WO2018105381A1

WO2018105381A1 - Liquid crystal display element

Info

Publication number: WO2018105381A1
Application number: PCT/JP2017/041792
Authority: WO
Inventors: 和樹栗沢; 雄一井ノ上
Original assignee: Dic株式会社
Priority date: 2016-12-05
Filing date: 2017-11-21
Publication date: 2018-06-14
Also published as: JPWO2018105381A1; JP6485723B2

Abstract

In order to address the problem described in the specification, the present invention provides a method for improving contrast when a liquid crystal display element is configured to have high characteristics as a liquid crystal display element and a narrowed cell gap. The present invention provides a liquid crystal display element configured from: a first substrate having an electrode A formed thereon; a second substrate that is arranged so as to face the first substrate and that has an electrode B formed thereon; and a liquid crystal layer that is provided between the first substrate and the second substrate in a state in which voltage is not applied between the electrodes and that is oriented so as to be approximately perpendicular to the first substrate and the second substrate. The electrode A has a fishbone pattern comprising branched parts. The interval (S µm) between adjacent individual branches in the fishbone pattern and the inter-substrate distance (d µm) between the first substrate and the second substrate satisfy the relationship indicated in formula (1). Formula (1): (d – 0.6)/1.25 < S < (d + 1.1)/1.25.

Description

Liquid crystal display element

The present invention relates to a liquid crystal display element useful as a constituent member for a liquid crystal television or the like.

Liquid crystal display elements are used in various measuring instruments, automobile panels, word processors, electronic notebooks, printers, computers, liquid crystal televisions, clocks, advertisement display boards, as well as clocks and calculators. Typical liquid crystal display methods include TN (twisted nematic) type, STN (super twisted nematic) type, vertical alignment type using TFT (thin film transistor) (vertical alignment; VA), IPS. (In-plane switching) type and FFS (fringe field switching) type.

These liquid crystal display elements are required to have a high-speed response in order to improve moving image characteristics, and there is an increasing demand for a narrow cell gap. Conventionally, the cell gap is about 4 μm, but further narrowing of the gap is required. In the liquid crystal display element, it is necessary to adjust the value of the product of the cell gap (d) and the refractive index anisotropy (Δn) of the liquid crystal composition to be used to the optimum value from the viewpoint of improving the contrast. There is a demand for high Δn. In the case of a conventional liquid crystal display device having a cell gap of about 4 μm, the contrast can be improved by adjusting Δn of the liquid crystal composition. However, when the cell gap is 3.6 μm or less and an electrode having a fishbone pattern is used, the contrast cannot be sufficiently improved only by adjusting Δn of the liquid crystal composition (for example, Patent Document 1).

JP 2014-74797 A

The present invention has been made in view of the above circumstances, and provides a method for improving the contrast when a narrow cell gap is achieved with high characteristics as a liquid crystal display element.

In order to solve the above-mentioned problems, the present inventors have studied the configurations of various liquid crystal display elements. As a result, the inventors have found that the above problems can be solved by using a specific electrode structure, and have completed the present invention. It was.

That is, the present invention
A first substrate on which an electrode A is formed;
A second substrate on which an electrode B is formed, disposed opposite to the first substrate;
In a state where no voltage is applied between the electrodes, the liquid crystal layer is provided between the first substrate and the second substrate and is aligned substantially perpendicular to the first and second substrates.
The electrode A has a fishbone pattern having a branch portion, and the distance between adjacent branches (S μm) of each branch in the fishbone pattern and the first substrate and the second substrate. A liquid crystal display element in which the distance between substrates (d μm) satisfies the relationship of the formula (1).
(D−0.6) /1.25 <S <(d + 1.1) /1.25 Formula (1)

According to the present invention, a liquid crystal display element exhibiting excellent contrast and response speed can be provided.

It is a schematic perspective view which shows one Embodiment of the liquid crystal display element of this invention. It is a schematic plan view which shows an example of the electrode (comb-shaped electrode) which has a fishbone-shaped pattern used for the liquid crystal display element of this invention. It is a figure which shows the definition of the pretilt angle in 1 domain in the liquid crystal display element of this invention. It is an example of the one side substrate electrode pattern top view used for the preferable liquid crystal display element of this invention. FIG. 5 is an example of a cross-sectional view of a preferred liquid crystal display element of the present invention using the electrode described in FIG. 4, and is a conceptual diagram of alignment of a liquid crystal compound in a state where no voltage is applied between the electrodes. Relationship between d, S and transmittance Relationship between S and d when transmittance (T) is a specific value In the liquid crystal display element shown in FIG. 5, d = 3.8 μm, S = 3.0 μm, L = 3.0 μm, and equipotential when a voltage of 10 V is applied between the first electrode and the second electrode. It is the simulation result which represents typically the mode of a surface, and the state of the liquid crystal molecule at that time.

<Liquid crystal display element>
The liquid crystal display element of the present invention is a liquid crystal display element in which a liquid crystal layer containing a liquid crystal composition is sandwiched between a pair of substrates, and a voltage is applied to the liquid crystal layer to displace the liquid crystal molecules in the liquid crystal layer. This is based on the principle of acting as an optical switch by transferring, and a well-known and conventional technique can be used in this respect.

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

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

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

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

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

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

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

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

In order to perform pixel division, an electrode having a fishbone pattern is used in each pixel. The pixel electrode may be an electrode having a fishbone pattern, and the common electrode may be an electrode having a fishbone pattern, but the pixel electrode is preferably an electrode having a fishbone pattern. FIG. 2 is a schematic plan view showing a typical form of an electrode having a fishbone pattern when a pixel electrode is divided into four regions. The slit electrode has comb-like slits in four directions from the center of the pixel, so that the liquid crystal molecules in each pixel that are substantially perpendicularly aligned with respect to the substrate when no voltage is applied are applied with voltage application. The liquid crystal molecules are directed in four different directions, approaching horizontal alignment. As a result, the alignment direction of the liquid crystal molecules in the pixel can be divided into a plurality of parts, so that the viewing angle characteristic is extremely wide.

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

As a method for dividing a pixel, a method for providing a pixel bone with a structure such as a linear protrusion in addition to a method for providing the pixel electrode with a fishbone pattern, and a method for providing an electrode other than the pixel electrode and the common electrode. A method of providing a structure made of a polymer of a polymerizable compound different from the alignment film can be used in combination, but a method of providing a structure (alignment control layer) made of a polymer of a polymerizable compound different from the alignment film (PSA) ) Is preferred. It is sufficient that at least one of the first substrate 11 and the second substrate 12 is included in the structure, and both may be included or may be present in the liquid crystal composition.

However, only an electrode having a fishbone pattern does not have a driving force for liquid crystal molecules when no voltage is applied, and therefore a pretilt angle cannot be given to the liquid crystal molecules. However, in the present invention, a pretilt angle can be imparted by providing an alignment control layer described later, and a wide viewing angle by pixel division can be achieved by combining with a slit electrode obtained by pixel division.

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

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

In the present invention, “the liquid crystal molecules are substantially vertically aligned” means a state in which the director of the vertically aligned liquid crystal molecules is slightly tilted from the vertical direction to give a pretilt angle. When the liquid crystal molecules are perfectly vertically aligned, the angle formed by the direction completely parallel to the substrate surface and the direction of the director of the liquid crystal molecules is 90 °, and the liquid crystal molecules are completely homogeneously aligned ( When the liquid crystal molecules are aligned substantially vertically, the angle is preferably 89.7 to 85 °, more preferably 89. 5 to 87 °.

The liquid crystal display element of the present invention may have a polyimide alignment film for aligning the liquid crystal composition on both the first substrate and the second substrate, or may be provided only on one side. It is not necessary to have both of the substrates.

When the liquid crystal display element of the present invention does not have a polyimide alignment film, the liquid crystal composition may be aligned by a polymer of a polymerizable compound having a reactive group in order to align the liquid crystal composition. Well, even when it has a polyimide alignment film, the liquid crystal composition is aligned by a polymer of a polymerizable compound having a reactive group in order to auxiliary align the liquid crystal composition in a direction different from the alignment direction of the polyimide. The structure to be made may be sufficient.

Specifically, the polymerizable compound having a reactive group for forming the alignment control layer of the liquid crystal display element of the present invention is represented by the general formula (ii)

(Where
Z ⁱ¹ represents a single bond, —CH═CH—, —CF═CF—, —C≡C—, —COO—, —OCO—, —CF ₂ O—, —OCF ₂ —, or 2 to 20 alkylene groups, and one or two or more non-adjacent —CH ₂ — in the alkylene group may be substituted with —O—, —COO— or —OCO—,
A ⁱ¹ represents a divalent 6-membered aromatic group, a divalent 6-membered heteroaromatic group, a divalent 6-membered aliphatic group, a divalent 6-membered heteroaliphatic group, or a single bond. A hydrogen atom in these ring structures may be substituted with a halogen atom and / or —Sp ⁱ¹ —R ⁱ¹ ,
When there are a plurality of Z ⁱ¹ and A ⁱ¹ , they may be the same as or different from each other;
m ⁱ¹ represents an integer of 1 to 5;
K ⁱ¹ represents a hydroxyl group, an amino group, —Sp ⁱ¹ —R ⁱ¹ or the following formulas (K-1) to (K-8):

(Where
W ^K1 represents a methine group or a nitrogen atom,
X ^K1 and Y ^K1 each independently represent —CH ₂ —, an oxygen atom or a sulfur atom,
Z ^K1 represents an oxygen atom or a sulfur atom,
U ^K1 , V ^K1 and S ^K1 each independently represent a methine group or a nitrogen atom,
Combinations in which ^K1 is a methine group, V ^K1 is a methine group, and S ^K1 is a nitrogen atom] are excluded. )
Represents a structure represented by
In formula (i) and formula (K-1) to formula (K-8), the black dot at the left end represents a bond,
Sp ⁱ¹ represents a linear alkylene group having 1 to 18 carbon atoms, a branched alkylene group having 1 to 18 carbon atoms, or a single bond, and one or two or more non-adjacent —
CH ₂ — may be substituted with —O—, —COO— or —OCO—,
R ⁱ¹ represents a hydrogen atom or formula (R-1) to formula (R-15):

(In the formula, the black dot at the right end represents a bond.)
Represents a substituent selected from the group consisting of
In addition, when the same description substituent exists in a molecule | numerator, they may be the same or different. ) Is preferred.

In formulas (i) and (ii), Z ⁱ¹ is preferably a single bond, a linear or branched alkylene group having 2 to 20 carbon atoms, or one or two not adjacent in the alkylene group The above —CH ₂ — represents a group substituted with —O—, more preferably a single bond, a linear alkylene group having 2 to 15 carbon atoms, or one or not adjacent to the alkylene group. Represents a group in which two or more —CH ₂ — are substituted with —O—, and more preferably a single bond, an alkylene group having 2 carbon atoms (ethylene group (—CH ₂ CH ₂ —)) or an ethylene group A group in which one of —CH ₂ — is substituted with —O— (—CH ₂ O—, —OCH ₂ —), a linear alkylene group having 3 to 13 carbon atoms, or one or not adjacent two or more -CH ₂ - is replaced by -O- It represents a group.

A ⁱ¹ preferably represents a divalent 6-membered aromatic group or a divalent 6-membered aliphatic group (the hydrogen atom in these ring structures may be substituted with a halogen atom), and more Preferably, it represents a divalent unsubstituted 6-membered aromatic group, a divalent unsubstituted 6-membered aliphatic group, or a group in which a hydrogen atom in these ring structures is substituted with a fluorine atom, Preferably, it represents a divalent unsubstituted 6-membered aromatic group, a group in which a hydrogen atom in the ring structure is substituted with a fluorine atom, or a divalent unsubstituted 6-membered cyclic aliphatic group.

m ⁱ¹ preferably represents an integer of 1 to 4, more preferably an integer of 1 to 3.

K ⁱ¹ preferably represents a structure represented by any one of the formulas (K-1) to (K-5) and (K-8), and more preferably the formula (K-1) and the formula (K -5) represents a structure represented by any one of formulas (K-8).

In formulas (K-1) to (K-8), W ^K1 preferably represents a methine group. X ^K1 and Y ^K1 each independently preferably represent —CH ₂ — or an oxygen atom. Z ^K1 preferably represents an oxygen atom. It is preferable to represent the one or both nitrogen atoms of U ^K1 and V ^K1, one of U ^K1 and V ^K1 represents a methine group, and more preferably the other represents a nitrogen atom. S ^K1 preferably represents a nitrogen atom.

In formula (ii), Sp ⁱ¹ preferably represents a linear alkylene group having 1 to 18 carbon atoms or a single bond, more preferably a linear alkylene group having 2 to 15 carbon atoms or a single bond. More preferably, it represents a linear alkylene group having 3 to 12 carbon atoms or a single bond.

R ⁱ¹ preferably represents a hydrogen atom or a substituent of any one of the formulas (R-1) and (R-2).

As general formula (ii), the following general formula (V)

(Wherein X ¹ and X ² each independently represent a hydrogen atom or a methyl group, and Sp ¹ and Sp ² each independently represent a single bond, an alkylene group having 1 to 8 carbon atoms or —O— (CH ₂ ) _s — (wherein _s represents an integer of 2 to 7 and an oxygen atom is bonded to an aromatic ring), and U is a linear or branched chain having 2 to 20 carbon atoms Represents a valent alkylene group or a polyvalent cyclic substituent having 5 to 30 carbon atoms, and the alkylene group in the polyvalent alkylene group may be substituted with an oxygen atom within a range in which the oxygen atom is not adjacent to each other. An alkyl group of ˜20 (the alkylene group in the group may be substituted with an oxygen atom within the range where the oxygen atom is not adjacent), may be substituted with a cyclic substituent, and k is an integer of 1 to 5 The polymerizable compound represented by

In the general formula (V), X ¹ and X ² each independently represent a hydrogen atom or a methyl group. However, when importance is attached to the reaction rate, a hydrogen atom is preferable, and importance is placed on reducing the amount of residual reaction. In this case, a methyl group is preferred.

In the general formula (V), Sp ¹ and Sp ² are each independently a single bond, an alkylene group having 1 to 8 carbon atoms, or —O— (CH ₂ ) _s — (wherein s is 2 to 7 Wherein the oxygen atom is bonded to the aromatic ring), the carbon chain is preferably not so long, a single bond or an alkylene group having 1 to 5 carbon atoms is preferable, and a single bond or An alkylene group having 1 to 3 carbon atoms is more preferred. Also, when Sp ¹ and Sp ² represent —O— (CH ₂ ) _s —, s is preferably 1 to 5, more preferably 1 to 3, and at least one of Sp ¹ and Sp ² is a single bond. More preferably, it is particularly preferable that both are single bonds.

In the general formula (V), U represents a linear or branched polyvalent alkylene group having 2 to 20 carbon atoms or a polyvalent cyclic substituent having 5 to 30 carbon atoms, and an alkylene group in the polyvalent alkylene group May be substituted with an oxygen atom in the range where the oxygen atom is not adjacent, and an alkyl group having 5 to 20 carbon atoms (the alkylene group in the group may be substituted with an oxygen atom within the range where the oxygen atom is not adjacent) ), May be substituted with a cyclic substituent, and is preferably substituted with two or more cyclic substituents.

In the general formula (V), U specifically preferably represents the following formula (Va-1) to formula (Va-5), and the formula (Va-1) to formula (Va-3) It is more preferable to represent, and it is particularly preferable to represent the formula (Va-1).

(In the formula, both ends shall be bonded to Sp ¹ or Sp ^2. )
When U has a ring structure, at least one of the Sp ¹ and Sp ² preferably represents a single bond, and it is also preferable that both are single bonds.

In the above general formula (V), k represents an integer of 1 to 5, but k is preferably a bifunctional compound of 1 or k is a trifunctional compound of 2, more preferably a bifunctional compound. .

Specifically, the compound represented by the general formula (V) is preferably a compound represented by the following general formula (Vb).

(Wherein X ¹ and X ² each independently represent a hydrogen atom or a methyl group, and Sp ¹ and Sp ² each independently represent a single bond, an alkylene group having 1 to 8 carbon atoms or —O— (CH ₂ ) _s — (wherein _s represents an integer of 2 to 7 and an oxygen atom is bonded to an aromatic ring), Z ¹ represents —OCH ₂ —, —CH ₂ O—, —COO—, —OCO—, —CF ₂ O—, —OCF ₂ —, —CH ₂ CH ₂ —, —CF ₂ CF ₂ —, —CH═CH—COO—, —CH═CH—OCO—, — _{_{COO-CH = CH -, -}} OCO-CH = CH -, - COO-CH 2 CH 2 -, - OCO-CH 2 CH 2 -, - CH 2 CH 2 -COO -, - CH 2 CH 2 -OCO- _{_{, -COO-CH 2 -, -}} OCO-CH 2 -, - CH 2 -COO -, - CH ^{^{-OCO -, - CY 1 = CY}} 2 -, - C≡C- or a single bond, C represents 1,4-phenylene group, represents trans-1,4-cyclohexylene group or a single bond, in formula All 1,4-phenylene groups may have any hydrogen atom substituted with a fluorine atom.)
In the general formula (Vb), X ¹ and X ² each independently represent a hydrogen atom or a methyl group, both of which are diacrylate derivatives each representing a hydrogen atom, or both are dimethacrylate derivatives having a methyl group. A compound in which one represents a hydrogen atom and the other represents a methyl group is also preferable. As for the polymerization rate of these compounds, diacrylate derivatives are the fastest, dimethacrylate derivatives are slow, asymmetric compounds are in the middle, and a preferred embodiment can be used depending on the application. In the PSA liquid crystal display element, a dimethacrylate derivative is particularly preferable.

In the general formula (Vb), Sp ¹ and Sp ² each independently represent a single bond, an alkylene group having 1 to 8 carbon atoms, or —O— (CH ₂ ) s—. In the PSA liquid crystal display element, Is preferably a compound in which at least one is a single bond, and both represent a single bond or one represents a single bond and the other represents an alkylene group having 1 to 8 carbon atoms or —O— (CH ₂ ) s—. preferable. In this case, an alkylene group having 1 to 4 carbon atoms is preferable, and s is preferably 1 to 4.

In the above general formula (Vb), Z ¹ represents —OCH ₂ —, —CH ₂ O—, —COO—, —OCO—, —CF ₂ O—, —OCF ₂ —, —CH ₂ CH ₂ —, — CF ₂ CF ₂ —, —CH═CH—COO—, —CH═CH—OCO—, —COO—CH═CH—, —OCO—CH═CH—, —COO—CH ₂ CH ₂ —, —OCO— CH ₂ CH ₂ —, —CH ₂ CH ₂ —COO—, —CH ₂ CH ₂ —OCO—, —COO—CH ₂ —, —OCO—CH ₂ —, —CH ₂ —COO—, —CH ₂ —OCO —, —CY ¹ ═CY ² —, —C≡C— or a single bond, —OCH ₂ —, —CH ₂ O—, —COO—, —OCO—, —CF ₂ O—, —OCF ₂ —, —CH ₂ CH ₂ —, —CF ₂ CF ₂ — or a single bond is preferred, and —COO -, -OCO- or a single bond is more preferable, and a single bond is particularly preferable.

In the general formula (Vb), C represents a 1,4-phenylene group, a trans-1,4-cyclohexylene group or a single bond in which any hydrogen atom may be substituted with a fluorine atom. -A phenylene group or a single bond is preferred.

When C represents a ring structure other than a single bond, Z ¹ is preferably a linking group other than a single bond. When C is a single bond, Z ¹ is preferably a single bond.

As described above, in the general formula (Vb), it is preferable that C represents a single bond and the ring structure is formed of two rings. Specific examples of the polymerizable compound having a ring structure include the following Compounds represented by formulas (V-1) to (V-6) are preferred, compounds represented by formulas (V-1) to (V-4) are particularly preferred, and compounds represented by formula (V-2) The compounds represented are most preferred.

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

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

The compound represented by the general formula (V) is preferably contained in an amount of 0.1 to 15% by weight, more preferably 0.1 to 10% by weight, based on the liquid crystal-containing polymerization composition. More preferably, the content is 1 to 8% by mass.

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

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

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

The liquid crystal display element of the present invention is a conventional liquid crystal display element by using a liquid crystal composition in combination with the following specific compound as a liquid crystal molecule and an alignment control layer formed from a specific polymerizable compound. Unlike the first substrate and the liquid crystal layer, and between the second substrate and the liquid crystal layer, the liquid crystal molecules are formed on the surface of the substrate when no voltage is applied, even if there is an alignment film. Is substantially perpendicular to the substrate. Then, the occurrence of image sticking is suppressed without deteriorating various properties such as dielectric anisotropy, viscosity, nematic phase upper limit temperature, rotational viscosity (γ ₁ ) and the like.

FIG. 4 is a partial cutout of FIG. The electrode A in the present invention has a fishbone pattern having branch portions, and the first substrate when the distance between adjacent branches of each branch in the fishbone pattern is S (μm). And a distance (d μm) between the second substrates satisfy the formula (1).
(D−0.6) /1.25 <S <(d + 1.1) /1.25 Formula (1)
Here, the upper limit value of α when S = (d−α) /1.25 is 0.6, 0.5 is preferable, 0.4 is preferable, 0.3 is preferable, and 0.2 Is preferable, 0.1 is preferable, and 0 is preferable. The lower limit is −1.1, −1.06 is preferable, −1.03 is preferable, −1.00 is preferable, −0.97 is preferable, −0.93 is preferable, and −0.9 is -0.87 is preferred, -0.83 is preferred, -0.8 is preferred, -0.77 is preferred, -0.73 is preferred, -0.7 is preferred, -0.67 is preferred -0.63, -0.6 is preferred, -0.57 is preferred, -0.53 is preferred, -0.5 is preferred, -0.47 is preferred, -0.43 is preferred, -0.4 is preferred.

¡By optimizing α, the transmittance of the liquid crystal display element can be improved. If S is outside the range defined in the present invention, it is not preferable from the viewpoint of transmittance, and if S is outside the range defined in the present invention, it is not preferable from the viewpoint of transmittance and response speed. S is preferably in the range of 1 to 4, and more preferably in the range of 1.5 to 3.3. d is preferably in the range of 0.7 to 3.6, preferably in the range of 1.0 to 3.6, and preferably in the range of 1.5 to 3.6. d is never less than 0.6.

The transmittance (T) is preferably larger in view of the characteristics of the liquid crystal display element, but is preferably 0.26 or more, preferably 0.27 or more, preferably 0.28 or more, and 0.29 or more from the viewpoint of human visual characteristics. Preferably, 0.30 or more is preferable. In particular, when used for a liquid crystal television or the like, it is preferably 0.28 or more.

Note that the cause of the decrease in contrast due to the decrease in transmittance due to the narrowing of the cell gap is considered to be complex, but in particular, it is caused by applying a voltage between the electrodes due to the narrowing of the cell gap, etc. The liquid crystal composition in the inter-substrate direction is affected by the fact that the potential surface becomes more complicated and is greatly affected by the electrode width and the interval thereof, and Δn of the liquid crystal composition, elastic constants K11 and K33, and the like. It is mentioned that the orientation state is greatly affected. This makes it necessary to satisfy a specific relationship between S and d. Moreover, since a specific physical property is requested | required also as a liquid-crystal composition, it is preferable that the liquid crystal compound which comprises this is also a specific combination.
<Method for manufacturing liquid crystal display element>
The liquid crystal display element 10 shown in FIG. 1 can be manufactured by the following method, for example.

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

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

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

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

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

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

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

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

The applied voltage may be alternating current or direct current.

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

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

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

Further, by irradiation with active energy rays, the two or more kinds of polymerizable compounds are preferentially polymerized with each other having similar structures to align liquid crystal molecules in the vicinity region of the substrate, and the direction of the pretilt. It is presumed that the orientation is controlled by defining the value in a predetermined direction.
(Liquid crystal composition)
The liquid crystal composition in the present invention contains one or more compounds represented by general formula (N-1), general formula (N-2), and general formula (N-3).

In the formula, R ^N11 , R ^N12 , R ^N21 , R ^N22 , R ^N31 and R ^N32 each independently represent an alkyl group having 1 to 8 carbon atoms, and one or two non-adjacent groups in the alkyl group The above —CH ₂ — may be independently substituted with —CH═CH—, —C≡C—, —O—, —CO—, —COO— or —OCO—,
A ^N11 , A ^N12 , A ^N21 , A ^N22 , A ^N31, and A ^N32 are each independently (a) a 1,4-cyclohexylene group (one —CH ₂ — or adjacent to each other in this group). And two or more —CH ₂ — may be replaced by —O—) and (b) a 1,4-phenylene group (one —CH═ present in this group or not adjacent 2 More than one -CH = may be replaced by -N =.)
(C) Naphthalene-2,6-diyl group, 1,2,3,4-tetrahydronaphthalene-2,6-diyl group or decahydronaphthalene-2,6-diyl group (naphthalene-2,6-diyl group or One —CH═ present in the 1,2,3,4-tetrahydronaphthalene-2,6-diyl group or two or more non-adjacent —CH═ may be replaced by —N═. )
The group (a), the group (b) and the group (c) may be each independently substituted with a cyano group, a fluorine atom or a chlorine atom,
Z ^N11 , Z ^N12 , Z ^N21 , Z ^N22 , Z ^N31 and Z ^N32 are each independently a single bond, —CH ₂ CH ₂ —, — (CH ₂ ) ₄ —, —OCH ₂ —, —CH ₂ O—. , —COO—, —OCO—, —OCF ₂ —, —CF ₂ O—, —CH═N—N═CH—, —CH═CH—, —CF═CF— or —C≡C—,
^XN21 represents a hydrogen atom or a fluorine atom,
T ^N31 represents —CH ₂ — or —O—.
n ^N11 , n ^N12 , n ^N21 , n ^N22 , n ^N31, and n ^N32 each independently represent an integer of 0 to 3, but n ^N11 + n ^N12 , n ^N21 + n ^N22, and n ^N31 + n ^N32 are each independently When there are a plurality of A ^N11 to A ^N32 and Z ^N11 to Z ^N32 , they may be the same or different.

The compounds represented by the general formulas (N-1), (N-2) and (N-3) are preferably compounds having a negative Δε and an absolute value larger than 3.

In the general formulas (N-1), (N-2) and (N-3), R ^N11 , R ^N12 , R ^N21 , R ^N22 , R ^N31 and R ^N32 each independently represent 1 to 8 carbon atoms. An alkyl group having 1 to 8 carbon atoms, an alkenyl group having 2 to 8 carbon atoms, or an alkenyloxy group having 2 to 8 carbon atoms, preferably an alkyl group having 1 to 5 carbon atoms, An alkoxy group having 1 to 5 carbon atoms, an alkenyl group having 2 to 5 carbon atoms or an alkenyloxy group having 2 to 5 carbon atoms is preferable, and an alkyl group having 1 to 5 carbon atoms or an alkenyl group having 2 to 5 carbon atoms is preferable. More preferably, an alkyl group having 2 to 5 carbon atoms or an alkenyl group having 2 to 3 carbon atoms is more preferable, and an alkenyl group having 3 carbon atoms (propenyl group) is particularly preferable.

Further, when the ring structure to which it is bonded is a phenyl group (aromatic), a linear alkyl group having 1 to 5 carbon atoms, a linear alkoxy group having 1 to 4 carbon atoms and carbon An alkenyl group having 4 to 5 atoms is preferable, and when the ring structure to which the alkenyl group is bonded is a saturated ring structure such as cyclohexane, pyran and dioxane, a linear alkyl group having 1 to 5 carbon atoms, a straight chain A straight-chain alkoxy group having 1 to 4 carbon atoms and a straight-chain alkenyl group having 2 to 5 carbon atoms are preferred. In order to stabilize the nematic phase, the total of carbon atoms and oxygen atoms, if present, is preferably 5 or less, and is preferably linear.

The alkenyl group is preferably selected from groups represented by any of the formulas (R1) to (R5). (The black dots in each formula represent carbon atoms in the ring structure.)

A ^N11 , A ^N12 , A ^N21 , A ^N22 , A ^N31, and A ^N32 are preferably aromatic when it is required to increase Δn independently, and in order to improve the response speed, fat Preferably a trans-1,4-cyclohexylene group, 1,4-phenylene group, 2-fluoro-1,4-phenylene group, 3-fluoro-1,4-phenylene group, 3,5 -Difluoro-1,4-phenylene group, 2,3-difluoro-1,4-phenylene group, 1,4-cyclohexenylene group, 1,4-bicyclo [2.2.2] octylene group, piperidine-1 , 4-diyl group, naphthalene-2,6-diyl group, decahydronaphthalene-2,6-diyl group or 1,2,3,4-tetrahydronaphthalene-2,6-diyl group Preferred, it is more preferable that represents the following structures,

More preferably, it represents a trans-1,4-cyclohexylene group or a 1,4-phenylene group.

^{^{^{^{Z N11, Z N12, Z N21}}}} , Z N22, Z N31 and ^{Z N32} _-CH 2 each _{independently} _{O -, - CF 2 O -} , - CH 2 CH 2 -, - CF 2 CF 2 - or a single bond preferably represents _{_{an, -CH 2 O -, - CH}} 2 CH 2 - or a single bond is more preferable, _-CH 2 O-or a single bond is particularly preferred.

^XN21 is preferably a fluorine atom.

T ^N31 is preferably —O—.

n ^N11 + n ^N12 , n ^N21 + n ^N22 and n ^N31 + n ^N32 are preferably 1 or 2, a combination in which n ^N11 is 1 and n ^N12 is 0, a combination in which n ^N11 is 2 and n ^N12 is 0, n ^A combination in which ^N11 is 1 and n ^N12 is 1, a combination in which n ^N11 is 2 and n ^N12 is 1, a combination in which n ^N21 is 1 and n ^N22 is 0, n ^N21 is 2 and n ^N22 is n A combination in which n ^N31 is 1 and n ^N32 is 0, and a combination in which n ^N31 is 2 and n ^N32 is 0 are preferable.

The lower limit of the preferable content of the compound represented by the general formula (N-1) with respect to the total amount of the liquid crystal composition of the present invention (the total amount of liquid crystal compounds contained in the liquid crystal composition; hereinafter the same) is 1% by mass (hereinafter referred to simply as%), 10%, 20%, 30%, 40%, 50%, 55%, 60% Yes, 65%, 70%, 75%, 80%. The upper limit of the preferred content is 95%, 85%, 75%, 65%, 55%, 45%, 35%, 25%, 20% It is.

The lower limit of the preferable content of the compound represented by the general formula (N-2) with respect to the total amount of the liquid crystal composition of the present invention is 1% by mass (hereinafter, mass% is simply expressed as%), 10%, 20%, 30%, 40%, 50%, 55%, 60%, 65%, 70%, 75%, 80%. The upper limit of the preferred content is 95%, 85%, 75%, 65%, 55%, 45%, 35%, 25%, 20% It is.

The lower limit of the preferable content of the compound represented by the general formula (N-3) with respect to the total amount of the liquid crystal composition of the present invention is 1% by mass (hereinafter, mass% is simply expressed as%). 10%, 20%, 30%, 40%, 50%, 55%, 60%, 65%, 70%, 75%, 80%. The upper limit of the preferred content is 95%, 85%, 75%, 65%, 55%, 45%, 35%, 25%, 20% It is.

When the liquid crystal composition of the present invention maintains a low viscosity and a composition having a high response speed is required, the above lower limit value is preferably low and the upper limit value is preferably low. Furthermore, when the composition of the present invention keeps Tni high and a composition having good temperature stability is required, the above lower limit value is preferably low and the upper limit value is preferably low. When it is desired to increase the dielectric anisotropy in order to keep the driving voltage low, it is preferable that the above lower limit value is increased and the upper limit value is high.

The compound represented by the general formula (N-1) is preferably a compound selected from the group of compounds represented by the general formulas (N-1-1) to (N-1-21).

The compound represented by the general formula (N-1-1) is the following compound.

( ^Wherein , R ^N111 and R ^N112 each independently represent the same meaning as R ^N11 and R ^N12 in formula (N-1)).
R ^N111 is preferably an alkyl group having 1 to 5 carbon atoms or an alkenyl group having 2 to 5 carbon atoms, and preferably a propyl group or a pentyl group. ^RN112 is preferably an alkyl group having 1 to 5 carbon atoms, an alkenyl group having 4 to 5 carbon atoms, or an alkoxy group having 1 to 4 carbon atoms, and preferably an ethoxy group or a butoxy group.

The compound represented by the general formula (N-1-1) can be used alone, or two or more compounds can be used in combination. There are no particular restrictions on the types of compounds that can be combined, but they are used in appropriate combinations according to the required properties such as solubility at low temperatures, transition temperatures, electrical reliability, and birefringence. The kind of the compound used is, for example, one kind as one embodiment of the present invention, two kinds, three kinds, four kinds, and five kinds or more.

It is preferable to set a higher content in the case of emphasizing improved [Delta] [epsilon], to emphasize the solubility at low temperature highly effective when larger amount to set the content, when importance is attached to T _NI content Setting to a small value is highly effective. Furthermore, when improving dripping marks and image sticking characteristics, it is preferable to set the content range in the middle.

The lower limit of the preferable content of the compound represented by the formula (N-1-1) with respect to the total amount of the liquid crystal composition of the present invention is 5 mass% (hereinafter, mass% is simply expressed as%). 10%, 13%, 15%, 17%, 20%, 23%, 25%, 27%, 30%, 33% 35%. The upper limit of the preferable content is 50%, 40%, 38%, 35%, 33%, 30%, and 30% with respect to the total amount of the liquid crystal composition of the present invention. 28%, 25%, 23%, 20%, 18%, 15%, 13%, 10%, 8%, 7%, 6%, 5%, 3%.

Further, the compound represented by the general formula (N-1-1) is a compound selected from the group of compounds represented by the formula (N-1-1.1) to the formula (N-1-1.14). Preferably, it is a compound represented by the formulas (N-1-1.1) to (N-1-1.4), and the formula (N-1-1.1) and the formula (N The compound represented by -1-1.3) is preferable.

The compounds represented by the formulas (N-1-1.1) to (N-1-1.4) can be used alone or in combination, but the liquid crystal composition of the present invention The lower limit of the preferred content of these compounds alone or with respect to the total amount is 5% by mass (hereinafter, mass% is simply expressed as%), 10%, 13%, and 15%. 17%, 20%, 23%, 25%, 27%, 30%, 33%, and 35%. The upper limit of the preferable content is 50%, 40%, 38%, 35%, 33%, 30%, and 30% with respect to the total amount of the liquid crystal composition of the present invention. 28%, 25%, 23%, 20%, 18%, 15%, 13%, 10%, 8%, 7%, 6%, 5%, 3%.

The compound represented by the general formula (N-1-2) is the following compound.

(In the formula, R ^N121 and R ^N122 each independently represent the same meaning as R ^N11 and R ^N12 in formula (N-1)).
^RN121 is preferably an alkyl group having 1 to 5 carbon atoms or an alkenyl group having 2 to 5 carbon atoms, and preferably an ethyl group, a propyl group, a butyl group or a pentyl group. ^RN122 is preferably an alkyl group having 1 to 5 carbon atoms, an alkenyl group having 4 to 5 carbon atoms, or an alkoxy group having 1 to 4 carbon atoms, and includes a methyl group, a propyl group, a methoxy group, an ethoxy group, or a propoxy group. preferable.

The compound represented by the general formula (N-1-2) can be used alone, or two or more compounds can be used in combination. There are no particular restrictions on the types of compounds that can be combined, but they are used in appropriate combinations according to the required properties such as solubility at low temperatures, transition temperatures, electrical reliability, and birefringence. The kind of the compound used is, for example, one kind as one embodiment of the present invention, two kinds, three kinds, four kinds, and five kinds or more.

When emphasizing the improvement of Δε, it is preferable to set the content higher. When emphasizing the solubility at low temperature, it is more effective to set the content lower. When emphasizing T _NI , the content is preferable. Setting a large number of is highly effective. Furthermore, when improving dripping marks and image sticking characteristics, it is preferable to set the content range in the middle.

The lower limit of the preferable content of the compound represented by the formula (N-1-2) with respect to the total amount of the liquid crystal composition of the present invention is 5% by mass (hereinafter, mass% is simply expressed as%). 7%, 10%, 13%, 15%, 17%, 20%, 23%, 25%, 27%, 30% 33%, 35%, 37%, 40%, 42%. The upper limit of the preferred content is 50%, 48%, 45%, 43%, 40%, 38%, with respect to the total amount of the liquid crystal composition of the present invention, 35%, 33%, 30%, 28%, 25%, 23%, 20%, 18%, 15%, 13%, 10%, 8%, 7%, 6%, 5%.

Further, the compound represented by the general formula (N-1-2) is a compound selected from the group of compounds represented by the formula (N-1-2.1) to the formula (N-1-2.13). Preferably, the formula (N-1-2.3) to the formula (N-1-2.7), the formula (N-1-2.10), the formula (N-1-2.11) and the formula The compound represented by (N-1-2.13) is preferable, and when importance is placed on the improvement of Δε, the formula (N-1-2.3) to the formula (N-1-2.7) in the compounds _represented, when emphasizing improvements in _{T NI} formula (N-1-2.10), formula (N-1-2.11) and formula (N-1-2.13) It is preferable that it is a compound represented by these.

The compounds represented by the formulas (N-1-2.1) to (N-1-2.13) can be used alone or in combination. The lower limit of the preferred content of these compounds alone or with respect to the total amount of the product is 5% by mass (hereinafter, mass% is simply expressed as%), 10%, 13%, 15% Yes, 17%, 20%, 23%, 25%, 27%, 30%, 33%, 35%. The upper limit of the preferable content is 50%, 40%, 38%, 35%, 33%, 30%, and 30% with respect to the total amount of the liquid crystal composition of the present invention. 28%, 25%, 23%, 20%, 18%, 15%, 13%, 10%, 8%, 7%, 6%, 5%, 3%.

The compound represented by the general formula (N-1-3) is the following compound.

( ^Wherein , R ^N131 and R ^N132 each independently represent the same meaning as R ^N11 and R ^N12 in formula (N-1)).
R ^N131 is preferably an alkyl group having 1 to 5 carbon atoms or an alkenyl group having 2 to 5 carbon atoms, and preferably an ethyl group, a propyl group or a butyl group. R ^N132 is preferably an alkyl group having 1 to 5 carbon atoms, an alkenyl group having 4 to 5 carbon atoms, or an alkoxy group having 1 to 4 carbon atoms, and preferably an ethoxy group, a propoxy group, or a butoxy group.

The compound represented by the general formula (N-1-3) can be used alone, or two or more compounds can be used in combination. There are no particular restrictions on the types of compounds that can be combined, but they are used in appropriate combinations according to the required properties such as solubility at low temperatures, transition temperatures, electrical reliability, and birefringence. The kind of the compound used is, for example, one kind as one embodiment of the present invention, two kinds, three kinds, four kinds, and five kinds or more.

It is preferable to set a higher content in the case of emphasizing improved [Delta] [epsilon], to emphasize the solubility at low temperature highly effective when larger amount to set the content, when importance is attached to T _NI content Highly effective when set to. Furthermore, when improving dripping marks and image sticking characteristics, it is preferable to set the content range in the middle.

The lower limit of the preferable content of the compound represented by the formula (N-1-3) with respect to the total amount of the liquid crystal composition of the present invention is 5% by mass (hereinafter, mass% is simply expressed as%). 10%, 13%, 15%, 17%, 20%. The upper limit of the preferable content is 35%, 30%, 28%, 25%, 23%, 20%, and 18% with respect to the total amount of the composition of the present invention. %, 15%, and 13%.

Further, the compound represented by the general formula (N-1-3) is a compound selected from the group of compounds represented by the formula (N-1-3.1) to the formula (N-1-3.11). Preferably, it is a compound represented by the formulas (N-1-3.1) to (N-1-3.7), and the formula (N-1-3.1) and the formula (N -1-3.2), formula (N-1-3.3), formula (N-1-3.4) and compounds represented by formula (N-1-3.6) are preferred.

The compounds represented by formula (N-1-3.1) to formula (N-1-3.4) and formula (N-1-3.6) may be used alone or in combination. Is possible, but the combination of formula (N-1-3.1) and formula (N-1-3.2), formula (N-1-3.3), formula (N-1-3.4) ) And a combination of two or three selected from formula (N-1-3.6) are preferred. The lower limit of the preferred content of these compounds alone or with respect to the total amount of the liquid crystal composition of the present invention is 5% by mass (hereinafter, mass% is simply expressed as%), 10%, and 13%. Yes, 15%, 17%, 20%. The upper limit of the preferable content is 35%, 30%, 28%, 25%, 23%, and 20% with respect to the total amount of the liquid crystal composition of the present invention. 18%, 15% and 13%.

The compound represented by the general formula (N-1-4) is the following compound.

^{(Wherein, R N141} and ^{R N142} each independently represents the same meaning as ^{R N11} and ^{R N12} in the general formula (N-1).)
R ^N141 and ^{R N142} are each independently an alkyl group having 1 to 5 carbon atoms, an alkenyl group or an alkoxy group having 1 to 4 carbon atoms carbon atoms 4-5 preferably a methyl group, a propyl group, an ethoxy Group or butoxy group is preferred.

The compound represented by the general formula (N-1-4) can be used alone, or two or more compounds can be used in combination. There are no particular restrictions on the types of compounds that can be combined, but they are used in appropriate combinations according to the required properties such as solubility at low temperatures, transition temperatures, electrical reliability, and birefringence. The kind of the compound used is, for example, one kind as one embodiment of the present invention, two kinds, three kinds, four kinds, and five kinds or more.

The lower limit of the preferable content of the compound represented by the formula (N-1-4) with respect to the total amount of the liquid crystal composition of the present invention is 3% by mass (hereinafter, mass% is simply expressed as%). 5%, 7%, 10%, 13%, 15%, 17%, 20%. The upper limit of the preferable content is 35%, 30%, 28%, 25%, 23%, and 20% with respect to the total amount of the liquid crystal composition of the present invention. 18%, 15%, 13%, 11%, 10%, 8%.

Further, the compound represented by the general formula (N-1-4) is a compound selected from the group of compounds represented by the formula (N-1-4.1) to the formula (N-1-4.14). Preferably, it is a compound represented by the formulas (N-1-4.1) to (N-1-4.4), and the formula (N-1-4.1) and the formula (N The compound represented by -1-4.2) is preferable.

The compounds represented by the formulas (N-1-4.1) to (N-1-4.4) can be used alone or in combination, but the liquid crystal composition of the present invention The lower limit of the preferable content of these compounds alone or with respect to the total amount of 3% is 3% by mass (hereinafter, mass% is simply expressed as%), 5%, 7%, and 10%. 13%, 15%, 17%, 20%. The upper limit of the preferable content is 35%, 30%, 28%, 25%, 23%, and 20% with respect to the total amount of the liquid crystal composition of the present invention. 18%, 15%, 13%, 11%, 10%, 8%.

The compound represented by the general formula (N-1-5) is the following compound.

(In the formula, R ^N151 and R ^N152 each independently represent the same meaning as R ^N11 and R ^N12 in formula (N-1).)
R ^N151 and R ^N152 are each independently an alkyl group having 1 to 5 carbon atoms, an alkenyl group having 4 to 5 carbon atoms, or an alkoxy group having 1 to 4 carbon atoms, and preferably an ethyl group, a propyl group, or a butyl group. Is preferred.

The compound represented by the general formula (N-1-5) can be used alone, or two or more compounds can be used in combination. There are no particular restrictions on the types of compounds that can be combined, but they are used in appropriate combinations according to the required properties such as solubility at low temperatures, transition temperatures, electrical reliability, and birefringence. The kind of the compound used is, for example, one kind as one embodiment of the present invention, two kinds, three kinds, four kinds, and five kinds or more.

The lower limit of the preferable content of the compound represented by the formula (N-1-5) with respect to the total amount of the liquid crystal composition of the present invention is 5% by mass (hereinafter, mass% is simply expressed as%). 8%, 10%, 13%, 15%, 17%, 20%. The upper limit of the preferable content is 35%, 33%, 30%, 28%, 25%, and 23% with respect to the total amount of the liquid crystal composition of the present invention, 20%, 18%, 15%, 13%.

Further, the compound represented by the general formula (N-1-5) is a compound selected from the group of compounds represented by the formula (N-1-5.1) to the formula (N-1-5.6). It is preferable that a compound represented by the formula (N-1-3.2 and the formula (N-1-3.4) is preferable.

The compounds represented by formula (N-1-3.2) and formula (N-1-3.4) can be used alone or in combination, but the liquid crystal composition of the invention The lower limit value of the preferred content of these compounds alone or with respect to the total amount of is 5% by mass (hereinafter, mass% is simply expressed as%), 8%, 10%, and 13%. 15%, 17%, and 20% The upper limit of the preferred content is 35%, 33%, and 30% with respect to the total amount of the liquid crystal composition of the present invention. 28%, 25%, 23%, 20%, 18%, 15%, 13%.

The compound represented by the general formula (N-1-10) is the following compound.

(In the formula, R ^N1101 and R ^N1102 each independently represent the same meaning as R ^N11 and R ^N12 in formula (N-1).)
R ^N1101 is preferably an alkyl group having 1 to 5 carbon atoms or an alkenyl group having 2 to 5 carbon atoms, and preferably an ethyl group, a propyl group or a butyl group. R ^N1102 is preferably an alkyl group having 1 to 5 carbon atoms, an alkenyl group having 4 to 5 carbon atoms, or an alkoxy group having 1 to 4 carbon atoms, and preferably an ethoxy group, a propoxy group, or a butoxy group.

The compound represented by the general formula (N-1-10) can be used alone, or two or more compounds can be used in combination. There are no particular restrictions on the types of compounds that can be combined, but they are used in appropriate combinations according to the required properties such as solubility at low temperatures, transition temperatures, electrical reliability, and birefringence. The kind of the compound used is, for example, one kind as one embodiment of the present invention, two kinds, three kinds, four kinds, and five kinds or more.

The lower limit of the preferable content of the compound represented by the formula (N-1-10) with respect to the total amount of the liquid crystal composition of the present invention is 5% by mass (hereinafter, mass% is simply expressed as%). 10%, 13%, 15%, 17%, 20%. The upper limit of the preferable content is 35%, 30%, 28%, 25%, 23%, 20%, and 18% with respect to the total amount of the composition of the present invention. %, 15%, and 13%.

Further, the compound represented by the general formula (N-1-10) is a compound selected from the group of compounds represented by the formula (N-1-10.1) to the formula (N-1-10.11). Preferably, it is a compound represented by the formulas (N-1-10.1) to (N-1-10.5), and the formula (N-1-10.1) and the formula (N The compound represented by (1-10.2) is preferable.

The compounds represented by the formula (N-1-10.1) and the formula (N-1-10.2) can be used alone or in combination. The lower limit of the preferred content of these compounds alone or with respect to the total amount of the product is 5% by mass (hereinafter, mass% is simply expressed as%), 10%, 13%, 15% Yes, 17%, 20%. The upper limit of the preferable content is 35%, 30%, 28%, 25%, 23%, and 20% with respect to the total amount of the liquid crystal composition of the present invention. 18%, 15% and 13%.

The compound represented by the general formula (N-1-11) is the following compound.

(In the formula, R ^N1111 and R ^N1112 each independently represent the same meaning as R ^N11 and R ^N12 in formula (N-1).)
R ^N1111 is preferably an alkyl group having 1 to 5 carbon atoms or an alkenyl group having 2 to 5 carbon atoms, and preferably an ethyl group, a propyl group or a butyl group. R ^N1112 is preferably an alkyl group having 1 to 5 carbon atoms, an alkenyl group having 4 to 5 carbon atoms or an alkoxy group having 1 to 4 carbon atoms, and preferably an ethoxy group, a propoxy group or a butoxy group.

The compound represented by the general formula (N-1-11) can be used alone, or two or more compounds can be used in combination. There are no particular restrictions on the types of compounds that can be combined, but they are used in appropriate combinations according to the required properties such as solubility at low temperatures, transition temperatures, electrical reliability, and birefringence. The kind of the compound used is, for example, one kind as one embodiment of the present invention, two kinds, three kinds, four kinds, and five kinds or more.

The lower limit of the preferable content of the compound represented by the formula (N-1-11) with respect to the total amount of the liquid crystal composition of the present invention is 5% by mass (hereinafter, mass% is simply expressed as%). 10%, 13%, 15%, 17%, 20%. The upper limit of the preferable content is 35%, 30%, 28%, 25%, 23%, and 20% with respect to the total amount of the liquid crystal composition of the present invention. 18%, 15% and 13%.

Further, the compound represented by the general formula (N-1-11) is a compound selected from the group of compounds represented by the formula (N-1-11.1) to the formula (N-1-11.15). Preferably, it is a compound represented by the formulas (N-1-11.1) to (N-1-11.15), and is preferably a compound represented by the formula (N-1-11.2) or the formula (N-- The compound represented by 1-11.4) is preferable.

The compounds represented by the formulas (N-1-11.2 and (N-1-11.4) can be used alone or in combination, but the liquid crystal composition of the present invention The lower limit of the preferred content of these compounds alone or with respect to the total amount is 5% by mass (hereinafter, mass% is simply expressed as%), 10%, 13%, and 15%. The upper limit of the preferable content is 35%, 30%, 28%, and 25% with respect to the total amount of the liquid crystal composition of the present invention. 23%, 20%, 18%, 15%, 13%.

General formula (N-1), general formula (N-2), and general formula (N-3) with respect to the total amount of the liquid crystal composition of the present invention (total amount of liquid crystal compounds contained in the liquid crystal composition) The total amount of the compound represented by the formula is preferably 10 to 90% by mass, more preferably 20 to 80% by mass, further preferably 20 to 70% by mass, further preferably 20 to 60% by mass, Is more preferably 55 to 55% by mass, further preferably 25 to 55% by mass, and particularly preferably 30 to 55% by mass.

More specifically, the total amount of the compounds represented by the general formula (N-1), the general formula (N-2), and the general formula (N-3) is a lower limit in the liquid crystal composition. 1% by mass (hereinafter, mass% is simply expressed as%), preferably 5% or more, preferably 10% or more, preferably 13% or more, 15 %, Preferably 18% or more, preferably 20% or more, preferably 23% or more, preferably 25% or more, 28% or more. 30% or more, preferably 33% or more, preferably 35% or more, preferably 38% or more, preferably 40% or more Masui. Further, the upper limit value is preferably 95% or less, preferably 90% or less, preferably 88% or less, preferably 85% or less, and preferably 83% or less. 80% or less, preferably 78% or less, preferably 75% or less, preferably 73% or less, preferably 70% or less, preferably 68% or less Preferably 65% or less, preferably 63% or less, preferably 60% or less, preferably 55% or less, preferably 50% or less, It is preferable to contain 40% or less.

The liquid crystal composition in the present invention preferably contains one or more compounds represented by the general formula (L). The compound represented by the general formula (L) corresponds to a dielectrically neutral compound (Δε value is −2 to 2).

(Wherein R ^L1 and R ^L2 each independently represents an alkyl group having 1 to 8 carbon atoms, and one or two or more non-adjacent —CH ₂ — in the alkyl group are each independently Optionally substituted by —CH═CH—, —C≡C—, —O—, —CO—, —COO— or —OCO—,
n ^L1 represents 0, 1, 2 or 3,
A ^L1 , A ^L2 and A ^L3 each independently represent (a) a 1,4-cyclohexylene group (one —CH ₂ — present in the group or two or more —CH ₂ — not adjacent to each other). May be replaced by —O—) and (b) a 1,4-phenylene group (one —CH═ present in this group or two or more —CH═ not adjacent to each other —N May be replaced by =.)
(C) Naphthalene-2,6-diyl group, 1,2,3,4-tetrahydronaphthalene-2,6-diyl group or decahydronaphthalene-2,6-diyl group (naphthalene-2,6-diyl group or One —CH═ present in the 1,2,3,4-tetrahydronaphthalene-2,6-diyl group or two or more non-adjacent —CH═ may be replaced by —N═. )
The group (a), the group (b) and the group (c) may be each independently substituted with a cyano group, a fluorine atom or a chlorine atom,
Z ^L1 and Z ^L2 are each independently 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 n ^L1 is 2 or 3, and a plurality of A ^L2 are present, they may be the same or different, and when n ^L1 is 2 or 3, and a plurality of Z ^L3 are present, May be the same or different, but excludes compounds represented by general formula (N-1), general formula (N-2) and general formula (N-3). )
Although the compound represented by general formula (L) may be used independently, it can also be used in combination. There are no particular restrictions on the types of compounds that can be combined, but they are used in appropriate combinations according to desired properties such as solubility at low temperatures, transition temperatures, electrical reliability, and birefringence. The kind of the compound used is, for example, one kind as one embodiment of the present invention. Alternatively, in another embodiment of the present invention, there are two types, three types, four types, five types, six types, seven types, eight types, nine types, 10 types, More than types.

In the composition of the present invention, the content of the compound represented by the general formula (L) is low-temperature solubility, transition temperature, electrical reliability, birefringence, process compatibility, dripping marks, image sticking, It is necessary to appropriately adjust according to required performance such as dielectric anisotropy.

The lower limit of the preferable content of the compound represented by the formula (L) with respect to the total amount of the liquid crystal composition of the present invention is 1% by mass (hereinafter, mass% is simply expressed as%), which is 10%. Yes, 20%, 30%, 40%, 50%, 55%, 60%, 65%, 70%, 75%, 80% is there. The upper limit of the preferable content is 95%, 85%, 75%, 65%, 55%, 45%, 35%, and 25%.

When the viscosity of the composition of the present invention is kept low and a composition having a high response speed is required, the above lower limit value is preferably high and the upper limit value is preferably high. Furthermore, when the composition of the present invention maintains a high Tni and requires a composition having good temperature stability, the above lower limit value is preferably high and the upper limit value is preferably high. Further, when it is desired to increase the dielectric anisotropy in order to keep the driving voltage low, it is preferable that the above lower limit value is lowered and the upper limit value is low.

When importance is attached to reliability, R ^L1 and R ^L2 are preferably both alkyl groups, and when importance is placed on reducing the volatility of the compound, it is preferably an alkoxy group, and importance is placed on viscosity reduction. In this case, at least one is preferably an alkenyl group.

R ^L1 and R ^L2 are each a linear alkyl group having 1 to 5 carbon atoms or a linear alkyl group having 1 to 4 carbon atoms when the ring structure to which R ^L1 is bonded is a phenyl group (aromatic). When the ring structure to which it is bonded is a saturated ring structure such as cyclohexane, pyran and dioxane, a straight-chain C 1-5 carbon atom is preferred. Alkyl groups, linear alkoxy groups having 1 to 4 carbon atoms and linear alkenyl groups having 2 to 5 carbon atoms are preferred. In order to stabilize the nematic phase, the total of carbon atoms and oxygen atoms, if present, is preferably 5 or less, and is preferably linear.

n ^L1 is preferably 0 when importance is attached to the response speed, 2 or 3 is preferred for improving the upper limit temperature of the nematic phase, and 1 is preferred for balancing these. In order to satisfy the properties required for the composition, it is preferable to combine compounds having different values.

A ^L1 , A ^L2, and A ^L3 are preferably aromatic when it is required to increase Δn, and are preferably aliphatic for improving the response speed, and are each independently trans- 1,4-cyclohexylene group, 1,4-phenylene group, 2-fluoro-1,4-phenylene group, 3-fluoro-1,4-phenylene group, 3,5-difluoro-1,4-phenylene group 1,4-cyclohexenylene group, 1,4-bicyclo [2.2.2] octylene group, piperidine-1,4-diyl group, naphthalene-2,6-diyl group, decahydronaphthalene-2,6 -It preferably represents a diyl group or a 1,2,3,4-tetrahydronaphthalene-2,6-diyl group, and more preferably represents the following structure:

Z ^L1 and Z ^L2 are preferably single bonds when the response speed is important.

The compound represented by the general formula (L) is preferably a compound selected from the group of compounds represented by the general formulas (L-1) to (L-7).

The compound represented by the general formula (L-1) is the following compound.

(In the formula, R ^L11 and R ^L12 each independently represent the same meaning as R ^L1 and R ^L2 in the general formula (L).)
R ^L11 and R ^L12 are preferably a linear alkyl group having 1 to 5 carbon atoms, a linear alkoxy group having 1 to 4 carbon atoms, and a linear alkenyl group having 2 to 5 carbon atoms. .

The compound represented by the general formula (L-1) can be used alone, or two or more compounds can be used in combination. There are no particular restrictions on the types of compounds that can be combined, but they are used in appropriate combinations according to the required properties such as solubility at low temperatures, transition temperatures, electrical reliability, and birefringence. The kind of the compound used is, for example, one kind as one embodiment of the present invention, two kinds, three kinds, four kinds, and five kinds or more.

The lower limit of the preferable content is 1% by mass (hereinafter, mass% is simply expressed as%), 2%, 3%, and 5% with respect to the total amount of the liquid crystal composition of the present invention. Yes, 7%, 10%, 15%, 20%, 25%, 30%, 35%, 40%, 45%, 50% Yes, 55%. The upper limit of the preferable content is 95%, 90%, 85%, 80%, 75%, 70%, 65%, based on the total amount of the composition of the present invention. %, 60%, 55%, 50%, 45%, 40%, 35%, 30%, 25%.

When the viscosity of the composition of the present invention is kept low and a composition having a high response speed is required, the above lower limit value is preferably high and the upper limit value is preferably high. Furthermore, when the composition of the present invention requires a high Tni and a composition having good temperature stability, it is preferable that the lower limit value is moderate and the upper limit value is moderate. When it is desired to increase the dielectric anisotropy in order to keep the driving voltage low, it is preferable that the lower limit value is low and the upper limit value is low.

The compound represented by the general formula (L-1) is preferably a compound selected from the group of compounds represented by the general formula (L-1-1).

(Wherein R ^L12 represents the same meaning as in general formula (L-1).)
The compound represented by the general formula (L-1-1) is a compound selected from the group of compounds represented by the formula (L-1-1.1) to the formula (L-1-1.3). And is preferably a compound represented by formula (L-1-1.2) or formula (L-1-1.3), and particularly represented by formula (L-1-1.3). It is preferable that it is a compound.

The lower limit of the preferable content of the compound represented by the formula (L-1-1.3) with respect to the total amount of the liquid crystal composition of the present invention is 1% by mass (hereinafter, the mass% is simply expressed as%). 2% 3% 5% 7% 10% The upper limit of the preferable content is 20%, 15%, 13%, 10%, 8%, 7%, and 6% with respect to the total amount of the composition of the present invention. %, 5%, 3%.

The compound represented by the general formula (L-1) is preferably a compound selected from the group of compounds represented by the general formula (L-1-2).

(Wherein R ^L12 represents the same meaning as in general formula (L-1).)
The lower limit of the preferable content of the compound represented by the formula (L-1-2) with respect to the total amount of the liquid crystal composition of the present invention is 1% by mass (hereinafter, mass% is simply expressed as%). 5%, 10%, 15%, 17%, 20%, 23%, 25%, 27%, 30%, 35% . The upper limit of the preferable content is 60%, 55%, 50%, 45%, 42%, 40%, and 38% with respect to the total amount of the composition of the present invention. %, 35%, 33%, and 30%.

Further, the compound represented by the general formula (L-1-2) is a compound selected from the group of compounds represented by the formula (L-1-2.1) to the formula (L-1-2.4). Preferably, it is a compound represented by the formula (L-1-2.2) to the formula (L-1-2.4). In particular, the compound represented by the formula (L-1-2.2) is preferable because the response speed of the composition of the present invention is particularly improved. When obtaining Tni higher than the response speed, it is preferable to use a compound represented by the formula (L-1-2.3) or the formula (L-1-2.4). The content of the compounds represented by formula (L-1-2.3) and formula (L-1-2.4) is not preferably 30% by mass or more in order to improve the solubility at low temperatures. .

The lower limit of the preferable content of the compound represented by the formula (L-1-2.2) with respect to the total amount of the liquid crystal composition of the present invention is 10% by mass (hereinafter, mass% is simply expressed as%). 15%, 18%, 20%, 23%, 25%, 27%, 30%, 33%, 35%, 38% And 40%. The upper limit of the preferable content is 60%, 55%, 50%, 45%, 43%, 40%, and 38% with respect to the total amount of the composition of the present invention. %, 35%, 32%, 30%, 27%, 25%, and 22%.

The preferred total content of the compound represented by the formula (L-1-1.3) and the compound represented by the formula (L-1-2.2) with respect to the total amount of the liquid crystal composition of the present invention The lower limit is 10% by mass (hereinafter, mass% is simply expressed as%), 15%, 20%, 25%, 27%, 30%, and 35%. 40%. The upper limit of the preferable content is 60%, 55%, 50%, 45%, 43%, 40%, and 38% with respect to the total amount of the composition of the present invention. %, 35%, 32%, 30%, 27%, 25%, and 22%.

The compound represented by the general formula (L-1) is preferably a compound selected from the group of compounds represented by the general formula (L-1-3).

(Wherein R ^L13 and R ^L14 each independently represents an alkyl group having 1 to 8 carbon atoms or an alkoxy group having 1 to 8 carbon atoms.)
R ^L13 and R ^L14 are preferably a linear alkyl group having 1 to 5 carbon atoms, a linear alkoxy group having 1 to 4 carbon atoms, and a linear alkenyl group having 2 to 5 carbon atoms. .

The lower limit of the preferable content of the compound represented by the formula (L-1-3) with respect to the total amount of the liquid crystal composition of the present invention is 1% by mass (hereinafter, mass% is simply expressed as%). 5%, 10%, 13%, 15%, 17%, 20%, 23%, 25%, 30%. The upper limit of the preferable content is 60%, 55%, 50%, 45%, 40%, 37%, and 35% with respect to the total amount of the composition of the present invention. %, 33%, 30%, 27%, 25%, 23%, 23%, 20%, 17%, 15%, 13%, 10% %.
Further, the compound represented by the general formula (L-1-3) is a compound selected from the group of compounds represented by the formula (L-1-3.1) to the formula (L-1-3.12). Preferably, it is a compound represented by formula (L-1-3.1), formula (L-1-3.3) or formula (L-1-3.4). In particular, the compound represented by the formula (L-1-3.1) is preferable because the response speed of the composition of the present invention is particularly improved. Further, when obtaining Tni higher than the response speed, the equation (L-1-3.3), the equation (L-1-3.4), the equation (L-1-3.11), and the equation (L− It is preferable to use a compound represented by 1-3.12). Sum of compounds represented by formula (L-1-3.3), formula (L-1-3.4), formula (L-1-3.11) and formula (L-1-3.12) The content of is not preferably 20% by mass or more in order to improve the solubility at low temperatures.

The lower limit of the preferable content of the compound represented by the formula (L-1-3.1) with respect to the total amount of the liquid crystal composition of the present invention is 1% by mass (hereinafter, the mass% is simply expressed as%). 2%, 3%, 5%, 7%, 10%, 13%, 15%, 18%, and 20%. The upper limit of the preferable content is 20%, 17%, 15%, 13%, 10%, 8%, and 7% with respect to the total amount of the composition of the present invention. % And 6%.

The compound represented by the general formula (L-1) is preferably a compound selected from the group of compounds represented by the general formula (L-1-4) and / or (L-1-5).

(In the formula, R ^L15 and R ^L16 each independently represent an alkyl group having 1 to 8 carbon atoms or an alkoxy group having 1 to 8 carbon atoms.)
R ^L15 and R ^L16 are preferably a linear alkyl group having 1 to 5 carbon atoms, a linear alkoxy group having 1 to 4 carbon atoms, and a linear alkenyl group having 2 to 5 carbon atoms. .

The lower limit of the preferable content of the compound represented by the formula (L-1-4) with respect to the total amount of the liquid crystal composition of the present invention is 1% by mass (hereinafter, mass% is simply expressed as%). 5%, 10%, 13%, 15%, 17%, 20%. The upper limit of the preferable content is 25%, 23%, 20%, 17%, 15%, 13%, and 10% with respect to the total amount of the composition of the present invention. %.

The lower limit of the preferable content of the compound represented by the formula (L-1-5) with respect to the total amount of the liquid crystal composition of the present invention is 1% by mass (hereinafter, mass% is simply expressed as%). 5%, 10%, 13%, 15%, 17%, 20%. The upper limit of the preferable content is 25%, 23%, 20%, 17%, 15%, 13%, and 10% with respect to the total amount of the composition of the present invention. %.

Furthermore, the compounds represented by the general formulas (L-1-4) and (L-1-5) are represented by the formulas (L-1-4.1) to (L-1-5.3). And a compound represented by the formula (L-1-4.2) or the formula (L-1-5.2) is preferable.

The lower limit of the preferable content of the compound represented by the formula (L-1-4.2) with respect to the total amount of the liquid crystal composition of the present invention is 1% by mass (hereinafter, the mass% is simply expressed as%). 2%, 3%, 5%, 7%, 10%, 13%, 15%, 18%, and 20%. The upper limit of the preferable content is 20%, 17%, 15%, 13%, 10%, 8%, and 7% with respect to the total amount of the composition of the present invention. % And 6%.

Formula (L-1-1.3), Formula (L-1-2.2), Formula (L-1-3.1), Formula (L-1-3.3), Formula (L-1- 3.4), it is preferable to combine two or more compounds selected from the compounds represented by formula (L-1-3.11) and formula (L-1-3.12). -1.3), formula (L-1-2.2), formula (L-1-3.1), formula (L-1-3.3), formula (L-1-3.4) and It is preferable to combine two or more compounds selected from the compounds represented by formula (L-1-4.2), and the lower limit of the preferable content of the total content of these compounds is the liquid crystal composition of the present invention. 1% by mass (hereinafter referred to simply as%), 2%, 3%, 5%, 7%, 10% with respect to the total amount of the product, 13% %, 15%, 1 %, 20%, 23%, 25%, 27%, 30%, 33%, 35%, and the upper limit of the liquid crystal composition of the present invention 80%, 70%, 60%, 50%, 45%, 40%, 37%, 35%, 33% with respect to the total amount, 30%, 28%, 25%, 23%, 20%. When emphasizing the reliability of the composition, compounds represented by formula (L-1-3.1), formula (L-1-3.3) and formula (L-1-3.4)) It is preferable to combine two or more compounds selected from the group consisting of formulas (L-1-1.3) and (L-1-2.2) when the response speed of the composition is important. It is preferable to combine two or more compounds selected from the following compounds.

The compound represented by the general formula (L-2) is the following compound.

(In the formula, R ^L21 and R ^L22 each independently represent the same meaning as R ^L1 and R ^L2 in the general formula (L).)
R ^L21 is preferably an alkyl group having 1 to 5 carbon atoms or an alkenyl group having 2 to 5 carbon atoms, and R ^L22 is an alkyl group having 1 to 5 carbon atoms, an alkenyl group having 4 to 5 carbon atoms, or a carbon atom. An alkoxy group of 1 to 4 is preferable.

When emphasizing solubility at low temperatures, it is highly effective to set a large amount of content. Conversely, when emphasizing response speed, setting a small amount of content is highly effective. Furthermore, when improving dripping marks and image sticking characteristics, it is preferable to set the content range in the middle.

The lower limit of the preferable content of the compound represented by the formula (L-2) with respect to the total amount of the liquid crystal composition of the present invention is 1% by mass (hereinafter, mass% is simply expressed as%). %, 3%, 5%, 7%, 10%. The upper limit of the preferable content is 20%, 15%, 13%, 10%, 8%, 7% with respect to the total amount of the liquid crystal composition of the present invention, 6%, 5%, 3%.

Further, the compound represented by the general formula (L-2) is preferably a compound selected from the group of compounds represented by the formulas (L-2.1) to (L-2.6). A compound represented by formula (L-2.1), formula (L-2.3), formula (L-2.4) and formula (L-2.6) is preferred.

The compound represented by the general formula (L-3) is the following compound.

(In the formula, R ^L31 and R ^L32 each independently represent the same meaning as R ^L1 and R ^L2 in General Formula (L).)
R ^L31 and R ^L32 are each independently preferably an alkyl group having 1 to 5 carbon atoms, an alkenyl group having 4 to 5 carbon atoms, or an alkoxy group having 1 to 4 carbon atoms.

The compound represented by the general formula (L-3) can be used alone, or two or more compounds can be used in combination. There are no particular restrictions on the types of compounds that can be combined, but they are used in appropriate combinations according to the required properties such as solubility at low temperatures, transition temperatures, electrical reliability, and birefringence. The kind of the compound used is, for example, one kind as one embodiment of the present invention, two kinds, three kinds, four kinds, and five kinds or more.

The lower limit of the preferable content of the compound represented by the formula (L-3) with respect to the total amount of the liquid crystal composition of the present invention is 1% by mass, 2%, 3%, 5% 7% and 10%. The upper limit of the preferable content is 20%, 15%, 13%, 10%, 8%, 7% with respect to the total amount of the liquid crystal composition of the present invention, 6%, 5%, 3%.

When a high birefringence is obtained, the effect is high when the content is set to be large. On the other hand, when high Tni is emphasized, the effect is high when the content is set low. Furthermore, when improving dripping marks and image sticking characteristics, it is preferable to set the content range in the middle.

Further, the compound represented by the general formula (L-3) is preferably a compound selected from the group of compounds represented by the formulas (L-3.1) to (L-3.4). A compound represented by the formula (L-3.7) from (L-3.2) is preferable.

The compound represented by the general formula (L-4) is the following compound.

(In the formula, R ^L41 and R ^L42 each independently represent the same meaning as R ^L1 and R ^L2 in General Formula (L).)
R ^L41 is preferably an alkyl group having 1 to 5 carbon atoms or an alkenyl group having 2 to 5 carbon atoms, and R ^L42 is an alkyl group having 1 to 5 carbon atoms, an alkenyl group having 4 to 5 carbon atoms, or a carbon atom. An alkoxy group of 1 to 4 is preferable. )
The compound represented by the general formula (L-4) can be used alone, or two or more compounds can be used in combination. There are no particular restrictions on the types of compounds that can be combined, but they are used in appropriate combinations according to the required properties such as solubility at low temperatures, transition temperatures, electrical reliability, and birefringence. The kind of the compound used is, for example, one kind as one embodiment of the present invention, two kinds, three kinds, four kinds, and five kinds or more.

In the composition of the present invention, the content of the compound represented by the general formula (L-4) is low-temperature solubility, transition temperature, electrical reliability, birefringence, process compatibility, dripping marks, It is necessary to adjust appropriately according to required performance such as image sticking and dielectric anisotropy.

The lower limit of the preferable content of the compound represented by the formula (L-4) with respect to the total amount of the liquid crystal composition of the present invention is 1% by mass (hereinafter, the mass% is simply expressed as%). %, 3%, 5%, 7%, 10%, 14%, 16%, 20%, 23%, 26%, 30% %, 35%, and 40%. The upper limit of the preferable content of the compound represented by the formula (L-4) with respect to the total amount of the liquid crystal composition of the present invention is 50%, 40%, 35%, and 30%. Yes, 20%, 15%, 10%, 5%.

The compound represented by general formula (L-4) is preferably a compound represented by formula (L-4.1) to formula (L-4.3), for example.

Depending on the required performance such as solubility at low temperature, transition temperature, electrical reliability, and birefringence, even if the compound represented by the formula (L-4.1) is contained, the formula (L -4.2) Even if it contains a compound represented by formula (L-4.1), it contains both a compound represented by formula (L-4.1) and a compound represented by formula (L-4.2). Or all of the compounds represented by formulas (L-4.1) to (L-4.3) may be included. The lower limit of the preferable content of the compound represented by the formula (L-4.1) or the formula (L-4.2) with respect to the total amount of the liquid crystal composition of the present invention is 3%, and 5% 7%, 9%, 11%, 12%, 13%, 18%, 21%, and a preferred upper limit is 45, 40%. Yes, 35%, 30%, 25%, 23%, 20%, 18%, 15%, 13%, 10%, 8% is there.

When both the compound represented by the formula (L-4.1) and the compound represented by the formula (L-4.2) are contained, both compounds relative to the total amount of the liquid crystal composition of the present invention The lower limit of the preferable content of is 15% by mass (hereinafter, mass% is simply expressed as%), 19%, 24%, 30%, and the preferable upper limit is 45. 40%, 35%, 30%, 25%, 23%, 20%, 18%, 15%, 13%.

The compound represented by the general formula (L-4) is preferably, for example, a compound represented by the formula (L-4.4) to the formula (L-4.6). It is preferable that it is a compound represented by this.

Depending on the required performance such as solubility at low temperature, transition temperature, electrical reliability, birefringence and the like, even if the compound represented by the formula (L-4.4) is contained, the formula (L -4.5) contains both the compound represented by formula (L-4.4) and the compound represented by formula (L-4.5). May be.

The lower limit of the preferable content of the compound represented by the formula (L-4.4) or the formula (L-4.5) with respect to the total amount of the liquid crystal composition of the present invention is 3% by mass (hereinafter referred to as mass%). Is simply expressed as%), 5%, 7%, 9%, 11%, 12%, 13%, 18%, and 21%. Preferred upper limit values are 45, 40%, 35%, 30%, 25%, 23%, 20%, 18%, 15%, 13% %, 10%, and 8%.

When both the compound represented by formula (L-4.4) and the compound represented by formula (L-4.5) are contained, both compounds relative to the total amount of the liquid crystal composition of the present invention The lower limit of the preferable content of is 15% by mass (hereinafter, mass% is simply expressed as%), 19%, 24%, 30%, and the preferable upper limit is 45. 40%, 35%, 30%, 25%, 23%, 20%, 18%, 15%, 13%.

The compound represented by the general formula (L-4) is preferably a compound represented by the formula (L-4.7) to the formula (L-4.10), and particularly the formula (L-4. The compound represented by 9) is preferred.

The compound represented by the general formula (L-5) is the following compound.

(In the formula, R ^L51 and R ^L52 each independently represent the same meaning as R ^L1 and R ^L2 in the general formula (L).)
R ^L51 is preferably an alkyl group having 1 to 5 carbon atoms or an alkenyl group having 2 to 5 carbon atoms, and R ^L52 is an alkyl group having 1 to 5 carbon atoms, an alkenyl group having 4 to 5 carbon atoms, or a carbon atom. An alkoxy group of 1 to 4 is preferable.

The compound represented by the general formula (L-5) can be used alone, or two or more compounds can be used in combination. There are no particular restrictions on the types of compounds that can be combined, but they are used in appropriate combinations according to the required properties such as solubility at low temperatures, transition temperatures, electrical reliability, and birefringence. The kind of the compound used is, for example, one kind as one embodiment of the present invention, two kinds, three kinds, four kinds, and five kinds or more.

In the composition of the present invention, the content of the compound represented by the general formula (L-5) includes solubility at low temperature, transition temperature, electrical reliability, birefringence index, process suitability, dripping marks, It is necessary to adjust appropriately according to required performance such as image sticking and dielectric anisotropy.

The lower limit of the preferable content of the compound represented by the formula (L-5) with respect to the total amount of the liquid crystal composition of the present invention is 1% by mass (hereinafter, mass% is simply expressed as%). %, 3%, 5%, 7%, 10%, 14%, 16%, 20%, 23%, 26%, 30% %, 35%, and 40%. The upper limit of the preferable content of the compound represented by the formula (L-5) with respect to the total amount of the liquid crystal composition of the present invention is 50%, 40%, 35%, 30% Yes, 20%, 15%, 10%, 5% The compound represented by the general formula (L-5) is represented by the formula (L-5.1) or the formula (L-5. The compound represented by 2) is preferred, and the compound represented by the formula (L-5.1) is particularly preferred.

The lower limit of the preferable content of these compounds with respect to the total amount of the liquid crystal composition of the present invention is 1% by mass (hereinafter, mass% is simply expressed as%), 2%, 3%, 5% and 7%. The upper limit of the preferable content of these compounds is 20%, 15%, 13%, 10%, and 9%.

The compound represented by the general formula (L-5) is preferably a compound represented by the formula (L-5.3) or the formula (L-5.4).

The compound represented by the general formula (L-5) is preferably a compound selected from the group of compounds represented by the formulas (L-5.5) to (L-5.7). The compound represented by L-5.7) is preferred.

The compound represented by the general formula (L-6) is the following compound.

(In the formula, R ^L61 and R ^L62 each independently represent the same meaning as R ^L1 and R ^L2 in the general formula (L), and X ^L61 and X ^L62 each independently represent a hydrogen atom or a fluorine atom. )
R ^L61 and R ^L62 are each independently preferably an alkyl group having 1 to 5 carbon atoms or an alkenyl group having 2 to 5 carbon atoms, and one of X ^L61 and X ^L62 is a fluorine atom and the other is a hydrogen atom. Is preferred.

The compound represented by the general formula (L-6) can be used alone, or two or more compounds can be used in combination. There are no particular restrictions on the types of compounds that can be combined, but they are used in appropriate combinations according to the required properties such as solubility at low temperatures, transition temperatures, electrical reliability, and birefringence. The kind of the compound used is, for example, one kind as one embodiment of the present invention, two kinds, three kinds, four kinds, and five kinds or more.

The lower limit of the preferable content of the compound represented by the formula (L-6) with respect to the total amount of the liquid crystal composition of the present invention is 1% by mass (hereinafter, mass% is simply expressed as%). %, 3%, 5%, 7%, 10%, 14%, 16%, 20%, 23%, 26%, 30% %, 35%, and 40%. The upper limit of the preferable content of the compound represented by the formula (L-6) with respect to the total amount of the liquid crystal composition of the present invention is 50%, 40%, 35%, 30% Yes, 20%, 15%, 10%, 5%. When emphasizing to increase Δn, it is preferable to increase the content, and when emphasizing the precipitation at low temperature, it is preferable to decrease the content.

The compound represented by the general formula (L-6) is preferably a compound represented by the formula (L-6.1) to the formula (L-6.9).

There are no particular restrictions on the types of compounds that can be combined, but 1 to 3 types of these compounds are preferably contained, more preferably 1 to 4 types. Further, since the wide molecular weight distribution of the selected compound is also effective for the solubility, for example, one type of the compound represented by the formula (L-6.1) or (L-6.2), the formula (L- 6.4) or one type from the compound represented by (L-6.5), one type from the compound represented by formula (L-6.6) or formula (L-6.7), It is preferable to select one compound from the compounds represented by -6.8) or (L-6.9) and combine them as appropriate. Among them, represented by formula (L-6.1), formula (L-6.3), formula (L-6.4), formula (L-6.6) and formula (L-6.9). It is preferable to include a compound.

Further, the compound represented by the general formula (L-6) is preferably, for example, a compound represented by the formula (L-6.10) to the formula (L-6.17). A compound represented by L-6.11) is preferable.

The compound represented by the general formula (L-7) is the following compound.

^{(Wherein, R L71} and ^{R L72} each independently represent the same meaning as ^{R L1} and ^{R L2} in Formula ^{(L), A L71} and ^{A L72} is ^{A L2} and in the general formula (L) independently A ^L3 represents the same meaning, but the hydrogen atoms on A ^L71 and A ^L72 may be each independently substituted with a fluorine atom, Z ^L71 represents the same meaning as Z ^L2 in formula (L), X ^L71 and X ^L72 each independently represent a fluorine atom or a hydrogen atom.)
In the formula, R ^L71 and R ^L72 are each independently preferably an alkyl group having 1 to 5 carbon atoms, an alkenyl group having 2 to 5 carbon atoms, or an alkoxy group having 1 to 4 carbon atoms, and A ^L71 and A ^L72 Are each independently preferably a 1,4-cyclohexylene group or a 1,4-phenylene group, the hydrogen atoms on A ^L71 and A ^L72 may be each independently substituted with a fluorine atom, and Q ^L71 is a single group. A bond or COO- is preferable, a single bond is preferable, and X ^L71 and X ^L72 are preferably a hydrogen atom.

There are no particular restrictions on the types of compounds that can be combined, but they are combined according to the required performance, such as solubility at low temperatures, transition temperature, electrical reliability, and birefringence. The kind of the compound used is, for example, one kind as one embodiment of the present invention, two kinds, three kinds, and four kinds.

In the liquid crystal composition of the present invention, the content of the compound represented by the general formula (L-7) includes solubility at low temperature, transition temperature, electrical reliability, birefringence, process suitability, dropping trace Therefore, it is necessary to adjust appropriately according to required performance such as image sticking and dielectric anisotropy.

The lower limit of the preferable content of the compound represented by the formula (L-7) with respect to the total amount of the liquid crystal composition of the present invention is 1% by mass (hereinafter, mass% is simply expressed as%). %, 3%, 5%, 7%, 10%, 14%, 16%, 20%. The upper limit of the preferable content of the compound represented by the formula (L-7) with respect to the total amount of the composition of the present invention is 30%, 25%, 23%, and 20%. 18%, 15%, 10%, 5%.

When an embodiment with high Tni is desired for the composition of the present invention, the content of the compound represented by formula (L-7) is preferably increased, and when an embodiment with low viscosity is desired, the content is It is preferable to reduce the amount.

Further, the compound represented by the general formula (L-7) is preferably a compound represented by the formula (L-7.1) to the formula (L-7.4), and the formula (L-7. It is preferable that it is a compound represented by 2).

Further, the compound represented by the general formula (L-7) is preferably a compound represented by the formula (L-7.11) to the formula (L-7.13). It is preferable that it is a compound represented by 11).

Furthermore, the compound represented by the general formula (L-7) is a compound represented by the formula (L-7.21) to the formula (L-7.23). A compound represented by formula (L-7.21) is preferable.

Further, the compound represented by the general formula (L-7) is preferably a compound represented by the formula (L-7.31) to the formula (L-7.34), and the formula (L-7. 31) or / and a compound represented by the formula (L-7.32).

Further, the compound represented by the general formula (L-7) is preferably a compound represented by the formula (L-7.41) to the formula (L-7.44), and the formula (L-7. 41) or / and a compound represented by formula (L-7.42).

The additive (antioxidant, UV absorber, etc.) in the liquid crystal composition according to the present invention is preferably 100 ppm to 1% by mass.

The liquid crystal composition of the present invention can use a nematic phase-isotropic liquid phase transition temperature (Tni) in a wide range, but the nematic phase-isotropic liquid phase transition temperature (Tni) is 60. It is preferably from ˜120 ° C., more preferably from 70 to 100 ° C., particularly preferably from 70 to 85 ° C.

The dielectric anisotropy Δε of the liquid crystal composition in the present invention is preferably −2.0 to −6.0, more preferably −2.5 to −5.0 at 25 ° C. A value of −2.5 to −3.5 is particularly preferable.

The refractive index anisotropy Δn of the liquid crystal composition in the present invention is preferably 0.08 to 0.13 at 25 ° C., more preferably 0.09 to 0.12. More specifically, the refractive index anisotropy of the liquid crystal composition in the present invention is preferably 0.10 to 0.12 at 25 ° C. when dealing with a thin cell gap. When it corresponds to a cell gap (cell gap of 3.4 μm or less), it is preferably about 0.9 to about 0.12, and when it corresponds to a thick cell gap (cell gap of 3.5 μm or more), it is about 0. It is preferably about 08 to about 0.1.

The upper limit of the rotational viscosity (γ ₁ ) of the liquid crystal composition according to the present invention is preferably 150 (mPa · s) or less, more preferably 130 (mPa · s) or less, and particularly preferably 120 (mPa · s) or less. . On the other hand, the lower limit of the rotational viscosity (γ ₁ ) is preferably 20 (mPa · s) or more, more preferably 30 (mPa · s) or more, still more preferably 40 (mPa · s) or more, and 50 (mPa · s). s) or more is more preferable, 60 (mPa · s) or more is further more preferable, and 70 (mPa · s) or more is particularly preferable.

In the liquid crystal composition according to the present invention, it is preferable that Z as a function of rotational viscosity and refractive index anisotropy shows a specific value.

(In the above formula, γ ₁ represents rotational viscosity and Δn represents refractive index anisotropy.)
Z is preferably 13000 or less, more preferably 12000 or less, and particularly preferably 11000 or less.

When used in an active matrix display device, the liquid crystal composition according to the present invention needs to have a specific resistance of 10 ¹¹ (Ω · m) or more, preferably 10 ¹² (Ω · m). ¹³ (Ω · m) or more is more preferable.

The liquid crystal composition according to the present invention can use a nematic phase-isotropic liquid phase transition temperature (T _NI ) in a wide range, and the phase transition temperature (T _NI ) is 60 to 120 ° C. It is preferably 70 to 110 ° C, particularly preferably 75 to 100 ° C.
[Method of manufacturing liquid crystal display element]
Next, with reference to FIG. 1, the manufacturing method of the liquid crystal display element of this invention is demonstrated.

An alignment film material or a polymerizable liquid crystal containing a polymerizable compound having a polymerizable group on the surface of the first substrate 11 on which the common electrode 14 is formed and on the surface of the second substrate 12 on which the pixel electrode 15 is formed. The

vertical alignment films

16 and 17 are formed by applying a compound and heating. In addition, when using a polymerizable liquid crystal compound as the alignment film, a normal alignment film may be provided as the base alignment film.

Here, first, an alignment film material containing a polymer having a thermally decomposable group is prepared by any one of the three methods described above.

When the first polymer compound is polyimide, examples of the polymer compound precursor include a mixture of tetracarboxylic dianhydride and diisocyanate, polyamic acid, and a polyimide solution in which polyimide is dissolved or dispersed in a solvent. Etc. The polyimide content in the polyimide solution is preferably 1% by mass or more and 10% by mass or less, and more preferably 3% by mass or more and 5% by mass or less.

When the first polymer compound is polysiloxane, examples of the polymer compound precursor include a silicon compound having an alkoxy group, a silicon compound having a halogenated alkoxy group, alcohol, and oxalic acid. Examples thereof include a polysiloxane solution prepared by synthesizing polysiloxane by mixing at a quantitative ratio and heating, and dissolving it in a solvent.

In addition, you may add the compound which has photocrosslinkability, a photoinitiator, a solvent, etc. to alignment film material as needed.

After the alignment film material is adjusted, the alignment film material is applied to each of the first substrate 11 and the second substrate 12 so as to cover the common electrode 14, the pixel electrode 15, and its slit portion (not shown). Or print. Moreover, it will be in the state which the polymer which has a thermally decomposable group containing a fluorine atom and / or a silicon atom segregated on the application | coating surface by passing through a drying process as needed.

Next, heat treatment (baking treatment) is performed in an environment of 120 to 300 ° C. As a result, the polymer compound precursor and / or the compound represented by the general formula (V-3) or the polymerizable liquid crystal compound contained in the coated or printed alignment film material is polymerized and cured to form a polymer. At the same time, among the polymers having a thermally decomposable group containing fluorine atoms and / or silicon atoms segregated on the coating surface, the thermally decomposable group portion containing fluorine atoms and / or silicon atoms is optically anisotropic. It is detached from the polymer contained in the body, and the coated surface becomes smooth.

In order to remove the thermally decomposable group portion bonded to the polymer having a thermally decomposable group, a baking treatment is preferably performed at 150 to 300 ° C. for 5 to 120 minutes, and at 180 to 250 ° C. for 10 to 60 minutes. It is more preferable to perform a baking treatment for a minute.

In the stage of this heat treatment, the vertical alignment ability to align the liquid crystal molecules in the liquid crystal composition layer in the direction perpendicular to the substrate surface is formed.

Next, the first substrate 11 and the second substrate 12 are overlapped, and the liquid crystal composition layer 13 containing liquid crystal molecules is sealed between them.

Specifically, spacer protrusions for securing a cell gap with respect to the surface on which the

vertical alignment films

16 and 17 are formed on either one of the first substrate 11 and the second substrate 12, for example, In addition to spraying plastic beads or the like, for example, the seal portion is printed using an epoxy adhesive or the like by a screen printing method.

Thereafter, the first substrate 11 and the second substrate 12 are bonded together through spacer protrusions and a seal portion so that the

vertical alignment films

16 and 17 are opposed to each other, and liquid crystal molecules and, if necessary, polymerizable. A liquid crystal composition containing the compound is injected.

Thereafter, the liquid crystal composition is sealed between the first substrate 11 and the second substrate 12 by curing the seal portion by UV irradiation or heating.

Next, a voltage is applied between the common electrode 14 and the pixel electrode 15 using voltage applying means. The voltage is applied with a magnitude of 5 to 30 (V), for example. The application may apply a charge substantially perpendicularly to the first substrate and the second substrate. Thereby, the surface adjacent to the liquid crystal composition layer 13 in the first substrate 11 (surface facing the liquid crystal composition layer 13) and the surface adjacent to the liquid crystal composition layer 13 in the second substrate 12 (liquid crystal An electric field in a direction forming a predetermined angle with respect to the surface facing the composition layer 13 is generated, and the liquid crystal molecules 19 are oriented in a predetermined direction with respect to the normal direction of the first substrate 11 and the second substrate 12. Will be. At this time, the tilt angle of the liquid crystal molecules 19 is approximately equal to the pretilt θ given to the liquid crystal molecules 19 in a process described later. Therefore, the magnitude of the pretilt θ of the liquid crystal molecules 19 can be controlled by appropriately adjusting the magnitude of the voltage (see FIG. 3).

Further, the liquid crystal composition in the

vertical alignment films

16 and 17 is irradiated with ultraviolet light (UV), for example, from the outside of the first substrate 11 while the voltage is applied. A polymer having a polymerizable group for controlling the alignment direction of liquid crystal molecules in the layer or a polymerizable liquid crystal compound and a polymerizable compound in the liquid crystal composition are polymerized to form a polymer.

In this case, the intensity of the ultraviolet light UV to be irradiated may or may not be constant, and the irradiation time at each intensity when the irradiation intensity is changed is arbitrary, but two or more stages of irradiation processes are performed. When employed, it is preferable to select an irradiation intensity in the irradiation process in the second stage and after that which is weaker than the irradiation intensity in the first stage, and the total irradiation time in the second stage and after is more than the irradiation time in the first stage. It is preferable that the total irradiation energy amount is long and long. When the irradiation intensity is changed discontinuously, it is desirable that the average irradiation light intensity in the first half of the entire irradiation process time is stronger than the average irradiation intensity in the second half, and the intensity immediately after the start of irradiation is the strongest. More desirably, it is further preferable that the irradiation intensity always decreases to a certain value as the irradiation time elapses. In this case, the ultraviolet UV intensity is preferably 0.5 mW / cm ⁻² to 100 mW / cm ⁻² , but during the first irradiation stage in the case of multi-stage irradiation or all irradiation processes in the case of changing the irradiation intensity discontinuously. The maximum irradiation intensity is 10 mW / cm ⁻² to 100 mW / cm ⁻² and the minimum irradiation intensity is 0.5 mW / cm after the second stage in the case of multistage irradiation or when the irradiation intensity is changed discontinuously. More preferably, it is cm ⁻² to 50 mW / cm ⁻² . The total irradiation energy is preferably 10 J to 300 J, more preferably 50 J to 250 J, and even more preferably 100 J to 250 J.

In this case, the applied voltage may be alternating current or direct current.

As a result, it has an alignment control ability (not shown) including a vertical alignment film material fixed to the alignment control portions of the

vertical alignment films

16 and 17, and further, the polymer layer 20 is formed on the surface thereof as necessary. , 21 are formed. This alignment control unit has a function of imparting a pretilt θ to the liquid crystal molecules 19 located in the vicinity of the interface of the liquid crystal composition layer 13 with the polymer layers 20 and 21 (vertical alignment films 16 and 17) in the non-driven state (alignment) Controllability). Here, although the ultraviolet light UV is irradiated from the outside of the first substrate 11, it may be irradiated from the outside of the second substrate 12, and both the first substrate 11 and the second substrate 12 may be irradiated. You may irradiate from the outer side of a board | substrate.

Thus, in the liquid crystal display element of the present invention, the liquid crystal molecules 19 in the liquid crystal composition layer 13 have a predetermined pretilt θ. As a result, the response speed to the drive voltage can be greatly improved as compared with a liquid crystal display element that has not been subjected to any pretilt processing and a liquid crystal display device having the liquid crystal display element.

In the liquid crystal display element of the present invention, a non-photosensitive polyimide precursor is preferable as the polymer compound precursor constituting the

vertical alignment films

16 and 17.
A predetermined amount of a monomer that polymerizes with light (= a precursor of a liquid crystal alignment aid) is mixed with at least one liquid crystal alignment material. The liquid crystal alignment material is applied and formed on each substrate as a liquid crystal alignment film, and the liquid crystal is sandwiched between the two substrates. Thereafter, a pretilt angle is imparted to the liquid crystal by irradiating UV light while applying a predetermined voltage to the liquid crystal driving electrode. This is thought to be because the monomer in the alignment film was dissolved in the liquid crystal and polymerized (= liquid crystal alignment aid) by this UV light treatment.

In general, the process of forming the liquid crystal alignment film includes a step of baking at a high temperature of 200 ° C. or higher in order to completely remove the organic solvent. In the case of a monomer having a general polymerization group, the thermal stability is poor, the polymerization group reacts by baking at a high temperature and is difficult to withstand, and the monomer is hardly dissolved in the liquid crystal layer.
Thus, as a result of intensive studies by the present inventors, it was found that the above problems can be solved by using an alignment film material mixed with a polymerizable compound having a specific chemical structure, and the present invention has been completed.

<liquid crystal>
(Side chain)
-N -C _n H _{2n + 1} linear alkyl group having n carbon atoms n-C _n H _{2n + 1-} linear alkyl group having n carbon atoms -On -OC _n H _{2n + 1} linear alkoxy group having n carbon atoms Group nO— C _n H _{2n + 1} O— Linear alkoxy group having n carbon atoms —V ₂ —CH═CH ₂
V- CH ₂ = CH-
-V- -CH = 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 —
-F -F
-OCF3 -OCF ₃
(Linking group)
—CF ₂ O——CF ₂ —O—
-OCF2- -O-CF _2-
-1O- -CH ₂ -O-
-O1- -O-CH _2-
-COO- -COO-
-OCO- -OCO-
(Ring structure)

In the examples, the measured characteristics are as follows. Unless otherwise specified, the measurement was performed according to the method specified in JEITA ED-2521B.

Tni: Nematic phase-isotropic liquid phase transition temperature (° C)
Δn: Refractive index anisotropy at 25 ° C. T: Transmittance: Simulation by LCD Master γ1: Rotational viscosity at 25 ° C. (mPa · s)
Δε: dielectric anisotropy at 25 ° C. K11: elastic constant K11 (pN) at 25 ° C.
K33: elastic constant K33 (pN) at 25 ° C.
S: Interval between adjacent branches (μm): measured using a microscope d: cell gap (μm): optically measured using an Optipro manufactured by Shintech (Examples 1 to 9, Comparative Example 1)
LC-1 to LC-4 liquid crystal compositions were prepared.
LC-2 to 4 appropriately changed Δn according to d from LC-1. In addition, the following compounds were appropriately used in the preparation of LC-2 to 4.
・ 3-Cy-Cy-V
・ 3-Cy-Cy-V1
・ R-Cy-Ph5-OR '
・ R-Ph-Ph5-OR '
・ R-Cy-Cy-Ph5-OR '

FIG. 6 is a plot of changes in T due to d when S is a specific value. The results shown in FIGS. 6 and 7 are the results of simulation using the physical property values described in Table 2 based on the physical properties of the liquid crystal composition actually adjusted.

○ is a plot of the relationship between d and T when S is 0, x is a plot of S is 1, Δ is S is 2, □ is S is 3, and + is a plot of S is 4. is there. It was found that T decreases as d decreases.

The results of physical properties using the above liquid crystal composition are as shown in FIG. In FIG. 7, ◯ is a plot of values of S and d when T is 0.26, Δ is 0.27, □ is 0.28, | is 0.29, and X is 0.3. Is a plot of the values of S and d.

From the above results, by setting α in S = (d−α) /1.25 from −1.1 to 0.6, the transmittance becomes 0.26 or more, and the liquid crystal display element of the present invention is excellent. It was found to have display characteristics.

Claims

A first substrate on which an electrode A is formed;
A second substrate on which an electrode B is formed, disposed opposite to the first substrate;
In a state where no voltage is applied between the electrodes, the liquid crystal layer is provided between the first substrate and the second substrate and is aligned substantially perpendicular to the first and second substrates.
The electrode A has a fishbone pattern having a branch portion, and the distance between adjacent branches (S μm) of each branch in the fishbone pattern and the first substrate and the second substrate. A liquid crystal display element in which the distance between substrates (d μm) satisfies the relationship of the formula (1).
(D−0.6) /1.25 <S <(d + 1.1) /1.25 Formula (1)
The liquid crystal display element according to claim 1, wherein d is smaller than 3.6.
The liquid crystal display element according to claim 1 or 2, wherein S is smaller than 3.4.
The liquid crystal display element according to any one of claims 1 to 3, wherein a value of a product Δn · d of refractive index anisotropy (Δn) and d of the liquid crystal layer is 320 to 360.
5. The liquid crystal display element according to claim 1, wherein Δn is 0.089 to 0.360.
The liquid crystal display element according to claim 1, wherein a liquid crystal material having negative dielectric anisotropy is used.
The liquid crystal display element according to any one of claims 1 to 4, wherein an average angle (θ) between the liquid crystal molecules in the liquid crystal layer and the first substrate is 85 ° to 89.8 °.
The liquid crystal display element according to claim 5, further comprising a polymer for adjusting θ between the first and second substrates.
The liquid crystal composition in the liquid crystal layer has the following general formula (N-1), general formula (N-2), and general formula (N-3).

(Wherein, R N11 , R N12 , R N21 , R N22 , R N31 and R N32 each independently represents an alkyl group having 1 to 8 carbon atoms, and one or non-adjacent 2 in the alkyl group Two or more —CH 2 — may be each independently substituted by —CH═CH—, —C≡C—, —O—, —CO—, —COO— or —OCO—,
A N11 , A N12 , A N21 , A N22 , A N31, and A N32 are each independently (a) a 1,4-cyclohexylene group (one —CH 2 — or adjacent to each other in this group). And two or more —CH 2 — may be replaced by —O—) and (b) a 1,4-phenylene group (one —CH═ present in this group or not adjacent 2 More than one -CH = may be replaced by -N =.)
(C) Naphthalene-2,6-diyl group, 1,2,3,4-tetrahydronaphthalene-2,6-diyl group or decahydronaphthalene-2,6-diyl group (naphthalene-2,6-diyl group or One —CH═ present in the 1,2,3,4-tetrahydronaphthalene-2,6-diyl group or two or more non-adjacent —CH═ may be replaced by —N═. )
The group (a), the group (b) and the group (c) may be each independently substituted with a cyano group, a fluorine atom or a chlorine atom,
Z N11 , Z N12 , Z N21 , Z N22 , Z N31 and Z N32 are each independently a single bond, —CH 2 CH 2 —, — (CH 2 ) 4 —, —OCH 2 —, —CH 2 O—. , —COO—, —OCO—, —OCF 2 —, —CF 2 O—, —CH═N—N═CH—, —CH═CH—, —CF═CF— or —C≡C—,
XN21 represents a hydrogen atom or a fluorine atom,
T N31 represents —CH 2 — or an oxygen atom,
n N11 , n N12 , n N21 , n N22 , n N31, and n N32 each independently represent an integer of 0 to 3, but n N11 + n N12 , n N21 + n N22, and n N31 + n N32 are each independently When there are a plurality of A N11 to A N32 and Z N11 to Z N32 , they may be the same or different. The liquid crystal display device according to any one of claims 1 to 7, which comprises one or more compounds selected from the group of compounds represented by:
The liquid crystal composition in the liquid crystal layer further has the general formula (L)

(Wherein R L1 and R L2 each independently represents an alkyl group having 1 to 8 carbon atoms, and one or two or more non-adjacent —CH 2 — in the alkyl group are each independently Optionally substituted by —CH═CH—, —C≡C—, —O—, —CO—, —COO— or —OCO—,
n L1 represents 0, 1, 2 or 3,
A L1 , A L2 and A L3 each independently represent (a) a 1,4-cyclohexylene group (one —CH 2 — present in the group or two or more —CH 2 — not adjacent to each other). May be replaced by —O—) and (b) a 1,4-phenylene group (one —CH═ present in this group or two or more —CH═ not adjacent to each other —N May be replaced by =.)
(C) Naphthalene-2,6-diyl group, 1,2,3,4-tetrahydronaphthalene-2,6-diyl group or decahydronaphthalene-2,6-diyl group (naphthalene-2,6-diyl group or One —CH═ present in the 1,2,3,4-tetrahydronaphthalene-2,6-diyl group or two or more non-adjacent —CH═ may be replaced by —N═. )
The group (a), the group (b) and the group (c) may be each independently substituted with a cyano group, a fluorine atom or a chlorine atom,
Z L1 and Z L2 are each independently 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 n L1 is 2 or 3, and a plurality of A L2 are present, they may be the same or different, and when n L1 is 2 or 3, and a plurality of Z L3 are present, May be the same or different, but excludes compounds represented by general formula (N-1), general formula (N-2) and general formula (N-3). The liquid crystal display device according to any one of claims 1 to 7, which comprises one or more compounds selected from a compound group represented by a compound represented by:
The polymer according to claim 7 is represented by the general formula (ii)

(Where
Z i1 represents a single bond, —CH═CH—, —CF═CF—, —C≡C—, —COO—, —OCO—, —CF 2 O—, —OCF 2 —, or 2 to 20 alkylene groups, and one or two or more non-adjacent —CH 2 — in the alkylene group may be substituted with —O—, —COO— or —OCO—,
A i1 represents a divalent 6-membered aromatic group, a divalent 6-membered heteroaromatic group, a divalent 6-membered aliphatic group, a divalent 6-membered heteroaliphatic group, or a single bond. A hydrogen atom in these ring structures may be substituted with a halogen atom and / or —Sp i1 —R i1 ,
When there are a plurality of Z i1 and A i1 , they may be the same as or different from each other;
m i1 represents an integer of 1 to 5;
K i1 represents a hydroxyl group, an amino group, —Sp i1 —R i1 or the following formulas (K-1) to (K-8):

(Where
W K1 represents a methine group or a nitrogen atom,
X K1 and Y K1 each independently represent —CH 2 —, an oxygen atom or a sulfur atom,
Z K1 represents an oxygen atom or a sulfur atom,
U K1 , V K1 and S K1 each independently represent a methine group or a nitrogen atom,
Combinations in which K1 is a methine group, V K1 is a methine group, and S K1 is a nitrogen atom] are excluded. )
Represents a structure represented by
In formula (i) and formula (K-1) to formula (K-8), the black dot at the left end represents a bond,
Sp i1 represents a linear alkylene group having 1 to 18 carbon atoms, a branched alkylene group having 1 to 18 carbon atoms, or a single bond, and one or two or more non-adjacent —
CH 2 — may be substituted with —O—, —COO— or —OCO—,
R i1 represents a hydrogen atom or formula (R-1) to formula (R-15):

(In the formula, the black dot at the right end represents a bond.)
Represents a substituent selected from the group consisting of
In addition, when the same description substituent exists in a molecule | numerator, they may be the same or different. The liquid crystal display device according to any one of claims 7 to 9, which is a polymer of a polymerizable compound represented by
11. The liquid crystal display element according to claim 1, wherein a polyimide alignment film is not provided on at least one of the first substrate and the second substrate according to claim 1.