TW202136480A - Method for manufacturing liquid crystal display element and liquid crystal display element wherein the liquid crystal display element is capable of realizing high speed response and high VHR - Google Patents

Abstract

An object of the present invention is to manufacture a PSA-type or PSVA-type liquid crystal display element that realizes high speed response and high VHR. A method of manufacturing a liquid crystal display element includes: a step of arranging a pair of substrates, of which at least one is provided with an alignment film, in a manner that they face each other with a liquid crystal composition containing a polymerizable compound in between; and a step of irradiating the liquid crystal composition with ultraviolet rays to polymerize the polymerizable compound. The present invention is characterized in that, as the ultraviolet rays, the ultraviolet rays that satisfy I365/I313>20 (I365 represents the illuminance at a wavelength of 365 nm (mW.cm2), and I313 represents the illuminance at a wavelength of 313 nm (mW.cm2)) are used for irradiation for at least once, and the liquid crystal composition contains one or two or more of the liquid crystal compounds represented by formula (I) and one or two or more of polymerizable compounds represented by formula (P).

Description

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

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

Liquid crystal display elements are represented by clocks and electronic computers and are used in various measuring equipment, automotive panels, electronic notebooks, printers, computers, televisions, clocks, advertising display boards, etc. As a representative of the liquid crystal display method, it can be cited: Twisted Nematic (TN) type, Super Twisted Nematic (STN) type, and Thin Film Transistor (TFT) are used. Vertical alignment type (Vertical Alignment; VA (Vertical Alignment)) or in-plane switching (IPS) type, etc. The liquid crystal composition used in these liquid crystal display elements is required to be stable against external factors such as moisture, air, heat, light, etc., and to display a liquid crystal phase in the widest possible temperature range centered on room temperature, with low viscosity, and driving The voltage is low. Furthermore, in order to make the dielectric constant anisotropy (Δε), the refractive index anisotropy (Δn), etc., an optimal value for each liquid crystal display element, the liquid crystal composition contains several to several tens of compounds.

In the VA type display, a liquid crystal composition in which Δε is negative is used, and it is widely used in liquid crystal televisions (television, TV) and the like. Among them, the polymer stabilized alignment (Polymer Sustained Alignment, PSA) mode is a mode in which polymerizable compounds (monomers) dissolved in liquid crystals are polymerized to impart a desired pretilt angle to vertically aligned liquid crystal molecules. Expanded or high-speed response and high transmittance, so it has become the mainstream of the current TV. In addition, in recent years, further high-speed response of liquid crystal display elements has been studied. As the technology, a liquid crystal composition containing a liquid crystal compound (alkenyl liquid crystal compound) having an alkenyl partial structure such as an alkenyl group has been used. Attempts of the liquid crystal layer (for example, refer to Patent Document 1 and Patent Document 2).

In addition, in recent years, in the manufacture of liquid crystal elements, for the purpose of improving production efficiency, a PSA liquid crystal composition having a moderately fast polymerization rate has been required. In the step of polymerizing the polymerizable compound in the liquid crystal composition, the polymerization rate of the polymerizable compound is very important. When the polymerization rate is fast, the residual amount of the polymerizable compound decreases in a short irradiation time such as ultraviolet rays, so that deterioration of the liquid crystal composition caused by ultraviolet rays and the like is less likely to occur. In addition, it also has advantages such as increased productivity, such as enabling production with less energy and shortening the production time. On the other hand, when the polymerization rate 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 or the like. In addition, when strong ultraviolet rays are irradiated for a long period of time in the polymerization step, the size of the manufacturing apparatus will be increased, the manufacturing efficiency will be reduced, and degradation of the liquid crystal composition caused by ultraviolet rays and the like will also occur. However, if the irradiation time of ultraviolet rays or the like is shortened, the residual amount of the polymerizable compound increases, and the remaining polymerizable compound causes display defects called unevenness or burn-in. In summary, a polymerizable liquid crystal composition that can realize a sufficient polymerization rate is desired. As a method for improving the polymerization rate of a polymerizable compound (approach), as shown in the examples of Patent Document 3, it is proposed to use a compound of the following formula (A) to increase the absorption wavelength of the liquid crystal material used. A method of extending the wavelength side to improve the polymerization rate of a polymerizable compound.

[現有技術文獻] [專利文獻][化1]

[Prior Art Document] [Patent Document]

[Patent Document 1] Japanese Patent Laid-Open No. 2014-112192 [Patent Document 2] Japanese Patent Laid-Open No. 2010-285499 [Patent Document 3] Japanese Patent Publication No. 2013-503952

[The problem to be solved by the invention] As described above, a liquid crystal composition containing an alkenyl liquid crystal compound is useful for high-speed response of liquid crystal display elements, but such liquid crystal composition is likely to be irradiated by light emitted from a backlight or during the manufacturing process of the liquid crystal display element. Active energy rays such as ultraviolet rays are degraded, and there is a problem that the voltage holding ratio (VHR) of the liquid crystal panel decreases due to impurities generated by the light degradation of the liquid crystal composition.

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

[Technical means to solve the problem] The inventors have conducted intensive research, and as a result, found that in the manufacturing method of an alkenyl-based polymerizable liquid crystal display element, the problem can be solved by irradiating ultraviolet rays with a specific illuminance ratio, and completed the invention of the present 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 includes: at least one of a pair of substrates having an alignment film is arranged so as to face each other via a liquid crystal composition containing a polymerizable compound; and irradiating the liquid crystal composition with ultraviolet rays The step of polymerizing the polymerizable compound, wherein as the ultraviolet rays, the ultraviolet rays satisfying the following formula (P-1) are irradiated at least once, and I ₃₆₅ /I ₃₁₃ > 20···(P-1) ( In the 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 the following general formula ( I) or one or two or more of liquid crystal compounds represented by the following general formula (II) and one or two or more of polymerizable compounds represented by the following general formula (P),

[化2]

(In the formula, R ¹¹ and R ¹² each independently represent an alkyl group having 1 to 8 carbon atoms, and one of the alkyl groups or two or more non-adjacent -CH ₂ -s can each independently be represented by -CH= CH-, -C≡C-, -O-, -CO-, -COO- or -OCO- substituted, ^{at least one of R 11} and R ¹² represents an alkenyl group having 2 to 8 carbon atoms, the alkene One or two or more of -CH ₂ -in the group may be further substituted with oxygen atoms as long as the oxygen atoms are not adjacent to each other. n ¹¹ and n ¹² represent 0, 1, 2 or 3, and n ¹¹ + n ¹² represent 1, 2 or 3, A ¹¹ and A ¹² are each independently selected from (a) 1,4-cyclohexylene (one -CH ₂ -present in this group or two or more non-adjacent -CH _2- Can be substituted with -O-.) and (b) 1,4-phenylene (one -CH= or two or more non-adjacent -CH= in this group can be substituted with -N=.) In the group consisting of, the hydrogen atoms in the groups (a) and (b) may be independently substituted by a cyano group, a fluorine atom or a chlorine atom, and 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 can be the same or different. When there are multiple Z ¹¹ And/or Z ¹² , they may be the same or different.),

[化3]

(In the formula, R ²¹ and R ²² each independently represent an alkyl group having 1 to 8 carbon atoms, and one of the alkyl groups or two or more non-adjacent -CH ₂ -s can each independently be represented by -CH= CH-, -C≡C-, -O-, -CO-, -COO- or -OCO- substituted, ^{at least one of R 21} and R ²² represents an alkenyl group having 2 to 8 carbon atoms, the alkene One or two or more -CH ₂ -in the group may be further substituted with an oxygen atom as long as the oxygen atoms are not adjacent to each other. A ²¹ , A ²² and A ²³ are independently selected from (a) 1, 4 -Cyclohexylene (one -CH ₂ -or two or more unadjacent -CH ₂ -in this group may be substituted with -O-.) and (b) 1,4-phenylene (this group One -CH= or two or more unadjacent -CH= can be substituted with -N=.) A group in the group, the hydrogen in the group (a) and group (b) Atoms may be independently substituted by cyano, fluorine or chlorine atoms. 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, and when ^{there are a plurality of A 22} and Z ²² respectively, they may be the same or different, except for the compound represented by the formula (I).)

[化4]

(In the formula, P ^p1 and P ^p2 each independently represent a polymerizable group, Sp ^p1 and Sp ^p2 each independently represent a spacer or a single bond, and 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- (where R ^ZP1 independently represents a hydrogen atom or an alkyl group with 1 to 4 carbon atoms, in the molecule When there are a plurality of R ^ZP1 , they may be the same or different.), A ^p1 , A ^p2 and A ^p3 each independently represent a group selected from (a ^p ) 1,4-cyclohexylene (the group exists One or two or more of -CH ₂ -in the group can be substituted by -O- as long as the oxygen atoms are not adjacent.) (b ^p ) 1,4-phenylene (one or more than two in the group The -CH= can 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 of the groups or Two or more -CH= can be substituted by -N=.) A group in the group consisting of, one or two of ^{the group (a p} ), group (b ^p ) and group (c ^p) The above hydrogen atoms may be independently substituted with a halogen atom, a cyano group, an alkyl group having 1 to 18 carbon atoms which may be substituted with a fluorine atom, or -Sp ^p2 -P ^p2 , and one of the alkyl groups may not be adjacent to each other. The two or more -CH ₂ -can be independently changed from -CH=CH-, -C≡C-, -O-, -CO-, -CO O- or -OCO- is substituted to prevent the oxygen atom from directly adjacent to each other. In addition, when m ^p1 is 0 and A ^p1 is the group represented by the group ^{(c p ), A p3} may be a single bond, and 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. ). A liquid crystal display element is manufactured by the manufacturing method of the liquid crystal display element.

[Effects of the invention] 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 a peak at a wavelength of 313 nm and a wavelength of 365 nm is used at a predetermined illuminance ratio, thereby enabling high productivity Display defects such as manufacturing unevenness and burn-in are reduced to display good display quality, and achieve a high-speed response and high-reliability liquid crystal display element.

Hereinafter, the method of manufacturing the liquid crystal display element of the present invention will be described in detail based on suitable embodiments. First, the liquid crystal display element manufactured by the manufacturing method of the liquid crystal display element of this invention is demonstrated.

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

In addition, in FIG. 1 and FIG. 2, for convenience, the size of each part and their ratio are exaggeratedly displayed, which may not match the actual situation. In addition, the materials, dimensions, etc. shown below are just examples, and the present invention is not limited to these, and can be appropriately changed within a range that does not change the gist.

The liquid crystal display element 1 shown in FIG. 1 includes an active matrix substrate AM and a color filter substrate CF arranged opposite to 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 side of the liquid crystal layer 4, and a first substrate provided on the surface of the first substrate 2 on the opposite side of the liquid crystal layer 4. Polarizing plate 7.

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, and a common electrode layer 6 provided on the surface of the second substrate 3 opposite to the liquid crystal layer 4. The second polarizer 8 and the 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, in the state where no voltage is applied between the electrode layer 5 and the electrode layer 6, the liquid crystal molecules are relative to the substrate AM and the substrate CF. Orient almost vertically.

That is, the liquid crystal display element 1 of this embodiment has 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 the structure of the second polarizing plate 8.

The first substrate 2 and the second substrate 3 are each formed of, for example, a glass material or a material having flexibility (flexibility) such as a plastic material.

Regarding the first substrate 2 and the second substrate 3, both of them may be translucent, or only one of them may be translucent. In the latter case, the other substrate may include, for example, an opaque material such as a metal material or a silicon material.

As shown in FIG. 2, the pixel electrode layer 5 has a plurality of gate bus lines 11 for supplying scanning signals, a plurality of data bus lines 12 for supplying display signals, and a plurality of pixel electrodes 13. In addition, a pair of gate bus lines 11 and 11 and a pair of data bus lines 12 and 12 are shown in FIG. 2.

The plurality of gate bus lines 11 and the plurality of data bus lines 12 are arranged in a matrix to cross each other, and the area surrounded by them forms a unit pixel of the liquid crystal display element 1. One 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 stems orthogonal to each other in a cross shape, and a plurality of branch portions branched from each main stem and inclined at an angle of about 45° with respect to each main stem (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 portions.

According to the pixel electrode 13 of the above structure, the liquid crystal molecules are uniformly tilted and aligned in the four directions in which the branch portion is tilted with respect to the trunk portion. Therefore, a domain divided into four is formed in one pixel, so that the viewing angle of the liquid crystal display element 1 can be widened.

The width of each branch is preferably about 1 μm to 5 μm, more preferably about 2 μm to 4 μm. In addition, the distance S between adjacent branch portions is preferably about 1 μm to 5 μm, and more preferably about 2 μm to 4 μm. With this structure, the liquid crystal molecules can be more reliably oriented obliquely in a predetermined direction.

Between the pair of gate bus lines 11, 11, a Cs electrode 14 is provided almost in parallel with the gate bus line 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 line 11 and the data bus line 12 intersect each other. The drain electrode 16 is provided with a contact hole 17.

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

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

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

On the other hand, the common electrode layer 6 has, for example, a plurality of striped 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 by, for example, a pigment dispersion method, a printing method, an electrodeposition method, or a dyeing method.

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

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

In addition, from the viewpoint of preventing light leakage, the liquid crystal display element 1 may be provided with a black matrix (not shown). The black matrix is preferably formed in a 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. The color filter 9 is arranged on the second substrate 3 side. In addition, the black matrix may include a portion that overlaps the colors of the color filter 9 to reduce the transmittance.

The active matrix substrate AM and the color filter substrate CF are formed on their peripheral regions by a sealing material (sealing material) containing epoxy-based thermosetting composition or acrylic-based ultraviolet (ultraviolet, UV) curing composition, etc. And fit each other.

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

The average separation distance between the active matrix substrate AM and the color filter substrate CF (that is, the average thickness of the liquid crystal layer 4) is preferably about 1 μm to 100 μm.

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

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

In addition, in the liquid crystal display element 1, on the liquid crystal layer 4 side of at least one of the active matrix substrate AM and the color filter substrate CF, an alignment film such as a polyimide alignment film is provided in contact with the liquid crystal layer 4. In the present invention, two substrates may have an alignment film, or only one of the substrates may have an alignment film.

(Method of manufacturing liquid crystal display element) The method of manufacturing a liquid crystal display element of the present invention includes a step of arranging a pair of substrates having an alignment film in at least one of them so as to face each other via a liquid crystal composition containing a polymerizable compound; and irradiating the liquid crystal composition with ultraviolet rays To polymerize the polymerizable compound.

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

The manufacturing method of the liquid crystal display element of this embodiment has: preparation step [1], preparing substrate AM, substrate CF, and liquid crystal composition; assembly step [2], assembling each part; liquid crystal layer forming step [3], in the liquid crystal Under the voltage applied to the composition, the polymerizable monomer is polymerized by ultraviolet irradiation to form the liquid crystal layer 4; and the monomer consumption step [4], the liquid crystal layer 4 is irradiated with ultraviolet light without applying a voltage to the liquid crystal layer 4, by This polymerizes and consumes the remaining polymerizable monomer.

As long as the performance as the liquid crystal display element 1 can be sufficiently obtained, any one of the liquid crystal layer formation step [3] and the monomer consumption step [4], particularly the monomer consumption step [4] may be omitted.

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

[2] Assembly steps Next, along the edge of at least one of the active matrix substrate AM and the color filter substrate CF, a dispenser is used to draw the sealing material into a closed-loop dam shape.

After that, a predetermined amount of the liquid crystal composition is dropped on the inside of the sealing material, and the active matrix substrate AM and the color filter substrate CF are arranged so as to face the liquid crystal composition under reduced pressure. That is, the pair of substrates AM and CF are arranged such that the electrode layer 5 and the electrode layer 6 (electrodes) face each other with the liquid crystal composition interposed therebetween.

In such a drop filling (One Drop Fill, ODF) method, it is necessary to drop an optimal injection amount according to the size of the liquid crystal display element 1. The liquid crystal composition described later has little influence on, for example, a sudden pressure change or impact in the dropping device that occurs during dropping, and can be dropped stably for a long period of 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 frequently used in smartphones, the optimal injection amount of the liquid crystal composition is small, and therefore, it is inherently difficult to control the deviation amount within a certain range. However, by using the above-mentioned liquid crystal composition, a stable and optimal injection amount can be accurately dropped even in a small liquid crystal display element.

After that, the sealing material is cured by irradiation with ultraviolet rays (active energy rays) and heating. In addition, depending on the type of the sealing material, the sealing material may be cured by only one of ultraviolet irradiation and heating.

[3] Liquid crystal layer formation step (first ultraviolet irradiation step) Next, the liquid crystal composition is irradiated with ultraviolet rays while applying a voltage. Thereby, 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, and the alignment film provided on the surface of the electrode layer 5 and/or the electrode layer 6 A polymer layer containing a polymer of a polymerizable monomer is formed at the interface). Through the formation of the polymer layer, the liquid crystal molecules are aligned vertically, or a pretilt angle is further imparted to the liquid crystal molecules.

The voltage may be applied between the pixel electrode 13 and the common electrode (opposing 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, more preferably about 5V to 15V. If a voltage of such a value is applied to the liquid crystal composition, a sufficient pretilt 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, a further increase in the effect cannot be expected.

At least any one of the ultraviolet ray irradiated in this step [3] and the ultraviolet ray irradiated in the next step [4] in the presence of the next step [4] has a peak at a wavelength of 313 nm and a wavelength of 365 nm , And satisfy the following formula (P-1). I ₃₆₅ /I ₃₁₃ ＞20・・・(P-1) (In the formula, I ₃₆₅ represents the illuminance at a wavelength of 365 nm (mW·cm ² ), and I ₃₁₃ represents the illuminance at a wavelength of 313 nm (mW·cm ² ).) From the viewpoint of increasing the VHR of the liquid crystal display element 1, it is preferable to take time to irradiate a relatively long wavelength of 365 nm ultraviolet rays to the liquid crystal composition to polymerize the polymerizable monomer at a moderate polymerization rate . In particular, when an alkenyl-based liquid crystal composition is used for the purpose of high-speed response, there is a strong demand for improvement in VHR, which is easy to decrease. Therefore, the inventors have repeatedly conducted active studies and found that there is an appropriate intensity ratio between the peak at the wavelength of 313 nm and the peak at the wavelength of 365 nm, thereby completing the present invention.

From such a viewpoint, in this step [3] which is mainly carried out by polymerization of a polymerizable compound, it is preferable to use ultraviolet rays satisfying the above-mentioned formula (P-1).

Among the ultraviolet rays satisfying the above formula (P-1), if I ₃₆₅ /I ₃₁₃ is 20 or less, the amount of ultraviolet rays with a wavelength of 313 nm is too much, and the quality or deterioration of the liquid crystal molecules occurs, and the VHR of the liquid crystal display element 1 reduce.

I ₃₆₅ /I ₃₁₃ only needs to exceed 20, but it is preferably 25 or more, and particularly preferably 30 or more. By setting _{the ratio of I 365} /I ₃₁₃ within the above-mentioned range, it is possible to efficiently manufacture a liquid crystal display element with high VHR and reduced display defects while preventing the deterioration or deterioration of liquid crystal molecules. In addition, _{the upper limit of I 365} /I ₃₁₃ is not particularly limited, and it may be 10,000 or more, or it may 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 remaining polymerizable monomers and manufacture 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 . As a result, the effect can be further improved.

In addition, from the viewpoint of more reliably preventing the deterioration or deterioration of the liquid crystal molecules, it is preferable that the ultraviolet rays have no peak in the wavelength of less than 313 nm (especially the wavelength of the short-wave ultraviolet (UVC) region), or even if there is Peak, its intensity is also extremely small.

The irradiation time of ultraviolet rays in this step [3] can be specified according to the relationship with the temperature of the liquid crystal layer 4. That is, in this step [3], it is preferable to irradiate ultraviolet rays until the temperature of the liquid crystal layer 4 rises by 0.1°C to 5°C, more preferably to raise it to 0.5°C to 5°C, and more preferably to raise it to 1°C. ℃～5℃. The temperature rise of the liquid crystal layer 4 within the above-mentioned range indicates that the polymerizable monomer is sufficiently polymerized.

The specific irradiation time also depends on the type of ultraviolet rays used, and is preferably about 10 seconds to 7,200 seconds, and more preferably about 20 seconds to 3600 seconds. In order to reduce the amount of remaining polymerizable monomers to manufacture a liquid crystal display element 1 having a high voltage holding ratio, it is preferably about 600 seconds to 7200 seconds. In addition, in order to provide a good pretilt 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 may be set to coincide with the voltage application time, or may be set to be shorter than the voltage application time.

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

In addition, the irradiation amount of ultraviolet rays 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, when irradiating ultraviolet rays, the intensity can also be changed.

In addition, in the case of polymerizing in a state where the two substrates are opposed to each other so as to contact the liquid crystal composition as in the present embodiment, at least the substrate located on the side of the irradiation surface needs to have an appropriate transmittance to ultraviolet rays.

In addition, the applied voltage may be any of direct current and alternating current, and is preferably alternating current. If voltage is applied by alternating current, it is easy to obtain the liquid crystal layer 4 in which the alignment state of the liquid crystal molecules is good.

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

The temperature when irradiated with ultraviolet rays is preferably within a temperature range that maintains the liquid crystal state of the liquid crystal composition. The specific temperature is preferably about 10°C to 50°C, more preferably about 15°C to 45°C. If it is in the above temperature range, in the liquid crystal composition, the polymerizable monomer is polymerized while being moderately diffused. Therefore, the polymerization proceeds well and the formation of the pretilt angle after the polymerization becomes good.

As a lamp that generates 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 rays can also be used by cutting a predetermined wavelength as necessary. A cut-off filter can be used for the cut-off of the wavelength. For example, by cutting off ultraviolet rays in a wavelength region including a wavelength of 313 nm, ultraviolet rays satisfying I ₃₆₅ /I ₃₁₃ > 20 can also be obtained. By almost completely cutting off the ultraviolet rays in the wavelength region including the wavelength of 313 nm, I ₃₁₃ =0. In this case, I ₃₆₅ /I ₃₁₃ becomes infinite.

In addition, the pretilt angle imparted to the liquid crystal molecules is preferably about 85° to 89.5°, more preferably about 87.5° to 89°. By adjusting the pretilt angle of the liquid crystal molecules to the above range, it is possible to sufficiently improve the response speed of the liquid crystal display element 1 while preventing a decrease in contrast.

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

The ultraviolet ray irradiated in this step [4] may be the same as or different from the first ultraviolet ray irradiation step. In addition, when the present invention performs ultraviolet irradiation at the intensity ratio of the present invention in the step [3], it does not prevent the peak intensity at the wavelength of 313 nm and the peak intensity at the wavelength of 365 nm in the step [4]. And their intensity ratios are ultraviolet rays outside the scope of the present invention.

Among them, it is preferable to irradiate ultraviolet rays having peaks at a wavelength of 313 nm and a wavelength of 365 nm as in the first ultraviolet irradiation step even when ultraviolet rays different from the first ultraviolet rays irradiation step are used. Regarding ultraviolet rays different from the first ultraviolet irradiation step, I ₃₆₅ /I _{313 is} preferably 20 or more, more preferably 25 or more, and still more preferably 30 or more. By setting it as the said range, the deterioration or deterioration of liquid crystal molecules can be prevented. As a result, the occurrence of display failure (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 remaining polymerizable monomers and manufacture 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 . As a result, the effect can be further improved.

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

The irradiation time of ultraviolet rays in this step [4] can also be specified in accordance with the relationship with the temperature of the liquid crystal layer 4. That is, in this step [4], it is preferable to irradiate ultraviolet rays until the temperature of the liquid crystal layer 4 rises by 1°C to 20°C, more preferably to raise it to 2°C to 15°C, and still more preferably to raise it to 3°C. ℃～10℃. The temperature rise of the liquid crystal layer 4 within the above range indicates that the remaining polymerizable monomer is sufficiently consumed.

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

The temperature when irradiated with ultraviolet rays is preferably within a temperature range that maintains the liquid crystal state of the liquid crystal composition. The specific temperature is preferably about 10°C to 50°C, more preferably about 15°C to 45°C. Within the above temperature range, the polymerizable monomer is polymerized while being moderately diffused in the liquid crystal composition. Therefore, the polymerization proceeds well, and the remaining polymerizable monomer can be fully consumed.

As a lamp that generates 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 rays can also be used by cutting off a predetermined wavelength as necessary. A cut-off filter can be used for the cut-off of the wavelength. For example, by cutting off ultraviolet rays in a wavelength region including a wavelength of 313 nm, ultraviolet rays satisfying I ₃₆₅ /I ₃₁₃ > 20 can also be obtained. By almost completely cutting off the ultraviolet rays in the wavelength region including the wavelength of 313 nm, I ₃₁₃ =0. In this case, I ₃₆₅ /I ₃₁₃ becomes infinite.

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

In addition, in the assembly step [2], instead of the drop injection (ODF) method, the vacuum injection method can also be used. For example, in the vacuum injection method, first, the sealing material is screen printed along the edge of at least one of the active matrix substrate AM and the color filter substrate CF with the injection port remaining. After that, the two substrates AM and CF are bonded together, and the sealing material is cured by at least one of heating and ultraviolet irradiation. Next, the liquid crystal composition is injected into the space partitioned by the sealing material between the two substrates AM and CF through the injection port under vacuum, and then the injection port is sealed. After that, transfer to [3] liquid crystal layer formation step and [4] monomer consumption step.

In addition, in other configuration examples, the intensity ratio of the peak at the wavelength of 313 nm to the peak at the wavelength of 365 nm in the liquid crystal layer formation step may be set as the relationship in the monomer consumption step. On the other hand, the monomer consumption The intensity ratio of the peak at the wavelength of 313 nm to the peak at the wavelength of 365 nm in the step is set as the relationship in the liquid crystal layer forming step. In this case, the specific intensity value of each peak or the irradiation time of ultraviolet rays is set so that the target voltage holding ratio or pretilt angle can be given to the obtained liquid crystal display element 1. In the above structure, the same action/effect as described above can also be obtained.

In addition to the above-mentioned steps [3] and [4], the peak intensity at 313 nm, the peak intensity at 365 nm, and their intensity ratio may be irradiated with ultraviolet rays outside the scope of the present invention in an additional step. . [Liquid crystal composition] In the production method of the present invention, the liquid crystal composition contains a polymerizable compound. More specifically, the liquid crystal composition used in the present invention contains one or two or more of the compounds represented by the general formula (I) or (II) and one or more of the polymerizable compounds represented by the general formula (P) Two or more. (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 anisotropy in dielectric. The "compound having negative anisotropy in dielectric" refers to a compound in which the sign of Δε is negative and the absolute value thereof shows a value greater than 2. In addition, the Δε of the compound is a value extrapolated from the measured value of the dielectric constant anisotropy of a composition obtained by adding the compound to a composition that is almost dielectrically 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 improved.

[化5]

(In the formula, R ¹¹ and R ¹² each independently represent an alkyl group having 1 to 8 carbon atoms, and one of the alkyl groups or two or more non-adjacent -CH ₂ -s can each independently be represented by -CH= CH-, -C≡C-, -O-, -CO-, -COO- or -OCO- substituted, ^{at least one of R 11} and R ¹² represents an alkenyl group having 2 to 8 carbon atoms, the alkene One or two or more of -CH ₂ -in the group may be further substituted with oxygen atoms as long as the oxygen atoms are not adjacent to each other. n ¹¹ and n ¹² represent 0, 1, 2 or 3, and n ¹¹ + n ¹² represent 1, 2 or 3, A ¹¹ and A ¹² are each independently selected from (a) 1,4-cyclohexylene (one -CH ₂ -present in this group or two or more non-adjacent -CH _2- Can be substituted with -O-.) and (b) 1,4-phenylene (one -CH= or two or more non-adjacent -CH= in this group can be substituted with -N=.) In the group consisting of, the hydrogen atoms in the groups (a) and (b) may be independently substituted by a cyano group, a fluorine atom or a chlorine atom, and 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 can be the same or different. When there are multiple Z ¹¹ And/or ^{in the case of Z 12} , they may be the same or different.) In the general formula (I), it is preferable ^{that at least one of R 11} and R ¹² is an alkenyl group having 2 to 8 carbon atoms, and the other It 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 alkenyl group having 2 to 8 carbon atoms. More specifically, it is preferable ^{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, or one having 1 to 5 carbon atoms. Alkoxy group, alkenyl group having 2 to 5 carbon atoms, or alkenyl group having 2 to 5 carbon atoms; more preferably at least one is alkenyl group having 2 to 5 carbon atoms, and the other is carbon number An alkyl group or an alkoxy group having 1 to 5 or an alkenyl group having 2 to 5 carbon atoms; more preferably at least one is an alkenyl group having 2 to 5 carbon atoms, and the other is 1 to 5 carbon atoms At least one of the alkyl groups or alkoxy groups is particularly preferably 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 the alkenyl group is bonded in R 11} and R ¹² is a phenyl group (aromatic), the group other than the alkenyl group is preferably a straight chain with 1 carbon atom number. The alkoxy group of -5 is preferably a linear alkyl group having 1 to 5 carbon atoms when the ring structure to which it is bonded is a cyclohexane structure. In order to stabilize the nematic phase, the total of carbon atoms and oxygen atoms when present is preferably 5 or less, preferably linear. As the alkenyl group, a group selected from the group represented by any one of the following formulas (R1) to (R5) is preferred. Among them, a group represented by the formula (R1) or the formula (R2) is particularly preferred. Preferably, R ¹¹ is a group represented by formula (R1) or formula (R2).

[化6]

(The black dots in each formula represent the carbon atoms in the ring structure.) In the case where an increase in Δn is required, A ¹¹ and A ^{12 are} preferably aromatic. In order to improve the response speed, they are preferably aliphatic, and more preferably Represents 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, more preferably represents trans-1,4-cyclohexylene or 1,4-phenylene.

Z ¹¹ and Z ¹² each independently preferably represent -CH ₂ O-, -CF ₂ O-, -CH ₂ CH ₂ -, -CF ₂ CF ₂ -or a single bond, and more preferably represent -CH ₂ O -, -CH ₂ CH ₂ -or a single bond, particularly preferably represents -CH ₂ O- or a single bond.

n ¹¹ +n ^{12 is} preferably 1 or 2, preferably ^{a composition in which n 11} is 1 and n ¹² is 0, a composition in which n ¹¹ is 2 and n ¹² is 0, and a composition in which n ¹¹ is 1 and n ¹² is 1 , N ¹¹ is 2 and n ¹² is 1 composition.

The compound represented by general formula (I) preferably contains one or two or more compounds selected from the group of compounds represented by general formula (I-01) to general formula (I-05), more preferably It contains one or two or more compounds selected from the group of compounds represented by general formula (I-01) to general formula (I-04).

[化7]

In the formula, R ¹¹⁰ and R ¹²⁰ are each independently the same as ^{R 11} and R ^{12 , and at least one of R 110} and R ¹²⁰ represents an alkenyl group having 2 to 8 carbon atoms which may be substituted with 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 the above The group represented by the formula (R1) or the formula (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 its preferred bases are the same as ^{Z 11} and Z ^{12 described above.}

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

The fluorine atom of the compounds represented by the general formula (I-01) to the general formula (I-05) may be substituted with a chlorine atom of the same halogen group. Among them, the content of the compound substituted with a chlorine atom is preferably as small as possible, and preferably not contained.

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

The compound represented by general formula (I-01) to general formula (I-05) is preferably a compound in which Δε is negative and its absolute value is greater than 3. Specifically, R ¹²⁰ preferably represents an alkoxy group having 1 to 8 carbon atoms or an alkenyloxy group having 2 to 8 carbon atoms, and 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 preferable to contain a compound selected from general formula (I-01-1) to general formula (I-01-4), general formula ( I-02-1)～Compounds represented by general formula (I-02-3), general formula (I-03-1), general formula (I-04-1) and general formula (I-05-1) One or more than two.

[化8]

[化9]

[化10]

(In the 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, the compound represented by formula (I) is preferably formula (I- 01-1) ~ Formula (I-01-4), Formula (I-02-1), and Formula (I-03-1) represented by compounds, more preferably Formula (I-01-3) ~ Formula ( The compound represented by I-01-4) is most preferably the compound represented by formula (I-01-4).

Relative to the total amount of the liquid crystal composition, the lower limit of the preferable content of the compound represented by the general formula (I) is 1%, 3%, 5%, 7%, 10%, 12%, 15%, 18%, 20%, 30%, 40%, 50%, 55%, 60%. The upper limit of the preferred content is 40%, 35%, 25%, 20%, 18%, 15%, 12%, 9%, and 5%. In addition, in this specification, as long as there is no special definition or description, "%" means "mass %". (Liquid crystal compound represented by formula (II)) The compound represented by the general formula (II) is as follows, and corresponds to a compound that is almost dielectrically neutral. "A compound that is almost dielectrically neutral" refers to a compound having a value of Δε of -2 to 2.

The compound represented by the general formula (II) is characterized by having at least one alkenyl group at the terminal similar to the compound represented by the general formula (I). By using the compound, the viscosity of the liquid crystal composition as a whole can be lowered. Improve the response speed of liquid crystal display elements.

[化11]

(In the formula, R ²¹ and R ²² each independently represent an alkyl group having 1 to 8 carbon atoms, and one of the alkyl groups or two or more non-adjacent -CH ₂ -s can each independently be represented by -CH= CH-, -C≡C-, -O-, -CO-, -COO- or -OCO- substituted, ^{at least one of R 21} and R ²² represents an alkenyl group having 2 to 8 carbon atoms, the alkene One or two or more -CH ₂ -in the group may be further substituted with an oxygen atom as long as the oxygen atoms are not adjacent to each other. A ²¹ , A ²² and A ²³ are independently selected from (a) 1, 4 -Cyclohexylene (one -CH ₂ -or two or more unadjacent -CH ₂ -in this group may be substituted with -O-.) and (b) 1,4-phenylene (this group One -CH= or two or more unadjacent -CH= can be substituted with -N=.) A group in the group, the hydrogen in the group (a) and group (b) Atoms may be independently substituted by cyano, fluorine or chlorine atoms. 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, and when ^{there are multiple A 22} and Z ²² respectively, they may be the same or different, except for the compound represented by the formula (I).) In the general formula (II) Preferably, 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, Alkenyl group having 2 to 8 carbon atoms or alkenyloxy group having 2 to 8 carbon atoms. More specifically, it is preferable ^{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, or one having 1 to 5 carbon atoms. Alkoxy group, alkenyl group having 2 to 5 carbon atoms, or alkenyl group having 2 to 5 carbon atoms; more preferably at least one is alkenyl group having 2 to 5 carbon atoms, and the other is carbon number An alkyl group or an alkoxy group having 1 to 5 or an alkenyl group having 2 to 5 carbon atoms; more preferably at least one is an alkenyl group having 2 to 5 carbon atoms, and the other is 1 to 5 carbon atoms It is particularly preferred that 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 of carbon atoms and oxygen atoms when present is preferably 8 or less, more preferably 5 or less, and more preferably linear. The alkenyl group is preferably a group selected from the group represented by any one of the above-mentioned formulas (R1) to (R5), and among them, a group represented by the formula (R1) or the formula (R2) is particularly preferable, and the most Preferably, R ²¹ is a group represented by formula (R1) or formula (R2).

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

Z ²¹ and Z ²² each independently preferably represent -CH ₂ O-, -CF ₂ O-, -CH ₂ CH ₂ -, -CF ₂ CF ₂ -or a single bond, and more preferably represent -CH ₂ O -, -CH ₂ CH ₂ -or a single bond, particularly preferably a single bond.

n ^{21 is} preferably 0 or 1, and most preferably 0.

The compound represented by general formula (II) preferably contains one or two or more compounds selected from the group of compounds represented by general formula (II-01) to general formula (II-06), more preferably Contains one or two or more compounds selected from the group of compounds represented by general formula (II-01) to general formula (II-05).

[化12]

In the formula, R ²¹⁰ and R ²²⁰ are each independently the same as ^{R 21} and R ^{22 , and at least one of R 210} and R ²²⁰ represents an alkenyl group having 2 to 8 carbon atoms which may be substituted with 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, still more preferably an alkenyl group having 2 to 3 carbon atoms, and particularly preferably the above The group represented by the formula (R1) or the formula (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 the general formula (II-01) to the general formula (II-06), it is preferable to contain one or two or more selected from the general formula (II-01-1) to the general formula (II-01-5). ) Represented by the compound.

[化13]

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 to 3 carbon atoms. .

n ²² each independently represents an integer of 0 to 5, and the sum of the number ^{of carbon atoms when R 211} is an alkyl group and ^{the value of n 22} does not exceed 6. n ^{22 is} preferably 0 or 1, 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 the number of carbon atoms 1-5 alkoxy groups.

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

With respect to the total amount of the liquid crystal composition, the lower limit of the preferable content of the compound represented by the 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% , Is 9%, is 5%. (Polymerizable compound represented by formula (P)) The compound represented by the general formula (P) is a polymerizable compound that is polymerized by irradiation with energy rays such as ultraviolet rays. More specifically, the polymerizable compound represented by the formula (P) is polymerized in the liquid crystal layer formation step [3] or the monomer consumption step [4].

[化14]

(In the formula, P ^p1 and P ^p2 each independently represent a polymerizable group, Sp ^p1 and Sp ^p2 each independently represent a spacer or a single bond, and 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- (where R ^ZP1 independently represents a hydrogen atom or an alkyl group with 1 to 4 carbon atoms, in the molecule When there are a plurality of R ^ZP1 , they may be the same or different.), A ^p1 , A ^p2 and A ^p3 each independently represent a group selected from (a ^p ) 1,4-cyclohexylene (the group exists One or two or more of -CH ₂ -in the group can be substituted by -O- as long as the oxygen atoms are not adjacent.) (b ^p ) 1,4-phenylene (one or more than two in the group The -CH= can 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 of the groups or Two or more -CH= can be substituted by -N=.) A group in the group consisting of, one or two of ^{the group (a p} ), group (b ^p ) and group (c ^p) The above hydrogen atoms may be independently substituted with a halogen atom, a cyano group, an alkyl group having 1 to 18 carbon atoms which may be substituted with a fluorine atom, or -Sp ^p2 -P ^p2 , and one of the alkyl groups may not be adjacent to each other. The two or more -CH ₂ -can be independently changed from -CH=CH-, -C≡C-, -O-, -CO-, -CO O- or -OCO- is substituted to prevent oxygen atoms from directly adjacent to each other. In addition, when m ^p1 is 0 and A ^p1 is the group represented by the group ^{(c p ), A p3} may be a single bond, and m ^p1 represents 0, 1, 2, or 3, when there are a plurality of Z ^p1 , A ^p2 , Sp ^p2 and/or P ^p2 in the molecule, they may be the same or different. ) A ^p1 , A ^p2 and A ^p3 are each independently selected from (a ^p ) 1,4-cyclohexylene (one -CH ₂ -existing in this group or two or more non-adjacent -CH _2- Is substituted with -O-.) (b ^p ) 1,4-phenylene (one -CH= or two or more non-adjacent -CH= in this group can be substituted with -N=.) and (C ^p ) Naphthalene-2,6-diyl, naphthalene-1,4-diyl, 1,2,3,4-tetrahydronaphthalene-2,6-diyl, decalin-2,6-diyl Group, phenanthrene-2,7-diyl or anthracene-2,6-diyl (One -CH= or two or more non-adjacent -CH= in the group can be substituted with -N=.) One or two or more hydrogen atoms present in the group (a ^p ), group (b ^p ) and group (c ^p ) can be independently replaced by halogen atoms, cyano groups, and A C 1-8 alkyl group or -Sp ^p2 -P ^{p2 is} substituted, and one of the alkyl groups or two or more non-adjacent -CH ₂ -s may be independently replaced by -CH=CH-, -C ≡C-, -O-, -CO-, -COO- or -OCO- substitution, m ^p1 represents 0, 1, 2 or 3, there are multiple Z ^p1 , A ^p2 , Sp ^p2 and/or P in the molecule ^In the case of p2, 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).}

[化15]

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 preferably represents 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, and is preferably a single bond, methylene group or ethylene group.

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

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

Among them, P ^p1 and P ^p2 are each independently preferably any one of formula (P ^p1 -1) to formula (P ^p1 -3), more preferably formula (P ^p1 -1), and more preferably a molecule ^{All P p1} and P ^p2 existing in the memory are represented by the formula (P ^p1 -1). In addition, it is preferable to have a total of two ^{polymerizable groups represented by P p1} and P ^p2 in the molecule, and both of the two P ^p1 and P ^p2 are preferably (P ^p1 -1), and the two (P ^{R p11 in p1} -1) is preferably all 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.

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

When Sp ^p1 and Sp ^p2 are spacers, the spacer is preferably an alkylene group having 1 to 30 carbon atoms. The -CH ₂ -in the alkylene group is as long as the oxygen atoms are not directly connected to each other. It can also be substituted by -O-, -CO-, -COO-, -OCO-, -CH=CH- or -C≡C-, and the hydrogen atom in the alkylene group can also be substituted by a halogen atom. Sp ^p1 and Sp ^{p2 are} preferably a linear alkylene group having 1 to 10 carbon atoms or a single bond.

A ^p1 , A ^p2 and A ^p3 are each independently preferably 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 preferable to have one or more 1,4-phenylene groups in the molecule. In order to improve the compatibility with the liquid crystal compound, these rings are preferably substituted with a fluorine atom, a methyl group or a methoxy group.

Below, suitable examples of the polymerizable compound represented by formula (P) are shown.

[化16]

[化17]

[化18]

[化19]

[化20]

[化21]

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

[化22]

[化23]

[化24]

[化25]

[化26]

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

[化27]

[化28]

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

[化29]

[化30]

[化31]

[化32]

(In the formula, P ^p41 , P ^p42 , Sp ^p41 and Sp ^{p42 represent the same meaning 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 Can be different.)

[化33]

[化34]

[化35]

(In the formula, P ^p51 , P ^p52 , Sp ^p51 and Sp ^{p52 represent the same meaning 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 It can be different. Me represents a methyl group.) In the present invention, the high-speed response of the liquid crystal display element is achieved by using an alkenyl liquid crystal compound, but by using an alkenyl liquid crystal compound, the polymerization speed of the polymerizable compound may be It will be slightly slower. Therefore, by using a highly reactive compound as the polymerizable compound, a decrease in the polymerization rate can be prevented. Furthermore, by obtaining a sufficient polymerization rate, productivity at the time of manufacturing a liquid crystal display element is improved, and display defects such as unevenness or burn-in of the obtained liquid crystal display element are reduced, and a good display quality can be achieved. As the highly reactive polymerizable compound, the formula (P-1-21) to (P-1-46) and the formula (P-5-1) to (P-5-19) are preferably listed compound of.

The compound represented by formula (P) may be used singly or in combination of two or more kinds. Among them, it is preferable to use two or three or more polymerizable monomers with different polymerization reaction speeds according to the composition, so that the polymerization reaction speed can be appropriately controlled, the amount of residual monomers can be reduced, and an appropriate pretilt angle can be imparted. In addition, from the viewpoint of the balance between storage stability and polymerization reaction rate, it is also preferable to use two or more kinds of polymerizable monomers in combination.

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

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

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

If the content is small, it is difficult to show the effect of adding the compound represented by formula (P), causing problems such as weak alignment restriction of the liquid crystal composition or weakening with time. If the content is too large, the amount remaining after curing will increase. , Hardening takes time, and the reliability of the liquid crystal is reduced. Therefore, the content is set in consideration of the balance of these. (Other liquid crystal compounds) The liquid crystal composition used in the present invention contains one or two or more of the compounds represented by the formula (I) or (II) and one or two of the polymerizable compounds represented by the formula (P) In addition to the above, other liquid crystal compounds may be further contained.

Examples of other liquid crystal compounds include compounds in ^{which neither R 11} nor R ¹² in the formula (I) is an alkenyl group having 2 to 8 carbon atoms (hereinafter referred to as "compound (I')"), In the formula (II), a compound in ^{which neither R 21} nor R ²² is an alkenyl group having 2 to 8 carbon atoms (hereinafter referred to as "compound (II')") is a preferable compound. · Compound (I') As the compound (I'), a compound represented by the following formula (I') can be mentioned.

[化36]

In formula (I'), R ^11' and R ^12' each independently represent an alkyl group having 1 to 8 carbon atoms, and one or two or more non-adjacent -CH ₂ -in the alkyl group may be independently The ground is substituted by -C≡C-, -O-, -CO-, -COO- or -OCO-, preferably an alkyl group having 1 to 5 carbons or an alkoxy group having 1 to 5 carbons. 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. In the case of a cyclohexylene group, it is preferably an alkyl group having 1 to 5 carbon atoms.

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

The compound (I') preferably contains one or two or more compounds selected from the group of compounds represented by the general formula (I'-01) to the general formula (I'-05), and more preferably contains one Or two or more kinds of compounds selected from the group of compounds represented by general formula (I'-01) to general formula (I'-04).

[化37]

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

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

The fluorine atom of the compound may be substituted by a chlorine atom of the same halogen group. Among them, the content of the compound substituted with a chlorine atom is preferably as small as possible, and preferably not contained. In addition, the hydrogen atom present on the ring of the compound may be substituted by a fluorine atom or a chlorine atom, but the chlorine atom is not preferable. The compound is preferably a compound whose Δε is negative and its absolute value is 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%, and 30% , Is 40%, is 50%, is 55%, is 60%, is 65%, is 70%, is 75%, is 80%. The upper limit of the preferred content is 95%, 85%, 75%, 65%, 55%, 45%, 35%, 25%, 20%, 15%, 10% . ·Compound (II') As a compound (II'), the compound represented by following formula (II') is mentioned.

[化38]

In the formula (II'), R ^21' and R ^22' each independently represent an alkyl group having 1 to 8 carbon atoms, and one or two or more non-adjacent -CH ₂ -in the alkyl group may be independently The ground is substituted by -C≡C-, -O-, -CO-, -COO- or -OCO-, preferably an alkyl group having 1 to 5 carbons or an alkoxy group having 1 to 5 carbons. 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. In the case of a cyclohexylene group, it is preferably an alkyl group having 1 to 5 carbon atoms.

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

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

[化39]

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 in the formula - (II'-06) R in the formula (II'-01) ^220.

The lower limit of the preferable content of the compound represented by the general formula (II') is 0%, 1%, 5%, 10%, and 20% relative to the total amount of the liquid crystal composition used in the present invention. %, 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 be added to the liquid crystal composition used in the present invention. Here, the sensitizer refers to a compound having an effect of promoting the polymerization reaction of the polymerizable compound, and in the present invention means to promote the polymerization of the polymerizable compound represented by the formula (P).

In the present invention, the high-speed response of the liquid crystal display element is achieved by using the alkenyl liquid crystal compound. However, by using the alkenyl liquid crystal compound, the polymerization speed of the polymerizable compound may be slightly slower. When the polymerization rate of the composition used in the present invention is insufficient, the polymerization rate can be increased by using the polymerizable compound and the sensitizer in combination. Furthermore, by improving the polymerization rate, the productivity at the time of manufacturing the liquid crystal display element can be improved, and display defects such as unevenness or burn-in of the obtained liquid crystal display element can be reduced, and good display quality can be achieved.

The sensitizer is preferably a compound represented by the following general formula (S).

[化40]

In the formula, R ^s1 and R ^s2 each independently represent an alkyl group with 1 to 10 carbon atoms, an alkoxy group with 1 to 10 carbon atoms, an alkenyl group with 2 to 10 carbon atoms, or an alkene with 2 to 10 carbon atoms. For oxy groups, one or two or more hydrogen atoms in these groups may be replaced by fluorine atoms.

In terms of the high effect of improving reliability such as 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 a carbon atom An alkyl group having 1 to 3 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 with fluorine atoms, but R s1} and R ^{s2 are} preferably not substituted with fluorine atoms.

Ring A ^s1 and ring B ^s1 each independently represent a group selected from (a) 1,4-cyclohexylene (one -CH ₂ -present in this group or two or more non-adjacent -CH ₂ -may be substituted with- O-.) (b) 1,4-phenylene (one -CH= or two or more unadjacent -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 (naphthalene-2,6-diyl or 1,2,3, One -CH= or two or more non-adjacent -CH= in 4-tetrahydronaphthalene-2,6-diyl can be substituted with -N=.) and (d) 1,4-cyclohexylene In the group consisting of alkenyl groups, the groups (a), group (b), group (c) and group (d) may each independently be substituted with fluorine atoms and the number of carbon atoms is 1-8 The alkyl group of may be substituted by a C 1-8 alkoxy group substituted with a fluorine atom, a cyano group or a fluorine atom.

Among them, the ring A ^s1 and the ring B ^{s1 are more} preferably 1,4-cyclohexylene, unsubstituted 1,4-phenylene, 2-fluoro-1,4-phenylene, 3-fluoro- 1,4-phenylene or 2,3-difluoro-1,4-phenylene.

If described in more detail, for the reason that the polymerization rate of the polymerizable compound can be further accelerated, the ring A ^s1 and the ring B ^s1 are each independently preferably an unsubstituted 1,4-phenylene group or 2-fluoro group. -1,4-phenylene, 3-fluoro-1,4-phenylene or 2,3-difluoro-1,4-phenylene, particularly preferably unsubstituted 1,4-phenylene base. Compared with phenylene substituted with other atoms such as fluorine atom, the UV absorption band of unsubstituted phenylene is on the longer wavelength side. Therefore, compared with the case of containing the compound represented by the general formula (S) having a substituent, the polymerizable compound of the present invention containing the compound represented by the general formula (S) having an unsubstituted phenylene group The liquid crystal composition can further accelerate the reaction rate of the polymerizable compound, and can sufficiently suppress the decrease in VHR.

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

When there are a plurality of ring A ^s1 and the ring B ^s1, the plurality of rings A ^s1 and a plurality of ring B ^s1, respectively, 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, preferably -OCH ₂ -, -CH ₂ O-, -CH ₂ CH ₂ -or a single bond. In order to accelerate the polymerization rate of the polymerizable compound, a single bond is particularly preferred key.

n ^s1 and n ^s2 independently represent 0, 1, or 2, respectively. In terms of better mixing with other liquid crystal molecules, it is preferable 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 from 1 to 4, but from the viewpoint of the miscibility with other liquid crystal molecules, it is preferably 1 or 2, and the miscibility with other liquid crystal molecules and tilt stability become more It is better to be 1.

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, Preferably, it is 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, and particularly preferably a hydrogen atom.

The number of groups as hydrogen atoms in X ^s1 to X ^{s6 is preferably at least three.} Specifically, ^{the number of groups as hydrogen atoms in X s1} to X ^s6 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 general formula (S) is preferably each compound represented by the following general formula (S-1) to general formula (S-5), more preferably general formula (S-1), general formula (S- 2) Or the compound represented by general formula (S-4) is particularly preferably a compound represented by general formula (S-1).

[化41]

In the formula, R ^s1 and R ^s2, respectively in the general formula (S) R ^s1 and R ^s2 same, wherein the hydrogen atom bonded to the ring may be a fluorine atom, carbon atoms and 1 to 3 Alkyl (preferably methyl) or alkoxy (preferably methoxy) with 1 to 3 carbon atoms.

The compound of the general formula (S) can promote the polymerization reaction of the polymerizable compound by its sensitization effect. On the other hand, if the content of the compound of the general formula (S) is too large, it is difficult to form a sufficient size by a short time reaction. Inclination, or VHR reduction, etc. In contrast, by adjusting the content of the compound of the general formula (S) in the polymerizable compound-containing liquid crystal composition of the present invention to a predetermined range, the polymerizable compound can be fully polymerized at a relatively fast rate, and the polymerizable compound can be fully polymerized in a short time. A sufficiently large inclination is formed inside, which can suppress the decrease in VHR caused by UV irradiation, and can satisfy various characteristics in a well-balanced manner.

The content of the compound of the general formula (S) only needs to be less than 2.0% in the total amount of the liquid crystal composition, and the upper limit of the content is preferably 1.9%, 1.8%, 1.7%, 1.6%, 1.5%, 1.4 %, 1.3%, 1.2%, 1.0%, 0.9%, 0.8%, 0.7%, 0.6%, 0.5%. In addition, the content of the compound of the general formula (S) only needs to exceed 0% in the total amount of the liquid crystal composition, and the lower limit of the content is preferably 0.01%, 0.05%, 0.1%, 0.2%, 0.3% , 0.4%, 0.5%, 0.6%, 0.7%, 0.8%, 0.9%, 1.0%. (Other additives) ·The compound represented by formula (A) In the liquid crystal composition used in the present invention, a compound represented by the following general formula (A) can be added.

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

[化42]

In the formula, R ^AK1 represents a straight chain or branched alkyl group having 1 to 20 carbon atoms, preferably a straight chain or branched alkyl group having 1 to 20 carbon atoms, and more preferably a straight chain or branched alkyl group having 1 to 20 carbon atoms. The chain alkyl group is more preferably a linear alkyl group having 1 to 8 carbon atoms. One of the alkyl groups or two or more non-adjacent -CH ₂ -s may be independently -CH=CH-, -C≡C-, -O-, -CO-, -COO- or -OCO. -Substitution, so as not to directly adjoin the oxygen atoms. In addition, one or two or more hydrogen atoms in the alkyl group may be independently substituted with a halogen atom. As the halogen atom, a fluorine atom or a chlorine atom is preferable, and a fluorine atom is more preferable.

A ^AL1 and A ^AL2 each independently represent a divalent cyclic group. The divalent cyclic group 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) octyl Base, 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-naphthylene, 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] One of the group consisting of thiophene-2,7-diyl, [1]benzoselenophene [3,2-b]selenophene-2,7-diyl and stilbene-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 more preferably 1,4-phenylene or 1,4-cyclohexyl.

The divalent cyclic group may be unsubstituted, and one or two or more hydrogen atoms in the cyclic group may be substituted by a substituent. Substituted or a monovalent organic group, are alkyl groups, said alkyl group may be a fluorine atom or a monovalent organic group hydroxy - as a substituent include a halogen group, a polar group, P ^AP1 -Sp ^AP1. Examples of the halogen group include a fluorine group, a chlorine group, and the like, and a fluorine group is preferred.

Here, the "monovalent organic group" refers to a group that has a chemical structure as an organic compound becomes a monovalent group, and refers to an atomic group obtained by removing one 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 those having 2 to 15 carbon atoms. Alkenyloxy and so on. _{One or more of -CH 2} -in the alkyl group, the alkenyl group, the alkoxy group, and the alkenoxy group may be substituted by -O-, -COO- or -OCO-, respectively, so as not to The oxygen atom is directly adjacent.

Among them, the monovalent organic group is preferably an alkyl group having 1 to 15 carbon atoms or an alkoxy group having 1 to 14 carbon atoms, and more preferably an alkyl group having 1 to 8 carbon atoms or an alkyl group having 1 to 14 carbon atoms. The alkoxy group of 8 is more preferably an alkyl group having 1 to 5 carbon atoms or an alkoxy group having 1 to 4 carbon atoms, and particularly preferably an alkyl group having 1 to 3 carbon atoms or an alkyl group having 1 to 4 carbon atoms. The alkoxy group of 2 is most preferably a C 1 or 2 alkyl group or a C 1 alkoxy group. _{One or more of -CH 2} -in the alkyl group, the alkenyl group, the alkoxy group, and the alkenoxy group may be substituted by -O-, -COO- or -OCO-, respectively, so as not to The oxygen atom is directly adjacent.

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, one of which may not be adjacent Two or more -CH ₂ -can be substituted by cyclic group, -CH=CH-, -C≡C-, -O-, -CO-, -COO- or -OCO- to avoid direct bonding of oxygen atoms . Among them, a single bond or an alkylene having 2 to 20 carbon atoms is preferred, a single bond or an alkylene having 2 to 10 carbon atoms is more preferred, and a single bond, -(CH ₂ ) ₂ -is more preferred. Or -(CH ₂ ) ₄ -. One or more than two -CH ₂ -in the alkylene group may be substituted by -O-, -COO- or -OCO- to avoid direct adjacent oxygen atoms.

In the case of improving 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 connecting the ring and the ring is an even number. One or two or more non-adjacent -CH ₂ -in the alkylene group may be substituted by -O-, -COO- or -OCO- to avoid direct adjacent oxygen atoms. The number of atoms directly linking the ring to the ring is, for example, 4 in the case of _{-CH 2} -CH _{2 COO-.}

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

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

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

[化43]

(In the formula, Sp ^WAT1 and Sp ^WAT2 each independently represent a single bond or a linear or branched alkylene group having 1 to 25 carbon atoms. One or more hydrogen atoms in the alkylene group may be- OH, -CN or P ^AP1 -Sp ^AP1 -substituted, one or more than two non-adjacent -CH ₂ -in the alkylene group may be cyclic group, -CH=CH-, -C≡C-, -O-, -CO-, -COO- or -OCO- substitution, so as to prevent the oxygen atom from being directly adjacent. The * in the formula represents a bonding bond.), Z ^AT1 represents a univalent polar group containing polar elements, and the Z ^AT1 One or more than two hydrogen atoms may be replaced 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).

[化44]

(In the formula, Sp ^ZAT11 represents a single bond or a linear or branched alkylene group having 1 to 25 carbon atoms, and one or two or more hydrogen atoms in the alkylene group may be replaced by -OH, -CN or- Z ^ZAT11 -R ^ZAT11 or P ^AP1 -Sp ^AP1 -is substituted, one of the alkylene groups or two or more non-adjacent -CH ₂ -may be substituted by a cyclic group, -O-, -COO-, -C (=O)-, -OCO-, or -CH=CH-substitution, so as not to directly adjoin the oxygen atom. Sp ^ZAT12 represents a single bond or a straight chain or branched alkylene group with 1 to 25 carbon atoms. One or two or more hydrogen atoms in the group may be substituted by -OH, -CN or P ^AP1 -Sp ^AP1 -, and one or two or more non-adjacent -CH ₂ -in the alkylene group may be cyclic group , -O-, -COO-, -C(=O)-, -OCO-, -CH=CH-, or -Z ^ZAT11 -substitution, so as not to directly adjoin the oxygen atom. Z ^ZAT11 represents a group containing a polar element. Contains Z ^{The structure represented by the ring of ZAT12} represents a five-member ring to a seven-member ring. ^{One or more of the hydrogen atoms in Z ZAT11} and Z ^ZAT12 may be substituted by -OH, -CN or P ^AP1 -Sp ^AP1 -. R ^ZAT11 and R ^ZAT12 each independently represents a hydrogen atom, a linear or branched alkyl group having 1 to 8 carbon atoms, and one or two or more hydrogen atoms in the alkyl group may be replaced by -OH, -CN or P ^AP1 -Sp ^AP1 -is substituted, one of the alkyl groups or two or more non-adjacent -CH ₂ -may be cyclic groups, -O-, -COO-, -C(=O)-, -OCO-,- CH=CH- or -Z ^ZAT11 -is substituted to avoid direct bonding of oxygen atoms. P ^AP1 represents a polymerizable group, and Sp ^AP1 represents a spacer group. The * in the formula represents a bonding bond.) Represented by the general formula (ZAT1-1) The group of is preferably a group represented by the following general formula (ZAT1-1-1) to (ZAT1-1-30).

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(In the formula, Sp ^ZAT11 and R ^ZAT11 respectively have the same meaning as described above, and the hydrogen atom bonded to the carbon atom can be replaced by -OH, -CN or P ^AP1 -Sp ^AP1 -. The * in the formula represents a bond Bonding.) In addition, as the group represented by the general formula (ZAT1-1), the following groups can be preferably cited.

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(In the formula, R ^tc represents a hydrogen atom, a linear or branched alkyl group having 1 to 20 carbon atoms or P ^AP1 -Sp ^AP1 -, and one or more hydrogen atoms in the alkyl group may be -OH , -CN or P ^AP1 -Sp ^AP1 -, one of the alkyl groups or two or more non-adjacent -CH ₂ -groups may be substituted by cyclic groups, -O-, -COO-, -C(=O )-, -OCO-, -CH=CH- or -Z ^ZAT11 -to avoid direct adjacent oxygen atoms. Hydrogen atoms in the molecule can be replaced by P ^AP1 -Sp ^AP1 -. The * in the formula represents a bonding bond.) The group represented by the general formula (ZAT1-2) is preferably a group represented by the following general formulas (ZAT1-2-1) to (ZAT1-2-9).

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(In the formula, Sp ^ZAT12 has the same meaning as described above, and one or two or more hydrogen atoms bonded to carbon atoms may be substituted by halogen atoms, -OH, -CN or P ^AP1 -Sp ^AP1 -. The * represents a bonding bond.) P ^AP1 represents a polymerizable group, preferably a group represented by any of the above formulas (P ^p1 -1) to (P ^p1 -9), and more preferably the above The group represented by any one of formula (P ^p1 -1) to formula (P ^p1 -7) is more preferably one of the formula (P ^p1 -1) to formula (P ^p1 -2) The group represented is most preferably the group represented by the above formula (P ^p1 -1).

Sp ^AP1 represents a spacer, preferably represents a single bond or a linear or branched alkylene group having 1 to 20 carbon atoms, more preferably represents a single bond or a linear alkylene group having 1 to 20 carbon atoms, and further Preferably, it represents a single bond or a linear alkylene group having 2 to 10 carbon atoms. In addition, in Sp ^AP1 , one of the alkylene groups or two or more non-adjacent -CH ₂ -s may be -CH=CH-, -C≡C-, -O-, -CO-,- COO- or -OCO- substitution, so as to avoid direct adjacent oxygen atoms. In addition, "substitution with a polymerizable group" may be ^{a form substituted with only a polymerizable group P AP1} , or a form substituted with P ^AP1 -Sp ^AP1 - ^{containing a spacer Sp AP1.} The same applies to other polymerizable groups.

In the compound represented by the 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, still more preferably 2 or more and 4 or less, particularly preferred It is 2 or 3, and 2 is most preferred.

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 multiple A ^AL1 , Z ^AL1 , Z ^AT1 , W ^AT1 , P ^AP1 , Sp ^AP1 , Sp ^WAT1 , Sp ^WAT2 , they may be the same or different.

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

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The lower limit of the content of the compound represented by the formula (A) is preferably 0.01% relative to the total amount of the liquid crystal composition, and among them, from the viewpoint of improving the specific resistance and VHR, it is more preferably 0.05%, and more preferably Is 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%, which is 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. The polymerization proceeds even in the absence of a polymerization initiator, but in order to promote polymerization, a polymerization initiator may be contained. Examples of the polymerization initiator include benzoin ethers, benzophenones, acetophenones, benzyl ketals, and phosphine oxides. ·Antioxidants The composition in the present invention may further contain the compound represented by the general formula (Q1) to the general formula (Q2) as an antioxidant.

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(In the formula, R ^Q represents a linear or branched alkyl group having 1 to 22 carbon atoms, and one or two or more CH ₂ groups in the alkyl group may be replaced by -O-, -CH=CH- , -CO-, -OCO-, -COO-, -C≡C-, -CF ₂ O-, -OCF ₂ -to replace, so as not to directly adjacent to the oxygen atom ^{, the hydrogen atom in R Q} can be 4-hydroxy-3 ,5-Di-tert-butylphenyl substituted, M ^Q represents one of trans-1,4-cyclohexylene, 1,4-phenylene or single bond, trans-1,4-cyclohexylene Or two non-adjacent -CH ₂ -can be substituted by -O-.

In the formula, X ^y represents an alkylene group having 1 to 15 carbon atoms (one or two or more -CH ₂ -in the alkylene group may be substituted with -O-, -CO-, -COO-, -OCO-, so as not to directly adjacent to oxygen atoms.), -OCH ₂ -, -CH ₂ O-, -COO-, -OCO-, -CF ₂ O-, -OCF ₂ -, -CF ₂ CF ₂ -,- CH=CH-COO-, -CH=CH-OCO-, -COO-CH=CH-, -OCO-CH=CH-, -CH=CH-, -C≡C-, 1,4-phenylene , Trans-1,4-cyclohexylene or a single bond. Regarding 1,4-phenylene, any hydrogen atom may be substituted with a fluorine atom, M ^y represents a monovalent linking group, and l represents an integer of 2-6. ) R ^Q represents a linear or branched alkyl group having 1 to 22 carbon atoms. One or two or more CH ₂ groups in the alkyl group may be replaced by -O-, -CH=CH-, -CO -, -OCO-, -COO-, -C≡C-, -CF ₂ O-, -OCF ₂ -Substitution, so as to avoid direct adjacent oxygen atoms, preferably straight chain alkyl with 1 to 10 carbon atoms, straight alkanoyl group, a CH ₂ group is substituted -OCO- or -COO- straight chain alkyl, branched alkyl, branched alkoxy group, a CH ₂ group is substituted with -OCO- or -COO- The branched chain alkyl group is more preferably a straight chain alkyl group having 1 to 20 carbon atoms, a straight chain alkyl group having one CH ₂ group substituted with -OCO- or -COO-, a branched chain alkyl group, and a branched chain alkyl group. Oxy, a CH ₂ group is substituted with -OCO- or -COO- branched chain alkyl. M ^Q represents trans-1,4-cyclohexylene, 1,4-phenylene or a single bond, but is preferably trans-1,4-cyclohexylene or 1,4-phenylene.

M ^{y is} preferably a hydrocarbon group with 1 to 25 carbon atoms, and one or two or more -CH ₂ -in the hydrocarbon group may be substituted with -O-, -CO-, -COO-, -OCO- to avoid The oxygen atom is directly adjacent.

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. If volatility is considered, the number of carbon atoms is preferably a large value. If viscosity is considered, the number of carbon atoms is preferably not too large. Therefore, the number of carbon atoms is preferably 2-12, and more preferably 3-10. More preferably, it has 4 to 10 carbon atoms, particularly preferably 5 to 10 carbon atoms, and most preferably 6 to 10 carbon atoms.

X ^{y is} preferably a single bond.

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

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In the formula, R ^{Q1 is} preferably a linear or branched alkyl group with 1 to 10 carbon atoms, R ^{Q2 is} preferably a linear or branched alkyl group with 1 to 20 carbon atoms, and R ^Q3 is more It is preferably a linear alkyl group having 1 to 8 carbon atoms, a branched chain alkyl group, a linear alkoxy group or a branched alkoxy group, and L ^{Q is} preferably a linear extended alkyl group having 1 to 8 carbon atoms or a branched alkyl group. Alkylene. 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 preferable.

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

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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%, particularly preferably 0.001% to 0.05%.

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

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(In the formula, n represents an integer of 0-20.) It preferably contains one or two or more compounds represented by general formula (Q1) to general formula (Q2) or a compound selected from general formula (III-1) to general formula (III-41), and more preferably contains One to five, the content of which is preferably 0.001% to 1%, more preferably 0.001% to 0.1%, particularly preferably 0.001% to 0.05%.

The liquid crystal display element manufactured by the manufacturing method of the present invention is useful for realizing high-speed response, high reliability, and suppression of display failures at the same time, and is particularly effective as a liquid crystal display element for active matrix driving, and can be applied to VA mode, polymer Liquid crystal display elements for polymer stabilized vertical alignment (PSVA) mode, PSA mode, IPS mode or Electrically Controlled Birefringence (ECB) mode. Especially suitable for VA mode, PSVA mode and PSA mode. [Example]

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

In the examples, the measured specificities are as follows. T _ni : nematic-isotropic liquid phase transition temperature (℃) Δn: refractive index anisotropy at 293 K Δε: dielectric constant anisotropy at 293 K γ1: rotational viscosity at 293 K (mPa ·S)

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

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[Table 1] <Side chain structure> Abbreviation Chemical structure -n -C _n H _2n+1 n- C _n H _2n+1- -On -OC _n H _2n+1 nO- C _n H _2n+1 O- -V -CH=CH ₂ V- CH ₂ =CH- -V1 -CH=CH-CH ₃ 1V- CH ₃ -CH=CH- -2V -CH ₂ -CH ₂ -CH=CH ₂ V2- CH ₂ =CH-CH ₂ -CH _2- -2V1 -CH ₂ -CH ₂ -CH=CH-CH ₃ 1V2- CH ₃ -CH=CH-CH ₂ -CH _2- (Among them, n in the table is a natural number.)

[Table 2] <Link structure> Abbreviation Chemical structure -n- -C _n H _2n- -nO- -C _n H _2n O- -On- -OC _n H _2n- -COO- -C(=O)-O- -OCO- -OC(=O)- -V- -CH=CH- -nV- -C _n H _2n -CH=CH- -Vn- -CH=CH-C _n H _2n- -T- -C=C- -CF2O- -CF ₂ -O- -OCF2- -O-CF _2- (Among them, n in the table is a natural number.)

In the examples, the properties evaluated are as follows. Reliability (VHR): The voltage retention rate (%) when the liquid crystal display element is prepared to be irradiated with UV light for 90 minutes and measured at 1 V, 0.6 Hz, and 60°C. For the UV irradiation lamp used in the example, Toshiba Lighting Technology is used (Toshiba lighting&technology) The FL15UV34A manufactured by the company adjusts the illuminance at 365 nm to 4 mW/cm ² . This lamp is I ₃₆₅ /I ₃₁₃ > 20 (in the 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.). For the UV irradiation lamp for the comparative example, FL15UV32A manufactured by Toshiba Lighting & Technology was used, and the illuminance of 313 nm was adjusted to 4 mW/cm ² . This lamp is I ₃₆₅ /I ₃₁₃ ＜20.

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

[table 3] LC-1 LC-2 LC-3 LC-4 LC-5 LC-6 3-Cy-Cy-2 4 6 17 20 3-Cy-Cy-4 7 5 3-Cy-Cy-5 3 3-Cy-Cy-V 29 29 32 twenty four 3-Cy-Cy-V1 10 8 3-Cy-Ph-01 5.5 4.5 3 3-Ph-Ph-1 10 10 9 10 3-Cy-Cy-Ph-1 7 5.5 2 3-Cy-Ph-Ph-1 2 4.5 2 3-Cy-Ph-Ph-2 3 6.5 1V2-Ph-Ph-1 5 3-Cy-10-Ph5-01 5 3 3-Cy-10-Ph5-02 10 12.5 13 11 2-Cy-Cy-10-Ph5-02 10 3-Cy-Cy-10-Ph5-02 15 3 15 1V-Cy-Cy-10-Ph5-02 5 4 7 3-Ph-2-Ph-Ph5-02 6 4 3-Cy-Ph5-02 7.5 15.5 3-Ph-Ph5-02 16 5 3-Cy-Cy-Ph5-01 3.5 3-Cy-Cy-Ph5-02 8.5 12.5 2-Cy-Ph-Ph5-02 8 8 6 5.5 8 3-Cy-Ph-Ph5-02 11 13 9 10 9 3-Cy-Ph-Ph5-04 9.5 5.5 9 3-Cy-Ph-Ph5-02 10 3 Total (Total) [%] 100 100 100 100 100 100 Tni 75 74 74 74 75 75 Δn 0.103 0.109 0.100 0.105 0.102 0.107 Δε -3.6 -2.7 -2.8 -3.2 -2.7 -3.3 γ1 89 76 74 75 81 100

It can be seen that LC-1 to LC-5 containing alkenyl compounds have a small γ1 and a fast response speed. It can be seen that LC-6 without an alkenyl compound has a large γ1 and a slow response speed. LC-6 with a poor response speed was excluded from the evaluation target, and the other LC-1 to LC-5 were included in the target, and the following evaluations were performed.

The liquid crystal composition mixed with the liquid crystal composition of LC-1 to LC-5, the polymerizable compound represented by RM1 to RM5, and the additive represented by AD1 and AD2 was used in the examples to irradiate UV with a UV lamp to measure the VHR Examples (E-01) to Example (E-25), and Comparative Example (C-01) to Comparative Example (C-10) in which VHR was measured by irradiating UV with a UV lamp using a comparative example are as shown in Table 4.

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[Table 4] E-01 E-02 E-03 E-04 E-05 C-01 C-02 LC-1 99.695 - - - - 99.695 - LC-2 - 99.695 - - - - - LC-3 - - 99.695 - - - - LC-4 - - - 99.695 - - 99.695 LC-5 - - - - 99.695 - - RM1 0.30 0.30 0.30 0.30 0.30 0.30 0.30 AD1 0.005 0.005 0.005 0.005 0.005 0.005 0.005 VHR 95.0 95.5 95.5 96.0 97.0 80.0 84.0

[table 5] E-06 E-07 E-08 E-09 E-10 C-03 C-04 LC-1 99.695 - - - - 99.695 - LC-2 - 99.695 - - - - - LC-3 - - 99.695 - - - - LC-6 - - - 99.695 - - - LC-7 - - - - 99.695 - - RM1 0.25 0.25 0.25 0.25 0.25 0.25 0.25 RM2 0.05 0.05 0.05 0.05 0.05 0.05 0.05 AD1 0.005 0.005 0.005 0.005 0.005 0.005 0.005 VHR 95.0 95.5 95.5 96.0 97.0 80.0 84.0

[Table 6] E-11 E-12 E-13 E-14 E-15 C-05 C-06 LC-1 99.195 - - - - 99.195 - LC-2 - 99.195 - - - - - LC-3 - - 99.195 - - - - LC-6 - - - 99.195 - - 99.195 LC-7 - - - - 99.195 - - RM2 0.03 0.03 0.03 0.03 0.03 0.03 0.03 RM3 0.27 0.27 0.27 0.27 0.27 0.27 0.27 AD1 0.005 0.005 0.005 0.005 0.005 0.005 0.005 AD2 0.50 0.50 0.50 0.50 0.50 0.50 0.50 VHR 95.0 95.5 95.5 96.0 97.0 80.0 84.0

[Table 7] E-16 E-17 E-18 E-19 E-20 C-07 C-08 LC-1 99.295 - - - - 99.295 - LC-2 - 99.295 - - - - - LC-3 - - 99.295 - - - - LC-6 - - - 99.295 - - 99.295 LC-7 - - - - 99.295 - - RM3 0.30 0.30 0.30 0.30 0.30 0.30 0.30 RM5 0.40 0.40 0.40 0.40 0.40 0.40 0.40 AD1 0.005 0.005 0.005 0.005 0.005 0.005 0.005 VHR 97.0 97.3 97.3 97.5 98.0 90.0 92.0

[Table 8] E-21 E-22 E-23 E-24 E-25 C-09 C-10 LC-1 98.795 - - - - 98.795 - LC-2 - 98.795 - - - - - LC-3 - - 98.795 - - - - LC-6 - - - 98.795 - - 98.795 LC-7 - - - - 98.795 - - RM3 0.27 0.25 0.25 0.25 0.25 0.25 0.25 RM4 0.03 0.05 0.05 0.05 0.05 0.05 0.05 RM5 0.40 0.40 0.40 0.40 0.40 0.40 0.40 AD1 0.005 0.005 0.005 0.005 0.005 0.005 0.005 AD2 0.50 0.50 0.50 0.50 0.50 0.50 0.50 VHR 97.0 97.3 97.3 97.5 98.0 90.0 92.0

It can be confirmed that the VHR of Example 1 (E-01) to Example 5 (E-05) is a sufficiently high value. In addition, it was confirmed that these examples showed a reduction in defects. In contrast, it was confirmed that the VHR of Comparative Example 1 (C-01) and Comparative Example 2 (C-02) was low, and the problem of the present invention could not be solved.

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

AM: Active matrix substrate (substrate) CF: Color filter substrate (substrate) 1: liquid crystal display element 2: The first substrate 3: The second substrate 4: liquid crystal layer 5: Pixel electrode layer (electrode layer) (electrode) 6: Common electrode layer (electrode layer) (electrode) 7: The first polarizer 8: The second polarizer 9: Color filter 11: Gate bus 12: Data bus 13: Pixel electrode 14: Cs electrode 15: Source electrode 16: drain electrode 17: Contact hole S: separation distance

Fig. 1 is an exploded perspective view schematically showing an embodiment of a liquid crystal display element. Fig. 2 is an enlarged plan view of an area enclosed by line I in Fig. 1.

AM: active matrix substrate (substrate)

CF: Color filter substrate (substrate)

1: liquid crystal display element

2: The first substrate

3: The second substrate

4: liquid crystal layer

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

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

7: The first polarizer

8: The second polarizer

9: Color filter

Claims (5)

A method for manufacturing a liquid crystal display element includes: at least one of a pair of substrates having an alignment film is arranged so as to face each other via a liquid crystal composition containing a polymerizable compound; and irradiating the liquid crystal composition with ultraviolet rays The step of polymerizing the polymerizable compound, wherein, as the ultraviolet rays, the ultraviolet rays satisfying the following formula (P-1) are irradiated at least once, I ₃₆₅ /I ₃₁₃ > 20···(P-1) In the 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 the following general formula (I) , Or one or two or more of liquid crystal compounds represented by the following general formula (II) and one or two or more of polymerizable compounds represented by the following general formula (P),

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

In the formula, R ²¹ and R ²² each independently represent an alkyl group having 1 to 8 carbon atoms, and one of the alkyl groups or two or more non-adjacent -CH ₂ -s can each independently be represented by -CH=CH -, -C≡C-, -O-, -CO-, -COO- or -OCO- substituted, ^{at least one of R 21} and R ²² represents an alkenyl group having 2 to 8 carbon atoms, the alkenyl group One or two or more of -CH ₂ -in -CH 2-as long as they are not adjacent to each other may be further substituted with oxygen atoms. A ²¹ , A ²² and A ²³ are each independently selected from (a) 1,4- cyclohexylene, in this group present in a -CH ₂ - or more than two adjacent -CH ₂ - may be substituted with -O-, and (b) 1,4- phenylene, this group is present One -CH= or two or more non-adjacent -CH= can be substituted with -N=, and the hydrogen atoms in the group (a) and group (b) can be replaced by -N=. Independently substituted by 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 means 0 , 1, 2, or 3, when ^{there are multiple A 22} and Z ²² respectively, they may be the same or different, except for the compound represented by the formula (I),

In the formula, P ^p1 and P ^p2 each independently represent a polymerizable group, Sp ^p1 and Sp ^p2 each independently represent a spacer or a single bond, and 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-, where R ^ZP1 each independently represents a hydrogen atom or an alkyl group with 1 to 4 carbon atoms, in the molecule When there are a plurality of R ^ZP1 , they may be the same or different. A ^p1 , A ^p2 and A ^p3 each independently represent a group selected from (a ^p ) 1,4-cyclohexylene, and one of the groups is or Two or more -CH ₂ -as long as the oxygen atoms are not adjacent to each other can be substituted by -O-, (b ^p ) 1,4-phenylene, one or more than two -CH= Can 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 of the groups present- CH= may be substituted by -N=, a group in the group consisting of, one or more hydrogen atoms in ^{the group (a p} ), group (b ^p ) and group (c ^{p) may be independent of each other} Ground is substituted with a halogen atom, a cyano group, an alkyl group having 1 to 18 carbon atoms which may be substituted with a fluorine atom, or -Sp ^p2 -P ^p2 , one or two or more non-adjacent -CH in the alkyl group ₂ -Can be independently set by -CH=CH-, -C≡C-, -O-, -CO-, -COO- or -OC O-substitution prevents oxygen atoms from directly adjacent to each other. In addition, when m ^p1 is 0 and A ^p1 is a group represented by a group (c ^p ), A ^p3 may be a single bond, and 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. The method for manufacturing a liquid crystal display element according to claim 1, wherein the compound represented by the formula (II) is selected from the group consisting of compounds represented by the following general formulas (II-01) to (II-06) The compounds in the group,

In the formula, R ²¹⁰ and R ²²⁰ each independently represent an alkyl group having 1 to 8 carbon atoms, and one of the alkyl groups or two or more non-adjacent -CH ₂ -s can each independently be represented by -CH=CH -, -C≡C-, -O-, -CO-, -COO- or -OCO- substituted, ^{at least one of R 210} and R ²²⁰ represents an alkenyl group having 2 to 8 carbon atoms, the alkenyl group One or two or more of -CH ₂ -in the -CH 2-may be further substituted with oxygen atoms as long as the oxygen atoms are not adjacent to each other. The method for manufacturing a liquid crystal display element according to claim 2, wherein the compound represented by the formula (II) is selected from the following general formulas (II-01-1) to (II-01-5) Compounds in the group consisting of the represented compounds,

In the formula, R ²¹¹ each independently represents a hydrogen atom or an alkyl group having 1 to 5 ^{carbon atoms, and R 221} each independently represents an alkyl group having 1 to 8 carbon atoms. One of the alkyl groups or two non-adjacent ones The above -CH ₂ -can be substituted by -CH=CH-, -C≡C-, -O-, -CO-, -COO- or -OCO- as long as the oxygen atoms are not adjacent to each other, and n ^{22 is} each independently It represents an integer of 0-5, and the sum of the number ^{of carbon atoms when R 211} is an alkyl group and ^{the value of n 22} does not exceed 6. The method for manufacturing a liquid crystal display element according to any one of claims 1 to 3, wherein the liquid crystal composition further contains a sensitizer represented by the following general formula (S),

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 alkyl group having 2 to 10 carbon atoms. Alkenyloxy, one or more of the hydrogen atoms in these groups may be replaced by fluorine atoms. A ^s1 and B ^s1 are each independently selected from (a) 1,4-cyclohexylene, one of the groups present -CH ₂ -or two or more non-adjacent -CH ₂ -can be substituted with -O-, (b) 1,4-phenylene, one -CH= or two non-adjacent existing in this group The above -CH= can be substituted with -N=, (c) naphthalene-2,6-diyl, 1,2,3,4-tetrahydronaphthalene-2,6-diyl or decahydronaphthalene-2, 6-diyl group, one of the naphthalene-2,6-diyl group or 1,2,3,4-tetrahydronaphthalene-2,6-diyl group -CH= or two or more unadjacent -CH = Can be substituted with -N=, and (d) the group consisting of 1,4-cyclohexenylene group, group (a), group (b), group (c) and group (d) It 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. ^When there are a plurality of s1 and ring B ^s1 respectively, the plurality of rings A ^s1 and the plurality of rings B ^s1 may be the same or different, ^{respectively, and 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 single bond, n ^s1 and n ^s2 are independent Represents 0, 1, or 2, n ^s1 + n ^s2 represents an integer of 1 to 4, and X ^s1 to X ^s6 each independently represent an alkyl group with 1 to 8 carbon atoms that may be substituted with fluorine atoms, which may be substituted with fluorine The atom has an alkoxy group having 1 to 8 carbon atoms, a fluorine atom, or a hydrogen atom. A liquid crystal display element manufactured by the method for manufacturing a liquid crystal display element according to any one of Claims 1 to 4.

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