JP6355009B1 - Liquid crystal display element and manufacturing method thereof - Google Patents

Abstract

[Problem] Alignment stability is improved by an alignment control layer having good adhesion to a substrate without deteriorating various properties such as dielectric anisotropy, viscosity, nematic phase upper limit temperature, rotational viscosity (γ1), etc. Providing a liquid crystal display element in which image sticking and generation of dripping marks during production are suppressed, and a method for producing the same. [Solution] A liquid crystal containing a liquid crystal composition between a first substrate having a common electrode and a color filter and a second substrate having a plurality of pixels and a pixel electrode for each of the pixels. A polymerizable compound comprising a compound represented by the general formula (1) [Chemical Formula 1] having a layer sandwiched and having no alignment film on one or both of the first substrate and the second substrate; A liquid crystal display element comprising an alignment control layer made of a polymer.

Description

  The present invention relates to a liquid crystal display element useful as a constituent member for a liquid crystal TV and the like, and a method for manufacturing the same.

  Liquid crystal display elements are used in various measuring instruments, automobile panels, word processors, electronic notebooks, printers, computers, televisions, watches, advertisement display boards, as well as watches and calculators. Typical liquid crystal display methods include TN (twisted nematic) type, STN (super twisted nematic) type, vertical alignment type (vertical alignment; VA) using TFT (thin film transistor), and IPS. (In-plane switching) type. The liquid crystal composition used in these liquid crystal display elements is stable against external factors such as moisture, air, heat, and light, and exhibits a liquid crystal phase in the widest possible temperature range centering on room temperature. It is required to be viscous and have a low driving voltage. Furthermore, the liquid crystal composition is composed of several to several tens of kinds of compounds in order to optimize dielectric anisotropy (Δε), refractive index anisotropy (Δn), etc. for each liquid crystal display element. It is composed of

In the VA type display, a liquid crystal composition having a negative Δε is used, which is widely used for liquid crystal TVs and the like. On the other hand, in all driving methods, low voltage driving, high-speed response, and a wide operating temperature range are required. That is, the absolute value of Δε is large, the viscosity (η) is small, and a high nematic phase-isotropic liquid phase transition temperature (T _NI ) is required. Further, from the setting of Δn × d, which is the product of Δn and the cell gap (d), it is necessary to adjust Δn of the liquid crystal composition to an appropriate range according to the cell gap. In addition, when applying a liquid crystal display element to a television or the like, since high-speed response is important, a liquid crystal composition having a low rotational viscosity (γ ₁ ) is required.

  On the other hand, in order to improve the viewing angle characteristics of a VA display, an MVA (multi-domain vertical alignment) type that divides the alignment direction of liquid crystal molecules in a pixel into a plurality of parts by providing a protrusion structure on the substrate. Liquid crystal display elements have been widely used. Although the MVA type liquid crystal display element is excellent in view angle characteristics, the response speed of liquid crystal molecules is different between the vicinity of the protrusion structure on the substrate and the part away from the protrusion structure, and the liquid crystal having a slow response speed away from the protrusion structure. Due to the influence of the molecules, there is a problem that the overall response speed is insufficient, and there is a problem of a decrease in transmittance due to the protruding structure. In order to solve this problem, PSA is a method for providing a uniform pretilt angle in a divided pixel without providing a non-transparent protrusion structure in a cell, unlike a normal MVA liquid crystal display element. Liquid crystal display elements (including polymer sustained alignment, including PS liquid crystal display elements (polymer stabilized)) have been developed. A PSA liquid crystal display element is obtained by adding a small amount of a polymerizable compound to a liquid crystal composition, introducing the liquid crystal composition into a liquid crystal cell, and then applying active energy rays while applying a voltage between the electrodes. It is produced by polymerizing the polymerizable compound. Therefore, an appropriate pretilt angle can be given in the divided pixels, and as a result, it is possible to achieve an improvement in contrast by improving the transmittance and a high-speed response by giving a uniform pretilt angle (for example, Patent Documents). 1).

  In the PSA liquid crystal display element, a vertical alignment film is formed on two substrates. By omitting such a vertical alignment film formation process, the manufacturing process is simplified, the yield is improved, and the result is low. A liquid crystal display element that can be reduced in cost has also been proposed. (For example, refer to Patent Document 2).

  It is described that the liquid crystal display element of this system can improve the transmittance and can be expected to have a high-speed response because it can improve the transmittance, like the PSA liquid crystal display element. However, there is a case where the manufactured element generates display unevenness due to the manufacturing process, and a method using a specific liquid crystal material is disclosed as an improvement method (see Patent Document 3).

  In a liquid crystal display device that can simplify the process of forming such a vertical alignment film and reduce the cost, a polymerizable compound in the liquid crystal composition is polymerized, and the polymer does not form a vertical alignment film. Since it is formed directly on the electrode substrate as an alignment control layer, it is required that the alignment control layer itself is stable and does not change for a long time from the viewpoint of alignment uniformity and alignment stability of liquid crystal molecules in the liquid crystal element. It was.

JP 2002-357830 A JP 2004-302061 A WO2014 / 123056A1 publication

  The present invention has been made in view of the above circumstances, simplifying the process of forming a vertical alignment film on an electrode substrate, polymerizing a polymerizable compound in a liquid crystal composition, and aligning the alignment control layer on the electrode substrate In the liquid crystal display device manufactured by forming the electrode substrate, the adhesion of the alignment control layer formed on the electrode substrate to the electrode substrate is improved, the alignment uniformity of the alignment control layer is improved together, and the change in the alignment uniformity over time is further suppressed. It is an object of the present invention to provide a liquid crystal display element with improved alignment stability of liquid crystal molecules and, as a result, improved display quality and long-term reliability thereof, and a method for manufacturing the same.

  In order to solve the above problems, the present inventors have studied various liquid crystal compositions and polymerizable compounds in the liquid crystal composition. As a result, the liquid crystal composition contains the polymerizable compound, and the liquid crystal composition is contained in the liquid crystal cell. In the system in which the polymerizable compound in the liquid crystal composition is polymerized by irradiation with active energy rays while applying a voltage between the electrodes while applying a voltage between the electrodes, on one or both substrates on the substrate constituting the liquid crystal cell. It has been found that the above problems can be solved by using a specific compound as the liquid crystal compound and the polymerizable compound without providing a vertical alignment film, and the present invention has been completed.

That is, the present invention is a liquid crystal display element in which a liquid crystal layer containing a liquid crystal composition is sandwiched between a first substrate and a second substrate,
There is no alignment film on one or both of the first substrate and the second substrate, and the general formula (1)

(Wherein Z ¹ represents formula (i) or formula (ii)

Z ² is represented by formula (iii) or formula (iv)

M ¹ represents any of the formulas (v), (vi), (vii), or (viii)

X ¹ to X ⁴⁷ each independently represent a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, a halogenated alkyl group having 1 to 8 carbon atoms, or an alkoxy having 1 to 8 carbon atoms. Group, halogen, cyano group, formula (2)

Or formula (3)

Wherein at least one of the existing X ¹ to X ⁴⁷ represents formula (2),
Y ¹ , Y ² and Z ³ are each independently a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, a halogenated alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, carbon Represents a halogenated alkoxy group having 1 to 8 atoms, halogen, cyano group, nitro group or R ³ , and S ¹ , S ² , S ³ , S ⁴ and S ⁵ each independently represent 1 to 12 carbon atoms; number of an alkylene group or a single bond, one -CH ₂ in the alkylene group - or nonadjacent two or more _-CH 2 - may, -O -, - COO -, - OCO- or - OCOO- may be substituted, and R ¹ , R ² , R ³ and R ⁴ are each independently a hydrogen atom or formula (R-1) to formula (R-15)

L ¹ , L ² and L ⁴ each independently represent a single bond, —O—, —CH═CH—, —OCH ₂ —, —CH ₂ O—, —CO—, —C _{2 H 4 -, - COO -} , - OCO -, - OCOOCH 2 -, - CH 2 OCOO -, - OCH 2 CH 2 O -, - CH = CR a -COO -, - CH = CR a -OCO-, ^{-COO-CR a = CH -,} - OCO-CR a = CH -, - COOC 2 H 4 -, - OCOC 2 H 4 -, - C 2 H 4 OCO -, - (CH 2) j -C (= _{O) -O -, - (CH} 2) j -O- (C = O) -, - O- (C = O) - (CH 2) j -, - (C = O) -O- (CH 2 _{) j -, - CH 2 OCO} -, - COOCH 2 -, - OCOCH 2 -, - CF 2 -, - CF 2 O -, - OCF 2 -, _{CF 2 CH 2 -, - CH} 2 CF 2 -, - CF 2 CF 2 - or -C≡C- (wherein, ^{R a} is each independently a hydrogen atom or an alkyl group having 1 to 4 carbon atoms , J represents an integer of 1 to 4, and L ³ represents a single bond, —O—, —OCH ₂ —, —CH ₂ O—, —CO—, —C ₂ H ₄ —, —COO. ^{_{-, - OCO -, - OCH}} 2 CH 2 O -, - CH = CR a -COO -, - CH = CR a -OCO -, - COO-CR a = CH -, - OCO-CR a = CH-, —CH═CH— or —C≡C— (wherein R ^a each independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms), and M ² and M ³ each independently 1,4-phenylene group, 1,4-cyclohexylene group, cyclohexene-1,4-diyl group, 2,5-diyl group, pyrimidine-2,5-diyl group, naphthalene-2,6-diyl group, naphthalene-1,4-diyl group, tetrahydronaphthalene-2,6-diyl group, 1,3- Dioxane-2,5-diyl group, phenanthrene-2,7diyl group, cyclopentane-1,3-diyl or cyclopentene-1,3-diyl are represented, and M ² and M ³ are each independently unsubstituted. Or an alkyl group having 1 to 8 carbon atoms, a halogenated alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, a halogen, a cyano group, or a nitro group. Well, m represents 0, 1 or 2, and p represents 0, 1 or 2, but when m is 2, the plurality of L ¹ and M ¹ may be the same or different. , P is 2, a plurality of L ⁴ and M ³ May be the same or different. The liquid crystal display device is characterized by having an orientation control layer made of a polymer of a polymerizable compound containing a compound represented by (1).

In the present invention, a liquid crystal layer containing a liquid crystal composition is sandwiched between a first substrate having a color filter layer and a second substrate, and two or more different directions of pretilt are different in the pixel. A method of manufacturing a liquid crystal display element having a region,
Without providing an alignment film on one or both of the first substrate and the second substrate, the following general formula (I)

(In the formula, R ^1α and R ^2α are each independently an alkyl group having 1 to 8 carbon atoms, an alkenyl group having 2 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, or 2 to 2 carbon atoms. 8 represents an alkenyloxy group, Q ¹ represents a 1,4-phenylene group or a trans-1,4-cyclohexylene group, l ¹ represents 1 or 2, and when l ¹ is 2, Q ¹ may be the same or different.)

(In the formula, R ^3α represents an alkyl group having 1 to 8 carbon atoms, an alkenyl group having 2 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, or an alkenyloxy group having 2 to 8 carbon atoms, R ^4α represents an alkyl group having 1 to 8 carbon atoms, an alkenyl group having 4 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, or an alkenyloxy group having 3 to 8 carbon atoms, and present Q ² And Q ³ each independently represents a 1,4-phenylene group or a trans-1,4-cyclohexylene group, and G ¹ and G ² present are each independently a single bond, —CH ₂ CH ₂ — , —CH ₂ O—, —OCH ₂ —, —CF ₂ O— or —OCF ₂ —, wherein l ² represents 0, 1 or 2, but when l ² is 2, two Q ² and G ² is represented by may be the same or different.) Compounds, and the general formula (1)

(Wherein Z ¹ represents formula (i) or formula (ii)

Z ² is represented by formula (iii) or formula (iv)

M ¹ represents any of the formulas (v), (vi), (vii), or (viii)

X ¹ to X ⁴⁷ each independently represent a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, a halogenated alkyl group having 1 to 8 carbon atoms, or an alkoxy having 1 to 8 carbon atoms. Group, halogen, cyano group, formula (2)

Or formula (3)

Wherein at least one of the existing X ¹ to X ⁴⁷ represents formula (2),
Y1 and Y2 are each independently a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, a halogenated alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, or 1 to 8 carbon atoms. Represents a halogenated alkoxy group, a halogen, a cyano group, a nitro group or R ³ , wherein S ¹ , S ² , S ³ , S ⁴ and S ⁵ are each independently an alkylene group having 1 to 12 carbon atoms or It represents a single bond, one -CH ₂ in the alkylene group - or nonadjacent two or more _-CH 2 - may, -O -, - COO -, - replaced by OCO- or -OCOO- R ¹ , R ² , R ³ and R ⁴ are each independently a hydrogen atom or formula (R-1) to formula (R-15).

L ¹ , L ² and L ⁴ each independently represent a single bond, —O—, —CH═CH—, —OCH ₂ —, —CH ₂ O—, —CO—, —C _{2 H 4 -, - COO -} , - OCO -, - OCOOCH 2 -, - CH 2 OCOO -, - OCH 2 CH 2 O -, - CH = CR a -COO -, - CH = CR a -OCO-, ^{-COO-CR a = CH -,} - OCO-CR a = CH -, - COOC 2 H 4 -, - OCOC 2 H 4 -, - C 2 H 4 OCO -, - (CH 2) j -C (= _{O) -O -, - (CH} 2) j -O- (C = O) -, - O- (C = O) - (CH 2) j -, - (C = O) -O- (CH 2 _{) j -, - CH 2 OCO} -, - COOCH 2 -, - OCOCH 2 -, - CF 2 -, - CF 2 O -, - OCF 2 -, _{CF 2 CH 2 -, - CH} 2 CF 2 -, - CF 2 CF 2 - or -C≡C- (wherein, ^{R a} is each independently a hydrogen atom or an alkyl group having 1 to 4 carbon atoms , J represents an integer of 1 to 4, and L ³ represents a single bond, —O—, —OCH ₂ —, —CH ₂ O—, —CO—, —C ₂ H ₄ —, —COO. ^{_{-, - OCO -, - OCH}} 2 CH 2 O -, - CH = CR a -COO -, - CH = CR a -OCO -, - COO-CR a = CH -, - OCO-CR a = CH-, —CH═CH— or —C≡C— (wherein R ^a each independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms), and M ² and M ³ each independently 1,4-phenylene group, 1,4-cyclohexylene group, cyclohexene-1,4-diyl group, 2,5-diyl group, pyrimidine-2,5-diyl group, naphthalene-2,6-diyl group, naphthalene-1,4-diyl group, tetrahydronaphthalene-2,6-diyl group or 1,3- Dioxane-2,5-diyl group, phenanthrene-2,7diyl group, cyclopentane-1,3-diyl, cyclopentene-1,3-diyl are represented, and M ² and M ³ are each independently unsubstituted. Or an alkyl group having 1 to 8 carbon atoms, a halogenated alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, a halogen, a cyano group, or a nitro group. Well, m represents 0, 1 or 2, and p represents 0, 1 or 2, but when m is 2, the plurality of L ¹ and M ¹ may be the same or different. , P is 2, a plurality of L ⁴ and M ³ May be the same or different. ) Sandwiching a liquid crystal-containing polymerization composition containing a compound represented by
By irradiating an active energy ray between the pixel electrode and the common electrode while applying a voltage for applying a pretilt angle to the liquid crystal molecules in the liquid crystal-containing polymerization composition, the two or more types are used. And forming an alignment control layer between the first substrate and the second substrate and the liquid crystal layer using the liquid crystal-containing polymerization composition as the liquid crystal composition. A method of manufacturing a liquid crystal display device is provided.

According to the present invention, the orientation of the liquid crystal molecules is remarkably improved without deteriorating various properties such as dielectric anisotropy, viscosity, nematic phase upper limit temperature, rotational viscosity (γ ₁ ), etc. Occurrence of traces of dripping is suppressed, the adhesion to the substrate is good, and the alignment control layer that suppresses changes over time has good alignment stability over time, and the formation of a vertical alignment film Provided are a liquid crystal display element capable of simplifying the process and reducing the cost, and a manufacturing method thereof.

It is a schematic perspective view which shows one Embodiment of the liquid crystal display element of this invention. It is a schematic plan view which shows an example of the slit electrode (comb-shaped electrode) used for the liquid crystal display element of this invention. It is a figure which shows the definition of the pretilt angle in the liquid crystal display element of this invention. It is a schematic sectional drawing which shows the IPS mode which is one Embodiment of the liquid crystal display element of this invention. It is a schematic sectional drawing which shows FFS mode which is one Embodiment of the liquid crystal display element of this invention.

  Hereinafter, embodiments of the liquid crystal display element of the present invention and the manufacturing method thereof will be described.

Note that this embodiment is specifically described for better understanding of the gist of the invention, and does not limit the present invention unless otherwise specified.
<Liquid crystal display element>
The liquid crystal display element of the present invention is a liquid crystal display element in which a liquid crystal layer containing a liquid crystal composition is sandwiched between a pair of substrates, and a voltage is applied to the liquid crystal layer to displace the liquid crystal molecules in the liquid crystal layer. This is based on the principle of acting as an optical switch by transferring, and a well-known and conventional technique can be used in this respect.

  In a normal vertical alignment liquid crystal display element in which two substrates have electrodes for causing the Fredericks transition of liquid crystal molecules, a method of applying a charge vertically between the substrates is generally employed. In this case, one electrode is a common electrode and the other electrode is a pixel electrode. The most typical embodiment of this scheme will be shown below.

  FIG. 1 is a schematic perspective view showing an embodiment of the liquid crystal display element of the present invention.

  The liquid crystal display element 10 of the present embodiment includes a first substrate 11, a second substrate 12, and a liquid crystal layer that is sandwiched between the first substrate 11 and the second substrate 12 and contains a liquid crystal composition. 13, a common electrode 14 provided on the surface of the first substrate 11 facing the liquid crystal layer 13, a pixel electrode 15 provided on the surface of the second substrate 12 facing the liquid crystal layer 13, A color filter 18 provided between one substrate 11 and the common electrode 14 is schematically configured.

  For example, a glass substrate or a plastic substrate is used as the first substrate 11 and the second substrate 12.

  As the plastic substrate, a substrate made of a resin such as acrylic resin, methacrylic resin, polyethylene terephthalate, polycarbonate, or cyclic olefin resin is used.

  The common electrode 14 and the pixel electrode 15 are usually made of a transparent material such as indium-added tin oxide (ITO).

  The pixel electrodes 15 are arranged in a matrix on the second substrate 12. The pixel electrode 15 is controlled by a drain electrode of an active element typified by a TFT switching element (not shown). The TFT switching element has a gate line as an address signal line and a source line as a data line in a matrix. doing.

  The pixel electrode 15 has two or more regions having different pretilt directions of liquid crystal molecules in the pixel. In this way, by defining the pretilt direction of the liquid crystal molecules and dividing the direction in which the liquid crystal molecules fall within the pixel into several regions, the viewing angle characteristics are improved.

  When pixel division is performed, for example, a pixel electrode having a slit (a portion where no electrode is formed) having a pattern such as a stripe shape or a V shape may be provided in each pixel.

  FIG. 2 is a schematic plan view showing a typical form of a slit electrode (comb electrode) when the inside of a pixel is divided into four regions. The slit electrode has comb-like slits in four directions from the center of the pixel, so that the liquid crystal molecules in each pixel that are substantially perpendicularly aligned with respect to the substrate when no voltage is applied are applied with voltage application. The liquid crystal molecules are directed in four different directions, approaching horizontal alignment. As a result, the alignment direction of the liquid crystal molecules in the pixel can be divided into a plurality of parts, so that the viewing angle characteristic is extremely wide.

  As the liquid crystal display element 10, it is preferable that the pixel electrode 15 has a slit (is a slit electrode).

  As a method of dividing the pixel, in addition to the method of providing the slit electrode, a method of providing a structure such as a linear protrusion in the pixel, a method of providing an electrode other than the pixel electrode and the common electrode, and the like are applied (not shown). And a method of providing the structure is preferable. The said structure should just have at least one of the 1st board | substrate 11 and the 2nd board | substrate 12, and both may have.

  However, a configuration using a slit electrode is preferable from the viewpoint of transmittance and ease of manufacture. Since the slit electrode does not have a driving force for the liquid crystal molecules when no voltage is applied, it cannot give a pretilt angle to the liquid crystal molecules. However, in the present invention, a pretilt angle can be imparted by providing an alignment control layer described later, and a wide viewing angle by pixel division can be achieved by combining with a slit electrode obtained by pixel division.

  In the present invention, having a pretilt angle means that in a state where no voltage is applied, the direction perpendicular to the substrate surface (the surface adjacent to the liquid crystal layer 13 in the first substrate 11 and the second substrate 12) and the liquid crystal molecules This means that the direction of the director is slightly different.

  Since the liquid crystal display element of the present invention is a vertical alignment (VA) type liquid crystal display element, the director of the liquid crystal molecules is aligned substantially perpendicular to the substrate surface when no voltage is applied. In general, in order to vertically align liquid crystal molecules in a VA liquid crystal display element, polyimide, polyamide, polysiloxane, or the like is provided between the first substrate and the liquid crystal layer and between the second substrate and the liquid crystal layer, respectively. Although a vertical alignment film is disposed, in the liquid crystal display element of the present invention, at least one substrate does not have such a vertical alignment film. However, if a vertical alignment film is provided on one substrate, for example, a transparent organic material such as polyimide, polyamide, BCB (Penzocyclobutene Polymer), or polyvinyl alcohol can be used. In the liquid crystal display element of the present invention, as in the above-described PSA type liquid crystal display element, a voltage is applied between the electrodes and the liquid crystal molecules are slightly tilted and irradiated with active energy rays such as ultraviolet rays. An appropriate pretilt angle is imparted by polymerizing the polymerizable compound in the liquid crystal composition. However, in the liquid crystal display element of the present invention, as the polymerizable compound, specifically, a polymerizable compound described later is polymerized to form the alignment control layer.

  In the present invention, “liquid crystal molecules are substantially vertically aligned” means a state in which a director of liquid crystal molecules that are vertically aligned is slightly tilted from the vertical direction to give a pretilt angle. When the liquid crystal molecules are perfectly vertically aligned, the angle formed by the direction completely parallel to the substrate surface and the direction of the director of the liquid crystal molecules is 90 °, and the liquid crystal molecules are completely homogeneously aligned ( When the liquid crystal molecules are aligned substantially vertically, the angle is preferably 89.7 to 85 °, and more preferably 89.85. 5 to 87 °.

  In addition, as the liquid crystal display element of the present invention, one in which an electrode is applied only to one substrate can be used. 4 and 5 are examples of schematic cross-sectional views of a liquid crystal display element in which an electrode is applied to one substrate. FIG. 4 shows a configuration of a liquid crystal display element generally referred to as an IPS mode, in which a first electrode 20 and a second electrode 21 are provided on a second substrate 12. FIG. 5 shows a configuration of a liquid crystal display element generally referred to as an FFS mode. A common electrode 14 and a pixel electrode 15 are provided on a second substrate 12.

  In order to form the alignment control layer of the liquid crystal display element of the present invention, the general formula (1)

(Wherein Z ¹ represents formula (i) or formula (ii)

Z ² is represented by formula (iii) or formula (iv)

M ¹ represents any of the formulas (v), (vi), (vii), or (viii)

X ¹ to X ⁴⁷ each independently represent a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, a halogenated alkyl group having 1 to 8 carbon atoms, or an alkoxy having 1 to 8 carbon atoms. Group, halogen, cyano group, formula (2)

Or formula (3)

Wherein at least one of the existing X ¹ to X ⁴⁷ represents formula (2),
Y ¹ , Y ² and Z ³ are each independently a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, a halogenated alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, carbon Represents a halogenated alkoxy group having 1 to 8 atoms, halogen, cyano group, nitro group or R ³ , and S ¹ , S ² , S ³ , S ⁴ and S ⁵ each independently represent 1 to 12 carbon atoms; number of an alkylene group or a single bond, one -CH ₂ in the alkylene group - or nonadjacent two or more _-CH 2 - may, -O -, - COO -, - OCO- or - OCOO- may be substituted, and R ¹ , R ² , R ³ and R ⁴ are each independently a hydrogen atom or formula (R-1) to formula (R-15)

L ¹ , L ² and L ⁴ each independently represent a single bond, —O—, —CH═CH—, —OCH ₂ —, —CH ₂ O—, —CO—, —C _{2 H 4 -, - COO -} , - OCO -, - OCOOCH 2 -, - CH 2 OCOO -, - OCH 2 CH 2 O -, - CH = CR a -COO -, - CH = CR a -OCO-, ^{-COO-CR a = CH -,} - OCO-CR a = CH -, - COOC 2 H 4 -, - OCOC 2 H 4 -, - C 2 H 4 OCO -, - (CH 2) j -C (= _{O) -O -, - (CH} 2) j -O- (C = O) -, - O- (C = O) - (CH 2) j -, - (C = O) -O- (CH 2 _{) j -, - CH 2 OCO} -, - COOCH 2 -, - OCOCH 2 -, - CF 2 -, - CF 2 O -, - OCF 2 -, _{CF 2 CH 2 -, - CH} 2 CF 2 -, - CF 2 CF 2 - or -C≡C- (wherein, ^{R a} is each independently a hydrogen atom or an alkyl group having 1 to 4 carbon atoms , J represents an integer of 1 to 4, and L ³ represents a single bond, —O—, —OCH ₂ —, —CH ₂ O—, —CO—, —C ₂ H ₄ —, —COO. ^{_{-, - OCO -, - OCH}} 2 CH 2 O -, - CH = CR a -COO -, - CH = CR a -OCO -, - COO-CR a = CH -, - OCO-CR a = CH-, —CH═CH— or —C≡C— (wherein R ^a each independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms), and M ³ and M ⁴ each independently 1,4-phenylene group, 1,4-cyclohexylene group, cyclohexene-1,4-diyl group, 2,5-diyl group, pyrimidine-2,5-diyl group, naphthalene-2,6-diyl group, naphthalene-1,4-diyl group, tetrahydronaphthalene-2,6-diyl group, 1,3- Dioxane-2,5-diyl group, phenanthrene-2,7diyl group, cyclopentane-1,3-diyl or cyclopentene-1,3-diyl are represented, and M ³ and M ⁴ are each independently unsubstituted. Or an alkyl group having 1 to 8 carbon atoms, a halogenated alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, a halogen, a cyano group, or a nitro group. Well, m represents 0, 1 or 2, and p represents 0, 1 or 2, but when m is 2, the plurality of L ¹ and M ¹ may be the same or different. , P is 2, a plurality of L ⁴ and M ³ May be the same or different. ) Is used.

In the compound represented by the general formula (1), at least one side chain group (side) of at least one ring skeleton is present at a lateral position of a mesogen skeleton (main skeleton) in which a plurality of rings are directly connected or linearly connected via a linking group. A structural feature having a chain skeleton). That is, by forming an alignment control layer using a polymerizable compound having a ring structure in both the main skeleton portion and the side chain skeleton portion, in the liquid crystal display element of the present invention, the adhesion between the alignment control layer and the substrate. At the same time, the alignment uniformity and alignment stability of the liquid crystal molecules become excellent.

In the formula of the general formula (1), Z ¹ represents the formula (i) or the formula (ii)

Z ² is represented by formula (iii) or formula (iv)

Z ¹ preferably represents formula (i), and Z ² preferably represents formula (iii).

M ¹ represents the formula (v), the formula (vi), the formula (vii), or the formula (viii).

Is preferably represented by formula (v).

X ¹ to X ⁴⁷ are each independently a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, a halogenated alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, a halogen, or a cyano group. , Formula (2)

Or formula (3)

Wherein at least one of the existing X ¹ to X ⁴⁷ represents the formula (2). When X ¹ to X ⁴⁷ represent other than formula (2), it is preferable to represent a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, halogen, or formula (3). When any of X ¹ to X ⁴⁷ represents formula (3), any of X ¹ , X ² , X ⁵ , X ⁶ , X ¹¹ , X ¹² , X ¹⁵ and X ¹⁶ represents formula (3). Is preferably represented.

Y ¹ and Y ² are each independently a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, a halogenated alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, or 1 carbon atom. Represents a halogenated alkoxy group of ˜8, halogen, cyano group, nitro group or R ³ , but represents an alkyl group of 1 to 8 carbon atoms, an alkoxy group of 1 to 8 carbon atoms, halogen or R ³ Preferably, R ³ is more preferable.

Z ³ is a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, a halogenated alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, or a halogenated alkoxy group having 1 to 8 carbon atoms. , Halogen, cyano group, nitro group or R ³ , preferably a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, halogen or cyano group, and a carbon atom More preferably, it represents an alkyl group having 1 to 5 carbon atoms or an alkoxy group having 1 to 5 carbon atoms.

S ¹ , S ² , S ³ , S ⁴ and S ⁵ each independently represents an alkylene group having 1 to 12 carbon atoms or a single bond, and one —CH ₂ — or adjacent group in the alkylene group. Two or more —CH ₂ — that are not present may be replaced by —O—, —COO—, —OCO—, or —OCOO—, and are alkylene groups having 1 to 8 carbon atoms, It is preferable that one —CH ₂ — in the alkylene group is replaced by —O— or a single bond, and more preferably a single bond.

R ¹ , R ² , R ³ and R ⁴ are each independently a hydrogen atom or formula (R-1) to formula (R-15)

In particular, it is preferable to represent the formula (R-1) or the formula (R-2).

L ¹ , L ² and L ⁴ are each independently a single bond, —O—, —CH═CH—, —OCH ₂ —, —CH ₂ O—, —CO—, —C ₂ H ₄ —, — _{COO -, - OCO -, -} OCOOCH 2 -, - CH 2 OCOO -, - OCH 2 CH 2 O -, - CH = CR a -COO -, - CH = CR a -OCO -, - COO-CR a = CH—, —OCO—CR ^a ═CH—, —COOC ₂ H ₄ —, —OCOC ₂ H ₄ —, —C ₂ H ₄ OCO—, — (CH ₂ ) _j —C (═O) —O—, _{- (CH 2) j -O- (} C = O) -, - O- (C = O) - (CH 2) j -, - (C = O) -O- (CH 2) j -, - CH _{2 OCO -, - COOCH 2 -} , - OCOCH 2 -, - CF 2 -, - CF 2 O -, - OCF 2 -, - CF 2 CH 2 - _{-CH 2 CF 2 -, - CF} 2 CF 2 - or -C≡C- (wherein, ^{R a} represents hydrogen atom or an alkyl group having a carbon number of 1 to 4 independently, j is 1 to 4 A single bond, —O—, —CH═CH—, —OCH ₂ —, —CH ₂ O—, —C ₂ H ₄ —, —COO—, —OCO—, — CH═CR ^a —COO—, —OCO—CR ^a ═CH—, —OCOC ₂ H ₄ —, —C ₂ H ₄ OCO— or —C≡C— (wherein each R ^a is independently a hydrogen atom Or an alkyl group having 1 to 2 carbon atoms.), Preferably a single bond, —C ₂ H ₄ —, —COO—, —OCO—, —CH═CR ^a —COO—, —OCO—. CR ^a ═CH—, —OCOC ₂ H ₄ —, —C ₂ H ₄ OCO— or —C≡C— (wherein R ^a is hydrogen More preferably, it represents an atom.

L ³ represents a single bond, —O—, —OCH ₂ —, —CH ₂ O—, —CO—, —C ₂ H ₄ —, —COO—, —OCO—, —OCH ₂ CH ₂ O—, — CH═CR ^a —COO—, —CH═CR ^a —OCO—, —COO—CR ^a ═CH—, —OCO—CR ^a ═CH—, —CH═CH—, or —C≡C— (wherein And R ^a each independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.), A single bond, —O—, —OCH ₂ —, —CH ₂ O—, —C ₂ H ₄ -, - it is preferable to represent a COO- or -OCO-, and more preferably a single bond.

M ² and M ³ are each independently 1,4-phenylene group, 1,4-cyclohexylene group, cyclohexene-1,4-diyl group, pyridine-2,5-diyl group, pyrimidine-2,5- Diyl group, naphthalene-2,6-diyl group, naphthalene-1,4-diyl group, tetrahydronaphthalene-2,6-diyl group, 1,3-dioxane-2,5-diyl group, phenanthrene-2,7 diyl Group, cyclopentane-1,3-diyl or cyclopentene-1,3-diyl, and each of M ³ and M ⁴ is independently an unsubstituted alkyl group having 1 to 8 carbon atoms, carbon It may be substituted with a halogenated alkyl group having 1 to 8 atoms, an alkoxy group having 1 to 8 carbon atoms, a halogen, a cyano group, or a nitro group, but is unsubstituted or substituted with an alkyl having 1 to 3 carbon atoms. A 1,3-phenylene group, a 1,4-cyclohexylene group, or a 1,3-dioxane-2,5-diyl group substituted with a halogen group, an alkoxy group having 1 to 3 carbon atoms, a halogen. Is preferably unsubstituted, an alkyl group having 1 carbon atom, an alkoxy group having 1 carbon atom, a 1,4-phenylene group substituted with a halogen, a 1,4-cyclohexylene group, or a 1,3-dioxane. It is more preferably a -2,5-diyl group, and further preferably an unsubstituted 1,4-phenylene group or a 1,4-cyclohexylene group.

  m represents 0, 1 or 2, but 0 or 1 is preferable, and p represents 0, 1 or 2, and 0 or 1 is preferable.

When m is 2, the plurality of L ¹ and M ¹ may be the same or different, and when p is 2, the plurality of L ⁴ and M ³ may be the same or different. good.

In the present specification, “(meth) acrylate” means both acrylate and methacrylate. Similarly, “(meth) acryloyl group” means acryloyl group (H ₂ C═CH—CO). -) and is intended to mean both methacryloyl group _{(H 2 C = C (CH} 3) -CO-). Unless otherwise specified, “—COO—” means “—C (═O) —O—” and “—OCO—” means “—O—C (═O) —”. And

  As the compound represented by the general formula (1), for example, compounds represented by the following general formulas (1-A) to (1-F) are preferable.

Wherein X ⁵⁰ to X ⁵⁴ are each independently a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, a halogenated alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, Halogen, cyano group, or formula (3)

Z ⁴ represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, a halogenated alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, or a halogen having 1 to 8 carbon atoms. Represents an alkoxy group, halogen, cyano group, nitro group,
L ⁵ , L ⁷ and L ⁸ are each independently a single bond, —O—, —CH═CH—, —OCH ₂ —, —CH ₂ O—, —CO—, —C ₂ H ₄ —, — _{COO -, - OCO -, -} OCOOCH 2 -, - CH 2 OCOO -, - OCH 2 CH 2 O -, - CH = CR a -COO -, - CH = CR a -OCO -, - COO-CR a = CH—, —OCO—CR ^a ═CH—, —COOC ₂ H ₄ —, —OCOC ₂ H ₄ —, —C ₂ H ₄ OCO—, — (CH ₂ ) _j —C (═O) —O—, _{- (CH 2) j -O- (} C = O) -, - O- (C = O) - (CH 2) j -, - (C = O) -O- (CH 2) j -, - CH _{2 OCO -, - COOCH 2 -} , - OCOCH 2 -, - CF 2 -, - CF 2 O -, - OCF 2 -, - CF 2 CH 2 - _{-CH 2 CF 2 -, - CF} 2 CF 2 - or -C≡C- (wherein, ^{R a} represents hydrogen atom or an alkyl group having a carbon number of 1 to 4 independently, j is 1 to 4 . that of an integer) ^represents, L 6 _{is, -O -, - OCH 2 -} , - CH 2 O -, - CO -, - C 2 H 4 -, - COO -, - OCO -, - OCH 2 _{^{CH 2 O -, - CH =}} CR a -COO -, - CH = CR a -OCO -, - COO-CR a = CH -, - OCO-CR a = CH -, - CH = CH-, or -C ≡C— (wherein R ^a independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms), and M ³ and M ⁴ each independently represent a 1,4-phenylene group. 1,4-cyclohexylene group, cyclohexene-1,4-diyl group, pyridine-2,5-diyl group, Spermidine-2,5-diyl group, or 1,3-dioxane-2,5-diyl group, ^{M 3} and ^{M 4} each independently may be unsubstituted, having 1 to 3 carbon atoms An alkyl group, a halogenated alkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, a halogen, a cyano group, or a nitro group, and n represents 0 or 1, R ¹ , R ³ , R ⁴ , S ¹ , S ² , S ⁵ and p have the same contents as described above. )
Of the compounds represented by the general formulas (1-A) to (1-F), more specifically, compounds represented by the formulas (1-1) to (1-79) are preferable.

  The alignment control layer is formed by preparing a liquid crystal-containing polymerization composition containing the compound represented by the general formula (1) in the liquid crystal composition. A specific method of forming the orientation control layer will be described in <Liquid crystal display device manufacturing method> in the subsequent stage.

The composition for liquid crystal-containing polymerization contains the compound represented by the general formula (1), but can also contain other polymerizable compounds. For example, a trifunctional or higher functional (meth) acrylate compound, a bifunctional (meth) acrylate compound, a monofunctional (meth) acrylate compound, and the like can be given.


The compound represented by the general formula (1) is preferably contained in an amount of 0.1 to 15% by mass, more preferably 0.1 to 10% by mass with respect to the liquid crystal-containing polymerization composition. It is still more preferable to contain 1-8 mass%.

  The liquid crystal composition used in the present invention has the general formula (I)

(In the formula, R ^1α and R ^2α are each independently an alkyl group having 1 to 8 carbon atoms, an alkenyl group having 2 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, or 2 to 2 carbon atoms. 8 represents an alkenyloxy group, Q ¹ represents a 1,4-phenylene group or a trans-1,4-cyclohexylene group, l ¹ represents 1 or 2, and when l ¹ is 2, Q ¹ may be the same or different.)
And general formula (II)

(In the formula, R ^3α represents an alkyl group having 1 to 8 carbon atoms, an alkenyl group having 2 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, or an alkenyloxy group having 2 to 8 carbon atoms, R ^4α represents an alkyl group having 1 to 8 carbon atoms, an alkenyl group having 4 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, or an alkenyloxy group having 3 to 8 carbon atoms, and present Q ² And Q ³ each independently represents a 1,4-phenylene group or a trans-1,4-cyclohexylene group, and G ¹ and G ² present are each independently a single bond, —CH ₂ CH ₂ — , —CH ₂ O—, —OCH ₂ —, —CF ₂ O— or —OCF ₂ —, wherein l ² represents 0, 1 or 2, but when l ² is 2, two Q ² and G ² is represented by may be the same or different.) Preferably contains a compound represented by the compound.

In general formula (I), the alkyl group having 1 to 8 carbon atoms in R ^1α and R ^2α may be linear, branched or cyclic, but may be linear or branched. Preferably, for example, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, n-pentyl group, isopentyl group, neopentyl group, tert-pentyl Group, 1-methylbutyl group, n-hexyl group, 2-methylpentyl group, 3-methylpentyl group, 2,2-dimethylbutyl group, 2,3-dimethylbutyl group, n-heptyl group, 2-methylhexyl group 3-methylhexyl group, 2,2-dimethylpentyl group, 2,3-dimethylpentyl group, 2,4-dimethylpentyl group, 3,3-dimethylpentyl group, 3-ethyl Pentyl group, 2,2,3-trimethyl butyl group, n- octyl group, and isooctyl group.

The alkyl group in R ^1α and R ^2α preferably has 1 to 6 carbon atoms.

In general formula (I), examples of the alkenyl group having 2 to 8 carbon atoms in R ^1α and R ^2α include an ethenyl group (vinyl group), a 2-propenyl group (allyl group), and the like, and carbon atoms in R ^1α and R ^2α . Examples of the alkyl group represented by Formulas 2 to 8 include monovalent groups in which one single bond (C—C) between carbon atoms is substituted with a double bond (C═C).

The alkenyl group in R ^1α and R ^2α preferably has 2 to 6 carbon atoms, and more preferably has the following structure.

(In the formula, the rightmost carbon atom of the alkenyl group is bonded to the ring structure.)
In the formula (I), the alkoxy group having 1 to 8 carbon atoms in ^{R l [alpha]} and ^{R 2.alpha,} a methoxy group, an ethoxy group or the like, said alkyl group having 1 to 8 carbon atoms in ^{R l [alpha]} and ^{R 2.alpha} oxygen A monovalent group formed by bonding to an atom is exemplified.

The alkoxy group in R ^1α and R ^2α preferably has 1 to 6 carbon atoms, more preferably 1 to 5 carbon atoms, and particularly preferably 1 to 3 carbon atoms.

In general formula (I), examples of the alkenyloxy group having 2 to 8 carbon atoms in R ^1α and R ^2α include ethenyloxy group, 2-propenyloxy group, etc., and those having 2 to 8 carbon atoms in R ^1α and R ^2α . Examples thereof include a monovalent group in which an alkenyl group is bonded to an oxygen atom.

The alkenyloxy group in R ^1α and R ^2α preferably has 2 to 6 carbon atoms.

Preferred compounds represented by the general formula (I) include those in which the combination of R ^1α and R ^2α is the alkyl group, the alkyl group and the alkoxy group, the alkyl group and the alkenyl group. Some are listed.

  Moreover, as what is preferable with the compound represented by general formula (I), what is represented by the following general formula (I-1)-(I-4) is mentioned, for example.

(In the formula, R ^1α and R ^2α are the same as described above.)
The content of the compound represented by the general formula (I) in the liquid crystal composition is preferably 30 to 65% by mass, and more preferably 35 to 55% by mass.

In the general formula (II), R ^3α is the same as R ^1α and R ^2α .

In general formula (II), ^examples of the alkyl group and alkoxy group having 1 to 8 carbon atoms in R ^4α include the same as the alkyl group and alkoxy group having 1 to 8 carbon atoms in R ^1α and R ^2α . .

In the general formula (II), the alkenyl group having 4 to 8 carbon atoms and the alkenyloxy group having 3 to 8 carbon atoms in R ^4α are the same as those in R ^1α and R ^2α except that the number of carbon atoms is different. The same thing as an alkenyl group and an alkenyloxy group is mentioned.

The alkyl group in R ^3α and R ^4α is preferably independently of 1 to 6 carbon atoms, more preferably 1 to 5 carbon atoms.

The alkoxy groups in R ^3α and R ^4α are preferably each independently having 1 to 6 carbon atoms, and more preferably 1 to 5 carbon atoms.

Preferred compounds represented by the general formula (II) are those in which R ^3α is the alkyl group, R ^4α is the alkoxy group, l ² is 0 or 1, and G ¹ is simple. Examples include a bond, —CH ₂ CH ₂ — or —CH ₂ O—, and G ² is a single bond or —CH ₂ CH ₂ —.

  Moreover, as what is preferable with the compound represented by general formula (II), what is represented by the following general formula (II-1)-(II-8) is mentioned, for example.

(In the formula, R ^3α and R ^4α are the same as described above.)
The content of the compound represented by the general formula (II) in the liquid crystal composition is preferably 30 to 65% by mass, and more preferably 35 to 55% by mass.

In the liquid crystal composition, [content of compound represented by general formula (II)] / [content of compound represented by general formula (I)] (mass ratio) is 8/2 to 2/8. Is preferable, 7/3 to 3/7 is more preferable, and 6/4 to 4/6 is particularly preferable.

  As a compound represented by the general formula (II), the following general formula (V)

(Wherein R ^9α and R ^10α are each independently an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, an alkoxy group having 1 to 18 carbon atoms, or 2 to 2 carbon atoms. 18 represents an alkenyloxy group, Q ⁴ represents a 1,4-phenylene group or a trans-1,4-cyclohexylene group, and l ⁴ represents 0 or 1. Good.

In general formula (V), the alkyl group having 1 to 18 carbon atoms in R ^9α and R ^10α may be linear, branched or cyclic, but may be linear or branched. Preferably, for example, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, n-pentyl group, isopentyl group, neopentyl group, tert-pentyl Group, 1-methylbutyl group, n-hexyl group, 2-methylpentyl group, 3-methylpentyl group, 2,2-dimethylbutyl group, 2,3-dimethylbutyl group, n-heptyl group, 2-methylhexyl group 3-methylhexyl group, 2,2-dimethylpentyl group, 2,3-dimethylpentyl group, 2,4-dimethylpentyl group, 3,3-dimethylpentyl group, 3-e Rupentyl, 2,2,3-trimethylbutyl, n-octyl, isooctyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl Is mentioned.

The alkyl group in R ^9α and R ^10α preferably has 1 to 10 carbon atoms, and more preferably 1 to 6 carbon atoms.

In formula (V), Examples of the alkenyl group having 2 to 18 carbon atoms in ^{R 9.alpha} and ^{R 10 [alpha],} in the alkyl group having 2 to 18 carbon atoms in ^{R 9.alpha} and ^{R 10 [alpha],} the one between carbon atoms A monovalent group formed by substituting a single bond (C—C) with a double bond (C═C) is exemplified.

The alkenyl group in R ^9α and R ^10α preferably has 2 to 6 carbon atoms, and examples thereof include the same as those in R ^1α and R ^2α .

In general formula (V), ^examples of the alkoxy group having 1 to 18 carbon atoms in R ^9α and R ^10α include a methoxy group and an ethoxy group, and the alkyl group having 1 to 18 carbon atoms in R ^9α and R ^10α is oxygen. A monovalent group formed by bonding to an atom is exemplified.

The alkoxy group in R ^9α and R ^10α preferably has 1 to 10 carbon atoms, and more preferably 1 to 6 carbon atoms.

In the general formula (V), examples of the alkenyloxy group having 2 to 18 carbon atoms in R ^9α and R ^10α include ethenyloxy group, 2-propenyloxy group, etc., and those having 2 to 18 carbon atoms in R ^9α and R ^10α . Examples thereof include a monovalent group in which an alkenyl group is bonded to an oxygen atom.

  Preferred examples of the compound represented by the general formula (V) include the following general formula (V-1):

(Wherein, R ^9α and R ^10α are the same as described above).

  The content of the components other than the compounds represented by the general formulas (I) and (II) such as the compounds represented by the general formulas (III), (IV), and (V) in the liquid crystal composition is 25. It is preferable that it is mass% or less, and it is more preferable that it is 20 mass% or less.

  In addition to the compounds represented by the general formulas (I) to (II), the liquid crystal composition has the following general formula (III)

Wherein R ^5α and R ^6α are each independently an alkyl group having 1 to 8 carbon atoms, an alkenyl group having 2 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, or 2 to 2 carbon atoms. 8 alkenyloxy groups (one or two or more methylene groups in the alkyl group, alkenyl group, alkoxy group or alkenyloxy group independently represent oxygen atoms or -CO- may be substituted, and one or two or more hydrogen atoms in the alkylene group may be substituted with a fluorine atom), and Q ³ represents a 1,4-phenylene group or Represents a tetrahydropyran-2,5-diyl group, l ³ represents 0 or 1, G ² represents a single bond, —CH ₂ O—, —OCH ₂ —, —CF ₂ O— or —OCF ₂ —. , ^L 1 ~L ⁶ is, If represents the respectively independently a hydrogen atom or a fluorine atom, at least two L ¹ ~L ⁶ represents a fluorine atom, which l ³ represents represents and G ² is a single bond to 0, L ⁵ and L ⁶ may not contain a fluorine atom.) May be contained.

In the general formula (III), R ^5α and R ^6α are alkyl groups having 1 to 8 carbon atoms, alkenyl groups having 2 to 8 carbon atoms, alkoxy groups having 1 to 8 carbon atoms, and 2 to 8 carbon atoms. The alkenyloxy group is the same as in R ^1α and R ^2α .

  Preferred examples of the compound represented by the general formula (III) include, for example, the following general formula (III-1)

(Wherein, R ^5α and R ^6α are the same as described above).

  In addition to the compounds represented by the general formulas (I) and (II), the liquid crystal composition has the following general formula (IV-1):

( ^Wherein R ^7α and R ^8α each independently represents an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, or an alkoxy group having 1 to 10 carbon atoms). It may contain the compound.

In general formula (IV-1), the alkyl group having 1 to 10 carbon atoms in R ^7α and R ^8α may be linear, branched or cyclic, but is linear or branched. For example, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, n-pentyl group, isopentyl group, neopentyl group, tert -Pentyl group, 1-methylbutyl group, n-hexyl group, 2-methylpentyl group, 3-methylpentyl group, 2,2-dimethylbutyl group, 2,3-dimethylbutyl group, n-heptyl group, 2-methyl Hexyl group, 3-methylhexyl group, 2,2-dimethylpentyl group, 2,3-dimethylpentyl group, 2,4-dimethylpentyl group, 3,3-dimethylpentyl group, 3 Ethylpentyl group, 2,2,3-trimethyl butyl group, n- octyl group, an isooctyl group, a nonyl group, decyl group.

The alkyl group in R ^7α and R ^8α preferably has 1 to 6 carbon atoms.

In the general formula (IV-1), as the alkenyl group having 2 to 10 carbon atoms in ^{R 7.alpha} and ^{R 8α,} in the alkyl group of 2 to 10 carbon atoms in ^{R 7.alpha} and ^{R 8α,} 1 between carbon atoms A monovalent group in which a single bond (C—C) is substituted with a double bond (C═C) is exemplified.

The alkenyl group in R ^7α and R ^8α preferably has 2 to 6 carbon atoms, and examples thereof include the same ones as in R ^1α and R ^2α .

In the general formula (IV-1), the alkoxy group having 1 to 10 carbon atoms in ^{R 7.alpha} and ^{R 8Arufa,} a methoxy group, an ethoxy group or the like, the alkyl group having 1 to 10 carbon atoms in ^{R 7.alpha} and ^{R 8Arufa} A monovalent group formed by bonding to an oxygen atom.

  Furthermore, the liquid crystal composition has the following general formula (IV-2) in addition to the compounds represented by the general formulas (I) and (II).

( ^Wherein R ^7α and R ^8α each independently represent an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, or an alkoxy group having 1 to 10 carbon atoms, and X ^7α and X ^8α each independently represents a hydrogen atom or a fluorine atom.

In general formula (IV-2), the alkyl group having 1 to 10 carbon atoms in R ^7α and R ^8α may be linear, branched or cyclic, but is linear or branched. For example, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, n-pentyl group, isopentyl group, neopentyl group, tert -Pentyl group, 1-methylbutyl group, n-hexyl group, 2-methylpentyl group, 3-methylpentyl group, 2,2-dimethylbutyl group, 2,3-dimethylbutyl group, n-heptyl group, 2-methyl Hexyl group, 3-methylhexyl group, 2,2-dimethylpentyl group, 2,3-dimethylpentyl group, 2,4-dimethylpentyl group, 3,3-dimethylpentyl group, 3 Ethylpentyl group, 2,2,3-trimethyl butyl group, n- octyl group, an isooctyl group, a nonyl group, decyl group.

The alkyl group in R ^7α and R ^8α preferably has 1 to 6 carbon atoms.

In the general formula (IV-2), as the alkenyl group having 2 to 10 carbon atoms in ^{R 7.alpha} and ^{R 8α,} in the alkyl group of 2 to 10 carbon atoms in ^{R 7.alpha} and ^{R 8α,} 1 between carbon atoms A monovalent group in which a single bond (C—C) is substituted with a double bond (C═C) is exemplified.

The alkenyl group in R ^7α and R ^8α preferably has 2 to 6 carbon atoms, and examples thereof include the same ones as in R ^1α and R ^2α .

In the general formula (IV-2), the alkoxy group having 1 to 10 carbon atoms in R ^7α and R ^8α includes a methoxy group, an ethoxy group, and the like, and the alkyl group having 1 to 10 carbon atoms in R ^7α and R ^8α . A monovalent group formed by bonding to an oxygen atom.

In general formula (IV-2), X ^7α and X ^8α each independently represent a hydrogen atom or a fluorine atom, and either one is preferably a fluorine atom.

  The liquid crystal display element 10 may further include a passivation film between at least one of the first substrate 11 and the liquid crystal layer 13 and between the second substrate 12 and the liquid crystal layer 13 ( (Not shown). As described above, the surface of the first substrate 11 or the second substrate 12 in the vicinity is protected by having the passivation film.

  The liquid crystal display element 10 may further include a planarization film between at least one of the first substrate 11 and the liquid crystal layer 13 and between the second substrate 12 and the liquid crystal layer 13. (Not shown). When the flatness of the surface of this film is high, such a passivation film may be handled as a flattening film.

  As the passivation film and the planarizing film, known ones can be used as appropriate.

The liquid crystal display element of the present invention includes a liquid crystal composition using a specific compound represented by general formulas (I) and (II) as liquid crystal molecules, an alignment control layer formed from two or more polymerizable compounds, and By using in combination, unlike a conventional liquid crystal display element, an alignment film may not be provided between the first substrate and the liquid crystal layer and between the second substrate and the liquid crystal layer. When no voltage is applied, the liquid crystal molecules are aligned substantially perpendicular to the substrate surface. Further, image sticking and generation of dripping marks during production are suppressed without deteriorating various properties such as dielectric anisotropy, viscosity, nematic phase upper limit temperature, rotational viscosity (γ ₁ ) and the like.
<Method for manufacturing liquid crystal display element>
The liquid crystal display element 10 shown in FIG. 1 can be manufactured by the following method, for example.

  First, the first substrate 11 and the second substrate 12 are overlapped, and a liquid crystal-containing polymerization composition for forming the liquid crystal layer 13 and the alignment control layer is sandwiched between them by a process described later. The liquid crystal-containing polymerization composition contains the compound represented by the general formula (1) as an essential component with respect to the liquid crystal composition, but the compound constituting the liquid crystal composition has the general formula ( It is preferable to contain the compound represented by I) and the compound represented by the general formula (II).

  More specifically, spacer protrusions for securing a cell gap, such as plastic beads, are sprayed on the facing surfaces of either the first substrate 11 or the second substrate 12. At the same time, for example, the seal portion is printed (formed) by screen printing using an epoxy adhesive or the like. The surface of the first substrate 11 facing the second substrate 12 is the surface having the common electrode 14 and the color filter 18, and the surface of the second substrate 12 facing the first substrate 11 is The surface having the pixel electrode 15.

  Next, the first substrate 11 and the second substrate 12 are made to face each other, and these are bonded together via the spacer protrusion and the seal portion, and then the liquid crystal-containing polymerization composition is injected into the formed space. To do. Then, the liquid crystal-containing polymerization composition is sandwiched between the first substrate 11 and the second substrate 12 by curing the seal portion by heating or the like.

  Next, a voltage is applied between the common electrode 14 and the pixel electrode 15 using voltage applying means. The voltage at this time is 5 to 30 V, for example. Thereby, the adjacent surface (surface which opposes the composition for liquid crystal containing polymerization) of the 1st board | substrate 11 and the composition for liquid crystal containing polymerization of the 2nd board | substrate 12 (surface facing the composition for liquid crystal containing polymerization) An electric field having a predetermined angle is generated with respect to the liquid crystal-containing polymerization composition, and the liquid crystal molecules in the liquid crystal-containing polymerization composition (compound represented by general formula (I), general formula The compound (II) (19) is oriented in a predetermined direction with respect to the normal direction of the first substrate 11 and the second substrate 12, and as shown in FIG. Is granted. The magnitude of the pretilt angle θ can be controlled by appropriately adjusting the magnitude of the voltage.

  Next, the two or more polymerizable compounds are polymerized by irradiating an active energy ray such as ultraviolet rays from the outside of the first substrate 11 to the liquid crystal-containing polymerization composition while the voltage is applied. Let The active energy ray may be irradiated from the outside of the second substrate 12 or may be irradiated from both the outside of the first substrate 11 and the outside of the second substrate 12.

  By irradiation with active energy rays, two or more kinds of the polymerizable compounds in the liquid crystal-containing polymerization composition react, and the liquid crystal-containing polymerization composition becomes a liquid crystal composition having a desired composition to form the liquid crystal layer 13. At the same time, an alignment control layer is formed between the first substrate 11 and the liquid crystal layer 13 and between the second substrate 12 and the liquid crystal layer 13.

  The formed alignment control layer imparts a pretilt angle θ to the liquid crystal molecules 19 located in the vicinity of the first substrate 11 and in the vicinity of the second substrate 12 in the liquid crystal layer 13 in a non-driven state.

The irradiation intensity of the active energy ray may or may not be constant, and when changing the irradiation intensity, the irradiation time at each irradiation intensity can be arbitrarily set, but two or more stages When the irradiation process is adopted, the irradiation intensity of the irradiation process after the second stage is preferably weaker than the irradiation intensity of the irradiation process of the first stage, and the total irradiation time of the irradiation process after the second stage is It is preferable that the irradiation time is longer than the first stage irradiation time and the total irradiation energy amount is large. In addition, when the irradiation intensity is changed discontinuously, the average irradiation light intensity in the first half of the entire irradiation process time is preferably stronger than the average irradiation intensity in the second half, and the intensity immediately after the start of irradiation is the strongest. More preferably, the irradiation intensity always decreases to a certain value as the irradiation time elapses. In this case, the irradiation intensity of the active energy ray is preferably ² to 100 mW / cm ² , but it is the highest in the entire irradiation process in the first stage in the case of multistage irradiation or when the irradiation intensity is changed discontinuously. The irradiation intensity is 10 to 100 mW / cm ² , and the minimum irradiation intensity is ² to 50 mW / cm ² after the second stage in the case of multistage irradiation or when the irradiation intensity is changed discontinuously. It is more preferable. Moreover, it is preferable that irradiation total energy amount is 10-300J, It is more preferable that it is 50-250J, It is further more preferable that it is 100-250J.

  The applied voltage may be alternating current or direct current.

  The active energy rays to be irradiated preferably have a plurality of spectra, and ultraviolet rays having a plurality of spectra are preferable. By irradiation with active energy rays having a plurality of spectra, two or more kinds of the polymerizable compounds can be polymerized by active energy rays having a spectrum (wavelength) suitable for each type, and in this case, the orientation control layer Is formed more efficiently.

  The alignment control layer is composed of a polymer of the polymerizable compound. For example, the first substrate 11 and the liquid crystal layer 13 are not clearly separated and formed between them. In the vicinity of the substrate 11, it is estimated that the first substrate 11 may be formed so as to enter the liquid crystal layer 13 from a surface adjacent to the liquid crystal layer 13 (a surface facing the liquid crystal layer 13). The The same is true in the vicinity of the second substrate 12, and the alignment control layer is not necessarily formed between the second substrate 12 and the liquid crystal layer 13 by clearly dividing the second substrate 12. In the vicinity of, it is estimated that the second substrate 12 may be formed so as to enter the liquid crystal layer 13 from a surface adjacent to the liquid crystal layer 13 (a surface facing the liquid crystal layer 13).

  However, it is difficult to accurately indicate the structure of the orientation control layer.

  Further, by irradiation with active energy rays, the two or more kinds of polymerizable compounds are preferentially polymerized with each other having similar structures to align liquid crystal molecules in the vicinity region of the substrate, and the direction of the pretilt. It is presumed that the orientation is controlled by defining the value in a predetermined direction.

  Hereinafter, although an example is given and this invention is further explained in full detail, this invention is not limited by these.

In the following Examples and Comparative Examples, Tni, Δn, Δε, η , γ 1 respectively are defined as follows.
T _ni : Nematic phase-isotropic liquid phase transition temperature (° C.)
Δn: refractive index anisotropy at 25 ° C. Δε: dielectric anisotropy at 25 ° C. η: viscosity at 20 ° C. (mPa · s)
γ ₁ : rotational viscosity at 25 ° C. (mPa · s)
The pretilt stability of the liquid crystal display elements in the following examples and comparative examples was evaluated by the following methods.
(Pretilt stability)
The pretilt stability of the liquid crystal display device was evaluated by measuring the amount of pretilt shift before and after voltage application after applying a predetermined voltage in the display area.
Example 1
A first substrate (common electrode substrate) having a transparent electrode layer and a color filter layer made of a transparent common electrode, and a second substrate (pixel) having a pixel electrode layer having a transparent pixel electrode driven by an active element Electrode substrate).
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.

  The polymerizable compound shown below with respect to liquid crystal composition LC-1 98.0 wt%

Was added and dissolved uniformly to prepare a liquid crystal-containing polymerization composition CLC-1.

  After sandwiching the liquid crystal-containing polymerization composition CLC-1 on the common electrode substrate and the pixel electrode substrate having no alignment film layer, the sealing material was cured. At this time, a spacer having a thickness of 3.2 μm was used, and the thickness of the liquid crystal layer was set to 3.2 μm. The obtained liquid crystal display was irradiated with ultraviolet rays while a voltage was applied to cure the polymerizable compound having a reactive group. As an irradiation apparatus, USH-250BY manufactured by Ushio Electric Co., Ltd. was used, and the liquid crystal display element was irradiated with ultraviolet rays at 100 mW for 10 minutes to obtain a liquid crystal display element CLCD-1 of Example 1. By this step, an alignment control layer containing a polymer of a polymerizable compound having a reactive group is formed, and a pretilt angle is imparted to the liquid crystal molecules in the liquid crystal layer.

Here, the pretilt angle is defined as 90 ° when the pretilt angle is completely vertical, and when the pretilt angle is given, the pretilt angle (θ) is smaller than 90 °.
The liquid crystal display element of Example 1 had a pretilt angle in different directions in the four sections according to the slits of the pixel electrode, and the pretilt angle was maintained even when the AC electric field was turned off after the polymerizable compound was cured. . The pretilt angle maintained was 89.1 °.

  Various characteristics of the liquid crystal composition LC-1 used in this example are shown in the following table.

As a result of measuring the pretilt stability of the liquid crystal display element, the pretilt shift amount was -0.3 degrees, indicating that the pretilt shift amount was small and the stability was excellent. In other words, it is clear that a liquid crystal display element having good alignment stability over time can be obtained by the alignment control layer in which changes over time are greatly suppressed.
(Comparative Example 1)
In the same experiment as in Example 1, the polymerizable compound shown below with respect to 98.0 wt% of the liquid crystal composition LC-1

1.5 wt% of the polymerizable compound shown below

Of 0.1 wt% of a photopolymerization initiator Igacure 651 was added and dissolved uniformly to prepare a polymerizable liquid crystal composition CLC-1a.

After sandwiching the polymerizable liquid crystal composition CLC-1a between the common electrode substrate and the pixel electrode substrate having no alignment film layer, the sealing material was cured to form a liquid crystal composition layer. At this time, a spacer having a thickness of 3.2 μm was used, and the thickness of the liquid crystal composition layer was set to 3.2 μm. The obtained liquid crystal display was irradiated with ultraviolet rays while a voltage was applied to cure the polymerizable compound having the reactive group. As an irradiation apparatus, USH-250BY manufactured by Ushio Electric Co., Ltd. was used, and the liquid crystal display element was irradiated with ultraviolet rays at 100 mW for 10 minutes to obtain a liquid crystal display element CLCD-1a of Comparative Example 1.
The liquid crystal display element of Comparative Example 1 had pretilt angles in different directions in the four sections according to the slits of the pixel electrode, and the pretilt angle was maintained even when the AC electric field was turned off after the polymerizable compound was cured. . The pretilt angle maintained was 87.0 °.

As a result of measuring the pretilt stability of the liquid crystal display element, it was found that the pretilt shift amount was −0.9 degrees and the pretilt angle was greatly changed.
(Example 2)
In the same experiment as in Example 1, the liquid crystal composition used was changed to a liquid crystal composition LC-2 containing a compound selected from general formula (I) and a compound selected from general formula (II). The constituent compounds and the ratios contained are as follows.

  The polymerizable compound shown below with respect to 97.7 wt% of liquid crystal composition LC-2

Was added in an amount of 2.3 wt% and dissolved uniformly to prepare a polymerizable liquid crystal composition CLC-2.

  After sandwiching the polymerizable liquid crystal composition CLC-2 between the common electrode substrate and the pixel electrode substrate having no alignment film layer, the sealing material was cured to form a liquid crystal composition layer. At this time, the thickness of the liquid crystal composition layer was set to 3.5 μm using a spacer having a thickness of 3.5 μm. The obtained liquid crystal display was irradiated with ultraviolet rays while a voltage was applied to cure the polymerizable compound having the reactive group. As an irradiation apparatus, USH-250BY manufactured by Ushio Electric Co., Ltd. was used, and the liquid crystal display element was irradiated with ultraviolet rays at 100 mW for 10 minutes to obtain a liquid crystal display element CLCD-2 of Example 2. The liquid crystal display element of Example 2 had pretilt angles in different directions in the four sections according to the slits of the pixel electrode, and the pretilt angle was maintained even when the AC electric field was turned off after the polymerizable compound was cured. . The pretilt angle maintained was 88.9 °.

  Various characteristics of the liquid crystal composition LC-2 used in this example are shown in the following table.

As a result of measuring the pretilt stability of the liquid crystal display element, it was shown that the pretilt shift amount was -0.2 degrees and the pretilt shift amount was small, and the stability was excellent. In other words, it is clear that a liquid crystal display element having good alignment stability over time can be obtained by the alignment control layer in which changes over time are greatly suppressed.
(Comparative Example 2)
In the same experiment as in Example 1, the polymerizable compound shown below with respect to 98.0 wt% of the liquid crystal composition LC-2

Is added at 1.5 wt%, and the polymerizable compound shown below

Of 0.1 wt% of a photopolymerization initiator Igacure 651 was added and dissolved uniformly to prepare a polymerizable liquid crystal composition CLC-2a.

  After sandwiching the polymerizable liquid crystal composition CLC-2a between the common electrode substrate and the pixel electrode substrate having no alignment film layer, the sealing material was cured to form a liquid crystal composition layer. At this time, the thickness of the liquid crystal composition layer was set to 3.5 μm using a spacer having a thickness of 3.5 μm. The obtained liquid crystal display was irradiated with ultraviolet rays while a voltage was applied to cure the polymerizable compound having the reactive group. As an irradiation apparatus, USH-250BY manufactured by Ushio Electric Co., Ltd. was used, and the liquid crystal display element was irradiated with ultraviolet rays at 100 mW for 10 minutes to obtain a liquid crystal display element CLCD-2a of Comparative Example 2. The liquid crystal display element of Comparative Example 2 had pretilt angles in different directions in the four sections according to the slits of the pixel electrode, and the pretilt angle was maintained even when the AC electric field was turned off after the polymerizable compound was cured. . The pretilt angle maintained was 87.5 °.

As a result of measuring the pretilt stability of the liquid crystal display element, it was found that the pretilt shift amount was -1.0 degrees and the pretilt angle was greatly changed.
(Example 3)
In the same experiment as in Example 1, the liquid crystal composition used was changed to a liquid crystal composition LC-3 containing a compound selected from general formula (I) and a compound selected from general formula (II). The constituent compounds and the ratios contained are as follows.

  The polymerizable compound shown below with respect to 98.0 wt% of liquid crystal composition LC-3

Was added at 2.0 wt% and dissolved uniformly to prepare a polymerizable liquid crystal composition CLC-3.
After sandwiching the polymerizable liquid crystal composition CLC-3 between the common electrode substrate and the pixel electrode substrate having no alignment film layer, the sealing material was cured to form a liquid crystal composition layer. At this time, the thickness of the liquid crystal composition layer was set to 3.5 μm using a spacer having a thickness of 3.5 μm. The obtained liquid crystal display was irradiated with ultraviolet rays while a voltage was applied to cure the polymerizable compound having the reactive group. As an irradiation apparatus, USH-250BY manufactured by Ushio Electric Co., Ltd. was used, and the liquid crystal display element was irradiated with ultraviolet rays at 100 mW for 10 minutes to obtain a liquid crystal display element CLCD-3 of Example 3. The liquid crystal display element of Example 3 had pretilt angles in different directions in the four sections according to the slits of the pixel electrode, and the pretilt angle was maintained even when the AC electric field was turned off after the polymerizable compound was cured. . The pretilt angle maintained was 89.3 °.

  Various characteristics of the liquid crystal composition LC-3 used in this example are shown in the following table.

As a result of measuring the pretilt stability of the liquid crystal display element, it was shown that the pretilt shift amount is -0.4 degrees, which is small and the stability is excellent. In other words, it is clear that a liquid crystal display element having good alignment stability over time can be obtained by the alignment control layer in which changes over time are greatly suppressed.
(Comparative Example 3)
In the same experiment as in Example 1, the polymerizable compound shown below with respect to 98.0 wt% of the liquid crystal composition LC-3

Is added at 1.5 wt%, and the polymerizable compound shown below

Of 0.1 wt% of a photopolymerization initiator Igacure 651 was added and dissolved uniformly to prepare a polymerizable liquid crystal composition CLC-3a.

  After sandwiching the polymerizable liquid crystal composition CLC-3a between the common electrode substrate and the pixel electrode substrate having no alignment film layer, the sealing material was cured to form a liquid crystal composition layer. At this time, the thickness of the liquid crystal composition layer was set to 3.5 μm using a spacer having a thickness of 3.5 μm. The obtained liquid crystal display was irradiated with ultraviolet rays while a voltage was applied to cure the polymerizable compound having the reactive group. As an irradiation apparatus, USH-250BY manufactured by Ushio Electric Co., Ltd. was used, and the liquid crystal display element was irradiated with ultraviolet rays at 100 mW for 10 minutes to obtain a liquid crystal display element CLCD-3a of Comparative Example 3. The liquid crystal display element of Comparative Example 3 had pretilt angles in different directions in the four sections according to the slits of the pixel electrode, and the pretilt angle was maintained even when the AC electric field was turned off after the polymerizable compound was cured. . The pretilt angle maintained was 87.7 °.

As a result of measuring the pretilt stability of the liquid crystal display element, it was found that the pretilt shift amount was −0.8 degrees and the pretilt angle was greatly changed.
Example 4
In the same experiment as in Example 1, the liquid crystal composition used was changed to a liquid crystal composition LC-4 containing a compound selected from general formula (I) and a compound selected from general formula (II). The constituent compounds and the ratios contained are as follows.

  The polymerizable compound shown below with respect to liquid crystal composition LC-4 97.8 wt%

Was added at 2.2 wt% and dissolved uniformly to prepare a polymerizable liquid crystal composition CLC-4.
After sandwiching the polymerizable liquid crystal composition CLC-4 between the common electrode substrate and the pixel electrode substrate having no alignment film layer, the sealing material was cured to form a liquid crystal composition layer. At this time, the thickness of the liquid crystal composition layer was set to 3.5 μm using a spacer having a thickness of 3.5 μm. The obtained liquid crystal display was irradiated with ultraviolet rays while a voltage was applied to cure the polymerizable compound having the reactive group. As an irradiation apparatus, USH-250BY manufactured by Ushio Electric Co., Ltd. was used, and the liquid crystal display element was irradiated with ultraviolet rays at 100 mW for 10 minutes to obtain a liquid crystal display element CLCD-4 of Example 4. The liquid crystal display element of Example 4 had pretilt angles in different directions in the four sections according to the slits of the pixel electrodes, and the pretilt angle was maintained even when the AC electric field was turned off after the polymerizable compound was cured. . The pretilt angle maintained was 89.3 °.

  Various characteristics of the liquid crystal composition LC-4 used in this example are shown in the following table.

As a result of measuring the pretilt stability of the liquid crystal display element, the pretilt shift amount was -0.3 degrees, indicating that the pretilt shift amount was small and the stability was excellent. In other words, it is clear that a liquid crystal display element having good alignment stability over time can be obtained by the alignment control layer in which changes over time are greatly suppressed.
(Comparative Example 4)
In the same experiment as in Example 1, the polymerizable compound shown below with respect to 98.0 wt% of the liquid crystal composition LC-4

Is added at 1.5 wt%, and the polymerizable compound shown below

Was added in an amount of 0.4 wt%, and photopolymerization initiator Igacure 651 was added in an amount of 0.1 wt%, and dissolved uniformly to prepare a polymerizable liquid crystal composition CLC-4a.

  After sandwiching the polymerizable liquid crystal composition CLC-4a between the common electrode substrate and the pixel electrode substrate having no alignment film layer, the sealing material was cured to form a liquid crystal composition layer. At this time, the thickness of the liquid crystal composition layer was set to 3.5 μm using a spacer having a thickness of 3.5 μm. The obtained liquid crystal display was irradiated with ultraviolet rays while a voltage was applied to cure the polymerizable compound having the reactive group. As an irradiation apparatus, USH-250BY manufactured by Ushio Electric Co., Ltd. was used, and the liquid crystal display element was irradiated with ultraviolet rays at 100 mW for 10 minutes to obtain a liquid crystal display element CLCD-4a of Comparative Example 4. The liquid crystal display element of Comparative Example 4 had pretilt angles in different directions in the four sections according to the slits of the pixel electrodes, and the pretilt angle was maintained even when the AC electric field was turned off after the polymerizable compound was cured. . The pretilt angle maintained was 88.0 °.

As a result of measuring the pretilt stability of the liquid crystal display element, it was found that the pretilt shift amount was −1.1 degrees and the pretilt angle was greatly changed.
(Example 5)
In the same experiment as in Example 1, the liquid crystal composition used was changed to a liquid crystal composition LC-5 containing a compound selected from general formula (I) and a compound selected from general formula (II). The constituent compounds and the ratios contained are as follows.

The polymerizable compound shown below with respect to 97.8 wt% of liquid crystal composition LC-5

Was added in an amount of 2.2 wt% and uniformly dissolved to prepare a polymerizable liquid crystal composition CLC-5.

  After sandwiching the polymerizable liquid crystal composition CLC-5 between the common electrode substrate and the pixel electrode substrate having no alignment film layer, the sealing material was cured to form a liquid crystal composition layer. At this time, the thickness of the liquid crystal composition layer was set to 3.5 μm using a spacer having a thickness of 3.5 μm. The obtained liquid crystal display was irradiated with ultraviolet rays while a voltage was applied to cure the polymerizable compound having the reactive group. As an irradiation apparatus, USH-250BY manufactured by Ushio Electric Co., Ltd. was used, and the liquid crystal display element was irradiated with ultraviolet rays at 100 mW for 10 minutes to obtain a liquid crystal display element CLCD-5 of Example 5. The liquid crystal display element of Example 5 had pretilt angles in different directions in the four sections according to the slits of the pixel electrode, and the pretilt angle was maintained even when the AC electric field was turned off after the polymerizable compound was cured. . The pretilt angle maintained was 89.4 °.

  Various characteristics of the liquid crystal composition LC-5 used in this example are shown in the following table.

As a result of measuring the pretilt stability of the liquid crystal display element, it was shown that the pretilt shift amount is -0.4 degrees, which is small and the stability is excellent. In other words, it is clear that a liquid crystal display element having good alignment stability over time can be obtained by the alignment control layer in which changes over time are greatly suppressed.
(Comparative Example 5)
In the same experiment as in Example 1, the polymerizable compound shown below with respect to 98.0 wt% of the liquid crystal composition LC-5

Is added at 1.5 wt%, and the polymerizable compound shown below

Was added in an amount of 0.4 wt%, and photopolymerization initiator Igacure 651 was added in an amount of 0.1 wt%, and dissolved uniformly to prepare a polymerizable liquid crystal composition CLC-5a.

  After sandwiching the polymerizable liquid crystal composition CLC-5a between the common electrode substrate and the pixel electrode substrate having no alignment film layer, the sealing material was cured to form a liquid crystal composition layer. At this time, the thickness of the liquid crystal composition layer was set to 3.5 μm using a spacer having a thickness of 3.5 μm. The obtained liquid crystal display was irradiated with ultraviolet rays while a voltage was applied to cure the polymerizable compound having the reactive group. As an irradiation apparatus, USH-250BY manufactured by Ushio Electric Co., Ltd. was used, and the liquid crystal display element was irradiated with ultraviolet rays at 100 mW for 10 minutes to obtain a liquid crystal display element CLCD-5a of Comparative Example 5. The liquid crystal display element of Comparative Example 5 had pretilt angles in different directions in the four sections according to the slits of the pixel electrode, and the pretilt angle was maintained even when the alternating electric field was turned off after the polymerizable compound was cured. . The pretilt angle maintained was 87.9 °.

As a result of measuring the pretilt stability of the liquid crystal display element, it was found that the pretilt shift amount was −0.7 degrees and the pretilt angle was greatly changed.
(Example 6)
In the same experiment as in Example 1, the liquid crystal composition used was changed to a liquid crystal composition LC-6 containing a compound selected from general formula (I) and a compound selected from general formula (II). The constituent compounds and the ratios contained are as follows.

The polymerizable compound shown below with respect to liquid crystal composition LC-6 98.1 wt%

1.9 wt% was added and dissolved uniformly to prepare a polymerizable liquid crystal composition CLC-6.

  After sandwiching the polymerizable liquid crystal composition CLC-6 between the common electrode substrate and the pixel electrode substrate having no alignment film layer, the sealing material was cured to form a liquid crystal composition layer. At this time, the thickness of the liquid crystal composition layer was set to 3.5 μm using a spacer having a thickness of 3.5 μm. The obtained liquid crystal display element was irradiated with ultraviolet rays while a voltage was applied to cure the polymerizable compound having the reactive group. As an irradiation apparatus, USH-250BY manufactured by Ushio Electric Co., Ltd. was used, and the liquid crystal display element was irradiated with ultraviolet rays at 100 mW for 10 minutes to obtain a liquid crystal display element CLCD-6 of Example 6. The liquid crystal display element of Example 6 had pretilt angles in different directions in the four sections according to the slits of the pixel electrodes, and the pretilt angle was maintained even when the AC electric field was turned off after the polymerizable compound was cured. . The pretilt angle maintained was 89.0 °.

  Various characteristics of the liquid crystal composition LC-6 used in this example are shown in the following table.

As a result of measuring the pretilt stability of the liquid crystal display element, it was shown that the pretilt shift amount was -0.2 degrees and the pretilt shift amount was small, and the stability was excellent. In other words, it is clear that a liquid crystal display element having good alignment stability over time can be obtained by the alignment control layer in which changes over time are greatly suppressed.
(Comparative Example 6)
In the same experiment as in Example 1, the polymerizable compound shown below with respect to 98.5 wt% of the liquid crystal composition LC-6

1.0 wt%, and the polymerizable compound shown below

Was added in an amount of 0.4 wt%, and photopolymerization initiator Igacure 651 was added in an amount of 0.1 wt%, and dissolved uniformly to prepare a polymerizable liquid crystal composition CLC-6a.
After sandwiching the polymerizable liquid crystal composition CLC-6a between the common electrode substrate and the pixel electrode substrate having no alignment film layer, the sealing material was cured to form a liquid crystal composition layer. At this time, the thickness of the liquid crystal composition layer was set to 3.5 μm using a spacer having a thickness of 3.5 μm. The obtained liquid crystal display was irradiated with ultraviolet rays while a voltage was applied to cure the polymerizable compound having the reactive group. As an irradiation apparatus, USH-250BY manufactured by Ushio Electric Co., Ltd. was used, and the liquid crystal display element was irradiated with ultraviolet rays at 100 mW for 10 minutes to obtain a liquid crystal display element CLCD-6a of Comparative Example 6. The liquid crystal display element of Comparative Example 6 had pretilt angles in different directions in the four sections according to the slits of the pixel electrode, and the pretilt angle was maintained even when the AC electric field was turned off after the polymerizable compound was cured. . The pretilt angle maintained was 87.5 °.

As a result of measuring the pretilt stability of the liquid crystal display element, it was found that the pretilt shift amount was −0.9 degrees and the pretilt angle was greatly changed.
(Example 7)
In the same experiment as in Example 1, the liquid crystal composition used was based on 98.1 wt% of LC-6 and the polymerizable compound shown below

Was added in an amount of 1.9 wt% and dissolved uniformly to prepare a polymerizable liquid crystal composition CLC-7.

After sandwiching the polymerizable liquid crystal composition CLC-7 between the common electrode substrate and the pixel electrode substrate having no alignment film layer, the sealing material was cured to form a liquid crystal composition layer. At this time, the thickness of the liquid crystal composition layer was set to 3.5 μm using a spacer having a thickness of 3.5 μm. The obtained liquid crystal display element was irradiated with ultraviolet rays while a voltage was applied to cure the polymerizable compound having the reactive group. As an irradiation apparatus, USH-250BY manufactured by Ushio Electric Co., Ltd. was used, and the liquid crystal display element was irradiated with ultraviolet rays at 100 mW for 10 minutes to obtain a liquid crystal display element CLCD-7 of Example 7. The liquid crystal display element of Example 7 had pretilt angles in different directions in the four sections according to the slits of the pixel electrode, and the pretilt angle was maintained even when the AC electric field was turned off after the polymerizable compound was cured. . The pretilt angle maintained was 88.5 °.
(Example 8)
In the same experiment as in Example 1, the liquid crystal composition used was based on 98.1 wt% of LC-6 and the polymerizable compound shown below

Was added in an amount of 1.9 wt% and dissolved uniformly to prepare a polymerizable liquid crystal composition CLC-8.

After sandwiching the polymerizable liquid crystal composition CLC-8 between the common electrode substrate and the pixel electrode substrate having no alignment film layer, the sealing material was cured to form a liquid crystal composition layer. At this time, the thickness of the liquid crystal composition layer was set to 3.5 μm using a spacer having a thickness of 3.5 μm. The obtained liquid crystal display element was irradiated with ultraviolet rays while a voltage was applied to cure the polymerizable compound having the reactive group. As the irradiation device, USH-250BY manufactured by Ushio Electric Co., Ltd. was used, and the liquid crystal display element was irradiated with ultraviolet rays at 100 mW for 10 minutes to obtain a liquid crystal display element CLCD-8 of Example 8. The liquid crystal display element of Example 8 had pretilt angles in different directions in the four sections according to the slits of the pixel electrode, and the pretilt angle was maintained even when the AC electric field was turned off after the polymerizable compound was cured. . The pretilt angle maintained was 88.1 °.
Example 9
In the same experiment as in Example 1, the liquid crystal composition used was based on 98.1 wt% of LC-6 and the polymerizable compound shown below

1.4 wt%,
Polymerizable compounds shown below

Was added at 0.5 wt% and uniformly dissolved to prepare a polymerizable liquid crystal composition CLC-9.

After sandwiching the polymerizable liquid crystal composition CLC-9 between the common electrode substrate and the pixel electrode substrate having no alignment film layer, the sealing material was cured to form a liquid crystal composition layer. At this time, the thickness of the liquid crystal composition layer was set to 3.5 μm using a spacer having a thickness of 3.5 μm. The obtained liquid crystal display element was irradiated with ultraviolet rays while a voltage was applied to cure the polymerizable compound having the reactive group. As an irradiation apparatus, USH-250BY manufactured by Ushio Electric Co., Ltd. was used, and the liquid crystal display element was irradiated with ultraviolet rays at 100 mW for 10 minutes to obtain a liquid crystal display element CLCD-9 of Example 6. The liquid crystal display element of Example 9 had pretilt angles in different directions in the four sections according to the slits of the pixel electrodes, and the pretilt angle was maintained even when the AC electric field was turned off after the polymerizable compound was cured. . The pretilt angle maintained was 88.4 °.
(Example 10)
In the same experiment as in Example 1, the liquid crystal composition used was changed to a liquid crystal composition LC-7 containing a compound selected from general formula (I) and a compound selected from general formula (II). The constituent compounds and the ratios contained are as follows.

  The polymerizable compound shown below with respect to 97.7 wt% of liquid crystal composition LC-7

Was added in an amount of 2.3 wt% and dissolved uniformly to prepare a polymerizable liquid crystal composition CLC-10.

  After sandwiching the polymerizable liquid crystal composition CLC-10 between the common electrode substrate and the pixel electrode substrate having no alignment film layer, the sealing material was cured to form a liquid crystal composition layer. At this time, the thickness of the liquid crystal composition layer was set to 3.5 μm using a spacer having a thickness of 3.5 μm. The obtained liquid crystal display was irradiated with ultraviolet rays while a voltage was applied to cure the polymerizable compound having the reactive group. As an irradiation apparatus, USH-250BY manufactured by Ushio Electric Co., Ltd. was used, and the liquid crystal display element was irradiated with ultraviolet rays at 100 mW for 10 minutes to obtain a liquid crystal display element CLCD-10 of Example 10. The liquid crystal display element of Example 10 had pretilt angles in different directions in the four sections according to the slits of the pixel electrodes, and the pretilt angle was maintained even when the AC electric field was turned off after the polymerizable compound was cured. . The pretilt angle maintained was 89.1 °.

  Various characteristics of the liquid crystal composition LC-7 used in this example are shown in the following table.

  As a result of measuring the pretilt stability of the liquid crystal display element, the pretilt shift amount was -0.3 degrees, indicating that the pretilt shift amount was small and the stability was excellent. In other words, it is clear that a liquid crystal display element having good alignment stability over time can be obtained by the alignment control layer in which changes over time are greatly suppressed.

  DESCRIPTION OF SYMBOLS 10 ... Liquid crystal display element, 11 ... 1st board | substrate, 12 ... 2nd board | substrate, 13 ... Liquid crystal layer, 14 ... Common electrode, 15 ... Pixel electrode, 18 ... -Color filter, 19 ... Liquid crystal molecule, 20 ... First electrode, 21 ... Second electrode, 22 ... Insulating protective layer, 23 ... Insulating layer

Claims (7)

A liquid crystal display element in which a liquid crystal layer containing a liquid crystal composition is sandwiched between a first substrate and a second substrate,
There is no alignment film on one or both of the first substrate and the second substrate, and the general formula (1-A) to the general formula (1-F)

Wherein X ⁵⁰ to X ⁵⁴ are each independently a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, a halogenated alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, Halogen, cyano group, or formula (3)

Z ⁴ represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, a halogenated alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, or a halogen having 1 to 8 carbon atoms. Represents an alkoxy group, a halogen, a cyano group, or a nitro group,
L ⁵ , L ⁷ and L ⁸ are each independently a single bond, —O—, —CH═CH—, —OCH ₂ —, —CH ₂ O—, —CO—, —C ₂ H ₄ —, — _{COO -, - OCO -, -} OCOOCH 2 -, - CH 2 OCOO -, - OCH 2 CH 2 O -, - CH = CR a -COO -, - CH = CR a -OCO -, - COO-CR a = CH—, —OCO—CR ^a ═CH—, —COOC ₂ H ₄ —, —OCOC ₂ H ₄ —, —C ₂ H ₄ OCO—, — (CH ₂ ) _j —C (═O) —O—, _{- (CH 2) j -O- (} C = O) -, - O- (C = O) - (CH 2) j -, - (C = O) -O- (CH 2) j -, - CH _{2 OCO -, - COOCH 2 -} , - OCOCH 2 -, - CF 2 -, - CF 2 O -, - OCF 2 -, - CF 2 CH 2 - _{-CH 2 CF 2 -, - CF} 2 CF 2 - or -C≡C- (wherein, ^{R a} represents hydrogen atom or an alkyl group having a carbon number of 1 to 4 independently, j is 1 to 4 . that of an integer) ^represents, L 6 _{is, -O -, - OCH 2 -} , - CH 2 O -, - CO -, - C 2 H 4 -, - COO -, - OCO -, - OCH 2 _{^{CH 2 O -, - CH =}} CR a -COO -, - CH = CR a -OCO -, - COO-CR a = CH -, - OCO-CR a = CH -, - CH = CH-, or -C ≡C— (wherein R ^a each independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms), and M ⁵ and M ⁶ each independently represent a 1,4-phenylene group. 1,4-cyclohexylene group, cyclohexene-1,4-diyl group, pyridine-2,5-diyl group, Spermidine-2,5-diyl group, or 1,3-dioxane-2,5-diyl group, ^{M 5} and ^{M 6} are each independently may be unsubstituted, having 1 to 3 carbon atoms An alkyl group, a halogenated alkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, a halogen, a cyano group, or a nitro group, and n represents 0 or 1 ,
R ¹ , R ³ and R ⁴ are each independently a hydrogen atom or formula (R-1) to formula (R-15)

Represents one of the following:
S ¹ , S ² and S ⁵ each independently represents an alkylene group having 1 to 12 carbon atoms or a single bond, one —CH ₂ — in the alkylene group or two or more not adjacent to each other is, -O - - _-CH 2 of, - COO -, - OCO- or -OCOO- may be replaced with,
p represents 0, 1 or 2. )
A liquid crystal display element comprising an alignment control layer made of a polymer of a polymerizable compound containing one or more compounds selected from the group consisting of: The liquid crystal composition has the following general formula (I)

(In the formula, R ^1α and R ^2α are each independently an alkyl group having 1 to 8 carbon atoms, an alkenyl group having 2 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, or 2 to 2 carbon atoms. 8 represents an alkenyloxy group, Q ¹ represents a 1,4-phenylene group or a trans-1,4-cyclohexylene group, l ¹ represents 1 or 2, and when l ¹ is 2, Q ¹ may be the same or different.), And the following general formula (II)

(In the formula, R ^3α represents an alkyl group having 1 to 8 carbon atoms, an alkenyl group having 2 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, or an alkenyloxy group having 2 to 8 carbon atoms, R ^4α represents an alkyl group having 1 to 8 carbon atoms, an alkenyl group having 4 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, or an alkenyloxy group having 3 to 8 carbon atoms, and present Q ² And Q ³ each independently represents a 1,4-phenylene group or a trans-1,4-cyclohexylene group, and G ¹ and G ² present are each independently a single bond, —CH ₂ CH ₂ — , —CH ₂ O—, —OCH ₂ —, —CF ₂ O— or —OCF ₂ —, wherein l ² represents 0, 1 or 2, but when l ² is 2, two Q ² and G ² is represented by may be the same or different.) The liquid crystal display device according to claim 1, characterized in that it contains a compound. The liquid crystal display element according to claim 1 , wherein at least one of the first substrate and the second substrate has a pixel electrode, and the pixel electrode has a slit.   The liquid crystal display element according to claim 1, wherein at least one of the first substrate and the second substrate has a structure that defines a pretilt direction. A liquid crystal display element having a liquid crystal layer containing a liquid crystal composition sandwiched between a first substrate having a color filter layer and a second substrate, and having two or more regions having different pretilt directions in the pixel A manufacturing method of
Without providing an alignment film on one or both of the first substrate and the second substrate, the following general formula (I)

(In the formula, R ^1α and R ^2α are each independently an alkyl group having 1 to 8 carbon atoms, an alkenyl group having 2 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, or 2 to 2 carbon atoms. 8 represents an alkenyloxy group, Q ¹ represents a 1,4-phenylene group or a trans-1,4-cyclohexylene group, l ¹ represents 1 or 2, and when l ¹ is 2, Q ¹ may be the same or different.)

(In the formula, R ^3α represents an alkyl group having 1 to 8 carbon atoms, an alkenyl group having 2 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, or an alkenyloxy group having 2 to 8 carbon atoms, R ^4α represents an alkyl group having 1 to 8 carbon atoms, an alkenyl group having 4 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, or an alkenyloxy group having 3 to 8 carbon atoms, and present Q ² And Q ³ each independently represents a 1,4-phenylene group or a trans-1,4-cyclohexylene group, and G ¹ and G ² present are each independently a single bond, —CH ₂ CH ₂ — , —CH ₂ O—, —OCH ₂ —, —CF ₂ O— or —OCF ₂ —, wherein l ² represents 0, 1 or 2, but when l ² is 2, two Q ² and G ² is represented by may be the same or different.) Compounds, and general formulas formulas (1-A) (1-F)

Wherein X ⁵⁰ to X ⁵⁴ are each independently a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, a halogenated alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, Halogen, cyano group, or formula (3)

Z ⁴ represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, a halogenated alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, or a halogen having 1 to 8 carbon atoms. Represents an alkoxy group, a halogen, a cyano group, or a nitro group,
L ⁵ , L ⁷ and L ⁸ are each independently a single bond, —O—, —CH═CH—, —OCH ₂ —, —CH ₂ O—, —CO—, —C ₂ H ₄ —, — _{COO -, - OCO -, -} OCOOCH 2 -, - CH 2 OCOO -, - OCH 2 CH 2 O -, - CH = CR a -COO -, - CH = CR a -OCO -, - COO-CR a = CH—, —OCO—CR ^a ═CH—, —COOC ₂ H ₄ —, —OCOC ₂ H ₄ —, —C ₂ H ₄ OCO—, — (CH ₂ ) _j —C (═O) —O—, _{- (CH 2) j -O- (} C = O) -, - O- (C = O) - (CH 2) j -, - (C = O) -O- (CH 2) j -, - CH _{2 OCO -, - COOCH 2 -} , - OCOCH 2 -, - CF 2 -, - CF 2 O -, - OCF 2 -, - CF 2 CH 2 - _{-CH 2 CF 2 -, - CF} 2 CF 2 - or -C≡C- (wherein, ^{R a} represents hydrogen atom or an alkyl group having a carbon number of 1 to 4 independently, j is 1 to 4 . that of an integer) ^represents, L 6 _{is, -O -, - OCH 2 -} , - CH 2 O -, - CO -, - C 2 H 4 -, - COO -, - OCO -, - OCH 2 _{^{CH 2 O -, - CH =}} CR a -COO -, - CH = CR a -OCO -, - COO-CR a = CH -, - OCO-CR a = CH -, - CH = CH-, or -C ≡C— (wherein R ^a each independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms), and M ⁵ and M ⁶ each independently represent a 1,4-phenylene group. 1,4-cyclohexylene group, cyclohexene-1,4-diyl group, pyridine-2,5-diyl group, Spermidine-2,5-diyl group, or 1,3-dioxane-2,5-diyl group, ^{M 5} and ^{M 6} are each independently may be unsubstituted, having 1 to 3 carbon atoms An alkyl group, a halogenated alkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, a halogen, a cyano group, or a nitro group, and n represents 0 or 1 ,
R ¹ , R ³ and R ⁴ are each independently a hydrogen atom or formula (R-1) to formula (R-15)

Represents one of the following:
S ¹ , S ² and S ⁵ each independently represents an alkylene group having 1 to 12 carbon atoms or a single bond, one —CH ₂ — in the alkylene group or two or more not adjacent to each other is, -O - - _-CH 2 of, - COO -, - OCO- or -OCOO- may be replaced with,
p represents 0, 1 or 2. )
Sandwiching a liquid crystal-containing polymerization composition containing one or more compounds selected from:
By irradiating an active energy ray between the first substrate and the second substrate while applying a voltage for imparting a pretilt angle to the liquid crystal molecules in the liquid crystal-containing polymerization composition, While polymerizing more than one kind of polymerizable compound, the liquid crystal-containing polymerization composition is used as the liquid crystal composition, and an alignment control layer is formed between the first substrate and the second substrate and the liquid crystal layer. A method for producing a liquid crystal display element.   The method for manufacturing a liquid crystal display element according to claim 5, wherein the active energy ray is an ultraviolet ray having a plurality of spectra. At least one of the first substrate and the second substrate has a pixel electrode , the pixel electrode has a slit, or at least one of the first substrate and the second substrate is a pretilt. The manufacturing method of the liquid crystal display element of Claim 5 or 6 which has a structure which prescribes | regulates a direction.

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