JP2020200428A - Polymerizable compound-containing liquid crystal composition and liquid crystal display element - Google Patents

Abstract

To provide: a polymerizable compound-containing liquid crystal composition which is sufficiently polymerizable at high speed, can form a tilt with weak or little UV light, and can achieve high tilt stability; and a liquid crystal display element based on the same.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 and a liquid crystal display device using the same. In addition, in this specification, a liquid crystal composition containing a polymerizable compound is referred to as a polymerizable compound-containing liquid crystal composition. Further, the polymerizable compound means a compound having a polymerizable group.

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

In the production of a PSA type liquid crystal display element, a liquid crystal composition containing a polymerizable compound is injected between substrates, and UV light is irradiated in a state where a voltage is applied to orient the liquid crystal molecules to polymerize the polymerizable compound. This is done by fixing the orientation of the liquid crystal molecules.

In recent years, PSA type liquid crystal display elements such as 4K and 8K require high-definition pixels. For this reason, a considerable amount of UV light is cut by increasing the area of the wiring and the light-shielding portion, and in the same UV irradiation process as in the conventional case, the tilt formation is insufficient, and the polymerizable compound is not sufficiently polymerized. Problems such as the remaining of many polymerizable compounds occur. Further, as a result, afterimages due to deterioration of response speed and orientation, and display defects called burn-in (IS) have been confirmed because the remaining polymerizable compound gradually polymerizes during driving and the tilt changes. ..
From the above, in a high-definition PSA type liquid crystal display element, a liquid crystal composition that can be stably produced with weaker or less UV light than before is required.

As an approach from a liquid crystal composition for polymerizing a liquid crystal composition containing a polymerizable compound with weaker or less UV light than before, Patent Document 1 and Patent Document 2 contain a liquid crystal compound having a terphenyl skeleton or a dibenzofuran skeleton. Techniques for shortening the polymerization reaction rate by doing so have been introduced.

International Publication No. 2009/050869 Japanese Unexamined Patent Publication No. 2016-132779

As described above, in recent years, high-definition PSA-type liquid crystal display devices have been required to have a polymerizable compound-containing liquid crystal composition that can be stably produced with weaker or less UV light than before. However, the polymerizable compound-containing liquid crystal composition containing a liquid crystal compound having a terphenyl skeleton or a dibenzofuran skeleton introduced in Patent Document 1 and Patent Document 2 has a sufficient polymerization rate but insufficient tilt formation. Also, the tilt stability was not sufficiently high. Therefore, improvement of the characteristics of the polymerizable compound-containing liquid crystal composition is required.

The problem to be solved by the present invention is a polymerizable compound-containing liquid crystal composition which can sufficiently polymerize at a high speed, can form a tilt with weak or a small amount of UV light, and can achieve high tilt stability. It is an object of the present invention to provide the liquid crystal display element used.

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

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 ^{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. A polymerizable compound-containing liquid crystal composition containing one or more compounds represented by) and one or more polymerizable compounds.

Further, the present invention uses a polymerizable compound-containing liquid crystal composition containing one or more compounds represented by the general formula (i) and one or more polymerizable compounds. Provided are a liquid crystal display element, a liquid crystal display element for driving an active matrix, and a liquid crystal display element for PSA mode, PSVA mode, PS-IPS mode, or PS-FFS mode.

According to the polymerizable compound-containing liquid crystal composition of the present invention, it can be sufficiently polymerized at a high speed, tilt can be formed with weak or little UV light, and high tilt stability can be achieved. The liquid crystal display element using the polymerizable compound-containing liquid crystal composition of the present invention has a small residual amount of unreacted polymerizable compound, can form a tilt with weak or small UV light, and has high high-speed response. It shows tilt stability, and can show excellent display quality with no or suppressed display defects such as orientation defects and seizure due to changes in the pre-tilt angle.

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. 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.

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 contained in one kind or two or more kinds, and a polymerizable compound is contained in one kind or two or more kinds.

According to the polymerizable compound-containing liquid crystal composition of the present invention, by including the liquid crystal composition containing the compound represented by the general formula (i) and the polymerizable compound, the polymer can be sufficiently polymerized at a high speed and is weak or weak. Tilt can be formed with a small amount of UV light, and high tilt stability can be achieved. Therefore, the polymerizable compound-containing liquid crystal composition of the present invention has a small residual amount of unreacted polymerizable compound, can form a tilt with weak or a small amount of UV light, and has high-speed response and high tilt stability. A compatible liquid crystal display element can be manufactured. Further, according to the polymerizable compound-containing liquid crystal composition of the present invention, it is possible to manufacture a liquid crystal display element exhibiting excellent display quality with no or suppressed display defects such as orientation defects and seizure due to changes in the pretilt angle. ..

Above all, in the production of high-definition PSA type liquid crystal display elements such as 4K and 8K, the production efficiency is remarkably deteriorated as the UV irradiation time becomes long. On the other hand, according to the polymerizable compound-containing liquid crystal composition of the present invention, a high-definition PSA type liquid crystal display element such as 4K or 8K can be manufactured in a short UV irradiation time, so that it has industrial utility value. Very expensive.

Hereinafter, each component 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. More specifically, when it is important that the absolute value (| Δε |) of the dielectric anisotropy (Δε) at 20 ° C. is large, it is preferable that both ^Xi1 and ^Xi2 are fluorine atoms, and they are reliable. When the property is emphasized, it is preferable that both X ⁱ¹ and X ⁱ² are hydrogen atoms.

Y ⁱ¹ and ^{Y i2,} at least one of which is -O-, among them one is -O- other -CH ₂ - is preferably, or are both -O-, large | [Delta] [epsilon] |, When emphasis is placed on the polymerization rate and tilt formation, 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, respectively, in order to reduce rotational viscosity (γ ₁ ). Is preferably an alkyl group having 1 to 8 carbon atoms or an alkenyl group having 2 to 8 carbon atoms, and preferably an alkyl group having 1 to 5 carbon atoms or an alkenyl group having 2 to 5 carbon atoms. Especially preferable. Further, it is preferably linear. The hydrogen atom present 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.

Further, in order to increase the miscibility with other liquid crystal components, it is preferable that ^{Li 1} and ^{Li 2} are different. Either one of ^{Li 1} and ^{Li 2} is preferably an alkoxy group or an alkenyloxy group, more preferably ^{Li 1} is an alkoxy group or an alkenyloxy group, and further preferably ^{Li 1} is an alkoxy group. , ^Li1 is particularly preferably an ethoxy group, a propoxy group or a butoxy group. When ^Li1 is an alkoxy group, in addition to the miscibility with the other liquid crystal components described above, the effects of increasing | Δε |, facilitating the formation of tilt in a short time, and increasing the polymerization rate can be obtained. This is because it is easy to get rid of.

Further, in order to increase the miscibility with other liquid crystal components, ^Li2 is preferably an alkyl group, more preferably an ethyl group, a propyl group or a butyl group, and is a propyl group or a butyl group. Is even more preferable. Particularly in the case of improving the γ1 of the liquid crystal composition, L ⁱ² is preferably butyl group.

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. In order to increase | Δε |, it is preferable to use an alkoxy group having 1 to 8 carbon atoms or an alkenyloxy group having 2 to 8 carbon atoms, and an alkoxy group having 1 to 5 carbon atoms or 2 carbon atoms. It is particularly preferably an alkoxyoxy group of ~ 5. 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 is

It is preferable to represent a group selected from. 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 miscibility with other liquid crystal components, the trans-1,4-cyclohexylene group, 2-fluoro-1,4-phenylene group or 3-fluoro-1,4-phenylene group may be used. preferable. In order to raise the nematic phase-isotropic liquid phase transition temperature (T _ni ), an unsubstituted 1,4-phenylene group, an unsubstituted 1,4-cyclohexylene group, and a 1,4-cyclohexenylene group are used. Alternatively, it is preferably an unsubstituted naphthalene-2,6-diyl group. In order to show a negatively large Δε, it is preferably a 2-fluoro-1,4-phenylene group, a 3-fluoro-1,4-phenylene group or a 2,3-difluoro-1,4-phenylene group. 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. In order to increase T _ni , Z ⁱ¹ is preferably single-bonded, -COO-, -OCO-, -CH = CH- or -C≡C-, and is single-bonded, -CH = CH- or. It is more preferably −C≡C−. In order to improve the miscibility with other liquid crystal components, it is preferably a single bond, −CH ₂ CH ₂ −, −CH ₂ O− or −OCH ₂ −. A single bond is preferable in order to improve long-term reliability of the liquid crystal display element.

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 is preferably 1 when γ ₁ is important. When T _ni is emphasized, it is preferably 2.

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

^Wi2 is preferably a single bond.

^{Li 3} , ^{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 more preferably 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.

Among the compounds represented by the general formula (i), the compounds represented by the following general formulas (i-1) to (i-48) are preferable. 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 preferably present, and particularly preferably 0.5 to 10% by mass. Hereinafter, mass% is described as%.

The content of the compound of the general formula (i) is preferably small when reliability is important, and is preferably large when the reaction rate and tilt formation of the polymerizable compound are important.

[2] Polymerizable Compound The polymerizable compound-containing liquid crystal composition of the present invention contains one or more polymerizable compounds. As the polymerizable compound, the general formula (P)

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

(In the formula, R ^p11 and R ^p12 independently represent a hydrogen atom, an alkyl group having 1 to 5 carbon atoms or an alkyl halide group having 1 to 5 carbon atoms, and W ^p11 is a single bond, −O. -, -COO-, represents an alkylene group having 1 to 5 carbon atoms, and t ^p11 represents 0, 1 or 2, but there are a plurality of R ^p11 , R ^p12 , W ^p11 and / or t ^{p11 in} the molecule. If so, they may be the same or different.)
Sp ^p1 and Sp ^p2 independently represent a single bond or a spacer group, respectively.
Z ^p1 and Z ^p2 are independent, single-bonded, -O-, -S-, -CH _2- , -OCH _2- , -CH ₂ O-, -CO-, -C ₂ H ₄ -,-, respectively. _{COO -, - OCO -, -} OCOOCH 2 -, - CH 2 OCOO -, - OCH 2 CH 2 O -, - CO-NR ZP1 -, - NR ZP1 -CO -, - SCH 2 -, - CH 2 S- ^{, -CH = CR ZP1 -COO -,} - CH = CR ZP1 -OCO -, - COO-CR ZP1 = CH -, - OCO-CR ZP1 = CH -, - COO-CR ZP1 = CH-COO -, - COO -CR ^ZP1 = CH- ^{OCO-, -OCO} -CR ^ZP1 = CH- ^{COO-, -OCO} -CR ^ZP1 = CH-OCO-,-(CH ₂ ) _z- COO-,-(CH ₂ ) _z- OCO- , -OCO- (CH ₂ ) _z -,-(C = O) -O- (CH ₂ ) _z- , -CH = CH-, -CF = CF-, -CF = CH-, -CH = CF- _{, -CF 2 -, - CF 2} O -, - OCF 2 -, - CF 2 CH 2 -, - CH 2 CF 2 -, - CF 2 CF 2 - or -C≡C- (wherein, z are each They independently represent integers 1 to 4, and R ^ZP1 independently represent hydrogen atoms or alkyl groups with 1 to 4 carbon atoms, but if there are multiple R ^ZP1s in the molecule, they are the same. In addition, * in the formula represents the connection point to Sp ^p1 or Sp ^p2 ).
A ^p1 and A ^p2 are independent of each other.
^(A p) 1,4-cyclohexylene group (this is present in the group one -CH ₂ - or nonadjacent two or more -CH ₂ - may be replaced by -O-.)
^(B p) 1,4-phenylene group (the one present in the group -CH = or non-adjacent two or more -CH = may be replaced by -N =.) And (c ^p ) Naphthalene diyl group, 1,2,3,4-tetrahydronaphthalenediyl group, decahydronaphthalenediyl group, phenanthrene-2,7-diyl group or anthracene-2,6-diyl group (1 present in these groups) Two or more -CH = or two or more non-adjacent -CH = may be replaced with -N =.)
Represents a group selected from the group consisting of
A ^p3 represents a group described above ^(a p), group ^{(b p)} and group ^(c p), and a group selected from the group consisting of a single bond,
The above groups ^(a p), group ^{(b p)} and group ^{(c p)} are each independently hydrogen atoms present in this group, a cyano group, a halogen atom, an alkyl of 1 to 8 carbon atoms It may be substituted with a group, an alkoxy group having 1 to 8 carbon atoms, an alkenyl group having 1 to 8 carbon atoms, or −Sp ^p2 −P ^p2 .
m ^p1 represents 0, 1, 2 or 3, ^{if Z p1,} A ^{p2, Sp} p2 and / or ^{P p2} is more present in the molecule, they may be the same or different but,
When m ^p1 is 0 and A ^p1 is a group other than a naphthalene diyl group, a phenanthrene-2,7-diyl group and an anthracene-2,6-diyl group, A ^p3 represents a group other than a single bond. ) Is preferable.

In the above general formula (P), R ^p1 is preferably −Sp ^p2 −P ^p2 .

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

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

t ^p11 is preferably 0 or 1.

W ^p11 is preferably a single bond or an alkylene group having 1 to 5 carbon atoms. As the alkylene group having 1 to 5 carbon atoms, a methylene group or an ethylene group is preferable.

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

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

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

Sp ^p1 and Sp ^p2 each independently represent a single bond or a spacer group, but the spacer group is preferably an alkylene group having 1 to 30 carbon atoms, and −CH ₂ − in the alkylene group contains oxygen atoms. As long as it is not directly linked, it may be substituted with −O−, −CO−, −COO−, −OCO−, −CH = CH− or −C≡C−, and the hydrogen atom in the alkylene group is a halogen atom. It may be replaced with. Among them, Sp ^p1 and Sp ^p2 are each independently preferably a linear alkylene group having 1 to 10 carbon atoms or a single bond, and more preferably a single bond.

In the general formula (P), the total number of -Sp ^p1- P ^p1 and Sp ^p2- P ^p2 is preferably 2 or more, preferably 2 to 4, and preferably 2 to 3.

A ^p1 and A ^p2 are independent of each other.
^(A p) 1,4-cyclohexylene group (this is present in the group one -CH ₂ - or nonadjacent two or more -CH ₂ - may be replaced by -O-.)
^(B p) 1,4-phenylene group (the one present in the group -CH = or non-adjacent two or more -CH = may be replaced by -N =.) And (c ^p ) Naphthalene diyl group, 1,2,3,4-tetrahydronaphthalenediyl group, decahydronaphthalenedyl group, phenanthrene-2,7-diyl group or anthracene-2,6-diyl group (1 present in these groups Two or more -CH = or two or more non-adjacent -CH = may be replaced with -N =.)
Represents a group selected from the group consisting of. ^{Also, A p3} represents a group described above ^(a p), group ^{(b p)} and group ^(c p), and a group selected from the group consisting of a single bond.

Here, the naphthalenediyl groups and 1,2,3,4-tetrahydronaphthalenediyl groups that ^Ap1 , ^Ap2 and ^Ap3 can take are groups that are bonded at two positions selected from the 1 to 8 positions. Specifically, naphthalene-diyl group and a 1,2,3,4-tetrahydronaphthalene-diyl ^group, in the case of ^{A p1,} combined with ^{Sp p1} in one of two positions selected from 1-8 of On the other hand, it is a group that binds to Z ^p1 or Z ^p2, and in the case of A ^p2 , it binds to Z ^{p1 at} one of the two positions selected from the 1st to 8th positions, and Z ^p1 or Z ^p2 on the other side. In the case of A ^p3 , it is a group that binds to Z ^{p2 at} one of the two positions selected from the 1st to 8th positions and to R ^p1 at the other.

Further, the decahydronaphthalinyl group that can be taken by A ^p1 , A ^p2 and A ^p3 is a group that binds at two positions selected from the 1st to 10th positions. Specifically, in the case of A ^p1 , the decahydronaphthalinyl group binds to Sp ^{p1 at} one of the two positions selected from the 1 to 10 positions, and to Z ^p1 or Z ^p2 at the other. In the case of A ^p2 , it is a group that binds to Z ^{p1 at} one of the two positions selected from the 1st to 10th positions, and to Z ^p1 or Z ^p2 on the other, and in the case of A ^p3 . If so, it is a group that binds to Z ^{p2 on} one of the two positions selected from the 1st to 10th positions and to R ^p1 on the other.

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, a naphthalene-2,6-diyl group is 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.

A ^p1 , A ^p2 and A ^p3 are each independently preferably a 1,4-phenylene group or a 1,4-cyclohexylene group, and a 1,4-phenylene group is preferable from the viewpoint of reactivity. In order to improve the compatibility of the 1,4-phenylene group with the liquid crystal compound, at least one hydrogen atom present in the 1,4-phenylene group is a fluorine atom and an alkyl group having 1 to 8 carbon atoms. Alternatively, it is preferably substituted with an alkoxy group having 1 to 8 carbon atoms, and more preferably an alkyl group having 1 to 8 carbon atoms or an alkoxy group having 1 to 8 carbon atoms. This is because at least one hydrogen atom existing in the 1,4-phenylene group is substituted with these groups, so that the residual amount of the polymerizable compound after UV irradiation can be reduced. It is particularly preferable that at least one hydrogen atom present in the 1,4-phenylene group is substituted with an alkoxy group having 1 to 8 carbon atoms because the above-mentioned effect can be more easily exhibited. As the alkyl group, for example, a methyl group is preferably mentioned, and as the alkoxy group, for example, a methoxy group is preferably mentioned.

When m ^p1 is 0 and A ^p1 is a naphthalene diyl group, a phenanthrene-2,7-diyl group or an anthracene-2,6-diyl group, A ^p3 may represent a single bond.

When m ^p1 is 0 and A ^p1 is a group other than a naphthalene diyl group, a phenanthrene-2,7-diyl group and an anthracene-2,6-diyl group, A ^p3 is a group other than a single bond, that is, the above. group ^(a p), represents a group selected from the group consisting of group ^{(b p)} and group ^{(c p).}

The total content of the compounds represented by the general formula (P) is preferably in the range of 0.05 to 10% with respect to the total amount of the polymerizable compound-containing liquid crystal composition of the present invention. It is preferably in the range of 1 to 8%, preferably in the range of 0.1 to 5%, preferably in the range of 0.1 to 3%, and preferably in the range of 0.2 to 2%. It is preferably in the range, preferably in the range of 0.2 to 1.3%, preferably in the range of 0.2 to 1%, and preferably in the range of 0.2 to 0.56%. It is preferably inside.

The preferable lower limit of the total content of the compounds represented by the general formula (P) is 0.01% by mass and 0.03% by mass with respect to the total amount of the polymerizable compound-containing liquid crystal composition of the present invention. , 0.05% by mass, 0.08% by mass, 0.1% by mass, 0.15% by mass, 0.2% by mass, 0.25% by mass, 0 .3% by mass. The preferable upper limit of the total content of the compounds represented by the general formula (P) is 10% by mass, 8% by mass, and 5% by mass with respect to the total amount of the polymerizable compound-containing liquid crystal composition of the present invention. It is mass%, it is 3 mass%, it is 1.5 mass%, it is 1.2 mass%, it is 1 mass%, it is 0.8 mass%, and it is 0.5 mass%. If the content of the compound represented by the general formula (P) contained in the polymerizable compound-containing liquid crystal composition of the present invention is small, the effect of adding the compound represented by the general formula (P) is unlikely to appear, and the tilt Problems such as insufficient formation and inferior tilt stability are likely to occur. In addition, problems such as a weak orientation regulating force of the liquid crystal composition or a weakening with time are likely to occur. On the other hand, if the content is too large, problems such as a large amount remaining after curing, a long curing time, and a decrease in the reliability of the liquid crystal occur. Therefore, the content is set in consideration of these balances.

The compound represented by the general formula (P) can be, for example, a compound represented by the following general formula (P-a1) or (P-a2).

(In the general formula (P-a1) and ^{(P-a2), A p1a} , A p2a, and ^{A p3a} are each independently, the group ^(a p), group ^{(b p)} and group ^{(c p} ) represents a group selected from the group consisting of the above group (a ^p), group (b ^p) and group (c ^p) are each independently hydrogen atoms present in this group, a cyano group, It may be substituted with a halogen atom, an alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, an alkenyl group having 1 to 8 carbon atoms, or −Sp ^p2a −P ^p2a .
At least one of A ^p1a , A ^p2a , and A ^p3a has at least one hydrogen atom in the ring substituted with an alkyl group having 1 to 8 carbon atoms or an alkoxy group having 1 to 8 carbon atoms.
P ^p1a , Sp ^p1a , Z ^p1a , Z ^p2a and R ^p1a , and Sp ^p2a and P ^p2a are P ^p1 , Sp ^p1 , Z ^p1 , Z ^p2 and R ^p1 and Sp ^{p2 in} the above general formula (P). It is the same as the definition of P ^p2 , and when there are a plurality of Sp ^p2a or P ^p2a in the molecule, they may be the same or different. )

The compounds represented by the general formulas (P-a1) and (P-a2) contain two or three rings in their molecular structures, and at least one of these rings is an alkyl group or an alkoxy. Has a group. The compounds represented by the general formulas (P-a1) and (P-a2) have such a molecular structure, and thus exhibit excellent solubility in a liquid crystal composition and excellent polymerization reactivity. Therefore, it can be suitably used for the polymerizable compound-containing liquid crystal composition of the present invention.

Further, the compound represented by the general formula (P) can be, for example, a compound represented by the following general formula (P-b).

(In the above general formula (P-b), A ^p1b , A ^p2b , and A ^p3b each independently represent a 1,4-phenylene group or a naphthalenediyl group, and these groups are independent of each other. The hydrogen atom existing in the group is a cyano group, a halogen atom, an alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, an alkenyl group having 1 to 8 carbon atoms, or -Sp ^p2b- P ^p2b. May be replaced with
P ^p1b , Sp ^p1b , Z ^p1b , Z ^p2b and R ^p1b , and Sp ^p2b and P ^p2b are P ^p1 , Sp ^p1 , Z ^p1 , Z ^p2 and R ^p1 and Sp ^{p2 in} the above general formula (P). It is the same as the definition of P ^p2 , and when there are a plurality of Sp ^p2b or P ^p2b in the molecule, they may be the same or different. )

The compound represented by the above general formula (P-b) contains the polymerizable compound of the present invention because it can exhibit excellent polymerization reactivity by essentially having three ring structures in its molecular structure. It can be suitably used for a liquid crystal composition.

As the naphthalene diyl group that A ^p1b , A ^p2b , and A ^p3b can take, the naphthalene-2,6-diyl group is preferable.

Further, the compound represented by the general formula (P) can be, for example, a compound represented by the following general formula (P-c1) or (P-c2).

(In the general formula (P-c1) and ^{(P-c2), A p1c} , A p2c and ^{A p3c} each independently, from the group ^(a p), group ^{(b p)} and group ^{(c p)} comprising a group selected from the group, the above groups (a ^p), group (b ^p) and group (c ^p) are each independently hydrogen atoms present in this group, a cyano group, a halogen atom , An alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, an alkenyl group having 1 to 8 carbon atoms, or -Sp ^p2c- P ^p2c may be substituted.
P ^p1c , Sp ^p1c , Z ^p1c , Z ^p2c and R ^p1c , and Sp ^p2c and P ^p2c are P ^p1 , Sp ^p1 , Z ^p1 , Z ^p2 and R ^p1 and Sp ^{p2 in} the above general formula (P). It is the same as the definition of P ^p2 , and when there are multiple Sp ^p2c or P ^p2c in the molecule, they may be the same or different.
In the above formula (P-c1), Z ^p2C is -CH = CH- ^COO- , -COO-CH = CH-,-(CH ₂ ) _2- COO-,-(CH ₂ ) _2- OCO-, -O. _{-CO- (CH 2) 2 -,} - COO- (CH 2) 2 - is a linking group selected from the group consisting of,
In the above formula (P-c2), at least one of Z ^p1C and Z ^p2C is -CH = CH- ^COO- , -COO-CH = CH-,-(CH ₂ ) _2- COO-,-(CH ₂ ) _{2. -OCO -, - O-CO- (} CH 2) 2 -, - COO- (CH 2) 2 - is a linking group selected from the group consisting of. ) Is preferable.

The compounds represented by the general formulas (P-c1) and (P-c2) have excellent solubility in a liquid crystal composition by having a desired linking group in which two rings are linked in the molecule. Since it can exhibit excellent polymerization reactivity, it can be suitably used for the polymerizable compound-containing liquid crystal composition of the present invention.

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

(In the formula, P ^p11 , P ^p12 , Sp ^p11 and Sp ^p12 have the same meanings as P ^p1 , P ^p2 , Sp ^p1 and Sp ^p2 in the general formula (P).)

Preferred examples of the compound represented by the general formula (P) include polymerizable compounds represented by the following formulas (P-2-1) to (P-2-9).

(In the formula, P ^p21 , P ^p22 , Sp ^p21 and Sp ^p22 have the same meanings as P ^p1 , P ^p2 , Sp ^p1 and Sp ^p2 in the general formula (P).)

Preferred examples of the compound represented by the general formula (P) include polymerizable compounds represented by the following formulas (P-3-1) to (P-3-15).

(In the formula, P ^p31 , P ^p32 , Sp ^p31 and Sp ^p32 have the same meanings as P ^p1 , P ^p2 , Sp ^p1 and Sp ^p2 in the general formula (P).)

Preferred examples of the compound represented by the general formula (P) include polymerizable compounds represented by the following formulas (P-4-1) to (P-4-21).

(In the formula, P ^p41 , P ^p42 , Sp ^p41 and Sp ^p42 have the same meanings as P ^p1 , P ^p2 , Sp ^p1 and Sp ^p2 in the general formula (P).)

Preferred examples of the compound represented by the general formula (P) include polymerizable compounds represented by the following formulas (P-5-1) to (P-5-37).

(In the formula, P ^p51 , P ^p52 , Sp ^p51 and Sp ^p52 have the same meanings as P ^p1 , P ^p2 , Sp ^p1 and Sp ^p2 in the general formula (P).)

[3] 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 obtained by removing 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 of 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, respectively.

On the other hand, when the response speed is important, at least one of R ^NU11 , R ^NU21 , R ^NU41 and R ^NU51 is preferably an alkenyl group having 2 to 8 carbon atoms. As the alkenyl group, the formulas (R1) to (R5)

(The black dots in each equation represent carbon atoms in the ring structure.) 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% or less, preferably 30% or less, based on the total amount of the liquid crystal composition in the present invention. % Or less is preferable, 20% or less is preferable, 15% or less is preferable, 10% or less is preferable, and 5% or less is preferable. When high VHR is emphasized, the compound having an alkenyl group is preferably 10% or less, preferably 5% or less, preferably 1% or less, and preferably not contained.

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

The liquid crystal composition 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 to 40% 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-02) is preferably 1 to 40% by mass, more preferably 5 to 25% by mass, and 5 to 20% 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-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 to 10% 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-05) is preferably 1 to 30% by mass, more preferably 1 to 20% by mass, and 3 to 20% 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-06) is preferably 0 to 30% by mass, more preferably 0 to 20% by mass, and 0 to 10% 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-07) is preferably 0 to 30% by mass, more preferably 0 to 20% by mass, and 0 to 10% 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-08) is preferably 0 to 30% by mass, more preferably 0 to 20% by mass, and 0 to 10% by mass in the total amount of the liquid crystal composition. It is more preferably%.

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.)

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 even more preferably an alkyl group having 2 to 4 carbon atoms. 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 formula represent carbon atoms in the ring structure) are preferable, and formula (R1) or 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 is a compound represented by the general formula (N-01), from the general formula (N-01-1) to the 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 above-mentioned compound group.

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 is a compound represented by the general formula (N-02) from the general formula (N-02-1) to the 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 above-mentioned compound group.

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

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.) Contains one or more compounds. It is preferable to do so.

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 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.) Contains one or more compounds. It is preferable to do so.

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

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-03-1). It is particularly preferable to contain the compound.

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%, 1%, 5%, and 10%. 20%, 30%, 40%, 50%, 55%, 60%, 65%, 70%, 75%, 80%. The upper limit of the preferred content is 95%, 85%, 75%, 65%, 55%, 45%, 35%, 25%. , 20%, 15%, and 10%.

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

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

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

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

The liquid crystal composition in the present invention may contain one or more compounds having a positive dielectric anisotropy 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 reliability and long-term stability of the liquid crystal composition are emphasized, the content of the compound having a carbonyl group is preferably 5% or less, preferably 3% or less, based on the total mass of the composition. It is more preferably 1% or less, and most preferably not substantially contained.

When the liquid crystal composition in the present invention emphasizes stability against UV irradiation, the content of the compound substituted with chlorine atoms is preferably 15% or less with respect to the total mass of the composition, which is 10%. It is preferably 8% or less, more preferably 5% or less, preferably 3% or less, and further preferably substantially not contained.

The liquid crystal composition in the present invention preferably has a high content of a compound having an all 6-membered ring structure in the molecule, and the content of a compound having an all 6-membered ring structure in the molecule is the composition. It is preferably 80% or more, more preferably 90% or more, further preferably 95% or more, and substantially all of the ring structures in the molecule are 6-membered rings with respect to the total mass of the substance. It is most preferable to compose the composition only with a certain compound.

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% or less, preferably 8% or less, more preferably 5% or less, more preferably 3% or less, and substantially the total mass of the composition. It is more preferable that it is not contained in.

When the improvement of viscosity and the improvement of T _ni 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. The content of the compound is preferably reduced, and the content of the compound having a 2-methylbenzene-1,4-diyl group in the molecule is preferably 10% or less based on the total mass of the composition. , 8% or less, more preferably 5% or less, more preferably 3% or less, and further preferably substantially no content.

In addition, in this specification, "substantially not contained" means that it is not contained except for unintentionally contained substances.

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

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

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

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

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

The liquid crystal composition in the present invention has Δε of -1.7 to -4.0, preferably -2.5 to -3.8, more preferably -2.7 to -3.7, and -2. More preferably .6 to -3.6.

[4] 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.

[5] Others Among the entire polymerizable compound-containing liquid crystal composition of the present invention, the compound represented by the general formula (i), the compound represented by the general formula (P), and the general formulas (N-01) to (N). Upper limit of the proportion of the component composed only of the compound selected from the compound group represented by -05) and the compound selected from the compound group represented by the general formulas (NU-01) to (NU-08). The values are 100% by mass, 99% by mass, 98% by mass, 97% by mass, 96% by mass, 95% by mass, 94% by mass, 93% by mass, 92% by mass, 91% by mass, 90% by mass, 89% by mass. , 88% by mass, 87% by mass, 86% by mass, 85% by mass, and 84% by mass are preferable.

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

The preferred values of T _ni , Δn, γ ₁ and Δε of the polymerizable compound-containing liquid crystal composition of the present invention can be the same as those of the liquid crystal composition of the present invention described above.

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 has a polymerizable compound-containing liquid crystal composition containing one or more compounds represented by the general formula (i) and one or more polymerizable compounds. It is a liquid crystal display element using an object.

In the liquid crystal display element of the present invention, by using the above-mentioned polymerizable compound-containing liquid crystal composition, a sufficient tilt angle can be obtained, the residual amount of the polymerizable compound in the liquid crystal display element after polymerization is small, and 4K or Display defects such as seizure (IS) of a high-definition PSA type liquid crystal display element such as 8K do not occur or can be remarkably suppressed. Further, in the production of a high-definition PSA type liquid crystal display element such as 4K or 8K, the production efficiency is remarkably deteriorated when the UV irradiation time is long, but the liquid crystal display element of the present invention contains the above-mentioned polymerizable compound. Since the liquid crystal composition is used, it becomes a high-definition PSA type liquid crystal display element in the UV irradiation time, and has very high industrial utility value.

The liquid crystal display element of the present invention is particularly useful for an active matrix driving liquid crystal display element, and can be used for a PSA mode, PSVA mode, VA mode, PS-IPS mode, or PS-FFS mode liquid crystal display element.

Since the liquid crystal display element of the present invention uses the above-mentioned polymerizable compound-containing liquid crystal composition, it can be set to a liquid crystal display element having no alignment film, that is, a mode commonly called PI-less. In this case, the polymerizable compound-containing liquid crystal composition is preferably used in combination with a compound having spontaneous orientation. Examples of the compound having spontaneous orientation include Japanese Patent Laid-Open No. 2014-513150, Japanese Patent Application Laid-Open No. 2014-524951, Japanese Patent No. 06081361, Japanese Patent Publication No. 2016-501938, Japanese Patent Application Laid-Open No. 2018-023718, International. Examples thereof include compounds having spontaneous orientation described in Publication No. 2017/041893, Japanese Patent No. 06070973, International Publication No. 2017/0471777, and the like. ,
The liquid crystal display element of the present invention includes a first substrate and a second substrate arranged opposite to each other, a common electrode provided on the first substrate or the second substrate, and the first substrate or the first substrate. It is preferable to have a pixel electrode provided on the second substrate and having a thin film transistor, and a liquid crystal layer provided between the first substrate and the second substrate. The liquid crystal layer contains at least a compound represented by the general formula (i), a liquid crystal composition contained in the polymerizable compound-containing liquid crystal composition, and a polymer of the polymerizable compound.

The liquid crystal display element of the present invention is provided with an alignment film for controlling the orientation direction of liquid crystal molecules on the facing surface side of at least one substrate of the first substrate and the second substrate so as to be in contact with the liquid crystal layer, if necessary. The alignment film may not be provided on both the first substrate and the second substrate. As the alignment film, a vertical alignment film, a horizontal alignment film, or the like can be appropriately selected according to the drive mode of the liquid crystal display element, and a rubbing alignment film (for example, a polyimide alignment film) or a photoalignment film (for example, a decomposition type) can be selected. A known alignment film such as a polyimide alignment film) can be used. Further, the color filter may be appropriately provided on the first substrate or the second substrate, and the color filter can be provided on the pixel electrode or the common electrode.

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

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

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

The distance between the first substrate and the second substrate may be adjusted via a spacer. At this time, it is preferable to adjust the thickness of the obtained liquid crystal layer to be 1 to 100 μm, and more preferably 1.5 to 10 μm. When a polarizing plate is used, it is preferable to adjust the product of the refractive index anisotropy Δn of the liquid crystal and the cell thickness d so that the contrast is maximized. Further, when there are two polarizing plates, the polarization axis of each polarizing plate can be adjusted so that the viewing angle and contrast can be improved. Further, a retardation film for widening the viewing angle can also be used. Examples of the spacer include glass particles, plastic particles, alumina particles, photoresist material and the like. Then, a sealant such as an epoxy-based thermosetting composition is screen-printed on the substrate in the form of providing a liquid crystal injection port, the substrates are bonded to each other, and the sealant is thermoset by heating.

As a method for sandwiching the polymerizable compound-containing liquid crystal composition between the two substrates, a normal vacuum injection method, an ODF method, or the like can be used.

As a method for polymerizing the polymerizable compound contained in the polymerizable compound-containing liquid crystal composition, an appropriate polymerization rate is desirable in order to obtain good orientation performance of the liquid crystal. Therefore, active energy rays such as ultraviolet rays or electron beams are used. A method of polymerizing by irradiation alone, in combination, or in sequence is preferable. When ultraviolet rays are used, a polarized light source may be used, or a non-polarized light source may be used. Further, when the polymerization is carried out in a state where the polymerizable compound-containing liquid crystal composition is sandwiched between two substrates, at least the substrate on the irradiation surface side must be provided with appropriate transparency for active energy rays. Must be. In addition, after polymerizing only a specific part using a mask during light irradiation, the orientation state of the unpolymerized part is changed by changing conditions such as electric field, magnetic field, or temperature, and further irradiation with active energy rays. You may use the means of polymerizing. In particular, when exposed to ultraviolet rays, it is preferable to expose the liquid crystal composition containing the polymerizable compound to ultraviolet rays while applying an AC electric field. The AC electric field to be applied is preferably an AC having a frequency of 10 Hz to 10 kHz, more preferably a frequency of 60 Hz to 10 kHz, and the voltage is selected depending on a desired pretilt angle of the liquid crystal display element. That is, the pretilt angle of the liquid crystal display element can be controlled by the applied voltage. In the PSVA mode liquid crystal display element, it is preferable to control the pretilt angle within the range of 80 degrees to 89.9 degrees from the viewpoint of orientation stability and contrast.

The temperature at the time of irradiation with active energy rays such as ultraviolet rays or electron beams used for polymerizing the polymerizable compound contained in the polymerizable compound-containing liquid crystal composition is not particularly limited. For example, when a polymerizable compound-containing liquid crystal composition is applied to a liquid crystal display element provided with a substrate having an alignment film, it is preferably within a temperature range in which the liquid crystal state of the polymerizable compound-containing liquid crystal composition is maintained. .. It is preferable to polymerize at a temperature close to room temperature, that is, typically in the range of 15 to 35 ° C.

On the other hand, for example, when the polymerizable compound-containing liquid crystal composition is applied to a liquid crystal display element having a substrate having no alignment film, it is applied to the liquid crystal display element having the substrate having the alignment film at the time of irradiation. The temperature range may be wider than the temperature range of.

As the lamp that generates ultraviolet rays, a metal halide lamp, a high-pressure mercury lamp, an ultra-high pressure mercury lamp and the like can be used, and a USHIO ultra-high pressure UV lamp and a fluorescent ultraviolet lamp manufactured by TOSHIBA are preferable. Further, as the wavelength of the ultraviolet rays to be irradiated, it is preferable to irradiate the ultraviolet rays in a wavelength region other than the absorption wavelength range of the polymerizable compound-containing liquid crystal composition, and it is preferable to cut the ultraviolet rays before use. The intensity of the ultraviolet rays to be irradiated is preferably 0.1 mW / cm ^{2 to} 100 W / cm ^{2, and} more preferably ² mW / cm ^{2 to} 50 W / cm ² . The amount of energy of the ultraviolet rays to be irradiated can be appropriately adjusted, but is preferably 10 mJ / cm ² to 500 J / cm ^{2, and} more preferably 100 mJ / cm ² to 200 J / cm ² . The intensity may be changed when irradiating with ultraviolet rays. The time for irradiating the ultraviolet rays is appropriately selected depending on the intensity of the ultraviolet rays to be irradiated, but is preferably 10 seconds to 3600 seconds, more preferably 10 seconds to 600 seconds.

The 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. Moreover, "%" in the following Examples and Comparative Examples means "mass%".

The following abbreviations are used for the description of compounds in the following examples and comparative examples.

(Side chain)
−N −C _n H _{2n + 1} linear alkyl group with n −C _n H _{2n + 1} − linear alkyl group with _n −On −OC _n H _{2n + 1} linear alkoxy having n ₊ carbon Group (linking group)
-1O--CH _2- O-
(Ring structure)

The characteristics measured in the following examples and comparative examples are as follows.

T _ni : Nematic phase-isotropic liquid phase transition temperature (° C)
Δn: Refractive index anisotropy 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 ₃₃ : Elastic constant at 20 ° C K ₃₃ (pN)
The manufacturing method and evaluation method of the liquid crystal display element in the following examples and comparative examples are as follows.

(Manufacturing method of liquid crystal display element)
First, a polymerizable compound-containing liquid crystal composition described later was injected by a vacuum injection method into a liquid crystal cell having a cell gap of 3.5 μm containing a substrate with ITO coated and rubbed with a polyimide alignment film that induces vertical orientation. Then, the liquid crystal cell into which the polymerizable compound-containing liquid crystal composition was injected was irradiated with ultraviolet rays for an arbitrary time using a fluorescent UV lamp to obtain a liquid crystal display element. At this time, the fluorescent UV lamp was adjusted so that the illuminance measured under the condition of the center wavelength of 313 nm was 3 mW / cm ² .

(Evaluation method of residual amount of polymerizable compound)
Under the above irradiation conditions, the residual amount [ppm] of the polymerizable compound in the liquid crystal display element after irradiation with ultraviolet rays for 150 seconds was measured. A method for measuring the residual amount of this polymerizable compound will be described. First, the decomposed liquid crystal display element and acetonitrile were placed in a test tube and filtered by shaking to obtain an acetonitrile solution of an elution component containing a liquid crystal composition, a polymer, and an unreacted polymerizable compound. This was analyzed by a high performance liquid chromatograph (column: reverse phase non-polar column, developing solvent: mixed solvent of 70% acetonitrile and 30% water), and the peak area of each component was calculated. The amount of the remaining polymerizable compound was determined from the ratio of the peak area of the liquid crystal compound as an index to the peak area of the unreacted polymerizable compound. The residual amount of the polymerizable compound was determined from this value and the amount of the polymerizable compound initially added. The detection limit of the residual amount of the polymerizable compound was 100 ppm.

(Evaluation method of pre-tilt angle change amount)
Under the above irradiation conditions, the amount of change in pretilt angle [°] of the liquid crystal display element before and after irradiation with ultraviolet rays for 50 seconds was measured.
First, the pre-tilt angle of the liquid crystal display element was measured and used as the pre-tilt angle (initial). The liquid crystal display element was irradiated with ultraviolet rays for 50 seconds while applying a voltage of 10 V at a frequency of 100 Hz. Then, the pre-tilt angle was measured and used as the pre-tilt angle (after UV). The value obtained by subtracting the pretilt angle (after UV) from the measured pretilt angle (initial) was defined as the amount of change in the pretilt angle [°]. The pretilt angle was measured using OPTIPRO manufactured by Shintec.

(Preparation of liquid crystal composition and physical property values)
The liquid crystal composition LC-001 before the addition of the compound of formula (i) and the polymerizable compound was prepared, and the physical property values thereof were measured. Table 1 shows the composition of the liquid crystal composition LC-001 and the results of its physical property values.

(Comparative Examples 1 to 3 and Examples 1 to 7)
A polymerizable compound-containing liquid crystal composition obtained by adding 0.3 parts by mass of a polymerizable compound represented by the following formula (RM-A) to 99.7 parts by mass of the liquid crystal composition LC-001 was compared with Comparative Example 1. did.

The liquid crystal composition LC-001 was 94.7 parts by mass, the compound represented by the following formula (REF-A) was 5 parts by mass, and the polymerizable compound represented by the following formula (RM-A) was 0. A liquid crystal composition containing a polymerizable compound added in an amount of 3 parts by mass was designated as Comparative Example 2.

The liquid crystal composition LC-001 was 94.7 parts by mass, the compound represented by the following formula (REF-B) was 5 parts by mass, and the polymerizable compound represented by the following formula (RM-A) was 0. A liquid crystal composition containing a polymerizable compound added in an amount of 3 parts by mass was designated as Comparative Example 3.

The liquid crystal composition LC-001 is 94.7 parts by mass, 5 parts by mass of the compound represented by the following formula (A) and 0.3 parts by mass of the polymerizable compound represented by the following formula (RM-A). The partially added polymerizable compound-containing liquid crystal composition was designated as Example 1.

The liquid crystal composition LC-001 is 96.7 parts by mass, 3 parts by mass of the compound represented by the following formula (A) and 0.3 parts by mass of the polymerizable compound represented by the following formula (RM-A). The partially added polymerizable compound-containing liquid crystal composition was designated as Example 2.

The liquid crystal composition LC-001 is 94.7 parts by mass, 5 parts by mass of the compound represented by the following formula (B) and 0.3 parts by mass of the polymerizable compound represented by the following formula (RM-A). The partially added polymerizable compound-containing liquid crystal composition was designated as Example 3.

To 94.7 parts by mass of the liquid crystal composition LC-001, 5 parts by mass of the compound represented by the formula (A) and 0.3 parts by mass of the polymerizable compound represented by the formula (RM-B) were added. The above-mentioned polymerizable compound-containing liquid crystal composition was designated as Example 4.

To 96.7 parts by mass of the liquid crystal composition LC-001, 3 parts by mass of the compound represented by the formula (A) and 0.3 parts by mass of the polymerizable compound represented by the formula (RM-C) were added. The above-mentioned polymerizable compound-containing liquid crystal composition was designated as Example 5.

To 96.7 parts by mass of the liquid crystal composition LC-001, 3 parts by mass of the compound represented by the formula (A) and 0.3 parts by mass of the polymerizable compound represented by the formula (RM-D) were added. The above-mentioned polymerizable compound-containing liquid crystal composition was designated as Example 6.

To 96.7 parts by mass of the liquid crystal composition LC-001, 3 parts by mass of the compound represented by the formula (A) and 0.3 parts by mass of the polymerizable compound represented by the formula (RM-E) were added. The above-mentioned polymerizable compound-containing liquid crystal composition was designated as Example 7.

Regarding the polymerizable compound-containing liquid crystal compositions of Comparative Examples 1 to 3 and Examples 1 to 7, the amount of change in the pretilt angle and the content of the polymerizable compound due to ultraviolet irradiation were shown in Table 2 below.

The polymerizable compound-containing liquid crystal compositions of Comparative Examples 1 and 3 had a small amount of change in the pretilt angle and a large amount of the polymerizable compound remaining. In Comparative Example 2, the residual amount of the polymerizable compound was small, and the amount of change in the pretilt angle was larger than that in Comparative Example 1 and Comparative Example 3, but the amount of change in the pretilt angle was not sufficient.

On the other hand, Examples 1 to 7, which are the polymerizable compound-containing liquid crystal compositions of the present invention, show a value in which the amount of change in the pretilt angle is sufficiently larger than that of Comparative Examples 1 to 3, and the residual amount of the polymerizable compound. It was found that the polymerization rate was sufficiently high. From the above, it was confirmed that the polymerizable compound-containing liquid crystal composition of the present invention can form a pretilt angle with short or a small amount of UV light and reduce the residual amount of the polymerizable compound.

Further, when Example 1 and Example 4 are compared, Example 1 using the polymerizable compound represented by the formula (RM-A) has a more polymerizable compound represented by the formula (RM-B). The amount of change in the pretilt angle was larger and the residual amount of the polymerizable compound was smaller than in Example 4 used.

The liquid crystal cell in which the liquid crystal composition containing the polymerizable compound of Examples 1 to 7 was injected was irradiated with ultraviolet rays for 60 minutes under the above irradiation conditions, and then backlit while applying a voltage of 30 V at a frequency of 100 Hz using OPTIPRO manufactured by Shintec. Was irradiated for 3 hours, and display defects (burn-in) due to changes in the pretilt angle were evaluated. As a result, the change in the pretilt angle was extremely small, showing high pretilt stability.

(Examples 8 to 9)
A polymerizable compound-containing liquid crystal composition in which 0.005 parts by mass of an antioxidant represented by the formula (H-2-1) was further added to Example 1 was designated as Example 8.

A polymerizable compound-containing liquid crystal composition in which 0.005 parts by mass of an antioxidant represented by the formula (H-4-1) was further added to Example 1 was designated as Example 9.

The polymerizable compound-containing liquid crystal compositions of Examples 8 to 9 were also evaluated in the same manner as in Example 1. As a result, in Examples 8 to 9, the amount of change in the pretilt angle was the same as that in Example 1, and the amount of change in the pretilt angle was sufficiently large. Further, it was found that in Examples 8 to 9, the residual amount of the polymerizable compound was the same as that in Example 1, the residual amount of the polymerizable compound was small, and the polymerization rate was sufficiently high. From this, it was confirmed that the polymerizable compound-containing liquid crystal compositions of Examples 8 to 9 also solved the problem of the present invention.

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 ^{L i10} are each independently ^the same meaning as ^{L i1.)}
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. A polymerizable compound-containing liquid crystal composition containing one or more compounds represented by) and one or more polymerizable compounds. As the polymerizable compound, the general formula (P)

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

(In the formula, R ^p11 and R ^p12 independently represent a hydrogen atom, an alkyl group having 1 to 5 carbon atoms or an alkyl halide group having 1 to 5 carbon atoms, and W ^p11 is a single bond, −O. -, -COO-, represents an alkylene group having 1 to 5 carbon atoms, and t ^p11 represents 0, 1 or 2, but there are a plurality of R ^p11 , R ^p12 , W ^p11 and / or t ^{p11 in} the molecule. If so, they may be the same or different.)
Sp ^p1 and Sp ^p2 independently represent a single bond or a spacer group, respectively.
Z ^p1 and Z ^p2 are independent, single-bonded, -O-, -S-, -CH _2- , -OCH _2- , -CH ₂ O-, -CO-, -C ₂ H ₄ -,-, respectively. _{COO -, - OCO -, -} OCOOCH 2 -, - CH 2 OCOO -, - OCH 2 CH 2 O -, - CO-NR ZP1 -, - NR ZP1 -CO -, - SCH 2 -, - CH 2 S- ^{, -CH = CR ZP1 -COO -,} - CH = CR ZP1 -OCO -, - COO-CR ZP1 = CH -, - OCO-CR ZP1 = CH -, - COO-CR ZP1 = CH-COO -, - COO -CR ^ZP1 = CH- ^{OCO-, -OCO} -CR ^ZP1 = CH- ^{COO-, -OCO} -CR ^ZP1 = CH-OCO-,-(CH ₂ ) _z- COO-,-(CH ₂ ) _z- OCO- , -OCO- (CH ₂ ) _z -,-(C = O) -O- (CH ₂ ) _z- , -CH = CH-, -CF = CF-, -CF = CH-, -CH = CF- _{, -CF 2 -, - CF 2} O -, - OCF 2 -, - CF 2 CH 2 -, - CH 2 CF 2 -, - CF 2 CF 2 - or -C≡C- (wherein, z are each They independently represent integers 1 to 4, and R ^ZP1 independently represent hydrogen atoms or alkyl groups with 1 to 4 carbon atoms, but if there are multiple R ^ZP1s in the molecule, they are the same. In addition, * in the formula represents a binding point to Sp ^p1 or Sp ^p2 .)
Represents
A ^p1 and A ^p2 are independent of each other.
^(A p) 1,4-cyclohexylene group (this is present in the group one -CH ₂ - or nonadjacent two or more -CH ₂ - may be replaced by -O-.)
^(B p) 1,4-phenylene group (the one present in the group -CH = or non-adjacent two or more -CH = may be replaced by -N =.) And (c ^p ) Naphthalene diyl group, 1,2,3,4-tetrahydronaphthalenediyl group, decahydronaphthalenedyl group, phenanthrene-2,7-diyl group or anthracene-2,6-diyl group (1 present in these groups Two or more -CH = or two or more non-adjacent -CH = may be replaced with -N =.)
Represents a group selected from the group consisting of
A ^p3 represents a group described above ^(a p), group ^{(b p)} and group ^(c p), and a group selected from the group consisting of a single bond,
The above groups ^(a p), group ^{(b p)} and group ^{(c p)} are each independently hydrogen atoms present in this group, a cyano group, a halogen atom, an alkyl of 1 to 8 carbon atoms It may be substituted with a group, an alkoxy group having 1 to 8 carbon atoms, an alkenyl group having 1 to 8 carbon atoms, or −Sp ^p2 −P ^p2 .
m ^p1 represents 0, 1, 2 or 3, ^{if Z p1,} A ^{p2, Sp} p2 and / or ^{P p2} is more present in the molecule, they may be the same or different but,
When m ^p1 is 0 and A ^p1 is a group other than a naphthalene diyl group, a phenanthrene-2,7-diyl group or an anthracene-2,6-diyl group, A ^p3 represents a group other than a single bond. )
The liquid crystal composition according to claim 1, which contains one or more compounds represented by. 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 formula (N-01), the general formula (N-02), the general formula (N-03), the general formula (N-03) and the general formula (N-05)

(In the formula, R ²¹ and R ²² are independently an alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, an alkenyl group having 2 to 8 carbon atoms, or 2 carbon atoms. represents 8 alkenyloxy group, two or more -CH of one or non-adjacent in the group ₂ - each independently -CH = CH -, - C [identical to] C -, - O -, - CO 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 PSA mode, PSVA mode, PS-IPS mode or PS-FFS mode using the polymerizable compound-containing liquid crystal composition according to any one of claims 1 to 4.