JP2021148973A - Manufacturing method of liquid crystal display element - Google Patents

Abstract

To provide a PSA-type or PSVA-type liquid crystal display element achieving high-speed response and high VHR.SOLUTION: A manufacturing method of liquid crystal display element includes the steps of: arranging a pair of substrates at least one of which includes an orientation film, with a liquid crystal composition containing polymerizable compound interposed therebetween; and irradiating the liquid crystal composition with UV light to polymerize the polymerizable compound. The UV light irradiation is performed using UV light satisfying I365/I313>20 (I365 represents illuminance (mW cm2) at wavelength of 365 nm, and I313 represents illuminance (mW cm2) at wavelength of 313 nm) at lease once. The liquid crystal composition contains one or two types of liquid crystal compounds represented by formula (I) and one or two types of polymerizable compounds represented by formula (P).SELECTED DRAWING: None

Description

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

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

In the VA type display, a liquid crystal composition having a negative Δε is used, and it is widely used in liquid crystal TVs and the like. Among them, the PSA (Polymer Sustained Realinment) mode is a mode in which a polymerizable compound (monomer) dissolved in a liquid crystal is polymerized to give a desired pretilt angle to vertically oriented liquid crystal molecules, and the viewing angle can be expanded. It has become the mainstream of current TVs because it provides high-speed response and high transmittance. Further, in recent years, further high-speed response of liquid crystal display elements has been studied, and as such a technique, a liquid crystal layer is formed by using a liquid crystal composition containing a liquid crystal compound (alkenyl liquid crystal compound) having an alkenyl partial structure such as an alkenyl group. Attempts have been made to form (see, for example, Patent Documents 1 and 2).

Further, in recent years, in the production of liquid crystal elements, a PSA liquid crystal composition having an appropriately high polymerization rate has been required for the purpose of improving production efficiency. In the step of polymerizing the polymerizable compound in the liquid crystal composition, the polymerization rate of the polymerizable compound is very important. When the polymerization rate is high, the residual amount of the polymerizable compound is reduced in a short irradiation time of ultraviolet rays or the like, so that deterioration of the liquid crystal composition due to ultraviolet rays or the like is unlikely to occur. It also has the advantage of improving productivity, such as being able to manufacture with less energy and shortening the manufacturing time. On the other hand, when the polymerization rate of the polymerizable compound is slow, it is necessary to lengthen the irradiation time of ultraviolet rays or the like in order to reduce the unreacted residual amount of the polymerizable compound. When a strong ultraviolet ray or the like is irradiated for a long time in the polymerization step, the size of the manufacturing apparatus is increased, the manufacturing efficiency is lowered, and the liquid crystal composition is deteriorated by the ultraviolet rays or the like. However, when the irradiation time of ultraviolet rays or the like is shortened, the residual amount of the polymerizable compound increases, and the remaining polymerizable compound causes display defects called unevenness and seizure. From the above, a polymerizable liquid crystal composition capable of achieving a sufficient polymerization rate is desired.
As an approach for improving the polymerization rate of the polymerizable compound, as shown in Examples of Patent Document 3, a compound as shown in the following formula (A) is used, and the absorption wavelength of the liquid crystal material used is set to a long wavelength. A method of extending to the side to improve the polymerization rate of the polymerizable compound has been proposed.

Japanese Unexamined Patent Publication No. 2014-112192 Japanese Unexamined Patent Publication No. 2010-285499 Special Table 2013-503952

As described above, a liquid crystal composition containing an alkenyl liquid crystal compound is useful for high-speed response of the liquid crystal display element, and such a liquid crystal composition is used for light emitted from a backlight or a manufacturing process of the liquid crystal display element. There is a problem that it is easily deteriorated by active energy rays such as ultraviolet rays irradiated in the liquid crystal display, and impurities generated by photodeterioration of the liquid crystal composition cause a decrease in the voltage retention rate (VHR) of the liquid crystal panel.

The present invention has been made in view of the above circumstances, and an object of the present invention is to provide a method for manufacturing a liquid crystal display element having excellent characteristics. More specifically, an object of the present invention is to manufacture a PSA type or PSVA type liquid crystal display element that achieves high-speed response and high VHR.

As a result of diligent studies by the present inventors, it has been found that the above-mentioned problems can be solved by irradiating ultraviolet rays having a specific illuminance ratio in a method for producing an alkenyl-based polymerizable liquid crystal display element, and the present invention has been completed. ..

That is, the present invention provides a method for manufacturing a liquid crystal display element having the following features.
A step of arranging a pair of substrates having an alignment film on at least one of them so as to face each other via a liquid crystal composition containing a polymerizable compound.
A method for producing a liquid crystal display element, which comprises a step of irradiating the liquid crystal composition with ultraviolet rays to polymerize the polymerizable compound.
As the ultraviolet rays, the following formula (P-1)
I ₃₆₅ / I ₃₁₃ > 20 ... (P-1)
(In the above formula, I ₃₆₅ represents the illuminance (mW · cm ² ) at a wavelength of 365 nm.
I ₃₁₃ represents the illuminance (mW · cm ² ) at a wavelength of 313 nm. ) Is used at least once to irradiate.
The liquid crystal composition has the following general formula (I).

(In the formula, R ¹¹ and R ¹² each independently represent an alkyl group having 1 to 8 carbon atoms, and one or two or more non-adjacent −CH ₂ − in the alkyl group are independent of each other. It may be replaced by -CH = CH-, -C≡C-, -O-, -CO-, -COO- or -OCO-, but ^{at least one of R 11} and R ¹² has 2 carbon atoms. represents 8 alkenyl group, one or two or more -CH 2 in the alkenyl group _- may be further substituted on the oxygen atom to the extent that the oxygen atom not adjacent,
n ¹¹ and n ¹² represent 0, 1, 2 or 3, while n ¹ + n ² represents 1, 2 or 3.
A ¹¹ and ^{A 12} are each independently (a) 1,4-cyclohexylene group (this is present in the group one -CH ₂ - or nonadjacent two or more -CH ₂ - is -O (May be replaced with −) and (b) 1,4-phenylene group (one -CH = existing in this group or two or more -CH = not adjacent to each other is replaced with -N =. May be done.)
Represents a group selected from the group consisting of, and the hydrogen atoms in the above groups (a) and (b) may be independently substituted with cyano groups, fluorine atoms or chlorine atoms, respectively.
Z ¹¹ and ^{Z 12} each independently represent a single _{bond, -CH 2 CH 2 -, -} (CH 2) 4 -, - OCH 2 -, - CH 2 O -, - COO -, - OCO -, - OCF 2 Represents −, −CF ₂ O−, −CH = NN = CH−, −CH = CH−, −CF = CF− or −C≡C−.
If A ¹¹ and / or A ¹² there are a plurality, they may be the same or different and if Z ¹¹ and / or Z ¹² there are multiple, they have be the same or different You may. ) Or
The following general formula (II)

(In the formula, R ²¹ and R ²² each independently represent an alkyl group having 1 to 8 carbon atoms, and one or two or more non-adjacent −CH ₂ − in the alkyl group are independent of each other. It may be replaced by -CH = CH-, -C≡C-, -O-, -CO-, -COO- or -OCO-, but ^{at least one of R 21} and R ²² has 2 carbon atoms. represents 8 alkenyl group, one or two or more -CH 2 in the alkenyl group _- may be further substituted on the oxygen atom to the extent that the oxygen atom not adjacent,
A ^{21, A 22} and ^{A 23} are each independently (a) 1,4-cyclohexylene group (this is present in the group one -CH ₂ - or nonadjacent two or more -CH ₂ - May be replaced with -O-) and (b) 1,4-phenylene group (one -CH = present in this group or two or more non-adjacent -CH = -N May be replaced with =)
Represents a group selected from the group consisting of, and the hydrogen atoms in the above groups (a) and (b) may be independently substituted with cyano groups, fluorine atoms or chlorine atoms, respectively.
Z ²¹ and ^{Z 22} each independently represent a single _{bond, -CH 2 CH 2 -, -} (CH 2) 4 -, - OCH 2 -, - CH 2 O -, - COO -, - OCO -, - OCF 2 Represents −, −CF ₂ O−, −CH = NN = CH−, −CH = CH−, −CF = CF− or −C≡C−.
n ²¹ represents 0, 1, 2 or 3
When a ^{plurality of A 22} and Z ²² are present, they may be the same or different, except for the compound represented by the above formula (I). ), And one or more of the liquid crystal compounds represented by).
The following general formula (P)

(In the above formula, P ^p1 and P ^p2 each independently represent a polymerizable group.
Sp ^p1 and Sp ^p2 independently represent a spacer group or a single bond, respectively.
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-} (in the formula, R ZP 1) Each independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, ^{but when there are a plurality of R ZP1s} in the molecule, they may be the same or different).
A ^p1 , A ^p2 and A ^p3 are independent of each other.
^(A p) 1,4-cyclohexylene group (one present in the base or two or more -CH ₂ - may be replaced by -O- to the extent that the oxygen atom not adjacent. )
^(B p) 1,4-phenylene group (one or more -CH present in the base = may be replaced by -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 , Phenylene-2,7-diyl group or anthracene-2,6-diyl group (one or more -CH = present in the group may be substituted with -N =).
Represents a group selected from the group consisting of the group (a ^p), group (b ^p) and one or more hydrogen atoms present in the radical (c ^p) are each independently a halogen atom, It may be substituted with a cyano group, an alkyl group having 1 to 18 carbon atoms which may be substituted with a fluorine atom, or −Sp ^p2 −P ^p2 , and one of the alkyl groups or two or more non-adjacent − Even if CH ₂ − is independently substituted with −CH = CH −, −C≡C−, −O−, −CO−, −COO− or −OCO− so that oxygen atoms are not directly adjacent to each other. Often,
^Further, when ^{m p1} is a ^{group A p1} is represented by group ^{(c p)} in 0 ^{A p3} may be a single bond,
m ^p1 represents 0, 1, 2 or 3
If there are a plurality of Z ^p1 , A ^p2 , Sp ^p2 and / or P ^{p2 in the} molecule, they may be the same or different. A method for producing a liquid crystal display device, which comprises one or more of the polymerizable compounds represented by).

According to the present invention, in the production of a liquid crystal display element using a polymerizable liquid crystal composition having a specific composition, unevenness, seizure, etc. are caused by using ultraviolet rays having peaks at a wavelength of 313 nm and a wavelength of 365 nm at a predetermined illuminance ratio. It is possible to manufacture a liquid crystal display element with high productivity, in which display defects are reduced, good display quality is exhibited, and high-speed response and high reliability are achieved.

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

Hereinafter, the method for manufacturing a liquid crystal display element of the present invention will be described in detail based on a preferred embodiment. First, a 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 shown in one embodiment of a liquid crystal display element, and FIG. 2 is an enlarged plan view of a region surrounded by line I in FIG.

In addition, in FIGS. 1 and 2, for convenience, the dimensions of each part and their ratios are exaggerated and may differ from the actual ones. Further, the materials, dimensions, etc. shown below are examples, and the present invention is not limited thereto, and can be appropriately changed without changing the gist thereof.

The liquid crystal display element 1 shown in FIG. 1 includes an active matrix substrate AM and a color filter substrate CF arranged so as 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 is formed on the first substrate 2, the pixel electrode layer 5 provided on the surface of the first substrate 2 on the liquid crystal layer 4 side, and the surface of the first substrate 2 opposite to the liquid crystal layer 4. It has a first polarizing plate 7 provided.

On the other hand, the color filter substrate CF is provided on the second substrate 3, the common electrode layer 6 provided on the liquid crystal layer 4 side of the second substrate 3, 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 a vertically oriented type using negative dielectric anisotropy, and in the liquid crystal layer 4, the liquid crystal molecules are attached to the substrates AM and CF without applying a voltage between the electrode layers 5 and 6. Oriented almost vertically.

That is, the liquid crystal display element 1 according to the present 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, and a color filter 9. 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 of the first substrate 2 and the second substrate 3 may have translucency, or only one of them may have translucency. In the latter case, the other substrate can be made of an opaque material such as a metal material, a silicon material.

As shown in FIG. 2, 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. Have. Note that FIG. 2 shows a pair of gate bus lines 11 and 11 and a pair of data bus lines 12 and 12.

The plurality of gate bus lines 11 and the plurality of data bus lines 12 are arranged in a matrix so as to intersect with each other, and a unit pixel of the liquid crystal display element 1 is formed by a region surrounded by these. One pixel electrode 13 is formed in each unit pixel. In addition, each pixel may be composed of a plurality of sub-pixels.

The pixel electrode 13 has a structure (so-called fishbone) including two trunks that are orthogonal to each other and have a cross shape, and a plurality of branches that branch from each trunk and are 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 a slit formed between the branch portions.

According to the pixel electrode 13 having such a structure, the liquid crystal molecules are tilted or oriented in the four directions in which the branches are tilted with respect to the trunk. 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. Further, the separation distance S between the adjacent branch portions is preferably about 1 to 5 μm, more preferably about 2 to 4 μm. With such a configuration, the liquid crystal molecules can be more reliably inclined or oriented in a predetermined direction.

A Cs electrode 14 is provided between the pair of gate bus lines 11 and 11 substantially parallel to the gate bus line 11. Further, a thin film transistor including a source electrode 15 and a drain electrode 16 is provided in the vicinity of the intersection where the gate bus line 11 and the data bus line 12 intersect with each other. The drain electrode 16 is provided with a contact hole 17.

The gate bus line 11 and the data bus line 12 are preferably formed of, for example, Al, Cu, Au, Ag, Cr, Ta, Ti, Mo, W, Ni or an alloy containing these, respectively, preferably Mo, Al or It is more preferable to form an alloy containing these.

The pixel electrode 13 is composed of, for example, a transparent electrode in order to improve the 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, and AZTO (AlZnSnO).

The average thickness of the transparent electrode is preferably about 10 to 200 nm. Further, in order to reduce the electrical resistance, a 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 striped common electrodes (transparent electrodes) arranged side by side. 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 a color filter is supplied onto a second substrate 3 in a predetermined pattern, and then cured by heating or irradiating with light. By performing this operation for the three colors of red, green, and blue, the color filter 9 can be obtained.

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 light leakage. It is preferable that this black matrix is formed in a portion corresponding to the thin film transistor.

The black matrix may be arranged together with the color filter 9 on the second substrate 3 side, may be arranged together with the color filter 9 on the first substrate 2 side, and the black matrix may be arranged on the first substrate 2 side. The color filters 9 may be individually arranged on the second substrate 3 side. Further, the black matrix can also be composed of a portion in which each color of the color filter 9 is superposed to reduce the transmittance.

The active matrix substrate AM and the color filter substrate CF are bonded to each other in their peripheral regions by a sealing material (sealing material) composed of an epoxy-based thermosetting composition, an acrylic-based UV curable composition, or the like. There is.

A spacer for maintaining the separation distance between the active matrix substrate AM and the color filter substrate CF may be arranged. Examples of the spacer include granular spacers such as glass particles, plastic particles, and alumina particles, and resin spacer columns formed by a photolithography method.

The average separation 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 so that the viewing angle and contrast are improved by adjusting the positional relationship of their transmission axes. Specifically, it is preferable that the first polarizing plate 7 and the second polarizing plate 8 are arranged so as to be orthogonal to each other so that their transmission axes operate in the normal black mode. In particular, it is preferable that either one of the first polarizing plate 7 and the second polarizing plate 8 is arranged so that its transmission axis is approximately 45 ° with the orientation direction of the liquid crystal molecules when a 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 so as to maximize the contrast. It is preferable to adjust. Further, the liquid crystal display element 1 may include a retardation film for widening the viewing angle.

In the liquid crystal display element 1, an alignment film such as a polyimide alignment film is 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. .. In the present invention, both substrates may have an alignment film, and only one substrate may have an alignment film.

(Manufacturing method of liquid crystal display element)
The method for producing a liquid crystal display element of the present invention includes a step of arranging a pair of substrates having an alignment film on at least one of them so as to face each other via a liquid crystal composition containing a polymerizable compound, and ultraviolet rays on the liquid crystal composition. It has a step of irradiating with the above-mentioned to polymerize the polymerizable compound.

Next, a method for manufacturing such a liquid crystal display element 1 will be described in detail based on a preferred embodiment.

The method for manufacturing the liquid crystal display element of the present embodiment includes a preparatory step [1] for preparing the substrate AM, CF and the liquid crystal composition, an assembly step [2] for assembling each part, and a state in which a voltage is applied to the liquid crystal composition. The liquid crystal layer forming step [3] of forming the liquid crystal layer 4 by polymerizing the polymerizable monomer by irradiation with ultraviolet rays, and the remaining by irradiating the liquid crystal layer 4 with ultraviolet rays without applying a voltage to the liquid crystal layer 4. It has a monomer consumption step [4] of polymerizing and consuming the polymerizable monomer.

If the performance of the liquid crystal display element 1 can be sufficiently obtained, one of the liquid crystal layer forming step [3] and the monomer consumption step [4], particularly the monomer consumption step [4], may be omitted.

[1] Preparation Step First, a liquid crystal composition containing an active matrix substrate AM, a color filter substrate CF, a liquid crystal molecule, and at least one polymerizable monomer is prepared.

[2] Assembly Step Next, the sealing material is drawn in a closed loop bank shape using a dispenser along at least one edge of the active matrix substrate AM and the color filter substrate CF.

Then, a predetermined amount of the liquid crystal composition is dropped inside the sealing material, and then the active matrix substrate AM and the color filter substrate CF are arranged so as to face each other so as to come into contact with the liquid crystal composition under reduced pressure. That is, the pair of substrates AM and CF are arranged so that the electrode layers 5 and 6 (electrodes) face each other via the liquid crystal composition.

In such a drop injection (ODF: One Drop Fill) 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 described later has little influence on a sudden pressure change or impact in the dropping device, which occurs at the time of dropping, and can be stably dropped for a long period of time. Therefore, the yield of the liquid crystal display element 1 can be maintained high.

In particular, in a small liquid crystal display element often used in smartphones, since the optimum injection amount of the liquid crystal composition is small, it is difficult to control the deviation amount within a certain range. However, by using the liquid crystal composition as described above, a stable and optimum injection amount can be accurately dropped even in a small liquid crystal display element.

Then, the sealing material is cured by irradiation with ultraviolet rays (active energy rays) and heating. Depending on the type of the sealing material, the sealing material may be cured only by either ultraviolet irradiation or heating.

[3] Liquid crystal layer forming step (first ultraviolet irradiation step)
Next, while applying a voltage to the liquid crystal composition, the liquid crystal composition is irradiated with ultraviolet rays. As a result, at the interface with the electrode layers 5 and 6 of the liquid crystal composition (in the electrodes 5 and 6 of the substrate having the alignment film, the interface with the alignment film provided on the surface of the electrode layers 5 and / or 6). A polymer layer containing a polymer of polymerizable monomers is formed. The formation of the polymer layer causes the liquid crystal molecules to be vertically oriented or even imparts a pretilt angle to the liquid crystal molecules.

The voltage may be applied between the pixel electrode 13 and the common electrode (opposite 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, and 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 value is applied to the liquid crystal composition, no further increase in the effect can be expected.

At least one of the ultraviolet rays to be irradiated in this step [3] and the ultraviolet rays to be irradiated in the next step [4] when the next step [4] is present has peaks at a wavelength of 313 nm and a wavelength of 365 nm. It satisfies the following equation (P-1).
I ₃₆₅ / I ₃₁₃ > 20 ... (P-1)
(In the above formula, I ₃₆₅ represents the illuminance (mW · cm ² ) at a wavelength of 365 nm.
I ₃₁₃ represents the illuminance (mW · cm ² ) at a wavelength of 313 nm. )
From the viewpoint of increasing the VHR of the liquid crystal display element 1, it is preferable to irradiate the liquid crystal composition with ultraviolet rays having a wavelength of 365 nm, which is a relatively long wavelength, over a period of time to polymerize the polymerizable monomer at an appropriate polymerization rate. .. In particular, when an alkenyl liquid crystal display is used for the purpose of increasing the response speed, improvement of VHR, which tends to decrease, is strongly required. Therefore, the present inventors have made extensive studies and found that an appropriate intensity ratio exists between the peak having a wavelength of 313 nm and the peak having a wavelength of 365 nm, and have completed the present invention.

From this point of view, in this step [3] in which the polymerization of the polymerizable compound is mainly carried out, it is preferable to use ultraviolet rays satisfying the above formula (P1).

_{When I 365} / I ₃₁₃ is 20 or less in the ultraviolet rays satisfying the above formula (P1), the amount of ultraviolet rays having a wavelength of 313 nm becomes too large, the liquid crystal molecules are deteriorated or deteriorated, and the VHR of the liquid crystal display element 1 becomes descend.

I ₃₆₅ / I ₃₁₃ may be more than 20, but 25 or more is preferable, and 30 or more is particularly preferable. By _{setting I 365} / I ₃₁₃ to a ratio within the above range, a liquid crystal display element having a high VHR and reduced display defects while preventing deterioration and deterioration of liquid crystal molecules can be manufactured with high efficiency. be able to. The upper limit of I ₃₆₅ / I ₃₁₃ is not particularly limited, and may be 10,000 or more or infinite.

Specifically, the peak intensity _{I 365} is preferably about 2.5~105mW / cm ^2, and more preferably about 3.5~95mW / cm ^2. In order to reduce the amount of residual polymerizable monomer and produce the liquid crystal display element 1 having a high voltage holding ratio, I ₃₆₅ is preferably 2.5 to 20 mW / cm ² . Further, in order to give a good pre-tilt angle, I ₃₆₅ is preferably 3.5 to 95 mW / cm ² .

On the other hand, the peak intensity _{I 313} is preferably less than 10 mW / cm ^2, is preferably about 0~10mW / cm ^2, and more preferably about 0~5mW / cm ^2. Thereby, the above-mentioned effect can be further improved.

From the viewpoint of more reliably preventing deterioration and deterioration of the liquid crystal molecules, ultraviolet rays do not have a peak in the wavelength region of less than 313 nm (particularly, the wavelength in the UVC region), or even if they have a peak. , It is preferable that the strength is extremely small.

The irradiation time of ultraviolet rays in this step [3] can be defined in relation to the temperature of the liquid crystal layer 4. That is, in this step [3], the irradiation of ultraviolet rays is preferably carried out until the temperature of the liquid crystal layer 4 rises by 0.1 to 5 ° C, more preferably 0.5 to 5 ° C. It is more preferable to carry out until the temperature rises by about 5 ° C. The temperature rise of the liquid crystal layer 4 in such a range indicates that the polymerizable monomer was sufficiently polymerized.

The specific irradiation time depends on the type of ultraviolet rays used, but is preferably about 10 to 7200 seconds, and 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, it is preferably about 600 to 7200 seconds. Further, in order to impart the pre-tilt angle satisfactorily, it is preferably about 10 to 1200 seconds, and 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.

Is illuminated by the above irradiation conditions, the irradiation amount of ultraviolet rays having a wavelength of 313nm ^is preferably ^{0mJ / cm 2 ~50J / cm 2} , more preferably ^{0mJ / cm 2 ~20J / cm 2} . In order to perform a pre-tilt angle imparting good ^is preferably ^{0mJ / cm 2 ~10J / cm 2} , more preferably ^{0mJ / cm 2 ~3J / cm 2} . Reducing the amount of the polymerizable monomer remaining, to produce a liquid crystal display device 1 having a high voltage holding ratio ^is preferably ^{0mJ / cm 2 ~10J / cm 2} , 0mJ / cm 2 ~10J / It is more preferably cm ^2.

The irradiation amount of ultraviolet rays having a wavelength of 365nm ^is more preferably is preferably ^{10mJ / cm 2 ~500J / cm 2} , is ^{100mJ / cm 2 ~200J / cm 2} . The above irradiation amount can be appropriately adjusted according to the desired characteristics. Further, the intensity may be changed when irradiating with ultraviolet rays.

When the polymerization is carried out with the 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 located on the irradiation surface side transmits ultraviolet rays appropriately. Must have sex.

The voltage to be applied may be either direct current or alternating current, but is preferably alternating current. If the voltage is applied by alternating current, it is easy to obtain the liquid crystal layer 4 having a good orientation state of the liquid crystal molecules.

The frequency of the alternating current to be applied is preferably about 10 Hz to 10 kHz, more preferably about 60 Hz to 10 kHz.

The temperature when irradiating with ultraviolet rays is preferably within a temperature range in which the liquid crystal state of the liquid crystal composition is maintained. The specific temperature is preferably about 10 to 50 ° C., preferably about 15 to 45 ° C. Within such a temperature range, the polymerization proceeds while the polymerizable monomer is appropriately diffused in the liquid crystal composition, so that the polymerization proceeds well and the pretilt angle formation after the polymerization is good.

As the lamp that generates ultraviolet rays, a metal halide lamp, a high-pressure mercury lamp, an ultra-high-pressure mercury lamp, a fluorescent tube, or the like can be used.

Further, the ultraviolet rays to be irradiated may be used by cutting a predetermined wavelength if necessary. A cut filter can be used to cut the wavelength. For example, by cutting ultraviolet rays in a wavelength range including a wavelength of ₃₁₃ nm, it is possible to obtain ultraviolet rays satisfying _{I 365} / I 313> 20. By almost completely cutting ultraviolet rays in the wavelength range including the wavelength of ₃₁₃ nm, I 313 = 0, and in this case, I ₃₆₅ / I ₃₁₃ becomes infinite.

The pretilt angle imparted 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] may be the same as or different from those in the first ultraviolet irradiation step. Further, in the present invention, when ultraviolet irradiation is performed at the intensity ratio of the present invention in the above step [3], the peak intensity at a wavelength of 313 nm, the peak intensity at a wavelength of 365 nm and the intensity ratio thereof are the present application in the present step [4]. It does not prevent the irradiation of ultraviolet rays outside the scope of the invention.

However, even when an ultraviolet ray different from the first ultraviolet irradiation step is used, it is preferable to irradiate the ultraviolet ray having peaks at a wavelength of 313 nm and a wavelength of 365 nm as in the first ultraviolet irradiation step. The ultraviolet rays different from the first ultraviolet irradiation step _{preferably have I 365} / I ₃₁₃ of 20 or more, more preferably about 25 or more, and even more preferably 30 or more. Within the above range, deterioration and deterioration of liquid crystal molecules can be prevented. As a result, it is possible to prevent or suppress the occurrence of display defects (burn-in) in the liquid crystal display element 1.

_{Specifically, I 365} is preferably about 0.05~50mW / cm ^2, and more preferably about 0.05~30mW / cm ^2. In order to reduce the amount of residual polymerizable monomer and produce the liquid crystal display element 1 having a high voltage holding ratio, I ₃₆₅ is preferably 1 to 20 mW / cm ^2. On the other _{hand, I 313} is preferably about 0~10mW / cm ^2, and more preferably about 0~5mW / cm ^2. Thereby, the above-mentioned effect can be further improved.

From the viewpoint of more reliably preventing deterioration and deterioration of the liquid crystal molecules, ultraviolet rays do not have a peak in the wavelength region of less than 313 nm (particularly, the wavelength in the UVC region), or even if they have a peak. , It is preferable that the strength is extremely small.

The irradiation time of ultraviolet rays in this step [4] can also be defined in relation to the temperature of the liquid crystal layer 4. That is, in this step [4], the irradiation of ultraviolet rays is preferably performed until the temperature of the liquid crystal layer 4 rises by 1 to 20 ° C, more preferably 2 to 15 ° C, and the temperature rises by 3 to 10 ° C. It is more preferable to carry out until The temperature rise of the liquid crystal layer 4 in such a range indicates that the remaining polymerizable monomer was sufficiently consumed.

The specific irradiation time of ultraviolet rays depends on the type of ultraviolet rays used, but is preferably about 1 to 150 minutes, more preferably about 30 to 120 minutes.

The temperature when irradiating with ultraviolet rays is preferably within a temperature range in which the liquid crystal state of the liquid crystal composition is maintained. The specific temperature is preferably about 10 to 50 ° C., preferably about 15 to 45 ° C. Within such a temperature range, the polymerization proceeds while the polymerizable monomer is appropriately diffused in the liquid crystal composition, so that the polymerization proceeds satisfactorily and the remaining polymerizable monomer can be sufficiently consumed.

As the lamp that generates ultraviolet rays, a metal halide lamp, a high-pressure mercury lamp, an ultra-high-pressure mercury lamp, a fluorescent tube, or the like can be used.

Further, the ultraviolet rays to be irradiated may be used by cutting a predetermined wavelength as required by the liquid. A cut filter can be used to cut the wavelength. For example, by cutting ultraviolet rays in a wavelength range including a wavelength of ₃₁₃ nm, it is possible to obtain ultraviolet rays satisfying _{I 365} / I 313> 20. By almost completely cutting ultraviolet rays in the wavelength range including the wavelength of ₃₁₃ nm, I 313 = 0, and in this case, I ₃₆₅ / I ₃₁₃ becomes infinite.

The liquid crystal display element 1 is obtained through the above steps.

In the [2] assembly step, the vacuum injection method may be used instead of the drop injection (ODF) method. For example, in the vacuum injection method, first, the 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 proceeds to [3] a liquid crystal layer forming step and [4] a monomer consumption step.

Further, in another configuration example, the intensity ratio of the peak having a wavelength of 313 nm and the peak having a wavelength of 365 nm in the liquid crystal layer forming step is the relationship in the above-mentioned monomer consumption step, while the peak having a wavelength of 313 nm and the peak having a wavelength of 365 nm in the monomer consumption step are related. The strength ratio with and may be the relationship in the liquid crystal layer forming step. In this case, the specific intensity value of each peak and the irradiation time of ultraviolet rays are set so that the desired voltage retention rate and pretilt angle can be given to the obtained liquid crystal display element 1. Even in such a configuration, the same actions and effects as described above can be obtained.

In addition to the steps [3] and [4] above, in a further step, the peak intensity at a wavelength of 313 nm, the peak intensity at a wavelength of 365 nm, and the intensity ratio thereof may be irradiated with ultraviolet rays that are outside the range of the present invention. ..
[Liquid crystal composition]
In the production method of the present invention, the liquid crystal composition contains a polymerizable compound. More specifically, the liquid crystal composition used in the present invention comprises one or more compounds represented by the general formula (I) or the general formula (II) and a polymerization represented by the general formula (P). It contains one or more sex compounds.
(Liquid crystal compound represented by the formula (I))
The compound represented by the general formula (I) is as follows, and corresponds to a compound having a dielectric negative anisotropy. The “dielectrically negative anisotropy compound” refers to a compound having a negative sign of Δε and an absolute value greater than 2. The Δε of the compound is a value extrapolated from the measured value of the dielectric anisotropy of the composition obtained by adding the compound to the composition which is dielectrically substantially neutral at 25 ° C.

The compound represented by the general formula (I) is characterized by having at least one alkenyl group at the terminal, and by using the compound, the viscosity of the entire liquid crystal composition is lowered, and as a result, the response speed of the liquid crystal display element is reduced. Can be improved.

(In the formula, R ¹¹ and R ¹² each independently represent an alkyl group having 1 to 8 carbon atoms, and one or two or more non-adjacent −CH ₂ − in the alkyl group are independent of each other. It may be replaced by -CH = CH-, -C≡C-, -O-, -CO-, -COO- or -OCO-, but ^{at least one of R 11} and R ¹² has 2 carbon atoms. represents 8 alkenyl group, one or two or more -CH 2 in the alkenyl group _- may be further substituted on the oxygen atom to the extent that the oxygen atom not adjacent,
n ¹¹ and n ¹² represent 0, 1, 2 or 3, while n ¹ + n ² represents 1, 2 or 3.
A ¹¹ and ^{A 12} are each independently (a) 1,4-cyclohexylene group (this is present in the group one -CH ₂ - or nonadjacent two or more -CH ₂ - is -O (May be replaced with −) and (b) 1,4-phenylene group (one -CH = existing in this group or two or more -CH = not adjacent to each other is replaced with -N =. May be done.)
Represents a group selected from the group consisting of, and the hydrogen atoms in the above groups (a) and (b) may be independently substituted with cyano groups, fluorine atoms or chlorine atoms, respectively.
Z ¹¹ and ^{Z 12} each independently represent a single _{bond, -CH 2 CH 2 -, -} (CH 2) 4 -, - OCH 2 -, - CH 2 O -, - COO -, - OCO -, - OCF 2 Represents −, −CF ₂ O−, −CH = NN = CH−, −CH = CH−, −CF = CF− or −C≡C−.
If A ¹¹ and / or A ¹² there are a plurality, they may be the same or different and if Z ¹¹ and / or Z ¹² there are multiple, they have be the same or different You may. )
In the general formula (I), ^{at least one of R 11} and R ¹² is an alkenyl group having 2 to 8 carbon atoms, and the other is an alkyl group having 1 to 8 carbon atoms and an alkoxy group having 1 to 8 carbon atoms. It is preferably an alkenyl group having 2 to 8 carbon atoms or an alkenyloxy group having 2 to 8 carbon atoms. More specifically, ^{at least one of R 11} and R ¹² is an alkenyl group having 2 to 5 carbon atoms, and the other is an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, and carbon. It is preferably an alkenyl group having 2 to 5 atoms or an alkenyloxy group having 2 to 5 carbon atoms; at least one is an alkenyl group having 2 to 5 carbon atoms and the other is an alkyl having 1 to 5 carbon atoms. More preferably, it is a group or alkoxy group, or an alkenyl group having 2 to 5 carbon atoms; at least one is an alkenyl group having 2 to 5 carbon atoms and the other is an alkyl group or alkoxy having 1 to 5 carbon atoms. It is more preferably a group; it is particularly preferable that at least one is an alkenyl group having 2 to 3 carbon atoms and the other is an alkyl group or an alkoxy group having 1 to 3 carbon atoms.

When ^{the ring structure to which a group other than the alkoxy group is bonded among R 11} and R ¹² is a phenyl group (aromatic), the group other than the alkoxy group has a linear carbon atom number of 1 to 1. It is preferably an alkoxy group of 5, and when the ring structure to which it is bonded is a cyclohexane structure, it is preferably a linear alkyl group having 1 to 5 carbon atoms. In order to stabilize the nematic phase, the total of carbon atoms and, if present, oxygen atoms is preferably 5 or less, preferably linear. The alkenyl group is preferably selected from the groups represented by any of the following formulas (R1) to (R5), and the group represented by the formula (R1) or (R2) is particularly preferable, and R ¹¹ Is most preferably a group represented by the formula (R1) or (R2).

(The black dots in each equation represent carbon atoms in the ring structure.)
A ¹¹ and A ¹² are preferably aromatic when it is required to increase Δn, and preferably aliphatic in order to improve the response rate, to trans-1,4-cyclo. Xylene group, 1,4-phenylene group, 2-fluoro-1,4-phenylene group, 3-fluoro-1,4-phenylene group, 3,5-difluoro-1,4-phenylene group or 2,3-difluoro It preferably represents a -1,4-phenylene group, and more preferably a trans-1,4-cyclohexylene group or a 1,4-phenylene group.

Z ¹¹ and ^{Z 12} are each _{independently -CH} 2 and _{O -, - CF 2 O -} , - CH 2 CH 2 -, - CF 2 CF 2 - or preferably a single bond, _-CH 2 O- , -CH ₂ CH _2- or single bond is more preferred, and -CH ₂ O- or single bond is particularly preferred.

n ¹¹ + n ¹² is preferably 1 or 2, a ^{combination of n 11} being 1 and n ¹² being 0, a combination of n ¹¹ being 2 and n ¹² being 0, and n ¹¹ being 1 and n. ^A combination in which 12 is 1 and a combination in which n ¹¹ is 2 and n ¹² is 1 are preferable.

As the compound represented by the general formula (I), it is preferable to contain one or more compounds selected from the compound group represented by the general formulas (I-01) to (I-05), and the general formula is preferable. It is more preferable to contain one or more compounds selected from the compound group represented by (I-01) to (I-04).

In the formula, R ¹¹⁰ and R ¹²⁰ are independently similar ^{to R 11} and R ^{12 , respectively, and at least one of R 110} and R ¹²⁰ may be substituted with an oxygen atom. An alkenyl having 2 to 8 carbon atoms. Represents a group.

As R ¹¹⁰ , an alkenyl group having 2 to 8 carbon atoms is preferable, an alkenyl group having 2 to 5 carbon atoms is more preferable, and an alkenyl group having 2 to 3 carbon atoms is particularly preferable. The group represented by R2) is particularly preferable.

When R ¹¹⁰ is an alkenyl group, R ¹²⁰ is preferably an alkyl group having 1 to 5 carbon atoms or an alkoxy group having 1 to 5 carbon atoms, and particularly preferably an alkoxy group having 1 to 5 carbon atoms.

Z ¹¹⁰ and its preferred groups are similar ^{to Z 11} and Z ^{12 described above.}

m independently represents 1 or 2, and when m is 1, Z ¹ is preferably a single bond. When m is 2, Z ¹ is preferably −CH ₂ CH _2- or −CH ₂ O−.

The fluorine atom of the compound represented by the general formulas (I-01) to (I-05) may be replaced with a chlorine atom having the same halogen group. However, the content of the compound substituted with the chlorine atom should be as small as possible, and it is preferable not to contain the compound.

The hydrogen atom existing on the ring of the compound represented by the general formulas (I-01) to (I-05) may be substituted with a fluorine atom or a chlorine atom, but the chlorine atom is not preferable.

The compounds represented by the general formulas (I-01) to (I-05) are preferably compounds having a negative Δε and an absolute value of more than 3. Specifically, R ¹²⁰ preferably represents an alkoxy group having 1 to 8 carbon atoms or an alkenyloxy group having 2 to 8 carbon atoms, and an alkoxy group having 1 to 5 carbon atoms is particularly preferable.

Examples of the compounds represented by the general formulas (I-01) to (I-05) include general formulas (I-01-1) to (I-01-4) and general formulas (I-02-1) to ( One or more selected from the compounds represented by I-02-3), general formula (I-03-1), general formula (I-04-1) and general formula (I-05-1). Is preferably contained.

(In the above formula, R ¹¹⁰ is the same as above, and R ¹²¹ independently represents an alkoxy group having 1 to 5 carbon atoms.)
Among them, the compounds represented by the formula (I) are represented by the formulas (I-01-1) to (I-01-4), (I-02-1) and (I-03-1). The compounds represented by (I-01-3) to (I-01-4) are more preferable, and the compounds represented by (I-01-4) are most preferable.

The lower limit of the preferable content of the compound represented by the general formula (I) with respect to the total amount of the liquid crystal composition is 1%, 3%, 5%, 7%, and 10%. 12%, 15%, 18%, 20%, 30%, 40%, 50%, 55%, 60%. The preferred upper limit of content is 40%, 35%, 25%, 20%, 18%, 15%, 12%, 9%, 5%. Is. In this specification, "%" means "mass%" unless otherwise defined or described.
(Liquid crystal compound represented by formula (II))
The compound represented by the general formula (II) is as follows, and corresponds to a dielectrically substantially neutral compound. The "dielectrically substantially neutral compound" means a compound having a value of Δε of -2 to 2.

The compound represented by the general formula (II) is characterized by having at least one alkenyl group at the terminal like the compound represented by the general formula (I), and by using the compound, the entire liquid crystal composition can be used. As a result, the response speed of the liquid crystal display element can be improved.

(In the formula, R ²¹ and R ²² each independently represent an alkyl group having 1 to 8 carbon atoms, and one or two or more non-adjacent −CH ₂ − in the alkyl group are independent of each other. It may be replaced by -CH = CH-, -C≡C-, -O-, -CO-, -COO- or -OCO-, but ^{at least one of R 21} and R ²² has 2 carbon atoms. represents 8 alkenyl group, one or two or more -CH 2 in the alkenyl group _- may be further substituted on the oxygen atom to the extent that the oxygen atom not adjacent,
A ^{21, A 22} and ^{A 23} are each independently (a) 1,4-cyclohexylene group (this is present in the group one -CH ₂ - or nonadjacent two or more -CH ₂ - May be replaced with -O-) and (b) 1,4-phenylene group (one -CH = present in this group or two or more non-adjacent -CH = -N May be replaced with =)
Represents a group selected from the group consisting of, and the hydrogen atoms in the above groups (a) and (b) may be independently substituted with cyano groups, fluorine atoms or chlorine atoms, respectively.
Z ²¹ and ^{Z 22} each independently represent a single _{bond, -CH 2 CH 2 -, -} (CH 2) 4 -, - OCH 2 -, - CH 2 O -, - COO -, - OCO -, - OCF 2 Represents −, −CF ₂ O−, −CH = NN = CH−, −CH = CH−, −CF = CF− or −C≡C−.
n ²¹ represents 0, 1, 2 or 3
When a ^{plurality of A 22} and Z ²² are present, they may be the same or different, except for the compound represented by the above formula (I). )
In the general formula (II), ^{at least one of R 21} and R ²² is an alkenyl group having 2 to 8 carbon atoms, and the other is an alkyl group having 1 to 8 carbon atoms and an alkoxy group having 1 to 8 carbon atoms. It is preferably an alkenyl group having 2 to 8 carbon atoms or an alkenyloxy group having 2 to 8 carbon atoms. More specifically, ^{at least one of R 21} and R ²² is an alkenyl group having 2 to 5 carbon atoms, and the other is an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, and carbon. It is preferably an alkenyl group having 2 to 5 atoms or an alkenyloxy group having 2 to 5 carbon atoms; at least one is an alkenyl group having 2 to 5 carbon atoms and the other is an alkyl having 1 to 5 carbon atoms. More preferably, it is a group or alkoxy group, or an alkenyl group having 2 to 5 carbon atoms; at least one is an alkenyl group having 2 to 5 carbon atoms and the other is an alkyl group or alkoxy having 1 to 5 carbon atoms. It is more preferably a group; it is particularly preferable that at least one is an alkenyl group having 2 to 3 carbon atoms and the other is an alkyl group or an alkoxy group having 1 to 3 carbon atoms.

In order to stabilize the nematic phase, the total of carbon atoms and, if present, oxygen atoms is preferably 8 or less, more preferably 5 or less, and preferably linear. .. The alkenyl group is preferably selected from the groups represented by any of the above formulas (R1) to (R5), and the group represented by the formula (R1) or (R2) is particularly preferable, and R ²¹ Is most preferably a group represented by the formula (R1) or (R2).

A ²¹ , A ²² and A ²³ have a trans-1,4-cyclohexylene group, a 1,4-phenylene group, a 2-fluoro-1,4-phenylene group, and a 3-fluoro-1,4-phenylene group. It is preferably represented, and more preferably represented as a trans-1,4-cyclohexylene group or a 1,4-phenylene group.

Z ²¹ and ^{Z 22} are each _{independently -CH} 2 and _{O -, - CF 2 O -} , - CH 2 CH 2 -, - CF 2 CF 2 - or preferably a single bond, _-CH 2 O- , -CH ₂ CH _2- or a single bond is more preferred, and a single bond is particularly preferred.

n ²¹ is preferably 0 or 1, most preferably 0.

As the compound represented by the general formula (II), it is preferable to contain one or more compounds selected from the compound group represented by the general formulas (II-01) to (II-06), and the general formula is preferable. It is more preferable to contain one or more compounds selected from the compound group represented by (II-01) to (II-05).

In the formula, R ²¹⁰ and R ²²⁰ are independently similar ^{to R 21} and R ^{22 , respectively, and at least one of R 210} and R ²²⁰ is an alkenyl having 2 to 8 carbon atoms which may be substituted with an oxygen atom. Represents a group.

As R ²¹⁰ , an alkenyl group having 2 to 8 carbon atoms is preferable, an alkenyl group having 2 to 5 carbon atoms is more preferable, and an alkenyl group having 2 to 3 carbon atoms is further preferable. The group represented by R2) is particularly preferable.

When R ²¹⁰ is an alkenyl group, R ²²⁰ is preferably an alkyl group having 1 to 5 carbon atoms or an alkoxy group having 1 to 5 carbon atoms.

As the compound represented by the general formulas (II-01) to (II-06), one or 2 selected from the compounds represented by the general formulas (II-01-1) to (II-01-5). It preferably contains more than a seed.

In the formula, R ²¹¹ independently represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms.
A hydrogen atom or an alkyl group having 1 to 3 carbon atoms is preferable, and a hydrogen atom or an alkyl group having 1 carbon number is particularly preferable.

Although n ²² independently represents an integer of 0 to 5, the total of the number of carbon atoms and the number of n ^{22 when R 211 is an alkyl group does not exceed 6.} n ²² is preferably 0 or 1, and 0 is particularly preferable.

^R221 represents 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 5 carbon atoms, and an alkyl group having 1 to 5 carbon atoms or 1 to 5 carbon atoms. Alkoxy group of 5 is preferable.

Among them, as the compound represented by the formula (II), the compound represented by the formula (II-01-1) is preferable, and in the formula (II-01-1), R ²¹¹ is a hydrogen atom or a methyl group. A compound in which n ²² is 0 or 1 is more preferable, a compound in which R ²¹¹ is a hydrogen atom or a methyl group, and ^{a compound in which n 22} is 0 is more preferable, and a compound in which R ²¹¹ is a hydrogen atom and n ²² is 0. Especially preferable. At this time, R ²²¹ is preferably a propyl group.

The lower limit of the preferable content of the compound represented by the general formula (II) with respect to the total amount of the liquid crystal composition is 1%, 3%, 5%, 7%, and 10%. 12%, 15%, 18%, 20%, 22%, 25%, 27%, 30%, 40%, 50%. , 55%, 60%, 65%, 70%, 75%, 80%. The preferred upper limit of content is 65%, 55%, 45%, 35%, 30%, 27%, 25%, 20%, 18%. , 15%, 12%, 9%, 5%.
(Polymerizable compound represented by the formula (P))
The compound represented by the general formula (P) is a polymerizable compound whose polymerization proceeds by irradiation with energy rays such as ultraviolet rays. More specifically, the polymerizable compound represented by the formula (P) is polymerized in the liquid crystal layer forming step [3] and the monomer consumption step [4] described above.

(In the above formula, P ^p1 and P ^p2 each independently represent a polymerizable group.
Sp ^p1 and Sp ^p2 independently represent a spacer group or a single bond, respectively.
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-} (in the formula, R ZP 1) Each independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, ^{but when there are a plurality of R ZP1s} in the molecule, they may be the same or different).
A ^p1 , A ^p2 and A ^p3 are independent of each other.
^(A p) 1,4-cyclohexylene group (one present in the base or two or more -CH ₂ - may be replaced by -O- to the extent that the oxygen atom not adjacent. )
^(B p) 1,4-phenylene group (one or more -CH present in the base = may be replaced by -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 , Phenylene-2,7-diyl group or anthracene-2,6-diyl group (one or more -CH = present in the group may be substituted with -N =).
Represents a group selected from the group consisting of the group (a ^p), group (b ^p) and one or more hydrogen atoms present in the radical (c ^p) are each independently a halogen atom, It may be substituted with a cyano group, an alkyl group having 1 to 18 carbon atoms which may be substituted with a fluorine atom, or −Sp ^p2 −P ^p2 , and one of the alkyl groups or two or more non-adjacent − Even if CH ₂ − is independently substituted with −CH = CH −, −C≡C−, −O−, −CO−, −COO− or −OCO− so that oxygen atoms are not directly adjacent to each other. Often,
^Further, when ^{m p1} is a ^{group A p1} is represented by group ^{(c p)} in 0 ^{A p3} may be a single bond,
m ^p1 represents 0, 1, 2 or 3
When there are a plurality of Z ^p1 , A ^p2 , Sp ^p2 and / or P ^{p2 in the} molecule, they may be the same or different. )
A ^p1 , A ^p2 and A ^p3 are independent of each other.
^(A p) 1,4-cyclohexylene group (this is present in the group one -CH ₂ - or nonadjacent two or more -CH ₂ - may be replaced by -O-.)
^(B p) 1,4-phenylene group (the one present in the group -CH = or non-adjacent two or more -CH = may be replaced by -N =.) And (c ^p ) Naphthalene-2,6-diyl group, naphthalene-1,4-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 = existing in these groups or two or more non-adjacent -CH = may be replaced with -N = good.)
Represents a group selected from the group consisting of the above group (a ^p), group (b ^p) and one or more hydrogen atoms present in the radical (c ^p) are each independently a halogen atom , a cyano group, may be substituted with an alkyl group or ^-Sp p2 ^{-P p2} having 1 to 8 carbon atoms, one or two or more -CH ₂ non-adjacent in the alkyl group - each independently Then, it may be replaced by −CH = CH−, −C≡C−, −O−, −CO−, −COO− or −OCO−.
m ^p1 represents 0, 1, 2 or 3, ^{and when a plurality of Z p1} , ^Ap2 , Sp ^p2 and / or P ^p2 are present in the molecule, they may be the same or different. A ^p3 represents a single bond when m ^p1 is 0 and A ^p1 is a phenanthrene-2,7-diyl group or an anthracene-2,6-diyl group. )
P ^p1 and P ^p2 are independently polymerizable groups, and are preferably groups represented by any of the following ^{general formulas (P p1-1} ) to (P ^p1-9).

In the formula, R ^p11 and R ^p12 independently represent a hydrogen atom, an alkyl group having 1 to 5 carbon atoms or an alkyl halide group having 1 to 5 carbon atoms, and independently represent a hydrogen atom or methyl. It is preferably a group.

W ^p11 represents a single bond, -O-, -COO- or an alkylene group having 1 to 3 carbon atoms, and a single bond, a methylene group or an ethylene group is preferable.

t ^p11 represents 0, 1 or 2, and 0 or 1 is preferable.

When a ^{plurality of R p11} , R ^p12 , W ^p11 and / or t ^p11 are present in the molecule, they may be the same or different.

Among ^{them, P p1} and ^{P p2} is able independently is preferably one of the formula ^(P p1 -1) ~ formula ^(P p1 -3), an expression ^(P p1 -1) More preferably, all P ^p1 and P ^p2 present in the molecule are of the formula (P ^p1-1 ). Further, it is preferable to have a total of two polymerizable groups represented by ^{P p1} and P ^p2 in the molecule, and ^{it is preferable that the two P p1} and P ^p2 are both (P ^p1-1 ). ^{R p11} in the two (P ^p1-1 ) is preferably a methyl group, or a combination of a hydrogen atom and a methyl group is preferable.

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

Z ^p1 and ^{Z p2} are each independently a single _{bond, -OCH 2 -, - CH 2} O -, - CO -, - C 2 H 4 -, - COO -, - OCO -, - CH = CH-, _{-CF 2 -, - CF 2 O} -, - (CH 2) 2 -COO -, - (CH 2) 2 -OCO -, - COO- (CH 2) 2 -, - OCO- (CH 2) 2 - , -CH = CH-COO-, -CH = CH-OCO-, -COO-CH = CH-, -OCO-CH = CH-, -OCF _2- or -C≡C-; each independently a single _{bond, -OCH 2 -, - CH 2} O -, - C 2 H 4 -, - COO -, - OCO -, - CH = CH -, - (CH 2) 2 -COO -, - (CH 2 ) _2- OCO-, -COO- (CH ₂ ) _2- , -OCO- (CH ₂ ) _2- , -CH = CH-COO-, -CH = CH-OCO-, -COO-CH = CH-, -OCO-CH = CH- or -C≡C- is more preferred. Furthermore, only one present in the molecule is _{-OCH 2 -, - CH 2 O} -, - C 2 H 4 -, - COO -, - OCO -, - CH = CH -, - (CH 2) 2 -COO-,-(CH ₂ ) _2- OCO-, -COO- (CH ₂ ) _2- , -OCO- (CH ₂ ) _2- , -CH = CH-COO-, -CH = CH-OCO-, It is particularly preferred that -COO-CH = CH-, -OCO-CH = CH- or -C≡C-, all others are single bonds, or all are single bonds.

When Sp ^p1 and Sp ^p2 are spacer groups, the spacer group is preferably an alkylene group having 1 to 30 carbon atoms, and −CH ₂ − in the alkylene group is −O−, unless oxygen atoms are directly linked to each other. It may be substituted with −CO−, −COO−, −OCO−, −CH = CH− or −C≡C−, and the hydrogen atom in the alkylene group may be substituted with a halogen atom. As Sp ^p1 and Sp ^p2 , a linear alkylene group having 1 to 10 carbon atoms or a single bond is preferable.

A ^p1 , A ^p2 and A ^p3 are independently 1,4-cyclohexylene group, 1,4-phenylene group or naphthalene-1,4-diyl group, respectively, preferably 1,4-phenylene group or naphthalene-1. , 4-Diyl groups are more preferred. It is particularly preferred to have one or more 1,4-phenylene groups in the molecule. These rings are preferably substituted with one fluorine atom, one methyl group or one methoxy group in order to improve the compatibility with the liquid crystal compound.

A suitable example of the polymerizable compound represented by the formula (P) is shown below.

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

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

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

(In the formula, P ^p41 , P ^p42 , Sp ^p41 and Sp ^{p42 have the same meanings as P p1} , P ^p2 , Sp ^p1 and Sp ^p2 in the general formula (P), and a plurality of P ^p42 and Sp ^p42 are the same, respectively. It may be different.)

(In the formula, P ^p51 , P ^p52 , Sp ^p51 and Sp ^{p52 have the same meanings as P p1} , P ^p2 , Sp ^p1 and Sp ^p2 in the general formula (P), and a plurality of P ^p52 and Sp ^p52 are the same, respectively. It may be different. Me indicates a methyl group.)
In the present invention, the high-speed response of the liquid crystal display element is achieved by using the alkenyl liquid crystal compound, but the polymerization rate of the polymerizable compound may be slightly slowed down by using the alkenyl liquid crystal compound. Therefore, by using a highly reactive compound as the polymerizable compound, it is possible to prevent a decrease in the polymerization rate. By obtaining a sufficient polymerization rate, the productivity at the time of manufacturing the liquid crystal display element is improved, and the obtained liquid crystal display element can have good display quality by reducing display defects such as unevenness and seizure. As the highly reactive polymerizable compound, the compounds listed in the above formulas (P-1-21) to (P-1-46) and (P-5-1) to (P-5-19) are preferable.

The compound represented by the formula (P) may be used alone or in combination of two or more. In particular, by using two or three or more kinds of polymerizable monomers having different polymerization reaction rates in combination, the polymerization reaction rate can be appropriately controlled, the amount of residual monomers can be reduced, and an appropriate pretilt can be achieved. It is preferable because it can impart horns. Further, from the viewpoint of the balance between storage stability and polymerization reaction rate, it is preferable to use two or more kinds of polymerizable monomers in combination.

The total content of the compounds represented by the formula (P) is preferably 0.05 to 10%, preferably 0.1 to 8%, based on the composition containing the compounds. It preferably contains 0.1 to 5%, preferably 0.1 to 3%, preferably 0.2 to 2%, and preferably 0.2 to 1.3%. It is preferable that it contains 0.2 to 1%, and it is preferable that it contains 0.2 to 0.56%.

The preferable lower limit of the total content of the compounds represented by the formula (P) is 0.01%, 0.03%, and 0.05% with respect to the composition containing those compounds. , 0.08%, 0.1%, 0.15%, 0.2%, 0.25%, 0.3%.

The preferable upper limit of the total content of the compounds represented by the formula (P) is 10%, 8%, 5%, and 3% with respect to the composition containing those compounds. It is 1.5%, 1.2%, 1%, 0.8%, and 0.5%.

If the content is low, the effect of adding the compound represented by the formula (P) is unlikely to appear, and problems such as weak orientation control force of the liquid crystal composition or weakening over time occur. If the content is too high, after curing Problems such as a large amount remaining, a long curing time, and a decrease in the reliability of the liquid crystal display occur. Therefore, the content is set in consideration of these balances.
(Other liquid crystal compounds)
The liquid crystal composition used in the present invention is one or more of the compounds represented by the above formula (I) or (II) and one or two kinds of the polymerizable compound represented by the above formula (P). In addition to the above, other liquid crystal compounds may be further contained.

Other liquid crystal compounds include compounds in the above formula (I) in which ^{both R 11} and R ¹² are not alkenyl groups having 2 to 8 carbon atoms (hereinafter referred to as "compound (I')"), and the above formula (hereinafter referred to as "compound (I')"). In II), a ^{compound in which both R 21} and R ²² are not alkenyl groups having 2 to 8 carbon atoms (hereinafter, referred to as “compound (II ′)”) is mentioned as a preferable compound.
-Compound (I')
Examples of the compound (I') include compounds represented by the following formula (I').

'In, ^{R 11} Formula ^(I)' is independently each and ^{R 12 'represents} an alkyl group having 1 to 8 carbon atoms, one or non-adjacent two or more -CH ₂ in the alkyl group − May be independently substituted with −C≡C−, −O−, −CO−, −COO− or −OCO−, respectively, and an alkyl group having 1 to 5 carbon atoms or an alkyl group having 1 to 5 carbon atoms. It is preferably an alkoxy group. When the ring structure R ^{11 'and} R ^12' are attached is a phenyl group is preferably an alkyl group or an alkoxy group having 1 to 5 carbon atoms of 1 to 5 carbon atoms, bonded to the ring structure When is a cyclohexylene group, it is preferably an alkyl group having 1 to 5 carbon atoms.

In the formula ^{(I '), A 11,} A 12, Z 11, Z 12, n 11, n 12 respectively the same as ^{A 11, A 12, Z 11} , Z 12, n 11, n 12 in the formula (I) Is.

The compound (I') preferably contains one or more compounds selected from the compound group represented by the general formulas (I'-01) to (I'-05), and preferably contains the general formula (I'). It is more preferable to contain one or more compounds selected from the compound group represented by'-01) to (I'-04).

In the formula, R ^110'is independently the same as R ^11', and an alkyl group having 1 to 5 carbon atoms or an alkoxy group having 1 to 5 carbon atoms is preferable, and an alkyl having 1 to 3 carbon atoms is preferable. Groups are more preferred.

R ^{120, Z 110,} m is the same as ^{R 120, Z 110,} m in each of the formulas (I-01) ~ (I -05).

The fluorine atom of the above compound may be substituted with a chlorine atom of the same halogen group. However, the content of the compound substituted with the chlorine atom should be as small as possible, and it is preferable not to contain the compound. Further, the hydrogen atom existing on the ring of the compound may be substituted with a fluorine atom or a chlorine atom, but the chlorine atom is not preferable. The above compound is preferably a compound in which Δε is negative and its absolute value is larger than 3.

The lower limit of the preferable content of the compound represented by the general formula (I') with respect to the total amount of the liquid crystal composition is 0%, 1%, 5%, 10%, and 20. %, 30%, 40%, 50%, 55%, 60%, 65%, 70%, 75%, 80%. The preferred upper limit of content is 95%, 85%, 75%, 65%, 55%, 45%, 35%, 25%, 20%. It is 15% and 10%.
-Compound (II')
Examples of the compound (II') include compounds represented by the following formula (II').

'In, ^{R 21} Formula ^(II)' is independently each and ^{R 22 'represents} an alkyl group having 1 to 8 carbon atoms, one or non-adjacent two or more -CH ₂ in the alkyl group − May be independently substituted with −C≡C−, −O−, −CO−, −COO− or −OCO−, respectively, and an alkyl group having 1 to 5 carbon atoms or an alkyl group having 1 to 5 carbon atoms. It is preferably an alkoxy group. When the ring structure R ^{21 'and} R ^22' are attached is a phenyl group is preferably an alkyl group or an alkoxy group having 1 to 5 carbon atoms of 1 to 5 carbon atoms, bonded to the ring structure When is a cyclohexylene group, it is preferably an alkyl group having 1 to 5 carbon atoms.

In the formula ^{(II '), A 21,} A 22, A 23, Z 21, Z 22, n 21 respectively the same as ^{A 21, A 22, A 23} , Z 21, Z 22, n 21 in the formula (II) Is.

The compound (II') preferably contains one or more compounds selected from the compound group represented by the general formulas (II'-01) to (II'-06).

In the formula, R ^210'is independently the same as R ^21', and an alkyl group having 1 to 5 carbon atoms or an alkoxy group having 1 to 5 carbon atoms is preferable.

R ²²⁰ is the same as ^{R 220} in formula (II'-01) ~ (II' -06).

The lower limit of the preferable content of the compound represented by the general formula (II') with respect to the total amount of the liquid crystal composition used in the present invention is 0%, 1%, 5%, and 10%. 20%, 30%, 40%, 50%, 55%, 60%, 65%, 70%, 75%, 80%. Is. The preferred upper limit of content is 95%, 85%, 75%, 65%, 55%, 45%, 35%, 25%, 20%. It is 15% and 10%.
(Sensitizer)
A sensitizer can also be added to the liquid crystal composition used in the present invention. Here, the sensitizer refers to a compound having an action of promoting the polymerization reaction of the polymerizable compound, and in the present invention, it means promoting the polymerization of the polymerizable compound represented by the formula (P).

In the present invention, the high-speed response of the liquid crystal display element is achieved by using the alkenyl liquid crystal compound, but the polymerization rate of the polymerizable compound may be slightly slowed down by using the alkenyl liquid crystal compound. When the polymerization rate of the composition used in the present invention is not sufficient, the polymerization rate can be improved by using the above-mentioned polymerizable compound and a sensitizer in combination. By improving the polymerization rate, the productivity at the time of manufacturing the liquid crystal display element is improved, and the obtained liquid crystal display element can have good display quality by reducing display defects such as unevenness and seizure.

As the sensitizer, a compound represented by the following general formula (S) is preferable.

In the formula, R ^s1 and R ^s2 are independently an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, or 2 to 2 carbon atoms. It represents 10 alkoxyoxy groups, and one or more hydrogen atoms present in these groups may be substituted with fluorine atoms.

Since the effect of improving the reliability of VHR and the like is high, it is preferable that R ^s1 and R ^s2 are independently an alkyl group having 1 to 5 carbon atoms or an alkoxy group having 1 to 5 carbon atoms. , An alkyl group having 1 to 3 carbon atoms or an alkoxy group having 1 to 3 carbon atoms is particularly preferable.

One or more hydrogen atoms present in the groups of R ^s1 and R ^s2 may or may not be substituted with a fluorine atom, ^{but R s1} and R ^{s2 are fluorine atoms.} It is preferable that it is not replaced with.

Ring A ^s1 and ring B ^s1 are independent of each other.
(A) 1,4-cyclohexylene group (this is present in the group one -CH ₂ - or nonadjacent two or more -CH ₂ - may be replaced by -O-.)
(B) 1,4-Phenylene group (one -CH = existing in this group or two or more -CH = not adjacent to each other may be replaced with -N =).
(C) Naphthalene-2,6-diyl group, 1,2,3,4-tetrahydronaphthalene-2,6-diyl group or decahydronaphthalene-2,6-diyl group (naphthalene-2,6-diyl group or One -CH = present in the 1,2,3,4-tetrahydronaphthalene-2,6-diyl group or two or more non-adjacent -CH = may be replaced with -N =. ) And (d) represent a group selected from the group consisting of 1,4-cyclohexenylene groups, and the above groups (a), group (b), group (c) and group (d) are independently fluorine. It may be substituted with an alkyl group having 1 to 8 carbon atoms which may be substituted with an atom, an alkoxy group having 1 to 8 carbon atoms which may be substituted with a fluorine atom, a cyano group, or a fluorine atom.

Among them, the ring ^As1 and the ring ^Bs1 include a 1,4-cyclohexylene group, an unsubstituted 1,4-phenylene group, a 2-fluoro-1,4-phenylene group, and a 3-fluoro-1,4-phenylene. More preferably, it is a group or a 2,3-difluoro-1,4-phenylene group.

To elaborate further. ^{Ring As1} and ring B ^s1 are independently unsubstituted 1,4-phenylene group, 2-fluoro-1,4-phenylene group, 3-, respectively, because the polymerization rate of the polymerizable compound can be increased. It is preferably a fluoro-1,4-phenylene group or a 2,3-difluoro-1,4-phenylene group, and particularly preferably an unsubstituted 1,4-phenylene group. The unsubstituted phenylene group has a UV absorption wavelength band located on the longer wavelength side than the phenylene group substituted with another atom such as a fluorine atom. As a result, the polymerizable compound-containing liquid crystal composition of the present invention containing the compound represented by the general formula (S) having an unsubstituted phenylene group contains the compound represented by the general formula (S) having a substituent. The reaction rate of the polymerizable compound can be increased, and the decrease in VHR can be sufficiently suppressed.

^{On the other hand, ring As1} and ring B ^s1 independently have 2-fluoro-1,4-phenylene groups and 3-fluoro-1,4, respectively, because the miscibility with other liquid crystal components is further improved. -Preferably a phenylene group or a 2,3-difluoro-1,4-phenylene group.

When a ring A ^s1 and the ring B ^s1 is present in plural, the plurality of rings A ^s1 and a plurality of rings B ^s1 may each be the same or different.

Z ^s1 and Z ^s2 are independently -OCH _2- , -CH ₂ O-, -COO-, -OCO-, -CF ₂ O-, -OCF _2- , -CH ₂ CH ₂ -,-, respectively. CF ₂ CF _2- , -C ≡ C- or a single bond, _{preferably -OCH 2-} , -CH ₂ O-, -CH ₂ CH _2- or a single bond, in order to increase the polymerization rate of the polymerizable compound. Is particularly preferred for single bonds.

Since n ^s1 and n ^s2 independently represent 0, 1 or 2, respectively, and the miscibility with other liquid crystal molecules becomes better, one of n ^s1 or n ^s2 represents 1 or 2 and the other represents 0. It is preferable to represent. Further, n ^s1 + n ^s2 represents an integer of 1 to 4, but is preferably 1 or 2 from the viewpoint of miscibility with other liquid crystal molecules, and miscibility with other liquid crystal molecules and tilt stability are further improved. It is more preferably 1 because it is good.

X ^{s1 to} X ^s6 are independently an alkyl group having 1 to 8 carbon atoms which may be substituted with a fluorine atom, an alkoxy group having 1 to 8 carbon atoms which may be substituted with a fluorine atom, and a fluorine atom. Alternatively, it represents a hydrogen atom, preferably an alkyl group having 1 to 5 hydrogen atoms, an alkoxy group having 1 to 5 carbon atoms, a fluorine atom or a hydrogen atom, more preferably a fluorine atom or a hydrogen atom, and hydrogen. It is particularly preferred to be an atom.

The number of groups that are hydrogen atoms in X ^{s1 to} X ^{s6 is preferably at least 3.} Specifically, ^{the number of groups that are hydrogen atoms in X s1 to} X ^s6 is preferably 3, 4, 5 or 6, preferably 4, 5 or 6, and is 5 or 6. It is preferably 6, and more preferably 6.

As the compound represented by the general formula (S), each compound represented by the following general formulas (S-1) to (S-5) is preferable, and the general formulas (S-1), (S-2) or The compound represented by (S-4) is more preferable, and the compound represented by the general formula (S-1) is particularly preferable.

In the above ^{formulas, R s1} and ^{R s2} are the same as ^{R s1} and ^{R s2,} respectively in the general formula (S), a hydrogen atom bonded to the ring in the formula, a fluorine atom, carbon atoms 1-3 It may be substituted with an alkyl group (preferably a methyl group) or an alkoxy group having 1 to 3 carbon atoms (preferably a methoxy group).

The compound of the general formula (S) can accelerate the polymerization reaction of the polymerizable compound by its sensitizing action, but on the other hand, if the content of the compound of the general formula (S) is too large, the reaction takes a short time. In some cases, it is difficult to form a tilt having a sufficient size, or in some cases, the VHR is lowered. On the other hand, in the polymerizable compound-containing liquid crystal composition of the present invention, the polymerizable compound can be sufficiently polymerized at a high speed by adjusting the content of the compound of the general formula (S) within a predetermined range. Therefore, it is possible to form a tilt having a sufficient size in a short time, it is possible to suppress a decrease in VHR due to UV irradiation, and various characteristics can be satisfied in a well-balanced manner.

The content of the compound of the general formula (S) may be less than 2.0% of the total amount of the liquid crystal composition, and the upper limit of the content is preferably 1.9%, 1.8%, 1. 7%, 1.6%, 1.5%, 1.4%, 1.3%, 1.2%, 1.0%, 0.9%, 0.8%, 0.7%, 0. It is 6% and 0.5%. The content of the compound of the general formula (S) may be more than 0% of the total amount of the liquid crystal composition, and the lower limit of the content is preferably 0.01%, 0.05%, 0. .1%, 0.2%, 0.3%, 0.4%, 0.5%, 0.6%, 0.7%, 0.8%, 0.9%, 1.0%. ..
(Other additives)
-Compound represented by the formula (A) A compound represented by the following general formula (A) can be added to the liquid crystal composition used in the present invention.

The compound represented by the general formula (A) has a monovalent polar group Z ^AT1 containing a polar element in its structure, and this polar group adsorbs and collects impurities. As a result, it is considered that impurities are not diffused in the entire liquid crystal layer, and the decrease in specific resistance and the decrease in VHR due to the impurities can be suppressed.

In the formula, ^RAK1 represents a linear or branched alkyl group having 1 to 20 carbon atoms, preferably a linear or branched alkyl group having 1 to 20 carbon atoms, and a straight chain having 1 to 20 carbon atoms. Alkyl groups are more preferred, and linear alkyl groups having 1 to 8 carbon atoms are even more preferred. One or two or more non-adjacent −CH ₂ −s in the alkyl group are independently −CH = CH−, −C≡C−, −O−, − so that the oxygen atoms are not directly adjacent to each other. It may be replaced with CO-, -COO- or -OCO-. Further, one or more hydrogen atoms in the alkyl group may be independently substituted with halogen atoms. As the halogen atom, a fluorine atom or a chlorine atom is preferable, and a fluorine atom is more preferable.

A ^AL1 and A ^AL2 each independently represent a divalent cyclic group. The divalent cyclic group includes 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 , Pyridin-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] selenophen It is preferably one selected from the group consisting of a -2,7-diyl group and a fluorene-2,7-diyl group. Among them, A ^AL1 and A ^AL2 are more preferably 1,4-phenylene group, 1,4-cyclohexylene group, 2,6-naphthylene group or phenanthrene-2,7-diyl group, respectively. , 4-Phenylene group or 1,4-cyclohexylene group is more preferable.

The divalent cyclic group may be unsubstituted, and one or more hydrogen atoms in the cyclic group may be substituted with the substituent. Examples of the substituent include a halogeno group, a polar group, P ^{AP1 -Sp} AP1 ^- or a monovalent organic group and the like, and a monovalent organic group is the alkyl group, the alkyl group is substituted with a fluorine atom or a hydroxyl group You may. Examples of the halogeno group include a fluoro group and a chloro group, and a fluoro group is preferable.

Here, the "monovalent organic group" is a group having a chemical structure formed by the organic compound in the form of a monovalent group, and refers to an atomic group obtained by removing one hydrogen atom from the organic compound. .. Examples of the monovalent organic group include an alkyl group having 1 to 15 carbon atoms, an alkenyl group having 2 to 15 carbon atoms, an alkoxy group having 1 to 14 carbon atoms, and an alkenyloxy having 2 to 15 carbon atoms. The group and the like can be mentioned. The alkyl group, the alkenyl group, the alkoxy group, and one or more of -CH _2- in the alkenyloxy group are -O-, -COO-, or-so that oxygen atoms are not directly adjacent to each other. It may be replaced with OCO−.

Among them, the monovalent organic group is preferably an alkyl group having 1 to 15 carbon atoms or an alkoxy group having 1 to 14 carbon atoms, and an alkyl group having 1 to 8 carbon atoms or 1 to 1 carbon atoms. It is more preferably an alkoxy group having 8 carbon atoms, further preferably an alkyl group having 1 to 5 carbon atoms or an alkoxy group having 1 to 4 carbon atoms, and an alkyl group having 1 to 3 carbon atoms or an alkoxy group having 1 to 4 carbon atoms. It is particularly preferably an alkoxy group having 1 or 2, and most preferably an alkyl group having 1 or 2 carbon atoms or an alkoxy group having 1 carbon atom. The alkyl group, the alkenyl group, the alkoxy group, and one or more of -CH _2- in the alkenyloxy group are -O-, -COO-, or-so that oxygen atoms are not directly adjacent to each other. It may be replaced with OCO−.

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, one or adjacent to the alkylene group. two or more -CH ₂ not -, the cyclic group such that oxygen atoms are not directly bonded, -CH = CH -, - C≡C -, - O -, - CO -, - COO- or -OCO- May be replaced with. Among them, an alkylene group of a single bond or a C2-20 is preferred, more preferably an alkylene group of a single bond or a C2-10 a single bond, - _{(CH 2) 2} - or - _(CH 2) ₄ -is more preferable. One or more -CH _2- in the alkylene group may be substituted with -O-, -COO- or -OCO- so that oxygen atoms are not directly adjacent to each other.

When increasing the linearity of the compound represented by the formula (A), Z ^AL1 is an alkylene group having an even number of atoms having an even number of carbon atoms, which is a single bond or directly connects the ring to the ring. Is preferable. One or two or more non-adjacent -CH _2- in the alkylene group may be substituted with -O-, -COO- or -OCO- so that the oxygen atom is not directly adjacent. The number of atoms that directly connect the ring to the ring is, for example, four in the case of _{-CH 2-} CH _{2 COO-.}

m ^AL1 represents an integer of 1 to 5, preferably an integer of 1 to 4, more preferably an integer of 1 to 3, and even more preferably 2 or 3.

Sp ^AT1 represents a single bond or a linear or branched alkylene group having 1 to 25 carbon atoms, and one or more hydrogen atoms in the alkylene group are -OH, -CN, -W ^AT1- Z ^AT1 or ^P AP1 ^{-Sp AP1} - may be substituted with, one or nonadjacent two or more -CH ₂ in the alkylene group - is, as the oxygen atoms are not directly bonded cyclic group, -CH = CH-, -C≡C-, -O-, -CO-, -COO- or -OCO- may be substituted. Among them, it is preferable to represent a single bond or a linear or branched alkylene group having 1 to 20 carbon atoms, and more preferably to represent a single bond or a linear alkylene group having 1 to 20 carbon atoms. It is more preferable to represent a linear alkylene group having 2 to 10 carbon atoms.

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

(In the formula, Sp ^WAT1 and Sp ^WAT2 each independently represent a single bond or a linear or branched alkylene group having 1 to 25 carbon atoms, and one or two or more hydrogen atoms in the alkylene group. is -OH, -CN or ^P AP1 ^{-Sp AP1} - may be substituted with, not one or adjacent in the alkylene group two or more -CH ₂ -, the ring so that oxygen atoms are not directly adjacent It may be substituted with the formula group, -CH = CH-, -C≡C-, -O-, -CO-, -COO- or -OCO-. * In the formula represents a bond). ,
Z ^AT1 represents a monovalent polar group comprising a polar ^component, one or more hydrogen atoms in ^{Z AT1} is -OH, -CN or ^P AP1 ^{-Sp AP1} - may be substituted with.
It is preferably a group represented by the following general formula (ZAT1-1) or (ZAT1-2).

(In the formula, Sp ^ZAT11 represents a single bond or a linear or branched alkylene group having 1 to 25 carbon atoms, and one or more hydrogen atoms in the alkylene group are -OH, -CN, -Z ^ZAT11 -R ^ZAT11 or ^P AP1 ^{-Sp AP1} - may be substituted with, one or not adjacent two or more -CH ₂ in the alkylene group - is, as the oxygen atoms are not directly adjacent cyclic It may be substituted with an atom, −O−, −COO−, −C (= O) −, −OCO− or −CH = CH−.
Sp ^ZAT12 represents a single bond or a linear or branched alkylene group having 1 to 25 carbon atoms, and one or more hydrogen atoms in the alkylene group are -OH, -CN or P ^AP1 -Sp. ^{It may be substituted with AP1} −, and one or two or more −CH _2−s in the alkylene group are cyclic groups, −O−, −COO−, −C so that oxygen atoms are not directly adjacent to each other. It may be substituted with (= O) −, ^{−OCO−, −CH = CH− or −Z ZAT11−.}
Z ^ZAT11 represents a polar group containing a polar element.
The ^{structure represented by the ring containing Z ZAT12} represents a 5- to 7-membered ring.
Z ^ZAT11 and one or more hydrogen atoms in ^{Z ZAT12} is, -OH, -CN or ^P AP1 ^{-Sp AP1} - may be substituted with.
R ^ZAT11 and R ^ZAT12 independently represent a hydrogen atom and a linear or branched alkyl group having 1 to 8 carbon atoms, and one or more hydrogen atoms in the alkyl group are -OH. , -CN or ^P AP1 ^{-Sp AP1} - it may be substituted with, one or nonadjacent two or more -CH ₂ in the alkyl group - is, as the oxygen atoms are not directly bonded cyclic group, - It may be substituted with O-, -COO-, -C (= O)-, ^{-OCO-, -CH = CH- or -Z ZAT11-.}
P ^AP1 represents a polymerizable group
Sp ^AP1 represents a spacer group.
* In the formula represents a bond. )
The group represented by the general formula (ZAT1-1) is preferably a group represented by the following general formulas (ZAT1-1-1) to (ZAT1-1-30).

^{(Wherein, Sp ZAT11} and ^{R ZAT11} are the same meanings respectively as described above, the hydrogen atom bonded to a carbon atom, -OH, -CN or ^{P AP1 -Sp} AP1 -. Which may be of the formula substituted in * Represents a bond.)
Further, as the group represented by the general formula (ZAT1-1), the following groups are preferably mentioned.

^{(Wherein, R tc} represents a hydrogen atom, a linear or branched alkyl group or ^P AP1 ^-Sp carbon atoms 1 to 20 ^AP1 - represents one or two or more hydrogen atoms in the alkyl group , -OH, -CN or ^P AP1 ^{-Sp AP1} - may be substituted with, one or non-adjacent two or more -CH ₂ in the alkyl group -, the ring so that oxygen atoms are not directly adjacent formula It may be substituted with an ^atom, −O−, −COO−, −C (= O) −, −OCO−, −CH = CH− or −Z ZAT11−.
Hydrogen atoms in the ^molecule, P ^{AP1 -Sp} AP1 - may be substituted with.
* In the formula represents a bond. )
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).

^{(Wherein, Sp ZAT12} is the same meaning as described above, one or more hydrogen atoms bonded to a carbon atom, a halogen atom, -OH, -CN or ^P AP1 ^{-Sp AP1} - be substituted by good.
* In the formula represents a bond. )
P ^AP1 represents a polymerizable group, and a group represented by any of the above formulas (P ^p1-1 ) to (P ^p1-9 ) is preferable, and the above formulas (P ^p1-1 ) to (P ^p1 −) are preferable. The group represented by any of the formulas (7) is more preferable, and the group represented by any of the formulas (P ^p1-1 ) to (P ^p1-2 ) is more preferable, and the group represented by the formula (P ^p1-1 ) is more preferable. The group represented by is most preferable.

Sp ^AP1 represents a spacer group, preferably a single bond or a linear or branched alkylene group having 1 to 20 carbon atoms, and preferably a single bond or a linear alkylene group having 1 to 20 carbon atoms. More preferably, it represents a single bond or a linear alkylene group having 2 to 10 carbon atoms. Further, in Sp ^AP1 , one or two or more −CH ₂ −s in the alkylene group are −CH = CH−, −C≡C−, −O−, so that oxygen atoms are not directly adjacent to each other. It may be substituted with −CO−, −COO− or −OCO−. Incidentally, "substituted with a polymerizable group" Rutowa may be a mode that is substituted only with a polymerizable group ^{P AP1,} the group ^P AP1 ^{-Sp AP1} including spacer group ^{Sp AP1} - aspects that are replaced by May be. The same applies to other polymerizable groups.

In the compounds of the formula ^{(A), P AP1 -Sp AP1} - that the number of is preferably 1 or more 5 or less, more preferably 1 to 4, it is 2 to 4 More preferably, it is particularly preferably 2 or 3, and most preferably 2.

P ^AP1 -Sp ^AP1 - hydrogen atoms in may be substituted with a polymerizable group or a polar group.

When a ^{plurality of A AL1} , Z ^AL1 , Z ^AT1 , W ^AT1 , P ^AP1 , Sp ^AP1 , Sp ^WAT1 , and Sp ^{WAT 2} are present in the formula, they may be the same or different from each other.

Preferred examples of the compound represented by the general formula (A) are shown below.

The lower limit of the content of the compound represented by the formula (A) is preferably 0.01% with respect to the total amount of the liquid crystal composition, and more preferably from the viewpoint of improving the specific resistance and VHR. It is 0.05%, more preferably 0.1%. On the other hand, the upper limit of the content of the first polymerizable compound and its polymer is preferably 50%, 10%, 7%, 5% and 4% with respect to the total amount of the liquid crystal composition in the present invention. 3%, 2%, 1%.
-Polymerization Initiator The liquid crystal composition used in the present invention contains a polymerizable compound as described above. Although the polymerization proceeds even in the absence of the polymerization initiator, the polymerization initiator may be contained in order to promote the polymerization. Examples of the polymerization initiator include benzoin ethers, benzophenones, acetophenones, benzyl ketals, acylphosphine oxides and the like.
-Antioxidant The composition in the present invention can further contain compounds represented by the general formulas (Q1) to (Q2) as an antioxidant.

(Wherein, R ^Q represents a straight-chain alkyl group or branched alkyl group having 1 to 22 carbon atoms, one or two or more CH ₂ groups in the alkyl group, so that the oxygen atoms are not directly adjacent a, -O -, - CH = CH -, - CO -, - OCO -, - COO -, - C≡C -, - CF 2 O -, - OCF 2 - may be substituted with, in ^{R Q} hydrogen atoms, 4-hydroxy-3,5-di -t- butyl phenyl group may be substituted by, ^{M Q} is trans-1,4-cyclohexylene group, 1,4-phenylene group or a single bond It represents a one in a trans-1,4-cyclohexylene group or non-adjacent two -CH ₂ - may be replaced by -O-.

In the formula, X ^y is an alkylene group having 1 to 15 carbon atoms (one or two or more -CH _2- in the alkylene group is -O-, -CO-, so that oxygen atoms are not directly adjacent to each other. It may be replaced with −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-, 1, It represents a 4-phenylene group, a trans-1,4-cyclohexylene group, or a single bond, and the 1,4-phenylene group may have any hydrogen atom substituted with a fluorine atom.
M ^y represents a l-valent linking group,
l represents an integer of 2-6. )
R ^Q represents a straight-chain alkyl group or branched alkyl group having 1 to 22 carbon atoms, one or two or more CH ₂ groups in the alkyl groups, so that oxygen atoms are not directly adjacent, -O −, −CH = CH−, −CO−, −OCO−, −COO−, −C≡C−, −CF ₂ O−, −OCF ₂₋ may be substituted, but the number of carbon atoms is 1 to 10. Linear alkyl group, linear alkoxy group, linear alkyl group in which one CH ₂ group is substituted with -OCO- or -COO-, branched chain alkyl group, branched alkoxy group, one CH ₂ group is -OCO- Alternatively, a branched chain alkyl group substituted with −COO− is preferable, a linear alkyl group having 1 to 20 carbon atoms, and a linear alkyl group in which one CH ₂ group is substituted with −OCO− or −COO−, or branched. A chain alkyl group, a branched alkoxy group, _{and a branched chain alkyl group in which one CH 2} group is substituted with -OCO- or -COO- are further preferable. ^MQ represents a trans-1,4-cyclohexylene group, a 1,4-phenylene group or a single bond, with a trans-1,4-cyclohexylene group or a 1,4-phenylene group being preferred.

M ^y is preferably a hydrocarbon group having 1 to 25 carbon atoms, one or two or more -CH 2 in the hydrocarbon group _- is, as the oxygen atoms are not directly adjacent, -O- , -CO-, -COO-, -OCO- may be substituted.

l is preferably 2 or 3, more preferably 2. when l is 2, ^{M y} is preferably an alkylene group having 1 to 14 carbon atoms. Considering volatileness, a large number of carbon atoms is preferable, but considering viscosity, it is preferable that the number of carbon atoms is not too large. Therefore, the number of carbon atoms is preferably 2 to 12, and more preferably 3 to 10 carbon atoms. , 4 to 10 carbon atoms are more preferable, 5 to 10 carbon atoms are particularly preferable, and 6 to 10 carbon atoms are most preferable.

X ^y is preferably a single bond.

More specifically, the compound represented by the general formula (Q1) is preferably a compound represented by the following general formulas (Q1-a) to (Q1-d).

^{Wherein, R Q1} is preferably a linear alkyl group or branched alkyl group having 1 to 10 carbon ^{atoms, R Q2} is preferably a linear alkyl group or branched alkyl group having a carbon number of 1 to ^{20, R Q3} is linear alkyl group having 1 to 8 carbon atoms, branched chain alkyl group, preferably a straight chain alkoxy group or a branched chain alkoxy group, L ^Q is preferably a linear alkylene group or branched alkylene group having 1 to 8 carbon atoms .. Among the compounds represented by the general formulas (Q1-a) to (Q1-d), the compounds represented by the general formulas (Q1-c) and the general formula (Q1-d) are more preferable.

More specifically, the compound represented by the general formula (Q2) is preferably a compound represented by the following general formulas (Q2-a) to (Q2-c).

The composition of the present invention preferably contains 1 or 2 compounds represented by the general formulas (Q1) to (Q2), more preferably 1 to 5 compounds, and the content thereof is It is preferably 0.001 to 1%, more preferably 0.001 to 0.1%, and particularly preferably 0.001 to 0.05%.

Further, as the antioxidant or light stabilizer that can be used in the present invention, more specifically, the compounds represented by the following (III-1) to (III-41) are preferable.

(In the formula, n represents an integer from 0 to 20.)
It is preferable to contain one or more compounds represented by the general formulas (Q1) to (Q2) or compounds selected from the general formulas (III-1) to (III-41), and one to five kinds. It is more preferably contained, and the content thereof is preferably 0.001 to 1%, more preferably 0.001 to 0.1%, and particularly preferably 0.001 to 0.05%.

The liquid crystal display element manufactured by the manufacturing method of the present invention is useful in achieving both high-speed response, high reliability, and suppression of display defects, and is particularly useful for the liquid crystal display element for driving an active matrix, and is in VA mode. , PSVA mode, PSA mode, IPS mode or ECB mode liquid crystal display element. It is particularly suitable for VA mode, PSVA mode and PSA mode.

The present invention will be described in more detail with reference to Examples below, but the present invention is not limited to these Examples. In addition, "%" in the compositions of the following Examples and Comparative Examples means "mass%".

In the examples, the measured characteristics are as follows.
T _ni : Nematic phase-isotropic liquid phase transition temperature (° C)
Δn: Refractive index anisotropy at 293K Δε: Dielectric anisotropy at _{293K γ 1} : Rotational viscosity at 293K (mPa · s)

In the examples, the following abbreviations are used for the description of the compound.
<Ring structure>

（ただし、表中のｎは自然数である。）

(However, n in the table is a natural number.)

（ただし、表中のｎは自然数である。）

(However, n in the table is a natural number.)

The characteristics evaluated in the examples are as follows.
Reliability (VHR):
Prepare a liquid crystal display element after irradiating with UV light for 90 minutes, and the voltage retention rate (%) when measured at 1 V, 0.6 Hz, and 60 ° C.
FL15UV34A manufactured by Toshiba Lighting & Technology Corporation was used as the UV irradiation lamp for the example, and the illuminance at 365 nm was adjusted to ^{4 mW / cm 2.} This lamp has I ₃₆₅ / I ₃₁₃ > 20 (in the above formula, I ₃₆₅ represents the illuminance at a wavelength of 365 nm (mW · cm ² ), and I ₃₁₃ represents the illuminance at a wavelength of ^{313 nm (mW · cm 2} )). ..
FL15UV32A manufactured by Toshiba Lighting & Technology Corporation was used as the UV irradiation lamp for the comparative example, and the illuminance at 313 nm was adjusted to ^{4 mW / cm 2.} This lamp is I ₃₆₅ / I ₃₁₃ <20.

(Preparation and evaluation results of liquid crystal composition)
(LC-6) was prepared from the liquid crystal composition (LC-1), and its physical characteristics were measured. The component ratios of these liquid crystal compositions and their physical property values are as shown in the table below.

It was found that LC-1 to LC-5 containing the alkenyl compound had a small γ1 and a high response rate. It was found that LC-6 containing no alkenyl compound had a large γ1 and a slow response rate. The LC-6, which is inferior in response speed, was excluded from the evaluation, and the other LC-1 to LC-5 were evaluated as follows.

The liquid crystal composition obtained by mixing the liquid crystal compositions of LC-1 to LC-5, the polymerizable compounds represented by RM1 to RM5, and the additives represented by AD1 and AD2 is mixed with UV by an example UV irradiation lamp. From Examples (E-01) to (E-25) in which VHR was measured by irradiating with UV, and from Comparative Examples (C-01) to (C-01) in which UV was irradiated with a UV irradiation lamp for comparative examples and VHR was measured. 10) is as shown in Table 4.

It was confirmed that VHR was sufficiently high in Examples 1 (E-01) to 5 (E-05). In addition, it was confirmed that these display defects in the examples were also reduced. On the other hand, it was confirmed that Comparative Example 1 (C-01) and Comparative Example 2 (C-02) had low VHR and could not solve the problem of the present invention.

Results similar to those of Example 1 (E-01) to Example 5 (E-05) and Comparative Example 1 (C-01) and Comparative Example 2 (C-02) were obtained from Example 6 (E-06). It was also obtained in Example 25 (E-25) and Comparative Example 3 (C-03) to Comparative Example 10 (C-10), respectively.

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 (5)

A step of arranging a pair of substrates having an alignment film on at least one of them so as to face each other via a liquid crystal composition containing a polymerizable compound.
A method for producing a liquid crystal display element, which comprises a step of irradiating the liquid crystal composition with ultraviolet rays to polymerize the polymerizable compound.
As the ultraviolet rays, the following formula (P-1)
I ₃₆₅ / I ₃₁₃ > 20 ... (P-1)
(In the above formula, I ₃₆₅ represents the illuminance (mW · cm ² ) at a wavelength of 365 nm.
I ₃₁₃ represents the illuminance (mW · cm ² ) at a wavelength of 313 nm. ) Is used at least once to irradiate.
The liquid crystal composition has the following general formula (I).

(In the formula, R ¹¹ and R ¹² each independently represent an alkyl group having 1 to 8 carbon atoms, and one or two or more non-adjacent −CH ₂ − in the alkyl group are independent of each other. It may be replaced by -CH = CH-, -C≡C-, -O-, -CO-, -COO- or -OCO-, but ^{at least one of R 11} and R ¹² has 2 carbon atoms. represents 8 alkenyl group, one or two or more -CH 2 in the alkenyl group _- may be further substituted on the oxygen atom to the extent that the oxygen atom not adjacent,
n ¹¹ and n ¹² represent 0, 1, 2 or 3, while n ¹ + n ² represents 1, 2 or 3.
A ¹¹ and ^{A 12} are each independently (a) 1,4-cyclohexylene group (this is present in the group one -CH ₂ - or nonadjacent two or more -CH ₂ - is -O (May be replaced with −) and (b) 1,4-phenylene group (one -CH = existing in this group or two or more -CH = not adjacent to each other is replaced with -N =. May be done.)
Represents a group selected from the group consisting of, and the hydrogen atoms in the above groups (a) and (b) may be independently substituted with cyano groups, fluorine atoms or chlorine atoms, respectively.
Z ¹¹ and ^{Z 12} each independently represent a single _{bond, -CH 2 CH 2 -, -} (CH 2) 4 -, - OCH 2 -, - CH 2 O -, - COO -, - OCO -, - OCF 2 Represents −, −CF ₂ O−, −CH = NN = CH−, −CH = CH−, −CF = CF− or −C≡C−.
If A ¹¹ and / or A ¹² there are a plurality, they may be the same or different and if Z ¹¹ and / or Z ¹² there are multiple, they have be the same or different You may. ) Or
The following general formula (II)

(In the formula, R ²¹ and R ²² each independently represent an alkyl group having 1 to 8 carbon atoms, and one or two or more non-adjacent −CH ₂ − in the alkyl group are independent of each other. It may be replaced by -CH = CH-, -C≡C-, -O-, -CO-, -COO- or -OCO-, but ^{at least one of R 21} and R ²² has 2 carbon atoms. represents 8 alkenyl group, one or two or more -CH 2 in the alkenyl group _- may be further substituted on the oxygen atom to the extent that the oxygen atom not adjacent,
A ^{21, A 22} and ^{A 23} are each independently (a) 1,4-cyclohexylene group (this is present in the group one -CH ₂ - or nonadjacent two or more -CH ₂ - May be replaced with -O-) and (b) 1,4-phenylene group (one -CH = present in this group or two or more non-adjacent -CH = -N May be replaced with =)
Represents a group selected from the group consisting of, and the hydrogen atoms in the above groups (a) and (b) may be independently substituted with cyano groups, fluorine atoms or chlorine atoms, respectively.
Z ²¹ and ^{Z 22} each independently represent a single _{bond, -CH 2 CH 2 -, -} (CH 2) 4 -, - OCH 2 -, - CH 2 O -, - COO -, - OCO -, - OCF 2 Represents −, −CF ₂ O−, −CH = NN = CH−, −CH = CH−, −CF = CF− or −C≡C−.
n ²¹ represents 0, 1, 2 or 3
When a ^{plurality of A 22} and Z ²² are present, they may be the same or different, except for the compound represented by the above formula (I). ), And one or more of the liquid crystal compounds represented by).
The following general formula (P)

(In the above formula,
P ^p1 and P ^p2 each independently represent a polymerizable group.
Sp ^p1 and Sp ^p2 independently represent a spacer group or a single bond, respectively.
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-} (in the formula, R ZP 1) Each independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, ^{but when there are a plurality of R ZP1s} in the molecule, they may be the same or different).
A ^p1 , A ^p2 and A ^p3 are independent of each other.
^(A p) 1,4-cyclohexylene group (one present in the base or two or more -CH ₂ - may be replaced by -O- to the extent that the oxygen atom not adjacent. )
^(B p) 1,4-phenylene group (one or more -CH present in the base = may be replaced by -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 , Phenylene-2,7-diyl group or anthracene-2,6-diyl group (one or more -CH = present in the group may be substituted with -N =).
Represents a group selected from the group consisting of the group (a ^p), group (b ^p) and one or more hydrogen atoms present in the radical (c ^p) are each independently a halogen atom, It may be substituted with a cyano group, an alkyl group having 1 to 18 carbon atoms which may be substituted with a fluorine atom, or −Sp ^p2 −P ^p2 , and one of the alkyl groups or two or more non-adjacent − Even if CH ₂ − is independently substituted with −CH = CH −, −C≡C−, −O−, −CO−, −COO− or −OCO− so that oxygen atoms are not directly adjacent to each other. Often,
^Further, when ^{m p1} is a ^{group A p1} is represented by group ^{(c p)} in 0 ^{A p3} may be a single bond,
m ^p1 represents 0, 1, 2 or 3
When there are a plurality of Z ^p1 , A ^p2 , Sp ^p2 and / or P ^{p2 in the} molecule, they may be the same or different. A method for producing a liquid crystal display device, which comprises one or more of the polymerizable compounds represented by). The compounds represented by the formula (II) are represented by the following general formulas (II-01) to (II-06).

(In the formula, R ²¹⁰ and R ²²⁰ each independently represent an alkyl group having 1 to 8 carbon atoms, and one or two or more non-adjacent −CH ₂ − in the alkyl group are independent of each other. It may be replaced by -CH = CH-, -C≡C-, -O-, -CO-, -COO- or -OCO-, but ^{at least one of R 210} and R ²²⁰ has 2 carbon atoms. represents 8 alkenyl group, one or two or more -CH 2 in the alkenyl group _- may be further substituted on the oxygen atom to the extent that the oxygen atom not adjacent).
The method for manufacturing a liquid crystal display element according to claim 1, which is a compound selected from the group consisting of the compounds represented by. The compounds represented by the formula (II) are the following general formulas (II-01-1) to (II-01-5).

(In the formula, R ²¹¹ independently represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms.
R ²²¹ each independently represents an alkyl group having from 1 to 8 carbon atoms, not one or adjacent in the alkyl group two or more -CH 2 _- is -CH long as the oxygen atom not adjacent = CH-, -C≡C-, -O-, -CO-, -COO- or -OCO- may be substituted.
Although n ²² independently represents an integer of 0 to 5, the total of the number of carbon atoms and the number of n ^{22 when R 211 is an alkyl group does not exceed 6.} )
The method for manufacturing a liquid crystal display element according to claim 2, which is a compound selected from the group consisting of the compounds represented by. The liquid crystal composition is further described by the following general formula (S).

(In the formula, R ^s1 and R ^s2 are independently an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, or 2 carbon atoms. It represents 10 to 10 alkoxyoxy groups, and one or more hydrogen atoms present in these groups may be substituted with fluorine atoms.
A ^s1 and B ^s1 are independent of each other.
(A) 1,4-cyclohexylene group (this is present in the group one -CH ₂ - or nonadjacent two or more -CH ₂ - may be replaced by -O-.)
(B) 1,4-Phenylene group (one -CH = existing in this group or two or more -CH = not adjacent to each other may be replaced with -N =).
(C) Naphthalene-2,6-diyl group, 1,2,3,4-tetrahydronaphthalene-2,6-diyl group or decahydronaphthalene-2,6-diyl group (naphthalene-2,6-diyl group or One -CH = present in the 1,2,3,4-tetrahydronaphthalene-2,6-diyl group or two or more non-adjacent -CH = may be replaced with -N =. ) And (d) represent a group selected from the group consisting of 1,4-cyclohexenylene groups, and the groups (a), group (b), group (c) and group (d) are independently converted into fluorine atoms. It may be substituted with an alkyl group having 1 to 8 carbon atoms which may be substituted, an alkoxy group having 1 to 8 carbon atoms which may be substituted by a fluorine atom, a cyano group, or a fluorine atom, and ring ^As1. and the ring if the B ^s1 is present in plural, the plurality of rings a ^s1 and a plurality of rings B ^s1 or different and a respectively identical,
Z ^s1 and Z ^s2 are independently -OCH _2- , -CH ₂ O-, -COO-, -OCO-, -CF ₂ O-, -OCF _2- , -CH ₂ CH ₂ -,-, respectively. CF ₂ Represents CF _2- , -C≡C- or a single bond,
n ^s1 and n ^s2 independently represent 0, 1 or 2, respectively, and n ^s1 + n ^s2 represent an integer of 1 to 4, and X ^{s1 to} X ^s6 may be independently substituted with a hydrogen atom. It represents an alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms which may be substituted with a fluorine atom, a fluorine atom or a hydrogen atom. )
The method for manufacturing a liquid crystal display element according to any one of claims 1 to 3, which contains a sensitizer represented by. A liquid crystal display element manufactured by the manufacturing method according to any one of claims 1 to 4.

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