JP6940015B1 - Liquid crystal composition and liquid crystal display element - Google Patents

Abstract

The present invention contains one or more compounds represented by the general formula (i) and one or more polymerizable compounds represented by the general formula (ii), and has a nematic phase and the like. It relates to a liquid crystal composition having a square liquid phase transition temperature of 100 ° C. or higher and a negative dielectric anisotropy. (Ri1 and Ri2 represent alkyl groups having 1 to 8 carbon atoms, ni1 represents 1 or 2, P1 and P2 represent polymerizable groups of formulas (PG-1) to (PG-5), and S1 And S2 represent a single bond or an alkylene group having 1 to 5 carbon atoms, and X1 to X8 represent a hydrogen atom, a fluorine atom, an alkyl group having 1 to 5 carbon atoms, or an alkoxy group having 1 to 5 carbon atoms. ) [Chemical 1]

Description

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

The PSA (Polymer Sustained Position) type liquid crystal display device 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 a liquid crystal display element (patented) because of its high-speed response and high contrast. Development is underway as Document 1).

The requirements for PSA liquid crystal compositions used for PID (Public Information Display), which is expected to be used outdoors, are that the nematic phase-isotropic liquid phase transition temperature ( _TNI ) is high and the solid phase-nematic phase transition. Low temperature ( _TCN ), excellent low temperature storage stability (Low Temperature Storage test) is essential, drive voltage is low, elastic constant (K ₃₃ ) is large, and rotational viscosity (γ ₁ ) is sufficiently small. Is required.

International Publication No. 2016/017569

The subject of the present invention is that the dielectric anisotropy (Δε) is negative, and the liquid crystal display while satisfying the display in a wide temperature range, low voltage driveability, high-speed response and high VHR normally required for a liquid crystal composition. It is an object of the present invention to provide a polymerizable liquid crystal composition having no or extremely few display defects when used as an element, and to provide a liquid crystal display element using the liquid crystal composition.

The present invention has the general formula (i).

(In the formula, R ⁱ¹ and R ⁱ² each independently represent an alkyl group having 1 to 8 carbon atoms, and one or two or more non-adjacent −CH ₂ − in the alkyl group are independent of each other. to -C≡C -, - O -, - CO -, -. COO- or -OCO- may be substituted ^{by, n i1} is one of the compounds represented by the representative) 1 or 2 or Two or more types, and general formula (ii)

(In the formula, P ¹ and P ² are independent of each other, formulas (PG-1) to formulas (PG-5).

(In the formula, the hydrogen atom in the methyl group, ethyl group, n-propyl group and i-propyl group bonded to the vinyl group may be substituted with one or more fluorine atoms, and the group may be substituted. -CH _2- inside may be substituted with an oxygen atom.) Represents a polymerizable group represented by.
S ¹ and S ² 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-CHs in the alkylene group. ₂ − may be replaced with −O−, −OCO− or −COO−.
X ^{1 to} X ⁸ independently represent a hydrogen atom, a fluorine atom, an alkyl group having 1 to 5 carbon atoms or an alkoxy group having 1 to 5 carbon atoms, and the alkyl group and the alkoxy group are fluorine. It may be replaced by an atom. ) Contains one or more of the polymerizable compounds represented by).
T _NI is at 100 ° C. or more, [Delta] [epsilon] is negative liquid crystal composition, as well as a liquid crystal display device using the liquid crystal composition.

By using the liquid crystal composition of the present invention, it is possible to display in a wide temperature range due to excellent low temperature storage stability, and a liquid crystal display element that achieves both low drive voltage, fast response speed and high VHR. Therefore, it is possible to provide a liquid crystal display element that can be sufficiently used outdoors.

It is a figure which shows one Embodiment of the liquid crystal display element schematically. It is an enlarged plan view of the area surrounded by line I in FIG.

[Liquid crystal composition]
The liquid crystal composition of the present invention has a negative dielectric constant anisotropy, has a transition temperature ( _TNI ) of a nematic phase-isotropic liquid of 100 ° C. or higher, and is represented by the following general formula (i). Contains one or more of the compounds, and one or more of the compounds represented by the following general formula (ii).

(Compound represented by formula (i))
The liquid crystal composition of the present invention contains one or more compounds represented by the general formula (i). The compound represented by the general formula (i) corresponds to a dielectrically negative compound (the sign of Δε is negative and its absolute value is larger than 2).

In the compound represented by the general formula (i), ^Ri1 is preferably an alkyl group having 1 to 5 carbon atoms or an alkenyl group having 2 to 5 carbon atoms, and a methyl group, an ethyl group, a propyl group, and the like. It is preferably a butyl group, a vinyl group or a 1-propenyl group. R ⁱ² is preferably an alkyl group having 1 to 5 carbon atoms, an alkenyl group having 4 to 5 carbon atoms, or an alkoxy group having 1 to 4 carbon atoms, and is an ethoxy group, a propoxy group, or a butoxy group. Is preferable.

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

When the improvement of Δε is emphasized, it is preferable to set a large content of the compound represented by the general formula (i), and when the solubility at a low temperature is emphasized, the compound represented by the general formula (i) is set. If the content of TNI is set low, the effect is high, and _{if TNI} is emphasized, a compound with three rings, that ^{is, a compound in which ni1} is 2 in the general formula (i) is used, and the effect is set if the content is set high. Is high. Further, when improving the dripping marks and the seizure characteristics, it is preferable to set the content range in the middle.

The lower limit of the preferable content of the compound represented by the formula (i) with respect to the total amount of the liquid crystal composition of the present invention is 5%, 10%, 13% and 15%. It is 17% and 20%. The upper limit of the preferable content is 35%, 30%, 28%, 25%, 23%, and 20% with respect to the total amount of the liquid crystal composition of the present invention. It is 18%, 15%, and 13%. ^{Further, the lower limit of the preferable content of the compound in which ni1} is 1 in the formula (i) is 1%, 2%, 5%, 10%, 13%, and 15%. It is 17% and 20%. The preferred upper limit of the content is 35%, 30%, 28%, 25%, 23%, 20%, and 18% with respect to the total amount of the composition of the present invention. %, 15%, 13%, 10%, 8%. ^{Further, the lower limit of the preferable content of the compound in which ni1} is 2 in the formula (i) is 5%, 7%, 9%, and 12%. The preferred upper limit of the content is 35%, 30%, 28%, 25%, 23%, 20%, and 18% with respect to the total amount of the composition of the present invention. % And 15%.

The compound represented by the general formula (i) is preferably a compound selected from the compound group represented by the formulas (i-1) to (i-34), and the compounds represented by the formulas (i-1) to (i-1) to (i-1). More preferably, it is a compound represented by i-8) and formulas (i-21) to (i-44). The most preferable compound is a compound represented by the formula (i-2), the formula (i-5), the formula (i-23) and the formula (i-25).

The compounds represented by the formula (i) can be used alone or in combination, but the lower limit of the preferable content of these compounds with respect to the total mass of the liquid crystal composition of the present invention is set. It is 5% by mass, 10% by mass, 13% by mass, 15% by mass, 17% by mass, and 20% by mass. The upper limit of the preferable content is 40% by mass, 38% by mass, 35% by mass, 30% by mass, and 28% by mass with respect to the total amount of the liquid crystal composition of the present invention. It is 25% by mass, 23% by mass, 20% by mass, 18% by mass, 15% by mass, and 13% by mass. Hereinafter, mass% may be simply described as "%".

(Compound represented by formula (ii))

P ¹ and P ² independently represent polymerizable groups represented by the following formulas (PG-1) to (PG-5).

(In the formula, the hydrogen atom in the methyl group, ethyl group, n-propyl group and i-propyl group bonded to the vinyl group may be substituted with one or more fluorine atoms, and the group may be substituted. -CH _2- inside may be substituted with an oxygen atom.) It ^{is preferable that the polymerizable groups of P 1} and P ² are independently of the formula (PG-1) or the formula (PG-2), respectively. , P ¹ and P ² are both of the formula (PG-1), which is particularly preferable.

S ¹ and S ² 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-CHs in the alkylene group. ₂ − may be substituted with −O−, −OCO− or −COO−. Among them, S ¹ and S ² are preferably single bonds or unsubstituted alkylene groups having 1 to 5 carbon atoms, respectively, and it is particularly preferable that both ^{S 1} and S ^{2 are single bonds.}

X ^{1 to} X ⁸ independently represent a hydrogen atom, a fluorine atom, an alkyl group having 1 to 5 carbon atoms, or an alkoxy group having 1 to 5 carbon atoms, and the alkyl group and the alkoxy group are fluorine atoms. May be replaced by. Among them, ^{at least one of X 1 to} X ⁸ is preferably a fluorine atom, an alkyl group having 1 to 5 carbon atoms or an alkoxy group having 1 to 5 carbon atoms, and at least one of ^{X 1 to} X ^{8 is fluorine.} It is more preferably an atom, a methyl group or a methoxy group, ^{and it is particularly preferable that one of X 1 to} X ⁸ is a fluorine atom or a methoxy group.

When ^{two or more of X 1 to} X ⁸ are groups or atoms other than hydrogen atoms, the two or more of those groups or atoms may be the same or different from each other. Further, a group or atom other than two or more hydrogen atoms may be substituted with a hydrogen atom bonded to the same benzene ring in terphenyl, or may be substituted with a hydrogen atom bonded to a different ring.

The compound represented by the general formula (ii) is preferably a compound selected from the compound group represented by the formulas (ii-1) to (ii-26), and the compounds represented by the formulas (ii-1) to (ii-26) are preferable. It is more preferable that the compounds are represented by the formulas i-3) and (and formulas (i-21) to (i-44). The most preferable compounds are formulas (i-2) and (i-5). ), Formula (i-23) and formula (i-25).

The compounds represented by the formula (ii) can be used alone or in combination, but the lower limit of the preferable content of these compounds with respect to the total amount of the liquid crystal composition of the present invention is set. It is 0.005%, 0.010%, 0.015%, 0.020%, 0.030%, 0.035%, and 0.040%. As the upper limit value, the upper limit value of the preferable content is 0.10%, 0.09%, 0.08%, 0.07%, and 0.06%.
(Arbitrary ingredient)
-Compound represented by the formula (N-1) The liquid crystal composition of the present invention preferably contains one or more compounds represented by the formula (N-1). The compound represented by the formula (N-1) corresponds to a dielectrically negative compound (the sign of Δε is negative and its absolute value is greater than 2), Δε is negative and its absolute value is greater than 3. It is preferably a large compound.

In the general formula (N-1), ^RN11 and ^RN12 are independently an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, or an alkenyl group having 2 to 6 carbon atoms. An alkenyloxy group having 2 to 6 carbon atoms is preferable, an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, an alkenyl group having 2 to 5 carbon atoms, or an alkenyl group having 2 to 5 carbon atoms. An alkenyloxy group is more preferable, an alkyl group having 1 to 5 carbon atoms or an alkenyl group having 2 to 5 carbon atoms is further preferable, and an alkyl group having 1 to 5 carbon atoms or an alkenyl group having 2 to 3 carbon atoms is preferable. Particularly preferably, an alkyl group having 1 to 3 carbon atoms or an alkenyl group (propenyl group) having 3 carbon atoms is particularly preferable.

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

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

A ^N11 and ^AN12 are preferably aromatic when it is required to increase Δn independently, and are preferably aliphatic in order to improve the response rate, and trans-1,4. -Cyclohexylene group, 1,4-phenylene group, 2-fluoro-1,4-phenylene group, 3-fluoro-1,4-phenylene group, 3,5-difluoro-1,4-phenylene group, 2, 3-Difluoro-1,4-phenylene group, 1,4-cyclohexenylene group, 1,4-bicyclo [2.2.2] octylene group, piperidine-1,4-diyl group, naphthalene-2,6- It is preferable to represent a diyl group, a decahydronaphthalene-2,6-diyl group or a 1,2,3,4-tetrahydronaphthalene-2,6-diyl group, and more preferably to represent the following structure.

It is more preferable to represent a trans-1,4-cyclohexylene group, a 1,4-cyclohexenylene group or a 1,4-phenylene group.

Z ^N11 and ^{Z N12} are each _{independently -CH 2 O -, - CF 2} O -, - CH 2 CH 2 -, - CF 2 CF 2 - or preferably a single bond, _-CH 2 O-, -CH ₂ CH _2- or single bond is more preferred, and -CH ₂ O- or single bond is particularly preferred.

n ^N11 + n ^N12 is preferably 1 or 2, n ^N11 is 1 and n ^N12 is 0, n ^N11 is 2 and n ^N12 is 0, n ^N11 is 1 and n ^N12 is 1. A certain combination, a combination in which n ^N11 is 2 and n ^N12 is 1, is preferable.

The compounds represented by the formula (N-1) can be used alone or in combination, but the lower limit of the preferable content of these compounds with respect to the total amount of the liquid crystal composition of the present invention. Is 1%, 10%, 20%, 30%, 40%, 50%, 55%, 60%, 65%, 70%. Yes, 75%, and 80%. The preferred upper limit of content is 95%, 85%, 75%, 65%, 55%, 45%, 35%, 25%, 20%. Is.

The compound represented by the general formula (N-1) is preferably a compound selected from the compound group represented by the general formulas (N-1-1) to (N-1-21).

The compound represented by the general formula (N-1-1) is the following compound, and the compound can be used alone or in combination of two or more.

^{(Wherein, R N111} and ^{R N112} each independently represents the same meaning as ^{R N11} and ^{R N12} in the general formula (N-1).)
^RN111 is preferably an alkyl group having 1 to 5 carbon atoms or an alkenyl group having 2 to 5 carbon atoms, and preferably a propyl group, a pentyl group or a vinyl group. ^RN112 is preferably an alkyl group having 1 to 5 carbon atoms, an alkenyl group having 4 to 5 carbon atoms, or an alkoxy group having 1 to 4 carbon atoms, and preferably an ethoxy group or a butoxy group.

It is preferable to set the content higher when the improvement of Δε is emphasized, the effect is higher when the content is set higher when the solubility at low temperature is emphasized, and the content is set _{when the TNI} is emphasized. The effect is high when is set low. Further, when improving the dripping marks and the seizure characteristics, it is preferable to set the content range in the middle.

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

Further, the compound represented by the general formula (N-1-1) is a compound selected from the compound group represented by the formulas (N-1-1.1) to (N1-1.22). It is preferable that the compound is represented by the formulas (N-1-1.1) to (N-1-1.5), and the formulas (N-1-1.1) and the formula (N-1-1.5) are preferable. The compound represented by -1-1.4) is preferable.

The compound represented by the general formula (N-1-2) is the following compound, and the compound can be used alone or in combination of two or more.

^{(Wherein, R N121} and ^{R N122} each independently represents the same meaning as ^{R N11} and ^{R N12} in the general formula (N-1).)
^RN121 is preferably an alkyl group having 1 to 5 carbon atoms or an alkenyl group having 2 to 5 carbon atoms, preferably an ethyl group, a propyl group, a butyl group or a pentyl group. ^RN122 is preferably an alkyl group having 1 to 5 carbon atoms, an alkenyl group having 4 to 5 carbon atoms or an alkoxy group having 1 to 4 carbon atoms, and a methyl group, a propyl group, a methoxy group, an ethoxy group or a propoxy group. preferable.

When the improvement of Δε is emphasized, it is preferable to set the content high, when the solubility at low temperature is emphasized, the content is set low, and _{when the TNI} is emphasized, the content is high. The effect is high when is set high. Further, when improving the dripping marks and the seizure characteristics, it is preferable to set the content range in the middle.

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

Further, the compound represented by the general formula (N-1-2) is a compound selected from the compound group represented by the formulas (N-1-2.1) to (N-1-2.22). It is preferable that there are formulas (N-1-2.3) to formulas (N-1-2.7), formulas (N1-2.10), formulas (N-1-2.11), and formulas. It is preferable that the compound is represented by (N-1-2.13) and the formula (N1-2.20), and when the improvement of Δε is emphasized, the formula (N-1-2.3) is used. is preferably a compound represented by the formula (N-1-2.7) _from when emphasizing improvements in _{T NI} formula (N-1-2.10), formula (N-1-2.11) And the compound represented by the formula (N-1-2.13) is preferable, and the compound represented by the formula (N-1-2.20) is used when the improvement of the response speed is emphasized. Is preferable.

The compound represented by the general formula (N-1-3) is the following compound, and the compound can be used alone or in combination of two or more.

^{(Wherein, R N131} and ^{R N132} each independently represents the same meaning as ^{R N11} and ^{R N12} in the general formula (N-1).)
^RN131 is preferably an alkyl group having 1 to 5 carbon atoms or an alkenyl group having 2 to 5 carbon atoms, preferably an ethyl group, a propyl group or a butyl group. ^RN132 is preferably an alkyl group having 1 to 5 carbon atoms, an alkenyl group having 3 to 5 carbon atoms or an alkoxy group having 1 to 4 carbon atoms, and preferably a 1-propenyl group, an ethoxy group, a propoxy group or a butoxy group. ..

It is preferable to set the content higher when the improvement of Δε is emphasized, the effect is higher when the content is set higher when the solubility at low temperature is emphasized, and the content is set _{when the TNI} is emphasized. The effect is high when is set high. Further, when improving the dripping marks and the seizure characteristics, it is preferable to set the content range in the middle.

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

Further, the compound represented by the general formula (N-1--3) is a compound selected from the compound group represented by the formulas (N-1-3.21) to (N-1-3.21). It is preferable that the compound is represented by the formulas (N-1-3.1) to (N-1-3.7) and (N-1-3.21), and is preferably the compound represented by the formula (N-1-3.21). -1-3.1), Eq. (N-1-3.2), Eq. (N-1-3.3), Eq. (N-1-3.4) and Eq. (N-1-3.6) ) Is preferable, and the compounds represented by the formulas (N-1-3.1) and (N-1-3.2) are remarkably preferable, and the compounds represented by the formula (N-1-3.2) are remarkably preferable. The compound represented by is most preferable.

The compound represented by the general formula (N-1-4) is the following compound, and the compound can be used alone or in combination of two or more.

^{(Wherein, R N141} and ^{R N142} each independently represents the same meaning as ^{R N11} and ^{R N12} in the general formula (N-1).)
Independently R ^N141 and ^{R N142} are each an alkyl group having 1 to 5 carbon atoms, preferably an alkenyl group or an alkoxy group having 1 to 4 carbon atoms carbon atoms 4-5, methyl group, propyl group, ethoxy Groups or butoxy groups are preferred.

It is preferable to set the content higher when the improvement of Δε is emphasized, the effect is higher when the content is set higher when the solubility at low temperature is emphasized, and the content is set _{when the TNI} is emphasized. The effect is high when is set low. Further, when improving the dripping marks and the seizure characteristics, it is preferable to set the content range in the middle.

The lower limit of the preferable content of the compound represented by the formula (N-1-4) with respect to the total amount of the composition of the present invention is 3%, 5%, 7% and 10%. It is 13%, it is 15%, it is 17%, and it is 20%. The preferred upper limit of the content is 35%, 30%, 28%, 25%, 23%, 20%, and 18% with respect to the total amount of the composition of the present invention. %, 15%, 13%, 11%, 10%, 8%.

Further, the compound represented by the general formula (N-1--4) is a compound selected from the compound group represented by the formulas (N-1-4.1) to (N-1-4.14). It is preferable that the compound is represented by the formulas (N-1-4.1) to (N-1-4.4), and the compounds are preferably of the formulas (N-1-4.1) and (N-1-4.4). The compounds represented by -1-4.2) and the formula (N-1-4.4) are preferable, and the compounds represented by N-1-4.2) are particularly preferable.

The compound represented by the general formula (N-1-5) is the following compound, and the compound can be used alone or in combination of two or more.

^{(Wherein, R N151} and ^{R N152} each independently represents the same meaning as ^{R N11} and ^{R N12} in the general formula (N-1).)
^RN151 and ^RN152 are independent of each other, preferably an alkyl group having 1 to 5 carbon atoms, an alkenyl group having 4 to 5 carbon atoms, or an alkoxy group having 1 to 4 carbon atoms, and an ethyl group, a propyl group, or a butyl group. Is preferable.

When the improvement of Δε is emphasized, it is preferable to set the content high, when the solubility at low temperature is emphasized, the content is set low, and _{when the TNI} is emphasized, the content is high. The effect is high when is set high. Further, when improving the dripping marks and the seizure characteristics, it is preferable to set the content range in the middle.

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

Further, the compound represented by the general formula (N-1-5) is a compound selected from the compound group represented by the formulas (N-1-5.1) to (N-1-5.6). It is preferable that the compound is represented by the formula (N-1-5.1), the formula (N-1-5.2) and the formula (N-1-5.4).

The compound represented by the general formula (N-1-12) is the following compound, and the compound can be used alone or in combination of two or more.

^{(Wherein, R N1121} and ^{R N1122} independently represents the same meaning as ^{R N11} and ^{R N12} in the general formula (N-1).)
^RN1121 is preferably an alkyl group having 1 to 5 carbon atoms or an alkenyl group having 2 to 5 carbon atoms, preferably an ethyl group, a propyl group or a butyl group. ^RN1122 is preferably an alkyl group having 1 to 5 carbon atoms, an alkenyl group having 4 to 5 carbon atoms or an alkoxy group having 1 to 4 carbon atoms, and preferably an ethoxy group, a propoxy group or a butoxy group.

It is preferable to set the content higher when the improvement of Δε is emphasized, the effect is higher when the content is set higher when the solubility at low temperature is emphasized, and the content is set _{when the TNI} is emphasized. The effect is high when is set low. Further, when improving the dripping marks and the seizure characteristics, it is preferable to set the content range in the middle.

The lower limit of the preferable content of the compound represented by the formula (N-1-12) with respect to the total amount of the composition of the present invention is 5%, 10%, 13% and 15%. It is 17% and 20%. The preferred upper limit of the content is 35%, 30%, 28%, 25%, 23%, 20%, and 18% with respect to the total amount of the composition of the present invention. %, 15%, and 13%.

The compound represented by the general formula (N-1-13) is the following compound, and the compound can be used alone or in combination of two or more.

^{(Wherein, R N1131} and ^{R N1132} independently represents the same meaning as ^{R N11} and ^{R N12} in the general formula (N-1).)
^RN1131 is preferably an alkyl group having 1 to 5 carbon atoms or an alkenyl group having 2 to 5 carbon atoms, preferably an ethyl group, a propyl group or a butyl group. ^RN1132 is preferably an alkyl group having 1 to 5 carbon atoms, an alkenyl group having 4 to 5 carbon atoms or an alkoxy group having 1 to 4 carbon atoms, and preferably an ethoxy group, a propoxy group or a butoxy group.

It is preferable to set the content higher when the improvement of Δε is emphasized, the effect is higher when the content is set higher when the solubility at low temperature is emphasized, and the content is set _{when the TNI} is emphasized. The effect is high when is set high. Further, when improving the dripping marks and the seizure characteristics, it is preferable to set the content range in the middle.

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

The compound represented by the general formula (N-1-14) is the following compound, and the compound can be used alone or in combination of two or more.

^{(Wherein, R N1141} and ^{R N1142} independently represents the same meaning as ^{R N11} and ^{R N12} in the general formula (N-1).)
^RN1141 is preferably an alkyl group having 1 to 5 carbon atoms or an alkenyl group having 2 to 5 carbon atoms, preferably an ethyl group, a propyl group or a butyl group. ^RN1142 is preferably an alkyl group having 1 to 5 carbon atoms, an alkenyl group having 4 to 5 carbon atoms or an alkoxy group having 1 to 4 carbon atoms, and preferably an ethoxy group, a propoxy group or a butoxy group.

It is preferable to set the content higher when the improvement of Δε is emphasized, the effect is higher when the content is set higher when the solubility at low temperature is emphasized, and the content is set _{when the TNI} is emphasized. The effect is high when is set low. Further, when improving the dripping marks and the seizure characteristics, it is preferable to set the content range in the middle.

The lower limit of the preferable content of the compound represented by the formula (N-1-14) with respect to the total amount of the composition of the present invention is 5%, 10%, 13% and 15%. It is 17% and 20%. The preferred upper limit of the content is 35%, 30%, 28%, 25%, 23%, 20%, and 18% with respect to the total amount of the composition of the present invention. %, 15%, and 13%.

The compound represented by the general formula (N-1-15) is the following compound, and the compound can be used alone or in combination of two or more.

^{(Wherein, R N1151} and ^{R N1152} independently represents the same meaning as ^{R N11} and ^{R N12} in the general formula (N-1).)
^RN1151 is preferably an alkyl group having 1 to 5 carbon atoms or an alkenyl group having 2 to 5 carbon atoms, preferably an ethyl group, a propyl group or a butyl group. ^RN1152 is preferably an alkyl group having 1 to 5 carbon atoms, an alkenyl group having 4 to 5 carbon atoms or an alkoxy group having 1 to 4 carbon atoms, and preferably an ethoxy group, a propoxy group or a butoxy group.

It is preferable to set the content higher when the improvement of Δε is emphasized, the effect is higher when the content is set higher when the solubility at low temperature is emphasized, and the content is set _{when the TNI} is emphasized. The effect is high when is set high. Further, when improving the dripping marks and the seizure characteristics, it is preferable to set the content range in the middle.

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

The compound represented by the general formula (N-1-16) is the following compound, and the compound can be used alone or in combination of two or more.

^{(Wherein, R N1161} and ^{R N1162} independently represents the same meaning as ^{R N11} and ^{R N12} in the general formula (N-1).)
^RN1161 is preferably an alkyl group having 1 to 5 carbon atoms or an alkenyl group having 2 to 5 carbon atoms, and preferably an ethyl group, a propyl group or a butyl group. ^RN1162 is preferably an alkyl group having 1 to 5 carbon atoms, an alkenyl group having 4 to 5 carbon atoms or an alkoxy group having 1 to 4 carbon atoms, and preferably an ethoxy group, a propoxy group or a butoxy group.

It is preferable to set the content higher when the improvement of Δε is emphasized, the effect is higher when the content is set higher when the solubility at low temperature is emphasized, and the content is set _{when the TNI} is emphasized. The effect is high when is set high. Further, when improving the dripping marks and the seizure characteristics, it is preferable to set the content range in the middle.

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

The compound represented by the general formula (N-1-17) is the following compound, and the compound can be used alone or in combination of two or more.

^{(Wherein, R N1171} and ^{R N1172} independently represents the same meaning as ^{R N11} and ^{R N12} in the general formula (N-1).)
^RN1171 is preferably an alkyl group having 1 to 5 carbon atoms or an alkenyl group having 2 to 5 carbon atoms, preferably an ethyl group, a propyl group or a butyl group. ^RN1172 is preferably an alkyl group having 1 to 5 carbon atoms, an alkenyl group having 4 to 5 carbon atoms or an alkoxy group having 1 to 4 carbon atoms, and preferably an ethoxy group, a propoxy group or a butoxy group.

It is preferable to set the content higher when the improvement of Δε is emphasized, the effect is higher when the content is set higher when the solubility at low temperature is emphasized, and the content is set _{when the TNI} is emphasized. The effect is high when is set high. Further, when improving the dripping marks and the seizure characteristics, it is preferable to set the content range in the middle.

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

The compound represented by the general formula (N-1-18) is the following compound, and the compound can be used alone or in combination of two or more.

^{(Wherein, R N1181} and ^{R N1182} independently represents the same meaning as ^{R N11} and ^{R N12} in the general formula (N-1).)
^RN1181 is preferably an alkyl group having 1 to 5 carbon atoms or an alkenyl group having 2 to 5 carbon atoms, and preferably a methyl group, an ethyl group, a propyl group or a butyl group. ^RN1182 is preferably an alkyl group having 1 to 5 carbon atoms, an alkenyl group having 4 to 5 carbon atoms or an alkoxy group having 1 to 4 carbon atoms, and preferably an ethoxy group, a propoxy group or a butoxy group.

It is preferable to set the content higher when the improvement of Δε is emphasized, the effect is higher when the content is set higher when the solubility at low temperature is emphasized, and the content is set _{when the TNI} is emphasized. The effect is high when is set high. Further, when improving the dripping marks and the seizure characteristics, it is preferable to set the content range in the middle.

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

Further, the compound represented by the general formula (N-1-18) is a compound selected from the compound group represented by the formulas (N-1-18.1) to (N-1-18.5). It is preferable that the compound is represented by the formulas (N-1-18.1) to (N-1-18.3), and the compounds are preferably represented by the formulas (N-1-18.2) and (N-1-18.2). The compound represented by -1-18.3) is preferable.

The compound represented by the general formula (N-1-20) is the following compound, and the compound can be used alone or in combination of two or more.

^{(Wherein, R N1201} and ^{R N1202} independently represents the same meaning as ^{R N11} and ^{R N12} in the general formula (N-1).)
^RN1201 and ^RN1202 are each independently preferably an alkyl group having 1 to 5 carbon atoms or an alkenyl group having 2 to 5 carbon atoms, preferably an ethyl group, a propyl group or a butyl group.

It is preferable to set the content higher when the improvement of Δε is emphasized, the effect is higher when the content is set higher when the solubility at low temperature is emphasized, and the content is set _{when the TNI} is emphasized. The effect is high when is set high. Further, when improving the dripping marks and the seizure characteristics, it is preferable to set the content range in the middle.

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

The compound represented by the general formula (N-1-21) is the following compound, and the compound can be used alone or in combination of two or more.

^{(Wherein, R N1211} and ^{R N1212} independently represents the same meaning as ^{R N11} and ^{R N12} in the general formula (N-1).)
^RN1211 and ^RN1212 are each independently preferably an alkyl group having 1 to 5 carbon atoms or an alkenyl group having 2 to 5 carbon atoms, preferably an ethyl group, a propyl group or a butyl group.

It is preferable to set the content higher when the improvement of Δε is emphasized, the effect is higher when the content is set higher when the solubility at low temperature is emphasized, and the content is set _{when the TNI} is emphasized. The effect is high when is set high. Further, when improving the dripping marks and the seizure characteristics, it is preferable to set the content range in the middle.

The lower limit of the preferable content of the compound represented by the formula (N-1-21) with respect to the total amount of the composition of the present invention is 5%, 10%, 13% and 15%. It is 17% and 20%. The preferred upper limit of the content is 35%, 30%, 28%, 25%, 23%, 20%, and 18% with respect to the total amount of the composition of the present invention. %, 15%, and 13%.

The compound represented by the general formula (N-1-22) is the following compound, and the compound can be used alone or in combination of two or more.

^{(Wherein, R N1221} and ^{R N1222} independently represents the same meaning as ^{R N11} and ^{R N12} in the general formula (N-1).)
^RN1221 and ^RN1222 are each independently preferably an alkyl group having 1 to 5 carbon atoms or an alkenyl group having 2 to 5 carbon atoms, preferably an ethyl group, a propyl group or a butyl group.

It is preferable to set the content higher when the improvement of Δε is emphasized, the effect is higher when the content is set higher when the solubility at low temperature is emphasized, and the content is set _{when the TNI} is emphasized. The effect is high when is set high. Further, when improving the dripping marks and the seizure characteristics, it is preferable to set the content range in the middle.

Further, the compound represented by the general formula (N-1-22) is a compound selected from the compound group represented by the formulas (N-1-22.1) to (N-1-2.12.2). It is preferable that the compound is represented by the formulas (N-1-22.1) to (N-1-22.5), and the compounds are preferably represented by the formulas (N-1-22.1) to (N-). The compound represented by 1-22.4) is preferable.

-Compound represented by the formula (L) The liquid crystal composition of the present invention preferably further contains one or more compounds represented by the general formula (L). The compound represented by the general formula (L) corresponds to a dielectrically substantially neutral compound (the value of Δε is -2 to 2). Therefore, in the compound represented by the general formula (L), the number of polar groups such as halogen in the molecule is preferably 2 or less, more preferably 1 or less, and polar groups such as halogen. It is particularly preferable not to have.

(Wherein, R ^L1 and R ^L2 represent each independently an alkyl group having 1 to 8 carbon atoms, one or non-adjacent two or more -CH 2 in the alkyl group _- is independently It may be replaced by −CH = CH−, −C≡C−, −O−, −CO−, −COO− or −OCO−.
n ^L1 represents 0, 1, 2 or 3
A ^{L1, A L2,} and ^{A L3} each independently (a) 1,4-cyclohexylene group (this is present in the group one -CH ₂ - or nonadjacent two or more -CH ₂ - May be replaced with -O-) and (b) 1,4-phenylene group (one -CH = present in this group or two or more non-adjacent -CH = -N May be replaced with =)
(C) Naphthalene-2,6-diyl group, 1,2,3,4-tetrahydronaphthalene-2,6-diyl group or decahydronaphthalene-2,6-diyl group (naphthalene-2,6-diyl group or One -CH = present in the 1,2,3,4-tetrahydronaphthalene-2,6-diyl group or two or more non-adjacent -CH = may be replaced with -N =. )
Represents a group selected from the group consisting of, and the above groups (a), groups (b) and groups (c) may be independently substituted with cyano groups, fluorine atoms or chlorine atoms, respectively.
Z ^L1 and ^{Z L2} each independently represent a single _{bond, -CH 2 CH 2 -, -} (CH 2) 4 -, - OCH 2 -, - CH 2 O -, - COO -, - OCO -, - OCF 2 Represents −, −CF ₂ O−, −CH = NN = CH−, −CH = CH−, −CF = CF− or −C≡C−.
If n ^L1 is 2 or 3 and there ^{are a plurality of A L2s} , they may be the same or different, and if n ^L1 is 2 or 3 and there are a plurality of ^{Z L3s, they may be the same or different.} May be the same or different, except for the compound represented by the general formula (N-1). )
When reliability is important, ^{both RL1} and ^RL2 are preferably alkyl groups, and when reducing the volatility of the compound is important, they are preferably alkoxy groups, and reduction of viscosity is important. It is preferable that at least one of them is an alkenyl group.

The number of halogen atoms present in the molecule is preferably 0, 1, 2 or 3, preferably 0 or 1, and preferably 1 when compatibility with other liquid crystal molecules is important.

^RL1 and ^RL2 are linear alkyl groups having 1 to 5 carbon atoms and linear carbon atoms 1 to 4 when the ring structure to which they are bonded is a phenyl group (aromatic). Alkoxy group and alkenyl group having 4 to 5 carbon atoms are preferable, and when the ring structure to which the alkoxy group is bonded is a saturated ring structure such as cyclohexane, pyran and dioxane, the linear carbon atom number is 1 to 5. Alkoxy groups, linear alkoxy groups having 1 to 4 carbon atoms and linear alkenyl groups having 2 to 5 carbon atoms are preferable. In order to stabilize the nematic phase, the total of carbon atoms and oxygen atoms, if present, is preferably 5 or less, and is preferably linear.

The alkenyl group is preferably selected from the groups represented by any of the above formulas (R1) to (R5).

n ^L1 is preferably 0 when the response speed is important, 2 or 3 is preferable for improving the upper limit temperature of the nematic phase, and 1 is preferable for balancing these. Further, in order to satisfy the properties required for the composition, it is preferable to combine compounds having different values.

Preferably A ^L1, A ^L2, and A ^L3 if it is required to increase the Δn is aromatic, preferably to improve the response speed is an aliphatic, independently trans - 1,4-Cyclohexylene group, 1,4-phenylene group, 2-fluoro-1,4-phenylene group, 3-fluoro-1,4-phenylene group, 3,5-difluoro-1,4-phenylene group , 1,4-Cyclohexenylene group, 1,4-bicyclo [2.2.2] octylene group, piperidine-1,4-diyl group, naphthalene-2,6-diyl group, decahydronaphthalene-2,6 It preferably represents a −diyl group or 1,2,3,4-tetrahydronaphthalene-2,6-diyl group, more preferably the following structure.

It is more preferable to represent a trans-1,4-cyclohexylene group or a 1,4-phenylene group.

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

The compound represented by the general formula (L) may be used alone or in combination. The types of compounds that can be combined are not particularly limited, but they are appropriately combined and used according to desired performance such as solubility at low temperature, transition temperature, electrical reliability, and birefringence. The type of compound used is, for example, one type as one embodiment of the present invention. Alternatively, in another embodiment of the present invention, there are two types, three types, four types, five types, six types, seven types, eight types, nine types, and ten. More than a kind.

In the composition of the present invention, the content of the compound represented by the general formula (L) includes solubility at low temperature, transition temperature, electrical reliability, birefringence, process compatibility, dripping marks, seizure, and the like. It is necessary to make appropriate adjustments according to the required performance such as dielectric anisotropy.

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

When a composition having a low viscosity and a high response rate is required, it is preferable that the above lower limit value is high and the upper limit value is high. Moreover, maintaining high T _NI of the compositions of the present invention, it is preferable if the temperature stability good composition is required upper limit higher the lower limit of the above is high. Further, when it is desired to increase the dielectric anisotropy in order to keep the drive voltage low, it is preferable that the above lower limit value is low and the upper limit value is low.

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

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

The compound represented by the general formula (L-1) is the following compound, and the compound can be used alone or in combination of two or more.

^{(Wherein, R L11} and ^{R L12} are each independently the same meaning as ^{R L1} and ^{R L2} in Formula (L).)
^RL11 and ^RL12 are preferably a linear alkyl group having 1 to 5 carbon atoms, a linear alkoxy group having 1 to 4 carbon atoms, and a linear alkenyl group having 2 to 5 carbon atoms. ..

The lower limit of the preferable content is 1%, 2%, 3%, 5%, 7%, 10%, and 15% with respect to the total amount of the composition of the present invention. %, 20%, 25%, 30%, 35%, 40%, 45%, 50%, 55%. The preferred upper limit of the content is 95%, 90%, 85%, 80%, 75%, 70%, 65% with respect to the total amount of the composition of the present invention. %, 60%, 55%, 50%, 45%, 40%, 35%, 30%, 25%.

When a composition having a low viscosity and a high response rate is required, it is preferable that the above lower limit value is high and the upper limit value is high. Moreover, maintaining high T _NI of the compositions of the present invention, it is preferred if a good composition temperature stability is required is the upper limit value in the lower limit of the above is moderate is moderate. Further, when it is desired to increase the dielectric anisotropy in order to keep the drive voltage low, it is preferable that the above lower limit value is low and the upper limit value is low.

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

(In the formula, ^RL12 has the same meaning as in the general formula (L-1).)
The compound represented by the general formula (L-1-1) is a compound selected from the compound group represented by the formulas (L-1-1.1) to (L-1-1.3). Is preferable, and it is preferable that the compound is represented by the formula (L-1-1.2) or the formula (L-1-1.3), and in particular, the compound is represented by the formula (L-1-1.3). It is preferably a compound.

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

(In the formula, ^RL12 has the same meaning as in the general formula (L-1).)
Further, the compound represented by the general formula (L-1-2) is a compound selected from the compound group represented by the formulas (L-1-2.1) to (L-1-2.4). It is preferable that the compound is represented by the formulas (L-1-2.2) to (L-1-2.4). In particular, the compound represented by the formula (L-1-2.2) is preferable because it particularly improves the response rate of the composition of the present invention. Further, when obtaining the high _{T NI} than the response speed, it is preferable to use a compound represented by formula (L-1-2.3) or the formula (L-1-2.4). The content of the compounds represented by the formulas (L-1-2.3) and (L-1-2.4) is not preferably 30% or more in order to improve the solubility at a low temperature.

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

(In the formula, ^RL13 and ^RL14 independently represent an alkyl group having 1 to 8 carbon atoms or an alkoxy group having 1 to 8 carbon atoms.)
^RL13 and ^RL14 are preferably a linear alkyl group having 1 to 5 carbon atoms, a linear alkoxy group having 1 to 4 carbon atoms, and a linear alkenyl group having 2 to 5 carbon atoms. ..

Further, the compound represented by the general formula (L-1--3) is a compound selected from the compound group represented by the formulas (L-1-3.1) to (L-1-3.13). It is preferable that the compound is represented by the formula (L-1-3.1), the formula (L-1-3.3) or the formula (L-1-3.4). In particular, the compound represented by the formula (L-1-3.1) is preferable because it particularly improves the response rate of the composition of the present invention. Further, when obtaining the high _{T NI} than the response speed of the formula (L-1-3.3), the formula (L-1-3.4), the formula (L-1-3.11) and formula (L It is preferable to use the compound represented by -1-3.12). The sum of the compounds represented by the formulas (L-1-3.3), (L-1-3.4), (L-1-3.11) and (L-1-3.13). The content of is not preferably 20% or more in order to improve the solubility at low temperature.

The compound represented by the general formula (L-1) is also preferably a compound selected from the compound group represented by the general formula (L-1-4) and / or (L-1-5).

(In the formula, ^RL15 and ^RL16 independently represent an alkyl group having 1 to 8 carbon atoms or an alkoxy group having 1 to 8 carbon atoms.)
^RL15 and ^RL16 are preferably a linear alkyl group having 1 to 5 carbon atoms, a linear alkoxy group having 1 to 4 carbon atoms, and a linear alkenyl group having 2 to 5 carbon atoms. ..

Further, the compounds represented by the general formulas (L-1-4) and (L-1-5) are represented by the formulas (L-1-5.3) from the formulas (L-1-4.1). It is preferable that the compound is selected from the above-mentioned compound group, and the compound represented by the formula (L-1-4.2) or the formula (L-1-5.2) is preferable.

Equation (L-1-1.3), Equation (L-1-2.2), Equation (L-1-3.1), Equation (L-1-3.3), Equation (L-1- It is preferable to combine two or more compounds selected from the compounds represented by 3.4), the formula (L-1-3.11) and the formula (L-1-3.12), and the formula (L-1). -1.3), formula (L-1-2.2), formula (L-1-3.1), formula (L-1-3.3), formula (L-1-3.4) and It is preferable to combine two or more compounds selected from the compounds represented by the formula (L-1-4.2).

When the reliability of the composition is emphasized, the compounds represented by the formulas (L-1-3.1), (L-1-3.3) and (L-1-3.4)) are used. It is preferable to combine two or more compounds selected from the above, and when the response speed of the composition is important, it is represented by the formulas (L-1-1.3) and (L-1-2.2). It is preferable to combine two or more compounds selected from the above compounds.

As the compound represented by the general formula (L-1), a compound selected from the compound group represented by the general formula (L-1-6) can also be used.

(In the formula, ^RL17 and ^RL18 each independently represent a methyl group or a hydrogen atom.)
Further, the compound represented by the general formula (L-1-6) is a compound selected from the compound group represented by the formulas (L-1-6.1) to (L-1-6.3). It is preferable to have.

The compound represented by the general formula (L-2) is the following compound, and the compound can be used alone or in combination of two or more.

^{(Wherein, R L21} and ^{R L22} are each independently the same meaning as ^{R L1} and ^{R L2} in Formula (L).)
^RL21 is preferably an alkyl group having 1 to 5 carbon atoms or an alkoxy group having 2 to 5 carbon atoms, and ^RL22 is an alkyl group having 1 to 5 carbon atoms, an alkenyl group having 4 to 5 carbon atoms or a carbon atom. Alkoxy groups of numbers 1 to 4 are preferred.

When the solubility at low temperature is emphasized, the effect is high when the content is set high, and conversely, when the response speed is emphasized, the effect is high when the content is set low. Further, when improving the dripping marks and the seizure characteristics, it is preferable to set the content range in the middle.

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

Further, the compound represented by the general formula (L-2) is preferably a compound selected from the compound group represented by the formulas (L-2.1) to (L-2.6), preferably the formula. It is preferably a compound represented by (L-2.1), the formula (L-2.3), the formula (L-2.4) and the formula (L-2.6), and the compound is preferably the formula (L-2). The compound represented by .3) is more preferable.

The compound represented by the general formula (L-3) is the following compound, and the compound can be used alone or in combination of two or more.

^{(Wherein, R L31} and ^{R L32} are each independently the same meaning as ^{R L1} and ^{R L2} in Formula (L).)
^RL31 and ^RL32 are preferably alkyl groups having 1 to 5 carbon atoms, alkenyl groups having 4 to 5 carbon atoms, or alkoxy groups having 1 to 4 carbon atoms, respectively.

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

When obtaining a high birefringence index higher effective to set a higher content, on the contrary, when importance is attached to high T _NI is highly effective Setting content lower. Further, when improving the dripping marks and the seizure characteristics, it is preferable to set the content range in the middle.

Further, the compound represented by the general formula (L-3) is preferably a compound selected from the compound group represented by the formulas (L-3.1) to (L-3.7), preferably the formula. It is preferable that the compound is represented by the formula (L-3.1) or the formula (L-3.5), but the formula (L-3.6) or the formula (L-3) is used to improve the monomer polymerization rate. It is also preferable to use the compound represented by 0.7) in combination.

The compound represented by the general formula (L-4) is the following compound, and the compound can be used alone or in combination of two or more.

^{(Wherein, R L41} and ^{R L42} are each independently the same meaning as ^{R L1} and ^{R L2} in Formula (L).)
^RL41 is preferably an alkyl group having 1 to 5 carbon atoms or an alkenyl group having 2 to 5 carbon atoms, and ^RL42 is an alkyl group having 1 to 5 carbon atoms, an alkenyl group having 4 to 5 carbon atoms or a carbon atom. Alkoxy groups of numbers 1 to 4 are preferred. )
In the composition of the present invention, the content of the compound represented by the general formula (L-4) includes solubility at low temperature, transition temperature, electrical reliability, birefringence, process compatibility, dropping marks, and the like. It is necessary to make appropriate adjustments according to the required performance such as seizure and dielectric anisotropy.

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

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

Depending on the required performance such as solubility at low temperature, transition temperature, electrical reliability, birefringence, etc., even if the compound represented by the formula (L-4.1) is contained, the formula (L) is contained. Even if it contains the compound represented by 4.2), it contains both the compound represented by the formula (L-4.1) and the compound represented by the formula (L-4.2). It may contain all the compounds represented by the formulas (L-4.1) to (L-4.3).

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

Depending on the required performance such as solubility at low temperature, transition temperature, electrical reliability, birefringence, etc., even if the compound represented by the formula (L-4.4) is contained, the formula (L) is contained. Even if it contains the compound represented by −4.5), it contains both the compound represented by the formula (L-4.4) and the compound represented by the formula (L-4.5). May be.

The compound represented by the general formula (L-4) is preferably a compound represented by the formulas (L-4.7) to (L-4.10), and in particular, the compound represented by the formula (L-4. The compound represented by 9) is preferable.

The compound represented by the general formula (L-5) is the following compound, and the compound can be used alone or in combination of two or more.

^{(Wherein, R L51} and ^{R L52} are each independently the same meaning as ^{R L1} and ^{R L2} in Formula (L).)
^RL51 is preferably an alkyl group having 1 to 5 carbon atoms or an alkenyl group having 2 to 5 carbon atoms, and ^RL52 is an alkyl group having 1 to 5 carbon atoms, an alkenyl group having 4 to 5 carbon atoms or a carbon atom. Alkoxy groups of numbers 1 to 4 are preferred.

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

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

The compound represented by the general formula (L-5) is preferably a compound represented by the formula (L-5.3) or the formula (L-5.4).

The compound represented by the general formula (L-5) is preferably a compound selected from the compound group represented by the formulas (L-5.5) to (L-5.7), and particularly the compound represented by the formula (L-5). It is preferably a compound represented by L-5.7).

The compound represented by the general formula (L-6) is the following compound, and the compound can be used alone or in combination of two or more.

^{(Wherein, R L61} and ^{R L62} each independently represent the same meaning as ^{R L1} and ^{R L2} in Formula ^{(L), X L61} and ^{X L62} each independently represents a hydrogen atom or a fluorine atom. )
^{Each of RL61} and ^RL62 is preferably an alkyl group having 1 to 5 carbon atoms or an alkenyl group having 2 to 5 carbon atoms, and ^{one of XL61 and XL62} is a fluorine atom and the other is a hydrogen atom. Is preferable.

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

The compound represented by the general formula (L-6) is preferably a compound represented by the formulas (L-6.1) to (L-6.9).

The types of compounds that can be combined are not particularly limited, but it is preferable to contain 1 to 3 types of these compounds, and even more preferably 1 to 4 types. Further, since the wide molecular weight distribution of the selected compound is also effective for solubility, for example, one kind from the compounds represented by the formula (L-6.1) or (L-6.2), the formula (L-). One type from the compound represented by 6.4) or (L-6.5), one type from the compound represented by the formula (L-6.6) or the formula (L-6.7), one type from the compound represented by the formula (L-6.7), the formula (L). It is preferable to select one kind of compound from the compounds represented by −6.8) or (L-6.9) and combine these appropriately. Among them, it is represented by the formula (L-6.1), the formula (L-6.3), the formula (L-6.4), the formula (L-6.6) and the formula (L-6.9). It preferably contains a compound.

Further, the compound represented by the general formula (L-6) is preferably a compound represented by the formulas (L-6.10) to (L-6.17), for example, and among them, the compound represented by the formula (L-6.17) is preferable. It is preferably a compound represented by L-6.11).

The compound represented by the general formula (L-7) is the following compound, and the compound can be used alone or in combination of two or more.

^{(Wherein, R L71} and ^{R L72} each independently represent the same meaning as ^{R L1} and ^{R L2} in Formula ^{(L), A L71} and ^{A L72} is ^{A L2} and in the general formula (L) independently Although it has the same meaning as ^{A L3 , the hydrogen atoms on A L71} and A ^L72 may be independently substituted with fluorine atoms, and Z ^L71 has the same meaning as ^{Z L2} in the general formula (L). X ^L71 and ^{XL 72} independently represent a fluorine atom or a hydrogen atom.)
In the formula, ^RL71 and ^RL72 are each independently preferably an alkyl group having 1 to 5 carbon atoms, an alkenyl group having 2 to 5 carbon atoms, or an alkoxy group having 1 to 4 carbon atoms, respectively, and ^{AL71 and AL72.} Are each independently preferably a 1,4-cyclohexylene group or a 1,4-phenylene group ^{, the hydrogen atoms on AL71} and ^AL72 may be independently substituted with fluorine atoms, and Z L71 is ^simply. Bonds or COO− are preferable, single bonds are preferable, and hydrogen atoms are preferable for ^{XL71 and XL72.}

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

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

Preferably, to larger amount of content of the compound represented by the formula (L-7) if the composition of the present invention is desired embodiment of the high T _NI, if the embodiment of the low viscosity is desired containing It is preferable to reduce the amount.

Further, the compound represented by the general formula (L-7) is preferably a compound represented by the formulas (L-7.1) to (L-7.4), and the compound represented by the formula (L-7. It is preferably a compound represented by 2).

Further, the compound represented by the general formula (L-7) is preferably a compound represented by the formulas (L-7.11) to (L-7.13), and the compound represented by the formula (L-7. It is preferably a compound represented by 11).

Further, the compound represented by the general formula (L-7) is a compound represented by the formulas (L-7.21) to (L-7.23). It is preferably a compound represented by the formula (L-7.21).

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

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

Further, the compound represented by the general formula (L-7) is preferably a compound represented by the formulas (L-7.51) to (L-7.53).

The lower limit of the total preferable content of the compounds represented by the general formulas (i), (ii), (L) and (N) with respect to the total amount of the composition of the present invention is 80%, which is 85. %, 88%, 90%, 92%, 93%, 94%, 95%, 96%, 97%, 98%, 99. % And 100%. The preferred upper limit of the content is 100%, 99%, 98% and 95%.

The lower limit of the total preferable content of the compounds represented by the general formulas (i), (N-1), and (L) with respect to the total amount of the composition of the present invention is 80%, which is 85%. 88%, 90%, 92%, 93%, 94%, 95%, 96%, 97%, 98%, 99%. It is 99.5%. The upper limit of the preferable content is 99.7%, 99.5%, 99%, 98%, and 95%.

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

When the reliability and long-term stability of the composition are emphasized, the content of the compound having a carbonyl group is preferably 5% or less, more preferably 3% or less, based on the total mass of the composition. It is preferably 1% or less, and most preferably not substantially contained.

When the stability by UV irradiation is emphasized, the content of the compound substituted with chlorine atoms is preferably 15% or less, preferably 10% or less, and 8% or less, based on the total mass of the composition. % Or less, more preferably 5% or less, more preferably 3% or less, and even more preferably substantially no content.

It is preferable to increase the content of the compound having all 6-membered ring structures in the molecule, and the content of the compound having all 6-membered ring structures in the molecule is 80 with respect to the total mass of the composition. % Or more, more preferably 90% or more, further preferably 95% or more, and the composition is composed only of a compound in which substantially all the ring structures in the molecule are 6-membered rings. It is most preferable to do so.

In order to suppress deterioration of the composition due to oxidation, it is preferable to reduce the content of the compound having a cyclohexenylene group as a ring structure, and the content of the compound having a cyclohexenylene group is added to the total mass of the composition. On the other hand, it is preferably 10% or less, preferably 8% or less, more preferably 5% or less, preferably 3% or less, and further preferably substantially not contained.

When the improvement of viscosity and the improvement of _TNI are emphasized, the content of the compound having a 2-methylbenzene-1,4-diyl group in which the hydrogen atom may be substituted with halogen should be reduced. The content of the compound having a 2-methylbenzene-1,4-diyl group in the molecule is preferably 10% or less, preferably 8% or less, based on the total mass of the composition. It is preferably 5% or less, more preferably 3% or less, and even more preferably substantially absent.

In the present application, substantially not contained means that it is not contained except for an unintentionally contained substance.

When the compound contained in the composition of the present invention has an alkenyl group as a side chain, the number of carbon atoms of the alkenyl group is preferably 2 to 5 when the alkenyl group is bonded to cyclohexane. When the alkenyl group is bonded to benzene, the number of carbon atoms of the alkenyl group is preferably 4 to 5, and the unsaturated bond of the alkenyl group and benzene are preferably not directly bonded.

_{The average elastic constant (KAVG} ) of the liquid crystal composition used in the present invention is preferably 10 to 25, but the lower limit thereof is preferably 10 is preferable, 10.5 is preferable, 11 is preferable, and 11.5 is preferable. , 12 is preferred, 12.3 is preferred, 12.5 is preferred, 12.8 is preferred, 13 is preferred, 13.3 is preferred, 13.5 is preferred, 13.8 is preferred, 14 is preferred, 14 .3 is preferred, 14.5 is preferred, 14.8 is preferred, 15 is preferred, 15.3 is preferred, 15.5 is preferred, 15.8 is preferred, 16 is preferred, 16.3 is preferred, 16 .5 is preferable, 16.8 is preferable, 17, is preferable, 17.3 is preferable, 17.5 is preferable, 17.8 is preferable, 18 is preferable, and 25 is preferable and 24.5 is preferable as the upper limit value thereof. Is preferred, 24 is preferred, 23.5 is preferred, 23 is preferred, 22.8 is preferred, 22.5 is preferred, 22.3 is preferred, 22 is preferred, 21.8 is preferred, and 21.5 is preferred. , 21.3 is preferable, 21 is preferable, 20.8 is preferable, 20.5 is preferable, 20.3 is preferable, 20 is preferable, 19.8 is preferable, 19.5 is preferable, and 19.3 is preferable. , 19 is preferred, 18.8 is preferred, 18.5 is preferred, 18.3 is preferred, 18 is preferred, 17.8 is preferred, 17.5 is preferred, 17.3 is preferred, and 17 is preferred. When emphasizing power reduction, it is effective to suppress the amount of light of the backlight, it is preferred that the liquid crystal display device to improve the light transmittance, it To achieve this the set lower value of K _AVG preferable. When the improvement of the response speed is emphasized, it is preferable to set the value of _{KAVG to a high value.}
-Polymerizable compound The composition of the present invention contains, in addition to the polymerizable compound represented by the formula (ii), another polymerizable compound (hereinafter, may be referred to as "polymerizable monomer"). Is also preferable. As the polymerizable compound, a compound represented by the following general formula (P) is preferable. The compounds listed in the following general formula (P) may be used alone or in combination of two or more.

(In the above general formula (P), R ^p1 represents a hydrogen atom, a fluorine atom, a cyano group, an alkyl group having 1 to 15 carbon atoms or -Sp ^p2- P ^p2 , and one or a non-alkyl group. Two or more adjacent −CH ₂ −s may be independently substituted by −CH = CH−, −C≡C−, −O−, −CO−, −COO− or −OCO−. One or more hydrogen atoms in the alkyl group may be independently substituted with a cyano group, a fluorine atom or a chlorine atom.
P ^p1 and P ^p2 are independent of each other, and the general formulas (P ^p1-1 ) to (P ^{p1-9) are respectively.}

(In the formula, R ^p11 and R ^p12 independently represent a hydrogen atom, an alkyl group having 1 to 5 carbon atoms or an alkyl halide group having 1 to 5 carbon atoms, and W ^p11 is a single bond, −O. Representing a −, −COO− or methylene group, t ^p11 represents 0, 1 or 2, but ^{if there are multiple R p11} , R ^p12 , W ^p11 and / or t ^{p11 in} the molecule, they are the same. It may or may not be different.)
Represents one of
Sp ^p1 and Sp ^p2 independently represent a single bond or a spacer group, respectively.
Z ^p1 and Z ^p2 are independent, single-bonded, -O-, -S-, -CH _2- , -OCH _2- , -CH ₂ O-, -CO-, -C ₂ H ₄ -,-, respectively. _{COO -, - OCO -, -} OCOOCH 2 -, - CH 2 OCOO -, - OCH 2 CH 2 O -, - CO-NR ZP1 -, - NR ZP1 -CO -, - SCH 2 -, - CH 2 S- ^{, -CH = CR ZP1 -COO -,} - CH = CR ZP1 -OCO -, - COO-CR ZP1 = CH -, - OCO-CR ZP1 = CH -, - COO-CR ZP1 = CH-COO -, - COO -CR ZP1 = CH- ^{OCO-, -OCO -CR ZP1} = CH- ^{COO-, -OCO} -CR ZP1 = CH-OCO-,-(CH ₂ ) _z- COO-,-(CH ₂ ) _2- OCO- , -OCO- (CH ₂ ) ₂ -,-(C = O) -O- (CH ₂ ) _2- , -CH = CH-, -CF = CF-, -CF = CH-, -CH = CF- _{, -CF 2 -, - CF 2} O -, - OCF 2 -, - CF 2 CH 2 -, - CH 2 CF 2 -, - CF 2 CF 2 - or -C≡C- ^{(wherein, R ZP1} is Each independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, ^{but when a plurality of R ZP1s} are present in the molecule, they may be the same or different.)
Represents
A ^p1 , A ^p2 and A ^p3 are independent of each other.
^(A p) 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 p) 1,4-phenylene group (the one present in the group -CH = or non-adjacent two or more -CH = may be replaced by -N =.) And (c ^p ) Naphthalene-2,6-diyl group, naphthalene-1,4-diyl group, 1,2,3,4-tetrahydronaphthalene-2,6-diyl group, decahydronaphthalene-2,6-diyl group, phenanthrene -2,7-Diyl group or anthracene-2,6-diyl group (one -CH = existing in these groups or two or more non-adjacent -CH = may be replaced with -N = good.)
Represents a group selected from the group consisting of the above group (a ^p), group (b ^p) and one or more hydrogen atoms present in the radical (c ^p) are each independently a halogen atom , a cyano group, may be substituted with an alkyl group or ^-Sp p2 ^{-P p2} having 1 to 8 carbon atoms, one or two or more -CH ₂ non-adjacent in the alkyl group - each independently Then, it may be replaced by −CH = CH−, −C≡C−, −O−, −CO−, −COO− or −OCO−.
m ^p1 represents 0, 1, 2 or 3, ^{and when a plurality of Z p1} , ^Ap2 , Sp ^p2 and / or P ^p2 are present in the molecule, they may be the same or different. A ^p3 represents a single bond when m ^p1 is 0 and A ^p1 is a phenanthrene-2,7-diyl group or an anthracene-2,6-diyl group. However, the compound represented by the general formula (ii) is excluded. )
In formula (P), R ^p1 is preferably −Sp ^p2 −P ^p2 .

It is preferable that P ^p1 and P ^p2 are independently one of the formulas (P ^p1-1 ) to (P ^p1 -3), and preferably (P ^p1-1 ).

It is preferable that R ^p11 and R ^p12 are independently hydrogen atoms or methyl groups, respectively.

t ^p11 is preferably 0 or 1.

W ^p11 is preferably a single bond, a methylene group or an ethylene group.

m ^p1 is preferably 0, 1 or 2, preferably 0 or 1.

Z ^p1 and ^{Z p2} are each independently a single _{bond, -OCH 2 -, - CH 2} O -, - CO -, - C 2 H 4 -, - COO -, - OCO -, - COOC 2 H 4 - _{, -OCOC 2 H 4 -, -} C 2 H 4 OCO -, - C 2 H 4 COO -, - CH = CH -, - CF 2 -, - CF 2 O -, - (CH 2) 2 -COO- ,-(CH ₂ ) _2- OCO-, -OCO- (CH ₂ ) _2- , -CH = CH-COO-, -COO-CH = CH-, -OCOCH = CH-, -COO- (CH ₂ ) ₂ -, - OCF ₂ - or -C≡C-, more preferably a single _{bond, -OCH 2 -, - CH 2} O -, - C 2 H 4 -, - COO -, - OCO -, - COOC 2 H 4 _{-, - OCOC 2 H 4 -} , - C 2 H 4 OCO -, - C 2 H 4 COO -, - CH = CH -, - (CH 2) 2 -COO -, - (CH 2) 2 -OCO- , -OCO- (CH ₂ ) _2- , -CH = CH-COO-, -COO-CH = CH-, -OCOCH = CH-, -COO- (CH ₂ ) ₂ -or -C≡C- are preferable. , only one -OCH ₂ present in the molecule _{-, - CH 2 O -,} - C 2 H 4 -, - COO -, - OCO -, - COOC 2 H 4 -, - OCOC 2 H 4 -, _{-C 2 H 4 OCO -, -} C 2 H 4 COO -, - CH = CH -, - (CH 2) 2 -COO -, - (CH 2) 2 -OCO -, - OCO- (CH 2) 2 -, -CH = CH-COO-, -COO-CH = CH-, -OCOCH = CH-, -COO- (CH ₂ ) _2- or -C≡C-, and all others are single-bonded. preferably, only one present in the _{molecule, -OCH 2 -, - CH 2} O -, - C 2 H 4 -, - COO- or a -OCO-, that other are all single bonds Preferably, all are single-bonded.

^{Also, only one of Z p1} and Z ^p2 present in the molecule is -CH = CH-COO-, -COO-CH = CH-,-(CH ₂ ) _2- COO-,-(CH ₂ ) _{2. -OCO -, - O-CO- (} CH 2) 2 -, - COO- (CH 2) 2 - is a linking group selected from the group consisting of, it is preferred the other is a single bond.

Sp ^p1 and Sp ^p2 independently represent a single bond or a spacer group, but the spacer group is preferably an alkylene group having 1 to 30 carbon atoms, and −CH ₂ − in the alkylene group contains oxygen atoms. As long as it is not directly linked, it may be substituted with −O−, −CO−, −COO−, −OCO−, −CH = CH− or −C≡C−, and the hydrogen atom in the alkylene group is a halogen atom. Although it may be substituted with, a linear alkylene group having 1 to 10 carbon atoms or a single bond is preferable.
A ^p1 , A ^p2 and A ^p3 are independently 1,4-phenylene group, naphthalene-1,4-diyl group or 1,4-cyclohexylene group, respectively, preferably 1,4-phenylene group or naphthalene-1. , 4-Diyl group is preferable, and it is particularly preferable that at least one of the molecules has a 1,4-phenylene group. The 1,4-phenylene group is preferably substituted with one fluorine atom, one methyl group or one methoxy group in order to improve the compatibility with the liquid crystal compound.

The total content of the compounds represented by the formula (P) is preferably 0.05 to 10%, more preferably 0.1 to 8%, and 0.1 to 0% with respect to the total amount of the composition of the present invention. 5% is very preferable, 0.1 to 3% is more preferable, 0.2 to 2% is particularly preferable, and 0.2 to 1% is particularly preferable.

The preferable lower limit of the total content of the compounds represented by the formula (P) is 0.01%, 0.03%, or 0.05% with respect to the total amount of the composition of the present invention. Yes, 0.08%, 0.1%, 0.15%, 0.2%, 0.25%, 0.3%.

The preferable upper limit of the total content of the compound represented by the formula (P) is 10%, 8%, 5%, and 3% with respect to the total amount of the composition of the present invention. , 1.5%, 1.2%, 1%, 0.8%, 0.5%.

When the content of the compound represented by the formula (P) is small, the effect of adding the compound represented by the formula (P) is unlikely to appear, and the orientation regulating force of the liquid crystal composition becomes weak or weak with time. Problem occurs. Further, if the content of the compound represented by the formula (P) 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 display occur. Therefore, the content is set in consideration of these balances.

Preferred examples of the compound represented by the formula (P) include polymerizable compounds represented by the following formulas (P-1-21) to (P-1-46).

(In the formula, P ^p11 , P ^p12 , Sp ^p11 and Sp ^p12 have the same meanings as ^{P p1} , P ^p2 , Sp ^p1 and Sp ^p2 in the general formula (P).)
Preferred examples of the compound represented by the general formula (P) according to the present invention include polymerizable compounds represented by the following formulas (P-2-1) to (P-2-29).

(In the formula, P ^p21 , P ^p22 , Sp ^p21 and Sp ^p22 have the same meanings as ^{P p1} , P ^p2 , Sp ^p1 and Sp ^p2 in the general formula (P).)
Preferred examples of the compound represented by the general formula (P) according to the present invention include polymerizable compounds represented by the following formulas (P-3-1) to (P-3-15).

(In the formula, P ^p31 , P ^p32 , Sp ^p31 and Sp ^p32 have the same meanings as ^{P p1} , P ^p2 , Sp ^p1 and Sp ^p2 in the general formula (P).)
Preferred examples of the compound represented by the general formula (P) according to the present invention include polymerizable compounds represented by the following formulas (P-4-1) to (P-4-19).

(In the formula, P ^p41 , P ^p42 , Sp ^p41 and Sp ^{p42 have the same meanings as P p1} , P ^p2 , Sp ^p1 and Sp ^p2 in the general formula (P), and a plurality of P ^p42 and Sp ^p42 are the same, respectively. It may be different.)
Preferred examples of the compound represented by the general formula (P) according to the present invention include polymerizable compounds represented by the following formulas (P-5-1) to (P-5-19).

(In the formula, P ^p51 , P ^p52 , Sp ^p51 and Sp ^{p52 have the same meanings as P p1} , P ^p2 , Sp ^p1 and Sp ^p2 in the general formula (P), and a plurality of P ^p52 and Sp ^p52 are the same, respectively. It may be different. Me indicates a methyl group.)
When a further polymerizable monomer is used in addition to the compound represented by the formula (ii) in the present invention, one type of polymerizable monomer may be used alone or two or more types may be used in combination. In particular, by using two or three or more kinds of polymerizable monomers having different polymerization reaction rates in combination, the polymerization reaction rate can be appropriately controlled, the amount of residual monomers can be reduced, and an appropriate pretilt can be achieved. It is preferable because it can impart horns. Further, from the viewpoint of the balance between storage stability and polymerization reaction rate, it is preferable to use two or more kinds of polymerizable monomers in combination. When two or more types of polymerizable monomers are used, it is preferable to use two or more types of the compound represented by the above formula (P) in combination.

The total content of the compounds represented by the formula (P) is preferably 0.05 to 10%, preferably 0.1 to 8%, based on the composition containing the compounds. It preferably contains 0.1 to 5%, preferably 0.1 to 3%, preferably 0.2 to 2%, and preferably 0.2 to 1.3%. It is preferable that it contains 0.2 to 1%, and it is preferable that it contains 0.2 to 0.56%.

The preferable lower limit of the total content of the compounds represented by the formula (P) is 0.01%, 0.03%, and 0.05% with respect to the composition containing those compounds. , 0.08%, 0.1%, 0.15%, 0.2%, 0.25%, 0.3%.

The preferable upper limit of the total content of the compounds represented by the formula (P) is 10%, 8%, 5%, and 3% with respect to the composition containing those compounds. It is 1.5%, 1.2%, 1%, 0.8%, and 0.5%.

If the content is low, the effect of adding the compound represented by the formula (P) is unlikely to appear, and problems such as weak orientation control force of the liquid crystal composition or weakening over time occur. If the content is too high, after curing Problems such as a large amount remaining, a long curing time, and a decrease in the reliability of the liquid crystal display occur. Therefore, the content is set in consideration of these balances.
-Other Additives When a monomer is added to the composition of the present invention, the polymerization proceeds even in the absence of the polymerization initiator, but the polymerization initiator may be contained in order to promote the polymerization. Examples of the polymerization initiator include benzoin ethers, benzophenones, acetophenones, benzyl ketals, acylphosphine oxides and the like.

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

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

In the above formula, ^RQ1 independently has an alkyl group having 1 to 30 carbon atoms, an alkoxy group having 1 to 30 carbon atoms, an alkenyl group having 2 to 30 carbon atoms, or 2 to 30 carbon atoms. represents an alkenyloxy group, one -CH ₂ present in the radical - or non-adjacent two or more -CH ₂ - are each independently -O -, - COO -, - OCO- or -S It may be substituted with −, and one or more hydrogen atoms present in the group may be independently substituted with a fluorine atom or a chlorine atom, respectively.

^MQ1 is an alkylene group having 1 to 15 carbon atoms (one or two or more -CH _2- in the alkylene group is -O-, -CO-, -COO so that oxygen atoms are not directly adjacent to each other. -, -OCO- may be substituted.), -OCH _2- , -CH ₂ O-, -COO-, -OCO-, -CF ₂ O-, -OCF _2- , -CF ₂ CF ₂ -, -CH = CH-COO-, -CH = CH-OCO-, -COO-CH = CH-, -OCO-CH = CH-, -CH = CH-, -C≡C-, single bond, 1 , 4-Phenylene group (any hydrogen atom in the 1,4-phenylene group may be substituted with a fluorine atom) or trans-1,4-cyclohexylene group, which has 1 to 14 carbon atoms. It is preferably an alkylene group of.

In the general formula (Q-1) to the general formula (Q-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 (Q-2) and the general formula in (Q-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 preferably, the antioxidants include compounds represented by the following formulas (Q-11) to (Q-41).

In the above ^formulas, R Q11 ^{to R Q13} each independently represents an alkyl group having 1 to 20 carbon ^{atoms, M Q11} and ^{M Q12} each independently represents an alkylene group having 1 to 10 carbon atoms.

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

(In the formula, ^RH1 and ^RH2 each independently represent a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, and M represents an alkylene group having 1 to 15 carbon atoms, which are present in M. One or more -CH _2- is -O-, -CH = CH-, -C≡C-, -CO-, -OCO-, -COO-, trans-1,4-cyclohexylene group, 1, It may be substituted with a 4-phenylene group or a naphthalene-2,6-diyl group.)
In the general formula (I-2), ^RH1 and ^RH2 are particularly preferably hydrogen atoms. When it is an alkyl group, it preferably has 1 to 8 carbon atoms, more preferably 1 to 5 carbon atoms, further preferably 1 to 3 carbon atoms, and 1 carbon atom. Is particularly preferred.

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

Specific examples thereof include compounds represented by the general formula (I-24), the general formula (I-26) and the general formula (I-28). The ^{R H1} and ^{R H2} in these formulas are as previously described.

More specifically, the compounds represented by the general formula (I-24H), the general formula (I-26H) and the general formula (I-28H) can be mentioned, and the bis represented by the general formula (I-28H) can be mentioned. (2,2,6,6,-Tetramethyl-4-piperidyl) Sebacate is the most appropriate.

Further, a compound represented by the general formula (I-3) is also preferable. Since the compound represented by the general formula (I-3) has a high effective amine concentration, it is a compound that acts more effectively. Further, a light stabilizer having a small molecular weight is often adsorbed on the alignment film in the liquid crystal display element and induces display unevenness, but the compound represented by the general formula (I-3) has a large molecular weight. Therefore, it is possible to prevent the induction of display unevenness.

(In the formula, ^RH3 , ^RH4 and ^RH5 each independently represent a hydrogen atom or an alkyl group having 1 to 10 carbon atoms. N ^H1 and n ^H2 independently represent 0 to 2, respectively. ^H3 represents 1 or 2. ^{If there are multiple R H5s} , they may be the same or different.)
In the general formula (I-3), ^RH3 , ^RH4 and ^RH5 are particularly preferably hydrogen atoms. When it is an alkyl group, it preferably has 1 to 8 carbon atoms, more preferably 1 to 5 carbon atoms, further preferably 1 to 3 carbon atoms, and 1 carbon atom. Is even more preferable.

Specifically, compounds represented by the general formula (I-31), the general formula (I-32) and the general formula (I-33) are preferable. ^{R H3, R H4} and ^{R H5} in these formulas are as previously described.

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

The liquid crystal composition of the present invention preferably contains a light stabilizer (HALS) in the composition as a lower limit value of 0.01% or more, preferably 0.02% or more, and 0.03% or more. It is preferably contained, preferably 0.05% or more, preferably 0.07% or more, preferably 0.1% or more, and preferably 0.15% or more. It is preferably contained in an amount of 0.2% or more, preferably 0.25% or more, preferably 0.3% or more, preferably 0.5% or more, and preferably 1% or more. Is preferable. Further, as an upper limit value, it is preferably contained in an amount of 5% or less, preferably 3% or less, preferably 1% or less, preferably 0.5% or less, and 0.45% or less. It is preferably contained in an amount of 0.4% or less, preferably 0.35% or less, preferably 0.3% or less, preferably 0.25% or less, and 0. It is preferably contained in an amount of 2% or less, preferably 0.15% or less, preferably 0.1% or less, preferably 0.07% or less, and preferably 0.05% or less. Is preferable, and it is preferable that the content is 0.03% or less.

More specifically, it is preferably contained in an amount of 0.01 to 5% by mass, preferably 0.01 to 0.3% by mass, and even more preferably 0.02 to 0.3% by mass. It is particularly preferably 0.05 to 0.25% by mass. More specifically, when the suppression of precipitation at low temperature is emphasized, the content thereof is preferably 0.01 to 0.1% by mass.

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

The liquid crystal composition of this embodiment is applied to a liquid crystal display element. Hereinafter, an example of the liquid crystal display element according to the present embodiment will be described with reference to FIGS. 1 and 2 as appropriate.

FIG. 1 is a diagram schematically showing a configuration of a liquid crystal display element. In FIG. 1, for convenience of explanation, the components are shown separated from each other. As shown in FIG. 1, the liquid crystal display element 1 according to the present embodiment is provided between the first substrate 2 and the second substrate 3 arranged so as to face each other, and between the first substrate 2 and the second substrate 3. The liquid crystal layer 4 is provided with the above-mentioned liquid crystal layer 4, and the liquid crystal layer 4 is composed of the liquid crystal composition of the present embodiment described above.

A pixel electrode layer 5 is formed on the surface of the first substrate 2 on the liquid crystal layer 4 side. On the second substrate 3, a common electrode layer 6 is formed on the liquid crystal layer 4 side. The first substrate 2 and the second substrate 3 may be sandwiched by a pair of polarizing plates 7 and 8. A color filter 9 may be further provided on the liquid crystal layer 4 side of the second substrate 3.

That is, the liquid crystal display element 1 according to the embodiment includes a first polarizing plate 7, a first substrate 2, a pixel electrode layer 5, a liquid crystal layer 4 containing a liquid crystal composition, a common electrode layer 6, and a color filter. 9, the second substrate 3, and the second polarizing plate 8 are laminated in this order.

The first substrate 2 and the second substrate 3 are made of a flexible material such as glass or plastic. At least one of the first substrate 2 and the second substrate 3 may be formed of a transparent material, and the other may be formed of a transparent material or an opaque material such as metal or silicon. The first substrate 2 and the second substrate 3 are bonded to each other by a sealing material such as an epoxy-based thermosetting composition and a sealing material arranged in the peripheral region, and in order to maintain a distance between the substrates. For example, granular spacers such as glass particles, plastic particles, and alumina particles, or spacer columns made of resin formed by a photolithography method may be arranged.

The first polarizing plate 7 and the second polarizing plate 8 can be adjusted so that the viewing angle and contrast are good by adjusting the polarization axes of the respective polarizing plates, and their transmission axes operate in the normal black mode. As such, it is preferable to have transmission axes that are orthogonal to each other. In particular, it is preferable that any one of the first polarizing plate 7 and the second polarizing plate 8 is arranged so as to have a transmission axis parallel to the orientation direction of the liquid crystal molecules when no voltage is applied.

From the viewpoint of preventing light leakage, the color filter 9 preferably forms a black matrix, and preferably forms a black matrix (not shown) in a portion corresponding to the thin film transistor.

The black matrix may be installed together with the color filter on the substrate opposite to the array substrate, or may be installed together with the color filter on the array substrate side. The black matrix may be installed on the array substrate and the color filter may be installed on the other substrate. It may be installed separately. Further, the black matrix may be installed separately from the color filter, but the transmittance may be lowered by superimposing each color of the color filter.

FIG. 2 is an enlarged plan view of a region surrounded by an I line, which is a part of the pixel electrode layer 5 formed on the first substrate 2 in FIG. As shown in FIG. 2, in the pixel electrode layer 5 including the thin film transistor formed on the surface of the first substrate 2, a plurality of gate bus lines 11 for supplying scanning signals and a plurality of gate bus lines 11 for supplying display signals are provided. The data bus lines 12 are arranged so as to intersect each other in a matrix. Note that FIG. 2 shows only a pair of gate bus lines 11 and 11 and a pair of data bus lines 12 and 12.

A unit pixel of a liquid crystal display element is formed by a region surrounded by a plurality of gate bus lines 11 and a plurality of data bus lines 12, and a pixel electrode 13 is formed in the unit pixel. The pixel electrode 13 has a so-called fishbone structure including two trunks that are orthogonal to each other and have a cross shape, and a plurality of branches that extend from each trunk. Further, a Cs electrode 14 is provided between the pair of gate bus lines 11 and 11 substantially in parallel with the gate bus line 11. Further, a thin film transistor including a source electrode 15 and a drain electrode 16 is provided in the vicinity of the intersection where the gate bus line 11 and the data bus line 12 intersect with each other. The drain electrode 16 is provided with a contact hole 17.

The gate bus line 11 and the data bus line 12 are preferably formed of a metal film, and more preferably formed of Al, Cu, Au, Ag, Cr, Ta, Ti, Mo, W, Ni or an alloy thereof. It is more preferably formed of Mo, Al or an alloy thereof.

The pixel electrode 13 is preferably a transparent electrode in order to improve the transmittance. The transparent electrode is formed by sputtering an oxide semiconductor (ZnO, InGaZnO, SiGe, GaAs, IZO (Indium Zinc Oxide), ITO (Indium Tin Oxide), SnO, TiO, AZTO (AlZnSnO), etc.). At this time, the film thickness of the transparent electrode may be 10 to 200 nm. Further, in order to reduce the electrical resistance, a transparent electrode can be formed as a polycrystalline ITO film by firing an amorphous ITO film.

In the liquid crystal display element of the present embodiment, for example, wiring is formed by sputtering a metal material such as Al or an alloy thereof on the first substrate 2 and the second substrate 3, and the pixel electrode layer 5 and the common electrode layer 6 are formed. Each can be formed. Further, the color filter 9 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 produced. Further, the color filter 9 may be installed on the substrate side having the TFT or the like.

The first substrate 2 and the second substrate 3 face each other so that the pixel electrode layer 5 and the common electrode layer 6 are on the inner side, and at that time, the distance between the first substrate 2 and the second substrate 3 is provided via a spacer. May be adjusted. At this time, it is preferable to adjust the thickness of the liquid crystal layer 4 so that it is, for example, 1 to 100 μm.

When the polarizing plates 7 and 8 are used, it is preferable to adjust the product of the refractive index anisotropy Δn of the liquid crystal layer 4 and the thickness of the liquid crystal layer 4 so as to maximize the contrast. Further, when there are two polarizing plates 7 and 8, 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. 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 of sandwiching the composition between the two substrates 2 and 3, a normal vacuum injection method, a drop injection (ODF: One Drop Fill) method, or the like can be used, but in the vacuum injection method, there are dripping marks. Although it does not occur, it has a problem that a trace of injection remains, but in the present embodiment, it can be suitably used by a display element manufactured by using the ODF method. In the ODF method liquid crystal display element manufacturing process, a sealant such as epoxy-based photothermal combination curable is drawn on either the backplane or frontplane as a closed-loop bank using a dispenser, and then removed from the substrate. A liquid crystal display element can be manufactured by dropping a predetermined amount of the composition under air and then joining the front plane and the back plane. In the present embodiment, in the ODF method, it is possible to suppress the occurrence of dripping marks when the liquid crystal composition is dropped on the substrate. The dripping mark is defined as a phenomenon in which the dripping mark of the liquid crystal composition appears white when it is displayed in black.

Further, in the manufacturing process of the liquid crystal display element by the ODF method, it is necessary to drop the optimum liquid crystal injection amount according to the size of the liquid crystal display element, but the liquid crystal composition of the present embodiment is generated, for example, when the liquid crystal is dropped. Since the effect on sudden pressure changes and impacts in the dropping device is small and the liquid crystal can be stably dropped for a long period of time, the yield of the liquid crystal display element can be kept high. In particular, the small liquid crystal display element often used in smartphones, which has become popular recently, is difficult to control the deviation from the optimum value within a certain range because the optimum liquid crystal injection amount is small, but the liquid crystal of the present embodiment. By using the composition, a stable discharge amount of the liquid crystal material can be realized even in a small liquid crystal display element.

When the liquid crystal composition of the present embodiment contains a polymerizable compound, as a method for polymerizing the polymerizable compound, an appropriate polymerization rate is desirable in order to obtain good orientation performance of the liquid crystal. Therefore, ultraviolet rays or electron beams are used. A method of polymerizing by irradiating the active energy rays such as, etc. 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 the polymerization is carried out in a state where the polymerizable compound-containing composition is sandwiched between two substrates, at least the substrate on the irradiation surface side must be provided with appropriate transparency to the active energy rays. It doesn't become. 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 composition by ultraviolet rays while applying an AC electric field to the composition containing the polymerizable compound. The AC electric field to be applied is preferably an AC having a frequency of 10 Hz to 10 kHz, more preferably a frequency of 60 Hz to 10 kHz, and the voltage is selected depending on the desired pretilt angle of the liquid crystal display element. That is, the pre-tilt angle of the liquid crystal display element can be controlled by the applied voltage. In the horizontal electric field type MVA mode liquid crystal display element, it is preferable to control the pretilt angle to 80 degrees to 89.9 degrees from the viewpoint of orientation stability and contrast.

The temperature at the time of irradiation is preferably within a temperature range in which the liquid crystal state of the composition of the present embodiment is maintained. It is preferable to polymerize at a temperature close to room temperature, that is, typically at a temperature of 15 to 35 ° C. As the lamp that generates ultraviolet rays, a metal halide lamp, a high-pressure mercury lamp, an ultra-high pressure mercury lamp, or the like can be used. Further, as the wavelength of the ultraviolet rays to be irradiated, it is preferable to irradiate the ultraviolet rays in a wavelength region other than the absorption wavelength region of the composition, and it is preferable to cut the ultraviolet rays before use, if necessary. Intensity of ultraviolet irradiation is ^preferably from ^{0.1mW / cm 2 ~100W / cm 2} , 2mW / cm 2 ~50W / cm 2 is more preferable. Energy of ultraviolet light irradiation, can be appropriately ^adjusted, preferably ^{10mJ / cm 2 ~500J / cm 2} , 100mJ / cm 2 ~200J / cm 2 is more preferable. The intensity may be changed when irradiating with ultraviolet rays. The time for irradiating the ultraviolet rays is appropriately selected depending on the intensity of the ultraviolet rays to be irradiated, but is preferably 10 seconds to 3600 seconds, more preferably 10 seconds to 600 seconds.

The liquid crystal display element 1 may be a liquid crystal display element for driving an active matrix. The liquid crystal display element 1 may be a PSA type, PSVA type, VA type, IPS type, FFS type or ECB type liquid crystal display element, and is preferably a PSA type liquid crystal display element.

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%".

In the examples, the following abbreviations are used for the description of the liquid crystal compound.
(Ring structure)

(Side chain structure and connecting structure)

In the examples, the measured characteristics are as follows. Unless otherwise specified, the measurement was performed by the method specified in JEITA ED-2521B.

T _NI : Nematic phase-isotropic liquid phase transition temperature (° C)
T _CN : Solid phase-liquid crystal phase transition phase (° C)
Δn: Refractive index anisotropy at 25 ° C. γ1: Rotational viscosity at 25 ° C. (mPa · s)
Δε: Dielectric modulus anisotropy at 25 ° C. K11: Elastic constant at 25 ° C. K11 (pN)
K33: Elastic constant at 25 ° C. K33 (pN)
Solubility evaluation test: The liquid crystal composition was observed at -25 ° C. The presence or absence of precipitation was visually observed and judged in the following three stages. The observation is performed 10 days after the liquid crystal composition is prepared.

A: Precipitation cannot be confirmed B: Precipitation can be slightly confirmed but is within the permissible range C: Electro-optic characteristic evaluation test (V50) in which clear precipitation or solidification can be confirmed: Electro-optic characteristic evaluation was performed after irradiation with ultraviolet rays. The transmittance when a voltage of 0 to 10 V was applied was measured. The voltage at which the maximum transmittance was 50% was defined as V50. The electro-optical characteristics were measured using OPTIPRO manufactured by Shintec. The smaller the V50, the higher the transmittance in the liquid crystal panel, and a higher transmittance can be obtained at a lower voltage.

Voltage retention rate (VHR): Prepare a ^{liquid crystal display element after irradiating UV light with an illuminance of 3 mW / cm 2} at 313 nm for 60 minutes, and evaluate the voltage retention rate (%) when measured at 1 V, 60 Hz, and 60 ° C. bottom.
(Method of manufacturing liquid crystal evaluation cell)
First, a liquid crystal composition containing a polymerizable compound is coated with a polyimide alignment film that induces vertical orientation with a cell gap of 3.8 μm, and then a vacuum injection method is performed into a liquid crystal cell containing a substrate with ITO that has been rubbed with the polyimide alignment film. Injected with. As the vertical alignment film forming material, JALS2096 manufactured by JSR Corporation was used.

Then, a high-voltage mercury lamp was used in a state where a voltage of 10 V was applied at a frequency of 100 Hz to a liquid crystal cell in which a liquid crystal composition containing a polymerizable compound was injected, and ultraviolet rays were irradiated through a filter that cuts ultraviolet rays of 325 nm or less. At this time, the illuminance measured under the condition of a central wavelength of 365 nm ^{was adjusted to be 100 mW / cm 2} , and ultraviolet rays having an integrated light intensity of 30 J / cm ^{2 were irradiated.} The ultraviolet irradiation condition was defined as irradiation condition 1. The irradiation condition 1 imparts a pretilt angle to the liquid crystal molecules in the liquid crystal cell.

Then, using a fluorescent UV lamp, the illuminance was measured at a center wavelength of 313nm is adjusted to 3 mW / cm ^2, further irradiated with ultraviolet light at an accumulated light intensity 10J / cm ^2, to obtain a liquid crystal display device .. The ultraviolet irradiation condition was defined as irradiation condition 2. Irradiation condition 2 reduces the residual amount of the polymerizable compound in the unreacted liquid crystal cell under irradiation condition 1.
(Adjustment of liquid crystal composition)
The liquid crystal compositions of LC-1 to 4 and RLC-1 to 3 shown in the table below were prepared, and their physical characteristics were measured. The physical properties are as shown in the table below. Since T _NI of PSA liquid crystal composition used in the PID is more than 100 ° C. is generally, and the evaluation of the liquid crystal composition above 100 ° C. in this embodiment.

(Examples 1 to 13, Comparative Examples 1 to 6)
A total of 0.3 parts by mass of the polymerizable compounds shown in the table below was added to 100 parts by mass of the liquid crystal composition shown in the table below to obtain the polymerizable liquid crystal compositions of Examples 1 to 13 and Comparative Examples 1 to 6. Made.

The solubility evaluation test and V50 evaluation result of each example are as shown in the table below.

It was confirmed that the polymerizable liquid crystal compositions of Examples 1 to 13 had sufficient solubility and had sufficiently low electro-optical characteristics. When the response speed of the liquid crystal display element using this was measured, it was confirmed that the response speed was sufficiently high. The cell thickness was 3.8 um, the alignment film was JALS2096, the measurement conditions for the response speed were 6 V for Von, 1 V for Voff, the measurement temperature was 20 ° C., and OPTIPRO manufactured by Shintec was used as the measurement device. It was also confirmed that VHR was sufficiently high.

On the other hand, it was confirmed that the polymerizable liquid crystal compositions of Comparative Examples 1 to 4 had a narrow driving temperature range, were inferior in solubility and electro-optical characteristics, and had low transmittance.

Claims (4)

General formula (i)

(In the formula, R ⁱ¹ and R ⁱ² each independently represent an alkyl group having 1 to 8 carbon atoms, and one or two or more non-adjacent −CH ₂ − in the alkyl group are independent of each other. to -C≡C -, - O -, - CO -, -. COO- or -OCO- may be substituted ^{by, n i1} is one of the compounds represented by the representative) 1 or 2 or containing two or more,
As the compound represented by the general formula (i), a compound represented by the following formula (i-5), a compound represented by the formula (i-23), and a compound represented by the formula (i-26) are used. Contains,

General formula (ii)

(In the formula, P ¹ and P ² are independent of each other, formulas (PG-1) to formulas (PG-5).

(In the formula, the hydrogen atom in the methyl group, ethyl group, n-propyl group and i-propyl group bonded to the vinyl group may be substituted with one or more fluorine atoms, and the group may be substituted. -CH _2- inside may be substituted with an oxygen atom.) Represents a polymerizable group represented by.
S ¹ and S ² 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-CHs in the alkylene group. ₂ − may be replaced with −O−, −OCO− or −COO−.
Only one of X ^{1 to} X ⁸ represents a fluorine atom, and the others represent a hydrogen atom. ) Contains one or more of the polymerizable compounds represented by).
Further, as the compound represented by the general formula (N-1), only one or two or more compounds selected from the general formula (N-1-3) are contained.

^(Wherein, represents an alkyl group of ^{R N11} and ^{R N12} is 1 to 8 carbon atoms each independently, one or non-adjacent two or more -CH ₂ in the alkyl group - is independently It may be replaced by −C≡C−, −O−, −CO−, −COO− or −OCO−.
Independently A ^N11 and ^{A N12,} respectively (a) 1,4-cyclohexylene group (this is present in the group one -CH ₂ - or nonadjacent two or more -CH ₂ - is -O (May be replaced with −) and (b) 1,4-phenylene group (one -CH = existing in this group or two or more -CH = not adjacent to each other is replaced with -N =. May be done.)
(C) Naphthalene-2,6-diyl group, 1,2,3,4-tetrahydronaphthalene-2,6-diyl group or decahydronaphthalene-2,6-diyl group (naphthalene-2,6-diyl group or One -CH = present in the 1,2,3,4-tetrahydronaphthalene-2,6-diyl group or two or more non-adjacent -CH = may be replaced with -N =. )
(D) Represents a group selected from the group consisting of 1,4-cyclohexenylene groups, and the above groups (a), group (b), group (c) and group (d) are independently cyano groups, respectively. It may be substituted with a fluorine atom or a chlorine atom,
Z ^N11 and ^{Z N12} are each independently a single _{bond, -CH 2 CH 2 -, -} (CH 2) 4 -, - OCH 2 -, - CH 2 O -, - COO -, - OCO -, - OCF 2 Represents −, −CF ₂ O−, −CH = NN = CH−, −CH = CH−, −CF = CF− or −C≡C−.
Although n ^N11 and ^{n N12} represents an integer of independently ^{0~3, n} N11 ⁺ n ^N12 is 1, 2 or ^3, if ^{A N11 ~A N32, Z N11 ~Z} N32 there is a plurality, They may be the same or different. )

(In the formula, ^RN131 represents an alkyl group having 1 to 5 carbon atoms or an alkenyl group having 2 to 5 ^{carbon atoms, and RN132} is an alkyl group having 1 to 5 carbon atoms or an alkoxy having 1 to 4 carbon atoms. Represents a group.)
Further, one kind or two or more kinds of compounds represented by the general formula (L) are contained, and one kind or one compound represented by the general formula (L-2) is contained as the compound represented by the general formula (L). Containing two or more kinds and one kind or two or more kinds of compounds represented by the general formula (L-5),

(Wherein, R ^L1 and R ^L2 represent each independently an alkyl group having 1 to 8 carbon atoms, one or non-adjacent two or more -CH 2 in the alkyl group _- is independently It may be replaced by −CH = CH−, −C≡C−, −O−, −CO−, −COO− or −OCO−.
n ^L1 represents 0, 1, 2 or 3
A ^{L1, A L2,} and ^{A L3} each independently (a) 1,4-cyclohexylene group (this is present in the group one -CH ₂ - or nonadjacent two or more -CH ₂ - May be replaced with -O-) and (b) 1,4-phenylene group (one -CH = present in this group or two or more non-adjacent -CH = -N May be replaced with =)
(C) Naphthalene-2,6-diyl group, 1,2,3,4-tetrahydronaphthalene-2,6-diyl group or decahydronaphthalene-2,6-diyl group (naphthalene-2,6-diyl group or One -CH = present in the 1,2,3,4-tetrahydronaphthalene-2,6-diyl group or two or more non-adjacent -CH = may be replaced with -N =. )
Represents a group selected from the group consisting of, and the above groups (a), groups (b) and groups (c) may be independently substituted with cyano groups, fluorine atoms or chlorine atoms, respectively.
Z ^L1 and ^{Z L2} each independently represent a single _{bond, -CH 2 CH 2 -, -} (CH 2) 4 -, - OCH 2 -, - CH 2 O -, - COO -, - OCO -, - OCF 2 Represents −, −CF ₂ O−, −CH = NN = CH−, −CH = CH−, −CF = CF− or −C≡C−.
If n ^L1 is 2 or 3 and there ^{are a plurality of A L2s} , they may be the same or different, and if n ^L1 is 2 or 3 and there are a plurality of ^{Z L2s, they may be the same or different.} May be the same or different, except for the compounds represented by the general formula (i) and the general formula (N-1). )

^{(Wherein, R L21} and ^{R L22} are each independently table to the same meaning as ^{R L1} and ^{R L2} in Formula (L).)

^{(Wherein, R L51} and ^{R L52} each independently represent the same meaning as ^{R L1} and ^{R L2} in Formula ^{(L), R L52} does not represent an alkoxy group or alkenyloxy group.)
A liquid crystal display element having a PSA-type or PSVA-type vertically oriented film using a liquid crystal composition having a nematic phase-isotropic liquid phase transition temperature of 100 ° C. or higher and a negative dielectric anisotropy. Further, as the compound represented by the general formula (L), the general formula (L-1) and the general formulas (L-3) to (L-4) are further added.

^{(Wherein, R L11, R L12 R L31} , R L32, R L41 and ^{R L42} each independently represent the same meaning as ^{R L1} and ^{R L2} in Formula ^{(L), R L31} and ^{R L32} are The liquid crystal display having a PSA type or PSVA type vertical alignment film according to claim 1, which contains one or more compounds selected from the compound group represented by (does not represent an alkoxy group or an alkenyloxy group). element. The liquid crystal display element having the PSA type or PSVA type vertical alignment film according to claim 1 or 2, further containing the polymerizable compound represented by the general formula (P) in the liquid crystal composition.

(In the above general formula (P), R ^p1 represents a hydrogen atom, a fluorine atom, a cyano group, an alkyl group having 1 to 15 carbon atoms or -Sp ^p2- P ^p2 , and one or a non-alkyl group. Two or more adjacent −CH ₂ −s may be independently substituted by −CH = CH−, −C≡C−, −O−, −CO−, −COO− or −OCO−. One or more hydrogen atoms in the alkyl group may be independently substituted with a cyano group, a fluorine atom or a chlorine atom.
P ^p1 and P ^p2 are independent of each other, and the general formulas (P ^p1-1 ) to (P ^{p1-9) are respectively.}

(In the formula, R ^p11 and R ^p12 independently represent a hydrogen atom, an alkyl group having 1 to 5 carbon atoms or an alkyl halide group having 1 to 5 carbon atoms, and W ^p11 is a single bond, −O. Representing a −, −COO− or methylene group, t ^p11 represents 0, 1 or 2, but ^{if there are multiple R p11} , R ^p12 , W ^p11 and / or t ^{p11 in} the molecule, they are the same. It may or may not be different.)
Represents one of
Sp ^p1 and Sp ^p2 independently represent a single bond or a spacer group, respectively.
Z ^p1 and Z ^p2 are independent, single-bonded, -O-, -S-, -CH _2- , -OCH _2- , -CH ₂ O-, -CO-, -C ₂ H ₄ -,-, respectively. _{COO -, - OCO -, -} OCOOCH 2 -, - CH 2 OCOO -, - OCH 2 CH 2 O -, - CO-NR ZP1 -, - NR ZP1 -CO -, - SCH 2 -, - CH 2 S- ^{, -CH = CR ZP1 -COO -,} - CH = CR ZP1 -OCO -, - COO-CR ZP1 = CH -, - OCO-CR ZP1 = CH -, - COO-CR ZP1 = CH-COO -, - COO -CR ZP1 = CH- ^{OCO-, -OCO -CR ZP1} = CH- ^{COO-, -OCO} -CR ZP1 = CH-OCO-,-(CH ₂ ) _z- COO-,-(CH ₂ ) _2- OCO- , -OCO- (CH ₂ ) ₂ -,-(C = O) -O- (CH ₂ ) _2- , -CH = CH-, -CF = CF-, -CF = CH-, -CH = CF- _{, -CF 2 -, - CF 2} O -, - OCF 2 -, - CF 2 CH 2 -, - CH 2 CF 2 -, - CF 2 CF 2 - or -C≡C- ^{(wherein, R ZP1} is Each independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, ^{but when a plurality of R ZP1s} are present in the molecule, they may be the same or different.)
Represents
A ^p1 , A ^p2 and A ^p3 are independent of each other.
^(A p) 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 p) 1,4-phenylene group (the one present in the group -CH = or non-adjacent two or more -CH = may be replaced by -N =.) And (c ^p ) Naphthalene-2,6-diyl group, naphthalene-1,4-diyl group, 1,2,3,4-tetrahydronaphthalene-2,6-diyl group, decahydronaphthalene-2,6-diyl group, phenanthrene -2,7-Diyl group or anthracene-2,6-diyl group (one -CH = existing in these groups or two or more non-adjacent -CH = may be replaced with -N = good.)
Represents a group selected from the group consisting of the above group (a ^p), group (b ^p) and one or more hydrogen atoms present in the radical (c ^p) are each independently a halogen atom , a cyano group, may be substituted with an alkyl group or ^-Sp p2 ^{-P p2} having 1 to 8 carbon atoms, one or two or more -CH ₂ non-adjacent in the alkyl group - each independently Then, it may be replaced by −CH = CH−, −C≡C−, −O−, −CO−, −COO− or −OCO−.
m ^p1 represents 0, 1, 2 or 3, ^{and if there are multiple Z p1} , ^Ap2 , Sp ^p2 and / or P ^p2 in the molecule, they may be the same or different. A ^p3 represents a single bond when m ^p1 is 0 and A ^p1 is a phenanthrene-2,7-diyl group or an anthracene-2,6-diyl group. However, the compound represented by the general formula (ii) is excluded. ) In addition to the liquid crystal composition, formulas (Q-1) to formulas (Q-4)

(In the formula, ^RQ1 independently has an alkyl group having 1 to 30 carbon atoms, an alkoxy group having 1 to 30 carbon atoms, an alkenyl group having 2 to 30 carbon atoms, or 2 to 30 carbon atoms. represents an alkenyloxy group, one -CH ₂ present in the radical - or non-adjacent two or more -CH ₂ - are each independently -O -, - COO -, - OCO- or -S It may be substituted with −, and one or more hydrogen atoms present in the group may be independently substituted with fluorine atom or chlorine atom, respectively.
^MQ1 is an alkylene group having 1 to 15 carbon atoms, -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, with fluorine atom It represents a 1,4-phenylene group or a trans-1,4-cyclohexylene group which may be substituted, and one or more -CH _2- in the alkylene group is directly adjacent to an oxygen atom. It may be replaced with -O-, -CO-, -COO-, -OCO- so as not to be.
In formulas (Q-1) to (Q-4), one or two or more non-adjacent -CH = in the 1,4-phenylene group may be substituted by -N =, 1,4. -Hydrogen atoms in the phenylene group may be independently substituted with fluorine or chlorine atoms.
In formulas (Q-1) to (Q-4), one or two or more non-adjacent -CH _2- in the 1,4-cyclohexylene group is substituted with -O- or -S-. The hydrogen atom in the 1,4-cyclohexylene group may be independently substituted with a fluorine atom or a chlorine atom. )
The liquid crystal display element having a PSA type or PSVA type vertical alignment film according to any one of claims 1 to 3, which contains one or more compounds selected from the compound group represented by.

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