first component in the liquid crystal composition of the present invention is preferably 5.0% by mass, preferably 4.5% by mass, preferably 4.0% by mass, and 3.5% by mass. Preferably, 3.0% by mass is preferable, 2.5% by mass is preferable, 2% by mass is preferable, 1.5% by mass is preferable, 1.0% by mass is preferable, 0.95% by mass is preferable, and 0. 9% by mass is preferable, 0.85% by mass is preferable, 0.8% by mass is preferable, 0.75% by mass is preferable, 0.7% by mass is preferable, 0.65% by mass is preferable, and 0.6% by mass is preferable. % Is preferable, 0.55% by mass is preferable, 0.5% by mass is preferable, 0.45% by mass is preferable, and 0.4% by mass is preferable.

More specifically, in order to obtain a high voltage retention (VHR) when the liquid crystal display element has a small residual amount of the polymerizable compound, the general formula (i) which is the first component in the liquid crystal composition of the present invention. Specifically, the content of the polymerizable compound selected from the formulas (i-1) to (i-25) described below is 0.1% by mass to 1.5% by mass. It is preferably in the range of%. Further, when the suppression of precipitation of the polymerizable compound at a low temperature is emphasized, the content of the first component in the liquid crystal composition of the present invention is preferably in the range of 0.01% by mass to 1.0% by mass. Further, when the liquid crystal composition of the present invention contains a plurality of polymerizable compounds represented by the general formula (i) as the first component, the content of each is 0.01% by mass to 0.6% by mass. It is preferably within the range of. Further, in the liquid crystal composition of the present invention, a polymerizable compound other than the polymerizable compound represented by the general formula (i) is used as the main polymerizable compound, and the polymerizable compound represented by the general formula (i) is used as a sub. When used in combination as a polymerizable compound, the content of the polymerizable compound represented by the general formula (i) is preferably in the range of 0.01% by mass to 0.1% by mass. Therefore, in order to solve all these problems, it is particularly desirable to adjust the first component in the liquid crystal composition of the present invention in the range of 0.02% by mass to 1.0% by mass.

Specifically, as the polymerizable compound represented by the general formula (i), it is preferable to use one or more polymerizable compounds selected from the formulas (i-1) to (i-25). ..

Among the compounds represented by the above formulas (i-1) to (i-25), the formulas (i-1), (i-2), and (i) are obtained from the viewpoint of improving the solubility in the liquid crystal composition. -6), (i-7), (i-10), (i-11), (i-15), (i-16) may be selected from one or more polymerizable compounds. More preferred. Further, in addition to the above viewpoints, the formulas (i-1), (i-6), (i-10), from the viewpoints of high tilt stability (hard to seize) and sufficient polymerization at a high speed. It is preferable to use one or more polymerizable compounds selected from (i-15), and the compounds represented by the formulas (i-1), (i-6) and (i-10) are used. It is more preferable to use, and it is particularly preferable to use the compounds represented by the formulas (i-1) and (i-6).

In the liquid crystal composition of the present invention, in addition to the polymerizable compound represented by the general formula (i), the general formula (RM-22) or the general formula (RM-23) is used as the second component of the polymerizable compound. It can contain one kind or two or more kinds of polymerizable compounds represented by.

(In the equation, P ⁵ , P ⁶ , P ⁷ and P ⁸ are independently from equation (R-1) to equation (R-15).

Represents a polymerizable group represented by, and S ⁵ , S ⁶ , S ⁷ and S ⁸ independently represent a single bond or an alkylene group having 1 to 5 carbon atoms, and one of the alkylene groups. of -CH ₂ - or nonadjacent two or more _-CH 2 - may, -O -, - may be substituted OCO- or -COO-, the carbon atom from ^{a 1 a 8} are each independently 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 independently have an alkyl group having 1 to 5 carbon atoms and 1 carbon atom number. Represents an alkoxy group of ~ 5, a fluorine atom or a hydrogen atom. )
As the second component of the polymerizable compound, the polymerizable compounds represented by the general formula (RM-22) are from the general formula (RM-2221) to (RM-2229) and from the general formula (RM-221) to (RM-). It is preferably a compatible compound represented by 225) and the general formulas (RM-22M1) to (RM-22M9).

(In the formula, P ⁵ and P ⁶ are independently from formula (R-1) to formula (R-15).

Representing a polymerizable group represented by, 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 one of the alkylene groups. Two or more non-adjacent −CH _2−s may be replaced by −O−, −OCO− or −COO−. )
The above-mentioned compatibility compounds represented by the general formulas (RM-2221) to (RM-2229), the general formulas (RM-221) to (RM-225), and the general formulas (RM-22M1) to (RM-22M9). Among them, P ⁵ and P ⁶ are preferably groups selected from the formulas (R-1) to (R-3) independently of each other, and are selected from the formula (R-1) or the formula (R-2). The group to be used is preferable. Further, S ⁵ and S ⁶ are preferably single bonds.

As the second component of the polymerizable compound, 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). ..

(In the formula, P ⁷ and P ⁸ are independently from formula (R-1) to formula (R-15).

Representing a polymerizable group represented by, 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 one of the alkylene groups. Two or more non-adjacent −CH _2−s may be replaced by −O−, −OCO− or −COO−. )
Above, polymerizable compound represented by the general formulas (RM-2331) (RM- 2355), P 7 and ^{P 8} are each independently from the formula (R-1) ~ formula (R-3) The group selected is preferred, and the group selected from formula (R-1) or formula (R-2) is preferred. Further, S ⁷ and S ⁸ are preferably single bonds.

The polymerizable compound-containing liquid crystal composition of the present invention contains one or two polymerizable compounds selected from the general formula (RM-22) or the general formula (RM-23) as the second component of the polymerizable compound. Specifically, the general formulas (RM-2221) to (RM-2229), the general formulas (RM-221) to (RM-225), and the general formulas (RM-22M1) to (RM-22M9), One or two or more polymerizable compounds selected from the general formulas (RM-2331) to (RM-2355) may be contained, but the content of the second component of the polymerizable compound is set as the lower limit. It is 0% by mass, preferably 0.05% by mass, preferably 0.1% by mass, preferably 0.15% by mass, and preferably 0.20% by mass. , 0.22% by mass, preferably 0.23% by mass, preferably 0.24% by mass, and even more preferably 0.26% by mass. The upper limit is 0.50% by mass, preferably 0.45% by mass, preferably 0.40% by mass, preferably 0.35% by mass, and 0. It is preferably 30% by mass, more preferably 0.28% by mass.

The total content of the first component and the second component of the polymerizable compound in the liquid crystal composition of the present invention is preferably 0.1% by mass, preferably 0.15% by mass, as the lower limit. It is preferably 0.21% by mass, preferably 0.24% by mass, preferably 0.26% by mass, preferably 0.28% by mass, and 0.30% by mass. It is preferably%. The upper limit is preferably 0.60% by mass, preferably 0.50% by mass, preferably 0.48% by mass, and preferably 0.45% by mass. It is preferably 0.42% by mass, preferably 0.40% by mass, preferably 0.35% by mass, and even more preferably 0.30% by mass. In the liquid crystal composition of the present invention, the first component which is essential as a polymerizable compound and the second component which is an optional component may be used in combination. When the second component is used as the main polymerizable compound and the first component represented by the general formula (i) is used as a by-polymerizable compound, that is, as an auxiliary agent for the second polymerizable compound, the main component is used. The polymerizable compound represented by the general formula (i) can supplement the orientation-regulating force caused by the polymerizable compound of the second component.

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

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

In the general formulas (N-01) to (N-05), R ²¹ and R ²² are independently alkyl groups having 1 to 8 carbon atoms, alkoxy groups having 1 to 8 carbon atoms, and carbon atoms. Represents an alkenyl group of 2 to 8 and an alkenyloxy group having 2 to 8 carbon atoms, and one or two or more non-adjacent −CH ₂₋ in the group are independently −CH = CH−,. -C≡C -, - O -, - CO -, - may be substituted by COO- or -OCO-, ^{Z 1} are 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−, where m represents , Each independently represents 1 or 2.

In the general formulas (N-01) to (N-05), R ²¹ is preferably an alkoxy group having 2 to 8 carbon atoms or an alkyl group having 1 to 8 carbon atoms, preferably from 2 carbon atoms. An alkoxy group of 5 or an alkyl group having 1 to 5 carbon atoms is more preferable, and an alkoxy group having 2 carbon atoms or an alkyl group having 1 to 4 carbon atoms is more preferable. In -05), R ²² is preferably an alkyl group having 1 to 8 carbon atoms or an alkoxy group having 1 to 8 carbon atoms, and an alkyl group having 1 to 5 carbon atoms or 1 to 4 carbon atoms. Alkoxy groups of 1 to 4 are more preferable, and alkoxy groups having 1 to 4 carbon atoms are further preferable.

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

(The black dots in each formula represent carbon atoms in the ring structure.) It is preferable to be selected from the groups represented by any of the above, and the formula (R1) or the formula (R2) is more preferable. However, ^{the content of the compound in which R 21} and R ²² are alkenyl groups should be as small as possible, and preferably not contained. )
In the general formula (N-01), Z ¹ is preferably a single bond or −CH _{2 O−.}

In the general formula (N-02), Z ¹ is preferably a single bond.

In the general formula (N-04), Z ¹ is independently single-bonded, -CH ₂ CH _2- , -OCH _2- , -CH ₂ O-, -COO-, -OCO-, -OCF ₂ Represents −, −CF ₂ O−, −CH = CH−, −CF = CF− or −C≡C−, but single bond, −CH ₂ CH ₂ −, −OCH ₂ −, −CH ₂ O− Preferably, a single bond or −CH ₂ O− is more preferred.

The fluorine atoms of the compounds represented by the general formulas (N-01), (N-02), (N-03), (N-04) and (N-05) are replaced with chlorine atoms which are the same halogen group. It may have been done. However, the content of the compound substituted with the chlorine atom should be as small as possible, and it is preferable not to contain the compound.

The hydrogen atom existing on the ring of the compound represented by the general formulas (N-01), (N-02), (N-03), (N-04) and (N-05) is a fluorine atom or chlorine. It may be substituted with an atom, but a chlorine atom is not preferable.

The compounds represented by the general formulas (N-01), (N-02), (N-03), (N-04) and (N-05) have a negative Δε and an absolute value greater than 3. It is preferably 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 has a general formula (N-01-1), a general formula (N-01-2), and a general formula (N-01-3) as compounds represented by the general formula (N-01). ) And general formula (N-01-4)

(In the formula, R ²¹ has the same meaning as described above, and R ²³ independently represents an alkoxy group having 1 to 4 carbon atoms.) One kind of compound selected from the compound group represented by the above, or It is preferable to contain two or more types.

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

The liquid crystal composition of the present invention comprises a polymerizable compound as a first component, optionally a polymerizable compound second component, a compound represented by the general formula (N-01-1), and a general formula (N-01-2). It is preferable to contain the compound represented by.

The liquid crystal composition of the present invention includes a polymerizable compound as a first component, a second component of optionally a polymerizable compound, a compound represented by the general formula (N-01-3), and a general formula (N-01-4). ) Is preferably contained.

The liquid crystal composition of the present invention has the general formula (N-02-1), the general formula (N-02-2), and the general formula (N-02-) as compounds represented by the general formula (N-02). 3)

(In the formula, R ²¹ has the same meaning as described above, and R ²³ independently represents an alkoxy group having 1 to 4 carbon atoms.) One kind of compound selected from the compound group represented by the above, or 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, optionally a second component of the polymerizable compound, and a compound represented by the general formula (N-02-1).

The liquid crystal composition of the present invention includes a polymerizable compound as a first component, a second component of optionally a polymerizable compound, a compound represented by the general formula (N-02-1), and a general formula (N-02-3). ) Is preferably contained.

The liquid crystal composition of the present invention comprises a polymerizable compound as a first component, a second component of optionally a polymerizable compound, a compound represented by the general formula (N-02-1), and a general formula (N-01-1). ) And the compound represented by the general formula (N-01-2).

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

(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 compounds represented by.

The liquid crystal composition of the present invention preferably contains a polymerizable compound as a first component, optionally a second component of the polymerizable compound, and a 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 second component of optionally a polymerizable compound, a compound represented by the general formula (N-03-1), and a general formula (N-01-4). ) Is preferably contained.

The liquid crystal composition of the present invention comprises a polymerizable compound as a first component, a second component of optionally a polymerizable compound, a compound represented by the general formula (N-03-1), and a general formula (N-02-1). ) And the compound represented by the general formula (N-01-1) are preferably contained.

The liquid crystal composition of the present invention comprises a polymerizable compound as a first component, a second component of optionally a polymerizable compound, a compound represented by the general formula (N-03-1), and a general formula (N-02-1). ), The compound represented by the general formula (N-01-1) and the compound represented by the general formula (N-01-1) are preferably contained.

The liquid crystal composition of the present invention includes a polymerizable compound as a first component, a second component of optionally a polymerizable compound, a compound represented by the general formula (N-03-1), and a general formula (N-01-3). ) And the compound represented by the general formula (N-01-4) are preferably contained.

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

(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 compounds represented by.

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

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

The liquid crystal composition of the present invention includes a polymerizable compound as a first component, a second component of optionally a polymerizable compound, a compound represented by the general formula (N-04-1), and a general formula (N-01-3). ) And the compound represented by the general formula (N-01-4) are particularly preferably contained at the same time.

The liquid crystal composition of the present invention includes a polymerizable compound as a first component, a second component of optionally a polymerizable compound, a compound represented by the general formula (N-04-1), and a general formula (N-01-4). ) And the compound represented by the general formula (N-03-1) are particularly preferably contained at the same time.

The liquid crystal composition of the present invention includes a polymerizable compound as a first component, a second component of optionally a polymerizable compound, a compound represented by the general formula (N-04-1), and a general formula (N-02-1). ) And the compound represented by the general formula (N-03-1) are particularly preferably contained at the same time.

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

The liquid crystal composition of the present invention comprises a compound selected from the compound group represented by the formulas (N-05-1) to (N-05-3) as the compound represented by the general formula (N-05). It may be contained.

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

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

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

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

The lower limit of the preferable content of the compound represented by the formula (N-05) with respect to the total amount of the liquid crystal composition of the present invention is 0%, 2%, 5%, and 8%. Yes, 10%, 13%, 15%, 17%, 20%. The preferred upper limit of the content is 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 the general formula (N-06).

(In the formula, R ²¹ and R ²² have the same meaning as described above.)
The compound represented by the general formula (N-06) is effective when various physical properties are to be adjusted, but it should be used to obtain _{a large refractive index anisotropy (Δn), a high TNI, and a large Δε.} Can be done.

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

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

^{(Wherein, 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 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. , two or more -CH of one or non-adjacent in the group ₂ - each independently -CH = CH -, - C≡C - , - O -, - CO -, - COO- or -OCO It may contain one or more compounds selected from the group of compounds represented by −).

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 NU81 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 R ^NU11 , R ^NU21 , R ^NU41 and R ^NU51 are preferably alkenyl groups having 2 to 3 carbon atoms, and are represented by the above formula (R2). Alkenyl groups are preferred.

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 emphasized, 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, R NU81 is particularly preferably an alkyl group having 1 to 5 carbon ^{atoms, R NU12,} R ^NU22, R ^{The 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 more preferably contains a compound represented by the general formula (NU-01). Here in general formula ^{(NU-01), R NU51} particularly preferably an alkyl group having 1 to 5 carbon ^{atoms, R NU52} particularly preferably an alkyl group having 1 to 5 carbon atoms.

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

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

The liquid crystal composition of the present invention includes 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 general formula (NU-03). It is more preferable to contain the compound represented by NU-05).

The liquid crystal composition of the present invention more preferably contains a compound represented by the general formula (NU-02) and a compound represented by the general formula (NU-05).

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

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

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

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

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

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

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

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

The liquid crystal composition of the present invention may contain one or more compounds having a positive dielectric anisotropy described in paragraphs 0236 to 0509 of Patent Document 3 (Patent No. 6233550). More preferably, a compound having a terphenyl structure or a tetraphenyl structure and having a dielectric anisotropy Δε larger than +2 is preferable. The Δε of the compound is a value extrapolated from the measured value of the dielectric anisotropy of the composition obtained by adding the compound to the composition which is dielectrically substantially neutral at 25 ° C. The compounds are used in combination according to desired performances such as solubility at low temperature, transition temperature, electrical reliability, refractive index anisotropy, etc., and in particular, a liquid crystal containing a polymerizable compound. The reactivity of the polymerizable compound in the composition can be accelerated.

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

The liquid crystal composition of the present invention comprises one or two compounds having a substantially neutral dielectric anisotropy (Δε is -2 to +2) described in paragraphs 0624 to 0642 of Patent Document 3 (Patent No. 6233550). The above can be contained.

In addition to the above-mentioned compounds, the liquid crystal composition of the present invention may contain ordinary nematic liquid crystals, smectic liquid crystals, cholesteric liquid crystals, antioxidants, ultraviolet absorbers, light stabilizers, infrared absorbers and the like.

Examples of the antioxidant include hindered phenol represented by the general formula (H-1) to the general formula (H-4).

From the general formula (H-1) to the general formula (H-3), ^RH1 independently has an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, and 2 carbon atoms. represents a 10 alkenyl group or alkenyloxy group having 2 to 10 carbon atoms from which one of the -CH 2 that is present in the radical _- or non-adjacent two or more -CH 2 _- are each independently - It may be substituted with O- or -S-, and one or more hydrogen atoms present in the group may be independently substituted with a fluorine atom or a chlorine atom, respectively. 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. It is more preferable that it is an alkyl group having 3 to 7 carbon atoms or an alkenyl group having 2 to 7 carbon atoms.

In the general formula (H-4), ^MH4 is an alkylene group having 1 to 15 carbon atoms (one or more -CH ₂ − in the alkylene group is -CH 2 − so that oxygen atoms are not directly adjacent to each other. It may be replaced 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. It is expressed that it is preferably an alkylene group having 1 to 14 carbon atoms, and a large number of carbon atoms is preferable in consideration of volatility, but it is preferable that the number of carbon atoms is not too large in consideration of viscosity. The number of carbon atoms is more preferably 2 to 12, the number of carbon atoms is 3 to 10, the number of carbon atoms is 4 to 10, the number of carbon atoms is 5 to 10, and the number of carbon atoms is 6 to 10.

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

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

More specifically, for example, formulas (H-11) to formulas (H-15) can be mentioned.

When the liquid crystal composition of the present invention contains an antioxidant, its lower limit is preferably 10 mass ppm, preferably 20 mass ppm, preferably 50 mass ppm, and its 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 ( _TNI ) of 60 ° C. to 120 ° C., more preferably 70 ° C. to 100 ° C., and particularly preferably 70 ° C. to 85 ° C. In the present invention, 60 ° C. or higher is expressed as having a high _TNI.

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

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, preferably 0.09 to 0.12. Especially preferable. More specifically, it is preferably 0.10 to 0.13 when dealing with a thin cell gap, and preferably 0.08 to 0.10. When dealing with a thick cell gap. The liquid crystal composition of the present invention 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. From 90 to 150 mPa · s, preferably 90 to 140 mPa · s, preferably 90 to 130 mPa · s, and preferably 90 to 115 mPa · s.

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

The liquid crystal composition of the present invention contains a polymerizable compound as a first component and optionally a second component of a polymerizable compound, and further contains a general formula (N-01), a general formula (N-02), and a general formula (N). -03), contains one or more compounds selected from the compound group represented by the general formula (N-04), the general formula (N-05) and, if necessary, the general formula (N-06). Further, it is preferable to contain one or more compounds selected from the compound group represented by the general formulas (NU-01) to (NU-08), and the upper limit of the total of these contents is 100. 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, and the lower limit of the total of these contents is 78% by mass, 80% by mass, 81% by mass, 83% by mass, 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% by mass, 99% by mass, and 100% by mass are preferable.

The liquid crystal composition of the present invention contains a polymerizable compound as a first component and optionally a second component of a polymerizable compound, and further contains a general formula (N-01), a general formula (N-02), and a general formula (N). A compound containing one or more compounds selected from the group of compounds represented by -03) and the general formula (N-04), and further represented by the general formulas (NU-01) to (NU-08). It is particularly preferable to contain one or more compounds selected from the group, and the upper limit of the total content thereof 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, It is preferably 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 impart a sufficiently fast polymerization rate and a sufficiently large pretilt angle. Further, the liquid crystal display element using the liquid crystal composition of the present invention has a small residual amount of the polymerizable compound in the liquid crystal display element after polymerization, and is a high-definition PSA type or PSVA type liquid crystal display element such as 4K or 8K. Display defects such as IS (Image Sticking) do not occur or can be remarkably suppressed. From the above, the production efficiency of a high-definition PSA type or PSVA type liquid crystal display element such as 4K or 8K can be remarkably improved, and the industrial utility value is very high.

The liquid crystal composition of the present invention is useful for a liquid crystal display element for driving an active matrix, and can be used for a liquid crystal display element 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 the first substrate or the first 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 orientation direction of the liquid crystal molecules may be provided on the facing surface side of at least one substrate of the first substrate and / or the second substrate so as to come into 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 according to the drive mode of the liquid crystal display element, such as a rubbing alignment film (for example, polyimide) or a photoalignment film (decomposition type polyimide, etc.). A known alignment film of the above can be used. Further, the color filter may be appropriately provided on the first substrate or the second substrate, and the color filter can be provided on the pixel electrode or the common electrode.

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

The color filter can be produced 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 by 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 cured by heating or light irradiation. By performing this step for each of the three colors of red, green, and blue, a pixel portion for a color filter can be created. In addition, a pixel electrode provided with an active element such as a TFT, a thin film diode, or a metal insulator metal resistivity element may be installed 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 via a spacer. At this time, it is preferable to adjust the thickness of the obtained dimming layer to be 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. Further, when there are two polarizing plates, the polarization axis of each polarizing plate can be adjusted so that the viewing angle and contrast are improved. Further, a retardation film for widening the viewing angle can also be used. Examples of the spacer include glass particles, plastic particles, alumina particles, photoresist material and the like. Then, a sealant such as an epoxy-based thermosetting composition is screen-printed on the substrate in the form of providing a liquid crystal injection port, the substrates are bonded to each other, and the sealant is thermoset by heating.

As a method for sandwiching the liquid crystal composition between the two substrates, a normal 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 orientation performance of the liquid crystal. A method of polymerizing by irradiating the energy rays alone, in combination, or in sequence is preferable. When ultraviolet rays are used, a polarized light source may be used, 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 with respect to active energy rays. In addition, after polymerizing only a specific part using a mask during light irradiation, the orientation state of the unpolymerized part is changed by changing conditions such as electric field, magnetic field, or temperature, and further irradiation with active energy rays. You may use the means of polymerizing. In particular, when exposed to ultraviolet rays, it is preferable to expose the liquid crystal composition with ultraviolet rays while applying a DC electric field or an AC electric field. The AC electric field to be applied is preferably an AC having 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 a 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 element, it is preferable to control the pretilt angle from 80 degrees to 89.9 degrees from the viewpoint of orientation stability and contrast. Further, it is more preferable to control so that the pre-tilt angle is as large as 80 degrees to 89 degrees and an appropriate tilt is applied. In a PSA type or PSVA type liquid crystal display element, seizure (IS) occurs if the polymerizable compound remains as it is without being polymerized after the device 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, and 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 the liquid crystal composition of the present invention is applied to a liquid crystal display element provided with a substrate having an alignment film, it 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 that generates ultraviolet rays, a metal halide lamp, a high-pressure mercury lamp, an ultra-high pressure mercury lamp and the like can be used, and an ultra-high pressure UV lamp manufactured by USHIO and a fluorescent ultraviolet lamp manufactured by TOSHIBA are preferable. Further, as the wavelength of the ultraviolet rays to be irradiated, it is preferable to irradiate the ultraviolet rays in a wavelength region other than the absorption wavelength region of the liquid crystal composition, and it is preferable to cut the ultraviolet rays before use. The intensity of the ultraviolet rays to be irradiated ^{is preferably 0.1 mW / cm 2 to} 100 W / cm ^{2, and} more preferably 2 mW / cm ^{2 to} 50 W / cm ² . The amount of energy of the ultraviolet rays to be irradiated can be appropriately adjusted, ^{but is preferably 10 mJ / cm 2} to 500 J / cm ^{2, and} 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 "mass%". The following abbreviations are used for the description of compounds in the examples.

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

(Side chain)
−N −C _n H _{2n + 1} linear alkyl group having n carbon atoms n−C _n H _{2n + 1} − linear alkyl group having n carbon atoms _{−On −OC n} H _{2n + linear alkoxy group having n + 1 carbon atoms} group nO- C _n H _2n + 1 O- straight chain alkoxy group with carbon number n -V -CH = CH ₂
V-CH ₂ = CH-
−V1 −CH = CH-CH ₃
1V-CH _3- CH = CH-
−F −F
-OCF3 -OCF ₃
(Connecting group)
-1O--CH _2- O-
−O1-−O−CH ₂₋
-2- -CH ₂ -CH ₂ -
−COO− −COO−
-OCO- -OCO-
− Single bond (ring structure)

In the examples, the measured characteristics are as follows.

Tni: Nematic phase-isotropic liquid phase transition temperature (° C)
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 residual monomer (ppm) in the liquid crystal display element after irradiation with UV light having an illuminance of 3 mW / cm ^{2 at 313 nm for 60 minutes.}
Tilt: Pretilt angle (°) of the liquid crystal display element after irradiating UV light with an illuminance of 3 mW / cm ^{2 at 313 nm for 2 minutes.}
IS: A liquid crystal display element after irradiating UV light with an illuminance of 3 mW / cm ² at 313 nm for 60 minutes is prepared, and the value obtained by multiplying the amount of change in the pretilt angle after maintaining the driving state for a certain period of time VHR: illuminance at 313 nm Prepare a liquid crystal display element after irradiating 3 mW / cm ² UV light for 60 minutes, and the voltage retention rate (%) when measured at 1 V, 60 Hz, and 60 ° C.
(Preparation and evaluation results of liquid crystal composition)
(LC-5) was prepared from the liquid crystal composition (LC-1), and its physical characteristics were measured. Table 1 shows the component ratios of these liquid crystal compositions and their physical property values.

These liquid crystal compositions are mixed with the polymerizable compounds represented by the following formulas (RM-111) to (RM-112), formulas (RM-221) to (RM-222), and formulas (RM-C1). The following table shows the results of preparing the liquid crystal compositions of Examples (E-01) to (E-16) and Comparative Example (C-01) and evaluating RM, Tilt, IS, and VHR. ..

First, the liquid crystal compositions of Examples 1 (E-01) to 10 (E-10) were prepared, and the evaluation results were as shown in the table below.

The liquid crystal display element using the liquid crystal composition of Examples 1 (E-01) to 10 (E-10) has a sufficiently small RM value, an appropriate value for Til, and a small value for IS. Yes, it was confirmed that VHR was a sufficiently high value. From the above, it was confirmed that these examples solve the problems of the present invention.

Next, the liquid crystal composition of Comparative Example 1 (C-01) was prepared, and the evaluation results were as shown in the table below.

As a result, it was confirmed that the liquid crystal display element using the liquid crystal composition of Comparative Example 1 (C-01) has a large RM and the reliability of the liquid crystal display element is lowered. Further, although the monomer (RM-C1) used in the comparative example has a skeleton similar to that of the present invention, the monomer represented by the general formula (i) used in the present invention does not have an essential substituent. The result was low VHR. From the above, it was confirmed that these comparative examples cannot solve the problems of the present invention.

Further, Examples 11 (E-11) to 16 (E-16) were prepared, and the evaluation results were as shown in the table below.

Examples 11 (E-11) to 16 (E-16) are other than the general formula (i) together with the essential polymerizable compound represented by the general formula (i) which is the first component in the present invention. It is a liquid crystal composition containing RM-221 or RM-222 as a polymerizable compound. It was confirmed that the liquid crystal display element using the liquid crystal composition had a small RM value, an appropriate Til value, a small IS value, and a high VHR value. From the results of Examples 11 to 16, other polymerizable compounds are used as the main polymerizable compound, and the polymerizable compound represented by the general formula (i) is used in a small ratio so as to serve as an auxiliary agent thereof. It has been confirmed that a display element having a sufficient pre-tilt angle and not causing display defects due to a change in the pre-tilt angle has been obtained, and that the problem of the present invention has been solved.

Claims (9)

A liquid crystal composition containing a polymerizable compound represented by the general formula (i) as a first component.

(During the ceremony,
R ^{101 to} R ¹⁰⁴ are independently of hydrogen atom, fluorine atom, -O- (CH ₂ ) _m1- CH ₃ , -CH ₂ F, -CHF ₂ , -CF ₃ or -Sp ⁱ³ -P ⁱ³ . Representing any, m1 represents 0, 1, 2 or 3, and at least one or more groups of ^{R 101 to} R ¹⁰⁴ _{are -O- (CH 2} ) _m1- CH ₃ , -CH ₂ F,-. Represents CHF ₂ or -CF ₃
L ⁱ¹ represents a single _{bond, -C 2 H 4 -, -} C 3 H 6 -, - C 4 H 8 -, - OCH 2 -, - CH 2 O -, - CO -, - COO -, - OCO- , -OCOOCH _2- , -CH ₂ OCOO-, -OCH ₂ CH ₂ O-, -CH = CRa-COO-, -CH = CRa-OCO-, -COO-CRa = CH-, -OCO-CRa = CH -, -COO-CRa = CH-COO-, -COO-CRa = CH-OCO-, -OCO-CRa = CH-COO-, -OCO-CRa = CH-OCO-, -CH _{2 OCO-, -COOCH 2 -, - OCOCH 2 -,} - C 2 H 4 OCO -, - C 2 H 4 COO -, - COOC 2 H 4 -, - OCOC 2 H 4 -, - CH = CH -, - CF = CF-, -CF = CH-, -CH = CF-, -CF ₂ O-, -OCF _2- , -CF ₂ CH _2- , -CH ₂ CF _2- , -CF ₂ CF _2- or -C ≡ C-, (In the formula, Ra independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms).
A ⁱ¹ is
(A) 1,4-cyclohexylene group, (this is present in the group one -CH ₂ - - or nonadjacent two or more -CH ₂ may be replaced by -O-.)
(B) From the group consisting of 1,4-phenylene groups (one -CH = existing in this group or two or more -CH = not adjacent to each other may be replaced with -N =). Representing the group to be selected, the group (a) and the group (b) may be substituted with ^{an alkyl group having 1 to 8 carbon atoms or Pi3-} S ^i3-.
n ⁱ¹ represents 0 or 1 and represents
^{Pi 1} , ^{Pi 2} and ^{Pi 3} each independently represent a polymerizable group selected from formulas (R-1) to (R-15).

Sp ⁱ¹ , Sp ⁱ² and Sp ⁱ³ 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 alkylene groups in the alkylene group. of -CH ₂ -, as the oxygen atoms are not directly adjacent, -O -, - OCO- or -COO- in may be substituted. ) General formula (N-01), general formula (N-02), general formula (N-03), general formula (N-03) and general formula (N-05)

(In the formula, R ²¹ and R ²² are independently an alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, an alkenyl group having 2 to 8 carbon atoms, or 2 carbon atoms. represents 8 alkenyloxy group, two or more -CH of one or non-adjacent in the group ₂ - each independently -CH = CH -, - C [identical to] C -, - O -, - CO -, -COO- or -OCO- may be substituted, and Z ¹ is independently single-bonded, -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 independently represents 1 or 2, respectively. The liquid crystal composition according to claim 1, which contains one or more compounds selected from the compound group represented by). General formula (NU-01) to general formula (NU-08)

^{(Wherein, 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 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. , two or more -CH of one or non-adjacent in the group ₂ - each independently -CH = CH -, - C≡C - , - O -, - CO -, - COO- or -OCO The liquid crystal composition according to claim 1 or 2, which contains one or more compounds selected from the group of compounds represented by −). The first component, a compound selected from the compound group 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). The liquid crystal composition according to claim 3, wherein the total content of the compounds selected from the compound group represented by) is 80% by mass to 100% by mass with respect to the total amount of the composition. The liquid crystal composition according to any one of claims 1 to 4, further optionally containing an antioxidant, an ultraviolet absorber, a light stabilizer, and / or an infrared absorber. 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. The liquid crystal display element according to claim 6, which is for driving an active matrix. The liquid crystal display element according to claim 6 or 7, which is a PSA type or a PSVA type. The liquid crystal display element according to any one of claims 6 to 8, wherein at least one of the two substrates does not have an alignment film.