JP5712551B2 - Polymerizable compound-containing liquid crystal composition and liquid crystal display device using the same - Google Patents

Description

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

The PSA (Polymer Sustained Alignment) type liquid crystal display device has a structure in which a polymer structure is formed in a cell in order to control the pretilt angle of liquid crystal molecules. Development is progressing as an element.
A PSA-type liquid crystal display device is manufactured by injecting a polymerizable composition comprising a liquid crystalline compound and a polymerizable compound between substrates and applying a voltage to polymerize the polymerizable compound in a state in which the liquid crystal molecules are aligned to produce liquid crystal molecules. This is done by fixing the orientation. As a cause of image sticking which is a display defect of this PSA type liquid crystal display element, there are known impurities and changes in alignment of liquid crystal molecules (changes in pretilt angle).
The seizure due to impurities is caused by a polymerizable compound remaining incompletely and a polymerization initiator added to accelerate the progress of the polymerization. For this reason, it is necessary to minimize the residual amount of the polymerizable compound after completion of the polymerization and to suppress the amount of the polymerization initiator to be added. For example, when a large amount of a polymerization initiator is added in order to cause the polymerization to proceed completely, the voltage holding ratio of the display element is lowered due to the remaining polymerization initiator, and the display quality is adversely affected. In addition, if the amount of the polymerization initiator used in the polymerization is reduced in order to suppress the decrease in voltage holding ratio, the polymerization does not proceed completely, so the polymerizable compound remains, and the occurrence of seizure due to the remaining polymerizable compound. Is inevitable. In addition, in order to completely cure the polymerizable compound with a small addition amount of the polymerization initiator and suppress the residual of the polymerizable compound, there is a method of adding a large amount of energy by irradiating strong ultraviolet rays for a long time in the polymerization. . However, in this case, the manufacturing apparatus is increased in size and the manufacturing efficiency is lowered, and the liquid crystal material is deteriorated by ultraviolet rays. Therefore, in the conventional liquid crystal composition containing a polymerizable compound, it has been difficult to simultaneously reduce the remaining amounts of both the uncured polymerizable compound and the polymerization initiator. Therefore, there has been a demand for a liquid crystal composition containing a polymerizable compound that can be polymerized without using a polymerization initiator.
On the other hand, the occurrence of image sticking is also known to be caused by a change in the pretilt angle of liquid crystal molecules in a liquid crystal composition containing a polymerizable compound. In other words, if the polymer, which is a cured product of the polymerizable compound, is flexible, the structure of the polymer changes when the same pattern is displayed for a long time when the display element is configured, and as a result, the pretilt angle changes. Resulting in. Since the change in the pretilt angle causes burn-in, a polymerizable compound that forms a polymer having a rigid structure in which the polymer structure does not change is required.

Conventionally, in order to prevent image sticking by improving the rigidity of a polymer, a display element is configured using a polymerizable compound having a ring structure and a structure such as a 1,4-phenylene group having only a polymerizable functional group. (See Patent Document 1) and the construction of a display element using a polymerizable compound having a biaryl structure (see Patent Document 2) have been studied. However, since these polymerizable compounds have low compatibility with the liquid crystal compound, there is a possibility that problems such as precipitation of the polymerizable compound may occur when the liquid crystal composition is prepared.
Also, in order to prevent seizure by improving the rigidity of the polymer, a mixture of a bifunctional polymerizable compound and a trifunctional or higher functional polymerizable compound such as dipentaerythritol pentaacrylate or dipentaerythritol hexaacrylate It has been proposed to form a display element using a liquid crystal composition (see Patent Document 3). However, since dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate do not have a ring structure in the molecule, their affinity with liquid crystal compounds is weak and their ability to regulate alignment is weak, so sufficient alignment stability There was a problem that could not be obtained. In addition, it is essential to add a polymerization initiator in the polymerization of these polymerizable compounds. If the polymerization initiator is not added, the polymerizable compound remains after the polymerization.
As described above, characteristics such as seizure characteristics of display elements, alignment stability, stability as a composition that does not cause precipitation, and production efficiency in the production of PSA type liquid crystal display elements, which are required in a polymerizable compound-containing liquid crystal composition, are satisfied. It is difficult to do so, which has hindered the practical application of the display element.

JP 2003-307720 A JP 2008-116931 A JP 2004-302096 A

  The problem to be solved by the present invention is that the polymerization is completed without using a polymerization initiator or with a very small amount of addition, the liquid crystal alignment regulating power after polymerization is strong, and the polymerizable compound is well compatible with the liquid crystal material. Accordingly, it is an object of the present invention to provide a polymerizable compound-containing liquid crystal composition that does not cause defects such as precipitation. Furthermore, it is providing the liquid crystal display element which the liquid crystal aligning ability was provided by polymerizing the polymeric compound containing liquid crystal composition, and was excellent in display performance.

（式中Ｒ^１１及び、Ｒ^１２はお互い独立して炭素原子数１から１０のアルキル基又は炭素原子数２から１０のアルケニル基を表し、これらの基中に存在する１個の−ＣＨ_２−又は隣接していない２個以上の−ＣＨ_２−は−Ｏ−又は−Ｓ−に置換されていても良く、またこれらの基中に存在する１個又は２個以上の水素原子はフッ素原子又は塩素原子に置換されても良く、
ｎ_１は、０、１又は２を表し、
Ｍ^１１及びＭ^１２はお互い独立して、
（ａ） トランス−１，４−シクロへキシレン基（この基中に存在する１個の−ＣＨ_２−又は隣接していない２個以上の−ＣＨ_２−は−Ｏ−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個の−ＣＨ＝又は隣接していない２個以上の−ＣＨ＝は−Ｎ＝に置き換えられてもよい）及び、
（ｃ） １，４−シクロヘキセニレン基、１，４−ビシクロ［２．２．２］オクタン−１，４−ジイル基、ピペリジン−２，５−ジイル基、ナフタレン−２，６−ジイル基、１，２，３，４−テトラヒドロナフタレン−２，６−ジイル基及びデカヒドロナフタレン−２，６−ジイル基
からなる群より選ばれる基を表し、上記の基（ａ）、基（ｂ）又は基（ｃ）に含まれる水素原子はそれぞれシアノ基、ハロゲン、トリフルオロメチル基又はトリフルオロメトキシ基で置換されていても良いが、Ｍ^１２が複数存在する場合は、それらは同一でも良く異なっていても良く、
Ｌ^１１は単結合、−ＣＯＯ−、−ＯＣＯ−、−ＣＨ_２ＣＨ_２−、−（ＣＨ_２）_４−、−ＯＣＨ_２−、−ＣＨ_２Ｏ−、−ＯＣＦ_２−、−ＣＦ_２Ｏ−又は−Ｃ≡Ｃ−を表し、
Ｘ^１１、Ｘ^１２はお互い独立してトリフルオロメチル基、トリフルオロメトキシ基、フッ素原子又は塩素原子を表すが、Ｘ^１１及びＸ^１２の何れか一つはフッ素原子を表す。）で表される化合物からなる群から選ばれる化合物を一種又は二種以上含有し、
第二成分として、一般式（ＩＩ）

（式中、Ｒ^２１及びＲ^２２はお互い独立して炭素原子数１から１０のアルキル基又は炭素原子数２から１０のアルケニル基を表し、これらの基中に存在する１個の−ＣＨ_２−又は隣接していない２個以上の−ＣＨ_２−は−Ｏ−又は−Ｓ−に置換されても良く、またこれらの基中に存在する１個又は２個以上の水素原子はフッ素原子又は塩素原子に置換されても良く、
ｎ_２は０、１又は２を表し、
Ｍ^２１、Ｍ^２２及びＭ^２３はお互い独立して
（ｄ） トランス−１，４−シクロへキシレン基（この基中に存在する１個の−ＣＨ_２−又は隣接していない２個以上の−ＣＨ_２−は−Ｏ−又は−Ｓ−に置き換えられてもよい）、
（ｅ） １，４−フェニレン基（この基中に存在する１個の−ＣＨ＝又は隣接していない２個以上の−ＣＨ＝は−Ｎ＝に置き換えられてもよい）、２−フルオロ−１，４−フェニレン基、３−フルオロ−１，４−フェニレン基、３，５−ジフルオロ−１，４−フェニレン基、及び
（ｆ） １，４−シクロヘキセニレン基、１，４−ビシクロ［２．２．２］オクタン−１，４−ジイル基、ピペリジン−２，５−ジイル基、ナフタレン−２，６−ジイル基、デカヒドロナフタレン−２，６−ジイル基及び１，２，３，４−テトラヒドロナフタレン−２，６−ジイル基
からなる群より選ばれる基を表すが、Ｍ^２３が複数存在する場合には同一であっても異なっていても良く、
Ｌ^２１、及びＬ^２２はお互い独立して単結合、−ＣＨ_２ＣＨ_２−、−（ＣＨ_２）_４−、−ＯＣＨ_２−、−ＣＨ_２Ｏ−、−ＯＣＦ_２−、−ＣＦ_２Ｏ−、−ＣＨ＝ＣＨ−、−ＣＨ＝Ｎ−Ｎ＝ＣＨ−又は−Ｃ≡Ｃ−を表すが、Ｌ^２２が複数存在する場合は、それらは同一でも良く異なっていても良い。）で表される化合物を一種又は二種以上含有し、
第三成分として、一般式（ＩＩＩ）

（式中、Ｚは、水素原子、ハロゲン、シアノ基、チオシアナト基、トリフルオロメトキシ基、トリフルオロメチル基、ジフルオロメトキシ基、又は炭素原子数１〜１２のアルキル基を表し、該アルキル基中の１個の−ＣＨ_２−又は隣接していない２個以上の−ＣＨ_２−は−Ｏ−、−Ｓ−、−ＣＯ−、−ＣＯＯ−、−ＯＣＯ−、−ＯＣＯＯ−、−ＣＨ＝ＣＨ−、又は−Ｃ≡Ｃ−で置換されて良く、あるいはＺは、−Ｓ^３２−Ｒ^３２を表し、
Ｒ^３１及びＲ^３２はお互い独立して以下の式（Ｒ−１）から式（Ｒ−１５）

の何れかを表し、
Ｓ^３１及びＳ^３２はお互い独立して、炭素原子数１〜１２のアルキレン基、又は単結合を表し、該アルキレン基中の１個の−ＣＨ_２−又は隣接していない２個以上の−ＣＨ_２−は−Ｏ−、−ＣＯＯ−、−ＯＣＯ−、又は−ＯＣＯＯ−に置き換えられても良く、
ｎ_３は１、２又は３を表し、
Ｌ^３１は−ＯＣＯＣＨ＝ＣＨ−又は−Ｃ≡Ｃ−を表し、
Ｌ^３２及びＬ^３３はお互い独立して、単結合、−Ｏ−、−Ｓ−、−ＣＨ_２−、−ＯＣＨ_２−、−ＣＨ_２Ｏ−、−ＣＯ−、−Ｃ_２Ｈ_４−、−ＣＯＯ−、−ＯＣＯ−、−ＯＣＯＯＣＨ_２−、−ＣＨ_２ＯＣＯＯ−、−ＣＯ−ＮＲ^ａ−、−ＮＲ^ａ−ＣＯ−、−ＳＣＨ_２−、−ＣＨ_２Ｓ−、−ＣＨ＝ＣＨ−ＣＯＯ−、−ＣＯＯ−ＣＨ＝ＣＨ−、−ＯＣＯ−ＣＨ＝ＣＨ−、−ＣＨ＝ＣＨ−ＯＣＯ−、−ＣＯＯＣ_２Ｈ_４−、−ＯＣＯＣ_２Ｈ_４−、−Ｃ_２Ｈ_４ＯＣＯ−、−Ｃ_２Ｈ_４ＣＯＯ−、−ＯＣＯＣＨ_２−、−ＣＨ_２ＣＯＯ−、−ＣＨ_２ＯＣＯ−、−ＣＯＯＣＨ_２−、−ＣＨ＝ＣＨ−、−ＣＦ＝ＣＨ−、−ＣＨ＝ＣＦ−、−ＣＦ＝ＣＦ−、−ＣＦ_２−、−ＣＦ_２Ｏ−、−ＯＣＦ_２−、−ＣＦ_２ＣＨ_２−、−ＣＨ_２ＣＦ_２−、−ＣＦ_２ＣＦ_２−又は−Ｃ≡Ｃ−を表すが（式中、Ｒ^ａは炭素原子数１〜４のアルキル基を表す。）、Ｌ^３３が複数存在する場合には同一であっても異なっていても良く、
Ｍ^３１は１，４−フェニレン基又はナフタレン−２，６−ジイル基を表し、Ｍ^３２は１，４−フェニレン基、１，４−シクロヘキシレン基、ピリジン−２，５−ジイル基、ピリミジン−２，５−ジイル基、ピペリジン−２，５−ジイル基、ナフタレン−２，６−ジイル基、インダン−２，５−ジイル基、１，２，３，４−テトラヒドロナフタレン−２，６−ジイル基又は１，３−ジオキサン−２，５−ジイル基を表し、Ｍ^３１及びＭ^３２はお互い独立して無置換であるか又はこれらの基中に含まれる水素原子がハロゲン、シアノ基、炭素原子数１〜８のアルキル基、炭素原子数１〜８のハロゲン化アルキル基、炭素原子数１〜８のハロゲン化アルコキシ基、炭素原子数１〜８のアルコキシ基、又はニトロ基に置換されていても良く、Ｍ^３２が複数存在する場合には同一であっても異なっていても良い。）で表される重合性化合物を一種又は二種以上含有する重合性化合物含有液晶組成物を提供し、更に、当該液晶組成物を用いた液晶表示素子を提供する。 As a result of examining various polymerizable compounds and various non-polymerizable liquid crystal compounds, the inventors of the present application have found that a polymerizable compound-containing liquid crystal composition comprising a polymerizable compound having a specific structure and a non-polymerizable liquid crystal compound. Has found that the above-mentioned problems can be solved, and has completed the present invention.
That is, as the first component, the general formula (I)

(In the formula, R ¹¹ and R ¹² each independently represent an alkyl group having 1 to 10 carbon atoms or an alkenyl group having 2 to 10 carbon atoms, and one —CH ₂ — present in these groups. Or two or more non-adjacent —CH ₂ — may be substituted by —O— or —S—, and one or more hydrogen atoms present in these groups are fluorine atoms or May be substituted with chlorine atoms,
n ₁ represents 0, 1 or 2,
M ¹¹ and M ¹² are independent of each other
(A) trans-1,4-cyclohexylene group (the one present in the group -CH ₂ - or nonadjacent two or more -CH ₂ - is replaced by -O- or -S- May be)
(B) a 1,4-phenylene group (one -CH = present in the group or two or more non-adjacent -CH = may be replaced by -N =), and
(C) 1,4-cyclohexenylene group, 1,4-bicyclo [2.2.2] octane-1,4-diyl group, piperidine-2,5-diyl group, naphthalene-2,6-diyl group Represents a group selected from the group consisting of 1,2,3,4-tetrahydronaphthalene-2,6-diyl group and decahydronaphthalene-2,6-diyl group, and the above groups (a) and (b) Alternatively, the hydrogen atoms contained in the group (c) may be each substituted with a cyano group, a halogen, a trifluoromethyl group or a trifluoromethoxy group, but when a plurality of M ¹² are present, they may be the same or different. You may,
L ¹¹ represents a single bond, —COO—, —OCO—, —CH ₂ CH ₂ —, — (CH ₂ ) ₄ —, —OCH ₂ —, —CH ₂ O—, —OCF ₂ —, —CF ₂ O—. Or -C≡C-
X ¹¹ and X ¹² each independently represent a trifluoromethyl group, a trifluoromethoxy group, a fluorine atom or a chlorine atom, and any one of X ¹¹ and X ¹² represents a fluorine atom. ) Containing one or more compounds selected from the group consisting of compounds represented by:
As the second component, the general formula (II)

(In the formula, R ²¹ and R ²² each independently represent an alkyl group having 1 to 10 carbon atoms or an alkenyl group having 2 to 10 carbon atoms, and one —CH ₂ — present in these groups. Or two or more non-adjacent —CH ₂ — may be substituted with —O— or —S—, and one or more hydrogen atoms present in these groups are fluorine atoms or chlorine May be substituted with atoms,
n ₂ represents 0, 1 or 2,
M ²¹ , M ²² and M ²³ are each independently (d) a trans-1,4-cyclohexylene group (one —CH ₂ — present in this group or two or more non-adjacent — CH ₂ — may be replaced by —O— or —S—),
(E) a 1,4-phenylene group (one —CH═ present in the group or two or more non-adjacent —CH═ may be replaced by —N═), 2-fluoro- 1,4-phenylene group, 3-fluoro-1,4-phenylene group, 3,5-difluoro-1,4-phenylene group, and (f) 1,4-cyclohexenylene group, 1,4-bicyclo [ 2.2.2] Octane-1,4-diyl group, piperidine-2,5-diyl group, naphthalene-2,6-diyl group, decahydronaphthalene-2,6-diyl group and 1,2,3,3 It represents a group selected from the group consisting of 4-tetrahydronaphthalene-2,6-diyl group, in the case where M ²³ there are a plurality may be the same or different and
L ²¹ and L ²² are each independently a single bond, —CH ₂ CH ₂ —, — (CH ₂ ) ₄ —, —OCH ₂ —, —CH ₂ O—, —OCF ₂ —, —CF ₂ O—. , —CH═CH—, —CH═N—N═CH—, or —C≡C—, when two or more L ²² are present, they may be the same or different. ) Containing one or more compounds represented by
As the third component, the general formula (III)

(In the formula, Z represents a hydrogen atom, a halogen, a cyano group, a thiocyanato group, a trifluoromethoxy group, a trifluoromethyl group, a difluoromethoxy group, or an alkyl group having 1 to 12 carbon atoms. One —CH ₂ — or two or more non-adjacent —CH ₂ — are —O—, —S—, —CO—, —COO—, —OCO—, —OCOO—, —CH═CH—. , or it may be substituted by -C≡C-, or Z ^represents -S 32 ^{-R 32,}
R ³¹ and R ³² are independently of each other from the following formulas (R-1) to (R-15):

Any one of
S ³¹ and S ³² each independently represent an alkylene group having 1 to 12 carbon atoms or a single bond, and one —CH ₂ — in the alkylene group or two or more —CH 2 not adjacent to each other. _2- may be replaced by -O-, -COO-, -OCO-, or -OCOO-,
n ₃ represents 1, 2 or 3,
L ³¹ represents —OCOCH═CH— or —C≡C—
L ³² and L ³³ are each independently a single bond, —O—, —S—, —CH ₂ —, —OCH ₂ —, —CH ₂ O—, —CO—, —C ₂ H ₄ —, — _{COO -, - OCO -, -} OCOOCH 2 -, - CH 2 OCOO -, - CO-NR a -, - NR a -CO -, - SCH 2 -, - CH 2 S -, - CH = CH-COO- , -COO-CH = CH -, - OCO-CH = CH -, - CH = CH-OCO -, - COOC 2 H 4 -, - OCOC 2 H 4 -, - C 2 H 4 OCO -, - C 2 H ₄ COO—, —OCOCH ₂ —, —CH ₂ COO—, —CH ₂ OCO—, —COOCH ₂ —, —CH═CH—, —CF═CH—, —CH═CF—, —CF═CF— _{, -CF 2 -, - CF 2} O -, - OCF 2 -, - CF 2 CH 2 -, - CH _{CF 2 -, - CF 2 CF} 2 - or represents a -C≡C- (. Wherein, ^{R a} is represents an alkyl group having 1 to 4 carbon ^atoms), identical if ^{the L 33} there are a plurality Can be different,
M ³¹ represents a 1,4-phenylene group or a naphthalene-2,6-diyl group, and M ³² represents a 1,4-phenylene group, a 1,4-cyclohexylene group, a pyridine-2,5-diyl group, a pyrimidine- 2,5-diyl group, piperidine-2,5-diyl group, naphthalene-2,6-diyl group, indan-2,5-diyl group, 1,2,3,4-tetrahydronaphthalene-2,6-diyl Represents a group or a 1,3-dioxane-2,5-diyl group, and M ³¹ and M ³² are each independently unsubstituted or a hydrogen atom contained in these groups is a halogen, a cyano group or a carbon atom An alkyl group having 1 to 8 carbon atoms, a halogenated alkyl group having 1 to 8 carbon atoms, a halogenated alkoxy group having 1 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, or a nitro group. It may be, ^{M 3} There may be the same or different when there are multiple. The polymerizable compound-containing liquid crystal composition containing one or two or more polymerizable compounds represented by formula (1) is provided, and further, a liquid crystal display device using the liquid crystal composition is provided.

  Since the polymerizable compound represented by the general formula (III) of the present application has excellent compatibility with the compound represented by the general formula (I) and the compound represented by the general formula (II), a stable liquid crystal composition is obtained. Can be obtained. Further, since it has a skeleton similar to a liquid crystal compound, the alignment regulating power of the liquid crystal compound is strong. In particular, the compatibility between the compound represented by the general formula (I) and the polymerizable compound represented by the general formula (III) is good, and the alignment regulating power is strong. In addition, the liquid crystal composition containing the polymerizable compound can polymerize the polymerizable compound without using a photopolymerization initiator or with a very small amount of addition, and an unpolymerized polymerizable compound remaining after the polymerization can be obtained. No or very little. In addition, the energy required for polymerization of the polymerizable compound can be greatly reduced. As a result, display defects of the liquid crystal display element that imparts alignment by polymerizing the polymerizable compound in the liquid crystal composition are greatly reduced, and energy costs for manufacturing can be reduced and production efficiency can be improved. It is useful as a liquid crystal composition for the liquid crystal display element.

<Liquid crystal compound>
In the compound represented by the general formula (I) used as the first component, R ¹¹ and R ¹² each independently represent an alkyl group having 1 to 10 carbon atoms or an alkenyl group having 2 to 10 carbon atoms, present in these groups one -CH 2 _- or nonadjacent two or more -CH 2 _- may be substituted by -O- or -S-, also present in the group One or more hydrogen atoms may be substituted with a fluorine atom or a chlorine atom. More preferred is 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 3 to 6 carbon atoms, and 1 to 5 carbon atoms. In particular, an alkyl group having 1 to 5 carbon atoms or an alkoxy group having 1 to 5 carbon atoms is particularly preferable.
n ₁ is preferably 0, 1 or 2, and more preferably 0 or 1. May be the same or different in the case of M ¹² there are a plurality.

M ¹¹ and M ¹² are independent of each other
(A) trans-1,4-cyclohexylene group (the one present in the group -CH ₂ - or nonadjacent two or more -CH ₂ - is replaced by -O- or -S- May be)
(B) a 1,4-phenylene group (one -CH = present in the group or two or more non-adjacent -CH = may be replaced by -N =), and
(C) 1,4-cyclohexenylene group, 1,4-bicyclo [2.2.2] octane-1,4-diyl group, piperidine-2,5-diyl group, naphthalene-2,6-diyl group Represents a group selected from the group consisting of 1,2,3,4-tetrahydronaphthalene-2,6-diyl group and decahydronaphthalene-2,6-diyl group, and the above groups (a) and (b) Alternatively, each hydrogen atom contained in the group (c) may be substituted with a cyano group, a halogen, a trifluoromethyl group, or a trifluoromethoxy group. A trans-1,4-cyclohexylene group, a 1,4-phenylene group, or a 1,4-bicyclo [2.2.2] octane-1,4-diyl group is more preferable, and a trans-1,4-cyclohexylene group is preferred. Or a 1,4-phenylene group is particularly preferable.

L ¹¹ represents a single bond, —COO—, —OCO—, —CH ₂ CH ₂ —, — (CH ₂ ) ₄ —, —OCH ₂ —, —CH ₂ O—, —OCF ₂ —, —CF ₂ O—. Or -C≡C-, preferably a single bond, -CH ₂ CH _2- , -OCH _2- , -CH ₂ O-, -OCF _2- , -CF ₂ O- or -C≡C- A bond, —CH ₂ CH ₂ —, —CH ₂ O—, or —CF ₂ O— is more preferable.
X ¹¹ and X ¹² each independently represent a trifluoromethyl group, a trifluoromethoxy group, a fluorine atom or a chlorine atom, and any one of X ¹¹ and X ¹² represents a fluorine atom, preferable.

  More specifically, general formula (I) is preferably a compound represented by the following general formula (I-1) to general formula (I-17) as a specific structure.

In the formula, R ¹³ and R ¹⁴ each independently represent an alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, or an alkenyl group having 2 to 8 carbon atoms. R ¹³ and R ¹⁴ are each independently more preferably an alkyl group having 1 to 8 carbon atoms or an alkoxy group having 1 to 8 carbon atoms.
Among the compounds represented by general formula (I-1) to general formula (I-17), the compound represented by general formula (I-1) or general formula (I-2) is more preferable.

  High-speed response can be achieved by using the compound represented by the general formula (I) and the polymerizable compound represented by the general formula (III). It contains at least one compound selected from the group consisting of compounds represented by formula (I) used as the first component, but preferably contains 2 to 10 types, and preferably contains 2 to 8 types. It is particularly preferable that the lower limit of the content is 5% by mass, more preferably 10% by mass, more preferably 20% by mass, and the upper limit is 60% by mass. Preferably, it is 50 mass%, and it is more preferable that it is 40 mass%.

In the compound represented by the general formula (II) used as the second component, R ²¹ and R ²² each independently represent an alkyl group having 1 to 10 carbon atoms or an alkenyl group having 2 to 10 carbon atoms, present in these groups one -CH 2 _- or nonadjacent two or more -CH 2 _- may be substituted by -O- or -S-, also present in the group One or more hydrogen atoms may be substituted with a fluorine atom or a chlorine atom. More preferred is 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 3 to 6 carbon atoms, and 1 to 5 carbon atoms. And an alkyl group having 1 to 5 carbon atoms is particularly preferable.
n ₂ is preferably 0, 1 or 2, and more preferably 0 or 1. When a plurality of M ²³ are present, they may be the same or different. When a plurality of L ²² are present, they may be the same or different.

M ²¹ , M ²² and M ²³ are each independently (d) a trans-1,4-cyclohexylene group (one —CH ₂ — present in this group or two or more non-adjacent — CH ₂ — may be replaced by —O— or —S—),
(E) a 1,4-phenylene group (one —CH═ present in the group or two or more non-adjacent —CH═ may be replaced by —N═), 2-fluoro- 1,4-phenylene group, 3-fluoro-1,4-phenylene group, 3,5-difluoro-1,4-phenylene group, and (f) 1,4-cyclohexenylene group, 1,4-bicyclo [ 2.2.2] Octane-1,4-diyl group, piperidine-2,5-diyl group, naphthalene-2,6-diyl group, decahydronaphthalene-2,6-diyl group and 1,2,3,3 A group selected from the group consisting of 4-tetrahydronaphthalene-2,6-diyl group is preferred. A trans-1,4-cyclohexylene group, a 1,4-phenylene group, or a 1,4-bicyclo [2.2.2] octane-1,4-diyl group is more preferable, and a trans-1,4-cyclohexylene group is preferred. Or a 1,4-phenylene group is particularly preferable.

L ²¹ and L ²² are each independently a single bond, —CH ₂ CH ₂ —, — (CH ₂ ) ₄ —, —OCH ₂ —, —CH ₂ O—, —OCF ₂ —, —CF ₂ O—. , —CH═CH—, —CH═N—N═CH— or —C≡C— are preferred. A single bond, —CH ₂ CH ₂ —, — (CH ₂ ) ₄ —, —OCH ₂ — or —CH ₂ O— is more preferred, and a single bond or —CH ₂ CH ₂ — is still more preferred.

  More specifically, the general formula (II) is preferably a compound represented by the following general formula (II-A) to general formula (II-P) as a specific structure.

Wherein R ²³ and R ²⁴ are each independently an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, or an alkenyloxy group having 3 to 10 carbon atoms. Represents.)
R ²³ and R ²⁴ are each independently preferably an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms or an alkenyl group having 2 to 10 carbon atoms, and an alkyl group or carbon having 1 to 5 carbon atoms An alkoxy group having 1 to 10 is more preferable.
Among the compounds represented by general formula (II-A) to general formula (II-P), general formula (II-A), general formula (II-B), general formula (II-C), and general formula (II) -E), general formula (II-H), general formula (II-I) or a compound represented by general formula (II-K) is preferred, and general formula (II-A), general formula (II-C) The compound represented by formula (II-E), formula (II-H) or formula (II-I) is more preferable.
In this invention, although the compound represented by general formula (II) contains at least 1 sort (s), it is preferable to contain 1-10 types, and it is especially preferable to contain 2-8 types. The lower limit of the content of the compound represented by the general formula (II) is preferably 5% by mass, more preferably 10% by mass, still more preferably 20% by mass, and 30% by mass. The upper limit is preferably 90% by mass, preferably 80% by mass, more preferably 70% by mass, and still more preferably 60% by mass.

<Polymerizable compound>
The polymerizable compound used in the liquid crystal composition containing the polymerizable compound of the present invention is composed of a compound represented by the general formula (III).
In the general formula (III), Z represents a hydrogen atom, a halogen, a cyano group, a thiocyanato group, a trifluoromethoxy group, a trifluoromethyl group, a difluoromethoxy group, or an alkyl group having 1 to 12 carbon atoms. One —CH ₂ — or two or more non-adjacent —CH ₂ — in the group is —O—, —S—, —CO—, —COO—, —OCO—, —OCOO—, —CH. ═CH— or —C≡C— may be substituted, or Z is preferably —S ³² —R ³² .
Z represents a hydrogen atom, a fluorine atom, a chlorine atom, a trifluoromethoxy group, a trifluoromethyl group, a difluoromethoxy group, or an alkyl group having 1 to 12 carbon atoms, and one —CH in the alkyl group. ₂ or two or more non-adjacent —CH ₂ — are —O—, —S—, —CO—, —COO—, —OCO—, —OCOO—, —CH═CH—, or —C≡. You may be substituted by C-, or Z ^is preferably a -S 32 ^{-R 32.}

R ³¹ and R ³² represent a polymerizable group. When Z is —S ³² —R ³² , it has two of R ³¹ and R ³² as polymerizable groups in the molecule, and one of R ^{31 in} other cases. The number of polymerizable groups in the molecule is important in determining the strength of the cured product after polymerization. When the number of polymerizable groups increases, the cured product after polymerization increases the strength. Therefore, it is preferable to select from a balance between improvement in strength and improvement in compatibility with the compound represented by formula (I). .
Specific examples of the polymerizable group include the structures shown below.

  These polymerizable groups are cured by radical polymerization, radical addition polymerization, cationic polymerization, and anionic polymerization. In particular, when performing ultraviolet polymerization as a polymerization method, the formula (R-1), formula (R-2), formula (R-4), formula (R-5), formula (R-7), formula (R -11), formula (R-13) or formula (R-15) are preferred, and formula (R-1), formula (R-2), formula (R-7), formula (R-11) or formula ( R-13) is more preferred, and formula (R-1) or formula (R-2) is more preferred.

S ³¹ and S ³² each independently represent a spacer group or a single bond. S ³¹ and ^{S 32} represents an alkylene group having 1 to 12 carbon atoms, or a single bond are preferred, one -CH ₂ in the alkylene group - or nonadjacent two or more -CH ₂ - is - O-, -COO-, -OCO-, or -OCOO- may be substituted.
In order to suppress the amount of change in the pretilt angle, a single bond or an alkylene group having 1 to 4 carbon atoms is preferable. On the other hand, an alkylene group having a certain length is preferable for improving the solubility. However, if the length is too long, the flexibility of the polymer after polymerization is increased, which causes baking. For this reason, in order to improve solubility, a C1-C8 alkylene group is preferable and a C1-C5 alkylene group is more preferable.

L ³¹ is preferably —OCOCH═CH— or —C≡C—. In addition, —OCOCH═CH— in L ³¹ means that M ³¹ is linked with the rightmost CH group.
In order to proceed the polymerization with ultraviolet light more rapidly, it is preferable that L ³¹ having these π electrons is conjugated with the aromatic ring of M ³¹ .

L ³² and L ³³ are each independently a single bond, —O—, —S—, —CH ₂ —, —OCH ₂ —, —CH ₂ O—, —CO—, —C ₂ H ₄ —, — _{COO -, - OCO -, -} OCOOCH 2 -, - CH 2 OCOO -, - CO-NR a -, - NR a -CO -, - SCH 2 -, - CH 2 S -, - CH = CH-COO- , -COO-CH = CH -, - OCO-CH = CH -, - CH = CH-OCO -, - COOC 2 H 4 -, - OCOC 2 H 4 -, - C 2 H 4 OCO -, - C 2 H ₄ COO—, —OCOCH ₂ —, —CH ₂ COO—, —CH ₂ OCO—, —COOCH ₂ —, —CH═CH—, —CF═CH—, —CH═CF—, —CF═CF— _{, -CF 2 -, - CF 2} O -, - OCF 2 -, - CF 2 CH 2 -, - CH _{CF 2 -, - CF 2 CF} 2 - or -C≡C- is preferred (wherein, ^{R a} represents an alkyl group having 1 to 4 carbon atoms.). Furthermore, a single bond, —O—, —CH ₂ —, —OCH ₂ —, —CH ₂ O—, —CO—, —C ₂ H ₄ —, —COO—, —OCO—, —OCOOCH ₂ —, — _{CH 2 OCOO -, - CH =} CH-COO -, - COO-CH = CH -, - OCO-CH = CH -, - CH = CH-OCO -, - COOC 2 H 4 -, - OCOC 2 H 4 - _{, -C 2 H 4 OCO -,} - C 2 H 4 COO -, - OCOCH 2 -, - CH 2 COO -, - CH 2 OCO -, - COOCH 2 - or -CH = CH- are preferred.
In order to make polymerization by ultraviolet light proceed more rapidly, a linking group having π electrons is preferable, and other liquid crystal materials, particularly a compound represented by the general formula (I) and a compound represented by the general formula (II) In order to improve the compatibility, a linking group having an ether bond or an ester bond and a single bond are preferred.

M ³¹ is preferably a 1,4-phenylene group or a naphthalene-2,6-diyl group. M ³² is a 1,4-phenylene group, 1,4-cyclohexylene group, pyridine-2,5-diyl group, pyrimidine-2,5-diyl group, a piperidine-2,5-diyl group, naphthalene-2,6 -A diyl group, an indane-2,5-diyl group, a 1,2,3,4-tetrahydronaphthalene-2,6-diyl group or a 1,3-dioxane-2,5-diyl group is preferred. M ³¹ and M ³² are each independently unsubstituted or a hydrogen atom contained in these groups is a halogen, a cyano group, an alkyl group having 1 to 8 carbon atoms, or a halogenation having 1 to 8 carbon atoms An alkyl group, a halogenated alkoxy group having 1 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, or a nitro group may be substituted.
Further, M ³² is a 1,4-phenylene group or a naphthalene-2,6-diyl group (these groups are, independently of one another, unsubstituted or hydrogen atoms contained in these groups are halogen, carbon atoms (It may be substituted with an alkyl group having 1 to 4 carbon atoms, a halogenated alkyl group having 1 to 4 carbon atoms, a halogenated alkoxy group having 1 to 4 carbon atoms, or an alkoxy group having 1 to 4 carbon atoms.) Is preferred.
M ³² is at least one trans-1,4-cyclohexylene group for improving the compatibility with other components, particularly the compound represented by the general formula (I) and the compound represented by the general formula (II). Or at least one hydrogen atom in the group is preferably substituted with a fluorine atom, an alkyl group or an alkoxy group, or the spacer group is not a single bond. In order to give moderate flexibility, it is preferable that at least one of M ³² has a cyclohexane skeleton, and in order to improve polymerizability, it is preferable that at least two of M ³² have an aromatic ring, and three or more More preferably, it has an aromatic ring. When the polymerizability is high, the irradiation intensity at the time of polymerization can be suppressed, and since the amount of the remaining polymerizable compound is reduced, the productivity can be improved, the deterioration of the liquid crystal composition can be prevented and the burn-in can be prevented, It is possible to reduce display defects.

n ₃ represents 1, 2 or 3.
When a plurality of L ³³ are present, they may be the same or different.
When a plurality of M ³² are present, they may be the same or different.
When improvement of compatibility with other components, particularly the compound represented by the general formula (I) and the compound represented by the general formula (II) is particularly required, n ₃ is preferably 1, and the liquid crystal molecule, N ₃ is preferably 1 or 2 when improvement in the orientation regulating power of the compound represented by the general formula (I) and the compound represented by the general formula (II) is particularly required. If the compatibility with other components is low, precipitation or the like occurs during transportation or manufacture of the liquid crystal display element, which causes a change in content or a display defect. In addition, when the alignment regulating force is low, the alignment of the liquid crystal molecules is changed, which causes display defects.

  More specifically, the compounds represented by the general formula (III) are compounds represented by the following general formulas (IIIa-1) to (IIIa-77) and (IIIb-1) to (IIIb-74). Is preferred.

(In the formula, p and q each independently represent an integer of 0 to 12, but when 0 represents a structure in which oxygens are directly connected, one oxygen atom is removed.)
General formula (IIIa-1) to general formula (IIIa-24), general formula (IIIa-69) to general formula (IIIa-76), general formula (IIIb-1) to general formula (IIIb-36), general formula Compounds represented by (IIIb-63) to general formula (IIIb-74) are more preferable, and further, general formula (IIIa-1) to general formula (IIIa-18), general formula (IIIa-69) to general formula Compounds represented by (IIIa-71), general formula (IIIb-1) to general formula (IIIb-36), and general formula (IIIb-63) to general formula (IIIb-68) are more preferable.

In the polymerizable compound-containing liquid crystal composition of the present invention, it contains at least one polymerizable compound represented by the general formula (III), preferably 1 to 5 types, preferably 1 to 3 types. It is particularly preferable to do this. When the content of the polymerizable compound represented by the general formula (III) is small, the alignment regulation for the non-polymerizable liquid crystal compound, particularly the compound represented by the general formula (I) and the compound represented by the general formula (II). If the force becomes weak and the amount is too large, the required energy during polymerization increases, and the amount of the polymerizable compound that remains without being polymerized increases. Therefore, the lower limit is preferably 0.01% by mass. The upper limit is preferably 2.0% by mass, more preferably 1.0% by mass.
In the compound represented by the general formula (I), the compound represented by the general formula (II) and the polymerizable compound represented by the general formula (III) included in the nematic liquid crystal composition of the present application, -O-O- There is no partial structure in which heteroatoms such as —O—S— and —S—S— are directly bonded to each other.

<Liquid crystal composition and liquid crystal display element>
In the liquid crystal composition of the present invention, Δn is preferably in the range of 0.08 to 0.25.
In the liquid crystal composition of the present invention, Δε having a positive or negative Δε can be used depending on the display mode of the liquid crystal display element. In the MVA mode liquid crystal display element, a liquid crystal composition having a negative Δε is used. In that case, Δε is preferably −1 or less, and more preferably −2 or less.

The liquid crystal composition of the present invention has a wide liquid crystal phase temperature range (absolute value of the difference between the liquid crystal phase lower limit temperature and the liquid crystal phase upper limit temperature), but the liquid crystal phase temperature range is preferably 100 ° C or higher, and 120 ° C or higher. Is more preferable. The upper limit temperature of the liquid crystal phase is preferably 70 ° C. or higher, and more preferably 75 ° C. or higher. Furthermore, the lower limit temperature of the liquid crystal phase is preferably −20 ° C. or lower, and more preferably −25 ° C. or lower.
The liquid crystal composition of the present invention may contain a normal nematic liquid crystal, a smectic liquid crystal, a cholesteric liquid crystal and the like in addition to the above compounds.

In the polymerizable compound-containing liquid crystal composition of the present invention, polymerization proceeds even in the absence of a polymerization initiator, but may contain a polymerization initiator in order to promote polymerization. Examples of the polymerization initiator include benzoin ethers, benzophenones, acetophenones, benzyl ketals, acylphosphine oxides, and the like.
In order to improve the storage stability of the liquid crystal composition of the present invention, a stabilizer may be added. Examples of the stabilizer that can be used include hydroquinones, hydroquinone monoalkyl ethers, tert-butylcatechols, pyrogallols, thiophenols, nitro compounds, β-naphthylamines, β-naphthols, nitroso compounds, and the like. It is done. The addition amount in the case of using a stabilizer is preferably in the range of 0.005 to 1% by mass, more preferably 0.02 to 0.5% by mass, and 0.03 to 0.1% by mass with respect to the liquid crystal composition. % Is particularly preferred.

  In the liquid crystal composition of the present invention, the polymerizable compound represented by the general formula (III) in the liquid crystal composition is polymerized so that liquid crystal alignment ability is imparted, and light transmission is performed using the birefringence of the liquid crystal composition. Used in liquid crystal display elements that control the amount of light. As liquid crystal display elements, AM-LCD (active matrix liquid crystal display element), TN (nematic liquid crystal display element), STN-LCD (super twisted nematic liquid crystal display element), OCB-LCD and IPS-LCD (in-plane switching liquid crystal display element) However, it is particularly useful for AM-LCDs, and can be used for transmissive or reflective liquid crystal display elements.

The two substrates of the liquid crystal cell used in the liquid crystal display element can be made of a transparent material having flexibility such as glass or plastic, and one of them can be an opaque material such as silicon. A transparent substrate having a transparent electrode layer can be obtained, for example, by sputtering indium tin oxide (ITO) on a transparent substrate such as a glass plate.
The color filter can be prepared by, for example, a pigment dispersion method, a printing method, an electrodeposition method, or a dyeing method. A method for producing a color filter by a pigment dispersion method will be described as an example. A curable coloring composition for a color filter is applied on the transparent substrate, subjected to patterning treatment, and cured by heating or light irradiation. By performing this process for each of the three colors red, green, and blue, a pixel portion for a color filter can be created. In addition, a pixel electrode provided with an active element such as a TFT, a thin film diode, or a metal insulator metal specific resistance element may be provided on the substrate.

The said board | substrate is made to oppose so that a transparent electrode layer may become an inner side. In that case, you may adjust the space | interval of a board | substrate through a spacer. At this time, it is preferable to adjust so that the thickness of the light control layer obtained may be set to 1-100 micrometers. More preferably, the thickness is 1.5 to 10 μm. When a polarizing plate is used, it is preferable to adjust the product of the refractive index anisotropy Δn of the liquid crystal and the cell thickness d so that the contrast is maximized. In addition, when there are two polarizing plates, the polarizing axis of each polarizing plate can be adjusted so that the viewing angle and contrast are good. Furthermore, a retardation film for widening the viewing angle can also be used. Examples of the spacer include glass particles, plastic particles, alumina particles, and a photoresist material. Thereafter, a sealant such as an epoxy thermosetting composition is screen-printed on the substrates with a liquid crystal inlet provided, the substrates are bonded together, and heated to thermally cure the sealant.
As a method for sandwiching the polymer-stabilized liquid crystal composition between the two substrates, a normal vacuum injection method, an ODF method, or the like can be used.

  As a method for polymerizing a polymerizable compound, since rapid progress of polymerization is desirable, a method of polymerizing by irradiating active energy rays such as ultraviolet rays or electron beams is preferable. When ultraviolet rays are used, a polarized light source or a non-polarized light source may be used. Further, when the polymerization is carried out with the liquid crystal composition sandwiched between two substrates, at least the substrate on the irradiation surface side must be given appropriate transparency to the active energy rays. Moreover, after polymerizing only a specific part using a mask during light irradiation, the orientation state of the unpolymerized part is changed by changing conditions such as an electric field, a magnetic field, or temperature, and further irradiation with active energy rays is performed. Then, it is possible to use a means for polymerization. In particular, when ultraviolet exposure is performed, it is preferable to perform ultraviolet exposure while applying an alternating electric field to the polymerizable compound-containing liquid crystal composition. The alternating electric field to be applied is preferably an alternating current having a frequency of 10 Hz to 10 kHz, more preferably a frequency of 60 Hz to 10 kHz, and the voltage is selected depending on a desired pretilt angle of the liquid crystal display element. That is, the pretilt angle of the liquid crystal display element can be controlled by the applied voltage. In the MVA mode liquid crystal display element, the pretilt angle is preferably controlled from 80 degrees to 89 degrees from the viewpoint of alignment stability and contrast.

The temperature during irradiation is preferably within a temperature range in which the liquid crystal state of the liquid crystal composition of the present invention is maintained. Polymerization is preferably performed at a temperature close to room temperature, that is, typically at a temperature of 15 to 35 ° C. As a lamp for generating ultraviolet rays, a metal halide lamp, a high-pressure mercury lamp, an ultra-high pressure mercury lamp, or the like can be used. Moreover, as a wavelength of the ultraviolet-rays to irradiate, it is preferable to irradiate the ultraviolet-ray of the wavelength range which is not the absorption wavelength range of a liquid crystal composition, and it is preferable to cut and use an ultraviolet-ray as needed. Intensity of ultraviolet irradiation is ^preferably from ^{0.1mW / cm 2 ~100W / cm 2} , 2mW / cm 2 ~50W / cm 2 is more preferable. The amount of energy of ultraviolet rays to be irradiated can be adjusted as appropriate, but is preferably 10 mJ / cm ² to 500 J / cm ^{2, and} more preferably 100 mJ / cm ² to 200 J / cm ² . When irradiating with ultraviolet rays, the intensity may be changed. The time for irradiating with ultraviolet rays is appropriately selected depending on the intensity of the irradiated ultraviolet rays, but is preferably from 10 seconds to 3600 seconds, and more preferably from 10 seconds to 600 seconds.

  EXAMPLES Hereinafter, although an Example is given and this invention is further explained in full detail, this invention is not limited to these Examples. Further, “%” in the compositions of the following Examples and Comparative Examples means “% by mass”.

The physical properties of the liquid crystal composition are expressed as follows.
T _N-I (° C.): Nematic phase-isotropic liquid phase transition temperature (liquid crystal phase upper limit temperature)
Δε: Dielectric anisotropy Δn: Refractive index anisotropy Vth (V): Applied voltage (threshold voltage) at which the transmittance changes by 10% when a rectangular wave with a frequency of 1 KHz is applied

(Measurement method of residual amount of monomer after UV curing)
After injecting the liquid crystal composition into the liquid crystal cell, UV is irradiated to polymerize the polymerizable compound. Thereafter, the liquid crystal cell is disassembled to obtain an acetonitrile solution of an elution component containing a liquid crystal material, a polymer, and an unpolymerized polymerizable compound. The peak area of each component is measured by high performance liquid chromatography (column: reverse phase nonpolar column, developing solvent: acetonitrile). The amount of the remaining polymerizable compound was determined from the peak area ratio of the liquid crystal material as an index and the peak area ratio of the unpolymerized polymerizable compound. The residual monomer amount was determined from this value and the amount of the polymerizable compound initially added. The detection limit of the remaining amount of the polymerizable compound was 1000 ppm.
(Burn-in evaluation method)
A voltage was applied to the liquid crystal display element after polymerization so as to form a black and white checker pattern, and a luminance change state was visually observed when a halftone display was performed for each elapsed time.

Example 1
A liquid crystal composition LC-1 containing a compound selected from general formula (I) and a compound selected from general formula (II) was prepared. The constituent compounds and the ratios contained are as follows.

  Table 1 shows the physical properties of the liquid crystal composition LC-1.

  Polymerizable compound-containing liquid crystal composition CLC-1 by adding 0.3% of the polymerizable compound represented by the formula (IIIb-8-a) to 99.7% of the liquid crystal composition LC-1 and uniformly dissolving it. Was prepared.

The physical properties of CLC-1 were almost the same as the physical properties of LC-1. For this reason, it turned out that the polymeric compound represented by a formula (IIIb-8-a) does not reduce the liquid crystal property of the liquid crystal composition to add. Moreover, although this CLC-1 was preserve | saved for one week at the cold place (-20 degreeC), precipitation etc. did not occur. From this, it was found that the polymerizable compound represented by the formula (IIIb-8-a) was excellent in compatibility with other liquid crystal compounds.
CLC-1 was injected by a vacuum injection method into a cell with ITO coated with a polyimide alignment film that induces homeotropic alignment with a cell gap of 3.5 μm. After measuring the pretilt angle (crystal rotation method) of this cell, the liquid crystal cell is irradiated with ultraviolet light by a high-pressure mercury lamp through a filter that cuts ultraviolet light of 320 nm or less while applying a rectangular wave of 1.8 V at a frequency of 1 KHz. did. The cell surface was adjusted so that the irradiation intensity was 10 mW / cm ² and irradiated for 600 seconds to obtain a vertically aligned liquid crystal display element in which the polymerizable compound in the polymerizable compound-containing liquid crystal composition was polymerized. Table 2 shows the pretilt angle of the element before and after UV irradiation and the electro-optical characteristics of the element.

The pretilt angle before the ultraviolet irradiation of the element was 89.6 degrees, whereas the pretilt angle after the irradiation was 87.1 degrees, and a pretilt was given. From the measurement result of the above pretilt angle, the polymerizable compound is polymerized to produce an alignment regulating force on the liquid crystal compound, and the pretilt angle is fixed while the liquid crystal molecules are tilted 2.9 degrees from the vertical direction. It was found that an alignment liquid crystal display element was obtained.
Further, the content of the compound represented by the unpolymerized formula (IIIb-8-a) contained in the device was analyzed by liquid chromatographic analysis, but was not detected. Thereby, the polymerizable compound represented by the formula (IIIb-8-a) contained in the liquid crystal composition of the present invention can be polymerized without using a polymerization initiator, and remains unpolymerized after polymerization. It was confirmed that the product was below the detection limit.

(Comparative Example 1)
A polymerizable compound-containing liquid crystal composition CLC-A was prepared by adding 0.3% of the polymerizable compound represented by the general formula (A) to 99.7% of the liquid crystal composition LC-1 and uniformly dissolving it. .

CLC-A was injected by vacuum injection into a cell with ITO coated with a polyimide alignment film that induces homeotropic alignment with a cell gap of 3.5 μm. After measuring the pretilt angle of this cell, the liquid crystal cell was irradiated with ultraviolet rays by a high-pressure mercury lamp through a filter that cuts ultraviolet rays of 320 nm or less while applying a rectangular wave of 1.8 V at a frequency of 1 KHz. The cell surface was adjusted so that the irradiation intensity was 10 mW / cm ² and irradiated for 600 seconds to obtain a vertically aligned liquid crystal display element in which the polymerizable compound in the polymerizable compound-containing liquid crystal composition was polymerized.
The pretilt angle before the ultraviolet irradiation of the device was 89.6 degrees, whereas the pretilt angle after the irradiation was 89.5 degrees, the pretilt angle was not changed, and the liquid crystal molecules were hardly tilted from the vertical direction. It was. That is, no pretilt was given. Moreover, as a result of analyzing the content of the polymerizable compound represented by the general formula (A) contained in the element by liquid chromatographic analysis, there was no change in the content before the ultraviolet irradiation, and the polymerizable compound (A) Polymerization was not progressing.
Further, as a result of storing this CLC-A in a cold place (−20 ° C.) for 1 week, precipitation occurred, and the polymerizable compound represented by the formula (A) is represented by the general formula (I) contained in the liquid crystal composition of the present invention. It was found that the compatibility with the liquid crystal compounds represented by the general formulas (I) and (II) represented by (II) and (II) was poor.

(Example 2)
Polymerizable compound-containing liquid crystal composition CLC-2 by adding 0.3% of the polymerizable compound represented by the formula (IIIa-2-a) to 99.7% of the liquid crystal composition LC-1 and uniformly dissolving it Was prepared.

The physical properties of CLC-2 were almost the same as the physical properties of LC-1. For this reason, it turned out that the polymeric compound represented by a formula (IIIa-2-a) does not reduce the liquid crystal property of the liquid crystal composition to add. Moreover, although this CLC-2 was preserve | saved for one week at the cold place (-20 degreeC), precipitation etc. did not occur. From this, it was found that the polymerizable compound represented by the formula (IIIa-2-a) was excellent in compatibility with other liquid crystal compounds.
CLC-2 was injected by vacuum injection into a cell with ITO coated with a polyimide alignment film that induces homeotropic alignment with a cell gap of 3.5 μm. After measuring the pretilt angle (crystal rotation method) of this cell, the liquid crystal cell is irradiated with ultraviolet light by a high-pressure mercury lamp through a filter that cuts ultraviolet light of 320 nm or less while applying a rectangular wave of 1.8 V at a frequency of 1 KHz. did. The cell surface was adjusted so that the irradiation intensity was 10 mW / cm ² and irradiated for 600 seconds to obtain a vertically aligned liquid crystal display element in which the polymerizable compound in the polymerizable compound-containing liquid crystal composition was polymerized.
The pretilt angle before the ultraviolet irradiation of the element was 89.6 degrees, whereas the pretilt angle after the irradiation was 87.0 degrees, which was a pretilt. From the measurement result of the above pretilt angle, the polymerizable compound is polymerized, so that the alignment regulating force for the liquid crystal compound is generated, and the vertical tilt with the pretilt angle fixed with the liquid crystal molecules tilted by 3.0 degrees from the vertical direction. It was found that an alignment liquid crystal display element was obtained.
Further, the content of the compound represented by the unpolymerized formula (IIIa-2-a) contained in the device was analyzed by liquid chromatographic analysis, but was not detected. Thereby, the polymerizable compound represented by the formula (IIIa-2-a) contained in the liquid crystal composition of the present invention can be polymerized without using a polymerization initiator, and remains unpolymerized after polymerization. It was confirmed that the product was below the detection limit.

(Example 3)
Polymerizable compound-containing liquid crystal composition CLC-3 is obtained by uniformly adding 0.3% of the polymerizable compound represented by the formula (IIIa-8-a) to 99.7% of the liquid crystal composition LC-1 and dissolving it uniformly. Was prepared.

The physical properties of CLC-3 were almost the same as the physical properties of LC-1. For this reason, it turned out that the polymeric compound represented by a formula (IIIa-8-a) does not reduce the liquid crystal property of the liquid crystal composition to add. Further, although this CLC-3 was stored in a cold place (−20 ° C.) for 1 week, precipitation or the like did not occur. From this, it was found that the polymerizable compound represented by the formula (IIIa-8-a) has excellent compatibility with other liquid crystal compounds.
CLC-3 was injected by vacuum injection into a cell with ITO coated with a polyimide alignment film that induces homeotropic alignment with a cell gap of 3.5 μm. After measuring the pretilt angle (crystal rotation method) of this cell, the liquid crystal cell is irradiated with ultraviolet light by a high-pressure mercury lamp through a filter that cuts ultraviolet light of 320 nm or less while applying a rectangular wave of 1.8 V at a frequency of 1 KHz. did. The cell surface was adjusted so that the irradiation intensity was 10 mW / cm ² and irradiated for 600 seconds to obtain a vertically aligned liquid crystal display element in which the polymerizable compound in the polymerizable compound-containing liquid crystal composition was polymerized.
The pretilt angle before the ultraviolet irradiation of the element was 89.6 degrees, whereas the pretilt angle after the irradiation was 86.9 degrees, and a pretilt was imparted. From the measurement result of the above pretilt angle, the polymerizable compound is polymerized to produce an alignment regulating force on the liquid crystal compound, and the pretilt angle is fixed while the liquid crystal molecules are tilted 3.1 degrees from the vertical direction. It was found that an alignment liquid crystal display element was obtained.
Further, the content of the unpolymerized compound (IIIa-8-a) contained in the device was analyzed by liquid chromatographic analysis, but was not detected. Thus, the polymerizable compound represented by the formula (IIIa-8-a) contained in the liquid crystal composition of the present invention can be polymerized without using a polymerization initiator, and remains unpolymerized after polymerization. It was confirmed that the product was below the detection limit.

(Example 4 and Comparative Example 2)
A voltage was applied to the liquid crystal display elements after polymerization prepared in Examples 1 to 3 and Comparative Example 1, and the elapsed time and the state of image sticking were visually observed.
The liquid crystal display device manufactured in Comparative Example 1 burned in 48 hours after display, and display defects were observed over almost the entire surface after 168 hours. On the other hand, in the liquid crystal display elements produced in Examples 1 to 3, image sticking did not occur even after 500 hours had elapsed, and a good display state was maintained. Thereby, all the polymerizable compounds contained in the liquid crystal composition of the present invention are polymerized without remaining after the polymerization, and it can be confirmed that the liquid crystal display device using the liquid crystal composition of the present invention has high reliability. It was. Further, it was found that the polymer has sufficiently large rigidity without lowering the orientation regulating force.

Claims (6)

As the first component, the general formula (I)

(In the formula, R ¹¹ and R ¹² each independently represent an alkyl group having 1 to 10 carbon atoms or an alkenyl group having 2 to 10 carbon atoms, and one —CH ₂ — present in these groups. Or two or more non-adjacent —CH ₂ — may be substituted by —O— or —S—, and one or more hydrogen atoms present in these groups are fluorine atoms or May be substituted with chlorine atoms,
n ₁ represents 0, 1 or 2,
M ¹¹ and M ¹² are independent of each other
(A) trans-1,4-cyclohexylene group (the one present in the group -CH ₂ - or nonadjacent two or more -CH ₂ - is replaced by -O- or -S- May be)
(B) a 1,4-phenylene group (one -CH = present in the group or two or more non-adjacent -CH = may be replaced by -N =), and
(C) 1,4-cyclohexenylene group, 1,4-bicyclo [2.2.2] octane-1,4-diyl group, piperidine-2,5-diyl group, naphthalene-2,6-diyl group Represents a group selected from the group consisting of 1,2,3,4-tetrahydronaphthalene-2,6-diyl group and decahydronaphthalene-2,6-diyl group, and the above groups (a) and (b) Alternatively, the hydrogen atoms contained in the group (c) may be each substituted with a cyano group, a halogen, a trifluoromethyl group or a trifluoromethoxy group, but when a plurality of M ¹² are present, they may be the same or different. You may,
L ¹¹ represents a single bond, —COO—, —OCO—, —CH ₂ CH ₂ —, — (CH ₂ ) ₄ —, —OCH ₂ —, —CH ₂ O—, —OCF ₂ —, —CF ₂ O—. Or -C≡C-
X ¹¹ and X ¹² each independently represent a trifluoromethyl group, a trifluoromethoxy group, a fluorine atom or a chlorine atom, and any one of X ¹¹ and X ¹² represents a fluorine atom. ) Containing one or more compounds selected from the group consisting of compounds represented by:
As the second component, the general formula (II)

(In the formula, R ²¹ and R ²² each independently represent an alkyl group having 1 to 10 carbon atoms or an alkenyl group having 2 to 10 carbon atoms, and one —CH ₂ — present in these groups. Or two or more non-adjacent —CH ₂ — may be substituted with —O— or —S—, and one or more hydrogen atoms present in these groups are fluorine atoms or chlorine May be substituted with atoms,
n ₂ represents 0, 1 or 2,
M ²¹ , M ²² and M ²³ are each independently (d) a trans-1,4-cyclohexylene group (one —CH ₂ — present in this group or two or more non-adjacent — CH ₂ — may be replaced by —O— or —S—),
(E) a 1,4-phenylene group (one —CH═ present in the group or two or more non-adjacent —CH═ may be replaced by —N═), 2-fluoro- 1,4-phenylene group, 3-fluoro-1,4-phenylene group, 3,5-difluoro-1,4-phenylene group, and (f) 1,4-cyclohexenylene group, 1,4-bicyclo [ 2.2.2] Octane-1,4-diyl group, piperidine-2,5-diyl group, naphthalene-2,6-diyl group, decahydronaphthalene-2,6-diyl group and 1,2,3,3 It represents a group selected from the group consisting of 4-tetrahydronaphthalene-2,6-diyl group, in the case where M ²³ there are a plurality may be the same or different and
L ²¹ and L ²² are each independently a single bond, —CH ₂ CH ₂ —, — (CH ₂ ) ₄ —, —OCH ₂ —, —CH ₂ O—, —OCF ₂ —, —CF ₂ O—. , —CH═CH—, —CH═N—N═CH—, or —C≡C—, when two or more L ²² are present, they may be the same or different. ) Containing one or more compounds represented by
As the third component, the general formula (III)

(In the formula, Z represents —S ³² —R ³² ,
R ³¹ and R ³² are independently of each other from the following formulas (R-1) to (R-15):

Any one of
S ³¹ and S ³² each independently represent an alkylene group having 1 to 12 carbon atoms or a single bond, and one —CH ₂ — in the alkylene group or two or more —CH 2 not adjacent to each other. _2- may be replaced by -O-, -COO-, -OCO-, or -OCOO-,
n ₃ represents 1, 2 or 3,
L ³¹ represents —OCOCH═CH— or —C≡C—
L ³² represents a single bond,
L ³³ is a single bond, —O—, —S—, —CH ₂ —, —OCH ₂ —, —CH ₂ O—, —CO—, —C ₂ H ₄ —, —COO—, —OCO—, ^{_{-OCOOCH 2 -, - CH 2 OCOO}} -, - CO-NR a -, - NR a -CO -, - SCH 2 -, - CH 2 S -, - CH = CH-COO -, - COO-CH = CH _{-, - OCOCH = CH -,} - CH = CH-OCO -, - COOC 2 H 4 -, - OCOC 2 H 4 -, - C 2 H 4 OCO -, - C 2 H 4 COO -, - OCOCH _{2 -, - CH 2 COO -} , - CH 2 OCO -, - COOCH 2 -, - CH = CH -, - CF = CH -, - CH = CF -, - CF = CF -, - CF 2 -, - _{CF 2 O -, - OCF 2} -, - CF 2 CH 2 -, - CH 2 CF 2 -, - CF 2 C ₂ - or represents a -C≡C- (. Wherein, R ^a is represents an alkyl group having 1 to 4 carbon atoms), even if the L ³³ there are a plurality optionally substituted by one or more identical well,
M ³¹ represents a 1,4-phenylene group or a naphthalene-2,6-diyl group, and M ³² represents a 1,4-phenylene group, a 1,4-cyclohexylene group, a pyridine-2,5-diyl group, a pyrimidine- 2,5-diyl group, piperidine-2,5-diyl group, naphthalene-2,6-diyl group, indan-2,5-diyl group, 1,2,3,4-tetrahydronaphthalene-2,6-diyl Represents a group or a 1,3-dioxane-2,5-diyl group, and M ³¹ and M ³² are each independently unsubstituted or a hydrogen atom contained in these groups is a halogen, a cyano group or a carbon atom An alkyl group having 1 to 8 carbon atoms, a halogenated alkyl group having 1 to 8 carbon atoms, a halogenated alkoxy group having 1 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, or a nitro group. It may be, ^{M 3} There may be different even if the same in the case of plurality of. A polymerizable compound-containing liquid crystal composition containing one or two or more polymerizable compounds represented by formula (1). In the general formula ^{(III), R 31}及beauty ^{R 32} are independently of one another, are a formula (R-1) or the polymerizable compound-containing liquid crystal composition according to claim 1 which represents the (R-2). In the general formula (III), M ³² is a 1,4-phenylene group or a naphthalene-2,6-diyl group (these groups are, independently of each other, unsubstituted or contained in these groups) A hydrogen atom is substituted with halogen, an alkyl group having 1 to 4 carbon atoms, a halogenated alkyl group having 1 to 4 carbon atoms, a halogenated alkoxy group having 1 to 4 carbon atoms, or an alkoxy group having 1 to 4 carbon atoms 3. The polymerizable compound-containing liquid crystal composition according to claim 1, wherein the polymerizable compound-containing liquid crystal composition represents. A liquid crystal having a structure in which a liquid crystal is sandwiched between a pair of substrates, having at least a transparent electrode and a polarizing plate, and imparting liquid crystal alignment ability by polymerizing a polymerizable compound contained in the liquid crystal composition. The polymerizable compound-containing liquid crystal composition according to any one of claims 1 to 3 , which is used for a display element. 5 to 60% by mass of the compound selected from the general formula (I), 20 to 90% by mass of the compound selected from the general formula (II), and 0.01 to 0.01% of the polymerizable compound selected from the general formula (III). the polymerizable compound-containing liquid crystal composition according to any one of claims 1 to 4, characterized in that it contains 2% by weight. The polymerizable compound-containing liquid crystal composition according to any one of claims 1 to 5 is used, and liquid crystal alignment ability is imparted by polymerizing the polymerizable compound in the polymerizable compound-containing liquid crystal composition. A liquid crystal display element.