TWI865737B - Method for manufacturing liquid crystal display element and liquid crystal display element - Google Patents

Abstract

The subject 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. A method for manufacturing a liquid crystal display element comprises: a step of arranging a pair of substrates, at least one of which has an alignment film, in such a manner that they face each other with a liquid crystal composition containing a polymerizable compound interposed therebetween; a step of irradiating the liquid crystal composition with ultraviolet light to polymerize the polymerizable compound, wherein the ultraviolet light is at least once irradiated with ultraviolet light satisfying I ₃₆₅ /I ₃₁₃ >20 (I ₃₆₅ represents the illuminance (mW/cm ² ) at a wavelength of 365 nm, and I ₃₁₃ represents the illuminance (mW/cm ² ) at a wavelength of 313 nm, and the liquid crystal composition contains one or more liquid crystal compounds represented by formula (I) and one or more polymerizable compounds represented by formula (P).

Description

Method for manufacturing liquid crystal display element and liquid crystal display element

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

Liquid crystal display elements are used in various measuring machines, such as clocks and electronic calculators, automotive panels, electronic notebooks, printers, computers, televisions, clocks, advertising display boards, etc. As representative liquid crystal display methods, the following can be cited: vertical alignment (VA (Vertical Alignment)) or in-plane switching (IPS) using twisted nematic (TN), super twisted nematic (STN), thin film transistor (TFT) and the like. The liquid crystal composition used in these liquid crystal display elements is required to be stable to external factors such as moisture, air, heat, and light, and to display the liquid crystal phase in the widest possible temperature range centered at room temperature, have low viscosity, and have a low driving voltage. Furthermore, in order to make the dielectric constant anisotropy (△ε) or refractive index anisotropy (△n) etc. the most suitable value for each liquid crystal display element, the liquid crystal composition contains several to dozens of compounds.

In VA type displays, liquid crystal compositions with negative Δε are used, and are widely used in liquid crystal televisions (television, TV) and the like. Among them, the polymer sustained alignment (PSA) mode is a mode in which a polymerizable compound (monomer) dissolved in liquid crystal is polymerized to give a desired pre-tilt angle to vertically aligned liquid crystal molecules. Since it can achieve an expanded viewing angle or high-speed response and high transmittance, it has become the mainstream of current TVs. In addition, in recent years, further high-speed response of liquid crystal display elements has been studied, and as such a technology, attempts have been made to form a liquid crystal layer using a liquid crystal composition containing a liquid crystal compound having an alkenyl partial structure such as an alkenyl group (alkenyl-based liquid crystal compound) (for example, refer to Patent Documents 1 and 2).

In addition, in recent years, in the manufacture of liquid crystal elements, in order to improve production efficiency, PSA liquid crystal compositions with moderately fast polymerization speeds are required. In the step of polymerizing the polymerizable compound in the liquid crystal composition, the polymerization speed of the polymerizable compound is very important. When the polymerization speed is fast, the residual amount of the polymerizable compound in a short irradiation time of ultraviolet rays etc. becomes less, so it is not easy to produce the degradation of the liquid crystal composition caused by ultraviolet rays etc. In addition, it also has the advantages of improved productivity such as being able to produce with less energy and shortening the production time. On the other hand, when the polymerization speed of the polymerizable compound is slow, in order to reduce the unreacted residual amount of the polymerizable compound, it is necessary to extend the irradiation time of ultraviolet rays etc. Furthermore, if strong ultraviolet rays are irradiated for a long time during the polymerization step, the manufacturing equipment will be enlarged, the manufacturing efficiency will be reduced, and the liquid crystal composition will be degraded by ultraviolet rays. However, if the irradiation time of ultraviolet rays is shortened, the amount of residual polymerizable compounds will increase, and display defects called unevenness or burn-in will occur due to the residual polymerizable compounds. In summary, a polymerizable liquid crystal composition that can achieve a sufficient polymerization speed is desired.

As an approach for improving the polymerization rate of a polymerizable compound, as shown in the embodiment of Patent Document 3, a method is proposed to improve the polymerization rate of a polymerizable compound by extending the absorption wavelength of a liquid crystal material used to a long wavelength using a compound of the following formula (A).

[Prior art literature]

[Patent Literature]

[Patent document 1] Japanese Patent Publication No. 2014-112192

[Patent Document 2] Japanese Patent Publication No. 2010-285499

[Patent Document 3] Japanese Patent Publication No. 2013-503952

As mentioned above, liquid crystal compositions containing alkenyl liquid crystal compounds are useful for high-speed response of liquid crystal display elements, but such liquid crystal compositions are easily degraded by active energy rays such as light emitted from a backlight source or irradiated with ultraviolet rays during the manufacturing process of liquid crystal display elements. There is a problem that the voltage holding ratio (VHR) of the liquid crystal panel is reduced due to impurities generated by light degradation of the liquid crystal composition.

The present invention is completed in view of the above situation, and its subject is to provide a method for manufacturing a liquid crystal display element with excellent characteristics. More specifically, the subject 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.

The inventors of this invention have conducted intensive research and found that in the manufacturing method of olefin-based polymerizable liquid crystal display elements, the above-mentioned problem can be solved by irradiating ultraviolet light with a specific illumination ratio, thereby completing the invention of this application.

That is, the present invention provides a method for manufacturing a liquid crystal display element having the following characteristics.

A method for manufacturing a liquid crystal display element comprises: a step of arranging a pair of substrates, at least one of which has an alignment film, facing each other via a liquid crystal composition containing a polymerizable compound; and a step of irradiating the liquid crystal composition with ultraviolet light to polymerize the polymerizable compound, wherein the ultraviolet light is used as the ultraviolet light to irradiate at least once, and 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, and I ₃₁₃ represents the illuminance (mW/cm ² ) at a wavelength of 313 nm.) The liquid crystal composition contains one or more liquid crystal compounds represented by the following general formula (I) or the following general formula (II) and one or more polymerizable compounds represented by the following general formula (P),

(wherein, R ¹¹ and R ¹² each independently represent an alkyl group having 1 to 8 carbon atoms, one or two or more non-adjacent -CH ₂ - in the alkyl group may each independently be substituted by -CH=CH-, -C≡C-, -O-, -CO-, -COO- or -OCO-, at least one of R ¹¹ and R ¹² represents an alkenyl group having 2 to 8 carbon atoms, one or two or more -CH ₂ - in the alkenyl group may further be substituted by an oxygen atom as long as the oxygen atoms are not adjacent, n ¹¹ and n ¹² represent 0, 1, 2 or 3, n ¹¹ + n ¹² represent 1, 2 or 3, A ¹¹ and A ¹² each independently represent a group selected from (a) 1,4-cyclohexyl (one -CH ₂ - or two or more non-adjacent -CH _{2 -} in the group) - may be substituted with -O-. ) and (b) 1,4-phenylene (one -CH= or two or more non-adjacent -CH= in this group may be substituted with -N=.)

The groups in the group consisting of: the hydrogen atoms in the groups (a) and (b) may be independently substituted by cyano, fluorine or chlorine atoms; Z ¹¹ and Z ¹² independently represent a single bond, -CH ₂ CH ₂ -, -(CH ₂ ) ₄ -, -OCH ₂ -, -CH ₂ O-, -COO-, -OCO-, -OCF ₂ -, -CF ₂ O-, -CH=NN=CH-, -CH=CH-, -CF=CF- or -C≡C-; when there are multiple A ¹¹ and/or A ¹² , they may be the same or different; when there are multiple Z ¹¹ and/or Z ¹² , they may be the same or different. )

(wherein, R ²¹ and R ²² each independently represent an alkyl group having 1 to 8 carbon atoms, one or two or more non-adjacent -CH ₂ - in the alkyl group may each independently be substituted by -CH=CH-, -C≡C-, -O-, -CO-, -COO- or -OCO-, at least one of R ²¹ and R ²² represents an alkenyl group having 2 to 8 carbon atoms, one or two or more -CH ₂ - in the alkenyl group may further be substituted by oxygen atoms as long as the oxygen atoms are not adjacent, A ²¹ , A ²² and A ²³ each independently represent a group selected from (a) 1,4-cyclohexyl (one -CH ₂ - or two or more non-adjacent -CH ₂ - in the group may each independently be substituted by -CH=CH-, -C≡C-, -O-, -CO-, -COO- or -OCO-) - may be substituted with -O-. ) and (b) 1,4-phenylene (one -CH= or two or more non-adjacent -CH= in this group may be substituted with -N=.)

The groups in the group formed are: the hydrogen atoms in the groups (a) and (b) may be independently substituted by cyano, fluorine or chlorine atoms; Z ²¹ and Z ²² independently represent a single bond, -CH ₂ CH ₂ -, -(CH ₂ ) ₄ -, -OCH ₂ -, -CH ₂ O-, -COO-, -OCO-, -OCF ₂ -, -CF ₂ O-, -CH=NN=CH-, -CH=CH-, -CF=CF- or -C≡C-; n ²¹ represents 0, 1, 2 or 3; when A ²² and Z ²² exist in plural numbers, they may be the same or different, except for the compound represented by the formula (I).

(In the above formula, ^Pp1 and ^Pp2 each independently represent a polymerizable group, ^Spp1 and ^Spp2 each independently represent a spacer group or a single bond, ^Zp1 and ^Zp2 each independently represent a single bond, -O-, -S-, _-CH2- , -OCH2-, _-CH2O- , -CO-, _-C2H4- , -COO-, -OCO-, -OCOOCH2-, _-CH2OCOO- , -, _OCH2CH2O- , -CO-NRZP1-, -NRZP1-CO-, _-SCH2- ^, _{-CH2S- , -CH} = ^{CRZP1 ,} -COO- _, ^{-CH=CRZP1, -OCO-, -COO-CRZP1=CH-, -OCO-CRZP1=CH-, -COO-CRZP1} ₌ ^{CH -} _COO- ^, -COO- ^CRZP1 =CH-OCO-, -OCO-CR ^ZP1 =CH-COO-, -OCO-CR ^ZP1 =CH-OCO-, -(CH ₂ ) ₂ -COO-, -(CH ₂ ) ₂ -OCO-, -OCO-(CH ₂ ) ₂ -, -(C=O)-O-(CH ₂ ) ₂ -, -CH=CH-, -CF=CF-, -CF=CH-, -CH=CF-, -CF ₂ -, -CF ₂ O-, -OCF ₂ -, -CF 2 CH 2 -, -CH ₂ CF ₂ -, -CF ₂ CF ₂ -, or -C≡C- (wherein R ^ZP1 each independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. When a plurality of ^{R ZP1} are present in the molecule, they may be the same or different.), A ^p1 , _{A p2} and A p3 ^p3 independently expresses the choice of

(a ^p )1,4-cyclohexylene group (one or two or more -CH ₂ - groups in the group may be substituted by -O- as long as the oxygen atoms are not adjacent to each other.)

(b ^p ) 1,4-phenylene (one or more -CH= in the group may be substituted by -N=.) and

(c ^p ) naphthalene-2,6-diyl, naphthalene-1,4-diyl, naphthalene-1,5-diyl, 1,2,3,4-tetrahydronaphthalene-2,6-diyl, decahydronaphthalene-2,6-diyl, phenanthrene-2,7-diyl or anthracene-2,6-diyl (one or two or more -CH= in the above group may be substituted by -N=.)

In the group consisting of: one or more hydrogen atoms in the group ( ^ap ), group ( ^bp ) and group ( ^cp ) may be independently substituted by a halogen atom, a cyano group, an alkyl group having 1 to 18 carbon atoms which may be substituted by a fluorine atom, or ^-Spp2 - ^Pp2 ; one or more non-adjacent _-CH2- groups in the alkyl group may be independently substituted by -CH=CH-, -C≡C-, -O-, -CO-, -COO- or -OCO- to avoid direct adjacency of the oxygen atom; in addition, when ^mp1 is 0 and ^Ap1 is a group represented by group ( ^cp ), ^Ap3 may be a single bond, ^mp1 represents 0, 1, 2 or 3; when a plurality of ^Zp1 , ^Ap2 , ^Spp2 and/or ^Pp2 are present in the molecule, they may be the same or different.).

A liquid crystal display element is manufactured by the manufacturing method of the liquid crystal display element.

According to the present invention, in the manufacture of a liquid crystal display element using a polymerizable liquid crystal composition having a specific composition, ultraviolet light having peaks at wavelengths of 313nm and 365nm is used at a specified illuminance ratio, thereby achieving high productivity in manufacturing a liquid crystal display element that has good display quality with reduced display defects such as unevenness or burn-in, and has achieved high-speed response and high reliability.

AM: Active Matrix Substrate (Substrate)

CF: Color filter substrate (substrate)

1: Liquid crystal display element

2: First substrate

3: Second substrate

4: Liquid crystal layer

5: Pixel electrode layer (electrode layer) (electrode)

6: Common electrode layer (electrode layer) (electrode)

7: First polarizing plate

8: Second polarizing plate

9: Color filter

11: Grid bus

12: Data bus

13: Pixel electrode

14: Cs electrode

15: Source electrode

16: Drain electrode

17: Contact hole

S: Distance between

FIG1 is a schematic exploded perspective view of an embodiment of a liquid crystal display element.

Figure 2 is an enlarged plan view of the area surrounded by line I in Figure 1.

The following is a detailed description of the manufacturing method of the liquid crystal display element of the present invention based on an appropriate implementation method. First, the liquid crystal display element manufactured by the manufacturing method of the liquid crystal display element of the present invention is described.

FIG1 is a schematic exploded perspective view of an implementation of a liquid crystal display element, and FIG2 is an enlarged plan view of the area surrounded by line I in FIG1.

In addition, for the sake of convenience, the dimensions and ratios of each part in Figures 1 and 2 are exaggerated and may not match the actual situation. In addition, the materials, dimensions, etc. shown below are examples, and the present invention is not limited to these and can be appropriately changed within the scope of not changing its purpose.

The liquid crystal display element 1 shown in FIG1 includes an active matrix substrate AM and a color filter substrate CF arranged facing each other, and a liquid crystal layer 4 sandwiched between the active matrix substrate AM and the color filter substrate CF.

The active matrix substrate AM has a first substrate 2, a pixel electrode layer 5 provided on the surface of the first substrate 2 on the liquid crystal layer 4 side, and a first polarizing plate 7 provided on the surface of the first substrate 2 on the opposite side to the liquid crystal layer 4.

On the other hand, the color filter substrate CF has a second substrate 3, a common electrode layer 6 provided on the liquid crystal layer 4 side of the second substrate 3, a second polarizing plate 8 provided on the surface of the second substrate 3 opposite to the liquid crystal layer 4, and a color filter 9 provided between the second substrate 3 and the common electrode layer 6.

The liquid crystal layer 4 is a vertical alignment type using negative dielectric constant anisotropy. In the liquid crystal layer 4, when no voltage is applied between the electrode layers 5 and 6, the liquid crystal molecules are aligned almost vertically with respect to the substrates AM and CF.

That is, the liquid crystal display element 1 of the present embodiment has a structure in which a first polarizing plate 7, a first substrate 2, a pixel electrode layer 5, a liquid crystal layer 4, a common electrode layer 6, a color filter 9, a second substrate 3, and a second polarizing plate 8 are sequentially stacked.

The first substrate 2 and the second substrate 3 are respectively formed of a glass material or a flexible material such as a plastic material.

Regarding the first substrate 2 and the second substrate 3, both may be light-transmissive or only one may be light-transmissive. In the latter case, the other substrate may include an opaque material such as a metal material or a silicon material.

As shown in FIG2 , the pixel electrode layer 5 has a plurality of gate buses 11 for supplying scanning signals, a plurality of data buses 12 for supplying display signals, and a plurality of pixel electrodes 13. In addition, FIG2 shows a pair of gate buses 11, 11 and a pair of data buses 12, 12.

A plurality of gate buses 11 and a plurality of data buses 12 are arranged in a matrix shape in a cross-intersecting manner, and the area surrounded by them forms a unit pixel of the liquid crystal display element 1. A pixel electrode 13 is formed in each unit pixel. In addition, each pixel may also include a plurality of sub-pixels.

The pixel electrode 13 has a structure including two main trunks orthogonal to each other in a cross shape, and a plurality of branch parts branching from each main trunk and tilted at an angle of about 45° relative to each main trunk (so-called fishbone structure). In other words, the pixel electrode 13 can also be understood as an electrode having a structure including slits formed between the branch parts.

According to the pixel electrode 13 of the structure, the liquid crystal molecules are uniformly tilted and aligned in the four directions in which the branch portion is tilted relative to the main trunk. Therefore, a domain divided into four is formed in one pixel, thereby widening the viewing angle of the liquid crystal display element 1.

The width of each branch is preferably about 1μm~5μm, and more preferably about 2μm~4μm. In addition, the spacing S between adjacent branches is preferably about 1μm~5μm, and more preferably about 2μm~4μm. With this structure, the liquid crystal molecules can be more effectively tilted in a prescribed direction.

A Cs electrode 14 is provided between a pair of gate buses 11, 11 and is almost parallel to the gate bus 11. In addition, a thin film transistor including a source electrode 15 and a drain electrode 16 is provided near the intersection where the gate bus 11 and the data bus 12 intersect each other. A contact hole 17 is provided in the drain electrode 16.

The gate bus 11 and the data bus 12 are preferably formed of, for example, Al, Cu, Au, Ag, Cr, Ta, Ti, Mo, W, Ni or alloys containing them, and more preferably formed of Mo, Al or alloys containing them.

The pixel electrode 13 includes a transparent electrode, for example, in order to improve the transmittance of light. The transparent electrode is formed by sputtering a compound such as ZnO, InGaZnO, SiGe, GaAs, Indium Zinc Oxide (IZO), Indium Tin Oxide (ITO), SnO, TiO, AZTO (AlZnSnO), etc.

The average thickness of the transparent electrode is preferably about 10nm~200nm. In addition, in order to reduce the resistance, the transparent electrode can also be formed by sintering the amorphous ITO film to make a polycrystalline ITO film.

On the other hand, the common electrode layer 6 has, for example, a plurality of stripe-shaped common electrodes (transparent electrodes) arranged in parallel. This common electrode can also be formed in the same manner as the pixel electrode 13.

The color filter 9 can be produced, for example, by a pigment dispersion method, a printing method, an electroplating method, or a dyeing method.

In the pigment dispersion method, after the curable coloring composition for the color filter is supplied to the second substrate 3 in a prescribed pattern, it is heated or irradiated with light to cure it. By performing the above operation for the three colors of red, green, and blue, a color filter 9 can be obtained.

In addition, the color filter 9 can also be arranged on the side of the first substrate 2.

In addition, from the perspective of preventing light leakage, the liquid crystal display element 1 may also be provided with a black matrix (not shown). This black matrix is preferably formed in the portion corresponding to the thin film transistor.

In addition, the black matrix can be arranged on the second substrate 3 side together with the color filter 9, can be arranged on the first substrate 2 side together with the color filter 9, or the black matrix can be arranged on the first substrate 2 side and the color filter 9 can be arranged on the second substrate 3 side. In addition, the black matrix can also include a portion that makes the colors of the color filter 9 overlap and reduces the transmittance.

The active matrix substrate AM and the color filter substrate CF are bonded to each other in their peripheral areas by a sealing material (sealing material) including an epoxy-based thermosetting composition or an acrylic-based ultraviolet (UV) curing composition.

In addition, a spacer may be arranged between the active matrix substrate AM and the color filter substrate CF to maintain the distance between them. Examples of the spacer include granular spacers such as glass particles, plastic particles, and alumina particles, and resin spacer columns formed by photolithography.

The average spacing between the active matrix substrate AM and the color filter substrate CF (i.e., the average thickness of the liquid crystal layer 4) is preferably about 1μm~100μm.

The first polarizer 7 and the second polarizer 8 can be designed to improve the viewing angle or contrast by adjusting the positional relationship of their transmission axes. Specifically, the first polarizer 7 and the second polarizer 8 are preferably arranged in a mutually orthogonal manner so that their transmission axes operate in a normally black mode. In particular, it is preferred that either the first polarizer 7 or the second polarizer 8 is arranged in a manner such that its transmission axis is almost 45° to the orientation direction of the liquid crystal molecules when a voltage is applied.

In addition, when the first polarizing plate 7 and the second polarizing plate 8 are used, it is preferable to adjust the product of the refractive index anisotropy (△n) of the liquid crystal layer 4 and the average thickness of the liquid crystal layer 4 in such a way as to maximize the contrast. Furthermore, the liquid crystal display element 1 may also include a phase difference film for expanding the viewing angle.

In addition, 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 in a manner contacting the liquid crystal layer 4. In the present invention, both substrates may have an alignment film, or only one of the substrates may have an alignment film.

(Method for manufacturing liquid crystal display element)

The manufacturing method of the liquid crystal display element of the present invention comprises: a step of arranging a pair of substrates, at least one of which has an alignment film, facing each other via a liquid crystal composition containing a polymerizable compound; and a step of irradiating the liquid crystal composition with ultraviolet rays to polymerize the polymerizable compound.

Next, the manufacturing method of this liquid crystal display element 1 is described in detail based on the preferred implementation method.

The manufacturing method of the liquid crystal display element of the present embodiment comprises: a preparation step [1], preparing a substrate AM, a substrate CF and a liquid crystal composition; an assembly step [2], assembling the various parts; a liquid crystal layer forming step [3], polymerizing the polymerizable monomer by irradiating ultraviolet light under a voltage applied to the liquid crystal composition to form a liquid crystal layer 4; and a monomer consumption step [4], irradiating the liquid crystal layer 4 with ultraviolet light without applying a voltage to the liquid crystal layer 4, thereby polymerizing and consuming the remaining polymerizable monomer.

As long as the performance as the liquid crystal display element 1 can be fully obtained, either the liquid crystal layer forming step [3] or the monomer consuming step [4] may be omitted, especially the monomer consuming step [4].

[1] Preparation steps

First, prepare an active matrix substrate AM, a color filter substrate CF, and a liquid crystal composition containing liquid crystal molecules and at least one polymerizable monomer.

[2]Assembly steps

Next, a sealant is drawn into a closed-loop dam shape using a dispenser along the edge of at least one of the active matrix substrate AM and the color filter substrate CF.

After that, a predetermined amount of liquid crystal composition is dripped onto the inner side of the sealant, and the active matrix substrate AM and the color filter substrate CF are arranged facing each other in such a way that they are in contact with the liquid crystal composition under reduced pressure. That is, a pair of substrates AM and CF are arranged such that the electrode layer 5 and the electrode layer 6 (electrodes) face each other through the liquid crystal composition.

In this One Drop Fill (ODF) method, the optimal injection amount needs to be added according to the size of the liquid crystal display element 1. The liquid crystal composition described later is less affected by the rapid pressure change or impact in the dropper during the drop, and can be dropped stably for a long time. Therefore, the yield of the liquid crystal display element 1 can be maintained high.

In particular, in small liquid crystal display elements that are often used in smart phones, the optimal injection amount of the liquid crystal composition is small, so it is difficult to control its deviation within a certain range. However, by using the liquid crystal composition as described above, a stable and optimal injection amount can be accurately dripped even in small liquid crystal display elements.

Afterwards, the sealant is cured by ultraviolet ray (active energy ray) irradiation and heating. In addition, depending on the type of sealant, the sealant may be cured by only using ultraviolet ray irradiation or heating.

[3] Liquid crystal layer formation step (first ultraviolet irradiation step)

Next, a voltage is applied to the liquid crystal composition while ultraviolet rays are irradiated. As a result, a polymer layer containing a polymerizable monomer is formed at the interface between the liquid crystal composition and the electrode layer 5 and the electrode layer 6 (in the electrode 5 and the electrode 6 of the substrate having the alignment film, the interface with the alignment film provided on the surface of the electrode layer 5 and/or the electrode layer 6). By the formation of the polymer layer, the liquid crystal molecules are vertically aligned, or a pre-tilt angle is further given to the liquid crystal molecules.

The voltage can be applied between the pixel electrode 13 and the common electrode (opposite electrode), or between the Cs electrode 14 and the common electrode.

The voltage applied to the liquid crystal composition in this step [3] is preferably 3V or more, and more preferably about 5V to 15V. If a voltage of this value is applied to the liquid crystal composition, a sufficient pre-tilt angle can be given to the liquid crystal molecules. In addition, even if a voltage exceeding the upper limit is applied to the liquid crystal composition, no further increase in the effect can be expected.

At least one of the ultraviolet light irradiated in this step [3] and the ultraviolet light irradiated in the next step [4] when the next step [4] exists has a peak at a wavelength of 313nm and a wavelength of 365nm, and satisfies 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, and I ₃₁₃ represents the illuminance (mW/cm ² ) at a wavelength of 313 nm.)

From the perspective of improving the VHR of the liquid crystal display element 1, it is better to spend time irradiating the liquid crystal composition with ultraviolet light of a relatively long wavelength of 365nm so that the polymerizable monomer polymerizes at an appropriate polymerization rate. In particular, when an olefinic liquid crystal composition is used for the purpose of high-speed response, it is strongly required to improve the VHR that is easily reduced. Therefore, the inventors of the present invention have repeatedly conducted active research and found that there is an appropriate intensity ratio between the peak of the wavelength of 313nm and the peak of the wavelength of 365nm, thereby completing the present invention.

From the above viewpoint, in the present step [3] mainly carried out for the polymerization of the polymerizable compound, it is preferred to use ultraviolet light satisfying the above formula (P-1).

In ultraviolet rays satisfying the formula (P-1), if I ₃₆₅ /I ₃₁₃ is 20 or less, the amount of ultraviolet rays with a wavelength of 313 nm is excessive, causing alteration or degradation in liquid crystal molecules, and the VHR of the liquid crystal display element 1 decreases.

I ₃₆₅ /I ₃₁₃ only needs to be greater than 20, but is preferably greater than 25, and particularly preferably greater than 30. By making I ₃₆₅ /I ₃₁₃ a ratio within the above range, a liquid crystal display element having a high VHR and reduced display defects can be efficiently manufactured while preventing the deterioration or degradation of liquid crystal molecules. In addition, the upper limit value of I ₃₆₅ /I ₃₁₃ is not particularly limited, and can be greater than 10,000 or can be infinite.

Specifically, the peak intensity I ₃₆₅ is preferably about 2.5 mW/cm ² to 105 mW/cm ² , and more preferably about 3.5 mW/cm ² to 95 mW/cm ^2. In order to reduce the amount of residual polymerizable monomers and produce a liquid crystal display element 1 with a high voltage holding ratio, I ₃₆₅ is preferably 2.5 mW/cm ² to 20 mW/cm ^2. In addition, in order to provide a good pretilt angle, I ₃₆₅ is preferably 3.5 mW/cm ² to 95 mW/cm ² .

On the other hand, the peak intensity I ₃₁₃ is preferably less than 10 mW/cm ² , preferably about 0 mW/cm ² to 10 mW/cm ² , and more preferably about 0 mW/cm ² to 5 mW/cm ² . This can further enhance the above effect.

In addition, from the perspective of more effectively preventing the deterioration or degradation of liquid crystal molecules, it is preferable that the ultraviolet light has no peak in the wavelength region less than 313 nm (especially the wavelength in the short-wave ultraviolet (UVC) region), or even if there is a peak, its intensity is extremely small.

The irradiation time of ultraviolet light in this step [3] can be determined based on the relationship with the temperature of the liquid crystal layer 4. That is, in this step [3], it is preferred to irradiate ultraviolet light until the temperature of the liquid crystal layer 4 rises by 0.1°C to 5°C, more preferably until the temperature rises by 0.5°C to 5°C, and further preferably until the temperature rises by 1°C to 5°C. The temperature rise of the liquid crystal layer 4 within the above range indicates that the polymerizable monomer has been fully polymerized.

The specific irradiation time also depends on the type of ultraviolet light used, and is preferably about 10 seconds to 7200 seconds, and more preferably about 20 seconds to 3600 seconds. In order to reduce the amount of residual polymerizable monomers and manufacture a liquid crystal display element 1 with a high voltage retention rate, it is preferably about 600 seconds to 7200 seconds. In addition, in order to give a good pre-tilt angle, it is preferably about 10 seconds to 1200 seconds, and more preferably about 30 seconds to 600 seconds. In addition, the ultraviolet irradiation time can be set to be consistent with the voltage application time, and can also be set to be shorter than the voltage application time.

The irradiation amount of ultraviolet light with a wavelength of 313 nm irradiated under the irradiation conditions is preferably 0 mJ/cm ² to 50 J/cm ² , more preferably 0 mJ/cm ² to 20 J/cm ² . In order to give a good pretilt angle, it is preferably 0 mJ/cm ² to 10 J/cm ² , more preferably 0 mJ/cm ² to 3 J/cm ² . In order to reduce the amount of residual polymerizable monomers and manufacture a liquid crystal display element 1 with a high voltage holding ratio, it is preferably 0 mJ/cm ² to 10 J/cm ² .

The irradiation amount of ultraviolet light with a wavelength of 365 nm is preferably 10 mJ/cm ² to 500 J/cm ² , and more preferably 100 mJ/cm ² to 200 J/cm ² . The irradiation amount can be appropriately adjusted according to the target characteristics. In addition, the intensity can be changed when irradiating ultraviolet light.

In addition, when polymerizing is performed with two substrates facing each other in contact with the liquid crystal composition as in the present embodiment, at least the substrate on the irradiation side needs to have appropriate transmittance to ultraviolet rays.

In addition, the applied voltage may be either direct current or alternating current, preferably alternating current. If alternating current is used to apply the voltage, it is easy to obtain a liquid crystal layer 4 with a good alignment state of the liquid crystal molecules.

The frequency of the applied AC is preferably about 10Hz~10kHz, and more preferably about 60Hz~10kHz.

The temperature during ultraviolet irradiation is preferably within the temperature range that maintains the liquid crystal state of the liquid crystal composition. The specific temperature is preferably about 10°C to 50°C, and more preferably about 15°C to 45°C. If it is within the temperature range, the polymerizable monomer in the liquid crystal composition diffuses appropriately while polymerizing, so the polymerization proceeds well and the pre-tilt angle after polymerization becomes good.

As lamps that generate ultraviolet rays, metal halide lamps, high-pressure mercury lamps, ultra-high-pressure mercury lamps, fluorescent tubes, etc. can be used.

In addition, the irradiated ultraviolet light may be used by cutting off a specified wavelength as needed. A cutoff filter may be used for the wavelength cutoff. For example, by cutting off ultraviolet light in a wavelength region including a wavelength of 313 nm, ultraviolet light satisfying I ₃₆₅ /I ₃₁₃ >20 may be obtained. By almost completely cutting off ultraviolet light in a wavelength region including a wavelength of 313 nm, I ₃₁₃ =0 is achieved. In this case, I ₃₆₅ /I ₃₁₃ becomes infinite.

In addition, the pre-tilt angle given to the liquid crystal molecules is preferably about 85°~89.5°, and more preferably about 87.5°~89°. By adjusting the pre-tilt angle of the liquid crystal molecules to the above range, the response speed of the liquid crystal display element 1 can be fully improved while preventing the contrast from decreasing.

[4] Monomer consumption step (second UV irradiation step)

Next, without applying voltage to the liquid crystal composition, ultraviolet rays are irradiated to the liquid crystal layer 4. As a result, the residual polymerizable monomers in the liquid crystal layer 4 are polymerized and consumed.

The ultraviolet light irradiated in this step [4] may be the same as or different from the first ultraviolet light irradiation step. In addition, in the case where the ultraviolet light irradiation is performed at the intensity ratio of the present invention in the step [3], it does not prevent the ultraviolet light with a peak intensity of 313nm, a peak intensity of 365nm and their intensity ratio from being outside the scope of the present invention in the step [4].

Among them, it is preferred that even when using ultraviolet light different from the first ultraviolet light irradiation step, ultraviolet light having peaks at wavelengths of 313 nm and 365 nm is irradiated in the same manner as in the first ultraviolet light irradiation step. With regard to ultraviolet light different from the first ultraviolet light irradiation step, I ₃₆₅ /I ₃₁₃ is preferably 20 or more, more preferably 25 or more, and further preferably 30 or more. By setting it within the above range, deterioration or degradation of liquid crystal molecules can be prevented. As a result, the occurrence of display defects (burn-in) of the liquid crystal display element 1 can be prevented or suppressed.

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

In addition, from the perspective of more effectively preventing the deterioration or degradation of liquid crystal molecules, it is preferable that the ultraviolet light has no peak in the wavelength region less than 313 nm (especially the wavelength in the UVC region), or even if there is a peak, its intensity is extremely small.

The irradiation time of ultraviolet light in this step [4] can also be determined based on the relationship with the temperature of the liquid crystal layer 4. That is, in this step [4], it is preferred to irradiate ultraviolet light until the temperature of the liquid crystal layer 4 rises by 1°C to 20°C, more preferably until it rises by 2°C to 15°C, and further preferably until it rises by 3°C to 10°C. The temperature rise of the liquid crystal layer 4 within the above range indicates that the residual polymerizable monomers have been fully consumed.

The specific exposure time of ultraviolet light also depends on the type of ultraviolet light used, and is preferably about 1 minute to 150 minutes, and more preferably about 30 minutes to 120 minutes.

The temperature during ultraviolet irradiation is preferably within the temperature range that maintains the liquid crystal state of the liquid crystal composition. The specific temperature is preferably about 10°C to 50°C, and more preferably about 15°C to 45°C. Within the temperature range, the polymerizable monomers in the liquid crystal composition diffuse appropriately while polymerizing, so the polymerization proceeds well, thereby fully consuming the remaining polymerizable monomers.

As lamps that generate ultraviolet rays, metal halide lamps, high-pressure mercury lamps, ultra-high-pressure mercury lamps, fluorescent tubes, etc. can be used.

In addition, the irradiated ultraviolet light may be used by cutting off a specified wavelength as needed. A cutoff filter may be used for the cutoff of the wavelength. For example, by cutting off ultraviolet light in a wavelength region including a wavelength of 313 nm, ultraviolet light satisfying I ₃₆₅ /I ₃₁₃ >20 may be obtained. By almost completely cutting off ultraviolet light in a wavelength region including a wavelength of 313 nm, I ₃₁₃ =0 is achieved, and in this case, I ₃₆₅ /I ₃₁₃ becomes infinite.

After the above steps, the liquid crystal display element 1 can be obtained.

In addition, in the [2] assembly step, a vacuum injection method may be used instead of the drop injection (ODF) method. For example, in the vacuum injection method, first, a sealant is screen-printed along the edge of at least one of the active matrix substrate AM and the color filter substrate CF in a manner that leaves an injection port. Thereafter, the two substrates AM and CF are bonded together, and the sealant is cured by at least one of heating and ultraviolet irradiation. Next, a liquid crystal composition is injected into the space defined by the sealant between the two substrates AM and CF through the injection port under vacuum, and then the injection port is sealed. Thereafter, the process proceeds to the [3] liquid crystal layer formation step and the [4] monomer consumption step.

In addition, in other configuration examples, the intensity ratio of the peak value of wavelength 313nm to the peak value of wavelength 365nm in the liquid crystal layer forming step can be set to the relationship in the monomer consumption step, and on the other hand, the intensity ratio of the peak value of wavelength 313nm to the peak value of wavelength 365nm in the monomer consumption step can be set to the relationship in the liquid crystal layer forming step. In the above case, the specific intensity value of each peak or the irradiation time of ultraviolet light is set in a manner that can give the target voltage retention rate or pre-tilt angle to the obtained liquid crystal display element 1. In the above structure, the same action/effect as the above can also be obtained.

In addition to the steps [3] and [4], in an additional step, ultraviolet light having a peak intensity of 313 nm, a peak intensity of 365 nm, and a ratio of their intensities outside the scope of the present invention may be irradiated.

[Liquid crystal composition]

In the manufacturing method of the present invention, the liquid crystal composition contains a polymerizable compound. More specifically, the liquid crystal composition used in the present invention contains one or more compounds represented by general formula (I) or general formula (II) and one or more polymerizable compounds represented by general formula (P).

(Liquid crystal compound represented by formula (I))

The compound represented by the general formula (I) is as follows and corresponds to a compound having negative dielectric anisotropy. "Compound having negative dielectric anisotropy" refers to a compound whose sign of Δε is negative and whose absolute value shows a value greater than 2. In addition, the Δε of the compound is a value extrapolated from the measured value of the dielectric anisotropy of a composition obtained by adding the compound to a composition that is dielectrically almost neutral at 25°C.

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

(wherein, R ¹¹ and R ¹² each independently represent an alkyl group having 1 to 8 carbon atoms, one or two or more non-adjacent -CH ₂ - in the alkyl group may each independently be substituted by -CH=CH-, -C≡C-, -O-, -CO-, -COO- or -OCO-, at least one of R ¹¹ and R ¹² represents an alkenyl group having 2 to 8 carbon atoms, one or two or more -CH ₂ - in the alkenyl group may further be substituted by an oxygen atom as long as the oxygen atoms are not adjacent, n ¹¹ and n ¹² represent 0, 1, 2 or 3, n ¹¹ + n ¹² represent 1, 2 or 3, A ¹¹ and A ¹² each independently represent a group selected from (a) 1,4-cyclohexyl (one -CH ₂ - or two or more non-adjacent -CH _{2 -} in the group) - may be substituted with -O-. ) and (b) 1,4-phenylene (one -CH= or two or more non-adjacent -CH= in this group may be substituted with -N=.)

The groups in the group formed are: the hydrogen atoms in the groups (a) and (b) may be independently substituted by cyano, fluorine or chlorine atoms; Z ¹¹ and Z ¹² independently represent a single bond, -CH ₂ CH ₂ -, -(CH ₂ ) ₄ -, -OCH ₂ -, -CH ₂ O-, -COO-, -OCO-, -OCF ₂ -, -CF ₂ O-, -CH=NN=CH-, -CH=CH-, -CF=CF- or -C≡C-; when there are multiple A ¹¹ and/or A ¹² , they may be the same or different; when there are multiple Z ¹¹ and/or Z ¹² , they may be the same or different.)

In the general formula (I), it is preferred that 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, an alkoxy group having 1 to 8 carbon atoms, an alkenyl group having 2 to 8 carbon atoms, or an alkenyloxy group having 2 to 8 carbon atoms. More specifically, it is preferred that 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, an alkenyl group having 2 to 5 carbon atoms, or an alkenyloxy group having 2 to 5 carbon atoms; further preferably, at least one is an alkenyl group having 2 to 5 carbon atoms, and the other is an alkyl group or alkoxy group having 1 to 5 carbon atoms, or an alkenyl group having 2 to 5 carbon atoms; further preferably, at least one is an alkenyl group having 2 to 5 carbon atoms, and the other is an alkyl group or alkoxy group having 1 to 5 carbon atoms; particularly preferably, at least one is an alkenyl group having 2 to 3 carbon atoms, and the other is an alkyl group or alkoxy group having 1 to 3 carbon atoms.

In addition, when the ring structure to which the group other than alkenyl in ^R11 and ^R12 is bonded is phenyl (aromatic), the group other than alkenyl is preferably a linear alkoxy group having 1 to 5 carbon atoms, 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 number of carbon atoms and oxygen atoms, if present, is preferably 5 or less, and a linear chain is preferred. As the alkenyl, a group represented by any one of the following formulas (R1) to (R5) is preferred, and a group represented by formula (R1) or (R2) is particularly preferred, and ^R11 is most preferably a group represented by formula (R1) or (R2).

[Chemistry 6]

(The black dots in the formulas represent carbon atoms in the ring structure.)

When increasing Δn is required, ^A11 and ^A12 are preferably aromatic, and are preferably aliphatic in order to improve the response speed. They are preferably trans-1,4-cyclohexylene, 1,4-phenylene, 2-fluoro-1,4-phenylene, 3-fluoro-1,4-phenylene, 3,5-difluoro-1,4-phenylene or 2,3-difluoro-1,4-phenylene, and more preferably trans-1,4-cyclohexylene or 1,4-phenylene.

^Z11 and ^Z12 each independently preferably represent _-CH2O- , -CF2O-, _{-CH2CH2- , -CF2CF2- ,} or a single bond, further preferably represent _-CH2O- , _-CH2CH2- , or a single _bond , and particularly preferably represent _-CH2O- or _{a single} bond.

n ¹¹ +n ¹² is preferably 1 or 2, and preferably a combination of n ¹¹ being 1 and n ¹² being 0, a combination of n ¹¹ being 2 and n ¹² being 0, a combination of n ¹¹ being 1 and n ¹² being 1, and a combination of n ¹¹ being 2 and n ¹² being 1.

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

[Chemistry 7]

In the formula, R ¹¹⁰ and R ¹²⁰ are independently the same as R ¹¹ and R ¹² , respectively, and at least one of R ¹¹⁰ and R ¹²⁰ represents an alkenyl group having 2 to 8 carbon atoms which may be substituted by an oxygen atom.

R ¹¹⁰ is preferably an alkenyl group having 2 to 8 carbon atoms, more preferably an alkenyl group having 2 to 5 carbon atoms, particularly preferably an alkenyl group having 2 to 3 carbon atoms, and particularly preferably a group represented by the above formula (R1) or (R2).

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 preferred groups thereof are the same as those of Z ¹¹ and Z ¹² described above.

m independently represents 1 or 2. When m is 1, ^Z1 is preferably a single bond. When m is 2, ^Z1 is preferably -CH ₂ CH ₂ - or -CH ₂ O-.

The fluorine atoms of the compounds represented by general formula (I-01) to general formula (I-05) can be replaced by chlorine atoms of the same halogen group. The content of the compounds replaced by chlorine atoms is preferably as small as possible, and preferably not contained.

The hydrogen atoms on the rings of the compounds represented by general formula (I-01) to general formula (I-05) may be replaced by fluorine atoms or chlorine atoms, but chlorine atoms are less preferred.

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

As the compound represented by general formula (I-01) to general formula (I-05), it is preferred to contain one or more compounds selected from the group consisting of compounds represented by general formula (I-01-1) to general formula (I-01-4), general formula (I-02-1) to general formula (I-02-3), general formula (I-03-1), general formula (I-04-1) and general formula (I-05-1).

[Chemistry 8]

[Chemistry 10]

(In the above formula, R ¹¹⁰ is the same as described above, and R ¹²¹ each independently represents an alkoxy group having 1 to 5 carbon atoms.)

Among them, as the compound represented by formula (I), preferably, the compound represented by formula (I-01-1) to formula (I-01-4), formula (I-02-1) and formula (I-03-1) are preferred, and the compound represented by formula (I-01-3) to formula (I-01-4) is more preferred, and the compound represented by formula (I-01-4) is most preferred.

The lower limit of the preferred content of the compound represented by general formula (I) relative to the total amount of the liquid crystal composition is 1%, 3%, 5%, 7%, 10%, 12%, 15%, 18%, 20%, 30%, 40%, 50%, 55%, and 60%. The upper limit of the preferred content is 40%, 35%, 25%, 20%, 18%, 15%, 12%, 9%, and 5%. In addition, in this specification, unless otherwise defined or stated, "%" means "mass %".

(Liquid crystal compound represented by formula (II))

The compound represented by the general formula (II) is described below, and is equivalent to a dielectrically almost neutral compound. "Dielectrically almost neutral compound" refers to a compound having a Δε value of -2 to 2.

The compound represented by general formula (II) is characterized in that it has at least one alkenyl group at the end, similarly to the compound represented by general formula (I). By using the compound, the viscosity of the entire liquid crystal composition is reduced, and as a result, the response speed of the liquid crystal display element can be increased.

(wherein, R ²¹ and R ²² each independently represent an alkyl group having 1 to 8 carbon atoms, one or two or more non-adjacent -CH ₂ - in the alkyl group may each independently be substituted by -CH=CH-, -C≡C-, -O-, -CO-, -COO- or -OCO-, at least one of R ²¹ and R ²² represents an alkenyl group having 2 to 8 carbon atoms, one or two or more -CH ₂ - in the alkenyl group may further be substituted by oxygen atoms as long as the oxygen atoms are not adjacent, A ²¹ , A ²² and A ²³ each independently represent a group selected from (a) 1,4-cyclohexyl (one -CH ₂ - or two or more non-adjacent -CH ₂ - in the group may each independently be substituted by -CH=CH-, -C≡C-, -O-, -CO-, -COO- or -OCO-) - may be substituted with -O-. ) and (b) 1,4-phenylene (one -CH= or two or more non-adjacent -CH= in this group may be substituted with -N=.)

The groups formed therein, the hydrogen atoms in the groups (a) and (b) may be independently substituted by cyano, fluorine or chlorine atoms, Z ²¹ and Z ²² independently represent a single bond, -CH ₂ CH ₂ -, -(CH ₂ ) ₄ -, -OCH ₂ -, -CH ₂ O-, -COO-, -OCO-, -OCF ₂ -, -CF ₂ O-, -CH=NN=CH-, -CH=CH-, -CF=CF- or -C≡C-, n ²¹ represents 0, 1, 2 or 3, and when A ²² and Z ²² exist in plural numbers, they may be the same or different, except for the compound represented by the formula (I).

In the general formula (II), it is preferred that 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, an alkoxy group having 1 to 8 carbon atoms, an alkenyl group having 2 to 8 carbon atoms, or an alkenyloxy group having 2 to 8 carbon atoms. More specifically, it is preferred that 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, an alkenyl group having 2 to 5 carbon atoms, or an alkenyloxy group having 2 to 5 carbon atoms; further preferably, at least one is an alkenyl group having 2 to 5 carbon atoms, and the other is an alkyl group or alkoxy group having 1 to 5 carbon atoms, or an alkenyl group having 2 to 5 carbon atoms; further preferably, at least one is an alkenyl group having 2 to 5 carbon atoms, and the other is an alkyl group or alkoxy group having 1 to 5 carbon atoms; particularly preferably, at least one is an alkenyl group having 2 to 3 carbon atoms, and the other is an alkyl group or alkoxy group having 1 to 3 carbon atoms.

In order to stabilize the nematic phase, the total number of carbon atoms and oxygen atoms, if present, is preferably 8 or less, more preferably 5 or less, and a linear chain is preferred. The alkenyl group is preferably a group represented by any one of the formulas (R1) to (R5), particularly preferably a group represented by the formula (R1) or (R2), and most preferably ^R21 is a group represented by the formula (R1) or (R2).

A ²¹ , A ²² and A ²³ preferably represent trans-1,4-cyclohexylene, 1,4-phenylene, 2-fluoro-1,4-phenylene or 3-fluoro-1,4-phenylene, and more preferably represent trans-1,4-cyclohexylene or 1,4-phenylene.

^Z21 and ^Z22 each independently preferably represent _-CH2O- , -CF2O-, _-CH2CH2- , _-CF2CF2- , or _a single bond, further preferably represent _{-CH2O- , -CH2CH2-} , or a single _bond , and particularly preferably represent a single _bond .

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

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

[Chemistry 12]

In the formula, R ²¹⁰ and R ²²⁰ are independently the same as R ²¹ and R ²² , respectively, and at least one of R ²¹⁰ and R ²²⁰ represents an alkenyl group having 2 to 8 carbon atoms which may be substituted by an oxygen atom.

R ²¹⁰ is preferably an alkenyl group having 2 to 8 carbon atoms, more preferably an alkenyl group having 2 to 5 carbon atoms, further preferably an alkenyl group having 2 to 3 carbon atoms, and particularly preferably a group represented by the formula (R1) or (R2).

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 general formula (II-01) to general formula (II-06), it is preferred to contain one or more compounds represented by general formula (II-01-1) to general formula (II-01-5).

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

ⁿ²² each independently represents an integer of 0 to 5, and the total number of carbon atoms when ^R211 is an alkyl group and the value of ⁿ²² does not exceed 6. ⁿ²² is preferably 0 or 1, and particularly preferably 0.

R ²²¹ 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, preferably an alkyl group having 1 to 5 carbon atoms or an alkoxy group having 1 to 5 carbon atoms.

Among them, as the compound represented by formula (II), the compound represented by formula (II-01-1) is preferred, and in formula (II-01-1), R ²¹¹ is a hydrogen atom or a methyl group, and n ²² is 0 or 1 is more preferred, and R ²¹¹ is a hydrogen atom or a methyl group, and n ²² is 0 is further preferred, and R ²¹¹ is a hydrogen atom, and n ²² is 0 is particularly preferred. In this case, R ²²¹ is preferably a propyl group.

Relative to the total amount of the liquid crystal composition, the lower limit of the preferred content of the compound represented by general formula (II) is 1%, 3%, 5%, 7%, 10%, 12%, 15%, 18%, 20%, 22%, 25%, 27%, 30%, 40%, 50%, 55%, 60%, 65%, 70%, 75%, 80%. The upper limit of the preferred content is 65%, 55%, 45%, 35%, 30%, 27%, 25%, 20%, 18%, 15%, 12%, 9%, 5%.

(Polymerizable compound represented by formula (P))

The compound represented by the general formula (P) is a polymerizable compound that polymerizes by irradiation with energy rays such as ultraviolet rays. More specifically, the polymerizable compound represented by the formula (P) polymerizes in the liquid crystal layer formation step [3] or the monomer consumption step [4].

(In the above formula, P ^p1 and P ^p2 each independently represent a polymerizable group, Sp ^p1 and Sp ^p2 each independently represent a spacer group or a single bond, Z ^p1 and Z ^p2 each independently represent a single bond, -O-, -S-, -CH 2 -, -OCH ₂ -, -CH ₂ O-, -CO-, -C ₂ H ₄ -, -COO-, -OCO-, -OCOOCH ₂ -, -CH _{2 OCOO-} , -OCH ₂ CH ₂ O-, -CO-NR ^ZP1 -, -NR ^ZP1 -CO-, -SCH ₂ -, -CH ₂ S-, -CH=CR ^ZP1 -COO-, -CH=CR ^ZP1 -OCO-, -COO-CR ^{ZP1 =CH-, -OCO-CR ZP1 =} CH-, -COO-CR ^ZP1 =CH-COO-, -COO-CR ^ZP1 =CH-OCO-, -OCO-CR ^ZP1 =CH-COO-, -OCO-CR ^ZP1 =CH-OCO-, -(CH ₂ ) ₂ -COO-, -(CH ₂ ) ₂ -OCO-, -OCO-(CH ₂ ) ₂ -, -(C=O)-O-(CH ₂ ) ₂ -, -CH=CH-, -CF=CF-, -CF=CH-, -CH=CF-, -CF ₂ -, -CF ₂ O-, -OCF ₂ -, -CF ₂ CH ₂ -, -CH ₂ CF ₂ -, -CF ₂ CF ₂ -, or -C≡C- (wherein R ^ZP1 each independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. When a plurality of R ^ZP1 are present in the molecule, they may be the same or different.), ^Ap1 , ^Ap2 and A p1 ^p3 independently expresses the choice of

(a ^p )1,4-cyclohexylene group (one or two or more -CH ₂ - groups in the group may be substituted by -O- as long as the oxygen atoms are not adjacent to each other.)

(b ^p ) 1,4-phenylene (one or more -CH= in the group may be substituted by -N=.) and

(c ^p ) naphthalene-2,6-diyl, naphthalene-1,4-diyl, naphthalene-1,5-diyl, 1,2,3,4-tetrahydronaphthalene-2,6-diyl, decahydronaphthalene-2,6-diyl, phenanthrene-2,7-diyl or anthracene-2,6-diyl (one or two or more -CH= in the above group may be substituted by -N=.)

In the group composed of the above-mentioned groups, one or two or more hydrogen atoms present in the group (a ^p ), the group (b ^p ) and the group (c ^p ) may be independently substituted by a halogen atom, a cyano group, an alkyl group having 1 to 18 carbon atoms which may be substituted by a fluorine atom, or -Sp ^p2 -P ^p2 ; one or two or more non-adjacent -CH ₂ - groups in the above-mentioned alkyl group may be independently substituted by -CH=CH-, -C≡C-, -O-, -CO-, -COO- or -OCO- to avoid direct adjacency of the oxygen atom; furthermore, when m ^p1 is 0 and A ^p1 is the group represented by the group (c ^p ), A ^p3 may be a single bond, m ^p1 represents 0, 1, 2 or 3; and when a plurality of Z ^p1 , A ^p2 , Sp ^p2 and/or P ^p2 are present in the molecule, they may be the same or different. )

A ^p1 , A ^p2 and A ^p3 represent the selection independently.

(a ^p )1,4-cyclohexylene (One -CH ₂ - or two or more non-adjacent -CH ₂ - in this group may be substituted with -O-.)

(b ^p ) 1,4-phenylene (one -CH= or two or more non-adjacent -CH= in this group may be substituted with -N=.) and

(c ^p ) naphthalene-2,6-diyl, naphthalene-1,4-diyl, 1,2,3,4-tetrahydronaphthalene-2,6-diyl, decahydronaphthalene-2,6-diyl, phenanthrene-2,7-diyl or anthracene-2,6-diyl (one -CH= or two or more non-adjacent -CH= in the above group may be substituted with -N=.)

In the group composed of the above, one or more hydrogen atoms in the above mentioned groups (a ^p ), (b ^p ) and (c ^p ) may be independently substituted by a halogen atom, a cyano group, an alkyl group having 1 to 8 carbon atoms or -Sp ^p2 -P ^p2 , one or more non-adjacent -CH ₂ - in the above mentioned alkyl group may be independently substituted by -CH=CH-, -C≡C-, -O-, -CO-, -COO- or -OCO-, m ^p1 represents 0, 1, 2 or 3, when there are multiple Z ^p1 , A ^p2 , Sp ^p2 and/or P ^p2 in the molecule, they may be the same or different, when m ^p1 is 0 and A ^p1 is phenanthrene-2,7-diyl or anthracene-2,6-diyl, A ^p3 represents a single bond.)

P ^p1 and P ^p2 are each independently a polymerizable group, and are preferably a group represented by any one of the following general formulas (P ^p1 -1) to (P ^p1 -9).

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

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

t ^p11 represents 0, 1 or 2, preferably 0 or 1.

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

Among them, P ^p1 and P ^p2 are preferably independently any one of formula (P ^p1 -1) to formula (P ^p1 -3), more preferably formula (P ^p1 -1), and further preferably all P ^p1 and P ^p2 present in the molecule are formula (P ^p1 -1). In addition, it is preferred that the molecule has a total of two polymerizable groups represented by P ^p1 and P ^p2 , the two P ^p1 and P ^p2 are preferably (P ^p1 -1), and R ^p11 in the two (P ^p1 -1)s are preferably both methyl groups, or a composition of a hydrogen atom and a methyl group.

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

^Zp1 and ^Zp2 are each independently preferably a single bond, _-OCH2- , _-CH2O- , -CO-, _-C2H4- , -COO-, -OCO-, -CH=CH-, -CF2-, -CF2O-, -( _{CH2 ) 2} -COO-, -( _CH2 ) ₂ -OCO-, _-COO- ( _CH2 )2-, -OCO-( _CH2 ) _2- , -CH=CH _- COO-, _-CH =CH-OCO-, -COO-CH=CH-, -OCO-CH=CH-, _-OCF2- or -C≡C-; each is each independently more preferably a single bond, _-OCH2- , _{-CH2O- , -C2H4-} , -COO-, -OCO-, -CH=CH-, -( _CH2 ) _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-. Furthermore, it is particularly preferred that only one of _-OCH2- , _-CH2O- , _-C2H4- , -COO-, -OCO-, _-CH =CH-, -( _CH2 ) ₂ -COO-, -( _CH2 )2-OCO-, -COO-(CH2) _2- , -OCO-( _CH2 ) _2- , -CH=CH-COO-, _-CH =CH-OCO-, -COO-CH= _CH- , -OCO-CH=CH- or -C≡C- exists in the molecule, and the others are all single bonds, or all are single bonds.

When Sp ^p1 and Sp ^p2 are spacers, the spacers are preferably alkylene groups having 1 to 30 carbon atoms, wherein -CH ₂ - in the alkylene groups may be replaced by -O-, -CO-, -COO-, -OCO-, -CH=CH- or -C≡C- as long as the oxygen atoms are not directly linked to each other, and the hydrogen atom in the alkylene groups may be replaced by a halogen atom. Sp ^p1 and Sp ^p2 are preferably straight chain alkylene groups having 1 to 10 carbon atoms or single bonds.

^Ap1 , ^Ap2 and ^Ap3 are preferably independently 1,4-cyclohexylene, 1,4-phenylene or naphthalene-1,4-diyl, and more preferably 1,4-phenylene or naphthalene-1,4-diyl. It is particularly preferred that the molecule has one or more 1,4-phenylene groups. In order to improve compatibility with liquid crystal compounds, these rings are preferably substituted with a fluorine atom, a methyl group or a methoxy group.

Suitable examples of polymerizable compounds represented by formula (P) are shown below.

[Chemistry 16]

[Chemistry 17]

[Chemistry 18]

(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).)

[Chemistry 25]

[Chemistry 26]

(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).)

[Chemistry 27]

[Chemistry 28]

(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).)

[Chemistry 29]

[Chemistry 32]

(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 may be the same or different.)

[Chemistry 33]

[Chemistry 34]

[Chemistry 35]

(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 may be the same or different. Me represents a methyl group.)

In the present invention, high-speed response of liquid crystal display elements is achieved by using alkenyl liquid crystal compounds, but by using alkenyl liquid crystal compounds, the polymerization rate of polymerizable compounds may be slightly slowed down. Therefore, by using highly reactive compounds as polymerizable compounds, the reduction of polymerization rate can be prevented. Moreover, by obtaining a sufficient polymerization rate, the productivity during the manufacture of liquid crystal display elements is improved, and the display defects such as unevenness or burn-in of the obtained liquid crystal display elements are reduced, and good display quality can be achieved. As highly reactive polymerizable compounds, the compounds listed in the above formula (P-1-21) to formula (P-1-46) and formula (P-5-1) to formula (P-5-19) are preferred.

The compound represented by formula (P) may be used alone or in combination of two or more. Among them, it is preferred to use two or more polymerizable monomers with different polymerization reaction rates in combination, because the polymerization reaction rate can be properly controlled, the amount of residual monomers can be reduced, and a proper pre-tilt angle can be given. In addition, from the perspective of balancing the storage stability and the polymerization reaction rate, it is also preferred to use two or more polymerizable monomers in combination.

The total content of the compounds represented by formula (P) relative to the composition containing these compounds is preferably 0.05% to 10%, preferably 0.1% to 8%, preferably 0.1% to 5%, preferably 0.1% to 3%, preferably 0.2% to 2%, preferably 0.2% to 1.3%, preferably 0.2% to 1%, preferably 0.2% to 0.56%.

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

The preferred upper limit of the total content of the compounds represented by formula (P) relative to the composition containing these compounds is 10%, 8%, 5%, 3%, 1.5%, 1.2%, 1%, 0.8%, and 0.5%.

If the content is too low, it is difficult to show the effect of adding the compound represented by formula (P), resulting in problems such as weak alignment restriction of the liquid crystal composition or weakening over time. If the content is too high, the amount of residue after curing increases, curing takes time, and the reliability of the liquid crystal decreases. Therefore, the content is set by considering the balance of these factors.

(Other liquid crystal compounds)

The liquid crystal composition used in the present invention may contain other liquid crystal compounds in addition to one or more compounds represented by the above formula (I) or formula (II) and one or more polymerizable compounds represented by the above formula (P).

As other liquid crystal compounds, the compound in the formula (I) wherein both R ¹¹ and R ¹² are not alkenyl groups having 2 to 8 carbon atoms (hereinafter referred to as "compound (I')") and the compound in the formula (II) wherein both R ²¹ and R ²² are not alkenyl groups having 2 to 8 carbon atoms (hereinafter referred to as "compound (II')") can be listed as preferred compounds.

．Compound (I')

As compound (I'), compounds represented by the following formula (I') can be listed.

In formula (I'), R ^11' and R ^12' each independently represent an alkyl group having 1 to 8 carbon atoms, one or two or more non-adjacent -CH ₂ - in the alkyl group may be independently substituted by -C≡C-, -O-, -CO-, -COO- or -OCO-, and are preferably alkyl groups having 1 to 5 carbon atoms or alkoxy groups having 1 to 5 carbon atoms. When the ring structure to which R ^11' and R ^12' are bonded is a phenyl group, it is preferably an alkyl group having 1 to 5 carbon atoms or an alkoxy group having 1 to 5 carbon atoms, and when the ring structure to which R 11' and R 12' are bonded is a cyclohexyl group, it is preferably an alkyl group having 1 to 5 carbon atoms.

In formula (I'), A ¹¹ , A ¹² , Z ¹¹ , Z ¹² , n ¹¹ , and n ¹² are the same as A ¹¹ , A ¹² , Z ¹¹ , Z ¹² , n ¹¹ , and n ¹² in formula (I), respectively.

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

[Chemistry 37]

In the formula, R ^110′ is independently the same as R ^11′ , preferably an alkyl group having 1 to 5 carbon atoms or an alkoxy group having 1 to 5 carbon atoms, more preferably an alkyl group having 1 to 3 carbon atoms.

R ¹²⁰ , Z ¹¹⁰ , and m are the same as R ¹²⁰ , Z ¹¹⁰ , and m in the above-mentioned formula (I-01) to formula (I-05), respectively.

The fluorine atom of the compound can be replaced by a chlorine atom of the same halogen group. The content of the compound substituted by chlorine atoms is preferably as small as possible, and preferably not contained. In addition, the hydrogen atom on the ring of the compound can be replaced by a fluorine atom or a chlorine atom, but the chlorine atom is not preferred. The compound is preferably a compound with a negative Δε and an absolute value greater than 3.

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

．Compound (II')

As compound (II'), compounds represented by the following formula (II') can be listed.

In formula (II'), R ^21' and R ^22' each independently represent an alkyl group having 1 to 8 carbon atoms, one or two or more non-adjacent -CH ₂ - in the alkyl group may be independently substituted by -C≡C-, -O-, -CO-, -COO- or -OCO-, and are preferably alkyl groups having 1 to 5 carbon atoms or alkoxy groups having 1 to 5 carbon atoms. When the ring structure to which R ^21' and R ^22' are bonded is a phenyl group, it is preferably an alkyl group having 1 to 5 carbon atoms or an alkoxy group having 1 to 5 carbon atoms, and when the ring structure to which R 21' and R 22' are bonded is a cyclohexyl group, it is preferably an alkyl group having 1 to 5 carbon atoms.

In formula (II'), A ²¹ , A ²² , A ²³ , Z ²¹ , Z ²² , and n ²¹ are the same as A ²¹ , A ²² , A ²³ , Z ²¹ , Z ²² , and n ²¹ in formula (II), respectively.

As compound (II'), it is preferred to contain one or more compounds selected from the group of compounds represented by general formula (II'-01) to (II'-06).

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

R ²²⁰ is the same as R ²²⁰ in the formula (II'-01) to the formula (II'-06).

Relative to the total amount of the liquid crystal composition used in the present invention, the lower limit of the preferred content of the compound represented by the general formula (II') is 0%, 1%, 5%, 10%, 20%, 30%, 40%, 50%, 55%, 60%, 65%, 70%, 75%, 80%. The upper limit of the preferred content is 95%, 85%, 75%, 65%, 55%, 45%, 35%, 25%, 20%, 15%, 10%.

(Sensitizer)

A sensitizer may also be added to the liquid crystal composition used in the present invention. Here, the sensitizer refers to a compound that has the function of promoting the polymerization reaction of a polymerizable compound, and in the present invention, it refers to promoting the polymerization of the polymerizable compound represented by the formula (P).

In the present invention, a high-speed response of a liquid crystal display element is achieved by using an alkenyl liquid crystal compound, but by using an alkenyl liquid crystal compound, the polymerization rate of the polymerizable compound is sometimes slightly slowed down. When the polymerization rate of the composition used in the present invention is not sufficient, the polymerization rate can be increased by using the polymerizable compound and a sensitizer. Moreover, by improving the polymerization rate, the productivity of the liquid crystal display element can be improved, and the unevenness or burn-in of the obtained liquid crystal display element can be reduced, and good display quality can be achieved.

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

In the formula, ^Rs1 and ^Rs2 independently represent an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, or an alkenyloxy group having 2 to 10 carbon atoms, and one or more hydrogen atoms present in these groups may be substituted by fluorine atoms.

In terms of the effect of improving the reliability of VHR, R ^s1 and R ^s2 are each independently preferably an alkyl group having 1 to 5 carbon atoms or an alkoxy group having 1 to 5 carbon atoms, and particularly preferably an alkyl group having 1 to 3 carbon atoms or an alkoxy group having 1 to 3 carbon atoms.

One or two or more hydrogen atoms present in the groups of R ^s1 and R ^s2 may or may not be substituted by fluorine atoms, but R ^s1 and R ^s2 are preferably not substituted by fluorine atoms.

Ring A ^s1 and Ring B ^s1 are independently selected from

(a) 1,4-cyclohexylene (one -CH ₂ - or two or more non-adjacent -CH ₂ - in this group may be substituted with -O-.)

(b) 1,4-phenylene group (one -CH= or two or more non-adjacent -CH= in this group can be substituted with -N=.)

(c) naphthalene-2,6-diyl, 1,2,3,4-tetrahydronaphthalene-2,6-diyl or decahydronaphthalene-2,6-diyl (one -CH= or two or more non-adjacent -CH= in naphthalene-2,6-diyl or 1,2,3,4-tetrahydronaphthalene-2,6-diyl may be substituted with -N=.) and

(d) 1,4-cyclohexenyl

The groups in the group formed, the groups (a), (b), (c) and (d) can be independently substituted by an alkyl group having 1 to 8 carbon atoms which can be substituted by a fluorine atom, an alkoxy group having 1 to 8 carbon atoms which can be substituted by a fluorine atom, a cyano group or a fluorine atom.

Among them, more preferred as ring A ^s1 and ring B ^s1 are 1,4-cyclohexylene, unsubstituted 1,4-phenylene, 2-fluoro-1,4-phenylene, 3-fluoro-1,4-phenylene or 2,3-difluoro-1,4-phenylene.

To describe in more detail, ring A ^s1 and ring B ^s1 are each independently preferably an unsubstituted 1,4-phenylene group, 2-fluoro-1,4-phenylene group, 3-fluoro-1,4-phenylene group or 2,3-difluoro-1,4-phenylene group, and particularly preferably an unsubstituted 1,4-phenylene group, because the polymerization rate of the polymerizable compound can be further accelerated, and unsubstituted 1,4-phenylene group is particularly preferred. The UV absorption band of the unsubstituted phenylene group is located on the long-wavelength side compared to the phenylene group substituted with other atoms such as fluorine atoms. Therefore, the liquid crystal composition containing a polymerizable compound of the present invention, which contains a compound represented by the general formula (S) having an unsubstituted phenylene group, can further accelerate the reaction rate of the polymerizable compound, and can also sufficiently suppress the reduction of VHR, compared to the case of containing a compound represented by the general formula (S) having a substituent.

On the other hand, because the miscibility with other liquid crystal components is further improved, the ring A ^s1 and the ring B ^s1 are each independently preferably 2-fluoro-1,4-phenylene, 3-fluoro-1,4-phenylene or 2,3-difluoro-1,4-phenylene.

When there are plural rings A ^s1 and B ^s1 , the plural rings A ^s1 and the plural rings B ^s1 may be the same or different.

^Zs1 and ^Zs2 independently represent _-OCH2- , _-CH2O- , -COO-, -OCO-, _-CF2O- , -OCF2-, _-CH2CH2- , _-CF2CF2- , _-C≡C- , or a _single bond, preferably _-OCH2- , _-CH2O- , _-CH2CH2- , or a single bond, and particularly preferably a _single bond in _order to increase the polymerization rate of the polymerizable compound.

n ^s1 and n ^s2 independently represent 0, 1 or 2, respectively, and in terms of better mixing properties with other liquid crystal molecules, it is preferred that one of n ^s1 or n ^s2 represents 1 or 2 and the other represents 0. In addition, n ^s1 + n ^s2 represents an integer of 1 to 4, but in terms of better mixing properties with other liquid crystal molecules, it is preferably 1 or 2, and in terms of better mixing properties with other liquid crystal molecules and tilt stability, it is more preferably 1.

^Xs1 to ^Xs6 each independently represent 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, a fluorine atom or a hydrogen atom, preferably an alkyl group having 1 to 5 carbon 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, particularly preferably a hydrogen atom.

The number of groups serving as hydrogen atoms in ^Xs1 to ^Xs6 is preferably at least 3. Specifically, the number of groups serving as hydrogen atoms in ^Xs1 to ^Xs6 is preferably 3, 4, 5 or 6, more preferably 4, 5 or 6, more preferably 5 or 6, and more preferably 6.

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

[Chemistry 41]

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

The compound of general formula (S) can promote the polymerization reaction of the polymerizable compound by its sensitizing effect. On the other hand, if the content of the compound of general formula (S) is too much, it is difficult to form a sufficiently large tilt by a short reaction time, or the VHR is reduced. In contrast, the liquid crystal composition containing the polymerizable compound of the present invention can fully polymerize the polymerizable compound at a faster rate by adjusting the content of the compound of general formula (S) to a specified range, can form a sufficiently large tilt in a short time, can suppress the reduction of VHR caused by UV irradiation, and can satisfy various characteristics in a well-balanced manner.

The content of the compound of general formula (S) in the total amount of the liquid crystal composition only needs to be less than 2.0%, 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%, 0.6%, 0.5%. In addition, the content of the compound of general formula (S) in the total amount of the liquid crystal composition only needs to exceed 0%, 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 formula (A)

The liquid crystal composition used in the present invention may contain a compound represented by the following general formula (A).

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

In the formula, R ^AK1 represents a straight or branched alkyl group having 1 to 20 carbon atoms, preferably a straight or branched alkyl group having 1 to 20 carbon atoms, more preferably a straight alkyl group having 1 to 20 carbon atoms, and further preferably a straight alkyl group having 1 to 8 carbon atoms. One or two or more non-adjacent -CH ₂ - in the alkyl group may be independently substituted by -CH=CH-, -C≡C-, -O-, -CO-, -COO- or -OCO-, so as to avoid direct adjacency of oxygen atoms. In addition, one or two or more hydrogen atoms in the alkyl group may be independently substituted by halogen atoms. As the halogen atom, a fluorine atom or a chlorine atom is preferred, and a fluorine atom is more preferred.

A ^AL1 and A ^AL2 each independently represent a divalent cyclic group. The divalent cyclic group is preferably selected from 1,4-phenylene, 1,4-cyclohexylene, 1,4-cyclohexenyl, tetrahydropyran-2,5-diyl, 1,3-dioxane-2,5-diyl, tetrahydrothiopyran-2,5-diyl, thiophene-2,5-diyl, 1,4-bicyclo(2.2.2)octylene, decahydronaphthalene-2,6-diyl, pyridine-2,5-diyl, pyrimidine-2,5-diyl, pyrazine-2,5-diyl, thiophene-2,5-diyl, 1,2,3,4-tetrahydronaphthalene-2,6-diyl, 2,6-dicyclohexen ... One of the group consisting of naphthyl, phenanthrene-2,7-diyl, 9,10-dihydrophenanthrene-2,7-diyl, 1,2,3,4,4a,9,10a-octahydrophenanthrene-2,7-diyl, 1,4-naphthylene, benzo[1,2-b:4,5-b']dithiophene-2,6-diyl, benzo[1,2-b:4,5-b']diselenophene-2,6-diyl, [1]benzothiophene[3,2-b]thiophene-2,7-diyl, [1]benzoselenophene[3,2-b]selenophene-2,7-diyl and fluorene-2,7-diyl. Among them, A ^AL1 and A ^AL2 are each independently more preferably 1,4-phenylene, 1,4-cyclohexylene, 2,6-naphthylene or phenanthrene-2,7-diyl, and further preferably 1,4-phenylene or 1,4-cyclohexylene.

The divalent cyclic group may be unsubstituted, and one or more hydrogen atoms in the cyclic group may be substituted by a substituent. As the substituent, a halogen group, a polar group, P ^AP1 -Sp ^AP1 - or a monovalent organic group may be listed. When the monovalent organic group is an alkyl group, the alkyl group may be substituted by a fluorine atom or a hydroxyl group. As the halogen group, a fluoro group, a chloro group, etc. may be listed, and a fluoro group is preferred.

Here, "monovalent organic group" is a group having a chemical structure when an organic compound is in the form of a monovalent group, and refers to an atomic group obtained by removing a hydrogen atom from an 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 group having 2 to 15 carbon atoms. One or more _-CH2- groups in the alkyl group, the alkenyl group, the alkoxy group, and the alkenyloxy group may be substituted with -O-, -COO-, or -OCO-, respectively, so that the oxygen atom is not directly adjacent.

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, more preferably an alkyl group having 1 to 8 carbon atoms or an alkoxy group having 1 to 8 carbon atoms, further preferably an alkyl group having 1 to 5 carbon atoms or an alkoxy group having 1 to 4 carbon atoms, particularly preferably an alkyl group having 1 to 3 carbon atoms or an alkoxy group having 1 to 2 carbon atoms, and most preferably an alkyl group having 1 or 2 carbon atoms or an alkoxy group having 1 carbon atom. One or more _-CH2- in the alkyl group, the alkenyl group, the alkoxy group and the alkenyloxy group may be substituted by -O-, -COO- or -OCO-, respectively, to avoid direct adjacency of oxygen atoms.

Z ^AL1 represents 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, wherein one or two or more non-adjacent -CH ₂ - may be substituted by a cyclic group, -CH=CH-, -C≡C-, -O-, -CO-, -COO- or -OCO- to avoid direct bonding with the oxygen atom. Among them, a single bond or an alkylene group having 2 to 20 carbon atoms is preferred, a single bond or an alkylene group having 2 to 10 carbon atoms is more preferred, and a single bond, -(CH ₂ ) ₂ - or -(CH ₂ ) ₄ - is further preferred. One or more -CH ₂ - in the alkylene group may be substituted by -O-, -COO- or -OCO- to avoid direct bonding with the oxygen atom.

In order to improve the linearity of the compound represented by formula (A), Z ^AL1 is preferably a single bond or an alkylene group having 2 to 20 carbon atoms in which the number of atoms directly linking the rings is an even number. One or two or more non-adjacent -CH ₂ - in the alkylene group may be substituted with -O-, -COO- or -OCO- to prevent the oxygen atoms from being directly adjacent. The number of atoms directly linking the rings is, for example, 4 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 further preferably 2 or 3.

Sp ^AT1 represents a single bond or a straight or branched alkylene group having 1 to 25 carbon atoms, one or more hydrogen atoms in the alkylene group may be substituted by -OH, -CN, -W ^AT1 -Z ^AT1 or P ^AP1 -Sp ^AP1 -, and one or more non-adjacent -CH ₂ - in the alkylene group may be substituted by a cyclic group, -CH=CH-, -C≡C-, -O-, -CO-, -COO- or -OCO- to avoid direct bonding of the oxygen atom. Among them, preferably represents a single bond or a straight or branched alkylene group having 1 to 20 carbon atoms, more preferably represents a single bond or a straight chain alkylene group having 1 to 20 carbon atoms, and further preferably represents a single bond or a straight chain alkylene group having 2 to 10 carbon atoms.

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

(In the formula, Sp ^WAT1 and Sp ^WAT2 independently represent a single bond or a straight or branched alkylene group having 1 to 25 carbon atoms, one or more hydrogen atoms in the alkylene group may be substituted by -OH, -CN or P ^AP1 -Sp ^AP1 -, and one or more non-adjacent -CH ₂ - in the alkylene group may be substituted by a cyclic group, -CH=CH-, -C≡C-, -O-, -CO-, -COO- or -OCO- to avoid direct adjacency of the oxygen atom. The * in the formula represents a bond.), Z ^AT1 represents a monovalent polar group containing a polar element, and one or more hydrogen atoms in Z ^AT1 may be substituted by -OH, -CN or P ^AP1 -Sp ^AP1 -.

Preferably, it is a group represented by the following general formula (ZAT1-1) or general formula (ZAT1-2).

[Chemistry 44]

(wherein, Sp ^ZAT11 represents a single bond or a straight chain or branched alkylene group having 1 to 25 carbon atoms, one or more hydrogen atoms in the alkylene group may be substituted by -OH, -CN or -Z ^ZAT11 -R ^ZAT11 or P ^AP1 -Sp ^AP1 -, and one or more non-adjacent -CH ₂ - in the alkylene group may be substituted by a cyclic group, -O-, -COO-, -C(=O)-, -OCO-, or -CH=CH- to avoid direct adjacent oxygen atoms.

Sp ^ZAT12 represents a single bond or a straight chain or branched alkylene group having 1 to 25 carbon atoms, one or more hydrogen atoms in the alkylene group may be substituted by -OH, -CN or P ^AP1 -Sp ^AP1 -, and one or more non-adjacent -CH ₂ - in the alkylene group may be substituted by a cyclic group, -O-, -COO-, -C(=O)-, -OCO-, -CH=CH- or -Z ^ZAT11 - to avoid direct adjacency of the oxygen atom.

Z ^ZAT11 represents a group including polar elements.

The structure represented by the ring including Z ^ZAT12 represents a five-membered ring to a seven-membered ring.

One or more hydrogen atoms in Z ^ZAT11 and Z ^ZAT12 may be substituted by -OH, -CN or P ^AP1 -Sp ^AP1 -.

R ^ZAT11 and R ^ZAT12 independently represent a hydrogen atom, a linear or branched alkyl group having 1 to 8 carbon atoms, one or more hydrogen atoms in the alkyl group may be substituted by -OH, -CN or P ^AP1 -Sp ^AP1 -, and one or more non-adjacent -CH ₂ - groups in the alkyl group may be substituted by a cyclic group, -O-, -COO-, -C(=O)-, -OCO-, -CH=CH- or -Z ^ZAT11 - to prevent direct bonding with the oxygen atom.

P ^AP1 represents a polymerizing group, and Sp ^AP1 represents a spacer group.

The * in the formula represents a key. )

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).

[Chemistry 45]

[Chemistry 46]

(In the formula, Sp ^ZAT11 and R ^ZAT11 have the same meanings as described above, and the hydrogen atom bonded to the carbon atom may be substituted by -OH, -CN or P ^AP1 -Sp ^AP1 -. The * in the formula represents a bond.)

In addition, as the group represented by the general formula (ZAT1-1), the following groups can be preferably listed.

[Chemistry 50]

(wherein, R ^tc represents a hydrogen atom, a linear or branched alkyl group having 1 to 20 carbon atoms, or P ^AP1 -Sp ^AP1 -, one or more hydrogen atoms in the alkyl group may be substituted by -OH, -CN or P ^AP1 -Sp ^AP1 -, and one or more non-adjacent -CH ₂ - groups in the alkyl group may be substituted by a cyclic group, -O-, -COO-, -C(=O)-, -OCO-, -CH=CH- or -Z ^ZAT11 - to avoid direct adjacency of the oxygen atom.

The hydrogen atom in the molecule can be replaced by P ^AP1 -Sp ^AP1 -.

The * in the formula represents a key. )

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 has the same meaning as described above, and one or more hydrogen atoms bonded to the carbon atom may be substituted by a halogen atom, -OH, -CN or P ^AP1 -Sp ^AP1 -.

The * in the formula represents a key. )

P ^AP1 represents a polymerizable group, preferably a group represented by any one of the formulas (P ^p1 -1) to (P ^p1 -9), more preferably a group represented by any one of the formulas (P ^p1 -1) to (P ^p1 -7), further preferably a group represented by any one of the formulas (P ^p1 -1) to (P ^p1 -2), and most preferably a group represented by the formula (P ^p1 -1).

Sp ^AP1 represents a spacer group, preferably a single bond or a straight chain or branched alkylene group having 1 to 20 carbon atoms, more preferably a single bond or a straight chain alkylene group having 1 to 20 carbon atoms, and still more preferably a single bond or a straight chain alkylene group having 2 to 10 carbon atoms. In Sp ^AP1 , one or two or more non-adjacent -CH ₂ - in the alkylene group may be substituted with -CH=CH-, -C≡C-, -O-, -CO-, -COO- or -OCO-, so that the oxygen atom is not directly adjacent. In addition, "substituted with a polymerizable group" may be a form of being substituted with only the polymerizable group P ^AP1 or a form of being substituted with P ^AP1 -Sp ^AP1 - containing the spacer group Sp ^AP1 . The same applies to other polymerizable groups.

In the compound represented by formula (A), the number of P ^AP1 -Sp ^AP1 - is preferably 1 or more and 5 or less, more preferably 1 or more and 4 or less, further preferably 2 or more and 4 or less, particularly preferably 2 or 3, and most preferably 2.

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

In the formula, when there are a plurality of A ^AL1 , Z ^AL1 , Z ^AT1 , W ^AT1 , P ^AP1 , Sp ^AP1 , Sp ^WAT1 , and Sp ^WAT2 , they may be the same or different.

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

[Chemistry 53]

[Chemistry 54]

[Chemistry 55]

[Chemistry 56]

[Chemistry 59]

[Chemistry 60]

[Chemistry 61]

The lower limit of the content of the compound represented by formula (A) relative to the total amount of the liquid crystal composition is preferably 0.01%, and from the perspective of improving the specific resistance and VHR, it is further preferably 0.05%, and more preferably 0.1%. On the other hand, relative to the total amount of the liquid crystal composition in the present invention, the upper limit of the content of the first polymerizable compound and its polymer is preferably 50%, 10%, 7%, 5%, 4%, 3%, 2%, 1%.

．Polymerization initiator

The liquid crystal composition used in the present invention contains a polymerizable compound as described above. Polymerization proceeds even in the absence of a polymerization initiator, but a polymerization initiator may be contained to promote polymerization. Examples of polymerization initiators include benzoin ethers, benzophenones, acetophenones, benzyl ketones, acylphosphine oxides, and the like.

．Antioxidant

The composition of the present invention may further contain compounds represented by general formula (Q1) to general formula (Q2) as antioxidants.

(In the formula, R ^Q represents a straight chain alkyl group or a branched chain alkyl group having 1 to 22 carbon atoms, one or more CH ₂ groups in the alkyl group may be substituted by -O-, -CH=CH-, -CO-, -OCO-, -COO-, -C≡C-, -CF ₂ O-, -OCF ₂ - to avoid direct adjacent oxygen atoms, the hydrogen atom in R ^Q may be substituted by 4-hydroxy-3,5-di-tert-butylphenyl, M ^Q represents trans-1,4-cyclohexyl, 1,4-phenylene or a single bond, and one or two non-adjacent -CH ₂ - in the trans-1,4-cyclohexyl group may be substituted by -O-.

In the formula, ^Xy represents an alkylene group having 1 to 15 carbon atoms (one or more _-CH2- in the _alkylene group may be substituted with -O-, -CO-, -COO-, or -OCO- to prevent the oxygen atom from being directly adjacent.), _-OCH2- , -CH2O- _, -COO-, -OCO-, -CF2O-, _-OCF2- , _-CF2CF2- , -CH=CH-COO-, -CH=CH-OCO-, -COO-CH=CH-, -OCO-CH=CH-, -CH=CH-, -C≡C-, 1,4- _phenylene , trans-1,4-cyclohexylene or a single bond. With respect to 1,4-phenylene, any hydrogen atom may be substituted with a fluorine atom. ^My represents a monovalent linking group, and l represents an integer of 2 to 6.)

R ^Q represents a straight-chain alkyl group or a branched-chain alkyl group having 1 to 22 carbon atoms, wherein one or more CH ₂ groups in the alkyl group may be substituted by -O-, -CH=CH-, -CO-, -OCO-, -COO-, -C≡C-, -CF ₂ O-, or -OCF ₂ - to prevent the oxygen atom from being directly adjacent to the alkyl group. Preferably, the alkyl group is a straight-chain alkyl group, a straight-chain alkoxy group, a straight-chain alkyl group in which one CH ₂ group is substituted by -OCO- or -COO-, a branched alkyl group, a branched alkoxy group, or a branched alkyl group in which one CH ₂ group is substituted by -OCO- or -COO-. More preferably, the alkyl group is a straight-chain alkyl group, a straight-chain alkyl group, a branched alkyl group, a branched alkoxy group, or a branched alkyl group in which one CH ₂ group is substituted by -OCO- or -COO-. ^{M Q} represents a trans-1,4 _- cyclohexylene group, a 1,4-phenylene group or a single bond, and preferably a trans-1,4-cyclohexylene group or a 1,4-phenylene group.

^{My is} preferably a alkyl group having 1 to 25 carbon atoms. One or more -CH ₂ - in the alkyl group may be substituted with -O-, -CO-, -COO-, or -OCO- to avoid direct adjoining oxygen atoms.

l is preferably 2 or 3, more preferably 2. When l is 2, ^My is preferably an alkylene group having 1 to 14 carbon atoms. Considering volatility, the carbon number is preferably a large number, and considering viscosity, the carbon number is preferably not too large, so the carbon number is preferably 2 to 12, more preferably 3 to 10, further preferably 4 to 10, particularly preferably 5 to 10, and most preferably 6 to 10.

X ^y is preferably a single key.

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

In the formula, R ^Q1 is preferably a linear or branched alkyl group having 1 to 10 carbon atoms, R ^Q2 is preferably a linear or branched alkyl group having 1 to 20 carbon atoms, R ^Q3 is preferably a linear alkyl group, branched alkyl group, linear alkoxy group or branched alkoxy group having 1 to 8 carbon atoms, and L ^Q is preferably a linear or branched alkyl group having 1 to 8 carbon atoms. Among the compounds represented by general formula (Q1-a) to general formula (Q1-d), compounds represented by general formula (Q1-c) and general formula (Q1-d) are more preferred.

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

The composition of the present invention preferably contains one or two compounds represented by general formula (Q1) to general formula (Q2), and more preferably contains one to five compounds, 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%.

In addition, as antioxidants or light stabilizers that can be used in the present invention, more specifically, the compounds represented by the following (III-1) to (III-41) are preferred.

[Chemistry 68]

[Chemistry 73]

(In the formula, n represents an integer from 0 to 20.)

It is preferred to contain one or more compounds represented by general formula (Q1) to general formula (Q2) or compounds selected from general formula (III-1) to general formula (III-41), and it is further preferred to contain one to five compounds, and the content thereof is preferably 0.001% to 1%, further 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 for achieving high-speed response, high reliability and suppression of display defects at the same time, and is particularly effective as an active matrix driven liquid crystal display element, and can be applied to VA mode, polymer stabilized vertical alignment (PSVA) mode, PSA mode, IPS mode or electrically controlled birefringence (ECB) mode liquid crystal display element. It is particularly suitable for VA mode, PSVA mode and PSA mode.

[Implementation example]

The present invention is described in more detail with the following examples, but the present invention is not limited to these examples. In addition, the "%" in the compositions of the following examples and comparative examples refers to "mass %".

In the embodiment, the specific measured is as follows.

T _ni : Nematic-isotropic liquid phase transition temperature (℃)

△n: refractive index anisotropy at 293K

△ε: Dielectric constant anisotropy at 293K

γ1: Rotational viscosity at 293K (mPa.s)

In addition, the following abbreviations are used to describe the compounds in the examples.

<Ring structure>

[Chemistry 76]

(In the table, n is a natural number.)

(In the table, n is a natural number.)

In the embodiment, the characteristics evaluated are as follows.

Reliability (VHR): Voltage retention rate (%) of a liquid crystal display element after being exposed to UV light for 90 minutes and measured at 1V, 0.6Hz, and 60℃

As the UV irradiation lamp for the embodiment, FL15UV34A manufactured by Toshiba Lighting & Technology was used, and the illuminance at 365 nm was adjusted to 4 mW/cm ² . This lamp has I ₃₆₅ /I ₃₁₃ >20 (where 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 )).

As the comparative UV irradiation lamp, FL15UV32A manufactured by Toshiba Lighting & Technology was used, and the illuminance at 313 nm was adjusted to 4 mW/cm ² . This lamp has I ₃₆₅ /I ₃₁₃ <20.

(Preparation and evaluation results of liquid crystal compositions)

Liquid crystal compositions (LC-1) to (LC-6) were prepared and their physical properties were measured. The composition ratios and physical properties of these liquid crystal compositions are shown in the following table.

It can be seen that LC-1 to LC-5 containing alkenyl compounds have small γ1 and fast response speed. It can be seen that LC-6 without alkenyl compounds has large γ1 and slow response speed. LC-6 with poor response speed was set as the evaluation object, and the other LC-1 to LC-5 were set as the object for the following evaluation.

For the liquid crystal composition mixed with LC-1 to LC-5, the polymerizable compound represented by RM1 to RM5, and the additive represented by AD1 and AD2, the VHR of Example (E-01) to Example (E-25) was measured by irradiating UV with a UV irradiation lamp in the Example, and the VHR of Comparative Example (C-01) to Comparative Example (C-10) was measured by irradiating UV with a UV irradiation lamp in the Comparative Example, as shown in Table 4.

[Chemistry 78]

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

The same results as those of Example 1 (E-01) to Example 5 (E-05) and Comparative Example 1 (C-01) and Comparative Example 2 (C-02) can also be obtained in Example 6 (E-06) to Example 25 (E-25) and Comparative Example 3 (C-03) to Comparative Example 10 (C-10).

AM: Active Matrix Substrate (Substrate)

CF: Color filter substrate (substrate)

1: Liquid crystal display element

2: First substrate

3: Second substrate

4: Liquid crystal layer

5: Pixel electrode layer (electrode layer) (electrode)

6: Common electrode layer (electrode layer) (electrode)

7: First polarizing plate

8: Second polarizing plate

9: Color filter

Claims (4)

A method for manufacturing a liquid crystal display element comprises: a step of arranging a pair of substrates, at least one of which has an alignment film, facing each other with a liquid crystal composition containing a polymerizable compound interposed therebetween; a step of irradiating the liquid crystal composition with ultraviolet light to polymerize the polymerizable compound, wherein the ultraviolet light is at least once irradiated with ultraviolet light satisfying the following formula (P-1): I ₃₆₅ /I ₃₁₃ >20‧‧‧(P-1) wherein I ₃₆₅ represents the illuminance (mW/cm ² ) at a wavelength of 365 nm, and I ₃₁₃ represents the illuminance (mW/cm ² ) at a wavelength of 313 nm; the liquid crystal composition contains one or more liquid crystal compounds represented by the following general formula (I) or the following general formula (II), one or more polymerizable compounds represented by the following general formula (P), and a sensitizer represented by the following general formula (S),

wherein R ¹¹ and R ¹² each independently represent an alkyl group having 1 to 8 carbon atoms, one or two or more non-adjacent -CH ₂ - in the alkyl group may each independently be substituted by -CH=CH-, -C≡C-, -O-, -CO-, -COO- or -OCO-; at least one of R ¹¹ and R ¹² represents an alkenyl group having 2 to 8 carbon atoms, one or two or more -CH ₂ - in the alkenyl group may further be substituted by an oxygen atom as long as the oxygen atoms are not adjacent; n ¹¹ and n ¹² represent 0, 1, 2 or 3, n ¹¹ + n ¹² represent 1, 2 or 3; A ¹¹ and A ¹² each independently represent a group selected from (a) 1,4-cyclohexyl, one -CH ₂ - or two or more non-adjacent -CH ₂ - in the group may each independently be substituted by an oxygen atom; - may be substituted with -O-, and (b) 1,4-phenylene, one -CH= or two or more non-adjacent -CH= in this group may be substituted with -N=, in the group consisting of, the hydrogen atom in the group (a) and the group (b) may be independently substituted with a cyano group, a fluorine atom or a chlorine atom, 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 -, -CF ₂ O-, -CH=NN=CH-, -CH=CH-, -CF=CF- or -C≡C-, when there are multiple A ¹¹ and/or A ¹² , they may be the same or different, when there are multiple Z ¹¹ and/or Z 12 In the case of ¹² , they can be the same or different.

wherein R ²¹ and R ²² each independently represent an alkyl group having 1 to 8 carbon atoms, one or two or more non-adjacent -CH ₂ - in the alkyl group may be independently substituted by -CH=CH-, -C≡C-, -O-, -CO-, -COO- or -OCO-; at least one of R ²¹ and R ²² represents an alkenyl group having 2 to 8 carbon atoms, one or two or more -CH ₂ - in the alkenyl group may be further substituted by oxygen atoms as long as the oxygen atoms are not adjacent; A ²¹ , A ²² and A ²³ each independently represent a group selected from (a) 1,4-cyclohexyl, one -CH ₂ - or two or more non-adjacent -CH ₂ - in the group may be independently substituted by -CH=CH-, -C≡C-, -O-, -CO-, -COO- or -OCO-; - may be substituted with -O-, and (b) 1,4-phenylene, one -CH= or two or more non-adjacent -CH= in this group may be substituted with -N=, in the group consisting of, the hydrogen atom in the group (a) and the group (b) may be independently substituted with a cyano group, a fluorine atom or a chlorine atom, 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 -, -CF ₂ O-, -CH=NN=CH-, -CH=CH-, -CF=CF- or -C≡C-, n ²¹ represents 0, 1, 2 or 3, in A ²² , Z 22 ²² respectively exist in a plurality of cases, they may be the same or different, except for the compound represented by the formula (I),

In the above formula, P ^p1 and P ^p2 each independently represent a polymerizable group, Sp ^p1 and Sp ^p2 each independently represent a spacer group or a single bond, Z ^p1 and Z ^p2 each independently represent a single bond, -O-, -S-, -CH ₂ -, -OCH ₂ -, -CH ₂ O-, -CO-, -C ₂ H ₄ -, -COO-, -OCO-, -OCOOCH ₂ -, -CH ₂ OCOO-, -OCH ₂ CH ₂ O-, -CO-NR ^ZP1 -, -NR ^ZP1 -CO-, -SCH ₂ -, -CH ₂ S-, -CH=CR ^ZP1 -COO-, -CH=CR ^ZP1 -OCO-, -COO-CR ^ZP1 =CH-, -OCO-CR ^ZP1 =CH-, -COO-CR ^ZP1 =CH-COO-, -COO-CR ^ZP1 =CH-OCO-, -OCO-CR ^ZP1 =CH-COO-, -OCO-CR ^ZP1 =CH-OCO-, -(CH ₂ ) ₂ -COO-, -(CH ₂ ) ₂ -OCO-, -OCO-(CH ₂ ) ₂ -, -(C=O)-O-(CH ₂ ) ₂ -, -CH=CH-, -CF=CF-, -CF=CH-, -CH=CF-, -CF ₂ -, -CF ₂ O-, -OCF ₂ -, _-CF 2 CH 2 -, -CH ₂ CF ₂ -, -CF ₂ CF ₂ -, or -C≡C-, wherein R ^ZP1 each independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. When a plurality of R ^ZP1 are present in the molecule, they may be the same or different. _Ap1 , ^Ap2 and A ^p1 are ^p3 each independently represents a group selected from the group consisting of ( ^ap ) 1,4-cyclohexylene, wherein one or two or more _-CH2- in the group may be substituted with -O- as long as the oxygen atoms are not adjacent, ( ^bp ) 1,4-phenylene, wherein one or two or more -CH= in the group may be substituted with -N=, and ( ^cp ) naphthalene-2,6-diyl, naphthalene-1,4-diyl, naphthalene-1,5-diyl, 1,2,3,4-tetrahydronaphthalene-2,6-diyl, decahydronaphthalene-2,6-diyl, phenanthrene-2,7-diyl or anthracene-2,6-diyl, wherein one or two or more -CH= in the group may be substituted with -N=, and the groups ( ^ap ), ( ^bp ) and (cp ⁾ ) may be substituted independently by a halogen atom, a cyano group, an alkyl group having 1 to 18 carbon atoms which may be substituted by a fluorine atom, or -Sp ^p2 -P ^p2 ; one or more non-adjacent -CH ₂ - groups in the alkyl group may be substituted independently by -CH=CH-, -C≡C-, -O-, -CO-, -COO-, or -OCO- to avoid direct adjacency to the oxygen atom; in addition, when m ^p1 is 0 and A ^p1 is a group represented by group (c ^p ), A ^p3 may be a single bond, m ^p1 represents 0, 1, 2 or 3; when a plurality of Z ^p1 , A ^p2 , Sp ^p2 and/or P ^p2 are present in the molecule, they may be the same or different;

In the formula, R ^s1 and R ^s2 each independently represent an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, or an alkenyloxy group having 2 to 10 carbon atoms, and one or more hydrogen atoms in these groups may be substituted by fluorine atoms. A ^s1 and B ^s1 each independently represent a group selected from (a) 1,4-cyclohexylene, and one -CH ₂ - or two or more non-adjacent -CH ₂ - in this group may be substituted by fluorine atoms. - may be substituted with -O-, (b) 1,4-phenylene, in which one -CH= or two or more non-adjacent -CH= in the group may be substituted with -N=, (c) naphthalene-2,6-diyl, 1,2,3,4-tetrahydronaphthalene-2,6-diyl or decahydronaphthalene-2,6-diyl, in which one -CH= or two or more non-adjacent -CH= in the group may be substituted with -N=, and (d) a group consisting of 1,4-cyclohexenyl, wherein the group (a), the group (b), the group (c) and the group (d) may be independently substituted with 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, a cyano group or a fluorine atom, and in ring A When there are plural rings ^{A s1} and B ^s1 , the plural rings A ^s1 and B ^s1 may be the same or different, Z ^s1 and Z ^s2 each independently represent -OCH ₂ -, -CH ₂ O-, -COO-, -OCO-, -CF ₂ O-, -OCF ₂ -, -CH ₂ CH ₂ -, -CF ₂ CF ₂ -, -C≡C- or a single bond, n ^s1 and n ^s2 each independently represent 0, 1 or 2, n ^s1 +n ^s2 represents an integer from 1 to 4, and X ^s1 to X ^s6 each independently represent 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, a fluorine atom or a hydrogen atom. The method for manufacturing a liquid crystal display element as described in claim 1, wherein the compound represented by formula (II) is a compound selected from the group consisting of compounds 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 may be independently substituted by -CH=CH-, -C≡C-, -O-, -CO-, -COO- or -OCO-. At least one of R ²¹⁰ and R ²²⁰ represents an alkenyl group having 2 to 8 carbon atoms, and one or two or more -CH ₂ - in the alkenyl group may be further substituted by an oxygen atom as long as the oxygen atoms are non-adjacent. The method for manufacturing a liquid crystal display element as described in claim 2, wherein the compound represented by formula (II) is a compound selected from the group consisting of compounds represented by the following general formulas (II-01-1) to (II-01-5),

In the formula, R ²¹¹ each independently represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, R ²²¹ each independently represents an alkyl group having 1 to 8 carbon atoms, one or more non-adjacent -CH ₂ - in the alkyl group may be substituted by -CH=CH-, -C≡C-, -O-, -CO-, -COO- or -OCO- as long as the oxygen atoms are non-adjacent, n ²² each independently represents an integer of 0 to 5, and the total number of carbon atoms when R ²¹¹ is an alkyl group and the value of n ²² will not exceed 6. A liquid crystal display element is manufactured by the manufacturing method of a liquid crystal display element as described in any one of claim 1 to claim 3.