WO2020075509A1

WO2020075509A1 - Polymerizable liquid-crystal composition and liquid-crystal display element

Info

Publication number: WO2020075509A1
Application number: PCT/JP2019/037807
Authority: WO
Inventors: 淳子山本; 雄一井ノ上; 純一間宮; 正臣木村
Original assignee: Dic株式会社
Priority date: 2018-10-11
Filing date: 2019-09-26
Publication date: 2020-04-16
Also published as: TW202033749A; JP6844749B2; JPWO2020075509A1; CN112534022A; TWI828769B

Abstract

The present invention addresses the problem of providing: a liquid-crystal composition containing a polymerizable compound, the composition retaining the intact alignment control force for vertically aligning the liquid-crystal molecules, causing very few or no display failures due to a change in pretilt angle, and having a high voltage holding ratio; and a liquid-crystal display element including the liquid-crystal composition. The liquid-crystal composition of the present invention contains a specific polymerizable compound. The above problem is solved with the liquid-crystal composition and the liquid-crystal display element including said liquid-crystal composition.

Description

Polymerizable liquid crystal composition and liquid crystal display device

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

Generally, liquid crystal display devices such as liquid crystal panels and liquid crystal displays change the state of alignment of liquid crystal molecules by an external stimulus such as an electric field and use the resulting change in optical characteristics for display. Such a liquid crystal display device has a structure in which liquid crystal molecules are filled in a gap between two transparent substrates, and liquid crystal molecules are arranged in a specific direction in advance on the surface of the substrate which is in contact with the liquid crystal molecules. Generally, an alignment film is formed.

However, in the manufacturing process of the liquid crystal display device, alignment defects occur due to scratches and dust on the surface of the alignment film. There is a problem that it is difficult to design and manage the alignment film for obtaining the film.

Therefore, in recent years, a liquid crystal display element that does not require an alignment film has been developed by using a liquid crystal composition containing a spontaneous alignment material that controls the alignment of liquid crystal molecules in a liquid crystal layer (Patent Documents 1 and 2). .

The production of a liquid crystal display device that does not require an alignment film was performed by injecting a liquid crystal compound, a polymerizable compound-containing liquid crystal composition containing a spontaneous alignment material and a polymerizable compound between the substrates, and applying a voltage to align the liquid crystal molecules. In this state, the spontaneous alignment material and the polymerizable compound are polymerized to fix the alignment of the liquid crystal molecules. It is known that the cause of image sticking, which is a display failure of the liquid crystal display element, is due to impurities and a change in alignment of liquid crystal molecules (change in pretilt angle).

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

US Patent Publication No. 2017-0123275 Japanese Patent Publication No. 2015-168826

INDUSTRIAL APPLICABILITY The present invention suppresses a polymerizable compound that remains when a liquid crystal display device is formed without impeding the alignment regulating force for vertically aligning liquid crystal molecules, and is there a display defect due to a decrease in voltage holding ratio or a change in pretilt angle? Or to provide a liquid crystal composition containing an extremely small amount of a polymerizable compound, and to provide a liquid crystal display device using the same.

As a result of intensive studies by the present inventors, it was found that the above problems can be solved by a liquid crystal composition containing one or more polymerizable compounds represented by the general formula (i), and the present invention is completed. I arrived.

(In the formula, X ⁱ¹ , X ⁱ² , X ⁱ³ , X ⁱ⁴ , X ⁱ⁵ , X ⁱ⁶ , X ⁱ⁷ , X ⁱ⁸ , X ⁱ⁹ , X ⁱ¹⁰ , X ⁱ¹¹ and X ⁱ¹² each independently have 1 carbon atom. Represents an alkyl group having from 1 to 18, an alkoxy group having from 1 to 18 carbon atoms, a halogen atom or a hydrogen atom,
At least two selected from X ⁱ¹ to X ⁱ¹² each independently represent an alkyl group having 1 to 18 carbon atoms, an alkoxy group having 1 to 18 carbon atoms, or a halogen atom,
P ⁱ¹ and P ⁱ² each independently represent one of the following formulas (RI) to (R-IX),

(In the formula, R ²¹ , R ³¹ , R ⁴¹ , R ⁵¹ and R ⁶¹ each independently represent a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and W is a single bond, —O— or methylene. Represents a group, T represents a single bond or —COO—, and p, t and q each independently represent 0, 1 or 2.)
Sp ⁱ¹ and Sp ⁱ² each independently represent a single bond or an alkylene group having 1 to 15 carbon atoms, and one or two or more —CH ₂ — in the alkylene group are directly adjacent to an oxygen atom. May be substituted with -O-, -OCO- or -COO-,
n ⁱ¹ represents 0, 1 or 2,
L ⁱ¹ and L ⁱ² are each independently a single bond, —OCH ₂ —, —CH ₂ O—, —C ₂ H ₄ —, —OC ₂ H ₄ O—, —COO—, —OCO—, —. CH = CR ^a -COO-, -CH = CR ^a -OCO-, -COO-CR ^a = CH-, -OCO-CR ^a = CH-,-(CH ₂ ) _z -COO-,-(CH ₂ ) _z —OCO—, —OCO— (CH ₂ ) _z —, —COO— (CH ₂ ) _z —, —CH═CH—, —CF ₂ O—, —OCF ₂ — or —C≡C— (wherein , R ^a represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and z represents an integer of 1 to 4),
When there are a plurality of X ⁱ⁵ , X ⁱ⁶ , X ⁱ⁷ , X ⁱ⁸ and / or L ⁱ² , they may be the same or different. )
At the same time, the present invention provides a liquid crystal display device using the liquid crystal composition, an active matrix driving liquid crystal display device using the liquid crystal composition, a PSA mode, a PSVA mode, and a PS-IPS mode using the liquid crystal composition. Another object is to provide a liquid crystal display element for PS-FSS mode and a liquid crystal display element in which an alignment film is not provided on the surface of at least one of a pair of substrates using the liquid crystal composition.

By using the polymerizable liquid crystal composition of the present invention, it is possible to obtain a liquid crystal display device having a small change in pretilt angle. In addition, the liquid crystal display device produced by using the polymerizable liquid crystal composition of the present invention has a high voltage holding ratio (VHR) and is characterized in that the amount of unpolymerized polymerizable compound in the device is extremely small.

In the above general formula (i), X ⁱ¹ , X ⁱ² , X ⁱ³ , X ⁱ⁴ , X ⁱ⁵ , X ⁱ⁶ , X ⁱ⁷ , X ⁱ⁸ , X ⁱ⁹ , X ⁱ¹⁰ , X ⁱ¹¹ and X ⁱ¹² are each independently. It represents an alkyl group having 1 to 18 carbon atoms, an alkoxy group having 1 to 18 carbon atoms, a halogen atom or a hydrogen atom. The alkyl group and the alkoxy group are preferably linear, and a hydrogen atom, Methyl group, ethyl group, propyl group, methoxy group, ethoxy group, propoxy group, fluorine atom or chlorine atom is preferable, hydrogen atom, methyl group, ethyl group, methoxy group or fluorine atom is preferable, hydrogen atom, methyl group, methoxy Groups or fluorine atoms are preferred. Two or more are preferably other than hydrogen atoms, two or three are preferably other than hydrogen atoms, and two are preferably other than hydrogen atoms.

The preferable number of carbon atoms of the alkyl group and the alkoxy group is preferably 10 to 18 when the orientation of the liquid crystal is important, and 1 to 4 is preferable when the solubility in the liquid crystal compound is important. Further, when importance is attached to tilt angle stability, an alkyl group is preferable. Further, the alkyl group and the alkoxy group may be linear or branched, but linear is particularly preferable.

Two or more of X ⁱ¹ , X ⁱ² , X ⁱ³ , X ⁱ⁴ , X ⁱ⁵ , X ⁱ⁶ , X ⁱ⁷ , X ⁱ⁸ , X ⁱ⁹ , X ⁱ¹⁰ , X ⁱ¹¹ and X ⁱ¹² are alkyl having 1 to 18 carbon atoms. Group, an alkoxy group having 1 to 18 carbon atoms or a halogen atom is preferable, and the preferable number of carbon atoms of the alkyl group and the alkoxy group is 10 to 18 when the orientation of the liquid crystal is important. Is preferred, and 1 to 4 are preferred when importance is attached to the solubility in the liquid crystal compound. Further, when importance is attached to tilt angle stability, an alkyl group is preferable. Further, the alkyl group and the alkoxy group may be linear or branched, but linear is particularly preferable.

Further, at least one of X ⁱ⁵ , X ⁱ⁶ , X ^i7, X ⁱ⁸ , X ⁱ⁹ , X ⁱ¹⁰ , X ⁱ¹¹ and X ⁱ¹² has 1 to 18 carbon atoms when the voltage holding ratio is important. It is preferably an alkyl group. The number of carbon atoms of the alkyl group is preferably 10 to 18 when the orientation of the liquid crystal is important, and 1 to 4 is preferable when the solubility in the liquid crystal compound is important. Further, when importance is attached to tilt stability, 1 to 3 is preferable. The alkyl group may be linear or branched, but linear is particularly preferable.

In the above general formula (i), in order to reduce the amount of residual monomer after UV irradiation, it is preferable that one or two of X ⁱ¹¹ or X ⁱ¹² be a hydrogen atom.

In the general formula (i), when importance is attached to the solubility in the liquid crystal composition, at least one of X ⁱ⁵ , X ⁱ⁶ , X ^i7, X ⁱ⁸ , X ⁱ⁹ , X ⁱ¹⁰ , X ^i11, and X ^{i12 is} at least one. , A halogen atom is preferable, and fluorine is particularly preferable.

The general formula ^(i), the case ^{n i1} is 1, when emphasizing the tilt angle ^{^{^{stability, X i5, X i6, X}}} i7, and two are chosen from among ^{X i8,} 1 carbon atoms To an alkyl group having 1 to 18 carbon atoms, an alkoxy group having 1 to 18 carbon atoms, and a halogen atom are preferable, and an alkyl group having 1 to 3 carbon atoms and fluorine are particularly preferable.

In the general formula (i), L ⁱ¹ is a single bond, —OCH ₂ —, —CH ₂ O—, —C ₂ H ₄ —, —COO—, —OCO—, —CH═CH—COO—, — CH = CH-OCO -, - COO-CH = CH -, - OCO-CH = CH -, - C 2 H 4 -COO -, - C 2 H 4 -OCO -, - OCO-C 2 H 4 -, —COO—C ₂ H ₄ —, —CH═CH—, —CF ₂ O—, —OCF ₂ — or —C≡C— is preferred, and a single bond, —OCH ₂ —, —CH ₂ O—, —C. ₂ H ₄ —, —COO—, —OCO—, —C ₂ H ₄ —COO—, —C ₂ H ₄ —OCO—, —OCO—C ₂ H ₄ —, —COO—C ₂ H ₄ —, — CF ₂ O—, —OCF ₂ — or —C≡C— is more preferable, and a single bond is particularly preferable.

In the general formula (i), L ⁱ² is a single bond, —OCH ₂ —, —CH ₂ O—, —C ₂ H ₄ —, —COO—, —OCO—, —CH═CH—COO—, — CH = CH-OCO -, - COO-CH = CH -, - OCO-CH = CH -, - C 2 H 4 -COO -, - C 2 H 4 -OCO -, - OCO-C 2 H 4 -, —COO—C ₂ H ₄ —, —CH═CH—, —CF ₂ O—, —OCF ₂ — or —C≡C— is preferred, and a single bond, —OCH ₂ —, —CH ₂ O—, —C. ₂ H ₄ —, —COO—, —OCO—, —C ₂ H ₄ —COO—, —C ₂ H ₄ —OCO—, —OCO—C ₂ H ₄ —, —COO—C ₂ H ₄ —, — CH = CH-, -CF ₂ O-, -OCF ₂ -or -C≡C- is more preferable, and a single bond is particularly preferable.

In the above general formula (i), L ⁱ¹ and L ⁱ² may be the same or different from each other, but it is more preferable that L ⁱ¹ and L ⁱ² are the same.

In the general formula (i), P ⁱ¹ and P ⁱ² each independently represent one of the following formulas (RI) to (R-IX).

(In the formula, R ²¹ , R ³¹ , R ⁴¹ , R ⁵¹ and R ⁶¹ are each independently of each other a hydrogen atom, an alkyl group having 1 to 5 carbon atoms or a halogenated alkyl group having 1 to 5 carbon atoms. A group, W is a single bond, -O- or a methylene group, T is a single bond or -COO-, and p, t and q are each independently 0, 1 or 2.)
Among them, in the general formula (i), P ⁱ¹ and P ⁱ² are each independently a formula ( ^RI ), a formula (R-II), a formula (R-III), a formula (R-IV), Formula (RV) or formula (R-VII) is preferred, and formula (RI), formula (R-II), formula (R-III) or formula (R-IV) is preferred. More preferably, it is more preferably of the formula (RI), that is, an acryloxy group (a substituent in which R ²¹ is a hydrogen atom in (RI)) or a methacryloxy group (wherein R ²¹ is R ²¹ is It is more preferably a substituent group which is a methyl group), and more preferably a methacryloxy group.

In the general formula (i), Sp ⁱ¹ and Sp ⁱ² are preferably each independently a single bond or an alkylene group having 1 to 3 carbon atoms, and more preferably a single bond.

The polymerizable compound represented by the general formula (i) may be used alone or in combination of two or more.

The liquid crystal composition according to the present invention preferably contains 1 to 5 kinds of polymerizable compounds represented by the general formula (i), and 1 to 4 kinds of polymerizable compounds represented by the general formula (i). It is preferable to include a compound, and it is preferable to include one to three polymerizable compounds represented by the general formula (i).

The lower limit of the content of the polymerizable compound represented by the general formula (i) in the liquid crystal composition of the present invention is preferably 0.05% by mass, preferably 0.08% by mass, and preferably 0.1% by mass, 0.15 mass% is preferable, 0.17 mass% is preferable, 0.2 mass% is preferable, 0.22 mass% is preferable, 0.25 mass% is preferable, 0.27 mass% is preferable, and 0. 3 mass% is preferable, 0.32 mass% is preferable, 0.35 mass% is preferable, 0.37 mass% is preferable, 0.4 mass% is preferable, 0.42 mass% is preferable, 0.45 mass% % Is preferred, 0.48% by mass is preferred, 0.5% by mass is preferred, 0.53% by mass is preferred, 0.55% by mass is preferred, 0.58% by mass is preferred, 0.60% by mass is Preferably, 0.63 mass% is preferable, 0.65 mass% is preferable, 0.68 mass% is preferable, 0.70 mass% is preferable, 0.73 mass% is preferable, 0.75 mass% is preferable, 0.78 mass% is preferable, and 0.8 Mass% is preferred. The upper limit of the content of the polymerizable compound represented by the general formula (i) in the liquid crystal composition of the present invention is preferably 2.5% by mass, preferably 2.3% by mass, and preferably 2.1% by mass, 2 mass% is preferable, 1.8 mass% is preferable, 1.6 mass% is preferable, 1.5 mass% is preferable, 1 mass% is preferable, 0.95 mass% is preferable, and 0.9 mass% is. Preferably, 0.85 mass% is preferable, 0.8 mass% is preferable, 0.75 mass% is preferable, 0.7 mass% is preferable, 0.65 mass% is preferable, 0.6 mass% is preferable, 0.55 mass% is preferable, 0.5 mass% is preferable, 0.45 mass% is preferable, and 0.4 mass% is preferable.
When the polymerizable compound represented by the general formula (i) is used alone, the smaller amount is preferable from the viewpoint of storage stability at low temperature, and a plurality of polymerizable compounds represented by the general formula (i) are combined. When used, a larger amount is preferable because the effect of the present application can be further exhibited.

In order to achieve both storage stability at low temperature and change in pretilt angle, the content of the polymerizable compound represented by the general formula (i) in the liquid crystal composition of the present invention is 0.1 to 1%. Is preferable, 0.2 to 0.8% is preferable, 0.3 to 0.75% is preferable, 0.35 to 0.7% is preferable, and 0.4 to 0.7% is preferable. Suitable compounds of the polymerizable compound represented by the general formula (i) according to the present invention include the following formulas RM-1 to RM-33.

The above formulas RM-1 to RM-33 are preferable, RM-3 to RM-11, RM-22 to RM-30 are more preferable, and RM-3, RM-11 and RM-25, RM-28 to RM-30. And are more preferable.

The liquid crystal composition according to the present invention contains the polymerizable compound represented by the general formula (i), but other polymerizable compounds may be used in combination. As the other polymerizable compound, the following general formula (P) is used.

(In the 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 more of the alkyl groups Two or more adjacent —CH ₂ — may be each independently substituted by —CH ＝ CH—, —C≡C—, —O—, —CO—, —COO—, or —OCO—; One or more hydrogen atoms in the alkyl group may be each independently substituted with a cyano group, a fluorine atom or a chlorine atom,
P ^p1 and P ^p2 are each independently a general formula (P ^p1 -1) to a formula (P ^p1 -9)

(Wherein, R ^p11 and R ^p12 each independently represent a hydrogen atom, an alkyl group having 1 to 5 carbon atoms or a halogenated alkyl group having 1 to 5 carbon atoms, W ^p11 represents a single bond, —O Represents a —, —COO— or methylene group, and t ^p11 represents 0, 1, or 2. When a plurality of R ^p11 , R ^p12 , W ^p11 and / or t ^p11 are present in a molecule, they are the same. Or different.)
Represents one of
Sp ^p1 and Sp ^p2 each independently represent a single bond or a spacer group,
Z ^p1 and Z ^p2 are each independently a single bond, —O—, —S—, —CH ₂ —, —OCH ₂ —, —CH ₂ O—, —CO—, —C ₂ H ₄ —, — COO—, —OCO—, —OCOOCH ₂ —, —CH ₂ OCOO—, —OCH ₂ CH ₂ O—, —CO—NR ^ZP1 —, —NR ^ZP1 —CO—, ^—SCH ₂ —, —CH ₂ S— ^{^{^{, -CH = CR ZP1 -COO -,}}} - CH = CR ZP1 -OCO -, - COO-CR ZP1 = CH -, - OCO-CR ZP1 = CH -, - COO-CR ZP1 = CH-COO -, - COO -CR ^ZP1 = CH- ^{OCO-, -OCO} -CR ^ZP1 = CH- ^{COO-, -OCO} -CR ^ZP1 = CH-OCO-,-(CH ₂ ) _z -COO-,-(CH ₂ ) ₂ -OCO- , -OCO- _(CH ₂₎ 2 _{_{, - (C = O) -O-}} (CH 2) 2 -, - CH = CH -, - CF = CF -, - CF = CH -, - CH = CF -, - CF 2 -, - CF 2 O —, —OCF ₂ —, —CF ₂ CH ₂ —, —CH ₂ CF ₂ —, —CF ₂ CF ₂ — or —C≡C— (wherein, R ^ZP1 each independently represent a hydrogen atom or a carbon atom number. Represents an alkyl group of 1 to 4, but when there are a plurality of R ^ZP1 in the molecule, they may be the same or different.)
Represents
^Ap1 , ^Ap2 and ^Ap3 are each independently
^(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 (one —CH═ present in this group or two or more —CH═ which are not adjacent to each other may be replaced with —N═) and (c). ^p ) naphthalene-2,6-diyl group, 1,2,3,4-tetrahydronaphthalene-2,6-diyl group, decahydronaphthalene-2,6-diyl group, phenanthrene-2,7-diyl group or anthracene -2,6-diyl group (one -CH = present in these groups or two or more -CH = not adjacent to each other may be replaced with -N =).
Represents a group selected from the group consisting of the above group (a ^p), group (b ^p) and one or more hydrogen atoms present in the radical (c ^p) are each independently a halogen atom , A cyano group, an alkyl group having 1 to 8 carbon atoms, or -Sp ^p2 -P ^p2 may be substituted, and one or two or more non-adjacent -CH ₂ -in the alkyl group are independent of each other. And may be substituted with —CH═CH—, —C≡C—, —O—, —CO—, —COO— or —OCO—,
m ^p1 represents 0, 1, 2 or 3, and when a plurality of Z ^p1 , A ^p2 , Sp ^p2 and / or P ^p2 are present in the molecule, they may be the same or different, A ^p3 represents a single bond when m ^p1 is 0 and A ^p1 is a phenanthrene-2,7-diyl group or an anthracene-2,6-diyl group.
However, the compound represented by the general formula (i) is excluded. )
Compounds represented by are preferred. Moreover, it is preferable to contain 1 type or 2 types or more of the said polymerizable monomer.

In the general formula (P) according to the present invention, R ^p1 is preferably -Sp ^p2 -P ^p2 .

P ^p1 and P ^p2 are preferably each independently any of formulas (P ^p1 -1) to (P ^p1 -3), and more preferably (P ^p1 -1).

Preferably, R ^p11 and R ^p12 are each independently a hydrogen atom or a methyl group.

0 or 1 is preferable for ^tp11 .

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

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

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

Further, only one of Z ^p1 and Z ^p2 present in the molecule is represented by —CH ＝ CH—COO—, —COO—CH ＝ CH—, — (CH ₂ ) ₂ —COO—, — (CH ₂ ) ₂ It is a connecting group selected from the group consisting of —OCO—, —O—CO— (CH ₂ ) ₂ —, and —COO— (CH ₂ ) ₂ —, and the other is preferably a single bond.

Sp ^p1 and Sp ^p2 each independently represent a single bond or a spacer group, and the spacer group is preferably an alkylene group having 1 to 30 carbon atoms, and —CH ₂ — in the alkylene group has oxygen atoms connected to each other. As long as they are not directly linked, they 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 May be substituted, but a linear alkylene group having 1 to 10 carbon atoms or a single bond 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 more preferably a 1,4-phenylene group. The 1,4-phenylene group is preferably substituted with one fluorine atom, one methyl group or one methoxy group in order to improve the compatibility with the liquid crystal compound.

The total content of the compound represented by the general formula (P) is preferably 0.05 to 10% with respect to the composition containing the compound represented by the general formula (P) of the present application, Preferably, it contains 0.1 to 8%, preferably 0.1 to 5%, more preferably 0.1 to 3%, and 0.2 to 2%. Preferably, it contains 0.2 to 1.3%, more preferably 0.2 to 1%, and more preferably 0.2 to 0.56%.

The preferable lower limit of the total content of the compound represented by the general formula (P) is 0.01% with respect to the composition containing the compound represented by the general formula (P) of the present application, and is 0.1%. 03%, 0.05%, 0.08%, 0.1%, 0.15%, 0.2%, 0.25%, 0.3% %.

A preferred upper limit of the total content of the compound represented by the general formula (P) is 10% and 8% with respect to the composition containing the compound represented by the general formula (P) of the present application. 5%, 3%, 1.5%, 1.2%, 1%, 0.8%, and 0.5%.

If the content is small, the effect of adding the compound represented by the general formula (P) is difficult to appear, and problems such as weak alignment control force of the liquid crystal composition or weakening over time occur. Problems such as an increase in the amount remaining afterward, a long time for curing, and a decrease in the reliability of the liquid crystal occur. Therefore, the content is set in consideration of these balances.

好ましい Preferred examples of the compound represented by the general formula (P) according to the present invention include polymerizable compounds represented by the following formulas (P-1-1) to (P-1-46).

^(Wherein, P ^{^p11,} P p12, ^Sp ^p11 and ^{Sp p12} are the same as defined ^P ^{^p11,} ^P ^p12, ^Sp p11 and ^{Sp p12} in the general formula (P-1).)
Preferred examples of the compound represented by the general formula (P) according to the present invention include polymerizable compounds represented by the following formulas (P-2-1) to (P-2-12).

^(Wherein, P ^{^p21,} P p22, ^Sp ^p21 and ^{Sp p22} are the same as defined ^P ^{^p21,} ^P ^p22, ^Sp p21 and ^{Sp p22} in the general formula (P-2).)
Preferred examples of the compound represented by the general formula (P) according to the present invention include polymerizable compounds represented by the following formulas (P-3-1) to (P-3-15).

^(Wherein, P ^{^p31,} P p32, ^Sp ^p31 and ^{Sp p32} are the same as defined ^P ^{^p31,} ^P ^p32, ^Sp p31 and ^{Sp p32} in the general formula (P-3).)
Preferred examples of the compound represented by the general formula (P) according to the present invention include polymerizable compounds represented by the following formulas (P-4-1) to (P-4-15).

^(Wherein, P ^{^p41,} P p42, ^Sp ^p41 and ^{Sp p42} are the same as defined ^P ^{^p41,} ^P ^p42, ^Sp p41 and ^{Sp p42} in the general formula (P-4).)
The liquid crystal composition according to the present invention has 1 to 3 kinds of polymerizable compounds represented by the general formula (i) and 1 to 3 kinds of general formulas (P) having different structures from those of the general formula (i). ) Can be included in the polymerizable compound.

The lower limit of the total content of the compound represented by the general formula (i) and the polymerizable compound represented by the general formula (P) is preferably 0.01% by mass in the general formula (i), and 0.03% by mass. % Is preferable, 0.05% by mass is preferable, 0.08% by mass is preferable, 0.10% by mass is preferable, 0.12% by mass is preferable, 0.15% by mass is preferable, 0.17% by mass is Preferably, 0.2 mass% is preferable, 0.22 mass% is preferable, 0.25 mass% is preferable, 0.27 mass% is preferable, 0.3 mass% is preferable, 0.32 mass% is preferable, 0.35 mass% is preferable, 0.37 mass% is preferable, and 0.4 mass% is preferable.

The upper limit of the total content of the polymerizable compound represented by the general formula (i) and the polymerizable compound represented by the general formula (P) in the liquid crystal composition of the present invention is preferably 2.0% by mass. 0.8 mass% is preferable, 1.5 mass% is preferable, 1.0 mass% is preferable, 0.8 mass% is preferable, 0.5 mass% is preferable, 0.47 mass% is preferable, and 0.1 mass% is. Mass% is preferable, 0.45 mass% is preferable, 0.43 mass% is preferable, 0.40 mass% is preferable, 0.37 mass% is preferable, 0.35 mass% is preferable, 0.32 mass% Is preferable, 0.30 mass% is preferable, 0.27 mass% is preferable, 0.25 mass% is preferable, 0.23 mass% is preferable, and 0.20 mass% is preferable.

The liquid crystal composition may further contain liquid crystal molecules and an alignment aid having a function of spontaneously aligning the liquid crystal molecules and having an adsorption group (polar group).

(Alignment aid)
The alignment aid (spontaneous alignment compound) is a member (electrode (for example, ITO)), substrate (for example, glass substrate, acrylic substrate, transparent substrate, flexible substrate, or the like) that directly contacts the liquid crystal layer containing the liquid crystal composition, resin. Homeotropic alignment or homogeneous alignment of liquid crystal molecules contained in the liquid crystal layer by interacting with layers (for example, color filters, alignment films, overcoat layers, etc.) and insulating films (for example, inorganic material films, SiNx, etc.) It has a function to induce.

The alignment aid induces alignment of the liquid crystal molecules, a polymerizable group for polymerization, a mesogenic group similar to the liquid crystal molecules, an adsorption group (polar group) capable of interacting with a member that directly contacts the liquid crystal layer. It is preferable to have an orientation-inducing group.

It is preferable that the adsorption group and the orientation-inducing group are bonded to the mesogen group, and the polymerizable group is substituted for the mesogen group, the adsorption group and the orientation-inducing group directly or via a spacer group as necessary. In particular, the polymerizable group is preferably substituted with the mesogen group in a state of being incorporated in the adsorptive group.

In the following, * at the left end and * at the right end in the chemical formulas represent bond.

"Orientation-inducing group"
The orientation-inducing group has a function of inducing the orientation of liquid crystal molecules, and is preferably a group represented by the following general formula (AK).

In the formula, R ^AK1 represents a linear or branched alkyl group having 1 to 20 carbon atoms. However, one or more —CH ₂ — in the alkyl group do not have an oxygen atom directly bonded and are independently —CH═CH—, —C≡C—, —O—, — It may be substituted with CO—, —COO— or —OCO—, and one or more hydrogen atoms in the alkyl group may be independently substituted with a halogeno group.

R ^AK1 is preferably a linear or branched alkyl group having 1 to 20 carbon atoms, more preferably a linear alkyl group having 1 to 20 carbon atoms, and more preferably a linear alkyl group. It is more preferable to represent an alkyl group having 1 to 8 carbon atoms.

Further, one or two or more non-adjacent —CH ₂ — groups in the alkyl group are independently —CH═CH—, —C≡C—, —O—, —CO—, —COO— or It may be substituted with —OCO—.

Further, the hydrogen atom in the alkyl group may be substituted with a fluorine atom or a chlorine atom, or may be substituted with a fluorine atom.

From the viewpoint of imparting the so-called amphipathic property to the liquid crystal layer to the alignment aid, it is preferable that the above alignment inducing group is bonded to a mesogenic group.

"Polymerizable group"
Polymerizable ^group, P ^{AP1 -Sp} AP1 - is preferably represented by.

P ^AP1 is preferably a group selected from the group represented by the following general formulas (AP-1) to (AP-9).

In the formula, R ^AP1 and R ^AP2 each independently represent a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a halogenated alkyl group having 1 to 10 carbon atoms. However, one or two or more —CH ₂ — in the alkyl group may be substituted with —O— or —CO—, and one or two or more hydrogen atoms in the alkyl group are each independently. Then, it may be substituted with a halogen atom or a hydroxyl group.

W ^AP1 represents a single bond, —O—, —COO— or —CH ₂ —.

t ^AP1 represents 0, 1 or 2.

P ^AP1 is preferably a group represented by the following general formula (AP-1) to general formula (AP-7), and is represented by the following general formula (AP-1) or general formula (AP-2). Group represented by formula (AP-1) is more preferable.

Sp ^AP1 is preferably a single bond or a linear or branched alkylene group having 1 to 20 carbon atoms, and more preferably a single bond or a linear alkylene group having 1 to 20 carbon atoms. It is more preferable to represent a single bond or a linear alkylene group having 2 to 10 carbon atoms.

In Sp ^AP1 , one or two or more non-adjacent —CH ₂ — groups in the alkylene group are independently —CH═CH—, —C≡C—, —O—, —CO—, It may be substituted with —COO— or —OCO—.

In the alignment aid, the polymerizable group ^(P ^{AP1 -Sp} AP1 -) number of, preferably 1 to 5 or less, more preferably 1 to 4, further not less 2 to 4 Particularly preferred is 2 or 3, and most preferred is 2.

The hydrogen atom in P ^AP1- Sp ^AP1- may be substituted with a polymerizable group, an adsorptive group and / or an orientation-inducing group.

Polymerizable group ^(P ^{AP1 -Sp} AP1 -), the polymerizable group, mesogen group may be bonded to an adsorptive group and / or orientation-induced group.

The polymerizable group (P ^{AP1 -Sp AP1} ^-) is preferably binding to the mesogenic groups, the adsorption group or orientation-induced group, and more preferably binding to the mesogenic groups or adsorptive groups.

When there are a plurality of P ^AP1 and / or Sp ^AP1 − molecules in the molecule, they may be the same or different from each other.

"Mesogenic group"
The mesogen group means a group having a rigid portion, for example, a group having at least one cyclic group, preferably a group having 2 to 4 cyclic groups, and 3 to 4 cyclic groups. The groups provided are more preferred. In addition, if necessary, the cyclic group may be linked by a linking group. The mesogen group preferably has a skeleton similar to that of liquid crystal molecules (liquid crystal compound) used in the liquid crystal layer.

In the present specification, the “cyclic group” refers to an atomic group in which constituent atoms are cyclically bonded, and is a carbon ring, a heterocyclic ring, a saturated or unsaturated cyclic structure, a monocyclic or bicyclic structure, Including polycyclic structures, aromatic and non-aromatic.

Further, the cyclic group may contain at least one hetero atom, and may be further substituted with at least one substituent (halogeno group, polymerizable group, organic group (alkyl, alkoxy, aryl, etc.)). When the formula group has a single ring, the mesogenic group preferably contains two or more single rings.

The mesogen group is preferably represented, for example, by the general formula (AL).

In the formula, Z ^AL1 is a single bond, —CH ＝ CH—, —CF ＝ CF—, —C≡C—, —COO—, —OCO—, —OCOO—, —CF ₂ O—, —OCF ₂ — _{_{, -CH = CHCOO -, - OCOCH}} = CH -, - CH 2 -CH 2 COO -, - OCOCH 2 -CH 2 -, - CH = C (CH 3) COO -, - OCOC (CH 3) = CH- , —CH ₂ —CH (CH ₃ ) COO—, —OCOCH (CH ₃ ) —CH ₂ —, —OCH ₂ CH ₂ O—, or an alkylene group having 1 to 20 carbon atoms. However, one or two or more non-adjacent —CH ₂ — in the alkylene group may be substituted with —O—, —COO—, or —OCO—.

A ^AL1 and A ^AL2 each independently represent a divalent cyclic group.

One or more hydrogen atoms in Z ^AL1 , A ^AL1 and A ^AL2 may be independently substituted with a halogeno group, an adsorbing group, P ^AP1- Sp ^AP1 -or a monovalent organic group. ,
When a plurality of Z ^AL1 and A ^AL1 are present in the molecule, they may be the same or different from each other.

m ^AL1 represents an integer of 1 to 5.

In the general formula (AL), Z ^AL1 is preferably a single bond or an alkylene group having 2 to 20 carbon atoms, more preferably a single bond or an alkylene group having 2 to 10 carbon atoms, and a single bond is preferable. , — (CH ₂ ) ₂ — or — (CH ₂ ) ₄ —. One or two or more non-adjacent —CH ₂ — in the alkylene group may be substituted with —O—, —COO—, or —OCO—.

Furthermore, when it is intended to enhance the linearity of a rod-shaped molecule, Z ^AL1 is a single bond in which rings are directly connected to each other or an even number of atoms directly connecting the rings is even. The form is preferred. For example, in the case of —CH ₂ —CH ₂ COO—, the number of atoms directly connecting the rings is four.

In formula (AL), A ^AL1 and A ^AL2 each independently represent a divalent cyclic group. Examples of the divalent cyclic group include 1,4-phenylene group, 1,4-cyclohexylene group, 1,4-cyclohexenyl group, tetrahydropyran-2,5-diyl group, 1,3-dioxane-2, 5-diyl group, tetrahydrothiopyran-2,5-diyl group, thiophene-2,5-diyl group, 1,4-bicyclo (2.2.2) octylene group, decahydronaphthalene-2,6-diyl group , Pyridine-2,5-diyl group, pyrimidine-2,5-diyl group, pyrazine-2,5-diyl group, thiophene-2,5-diyl group-, 1,2,3,4-tetrahydronaphthalene-2 , 6-diyl group, 2,6-naphthylene group, phenanthrene-2,7-diyl group, 9,10-dihydrophenanthrene-2,7-diyl group, 1,2,3,4,4a, 9,10a- Octahydrofe Nentren-2,7-diyl group, 1,4-naphthylene group, benzo [1,2-b: 4,5-b '] dithiophen-2,6-diyl group, benzo [1,2-b: 4 5-b ′] diselenophen-2,6-diyl group, [1] benzothieno [3,2-b] thiophen-2,7-diyl group, [1] benzoselenopheno [3,2-b] selenophene-2 , 7-diyl group and fluorene-2,7-diyl group, preferably 1,4-phenylene group, 1,4-cyclohexylene group, 2,6-naphthylene group Alternatively, a phenanthrene-2,7-diyl group is more preferable, and a 1,4-phenylene group or 1,4-cyclohexylene group is more preferable.

These groups may be unsubstituted or substituted with a substituent. The substituent is preferably a fluorine atom or an alkyl group having 1 to 8 carbon atoms. Further, the alkyl group may be substituted with a fluorine atom or a hydroxyl group.

Further, one or more hydrogen atoms in the cyclic group may be substituted with a halogeno group, an adsorptive group, P ^AP1- Sp ^AP1 -or a monovalent organic group.

In the general formula (AL), the monovalent organic group is a group having a chemical structure formed by converting an organic compound into a monovalent group, and is obtained by removing one hydrogen atom from the organic compound. Refers to an atomic group.

Examples of such a monovalent organic group include an alkyl group having 1 to 15 carbon atoms, an alkenyl group having 2 to 15 carbon atoms, an alkoxy group having 1 to 14 carbon atoms, and an alkenyloxy group having 2 to 15 carbon atoms. And an alkyl group having 1 to 15 carbon atoms or an alkoxy group having 1 to 14 carbon atoms, 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, and more preferably an alkyl group having 1 to 3 carbon atoms or an alkyl group having 1 to 2 carbon atoms. An alkoxy group is particularly preferred, and an alkyl group having 1 or 2 carbon atoms or an alkoxy group having 1 carbon atom is most preferred.

Further, one or two or more non-adjacent —CH ₂ — in the above alkyl group, alkenyl group, alkoxy group and alkenyloxy group may be substituted with —O—, —COO— or —OCO—. Further, the monovalent organic group may have a role as an orientation inducing group described later.

In the general formula (AL), m ^AL1 is preferably an integer of 1 to 4, more preferably an integer of 1 to 3, and even more preferably 2 or 3.

The following formulas (me-1) to (me-44) are mentioned as preferable forms of the mesogen group.

The general formula (AL) is a structure in which two hydrogen atoms are eliminated from these compounds.

In these formulas (me-1) to (me-44), one or more hydrogen atoms in the cyclohexane ring, benzene ring or naphthalene ring are each independently a halogeno group, P ^AP1 -Sp ^AP1 -It may be substituted with a monovalent organic group (for example, an alkyl group having 1 to 15 carbon atoms, an alkoxy group having 1 to 14 carbon atoms), an adsorption group or an orientation inducing group.

Among the above mesogen groups, preferred forms are formulas (me-8) to (me-44), and more preferred forms are formulas (me-8) to (me-10) and formulas (me-12) to (Me-18), formulas (me-22) to (me-24), formulas (me-26) to (me-27) and formulas (me-29) to (me-44), and more preferable forms Are expressions (me-12), (me-15) to (me-16), (me-22) to (me-24), (me-29), (me-34), (me-36) To (me-37) and (me-42) to (me-44).

Among the above mesogen groups, a particularly preferred form is the following general formula (AL-1) or (AL-2), and a most preferred form is the following general formula (AL-1).

In the formula, X ^AL101 to X ^AL118 and X ^AL201 to X ^AL214 each independently represent a hydrogen atom, a halogeno group, P ^AP1- Sp ^AP1- , an adsorption group or an orientation-inducing group.

Ring ^{A AL11,} Ring ^{A AL12} and ring ^{A AL21} each independently represent a cyclohexane ring or a benzene ring.

Any one type or two or more types of X ^AL101 to X ^AL118 and X ^AL201 to X ^AL214 are substituted with an adsorption group.

Any one type or two or more types of X ^AL101 to X ^AL118 and X ^AL201 to X ^AL214 are substituted with an orientation-inducing group.

Adsorptive group and orientation derivative ^groups, P ^{AP1 -Sp} AP1 - may be substituted with.

The general formula (AL-1) or the general formula (AL-2) has one or more kinds of P ^AP1 -Sp ^APl- in its molecule.

In formula (AL-1), X ^AL101 is preferably an orientation-inducing group.

In the general formula (AL-1), at least one of X ^AL109 , X ^AL110 and X ^AL111 is preferably an adsorption group, and both X ^AL109 and X ^AL110 are adsorption groups or X ^AL110 is an adsorption group. Is more preferable, and X ^AL110 is even more preferably an adsorptive group.

In the general formula (AL-1), it is preferable that at least one of X ^AL109 , X ^AL110 and X ^AL111 is P ^AP1 —Sp ^AP1 − or an adsorption group having a polymerizable site in the structure, and X ^AL109 and X ^AL111 more preferably - one or both of ^P AP1 ^{-Sp AP1.}

In the general formula (AL-1), one or two of X ^AL104 to X ^AL108 and X ^AL112 to X ^AL116 are independently an alkyl group having 1 to 5 carbon atoms, or an alkoxy group having 1 to 5 carbon atoms. Alternatively, it is preferably a halogeno group, and more preferably an alkyl group having 1 to 3 carbon atoms or a fluorine atom. In particular, it is preferable that X ^AL105 , X ^{AL106, and} X ^AL107 are each independently an alkyl group having 1 to 3 carbon atoms or a fluorine atom.

In formula (AL-2), X ^AL201 is preferably an orientation-inducing group.

In formula (AL-2), at least one of X ^AL207 , X ^AL208 and X ^AL209 is preferably an adsorptive group, and both X ^AL207 and X ^AL208 are adsorptive groups or X ^AL208 is an adsorptive group. Is more preferable, and X ^AL208 is even more preferably an adsorptive group.

In the general formula (AL-2), at least one of X ^AL207 , X ^AL208 and X ^AL209 is preferably P ^AP1 -Sp ^AP1 -or an adsorbing group having a polymerizable site in the structure, and X ^AL207 and X ^AL209 more preferably - one or both of ^P AP1 ^{-Sp AP1.}

In formula (AL-2), one or two of X ^AL202 to X ^AL206 and X ^AL210 to X ^AL214 are independently an alkyl group having 1 to 5 carbon atoms or an alkoxy group having 1 to 5 carbon atoms. Alternatively, it is preferably a halogeno group, and more preferably an alkyl group having 1 to 3 carbon atoms or a fluorine atom. In ^particular, ^{X AL204,} X ^AL205 or ^{X AL206} are each independently preferably an alkyl group or a fluorine atom of 1 to 3 carbon atoms.

"Adsorption group"
The adsorptive group is a group having a role of adsorbing an adsorbent which is a layer that comes into contact with the liquid crystal composition such as a substrate, a film and an electrode.

Adsorption is generally classified into chemisorption in which a chemical bond (covalent bond, ionic bond, or metal bond) is created and adsorbed between an adsorbent and an adsorbate, and physical adsorption other than chemisorption. In the present specification, the adsorption may be either chemical adsorption or physical adsorption, but physical adsorption is preferable. Therefore, the adsorbing group is preferably a group capable of physically adsorbing to the adsorbent, and more preferably a group capable of bonding to the adsorbent by intermolecular force.

(4) Examples of the form of bonding with an adsorbent by an intermolecular force include forms by interaction such as permanent dipole, permanent quadrupole, dispersion force, charge transfer force, and hydrogen bond.

好ましい A preferred form of the adsorptive group is a form that can be bonded to the adsorbent by hydrogen bonding. In this case, the adsorptive group may serve as either a donor or an acceptor of a proton via a hydrogen bond, or may serve as both.

The adsorbing group is preferably a group including a polar element having an atomic group in which a carbon atom and a hetero atom are linked (hereinafter, the “adsorbing group” is also referred to as a “polar group”). In the present specification, a polar element refers to an atomic group in which a carbon atom and a hetero atom are directly connected.

The heteroatom is preferably at least one selected from the group consisting of N, O, S, P, B and Si, and is at least one selected from the group consisting of N, O and S Is more preferable, at least one selected from the group consisting of N and O is more preferable, and O is particularly preferable.

In addition, in the alignment assistant, the valence of the polar element is not particularly limited, such as monovalent, divalent, or trivalent, and the number of polar elements in the adsorptive group is not particularly limited.

The orientation aid preferably has 1 to 8 adsorption groups in one molecule, more preferably 1 to 4 adsorption groups, and further preferably 1 to 3 adsorption groups.

Incidentally, the adsorption group, excluding a polymerizable group and orientation induced group, a hydrogen atom is ^P AP1 ^{-Sp AP1} in adsorptive group - substituted with structural and ^P AP1 ^{-Sp AP1} - hydrogen atoms in the -OH The structure substituted with is included in the adsorption group.

Adsorption group contains one or more polar elements and is roughly classified into cyclic group type and chain type.

The cyclic base type is a form including a cyclic group having a cyclic structure containing a polar element in its structure, and the chain base form is a cyclic group having a cyclic structure containing a polar element in its structure. Is not included.

The -chain type is a form having a polar element in a linear or branched chain group, and may have a cyclic structure containing no polar element in a part thereof.

A cyclic group-type adsorptive group means a form having a structure containing at least one polar element in a cyclic atomic arrangement.

In the present specification, the cyclic group is as described above. Therefore, the cyclic group type adsorptive group only needs to contain a cyclic group containing a polar element, and the entire adsorptive group may be branched or linear.

On the other hand, a chain-type adsorptive group refers to a structure in which a molecule does not include a cyclic atomic arrangement including a polar element, and includes at least one polar element in a linear atomic arrangement (which may be branched). Means a form having

In the present specification, a chain group refers to an atomic group in which a structural atom does not include a cyclic atom arrangement, and constituent atoms are linearly (may be branched), and an acyclic group. Group. In other words, the chain group refers to a linear or branched aliphatic group, and may contain either a saturated bond or an unsaturated bond.

鎖 Thus, open-chain groups include, for example, alkyl, alkenyl, alkoxy, ester, ether or ketone. Note that the hydrogen atom in these groups may be substituted with at least one substituent (a reactive functional group (such as a vinyl group, an acryl group, or a methacryl group) or a chain organic group (such as an alkyl group or a cyano group)). . The chain group may be linear or branched.

The cyclic group type adsorptive group may be a heteroaromatic group having 3 to 20 carbon atoms (including a condensed ring) or a heteroalicyclic group having 3 to 20 carbon atoms (including a condensed ring). More preferably, it is a heteroaromatic group having 3 to 12 carbon atoms (including a condensed ring) or a heteroalicyclic group having 3 to 12 carbon atoms (including a condensed ring), more preferably a 5-membered heterocyclic group. More preferably, they are an aromatic group, a 5-membered heteroalicyclic group, a 6-membered heteroaromatic group, or a 6-membered heteroalicyclic group. The hydrogen atom in these ring structures may be substituted with a halogeno group, a linear or branched alkyl group having 1 to 5 carbon atoms or an alkyloxy group.

The chain type adsorptive group is preferably a linear or branched alkyl group having 1 to 20 carbon atoms in which a hydrogen atom or —CH ₂ — in the structure is substituted with a polar element. One or two or more non-adjacent —CH ₂ — groups in the alkyl group are —CH═CH—, —C≡C—, —O—, —CO—, —COO—, —OCO— or —. It may be substituted with OCO-COO-. In addition, the chain-type adsorptive group preferably contains one or more polar elements at the end thereof.

水素 The hydrogen atom in the adsorptive group may be replaced by a polymerizable group.

Specific examples of the polar element include a polar element containing an oxygen atom (hereinafter, oxygen-containing polar element), a polar element containing a nitrogen atom (hereinafter, nitrogen-containing polar element), and a polar element containing a phosphorus atom (hereinafter, phosphorus-containing polarity). Element), a polar element containing a boron atom (hereinafter, a boron-containing polar element), a polar element containing a silicon atom (hereinafter, a silicon-containing polar element), or a polar element containing a sulfur atom (hereinafter, a sulfur-containing polar element). . From the viewpoint of the adsorption ability, the polar element is preferably a nitrogen-containing polar element, a nitrogen-containing polar element, or an oxygen-containing polar element, and more preferably an oxygen-containing polar element.

As the oxygen-containing polar element, at least one group selected from the group consisting of a hydroxyl group, an alkylol group, an alkoxy group, a formyl group, a carboxyl group, an ether group, a carbonyl group, a carbonate group and an ester group, It is preferably a group linked to an atom.

Examples of the nitrogen-containing polar element include at least one group selected from the group consisting of a cyano group, a primary amino group, a secondary amino group, a tertiary amino group, a pyridyl group, a carbamoyl group, and a ureido group, It is preferably a group linked to an atom.

リン The phosphorus-containing polar element is preferably at least one group selected from the group consisting of a phosphinyl group and a phosphate group or a group in which the group is linked to a carbon atom.

Therefore, as the adsorptive group, a cyclic group having an oxygen-containing polar element (hereinafter, oxygen-containing cyclic group), a cyclic group having a nitrogen-containing polar element (hereinafter, nitrogen-containing cyclic group), a sulfur-containing polar group Cyclic group with an element (hereinafter, sulfur-containing cyclic group), a chain group with an oxygen-containing polar element (hereinafter, oxygen-containing chain group), and a chain group with a nitrogen-containing polar element (hereinafter, One or more groups selected from the group consisting of a nitrogen-containing chain group) or the group itself, and it is preferable to contain the group. From the viewpoint of adsorption ability, an oxygen-containing cyclic group, a sulfur-containing cyclic group, and oxygen-containing More preferably, it contains one or more groups selected from the group consisting of a chain type group and a nitrogen-containing chain type group.

The oxygen-containing cyclic group preferably contains any of the following groups having an oxygen atom as an ether group in the ring structure.

The oxygen-containing cyclic group preferably includes any of the following groups having an oxygen atom as a carbonyl group, a carbonate group, or an ester group in the ring structure.

窒素 The nitrogen-containing cyclic group preferably contains any of the following groups.

酸素 The oxygen-containing group preferably contains any of the following groups.

In the formula, R ^at1 represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms.

Z ^at1 represents a single bond, a linear or branched alkylene group having 1 to 15 carbon atoms, or a linear or branched alkenylene group having 2 to 18 carbon atoms. However, —CH ₂ — in the alkylene group or alkenylene group may be substituted with —O—, —COO—, —C (═O) —, or —OCO— so that oxygen atoms are not directly adjacent to each other.

X ^at1 represents an alkyl group having 1 to 15 carbon atoms. However, —CH ₂ — in the alkyl group may be substituted with —O—, —COO—, —C (＝ O) —, or —OCO— so that the oxygen atom is not directly adjacent.

窒素 The nitrogen-containing chain-type group preferably contains any of the following groups.

In the formula, R ^at , R ^bt , R ^ct and R ^dt each independently represent a hydrogen atom or an alkyl group having 1 to 5 carbon atoms.

The adsorbing group is preferably a group represented by the following general formula (AT).

In the formula, Sp ^AT1 represents a single bond or a linear or branched alkylene group having 1 to 25 carbon atoms. However, the hydrogen atom in the alkylene group may be substituted with —OH, —CN, —W ^AT1 —Z ^AT1 or P ^AP1 —Sp ^AP1 —, and —CH ₂ — in the alkylene group is directly bonded to the oxygen atom. It may be substituted with a cyclic group, -O-, -COO-, -C (= O)-, -OCO-, -CH = CH- or -OCO-COO- so as not to bond.

W ^AT1 represents a single bond or the following general formula (WAT1) or (WAT2).

Z ^AT1 represents a monovalent group containing a polar element. However, the hydrogen atom in Z ^AT1 may be replaced with —OH, —CN, —Sp ^AT1 —W ^AT1 —Z ^AT1 or P ^AP1 —Sp ^AP1 —.

(In the formula, Sp ^WAT1 and Sp ^WAT2 each independently represent a single bond or a linear or branched alkylene group having 1 to 25 carbon atoms, and the hydrogen atom in the alkylene group is —OH, — CN, —Sp ^AT1 —W ^AT1 —Z ^AT1 or P ^AP1 —Sp ^AP1 — may be substituted, and —CH ₂ — in the alkylene group is a cyclic group, —O— so that an oxygen atom is not directly bonded. , -COO-, -C (= O)-, -OCO- or -CH = CH-.)
It is preferable that Sp ^AT1 , Sp ^WAT1 and Sp ^WAT2 each independently represent a single bond or a linear or branched alkylene group having 1 to 20 carbon atoms, and a single bond or a linear carbon atom number. It is more preferable to represent an alkylene group having 1 to 20 carbon atoms, and it is more preferable to represent a single bond or a linear alkylene group having 2 to 10 carbon atoms.

Further, in Sp ^AT1 , Sp ^WAT1 and Sp ^WAT2 , one or two or more non-adjacent —CH ₂ — in the alkylene group are independently —CH═CH so that an oxygen atom is not directly bonded. It may be substituted with-, -C≡C-, -O-, -CO-, -COO- or -OCO-.

In addition, the hydrogen atoms in Sp ^AT1 and Sp ^WAT1 may be independently substituted with —Sp ^AT1 —W ^AT1 —Z ^AT1 or P ^AP1 —Sp ^AP1 —.

Z ^AT1 represents a monovalent group containing a polar element and is preferably a group represented by the following general formula (ZAT1-1) or (ZAT1-2).

In the formula, Sp ^ZAT11 and Sp ^ZAT12 each independently represent a linear or branched alkylene group having 1 to 25 carbon atoms. However, the hydrogen atom in the alkylene group may be substituted with —OH, —CN, —Sp ^AT1 —W ^AT1 —Z ^AT1 or P ^AP1 —Sp ^AP1 —, and —CH ₂ — in the alkylene group is oxygen. It may be substituted with a cyclic group, —O—, —COO—, —C (═O) —, —OCO— or —CH═CH— so that the atoms are not directly adjacent.

Z ^ZAT11 represents a group containing a polar element.

The structure represented by the ring containing Z ^ZAT12 in the general formula (ZAT1-2) represents a 5- to 7-membered ring.

The hydrogen atom in Z ^ZAT11 and Z ^ZAT12 may be substituted with —OH, —CN, —Sp ^AT1 —W ^AT1 —Z ^AT1 or P ^AP1 —Sp ^AP1 —.

R ^ZAT11 and R ^ZAT12 each independently represent a linear or branched alkyl group having 1 to 8 carbon atoms. However, the hydrogen atom in the alkyl group may be replaced by —OH, —CN, —Sp ^AT1 —W ^AT1 —Z ^AT1 or P ^AP1 —Sp ^AP1 —, and —CH ₂ — in the alkyl group is oxygen. It may be substituted with a cyclic group, —O—, —COO—, —C (═O) —, —OCO— or —CH═CH— so that the atoms are not directly bonded.

The group represented by the general formula (ZAT1-1) is preferably a group represented by the following general formulas (ZAT1-1-1) to (ZAT1-1-30).

In the formula, the hydrogen atom bonded to the carbon atom may be substituted with —OH, —CN, —Sp ^AT1 —W ^AT1 —Z ^AT1 or P ^AP1 —Sp ^AP1 —.

Sp ^ZAT11 represents a linear or branched alkylene group having 1 to 25 carbon atoms. However, the hydrogen atom in the alkylene group may be substituted with —OH, —CN, —Sp ^AT1 —W ^AT1 —Z ^AT1 or P ^AP1 —Sp ^AP1 —, and —CH ₂ — in the alkylene group is oxygen. It may be substituted with a cyclic group, —O—, —COO—, —C (═O) —, —OCO— or —CH═CH— so that the atoms are not directly adjacent.

R ^ZAT11 represents a linear or branched alkyl group having 1 to 8 carbon atoms. However, the hydrogen atom in the alkyl group may be replaced by —OH, —CN, —Sp ^AT1 —W ^AT1 —Z ^AT1 or P ^AP1 —Sp ^AP1 —, and —CH ₂ — in the alkyl group is oxygen. It may be substituted with a cyclic group, —O—, —COO—, —C (═O) —, —OCO— or —CH═CH— so that the atoms are not directly bonded.

The group represented by the general formula (ZAT1-2) is preferably a group represented by the following general formulas (ZAT1-2-1) to (ZAT1-2-9).

In the formula, the hydrogen atom bonded to the carbon atom may be substituted with a halogen atom, —OH, —CN, —Sp ^AT1 —W ^AT1 —Z ^AT1 or P ^AP1 —Sp ^AP1 —.

Examples of the group represented by the general formula (ZAT1-1) include the following groups.

In the formula, R ^tc represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, or P ^AP1 —Sp ^AP1 —. However, the hydrogen atom in the alkyl group may be replaced by —OH, —CN, —Sp ^AT1 —W ^AT1 —Z ^AT1 or P ^AP1 —Sp ^AP1 —, and —CH ₂ — in the alkyl group is oxygen. It may be substituted with a cyclic group, —O—, —COO—, —C (═O) —, —OCO— or —CH═CH— so that the atoms are not directly adjacent.

Hydrogen atoms in the ^molecule, P ^{AP1 -Sp} AP1 - may be substituted with.

* Represents a bond.

The orientation aid is preferably in a form in which the polar element contained in the adsorptive group or the polar element contained in the polymerizable group is localized. The adsorptive group is an important structure for vertically aligning liquid crystal molecules, and when the adsorptive group and the polymerizable group are adjacent to each other, a better alignment property can be obtained, and a favorable liquid crystal composition can be obtained. Shows solubility.

Specifically, the orientation aid preferably has a form having a polymerizable group and an adsorptive group on the same ring of the mesogen group. In such a form, one or more polymerizable groups and one or more adsorbing groups are respectively bonded on the same ring, and at least one of the one or more polymerizable groups or at least one of the one or more adsorbing groups. Of these, a form in which one is bonded to the other and has a polymerizable group and an adsorptive group on the same ring is included.

Further, in this case, a hydrogen atom in the spacer group of the polymerizable group may be replaced with an adsorptive group, and further, a hydrogen atom in the adsorptive group may be replaced with a polymerizable group through the spacer group. Good.

The orientation aid is preferably a compound represented by the following general formula (SAL).

In the formula, the hydrogen atom bonded to the carbon atom is a linear or branched alkyl group having 1 to 25 carbon atoms, —OH, —CN, —Sp ^AT1 —W ^AT1 —Z ^AT1 or P ^AP1 —Sp ^AP1. It may be replaced with-. However, the hydrogen atom in the alkyl group may be replaced by —OH, —CN, —Sp ^AT1 —W ^AT1 —Z ^AT1 or P ^AP1 —Sp ^AP1 —, and —CH ₂ — in the alkyl group is oxygen. It may be substituted with a cyclic group, —O—, —COO—, —C (═O) —, —OCO— or —CH═CH— so that the atoms are not directly bonded.

R ^AK1 has the same meaning as R ^AK1 in formula (AK).

A ^AL1 and A ^AL2 each independently have the same meaning as A ^AL1 and A ^AL2 in formula (AL).

Z ^AL1 has the same meaning as Z ^AL1 in formula (AL).

m ^AL1 has the same meaning as m ^AL1 in formula (AL).

Sp ^AT1 has the same meaning as Sp ^AT1 in formula (AT).

W ^AT1 has the same meaning as W ^AT1 in formula (AT).

Z ^AT1 has the same meaning as Z ^AT1 in formula (AT).

The compound represented by the general formula (SAL) is preferably a compound represented by the following formulas (SAL-1.1) to (SAL-2.9).

The amount of the alignment aid contained in the liquid crystal composition is preferably about 0.01 to 50% by mass. The more preferable lower limit values thereof are 0.05% by mass and 0.1% by mass from the viewpoint of aligning the liquid crystal molecules more preferably. On the other hand, the more preferable upper limit values thereof are 30% by mass, 10% by mass, 7% by mass, 5% by mass, 4% by mass and 3% by mass from the viewpoint of improving response characteristics.

A compound represented by the general formula (i), a compound represented by the general formula (SAL) (that is, an alignment aid which is a compound containing an adsorption group Z ^AT1 ) and a compound represented by the general formula (P) The total content of the liquid crystal composition is preferably 0.05 to 10% by mass, preferably 0.1 to 8% by mass, and 0.1 to 5% by mass. Preferably, it is 0.1 to 3% by mass, preferably 0.2 to 2% by mass, more preferably 0.2 to 1.3% by mass, and 0.2 to 1% by mass. And preferably 0.2 to 0.56% by mass.

The polymerizable liquid crystal composition of the present invention contains a compound represented by the general formula (i) as a polymerizable compound, and further contains a compound represented by the general formula (SAL) (that is, contains an adsorption group Z ^AT1) . It is preferable to contain a compound represented by the formula (P) and an alignment aid which is a compound.

Here, the compound represented by the general formula (SAL), which is an alignment aid, has a function of aligning the liquid crystal compound in the liquid phase composition substantially perpendicularly to the substrate, and is represented by the general formula (i). The compound represented and the compound represented by the general formula (P) are used for stabilizing the alignment in which the liquid crystal compound is tilted in a certain direction with respect to the substrate in the state where no voltage is applied. Stabilization of the tilt of the liquid crystal compound with respect to the substrate can be achieved to a certain extent by using only the compound represented by the general formula (P), but the compound represented by the general formula (i) is used. As a result, the problem to be solved by the present application can be achieved.

A compound represented by the general formula (i), a compound represented by the general formula (SAL) (that is, an alignment aid which is a compound containing an adsorption group Z ^AT1 ) and a compound represented by the general formula (P) The preferred lower limit of the total content is 0.01% by mass, 0.03% by mass, 0.05% by mass, 0.08% by mass, and 0% by mass with respect to the liquid crystal composition. 0.1% by mass, 0.15% by mass, 0.2% by mass, 0.25% by mass, and 0.3% by mass.

A preferable upper limit value of the total content of the compound represented by the general formula (SAL) and the compound represented by the general formula (P) is 10% by mass, and 8% by mass with respect to the liquid crystal composition. Yes, 5% by mass, 3% by mass, 1.5% by mass, 1.2% by mass, 1% by mass, 0.8% by mass, 0.5% by mass is there.

A compound represented by the general formula (i), a compound represented by the general formula (SAL) (that is, an alignment aid which is a compound containing an adsorption group Z ^AT1 ) and a compound represented by the general formula (P) When the total content is small, the effect of adding these compounds to the liquid crystal composition is difficult to appear, and for example, depending on the type of liquid crystal molecules, the alignment regulating force of the liquid crystal molecules becomes weak or becomes weak over time. May occur. On the other hand, if the total content of the compound represented by the general formula (SAL) and the compound represented by the general formula (P) is too large, the compound may remain after curing depending on, for example, the illuminance of active energy rays. In some cases, problems such as an increase in the amount to be applied, a long time for curing, and a decrease in reliability of the liquid crystal composition may occur. Therefore, it is preferable to set the contents of these in consideration of these balances.

The liquid crystal composition of the present invention contains a compound selected from the group consisting of compounds represented by general formulas (N-01), (N-02), (N-03), (N-04) and (N-05). It is preferable to contain one kind or two or more kinds. These compounds correspond to compounds having a negative dielectric anisotropy. The “compound having negative dielectric anisotropy” refers to a compound having a negative Δε sign and an absolute value larger than 2. In addition, 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 a composition that is dielectrically almost neutral at 25 ° C.

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

In the formula, R ²¹ and R ²² each independently represent an alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, an alkenyl group having 2 to 8 carbon atoms, or 2 carbon atoms. 8 represents an alkenyloxy group, and one or two or more non-adjacent —CH ₂ — groups in each group independently represent —CH═CH—, —C≡C—, —O—, —CO. It may be substituted with —, —COO— or —OCO—, and each Z ¹ independently represents a single bond, —CH ₂ CH ₂ —, —OCH ₂ —, —CH ₂ O—, —COO—. , —OCO—, —OCF ₂ —, —CF ₂ O—, —CH═CH—, —CF═CF— or —C≡C—, and m independently represents 1 or 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 further preferably an alkyl group having 1 to 4 carbon atoms. However, when Z ¹ is 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, more preferably an alkyl group having 1 to 5 carbon atoms or an alkoxy group having 1 to 4 carbon atoms. Of these, 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)

(A black dot in each formula represents a carbon atom in the ring structure.), And a formula (R1) or a formula (R2) is more preferable. However, the content of the compound in which R ²¹ and R ²² are alkenyl groups is preferably as small as possible, and preferably not contained.

Z ^{1 s} are each independently a single bond, —CH ₂ CH ₂ —, —OCH ₂ —, —CH ₂ O—, —COO—, —OCO—, —OCF ₂ —, —CF ₂ O—, — Represents CH = CH-, -CF = CF- or -C≡C-, preferably a single bond, -CH ₂ CH _2- , -OCH _2- , -CH ₂ O-, a single bond or -CH ₂ O -Is more preferable.

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

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

The fluorine atom of the compounds represented by the general formulas (N-01), (N-02), (N-03), (N-04) and (N-05) is replaced with a chlorine atom of the same halogen group. It may be done. However, the content of the compound substituted with a chlorine atom is preferably as small as possible, and is preferably not contained.

The hydrogen atom present on the ring of the compound represented by formula (N-01), (N-02), (N-03), (N-04) or (N-05) is a fluorine atom or chlorine. Although it may be substituted with an atom, a chlorine atom is not preferred.

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

(In the formula, R ²¹ and R ²² have the same meanings as described above.)
The compound represented by the general formula (N-06) is effective for adjusting various physical properties, but should be used for obtaining a large refractive index anisotropy (Δn), a high T _NI , and a large Δε. You can

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

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

^{^{^{^{(Wherein, R NU11, R NU12, R}}}} NU21, R NU22, R NU31, R NU32, R NU41, R NU42, R NU51, R NU52, R NU61, R NU62, R NU71, R NU72, R NU81 and R ^NU82 each independently represents an alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, an alkenyl group having 2 to 8 carbon atoms or an alkenyloxy group having 2 to 8 carbon atoms. , One or two or more non-adjacent —CH ₂ — groups in the group are each independently —CH═CH—, —C≡C—, —O—, —CO—, —COO— or —OCO. It may be substituted by-) and contains one or more compounds selected from the group of compounds represented by

More ^{^{^{^{specifically, R NU11, R NU12, R}}}} NU21, R NU22, R NU31, R NU32, R NU41, R NU42, R NU51, R NU52, R NU61, R NU62, R NU71, R NU72, R NU81 and R ^NU82 is preferably an alkyl group having 1 to 5 carbon atoms or an alkoxy group having 1 to 5 carbon atoms, and more preferably an alkyl group having 1 to 5 carbon atoms. When importance is attached to the response speed, at least one R ^NU11 , R ^NU21 , R ^NU41 and R ^NU51 is preferably an alkenyl group having 2 to 3 carbon atoms, and is an alkenyl represented by the formula (R2). Groups are preferred.

The compound having an alkenyl group is preferably 30% or less, more preferably 25% or less, preferably 20% or less, preferably 15% or less, and 10% or less with respect to the total amount of the liquid crystal composition of the present invention. % Or less is preferable. When importance is attached to high VHR, the compound having an alkenyl group is preferably 10% or less, preferably 5% or less, preferably 1% or less, and preferably not contained.

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

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

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

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

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

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

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

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

The liquid crystal composition of the present invention contains a compound represented by 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 of 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 of the present invention includes a compound represented by the general formula (NU-01), a compound represented by the general formula (NU-02), a compound represented by the general formula (NU-03) and a general formula (NU It is more preferable to contain a 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 further preferably 20 to 40% by mass. preferable.

The content of the compound represented by the general formula (NU-02) is preferably 1 to 40% by mass, more preferably 5 to 25% by mass, and further preferably 5 to 20% by mass. preferable.

The content of the compound represented by the general formula (NU-03) is preferably 1 to 20% by mass, more preferably 0 to 15% by mass, and further preferably 0 to 10% by mass. preferable.

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

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

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

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

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

The liquid crystal composition of the present invention may contain one kind or two or more kinds of compounds having positive dielectric anisotropy described in paragraphs 0236 to 0509 of Patent Document 4 (Patent No. 6233550).

It is preferable that the composition of the present invention 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 importance is placed on the reliability and long-term stability of the composition, the content of the compound having a carbonyl group is preferably 5% or less, and more preferably 3% or less with respect to the total mass of the composition. It is more preferably 1% or less, and most preferably substantially not contained.

When importance is attached to the stability by UV irradiation, the content of the compound in which the chlorine atom is substituted is preferably 15% or less, and more preferably 10% or less with respect to the total mass of the composition. % Or less, preferably 5% or less, more preferably 3% or less, and further preferably substantially not contained.

It is preferable to increase the content of the compound in which all the ring structures in the molecule are 6-membered rings, and the content of the compound in which all the ring structures in the molecule are 6-membered rings is 80 relative to the total mass of the composition. % Or more, more preferably 90% or more, still more preferably 95% or more, and the composition is composed of only compounds in which all the ring structures in the molecule are all 6-membered rings. Most preferably.

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

When importance is attached to the improvement of viscosity and the improvement of TNI, the content of the compound having a 2-methylbenzene-1,4-diyl group in which a hydrogen atom may be replaced by a halogen in the molecule may be reduced. It is preferable that the content of the compound having the 2-methylbenzene-1,4-diyl group in the molecule is 10% or less, and preferably 8% or less, based on the total mass of the composition. It is more preferably 5% or less, more preferably 3% or less, and further preferably substantially not contained.

In the present application, “substantially free of” means not including any substance that is unintentionally included.

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

The liquid crystal composition of the present invention preferably contains an antioxidant so that the liquid crystal composition does not polymerize in the heat treatment which is one of the manufacturing steps of the liquid crystal display element. When the antioxidant is not contained, the polymerization proceeds in the heat treatment before the UV irradiation step, and the desired orientation cannot be obtained.

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

In formulas (H-1) to (H-3), R ^H1's each independently represent an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, or 2 carbon atoms. Represents an alkenyl group having 1 to 10 carbon atoms or an alkenyloxy group having 2 to 10 carbon atoms. More specifically, R ^H1 is more preferably an alkyl group having 3 carbon atoms.

In the general formula (H-4), M ^H1 is an alkylene group having 4 to 10 carbon atoms (one or more —CH ₂ — in the alkylene group is O-, -CO-, -COO-, -OCO- may be substituted), -OCH _2- , -CH ₂ O-, -COO-, -OCO-, -CF ₂ O-,-. OCF ₂ —, —CF ₂ CF ₂ —, —CH═CH—COO—, —CH═CH—OCO—, —COO—CH═CH—, —OCO—CH═CH—, —CH═CH—, — C≡C-, a single bond, a 1,4-phenylene group (any hydrogen atom in the 1,4-phenylene group may be substituted with a fluorine atom) or a trans-1,4-cyclohexylene group is used. Represent

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

The liquid crystal composition of the present invention has a nematic phase-isotropic liquid phase transition temperature (T _NI ) of 60 ° C. to 120 ° C., more preferably 70 ° C. to 100 ° C., particularly preferably 70 ° C. to 85 ° C. In addition, in this invention, 60 degreeC or more is expressed as _TNI being high.

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 preferred.

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

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

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

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

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

The liquid crystal composition of the present invention can impart a sufficiently high polymerization rate and a sufficiently large pretilt angle. In addition, the liquid crystal display device using the liquid crystal composition of the present invention has a small residual amount of the polymerizable compound in the liquid crystal display device after the polymerization, and is a high-definition PSA type or PSVA type liquid crystal display device such as 4K or 8K. It is possible to prevent or significantly suppress display defects such as IS. From the above, the production efficiency of a 4K or 8K high-definition PSA type or PSVA type liquid crystal display device can be remarkably improved, and the industrial utility value is very high.
The liquid crystal composition of the present invention is suitable for producing a PSA type or PSVA type liquid crystal display element, and also suitable for producing an NPS type liquid crystal display element. Further, it is also suitable for producing a PI-less type liquid crystal display element characterized by not having an alignment film.

The liquid crystal composition of the present invention is also suitable for a liquid crystal display element having no alignment film, that is, a mode commonly referred to as PI-less. For example, the compounds having spontaneous orientation described in Japanese Patent Application No. 2013-552125, Japanese Patent Application No. 2014-517515, Japanese Patent Application No. 06081361, Japanese Patent Application No. 2015-546888, Japanese Patent Application No. 2017-12710, WO2017041893A, Japanese Patent No. 0607973, WO17 / 047177, etc. It is preferably used in combination with the liquid crystal composition of the invention.

The liquid crystal composition of the present invention is useful for a liquid crystal display device for driving an active matrix, and can be used for liquid crystal display devices such as PSA, PSVA, PS-IPS, PS-FFS, and NPS.

The liquid crystal display element of the present invention includes a first substrate and a second substrate which are arranged to face each other, a common electrode provided on the first substrate or the second substrate, and the first substrate or the first substrate. It is preferable to have a pixel electrode provided on the second substrate and having a thin film transistor, and a liquid crystal layer containing a liquid crystal composition provided between the first substrate and the second substrate. If necessary, an alignment film for controlling the alignment direction of liquid crystal molecules may be provided on the facing surface side of at least one of the first substrate and / or the second substrate so as to come into contact with the liquid crystal layer. As the alignment film, a vertical alignment film, a horizontal alignment film, or the like can be appropriately selected according to the driving mode of the liquid crystal display element, and a rubbing alignment film (eg, polyimide) or a photo alignment film (decomposition type polyimide, etc.), etc. The well-known alignment film can be used. Further, a color filter may be appropriately provided on the first substrate or the second substrate, and a color filter can be provided on the pixel electrode or the common electrode.

The two substrates of the liquid crystal cell used in the liquid crystal display element of the present invention can be made of a transparent transparent material such as glass or plastic, and one of them may be an opaque material such as silicon. The transparent substrate having the 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. The method for producing a color filter by the pigment dispersion method will be described as an example. A curable colored composition for a color filter is applied on the transparent substrate, subjected to 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 manufactured. In addition, a pixel electrode provided with an active element such as a TFT, a thin film diode, a metal insulator and a metal specific resistance element may be provided on the substrate.

It is preferable to face the first substrate and the second substrate so that the common electrode and the pixel electrode layer are 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 light control layer to be 1 to 100 μm. 1.5 to 10 μm is more preferable, and when a polarizing plate is used, it is preferable to adjust the product of the refractive index anisotropy Δn of the liquid crystal and the cell thickness d so as to maximize the contrast. When there are two polarizing plates, the polarizing axis of each polarizing plate can be adjusted so that the viewing angle and contrast are improved. Further, a retardation film for widening the viewing angle can also be used. Examples of the spacer include glass particles, plastic particles, alumina particles, photoresist materials, and the like. Then, a sealing agent such as an epoxy thermosetting composition is screen-printed on the substrates with a liquid crystal injection port provided if necessary, the substrates are bonded together and heated to heat-cure the sealing agent.

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

As a method for polymerizing the polymerizable compound contained in the liquid crystal composition of the present invention, in order to obtain good alignment performance of the liquid crystal, it is desirable to polymerize at an appropriate polymerization rate, and therefore, the activity of an ultraviolet ray, an electron beam, etc. A method of polymerizing by irradiating an energy ray singly or in combination or sequentially is preferable. When ultraviolet rays are used, a polarized light source or a non-polarized light source may be used. Further, when the polymerization is carried out in a state where the 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. Moreover, after polymerizing only a specific part using a mask at the time of 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 is performed. It is also possible to use a means of polymerizing the polymer. In particular, when exposing to ultraviolet light, it is preferable to apply ultraviolet light while applying a DC electric field or an AC electric field to the liquid crystal composition. The applied alternating electric field is preferably an alternating current having a frequency of 1 Hz to 10 kHz, more preferably a frequency of 60 Hz to 10 kHz, and the voltage is selected depending on the desired pretilt angle of the liquid crystal display element. That is, the pretilt angle of the liquid crystal display element can be controlled by the applied voltage. In a PSA type or PSVA type liquid crystal display device, it is preferable to control the pretilt angle from 80 degrees to 89.9 degrees from the viewpoint of alignment stability and contrast.
In a PSA type or PSVA type liquid crystal display device, IS occurs if the polymerizable compound remains unpolymerized after the device is manufactured. The amount of the remaining polymerizable compound is preferably 100 ppm or less, more preferably 50 ppm or less, particularly preferably 20 ppm or less, particularly preferably the detection lower limit or less, or 0.

The temperature at the time of irradiation with active energy rays such as ultraviolet rays or electron rays used when polymerizing the polymerizable compound contained in the liquid crystal composition of the present invention is not particularly limited. For example, when the liquid crystal composition of the present invention is applied to a liquid crystal display device including a substrate having an alignment film, it is preferably within a temperature range in which the liquid crystal state of the liquid crystal composition is maintained. That is, it is preferable to polymerize at 15 to 50 ° C.

A metal halide lamp, a high-pressure mercury lamp, an ultra-high-pressure mercury lamp, or the like can be used as a lamp for generating ultraviolet rays, and an ultra-high-pressure UV lamp manufactured by USHIO and a fluorescent ultraviolet lamp manufactured by TOSHIBA are preferable. Further, as the wavelength of the ultraviolet rays to be irradiated, it is preferable to irradiate the ultraviolet rays in a wavelength range other than the absorption wavelength range of the liquid crystal composition, and it is preferable to use the ultraviolet rays after cutting the ultraviolet rays if necessary. The intensity of ultraviolet rays to be applied is preferably 0.1 mW / cm ² to 100 W / cm ^{2, and} more preferably ² mW / cm ² to 50 W / cm ² . The amount of energy of the ultraviolet rays to be irradiated can be appropriately adjusted, but is preferably 10 mJ / cm ² to 500 J / cm ^{2, and} more preferably 100 mJ / cm ² to 200 J / cm ² .

The present invention will be described in more detail below with reference to examples, but the present invention is not limited to these examples. Moreover, "%" in the compositions of the following Examples and Comparative Examples means "mass%". The following abbreviations are used for describing the compounds in the examples.

(Side chain)
-N -C _n H _{2n + 1} linear carbon number n alkyl group n- C _n H _{2n + 1} - carbon number n linear alkyl group -On -OC _n H _{2n + 1} with carbon number n straight chain alkoxy Group nO- C _n H _{2n + 1} O- Linear alkoxy group having a carbon number of -V -CH = CH ₂
V- CH ₂ = CH-
-V- -CH = CH-
-O1V -O-CH ₂ -V
-V1 -CH = CH-CH ₃
1V- CH ₃ -CH = CH-
_{_{-2V -CH 2 -CH 2 -CH = CH}} 2
V2-CH ₂ = CH-CH ₂ -CH _2-
-2V1 -CH ₂ -CH ₂ -CH = CH-CH ₃
1V2- CH ₃ -CH = CH-CH ₂ -CH _2-
-F -F
-OCF3 -OCF ₃
(Linking group)
-CF2O- -CF ₂ -O-
-OCF2- -O-CF ₂ -
-1O- -CH ₂ -O-
-O1- -O-CH ₂ -
-COO- -COO-
-OCO- -OCO-
(Ring structure)

The characteristics measured in the 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 anisotropy at 20 ° C. K ₃₃ : elastic constant at 20 ° C. K ₃₃ (pN)
(Manufacturing method and evaluation method of liquid crystal display element)
(Evaluation of pretilt angle change amount)
First, the pretilt angle of the liquid crystal display element was measured and used as the pretilt angle (initial).

Next, while applying a rectangular voltage of 30 V at a frequency of 100 Hz to the liquid crystal display element, light was continuously emitted from the backlight for 10 hours. Then, the pretilt angle was measured and used as the pretilt angle (after the test).

The value obtained by subtracting the pretilt angle (after the test) from the measured pretilt angle (initial) was taken as the pretilt angle change amount (= absolute value of pretilt angle change) [°].

Note that the pretilt angle was measured using a pretilt angle measuring system (“OPTIPRO” manufactured by Shintech Co., Ltd.). Moreover, the magnitude of the applied voltage (30 V) is several times larger than the normal drive voltage, and this evaluation test is an acceleration test.

The closer the pretilt angle change amount is to 0 [°], the lower the possibility of display failure due to the change of the pretilt angle.

In this evaluation, the variation amount of 0.3 [°] was set as the allowable limit range of display defects.
(Evaluation of residual monomer amount)
First, a liquid crystal composition containing a polymerizable compound was injected by a vacuum injection method into a liquid crystal cell having a cell gap of 3.5 μm and including a substrate with ITO that was coated with a polyimide alignment film that induces vertical alignment and rubbed.

Then, the liquid crystal cell containing the polymerizable compound was injected into the liquid crystal cell using a fluorescent UV lamp so that the illuminance measured under the condition of the central wavelength of 365 nm was 3.5 mW / cm 2, and the ultraviolet light was 120%. A liquid crystal display element was obtained by irradiating for a minute (note that each characteristic value of the liquid crystal display element was evaluated using a liquid crystal display element prepared by a similar method).

Under the irradiation conditions described above, the residual amount [ppm] of the polymerizable compound in the liquid crystal display device after irradiation was measured. The method for measuring the residual amount of the polymerizable compound will be described. First, the liquid crystal display device was disassembled 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 high performance liquid chromatography to measure the peak area of each component. The amount of the remaining polymerizable compound was determined from the peak area ratio of the liquid crystal compound as an index and 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 10 ppm. In this evaluation, the residual amount of 100 ppm was set as the allowable limit range of display defects.
(Evaluation of voltage holding ratio)
First, a liquid crystal composition containing a polymerizable compound was injected by a vacuum injection method into a liquid crystal cell having a cell gap of 3.5 μm and including a substrate with ITO having no polyimide alignment film.
Next, after heating at 120 ° C. for 1 hour, a fluorescent UV lamp was used to adjust the illuminance measured under the condition of a central wavelength of 365 nm to be 3.5 mW / cm 2, and the liquid crystal display device was irradiated with ultraviolet rays for 120 minutes. Got The measurement conditions are 1 V, 0.6 Hz, and 60 ° C.
(Preparation of liquid crystal composition and evaluation results)
Liquid crystal compositions of LC-1 and LC-2 were prepared, and the physical properties thereof were measured. Table 1 shows the constitution of the liquid crystal composition and the results of its physical properties.

(Table 1)

(Comparative Examples 1 and 2, Examples 1 to 5)
To 100 parts by mass of the liquid crystal compositions (LC-1 and LC-2), each polymerizable compound was added by mass parts described below to prepare a polymerizable liquid crystal composition. Using the polymerizable liquid crystal composition, a liquid crystal display device was prepared by the above method, and each value was measured.

With respect to 100 parts by mass of the liquid crystal composition LC-1, 0.2 parts by mass of the compound represented by the formula (SAL-X1) and 0.4 parts by mass of the compound represented by the formula (SAL-X2), Comparative Example 1 was a liquid crystal composition containing a polymerizable compound to which 0.6 part by mass of the compound represented by the formula (RM-R1) was added.

With respect to 100 parts by mass of the liquid crystal composition LC-1, 0.2 parts by mass of the compound represented by the formula (SAL-X1) and 0.4 parts by mass of the compound represented by the formula (SAL-X2), Comparative Example 2 was a liquid crystal composition containing a polymerizable compound containing 0.6 part by mass of the compound represented by the formula (RM-R2).

With respect to 100 parts by mass of the liquid crystal composition LC-1, 0.2 parts by mass of the compound represented by the formula (SAL-X1) and 0.4 parts by mass of the compound represented by the formula (SAL-X2), Example 1 was a liquid crystal composition containing a polymerizable compound to which 0.6 part by mass of the compound represented by the formula (RM-11) was added.

With respect to 100 parts by mass of the liquid crystal composition LC-1, 0.2 parts by mass of the compound represented by the formula (SAL-X1) and 0.4 parts by mass of the compound represented by the formula (SAL-X2), Example 2 was a liquid crystal composition containing a polymerizable compound to which 0.6 part by mass of the compound represented by the formula (RM-3) was added.

With respect to 100 parts by mass of the liquid crystal composition LC-1, 0.2 parts by mass of the compound represented by the formula (SAL-X1) and 0.4 parts by mass of the compound represented by the formula (SAL-X2), Example 3 was a liquid crystal composition containing a polymerizable compound to which 0.6 part by mass of the compound represented by the formula (RM-4) was added.

With respect to 100 parts by mass of the liquid crystal composition LC-1, 0.2 parts by mass of the compound represented by the formula (SAL-X1) and 0.4 parts by mass of the compound represented by the formula (SAL-X2), Example 4 A liquid crystal composition containing a polymerizable compound containing 0.3 part by mass of the compound represented by the formula (RM-1) and 0.3 part by mass of the compound represented by the formula (RM-11) was prepared. And

With respect to 100 parts by mass of the liquid crystal composition LC-1, 0.2 parts by mass of the compound represented by the formula (SAL-X1) and 0.4 parts by mass of the compound represented by the formula (SAL-X2), Example 5 A liquid crystal composition containing a polymerizable compound obtained by adding 0.3 part by mass of the compound represented by the formula (RM-1) and 0.3 part by mass of the compound represented by the formula (RM-3) was used. And

The voltage holding ratio after ultraviolet irradiation, the amount of change in pretilt angle, and the residual amount of all polymerizable compounds in Comparative Examples 1 and 2 and Examples 1 to 5 are shown in Table 2 below.

It was found that the voltage holding ratios of Examples 1 to 3 which are liquid crystal compositions of the present invention clearly show higher values than those of Comparative Examples 1 and 2. As described above, by using the compound represented by the general formula (i), it is possible to prevent image sticking and the like.

Furthermore, it was found that the voltage holding ratios of Examples 4 and 5 were higher than those of Comparative Example 1.
As described above, it was found that even when a part of the polymerizable compound represented by the general formula (L) was replaced with the compound represented by the general formula (i), a high retention rate was exhibited.

It was found that the pretilt angle change amounts of Examples 1 to 5 were sufficiently small.

It was found that the residual amounts of the polymerized compounds of Examples 1 to 5 were also sufficiently small.
Further, even after the polymerizable liquid crystal compositions prepared in Examples 1 to 3 were stored at −20 ° C. for 240 hours, the nematic liquid crystal phase was retained, and precipitation of the polymerizable compound was not confirmed.

From the above, it can be confirmed that the liquid crystal composition of the present invention has a sufficiently high voltage holding ratio, is less likely to cause a display defect due to a change in the pretilt angle, and is free from deposition of a polymerizable compound.
(Comparative Examples 3 and 4, Examples 6 to 10)
With respect to 100 parts by mass of the liquid crystal composition LC-2, 0.4 parts by mass of the compound represented by the formula (SAL-X2) and 0.5 parts by mass of the compound represented by the formula (SAL-X3), Comparative Example 3 was a liquid crystal composition containing a polymerizable compound to which 0.6 part by mass of the compound represented by the formula (RM-R3) was added.

With respect to 100 parts by mass of the liquid crystal composition LC-2, 0.4 parts by mass of the compound represented by the formula (SAL-X2) and 0.5 parts by mass of the compound represented by the formula (SAL-X3), A liquid crystal composition containing a polymerizable compound containing 0.6 part by mass of the compound represented by the formula (RM-R3) was set as Comparative Example 4.

With respect to 100 parts by mass of the liquid crystal composition LC-2, 0.4 parts by mass of the compound represented by the formula (SAL-X2) and 0.5 parts by mass of the compound represented by the formula (SAL-X3), Example 6 was a liquid crystal composition containing a polymerizable compound to which 0.6 part by mass of the compound represented by the formula (RM-25) was added.

With respect to 100 parts by mass of the liquid crystal composition LC-2, 0.4 parts by mass of the compound represented by the formula (SAL-X2) and 0.5 parts by mass of the compound represented by the formula (SAL-X3), Example 7 was a liquid crystal composition containing a polymerizable compound to which 0.6 part by mass of the compound represented by the formula (RM-28) was added.

With respect to 100 parts by mass of the liquid crystal composition LC-2, 0.4 parts by mass of the compound represented by the formula (SAL-X2) and 0.5 parts by mass of the compound represented by the formula (SAL-X3), Example 8 was a liquid crystal composition containing a polymerizable compound to which 0.6 part by mass of the compound represented by the formula (RM-23) was added.

With respect to 100 parts by mass of the liquid crystal composition LC-2, 0.4 parts by mass of the compound represented by the formula (SAL-X2) and 0.5 parts by mass of the compound represented by the formula (SAL-X3), Example 9 was a liquid crystal composition containing a polymerizable compound to which 0.6 part by mass of the compound represented by the formula (RM-33) was added.

With respect to 100 parts by mass of the liquid crystal composition LC-2, 0.4 parts by mass of the compound represented by the formula (SAL-X2) and 0.5 parts by mass of the compound represented by the formula (SAL-X3), Example 10 A liquid crystal composition containing a polymerizable compound to which 0.3 part by mass of the compound represented by the formula (RM-25) and 0.3 part by mass of the compound represented by the formula (RM-28) were added. And

With respect to 100 parts by mass of the liquid crystal composition LC-2, 0.4 parts by mass of the compound represented by the formula (SAL-X2) and 0.5 parts by mass of the compound represented by the formula (SAL-X3), Example 11 A liquid crystal composition containing a polymerizable compound obtained by adding 0.3 part by mass of the compound represented by the formula (RM-25) and 0.3 part by mass of the compound represented by the formula (RM-23) was used. And

The voltage holding ratio after ultraviolet irradiation, the amount of change in pretilt angle, and the residual amount of all polymerizable compounds in Comparative Examples 3 and 4 and Examples 6 to 11 are as shown in the table.

It was found that the voltage holding ratios of Examples 6 to 9 which were the polymerizable liquid crystal compositions of the present invention clearly showed higher values than those of Comparative Examples 3 and 4. As described above, by using the compound represented by the general formula (i), display defects such as burn-in can be prevented.

It was found that the voltage holding ratios of Examples 10 and 11 were also higher than those of Comparative Examples 3 and 4.
Thus, it was found that even if two or more compounds represented by the general formula (i) were used, a high voltage holding ratio was exhibited.

It was found that the pretilt angle change amounts of Examples 6 to 11 were sufficiently small.

It was also found that the residual amount of the polymer compound of Examples 6 to 11 was sufficiently small.

Further, even after the polymerizable liquid crystal compositions prepared in Examples 6 to 11 were stored at −20 ° C. for 240 hours, the nematic liquid crystal phase was retained, and precipitation of the polymerizable compound was not confirmed.

From the above, by using the polymerizable liquid crystal composition of the present invention, a liquid crystal display device having a sufficiently high voltage holding ratio, hardly causing a display defect due to a change in the pretilt angle, and having no residual polymerizable compound can be obtained. I was able to confirm that.

Claims

A polymerizable liquid crystal composition containing a liquid crystal composition and one or more polymerizable compounds represented by formula (i).

(In the formula, X i1 , X i2 , X i3 , X i4 , X i5 , X i6 , X i7 , X i8 , X i9 , X i10 , X i11 and X i12 each independently have 1 carbon atom. Represents an alkyl group having from 1 to 18, an alkoxy group having from 1 to 18 carbon atoms, a halogen atom or a hydrogen atom,
At least two selected from X i1 to X i12 each independently represent an alkyl group having 1 to 18 carbon atoms, an alkoxy group having 1 to 18 carbon atoms, or a halogen atom,
P i1 and P i2 each independently represent one of the following formulas (RI) to (R-IX),

(In the formula, R 21 , R 31 , R 41 , R 51 and R 61 each independently represent a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and W is a single bond, —O— or methylene. Represents a group, T represents a single bond or —COO—, and p, t and q each independently represent 0, 1 or 2.)
Sp i1 and Sp i2 each independently represent a single bond or an alkylene group having 1 to 15 carbon atoms, and one or two or more —CH 2 — in the alkylene group are directly adjacent to an oxygen atom. May be substituted with -O-, -OCO- or -COO-,
n i1 represents 0, 1 or 2,
L i1 and L i2 are each independently a single bond, —OCH 2 —, —CH 2 O—, —C 2 H 4 —, —OC 2 H 4 O—, —COO—, —OCO—, —. CH = CR a -COO-, -CH = CR a -OCO-, -COO-CR a = CH-, -OCO-CR a = CH-,-(CH 2 ) z -COO-,-(CH 2 ) z —OCO—, —OCO— (CH 2 ) z —, —COO— (CH 2 ) z —, —CH═CH—, —CF 2 O—, —OCF 2 — or —C≡C— (wherein , R a represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and z represents an integer of 1 to 4),
When there are a plurality of X i5 , X i6 , X i7 , X i8 and / or L i2 , they may be the same or different. )
In the general formula (i), at least two selected from X i5 , X i6 , X i7 , X i8 , X i9 , X i10 , X i11 and X i12 each independently have 1 to 18 carbon atoms. 2. The polymerizable liquid crystal composition according to claim 1, which represents an alkyl group, an alkoxy group having 1 to 18 carbon atoms, or a halogen atom.
In the general formula (i), at least two selected from X i5 , X i6 , X i7 , X i8 , X i9 , X i10 , X i11 and X i12 each independently have 1 to 18 carbon atoms. 3. The polymerizable liquid crystal composition according to claim 1, which is an alkyl group or a halogen atom.
A polymerizable compound represented by the general formula (i),
4. The polymerizable liquid crystal according to claim 1, further comprising an alignment aid having a chemical structure different from that of the polymerizable compound represented by the general formula (i) and having an adsorption group. Composition.
In the general formula (i), n i1 is 0, and at least one selected from X i9 , X i10 , X i11 and X i12 is independently an alkyl group having 1 to 18 carbon atoms. The polymerizable liquid crystal composition according to any one of claims 1 to 4.
In the general formula (i), n i1 is 1 or 2, and at least one selected from X i5 , X i6 , X i7 , X i8 , X i9 , X i10 , X i11, and X i12 is each. The polymerizable liquid crystal composition according to any one of claims 1 to 4, which is independently an alkyl group having 1 to 18 carbon atoms.
In the general formula (i), n i1 is 0, and two selected from X i9 , X i10 , X i11 and X i12 are each independently an alkyl group having 1 to 3 carbon atoms or a halogen atom. The polymerizable liquid crystal composition according to any one of claims 1 to 4, which is
In the general formula (i), n i1 is 1 or 2, and two selected from X i5 , X i6 , X i7 and X i8 are each independently an alkyl group having 1 to 18 carbon atoms. 5. A halogen atom, or two selected from X i9 , X i10 , X i11 and X i12 are an alkyl group having 1 to 18 carbon atoms or a halogen atom. The polymerizable liquid crystal composition described.
The polymerizable liquid crystal composition according to any one of claims 1 to 4, wherein in the general formula (i), ni1 is 0 or 1.
The polymerizable liquid crystal composition according to any one of claims 1 to 9, wherein in the general formula (i), X i12 or X i11 is a hydrogen atom.
11. The polymerizable liquid crystal composition according to claim 1, wherein L i1 and L i2 in the general formula (i) are single bonds.
The polymerizable liquid crystal composition according to any one of claims 1 to 11, wherein the addition amount of the polymerizable compound represented by the general formula (i) is 0.20% by mass to 1.0% by mass.
The polymerizable liquid crystal according to any one of claims 1 to 12, containing one kind or two or more kinds of compounds selected from the group of compounds represented by formula (N-01) to formula (N-05). Composition.

(In the formula, R 21 and R 22 are each independently an alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, an alkenyl group having 2 to 8 carbon atoms, and 2 carbon atoms. To 8 alkenyloxy groups, wherein one or two or more non-adjacent —CH 2 — groups in the group are each independently —CH═CH—, —C≡C—, —O—, — It may be substituted with CO—, —COO— or —OCO—, and Z 1's are each independently a single bond, —CH 2 CH 2 —, —OCH 2 —, —CH 2 O—, —COO. Represents —, —OCO—, —OCF 2 —, —CF 2 O—, —CH═CH—, —CF═CF— or —C≡C—, and m independently represents 1 or 2. .)
The polymerizable liquid crystal according to any one of claims 1 to 13, which contains one kind or two or more kinds of compounds selected from the group of compounds represented by the general formula (NU-01) to the general formula (NU-08). Composition.

(Wherein, R NU11, R NU12, R NU21, R NU22, R NU31, R NU32, R NU41, R NU42, R NU51, R NU52, R NU61, R NU62, R NU71, R NU72, R NU81 and R NU82 each independently represents an alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, an alkenyl group having 2 to 8 carbon atoms or an alkenyloxy group having 2 to 8 carbon atoms. , One or two or more non-adjacent —CH 2 — groups in the group are each independently —CH═CH—, —C≡C—, —O—, —CO—, —COO— or —OCO. -May be replaced by.)
The alignment aid is a polymerizable group for polymerization, a mesogenic group similar to liquid crystal molecules, an adsorption group capable of interacting with a member in direct contact with the liquid crystal layer, and an alignment induction group for inducing alignment of the liquid crystal molecules. The polymerizable liquid crystal composition according to any one of claims 4 to 14, which is a compound having:
A liquid crystal display device using the polymerizable liquid crystal composition according to claim 1.
A liquid crystal display device for active matrix driving, comprising the polymerizable liquid crystal composition according to claim 1.
A liquid crystal display device for PSA mode, PSVA mode, PS-IPS mode or PS-FSS mode, which uses the polymerizable liquid crystal composition according to any one of claims 1 to 15.
The polymerizable liquid crystal composition according to any one of claims 1 to 15, which is used for a liquid crystal display device in which an alignment film is not provided on the surface of at least one of the pair of substrates.