JP2020200429A - Polymerizable compound-containing liquid crystal composition and liquid crystal display element - Google Patents

Abstract

To provide: a polymerizable compound-containing liquid crystal composition allowing production of a liquid crystal display element which inhibits increase in the drive voltage and decrease in the light transmittance while realizing fast switching-off response; and a liquid crystal display element based on the polymerizable compound-containing liquid crystal composition.SOLUTION: A polymerizable compound-containing liquid crystal composition contains one or more compounds represented by formula (i), and one or more polymerizable compounds. A liquid crystal display element is based on the polymerizable compound-containing liquid crystal composition. (Xi1 and Xi2 are each independently H, F, or the like; Yi1 and Yi2 are each independently -O-, -CF2-, or the like; Li1 to Li5 are each independently H, Br, or the like; Wi1 is an optionally substituted ethylene group or the like; and Wi2 is a single bond or the like.)SELECTED DRAWING: None

Description

The present invention relates to a liquid crystal composition containing a polymerizable compound, a liquid crystal display device using the same, and a polymerizable compound. In addition, in this specification, a liquid crystal composition containing a polymerizable compound is referred to as a polymerizable compound-containing liquid crystal composition or a polymerizable liquid crystal composition. Further, the polymerizable compound means a compound having a polymerizable group.

In recent years, as the size of liquid crystal televisions has increased, the moving speed of display objects moving on the screen has increased, and therefore, improvement in the response speed of liquid crystals has been required. Therefore, in order to speed up the display, for example, PS (polymer-stabilized) that mainly adopts the vertical orientation mode and imparts a tilt angle of the liquid crystal material to speed up the rising response (on response) when a voltage is applied. : Polymer-stabilized) or PSA (polymer-sustained oriented) display (see Patent Documents 1 to 4) is widely used.

Specifically, in such a PS or PSA display, a small amount of a polymerizable compound is added to the liquid crystal medium, an electric field is applied to the upper and lower electrodes to tilt the liquid crystal molecules in one direction, and UV light is irradiated in this state. It is obtained by polymerizing a polymerizable compound to form a polymer layer on an alignment film. This technology is used to fix the orientation state of the tilted liquid crystal by the polymer layer, thereby speeding up the rising response (on response) when a voltage is applied.

However, as a result of the recent increase in the size of liquid crystal televisions, the moving speed of the display object moving on the screen has become even faster, and therefore, further improvement in the response speed of the liquid crystal is required.

Therefore, conventionally, as a means for improving the response speed, an attempt has been made not only to speed up the rising response (on response) when a voltage is applied, but also to improve the response speed when the voltage is released from the application (switching off). For example, in Patent Document 5, a composition containing a liquid crystal compound and a mesogen group-containing diacrylate in a range of approximately 2 to 15% by mass of the diacrylate is injected into a liquid crystal cell and then irradiated with ultraviolet rays. Then, a liquid crystal display element in which a polymer network of the polymer of the diacrylate is formed in the liquid crystal cell is disclosed. The composition disclosed in Patent Document 5 contains a large amount of a polymerizable compound as compared with the case of a composition used in a PS or PSA display, and such a liquid crystal display element has a polymer network in the liquid crystal layer. It is formed. As a result, by utilizing the attractive interaction between the polymer and the liquid crystal molecule, the relaxation process to the initial orientation state during the switching off response (hereinafter abbreviated as "off response") is accelerated. It realizes high-speed off response.

However, in such a liquid crystal display element, since the polymer content in the liquid crystal layer increases, the amount of the liquid crystal compound has to be relatively small, which tends to cause an increase in the driving voltage and a decrease in the light transmittance. There was a challenge.

Japanese Patent No. 4175826 Japanese Patent No. 5020203 Japanese Patent No. 5383994 U.S. Pat. No. 8940375 International Publication 2015/122457

The problem to be solved by the present invention is a polymerizable compound-containing liquid crystal composition capable of producing a liquid crystal display element in which an increase in drive voltage and a decrease in light transmittance are suppressed while realizing a fast switching-off response. An object of the present invention is to provide a liquid crystal display element using the polymerizable compound-containing liquid crystal composition.

As a result of diligent studies by the present inventors on the above problems, the polymerizable compound-containing liquid crystal composition contains at least a compound having a specific structure (liquid crystal compound) and a polymerizable compound having a specific chemical structure. , The present invention has been completed by finding that the above problems can be solved.

That is, the present invention has the general formula (i).

(In the formula, X ⁱ¹ and X ⁱ² independently represent a hydrogen atom, a fluorine atom, a chlorine atom, a cyano group, a trifluoromethyl group, or a trifluoromethoxy group, respectively.
Y ⁱ¹ and Y ⁱ² independently represent -O-, -CF _2- , -CO-, or -CX ⁱ³ X ^i4- , but any one or more of Y ⁱ¹ and Y ⁱ² is -O-. X ⁱ³ and X ⁱ⁴ independently represent the same meaning as X ⁱ¹ .
^{Li 1} , ^{Li 2} , ^{Li 3} , ^{Li 4} and ^{Li 5} are independently hydrogen atom, bromine atom, iodine atom, hydroxyl group, alkyl group having 1 to 15 carbon atoms, and alkenyl having 2 to 15 carbon atoms. Group or general formula ( ^Li -1)

(In the formula, ^Ri1 is a hydrogen atom, an alkyl group having 1 to 15 carbon atoms, an alkoxy group having 1 to 15 carbon atoms, an alkenyl group having 2 to 15 carbon atoms, or an alkenyloxy group having 2 to 15 carbon atoms. Represents
A ⁱ¹ is (a) 1,4-cyclohexylene group (the one present in the group -CH ₂ - or nonadjacent two or more -CH ₂ - is -O- or -S- in May be replaced.)
(B) 1,4-Phenylene group (one -CH = existing in this group or two or more -CH = not adjacent to each other may be replaced with -N = and is present in this group. One hydrogen atom may be replaced with a fluorine atom.)
(C) 1,4-Cyclohexenylene group, naphthalene-2,6-diyl group, 1,2,3,4-tetrahydronaphthalene-2,6-diyl group, decahydronaphthalene-2,6-diyl group (c) The hydrogen atom present in these groups may be substituted with a fluorine atom, and is also present in the naphthalene-2,6-diyl group or the 1,2,3,4-tetrahydronaphthalene-2,6-diyl group. One -CH = or two or more non-adjacent -CH = may be replaced with -N =.)
Represents a group selected from the group consisting of
Z ⁱ¹ is -CH ₂ O-, -OCH _2- , -CF ₂ O-, -OCF _2- , -COO-, -OCO-, -CH ₂ CH _2- , -CF ₂ CF _2- , -CH = CH-, -CF = CF-, -C≡C- or single bond,
Although n ⁱ¹ represents 1 or 2, when n ⁱ¹ represents 2 and there are a plurality of A ⁱ¹ and Z ^{i 1} , they may be the same or different. )
Represents the group represented by
W ⁱ¹ is a general formula (W ^i1-1 ), (W ^i1-2 ) or (W ⁱ¹ -3).

(In the formula, the black dot (・) represents the bond point to ^{Li i2} or Y ⁱ² , * represents the bond point to the carbon atom adjacent to the carbon atom to which ^{Li i5} is bonded, and ^{Li i6} , ^{Li 7} and ^{Li 8} each independently represent a group represented by represents.) the same meaning as L ^i1,
W ⁱ² is a single bond or ^{-CL i9 L} i10 - ^(L i9 and ^{L i10} are each independently ^the same meaning as ^{L i1.)} Represent,
^{L i1, L i2, L i3} , L i4, L i5, L i6, L i7, L i8, L i9 and ^{L i10} in present in one -CH ₂ - or adjacent have not more than one - CH ₂ − may be replaced by −C≡C−, −O−, −COO−, −OCO− or −CO−, and a hydrogen atom present in an alkyl group or an alkenyl group is substituted with a fluorine atom. May be done. ) Is one or more compounds,
General formula (PI)

(In the above general formula (PI), R ¹⁰² , R ¹⁰³ , R ¹⁰⁴ , R ¹⁰⁵ , R ¹⁰⁶ , R ¹⁰⁷ , R ¹⁰⁸ and R ¹⁰⁹ are independently alkyl groups and carbon atoms having 1 to 18 carbon atoms, respectively. Represents any of the alkoxy groups, halogen atoms or hydrogen atoms of numbers 1-18,
P ¹¹ and P ¹² independently represent any of the following equations (R-1) to (R-9).

(In the above formulas (R-1) to (R-9), R ²¹ , R ³¹ , R ⁴¹ , R ⁵¹ and R ⁶¹ are independent of each other and have an alkyl group having a hydrogen atom and 1 to 5 carbon atoms. Alternatively, it represents an alkyl halide group having 1 to 5 carbon atoms, and W and T independently represent a single bond, -O-, -COO- or an alkylene group having 1 to 5 carbon atoms, p, t. And q independently represent 0, 1 or 2. * in the equation represents the point of connection to S ¹¹ or S ^12. )
S ¹¹ and S ¹² each independently represent a single bond or an alkylene group having 1 to 15 carbon atoms, but S ¹¹ and S ¹² do not represent a single bond at the same time, and one or one of the alkylene groups. two or more -CH ₂ -, as the oxygen atoms are not directly adjacent, -O -, - OCO- or -COO- in may be substituted,
At least one of R ¹⁰² , R ¹⁰³ , R ¹⁰⁴ , R ¹⁰⁵ , R ¹⁰⁶ , R ¹⁰⁷ , R ¹⁰⁸ and R ¹⁰⁹ is a halogen atom, an alkyl group with 1 to 18 carbon atoms, or an alkoxy with 1 to 18 carbon atoms. It is the basis. )
One or more polymerizable compounds represented by
To provide a liquid crystal composition containing a polymerizable compound containing the above.

The present invention also contains one or more compounds represented by the general formula (i) and one or more polymerizable compounds represented by the general formula (PI). Provided is a liquid crystal display element using a liquid crystal composition containing a polymerizable compound.

According to the present invention, a polymerizable compound-containing liquid crystal composition capable of producing a liquid crystal display device in which an increase in drive voltage and a decrease in light transmittance are suppressed while realizing a fast switching-off response, and the above-mentioned It is possible to provide a liquid crystal display element having the above-mentioned features.

Hereinafter, the polymerizable compound-containing liquid crystal composition of the present invention and the liquid crystal display device using the same will be described in detail.

A. Polymerizable Compound-Containing Liquid Crystal Composition The polymerizable compound-containing liquid crystal composition of the present invention has the general formula (i).

(In the formula, X ⁱ¹ and X ⁱ² independently represent a hydrogen atom, a fluorine atom, a chlorine atom, a cyano group, a trifluoromethyl group, or a trifluoromethoxy group, respectively.
Y ⁱ¹ and Y ⁱ² independently represent -O-, -CF _2- , -CO-, or -CX ⁱ³ X ^i4- , but any one or more of Y ⁱ¹ and Y ⁱ² is -O-. X ⁱ³ and X ⁱ⁴ independently represent the same meaning as X ⁱ¹ .
^{Li 1} , ^{Li 2} , ^{Li 3} , ^{Li 4} and ^{Li 5} are independently hydrogen atom, bromine atom, iodine atom, hydroxyl group, alkyl group having 1 to 15 carbon atoms, and alkenyl having 2 to 15 carbon atoms. Group or general formula ( ^Li -1)

(In the formula, ^Ri1 is a hydrogen atom, an alkyl group having 1 to 15 carbon atoms, an alkoxy group having 1 to 15 carbon atoms, an alkenyl group having 2 to 15 carbon atoms, or an alkenyloxy group having 2 to 15 carbon atoms. Represents
A ⁱ¹ is (a) 1,4-cyclohexylene group (the one present in the group -CH ₂ - or nonadjacent two or more -CH ₂ - is -O- or -S- in May be replaced.)
(B) 1,4-Phenylene group (one -CH = existing in this group or two or more -CH = not adjacent to each other may be replaced with -N = and is present in this group. One hydrogen atom may be replaced with a fluorine atom.)
(C) 1,4-Cyclohexenylene group, naphthalene-2,6-diyl group, 1,2,3,4-tetrahydronaphthalene-2,6-diyl group, decahydronaphthalene-2,6-diyl group (c) The hydrogen atom present in these groups may be substituted with a fluorine atom, and is also present in the naphthalene-2,6-diyl group or the 1,2,3,4-tetrahydronaphthalene-2,6-diyl group. One -CH = or two or more non-adjacent -CH = may be replaced with -N =.)
Represents a group selected from the group consisting of
Z ⁱ¹ is -CH ₂ O-, -OCH _2- , -CF ₂ O-, -OCF _2- , -COO-, -OCO-, -CH ₂ CH _2- , -CF ₂ CF _2- , -CH = CH-, -CF = CF-, -C≡C- or single bond,
Although n ⁱ¹ represents 1 or 2, when n ⁱ¹ represents 2 and there are a plurality of A ⁱ¹ and Z ^{i 1} , they may be the same or different. )
Represents the group represented by
W ⁱ¹ is a general formula (W ^i1-1 ), (W ^i1-2 ) or (W ⁱ¹ -3).

(In the formula, the black dot (・) represents the bond point to ^{Li i2} or Y ⁱ² , * represents the bond point to the carbon atom adjacent to the carbon atom to which ^{Li i5} is bonded, and ^{Li i6} , ^{Li 7} and ^{Li 8} each independently represent a group represented by represents.) the same meaning as L ^i1,
W ⁱ² is a single bond or ^{-CL i9 L} i10 - ^(L i9 and ^{L i10} are each independently ^the same meaning as ^{L i1.)} Represent,
^{L i1, L i2, L i3} , L i4, L i5, L i6, L i7, L i8, L i9 and ^{L i10} in present in one -CH ₂ - or adjacent have not more than one - CH ₂ − may be replaced by −C≡C−, −O−, −COO−, −OCO− or −CO−, and a hydrogen atom present in an alkyl group or an alkenyl group is substituted with a fluorine atom. May be done. ) Is one or more compounds,
General formula (PI)

(In the above general formula (PI), R ¹⁰² , R ¹⁰³ , R ¹⁰⁴ , R ¹⁰⁵ , R ¹⁰⁶ , R ¹⁰⁷ , R ¹⁰⁸ and R ¹⁰⁹ are independently alkyl groups and carbon atoms having 1 to 18 carbon atoms, respectively. Represents any of the alkoxy groups, halogen atoms or hydrogen atoms of numbers 1-18,
P ¹¹ and P ¹² independently represent any of the following equations (R-1) to (R-9).

(In the above formulas (R-1) to (R-9), R ²¹ , R ³¹ , R ⁴¹ , R ⁵¹ and R ⁶¹ are independent of each other and have an alkyl group having a hydrogen atom and 1 to 5 carbon atoms. Alternatively, it represents an alkyl halide group having 1 to 5 carbon atoms, and W and T independently represent a single bond, -O-, -COO- or an alkylene group having 1 to 5 carbon atoms, p, t. And q independently represent 0, 1 or 2. * in the equation represents the point of connection to S ¹¹ or S ^12. )
S ¹¹ and S ¹² each independently represent a single bond or an alkylene group having 1 to 15 carbon atoms, but S ¹¹ and S ¹² do not represent a single bond at the same time, and one or one of the alkylene groups. two or more -CH ₂ -, as the oxygen atoms are not directly adjacent, -O -, - OCO- or -COO- in may be substituted,
At least one of R ¹⁰² , R ¹⁰³ , R ¹⁰⁴ , R ¹⁰⁵ , R ¹⁰⁶ , R ¹⁰⁷ , R ¹⁰⁸ and R ¹⁰⁹ is a halogen atom, an alkyl group with 1 to 18 carbon atoms, or an alkoxy with 1 to 18 carbon atoms. It is the basis. )
One or more polymerizable compounds represented by
Contains.

In the following description, the compound represented by the general formula (i) may be referred to as a compound of the general formula (i) or a compound (i). The same applies to other compounds.

According to the present invention, the compound of the general formula (PI) can form a polymer network that does not easily inhibit the orientation state of the liquid crystal, that is, can suppress a decrease in light transmittance. Further, the compound of the general formula (i) increases the absolute value | Δε | of the anisotropy Δε of the dielectric constant and the birefringence Δn, and as a result, suppresses the increase in the driving voltage even if the polymer network is formed. be able to. Therefore, the polymerizable compound-containing liquid crystal composition of the present invention makes it possible to manufacture a liquid crystal display element exhibiting high light transmittance in which an increase in driving voltage is suppressed while maintaining a fast switching-off response. ..

Hereinafter, the components contained in the polymerizable compound-containing liquid crystal composition of the present invention will be described.

[1] Compound represented by the general formula (i) In the general formula (i), at least one of X ⁱ¹ and X ⁱ² preferably represents a hydrogen atom or a fluorine atom, and at least one of them is a fluorine atom. Is preferable, and both are preferably fluorine atoms.

Y ⁱ¹ and ^{Y i2,} at least one of which is -O-, among them one is -O- other -CH ₂ - is, or is preferably both -O-. When a large | Δε |, polymerization rate and tilt formation are emphasized, it is preferable that both Y ⁱ¹ and Y ⁱ² are −O−.

It is preferable that ^{Li 1} and ^{Li 2} independently represent a hydrogen atom, an alkyl group having 1 to 15 carbon atoms, and an alkenyl group having 2 to 15 carbon atoms. In order to reduce γ ₁ , ^{Li 1} and ^{Li 2} are each independently preferably an alkyl group having 1 to 8 carbon atoms or an alkenyl group having 2 to 8 carbon atoms, preferably having 1 to 8 carbon atoms. It is particularly preferably an alkyl group of 5 or an alkenyl group having 2 to 5 carbon atoms. Further, ^{Li 1} and ^{Li 2} are preferably linear. In order to increase | Δε |, ^Li1 and ^Li2 are each independently preferably an alkoxy group having 1 to 8 carbon atoms or an alkenyloxy group having 2 to 8 carbon atoms, and the number of carbon atoms is large. It is particularly preferably an alkoxy group of 1 to 5 or an alkenyloxy group having 2 to 5 carbon atoms. In order to increase the miscibility with other liquid crystal components, ^{Li 1} and ^{Li 2} are preferably different, and either one of ^{Li 1} and ^{Li 2} is preferably an alkoxy group or an alkenyloxy group, and ^{Li 1} Is particularly preferably an alkoxy group. The hydrogen atom existing in ^{Li 1} and ^{Li 2} may be substituted with a fluorine atom, but it is preferable that the hydrogen atom is not substituted with a fluorine atom.

In addition, ^{Li 1} and ^{Li 2} are

It is preferable to represent.

In order to reduce γ ₁ , R ⁱ¹ is preferably an alkyl group having 1 to 8 carbon atoms or an alkenyl group having 2 to 8 carbon atoms, and an alkyl group having 1 to 5 carbon atoms or an alkenyl group having 1 to 5 carbon atoms. It is particularly preferably 2 to 5 alkenyl groups. Further, it is preferably linear. On the other hand, in order to increase | Δε |, ^Ri1 is preferably an alkoxy group having 1 to 8 carbon atoms or an alkenyloxy group having 2 to 8 carbon atoms, and is an alkoxy having 1 to 5 carbon atoms. It is particularly preferably a group or an alkoxyoxy group having 2 to 5 carbon atoms. When a plurality of R ^i1s are present, the R ^i1s are preferably different from each other in order to increase the miscibility with other liquid crystal components, and any one of the plurality of R ^i1s is an alkoxy group or an alkenyloxy group. It is particularly preferable that ^Ri1 in ^Li1 is an alkoxy group or an alkenyloxy group. The hydrogen atom present in ^Ri1 may be substituted with a fluorine atom, but it is preferable that the hydrogen atom is not substituted with a fluorine atom.

A ⁱ¹ preferably represents a group selected from the following formula.

Specifically, A ¹ is a trans-1,4-cyclohexylene group, an unsubstituted 1,4-phenylene group, a 2-fluoro-1,4-phenylene group or a 3-fluoro to lower γ _1. It is preferably a -1,4-phenylene group, and particularly preferably a trans-1,4-cyclohexylene group. In order to improve the miscibility with other liquid crystal components, ^{A 1} is trans-1,4-cyclohexylene group, 2-fluoro-1,4-phenylene or 3-fluoro-1,4-phenylene group Is preferable. To increase _TNI , A ¹ is an unsubstituted 1,4-phenylene group, an unsubstituted 1,4-cyclohexylene group, a 1,4-cyclohexenylene group or an unsubstituted naphthalene-2, It is preferably a 6-diyl group. In order to show a negatively large Δε, A ¹ is a 2-fluoro-1,4-phenylene group, a 3-fluoro-1,4-phenylene group or a 2,3-difluoro-1,4-phenylene group. Is preferable. In order to achieve miscibility with other liquid crystal components while showing a negatively large Δε, the total number of fluorine atoms present in ^Ai1 is preferably 1 to 4, preferably 1 to 3. It is particularly preferable to have.

Z ⁱ¹ is preferably a single bond, −CH ₂ CH ₂ −, −CH ₂ O− or −OCH ₂ −, and is single bond or −CH ₂ CH ₂ − in order to reduce γ _1. Is more preferable. ^{Further, Z _i1,} in order to increase the _{T NI} represents a single bond, -COO -, - OCO -, - preferably CH = CH- or -C≡C-, a single bond, -CH = CH -Or -C≡C- is more preferable. In order to improve the miscibility with other liquid crystal components, Z ⁱ¹ is preferably a single bond, −CH ₂ CH ₂ −, −CH ₂ O− or −OCH ₂ −. In order to improve the long-term reliability of the liquid crystal display element, it is preferable that Z ⁱ¹ has a single bond.

When n ⁱ¹ represents 2, it is preferable that any one or more of a plurality of Z ⁱ¹ represents a single bond. n ⁱ¹ preferably represents 1 when γ ₁ is emphasized, and preferably 2 when T _NI is emphasized.

^{Wi 1} is preferably of the general formula (W ^i1-1 ) or (W ⁱ¹ -3).

^Wi2 is preferably a single bond.

^Li3 may represent a hydrogen atom, an alkyl group having 1 to 15 carbon atoms, an alkoxy group having 1 to 15 carbon atoms, an alkenyl group having 2 to 15 carbon atoms, and an alkenyloxy group having 2 to 15 carbon atoms. Preferably, in order to reduce γ ₁ , an alkyl group having 1 to 8 carbon atoms or an alkoxy group having 2 to 8 carbon atoms is preferable, and an alkyl group having 1 to 5 carbon atoms or 2 carbon atoms is preferable. It is particularly preferably an alkenyl group of ~ 5. Further, ^{Li 3} is preferably linear.

It is preferable that at least one of ^{Li 1} , ^{Li 2} and ^{Li 3} represents a hydrogen atom, and ^{Li 1} or ^{Li 3} preferably represents a hydrogen atom. It is preferable that ^{Li 1} is an alkyl group having 1 to 8 carbon atoms or an alkoxy group having 1 to 8 carbon atoms, ^{Li 2} is a hydrogen atom, ^{Li 3} is an alkyl group having 1 to 8 carbon atoms, and ^{Li 1} is It is preferable that the hydrogen atom and ^Li2 are an alkyl group having 1 to 8 carbon atoms or an alkoxy group having 1 to 8 carbon atoms, and ^Li3 is an alkyl group having 1 to 8 carbon atoms.

^{Li 4} and ^{Li 5} independently represent a hydrogen atom, an alkyl group having 1 to 15 carbon atoms, and an alkenyl group having 2 to 15 carbon atoms, and preferably represent a hydrogen atom.

^{Li 6} and ^{Li 7} each independently represent a hydrogen atom, an alkyl group having 1 to 15 carbon atoms, and an alkenyl group having 2 to 15 carbon atoms, and a hydrogen atom is preferable.

^Li8 may represent a hydrogen atom, an alkyl group having 1 to 15 carbon atoms, an alkoxy group having 1 to 15 carbon atoms, an alkenyl group having 2 to 15 carbon atoms, and an alkenyloxy group having 2 to 15 carbon atoms. Preferably, a hydrogen atom is preferred.

L ⁱ⁹ and ^{L i10} is preferably representative of at least one of hydrogen ^atom, it is more preferable ^{that L i9} and ^{L i10} represents both hydrogen atoms.

The compound represented by the general formula (i) does not have a structure in which heteroatoms are directly bonded to each other.

The compound represented by the general formula (i) is preferably one or more selected from the compound group represented by the following general formulas (i-1) to (i-48). .. Among them, particularly preferable compounds are compounds represented by the general formulas (i-1) to (i-12), and compounds represented by the general formulas (i-1) to (i-4). It is a compound represented by the general formulas (i-1) and (i-3), and is a compound represented by the general formula (i-1).

(In the formula, R ⁱ² and R ⁱ³ have the same meaning as R ⁱ¹ in the general formula (i).)

(In the formula, R ⁱ² and R ⁱ³ have the same meaning as R ⁱ¹ in the general formula (i).)

(In the formula, R ⁱ² and R ⁱ³ have the same meaning as R ⁱ¹ in the general formula (i).)

(In the formula, R ⁱ² and R ⁱ³ have the same meaning as R ⁱ¹ in the general formula (i).)

The content of the compound of the general formula (i) in the polymerizable compound-containing liquid crystal composition of the present invention is preferably 0.1% by mass, preferably 0.2% by mass, as a lower limit. It is preferably 0.3% by mass, preferably 0.5% by mass, preferably 1% by mass, preferably 2% by mass, preferably 3% by mass, and 4% by mass. It is preferably mass%. The content of the compound of the general formula (i) is preferably 20% by mass, preferably 15% by mass, preferably 13% by mass, and 10% by mass as the upper limit value. It is preferably 9% by mass, preferably 7% by mass, and preferably 5% by mass. The content of the compound of the general formula (i) is preferably 0.1 to 25% by mass, more preferably 0.1 to 20% by mass, and 0.1 to 15% by mass. It is more preferable, and 0.5 to 10% by mass is particularly preferable. Hereinafter, mass% is described as%.

The content of the compound of the general formula (i) is preferably small when the nematic phase-isotropic liquid phase transition temperature ( _TNI ) is important, and the ratio of the rotational viscosity γ _{1 to} the elastic constant K ₃₃ . It is preferable to improve (γ ₁ / K ₃₃ ) and increase it when the response speed is emphasized.

When the polymerizable compound-containing liquid crystal composition of the present invention contains two or more compounds of the general formula (i), the content of the compound of the general formula (i) means the total content.

[2] Polymerizable compound represented by the general formula (PI) In the above general formula (PI), R ¹⁰² , R ¹⁰³ , R ¹⁰⁴ , R ¹⁰⁵ , R ¹⁰⁶ , R ¹⁰⁷ , R ¹⁰⁸ and R ¹⁰⁹ are independent of each other. Represents any of an alkyl group having 1 to 18 carbon atoms, an alkoxy group having 1 to 18 carbon atoms, a halogen atom or a hydrogen atom, and R ¹⁰² , R ¹⁰³ , R ¹⁰⁴ , R ¹⁰⁵ , R ¹⁰⁶ , R. ^At least one of ¹⁰⁷ , R ¹⁰⁸ and R ¹⁰⁹ is a halogen atom, an alkyl group having 1 to 18 carbon atoms, or an alkoxy group having 1 to 18 carbon atoms. Of these, it is preferable that at least one of R ¹⁰² , R ¹⁰³ , R ¹⁰⁶ and R ¹⁰⁷ is a halogen atom. Further, the halogen atom is more preferably a fluorine atom.

An alkyl group having a carbon number of 1 to 18 (one or non-adjacent two or more -CH 2 in the alkyl group _-. Is which may optionally be substituted by independently -O-) is a straight-chain Alternatively, branching may be mentioned, but linear chain is preferable. Further, the preferable number of carbon atoms of the alkyl group is preferably 1 to 3 when the solubility and expandability of the liquid crystal composition are important, and 10 to 10 when the vertical orientation is important as the liquid crystal composition. 18 is preferable.

In the above general formula (PI), P ¹¹ and P ¹² independently represent any of the above-mentioned formulas (R-1) to (R-9). In addition, * in the formula (R-1) to the formula (R-9) represents the connection point to S ¹¹ or S ¹² . Among them, P ¹¹ and P ¹² are independently represented by the formula (R-1), the formula (R-2), the formula (R-3), the formula (R-4), the formula (R-5) or the formula (R-5). It is preferably R-7), more preferably the formula (R-1), the formula (R-2), the formula (R-3) or the formula (R-4), and the formula (R-1). Is more preferable, an acrylic group or a methacrylic group is further preferable, and a methacrylic group is even more preferable. Further, P ¹¹ and P ¹² may be the same or different, but are preferably the same.

In the above formulas (R-1) to (R-9), it is preferable that R ²¹ , R ³¹ , R ⁴¹ , R ⁵¹ and R ⁶¹ are independently hydrogen atoms or methyl groups, respectively.

In the formulas (R-1) to (R-9), p and t are preferably 0 or 1, respectively.

In the above formulas (R-1) to (R-9), W is preferably a single bond, —O— or a methylene group.

In the above formulas (R-1) to (R-9), T is preferably a single bond or -COO-.

In the above formulas (R-1) to (R-9), when there are a plurality of the same reference numerals in the formulas, they may be the same or different.

In the above general formula (PI), S ¹¹ and S ¹² each independently represent a single bond or an alkylene group having 1 to 15 carbon atoms, but S ¹¹ and S ¹² do not represent a single bond at the same time. That is, at least one of S ¹¹ and S ¹² is an alkylene group having a desired number of carbon atoms. The number of carbon atoms of the alkylene group is preferably 1 to 15, preferably 1 to 8, and preferably 1 to 4. Further, one or more -CH ₂ − in the alkylene group may be substituted with −O−, −OCO− or −COO− so that oxygen atoms are not directly adjacent to each other.

At least one of S ¹¹ and S ¹² are one or more -CH 2 in the group _- that is is desired that may be substituted alkylene group having carbon atoms, single bond S ¹¹ and S ¹² are both As compared with the case of, it is possible to easily form a polymer network in the liquid crystal layer in which the orientation of the liquid crystal is less likely to be disturbed. As a result, in the liquid crystal display element using the polymerizable compound-containing liquid crystal composition of the present invention, the light transmittance can be improved, and the off-response speed utilizing the attractive interaction between the polymer and the liquid crystal molecule can be achieved. Has the advantage of being able to speed up. Further, there is an advantage that the compatibility between the compound represented by the general formula (PI) and the liquid crystal compound is improved, and the compound is less likely to precipitate due to low temperature storage. Among them, S ¹¹ and S ¹² are independently alkylene groups having 1 to 15 carbon atoms (one -CH _2- in the group may be substituted with -O-). It is preferably an alkylene group having 1 to 8 carbon atoms (one −CH ₂ − in the group may be substituted with −O−), and an alkylene group having 1 to 4 carbon atoms (1 to 4 carbon atoms). one -CH in group ₂ -. which may be substituted with -O-) is preferably, one -CH ₂ in the group - number of carbon atoms is substituted with -O-. 1 to It is preferably an alkylene group of 4. Of these, it is preferable that -CH _2- bonded to the ring is an alkylene group substituted with -O-. Further, the two or more S ¹¹ and S ¹² of the above general formula (PI) may be the same or different, but are preferably the same.

The types of the polymerizable compound represented by the general formula (PI) contained in the polymerizable compound-containing liquid crystal composition of the present invention are 1 to 5 types, 1 to 4 types, 1 to 3 types, and 1 to 2 types. Is preferable. In another embodiment, from the viewpoint of improving vertical orientation and uneven orientation, the types of the polymerizable compound represented by the general formula (PI) are 2 to 5, 2 to 4, and 2 to. It is preferable to include 3 types.

A preferable example of the polymerizable compound represented by the general formula (PI) according to the present invention is a compound selected from the group consisting of compounds represented by the following formulas (PI-1) to (PI-17). Can be mentioned.

(In the formula, Sp ^xx independently represent an alkylene group having 1 to 8 carbon atoms or −O− (CH ₂ ) _s − (s is an integer from 1 to 7, and the oxygen atom is bonded to the ring. ) Represents.)

Among them, the polymerizable compound represented by the general formula (PI) is represented by the above formulas (PI-1), (PI-2), (PI-4), (PI-6) and (PI-7). One or more selected from the group consisting of compounds is more preferable, and one or more selected from the group consisting of compounds represented by the general formulas (PI-1), (PI-2), and (PI-4). One or more are particularly preferred. Among these, a compound in which Sp ^xx in the above formula is −O− (CH ₂ ) _s− and s is 2 or 3 is particularly preferable.

The higher the content of the polymerizable compound represented by the general formula (PI), the more a polymer network is formed in the liquid crystal layer in the liquid crystal display element manufactured by using the polymerizable compound-containing liquid crystal composition of the present invention. And the switching off response can be made faster. Specifically, the content of the polymerizable compound represented by the general formula (PI) in the polymerizable compound-containing liquid crystal composition of the present invention is preferably 0.4% by mass or more, preferably 1.0% by mass or more. Is more preferable, and 1.8% by mass or more is particularly preferable. In particular, a liquid crystal display element manufactured by using the polymerizable compound-containing liquid crystal composition of the present invention by containing 1.8% by mass or more of a polymerizable compound (monomer) represented by the general formula (PI) is a liquid crystal display. Since a polymer network (polymer network) is formed not only on the surface of the substrate but also in the liquid crystal medium, the polymer network strongly stabilizes the orientation when no voltage is applied, and as a result, switching more effectively. This is preferable because the off response is faster.

On the other hand, if the content of the polymerizable compound represented by the general formula (PI) is too high, the liquid crystal display element using the polymerizable compound-containing liquid crystal composition may cause a decrease in light transmittance and an increase in drive voltage. There is. Therefore, the content of the polymerizable compound represented by the general formula (PI) in the polymerizable compound-containing liquid crystal composition of the present invention is preferably 8.0% by mass or less, preferably 6.0% by mass or less. It is preferably 4.8% by mass or less, preferably 4.0% by mass or less, preferably 3.2% by mass or less, and preferably 3.0% by mass or less. The more specific content of the polymerizable compound represented by the general formula (PI) in the polymerizable compound-containing liquid crystal composition of the present invention can be set by combining the above-mentioned upper limit value and lower limit value. For example, it can be in the range of 0.4% by mass to 8.0% by mass, preferably in the range of 0.4% by mass to 4.8% by mass, and particularly 0.7% by mass to 4.0. The range of mass% is preferable, and the range of 1.8 mass% to 3.2 mass% is particularly preferable. When the polymerizable compound-containing liquid crystal composition of the present invention contains two or more kinds of polymerizable compounds represented by the general formula (PI), the content of the polymerizable compound represented by the general formula (PI) is used. Refers to the total content of the polymerizable compound represented by two or more general formulas (PI).

[3] Polymerizable compound represented by the general formula (PII) The liquid crystal composition according to the present invention has the general formula (PII).

^{(Wherein, R 201, R 202, R} 203, R 204, R 205, R 206, R 207, R 208, R 209 and ^{R 210} each ^{independently,} P 21 ^{-S 21} -, fluorine atom Represents any of an alkyl group having 1 to 18 carbon atoms which may be substituted, an alkoxy group having 1 to 18 carbon atoms which may be substituted by a fluorine atom, a fluorine atom or a hydrogen atom.
P ²¹ represents any of the formulas (R-1) to (R-9) in the general formula (PI).
S ²¹ represents a single bond or an alkylene group having 1 to 8 carbon atoms, and -CH _2- in the alkylene group is -O-, -CO-, -COO-, unless oxygen atoms are directly linked to each other. It may be substituted with −OCO−, −CH = CH− or −C≡C−, and the hydrogen atom in the alkylene group may be substituted with a halogen atom.
n ²¹ represents 0, 1 or 2,
A ²¹ is
(A) 1,4-cyclohexylene group (this is present in the group one -CH ₂ - or nonadjacent two or more -CH ₂ - may be replaced by -O-.)
(B) 1,4-phenylene group (one -CH = existing in this group or two or more -CH = not adjacent to each other may be replaced with -N =) and (c). One -CH = present in a naphthalenediyl group, a 1,2,3,4-tetrahydronaphthalenediyl group, or a decahydronaphthalenediyl group (naphthalenediyl group or a 1,2,3,4-tetrahydronaphthalenediyl group Alternatively, 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) are independently alkyl groups having 1 to 12 carbon atoms and 1 to 12 carbon atoms, respectively. It may be substituted with an alkoxy group, a halogen, a cyano group, a nitro group or P ²¹ −S ²¹ −.
It has at least one P ^21- S ^21- in one molecule of the above general formula (PII) and has at least one P ^21- S 21-.
L ²¹ represents a single _{bond, -OCH 2 -, - CH 2} O -, - C 2 H 4 -, - OC 2 H 4 O -, - COO -, - OCO -, - CH = CR a -COO -, - CH = CR ^a- OCO-, -COO-CR ^a = CH-, -OCO-CR ^a = CH-,-(CH ₂ ) _z- COO-,-(CH ₂ ) _z- OCO-, -OCO- ( CH ₂ ) _z- , -COO- (CH ₂ ) _z- , -CH = CH-, -CF ₂ O-, -OCF _2- or -C ≡ C- (In the formula, R ^a is hydrogen independently. It represents an atom or an alkyl group having 1 to 3 carbon atoms, and in the above formula, z independently represents an integer of 1 to 4).
When a plurality of P ²¹ , S ²¹ , and A ²¹ exist, they may be the same or different from each other. However, the compounds represented by the above general formula (PI) are excluded. )
The polymerizable compound represented by (1) or 2 or more may be further contained.

The polymerizable compound-containing liquid crystal composition of the present invention contains a polymerizable compound represented by the general formula (PII) in addition to the polymerizable compound represented by the general formula (PI), thereby causing display defects. It is effective in terms of being able to further reduce. It also has the effect of improving orientation stability and tilt stability.

In the above general formula (PII), it is preferable to have 1 or 2 or more P ²¹ −S ²¹ − in one molecule of the compound represented by the general formula (PII), and 4 or less P ²¹ −S ²¹ −. The number of P ²¹ −S ²¹ − present in one molecule of the above general formula (PII) is preferably 1 or more and 4 or less, more preferably 1 or more and 3 or less, and the above general formula (PII). The number of P ²¹ −S ²¹ − in the molecule of the compound represented by is particularly preferably 2 or 3.

That is, the compound represented by the general formula (PII) has a structure in which two benzene rings (phenyl groups) and, if necessary, ring A ²¹ are linked, and these two benzene rings (phenyl groups) and ring A ^{21 are connected.} Since it has at least one P ²¹ − S ²¹ − in the above, the compound represented by the general formula (PII) exhibits an action / effect as a polymerizable compound.

In the above general formula (PII), one or more selected from the group consisting of R ²⁰¹ , R ²⁰² , R ²⁰³ , R ²⁰⁴ , R ²⁰⁵ , R ²⁰⁶ , R ²⁰⁷ , R ²⁰⁸ , R ²⁰⁹ and R ^210. If it ^{is, R 201, R 202, R} 204, R 207, R 209 or one or two or more either ^{R 210} is ^{P 21 -S} 21 - - but ^P 21 ^{-S 21} is preferably , ^{R 201} and ^{R 210} are ^P 21 ^{-S 21} - is more preferable.

In the above general formula (PII), R ²⁰¹ and R ²¹⁰ are preferably P ²¹ −S ²¹ −, respectively, and in this case, R ²⁰¹ and R ²¹⁰ are the same P ²¹ −S ²¹ −. even different ^P 21 ^{-S 21} - may be.

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

In the above general formula (PII), R ²⁰² , R ²⁰³ , R ²⁰⁴ , R ²⁰⁵ , R ²⁰⁶ , R ²⁰⁷ , R ²⁰⁸ and R ²⁰⁹ are independently derived from P ²¹ − S ²¹ − and 1 carbon atom. 3 alkyl group, preferably a fluorine atom or a hydrogen atom, P ^{21 -S} 21 ^-, more preferably a fluorine atom or a hydrogen atom, more preferably a fluorine atom or a hydrogen atom.

P ²¹ represents any of the formulas (R-1) to (R-9) in the general formula (PI). In the general formula (PII), * in the formulas (R-1) to (R-9) represents a binding point to S ²¹ . Among them, P ²¹ is preferably of the formula (R-1), more preferably of an acrylic group or a methacrylic group, and even more preferably of a methacrylic group.

S ²¹ is preferably a single bond or an alkylene group having 1 to 3 carbon atoms, and more preferably a single bond.

In the above general formula (PII), n ²¹ is preferably 0 or 1.

In the above general formula (PII), A ²¹ represents a group selected from the group consisting of the above groups (a), (b) and (c). Here, in the above group (c), the naphthalenediyl group and the 1,2,3,4-tetrahydronaphthalenediyl group are groups that are bonded at two positions selected from the 1st to 8th positions, and specifically, Of the two sites selected from the 1st to 8th positions, one is a group that binds to an adjacent benzene ring (phenyl group) or an adjacent A ^21, and the other is a group that binds to an adjacent A ²¹ or L ²¹ .

Further, in the above group (c), the decahydronaphthalenedyl group is a group that binds at two positions selected from the 1 to 10 positions, and specifically, of the two positions selected from the 1 to 10 positions. On the one hand, it is a group that binds to an adjacent benzene ring (phenyl group) or an adjacent A ²¹ and on the other hand, it is a group that binds to an adjacent A ²¹ or L ²¹ .

Examples of the naphthalene diyl group include naphthalene-1,2-diyl group, naphthalene-1,3-diyl group, naphthalene-1,4-diyl group, naphthalene-1,5-diyl group and naphthalene-1,6-diyl group. Examples thereof include groups, naphthalene-1,7-diyl groups, naphthalene-1,8-diyl groups, naphthalene-2,3-diyl groups, naphthalene-2,6-diyl groups, naphthalene-2,7-diyl groups and the like. .. Of these, naphthalene-1,4-diyl group, naphthalene-1,5-diyl group or naphthalene-2,6-diyl group is preferable, and naphthalene-2,6-diyl group is more preferable.

Examples of the 1,2,3,4-tetrahydronaphthalenediyl group include 1,2,3,4-tetrahydronaphthalene-2,6-diyl group and 1,2,3,4-tetrahydronaphthalene-1,4-diyl. Groups, 1,2,3,4-tetrahydronaphthalene-1,5-diyl groups and the like can be mentioned. Of these, 1,2,3,4-tetrahydronaphthalene-2,6-diyl groups are preferable.

As the decahydronaphthalenedyl group, a decahydronaphthalene-2,6-diyl group is preferable.

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

In the general formula ^{(PII), L 21} represents a single _{bond, -OCH 2 -, - CH 2} O -, - C 2 H 4 -, - COO -, - OCO -, - CH = CH-COO -, - CH = CH-OCO -, - COO-CH = CH -, - OCO-CH = CH -, - C 2 H 4 -COO -, - C 2 H 4 -OCO -, - OCO-C 2 H 4 -, _{-COO-C 2 H 4 -,} - CH = CH -, - CF 2 O -, - OCF 2 - or -C≡C- is preferred.

The polymerizable compound represented by the general formula (PII) is more preferably one or more selected from the compound group represented by the formulas (PII-1) to (PII-7). , The compound represented by the formula (PII-5) is particularly preferable.

Further, as the polymerizable compound represented by the general formula (PII), for example, the polymerizable compound represented by the formulas (PII-8) to (PII-41) can also be exemplified.

The upper limit of the content of the polymerizable compound represented by the general formula (PII) in the polymerizable compound-containing liquid crystal composition of the present invention is preferably 1.0% by mass, more preferably 0.8% by mass, and 0. 6.6% by mass is particularly preferable.

The total content of the polymerizable compound represented by the general formula (PI) and the polymerizable compound represented by the general formula (PII) in the entire polymerizable compound-containing liquid crystal composition (100% by mass) of the present invention. The upper limit is preferably 9.0% by mass, preferably 7.0% by mass, preferably 5.8% by mass, preferably 5.0% by mass, preferably 4.2% by mass, and 4.0% by mass. Preferably, 3.0% by mass is preferable. The lower limit of the total content is preferably 0.4% by mass, preferably 1.8% by mass, preferably 2.5% by mass, and preferably 3.0% by mass.

[4] Liquid Crystal Compound The polymerizable compound-containing liquid crystal composition of the present invention contains one or more liquid crystal compounds as constituents in addition to the above-mentioned general formula (i) compound and polymerizable compound. The composition composed of one or more liquid crystal compounds excluding the polymerizable compound and the additive from the polymerizable compound-containing liquid crystal composition of the present invention is referred to as the liquid crystal composition in the present invention. ..

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

(In the formula, R ^NU11 , R ^NU12 , R ^NU21 , R ^NU22 , R ^NU31 , R ^NU32 , R ^NU41 , R ^NU42 , R ^NU51 , R ^NU52 , R ^NU61 , R ^NU62 , R ^NU71 , R ^NU72 , R ^NU71, R ^NU82 independently represents an alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, an alkenyl group having 2 to 8 carbon atoms, or an alkenyloxy group having 2 to 8 carbon atoms. It contains one or more compounds selected from the group of compounds represented by.).

More ^{specifically, R NU11, R NU12, R} NU21, R NU22, R NU31, R NU32, R NU41, R NU42, R NU51, R NU52, R NU61, R NU62, R NU71, R NU72, R NU81 and R ^NU82 is preferably an alkyl group having 1 to 5 carbon atoms or an alkoxy group having 1 to 5 carbon atoms, and more preferably an alkyl group having 1 to 5 carbon atoms. When the response speed is important, at least one R ^NU11 , R ^NU21 , R ^NU41 and R ^NU51 are preferably alkenyl groups having 2 to 3 carbon atoms. As the alkenyl group, the formulas (R1) to (R5)

(The black dots in each equation represent carbon atoms in the ring structure.)
Can be mentioned. Of these, an alkenyl group having 2 to 3 carbon atoms is preferable, and an alkenyl group represented by the formula (R1) or the formula (R2) is preferable.

The compound having an alkenyl group selected from the compound group represented by the general formula (NU-01) to the general formula (NU-08) is preferably 30% by mass or less based on the total amount of the liquid crystal composition in the present invention. , 25% by mass or less, preferably 20% by mass or less, preferably 15% by mass or less, preferably 10% by mass or less, and preferably 5% by mass or less. When high VHR is emphasized, the content of the compound having an alkenyl group is preferably 10% by mass or less, preferably 5% by mass or less, preferably 1% by mass or less, and preferably not contained.

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

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

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

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

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

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

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

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

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

The liquid crystal composition in the present invention contains a compound represented by the general formula (NU-01), a compound represented by the general formula (NU-03), and a compound represented by the general formula (NU-05). Is more preferable.

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

The content of the compound represented by the general formula (NU-01) is preferably 1 to 60% by mass, more preferably 10 to 50% by mass, and 20% by mass, based on the total amount of the liquid crystal composition in the present invention. It is more preferably ~ 40% by mass.

The content of the compound represented by the general formula (NU-02) is preferably 1 to 40% by mass, more preferably 5 to 25% by mass, based on the total amount of the liquid crystal composition in the present invention. It is more preferably ~ 20% by mass.

The content of the compound represented by the general formula (NU-03) is preferably 1 to 30% by mass, more preferably 1 to 20% by mass, and 3 to 15% by mass in the total amount of the liquid crystal composition. It is more preferably%.

The content of the compound represented by the general formula (NU-04) is preferably 0 to 30% by mass, more preferably 0 to 20% by mass, and 0, based on the total amount of the liquid crystal composition in the present invention. It is more preferably 10% by mass.

The content of the compound represented by the general formula (NU-05) is preferably 1 to 30% by mass, more preferably 1 to 20% by mass, based on the total amount of the liquid crystal composition in the present invention. It is more preferably ~ 20% by mass.

The content of the compound represented by the general formula (NU-06) is preferably 0 to 30% by mass, more preferably 0 to 20% by mass, and 0, based on the total amount of the liquid crystal composition in the present invention. It is more preferably 10% by mass.

The content of the compound represented by the general formula (NU-07) is preferably 0 to 30% by mass, more preferably 0 to 20% by mass, and 0, based on the total amount of the liquid crystal composition in the present invention. It is more preferably ~ 20% by mass.

The content of the compound represented by the general formula (NU-08) is preferably 0 to 30% by mass, more preferably 0 to 20% by mass, and 0, based on the total amount of the liquid crystal composition in the present invention. It is more preferably 10% by mass.

The liquid crystal composition in the present invention is a compound selected from the compound group represented by the general formulas (N-01), (N-02), (N-03), (N-04) and (N-05). It is preferable to contain one type or two or more types. These compounds correspond to compounds having a dielectric negative anisotropy. The “dielectrically negative anisotropy compound” refers to a compound having a negative sign of Δε and an absolute value greater than 2. Δε of the compound is a value extrapolated from the measured value of the dielectric anisotropy of the composition obtained by adding the compound to the composition which is dielectrically substantially neutral at 20 ° C.

(In the formula, R ²¹ and R ²² are independently an alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, an alkenyl group having 2 to 8 carbon atoms, and 2 carbon atoms. Represents alkoxyoxy groups from 8 to 8, where Z ¹ independently represents a single bond, -CH ₂ CH _2- , -OCH _2- or -CH ₂ O-, and m independently represents 1 Or represents 2.)

In the above general formulas (N-01) to (N-05), R ²¹ is preferably an alkyl group having 1 to 8 carbon atoms, more preferably an alkyl group having 1 to 5 carbon atoms, and a carbon atom. Alkyl groups of numbers 2 to 4 are more preferred. However, when Z ¹ represents a bond other than a single bond, R ²¹ is preferably an alkyl group having 1 to 3 carbon atoms.

R ²² is preferably an alkyl group having 1 to 8 carbon atoms or an alkoxy group having 1 to 8 carbon atoms, and more preferably an alkyl group having 1 to 5 carbon atoms or an alkoxy group having 1 to 4 carbon atoms. Preferably, an alkoxy group having 1 to 4 carbon atoms is more preferable.

When R ²¹ and R ²² are alkenyl groups, the formulas (R1) to (R5)

(The black dots in each equation represent carbon atoms in the ring structure.)
Is preferable, and the formula (R1) or the formula (R2) is more preferable.

Z ¹ is more preferably single-bonded, -CH ₂ CH _2- or -CH ₂ O- independently of each other.

When m is 1, Z ¹ is preferably single bond or −CH ₂ O−.

When m is 2, Z ¹ is preferably a single bond, −CH ₂ CH _2- or −CH ₂ O−.

The liquid crystal composition in the present invention has a general formula (N-01-1), a general formula (N-01-2), and a general formula (N-01-3) as compounds represented by the general formula (N-01). ) And general formula (N-01-4)

(In the formula, R ²⁴ independently represents an alkyl group having 1 to 5 carbon atoms, and R ²³ independently represents an alkoxy group having 1 to 4 carbon atoms.)
It is preferable to contain one or more compounds selected from the compound group represented by.

The liquid crystal composition in the present invention preferably contains a compound represented by the general formula (N-01-1) and a compound represented by the general formula (N-01-4).

The liquid crystal composition in the present invention preferably contains a compound represented by the general formula (N-01-3) and a compound represented by the general formula (N-01-4).

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

(In the formula, R ²⁴ independently represents an alkyl group having 1 to 5 carbon atoms, and R ²³ independently represents an alkoxy group having 1 to 4 carbon atoms.)
It is preferable to contain one or more compounds selected from the compound group represented by.

The liquid crystal composition in the present invention particularly preferably contains a compound represented by the general formula (N-02-1).

The liquid crystal composition in the present invention preferably contains a compound represented by the general formula (N-02-1) and a compound represented by the general formula (N-02-3).

The liquid crystal composition in the present invention preferably contains a compound represented by the general formula (N-02-1) and a compound represented by the general formula (N-01-4).

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

(In the formula, R ²⁴ represents an alkyl group having 1 to 5 carbon atoms, and R ²³ represents an alkoxy group having 1 to 4 carbon atoms.)
It is preferable to contain one or more compounds represented by.

The liquid crystal composition in the present invention preferably contains a compound represented by the general formula (N-03-1).

The liquid crystal composition in the present invention preferably contains a compound represented by the general formula (N-03-1) and a compound represented by the general formula (N-01-4).

The liquid crystal composition in the present invention preferably contains a compound represented by the general formula (N-03-1) and a compound represented by the general formula (N-02-1).

The liquid crystal composition in the present invention is represented by a compound represented by the general formula (N-03-1), a compound represented by the general formula (N-01-4), and a compound represented by the general formula (N-02-1). It preferably contains a compound.

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

(In the formula, R ²⁴ represents an alkyl group having 1 to 5 carbon atoms, and R ²³ represents an alkoxy group having 1 to 4 carbon atoms.)
It is preferable to contain one or more compounds represented by.

The liquid crystal composition in the present invention particularly preferably contains a compound represented by the general formula (N-04-1) and a compound represented by the general formula (N-01-4).

The liquid crystal composition in the present invention is represented by a compound represented by the general formula (N-04-1), a compound represented by the general formula (N-01-4), and a general formula (N-02-1). It is particularly preferable to simultaneously contain the compounds.

The liquid crystal composition in the present invention is represented by a compound represented by the general formula (N-04-1), a compound represented by the general formula (N-01-4), and a general formula (N-03-1). It is particularly preferable to simultaneously contain the compounds.

The liquid crystal composition in the present invention is represented by a compound represented by the general formula (N-04-1), a compound represented by the general formula (N-02-1), and a general formula (N-03-1). It is particularly preferable to simultaneously contain the compounds.

The liquid crystal composition in the present invention is represented by a compound represented by the general formula (N-04-1), a compound represented by the general formula (N-01-4), and a general formula (N-02-1). It is particularly preferable that the compound and the compound represented by the general formula (N-03-1) are simultaneously contained.

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

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

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

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

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

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

The liquid crystal composition in the present invention may contain one or more compounds having a positive dielectric anisotropy, which are described in paragraphs 0236 to 0509 of Japanese Patent No. 6233550.

The liquid crystal composition in 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 stability to UV irradiation is emphasized, the liquid crystal composition in the present invention has a content of a compound substituted with chlorine atoms of 15% by mass or less with respect to the total mass of the liquid crystal composition in the present invention. It is preferably 10% by mass or less, preferably 8% by mass or less, more preferably 5% by mass or less, preferably 3% by mass or less, and substantially not contained. Is even more preferable.

The liquid crystal composition in the present invention preferably has a high content of a compound having an intramolecular ring structure of all 6-membered rings, and the content of a compound having an intramolecular ring structure of all 6-membered rings is set to the present. The liquid crystal composition according to the invention is preferably 80% by mass or more, more preferably 90% by mass or more, further preferably 95% by mass or more, substantially intramolecularly, based on the total mass. It is most preferable that the liquid crystal composition in the present invention is composed only of a compound having a ring structure of all 6-membered rings.

In order to suppress deterioration of the liquid crystal composition due to oxidation, the liquid crystal composition in the present invention preferably contains a compound having a cyclohexenylene group as a ring structure, and contains a compound having a cyclohexenylene group. The amount is preferably 10% by mass or less, preferably 8% by mass or less, more preferably 5% by mass or less, and 3% by mass, based on the total mass of the liquid crystal composition in the present invention. It is preferably as follows, and more preferably not substantially contained.

When the improvement of viscosity and the improvement of _TNI are emphasized, the liquid crystal composition in the present invention has a 2-methylbenzene-1,4-diyl group in the molecule in which the hydrogen atom may be substituted with halogen. It is preferable to reduce the content of the compound, and the content of the compound having the 2-methylbenzene-1,4-diyl group in the molecule is 10% by mass or less based on the total mass of the liquid crystal composition in the present invention. It is preferably 8% by mass or less, more preferably 5% by mass or less, preferably 3% by mass or less, and further preferably substantially not contained.

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

In addition to the above-mentioned compounds, the liquid crystal composition in the present invention may contain ordinary nematic liquid crystal, smectic liquid crystal, cholesteric liquid crystal and the like.

T _NI of liquid crystal composition of the present _invention, [Delta] n, the preferred value of gamma ₁ and Δε can be similar to the respective physical properties of the polymerizable compound-containing liquid crystal composition of the present invention described below.

[5] Additives The polymerizable compound-containing liquid crystal composition of the present invention may contain an antioxidant, an ultraviolet absorber, a light stabilizer, an infrared absorber and the like. Above all, the polymerizable compound-containing liquid crystal composition of the present invention preferably contains an antioxidant so as not to polymerize in the heat treatment, which is one of the manufacturing steps of the liquid crystal display element.

The polymerizable compound-containing liquid crystal composition of the present invention preferably contains an antioxidant represented by the general formulas (H-1) to (H-4), and the lower limit of the content is 10 mass ppm. Is preferable, 20 mass ppm is preferable, 50 mass ppm is preferable, and the upper limit thereof is 10000 mass ppm, but 1000 mass ppm is preferable, 500 mass ppm is preferable, and 100 mass ppm is preferable.

From the general formula (H-1) to the general formula (H-3), ^RH1 independently represents an alkyl group having 3 to 7 carbon atoms. More specifically, ^{R H1} of the general formula (H1) represents an alkyl group having a carbon number of 7. ^{R H1} of the general formula (H-2) represents an alkyl group having a carbon number of 3. ^{R H1} of the general formula (H-3) represents an alkyl group having a carbon number of 3.

In the general formula (H-4), ^MH1 is an alkylene group having 4 to 10 carbon atoms (one or two or more -CH ₂ − in the alkylene group is -CH ₂ − so that oxygen atoms are not directly adjacent to each other. It may be substituted with COO- or -OCO-) single bond, 1,4-phenylene group (any hydrogen atom in the 1,4-phenylene group may be substituted with a fluorine atom) or. It represents trans-1,4-cyclohexylene ^{group, M H1} is preferably an alkylene group having 4 to 8 carbon atoms.

A polymerization initiator may be added to the polymerizable compound-containing liquid crystal composition of the present invention for the purpose of rapidly polymerizing the polymerizable compound. It is preferable to select a photopolymerization initiator as the polymerization initiator. Examples of the photopolymerization initiator include diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzyldimethylketal, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropane-. 1-one, 4- (2-hydroxyethoxy) phenyl- (2-hydroxy-2-propyl) ketone, 1-hydroxycyclohexyl-phenylketone, 2-methyl-2-morpholino (4-thiomethylphenyl) propane-1 -On, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone, 4'-phenoxyacetophenone, 4'-ethoxyacetophenone and other acetophenone systems; benzophenone, benzoin isopropyl ether, benzoin isobutyl ether, benzophenone Benzophenones such as methyl ethers and benzoin ethyl ethers; acylphosphine oxides such as 2,4,6-trimethylbenzoyldiphenylphosphine oxide; benzyls, methylphenylglioxyesters; benzophenones, methyl o-benzoylbenzoate, 4-phenyl Benzophenone, 4,4'-dichlorobenzophenone, hydroxybenzophenone, 4-benzoyl-4'-methyl-diphenylsulfide, acrylicized benzophenone, 3,3', 4,4'-tetra (t-butylperoxycarbonyl) benzophenone, Benzophenone systems such as 3,3'-dimethyl-4-methoxybenzophenone, 2,5-dimethylbenzophenone, 3,4-dimethylbenzophenone; 2-isopropylthioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2 , 4-Dichlorothioxanthone and other thioxanthone systems; Michler ketone, 4,4'-diethylaminobenzophenone and other aminobenzophenone systems; 10-butyl-2-chloroacrydone, 2-ethylanthraquinone, 9,10-phenanthrene quinone, Examples include benzophenone. The lower limit of the content is preferably 0.001% by mass, preferably 0.01% by mass, preferably 0.02% by mass, preferably 0.03% by mass, and preferably 0.04% by mass. The upper limit is preferably 0.2% by mass, preferably 0.1% by mass.

[6] Others The polymerizable compound-containing liquid crystal composition of the present invention is uniaxial by containing at least a compound represented by the general formula (i) and a polymerizable compound represented by the general formula (PI). It is preferable that a polymer network having sexual optical anisotropy, uniaxial refractive index anisotropy, or easy axial direction can be formed. At this time, it is more preferable that the optical axis or the easy axis of orientation of the polymer network and the easy axis of orientation of the low molecular weight liquid crystal substantially coincide with each other.

The polymerizable compound-containing liquid crystal composition of the present invention is represented by the compound represented by the general formula (i), the compound represented by the general formula (PI), and the general formulas (N-01) to (N-05). The upper limit of the ratio of the components composed only of the compounds represented by the general formulas (NU-01) to (NU-08) is 100% by mass, 99% by mass, 98% by mass, and 97% by mass. %, 96% by mass, 95% by mass, 94% by mass, 93% by mass, 92% by mass, 91% by mass, 90% by mass, 89% by mass, 88% by mass, 87% by mass, 86% by mass, 85% by mass, It is preferably 84% by mass.

Further, the polymerizable compound-containing liquid crystal composition of the present invention has a compound represented by the general formula (i), a compound represented by the general formula (P), and the general formulas (N-01) to (N-05). The lower limit of the proportion of the compound represented and the component composed only of the compounds represented by the general formulas (NU-01) to (NU-08) is 78% by mass, 80% by mass, 81% by mass, 83. Mass%, 85 mass%, 86 mass%, 87 mass%, 88 mass%, 89 mass%, 90 mass%, 91 mass%, 92 mass%, 93 mass%, 94 mass%, 95 mass%, 96 mass% , 97% by mass, 98% by mass, and 99% by mass are preferable.

The polymerizable compound-containing liquid crystal composition of the present invention has a nematic phase-isotropic liquid phase transition temperature ( _TNI ) of 60 ° C to 120 ° C, more preferably 70 ° C to 100 ° C, and 70 ° C to 85 ° C. Is particularly preferable. In the present invention, 60 ° C. or higher is expressed as having a high _TNI .

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

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

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

The polymerizable compound-containing liquid crystal composition of the present invention preferably has a dielectric anisotropy (Δε) at 20 ° C. of -1.7 to -4.5, preferably -2.5 to -4.3, and -2. It is more preferably .7 to -4.0 and more preferably -2.6 to -3.9.

B. Liquid crystal display element Next, the liquid crystal display element of the present invention will be described. The liquid crystal display element of the present invention is a liquid crystal display element using the polymerizable compound-containing liquid crystal composition described in the above-mentioned "A. Polymerizable compound-containing liquid crystal composition". That is, the liquid crystal display element of the present invention includes one or more compounds represented by the general formula (i) and one or more polymerizable compounds represented by the general formula (PI). It is a liquid crystal display element using a liquid crystal composition containing a polymerizable compound containing at least.

According to the liquid crystal display device of the present invention, a fast switching-off response is realized by using the polymerizable compound-containing liquid crystal composition described in the above-mentioned "A. Polymerizable compound-containing liquid crystal composition". While doing so, it is possible to suppress an increase in the drive voltage and to exhibit a high light transmittance.

The liquid crystal display element of the present invention can have the same structure as the liquid crystal display element according to the prior art. That is, the liquid crystal display element of the present invention has a structure in which a liquid crystal layer is sandwiched between two transparent substrates having electrodes on at least one of them, and the liquid crystal layer is the above-mentioned "A. polymerizable compound-containing liquid crystal." A polymer of a polymerizable compound represented by the general formula (PI) is contained in a liquid crystal composition containing at least the compound represented by the general formula (i) described in the section "Composition" and constituting the liquid crystal layer. It can be an embodiment in which a polymer network containing at least is formed.

The liquid crystal display element of the present invention preferably has an alignment layer for orienting liquid crystal molecules on at least one transparent substrate. A voltage is applied to the alignment layer provided on the substrate and the electrodes provided on the substrate to control the orientation of the liquid crystal molecules. It is preferable that the polymer network has uniaxial refractive index anisotropy or easy orientation axial direction, and the optical axis direction or easy orientation axial direction of the polymer network and the easy orientation axial direction of the low molecular weight liquid crystal are in the same direction.

Further, it is preferable that the easy axial direction of the alignment layer and the easy axial direction of the polymer network are the same.

The liquid crystal layer is a polymer having refractive index anisotropy by applying an AC electric field to the polymerizable compound-containing liquid crystal composition in a temperature range of -50 ° C to 30 ° C and irradiating the liquid crystal composition with ultraviolet rays or electron beams. It is formed in the liquid crystal so that the optical axis direction of the network forms a pretilt angle with respect to the substrate surface. By providing a polarizing plate, a retardation film, etc., this orientation state is used for display.

The liquid crystal display element of the present invention is useful for an active matrix driving liquid crystal display element. Further, the liquid crystal display element of the present invention can be applied to operation modes such as TN, STN, ECB, VA, VA-TN, IPS, FFS, π cell, OCB, and cholesteric liquid crystal. Among these, it can be used for VA mode, IPS mode, FFS mode, VA-TN mode, TN mode, or ECB mode. The liquid crystal display element of the present invention is a PSA (Polymer Sustained Alignment) type liquid crystal display element having a polymer or copolymer on an alignment film in that a polymer or copolymer is contained in the liquid crystal composition. Is different.

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

The liquid crystal display element of the present invention can have various members constituting a general liquid crystal display element such as a color filter, a pixel electrode, a spacer, and a polarizing plate. Further, the liquid crystal display device of the present invention can be manufactured by using a known method, and is manufactured by using, for example, the methods disclosed in Japanese Patent No. 6090482, International Publication No. 2017/027272, and the like. Can be done.

The present invention is not limited to the above embodiment. The above-described embodiment is an example, and any object having substantially the same configuration as the technical idea described in the claims of the present invention and exhibiting the same effect and effect is the present invention. Is included in the technical scope of.

The present invention will be described in more detail with reference to Examples below, but the present invention is not limited to these Examples.

The characteristics of the measured liquid crystal composition are as follows.

T _NI : Nematic phase-isotropic liquid phase transition temperature (° C)
Δn: Birefringence at 20 ° C. η: Viscosity at 20 ° C. (mPa · s)
γ ₁ : Rotational viscosity at 20 ° C (mPa · s)
Δε: Dielectric modulus anisotropy at 20 ° C K ₁₁ : Elastic constant at 20 ° C K ₁₁ (pN)
K ₃₃ : Elastic constant at 20 ° C K ₃₃ (pN)
ε _⊥ : Dielectric constant in the short axis direction of the liquid crystal at 20 ° C no: Normal light refractive index at a wavelength of 589 nm

(Reference Example 1) Preparation of liquid crystal composition LCN-R A liquid crystal composition LCN-R having the composition shown below was prepared.

(Reference example 2)
A liquid crystal composition LCN-1 having the composition shown below was prepared.

(Reference example 3)
A liquid crystal composition LCN-2 having the composition shown below was prepared.

(Reference example 4)
A liquid crystal composition LCN-3 having the composition shown below was prepared.

(Reference example 5)
A liquid crystal composition LCN-4 having the composition shown below was prepared.

(Reference example 6)
A liquid crystal composition LCN-5 having the composition shown below was prepared.

(Reference example 7)
A liquid crystal composition LCN-6 having the composition shown below was prepared.

The measurement results of the liquid crystal compositions prepared in Reference Examples 1 to 7 are summarized in Table 1 below.

(Example 1)
The liquid crystal composition "LCN-1" is 96.94% by mass, the following polymerizable compound "PI-1-2" is 2.4% by mass, and the following polymerizable compound "PI-1-3" is 0.6. A material composed of 0.06% by mass of mass% and 0.06% by mass of the photopolymerization initiator Omnirad 651 (IGM Resins VV) was uniformly heated and dissolved to prepare a polymerizable compound-containing liquid crystal composition "NPS-1". did. It was confirmed that the obtained polymerizable compound-containing liquid crystal composition showed a nematic liquid crystal phase at room temperature.

A liquid crystal cell was produced by facing two glass substrates with ITO on which a polyimide alignment film for vertical alignment was formed so as to have a pretilt angle of 88 °. The distance between the two substrates was set to 3.6 μm, and the rubbing direction was set to be anti-parallel.

The polymerizable compound-containing liquid crystal composition "NPS-1" was vacuum-injected into the produced liquid crystal cell. Then, the injection port was sealed by irradiating the injection port with UV light of 385 nm for 10 seconds using an ultraviolet curable adhesive "3026E" (manufactured by ThreeBond Co., Ltd.). At this time, the UV light was irradiated only in the vicinity of the injection port. Then, it was heated at 90 ° C. for 60 minutes using an oven. After cooling to room temperature, the entire cell was irradiated with UV light of 365 nm (illuminance 20 mW / cm ² ) for 10 seconds using a multi-light manufactured by Ushio, Inc. to polymerize the polymerizable compound. Then, using a fluorescent lamp, UV light of 313 nm (illuminance 0.3 mW / cm ² ) was further irradiated at room temperature for 5400 seconds. As a result, a VA mode liquid crystal display element having a phase-separated structure formed in the entire cell was obtained. Furthermore, this was sandwiched between two orthogonal polarizing plates and the characteristics were measured. At this time, the angle formed by the rubbing direction and the transmission axis of the polarizing plate was set to be 45 °.

When a 60 Hz square wave was applied to the obtained VA mode liquid crystal display element to specify the voltage-light transmittance and to measure the switching off response time (hereinafter abbreviated as off response time), the drive voltage V90 (hereinafter abbreviated as off response time) was measured. When the transmittance at the maximum transmittance is 100%, the transmittance of 90% is 6.1V, and the off response τoff (when the voltage is applied at the drive voltage V90 is changed to 0V). Response time) was 4.1 ms. Further, the transmittance at the time of applying 8V, which is a guideline for driving the liquid crystal driver IC, was 79.0%.

(Comparative Example 1)
A polymerizable compound-containing liquid crystal composition and a liquid crystal display element were obtained in the same manner as in Example 1 except that the liquid crystal composition "LCN-R" was used instead of the liquid crystal composition "LCN-1" in Example 1. It was. The drive voltage V90 of this liquid crystal display element was 6.5 V, the off response τoff was 4.4 ms, and the transmittance when 8 V was applied was 75.3%.

(Comparative Example 2)
Instead of adding the polymerizable compound "PI-1-2" and the polymerizable compound "PI-1-3" to the liquid crystal composition "LCN-1" in Example 1, the polymerizable compound "PII-5" A polymerizable compound-containing liquid crystal composition and a liquid crystal display element were obtained in the same manner as in Example 1 except that 3.0% by mass was added. The drive voltage V90 of this liquid crystal display element was 6.6 V, the off response τoff was 4.3 ms, and the light transmittance when 8 V was applied was 70.6%.

(Examples 2 to 6)
A polymerizable compound-containing liquid crystal composition in the same manner as in Example 1 except that one of "LCN-2" to "LCN-6" was used instead of the liquid crystal composition "LCN-1" in Example 1. A compound and a liquid crystal display element were obtained, respectively.

Table 2 below shows the characteristics of the devices obtained in Examples 1 to 6 and Comparative Examples 1 and 2.

From the comparison between Example 1 and Comparative Example 1, it was shown that the use of the polymerizable compound-containing liquid crystal composition of the present invention can improve the transmittance at the time of applying 8 V and the off-response τoff while lowering the driving voltage. .. Further, from the results of Example 1 and Comparative Example 2, it was suggested that Example 1 containing the compound of formula (PI) had a higher light transmittance when 8 V was applied than that of Comparative Example 2 not containing the compound. ..

Example 2-6 includes a compound represented by formula (i), and the liquid crystal composition in Comparative Example 1 A liquid crystal composition "LCN-R" and T _NI were prepared so that the same general It is obtained by adding the polymerizable compounds "PI-1-2" and "PI-1--3" represented by the formula (PI). From the comparison between Examples 2 to 6 and Comparative Example 1, it is possible to improve the light transmittance and the off-response τoff when 8 V is applied while lowering the driving voltage by using the polymerizable compound-containing liquid crystal composition of the present invention. Shown.

Claims (7)

General formula (i)

(In the formula, X ⁱ¹ and X ⁱ² independently represent a hydrogen atom, a fluorine atom, a chlorine atom, a cyano group, a trifluoromethyl group, or a trifluoromethoxy group, respectively.
Y ⁱ¹ and Y ⁱ² independently represent -O-, -CF _2- , -CO-, or -CX ⁱ³ X ^i4- , but any one or more of Y ⁱ¹ and Y ⁱ² is -O-. X ⁱ³ and X ⁱ⁴ independently represent the same meaning as X ⁱ¹ .
^{Li 1} , ^{Li 2} , ^{Li 3} , ^{Li 4} and ^{Li 5} are independently hydrogen atom, bromine atom, iodine atom, hydroxyl group, alkyl group having 1 to 15 carbon atoms, and alkenyl having 2 to 15 carbon atoms. Group or general formula ( ^Li -1)

(In the formula, ^Ri1 is a hydrogen atom, an alkyl group having 1 to 15 carbon atoms, an alkoxy group having 1 to 15 carbon atoms, an alkenyl group having 2 to 15 carbon atoms, or an alkenyloxy group having 2 to 15 carbon atoms. Represents
A ⁱ¹ is (a) 1,4-cyclohexylene group (the one present in the group -CH ₂ - or nonadjacent two or more -CH ₂ - is -O- or -S- in May be replaced.)
(B) 1,4-Phenylene group (one -CH = existing in this group or two or more -CH = not adjacent to each other may be replaced with -N = and is present in this group. One hydrogen atom may be replaced with a fluorine atom.)
(C) 1,4-Cyclohexenylene group, naphthalene-2,6-diyl group, 1,2,3,4-tetrahydronaphthalene-2,6-diyl group, decahydronaphthalene-2,6-diyl group (c) The hydrogen atom present in these groups may be substituted with a fluorine atom, and is also present in the naphthalene-2,6-diyl group or the 1,2,3,4-tetrahydronaphthalene-2,6-diyl group. One -CH = or two or more non-adjacent -CH = may be replaced with -N =.)
Represents a group selected from the group consisting of
Z ⁱ¹ is -CH ₂ O-, -OCH _2- , -CF ₂ O-, -OCF _2- , -COO-, -OCO-, -CH ₂ CH _2- , -CF ₂ CF _2- , -CH = CH-, -CF = CF-, -C≡C- or single bond,
Although n ⁱ¹ represents 1 or 2, when n ⁱ¹ represents 2 and there are a plurality of A ⁱ¹ and Z ^{i 1} , they may be the same or different. )
Represents the group represented by
W ⁱ¹ is a general formula (W ^i1-1 ), (W ^i1-2 ) or (W ⁱ¹ -3).

(In the formula, the black dot (・) represents the bond point to ^{Li i2} or Y ⁱ² , * represents the bond point to the carbon atom adjacent to the carbon atom to which ^{Li i5} is bonded, and ^{Li i6} , ^{Li 7} and ^{Li 8} each independently represent a group represented by represents.) the same meaning as L ^i1,
W ⁱ² is a single bond or ^-CL i9 ^{L i10} -
(L ⁱ⁹ and ^{Li i10} independently represent the same meaning as ^{Li 1} ).
Represents
^{L i1, L i2, L i3} , L i4, L i5, L i6, L i7, L i8, L i9 and ^{L i10} in present in one -CH ₂ - or adjacent have not more than one - CH ₂ − may be replaced by −C≡C−, −O−, −COO−, −OCO− or −CO−, and a hydrogen atom present in an alkyl group or an alkenyl group is substituted with a fluorine atom. May be done. ) Is one or more compounds,
General formula (PI)

(In the general formula (PI), R ¹⁰² , R ¹⁰³ , R ¹⁰⁴ , R ¹⁰⁵ , R ¹⁰⁶ , R ¹⁰⁷ , R ¹⁰⁸ and R ¹⁰⁹ are independently alkyl groups and carbon atoms having 1 to 18 carbon atoms, respectively. Represents any of the alkoxy groups, halogen atoms or hydrogen atoms of numbers 1-18,
P ¹¹ and P ¹² independently represent any of the following equations (R-1) to (R-9).

(In the above formulas (R-1) to (R-9), R ²¹ , R ³¹ , R ⁴¹ , R ⁵¹ and R ⁶¹ are independent of each other and have an alkyl group having a hydrogen atom and 1 to 5 carbon atoms. Alternatively, it represents an alkyl halide group having 1 to 5 carbon atoms, and W and T independently represent a single bond, -O-, -COO- or an alkylene group having 1 to 5 carbon atoms, p, t. And q independently represent 0, 1 or 2. * in the equation represents the point of connection to S ¹¹ or S ^12. )
S ¹¹ and S ¹² independently represent a single bond or an alkylene group having 1 to 15 carbon atoms, but S ¹¹ and S ¹² do not represent a single bond at the same time, and one or 2 of the alkylene groups. One or more of -CH ₂ -, as the oxygen atoms are not directly adjacent, -O -, - OCO- or -COO- in may be substituted,
At least one of R ¹⁰² , R ¹⁰³ , R ¹⁰⁴ , R ¹⁰⁵ , R ¹⁰⁶ , R ¹⁰⁷ , R ¹⁰⁸ and R ¹⁰⁹ is a halogen atom, an alkyl group with 1 to 18 carbon atoms, or an alkoxy with 1 to 18 carbon atoms. It is the basis. )
One or more polymerizable compounds represented by
A liquid crystal composition containing a polymerizable compound containing. The polymerizable compound-containing liquid crystal composition according to claim 1, wherein the content of the polymerizable compound represented by the general formula (PI) is 0.4% by mass to 8% by mass. Further, from the general formula (NU-01) to the general formula (NU-08)

(In the formula, R ^NU11 , R ^NU12 , R ^NU21 , R ^NU22 , R ^NU31 , R ^NU32 , R ^NU41 , R ^NU42 , R ^NU51 , R ^NU52 , R ^NU61 , R ^NU62 , R ^NU71 , R ^NU72 , R ^NU71, R ^NU82 independently represents an alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, an alkenyl group having 2 to 8 carbon atoms, or an alkenyloxy group having 2 to 8 carbon atoms. , One or two or more non-adjacent −CH ₂ −s in the group are independently −CH = CH−, −C≡C−, −O−, −CO−, −COO− or −OCO. May be replaced by-.)
The polymerizable compound-containing liquid crystal composition according to claim 1 or 2, which contains one or more compounds selected from the compound group represented by. Furthermore, the general formulas (N-01), (N-02), (N-03), (N-03) and (N-05)

(In the formula, R ²¹ and R ²² are independently an alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, an alkenyl group having 2 to 8 carbon atoms, or 2 carbon atoms. represents 8 alkenyloxy group, two or more -CH of one or non-adjacent in the group ₂ - each independently -CH = CH -, - C [identical to] C -, - O -, - CO It may be replaced by −, −COO− or −OCO−.
Z ¹ is independently single-bonded, -CH ₂ CH _2- , -OCH _2- , -CH ₂ O-, -COO-, -OCO-, -OCF _2- , -CF ₂ O-,- Represents CH = CH-, -CF = CF- or -C≡C-
m independently represents 1 or 2, respectively. )
The polymerizable compound-containing liquid crystal composition according to any one of claims 1 to 3, which contains one or more compounds selected from the compound group represented by. A liquid crystal display device using the polymerizable compound-containing liquid crystal composition according to any one of claims 1 to 4. An active matrix driving liquid crystal display device using the polymerizable compound-containing liquid crystal composition according to any one of claims 1 to 4. A liquid crystal display element for VA mode, IPS mode, FFS mode, VA-TN mode, TN mode, or ECB mode using the polymerizable compound-containing liquid crystal composition according to any one of claims 1 to 4.