JP7331361B2 - Liquid crystal display element manufacturing method and liquid crystal display element - Google Patents

Description

The present invention relates to a method for manufacturing a liquid crystal display element and a liquid crystal display element.

In order to improve the properties of liquid crystal display elements, the liquid crystal composition constituting the liquid crystal layer is mixed with a polymerizable monomer such as PSA (Polymer Sustained Alignment) to control the alignment state of the liquid crystal molecules. I have something to do.
Conventionally, polymerization of a polymerizable monomer is performed by continuously or stepwise increasing the voltage applied to a liquid crystal composition from 0 V to a predetermined value, and irradiating ultraviolet rays while maintaining the increased voltage. (See Patent Documents 1 and 2, for example).

From the viewpoint of increasing the voltage holding ratio (VHR), it is preferable to use ultraviolet light having a relatively long wavelength, but it takes a long time to fully polymerize the polymerizable monomer. In order to solve this problem, ultraviolet light with a shorter wavelength may be used to increase the rate of polymerization of the polymerizable monomer.

JP-A-2003-177408 JP 2011-221505 A

It is an object of the present invention to provide a method for manufacturing a liquid crystal display device capable of manufacturing a liquid crystal display device having a high voltage holding ratio in a relatively short period of time while preventing alteration and deterioration of liquid crystal molecules, and to have a high voltage holding ratio. To provide a liquid crystal display element exhibiting good display quality at low temperature.

Such objects are achieved by the present invention of the following (1) to (11).
(1) placing a pair of substrates facing each other with a liquid crystal composition containing liquid crystal molecules and at least one polymerizable monomer interposed therebetween;
and polymerizing the at least one polymerizable monomer by irradiating the liquid crystal composition with ultraviolet light,
A method for manufacturing a liquid crystal display element, wherein the ultraviolet rays have a ratio (X2/X1) of intensity X2 at a wavelength of 365 nm to intensity X1 at a wavelength of 313 nm of 5 to 70.

(2) The method of manufacturing a liquid crystal display element according to (1) above, wherein the intensity X1 is 0.05 to 50 mW/cm ² .
(3) Manufacture of a liquid crystal display element according to (1) or (2) above, wherein the step of irradiating with ultraviolet rays is a liquid crystal layer forming step of polymerizing the at least one polymerizable monomer to form a liquid crystal layer. Method.
(4) The method of manufacturing a liquid crystal display element according to (3), wherein in the liquid crystal layer forming step, the ultraviolet rays are applied while a voltage is applied to the liquid crystal composition.

(5) The method of manufacturing a liquid crystal display element according to (3) or (4), wherein in the liquid crystal layer forming step, the ultraviolet rays are irradiated until the temperature of the liquid crystal layer rises by 0.1 to 5°C.
(6) The liquid crystal according to (1) or (2) above, wherein the step of irradiating with ultraviolet rays is a monomer consumption step of irradiating with ultraviolet rays a liquid crystal layer formed by polymerizing the at least one polymerizable monomer. A method for manufacturing a display element.

(7) The method of manufacturing a liquid crystal display element according to (6) above, wherein in the monomer consumption step, the ultraviolet rays are applied until the temperature of the liquid crystal layer rises by 1 to 20.degree.
(8) in the step of arranging the pair of substrates to face each other, at least one of the substrates is arranged so as to be in direct contact with the liquid crystal composition without an alignment layer;
The method for producing a liquid crystal display element according to any one of (1) to (7) above, wherein the at least one polymerizable monomer includes a polymerizable monomer having at least one adsorptive group.
(9) The method for producing a liquid crystal display element according to any one of (1) to (8) above, wherein the at least one polymerizable monomer contains a polymerizable monomer having no adsorptive group.

（式（Ｐ）中、Ｒ^ｐ１は、水素原子、フッ素原子、シアノ基、炭素原子数１～１５のアルキル基又は－Ｓｐ^ｐ２－Ｐ^ｐ２を表し、前記アルキル基中に存在する１個又は２個以上の－ＣＨ_２－は、それぞれ独立して、－ＣＨ＝ＣＨ－、－Ｃ≡Ｃ－、－Ｏ－、－ＣＯ－、－ＣＯＯ－又は－ＯＣＯ－で置換されてもよいが、隣接する２個以上の－ＣＨ_２－が同時に－Ｏ－で置換されることはなく、前記アルキル基中に存在する１個又は２個以上の水素原子は、それぞれ独立して、シアノ基、フッ素原子又は塩素原子で置換されてもよく、
Ｐ^ｐ１及びＰ^ｐ２は、それぞれ独立して、下記一般式（Ｐ^ｐ１－１）～式（Ｐ^ｐ１－９）のいずれかを表し、

［式中、Ｒ^ｐ１１及びＲ^ｐ１２は、それぞれ独立して、水素原子、炭素原子数１～５のアルキル基又は炭素原子数１～５のハロゲン化アルキル基を表し、Ｗ^ｐ１１は、単結合、－Ｏ－、－ＣＯＯ－又は－ＣＨ_２－を表し、ｔ^ｐ１１は、０、１又は２を表すが、分子内にＲ^ｐ１１、Ｒ^ｐ１２、Ｗ^ｐ１１及び／又はｔ^ｐ１１が複数存在する場合、それらは同一であっても異なってもよい。］
Ｓｐ^ｐ１及びＳｐ^ｐ２は、それぞれ独立して、単結合又はスペーサ基を表し、
Ｚ^ｐ１及びＺ^ｐ２は、それぞれ独立して、単結合、－Ｏ－、－Ｓ－、－ＣＨ_２－、－ＯＣＨ_２－、－ＣＨ_２Ｏ－、－ＣＯ－、－Ｃ_２Ｈ_４－、－ＣＯＯ－、－ＯＣＯ－、－ＯＣＯＯＣＨ_２－、－ＣＨ_２ＯＣＯＯ－、－ＯＣＨ_２ＣＨ_２Ｏ－、－ＣＯ－ＮＲ^ＺＰ１－、－ＮＲ^ＺＰ１－ＣＯ－、－ＳＣＨ_２－、－ＣＨ_２Ｓ－、－ＣＨ＝ＣＲ^ＺＰ１－ＣＯＯ－、－ＣＨ＝ＣＲ^ＺＰ１－ＯＣＯ－、－ＣＯＯ－ＣＲ^ＺＰ１＝ＣＨ－、－ＯＣＯ－ＣＲ^ＺＰ１＝ＣＨ－、－ＣＯＯ－ＣＲ^ＺＰ１＝ＣＨ－ＣＯＯ－、－ＣＯＯ－ＣＲ^ＺＰ１＝ＣＨ－ＯＣＯ－、－ＯＣＯ－ＣＲ^ＺＰ１＝ＣＨ－ＣＯＯ－、－ＯＣＯ－ＣＲ^ＺＰ１＝ＣＨ－ＯＣＯ－、－（ＣＨ_２）_ｚ－ＣＯＯ－、－（ＣＨ_２）_２－ＯＣＯ－、－ＯＣＯ－（ＣＨ_２）_２－、－（Ｃ＝Ｏ）－Ｏ－（ＣＨ_２）_２－、－ＣＨ＝ＣＨ－、－ＣＦ＝ＣＦ－、－ＣＦ＝ＣＨ－、－ＣＨ＝ＣＦ－、－ＣＦ_２－、－ＣＦ_２Ｏ－、－ＯＣＦ_２－、－ＣＦ_２ＣＨ_２－、－ＣＨ_２ＣＦ_２－、－ＣＦ_２ＣＦ_２－又は－Ｃ≡Ｃ－［式中、Ｒ^ＺＰ１は、それぞれ独立して、水素原子又は炭素原子数１～４のアルキル基を表すが、分子内にＲ^ＺＰ１が複数存在する場合、それらは同一であっても異なってもよい。］を表し、
Ａ^ｐ１、Ａ^ｐ２及びＡ^ｐ３は、それぞれ独立して、
（ａ^ｐ） １，４－シクロヘキシレン基［この基中に存在する１個の－ＣＨ_２－又は隣接していない２個以上の－ＣＨ_２－は、－Ｏ－で置換されてもよい。］
（ｂ^ｐ） １，４－フェニレン基［この基中に存在する１個の－ＣＨ＝又は隣接していない２個以上の－ＣＨ＝は、－Ｎ＝で置換されてもよい。］及び
（ｃ^ｐ） ナフタレン－２，６－ジイル基、ナフタレン－１，４－ジイル基、ナフタレン－１，５－ジイル基、１，２，３，４－テトラヒドロナフタレン－２，６－ジイル基、デカヒドロナフタレン－２，６－ジイル基、フェナントレン－２，７－ジイル基又はアントラセン－２，６－ジイル基［これらの基中に存在する１個の－ＣＨ＝又は隣接していない２個以上の－ＣＨ＝は、－Ｎ＝で置換されてもよい。］
からなる群より選ばれる基［前記基（ａ^ｐ）、基（ｂ^ｐ）及び基（ｃ^ｐ）は、それぞれ独立して、この基中に存在する水素原子が、ハロゲン原子、炭素原子数１～８のアルキル基又は炭素原子数１～８のアルケニル基、シアノ基又は－Ｓｐ^ｐ２－Ｐ^ｐ２で置換されてもよい。］を表し、
ｍ^ｐ１は、０、１、２又は３を表し、分子内にＺ^ｐ１、Ａ^ｐ２、Ｓｐ^ｐ２及び／又はＰ^ｐ２が複数存在する場合、それらは同一であっても異なってもよいが、Ａ^ｐ３は、ｍ^ｐ１が０で、Ａ^ｐ１が前記基（ｃ^ｐ）である場合、単結合であってもよい。） (9) The method for producing a liquid crystal display element according to (9) above, wherein the polymerizable monomer having no adsorptive group is represented by the following general formula (P).

(In the formula (P), R ^p1 represents a hydrogen atom, a fluorine atom, a cyano group, an alkyl group having 1 to 15 carbon atoms or -Sp ^p2 -P ^p2 , and one or two One or more —CH ₂ — may each independently be replaced with —CH═CH—, —C≡C—, —O—, —CO—, —COO— or —OCO—, but adjacent two or more —CH ₂ — are not substituted with —O— at the same time, and one or more hydrogen atoms present in the alkyl group are each independently a cyano group, a fluorine atom or optionally substituted with a chlorine atom,
P ^p1 and P ^p2 each independently represent any one of the following general formulas (P ^p1 -1) to (P ^p1 -9);

[Wherein, R ^p11 and R ^p12 each independently represent a hydrogen atom, an alkyl group having 1 to 5 carbon atoms or a halogenated alkyl group having 1 to 5 carbon atoms, W ^p11 is a single bond, represents -O-, -COO- or -CH ₂ -, and t ^p11 represents 0, 1 or 2, but when a plurality of R ^p11 , R ^p12 , W ^p11 and/or t ^p11 are present in the molecule, They can be the same or different. ]
Sp ^p1 and Sp ^p2 each independently represent a single bond or a spacer group;
Z ^p1 and Z ^p2 are each independently a single bond, —O—, —S—, —CH ₂ —, —OCH ₂ —, —CH ₂ O—, —CO—, —C ₂ H ₄ —, -COO-, -OCO-, -OCOOCH ₂ -, -CH ₂ OCOO-, -OCH ₂ CH ₂ O-, -CO-NR ^ZP1 -, -NR ^ZP1 -CO-, -SCH ₂ -, -CH ₂ S -, -CH=CR ^ZP1 -COO-, -CH=CR ^ZP1 -OCO-, -COO-CR ^ZP1 =CH-, -OCO-CR ^ZP1 =CH-, -COO-CR ^ZP1 =CH-COO-, - COO-CR ^ZP1 =CH-OCO-, -OCO-CR ^ZP1 =CH-COO-, -OCO-CR ^ZP1 =CH-OCO-, -(CH ₂ ) _z -COO-, -(CH ₂ ) ₂ -OCO -, -OCO-(CH ₂ ) ₂ -, -(C=O)-O-(CH ₂ ) ₂ -, -CH=CH-, -CF=CF-, -CF=CH-, -CH=CF -, -CF ₂ -, -CF ₂ O-, -OCF ₂ -, -CF ₂ CH ₂ -, -CH ₂ CF ₂ -, -CF ₂ CF ₂ - or -C≡C- [wherein R ^ZP1 each independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and when multiple R ^ZP1 are present in the molecule, they may be the same or different. ] represents
A ^p1 , A ^p2 and A ^p3 are each independently
(a ^p ) 1,4-cyclohexylene group [one -CH ₂ - or two or more non-adjacent -CH ₂ - present in this group may be substituted with -O-; ]
(b ^p ) 1,4-phenylene group [One -CH= or two or more non-adjacent -CH= present in this group may be substituted with -N=. ] and (c ^p ) naphthalene-2,6-diyl group, naphthalene-1,4-diyl group, naphthalene-1,5-diyl group, 1,2,3,4-tetrahydronaphthalene-2,6-diyl group , decahydronaphthalene-2,6-diyl group, phenanthrene-2,7-diyl group or anthracene-2,6-diyl group [one —CH= present in these groups or two non-adjacent -CH= above may be replaced with -N=. ]
A group selected from the group consisting of [the group (a ^p ), the group (b ^p ) and the group (c ^p ) are each independently a hydrogen atom present in the group, a halogen atom, a ∼8 alkyl groups or alkenyl groups having 1 to 8 carbon atoms, a cyano group or -Sp ^p2 -P ^p2 . ] represents
m ^p1 represents 0, 1, 2 or 3, and when there are multiple Z ^p1 , A ^p2 , Sp ^p2 and/or P ^p2 in the molecule, they may be the same or different, but A ^p3 may be a single bond when m ^p1 is 0 and A ^p1 is the group (c ^p ). )

(11) comprising a pair of substrates and a liquid crystal layer disposed between the pair of substrates and containing at least one polymerizable monomer polymerized by ultraviolet irradiation,
A liquid crystal display device, wherein the ratio (X2/X1) of the intensity X2 at a wavelength of 365 nm to the intensity X1 at a wavelength of 313 nm is 5-70.

According to the present invention, by using ultraviolet rays having peaks at wavelengths of 313 nm and 365 nm at a predetermined intensity ratio, deterioration and deterioration of liquid crystal molecules are prevented, and good display quality is achieved by having a high voltage holding ratio. The liquid crystal display element shown can be manufactured in a relatively short time.

FIG. 1 is an exploded perspective view schematically showing an embodiment of a liquid crystal display element. FIG. 2 is an enlarged plan view of a region surrounded by line I in FIG. 1;

Hereinafter, the method for manufacturing the liquid crystal display element of the present invention will be described in detail based on preferred embodiments. First, the liquid crystal display element manufactured by the method for manufacturing a liquid crystal display element of the present invention will be described.
FIG. 1 is an exploded perspective view schematically showing an embodiment of a liquid crystal display element, and FIG. 2 is a plan view enlarging a region surrounded by line I in FIG.
In addition, in FIGS. 1 and 2, the dimensions of each part and their ratios are exaggerated for the sake of convenience, and may differ from the actual dimensions. Also, the materials, dimensions, and the like shown below are examples, and the present invention is not limited to them, and can be changed as appropriate without changing the gist of the invention.

The liquid crystal display element 1 shown in FIG. 1 includes an active matrix substrate AM and a color filter substrate CF which are arranged to face each other, and a liquid crystal layer 4 sandwiched between the active matrix substrate AM and the color filter substrate CF. ing.
The active matrix substrate AM includes a first substrate 2 , a pixel electrode layer 5 provided on the surface of the first substrate 2 facing the liquid crystal layer 4 , and an electrode layer 5 provided on the surface of the first substrate 2 opposite to the liquid crystal layer 4 . and a first polarizing plate 7 provided.
On the other hand, the color filter substrate CF includes the second substrate 3, the common electrode layer 6 provided on the second substrate 3 on the side of the liquid crystal layer 4, and the surface of the second substrate 3 opposite to the liquid crystal layer 4. It has a second polarizing plate 8 provided and a color filter 9 provided between the second substrate 3 and the common electrode layer 6 .
The liquid crystal layer 4 is of a vertical alignment type using negative dielectric anisotropy. Almost vertically oriented.

That is, the liquid crystal display element 1 according to this embodiment includes a first polarizing plate 7, a first substrate 2, a pixel electrode layer 5, a liquid crystal layer 4, a common electrode layer 6, a color filter 9, It has a structure in which the second substrate 3 and the second polarizing plate 8 are laminated in this order.
The first substrate 2 and the second substrate 3 are each made of a flexible material such as a glass material or a plastic material.
Both the first substrate 2 and the second substrate 3 may be translucent, or only one of them may be translucent. In the latter case, the other substrate can consist of an opaque material, such as a metal material, a silicon material, for example.

The pixel electrode layer 5 includes a plurality of gate bus lines 11 for supplying scanning signals, a plurality of data bus lines 12 for supplying display signals, and a plurality of pixel electrodes 13, as shown in FIG. have. A pair of gate bus lines 11, 11 and a pair of data bus lines 12, 12 are shown in FIG.
A plurality of gate bus lines 11 and a plurality of data bus lines 12 intersect each other and are arranged in a matrix, and the area surrounded by these lines forms a unit pixel of the liquid crystal display element 1 . One pixel electrode 13 is formed in each unit pixel. Note that each pixel may be composed of a plurality of sub-pixels.

The pixel electrode 13 has a structure (a so-called fishbone structure) comprising two cross-shaped trunks perpendicular to each other and a plurality of branch portions branched from each trunk and inclined at an angle of about 45° with respect to each trunk. structure). In other words, the pixel electrode 13 can also be regarded as an electrode having a structure having slits formed between branches.
According to the pixel electrode 13 having such a structure, the liquid crystal molecules are tilted in alignment with the four directions in which the branches are tilted with respect to the stem. Therefore, a domain divided into four is formed in one pixel, and the viewing angle of the liquid crystal display element 1 can be widened.

The width of each branch is preferably about 1 to 5 μm, more preferably about 2 to 4 μm. Also, the distance S between adjacent branches is preferably about 1 to 5 μm, more preferably about 2 to 4 μm. With such a configuration, the liquid crystal molecules can be tilted in a predetermined direction more reliably.
A Cs electrode 14 is provided between the pair of gate bus lines 11 , 11 substantially parallel to the gate bus line 11 . A thin film transistor including a source electrode 15 and a drain electrode 16 is provided in the vicinity of an intersection where the gate bus line 11 and the data bus line 12 intersect each other. A contact hole 17 is provided in the drain electrode 16 .

The gate bus lines 11 and the data bus lines 12 are preferably made of, for example, Al, Cu, Au, Ag, Cr, Ta, Ti, Mo, W, Ni, or alloys containing these. It is more preferable to form with an alloy containing these.
The pixel electrode 13 is composed of, for example, a transparent electrode in order to improve light transmittance. The transparent electrode is formed by sputtering a compound such as ZnO, InGaZnO, SiGe, GaAs, IZO (Indium Zinc Oxide), ITO (Indium Tin Oxide), SnO, TiO, AZTO (AlZnSnO).
The average thickness of the transparent electrode is preferably about 10 to 200 nm. Also, in order to reduce electric resistance, the transparent electrode can be formed as a polycrystalline ITO film by firing an amorphous ITO film.

On the other hand, the common electrode layer 6 has, for example, a plurality of parallel striped common electrodes (transparent electrodes). This common electrode can also be formed in the same manner as the pixel electrode 13 .
The color filter 9 can be produced by, for example, a pigment dispersion method, a printing method, an electrodeposition method, a dyeing method, or the like.
In the pigment dispersion method, a curable coloring composition for color filters is supplied in a predetermined pattern on the second substrate 3 and then cured by heating or light irradiation. The color filter 9 can be obtained by performing this operation for the three colors of red, green, and blue.
Note that the color filter 9 may be arranged on the first substrate 2 side.

Further, the liquid crystal display element 1 may be provided with a black matrix (not shown) from the viewpoint of preventing leakage of light. This black matrix is preferably formed in a portion corresponding to the thin film transistor.
The black matrix may be arranged on the second substrate 3 side together with the color filter 9, or may be arranged on the first substrate 2 side together with the color filter 9. Alternatively, the black matrix may be arranged on the first substrate 2 side. The color filters 9 may be arranged individually on the second substrate 3 side. Also, the black matrix can be configured by overlapping the colors of the color filters 9 to reduce the transmittance.

The active matrix substrate AM and the color filter substrate CF are bonded to each other at their peripheral regions with a sealing material (sealing material) composed of an epoxy thermosetting composition, an acrylic UV curable composition, or the like. there is
A spacer may be arranged between the active matrix substrate AM and the color filter substrate CF to maintain the separation distance therebetween. Examples of spacers include granular spacers such as glass particles, plastic particles, and alumina particles, and resin spacer columns formed by photolithography.
The average distance between the active matrix substrate AM and the color filter substrate CF (that is, the average thickness of the liquid crystal layer 4) is preferably about 1 to 100 μm.

The first polarizing plate 7 and the second polarizing plate 8 can be designed to improve the viewing angle and contrast by adjusting the positional relationship of their transmission axes. Specifically, the first polarizing plate 7 and the second polarizing plate 8 are preferably arranged so that their transmission axes are orthogonal to each other so that they operate in the normally black mode. In particular, one of the first polarizing plate 7 and the second polarizing plate 8 is preferably arranged such that its transmission axis is at approximately 45° to the alignment direction of the liquid crystal molecules when voltage is applied. .

When the first polarizing plate 7 and the second polarizing plate 8 are used, the product of the refractive index anisotropy (Δn) of the liquid crystal layer 4 and the average thickness of the liquid crystal layer 4 is adjusted so that the contrast is maximized. is preferably adjusted. Furthermore, the liquid crystal display element 1 may be provided with a retardation film for widening the viewing angle.
In the liquid crystal display element 1, an alignment film such as a polyimide alignment film may be provided on the liquid crystal layer 4 side of at least one of the active matrix substrate AM and the color filter substrate CF so as to be in contact with the liquid crystal layer 4. can. In other words, in the present invention, at least one of the active matrix substrate AM and the color filter substrate CF may not have an alignment film by using a liquid crystal composition as described later.

(Method for manufacturing liquid crystal display element)
Next, a method for manufacturing such a liquid crystal display element 1 will be described.
The manufacturing method of the liquid crystal display element of the present embodiment comprises a preparation step [1] for preparing the substrates AM, CF, and the liquid crystal composition, an assembly step [2] for assembling each part, and a voltage applied to the liquid crystal composition. a liquid crystal layer forming step [3] in which the liquid crystal layer 4 is formed by polymerizing the polymerizable monomers by irradiating ultraviolet rays; and a monomer consuming step [4] of polymerizing and consuming the polymerizable monomer.
The order of the liquid crystal layer forming step [3] and the monomer consuming step [4] is preferable, but the order may be changed, and if the performance of the liquid crystal display element 1 is sufficient, the liquid crystal layer forming step [3] and the monomer consumption step [4] can be omitted.
[1] Preparation Step First, an active matrix substrate AM, a color filter substrate CF, and a liquid crystal composition containing liquid crystal molecules and at least one polymerizable monomer are prepared.

[2] Assembly Process Next, along at least one edge of the active matrix substrate AM and the color filter substrate CF, a dispenser is used to draw a sealing material in the form of a closed loop bank.
Thereafter, a predetermined amount of liquid crystal composition is dropped inside the sealing material, and then the active matrix substrate AM and the color filter substrate CF are placed facing each other so as to be in contact with the liquid crystal composition under reduced pressure. That is, a pair of substrates AM and CF are arranged so that the electrode layers 5 and 6 (electrodes) face each other with the liquid crystal composition interposed therebetween.
In such a one drop fill (ODF) method, it is necessary to drop an optimum injection amount according to the size of the liquid crystal display element 1 . The liquid crystal composition, which will be described later, is less affected by, for example, abrupt pressure changes and shocks in the dropping device that occur during dropping, and can be stably dropped for a long period of time. Therefore, the yield of the liquid crystal display element 1 can be kept high.

In particular, in small liquid crystal display elements that are frequently used in smartphones, the optimal injection amount of the liquid crystal composition is small, so it is difficult to control the amount of deviation within a certain range. However, by using the liquid crystal composition as described above, it is possible to stably and accurately drop the optimum injection amount even in a small-sized liquid crystal display device.
After that, the sealing material is cured by ultraviolet (active energy ray) irradiation and heating. Depending on the type of sealing material, curing of the sealing material may be performed by only one of ultraviolet irradiation and heating.

[3] Liquid crystal layer forming step (first ultraviolet irradiation step)
Next, while applying a voltage to the liquid crystal composition, it is irradiated with ultraviolet rays. As a result, a polymer layer containing a polymer of the polymerizable monomer is formed at the interface with the electrode layers 5 and 6 of the liquid crystal composition, and the liquid crystal layer 4 is obtained. The formation of the polymer aligns the liquid crystal molecules vertically or imparts a pretilt angle to the liquid crystal molecules.
A voltage may be applied between the pixel electrode 13 and the common electrode (counter electrode), or may be applied between the CS electrode 14 and the common electrode.

The voltage applied to the liquid crystal composition in this step [3] is preferably 3 V or more, more preferably about 5 to 15 V. By applying a voltage of such a value to the liquid crystal composition, a sufficient pretilt angle can be imparted to the liquid crystal molecules. Even if a voltage exceeding the above upper limit is applied to the liquid crystal composition, no further increase in the effect can be expected.
The ultraviolet rays irradiated in this step [3] have a peak A1 at a wavelength of 313 nm (wavelength in the UVB region) and a peak A2 at a wavelength of 365 nm (wavelength in the UVA region). The ratio (X2/X1) of the intensity X2 of peak A2 to the intensity X1 of peak A1 is 5-70.

From the viewpoint of increasing the voltage holding ratio of the liquid crystal display element 1, the liquid crystal composition is irradiated with ultraviolet light having a relatively long wavelength of 365 nm over a long period of time to polymerize the polymerizable monomer at an appropriate polymerization rate. is preferred. However, when the irradiation time of the ultraviolet rays becomes long, the manufacturing efficiency of the liquid crystal display element 1 decreases. Therefore, in the present invention, the polymerization speed of the polymerizable monomer is increased by also irradiating ultraviolet rays having a wavelength of 313 nm, which is shorter than 365 nm. However, ultraviolet light with a wavelength of 313 nm is likely to cause alteration and deterioration of liquid crystal molecules. Therefore, the present inventors have made extensive studies and found that there is an appropriate intensity ratio (X2/X1 = 5 to 70) between the peak A1 at a wavelength of 313 nm and the peak A2 at a wavelength of 365 nm. I have completed my invention.

When X2/X1 is less than the above lower limit, the amount of ultraviolet rays with a wavelength of 313 nm becomes too large, causing alteration or deterioration of liquid crystal molecules and lowering the voltage holding ratio of the liquid crystal display element 1 . On the other hand, when X2/X1 exceeds the above upper limit, the amount of ultraviolet rays with a wavelength of 313 nm becomes too small, and the polymerization rate of the polymerizable monomer cannot be sufficiently increased, thereby reducing the manufacturing efficiency of the liquid crystal display element 1. At the same time, the residual amount of the polymerizable monomer increases, resulting in defective display.
X2/X1 may be 5 to 70, preferably about 5.3 to 60, more preferably about 5.7 to 50, particularly about 5.7 to 40. It is preferably about 5.7 to 30, and particularly preferably about 6.5 to 15. By setting X2/X1 within the above range, it is possible to manufacture a liquid crystal display element having a high voltage holding ratio in a relatively short time while preventing alteration and deterioration of liquid crystal molecules.

Specifically, the peak intensity X1 is preferably about 0.05 to 50 mW/cm ² and more preferably about 0.05 to 30 mW/cm ² . X1 is preferably 0.1 to 20 mW/cm ² in order to reduce the amount of residual polymerizable monomer and to manufacture the liquid crystal display element 1 having a high voltage holding ratio. Also, in order to give a good pretilt angle, X1 is preferably 5 to 30 mW/cm ² . On the other hand, the peak intensity X2 is preferably about 0.1 to 100 mW/cm ² and more preferably about 2 to 50 mW/cm ² . Thereby, the above effect can be further improved.
From the viewpoint of more reliably preventing alteration and deterioration of liquid crystal molecules, ultraviolet rays do not have a peak at wavelengths in the region of less than 313 nm (especially wavelengths in the UVC region), or even if they do have a peak. , the strength of which is preferably very small.

The UV irradiation time in step [3] can be defined in relation to the temperature of the liquid crystal layer 4 . That is, in this step [3], the ultraviolet irradiation is preferably performed until the temperature of the liquid crystal layer 4 rises by 0.1 to 5°C, more preferably until the temperature rises by 0.5 to 5°C. It is more preferable to carry out until the temperature rises by ~5°C. A rise in the temperature of the liquid crystal layer 4 within this range indicates that the polymerizable monomer has sufficiently polymerized.
Although the specific irradiation time depends on the type of ultraviolet light used, it is preferably about 10 to 7200 seconds, more preferably about 20 to 3600 seconds. In order to reduce the amount of the remaining polymerizable monomer and to manufacture the liquid crystal display element 1 having a high voltage holding ratio, the time is preferably about 600 to 7200 seconds. In order to give a good pretilt angle, the time is preferably about 10 to 1200 seconds, more preferably about 30 to 600 seconds. The ultraviolet irradiation time may be set to match the voltage application time, or may be set to be shorter than the voltage application time.

The irradiation amount of ultraviolet rays with a wavelength of 313 nm, which is irradiated under the above irradiation conditions, is preferably 1 mJ/cm ² to 50 J/cm ² , more preferably 10 mJ/cm ² to 20 J/cm ² . In order to give a good pretilt angle, it is preferably 1 mJ/cm ² to 10 J/cm ² , more preferably 10 mJ/cm ² to 3 J/cm ² . In order to reduce the amount of the remaining polymerizable monomer and to manufacture the liquid crystal display element 1 having a high voltage holding ratio, it is preferably 1 mJ/cm ² to 10 J/cm ² , more preferably 10 mJ/cm ² to 10 J/cm 2 . cm ² is even more preferred.
Also, the dose of ultraviolet rays with a wavelength of 365 nm is preferably 10 mJ/cm ² to 500 J/cm ² , more preferably 100 mJ/cm ² to 200 J/cm ² . The above irradiation dose can be appropriately adjusted according to the desired properties. Moreover, when irradiating an ultraviolet-ray, you may change intensity|strength.

When polymerization is performed with two substrates facing each other so as to be in contact with the liquid crystal composition, as in the present embodiment, at least the substrate positioned on the irradiation surface side must have an appropriate transmittance to ultraviolet rays. must have gender.
Moreover, although the voltage to be applied may be either direct current or alternating current, it is preferably alternating current. By applying an AC voltage, it is easy to obtain the liquid crystal layer 4 in which the liquid crystal molecules are well aligned.
The frequency of the applied alternating current is preferably about 10 Hz to 10 kHz, more preferably about 60 Hz to 10 kHz.

The temperature at which the ultraviolet rays are irradiated is preferably within a temperature range in which the liquid crystal state of the liquid crystal composition is maintained. A specific temperature is preferably about 10 to 50°C, more preferably about 15 to 45°C. Within this temperature range, the polymerization progresses while the polymerizable monomer diffuses moderately in the liquid crystal composition, so that the polymerization progresses well and the pretilt angle formation after the polymerization is good.
A metal halide lamp, a high-pressure mercury lamp, an extra-high pressure mercury lamp, a fluorescent tube, or the like can be used as a lamp for generating ultraviolet rays.
Moreover, the ultraviolet rays to be irradiated may be used after cutting a predetermined wavelength, if necessary.

The pretilt angle given to the liquid crystal molecules is preferably about 85 to 89.5°, more preferably about 87.5 to 89°. By adjusting the pretilt angle of the liquid crystal molecules within such a range, it is possible to sufficiently increase the response speed of the liquid crystal display element 1 and prevent a decrease in contrast.

[4] Monomer consumption step (second ultraviolet irradiation step)
Next, the liquid crystal layer 4 is irradiated with ultraviolet rays without applying a voltage to the liquid crystal composition. As a result, the polymerizable monomer remaining in the liquid crystal layer 4 is polymerized and consumed.

The ultraviolet rays irradiated in this step [4] have a peak B1 at a wavelength of 313 nm (wavelength in the UVB region) and a peak B2 at a wavelength of 365 nm (wavelength in the UVA region). Then, the ratio (Y2/Y1) of the intensity Y2 of the peak B2 to the intensity Y1 of the peak B1 is preferably 0.5 to 40, more preferably about 0.5 to 35, and more preferably 0.5 to 32 It is more preferable that it is a degree. By setting Y2/Y1 within the above range, the UV light with a wavelength of 313 nm becomes appropriate, and the remaining polymerizable monomers can be reduced more reliably and in a short time while preventing alteration and deterioration of liquid crystal molecules. As a result, it is possible to prevent or suppress the occurrence of display defects (burn-in) of the liquid crystal display element 1 while preventing a decrease in manufacturing efficiency of the liquid crystal display element 1 .

Specifically, the peak intensity Y1 is preferably about 0.05 to 50 mW/cm ² and more preferably about 0.05 to 30 mW/cm ² . Y1 is preferably 1 to 20 mW/cm ² in order to reduce the amount of the remaining polymerizable monomer and to manufacture the liquid crystal display element 1 having a high voltage holding ratio. On the other hand, the peak intensity Y2 is preferably about 0.1 to 100 mW/cm ² and more preferably about 2 to 50 mW/cm ² . Thereby, the above effect can be further improved.
From the viewpoint of more reliably preventing alteration and deterioration of liquid crystal molecules, ultraviolet rays do not have a peak at wavelengths in the region of less than 313 nm (especially wavelengths in the UVC region), or even if they do have a peak. , the strength of which is preferably very small.

The UV irradiation time in step [4] can also be defined in relation to the temperature of the liquid crystal layer 4 . That is, in this step [4], the ultraviolet irradiation is preferably performed until the temperature of the liquid crystal layer 4 rises by 1 to 20°C, more preferably until the temperature rises by 2 to 15°C, and is increased by 3 to 10°C. It is more preferable to carry out until the A rise in the temperature of the liquid crystal layer 4 within this range indicates that the remaining polymerizable monomer has been sufficiently consumed.
Although the specific irradiation time of ultraviolet rays depends on the type of ultraviolet rays used, it is preferably about 1 to 150 seconds, more preferably about 30 to 100 seconds.

The temperature at which the ultraviolet rays are irradiated is preferably within a temperature range in which the liquid crystal state of the liquid crystal composition is maintained. A specific temperature is preferably about 10 to 50°C, more preferably about 15 to 45°C. Within this temperature range, the polymerization progresses while the polymerizable monomer diffuses moderately in the liquid crystal composition, so that the polymerization progresses satisfactorily and the remaining polymerizable monomer can be sufficiently consumed.
A metal halide lamp, a high-pressure mercury lamp, an extra-high pressure mercury lamp, a fluorescent tube, or the like can be used as a lamp for generating ultraviolet rays.
Moreover, the ultraviolet rays to be irradiated may be used by cutting a predetermined wavelength according to liquid requirements.

Through the steps described above, the liquid crystal display element 1 is obtained.
In the [2] assembly process, a vacuum injection method may be used instead of the drop injection (ODF) method. For example, in the vacuum injection method, first, a sealing material is screen-printed along at least one edge of the active matrix substrate AM and the color filter substrate CF so as to leave an injection port. After that, the two substrates AM and CF are bonded together, and the sealing material is cured by at least one of heating and ultraviolet irradiation. Next, the liquid crystal composition is injected under vacuum into the space partitioned by the sealing material between the two substrates AM and CF through the injection port, and then the injection port is sealed. After that, the process shifts to [3] liquid crystal layer forming step and [4] monomer consuming step.
In another configuration example, the intensity ratio between the peak at a wavelength of 313 nm and the peak at a wavelength of 365 nm in the liquid crystal layer forming process is the relationship in the monomer consuming process, while the peak at a wavelength of 313 nm and the peak at a wavelength of 365 nm in the monomer consuming process. may be used as the relationship in the liquid crystal layer forming step. In this case, specific values of intensity of each peak and irradiation time of ultraviolet rays are set so that the liquid crystal display element 1 to be obtained can be provided with the desired voltage holding ratio and pretilt angle. Even in such a configuration, the same functions and effects as those described above can be obtained.
Further, when ultraviolet irradiation is performed at the intensity ratio of the present invention in either step [3] or step [4], in the remaining step, the peak intensity at a wavelength of 313 nm, the peak intensity at a wavelength of 365 nm, and these Ultraviolet rays whose intensity ratio is outside the scope of the present invention may be irradiated. Alternatively, in addition to the above steps [3] and [4], in an additional step, the peak intensity at a wavelength of 313 nm, the peak intensity at a wavelength of 365 nm, and the intensity ratio thereof are outside the scope of the present invention. good too.

(Liquid crystal composition)
The liquid crystal composition used to form the liquid crystal layer 4 contains liquid crystal molecules and at least one polymerizable monomer.
As described above, when at least one of the active matrix substrate AM and the color filter substrate CF is arranged in direct contact with the liquid crystal layer 4 (liquid crystal composition) without an alignment film interposed therebetween, at least one Preferably, the polymerizable monomer of (1) contains a polymerizable monomer A (orientation aid) having at least one adsorption group. Also, the liquid crystal composition preferably contains one or two or more of such polymerizable monomers A.

((polymerizable monomer A))
The polymerizable monomer A is a member (electrode (e.g., ITO), substrate (e.g., glass substrate, acrylic substrate, transparent substrate, flexible substrate, etc.) that directly contacts the liquid crystal layer containing the liquid crystal composition, resin layer (e.g., color filter, alignment film, overcoat layer, etc.), insulating film (e.g., inorganic material film, SiNx, etc.)), and has a function of inducing homeotropic alignment of liquid crystal molecules contained in the liquid crystal layer 4. there is

The polymerizable monomer A comprises a polymerizable group for polymerization, a mesogenic group similar to liquid crystal molecules, an adsorptive group capable of interacting with a member that is in direct contact with the liquid crystal layer, and an orientation-inducing group that induces the orientation of the liquid crystal molecules. It is preferred to have
It is preferable that the mesogenic group is bonded to the adsorptive group and the orientation-inducing group, and the polymerizable group is substituted directly or optionally through a spacer group on the mesogenic group, the adsorptive group and the orientation-inducing group. In particular, the polymerizable group preferably substitutes the mesogenic group while being incorporated into the adsorptive group.
In the following chemical formulas, * at the left end and * at the right end represent a bond.

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

In the formula, R ^AK1 represents a linear or branched alkyl group having 1 to 20 carbon atoms. provided that one or two or more non-adjacent -CH ₂ - in the alkyl group are each independently -CH=CH-, -C≡C-, -O-, -CO-, -COO- or It may be substituted with -OCO-, and one or more hydrogen atoms in the alkyl group may each independently be substituted with a halogeno group.

R ^AK1 preferably represents a linear or branched alkyl group having 1 to 20 carbon atoms, more preferably a linear alkyl group having 1 to 20 carbon atoms. More preferably, it represents an alkyl group having 1 to 8 carbon atoms.
In addition, one or two or more -CH ₂ - which are not adjacent to each other in the alkyl group are each independently selected from -CH=CH-, -C≡C-, -O-, -C≡C-, -O-, so that the oxygen atoms are not directly adjacent to each other. It may be substituted with -CO-, -COO- or -OCO-.

Furthermore, hydrogen atoms in the alkyl group may be substituted with fluorine atoms or chlorine atoms, or may be substituted with fluorine atoms.
From the viewpoint of imparting so-called amphiphilicity to the polymerizable monomer A with respect to the liquid crystal layer, the orientation-inducing group is preferably bonded to the mesogenic group.

"polymerizable group"
The polymerizable group is represented by P ^AP1 - and is preferably bonded to the mesogenic group via -Sp ^AP1 - (single bond or spacer group).
^PAP1 is preferably a group selected from the group represented by the following general formulas (AP-1) to (AP-9).

In the formula, R ^AP1 and R ^AP2 each independently represent a hydrogen atom, an alkyl group having 1 to 5 carbon atoms or a halogenated alkyl group having 1 to 10 carbon atoms. However, one or more —CH ₂ — in the alkyl group may be substituted with —O— or —CO— so that the oxygen atoms are not directly adjacent to each other, and one or more —CH 2 — in the alkyl group Each of the above hydrogen atoms may be independently substituted with a halogen atom or a hydroxyl group.
W ^AP1 represents a single bond, -O-, -COO- or -CH ₂ -.
^tAP1 represents 0, 1 or 2;

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

Sp ^AP1 preferably represents a single bond or a linear or branched alkylene group having 1 to 20 carbon atoms, more preferably a single bond or a linear alkylene group having 1 to 20 carbon atoms. It preferably represents a single bond or a linear alkylene group having 2 to 10 carbon atoms.
In Sp ^AP1 , one or two or more non-adjacent -CH ₂ - in the alkylene group are independently -CH=CH-, -C≡C-, -C≡C-, so that oxygen atoms are not directly adjacent to each other. It may be substituted with -O-, -CO-, -COO- or -OCO-.

In the polymerizable monomer A, the number of P ^AP1 -Sp ^AP1 - is preferably 1 or more and 5 or less, more preferably 1 or more and 4 or less, further preferably 2 or more and 4 or less, 2 or 3 is particularly preferred, and 2 is most preferred.
A hydrogen atom in P ^AP1 -Sp ^AP1 - may be substituted with a polymerizable group, an adsorptive group and/or an orientation-inducing group.

P ^AP1 -Sp ^AP1 - may be attached to a polymerizable group, a mesogenic group, an adsorptive group and/or an orientation-inducing group.
In addition, P ^AP1 -Sp ^AP1 - preferably binds to a mesogenic group, an adsorptive group or an orientation-inducing group, and more preferably binds to a mesogenic group or an adsorptive group.
When a plurality of P ^AP1 and/or Sp ^AP1 - are present in the molecule, they may be the same or different.

"Mesogenic group"
A mesogenic group refers to a group with a rigid portion, such as a group with one or more cyclic groups, preferably a group with 2 to 4 cyclic groups, and 3 to 4 cyclic groups. groups are more preferred. In addition, the cyclic group may be connected by a connecting group as necessary. The mesogenic group preferably has a skeleton similar to that of liquid crystal molecules (liquid crystal compounds) used in the liquid crystal layer.
As used herein, the term "cyclic group" refers to an atomic group in which constituent atoms are cyclically bonded, and includes a carbocyclic ring, a heterocyclic ring, a saturated or unsaturated cyclic structure, a monocyclic structure, a bicyclic structure, Including polycyclic structures, aromatics, non-aromatics, and the like.
The cyclic group may also contain at least one heteroatom and may be further substituted with at least one substituent (halogeno group, polymerizable group, organic group (alkyl, alkoxy, aryl, etc.). Ring If the formula group is monocyclic, the mesogenic group preferably contains two or more monocyclic rings.

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

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

A ^AL1 and A ^AL2 each independently represent a divalent cyclic group.
One or more hydrogen atoms in Z ^AL1 , A ^AL1 and A ^AL2 are each independently substituted with a halogeno group, an adsorptive group described later, P ^AP1 -Sp ^AP1 - or a monovalent organic group good too.
When multiple Z ^AL1 and A ^AL1 are present in the molecule, they may be the same or different.
m ^AL1 represents an integer of 1-5.

In the general formula (AL), Z ^AL1 is preferably a single bond or an alkylene group having 2 to 20 carbon atoms, more preferably a single bond or an alkylene group having 2 to 10 carbon atoms. , -(CH ₂ ) ₂ - or -(CH ₂ ) ₄ - is more preferred. One or more non-adjacent -CH ₂ - in an alkylene group may be replaced with -O-, -COO- or -OCO- such that the oxygen atoms are not directly adjacent.
Furthermore, when the purpose is to increase the linearity of the rod-like molecule, Z ^AL1 may be a single bond in which the rings are directly connected, or a single bond in which the number of atoms directly connecting the rings is an even number. Morphology is preferred. For example, in the case of -CH ₂ -CH ₂ COO-, the number of atoms directly connecting rings is four.

In general formula (AL), A ^AL1 and A ^AL2 each independently represent a divalent cyclic group. Divalent cyclic groups include 1,4-phenylene group, 1,4-cyclohexylene group, 1,4-cyclohexenyl group, tetrahydropyran-2,5-diyl group, 1,3-dioxane-2, 5-diyl group, tetrahydrothiopyran-2,5-diyl group, thiophene-2,5-diyl group, 1,4-bicyclo(2.2.2)octylene group, decahydronaphthalene-2,6-diyl group , pyridine-2,5-diyl group, pyrimidine-2,5-diyl group, pyrazine-2,5-diyl group, thiophene-2,5-diyl group-, 1,2,3,4-tetrahydronaphthalene-2 ,6-diyl group, 2,6-naphthylene group, phenanthrene-2,7-diyl group, 9,10-dihydrophenanthrene-2,7-diyl group, 1,2,3,4,4a,9,10a- octahydrophenanthrene-2,7-diyl group, 1,4-naphthylene group, benzo[1,2-b:4,5-b']dithiophene-2,6-diyl group, benzo[1,2-b: 4,5-b′]diselenophen-2,6-diyl group, [1]benzothieno[3,2-b]thiophene-2,7-diyl group, [1]benzoselenopheno[3,2-b]selenophene -2,7-diyl group and fluorene-2,7-diyl group, preferably one selected from the group consisting of 1,4-phenylene group, 1,4-cyclohexylene group, 2,6- A naphthylene group or a phenanthrene-2,7-diyl group is more preferred, and a 1,4-phenylene group or 1,4-cyclohexylene group is even more preferred.

In addition, these groups may be unsubstituted or substituted with a substituent. This substituent is preferably a fluorine atom or an alkyl group having 1 to 8 carbon atoms. Furthermore, alkyl groups may be substituted with fluorine atoms or hydroxyl groups.
Also, one or more hydrogen atoms in the cyclic group may be substituted with a halogeno group, an adsorptive group, P ^AP1 —Sp ^AP1 — or a monovalent organic group.

In the general formula (AL), the monovalent organic group is a group having a chemical structure formed by forming an organic compound in the form of a monovalent group, and is formed by removing one hydrogen atom from the organic compound. A group of atoms.
Examples of such monovalent organic groups include alkyl groups having 1 to 15 carbon atoms, alkenyl groups having 2 to 15 carbon atoms, alkoxy groups having 1 to 14 carbon atoms, and alkenyloxy groups having 2 to 15 carbon atoms. and the like, preferably an alkyl group having 1 to 15 carbon atoms or an alkoxy group having 1 to 14 carbon atoms, an alkyl group having 1 to 8 carbon atoms or an alkoxy group having 1 to 8 carbon atoms is more preferably an alkyl group having 1 to 5 carbon atoms or an alkoxy group having 1 to 4 carbon atoms, an alkyl group having 1 to 3 carbon atoms or an alkyl group having 1 to 2 carbon atoms An alkoxy group is particularly preferred, and an alkyl group having 1 or 2 carbon atoms or an alkoxy group having 1 carbon atom is most preferred.
In addition, one or two or more non-adjacent -CH ₂ - groups in the alkyl group, alkenyl group, alkoxy group and alkenyloxy group may be substituted with -O-, -COO- or -OCO-. Furthermore, the above-mentioned monovalent organic group may have a role as an orientation-inducing group, which will be described later.
In general formula (AL), m ^AL1 is preferably an integer of 1 to 4, more preferably an integer of 1 to 3, and even more preferably 2 or 3.

Preferred forms of the mesogenic group include the following formulas (me-1) to (me-44).

General formula (AL) is a structure in which two hydrogen atoms are eliminated from these compounds.
In these formulas (me-1) to (me-44), one or more hydrogen atoms in the cyclohexane ring, benzene ring or naphthalene ring are each independently a halogeno group, P ^AP1 -Sp ^AP1 -, a monovalent organic group (eg, an alkyl group having 1 to 15 carbon atoms, an alkoxy group having 1 to 14 carbon atoms), an adsorptive group, or an orientation-inducing group.

Among the above mesogenic groups, preferred forms are formulas (me-8) to (me-44), and more preferred forms are formulas (me-8) to (me-10), formulas (me-12) to (me-18), formulas (me-22) to (me-24), formulas (me-26) to (me-27) and formulas (me-29) to (me-44), more preferred forms is the formula (me-12), (me-14), (me-16), (me-22) ~ (me-24), (me-29), (me-34), (me-36) ~ (me-37), (me-42) ~ (me-44).

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

In the formulas, X ^AL101 to X ^AL118 and X ^AL201 to X ^AL214 each independently represent a hydrogen atom, a halogeno group, P ^APl —Sp ^APl —, an adsorptive group to be described later, or the orientation-inducing group.
Ring A ^AL11 , Ring A ^AL12 and Ring A ^AL21 each independently represent a cyclohexane ring or a benzene ring.
Any one or more of X ^AL101 to X ^AL118 and X ^AL201 to X ^AL214 is substituted with an adsorptive group described below.
Any one or more of X ^AL101 to X ^AL118 and X ^AL201 to X ^AL214 are substituted with the orientation-inducing group.
The adsorptive group and the orientation-inducing group described later may be substituted with P ^AP1 -Sp ^AP1 -.
General formula (AL-1) or general formula (AL-2) has one or more P ^AP1 -Sp ^APl - in its molecule.

In general formula (AL-1), ^XAL101 is preferably the orientation-inducing group.
In general formula (AL-1), it is preferable that at least one of X ^AL109 , X ^AL110 and X ^AL111 is an adsorptive group described later, and both X ^AL109 and X ^AL110 are adsorptive groups described later, or X ^AL110 is described later. and ^XAL110 is more preferably an adsorptive group described later.
In general formula (AL-1), at least one of X ^AL109 , X ^AL110 and X ^AL111 is preferably P ^AP1 -Sp ^AP1 - or one having a polymerizable site in the structure, among the adsorptive groups described later. , X ^AL109 and/or X ^AL111 are more preferably P ^AP1 -Sp ^AP1 -.
In general formula (AL-1), one or two of X ^AL104 to X ^AL108 and X ^AL112 to X ^AL116 are each independently an alkyl group having 1 to 5 carbon atoms and an alkoxy group having 1 to 5 carbon atoms. or a halogeno group, more preferably an alkyl group having 1 to 3 carbon atoms or a fluorine atom. In particular, X ^AL105 , X ^AL106 or X ^AL107 are each independently preferably an alkyl group having 1 to 3 carbon atoms or a fluorine atom.

In general formula (AL-2), X ^AL201 is preferably the orientation-inducing group.
In general formula (AL-2), it is preferable that at least one of X ^AL207 , X ^AL208 and X ^AL209 is an adsorptive group described later, and both X ^AL207 and X ^AL208 are adsorptive groups described later, or X ^AL208 is described later. is more preferably an adsorptive group, and ^XAL208 is more preferably an adsorptive group described later.
In general formula (AL-2), at least one of X ^AL207 , X ^AL208 and X ^AL209 is preferably P ^AP1 -Sp ^AP1 - or one having a polymerizable site in the structure, among the adsorptive groups described later. , X ^AL207 and/or X ^AL209 are more preferably P ^AP1 -Sp ^AP1 -.
In general formula (AL-2), one or two of X ^AL202 to X ^AL206 and X ^AL210 to X ^AL214 are each independently an alkyl group having 1 to 5 carbon atoms and an alkoxy group having 1 to 5 carbon atoms. or a halogeno group, more preferably an alkyl group having 1 to 3 carbon atoms or a fluorine atom. In particular, X ^AL204 , X ^AL205 or X ^AL206 are each independently preferably an alkyl group having 1 to 3 carbon atoms or a fluorine atom.

"adsorption group"
The adsorptive group is a group having a role of adsorbing an adsorbent, which is a layer in contact with the liquid crystal composition, such as a substrate, film, or electrode.
Adsorption is generally classified into chemisorption, in which a chemical bond (covalent bond, ionic bond, or metallic bond) is formed to adsorb between an adsorbent and an adsorbate, and physical adsorption other than chemisorption. In the present specification, adsorption may be either chemical adsorption or physical adsorption, but physical adsorption is preferred. Therefore, the adsorptive group is preferably a group capable of physically adsorbing the adsorbent, and more preferably a group capable of bonding with the adsorbent by intermolecular force.
The form of bonding with the adsorbent by intermolecular forces includes forms due to interactions such as permanent dipoles, permanent quadrupoles, dispersion forces, charge transfer forces, and hydrogen bonds.
A preferred form of the adsorptive group includes a form capable of binding to the adsorbent through hydrogen bonding. In this case, the adsorptive group may play the role of either a proton donor or an acceptor that mediates hydrogen bonding, or may play both roles.

The adsorptive group is preferably a group containing a polar element having an atomic group in which a carbon atom and a heteroatom are linked (hereinafter, "adsorptive group" is also referred to as "polar group"). As used herein, a polar element refers to an atomic group in which a carbon atom and a heteroatom are directly linked.
The heteroatom is preferably at least one selected from the group consisting of N, O, S, P, B and Si, and at least one selected from the group consisting of N, O and S. is more preferred, at least one selected from the group consisting of N and O is more preferred, and O is particularly preferred.

In the polymerizable monomer A, the valence of the polar element is not particularly limited, such as monovalent, divalent, or trivalent, and the number of polar elements in the adsorptive group is also not particularly limited.
The polymerizable monomer A preferably has 1 to 8 adsorptive groups in one molecule, more preferably 1 to 4 adsorptive groups, even more preferably 1 to 3 adsorptive groups. .
The adsorbing groups exclude polymerizable groups and orientation-inducing groups, but the structure in which the hydrogen atom in the adsorbing group is replaced with P ^AP1 -Sp ^AP1 - and the hydrogen atom in P ^AP1 -Sp ^AP1 - is -OH. The structure substituted with is included in the adsorptive group.

Adsorptive groups contain one or more polar elements and are broadly classified into cyclic group types and chain group types.
Cyclic radical types are those forms containing cyclic radicals with cyclic structures containing polar elements in their structures, and chain radical types are those containing cyclic radicals with cyclic structures containing polar elements in their structures. It is a form that does not contain
A chain group type is a form having a polar element in a linear or branched chain group, and may have a cyclic structure in which a part thereof does not contain a polar element.

A cyclic group-type adsorptive group means a form having a structure containing at least one polar element in a cyclic atomic arrangement.
In addition, in this specification, a cyclic group is as having mentioned above. Therefore, the cyclic group-type adsorptive group only needs to contain a cyclic group containing a polar element, and the adsorptive group as a whole may be branched or linear.

On the other hand, a chain group-type adsorbing group is a structure that does not contain a cyclic atomic arrangement containing a polar element in the molecule and contains at least one polar element in a linear atomic arrangement (which may be branched). means a form having
In the present specification, the chain group refers to an atomic group in which the constituent atoms are linearly (may be branched) and does not contain a cyclic atomic arrangement in the structural formula. base. In other words, a chain group refers to a straight or branched chain aliphatic group, which may contain either saturated or unsaturated bonds.
Chain groups thus include, for example, alkyls, alkenyls, alkoxys, esters, ethers or ketones. The hydrogen atoms in these groups may be substituted with at least one substituent (reactive functional group (vinyl group, acryl group, methacryl group, etc.), chain organic group (alkyl, cyano, etc.)). . Also, the chain group may be linear or branched.

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

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

A hydrogen atom in the adsorptive group may be substituted with a polymerizable group.
Specific examples of the polar element include a polar element containing an oxygen atom (hereinafter referred to as an oxygen-containing polar element), a polar element containing a nitrogen atom (hereinafter referred to as a nitrogen-containing polar element), and a polar element containing a phosphorus atom (hereinafter referred to as a phosphorus-containing polar element). element), a polar element containing a boron atom (hereinafter referred to as a boron-containing polar element), a polar element containing a silicon atom (hereinafter referred to as a silicon-containing polar element) or a polar element containing a sulfur atom (hereinafter referred to as a sulfur-containing polar element). . From the viewpoint of adsorption capacity, the polar element is preferably a nitrogen-containing polar element, a nitrogen-containing polar element or an oxygen-containing polar element, more preferably an oxygen-containing polar element.

The oxygen-containing polar element includes at least one group selected from the group consisting of a hydroxyl group, an alkylol group, an alkoxy group, a formyl group, a carboxyl group, an ether group, a carbonyl group, a carbonate group and an ester group, or the group is a carbon It is preferably an atom-linked group.
The nitrogen-containing polar element includes at least one group selected from the group consisting of a cyano group, a primary amino group, a secondary amino group, a tertiary amino group, a pyridyl group, a carbamoyl group and a ureido group; It is preferably an atom-linked group.
The phosphorus-containing polar element is preferably at least one group selected from the group consisting of a phosphinyl group and a phosphoric acid group, or a group in which the group is linked to a carbon atom.

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

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

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

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

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

In the formula, R ^at1 represents an alkyl group having 1 to 5 carbon atoms.
Z ^at1 represents a single bond, a linear or branched alkylene group having 1 to 15 carbon atoms, or a linear or branched alkenylene group having 2 to 18 carbon atoms. However, —CH ₂ — in an alkylene group or alkenylene group may be substituted with —O—, —COO—, —C(═O)—, or —OCO— so that an oxygen atom is not directly adjacent.
X ^at1 represents an alkyl group having 1 to 15 carbon atoms. However, -CH ₂ - in the alkyl group may be substituted with -O-, -COO-, -C(=O)-, or -OCO- so that the oxygen atom is not directly adjacent.

式中、Ｒ^ａｔ、Ｒ^ｂｔ、Ｒ^ｃｔ及びＲ^ｄｔは、それぞれ独立して、水素原子又は炭素原子数１～５のアルキル基を表す。 The nitrogen-containing chain group preferably contains any one of the following groups.

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

式中、Ｓｐ^ＡＴ１は、単結合、炭素原子数１～２５の直鎖状若しくは分岐状のアルキレン基を表す。ただし、アルキレン基中の水素原子は、－ＯＨ、－ＣＮ、－Ｗ^ＡＴ１－Ｚ^ＡＴ１又はＰ^ＡＰ１－Ｓｐ^ＡＰ１－で置換されてもよく、アルキレン基中の－ＣＨ_２－は、酸素原子が直接結合しないように環式基、－Ｏ－、－ＣＯＯ－、－Ｃ（＝Ｏ）－、－ＯＣＯ－、－ＣＨ＝ＣＨ－で置換されてもよい。
Ｗ^ＡＴ１は、単結合又は下記一般式（ＷＡＴ１）又は（ＷＡＴ２）を表す。
Ｚ^ＡＴ１は、極性要素を含む１価の基を表す。ただし、Ｚ^ＡＴ１中の水素原子は、－ＯＨ、－ＣＮ又はＰ^ＡＰ１－Ｓｐ^ＡＰ１－で置換されてもよい。 The adsorptive group is preferably a group represented by the following general formula (AT).

In the formula, Sp ^AT1 represents a single bond or a linear or branched alkylene group having 1 to 25 carbon atoms. However, a hydrogen atom in the alkylene group may be substituted with —OH, —CN, —W ^AT1 —Z ^AT1 or P ^AP1 —Sp ^AP1 —, and —CH ₂ — in the alkylene group is directly It may be substituted with a cyclic group, -O-, -COO-, -C(=O)-, -OCO-, -CH=CH- so as not to bond.
^WAT1 represents a single bond or the following general formula (WAT1) or (WAT2).
Z ^AT1 represents a monovalent group containing a polar element. However, a hydrogen atom in Z ^AT1 may be replaced with —OH, —CN or P ^AP1 —Sp ^AP1 —.

（式中、Ｓｐ^ＷＡＴ１及びＳｐ^ＷＡＴ２は、それぞれ独立して、単結合、炭素原子数１～２５の直鎖状若しくは分岐状のアルキレン基を表し、アルキレン基中の水素原子は、－ＯＨ、－ＣＮ又はＰ^ＡＰ１－Ｓｐ^ＡＰ１－で置換されてもよく、アルキレン基中の－ＣＨ_２－は、酸素原子が直接結合しないように環式基、－Ｏ－、－ＣＯＯ－、－Ｃ（＝Ｏ）－、－ＯＣＯ－又は－ＣＨ＝ＣＨ－で置換されてもよい。）

(Wherein, Sp ^WAT1 and Sp ^WAT2 each independently represent a single bond, a linear or branched alkylene group having 1 to 25 carbon atoms, and the hydrogen atoms in the alkylene group are —OH, — It may be substituted with CN or P ^AP1 -Sp ^AP1 -, and -CH ₂ - in the alkylene group is a cyclic group, -O-, -COO-, -C (=O )-, -OCO- or -CH=CH- may be substituted.)

Sp ^AT1 , Sp ^WAT1 and Sp ^WAT2 each independently preferably represents a single bond or a linear or branched alkylene group having 1 to 20 carbon atoms, and a single bond or a linear number of carbon atoms It more preferably represents an alkylene group of 1 to 20, and more preferably represents a single-bonded or linear alkylene group of 2 to 10 carbon atoms.
In Sp ^AT1 , Sp ^WAT1 and Sp ^WAT2 , one or two or more non-adjacent —CH ₂ — in the alkylene group are each independently —CH═CH so that the oxygen atoms are not directly bonded. -, -C≡C-, -O-, -CO-, -COO- or -OCO-.
Further, hydrogen atoms in Sp ^AT1 and Sp ^WAT1 may each independently be replaced with -W ^AT1 -Z ^AT1 or P ^AP1 -Sp ^AP1 -.

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

In the formula, Sp ^ZAT11 and Sp ^ZAT12 each independently represent a single bond or a linear or branched alkylene group having 1 to 25 carbon atoms. However, the hydrogen atom in the alkylene group may be substituted with —OH, —CN, —Z ^ZAT11 —R ^ZAT11 or P ^AP1 —Sp ^AP1 —, and —CH ₂ — in the alkylene group is directly attached to the oxygen atom. It may be substituted with non-adjacent cyclic groups -O-, -COO-, -C(=O)-, -OCO- or -CH=CH-.
Z ^ZAT11 represents a group containing a polar element.
The structure represented by the ring containing Z ^ZAT12 in general formula (ZAT1-2) represents a 5- to 7-membered ring.
A hydrogen atom in Z ^{2 ZAT11} and Z ^{2 ZAT12} may be replaced with —OH, —CN or P ^AP1 —Sp ^AP1 —.

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

As the group represented by the general formula (ZAT1-1), groups represented by the following general formulas (ZAT1-1-1) to (ZAT1-1-30) are preferable.

In the formula, a hydrogen atom bonded to a carbon atom may be replaced with -OH, -CN or P ^AP1 -Sp ^AP1 -.
Sp ^ZAT11 represents a single bond or a linear or branched alkylene group having 1 to 25 carbon atoms. However, the hydrogen atom in the alkylene group may be substituted with —OH, —CN, —Z ^ZAT11 —R ^ZAT11 or P ^AP1 —Sp ^AP1 —, and —CH ₂ — in the alkylene group is directly attached to the oxygen atom. It may be substituted with non-adjacent cyclic groups -O-, -COO-, -C(=O)-, -OCO- or -CH=CH-.

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

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

In the formula, a hydrogen atom bonded to a carbon atom may be substituted with a halogen atom, -OH, -CN or P ^AP1 -Sp ^AP1 -.
Sp ^ZAT11 represents a linear or branched alkylene group having 1 to 25 carbon atoms. However, a hydrogen atom in the alkylene group may be substituted with —OH, —CN or P ^AP1 —Sp ^AP1 —, and —CH ₂ — in the alkylene group is a cyclic group such that an oxygen atom is not directly adjacent. , -O-, -COO-, -C(=O)-, -OCO-, -CH=CH- or -Z ^ZAT11 -.

The groups represented by the general formula (ZAT1-1) include the following groups.

In the formula, R ^tc represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, or P ^AP1 -Sp ^AP1 -. However, a hydrogen atom in the alkyl group may be substituted with —OH, —CN or P ^AP1 —Sp ^AP1 —, and —CH ₂ — in the alkyl group is a cyclic group such that an oxygen atom is not directly adjacent. , -O-, -COO-, -C(=O)-, -OCO-, -CH=CH- or -Z ^ZAT11 -.
A hydrogen atom in the molecule may be replaced with P ^AP1 -Sp ^AP1 -.
* represents a bond.

The polymerizable monomer A preferably has a form in which the polar element contained in the adsorptive group or the polar element contained in the polymerizable group is localized. The adsorptive group is an important structure for vertically aligning the liquid crystal molecules, and the adjoining adsorptive group and the polymerizable group provide better alignment, and the liquid crystal composition also has a favorable structure. It is soluble.
Specifically, the polymerizable monomer A preferably has a form having a polymerizable group and an adsorptive group on the same ring of the mesogenic group. Such forms include a form in which one or more polymerizable groups and one or more adsorptive groups are respectively bonded on the same ring, and a form in which at least one of one or more polymerizable groups or at least one of one or more adsorptive groups are combined. Among them, a form in which one is bonded to the other and has a polymerizable group and an adsorptive group on the same ring is included.
Further, in this case, the hydrogen atom in the spacer group possessed by the polymerizable group may be substituted with the adsorptive group, or the hydrogen atom in the adsorptive group may be substituted with the polymerizable group via the spacer group. good.

The polymerizable monomer A (spontaneous alignment compound) is preferably a compound represented by the following general formula (SAL).

In the formula, a hydrogen atom bonded to a carbon atom is a linear or branched alkyl group having 1 to 25 carbon atoms, —OH, —CN, —Sp ^AT1 —W ^AT1 —Z ^AT1 or P ^AP1 —Sp ^AP1 - may be substituted. However, a hydrogen atom in the alkyl group may be substituted with —OH, —CN, —Sp ^AT1 —W ^AT1 —Z ^AT1 or P ^AP1 —Sp ^AP1 —, and —CH ₂ — in the alkyl group may be substituted with oxygen It may be substituted with a cyclic group, -O-, -COO-, -C(=O)-, -OCO- or -CH=CH- so that the atoms are not directly bonded.
R ^AK1 has the same meaning as R ^AK1 in general formula (AK).

A ^AL1 and A ^AL2 each independently represent the same meaning as A ^AL1 and A ^AL2 in general formula (AL).
Z ^AL1 has the same meaning as Z ^AL1 in general formula (AL).
m ^AL1 has the same meaning as m ^AL1 in general formula (AL).
Sp ^AT1 has the same meaning as Sp ^AT1 in general formula (AT).
W ^AT1 has the same meaning as W ^AT1 in general formula (AT).
Z ^AT1 has the same meaning as Z ^AT1 in general formula (AT).

Compounds represented by the general formula (SAL) are preferably compounds represented by the following formulas (SAL-1.1) to (SAL-2.10).

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

((polymerizable monomer B))
At least one polymerizable monomer may further contain a polymerizable monomer B that does not have an adsorptive group (polar group). Polymerizable monomer B is preferably a compound represented by the following general formula (P). Also, the liquid crystal composition preferably contains one or two or more of such polymerizable monomers B.

In formula (P), R ^p1 represents a hydrogen atom, a fluorine atom, a cyano group, an alkyl group having 1 to 15 carbon atoms, or -Sp ^p2 -P ^p2 . provided that one or more —CH ₂ — present in an alkyl group are each independently —CH═CH—, —C≡C—, —O—, —CO—, —COO—, or -OCO- may be substituted, but two or more adjacent -CH ₂ - are not simultaneously substituted with -O-. Also, one or more hydrogen atoms present in the alkyl group may each independently be substituted with a cyano group, a fluorine atom or a chlorine atom.

（式中、Ｒ^ｐ１１及びＲ^ｐ１２は、それぞれ独立して、水素原子、炭素原子数１～５のアルキル基又は炭素原子数１～５のハロゲン化アルキル基を表し、Ｗ^ｐ１１は、単結合、－Ｏ－、－ＣＯＯ－又はメチレン基を表し、ｔ^ｐ１１は、０、１又は２を表すが、分子内にＲ^ｐ１１、Ｒ^ｐ１２、Ｗ^ｐ１１及び／又はｔ^ｐ１１が複数存在する場合、それらは同一であっても異なってもよい。） P ^p1 and P ^p2 each independently represent any one of the following general formulas (P ^p1 -1) to (P ^p1 -9).

(Wherein, R ^p11 and R ^p12 each independently represent a hydrogen atom, an alkyl group having 1 to 5 carbon atoms or a halogenated alkyl group having 1 to 5 carbon atoms, W ^p11 is a single bond, -O-, -COO- or a methylene group, and t ^p11 represents 0, 1 or 2, but when multiple R ^p11 , R ^p12 , W ^p11 and/or t ^p11 are present in the molecule, they are may be the same or different).

Sp ^p1 and Sp ^p2 each independently represent a single bond or a spacer group.
Z ^p1 and Z ^p2 are each independently a single bond, —O—, —S—, —CH ₂ —, —OCH ₂ —, —CH ₂ O—, —CO—, —C ₂ H ₄ —, -COO-, -OCO-, -OCOOCH ₂ -, -CH ₂ OCOO-, -OCH ₂ CH ₂ O-, -CO-NR ^ZP1 -, -NR ^ZP1 -CO-, -SCH ₂ -, -CH ₂ S -, -CH=CR ^ZP1 -COO-, -CH=CR ^ZP1 -OCO-, -COO-CR ^ZP1 =CH-, -OCO-CR ^ZP1 =CH-, -COO-CR ^ZP1 =CH-COO-, - COO-CR ^ZP1 =CH-OCO-, -OCO-CR ^ZP1 =CH-COO-, -OCO-CR ^ZP1 =CH-OCO-, -(CH ₂ ) ₂ -COO-, -(CH ₂ ) ₂ -OCO -, -OCO-(CH ₂ ) ₂ -, -(C=O)-O-(CH ₂ ) ₂ -, -CH=CH-, -CF=CF-, -CF=CH-, -CH=CF -, -CF ₂ -, -CF ₂ O-, -OCF ₂ -, -CF ₂ CH ₂ -, -CH ₂ CF ₂ -, -CF ₂ CF ₂ - or -C≡C- (wherein R ^ZP1 each independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, but when multiple R ^ZP1 are present in the molecule, they may be the same or different).

A ^p1 , A ^p2 and A ^p3 are each independently
(a ^p ) 1,4-cyclohexylene group (one —CH ₂ — or two or more non-adjacent —CH ₂ — present in this group may be substituted with —O—; )
(b ^p ) 1,4-phenylene group (one —CH= or two or more non-adjacent —CH= present in this group may be substituted with —N=) and ( c ^p ) naphthalene-2,6-diyl group, naphthalene-1,4-diyl group, naphthalene-1,5-diyl group, 1,2,3,4-tetrahydronaphthalene-2,6-diyl group, decahydro naphthalene-2,6-diyl group, phenanthrene-2,7-diyl group or anthracene-2,6-diyl group (one -CH= present in these groups or two or more non-adjacent - CH= may be replaced with -N=.)
A group selected from the group consisting of (the group (a ^p ), the group (b ^p ) and the group (c ^p ) is each independently a hydrogen atom present in this group, a halogen atom, a carbon atom number 1 to 8 alkyl groups, alkenyl groups having 1 to 8 carbon atoms, cyano groups or -Sp ^p2 -P ^p2 ).

m ^p1 represents 0, 1, 2 or 3;
When multiple Z ^p1 , A ^p2 , Sp ^p2 and/or P ^p2 are present in the molecule, they may be the same or different. However, A ^p3 may be a single bond when m ^p1 is 0 and A ^p1 is the group (c ^p ).
In addition, the polymerizable monomer A is excluded from the polymerizable monomer B.

R ^p1 is preferably -Sp ^p2 -P ^p2 .
P ^p1 and P ^p2 are each independently preferably any one of general formulas (P ^p1 -1) to (P ^p1 -3), more preferably (P ^p1 -1).
R ^p11 and R ^p12 are each independently preferably a hydrogen atom or a methyl group.
Preferably, t ^p11 is 0 or 1.
W ^p11 is preferably a single bond, a methylene group or an ethylene group.
m ^p1 is preferably 0, 1 or 2, preferably 0 or 1.

Z ^p1 and Z ^p2 are each independently a single bond, -OCH ₂ -, -CH ₂ O-, -CO-, -C ₂ H ₄ -, -COO-, -OCO-, -COOC ₂ H ₄ -, -OCOC ₂ H ₄ -, -C ₂ H ₄ OCO-, -C ₂ H ₄ COO-, -CH=CH-, -CF ₂ -, -CF ₂ O-, -(CH ₂ ) ₂ -COO -, -(CH ₂ ) ₂ -OCO-, -OCO-(CH ₂ ) ₂ -, -CH=CH-COO-, -COO-CH=CH-, -OCOCH=CH-, -COO-(CH ₂ ) ₂ -, -OCF ₂ - or -C≡C-, a single bond, -OCH ₂ -, -CH ₂ O-, -C ₂ H ₄ -, -COO-, -OCO-, - COOC ₂ H ₄ -, -OCOC ₂ H ₄ -, -C ₂ H ₄ OCO-, -C ₂ H ₄ COO-, -CH=CH-, -(CH ₂ ) ₂ -COO-, -(CH ₂ ) ₂ -OCO-, -OCO-(CH ₂ ) ₂ -, -CH=CH-COO-, -COO-CH=CH-, -OCOCH=CH-, -COO-(CH ₂ ) ₂ - or -C≡ It is more preferably C-.

Only one of Z ^p1 and Z ^p2 present in the molecule is —OCH ₂ —, —CH ₂ O—, —C ₂ H ₄ —, —COO—, —OCO—, —COOC ₂ H ₄ —, -OCOC ₂ H ₄ -, -C ₂ H ₄ OCO-, -C ₂ H ₄ COO-, -CH=CH-, -(CH ₂ ) ₂ -COO-, -(CH ₂ ) ₂ -OCO-, - OCO-(CH ₂ ) ₂ -, -CH=CH-COO-, -COO-CH=CH-, -OCOCH=CH-, -COO-(CH ₂ ) ₂ - or -C≡C-, and other are all single bonds, and only one of Z ^p1 and Z ^p2 present in the molecule is —OCH ₂ —, —CH ₂ O—, —C ₂ H ₄ —, —COO— or —OCO - and all others are single bonds, and more preferably all of Z ^p1 and Z ^p2 present in the molecule are single bonds.
In addition, only one of Z ^p1 and Z ^p2 present in the molecule is —CH═CH—COO—, —COO—CH═CH—, —(CH ₂ ) ₂ —COO—, —(CH ₂ ) ₂ It is a linking group selected from the group consisting of -OCO-, -O-CO-(CH ₂ ) ₂ -, and -COO-(CH ₂ ) _{2 -} , and all others are preferably single bonds.

Sp ^p1 and Sp ^p2 each independently represent a single bond or a spacer group, and the spacer group is preferably an alkylene group having 1 to 30 carbon atoms. provided that —CH ₂ — in the alkylene group is substituted with —O—, —CO—, —COO—, —OCO—, —CH═CH— or —C≡C—, as long as the oxygen atoms are not directly connected to each other and a hydrogen atom in the alkylene group may be substituted with a halogen atom.
Among them, Sp ^p1 and Sp ^p2 are each independently preferably a linear alkylene group having 1 to 10 carbon atoms or a single bond.

A ^p1 , A ^p2 and A ^p3 are each independently preferably a 1,4-phenylene group or a 1,4-cyclohexylene group, more preferably a 1,4-phenylene group.
The 1,4-phenylene group is preferably substituted with one fluorine atom, one methyl group or one methoxy group in order to improve compatibility with liquid crystal molecules (liquid crystal compounds).

The amount of the polymerizable monomer B contained in the liquid crystal composition is preferably 0.05 to 10% by mass, more preferably 0.1 to 8% by mass, and 0.1 to 5% by mass. more preferably 0.1 to 3% by mass, more preferably 0.2 to 2% by mass, even more preferably 0.2 to 1.3% by mass, 0.2 to 1% by weight is particularly preferred, and 0.2 to 0.56% by weight is most preferred.

Preferred lower limits thereof are 0.01% by mass, 0.03% by mass, 0.05% by mass, 0.08% by mass, 0.1% by mass, and 0.15% by mass. %, 0.2% by mass, 0.25% by mass, and 0.3% by mass. On the other hand, the preferred upper limits are 10% by mass, 8% by mass, 5% by mass, 3% by mass, 1.5% by mass, 1.2% by mass, and 1% by mass. %, 0.8% by mass, and 0.5% by mass.

If the amount of the polymerizable monomer B is small, the effect of adding the polymerizable monomer B to the liquid crystal composition is difficult to appear. It may cause problems such as becoming weaker. On the other hand, if the amount of the polymerizable monomer B is too large, the amount of the polymerizable monomer B remaining after curing increases, the curing takes a long time, and the reliability of the liquid crystal composition decreases, depending on, for example, the illuminance of ultraviolet rays. and other problems may occur. Therefore, it is preferable to set the amount of the polymerizable monomer B in consideration of these balances.

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

式中、Ｐ^ｐ１１、Ｐ^ｐ１２、Ｓｐ^ｐ１１及びＳｐ^ｐ１２は、一般式（Ｐ）におけるＰ^ｐ１、Ｐ^ｐ２、Ｓｐ^ｐ１及びＳｐ^ｐ２と同じ意味を表す。

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

式中、Ｐ^ｐ２１、Ｐ^ｐ２２、Ｓｐ^ｐ２１及びＳｐ^ｐ２２は、一般式（Ｐ）におけるＰ^ｐ１、Ｐ^ｐ２、Ｓｐ^ｐ１及びＳｐ^ｐ２と同じ意味を表す。 Preferred examples of the compound represented by the general formula (P) also include polymerizable compounds represented by the following formulas (P-2-1) to (P-2-12).

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

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

式中、Ｐ^ｐ３１、Ｐ^ｐ３２、Ｓｐ^ｐ３１及びＳｐ^ｐ３２は、一般式（Ｐ）におけるＰ^ｐ１、Ｐ^ｐ２、Ｓｐ^ｐ１及びＳｐ^ｐ２と同じ意味を表す。

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

Preferred examples of the compound represented by the general formula (P) also include polymerizable compounds represented by the following formulas (P-4-1) to (P-4-19).

式中、Ｐ^ｐ４１、Ｐ^ｐ４２、Ｓｐ^ｐ４１及びＳｐ^ｐ４２は、一般式（Ｐ）におけるＰ^ｐ１、Ｐ^ｐ２、Ｓｐ^ｐ１及びＳｐ^ｐ２と同じ意味を表す。

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

Compounds represented by the general formula (P) are particularly preferably compounds represented by the following formulas (P-1.1) to (P-1.3).

((liquid crystal molecule))
In the liquid crystal composition of the present invention, in addition to the above polymerizable monomers, liquid crystal molecules represented by general formulas (N-01), (N-02), (N-03), (N-04) and (N-05) ) preferably contains one or more compounds selected from the group of compounds represented by These compounds correspond to compounds having negative dielectric anisotropy. These compounds have a negative sign of Δε and an absolute value of more than 2. The Δε of the compound is a value extrapolated from the measured value of the dielectric anisotropy of a composition obtained by adding the compound to a composition that is dielectrically neutral at 25°C.

In the formula, R ²¹ and R ²² are each independently an alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, an alkenyl group having 2 to 8 carbon atoms, or 2 to 2 carbon atoms. represents an alkenyloxy group of 8, wherein one or two or more non-adjacent -CH ₂ - in said group are each independently -CH=CH-, -C≡C-, -O-, - optionally substituted by CO-, -COO- or -OCO-, and Z ¹ is each independently a single bond, -CH ₂ CH ₂ -, -OCH ₂ -, -CH ₂ O-, -COO- , -OCO-, -OCF ₂ -, -CF ₂ O-, -CH=CH-, -CF=CF- or -C≡C-, and m each independently represents 1 or 2;

R ²¹ is preferably an alkyl group having 1 to 8 carbon atoms, more preferably an alkyl group having 1 to 5 carbon atoms, and even more preferably an alkyl group having 1 to 4 carbon atoms. . However, when Z ¹ represents other than a single bond, R ²¹ is preferably an alkyl group having 1 to 3 carbon atoms.
R ²² is preferably an alkyl group having 1 to 8 carbon atoms or an alkoxy group having 1 to 8 carbon atoms, and is an alkyl group having 1 to 5 carbon atoms or an alkoxy group having 1 to 4 carbon atoms. is more preferred, and an alkoxy group having 1 to 4 carbon atoms is even more preferred.

R ²¹ and R ²² can also be alkenyl groups. In this case, R ²¹ and R ²² are each independently selected from groups represented by the following formulas (R1) to (R5) (black dots in each formula represent carbon atoms in the ring structure). Formula (R1) or Formula (R2) is more preferred. However, the content of the compound in which R ²¹ and R ²² are alkenyl groups should be as low as possible, and in many cases it is preferable not to include it.

Z ¹ is each independently a single bond, -CH ₂ CH ₂ -, -OCH ₂ -, -CH ₂ O-, -COO-, -OCO-, -OCF ₂ -, -CF ₂ O-, - represents CH=CH-, -CF=CF- or -C≡C-, preferably a single bond, -CH ₂ CH ₂ -, -OCH ₂ - or -CH ₂ O-, a single bond or - CH ₂ O— is more preferred.
When m is 1, Z ¹ is preferably a single bond.
When m is 2, Z ¹ is preferably -CH ₂ CH ₂ - or -CH ₂ O-.

Fluorine atoms in compounds represented by general formulas (N-01), (N-02), (N-03), (N-04) and (N-05) are substituted with chlorine atoms which are the same halogen group. may have been However, the content of the compound substituted with a chlorine atom should be as low as possible, preferably not contained.
The hydrogen atoms present on the rings of the compounds represented by general formulas (N-01), (N-02), (N-03), (N-04) and (N-05) are further fluorine atoms or It may be substituted with a chlorine atom. However, the content of the compound substituted with a chlorine atom should be as low as possible, preferably not contained.
The compounds represented by the general formulas (N-01), (N-02), (N-03), (N-04) and (N-05) have a negative Δε and an absolute value greater than 3. Large compounds are preferred. Specifically, R ²² is preferably an alkoxy group having 1 to 8 carbon atoms or an alkenyloxy group having 2 to 8 carbon atoms.

（式中、Ｒ^２１は、上記と同じ意味を表し、Ｒ^２３は、それぞれ独立して、炭素原子数１～４のアルコキシ基を表す。） As compounds represented by general formula (N-01), general formula (N-01-1), general formula (N-01-2), general formula (N-01-3) and general formula (N-01 It is preferable to contain one or more selected from the compounds represented by -4).

(In the formula, R ²¹ has the same meaning as above, and each R ²³ independently represents an alkoxy group having 1 to 4 carbon atoms.)

The liquid crystal composition preferably contains a polymerizable monomer and compounds represented by general formulas (N-01-1) and (N-01-4).
When a high VHR is required, that is, when high reliability is required, in other words, when emphasizing obtaining a liquid crystal display element 1 free from display defects, general formula (N-01-3) It is preferred not to contain the represented compound.

（式中、Ｒ^２１は、上記と同じ意味を表し、Ｒ^２３は、それぞれ独立して、炭素原子数１～４のアルコキシ基を表す。） The compound represented by general formula (N-02) is selected from compounds represented by general formula (N-02-1), general formula (N-02-2) and general formula (N-02-3) It is preferable to contain one type or two or more types.

(In the formula, R ²¹ has the same meaning as above, and each R ²³ independently represents an alkoxy group having 1 to 4 carbon atoms.)

The liquid crystal composition preferably contains a polymerizable monomer and a compound represented by general formula (N-02-1).
The liquid crystal composition preferably contains a polymerizable monomer and a compound represented by general formula (N-02-3).
The liquid crystal composition includes a polymerizable monomer, a compound represented by the general formula (N-01-1), a compound represented by the general formula (N-01-4) and a compound represented by the general formula (N-02-1). It is particularly preferred to simultaneously contain the compound
The liquid crystal composition includes a polymerizable monomer, a compound represented by the general formula (N-01-1), a compound represented by the general formula (N-01-4) and a compound represented by the general formula (N-02-3). It is particularly preferred to simultaneously contain the compound

（式中、Ｒ^２１、上記と同じ意味を表し、Ｒ^２３は、炭素原子数１～４のアルコキシ基を表す。） As the compound represented by general formula (N-03), one or more compounds represented by general formula (N-03-1) are preferably contained.

(In the formula, R ²¹ has the same meaning as above, and R ²³ represents an alkoxy group having 1 to 4 carbon atoms.)

The liquid crystal composition preferably combines a polymerizable monomer and a compound represented by general formula (N-03-1).
The liquid crystal composition includes a polymerizable monomer, a compound represented by the general formula (N-01-1), a compound represented by the general formula (N-01-4) and a compound represented by the general formula (N-03-1). It is particularly preferred to simultaneously contain the compound

（式中、Ｒ^２１は、上記と同じ意味を表し、Ｒ^２３は、炭素原子数１～４のアルコキシ基を表す。） As the compound represented by general formula (N-04), one or more compounds represented by general formula (N-04-1) are preferably contained.

(In the formula, R ²¹ has the same meaning as above, and R ²³ represents an alkoxy group having 1 to 4 carbon atoms.)

The liquid crystal composition includes a polymerizable monomer, a compound represented by the general formula (N-01-1), a compound represented by the general formula (N-01-4) and a compound represented by the general formula (N-04-1). It is particularly preferred to simultaneously contain the compound

The compound represented by general formula (N-05) is preferably selected from compounds represented by formulas (N-05-1) to (N-05-3).

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

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

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

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

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

The liquid crystal composition contains 0.1 to 15% by mass of a polymerizable monomer, contains 1 to 20% by mass of a compound represented by the general formula (N-01-1), and has the general formula (N-01-4 ), and particularly preferably 1 to 20% by mass of the compound represented by general formula (N-04-1).

（式中、Ｒ^２１及びＲ^２２は、上記と同じ意味を表す。） The liquid crystal composition may further contain one or more compounds represented by general formula (N-06).

(In the formula, R ²¹ and R ²² have the same meanings as above.)

The compound represented by _the general formula (N-06) is effective when it is desired to adjust various physical properties. can be done.
The lower limit of the preferable content of the compound represented by the general formula (N-06) with respect to the total amount of the liquid crystal composition is 0% by mass, 2% by mass, 5% by mass, and 8% by mass. %, 10% by mass, 13% by mass, 15% by mass, 17% by mass, and 20% by mass. The upper limit of the preferred content is 30% by mass, 28% by mass, 25% by mass, 23% by mass, 20% by mass, 18% by mass, 15% by mass, 13% by mass, 10% by mass, and 5% by mass.

（式中、Ｒ^ＮＵ１１、Ｒ^ＮＵ１２、Ｒ^ＮＵ２１、Ｒ^ＮＵ２２、Ｒ^ＮＵ３１、Ｒ^ＮＵ３２、Ｒ^ＮＵ４１、Ｒ^ＮＵ４２、Ｒ^ＮＵ５１、Ｒ^ＮＵ５２、Ｒ^ＮＵ６１及びＲ^ＮＵ６２は、それぞれ独立して、炭素原子数１～８のアルキル基、炭素原子数１～８のアルコキシ基、炭素原子数２～８のアルケニル基又は炭素原子数２～８のアルケニルオキシ基を表し、該基中の１個又は非隣接の２個以上の－ＣＨ_２－は、それぞれ独立して－ＣＨ＝ＣＨ－、－Ｃ≡Ｃ－、－Ｏ－、－ＣＯ－、－ＣＯＯ－又は－ＯＣＯ－によって置換されてもよい。） The liquid crystal composition preferably contains one or more compounds selected from compounds represented by general formulas (NU-01) to (NU-06).

(wherein R ^NU11 , R ^NU12 , R ^NU21 , R ^NU22 , R ^NU31 , R ^NU32 , R ^NU41 , R ^NU42 , R ^NU51 , R ^NU52 , R ^NU61 and R ^NU62 each independently has 1 carbon atom; 8 alkyl group, alkoxy group having 1 to 8 carbon atoms, alkenyl group having 2 to 8 carbon atoms or alkenyloxy group having 2 to 8 carbon atoms, in which one or two non-adjacent One or more —CH ₂ — may be independently substituted with —CH═CH—, —C≡C—, —O—, —CO—, —COO— or —OCO—.)

More specifically, R ^NU11 , R ^NU12 , R ^NU21 , R ^NU22 , R ^NU31 , R ^NU32 , R ^NU41 , R ^{NU42 , R NU51} , R ^NU52 , R ^NU61 and ^{R NU62 each} independently have the number of carbon atoms It is preferably an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms or an alkenyl group having 2 to 3 carbon atoms, and an alkyl group having 1 to 5 carbon atoms or an alkenyl group having 2 to 3 carbon atoms. more preferably a group.
When the response speed is important, at least one of R ^NU11 , R ^NU21 , R ^NU31 , R ^NU41 , R ^NU51 and R ^NU61 is preferably an alkenyl group having 2 to 3 carbon atoms. A preferable content of the compound having such an alkenyl group is 10% by mass or more, 20% by mass or more, 25% by mass or more, and 30% by mass or more with respect to the total amount of the liquid crystal composition. , 40% by mass or more, 45% by mass or more, and 50% by mass or more.
When emphasizing high VHR, the content of the alkenyl group-containing compound is preferably 40% by mass or less, 35% by mass or less, and 30% by mass or less.

In order to achieve both high speed and high reliability, it is preferable to use only general formula (NU-01) as the compound having an alkenyl group. In this case, R ^NU11 is preferably an alkyl group having 2 to 4 carbon atoms, and R ^NU12 is preferably an alkenyl group having 2 to 3 carbon atoms.
In order to achieve both high speed and high reliability, it is preferable to use general formula (NU-01) and general formula (NU-05) as the compound having an alkenyl group. In this case, R ^NU11 is preferably an alkyl group having 2 to 4 carbon atoms, and R ^NU12 is preferably an alkenyl group having 2 to 3 carbon atoms. R ^NU51 is preferably an alkenyl group having 2 to 3 carbon atoms, and R ^NU52 is preferably an alkyl group having 2 to 3 carbon atoms.

In order to achieve both high speed and high reliability, it is preferable to use general formula (NU-01), general formula (NU-05) and general formula (NU-04) as compounds having alkenyl groups. In this case, R ^NU11 is preferably an alkyl group having 2 to 4 carbon atoms, and R ^NU12 is preferably an alkenyl group having 2 to 3 carbon atoms. R ^NU51 and R ^NU41 are each independently an alkenyl group having 2 to 3 carbon atoms, and R ^NU52 and R ^NU42 are each independently preferably an alkyl group having 2 to 3 carbon atoms. .

The liquid crystal composition preferably contains compounds represented by general formulas (NU-01) and (NU-02).
The liquid crystal composition preferably contains compounds represented by general formulas (NU-01) and (NU-03).
The liquid crystal composition preferably contains compounds represented by general formulas (NU-04) and (NU-05).
The liquid crystal composition preferably contains compounds represented by general formulas (NU-05) and (NU-06).

The liquid crystal composition preferably contains compounds represented by general formulas (NU-01) and (NU-05).
The liquid crystal composition preferably contains compounds represented by general formulas (NU-01) and (NU-06).
The liquid crystal composition preferably contains compounds represented by general formulas (NU-01), (NU-05) and (NU-06).

The content of the compound represented by the general formula (NU-01) is preferably 5 to 60% by mass, more preferably 10 to 50% by mass, and further preferably 25 to 45% by mass. preferable.
The content of the compound represented by the general formula (NU-02) is preferably 3 to 30% by mass, more preferably 5 to 25% by mass, and further preferably 5 to 20% by mass. preferable.
The content of the compound represented by the general formula (NU-03) is preferably 0 to 20% by mass, more preferably 0 to 15% by mass, and further preferably 0 to 10% by mass. preferable.

The content of the compound represented by the general formula (NU-04) is preferably 3 to 30% by mass, more preferably 3 to 20% by mass, and further preferably 3 to 10% by mass. preferable.
The content of the compound represented by the general formula (NU-05) is preferably 0 to 30% by mass, more preferably 1 to 20% by mass, and further preferably 3 to 20% by mass. preferable.
The content of the compound represented by the general formula (NU-06) is preferably 1 to 30% by mass, more preferably 3 to 20% by mass, and further preferably 3 to 10% by mass. preferable.

The liquid crystal composition of the present invention includes, as liquid crystal molecules, one or more compounds having a terphenyl structure or a tetraphenyl structure and a dielectric anisotropy Δε greater than +2, that is, a compound having a positive dielectric anisotropy. Two or more types can be contained. The Δε of the compound is a value extrapolated from the measured value of the dielectric anisotropy of a composition obtained by adding the compound to a composition that is dielectrically neutral at 25°C.
The compounds are used in combination according to desired properties such as solubility at low temperatures, transition temperature, electrical reliability, and refractive index anisotropy. can accelerate the reactivity of polymerizable monomers in the product.

For a compound having a terphenyl structure or a tetraphenyl structure and a dielectric anisotropy Δε greater than +2, the preferred lower limit of the content is 0.1% by mass with respect to the total amount of the liquid crystal composition. .5 wt%, 1 wt%, 1.5 wt%, 2 wt%, 2.5 wt%, 3 wt%, 4 wt%, 5 wt% and 10% by mass. Preferred upper limits of the content are 20% by mass, 15% by mass, 10% by mass, 9% by mass, 8% by mass, and 7% by mass with respect to the total amount of the liquid crystal composition. , 6% by mass, 5% by mass, 4% by mass, and 3% by mass.

Compounds having a terphenyl structure or a tetraphenyl structure and having a dielectric anisotropy greater than +2, which can be used in liquid crystal compositions, include formulas (M-8.51) to (M-8.54). Compounds represented by formulas (M-7.1) to compounds represented by formulas (M-7.4), formulas (M-7.11) to formulas (M-7.14) represented by It is preferable to contain compounds represented by formulas (M-7.21) to (M-7.24).

In order to increase the TNI of the liquid crystal composition, the formulas (L-7.1) to (L-7.4), the formulas (L-7.11) to (L-7.13), the formulas (L-7.21) ~ Formula (L-7.23), Formula (L-7.31) ~ Formula (L-7.34), Formula (L-7.41) ~ Formula (L-7. 44), 4-ring dielectric near-zero (approximately in the range of -2 to +2) compounds of formulas (L-7.51) to (L-7.53).

The liquid crystal composition of the present invention may contain ordinary nematic liquid crystals, smectic liquid crystals, cholesteric liquid crystals, antioxidants, ultraviolet absorbers, light stabilizers, infrared absorbers, and the like, in addition to the compounds described above.
Antioxidants include hindered phenols represented by general formulas (H-1) to (H-4).

In general formulas (H-1) to (H-3), each R ^H1 is independently an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, or 2 carbon atoms. to 10 alkenyl groups or alkenyloxy groups having 2 to 10 carbon atoms, wherein one —CH ₂ — or two or more non-adjacent —CH ₂ — present in the group are each independently , —O— or —S—, and one or more hydrogen atoms present in the group may each independently be substituted with a fluorine atom or a chlorine atom.
More specifically, each R ^H1 is independently an alkyl group having 2 to 7 carbon atoms, an alkoxy group having 2 to 7 carbon atoms, an alkenyl group having 2 to 7 carbon atoms, or 2 to 7 carbon atoms. 7 alkenyloxy group, more preferably an alkyl group having 3 to 7 carbon atoms or an alkenyl group having 2 to 7 carbon atoms.

In general formula (H-4), M ^H4 is an alkylene group having 1 to 15 carbon atoms (one or two or more —CH ₂ — in the alkylene group are (may be substituted with -O-, -CO-, -COO-, -OCO-), -OCH ₂ -, -CH ₂ O-, -COO-, -OCO-, -CF ₂ O-, -OCF ₂ -, -CF ₂ CF ₂ -, -CH=CH-COO-, -CH=CH-OCO-, -COO-CH=CH-, -OCO-CH=CH-, -CH=CH-, —C≡C—, a single bond, a 1,4-phenylene group (any hydrogen atom in the 1,4-phenylene group may be substituted with a fluorine atom) or trans-1,4-cyclohexylene is preferably an alkylene group having 1 to 14 carbon atoms. Considering volatility, a large number of carbon atoms is preferable, but considering viscosity, it is preferable that the number of carbon atoms is not too large, so M ^H4 has 2 to 12 carbon atoms. is preferably 3 to 10 carbon atoms, more preferably 4 to 10 carbon atoms, particularly preferably 5 to 10 carbon atoms, and 6 to 10 carbon atoms is most preferred.

In general formulas (H-1) to (H-4), one or two or more non-adjacent -CH= in the 1,4-phenylene group may be substituted with -N= . Also, each hydrogen atom in the 1,4-phenylene group may be independently substituted with a fluorine atom or a chlorine atom.
In general formulas (H-2) and (H-4), one or two or more non-adjacent —CH ₂ — in the 1,4-cyclohexylene group are replaced by —O— or —S— may be substituted. Also, each hydrogen atom in the 1,4-cyclohexylene group may be independently substituted with a fluorine atom or a chlorine atom.

More specifically, antioxidants include formulas (H-11) to (H-15).

When the liquid crystal composition contains an antioxidant, the preferred lower limits are 10 mass ppm or more, 20 mass ppm or more, and 50 mass ppm or more. On the other hand, the preferred upper limits are 10000 mass ppm, 1000 mass ppm, 500 mass ppm and 100 mass ppm.
The liquid crystal composition preferably has a nematic phase-isotropic liquid phase transition temperature (T _NI ) of 60 to 120°C, more preferably 70 to 100°C, even more preferably 70 to 85°C. In this specification, a temperature of 60° C. or higher is expressed as a high _TNI .
For liquid crystal television applications, the _TNI is preferably 70 to 80° C. For mobile applications, the _TNI is preferably 80 to 90° C. For outdoor display applications such as PID (Public Information Display), The _TNI is preferably between 90 and 110°C.

The liquid crystal composition preferably has a refractive index anisotropy (Δn) at 20° C. of 0.08 to 0.14, more preferably 0.09 to 0.13, and more preferably 0.09 to 0.09. 12 is more preferred. More specifically, the refractive index anisotropy (Δn) is preferably 0.10 to 0.13 when the cell gap is thin, and the refractive index anisotropy (Δn) is preferably 0.10 to 0.13 when the cell gap is thick. Δn) is preferably 0.08 to 0.10. In this specification, 0.09 or more is expressed as large Δn.
The liquid crystal composition preferably has a rotational viscosity (γ ₁ ) at 20° C. of 50 to 160 mPa·s, more preferably 55 to 160 mPa·s, and more preferably 60 to 160 mPa·s. It is more preferably 80 to 150 mPa·s, still more preferably 90 to 140 mPa·s, particularly preferably 90 to 130 mPa·s, and most preferably 100 to 130 mPa·s.

The liquid crystal composition preferably has a dielectric anisotropy (Δε) at 20° C. of −2.0 to −8.0, more preferably −2.0 to −6.0, and −2.0 to -5.0 is more preferred, -2.5 to -4.0 is particularly preferred, and -2.5 to -3.5 is most preferred.
Among the compounds constituting the liquid crystal composition, the preferable upper limit of the total content of the compounds having an alkenyl group is 10% by mass, 8% by mass, 6% by mass, and 5% by mass, 4% by mass, 3% by mass, 2% by mass, 1% by mass, and 0% by mass. Further, the preferred range of the total content of the compound having an alkenyl group is 0 to 10% by mass, 0 to 8% by mass, 0 to 5% by mass, 0 to 4% by mass, 0 ~3% by mass and 0 to 2% by mass. However, the compound represented by the general formula (NU-01) is excluded.

The liquid crystal composition contains a polymerizable monomer as an essential component, and further has general formula (N-01), general formula (N-02), general formula (N-03), general formula (N-04), general Compounds containing one or more selected from compounds represented by formula (N-05) and general formula (N-06), and further represented by general formulas (NU-01) to (NU-06) It is preferable to contain one or more selected from.
The upper limits of the total of these contents are 100% by mass, 99% by mass, 98% by mass, 97% by mass, 96% by mass, 95% by mass, 94% by mass, 93% by mass, 92% by mass, 91% by mass , 90% by mass, 89% by mass, 88% by mass, 87% by mass, 86% by mass, 85% by mass, and 84% by mass. % by mass, 81% by mass, 83% by mass, 85% by mass, 86% by mass, 87% by mass, 88% by mass, 89% by mass, 90% by mass, 91% by mass, 92% by mass, 93% by mass, 94% by mass , 95% by mass, 96% by mass, 97% by mass, 98% by mass, and 99% by mass.

The liquid crystal display device of the present invention is particularly useful as a liquid crystal display device for active matrix driving, and includes liquid crystal displays such as VA, FFS, IPS, PSA, PSVA, PS-IPS, PS-FFS, NPS and PI-less. It can be used as appropriate for the element.
Although the method for manufacturing a liquid crystal display element and the liquid crystal display element of the present invention have been described above based on the embodiments, the present invention is not limited to this, and each step can be performed in an arbitrary configuration having similar functions. Substitutions may be made and other optional steps may be added.

Examples of the present invention will be described below, but the present invention is not limited to the following examples.
The properties measured for the liquid crystal mixture are as follows.
Tni: nematic phase-isotropic liquid phase transition temperature (°C)
Δn: Refractive index anisotropy at 293K Δε: Dielectric anisotropy at 293K γ1: Rotational viscosity at 293K (mPa s)
K11: Elastic constant of broadening (pN) at 293K
K33: Elastic constant of bending at 293 K (pN)

1. Preparation of Liquid Crystal Mixtures Below, the following abbreviations are used for the description of compounds. n in the abbreviation is a natural number.
(side chain)
-n -C _n H _2n+1 : straight-chain alkyl group having n carbon atoms n- C _n H _2n+1 -: straight-chain alkyl group having n carbon atoms -On -OC _n H _2n+1 : n carbon atoms Linear alkoxy group -V1 -CH=CH-CH ₃ : propenyl group V- CH ₂ =CH-: vinyl group 1V2- CH ₃ -CH=CH-CH ₂ -CH ₂ -: pentenyl group

(connection structure)
_{-nO- -CnH2nO-}
(ring structure)

The compositions and physical properties of liquid crystal mixtures LC-1 and LC-2 are shown in Table 1 below.

2. Preparation of liquid crystal composition (Preparation of liquid crystal composition 1)
0.3 parts by mass of the following polymerizable monomer A and 0.3 parts by mass of the following polymerizable monomer B are mixed with 100 parts by mass of the liquid crystal mixture LC-1, and dissolved by heating to form a liquid crystal composition. Got item 1.

(Preparation of liquid crystal composition 2)
A liquid crystal composition 2 was obtained in the same manner as the liquid crystal composition 1, except that the liquid crystal mixture was changed to the liquid crystal mixture LC-2.

3. Preparation of liquid crystal display element (Example A1)
First, after applying a polyimide film to an ITO substrate, an orientation film was formed by rubbing the polyimide film. After that, an empty liquid crystal cell (cell gap 3.5 μm) including an ITO substrate with an alignment film and an ITO substrate without an alignment film was produced.
Next, the liquid crystal composition 1 was injected into the empty liquid crystal cell by a vacuum injection method.
Next, the liquid crystal cell into which the liquid crystal composition 1 was injected was irradiated with ultraviolet rays using the light source 1 while an AC voltage of 10 V was applied at a frequency of 100 Hz until the liquid crystal layer was raised by 3°C. Thus, a liquid crystal display device was obtained. As a UV illuminance meter, "UIT-150" manufactured by Ushio Inc. was used.

(Examples A2 to A7)
A liquid crystal display element was manufactured in the same manner as in Example A1, except that the light source was changed and the ultraviolet rays were irradiated until the temperature of the liquid crystal layer increased to that shown in Table 3.
(Examples B1 to B7)
Liquid crystal display devices were produced in the same manner as in Examples A1 to A7, except that Liquid Crystal Composition 2 was used.

(Examples C1 to C7)
Furthermore, liquid crystal display elements were manufactured in the same manner as in Examples A1 to A7, except that the ultraviolet light was applied using the light source R-4 without applying a voltage until the liquid crystal layer was heated by 5°C.
(Examples D1 to D7)
Furthermore, liquid crystal display elements were manufactured in the same manner as in Examples A1 to A7, except that ultraviolet light was applied using the light source 6 without applying voltage until the liquid crystal layer was heated by 3°C.

(Comparative Examples 1 to 7)
Liquid crystal display elements were manufactured in the same manner as in Examples A1 to A7, except that the light source was changed and the ultraviolet rays were applied until the temperature of the liquid crystal layer increased to that shown in Table 5.

4. Evaluation The liquid crystal display elements obtained in each example and each comparative example were evaluated as follows.
4-1. Evaluation of Pretilt Angle Formation In the obtained liquid crystal display element, the pretilt angle of liquid crystal molecules was measured using a pretilt angle measurement system (manufactured by Shintech, "OPTIPRO") and evaluated according to the following criteria.
[Evaluation criteria]
A: 88.5° or less B: Over 88.5°, 89° or less C: Over 89°, 89.5° or less D: Over 89.5°

4-2. Evaluation of Remaining Amount of Polymerizable Monomer A liquid crystal composition was extracted from the resulting liquid crystal display element, and the remaining polymerizable monomer was analyzed using high performance liquid chromatography and evaluated according to the following criteria.
[Evaluation criteria]
A: Below the detection limit B: 0.001% by mass or more and less than 0.01% by mass C: 0.01% by mass or more and less than 0.1% by mass D: 0.1% by mass or more

4-3. Evaluation of display defect (burn-in) A predetermined fixed pattern was displayed in the display area of the obtained liquid crystal display element for 1000 hours. After that, the level of the afterimage of the fixed pattern when performing uniform display on the whole screen was visually confirmed and evaluated according to the following criteria.
[Evaluation criteria]
A: No afterimage B: Slight afterimage but acceptable level C: Afterimage present, unacceptable level D: Afterimage present, considerably poor

4-4. Evaluation of VHR A pulsed AC voltage of 5 V was applied to the obtained liquid crystal display element with a pulse frequency of 60 Hz and a pulse width of 16.67 msec. Thereafter, VHR was measured before and after application of AC voltage using a liquid crystal property evaluation system ("6254 type" manufactured by Toyo Technica Co., Ltd.) and evaluated according to the following criteria.
[Evaluation criteria]
A: Decrease of less than 1% B: Decrease of 1% or more and less than 3% C: Decrease of 3% or more and less than 5% D: Decrease of 5% or more Tables 2 to 4 show the above results.

As shown in Tables 2 to 4, by setting the ratio of the intensity of the peak at a wavelength of 313 nm to the intensity of the peak at a wavelength of 365 nm in the irradiated ultraviolet rays within a predetermined range, the occurrence of display defects and the decrease in VHR are prevented. We were able to.
In addition, by adding the consuming step, it was possible to reduce the residual amount of the polymerizable monomer. Along with this, there was a tendency for the occurrence of display defects to decrease.
On the other hand, when the ratio of the intensity of the peak at a wavelength of 313 nm and the intensity of the peak at a wavelength of 365 nm in the irradiated ultraviolet rays deviates from the predetermined range, a sufficient pretilt angle cannot be provided or the VHR is significantly lowered.

In Examples A1 to A7, B1 to B7, C1 to C7, and D1 to D7, in place of the polymerizable monomer A, the compounds represented by the formulas (SAL-1.1) to (SAL-2.9), the polymerizable monomer B Also when the compounds of the above formulas (P-1.1) to (P-1.3) are used instead of , good performance is obtained in each evaluation of pretilt angle formation, residual amount of polymerizable monomer, display defect, and VHR. showed that.
Further, in Examples C1 to C7, when the ultraviolet irradiation conditions for the first time and the ultraviolet irradiation conditions for the second time were reversed and the liquid crystal composition and the liquid crystal layer were irradiated with ultraviolet light, the same tendency as in Examples C1 to C7 was observed. The results were obtained.

REFERENCE SIGNS LIST 1 liquid crystal display element AM active matrix substrate CF color filter substrate 2 first substrate 3 second substrate 4 liquid crystal layer 5 pixel electrode layer 6 common electrode layer 7 first polarizing plate 8 second polarizing plate 9 color filter 11 gate Bus line 12 Data bus line 13 Pixel electrode 14 Cs electrode 15 Source electrode 16 Drain electrode 17 Contact hole

Claims (11)

A step of arranging a pair of substrates so as to face each other with a liquid crystal composition containing liquid crystal molecules and at least one polymerizable monomer interposed therebetween;
and polymerizing the at least one polymerizable monomer by irradiating the liquid crystal composition with ultraviolet light,
The method for manufacturing a liquid crystal display element, wherein the ultraviolet rays have a ratio (X2/X1) of an intensity X2 at a wavelength of 365 nm to an intensity X1 at a wavelength of 313 nm of 5 to 70,
As the liquid crystal molecule, the general formula (N-03)
(In the formula,
R ²¹ and R ²² are each independently an alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, an alkenyl group having 2 to 8 carbon atoms, or an alkenyl group having 2 to 8 carbon atoms represents an oxy group,
One or two or more non-adjacent -CH ₂ - in the group are each independently -CH=CH-, -C≡C-, -O-, -CO-, -COO- or - It may be substituted by OCO-. )
One or two or more compounds represented by the general formula (NU-01)
(In the formula,
R ^NU11 and R ^NU12 are each independently an alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, an alkenyl group having 2 to 8 carbon atoms, or an alkenyl group having 2 to 8 carbon atoms represents an oxy group,
One or two or more non-adjacent -CH ₂ - in the group are each independently -CH=CH-, -C≡C-, -O-, -CO-, -COO- or -OCO may be replaced by -. )
Contains one or more compounds represented by
As the polymerizable monomer, the following general formula (P)
(In the formula,
R ^p1 represents -Sp ^p2 -P ^p2 ,
P ^p1 and P ^p2 are each independently represented by the following general formula (P ^p1 -1)
(In the formula,
R ^p11 each independently represents an alkyl group having 1 to 5 carbon atoms,
When multiple R ^p11 are present in the molecule, they may be the same or different. )
represents a group represented by
Sp ^p1 and Sp ^p2 each independently represent a single bond ,
Z ^p1 and Z ^p2 each independently represent a single bond ,
A ^p1 , A ^p2 and A ^p3 are each independently
(a ^p ) 1,4-cyclohexylene group (b ^p ) 1,4-phenylene group (one —CH= or two or more non-adjacent —CH= present in this group are —N = may be substituted.)
(c ^p ) represents a group selected from the group consisting of a naphthalene-2,6-diyl group and a phenanthrene-2,7-diyl group;
The hydrogen atoms present in the groups (a ^p ), (b ^p ) and (c ^p ) are each independently a halogen atom, an alkyl group having 1 to 8 carbon atoms, or -Sp ^p2 -P ^p2 may be substituted,
When representing a 1,4-phenylene group, it may be substituted with one methoxy group,
m ^p1 represents 0 ,
When multiple Sp ^p2 and/or P ^p2 are present in the molecule, they may be the same or different,
A ^p3 may be a single bond when m ^p1 is 0 and A ^p1 represents a phenanthrene-2,7-diyl group. )
A method for producing a liquid crystal display element containing one or more of the compounds represented by 2. The method of manufacturing a liquid crystal display element according to claim 1, wherein the intensity X1 is 0.05 to 50 mW/cm ² . 3. The method of manufacturing a liquid crystal display element according to claim 1, wherein the step of irradiating with ultraviolet rays is a liquid crystal layer forming step of polymerizing the at least one polymerizable monomer to form a liquid crystal layer. 4. The method of manufacturing a liquid crystal display element according to claim 3, wherein in the liquid crystal layer forming step, the ultraviolet rays are applied while a voltage is applied to the liquid crystal composition. 5. The method of manufacturing a liquid crystal display element according to claim 3, wherein in the liquid crystal layer forming step, the ultraviolet rays are applied until the temperature of the liquid crystal layer rises by 0.1 to 5.degree. 3. The method of manufacturing a liquid crystal display element according to claim 1, wherein the step of irradiating with ultraviolet rays is a monomer consumption step of irradiating the liquid crystal layer formed by polymerizing the at least one polymerizable monomer with ultraviolet rays. 7. The method of manufacturing a liquid crystal display element according to claim 6, wherein in the monomer consuming step, the ultraviolet rays are applied until the temperature of the liquid crystal layer rises by 1 to 20.degree. In the step of arranging the pair of substrates to face each other, at least one of the substrates is arranged so as to be in direct contact with the liquid crystal composition without an alignment layer therebetween,
8. The method of manufacturing a liquid crystal display element according to claim 1, wherein the at least one polymerizable monomer includes a polymerizable monomer having at least one adsorption group. 9. The method for producing a liquid crystal display element according to any one of claims 1 to 8, wherein the content of the compound represented by the general formula (N-03) with respect to the total amount of the liquid crystal composition is 10% by mass or more. 10. The method for producing a liquid crystal display element according to any one of claims 1 to 9, wherein the content of the compound represented by the general formula (NU-01) is 10 to 50% by mass with respect to the total amount of the liquid crystal composition. The method for producing a liquid crystal display element according to any one of claims 1 to 10, wherein the content of the compound represented by the general formula (P) is 0.05 to 10% by mass with respect to the total amount of the liquid crystal composition.

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