JP2023004890A - Polymerizable compound-containing liquid crystal composition and liquid crystal display device including the same - Google Patents

Abstract

To provide a polymerizable compound-containing liquid crystal composition capable of providing a liquid crystal display device that has a small amount of residual monomer and is excellent in a voltage holding ratio (VHR), pretilt angle formation, and cryopreservation. and a liquid crystal display device including the same.SOLUTION: A polymerizable compound-containing liquid crystal composition contains at least one polymerizable compound represented by a general formula (i), at least one sensitizing compound and at least one liquid crystal compound. There is also provided a liquid crystal display device including the polymerizable compound-containing liquid crystal composition.SELECTED DRAWING: None

Description

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

Liquid crystal display elements are used in clocks, calculators, various measuring instruments, automobile panels, word processors, electronic notebooks, printers, computers, televisions, clocks, advertising display boards, and the like. Typical liquid crystal display methods include TN (twisted nematic) type, STN (super twisted nematic) type, vertical alignment type using TFT (thin film transistor) (vertical alignment; VA), and IPS. (in-plane switching) type, and the like. The liquid crystal composition used in these liquid crystal display elements must be stable against external factors such as moisture, air, heat, and light, and must exhibit a liquid crystal phase over as wide a temperature range as possible centering on room temperature. Viscosity and low driving voltage are required. The liquid crystal composition is composed of several to several tens of compounds in order to optimize the dielectric anisotropy (Δε) and refractive index anisotropy (Δn) for each liquid crystal display element. It is
A liquid crystal composition having a negative Δε is used in a VA type display, and is widely used in liquid crystal TVs and the like. Among them, the PSA (Polymer Support Alignment) mode is a mode in which a desired pretilt angle is given to vertically aligned liquid crystal molecules by polymerizing a monomer dissolved in the liquid crystal. It is the mainstream of current liquid crystal TVs because it can obtain high efficiency.
Further, in recent years, there has been a demand for a liquid crystal display device with even higher response speed, and a liquid crystal composition that requires extremely high characteristics that are distinct from conventional technologies is in demand (Patent Documents 1 and 2).

JP 2014-112192 A JP 2010-285499 A

However, the liquid crystal composition is easily degraded by light emitted from the backlight or active energy rays such as ultraviolet rays irradiated during the manufacturing process of the liquid crystal display element. There is a problem of causing a decrease in voltage holding ratio (VHR). Therefore, a liquid crystal composition that can maintain a high voltage holding ratio (VHR) even with high-speed response is desired.
The problem to be solved by the present invention is to provide a liquid crystal composition having a low residual monomer amount, a high voltage holding ratio (VHR), good pretilt angle formation and low-temperature storage stability, and a liquid crystal display device using the same. That's what it is.

As a result of intensive studies, the present inventors have found that one or more polymerizable compounds represented by the general formula (i) described later, one or more sensitizing compounds, and one liquid crystal compound. The inventors have found that the above-mentioned problems can be solved by a polymerizable compound-containing liquid crystal composition containing at least two of them, and have completed the present invention.
The configuration of the present invention for solving the above problems is as follows.
The polymerizable compound-containing liquid crystal composition according to the present invention is
The following general formula (i)

(In the formula,
P ⁱ¹ and P ⁱ² each independently represent a polymerizable group,
Sp ⁱ¹ and Sp ⁱ² represent a single bond or an alkylene group having 1 to 20 carbon atoms,
one or more —CH ₂ — in the alkylene group may be independently substituted with —O—, —NH—,
one or more —CH ₂ —CH ₂ — in the alkylene group are each independently —CH═CH—, —C≡C—, —CO—O— or —O—CO—; may be substituted,
One or more hydrogen atoms in the alkylene group may each independently be substituted with a halogen atom,
There is no direct bond between oxygen atoms and oxygen atoms,
A ⁱ¹ , A ⁱ² and A ⁱ³ each independently represent a divalent aromatic group, a divalent cycloaliphatic group or a divalent heterocyclic compound group;
one or more hydrogen atoms in A ⁱ¹ , A ⁱ² and A ⁱ³ may each independently be substituted with a substituent Sr ⁱ¹ ;
The substituent Sr ⁱ¹ represents either a halogen atom or an alkyl group having 1 to 20 carbon atoms,
one or more —CH ₂ — in the alkyl group may be independently substituted with —O—, —NH—,
one or more —CH ₂ —CH ₂ — in the alkyl group are each independently —CH═CH—, —C≡C—, —CO—O— or —O—CO—; may be substituted,
One or more hydrogen atoms in the alkyl group may each independently be substituted with a halogen atom,
There is no direct bond between oxygen atoms and oxygen atoms,
When a plurality of substituents Sr ⁱ¹ are present, they may be the same or different, and at least one of Sp ⁱ¹ , Sp ⁱ² and/or substituents Sr ⁱ¹ is an alkylene group having 1 to 20 carbon atoms or represents an alkyl group having 1 to 20 carbon atoms,
In at least one of an alkylene group having 1 to 20 carbon atoms or an alkyl group having 1 to 20 carbon atoms represented by Sp ⁱ¹ , Sp ⁱ² and/or the substituent Sr ⁱ¹ ,
one or more —CH ₂ — in said group, and/or
One or more hydrogen atoms in the group are each independently represented by the following formulas (PG ⁱ -1) to (PG ⁱ -33)

(In the formulas (PG ⁱ -1) to (PG ⁱ -33),
X ^PGi and Z ^PGi each independently represent a methylene group (—CH ₂ —), an oxygen atom (—O—) or a sulfur atom (—S—),
Y ^PGi represents a carbonyl group (>C=O), a thionyl group (>C=S), an oxygen atom (-O-) or a sulfur atom (-S-),
W ^PGi represents a methylene group ( _-CH2- ), a carbonyl group (>C=O) or a thionyl group (>C=S),
S ^PGi , T ^PGi and U ^PGi each independently represent a methine group (=CH-) or a nitrogen atom (=N-),
In formula (PG ⁱ -18), S ^PGi and T ^PGi do not represent a methine group (=CH-) at the same time,
In formula (PG ⁱ -19), S ^PGi , T ^PGi and U ^PGi do not represent a methine group (=CH-) at the same time,
R ^PGi each independently represents an alkyl group having 1 to 20 carbon atoms,
one or more —CH ₂ — in the alkyl group may be independently substituted with —O—, —NH—,
one or more —CH ₂ —CH ₂ — in the alkyl group are each independently —CH═CH—, —C≡C—, —CO—O— or —O—CO—; may be substituted,
One or more hydrogen atoms in the alkyl group may each independently be substituted with a halogen atom,
There is no direct bond between oxygen atoms and oxygen atoms,
When there are multiple ^RPGi , they may be the same or different,
Sp ^PGi each independently represents a single bond, an alkylene group having 1 to 20 carbon atoms or an arylene group having 6 to 20 carbon atoms,
one or more —CH ₂ — in the alkylene group or the arylene group may be independently substituted with —O—, —NH—,
One or more —CH ₂ —CH ₂ — in the alkylene group or the arylene group are each independently —CH═CH—, —C≡C—, —CO—O— or —O -CO- may be substituted,
One or more hydrogen atoms in the alkylene group or the arylene group may each independently be substituted with a halogen atom or a hydroxyl group,
There is no direct bond between oxygen atoms and oxygen atoms,
When multiple Sp ^PGi are present, they may be the same or different,
* represents a bond.
provided that one or more —CH ₂ — in said group is substituted with a group selected from the group consisting of groups represented by formulas (PG ⁱ -1) to (PG ⁱ -7),
One or more hydrogen atoms in said group are substituted with a group selected from the group consisting of groups represented by formulas (PG ⁱ -8) to (PG ⁱ -33). )
is substituted with a group selected from the group consisting of groups represented by
L ⁱ¹ and L ⁱ² each independently represent a single bond or an alkylene group having 1 to 20 carbon atoms,
one or more hydrogen atoms in the alkylene group may be independently substituted with a halogen atom or an alkyl group having 1 to 6 carbon atoms,
n ⁱ¹ represents an integer from 0 to 1,
When a plurality of L ⁱ² and A ⁱ³ are present, they may be the same or different. )
One or two or more polymerizable compounds represented by
one or more sensitizing compounds;
one or more liquid crystal compounds;
characterized by including at least
Further, a liquid crystal display device according to the present invention is characterized by using the polymerizable compound-containing liquid crystal composition described above.
Furthermore, an example of the configuration of the present invention is as follows.

Section 1. The following general formula (i)

（式中、
Ｐ^ｉ１及びＰ^ｉ２は、それぞれ独立して、重合性基を表し、
Ｓｐ^ｉ１及びＳｐ^ｉ２は単結合又は炭素数１～２０のアルキレン基を表し、
該アルキレン基中の１つ又は２つ以上の－CＨ_２－は、それぞれ独立して、－Ｏ－、－ＮＨ－で置換されてもよく、
該アルキレン基中の１つ又は２つ以上の－CＨ_２－CＨ_２－は、それぞれ独立して、－ＣＨ＝ＣＨ－、－Ｃ≡Ｃ－、－ＣＯ－Ｏ－又は－Ｏ－ＣＯ－で置換されてもよく、
該アルキレン基中の１つ又は２つ以上の水素原子は、それぞれ独立して、ハロゲン原子で置換されていてもよいが、
酸素原子と酸素原子が直接結合することはなく、
Ａ^ｉ１、Ａ^ｉ２及びＡ^ｉ３は、それぞれ独立して、２価の芳香族基、２価の環式脂肪族基、２価の複素環式化合物基のいずれかを表し、
Ａ^ｉ１、Ａ^ｉ２及びＡ^ｉ３中の１つ又は２つ以上の水素原子は、それぞれ独立して、置換基Ｓｒ^ｉ１で置換されていてもよく、
置換基Ｓｒ^ｉ１は、ハロゲン原子、炭素原子数１～２０のアルキル基のいずれかを表し、
該アルキル基中の１つ又は２つ以上の－CＨ_２－は、それぞれ独立して、－Ｏ－、－ＮＨ－で置換されてもよく、
該アルキル基中の１つ又は２つ以上の－CＨ_２－CＨ_２－は、それぞれ独立して、－ＣＨ＝ＣＨ－、－Ｃ≡Ｃ－、－ＣＯ－Ｏ－又は－Ｏ－ＣＯ－で置換されてもよく、
該アルキル基中の１つ又は２つ以上の水素原子は、それぞれ独立して、ハロゲン原子で置換されていてもよいが、
酸素原子と酸素原子が直接結合することはなく、
置換基Ｓｒ^ｉ１が複数存在する場合は、それらは同一であっても異なっていても良く、 Ｓｐ^ｉ１、Ｓｐ^ｉ２及び／又は置換基Ｓｒ^ｉ１の少なくとも一つは、炭素数１～２０のアルキレン基又は炭素数１～２０のアルキル基を表し、
Ｓｐ^ｉ１、Ｓｐ^ｉ２及び／又は置換基Ｓｒ^ｉ１が表す炭素原子数１～２０のアルキレン基又は炭素数１～２０のアルキル基の少なくとも一つにおいて、
該基における１つ又は２つ以上の－CＨ_２－、及び／又は、
該基における１つ又は２つ以上の水素原子は、それぞれ独立して、下記式（ＰＧ^ｉ－１）～（ＰＧ^ｉ－３３）

(In the formula,
P ⁱ¹ and P ⁱ² each independently represent a polymerizable group,
Sp ⁱ¹ and Sp ⁱ² represent a single bond or an alkylene group having 1 to 20 carbon atoms,
one or more —CH ₂ — in the alkylene group may be independently substituted with —O—, —NH—,
one or more —CH ₂ —CH ₂ — in the alkylene group are each independently —CH═CH—, —C≡C—, —CO—O— or —O—CO—; may be substituted,
One or more hydrogen atoms in the alkylene group may each independently be substituted with a halogen atom,
There is no direct bond between oxygen atoms and oxygen atoms,
A ⁱ¹ , A ⁱ² and A ⁱ³ each independently represent a divalent aromatic group, a divalent cycloaliphatic group or a divalent heterocyclic compound group;
one or more hydrogen atoms in A ⁱ¹ , A ⁱ² and A ⁱ³ may each independently be substituted with a substituent Sr ⁱ¹ ;
The substituent Sr ⁱ¹ represents either a halogen atom or an alkyl group having 1 to 20 carbon atoms,
one or more —CH ₂ — in the alkyl group may be independently substituted with —O—, —NH—,
one or more —CH ₂ —CH ₂ — in the alkyl group are each independently —CH═CH—, —C≡C—, —CO—O— or —O—CO—; may be substituted,
One or more hydrogen atoms in the alkyl group may each independently be substituted with a halogen atom,
There is no direct bond between oxygen atoms and oxygen atoms,
When a plurality of substituents Sr ⁱ¹ are present, they may be the same or different, and at least one of Sp ⁱ¹ , Sp ⁱ² and/or substituents Sr ⁱ¹ is an alkylene group having 1 to 20 carbon atoms or represents an alkyl group having 1 to 20 carbon atoms,
In at least one of an alkylene group having 1 to 20 carbon atoms or an alkyl group having 1 to 20 carbon atoms represented by Sp ⁱ¹ , Sp ⁱ² and/or the substituent Sr ⁱ¹ ,
one or more —CH ₂ — in said group, and/or
One or more hydrogen atoms in the group are each independently represented by the following formulas (PG ⁱ -1) to (PG ⁱ -33)

（式（ＰＧ^ｉ－１）～（ＰＧ^ｉ－３３）中、
Ｘ^ＰＧｉ及びＺ^ＰＧｉは、それぞれ独立して、メチレン基（－ＣＨ_２－）、酸素原子（－Ｏ－）又は硫黄原子（－Ｓ－）を表し、
Ｙ^ＰＧｉは、カルボニル基（＞Ｃ＝Ｏ）、チオニル基（＞Ｃ＝Ｓ）、酸素原子（－Ｏ－）又は硫黄原子（－Ｓ－）を表し、
Ｗ^ＰＧｉは、メチレン基（－ＣＨ_２－）、カルボニル基（＞Ｃ＝Ｏ）又はチオニル基（＞Ｃ＝Ｓ）を表し、
Ｓ^ＰＧｉ、Ｔ^ＰＧｉ及びＵ^ＰＧｉは、それぞれ独立して、メチン基（＝ＣＨ－）又は窒素原子（＝Ｎ－）を表すが、
式（ＰＧ^ｉ－１８）において、Ｓ^ＰＧｉ及びＴ^ＰＧｉが、同時にメチン基（＝ＣＨ－）を表すことはなく、
式（ＰＧ^ｉ－１９）において、Ｓ^ＰＧｉ、Ｔ^ＰＧｉ及びＵ^ＰＧｉが、同時にメチン基（＝ＣＨ－）を表すことはなく、
Ｒ^ＰＧｉは、それぞれ独立して、炭素原子数１～２０のアルキル基を表し、
該アルキル基中の１つ又は２つ以上の－CＨ_２－は、それぞれ独立して、－Ｏ－、－ＮＨ－で置換されてもよく、
該アルキル基中の１つ又は２つ以上の－CＨ_２－CＨ_２－は、それぞれ独立して、－ＣＨ＝ＣＨ－、－Ｃ≡Ｃ－、－ＣＯ－Ｏ－又は－Ｏ－ＣＯ－で置換されてもよく、
該アルキル基中の１つ又は２つ以上の水素原子は、それぞれ独立して、ハロゲン原子で置換されていてもよいが、
酸素原子と酸素原子が直接結合することはなく、
Ｒ^ＰＧｉが複数存在する場合は、それらは同一であっても異なっていてもよく、
Ｓｐ^ＰＧｉは、それぞれ独立して、単結合、炭素数１～２０のアルキレン基又は炭素原子数６～２０のアリーレン基を表し、
該アルキレン基又は該アリーレン基中の１つ又は２つ以上の－CＨ_２－は、それぞれ独立して、－Ｏ－、－ＮＨ－で置換されてもよく、
該アルキレン基又は該アリーレン基中の１つ又は２つ以上の－CＨ_２－CＨ_２－は、それぞれ独立して、－ＣＨ＝ＣＨ－、－Ｃ≡Ｃ－、－ＣＯ－Ｏ－又は－Ｏ－ＣＯ－で置換されてもよく、
該アルキレン基又は該アリーレン基中の１つ又は２つ以上の水素原子は、それぞれ独立して、ハロゲン原子又は水酸基で置換されていてもよいが、
酸素原子と酸素原子が直接結合することはなく、
Ｓｐ^ＰＧｉが複数存在する場合は、それらは同一であっても異なっていてもよく、
＊は結合手を表す。
但し、前記該基における１つ又は２つ以上の－CＨ_２－は、式（ＰＧ^ｉ－１）～（ＰＧ^ｉ－７）で表される基からなる群から選ばれる基で置換され、
前記該基における１つ又は２つ以上の水素原子は、式（ＰＧ^ｉ－８）～（ＰＧ^ｉ－３３）で表される基からなる群から選ばれる基で置換される。）
で表される基からなる群から選ばれる基で置換されており、
Ｌ^ｉ１及びＬ^ｉ２は、それぞれ独立して、単結合又は炭素原子数１～２０のアルキレン基を表し、
該アルキレン基中の１つ又は２つ以上の水素原子は、それぞれ独立して、ハロゲン原子、炭素原子数１～６のアルキル基で置換されていてもよく、
ｎ^ｉ１は、０～１の整数を表し、
Ｌ^ｉ２、Ａ^ｉ３が複数存在する場合は、それらは同一であっても異なっていてもよい。）
で表される重合性化合物の１種又は２種以上と、
増感化合物の１種又は２以上と、
液晶化合物の１種又は２以上と、
を少なくとも含む重合性化合物含有液晶組成物。

(In the formulas (PG ⁱ -1) to (PG ⁱ -33),
X ^PGi and Z ^PGi each independently represent a methylene group (—CH ₂ —), an oxygen atom (—O—) or a sulfur atom (—S—),
Y ^PGi represents a carbonyl group (>C=O), a thionyl group (>C=S), an oxygen atom (-O-) or a sulfur atom (-S-),
W ^PGi represents a methylene group ( _-CH2- ), a carbonyl group (>C=O) or a thionyl group (>C=S),
S ^PGi , T ^PGi and U ^PGi each independently represent a methine group (=CH-) or a nitrogen atom (=N-),
In formula (PG ⁱ -18), S ^PGi and T ^PGi do not represent a methine group (=CH-) at the same time,
In formula (PG ⁱ -19), S ^PGi , T ^PGi and U ^PGi do not represent a methine group (=CH-) at the same time,
R ^PGi each independently represents an alkyl group having 1 to 20 carbon atoms,
one or more —CH ₂ — in the alkyl group may be independently substituted with —O—, —NH—,
one or more —CH ₂ —CH ₂ — in the alkyl group are each independently —CH═CH—, —C≡C—, —CO—O— or —O—CO—; may be substituted,
One or more hydrogen atoms in the alkyl group may each independently be substituted with a halogen atom,
There is no direct bond between oxygen atoms and oxygen atoms,
When there are multiple ^RPGi , they may be the same or different,
Sp ^PGi each independently represents a single bond, an alkylene group having 1 to 20 carbon atoms or an arylene group having 6 to 20 carbon atoms,
one or more —CH ₂ — in the alkylene group or the arylene group may be independently substituted with —O—, —NH—,
One or more —CH ₂ —CH ₂ — in the alkylene group or the arylene group are each independently —CH═CH—, —C≡C—, —CO—O— or —O -CO- may be substituted,
One or more hydrogen atoms in the alkylene group or the arylene group may each independently be substituted with a halogen atom or a hydroxyl group,
There is no direct bond between oxygen atoms and oxygen atoms,
When multiple Sp ^PGi are present, they may be the same or different,
* represents a bond.
provided that one or more —CH ₂ — in said group is substituted with a group selected from the group consisting of groups represented by formulas (PG ⁱ -1) to (PG ⁱ -7),
One or more hydrogen atoms in said group are substituted with a group selected from the group consisting of groups represented by formulas (PG ⁱ -8) to (PG ⁱ -33). )
is substituted with a group selected from the group consisting of groups represented by
L ⁱ¹ and L ⁱ² each independently represent a single bond or an alkylene group having 1 to 20 carbon atoms,
one or more hydrogen atoms in the alkylene group may be independently substituted with a halogen atom or an alkyl group having 1 to 6 carbon atoms,
n ⁱ¹ represents an integer from 0 to 1,
When a plurality of L ⁱ² and A ⁱ³ are present, they may be the same or different. )
One or two or more polymerizable compounds represented by
one or more sensitizing compounds;
one or more liquid crystal compounds;
A polymerizable compound-containing liquid crystal composition containing at least

Section 2. Item 1. The polymerizable compound-containing liquid crystal composition according to item 1, which is substituted with a group represented by formula (PG ⁱ -1).

Item 3. 3. The polymerizable compound-containing liquid crystal composition according to item 1 or 2, wherein Sp ⁱ² represents an alkylene group having 1 to 20 carbon atoms.

Section 4. 4. The polymerizable compound-containing liquid crystal composition according to any one of Items 1 to 3, wherein n ⁱ¹ is 0.

Item 5. Item 5. The polymerizable compound-containing liquid crystal composition according to any one of Items 1 to 4, wherein the ^Li1 is a single bond.

Item 6. The divalent aromatic group is a 1,4-phenylene group, naphthalene-2,6-diyl group, anthracene-2,6-diyl group, phenanthrene-2,7-diyl group, and indane-2,5-diyl group , 1,2,3,4-tetrahydronaphthalene-2,6-diyl group,
the divalent cycloaliphatic group represents any one of a 1,4-cyclohexylene group, a 1,4-cyclohexenylene group, and a 1,3-dioxane-2,5-diyl group;
Item 6. The polymerizable compound-containing liquid crystal according to any one of Items 1 to 5, wherein the divalent heterocyclic compound group is either a pyridine-2,5-diyl group or a pyrimidine-2,5-diyl group. Composition.

Item 7. The sensitizing compound has the following general formula (SC)

（ 式（ＳＣ）中、
Ｒ^ＳＣ１及びＲ^ＳＣ２、それぞれ独立して、炭素原子数１～２０のアルキル基を表し、
該アルキル基中の１つ又は２つ以上の－CＨ_２－は、それぞれ独立して、－Ｏ－、－ＮＨ－で置換されてもよく、
該アルキル基中の１つ又は２つ以上の－CＨ_２－CＨ_２－は、それぞれ独立して、－ＣＨ＝ＣＨ－、－Ｃ≡Ｃ－、－ＣＯ－Ｏ－又は－Ｏ－ＣＯ－で置換されてもよく、
該アルキル基中の１つ又は２つ以上の水素原子は、それぞれ独立して、ハロゲン原子で置換されていてもよいが、
酸素原子と酸素原子が直接結合することはなく、
Ｓ^ＳＣ２、Ｓ^ＳＣ３、Ｓ^ＳＣ５及びＳ^ＳＣ６は、それぞれ独立して、水素原子又はフッ素原子を表し、
Ａ^ＳＣ１は、それぞれ独立して、以下の基（ａ）及び基（ｂ）：
（ａ） １，４－シクロヘキシレン基（この基中に存在する１つの－ＣＨ_２－又は非隣接の２つ以上の－ＣＨ_２－は－Ｏ－及び／又は－Ｓ－に置き換えられてもよい。）、
（ｂ） １，４－フェニレン基（この基中に存在する１つの－ＣＨ＝又は非隣接の２つ以上の－ＣＨ＝は－Ｎ＝に置き換えられてもよい。）
からなる群より選ばれる基を表し、
前記Ａ^ＳＣ１中の一つ又は二つ以上の水素原子は、それぞれ独立して、置換基Ｓｒ^ＳＣ１で置換されていてもよく、
置換基Ｓｒ^ＳＣ１は、ハロゲン原子、炭素原子数１～２０のアルキル基のいずれかを表し、
該アルキル基中の１つ又は２つ以上の－CＨ_２－は、それぞれ独立して、－Ｏ－、－ＮＨ－で置換されてもよく、
該アルキル基中の１つ又は２つ以上の－CＨ_２－CＨ_２－は、それぞれ独立して、－ＣＨ＝ＣＨ－、－Ｃ≡Ｃ－、－ＣＯ－Ｏ－又は－Ｏ－ＣＯ－で置換されてもよく、
該アルキル基中の１つ又は２つ以上の水素原子は、それぞれ独立して、ハロゲン原子で置換されていてもよいが、
酸素原子と酸素原子が直接結合することはなく、
置換基Ｓｒ^ＳＣ１が複数存在する場合は、それらは同一であっても異なっていても良く、
ｎ^ＳＣ１は、０～１の整数を表す。）
で表される化合物である項１～６のいずれか一項に記載の重合性化合物含有液晶組成物。

(In formula (SC),
R ^SC1 and R ^SC2 each independently represent an alkyl group having 1 to 20 carbon atoms;
one or more —CH ₂ — in the alkyl group may be independently substituted with —O—, —NH—,
one or more —CH ₂ —CH ₂ — in the alkyl group are each independently —CH═CH—, —C≡C—, —CO—O— or —O—CO—; may be substituted,
One or more hydrogen atoms in the alkyl group may each independently be substituted with a halogen atom,
There is no direct bond between oxygen atoms and oxygen atoms,
S ^SC2 , S ^SC3 , S ^SC5 and S ^SC6 each independently represent a hydrogen atom or a fluorine atom,
A ^SC1 is each independently the following group (a) and group (b):
(a) a 1,4-cyclohexylene group (one —CH ₂ — or two or more non-adjacent —CH ₂ — present in this group may be replaced with —O— and/or —S—; good.),
(b) a 1,4-phenylene group (one -CH= or two or more non-adjacent -CH= present in this group may be replaced with -N=);
represents a group selected from the group consisting of
one or more hydrogen atoms in A ^SC1 may each independently be substituted with a substituent Sr ^SC1 ,
The substituent Sr ^SC1 represents either a halogen atom or an alkyl group having 1 to 20 carbon atoms,
one or more —CH ₂ — in the alkyl group may be independently substituted with —O—, —NH—,
one or more —CH ₂ —CH ₂ — in the alkyl group are each independently —CH═CH—, —C≡C—, —CO—O— or —O—CO—; may be substituted,
One or more hydrogen atoms in the alkyl group may each independently be substituted with a halogen atom,
There is no direct bond between oxygen atoms and oxygen atoms,
When multiple substituents Sr ^SC1 are present, they may be the same or different,
n ^SC1 represents an integer from 0 to 1; )
Item 7. The polymerizable compound-containing liquid crystal composition according to any one of Items 1 to 6, which is a compound represented by.

Item 8. Item 8. The polymerizable compound-containing liquid crystal composition according to any one of Items 1 to 7, further comprising a polymerizable compound having a structure different from that of general formula (i).

Item 9. As the liquid crystal compound, the following general formulas (NU-01) ~ (NU-08)

（一般式（ＮＵ－０１）～（ＮＵ－０８）中、
Ｒ^ＮＵ１及びＲ^ＮＵ２は、それぞれ独立して、炭素原子数１～８のアルキル基、炭素原子数１～８のアルコキシ基、炭素原子数２～８のアルケニル基又は炭素原子数２～８のアルケニルオキシ基のいずれかを表し、
該基中の１つ又は２つ以上の－ＣＨ_２－ＣＨ_２－は、それぞれ独立して、－Ｃ≡Ｃ－、－ＣＯ－、－ＣＯ－Ｏ－又は－Ｏ－ＣＯ－によって置換されていても良いが、
酸素原子と酸素原子が直接結合することはない。）
のいずれかで表される化合物からなる群から選ばれる化合物を含む項１～８のいずれか一項に記載の重合性化合物含有液晶組成物。

(In the general formulas (NU-01) to (NU-08),
R ^NU1 and R ^NU2 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, or an alkenyl group having 2 to 8 carbon atoms represents any of the oxy groups,
one or more —CH ₂ —CH ₂ — in said group are each independently substituted by —C≡C—, —CO—, —CO—O— or —O—CO— but
Oxygen atoms are never directly bonded to each other. )
Item 9. The polymerizable compound-containing liquid crystal composition according to any one of Items 1 to 8, containing a compound selected from the group consisting of compounds represented by any one of

Item 10. two substrates and
A liquid crystal display element having a liquid crystal layer containing the polymerizable compound-containing liquid crystal composition according to any one of Items 1 to 9 between the two substrates,
A liquid crystal display device in which a polymer obtained by polymerizing a polymerizable compound represented by the general formula (i) is present.

According to the present invention, one or two or more polymerizable compounds represented by general formula (i) described later, one or two or more sensitizing compounds, and one or two or more liquid crystal compounds. By using the polymerizable compound-containing liquid crystal composition containing, it is possible to provide a liquid crystal display element having a low residual monomer amount, good voltage holding ratio (VHR), formation of a pretilt angle, and low-temperature storage stability.

1 is an exploded perspective view showing an example of a liquid crystal display element according to the present invention; FIG.

(Polymerizable compound represented by general formula (i))
The polymerizable compound-containing liquid crystal composition according to the present invention contains one or more polymerizable compounds represented by the following general formula (i).

The polymerizable compound represented by general formula (i) has a polar group in its structure.
That is, in general formula (i), at least one of Sp ⁱ¹ , Sp ⁱ² and/or substituent Sr ⁱ¹ described later represents an alkylene group having 1 to 20 carbon atoms or an alkyl group having 1 to 20 carbon atoms, and Sp ⁱ¹ , Sp ⁱ² and/or substituent Sr ⁱ¹ represented by at least one alkylene group having 1 to 20 carbon atoms or alkyl group having 1 to 20 carbon atoms, one or two or more —CH ₂ in the group - and/or one or more hydrogen atoms in the group are each independently selected from the group consisting of groups represented by the following formulas (PG ⁱ -1) to (PG ⁱ -33) is substituted with a group that is

provided that one or more —CH ₂ — in the group is substituted with a group selected from the group consisting of groups represented by formulas (PG ⁱ -1) to (PG ⁱ -7), One or more hydrogen atoms in the group are substituted with a group selected from the group consisting of groups represented by formulas (PG ⁱ -8) to (PG ⁱ -33).

In formulas (PG ⁱ -1) to (PG ⁱ -33), X ^PGi and Z ^PGi are each independently a methylene group (—CH ₂ —), an oxygen atom (—O—) or a sulfur atom (—S -).
In formulas (PG ⁱ -1) to (PG ⁱ -33), Y ^PGi is a carbonyl group (>C=O), a thionyl group (>C=S), an oxygen atom (-O-) or a sulfur atom represents (-S-).
In formulas (PG ⁱ -1) to (PG ⁱ -33), W ^PGi represents a methylene group (-CH ₂ -), a carbonyl group (>C=O) or a thionyl group (>C=S). .
In formulas (PG ⁱ -1) to (PG ⁱ -33), S ^PGi , T ^PGi and U ^PGi each independently represent a methine group (=CH-) or a nitrogen atom (=N-) .
However, in formula (PG ⁱ -18), S ^PGi and T ^PGi do not simultaneously represent a methine group (=CH-).
In formula (PG ⁱ -19), S ^PGi , T ^PGi and U ^PGi do not all represent a methine group (=CH-) at the same time.

In formulas (PG ⁱ -1) to (PG ⁱ -33), each R ^PGi independently represents an alkyl group having 1 to 20 carbon atoms.
One or more —CH ₂ — in the alkyl group may be independently substituted with —O—, —NH—.
In addition, one or two or more —CH ₂ —CH ₂ — in the alkyl group are each independently —CH═CH—, —C≡C—, —CO—O— or —O—CO - may be substituted.
Also, one or more hydrogen atoms in the alkyl group may each independently be substituted with a halogen atom.
Halogen atoms include fluorine, chlorine, bromine and iodine atoms.
However, when the alkyl group is substituted with a predetermined group, the oxygen atoms are not directly bonded to each other.
The alkyl group having 1 to 20 carbon atoms is a linear, branched or cyclic alkyl group, preferably a linear alkyl group.
The number of carbon atoms in the alkyl group having 1 to 20 carbon atoms is preferably 2 to 10, preferably 2 to 6.

For example, R ^PGi can represent an alkoxy group having 1 to 19 carbon atoms by substituting one —CH ₂ — in the alkyl group with —O—.
The alkoxy group is a linear, branched or cyclic alkoxy group, preferably a linear alkoxy group.
The number of carbon atoms in the alkoxy group is preferably 2-10, preferably 2-6.

R ^PGi represents an alkenyl group having 2 to 20 carbon atoms by substituting -CH=CH- for one or more -CH ₂ -CH ₂ - in the alkyl group. be able to.
The alkenyl group is a linear, branched or cyclic alkenyl group, preferably a linear alkenyl group.
The number of carbon atoms in the alkenyl group is preferably 2-10, preferably 2-6.

R ^PGi represents an alkynyl group having 2 to 20 carbon atoms by substituting one or more —CH ₂ —CH ₂ — in the alkyl group with —C≡C— be able to.
The alkynyl group is a linear, branched or cyclic alkynyl group, preferably a linear alkynyl group.
The number of carbon atoms in the alkynyl group is preferably 2-10, preferably 2-6.

In R ^PGi , one -CH ₂ - in the alkyl group is substituted with -O-, and one or more -CH ₂ -CH ₂ - is substituted with -CH=CH- can represent an alkenyloxy group having 2 to 19 carbon atoms.
The alkenyloxy group is a linear, branched or cyclic alkenyloxy group, preferably a linear alkenyloxy group.
The number of carbon atoms in the alkenyloxy group is preferably 2-10, preferably 2-6.

R ^PGi can also represent a halogenated alkyl group having 1 to 20 carbon atoms by substituting one or more hydrogen atoms in the alkyl group with a halogen atom.
The halogenated alkyl group is a linear, branched or cyclic halogenated alkyl group, preferably a linear halogenated alkyl group.
The number of carbon atoms in the halogenated alkyl group is preferably 2-10, preferably 2-6.

In addition, R ^PGi is obtained by substituting one —CH ₂ — in the alkyl group with —O— and substituting one or more hydrogen atoms in the alkyl group with a halogen atom. , can represent a halogenated alkoxy group having 1 to 19 carbon atoms.
The halogenated alkoxy group is a linear, branched or cyclic halogenated alkoxy group, preferably a linear halogenated alkoxy group.
The number of carbon atoms in the halogenated alkoxy group is preferably 2-10, preferably 2-6.

Specific examples of the alkyl group (including substituted ones) having 1 to 20 carbon atoms in R ^PGi include groups represented by formulas (R ^PGi -1) to (R ^PGi -31).

In formulas (R ^PGi -1) to (R ^PGi -31), black dots represent bonds.
R ^PGi is preferably a straight-chain alkyl group having 1 to 6 carbon atoms.
When multiple ^RPGi are present, they may be the same or different.

In formulas (PG ⁱ -1) to (PG ⁱ -33), each Sp ^PGi independently represents a single bond, an alkylene group having 1 to 20 carbon atoms, or an arylene group having 6 to 20 carbon atoms.
One or more —CH ₂ — in the alkylene group or the arylene group may be independently substituted with —O— or —NH—.
In addition, one or two or more —CH ₂ —CH ₂ — in the alkylene group or the arylene group are each independently —CH═CH—, —C≡C—, —CO—O—, or -O-CO- may be substituted.
Also, one or more hydrogen atoms in the alkylene group or the arylene group may each independently be substituted with a halogen atom or a hydroxyl group.
Halogen atoms include fluorine, chlorine, bromine and iodine atoms.
However, when the alkylene group is substituted with a predetermined group, the oxygen atoms are not directly bonded to each other.

The alkylene group having 1 to 20 carbon atoms is a linear, branched or cyclic alkylene group, preferably a linear alkylene group.
The number of carbon atoms in the alkylene group having 1 to 20 carbon atoms is preferably 1 to 12, preferably 1 to 9, and preferably 1 to 6.

The arylene group having 6 to 20 carbon atoms is a linear, branched or cyclic arylene group, preferably a linear arylene group.
The number of carbon atoms in the arylene group having 6 to 20 carbon atoms is preferably 6 to 12, preferably 6 to 9.

Specific examples of the alkylene group having 1 to 20 carbon atoms (including substituted ones) and the arylene group having 6 to 20 carbon atoms (including substituted ones) in Sp ^PGi include the formula (Sp ^PGi -1 ) to (Sp ^PGi -14).

In formulas (Sp ^PGi -1) to (Sp ^PGi -14), the white dot represents a bond to an oxygen atom or a sulfur atom, and * represents a bond to a carbon atom, a nitrogen atom, or a silicon atom.
Sp 2 ^PGi is preferably a linear alkylene group having 1 to 6 carbon atoms.
When multiple Sp ^PGi are present, they may be the same or different.

In formulas (PG ⁱ -1) to (PG ⁱ -33), * represents a bond.

Specific examples of the group represented by formula (PG ⁱ -1) include groups represented by formulas (PG ⁱ -1-1) to (PG ⁱ -1-3).

In formulas (PG ⁱ -1-1) to (PG ⁱ -1-3), * represents a bond.

Specific examples of the group represented by formula (PG ⁱ -2) include groups represented by formulas (PG ⁱ -2-1) to (PG ⁱ -2-3).

In formulas (PG ⁱ -2-1) to (PG ⁱ -2-3), * represents a bond.

Specific examples of the group represented by formula (PG ⁱ -3) include a group represented by formula (PG ⁱ -3-1).

In formula (PG ⁱ -3-1), * represents a bond.

Specific examples of the group represented by formula (PG ⁱ -4) include a group represented by formula (PG ⁱ -4-1).

In formula (PG ⁱ -4-1), * represents a bond.

Specific examples of the group represented by formula (PG ⁱ -5) include a group represented by formula (PG ⁱ -5-1).

In formula (PG ⁱ -5-1), * represents a bond.

Specific examples of the group represented by formula (PG ⁱ -6) include a group represented by formula (PG ⁱ -6-1).

In formula (PG ⁱ -6-1), * represents a bond.

Specific examples of the group represented by formula (PG ⁱ -7) include a group represented by formula (PG ⁱ -7-1).

In formula (PG ⁱ -7-1), * represents a bond.

Specific examples of the group represented by formula (PG ⁱ -13) include a group represented by formula (PG ⁱ -13-1).

In formula (PG ⁱ -13-1), * represents a bond.

Specific examples of the group represented by formula (PG ⁱ -15) include a group represented by formula (PG ⁱ -15-1).

In formula (PG ⁱ -15-1), * represents a bond.

Specific examples of the group represented by formula (PG ⁱ -16) include a group represented by formula (PG ⁱ -16-1).

In formula (PG ⁱ -16-1), * represents a bond.

Specific examples of the group represented by formula (PG ⁱ -17) include groups represented by formulas (PG ⁱ -17-1) to (PG ⁱ -17-3).

In formulas (PG ⁱ -17-1) to (PG ⁱ -17-3), * represents a bond.

Specific examples of the group represented by formula (PG ⁱ -18) include groups represented by formulas (PG ⁱ -18-1) to (PG ⁱ -18-2).

In formulas (PG ⁱ -18-1) to (PG ⁱ -18-2), * represents a bond.

Specific examples of the group represented by formula (PG ⁱ -19) include groups represented by formulas (PG ⁱ -19-1) to (PG ⁱ -19-3).

In formulas (PG ⁱ -19-1) to (PG ⁱ -19-3), * represents a bond.

Specific examples of the group represented by formula (PG ⁱ -20) include groups represented by formulas (PG ⁱ -20-1) to (PG ⁱ -20-3).

In formulas (PG ⁱ -20-1) to (PG ⁱ -20-3), * represents a bond.

Specific examples of the group represented by formula (PG ⁱ -21) include groups represented by formulas (PG ⁱ -21-1) to (PG ⁱ -21-2).

In formulas (PG ⁱ -21-1) to (PG ⁱ -21-2), * represents a bond.

Specific examples of the group represented by formula (PG ⁱ -22) include a group represented by formula (PG ⁱ -22-1).

In formula (PG ⁱ -22-1), * represents a bond.

Specific examples of the group represented by formula (PG ⁱ -23) include groups represented by formulas (PG ⁱ -23-1) to (PG ⁱ -23-2).

In formulas (PG ⁱ -23-1) to (PG ⁱ -23-2), * represents a bond.

Specific examples of the group represented by formula (PG ⁱ -31) include a group represented by formula (PG ⁱ -31-1).

In formula (PG ⁱ -31-1), * represents a bond.

Specific examples of the group represented by formula (PG ⁱ -32) include a group represented by formula (PG ⁱ -32-1).

In formula (PG ⁱ -32-1), * represents a bond.

Specific examples of the group represented by formula (PG ⁱ -33) include a group represented by formula (PG ⁱ -33-1).

In formula (PG ⁱ -33-1), * represents a bond.

The polymerizable compound represented by the general formula (i) is preferably substituted with a group represented by the formula (PG ⁱ -1) from the viewpoint of improving the voltage holding ratio and solubility. It is more preferably substituted with a group represented by ⁱ -1-3).

In general formula (i), P ⁱ¹ and P ⁱ² each independently represent a polymerizable group.
Polymerizable groups are, for example, groups suitable for chain polymerization such as radical, cationic or anionic polymerization and/or sequential polymerization such as polyaddition or polycondensation.
The polymerizable group includes a carbon-carbon double bond (>C=C<), a carbon-carbon triple bond (-C≡C-) and/or an n-membered ring structure (n is 3 It is preferably a group containing an integer of to 7).

Further, the polymerizable group is preferably a group selected from the group consisting of formulas (P ^i1/2 -1) to (P ^i1/2 -8).

In formulas (P ^i1/2 −1) to (P ^i1/2 −8), S ^i1/2 is each independently a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or 1 to 5 carbon atoms. represents a halogenated alkyl group.
The alkyl group having 1 to 5 carbon atoms includes methyl group, ethyl group, propyl group and the like.
Examples of halogenated alkyl groups having 1 to 5 carbon atoms include trifluoromethyl group and difluoroethyl group.
Each ^Si1/2 preferably independently represents a hydrogen atom, a methyl group, an ethyl group or a propyl group.

In formulas (P ^i1/2 −1) to (P ^i1/2 −8), the black dot represents the point of attachment to Spi ⁱ¹ or to Spi ⁱ² .

From the viewpoint of ensuring appropriate reactivity, P ⁱ¹ and P ⁱ² each independently represent the formula (P ^i1/2 -1), the formula (P ^{i1 /2} -2), the formula ), formula (P ^i1/2 −4), formula (P ^i1/2 −5) or formula (P ^i1/2 −7), and formula (P ^i1/2 −1), formula (P ^i1/2 -2), formula (P ^i1/2 -3) or formula (P ^i1/2 -7), preferably formula (P ^i1/2 -1), acrylic group ( In formula (P ^i1/2 -1), S ^i1/2 = hydrogen atom) or a methacryl group (in formula (P ^i1/2 -1), S ^i1/2 = methyl group), preferably a methacryl group is preferably

Also, P ⁱ¹ and P ⁱ² may be the same or different.
When P ⁱ¹ and P ⁱ² select the same formulas (P ^i1/2 −1) to (P ^i1/2 −8), the same symbols (S ^i1/2 ) in the formulas are They may be the same or different.

In general formula (i), Sp ⁱ¹ and Sp ⁱ² each independently represent a single bond or an alkylene group having 1 to 20 carbon atoms.
One or more —CH ₂ — in the alkylene group may be independently substituted with —O—, —NH—.
In addition, one or more —CH ₂ —CH ₂ — in the alkylene group is substituted with —CH═CH—, —C≡C—, —CO—O— or —O—CO— may
Also, one or more hydrogen atoms in the alkylene group may be independently substituted with a halogen atom.
Halogen atoms include fluorine, chlorine, bromine and iodine atoms.
However, when the alkylene group is substituted with a predetermined group, the oxygen atoms are not directly bonded to each other.

The alkylene group having 1 to 20 carbon atoms is a linear, branched or cyclic alkylene group, preferably a linear alkylene group.
The number of carbon atoms in the alkylene group having 1 to 20 carbon atoms is preferably 1 to 12, preferably 1 to 9, and preferably 1 to 6.

Specific examples of the alkylene group having 1 to 20 carbon atoms (including substituted ones) in Sp ⁱ¹ and Sp ⁱ² are represented by formulas (Sp ^i1/2 −1) to (Sp ^i1/2 −5). and the like.

In formulas (Sp ⁱ¹ -1) to (Sp ⁱ¹ -5), white dots represent bonds to P ⁱ¹ or P ⁱ² and * represents bonds to A ⁱ¹ , A ⁱ² or A ⁱ³ .
In addition, it is preferable that Sp ⁱ² represents an alkylene group having 1 to 20 carbon atoms.
Moreover, Sp ⁱ² is preferably a straight-chain alkylene group having 1 to 6 carbon atoms or a straight-chain alkoxylylene group having 1 to 6 carbon atoms.

Specific examples of P ⁱ¹ -Sp ⁱ¹ - and P ⁱ² -Sp ⁱ² - are represented by formulas (P ^i1/2 -Sp ^i1/2 -1) to (P ^i1/2 -Sp ^i1/2 -19) and the like.

In formulas (P ^i1/2 -Sp ^i1/2 -1) to (P ^i1/2 -Sp ^i1/2 -19), * represents a bond to A ⁱ¹ , A ⁱ² or A ⁱ³ .

In general formula (i), A ⁱ¹ , A ⁱ² and A ⁱ³ are each independently a divalent aromatic group, a divalent cycloaliphatic group, or a divalent heterocyclic compound group. show.
Divalent aromatic groups include 1,4-phenylene group, naphthalene-2,6-diyl group, anthracene-2,6-diyl group, phenanthrene-2,7-diyl group and indane-2,5-diyl group. group, 1,2,3,4-tetrahydronaphthalene-2,6-diyl group, and the like.
Divalent cycloaliphatic groups include 1,4-cyclohexylene group, 1,4-cyclohexenylene group, 1,3-dioxane-2,5-diyl group and the like.
Examples of the divalent heterocyclic compound group include pyridine-2,5-diyl group and pyrimidine-2,5-diyl group.

One or more hydrogen atoms in A ⁱ¹ , A ⁱ² and A ⁱ³ may each independently be substituted with a substituent Sr ⁱ¹ .
The substituent Sr ⁱ¹ represents either a halogen atom or an alkyl group having 1 to 20 carbon atoms.
One or more —CH ₂ — in the alkyl group may be independently substituted with —O—, —NH—.
In addition, one or two or more —CH ₂ —CH ₂ — in the alkyl group are each independently —CH═CH—, —C≡C—, —CO—O— or —O—CO - may be substituted.
Also, one or more hydrogen atoms in the alkyl group may each independently be substituted with a halogen atom.
Halogen atoms include fluorine, chlorine, bromine and iodine atoms.
However, when the alkyl group is substituted with a predetermined group, the oxygen atoms are not directly bonded to each other.

The alkyl group having 1 to 20 carbon atoms is a linear, branched or cyclic alkyl group, preferably a linear alkyl group.
The number of carbon atoms in the alkyl group having 1 to 20 carbon atoms is preferably 2 to 10, preferably 2 to 6.

For example, the substituent Sr ⁱ¹ can represent an alkoxy group having 1 to 19 carbon atoms by substituting one —CH ₂ — in the alkyl group with —O—.
The alkoxy group having 1 to 19 carbon atoms is a linear, branched or cyclic alkoxy group, preferably a linear alkoxy group.
The number of carbon atoms in the alkoxy group having 1 to 19 carbon atoms is preferably 2 to 10, preferably 2 to 6.

Further, the substituent Sr ⁱ¹ can represent an alkoxyalkyl group having 1 to 19 carbon atoms by substituting one —CH ₂ — in the alkyl group with —O—.
The alkoxyalkyl group having 1 to 19 carbon atoms is a linear, branched or cyclic alkoxyalkyl group, preferably a linear alkoxyalkyl group.
The number of carbon atoms in the alkoxyalkyl group having 1 to 19 carbon atoms is preferably 2 to 10, preferably 2 to 6.

In addition, the substituent Sr ⁱ¹ is a halogenated alkyl group having 1 to 20 carbon atoms by independently substituting one or more hydrogen atoms in the alkyl group with a halogen atom. can be represented.
The halogenated alkyl group having 1 to 20 carbon atoms is a linear, branched or cyclic halogenated alkyl group, preferably a linear halogenated alkyl group.
The number of carbon atoms in the halogenated alkyl group having 1 to 20 carbon atoms is preferably 2 to 10, preferably 2 to 6.

The substituent Sr ⁱ¹ is obtained by substituting one —CH ₂ — in the alkyl group with —O— and substituting one or more hydrogen atoms in the alkyl group with a halogen atom. , can represent a halogenated alkoxy group having 1 to 19 carbon atoms.
The halogenated alkoxy group is a linear, branched or cyclic halogenated alkoxy group, preferably a linear halogenated alkoxy group.
The number of carbon atoms in the halogenated alkoxy group is preferably 2-10, preferably 2-6.

Specific examples of the alkyl group having 1 to 20 carbon atoms (including substituted ones) in the substituent Sr ⁱ¹ include groups represented by formulas (Sr ⁱ¹ -1) to (Sr ⁱ¹ -21). be done.

In formulas (Sr ⁱ¹ −1) to (Sr ⁱ¹ −21), the black dots represent bonds to A ⁱ¹ , A ⁱ² or A ⁱ³ .
When multiple substituents Sr ⁱ¹ are present, they may be the same or different.

The substitution position of the substituent Sr ⁱ¹ in A ⁱ¹ is preferably any one of the following formulas (A ⁱ¹ -SP-1) to (A ⁱ¹ -SP-3).

In the formulas (A ⁱ¹ -SP-1) to (A ⁱ¹ -SP-3), white dots represent bonds to Sp ⁱ¹ and black dots represent bonds to L ⁱ¹ .

The substitution position of the substituent Sr ⁱ¹ in A ⁱ² is preferably any one of the following formulas (A ⁱ² -SP-1) to (A ⁱ² -SP-2).

In formulas (A ⁱ² -SP-1) to (A ⁱ² -SP-2), white dots represent bonds to L ⁱ¹ and black dots represent bonds to L ⁱ² or Sp ⁱ² .

The substitution position of the substituent Sr ⁱ¹ in A ⁱ³ is preferably any one of the following formulas (A ⁱ³ -SP-1) to (A ⁱ³ -SP-2).

In formulas (A ⁱ³ -SP-1) to (A ⁱ³ -SP-2), white dots represent bonds to L ⁱ² and black dots represent bonds to Sp ⁱ² .

More specifically, A ⁱ¹ preferably represents any one of the following formulas (A ⁱ¹ -1) to (A ⁱ¹ -5).

In formulas (A ⁱ¹ -1) to (A ⁱ¹ -5), white dots represent bonds to Sp ⁱ¹ and black dots represent bonds to L ⁱ¹ .

More specifically, A ⁱ² preferably represents any one of the following formulas (A ⁱ² -1) to (A ⁱ² -6).

In formulas (A ⁱ² -1) to (A ⁱ² -6), white dots represent bonds to L ⁱ¹ and black dots represent bonds to L ⁱ² or Sp ⁱ² .

More specifically, A ⁱ³ preferably represents any one of the following formulas (A ⁱ³ -1) to (A ⁱ³ -4).

In the formulas (A ⁱ³ −S1) to (A ⁱ³ −4), white dots represent bonds to L ⁱ² and black dots represent bonds to Sp ⁱ² .

In general formula (i), L ⁱ¹ and L ⁱ² each independently represent a single bond or an alkylene group having 1 to 20 carbon atoms.
One or more hydrogen atoms in the alkylene group may each independently be substituted with a halogen atom or an alkyl group having 1 to 6 carbon atoms.
Halogen atoms include fluorine, chlorine, bromine and iodine atoms.
The alkylene group having 1 to 20 carbon atoms is a linear, branched or cyclic alkylene group, preferably a linear alkylene group.
The number of carbon atoms in the alkylene group having 1 to 20 carbon atoms is preferably 1 to 15, preferably 1 to 10.

Specific examples of the alkylene group having 1 to 20 carbon atoms (including substituted ones) in L ⁱ¹ and L ⁱ² are represented by formulas (L ^i1/2 −1) to (L ^i1/2 −2). and the like.

In formulas (L ^i1/2 −1) to (L ^i1/2 −2), white dots represent bonds to A ⁱ¹ or A ⁱ² , and black dots represent bonds to A ⁱ² or A ⁱ³ .
Also, ^Li1 is preferably a single bond.

In general formula (i), n ⁱ¹ represents an integer of 0 to 1, preferably 0.
When a plurality of L ⁱ² and A ⁱ³ are present, they may be the same or different.

The polymerizable compound represented by general formula (i) is preferably a compound selected from the group consisting of compounds represented by general formulas (i-1) to (i-13) below.

In general formulas (i-1) to (i-13), P ⁱ¹ , P ⁱ² , Sp ⁱ¹ and Sp ⁱ² and Sr ⁱ¹ are each independently P ⁱ¹ , P ⁱ² , Each has the same meaning as Sp ⁱ¹ , Sp ⁱ² and Sr ⁱ¹ .

Specific examples of the compound represented by general formula (i-1) include compounds represented by the following structural formulas (i-1-1) to (i-1-16).

Specific examples of the compound represented by general formula (i-2) include compounds represented by the following structural formulas (i-2-1) to (i-2-9).

Specific examples of the compound represented by general formula (i-3) include compounds represented by the following structural formulas (i-3-1) to (i-3-12).

Specific examples of the compound represented by the general formula (i-4) include compounds represented by the following structural formulas (i-4-1) to (i-4-15).

Specific examples of the compound represented by general formula (i-5) include compounds represented by the following structural formulas (i-5-1) to (i-5-12).

Specific examples of the compound represented by general formula (i-6) include compounds represented by the following structural formulas (i-6-1) to (i-6-12).

Specific examples of the compound represented by the general formula (i-7) include compounds represented by the following structural formulas (i-7-1) to (i-7-6).

Specific examples of the compound represented by general formula (i-8) include compounds represented by the following structural formulas (i-8-1) to (i-8-4).

Specific examples of the compound represented by general formula (i-9) include compounds represented by the following structural formulas (i-9-1) to (i-9-8).

Specific examples of the compound represented by general formula (i-10) include compounds represented by the following structural formulas (i-10-1) to (i-10-4).

Specific examples of the compound represented by general formula (i-11) include compounds represented by the following structural formulas (i-11-1) to (i-11-8).

Specific examples of the compound represented by general formula (i-12) include compounds represented by the following structural formulas (i-12-1) to (i-12-4).

Specific examples of the compound represented by the general formula (i-13) include compounds represented by the following structural formulas (i-13-1) to (i-13-4).

General formula (i), general formulas (i-1) to (i-13), structural formulas (i-1-1) to (i-1-16), structural formulas (i-2-1) to (i -2-9), structural formulas (i-3-1) to (i-3-12), structural formulas (i-4-1) to (i-4-15), structural formulas (i-5-1) ) to (i-5-12), structural formulas (i-6-1) to (i-6-12), structural formulas (i-7-1) to (i-7-6), structural formulas (i -8-1) ~ (i-8-4), structural formulas (i-9-1) ~ (i-9-8),
Structural formulas (i-10-1) to (i-10-4), structural formulas (i-11-1) to (i-11-8), structural formulas (i-12-1) to (i-12 -4) or the types of polymerizable compounds represented by structural formulas (i-13-1) to (i-13-4) used in the polymerizable compound-containing liquid crystal composition are one or more, preferably 1 to 5 types, preferably 1 to 4 types, preferably 1 to 3 types, preferably 1 to 2 types, preferably 1 type.

General formula (i), general formulas (i-1) to (i-13), structural formulas (i-1-1) to (i-1-16), structural formulas (i-2-1) to (i -2-9), structural formulas (i-3-1) to (i-3-12), structural formulas (i-4-1) to (i-4-15), structural formulas (i-5-1) ) to (i-5-12), structural formulas (i-6-1) to (i-6-12), structural formulas (i-7-1) to (i-7-6), structural formulas (i -8-1) ~ (i-8-4), structural formulas (i-9-1) ~ (i-9-8),
Structural formulas (i-10-1) to (i-10-4), structural formulas (i-11-1) to (i-11-8), structural formulas (i-12-1) to (i-12 -4) or the lower limit of the total content of polymerizable compounds represented by structural formulas (i-13-1) to (i-13-4) in 100% by mass of the polymerizable compound-containing liquid crystal composition is 0 It is preferably 0.01% by mass or more, preferably 0.05% by mass or more, and preferably 1.0% by mass or more.

General formula (i), general formulas (i-1) to (i-13), structural formulas (i-1-1) to (i-1-16), structural formulas (i-2-1) to (i -2-9), structural formulas (i-3-1) to (i-3-12), structural formulas (i-4-1) to (i-4-15), structural formulas (i-5-1) ) to (i-5-12), structural formulas (i-6-1) to (i-6-12), structural formulas (i-7-1) to (i-7-6), structural formulas (i -8-1) ~ (i-8-4), structural formulas (i-9-1) ~ (i-9-8),
Structural formulas (i-10-1) to (i-10-4), structural formulas (i-11-1) to (i-11-8), structural formulas (i-12-1) to (i-12 -4) or the upper limit of the total content of polymerizable compounds represented by structural formulas (i-13-1) to (i-13-4) in 100% by mass of the polymerizable compound-containing liquid crystal composition is 1 0% by mass or less is preferable, 0.7% by mass or less is preferable, and 0.5% by mass or less is preferable.

General formula (i), general formulas (i-1) to (i-13), structural formulas (i-1-1) to (i-1-16), structural formulas (i-2-1) to (i -2-9), structural formulas (i-3-1) to (i-3-12), structural formulas (i-4-1) to (i-4-15), structural formulas (i-5-1) ) to (i-5-12), structural formulas (i-6-1) to (i-6-12), structural formulas (i-7-1) to (i-7-6), structural formulas (i -8-1) ~ (i-8-4), structural formulas (i-9-1) ~ (i-9-8),
Structural formulas (i-10-1) to (i-10-4), structural formulas (i-11-1) to (i-11-8), structural formulas (i-12-1) to (i-12 -4) or the total content of polymerizable compounds represented by structural formulas (i-13-1) to (i-13-4) in 100% by mass of the polymerizable compound-containing liquid crystal composition has a high voltage holding rate. From the viewpoint of compatibility between (VHR) and low-temperature storage stability, it is preferably 0.01 to 1.0% by mass, preferably 0.05 to 0.7% by mass, and 0.1 to 0.5% by mass. % by mass is preferred.

A polymerizable compound (including subordinate concepts) represented by general formula (i) can be synthesized using a known synthesis method.

(sensitizing compound)
The polymerizable compound-containing liquid crystal composition according to the present invention contains one or more sensitizing compounds.
A sensitizing compound is a compound capable of sufficiently polymerizing a polymerizable compound at a higher rate due to its sensitizing action. The effect of using a sensitizing compound is that the polymerizable compound can be sufficiently polymerized at a high rate, so that a large pretilt can be formed with weak or little UV light, and high pretilt stability can be achieved. be able to. Furthermore, since the polymer can be polymerized at a high speed, the UV irradiation time can be shortened, so deterioration of the liquid crystal composition due to UV irradiation can be suppressed, and a decrease in voltage holding ratio (VHR) can be suppressed.

The sensitizing compound is preferably a naphthalene compound, more preferably a sensitizing compound represented by the following general formula (SC).

In general formula (SC), R ^SC1 and R ^SC2 each independently represent an alkyl group having 1 to 20 carbon atoms.
One or more —CH ₂ — in the alkyl group may be independently substituted with —O—, —NH—.
In addition, one or two or more —CH ₂ —CH ₂ — in the alkyl group are each independently —CH═CH—, —C≡C—, —CO—O— or —O—CO - may be substituted.
Also, one or more hydrogen atoms in the alkyl group may each independently be substituted with a halogen atom.
Halogen atoms include fluorine, chlorine, bromine and iodine atoms.
However, when the alkyl group is substituted with a predetermined group, the oxygen atoms are not directly bonded to each other.

The alkyl group having 1 to 20 carbon atoms is a linear, branched or cyclic alkyl group, preferably a linear alkyl group.
The number of carbon atoms in the alkyl group having 1 to 20 carbon atoms is preferably 2 to 10, preferably 2 to 6.

For example, R ^SC1 and R ^SC2 can represent an alkoxy group having 1 to 19 carbon atoms by substituting one —CH ₂ — in the alkyl group with —O—.
The alkoxy group is a linear, branched or cyclic alkoxy group, preferably a linear alkoxy group.
The number of carbon atoms in the alkoxy group is preferably 2-10, preferably 2-6.

In addition, R ^SC1 and R ^SC2 are alkenyl groups having 2 to 20 carbon atoms by substituting one or more —CH ₂ —CH ₂ — in the alkyl group with —CH═CH—. group.
The alkenyl group is a linear, branched or cyclic alkenyl group, preferably a linear alkenyl group.
The number of carbon atoms in the alkenyl group is preferably 2-10, preferably 2-6.

R ^SC1 and R ^SC2 are alkynyls having 2 to 20 carbon atoms, obtained by substituting one or more —CH ₂ —CH ₂ — in the alkyl group with —C≡C—. group.
The alkynyl group is a linear, branched or cyclic alkynyl group, preferably a linear alkynyl group.
The number of carbon atoms in the alkynyl group is preferably 2-10, preferably 2-6.

In R ^SC1 and R ^SC2 , one —CH ₂ — in the alkyl group is substituted with —O—, and one or two or more —CH ₂ —CH ₂ — are —CH═CH— can represent an alkenyloxy group having 2 to 19 carbon atoms.
The alkenyloxy group is a linear, branched or cyclic alkenyloxy group, preferably a linear alkenyloxy group.
The number of carbon atoms in the alkenyloxy group is preferably 2-10, preferably 2-6.

Further, R ^SC1 and R ^SC2 can represent a halogenated alkyl group having 1 to 20 carbon atoms by substituting one or more hydrogen atoms in the alkyl group with a halogen atom. .
The halogenated alkyl group is a linear, branched or cyclic halogenated alkyl group, preferably a linear halogenated alkyl group.
The number of carbon atoms in the halogenated alkyl group is preferably 2-10, preferably 2-6.

In R ^SC1 and R ^SC2 , one —CH ₂ — in the alkyl group is substituted with —O—, and one or more hydrogen atoms in the alkyl group are substituted with halogen atoms. can represent a halogenated alkoxy group having 1 to 19 carbon atoms.
The halogenated alkoxy group is a linear, branched or cyclic halogenated alkoxy group, preferably a linear halogenated alkoxy group.
The number of carbon atoms in the halogenated alkoxy group is preferably 2-10, preferably 2-6.

Specific examples of alkyl groups (including substituted ones) having 1 to 20 carbon atoms in R ^SC1 and R ^SC2 are represented by formulas (R ^SC1/2 -1) to (R ^SC1/2 -31). and the like.

In formulas (R ^SC1/2 -1) to (R ^SC1/2 -21), black dots represent bonds to naphthalene-2,6-diyl groups, 1,4-phenylene groups or A ^SC1 .

In general formula (SC), S ^SC2 , S ^SC3 , S ^SC5 and S ^SC6 each independently represent a hydrogen atom (H) or a fluorine atom (F).
Combinations of S ^SC2 , S ^SC3 , S ^SC5 and S ^SC6 (S ^SC2 , S ^SC3 , S ^SC5 , S ^SC6 ) are (H, H, H, H), (F, H, H, H), ( H, F, H, H) or (F, F, H, H) are preferred.

In general formula (SC), A ^SC1 is each independently the following group (a) and group (b):
(a) a 1,4-cyclohexylene group (one —CH ₂ — or two or more non-adjacent —CH ₂ — present in this group may be replaced with —O— and/or —S—; good.),
(b) a 1,4-phenylene group (one -CH= or two or more non-adjacent -CH= present in this group may be replaced with -N=);
represents a group selected from the group consisting of

One or more hydrogen atoms in A ^SC1 may each independently be substituted with a substituent Sr ^SC1 .
The substituent Sr 2 ^SC1 represents a halogen atom or an alkyl group having 1 to 20 carbon atoms.
One or more —CH ₂ — in the alkyl group may be independently substituted with —O—, —NH—.
In addition, one or two or more —CH ₂ —CH ₂ — in the alkyl group are each independently —CH═CH—, —C≡C—, —CO—O— or —O—CO - may be substituted.
Also, one or more hydrogen atoms in the alkyl group may each independently be substituted with a halogen atom.
Halogen atoms include fluorine, chlorine, bromine and iodine atoms.
However, when the alkyl group is substituted with a predetermined group, the oxygen atoms are not directly bonded to each other.

The alkyl group having 1 to 20 carbon atoms is a linear, branched or cyclic alkyl group, preferably a linear alkyl group.
The number of carbon atoms in the alkyl group having 1 to 20 carbon atoms is preferably 2 to 10, preferably 2 to 6.

For example, the substituent Sr 2 ^SC1 can represent an alkoxy group having 1 to 19 carbon atoms by substituting one —CH ₂ — in the alkyl group with —O—.
The alkoxy group having 1 to 19 carbon atoms is a linear, branched or cyclic alkoxy group, preferably a linear alkoxy group.
The number of carbon atoms in the alkoxy group having 1 to 19 carbon atoms is preferably 2 to 10, preferably 2 to 6.

Further, the substituent Sr 2 ^SC1 can represent an alkoxyalkyl group having 1 to 19 carbon atoms by substituting one —CH ₂ — in the alkyl group with —O—.
The alkoxyalkyl group having 1 to 19 carbon atoms is a linear, branched or cyclic alkoxyalkyl group, preferably a linear alkoxyalkyl group.
The number of carbon atoms in the alkoxyalkyl group having 1 to 19 carbon atoms is preferably 2 to 10, preferably 2 to 6.

Further, the substituent Sr 2 ^SC1 is a halogenated alkyl group having 1 to 20 carbon atoms by independently substituting one or more hydrogen atoms in the alkyl group with a halogen atom. can be represented.
The halogenated alkyl group having 1 to 20 carbon atoms is a linear, branched or cyclic halogenated alkyl group, preferably a linear halogenated alkyl group.
The number of carbon atoms in the halogenated alkyl group having 1 to 20 carbon atoms is preferably 2 to 10, preferably 2 to 6.

The substituent Sr ^SC1 is obtained by substituting one —CH ₂ — in the alkyl group with —O— and substituting one or more hydrogen atoms in the alkyl group with a halogen atom. , can represent a halogenated alkoxy group having 1 to 19 carbon atoms.
The halogenated alkoxy group is a linear, branched or cyclic halogenated alkoxy group, preferably a linear halogenated alkoxy group.
The number of carbon atoms in the halogenated alkoxy group is preferably 2-10, preferably 2-6.

Specific examples of the alkyl group (including substituted ones) having 1 to 20 carbon atoms in the substituent Sr 2 ^SC1 include groups represented by formulas (Sr 2 ^SC1 -1) to (Sr 2 ^SC1 -21). be done.

In the formulas (Sr ^SC1 −1) to (Sr ^SC1 −21), black dots represent bonds to A ^SC1 .
The substituent Sr ^{2 SC1} is preferably a halogen atom, preferably a fluorine atom.
When multiple substituents Sr ^{2 SC1} are present, they may be the same or different.

The substitution position of the substituent Sr 2 ^SC1 in A ^SC1 is preferably any one of the following formulas (A ^SC1 -SP-1) to (A ^SC1 -SP-3).

In formulas (A ^SC1 -SP-1) to (A ^SC1 -SP-3), white dots represent bonds to the 1,4-phenylene group, and black dots represent bonds to R ^SC2 .

More specifically, A ^SC1 preferably represents any one of the following formulas (A ^SC1 -1) to (A ^SC1 -3).

In formulas (A ^SC1 -1) to (A ^SC1 -3), white dots represent bonds to the 1,4-phenylene group, and black dots represent bonds to R ^SC2 .

In general formula (SC), n ^SC1 represents an integer of 0 to 1, preferably 0.

The polymerizable compound represented by general formula (SC) is preferably a compound selected from the group consisting of compounds represented by general formulas (SC-1) to (SC-14) below.

In general formulas (SC-1) to (SC-7), R ^SC1 and R ^SC2 each independently have the same meaning as R ^SC1 and R ^SC2 in general formula (SC) above.

Specific examples of the compound represented by general formula (SC-1) include compounds represented by the following structural formula (SC-1-1).

Specific examples of the compound represented by general formula (SC-4) include compounds represented by the following structural formula (SC-4-1).

Polymerizable compounds of sensitizing compounds represented by general formula (SC), general formulas (SC-1) to (SC-7), structural formula (SC-1-1) or structural formula (SC-4-1) The types used in the containing liquid crystal composition are 1 or 2 or more, preferably 1 to 5, preferably 1 to 4, preferably 1 to 3, preferably 1 to 2, preferably 1. .

Polymerizable compounds of sensitizing compounds represented by general formula (SC), general formulas (SC-1) to (SC-7), structural formula (SC-1-1) or structural formula (SC-4-1) The lower limit of the total content in 100% by mass of the liquid crystal composition is preferably 0.01% by mass or more, preferably 0.03% by mass or more, and 0.04% by mass or more. is preferred, and 0.05% by mass or more is preferred.

Polymerizable compounds of sensitizing compounds represented by general formula (SC), general formulas (SC-1) to (SC-7), structural formula (SC-1-1) or structural formula (SC-4-1) The upper limit of the total content in 100% by mass of the liquid crystal composition is preferably 0.25% by mass or less, preferably 0.2% by mass or less, and preferably 0.15% by mass or less.

Polymerizable compounds of sensitizing compounds represented by general formula (SC), general formulas (SC-1) to (SC-7), structural formula (SC-1-1) or structural formula (SC-4-1) The total content in 100% by mass of the liquid crystal composition is preferably 0.01 to 0.25% by mass, from the viewpoint of achieving both a high voltage holding ratio (VHR) and monomer reactivity, and 0.03 to 0.03% by mass. It is preferably 0.2 mass %, preferably 0.04 to 0.15 mass %, preferably 0.05 to 0.15 mass %.

A sensitizing compound represented by general formula (SC) (including subordinate concepts) can be synthesized using a known synthesis method.

(Polymerizable liquid crystal compound having a structure different from that of general formula (i))
The polymerizable compound-containing liquid crystal composition according to the present invention may contain one or more polymerizable compounds having a structure different from that of general formula (i).
For example, polymerizable compounds having a structure different from that of general formula (i) include polymerizable compounds represented by general formula (ii) below.

In general formula (ii), R ⁱⁱ¹ , R ⁱⁱ² , R ⁱⁱ³ , R ⁱⁱ⁴ , R ⁱⁱ⁵ , R ⁱⁱ⁶ , R ⁱⁱ⁷ and R ⁱⁱ⁸ each independently represent an alkyl group having 1 to 18 carbon atoms; represents any one of 1 to 18 alkoxy groups, halogen atoms, P ⁱⁱ³ -Sp ⁱⁱ³ - or hydrogen atoms;
The alkyl group having 1 to 18 carbon atoms may be straight chain, branched or cyclic, but straight chain is preferred from the viewpoint of obtaining good orientation.
The number of carbon atoms in the alkyl group having 1 to 18 carbon atoms is preferably 1 to 3 when the solubility in the polymerizable compound-containing liquid crystal composition is important, and the vertical alignment property of the polymerizable compound-containing liquid crystal composition is improved. 10 to 18 is preferable when it is important.
The alkoxy group having 1 to 18 carbon atoms may be straight-chain, branched or cyclic, but straight-chain is preferred from the viewpoint of obtaining good orientation.
The number of carbon atoms in the alkoxy group having 1 to 18 carbon atoms is preferably 1 to 3 when the solubility in the polymerizable compound-containing liquid crystal composition is emphasized, and the vertical alignment property of the polymerizable compound-containing liquid crystal composition is improved. 10 to 18 is preferable when it is important.
Halogen atoms include fluorine, chlorine, bromine and iodine atoms.

From the viewpoint of ensuring compatibility with the liquid crystal compound, at least one of R ⁱⁱ¹ , R ¹ⁱ² , R ⁱⁱ⁵ , R ⁱⁱ⁶ and R ⁱⁱ⁸ is preferably a halogen atom, more preferably a fluorine atom.

In general formula (ii), P ⁱⁱ¹ , P ⁱⁱ² and P ⁱⁱ³ each independently represent a polymerizable group.
Polymerizable groups are, for example, groups suitable for chain polymerization such as radical, cationic or anionic polymerization and/or sequential polymerization such as polyaddition or polycondensation.
The polymerizable group includes a carbon-carbon double bond (>C=C<), a carbon-carbon triple bond (-C≡C-) and/or an n-membered ring structure (n is 3 It is preferably a group containing an integer of to 7).

Also, the polymerizable group is preferably a group selected from the group consisting of the following general formulas (P ^ii1/2/3 −1) to (P ^ii1/2/3 −8).

In the general formulas (P ^ii1/2/3 −1) to (P ^ii1/2/3 −8), S ^ii1/2/3 are each independently a hydrogen atom, an alkyl group having 1 to 5 carbon atoms or represents a halogenated alkyl group having 1 to 5 carbon atoms.
The alkyl group having 1 to 5 carbon atoms includes methyl group, ethyl group, propyl group and the like.
Examples of halogenated alkyl groups having 1 to 5 carbon atoms include trifluoromethyl group and difluoroethyl group.
S ^ii1/2/3 are each independently preferably a hydrogen atom, a methyl group, an ethyl group or a propyl group.

In general formulas (P ^ii1/2/3 −1) to (P ^ii1/2/3 −8), * represents a point of attachment to Sp ⁱⁱ¹ , Sp ⁱⁱ² or Sp ⁱⁱ³ .

From the viewpoint of ensuring appropriate reactivity, among others, P ⁱⁱ¹ , P ⁱⁱ² and P ⁱⁱ³ are each independently represented by the formula (P ^ii1/2/3 −1), the formula (P ^ii1/2/3 −2), Formula (P ^ii1/2/3 −3), Formula (P ^ii1/2/3 −4), Formula (P ^ii1/2/3 −5) or Formula (P ^ii1/2/3 −7) is preferred, the formula (P ^ii1/2/3 -1), the formula (P ^ii1/2/3 -2), the formula (P ^ii1/2/3 -3) or the formula (P ^ii1/2/3 -7) is preferably a formula (P ^ii1/2/3 −1), an acrylic group (in the formula (P ^ii1/2/3 −1), S ^ii1/2/3 = hydrogen atom) or It is preferably a methacryl group (S ^ii1/2/3 =methyl group in the formula (P ^ii1/2/3 -1)), preferably a methacryl group.

P ⁱⁱ¹ , P ⁱⁱ² and P ⁱⁱ³ may be the same or different, but P ⁱⁱ¹ and P ⁱⁱ² are preferably the same.
When P ⁱⁱ¹ , P ⁱⁱ² and P ^{ii3 select} the same formula (P ^ii1/2/3 −1) to (P ^ii1/2/3 −8), the same code in the formula ( S ^ii1/2/3 ) may be the same or different.

Further, from the viewpoint of compatibility with the liquid crystal compound, in the polymerizable compound represented by the general formula (ii), R ⁱⁱ¹ , R ⁱⁱ² , R ⁱⁱ³ , R ⁱⁱ⁴ , R ⁱⁱ⁵ , R ⁱⁱ⁶ , R ⁱⁱ⁷ and R ⁱⁱ⁸ , at least one of R ⁱⁱ¹ , R ⁱⁱ² , R ⁱⁱ³ , R ⁱⁱ⁴ , R ⁱⁱ⁵ , R ⁱⁱ⁶ , R ⁱⁱ⁷ and R ⁱⁱ⁸ is a halogen atom, an alkyl group having 1 to 18 carbon atoms, It preferably represents an alkoxy group having 1 to 18 carbon atoms or P ⁱⁱ³ -Sp ⁱⁱ³ -.

In general formula (ii), Sp ⁱⁱ¹ , Sp ⁱⁱ² and Sp ⁱⁱ³ each independently represent a single bond or a spacer group.
A spacer group is a flexible group.
The spacer group more specifically represents an alkylene group having 1 to 15 carbon atoms.
One or more —CH ₂ — in the alkylene group may be independently substituted with —O—.
Also, one or more —CH ₂ —CH ₂ — in the alkylene group may be independently substituted with —O—CO— or —CO—O—.
However, when the alkylene group is substituted with a predetermined group, the oxygen atoms are not directly bonded to each other.
Also, Sp ⁱⁱ¹ , Sp ⁱⁱ² and Sp ⁱⁱ³ may be the same or different.

The alkylene group having 1 to 15 carbon atoms is a linear, branched or cyclic alkylene group, preferably a linear alkylene group.
The number of carbon atoms in the alkylene group having 1 to 15 carbon atoms is preferably 1 to 8, preferably 1 to 4, and preferably 2 to 3.

More specifically, Sp ⁱⁱ¹ , Sp ⁱⁱ² and Sp ⁱⁱ³ are each independently a single bond, —CH ₂ —, —CH ₂ —CH ₂ —, —CH ₂ —CH ₂ —CH ₂ —, —O -, -CH ₂ -O-, -CH ₂ -CH ₂ -O-, or -CH ₂ -CO-O- is preferred.
Moreover, both Sp ⁱⁱ¹ and Sp ⁱⁱ² are preferably single bonds.

In general formula (ii), L ⁱⁱ¹ represents either a single bond or an alkylene group having 1 to 20 carbon atoms.
The alkylene group is a linear, branched or cyclic alkylene group, preferably a linear alkylene group.
The number of carbon atoms in the alkylene group is preferably 2-10, preferably 2-6.
One or more —CH ₂ — in the alkylene group may each independently be replaced with —O—, —CF ₂ — and/or —CO—.
In addition, one or two or more —CH ₂ —CH ₂ — in the alkylene group are each independently —CH ₂ —CH(CH ₃ )—, —CH(CH ₃ )—CH ₂ —, -CH=CH-, -CF=CF-, -CH=C(CH ₃ )-, -C(CH ₃ )=CH-, -CH=N-, -N=CH-, -N=N-, may be substituted with -C≡C-, -CO-O- and/or -O-CO-.
However, when the alkylene group is substituted with a predetermined group, the oxygen atoms are not directly bonded to each other.

Specific examples of the alkylene group having 2 to 20 carbon atoms (including substituted ones) include groups represented by formulas (L ⁱⁱ¹ -1) to (L ⁱⁱ¹ -24).

In formulas (L ⁱⁱ¹ -1) to (L ⁱⁱ¹ -24), white dots and black dots represent bonds to 1,4-phenylene groups.

In general formula (ii), ⁿⁱⁱ¹ represents an integer of 1-2.
When n ⁱⁱ¹ represents 2, a plurality of R ⁱⁱ⁵ , R ⁱⁱ⁶ , R ⁱⁱ⁷ , R ⁱⁱ⁸ , and L ⁱⁱ¹ may be the same or different.

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

In general formulas (ii-1) to (ii-3), Sp ⁱⁱ¹ , Sp ⁱⁱ² , R ⁱⁱ⁶ and R ⁱⁱ⁷ have the same meanings as Sp ⁱⁱ¹ , ^{Spi ii2} , R ⁱⁱ⁶ and R ⁱⁱ⁷ in general formula (ii) above. represents

Specific examples of the polymerizable compound represented by the general formula (ii-1) include polymerizable compounds represented by the following structural formulas (ii-1-1) to (ii-1-4). .

Specific examples of the polymerizable compound represented by the general formula (ii-2) include polymerizable compounds represented by the following structural formulas (ii-2-1) to (ii-1-2). .

Specific examples of the polymerizable compound represented by general formula (ii-3) include polymerizable compounds represented by the following structural formula (ii-3-1).

general formula (ii), general formulas (ii-1) to (ii-3), structural formulas (ii-1-1) to (ii-1-4), structural formulas (ii-2-1) to (ii -2-2) or the type of the polymerizable liquid crystal compound represented by the structural formula (ii-3-1) used in the polymerizable compound-containing liquid crystal composition is preferably one or two or more. It is preferably 5 types, preferably 1 to 4 types, preferably 1 to 3 types, preferably 1 to 2 types, and preferably 1 type.

general formula (ii), general formulas (ii-1) to (ii-3), structural formulas (ii-1-1) to (ii-1-4), structural formulas (ii-2-1) to (ii -2-2) or the lower limit of the total content of the polymerizable compound represented by the structural formula (ii-3-1) in 100% by mass of the polymerizable compound-containing liquid crystal composition is 0.1% by mass or more. It is preferably 0.15% by mass or more, and preferably 0.2% by mass or more.

general formula (ii), general formulas (ii-1) to (ii-3), structural formulas (ii-1-1) to (ii-1-4), structural formulas (ii-2-1) to (ii -2-2) or the upper limit of the total content of the polymerizable compound represented by the structural formula (ii-3-1) in 100% by mass of the polymerizable compound-containing liquid crystal composition is 1.0% by mass or less. It is preferably 0.7% by mass or less, preferably 0.5% by mass or less.

general formula (ii), general formulas (ii-1) to (ii-3), structural formulas (ii-1-1) to (ii-1-4), structural formulas (ii-2-1) to (ii -2-2) or the total content of the polymerizable compound represented by the structural formula (ii-3-1) in 100% by mass of the polymerizable compound-containing liquid crystal composition is 0.1 to 1.0% by mass. preferably 0.15 to 0.7% by mass, preferably 0.2 to 0.5% by mass.

A polymerizable compound represented by general formula (ii) (including subordinate concepts) can be synthesized using a known synthesis method.

(Polymerizable compound-containing liquid crystal composition)
The polymerizable compound-containing liquid crystal composition according to the present invention includes, for example, the polymerizable compound represented by the above general formula (i), the sensitizing compound (SC), the liquid crystal composition used for the polymerizable compound-containing liquid crystal composition, It can be produced by mixing a polymerizable compound having a structure different from that of general formula (i) and an additive, if necessary.
The liquid crystal composition used for the polymerizable compound-containing liquid crystal composition contains one or more liquid crystal compounds.

(liquid crystal compound)
The liquid crystal compound has a dielectric anisotropy at 20° C. that is negative (Δε<−2), neutral (−2≦Δε≦2), and positive (2<Δε). A liquid crystal compound is mentioned.
The dielectric anisotropy (Δε) of the liquid crystal compound is a value extrapolated from the measured value of the dielectric anisotropy of a composition obtained by adding a liquid crystal compound to a composition that is dielectrically almost neutral at 20°C. is.

Further, the liquid crystal compound preferably does not contain a naphthalene ring structure in its structure.
That is, the liquid crystal compound is preferably not a naphthalene compound.

The liquid crystal compound having a negative dielectric anisotropy (Δε<−2) at 20° C. is selected from the group consisting of liquid crystal compounds represented by any of the following general formulas (N-01) to (N-05): It is preferably a compound of choice.

In general formulas (N-01) to (N-05), R ^N1 and R ^N2 are each independently an alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, and a number of carbon atoms. It represents an alkenyl group having 2 to 8 carbon atoms or an alkenyloxy group having 2 to 8 carbon atoms.
One or more —CH ₂ — in the group may each independently be substituted with —C≡C—, —CO—, —CO—O— or —O—CO— .
However, when the group is substituted with a predetermined group, the oxygen atoms are not directly bonded to each other.

R ^{1 N1} is preferably an alkyl group having 1 to 8 carbon atoms, preferably an alkyl group having 1 to 5 carbon atoms, and more preferably an alkyl group having 2 to 4 carbon atoms.
However, when Z ^{1 N1} represents other than a single bond, R ^{1 N1} is preferably an alkyl group having 1 to 3 carbon atoms.

R ^N2 is preferably an alkyl group having 1 to 8 carbon atoms or an alkoxy group having 1 to 8 carbon atoms, preferably an alkyl group having 1 to 5 carbon atoms or an alkoxy group having 1 to 4 carbon atoms. , an alkoxy group having 1 to 4 carbon atoms.

Examples of alkenyl groups having 2 to 8 carbon atoms include formulas (R1) to (R7), with formula (R1) or formula (R2) being preferred.

In formulas (R1) to (R7), a black dot represents a bond to a ring structure.

In general formulas (N-01) to (N-05), Z ^N1 is each independently a single bond, -CH ₂ -CH ₂ -, -O-CH ₂ -, -CH ₂ -O-, - represents CO—O—, —O—CO—, —O—CF ₂ —, —CF ₂ —O—, —CH═CH—, —CF═CF— or —C≡C—.

In general formulas (N-01) to (N-05), m ^N1 each independently represents 1 or 2.

When m ^N1 is 1, Z ¹ is preferably a single bond or -CH ₂ -O-.
When m ^N1 is 2, Z ¹ is preferably a single bond, -CH ₂ -CH ₂ - or -CH ₂ -O-.

Hydrogen atoms present on the rings of the liquid crystal compounds represented by general formulas (N-01) to (N-05) may each independently be substituted with a fluorine atom or a chlorine atom.

The polymerizable compound-containing liquid crystal composition according to the present invention is a compound group represented by general formulas (N-01-1) to (N-01-4) as the compound represented by general formula (N-01). It is preferable to contain one or two or more compounds selected from.

In general formulas (N-01-1) to (N-01-4), R ^N3 and R ^N4 are each independently an alkyl group having 1 to 5 carbon atoms and an alkenyl group having 2 to 5 carbon atoms. or represents an alkoxy group having 1 to 4 carbon atoms.

Examples of the liquid crystal compound represented by the general formula (N-01-1) include liquid crystal compounds represented by the following structural formulas (N-01-1.1) to (N-01-1.2). .

Examples of the liquid crystal compound represented by the general formula (N-01-2) include liquid crystal compounds represented by the following structural formulas (N-01-2.1) to (N-01-2.5). .

Examples of the liquid crystal compound represented by the general formula (N-01-3) include liquid crystal compounds represented by the following structural formulas (N-01-3.1) to (N-01-3.3). .

Examples of the liquid crystal compound represented by the general formula (N-01-4) include liquid crystal compounds represented by the following structural formulas (N-01-4.1) to (N-01-4.4). .

The polymerizable compound-containing liquid crystal composition according to the present invention is a compound group represented by general formulas (N-02-1) to (N-02-3) as compounds represented by general formula (N-02). It is preferable to contain one or two or more compounds selected from.

In general formulas (N-02-1) to (N-02-3), each R ^N3 independently represents an alkyl group having 1 to 5 carbon atoms.
In general formulas (N-02-1) to (N-02-3), each R ^N4 independently represents an alkoxy group having 1 to 4 carbon atoms.

Examples of the liquid crystal compound represented by the general formula (N-02-1) include liquid crystal compounds represented by the following structural formula (N-02-1.1).

In the liquid crystal composition containing a polymerizable compound according to the present invention, one or more liquid crystal compounds represented by the general formula (N-03-1) are used as the liquid crystal compound represented by the general formula (N-03). It is preferable to contain.

In general formula (N-03-1), R 3 ^N3 represents an alkyl group having 1 to 5 carbon atoms.
In general formula (N-03-1), R ^{4 N4} represents an alkoxy group having 1 to 4 carbon atoms.

Examples of the liquid crystal compound represented by the general formula (N-03-1) include liquid crystal compounds represented by the following structural formulas (N-03-1.1) to (N-03-1.5). .

In the liquid crystal composition containing a polymerizable compound according to the present invention, one or more liquid crystal compounds represented by general formula (N-04-1) are used as the liquid crystal compound represented by general formula (N-04). It is preferable to contain.

In general formula (N-04-1), R 3 ^N3 represents an alkyl group having 1 to 5 carbon atoms.
In general formula (N-04-1), R ^{4 N4} represents an alkoxy group having 1 to 4 carbon atoms.

Examples of the liquid crystal compound represented by the general formula (N-04-1) include liquid crystal compounds represented by the following structural formulas (N-04-1.1) to (N-04-1.3). .

The polymerizable compound-containing liquid crystal composition according to the present invention is a compound group represented by structural formulas (N-05-1) to (N-05-2) as compounds represented by general formula (N-05). It may contain a liquid crystal compound selected from.

General formulas (N-01) to (N-05), general formulas (N-01-1) to (N-01-4), general formulas (N-02-1) to (N-02-3), General formula (N-03-1), general formula (N-04-1), structural formulas (N-01-1.1) to (N-01-1.2), structural formula (N-01-2) .1) to (N-01-2.5), structural formulas (N-01-3.1) to (N-01-3.3), structural formulas (N-01-4.1) to (N -01-4.4), structural formula (N-02-1.1), structural formulas (N-03-1.1) to (N-03-1.5), structural formula (N-04-1 .1) to (N-04-1.3) or liquid crystal compounds represented by structural formulas (N-05-1) to (N-05-2) are used in the polymerizable compound-containing liquid crystal composition, It is preferably 1 to 15 species, preferably 1 to 13 species, preferably 2 to 13 species, preferably 2 to 11 species, preferably 2 to 8 species.

General formula (N-01), general formulas (N-01-1) to (N-01-4), structural formulas (N-01-1.1) to (N-01-1.2), structural formulas (N-01-2.1) to (N-01-2.5), structural formulas (N-01-3.1) to (N-01-3.3) or structural formulas (N-01-4 .1) to (N-01-4.4) in the polymerizable compound-containing liquid crystal composition 100% by mass, the preferred lower limit of the total content of the liquid crystal compounds is 0% by mass, 1% by mass. , 5% by mass, 10% by mass, 20% by mass, 30% by mass, 40% by mass, 50% by mass, 55% by mass, and 60% by mass , 65% by mass, 70% by mass, 75% by mass, and 80% by mass.

General formula (N-01), general formulas (N-01-1) to (N-01-4,) structural formulas (N-01-1.1) to (N-01-1.2), structural formulas (N-01-2.1) to (N-01-2.5), structural formulas (N-01-3.1) to (N-01-3.3) or structural formulas (N-01-4 .1) to (N-01-4.4), the preferred upper limit of the total content of the liquid crystal compounds represented by (N-01-4.4) in 100% by mass of the polymerizable compound-containing liquid crystal composition is 95% by mass, and 85% by mass. , 75% by mass, 65% by mass, 55% by mass, 45% by mass, 35% by mass, 25% by mass, 20% by mass, and 15% by mass , 10% by weight.

Liquid crystal composition containing polymerizable compound of liquid crystal compound represented by general formula (N-02), general formulas (N-02-1) to (N-02-3) or structural formula (N-02-1.1) Preferred lower limits for the total content in 100% by mass of the substance are 0% by mass, 1% by mass, 5% by mass, 10% by mass, 20% by mass, and 30% by mass. , 40% by mass, 50% by mass, 55% by mass, 60% by mass, 65% by mass, 70% by mass, 75% by mass, and 80% by mass.

Liquid crystal composition containing polymerizable compound of liquid crystal compound represented by general formula (N-02), general formulas (N-02-1) to (N-02-3) or structural formula (N-02-1.1) The preferred upper limit of the total content in 100% by mass of the substance is 95% by mass, 85% by mass, 75% by mass, 65% by mass, 55% by mass, and 45% by mass. , 35% by mass, 25% by mass, 20% by mass, 15% by mass, and 10% by mass.

Containing polymerizable compounds of liquid crystal compounds represented by general formula (N-03), general formula (N-03-1) or structural formulas (N-03-1.1) to (N-03-1.5) Preferred lower limits of the total content in 100% by mass of the liquid crystal composition are 0% by mass, 1% by mass, 5% by mass, 10% by mass, 15% by mass, and 20% by mass. , 30% by mass, 40% by mass, 50% by mass, 55% by mass, 60% by mass, 65% by mass, 70% by mass, and 75% by mass , 80 mass %.

Containing polymerizable compounds of liquid crystal compounds represented by general formula (N-03), general formula (N-03-1) or structural formulas (N-03-1.1) to (N-03-1.5) Preferred upper limits of the total content in 100% by mass of the liquid crystal composition are 95% by mass, 85% by mass, 75% by mass, 65% by mass, 55% by mass, and 45% by mass. , 35% by mass, 25% by mass, 20% by mass, 15% by mass, and 10% by mass.

Containing polymerizable compounds of liquid crystal compounds represented by general formula (N-04), general formula (N-04-1) or structural formulas (N-04-1.1) to (N-04-1.3) Preferred lower limits of the total content in 100% by mass of the liquid crystal composition are 0% by mass, 1% by mass, 5% by mass, 10% by mass, 20% by mass, and 30% by mass. , 40% by mass, 50% by mass, 55% by mass, 60% by mass, 65% by mass, 70% by mass, 75% by mass, and 80% by mass .

Containing polymerizable compounds of liquid crystal compounds represented by general formula (N-04), general formula (N-04-1) or structural formulas (N-04-1.1) to (N-04-1.2) Preferred upper limits of the total content in 100% by mass of the liquid crystal composition are 95% by mass, 85% by mass, 75% by mass, 65% by mass, 55% by mass, and 45% by mass. , 35% by mass, 25% by mass, 20% by mass, 15% by mass, and 10% by mass.

Preferred lower limit of the total content of the liquid crystal compounds represented by the general formula (N-05) or the structural formulas (N-05-1) to (N-05-2) in 100% by mass of the polymerizable compound-containing liquid crystal composition The values are 0% by weight, 2% by weight, 5% by weight, 8% by weight, 10% by weight, 13% by weight, 15% by weight and 17% by weight. , 20 mass %.

A preferred upper limit of the total content of liquid crystal compounds represented by general formula (N-05) or structural formulas (N-05-1) to (N-05-2) in 100% by mass of the polymerizable compound-containing liquid crystal composition The values are 30% by weight, 28% by weight, 25% by weight, 23% by weight, 20% by weight, 18% by weight, 15% by weight and 13% by weight. .

Liquid crystal compounds having a neutral dielectric anisotropy at 20° C. (−2≦Δε≦2) include liquid crystal compounds represented by any of the following general formulas (NU-01) to (NU-08). It is preferably a compound selected from the group consisting of

In general formulas (NU-01) to (NU-08), R ^NU1 and R ^NU2 are each independently an alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, and a number of carbon atoms. It represents either an alkenyl group having 2 to 8 carbon atoms or an alkenyloxy group having 2 to 8 carbon atoms.
one or more —CH ₂ —CH ₂ — in said group are each independently substituted by —C≡C—, —CO—, —CO—O— or —O—CO— can be
However, when the group is substituted with a predetermined group, the oxygen atoms are not directly bonded to each other.

R ^NU1 and R ^NU2 are preferably alkyl groups having 1 to 5 carbon atoms or alkoxy groups having 1 to 5 carbon atoms, more preferably alkyl groups having 1 to 5 carbon atoms.
In the case of aiming at high-speed response, in general formula (NU-01), R ^NU1 is an alkenyl group having 2 to 3 carbon atoms, and R ^NU2 is an alkyl group having 1 to 6 carbon atoms. By including the compound in the polymerizable compound-containing liquid crystal composition according to the present invention, high-speed response can be reliably realized. This is because the compound has low viscosity or low rotational viscosity, and greatly contributes to both reliability improvement and responsiveness improvement.

More specifically, R ^NU1 is particularly preferably an alkyl group having 1 to 5 carbon atoms, and R ^NU2 is particularly preferably an alkyl group having 1 to 5 carbon atoms or an alkoxy group having 1 to 5 carbon atoms.

Examples of alkenyl groups having 2 to 3 carbon atoms include formulas (R1) to (R2), with formula (R1) or formula (R2) being preferred.

In formulas (R1) to (R2), a black dot represents a bond to a ring structure.

Liquid crystal compounds represented by the general formula (NU-01) include liquid crystal compounds represented by the following structural formulas (NU-01-1) to (NU-01-6).

Examples of the liquid crystal compound represented by the general formula (NU-02) include liquid crystal compounds represented by the following structural formulas (NU-02-1) to (NU-02-2).

Liquid crystal compounds represented by the general formula (NU-03) include liquid crystal compounds represented by the following structural formulas (NU-03-1) to (NU-03-4).

Examples of the liquid crystal compound represented by the general formula (NU-04) include liquid crystal compounds represented by the following structural formulas (NU-04-1) to (NU-04-2).

Examples of the liquid crystal compound represented by the general formula (NU-05) include liquid crystal compounds represented by the following structural formulas (NU-05-1) to (NU-05-4).

Preferred range of total content of liquid crystal compounds represented by general formula (NU-01) or structural formulas (NU-01-1) to (NU-01-6) in 100% by mass of polymerizable compound-containing liquid crystal composition is 15 to 55% by mass, 20 to 50% by mass, and 25 to 45% by mass.

Preferred range of total content of liquid crystal compounds represented by general formula (NU-02) or structural formulas (NU-02-1) to (NU-02-2) in 100% by mass of polymerizable compound-containing liquid crystal composition is 0 to 30% by mass, 0.5 to 25% by mass, and 1 to 20% by mass.

Preferred range of total content of liquid crystal compounds represented by general formula (NU-03) or structural formulas (NU-03-1) to (NU-03-4) in 100% by mass of polymerizable compound-containing liquid crystal composition is 0 to 25% by mass, 1 to 20% by mass, and 3 to 15% by mass.

Preferred range of total content of liquid crystal compounds represented by general formula (NU-04) or structural formulas (NU-04-1) to (NU-04-2) in 100% by mass of liquid crystal composition containing polymerizable compound is 0 to 25% by mass, 0.5 to 15% by mass, and 1 to 10% by mass.

Preferred range of total content of liquid crystal compounds represented by general formula (NU-05) or structural formulas (NU-05-1) to (NU-05-4) in 100% by mass of liquid crystal composition containing polymerizable compound is 0 to 30% by mass, 1 to 25% by mass, and 3 to 20% by mass.

The preferred range of the total content of the liquid crystal compound represented by the general formula (NU-06) in 100% by mass of the polymerizable compound-containing liquid crystal composition is preferably 0 to 30% by mass, preferably 0 to 20% by mass. and preferably 0 to 10% by mass.

A preferable range of the total content of the liquid crystal compound represented by the general formula (NU-07) in 100% by mass of the polymerizable compound-containing liquid crystal composition is preferably 0 to 30% by mass, and preferably 0 to 20% by mass. and preferably 0 to 10% by mass.

A preferable range of the total content of the liquid crystal compound represented by the general formula (NU-08) in 100% by mass of the polymerizable compound-containing liquid crystal composition is preferably 0 to 30% by mass, and preferably 0 to 20% by mass. and preferably 0 to 10% by mass.

The liquid crystal compound having a positive dielectric anisotropy (2<Δε) at 20° C. is selected from the group consisting of liquid crystal compounds represented by any of the following general formulas (P-01) to (P-02). It is preferably a compound that can be

In general formulas (P-01) to (P-02), R ^P11 is each independently an alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, or 2 to 8 carbon atoms. or an alkenyloxy group having 2 to 8 carbon atoms.
R ^P11 is preferably an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, an alkenyl group having 2 to 5 carbon atoms or an alkenyloxy group having 2 to 5 carbon atoms. An alkyl group having 1 to 5 carbon atoms or an alkenyl group having 2 to 5 carbon atoms is preferable, an alkyl group having 2 to 5 carbon atoms or an alkenyl group having 2 to 3 carbon atoms is preferable, and an alkenyl group having 3 carbon atoms ( propenyl groups) are particularly preferred.
R ^P11 is preferably an alkyl group when reliability is important, and an alkenyl group is preferable when viscosity reduction is important.
Further, when the ring structure to which R ^P11 is bonded is a phenyl group (aromatic), a linear alkyl group having 1 to 5 carbon atoms, a linear alkoxy group having 1 to 4 carbon atoms, Any of alkenyl groups having 4 to 5 carbon atoms is preferable, and when the ring structure to which R 1 ^P11 is bonded is a saturated ring structure such as cyclohexane, pyran and dioxane, a straight chain having 1 to 5 carbon atoms An alkyl group, a linear alkoxy group having 1 to 4 carbon atoms, or a linear alkenyl group having 2 to 5 carbon atoms is preferred. In order to stabilize the nematic phase, the total number of carbon atoms and, if present, oxygen atoms is preferably 5 or less, and is preferably linear.

Examples of alkenyl groups having 2 to 8 carbon atoms include groups represented by formulas (R1) to (R7), and formula (R1) or formula (R2) is preferable.

In general formulas (P-01) and (P-02), in each of ring A ^P11 , at least one of -CH ₂ - in the ring may be substituted with -O- or -S- represents either a 1,4-cyclohexylene group or a 1,4-phenylene group in which at least one -CH= in the ring may be substituted with -N=, and at least hydrogen atoms in ring A ^P11 One may be substituted with halogen.
A halogen atom includes a chlorine atom, a bromine atom, and a fluorine atom.
In addition, when there are a plurality of ring A ^P11 , they may be the same or different.

Ring A ^P11 is each independently a 1,4-phenylene group in which at least one —CH= in the ring may be substituted with —N= when it is required to increase Δn is preferred, and in order to improve the response speed, at least one -CH ₂ - in the ring is preferably a 1,4-cyclohexylene group optionally substituted with -O- or -S-, Any one of the structures represented by the following formulas (A ^P11 -1) to (A ^P11 -6) is more preferable.

L ^P11 is each independently a single bond, -C ₂ H ₄ -, -CH=CH-, -C≡C-, -COO-, -OCO-, -CH ₂ O-, -OCH ₂ -, represents either -CF ₂ O- or -OCF ₂ -;
In addition, when multiple ^LP11 exist, they may be the same or different.

In general formulas (P-01) to (P-02), m ^P11 represents an integer of 1 to 4.

In general formulas (P-01) to (P-02), Y ^P11 and Y ^P12 each independently represent either a hydrogen atom or a fluorine atom.

In general formulas (P-01) to (P-02), X ^P11 is —F, —Cl, —CN, —NCS, —CF ₃ , —OCF ₃ , and at least one hydrogen atom is substituted with a halogen atom. an alkyl group having 1 to 6 carbon atoms, or an alkoxy group having 1 to 6 carbon atoms in which at least one hydrogen atom is substituted with a halogen atom.
A halogen atom includes a chlorine atom, a bromine atom, and a fluorine atom.

As the liquid crystal compound represented by general formula (P-01), compounds represented by general formulas (P-01-1) to (P-01-28) are preferable.

In general formulas (P-01-1) to (P-01-28), R ^P12 is an alkyl group having 1 to 7 carbon atoms, an alkoxy group having 1 to 7 carbon atoms, a represents an alkenyl group.

As the compound represented by general formula (P-02), compounds represented by general formulas (P-02-1) to (P-02-6) are preferred.

In general formulas (P-02-1) to (P-02-6), R ^P12 is an alkyl group having 1 to 7 carbon atoms, an alkoxy group having 1 to 7 carbon atoms, a represents an alkenyl group.

The liquid crystal compounds represented by the general formulas (P-01) to (P-02) may be selected from either one group and used, or may be selected from each group and used in combination. can.

When emphasizing the reliability of the polymerizable compound-containing liquid crystal composition according to the present invention, general formulas (P-01-1) to (P-01-11), (P-01-16) to (P-01) -20) and general formulas (P-02-1) ~ (P-02-4) it is preferable to use a liquid crystal compound selected from the group represented by the general formula (P-01-1), ( P-01-2), (P-01-4), (P-01-17) and (P-01-20) are more preferably selected from the group.

When emphasizing low viscosity of the polymerizable compound-containing liquid crystal composition according to the present invention, general formulas (P-01-12) to (P-01-15), (P-01-21) to (P-01) -28) and (P-01-5) ~ (P-01-6) it is preferable to use a liquid crystal compound selected from the group represented by (P-01-12), (P-01- 13), (P-01-22), (P-01-23) and (P-01-26).

While emphasizing low viscosity of the polymerizable compound-containing liquid crystal composition according to the present invention, when further emphasizing improvement of transmittance in FFS mode, general formulas (P-01-14) and (P-01-15) , (P-01-25), (P-01-27) and (P-01-28).

In order to shorten the UV irradiation process time in the manufacturing process of the liquid crystal display element according to the present invention, general formulas (P-01-4) to (P-01-7), (P-01-20) and ( It is preferable to use a liquid crystal compound selected from the group represented by P-01-4), and among them, a liquid crystal compound selected from (P-01-4) or (P-01-20) is particularly preferable. By using a liquid crystal compound of the group (1), problems such as deterioration of the polymerizable compound-containing liquid crystal composition during UV irradiation, a decrease in the voltage holding ratio of the liquid crystal display element, and the occurrence of image sticking do not occur or the degree thereof is reduced. be able to.

General formulas (P-01) ~ (P-02), general formulas (P-01-1) ~ (P-01-28) and / or general formulas (P-02-1) ~ (P-02-6 ) can be appropriately selected according to the properties required for the liquid crystal display element, and can be used in combination of a plurality of types as necessary. It is preferable to use 12 types, preferably 2 to 10 types, and particularly preferably 3 to 8 types.

General formulas (P-01) to (P-02), general formulas (P-01-1) to (P-01-28) or general formulas (P-02-1) to (P-02-6) Preferred lower limits of the total content of the represented liquid crystal compounds in 100% by mass of the polymerizable compound-containing liquid crystal composition are 1% by mass, 10% by mass, 20% by mass, and 30% by mass. , 40% by mass, 50% by mass, 55% by mass, 60% by mass, 65% by mass, 70% by mass, 75% by mass, and 80% by mass.

General formulas (P-01) to (P-02), general formulas (P-01-1) to (P-01-28) or general formulas (P-02-1) to (P-02-6) Preferred upper limits of the total content of the represented liquid crystal compounds in 100% by mass of the polymerizable compound-containing liquid crystal composition are 95% by mass, 85% by mass, 75% by mass, and 65% by mass. , 55% by mass, 45% by mass, 35% by mass, and 25% by mass.

In the polymerizable compound-containing liquid crystal composition according to the present invention, general formulas (P-01) to (P-02), general formulas (P-01-1) to (P-01-28), or general formula (P -02-1) ~ (P-02-6) The total content of the liquid crystal compounds represented by (P-02-6), solubility at low temperature, transition temperature, electrical reliability, birefringence, dielectric anisotropy, etc. may be appropriately adjusted according to the required performance.
When the viscosity of the polymerizable compound-containing liquid crystal composition according to the present invention is kept low and the response speed is increased, it is preferable to lower the lower limit and the upper limit.
In order to keep the _TNI of the polymerizable compound-containing liquid crystal composition according to the present invention high and improve the temperature stability, it is preferable to lower the lower limit and the upper limit.
When increasing the dielectric anisotropy in order to keep the driving voltage of the polymerizable compound-containing liquid crystal composition according to the present invention low, it is preferable to increase the lower limit and the upper limit.

The polymerizable compound-containing liquid crystal composition according to the present invention may contain ordinary nematic liquid crystals, smectic liquid crystals, cholesteric liquid crystals, etc., in addition to the liquid crystal compounds described above.

The polymerizable compound-containing liquid crystal composition according to the present invention may contain additives.
Examples of additives include antioxidants, ultraviolet absorbers, light stabilizers, infrared absorbers, and the like.

As the antioxidant, antioxidants represented by general formulas (H-1) to (H-4) are preferred.

The lower limit of the total content of the antioxidant in 100% by mass of the polymerizable compound-containing liquid crystal composition is preferably 10 ppm by mass, preferably 20 ppm by mass, preferably 50 ppm by mass, and the upper limit is preferably 10000 ppm by mass. 1000 mass ppm is preferred, 500 mass ppm is preferred, 100 mass ppm is preferred.

In general formulas (H-1) to (H-3), each R ^{1 H1} independently represents an alkyl group having 3 to 7 carbon atoms.
More specifically, R 1 H1 in general formula (H-1) represents an alkyl group having 7 carbon atoms, R ^{1 H1} in general formula (H-2) represents an alkyl group having 3 carbon atoms, R ^{1 H1} in general formula (H-3) represents 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 two or more non-adjacent —CH ₂ — in the group are , may be substituted with -CO-O- or -O-CO-), single bond, 1,4-phenylene group (any hydrogen atom in the 1,4-phenylene group is substituted with a fluorine atom ) or represents a trans-1,4-cyclohexylene group.
The number of carbon atoms in the alkylene group having 4 to 10 carbon atoms is preferably 4 to 8.

A polymerization initiator may be added to the polymerizable compound-containing liquid crystal composition of the present invention for the purpose of speeding up the polymerization of the polymerizable compound.
A photopolymerization initiator is preferably selected as the polymerization initiator.
Photopolymerization initiators include diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzyldimethylketal, 1-(4-isopropylphenyl)-2-hydroxy-2-methylpropane- 1-one, 4-(2-hydroxyethoxy)phenyl-(2-hydroxy-2-propyl)ketone, 1-hydroxycyclohexyl-phenylketone, 2-methyl-2-morpholino(4-thiomethylphenyl)propane-1 -one, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone, 4'-phenoxyacetophenone, 4'-ethoxyacetophenone and other acetophenone series; benzoin, benzoin isopropyl ether, benzoin isobutyl ether, benzoin Benzoins such as methyl ether and benzoin ethyl ether; acylphosphine oxides such as 2,4,6-trimethylbenzoyldiphenylphosphine oxide; benzyl, methylphenylglyoxyester; benzophenone, methyl o-benzoylbenzoate, 4-phenyl benzophenone, 4,4'-dichlorobenzophenone, hydroxybenzophenone, 4-benzoyl-4'-methyl-diphenylsulfide, acrylated benzophenone, 3,3',4,4'-tetra(t-butylperoxycarbonyl)benzophenone, Benzophenone series such as 3,3′-dimethyl-4-methoxybenzophenone, 2,5-dimethylbenzophenone, 3,4-dimethylbenzophenone; 2-isopropylthioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2 Thioxanthone series such as ,4-dichlorothioxanthone; Michler's ketone, aminobenzophenone series such as 4,4'-diethylaminobenzophenone; 10-butyl-2-chloroacridone, 2-ethylanthraquinone, 9,10-phenanthrenequinone, and camphorquinone.

The upper limit of the total content of the photopolymerization initiator in the polymerizable compound-containing liquid crystal composition in 100% by mass of the polymerizable compound-containing liquid crystal composition is preferably 100 mass ppm, preferably 56 mass ppm, It is preferably 48 mass ppm, preferably 36 mass ppm.

The dielectric anisotropy at 25° C. of the liquid crystal composition used for the polymerizable compound-containing liquid crystal composition is negative (Δε<−2), neutral (−2≦Δε≦2), or positive (2<Δε). However, it is preferably negative (Δε<−2).
The value of dielectric anisotropy (Δε: measured at 25° C.) can be calculated from the formula Δε=ε∥−ε⊥.
Dielectric constants (ε∥, ε⊥) were measured as follows.
A) Measurement of dielectric constant (ε∥): A vertical alignment film was applied to a well-cleaned glass substrate and baked. Two glass substrates are arranged so that the alignment film coated surfaces face each other, and a spacer agent and a sealing agent are sandwiched so that the gap (cell gap) between the glass substrates is about 10 μm, and the sealing agent is cured to produce a vertical alignment device. got A liquid crystal composition used for a polymerizable compound-containing liquid crystal composition was injected into the vertical alignment element, and sealed with an adhesive that was cured by ultraviolet rays. A sine wave (0.3 V, 1 kHz) was applied to this vertical alignment device, and the permittivity (ε∥) in the longitudinal direction of the liquid crystal composition used for the polymerizable compound-containing liquid crystal composition was measured.
B) Measurement of dielectric constant (ε⊥): A horizontal alignment film was applied to a well-cleaned glass substrate, baked, and then rubbed. Two glass substrates are placed so that the alignment film coated surfaces face each other and the rubbing direction is 180°. Then, the anti-parallel horizontal alignment element was obtained by curing the sealant. A liquid crystal composition used for a polymerizable compound-containing liquid crystal composition was injected into the anti-parallel horizontal alignment element, and sealed with an ultraviolet curable adhesive. A sine wave (20.0 V, 1 kHz) was applied to this anti-parallel horizontal alignment element, and the permittivity (ε⊥) in the minor axis direction of the liquid crystal composition used for the polymerizable compound-containing liquid crystal composition was measured.

When the dielectric anisotropy at 25° C. of the liquid crystal composition used for the polymerizable compound-containing liquid crystal composition is negative (Δε<−2), the dielectric anisotropy (Δε) of the liquid crystal composition at 25° C. is , preferably less than -2.0 and -4.5 or more, preferably -2.1 to -4.3, preferably -2.3 to -4.0, -2.5 to -3.9 is preferred.

The liquid crystal phase upper limit temperature (nematic phase-isotropic liquid phase transition temperature, T _ni ) is the temperature at which the liquid crystal composition transitions from the nematic phase to the isotropic phase.
T _ni is measured by preparing a preparation in which the liquid crystal composition is sandwiched between a slide glass and a cover glass, and observing it with a polarizing microscope while heating it on a hot stage.
It can also be measured by differential scanning calorimetry (DSC), and the unit is "°C".
The higher the _Tni , the more the nematic phase can be maintained even at high temperatures, and the wider the operating temperature range can be taken.

When the dielectric anisotropy at 25° C. of the liquid crystal composition used for the polymerizable compound-containing liquid crystal composition is negative (Δε<−2), the nematic phase-isotropic liquid phase transition temperature (T _ni ) is preferably 60 to 120°C, preferably 65 to 110°C, and preferably 65 to 95°C.

Δn (refractive index anisotropy) is obtained from the difference (n _e −n _o ) between the extraordinary refractive index (n _e ) and the ordinary refractive index (n _o ) of the liquid crystal composition at 25° C. using an Abbe refractometer. demand.

When the dielectric anisotropy at 25° C. of the liquid crystal composition used for the polymerizable compound-containing liquid crystal composition is negative (Δε<−2), the refractive index anisotropy (Δn) of the liquid crystal composition at 25° C. is , preferably 0.08 to 0.14, preferably 0.09 to 0.13, and preferably 0.09 to 0.12.

Rotational viscosity (γ ₁ ) is the viscosity associated with the rotation of liquid crystal molecules, and is measured using LCM-2 (manufactured by Toyo Technica) after filling a polymerizable compound-containing liquid crystal composition in a glass cell with a cell gap of about 10 μm. can do.
The measurement is performed at a temperature of 25° C., and the unit is mPa·s.
A horizontally aligned cell is used for a liquid crystal composition with a positive dielectric anisotropy, and a vertically aligned cell is used for a liquid crystal composition with a negative dielectric anisotropy.
_The smaller γ1 is, the faster the response speed of the liquid crystal composition is, so it is suitable for any liquid crystal display device.

When the dielectric anisotropy at 25° C. of the liquid crystal composition used for the polymerizable compound-containing liquid crystal composition is negative (Δε<−2), the rotational viscosity (γ ₁ ) of the liquid crystal composition at 25° C. is 50. It is preferably up to 160 mPa s, preferably 50 to 160 mPa s, preferably 55 to 140 mPa s, preferably 60 to 120 mPa s, preferably 65 to 110 mPa s. preferably 70 to 100 mPa·s.

As a combination of compounds used in the polymerizable compound-containing liquid crystal composition, 1) a compound represented by general formula (i) (including subordinate concepts) and a compound represented by general formula (ii) (including subordinate concepts ), a combination of a sensitizing compound (including subordinate concepts) and a compound represented by general formula (NU-01) (including subordinate concepts), 2) a compound represented by general formula (i) (including subordinate (including the concept), the compound represented by the general formula (ii) (including the subordinate concept), the sensitizing compound (including the subordinate concept), and the compound represented by the general formula (NU-05) (the subordinate concept 3) a compound represented by general formula (i) (including subordinate concepts), a compound represented by general formula (ii) (including subordinate concepts), and a sensitizing compound (including subordinate (including the concept) and the compound represented by the general formula (N-01) (including the subordinate concept), 4) the compound represented by the general formula (i) (including the subordinate concept) and the general formula A combination of a compound represented by (ii) (including subordinate concepts), a sensitizing compound (including subordinate concepts), and a compound represented by general formula (N-04) (including subordinate concepts), 5 ) a compound represented by general formula (i) (including subordinate concepts), a compound represented by general formula (ii) (including subordinate concepts), a sensitizing compound (including subordinate concepts), and general formula A combination of a compound represented by (NU-01) (including subordinate concepts) and a compound represented by general formula (NU-05) (including subordinate concepts), 6) represented by general formula (i) A compound (including a subordinate concept), a compound represented by the general formula (ii) (including a subordinate concept), a sensitizing compound (including a subordinate concept), and a general formula (N-01) A combination of a compound (including a subordinate concept) and a compound (including a subordinate concept) represented by the general formula (N-04), 7) a compound (including a subordinate concept) represented by the general formula (i) , a compound represented by general formula (ii) (including subordinate concepts), a sensitizing compound (including subordinate concepts), and a compound represented by general formula (NU-01) (including subordinate concepts), A compound (including subordinate concepts) represented by the general formula (NU-05), a compound (including subordinate concepts) represented by the general formula (N-01), and a compound represented by the general formula (N-04) 8) a compound represented by general formula (i) (including subordinate concepts) and a compound represented by general formula (ii) (including subordinate concepts); A sensitizing compound (including subordinate concepts), a compound represented by the general formula (NU-01) (including subordinate concepts), and a general formula ( NU-03) (including subordinate concepts), a compound (including subordinate concepts) represented by the general formula (NU-05), and a compound represented by the general formula (N-01) ( (including subordinate concepts) and a compound represented by general formula (N-04) (including subordinate concepts), 9) a compound represented by general formula (i) (including subordinate concepts), and general A compound represented by formula (ii) (including subordinate concepts), a sensitizing compound (including subordinate concepts), a compound represented by general formula (NU-01) (including subordinate concepts), and general formula A compound represented by (NU-02) (including a subordinate concept), a compound represented by the general formula (NU-05) (including a subordinate concept), and a compound represented by the general formula (N-01) (including a subordinate concept), a compound represented by the general formula (N-03) (including a subordinate concept), and a combination of a compound represented by the general formula (N-04) (including a subordinate concept), 10) compounds represented by general formula (i) (including subordinate concepts), compounds represented by general formula (ii) (including subordinate concepts), sensitizing compounds (including subordinate concepts), and general A compound represented by the formula (NU-01) (including subordinate concepts), a compound represented by the general formula (NU-03) (including subordinate concepts), and a general formula (NU-05) Compounds (including subordinate concepts), compounds represented by general formula (N-01) (including subordinate concepts), compounds represented by general formula (N-03) (including subordinate concepts), and general A combination with a compound represented by formula (N-04) (including subordinate concepts), 11) a compound represented by general formula (i) (including subordinate concepts) and general formula (ii) compounds (including subordinate concepts), sensitizing compounds (including subordinate concepts), compounds represented by general formula (NU-01) (including subordinate concepts), and general formula (NU-02) A compound (including a subordinate concept), a compound (including a subordinate concept) represented by the general formula (NU-03), and a compound (including a subordinate concept) represented by the general formula (NU-05), A combination of a compound (including a subordinate concept) represented by the general formula (N-01) and a compound (including a subordinate concept) represented by the general formula (N-03), 12) in the general formula (i) The compound represented by (including subordinate concepts), the compound represented by general formula (ii) (including subordinate concepts), the sensitizing compound (including subordinate concepts), and the general formula (NU-01) and the compound (including subordinate concepts) represented by the general formula (NU-03) and the compound (including subordinate concepts) represented by the general formula (NU-05) A combination of a compound (including a subordinate concept), a compound (including a subordinate concept) represented by the general formula (N-01), and a compound (including a subordinate concept) represented by the general formula (N-03) is preferred.

(liquid crystal display element)
Next, a liquid crystal display element having two substrates and a liquid crystal layer containing the polymerizable compound-containing liquid crystal composition between the two substrates, wherein the polymerizable compound-containing liquid crystal composition contains the general A liquid crystal display element in which a polymer obtained by polymerizing a polymerizable compound represented by formula (i) is present will be described.
More specifically, a liquid crystal display element having two substrates and a liquid crystal layer containing the polymerizable compound-containing liquid crystal composition that has been polymerized and sandwiched between the two substrates, wherein A polymer obtained by polymerizing the polymerizable compound represented by the general formula (i) exists in the treated liquid crystal composition containing the polymerizable compound.
When the polymerizable compound-containing composition contains a polymerizable liquid crystal compound having a structure different from that of general formula (i), a polymerizable liquid crystal compound having a structure different from that of general formula (i) is polymerized. Coalescing may also be present.
Ultraviolet irradiation etc. are mentioned as a polymerization process.

The two substrates are divided into a first substrate and a second substrate.
The first substrate may comprise a pixel electrode layer and/or an alignment film with transparent pixel electrodes driven by active elements corresponding to the second substrate.
The transparent electrode layer made of a transparent common electrode includes a plurality of gate bus lines and data bus lines arranged in a matrix, thin film transistors provided at intersections of the gate bus lines and the data bus lines, The structure may be an electrode layer having a pixel electrode driven by the thin film transistor for each pixel.
In addition, the second substrate may optionally include a transparent electrode layer made of a transparent common electrode, a color filter layer and/or an alignment film layer.

The liquid crystal display device according to the present invention is preferably driven by an active matrix system or a passive matrix system.

Further, the liquid crystal display element according to the present invention is preferably a liquid crystal display element that reversibly switches the dielectric constant by reversibly changing the alignment direction of the liquid crystal molecules of the liquid crystal composition.

Further, the liquid crystal display element according to the present invention may be a PSA type, PSVA type, VA type, IPS type, FFS type, PS-IPS type, PS-FFS type, NPS type or ECB type liquid crystal display element, PSA type, PSVA type, IPS type or FFS type liquid crystal display elements are preferable.
The VA type liquid crystal display element may be a general VA type, a TN-VA type, or a chiral VA type having a liquid crystal layer further containing a chiral agent.

A more specific description will be given below with reference to the drawings.
FIG. 1 is a schematic diagram showing an example of the liquid crystal display element of the present invention.
The structure of the liquid crystal display element of the present invention is not limited to this example.
Also, in FIG. 1, each component is shown separated for convenience of explanation.
The liquid crystal display element 1 shown in FIG. and
As illustrated in FIG. 1, a pixel electrode layer 5 is formed on the surface of the first substrate 2 facing the liquid crystal layer 4 .
A transparent electrode layer 6 is formed on the second substrate 3 on the liquid crystal layer 4 side.
The first substrate 2 and the second substrate 3 may be sandwiched between a pair of polarizing plates (first polarizing plate 7, second polarizing plate 8).
A color filter layer 9 may be further provided on the liquid crystal layer 4 side of the second substrate 3 .
The liquid crystal layer 4 contains the polymerizable compound-containing liquid crystal composition according to the present invention.
In the case of a liquid crystal display element manufactured using a liquid crystal composition containing a polymerizable compound, the polymer of the polymerizable compound generated by ultraviolet irradiation in the manufacturing process is formed on the first substrate 2 and the second substrate in the liquid crystal layer 4. It is unevenly distributed at the interface on the side.
That is, in the case of FIG. 1, a polymer of a polymerizable compound is formed at the interface between the liquid crystal layer 4 and the pixel electrode layer 5 and the transparent electrode layer 6 .

Although not shown, the liquid crystal display element of the present invention is provided between a first substrate and a second substrate facing each other and between the first substrate and the second substrate, and the polymerizable compound-containing liquid crystal according to the present invention a liquid crystal layer containing a composition, a first alignment film on the surface of the first substrate facing the liquid crystal layer, and a second alignment film on the surface of the second substrate facing the liquid crystal layer can have
That is, the liquid crystal display element of the present invention comprises a first polarizing plate, a first substrate, a first alignment film, a pixel electrode layer, a liquid crystal layer, a transparent electrode layer, a color filter layer, a first A configuration in which a second alignment film, a second substrate, and a second polarizing plate are laminated in this order can be employed.
The alignment film has a function of aligning liquid crystal molecules.
As the alignment film, a film such as a polyimide alignment film that is commonly used for liquid crystal display elements can be used.
The liquid crystal display device of the present invention can be manufactured by a known method.

EXAMPLES The present invention will be described in more detail below based on examples, but the present invention is not limited to the examples.
In the compositions of Examples and Comparative Examples below, the following abbreviations are used to describe compounds. Note that "n" represents a natural number.

<Ring structure>

<Side chain>
-n -C _n H _2n+1 straight chain alkyl group having n carbon atoms n- C _n H _2n+1 - straight chain alkyl group having n carbon atoms -On -OC _n H _2n+1 straight chain having n carbon atoms alkoxy group nO- H _2n+1 C _n O- straight-chain alkoxy group having n carbon atoms -V -CH=CH ₂
V- H ₂ C=CH-
-2V _-CH2 - _CH2 -CH= _CH2
V2- H ₂ C═CH—CH ₂ —CH ₂ —
-V1 -CH=CH-CH ₃
1V- H ₃ C-CH=CH-
1V2- H ₃ C-CH=CH-CH ₂ -CH ₂ -
-2V1 _-CH2 - _CH2 -CH=CH- _CH3
<Linking group>
_{-n- -CnH2n-}
-nO- -C _n H _2n -O-
_-On- -O- _CnH2n-

<Physical Properties of Liquid Crystal Composition Used for Polymerizable Compound-Containing Liquid Crystal Composition>
The following physical property values were measured for the liquid crystal composition used for the polymerizable compound-containing liquid crystal composition.
T _ni : nematic phase-isotropic liquid phase transition temperature (°C)
Δn: refractive index anisotropy at 25°C Δε: dielectric anisotropy at 25°C γ ₁ : rotational viscosity at 25°C (mPa s)

<Polymerizable compound represented by formula (i) (polymerizable compound a)>
The following compounds were used as the polymerizable compound represented by formula (i).

<Sensitizing compound (SC)>
The following compounds were used as the sensitizing compound (SC).

<Polymerizable liquid crystal compound (polymerizable compound b) having a structure different from that of general formula (i)>
The following compounds were used as the polymerizable liquid crystal compound having a structure different from that of general formula (i).

<Adjustment of liquid crystal composition (base composition) used for polymerizable compound-containing liquid crystal composition>
As shown in Table 1, liquid crystal compositions LC-1 to LC-10 used for the polymerizable compound-containing liquid crystal composition were prepared by mixing each liquid crystal compound at each ratio, and their physical properties were measured. Table 1 shows the results.

(Examples 1 to 35 and Comparative Examples 1 to 11)
<Adjustment of Liquid Crystal Composition Containing Polymerizable Compound>
Add the polymerizable compound a, the polymerizable compound b and the sensitizing compound (SC) in the amounts (parts by mass) shown in Table 2 to 100 parts by mass of each of the prepared LC-1 to LC-10. Thus, polymerizable compound-containing liquid crystal compositions of Examples 1 to 35 and Comparative Examples 1 to 11 were prepared.
<Production of liquid crystal display element>
A liquid crystal composition containing a polymerizable compound was injected by a vacuum injection method into a liquid crystal cell with a cell gap of 3.5 μm including a substrate with ITO coated with a polyimide alignment film that induces vertical alignment and rubbed. After that, the liquid crystal cell into which the polymerizable compound-containing liquid crystal composition was injected was irradiated with ultraviolet rays for 90 minutes using a fluorescent UV lamp to prepare a liquid crystal display element. The fluorescent UV lamp was used after being adjusted so that the illuminance measured at a center wavelength of 313 nm was 3.0 mW/cm ² .
<Evaluation test>
The following evaluation tests were performed on each polymerizable compound-containing liquid crystal composition of Examples and Comparative Examples. The results are shown in Tables 2-4.
(Method for evaluating monomer reactivity)
The liquid crystal composition was taken out from the prepared liquid crystal display device, and the total remaining amount of polymerizable compound a and polymerizable liquid crystal compound b was quantified by HPLC.
Evaluation criteria are as follows.
A: Less than 50 ppm B: 50 ppm or more and less than 100 ppm C: 100 ppm or more and less than 200 ppm D: 200 ppm or more (evaluation method of voltage holding rate)
The voltage holding ratio (VHR) of the produced liquid crystal display element was measured under conditions of 1 V, 0.6 Hz, and 60°C.
Evaluation criteria are as follows.
A: 95% or more B: less than 95% 90% or more C: less than 90% 80% or more D: less than 80% (evaluation method for pretilt angle formation)
First, the pretilt angle of the manufactured liquid crystal display element was measured and used as the pretilt angle (initial). Next, this liquid crystal display element was irradiated with ultraviolet rays for 200 seconds using a fluorescent UV lamp while applying a voltage of 10 V at a frequency of 100 Hz.
A value obtained by subtracting the pretilt angle (after UV) from the measured pretilt angle (initial) was taken as the pretilt angle change amount [°].
In addition, the pretilt angle was measured using OPTIPRO manufactured by Shintech.
Also, the fluorescent UV lamp was used after being adjusted so that the illuminance measured at a central wavelength of 313 nm was 3.0 mW/cm ² .
Evaluation criteria are as follows.
A: Pretilt angle variation is 2.0° or more B: Pretilt angle variation is less than 2.0° and 1.5° or more C: Pretilt angle variation is less than 1.5° and 1.0° or more D: Pretilt angle The amount of change is less than 1.0 ° (low temperature storage stability evaluation method)
The polymerizable compound-containing liquid crystal composition was filtered using a membrane filter (manufactured by Agilent Technologies, PTFE 13 mm-0.2 μm), and 0.5 g was weighed into a test tube. Then, after deaeration was performed for 15 minutes under vacuum and reduced pressure conditions (2.5 to 2.0 hPa), the sample was purged with nitrogen and sealed with a rubber stopper to obtain a sample for evaluation of low-temperature storage stability. This sample was stored in a freezer at -20°C, and the presence or absence of precipitation was observed every day.
Evaluation criteria are as follows.
◯: No precipitation was observed even after storage for 10 days.
Δ: Precipitation was confirmed within 6 to 9 days.
x: Deposited within 5 days was rated as x.

From Tables 2 to 4, it was confirmed that Examples 1 to 35 containing a sensitizing compound (SC) had better monomer reactivity than Comparative Examples 1 to 11 containing no sensitizing compound (SC). did it.
The liquid crystal compositions of Examples 1 to 30 containing both the polymerizable compound a and the polymerizable compound b shown in Tables 2 to 3 contain the polymerizable compound b shown in Table 4, but the polymerizable compound a and the sensitizing compound Compared to the liquid crystal compositions of Comparative Examples 1 to 10, which did not contain (SC) and had the same base composition, the voltage holding ratio and pretilt angle change amount were improved, and the low-temperature storage stability was also good. , was confirmed to have better performance. Comparing the liquid crystal composition of Example 1 and Comparative Example 1, which have the same base composition, Example 1 is superior to Comparative Example 1 in both the voltage holding ratio and the amount of pretilt change. This is probably because the liquid crystal composition of Example 1 contained the polymerizable compound a and the sensitizing compound (SC) as described above, thereby reducing the influence of impurities present in the liquid crystal cell.

Then, the liquid crystal compositions of Examples 1 to 21 in which the total content of the polymerizable compound a and the polymerizable compound b is 0.7% by mass, the polymerizable compound a and the sensitizing compound (SC) are not included but polymerizable Liquid crystal compositions of Comparative Examples 1 to 10 containing 0.3% by mass of compound b, and comparisons containing 0.7% by mass of polymerizable compound b but not containing polymerizable compound a and sensitizing compound (SC) From the comparison with Example 11, the three improvements in the voltage holding ratio, pretilt angle change amount, and low-temperature storage property were not due to an increase in the total content of the polymerizable compound a and the polymerizable compound b, but to the polymerizable compound a. and the addition of the sensitizing compound (SC) was confirmed to be the effect.

Further, from Examples 1 to 30, it was confirmed that a liquid crystal composition having better performance can be obtained by using the polymerizable compounds a and b in addition to the sensitizing compound (SC).

From the above results, it can be said that it is preferable to contain the polymerizable compound a, the polymerizable compound b, and the sensitizing compound SC in order to achieve both performances.

From the above, by including one or two or more polymerizable compounds represented by general formula (i), one or two or more sensitizing compounds, and one or two or more liquid crystal compounds, It was confirmed that a polymerizable compound-containing liquid crystal composition that can provide a liquid crystal display device having a low residual monomer amount, good voltage holding ratio (VHR), formation of a pretilt angle, and low-temperature storage stability can be obtained.

(Examples 36-50)
Furthermore, as shown in Table 5, liquid crystal compositions LC-11 to LC-12 used for the polymerizable compound-containing liquid crystal composition were prepared by mixing each liquid crystal compound in each ratio, and the physical properties thereof were measured. bottom. Then, with respect to 100 parts by mass of each of the adjusted LC-11 to LC-12, polymerizable compound a, polymerizable compound b and sensitizing compound (SC) are added in the amounts (parts by mass) shown in Table 6. Polymerizable compound-containing liquid crystal compositions of Examples 36 to 50 were prepared by adding these compounds, and evaluated in the same manner as in Examples 1 to 36. Similar effects were confirmed. Results are shown in Tables 5 and 6.

The polymerizable compound-containing liquid crystal composition according to the present invention can be used for liquid crystal display devices.

1: liquid crystal display element 2: first substrate 3: second substrate 4: liquid crystal layer 5: pixel electrode layer 6: transparent electrode layer (common electrode layer)
7: First polarizing plate 8: Second polarizing plate 9: Color filter

Claims (10)

The following general formula (i)

(In the formula,
P ⁱ¹ and P ⁱ² each independently represent a polymerizable group,
Sp ⁱ¹ and Sp ⁱ² represent a single bond or an alkylene group having 1 to 20 carbon atoms,
one or more —CH ₂ — in the alkylene group may be independently substituted with —O—, —NH—,
one or more —CH ₂ —CH ₂ — in the alkylene group are each independently —CH═CH—, —C≡C—, —CO—O— or —O—CO—; may be substituted,
One or more hydrogen atoms in the alkylene group may each independently be substituted with a halogen atom,
There is no direct bond between oxygen atoms and oxygen atoms,
A ⁱ¹ , A ⁱ² and A ⁱ³ each independently represent a divalent aromatic group, a divalent cycloaliphatic group or a divalent heterocyclic compound group;
one or more hydrogen atoms in A ⁱ¹ , A ⁱ² and A ⁱ³ may each independently be substituted with a substituent Sr ⁱ¹ ;
The substituent Sr ⁱ¹ represents either a halogen atom or an alkyl group having 1 to 20 carbon atoms,
one or more —CH ₂ — in the alkyl group may be independently substituted with —O—, —NH—,
one or more —CH ₂ —CH ₂ — in the alkyl group are each independently —CH═CH—, —C≡C—, —CO—O— or —O—CO—; may be substituted,
One or more hydrogen atoms in the alkyl group may each independently be substituted with a halogen atom,
There is no direct bond between oxygen atoms and oxygen atoms,
When a plurality of substituents Sr ⁱ¹ are present, they may be the same or different, and at least one of Sp ⁱ¹ , Sp ⁱ² and/or substituents Sr ⁱ¹ is an alkylene group having 1 to 20 carbon atoms or represents an alkyl group having 1 to 20 carbon atoms,
In at least one of an alkylene group having 1 to 20 carbon atoms or an alkyl group having 1 to 20 carbon atoms represented by Sp ⁱ¹ , Sp ⁱ² and/or the substituent Sr ⁱ¹ ,
one or more —CH ₂ — in said group, and/or
One or more hydrogen atoms in the group are each independently represented by the following formulas (PG ⁱ -1) to (PG ⁱ -33)

(In the formulas (PG ⁱ -1) to (PG ⁱ -33),
X ^PGi and Z ^PGi each independently represent a methylene group (—CH ₂ —), an oxygen atom (—O—) or a sulfur atom (—S—),
Y ^PGi represents a carbonyl group (>C=O), a thionyl group (>C=S), an oxygen atom (-O-) or a sulfur atom (-S-),
W ^PGi represents a methylene group ( _-CH2- ), a carbonyl group (>C=O) or a thionyl group (>C=S),
S ^PGi , T ^PGi and U ^PGi each independently represent a methine group (=CH-) or a nitrogen atom (=N-),
In formula (PG ⁱ -18), S ^PGi and T ^PGi do not represent a methine group (=CH-) at the same time,
In formula (PG ⁱ -19), S ^PGi , T ^PGi and U ^PGi do not represent a methine group (=CH-) at the same time,
R ^PGi each independently represents an alkyl group having 1 to 20 carbon atoms,
one or more —CH ₂ — in the alkyl group may be independently substituted with —O—, —NH—,
one or more —CH ₂ —CH ₂ — in the alkyl group are each independently —CH═CH—, —C≡C—, —CO—O— or —O—CO—; may be substituted,
One or more hydrogen atoms in the alkyl group may each independently be substituted with a halogen atom,
There is no direct bond between oxygen atoms and oxygen atoms,
When there are multiple ^RPGi , they may be the same or different,
Sp ^PGi each independently represents a single bond, an alkylene group having 1 to 20 carbon atoms or an arylene group having 6 to 20 carbon atoms,
one or more —CH ₂ — in the alkylene group or the arylene group may be independently substituted with —O—, —NH—,
One or more —CH ₂ —CH ₂ — in the alkylene group or the arylene group are each independently —CH═CH—, —C≡C—, —CO—O— or —O -CO- may be substituted,
One or more hydrogen atoms in the alkylene group or the arylene group may each independently be substituted with a halogen atom or a hydroxyl group,
There is no direct bond between oxygen atoms and oxygen atoms,
When multiple Sp ^PGi are present, they may be the same or different,
* represents a bond.
provided that one or more —CH ₂ — in said group is substituted with a group selected from the group consisting of groups represented by formulas (PG ⁱ -1) to (PG ⁱ -7),
One or more hydrogen atoms in said group are substituted with a group selected from the group consisting of groups represented by formulas (PG ⁱ -8) to (PG ⁱ -33). )
is substituted with a group selected from the group consisting of groups represented by
L ⁱ¹ and L ⁱ² each independently represent a single bond or an alkylene group having 1 to 20 carbon atoms,
one or more hydrogen atoms in the alkylene group may be independently substituted with a halogen atom or an alkyl group having 1 to 6 carbon atoms,
n ⁱ¹ represents an integer from 0 to 1,
When a plurality of L ⁱ² and A ⁱ³ are present, they may be the same or different. )
One or two or more polymerizable compounds represented by
one or more sensitizing compounds;
one or more liquid crystal compounds;
A polymerizable compound-containing liquid crystal composition containing at least 2. The polymerizable compound-containing liquid crystal composition according to claim 1, which is substituted with a group represented by the formula (PG ⁱ -1). 3. The polymerizable compound-containing liquid crystal composition according to claim 1, wherein Sp ⁱ² represents an alkylene group having 1 to 20 carbon atoms. 3. The polymerizable compound-containing liquid crystal composition according to claim 1, wherein n ⁱ¹ is 0. 3. The polymerizable compound-containing liquid crystal composition according to claim 1, wherein said ^Li1 is a single bond. The divalent aromatic group is a 1,4-phenylene group, naphthalene-2,6-diyl group, anthracene-2,6-diyl group, phenanthrene-2,7-diyl group, and indane-2,5-diyl group , 1,2,3,4-tetrahydronaphthalene-2,6-diyl group,
the divalent cycloaliphatic group represents any one of a 1,4-cyclohexylene group, a 1,4-cyclohexenylene group, and a 1,3-dioxane-2,5-diyl group;
3. The polymerizable compound-containing liquid crystal composition according to claim 1, wherein the divalent heterocyclic compound group represents either a pyridine-2,5-diyl group or a pyrimidine-2,5-diyl group. The sensitizing compound has the following general formula (SC)

(In formula (SC),
R ^SC1 and R ^SC2 each independently represent an alkyl group having 1 to 20 carbon atoms;
one or more —CH ₂ — in the alkyl group may be independently substituted with —O—, —NH—,
one or more —CH ₂ —CH ₂ — in the alkyl group are each independently —CH═CH—, —C≡C—, —CO—O— or —O—CO—; may be substituted,
One or more hydrogen atoms in the alkyl group may each independently be substituted with a halogen atom,
There is no direct bond between oxygen atoms and oxygen atoms,
S ^SC2 , S ^SC3 , S ^SC5 and S ^SC6 each independently represent a hydrogen atom or a fluorine atom,
A ^SC1 is each independently the following group (a) and group (b):
(a) a 1,4-cyclohexylene group (one —CH ₂ — or two or more non-adjacent —CH ₂ — present in this group may be replaced with —O— and/or —S—; good.),
(b) a 1,4-phenylene group (one -CH= or two or more non-adjacent -CH= present in this group may be replaced with -N=);
represents a group selected from the group consisting of
one or more hydrogen atoms in A ^SC1 may each independently be substituted with a substituent Sr ^SC1 ,
The substituent Sr ^SC1 represents either a halogen atom or an alkyl group having 1 to 20 carbon atoms,
one or more —CH ₂ — in the alkyl group may be independently substituted with —O—, —NH—,
one or more —CH ₂ —CH ₂ — in the alkyl group are each independently —CH═CH—, —C≡C—, —CO—O— or —O—CO—; may be substituted,
One or more hydrogen atoms in the alkyl group may each independently be substituted with a halogen atom,
There is no direct bond between oxygen atoms and oxygen atoms,
When multiple substituents Sr ^SC1 are present, they may be the same or different,
n ^SC1 represents an integer from 0 to 1; )
3. The polymerizable compound-containing liquid crystal composition according to claim 1, which is a compound represented by: 3. The polymerizable compound-containing liquid crystal composition according to claim 1, further comprising a polymerizable compound having a structure different from that of general formula (i). As the liquid crystal compound, the following general formulas (NU-01) ~ (NU-08)

(In the general formulas (NU-01) to (NU-08),
R ^NU1 and R ^NU2 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, or an alkenyl group having 2 to 8 carbon atoms represents any of the oxy groups,
one or more —CH ₂ —CH ₂ — in said group are each independently substituted by —C≡C—, —CO—, —CO—O— or —O—CO— but
Oxygen atoms are never directly bonded to each other. )
3. The polymerizable compound-containing liquid crystal composition according to claim 1, comprising a compound selected from the group consisting of compounds represented by any one of: two substrates and
A liquid crystal display element having a liquid crystal layer containing the polymerizable compound-containing liquid crystal composition according to claim 1 or 2 between the two substrates,
A liquid crystal display device in which a polymer obtained by polymerizing a polymerizable compound represented by the general formula (i) is present.

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