JP2021017520A - Nematic liquid crystal composition, liquid crystal display element and method for producing same - Google Patents

Abstract

To provide a liquid crystal composition that has extremely good orientation of liquid crystal molecules in an in-plane switching system, has excellent falling speed of liquid crystal molecules during non-application of voltage, and has extremely good rapid response.SOLUTION: A liquid crystal composition contains one or more compounds having a mesogenic group and a photoisomerization group or dimerization group bonded to the mesogenic group, a compound represented by formula (II), a compound with a dielectric anisotropy (Δε) of -2 to +2, and a compound with Δε of +2 or more or -2 or less, and the content of the compound of formula (II) is 1.8-4.8 mass%. (R202-R209 each denote a C1-18 alkyl group or the like; P21 is an acryloyloxy group or the like; S21 is a C1-15 alkylene group or the like).SELECTED DRAWING: Figure 1

Description

The present invention relates to a nematic liquid crystal composition using an orientation aid, a liquid crystal display element, and a method for producing the same.

Liquid crystal display elements are used in various measuring instruments such as clocks and calculators, automobile panels, printers, computers, televisions, clocks, advertisement display boards and the like. Typical liquid crystal display methods are TN (twisted nematic) type, STN (super twisted nematic) type, vertical alignment type using TFT (thin film transistor), and IPS (in-plane switching) type. And so on.

The liquid crystal compositions used in these liquid crystal display elements have several to several tens of types in order to optimize the dielectric anisotropy (Δε) or the refractive index anisotropy (Δn) for each display element. It is composed of the above compounds. For example, a liquid crystal composition having a negative Δε is used in a vertically oriented (VA: Vertical Alignment) type display, and Δε is used in a horizontally oriented display such as a TN type, STN type, or IPS (in-plane switching) type display. A positive liquid crystal composition is used.

In particular, as the latter horizontally oriented display, a fringe field switching mode liquid crystal display device (Fringe Field Switching mode Liquid Crystal Display; FFS mode liquid crystal display device), which is a kind of IPS mode liquid crystal display element, has high quality and visual characteristics. It is widely used as a liquid crystal display for smartphones because of its excellent points.

Such an FFS mode is a method introduced to improve the low aperture ratio and transmittance of the IPS mode, and the liquid crystal composition used has anisotropy of dielectric constant because it is easy to reduce the voltage. Materials using a positive p-type liquid crystal composition are widely used. In addition, since most of the applications of the FFS mode are mobile terminals, there is a strong demand for further power saving, and liquid crystal element manufacturers are continuing active development such as adoption of arrays using IGZO.

In a conventional liquid crystal display element, a polyimide alignment film (PI) layer is provided at a substrate interface in contact with a liquid crystal composition in order to obtain uniform orientation of liquid crystal molecules when no voltage is applied.

However, since the formation of the PI layer requires a great deal of cost, a method for realizing the orientation of the liquid crystal molecules while omitting the PI layer has been studied. Further, as a liquid crystal display element, improvement of transmittance and improvement of design are also being studied.

A large number of researches and developments have already been made on liquid crystal display elements that do not have a PI layer in VA type liquid crystal display elements, but they voluntarily exhibit horizontal orientation as represented by the IPS method and FFS method. There are few examples of studies on inducing devices.

For example, Patent Document 1 discloses a liquid crystal medium based on a mixture of polar compounds having negative dielectric anisotropy and containing at least one kind of spontaneous orientation additive. It is stated that is highly suitable for use in displays that do not have an alignment layer. Then, in Patent Document 1, a specific compound having a hydroxyl group is used as a spontaneous orientation additive in a VA type liquid crystal display.

Further, Patent Document 2 discloses a specific compound having a polymerizable group as a spontaneous orientation additive.

On the other hand, even in IPS type and FFS type liquid crystal displays, there is a demand for an orientation additive that does not require an alignment film. Therefore, an orientation additive that orients the liquid crystal molecules horizontally is required. Further, in a horizontal electric field type liquid crystal display such as an IPS method or an FFS method, horizontal uniaxial orientation is required when no voltage is applied, and when sufficient orientation is not ensured, light scattering occurs when a voltage is applied. There is a problem that it ends up.

Further, if the orientation regulating force of the spontaneous orientation additive is not sufficient, the falling speed of the liquid crystal molecules when no voltage is applied to the liquid crystal display device cannot be sufficiently obtained, and the response speed becomes low. Have.

Special Table 2014-524951 JP-A-2015-168826

Therefore, the problem to be solved by the present invention is that the orientation of the liquid crystal molecules can be made possible without providing the PI layer, and the orientation of the liquid crystal molecules in the transverse electric field method such as the IPS method and the FFS method is extremely good. It is an object of the present invention to provide a liquid crystal composition which is excellent in falling speed of liquid crystal molecules when no voltage is applied and is extremely excellent in high-speed response. Another object of the present invention is to provide a liquid crystal composition having excellent voltage retention and reliability, and a liquid crystal display device using the liquid crystal composition.

As a result of diligent studies to solve the above problems, the inventors of the present application have determined the configurations of various liquid crystal compositions suitable for liquid crystal display elements such as IPS and FFS modes, which do not have a PI layer on both sides or one side of the element. As a result of the examination, the present invention has been completed.

That is, the present invention includes one or more of a mesogen group and a compound (i) containing a photoisomerizing group or a dimerization group bonded to the mesogen group.
General formula (II)

(In the above general formula (I), R ²⁰² , R ²⁰³ , R ²⁰⁴ , R ²⁰⁵ , R ²⁰⁶ , R ²⁰⁷ , R ²⁰⁸ and R ²⁰⁹ are independently alkyl groups and carbon atoms having 1 to 18 carbon atoms, respectively. Represents any of the alkoxy groups, halogen atoms or hydrogen atoms of the numbers 1 to 18, and P ²¹ represents any of the following formulas (R-1) to (R-9).

(In the above formulas (R-1) to (R-9), R ²¹ , R ³¹ , R ⁴¹ , R ⁵¹ and R ⁶¹ are independent of each other and have an alkyl group having a hydrogen atom and 1 to 5 carbon atoms. Alternatively, it is an alkyl halide group having 1 to 5 carbon atoms, W is a single bond, -O- or a methylene group, T is a single bond or -COO-, and p, t and q are independent of each other. It is 0, 1 or 2.)
S ²¹ represents an alkylene group having 1 to 15 carbon atoms, and one or more -CH _2- in the alkylene group is -O-, -OCO- so that oxygen atoms are not directly adjacent to each other. Alternatively, it may be replaced with -COO-.
At least one of R ²⁰² , R ²⁰³ , R ²⁰⁴ , R ²⁰⁵ , R ²⁰⁶ , R ²⁰⁷ , R ²⁰⁸ and R ²⁰⁹ is a halogen atom, an alkyl group having 1 to 18 carbon atoms, and an alkoxy group having 1 to 18 carbon atoms. Is. ) And the compound
One or more compounds whose dielectric anisotropy (Δε) is greater than -2 and less than +2,
It contains one or more compounds selected from a compound having a dielectric anisotropy (Δε) of +2 or more and a compound having a dielectric anisotropy (Δε) of -2 or less, and
The present invention relates to a nematic liquid crystal composition characterized in that the content of the compound represented by the general formula (II) is in the range of 1.8 to 4.8% by mass.

The present invention further relates to a liquid crystal display device including two substrates and a liquid crystal layer containing the nematic liquid crystal composition provided between the two substrates.

The present invention is further represented by the general formula (II) by sandwiching two substrates and a liquid crystal layer containing the nematic liquid crystal composition provided between the two substrates and irradiating them with ultraviolet rays. The present invention relates to a method for producing a liquid crystal display element, which comprises forming a polymer of a compound on a substrate so as to be in contact with a liquid crystal layer.

According to the present invention, it is possible to orient the liquid crystal molecules without providing the PI layer, and in particular, the orientation of the liquid crystal molecules in the transverse electric field method such as the IPS method and the FFS method is extremely good, and the voltage is not marked. It is possible to provide a liquid crystal composition having excellent falling speed of liquid crystal molecules at the time of application and extremely excellent high-speed response. Further, it is possible to provide a liquid crystal composition having excellent voltage retention and reliability, and a liquid crystal display element using the liquid crystal composition.

The figure which shows typically the structure of the liquid crystal display element Enlarged plan view of the region surrounded by the line II of the electrode layer 3 Sectional view of the liquid crystal display element shown in FIG. 1 cut in the direction of lines III-III. The figure which shows the orientation direction of a liquid crystal schematically Another example of an enlarged plan view of the area surrounded by the line II of the electrode layer 3 Another example of a cross-sectional view obtained by cutting the liquid crystal display element shown in FIG. 1 in the direction of line III-III. The figure which shows the electrode structure of the FFS type display element.

The nematic liquid crystal composition of the present invention preferably exhibits a liquid crystal phase at room temperature (25 ° C.), and more preferably exhibits a nematic phase. Further, in the present invention, the dielectric anisotropy of the compound is a value extrapolated from the measured value of the dielectric anisotropy of the composition prepared by adding it to the composition which is dielectrically substantially neutral at 25 ° C. is there. In addition, although the content is described below in%, this means mass%.

F
The liquid crystal composition in the present embodiment is a compound (i) containing a mesogen group and a photoisomerizing group or a dimerization group bonded to the mesogen as a first component.
Containing one or more types,
General formula (II) as the second component

(In the above general formula (I), R ²⁰² , R ²⁰³ , R ²⁰⁴ , R ²⁰⁵ , R ²⁰⁶ , R ²⁰⁷ , R ²⁰⁸ and R ²⁰⁹ are independently alkyl groups and carbon atoms having 1 to 18 carbon atoms, respectively. Represents any of the alkoxy groups, halogen atoms or hydrogen atoms of the numbers 1 to 18, and P ²¹ represents any of the following formulas (R-1) to (R-9).

(In the above formulas (R-1) to (R-9), R ²¹ , R ³¹ , R ⁴¹ , R ⁵¹ and R ⁶¹ are independent of each other and have an alkyl group having a hydrogen atom and 1 to 5 carbon atoms. Alternatively, it is an alkyl halide group having 1 to 5 carbon atoms, W is a single bond, -O- or a methylene group, T is a single bond or -COO-, and p, t and q are independent of each other. It is 0, 1 or 2.)
S ²¹ represents an alkylene group having 1 to 15 carbon atoms, and one or more -CH _2- in the alkylene group is -O-, -OCO- so that oxygen atoms are not directly adjacent to each other. Alternatively, it may be replaced with -COO-.
At least one of R ²⁰² , R ²⁰³ , R ²⁰⁴ , R ²⁰⁵ , R ²⁰⁶ , R ²⁰⁷ , R ²⁰⁸ and R ²⁰⁹ is a halogen atom, an alkyl group having 1 to 18 carbon atoms, and an alkoxy group having 1 to 18 carbon atoms. Is. )
Contains 1.8 to 4.8% by mass of the polymerizable monomer represented by
As the second component, one or more compounds having a dielectric anisotropy (Δε) greater than -2 and less than +2 (hereinafter, may be abbreviated as "dielectrically neutral compound").
A compound having a dielectric constant anisotropy (Δε) of +2 or more (hereinafter, may be abbreviated as “dielectrically positive compound”) and a compound having a dielectric constant anisotropy (Δε) of -2 or less (hereinafter,). , May be abbreviated as "dielectrically negative compound"), and contains one or more compounds selected from the above.
Nematic liquid crystal composition characterized in that the content of the compound represented by the general formula (II) is in the range of 1.8 to 4.8% by mass. The compound (i) in the liquid crystal composition of the present invention is a compound (i). It is characterized by having a partial structure of a photoisomerizing group or a dimerizing group in the major axis direction of the mesogen. As a result, when the liquid crystal composition of the present invention is irradiated with light, only molecules whose absorption and photoreaction are oriented parallel to the mesogen react relatively, resulting in selective photoisomerization or selective photoisomerization. The photodimerization reaction is promoted. By repeating these reactions, as a result, the orientation axis of the liquid crystal composition of the entire system is uniquely determined. That is, the molecular structure of compound (i) serves as a driving force for determining the axis of orientation.

Therefore, according to the liquid crystal composition using the compound (i) of the present embodiment, the liquid crystal molecules are oriented even if the PI layer is not provided on both sides or one side of the element (uniform horizontal orientation of the liquid crystal molecules when no voltage is applied). (Realize) becomes possible. As described above, compound (i) is preferably used to assist the horizontal orientation of liquid crystal molecules in the liquid crystal composition.

The photoisomerization or photodimerization reactive group present in the molecular structure of the compound (i) is preferably any of the following (Z3-1) to (Z3-5). In the formula, the black circles and the black dots at both ends represent the bond.

By irradiating with polarized light, dimerization or isomerization occurs along the polarization direction, and the liquid crystal molecules can be held in a horizontally oriented state. Therefore, according to the liquid crystal composition using the compound of the present embodiment, the liquid crystal molecules can be oriented and switching by applying a voltage can be performed without providing the PI layer on both sides or one side of the device. As described above, compound (i) is preferably used to assist the orientation of liquid crystal molecules in the liquid crystal composition. When 365 nm is mainly used as the wavelength of polarization to be used, (Z3-1), (Z3-3) and (Z3-5) are preferable, and when a wavelength of 313 nm is used, (Z3-1), (Z3-2) and (Z3-4) are preferable, and (Z3-1) and (Z3-2) are more preferable in terms of orientation stability and reliability.

(Z3-1), (Z3-2), and (Z3-4) are preferable from the viewpoint of compatibility with the liquid crystal composition and ease of synthesis, and (Z3-1) and (Z3) are preferable from the viewpoint of durability. −2) and (Z3-3) are preferable.

Further, from the viewpoint of reaction rate and horizontal orientation, it is preferable that the photoisomerization or photodimerization reaction group site is bonded at least adjacent to the aromatic site. On the other hand, from the viewpoint of compatibility with the liquid crystal, it is preferable that the aliphatic groups are adjacent to each other. In actual use, it is preferable to use the above in an appropriate and well-balanced manner, and the same compound may have different photoisomerization or photodimerization reactive groups, or photoisomerization or photodimerization having different structures, respectively. A plurality of compounds having a reactive group may be used in combination.

The mesogen group refers to a group having a rigid portion, for example, a group having one or more cyclic groups, preferably a group having 2 to 4 cyclic groups, and 3 to 4 cyclic groups. The provided group is more preferable. If necessary, the cyclic group may be linked by a linking group. The mesogen group preferably has a skeleton similar to that of the liquid crystal molecule (liquid crystal compound) used in the liquid crystal layer.

In the present invention, the "cyclic group" refers to an atomic group in which constituent atoms are cyclically bonded, and is a carbocyclic ring, a heterocyclic ring, a saturated or unsaturated cyclic structure, a monocyclic or bicyclic structure, or a polycyclic ring. Includes formula structures, aromatics, non-aromatics, etc.

Further, the cyclic group may contain at least one heteroatom, and may be further substituted with at least one substituent (halogeno group, polymerizable group, organic group (alkyl, alkoxy, aryl, etc.)). When the formula group is monocyclic, the mesogen group preferably contains two or more monocyclic rings.

The mesogen group preferably has a structure represented by the general formula (AL), for example.

^{Wherein, Z AL1} is a single bond, -CH = CH -, - CF = CF -, - C≡C -, - COO -, - OCO -, - OCOO -, - CF 2 O -, - OCF 2 - , -CH = CHCOO-, -OCOCH = CH-, -CH _2- CH ₂ COO-, -OCOCH _2- CH _2- , -CH = C (CH ₃ ) COO-, -OCOC (CH ₃ ) = CH- , -CH _2- CH (CH ₃ ) COO-, -OCOCH (CH ₃ ) -CH _2- , -OCH ₂ CH ₂ O- or an alkylene group having 1 to 20 carbon atoms. However, one or two or more non-adjacent -CH _2- in the alkylene group may be substituted with -O-, -COO- or -OCO-.

A ^AL1 and A ^AL2 each independently represent a divalent cyclic group.

One or more hydrogen atoms in Z ^AL1 , A ^AL1 and A ^AL2 may be independently substituted with a halogeno group, an adsorbent group, a polymerization group or a monovalent organic group.
When a plurality of Z ^AL1 and A ^AL1 are present in the molecule, they may be the same or different from each other.

m ^AL1 represents an integer of 1-5.

In the general formula (AL), Z ^AL1 is preferably a single bond or an alkylene group having 2 to 20 carbon atoms, more preferably a single bond or an alkylene group having 2 to 10 carbon atoms, and is a single bond. , − (CH ₂ ) ₂ − or − (CH ₂ ) ₄ − is more preferable. One or two or more non-adjacent −CH ₂ −s in the alkylene group may be substituted with −O−, −COO− or −OCO−.

Further, when the purpose is to improve the linearity of the rod-shaped molecule, Z ^AL1 has a single bond in which the ring and the ring are directly connected, or an even number of atoms directly connecting the ring and the ring. The form is preferable. For example, in the case of −CH ₂ −CH ₂ COO−, the number of atoms directly connecting the rings is four.

In the general formula (AL), A ^AL1 and A ^AL2 each independently represent a divalent cyclic group. As the divalent cyclic group, 1,4-phenylene group, 1,4-cyclohexylene group, 1,4-cyclohexenyl group, tetrahydropyran-2,5-diyl group, 1,3-dioxane-2, 5-Diyl group, tetrahydrothiopyran-2,5-diyl group, thiophene-2,5-diyl group, 1,4-bicyclo (2,2,2) octylene group, decahydronaphthalene-2,6-diyl group , Pyridin-2,5-diyl group, pyrimidin-2,5-diyl group, pyrazine-2,5-diyl group, thiophene-2,5-diyl group-, 1,2,3,4-tetrahydronaphthalene-2 , 6-Diyl group, 2,6-naphthylene group, phenanthrene-2,7-diyl group, 9,10-dihydrophenanthrene-2,7-diyl group, 1,2,3,4,4a, 9,10a- Octahydrophenanthrene-2,7-diyl group, 1,4-naphthylene group, benzo [1,2-b: 4,5-b'] dithiophene-2,6-diyl group, benzo [1,2-b: 4,5-b'] diselenophen-2,6-diyl group, [1] benzothieno [3,2-b] thiophene-2,7-diyl group, [1] benzoselenopheno [3,2-b] serenophen It is preferably one selected from the group consisting of -2,7-diyl group and fluorene-2,7-diyl group, preferably 1,4-phenylene group, 1,4-cyclohexylene group, 2,6--. A naphthylene group or a phenanthrene-2,7-diyl group is more preferable, and a 1,4-phenylene group or a 1,4-cyclohexylene group is even more preferable.

In addition, these groups may be substituted or substituted with a substituent. The substituent is preferably a fluorine atom or an alkyl group having 1 to 8 carbon atoms. Further, the alkyl group may be substituted with a fluorine atom or a hydroxyl group.

Further, one or more hydrogen atoms in the cyclic group may be substituted with a halogeno group, an adsorbing group, a polymerization group or a monovalent organic group.

In the general formula (AL), a monovalent organic group is a group having a chemical structure formed by the organic compound in the form of a monovalent group, and is formed by removing one hydrogen atom from the organic compound. Atomic group.

Examples of the monovalent organic group include an alkyl group having 1 to 15 carbon atoms, an alkenyl group having 2 to 15 carbon atoms, an alkoxy group having 1 to 14 carbon atoms, and an alkenyloxy having 2 to 15 carbon atoms. Examples thereof include an alkyl group having 1 to 15 carbon atoms or an alkoxy group having 1 to 14 carbon atoms, and an alkyl group having 1 to 8 carbon atoms or an alkoxy group having 1 to 8 carbon atoms. It is more preferably an alkyl group having 1 to 5 carbon atoms or an alkoxy group having 1 to 4 carbon atoms, and an alkyl group having 1 to 3 carbon atoms or an alkyl group having 1 to 2 carbon atoms. It is particularly preferably an alkoxy group, and most preferably an alkyl group having 1 or 2 carbon atoms or an alkoxy group having 1 carbon atom.

Further, one or two or more -CH ₂ −s in the above alkyl group, alkenyl group, alkoxy group and alkenyloxy group may be substituted with —O−, −COO− or −OCO−. Furthermore, the monovalent organic group may have a role as an orientation-inducing group described later.

In the above general formula (AL), m ^AL1 is preferably an integer of 1 to 4, more preferably an integer of 1 to 3, and even more preferably 2 or 3.

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

The general formula (AL) is a structure in which two hydrogen atoms are eliminated from these compounds.

In these formulas (me-1) to (me-44), one or more hydrogen atoms in the cyclohexane ring, benzene ring or naphthalene ring are independently halogeno groups, polymerizable groups, and monovalent groups. (For example, an alkyl group having 1 to 15 carbon atoms, an alkoxy group having 1 to 14 carbon atoms), an adsorbing group or an orientation inducing group may be substituted.

Among the above-mentioned mesogen groups, preferred forms are formulas (me-8) to (me-44), and more preferable forms are formulas (me-8) to (me-10) and formulas (me-12) to. (Me-18), formulas (me-22) to (me-24), formulas (me-26) to (me-27) and formulas (me-29) to (me-44), which are more preferable forms. Formulations (me-12), (me-15) to (me-16), (me-22) to (me-24), (me-29), (me-34), (me-36). ~ (Me-37), (me-42) ~ (me-44).

More specifically, the above-mentioned compound (i) has the following general formula (i).

^{(Wherein, R i1} and ^{R i2} are each independently a hydrogen atom, a linear or branched alkyl group having 1 to 40 carbon atoms, a halogenated alkyl group, or ^P i1 ^{-Sp i1} - represents a, R at least one of ⁱ¹ and ^{R i2 are,} P i1 ^{-Sp i1} - a and, -CH ₂ in the alkyl group - is -CH = CH -, - C≡C - , - O -, - NH -, - OCOO -, - COO- or -OCO- may be substituted with, but -O- is not become a ^{continuous, P i1} represents a polymerizable group, ^{Sp i1} represents a spacer group or a single bond,
A, C and D each independently represent a divalent aromatic group, a divalent heteroarophatic group, a divalent aliphatic group, and a divalent heteroaliphatic group.
B represents an aromatic group
These ring structures A to D are unsubstituted or an alkyl group having 1 to 12 carbon atoms, an alkyl halide group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, and a carbon atom number. 1-12 halogenated alkoxy group, a halogen atom, a cyano group, a nitro ^group, P i1 ^{-Sp i1} - may be substituted with,
The ring structures of A, C, and D may be substituted with −Z ⁴ - ^Kil .
Z ¹ and Z ² are independently single-bonded, -CH = CH-, -CF = CF-, -C≡C-, -COO-, -OCO-, -OCOO-, -CF ₂ O-, -OCF _2- , -CH = CHCOO-, -OCOCH = CH-, -CH _2- CH ₂ COO-, -OCOCH _2- CH _2- , -CH = C (CH ₃ ) COO-, -OCOC (CH ₃₎ ) = CH-, -CH _2- CH (CH ₃ ) COO-, -OCOCH (CH ₃ ) -CH _2- , -OCH ₂ CH ₂ O-, or an alkylene group having 2 to 20 carbon atoms. One or two or more non-adjacent −CH _2−s in the alkylene group may be independently substituted with −O−, −COO− or −OCO−.
Z ³¹ and Z ³² each independently represent a group or single bond selected from the general formulas (Z3-1) to (Z3-5), but at least one of Z ³¹ and Z ³² is (Z3-1). ) ~ (Z3-5),

(In the formula, the black dots at both ends represent the bond.)
l, m and n independently represent integers 0, 1, 2 and
k represents an integer of 1 or 2,
Z ⁴ is a single bond, -O-, -CH = CH-, -COO-, -OCO-, -OCOO-, -CH _2- CH (CH ₃ ) COO-, -OCOCH (CH ₃ ) -CH ₂ -Or represents a linear or branched alkylene group having 1 to 20 carbon atoms, and one or two or more -CH _2- not adjacent to the alkylene group are -O-, -COO- or -OCO-. May be replaced,
^Ki1 represents an adsorbent group. )
It is particularly preferable that the structure is represented by.

By having the polymerizable group represented by ^Pi1 in the general formula (i), the polymerization reaction proceeds in addition to the above-mentioned photoisomerization reaction and photodimerization reaction to form a polymer in the vicinity of the substrate. be able to. This makes it possible to ensure the stability and durability of the horizontal orientation.

Here ^P i1 ^{-Sp i1} - of Der structure represented by, as described ^{above, P i1} represents a polymerizable group, the table in the following general formula (P-1) ~ formula (P-15) It is preferable that the substituent is selected from the group to be selected (in the formula, the black dot at the right end represents a bond). Among these, any of the substituents of the formulas (P-1) to (P-3), (P-14), and (P-15) is preferable from the viewpoint of ease of handling and reactivity. (P-1) and (P-2) are more preferable. Said

The Sp ⁱ¹ represents a spacer group, and is a single bond, -CH = CH-, -CF = CF-, -C≡C-, -COO-, -OCO-, -OCOO-, -OOCO-, -CF ₂ O. -, -OCF _2- , -CH = CHCOO-, -OCOCH = CH-, -CH _2- CH ₂ COO-, -OCOCH _2- CH _2- , -CH = C (CH ₃ ) COO-, -OCOC ( CH ₃ ) = CH-, -CH _2- CH (CH ₃ ) COO-, -OCOCH (CH ₃ ) -CH _2- , -OCH ₂ CH ₂ O-, or an alkylene group having 2 to 20 carbon atoms. , One or two or more non-adjacent -CH _2- in this alkylene group may be substituted with -O-, -COO- or -OCO-.

Furthermore K ^il in the general formula (i) an adsorptive group, the structure of compound (i), preferably has at least one adsorptive group (K ^il).

The adsorbing group ( ^Kil ) can be selectively adsorbed on a substrate that sandwiches the liquid crystal composition (liquid crystal layer) when used in the liquid crystal composition due to its relativity with other parts in the molecular structure. .. Therefore, the binding position of ( ^Kil ) is important, and the liquid crystal molecules are oriented in the horizontal direction by binding to the lateral position (lateral portion) of the structure "B" in the general formula (i). Can be held in a state of being. That is, in order to realize horizontal orientation, it is preferable to have at least one adsorption group ( ^Kil ).

Here, the adsorption group is a group having a role of adsorbing with an adsorption medium which is a layer that comes into contact with the liquid crystal composition such as a substrate, a film, and an electrode, and may be adsorbed by either chemical adsorption or physical adsorption. In particular, physical adsorption is preferable. Therefore, it is more preferable that the adsorption group is a group that can be bonded to the adsorption medium by an intermolecular force.

The adsorbing group is preferably a group containing a polar element having an atomic group in which a carbon atom and a hetero atom are linked (hereinafter, "adsorbing group" is also referred to as "polar group"). In the present invention, the polar element means an atomic group in which a carbon atom and a hetero atom are directly linked.

The heteroatom is preferably at least one selected from the group consisting of N, O, S, P, B and Si, and at least one selected from the group consisting of N, O and S. Is more preferable, at least one selected from the group consisting of N and O is further preferable, and O is particularly preferable.

Compound (i) preferably has 1 to 8 adsorbent groups in one molecule, more preferably 1 to 4 adsorbent groups, and even more preferably 1 to 3 adsorbent groups. ..

Incidentally, the adsorption group, excluding a polymerizable group and orientation derived groups, any hydrogen atom is ^P i1 ^{-Sp i1} in adsorptive group - hydrogen atoms in - that is substituted with structures and ^P i1 ^{-Sp i1} Structures substituted with −OH or the like are included in the adsorption group.

The adsorbent group contains one or more polar elements and is roughly classified into a cyclic group type and a chain type group type.

A cyclic base type is a form including a cyclic group having a cyclic structure containing a polar element in its structure, and a chain type base type is a cyclic group having a cyclic structure containing a polar element in its structure. It is a form that does not include.

The chain type is a form having a polar element in a linear or branched chain group, and may have a cyclic structure in which a polar element is not included in a part thereof.

The cyclic group-type adsorbent group means a form having a structure containing at least one polar element in a cyclic atomic arrangement. Therefore, the cyclic group-type adsorbent group may include only a cyclic group containing a polar element, and the adsorbent group as a whole may be branched or linear.

On the other hand, the chain-type adsorption group is a structure that does not contain a cyclic atomic arrangement containing a polar element in the molecule and contains at least one polar element in a linear atomic arrangement (which may be branched). Means a form having.

In the present invention, the chain type group means a linear or branched aliphatic group that does not contain a cyclic atomic arrangement in the structural formula, and may contain either a saturated bond or an unsaturated bond. ..

Thus, chain groups include, for example, alkyl, alkenyl, alkoxy, esters, ethers, ketones and the like. The hydrogen atom in these groups may be substituted with at least one substituent (reactive functional group (vinyl group, acrylic group, methacryl group, etc.), chain organic group (alkyl, cyano, etc.)). .. Further, the chain type group may be either linear or branched.

The cyclic group-type adsorption group may be a heteroaromatic group having 3 to 20 carbon atoms (including a fused ring) or a heterolipocyclic group having 3 to 20 carbon atoms (including a fused ring). It is more preferably a heteroaromatic group having 3 to 12 carbon atoms (including a fused ring) or a heterolipocyclic group having 3 to 12 carbon atoms (including a fused ring), and a 5-membered complex. More preferably, it is an aromatic group, a 5-membered heterolipid ring group, a 6-membered heteroaromatic group or a 6-membered heterolipocyclic group. The hydrogen atom in these ring structures may be substituted with a halogeno group, a linear or branched alkyl group having 1 to 5 carbon atoms, or an alkyloxy group.

The chain-type adsorbent group is preferably a linear or branched alkyl group having 1 to 20 carbon atoms in which a hydrogen atom or −CH ₂ − in the structure is substituted with a polar element. In addition, one or two or more −CH ₂ −s in the alkyl group are replaced with −CH = CH−, −C≡C−, −O−, −CO−, −COO− or −OCO−. May be done. Further, the chain-type adsorbent group preferably contains one or two or more polar elements at its end.

The hydrogen atom in the adsorbent group may be substituted with a polymerizable group.

Specific examples of the polar element include a polar element containing an oxygen atom (hereinafter, oxygen-containing polar element), a polar element containing a nitrogen atom (hereinafter, nitrogen-containing polar element), and a polar element containing a phosphorus atom (hereinafter, phosphorus-containing polar element). Elements), polar elements containing boron atoms (hereinafter, boron-containing polar elements), polar elements containing silicon atoms (hereinafter, silicon-containing polar elements), or polar elements containing sulfur atoms (hereinafter, sulfur-containing polar elements) can be mentioned. .. From the viewpoint of adsorptivity, the polar element is preferably a nitrogen-containing polar element, a nitrogen-containing polar element, or an oxygen-containing polar element, and more preferably an oxygen-containing polar element.

As the oxygen-containing polar element, at least one group selected from the group consisting of a hydroxyl group, an alkylol group, an alkoxy group, a formyl group, a carboxyl group, an ether group, a carbonyl group, a carbonate group and an ester group, or the group is carbon. It is preferably a group linked to an atom.

As the nitrogen-containing polar element, at least one group selected from the group consisting of a cyano group, a primary amino group, a secondary amino group, a tertiary amino group, a pyridyl group, a carbamoyl group and a ureido group, or the group is carbon. It is preferably a group linked to an atom.

The phosphorus-containing polar element is preferably at least one group selected from the group consisting of a phosphinyl group and a phosphoric acid group, or a group in which the group is linked to a carbon atom.

Therefore, as the adsorption group, a cyclic group having an oxygen-containing polar element (hereinafter, oxygen-containing cyclic group), a cyclic group having a nitrogen-containing polar element (hereinafter, nitrogen-containing cyclic group), and a sulfur-containing polar group. A cyclic group having an element (hereinafter, sulfur-containing cyclic group), a chain type group having an oxygen-containing polar element (hereinafter, oxygen-containing chain type group), and a chain-type group having a nitrogen-containing polar element (hereinafter, hereafter). It is preferable to contain one or more groups themselves or the group selected from the group consisting of nitrogen-containing chain-type groups), and from the viewpoint of adsorptivity, oxygen-containing cyclic groups, sulfur-containing cyclic groups, and oxygen-containing groups. It is more preferable to contain one or more groups selected from the group consisting of chain groups and nitrogen-containing chain groups.

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

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

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

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

In the formula, ^Rat1 represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms.

Z ^at1 represents a single bond, a linear or branched alkylene group having 1 to 15 carbon atoms, or a linear or branched alkenylene group having 2 to 18 carbon atoms. However, -CH _2- in the alkylene group or the alkenylene group may be substituted with -O-, -COO-, -C (= O)-, and -OCO- so that oxygen atoms are not directly adjacent to each other.

X ^at1 represents an alkyl group having 1 to 15 carbon atoms. However, −CH ₂₋ in the alkyl group may be substituted with −O−, −COO−, −C (= O) −, −OCO− so that oxygen atoms are not directly adjacent to each other. ^mat1 , ^mat2 , and ^mat3 represent 0 to 5.

The nitrogen-containing chain type group preferably contains any of the following groups.

^{Wherein, R at, R bt, R} ct and ^{R dt} are each independently represent a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. However, −CH ₂₋ in the alkyl group may be substituted with −O−, −COO−, −C (= O) −, −OCO− so that oxygen atoms are not directly adjacent to each other.

More preferably, the adsorbent group (K ^il ) in the compound (i) is represented by any of the following general formulas (K-1) to (K-18).

W ^K1 represents a methine group or a nitrogen atom, and the hydrogen atom in the methine group may be replaced with a linear or branched alkyl group having 1 to 6 carbon atoms.
X ^K1 and Y ^K1 independently represent −CH _2- , oxygen atom or sulfur atom, respectively.
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, T K1} are each independently formula (T-1) ~ (T-6)

Represents a group selected from, ^ST1 is a single-bonded, linear or branched alkylene group having 1 to 15 carbon atoms or a linear or branched alkenylene group having 2 to 18 carbon atoms. Represented, -CH _{2- of the} alkylene group or the alkylene group is -O-, -COO-, -C (= O)-, -C (= CH ₂ )-or -OCO so that oxygen atoms are not directly adjacent to each other. - may be substituted ^{by, R T1} represents an alkyl group having 1 to 5 carbon atoms, -CH ₂ of the alkyl groups - such that oxygen atoms are not directly adjacent are -O -, - COO -, - C (= O) -, - C (= CH 2) - or -OCO- may be substituted ^{by, R T2} and ^{R T3} are each independently a hydrogen atom or an alkyl group having 1 to 5 carbon atoms represents, compounds represented by the general formula (i) at least one ^P i1 ^{-Sp i1} - have a group, a, C, D, Z 1, Z 2, Z 3, Z 4, K i1, W K1 , X ^K1 , Y ^K1 , Z ^K1 , ^TK1 , U ^K1 , V ^K1 , ^SK1 , ^ST1 , ^RT1 , ^RT2 , ^RT3 , ^Pi1 and Sp ⁱ¹ are the same. May be different. )
As the partial structure represented by the general formulas (K-1) to (K-18), when the orientation of the liquid crystal is emphasized, the general formulas (K-1), (K-2), (K-) 5), (K-8), (K-11), (K-13), (K-14), (K-15), (K-17), and (K-18) are preferable and reliable. (K-1), (K-9), (K-11), (K-13), and (K-15) are preferable when the above is regarded as important. (K-11), (K-13) and (K-15) are more preferable when considering both orientation and reliability. Further, in (K-13) to (K-18), ^TK1 is preferably a group represented by the general formulas (T-1), (T-3) and (T-4), and particularly (T-1). And (T-3) are more preferable. S ^T1 in formula (T-3) is a single bond, -C 1-10 linear or branched alkylene group or a C2-10 straight-chain or branched alkenylene It preferably represents a group, preferably a linear or branched alkyl group having 1 to 7 carbon atoms or a linear or branched alkenylene group having 2 to 7 carbon atoms, and preferably having 1 to 3 carbon atoms. A linear alkyl group is preferable, and −CH ₂ − in the alkyl group or alkylene group is −O −, −C (= O) − or −C (= CH ₂ ) − so that oxygen atoms are not directly adjacent to each other. It is preferably substituted. R ^T1 in formula (T-3) represents a linear or branched alkyl group having 1 to 5 carbon atoms, -CH 2 of the alkyl groups _- is such that oxygen atoms are not directly adjacent - It is preferably substituted with O-, -C (= O)-, -C (= CH ₂ )-or -OCO-, and a linear alkyl group having 1 to 3 carbon atoms is preferable. In the general formula (T-3), it is preferable that at least two or more secondary carbon atoms contain -C (= O).

^RT2 and ^RT3 in the general formula (T-6) independently represent a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, but preferably represent a hydrogen atom.

Preferred examples of the general formulas (K-13) and (K-17) are the following (K-1-1) to (K-1-4), (K-3-1), and (K-5-1). ) Is preferable from the viewpoint of orientation and reactivity, and the formulas (K-1-1), (K-1-3), and (K-3-1) are particularly preferable.

(In the formula, ^Pi1 represents a polymerizable group, ^RT4 , ^RT5 and ^RT6 independently represent hydrogen and an alkyl group having 1 to 3 carbon atoms, and ^RK1 represents a hydrogen atom and the number of carbon atoms. Representing linear or branched alkyl groups 1 to 6, -CH _2- in the alkyl group is -CH = CH-, -C≡C-, -O-, -NH-, -OCOO-, -COO- Alternatively, it may be replaced with -OCO-, but -O- is not continuous and is not continuous.
n ^T1 and ^{n T2} is 0 or 1 each ^{independently, n T3} represents an integer of independently 0-3, there exist a plurality of ^{R T4, R T5, R T6} , n T1, n T2 and n ^T3 may be the same or different. )
Z ¹ and Z ^{2 in} formula (i) are preferably single bonds, -CH = CH-, -CF = CF-, -C≡C-, -COO-, -OCO-, -CF ₂ O-, -OCF _2- , -CH = CHCOO-, -OCOCH = CH-, -OCH ₂ CH ₂ O-, or an alkylene group having 1 to 10 carbon atoms, or one or two or more non-adjacent alkylene groups. -CH _2- represents a group substituted with -O-, -COO- or -OCO-, respectively, and more preferably single bond, -COO-, -OCO-, -CH = CHCOO-, -OCOCH = CH-, -OCH ₂ CH ₂ O-, a linear or branched alkylene group having 1 to 6 carbon atoms, or one or two or more non-adjacent -CH _2- in the alkylene group is -O. -, - COO- or -OCO- in represents the radicals substituted with substituted group, more preferably ^{Z 1} and ^{Z 2,} a single bond, -COO -, - OCO -, - OCH 2 CH 2 O- , Or an alkylene group having 2 carbon atoms (ethylene group (-CH ₂ CH ₂ −)) or a group in which one of −CH ₂ − in the ethylene group is substituted with −O− (−CH ₂ O−, − OCH _2- ), or one of -CH _2- in the ethylene group is a group substituted with -COO-, -OCO- (-CH _2- CH ₂ COO-, -OCOCH _2- CH _2- ). .. Z ⁴ is a single bond, -O-, -CH = CH-, -COO-, -OCO-, -OCOO-, -CH _2- CH (CH ₃ ) COO-, -OCOCH (CH ₃ ) -CH ₂ -Or a linear or branched alkylene group having 1 to 20 carbon atoms (one or two or more -CH ₂ − not adjacent to each other in the alkylene group is replaced with -O-, -COO- or -OCO-. (May be), but preferably -COO-, -OCO-, -OCH ₂ CH ₂ O-, or an alkylene group having 2 carbon atoms (ethylene group (-CH ₂ CH _2- )) or an ethylene group. One of the −CH ₂ − in the group is substituted with −O − (−CH ₂ O−, −OCH ₂ −), or one of the −CH ₂ − in the 2-8 alkyl carbon group is − It is a group substituted with O-, -COO-, -OCO-.

From the viewpoint of horizontal orientation, it is preferable that the adsorbent group ( ^Ki1 ) is selected from the above (K-13) to (K-18), and at least one of ^TK1 is (T-1).
Specific substructures include, but are not limited to, the following groups.

^{Wherein, R tc} represents a hydrogen atom, an alkyl group or ^P i1 ^-Sp carbon atoms 1 to 20 ⁱ¹ - represents a. However, the hydrogen atom in the alkyl group is an alkyl group having 1 to 12 carbon atoms, an alkyl halide group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, and a halogen having 1 to 12 carbon atoms. alkoxy group, a halogen atom, a cyano group, a nitro group, or ^P i1 ^{-Sp i1} group ^-, - Z 4 ^{-K il} may be substituted with, -CH in the alkyl group ₂ - directly oxygen atom It may be substituted with a cyclic group, −O−, −COO−, −C (= O) −, −OCO− or −CH = CH− so as not to be adjacent.

* Represents a bond.

On the other hand, from the balance of orientation and solution stability, at least one of said although definitive adsorption group (K ⁱ¹⁾ are selected from the (K-13) ~ (K -18), and T ^K1 is (T- 3) is preferable. Specific substructures include, but are not limited to, the following groups.

In the formula, R ^ct has the same meaning as described above.

Further, from the viewpoint of the balance between orientation and voltage retention, it is preferable that the adsorption group ( ^Ki1 ) is any one of (K-1) to (K-12).

The compound represented by Formula (i) has at least one ^P i1 ^{-Sp i1} group, from the viewpoint of improving the orientation property, have two or more or three or more ^P i1 ^{-Sp i1} group preferable. If the general formula (i) 2 or more at or more than two ^P i1 ^{-Sp i1} group ¹ is present, more preferably ^{R 2} is a linear or branched alkyl group having 1 to 40 carbon atoms, a halogenated represents an alkyl group, of two or more ^P i1 ^{-Sp i1} originally wherein in formula ^{(i) (Z3-1) ~ R} i1 side of group selected from (Z3-5) position It is more preferable that it is present in. Orientation, from the viewpoint of reliability, more preferably, are both ^P i1 ^{-Sp i1} group of ^{R i1} and ^{R i2,} it is further preferable that at least one of ^{Sp i1} is a single bond.

The ring B in the general formula (i) is preferably a phenylene group or a naphthylene group, and more preferably 1,2,4-phenylentryyl and 1,3,4-phenylentryyl groups.

Rings A, C and D are a divalent ring aromatic group, a divalent ring heteroaromatic group, a divalent ring aliphatic group, or a divalent ring heteroaliphatic group, and a divalent ring aromatic group. A group, a divalent ring complex aromatic group, a divalent ring aliphatic group, or a divalent ring complex aliphatic group is preferable, and specifically, a 1,4-phenylene group and a 1,4-cyclohexylene group. , Anthracene-2,6-diyl group, phenanthrene-2,7-diyl group, pyridine-2,5-diyl group, pyrimidine-2,5-diyl group, naphthalene-2,6-diyl group, indan-2, A 5-diyl group, a chromane-3,7-diyl, a 1,2,3,4-tetrahydronaphthalene-2,6-diyl group and a 1,3-dioxane-2,5-diyl group are preferable, and the ring structure thereof is it is preferably substituted with or is L ¹ is unsubstituted. L ¹ is an alkyl group having 1 to 12 carbon atoms, an alkyl halide group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, a halogenated alkoxy group having 1 to 12 carbon atoms, a halogen atom, and the like. a cyano group, a nitro ^group, P i1 ^{-Sp i1} - group, or ^Z 4 ^{-K i1} is preferably an alkyl group having 1 to 6 carbon atoms, radicals substituted with an alkoxy group or a halogen atom having 1 to 6 carbon atoms Is more preferable. Between rings A, C and ring D, more preferably, an alkyl group having 1 to 12 carbon atoms, an alkyl halide group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, a halogen atom, or P ^i1- Sp ⁱ¹ -group may be substituted with 1,4-phenylene group, 2,6-naphthalene group, 1,4-cyclohexyl group or 1,3-dioxane-2,5-diyl. Although l, m and n represent integers of 0, 1, and 2, l + m + n ≦ 1 is preferable, l + m + n ≦ 2 is preferable, and l + m + n ≦ 3 is more preferable.
From the viewpoint of solution stability, k is preferably 0, and from the viewpoint of orientation, 1 or 2 is preferable.

More specific examples of the general formula (i) are represented by the following formulas (R-1) to (R-57), but are not limited thereto. Further, in the following formula, the description of the substituent is omitted.

(Wherein, ^{R i1, R i2, Z 4} , K i1 and k represents an ^{R i1, R i2, Z 4} , K i1 and k respectively the same meanings independently in the general formula (i). )

When added for a liquid crystal composition, one or more compounds represented by the general formula (i) of the present invention may be added, and in addition to the compound represented by the general formula (i), It may further contain a known polymerizable compound, an antioxidant or the like used in the liquid crystal composition. Examples of more specific compounds of the compound (i) are represented by the following (P-0-1) to (P-0-30) and (P-1-1) to (P-1-45).

(Liquid crystal composition)
The liquid crystal composition of the present embodiment contains one or more of the above compounds (i). The liquid crystal composition preferably has positive or negative dielectric anisotropy (Δε). The compounds represented by the general formula (i) contained in the liquid crystal composition include the compounds represented by the formulas (R-1-1) to (R-1-25), and the above-mentioned compounds (i). ), So the description is omitted here.

The content of the compound (i) is preferably 0.01 to 50% by mass, but the lower limit thereof is preferably based on the total amount of the liquid crystal composition from the viewpoint of more preferably oriented the liquid crystal molecules. It is 0.01% by mass or more, 0.1% by mass or more, 0.5% by mass or more, 0.7% by mass or more, or 1% by mass or more. The upper limit of the content of the compound (i) is preferably 50% by mass or less, 30% by mass or less, 10% by mass or less, and 7% by mass, based on the total amount of the liquid crystal composition from the viewpoint of excellent response characteristics. Hereinafter, it is 5% by mass or less, 4% by mass or less, or 3% by mass or less.

In the present invention, the general formula (II) is further used as the second component.

(In the above general formula (I), R ²⁰² , R ²⁰³ , R ²⁰⁴ , R ²⁰⁵ , R ²⁰⁶ , R ²⁰⁷ , R ²⁰⁸ and R ²⁰⁹ are independently alkyl groups and carbon atoms having 1 to 18 carbon atoms, respectively. Represents any of the alkoxy groups, halogen atoms or hydrogen atoms of the numbers 1 to 18, and P ²¹ represents any of the following formulas (R-1) to (R-9).

(In the above formulas (R-1) to (R-9), R ²¹ , R ³¹ , R ⁴¹ , R ⁵¹ and R ⁶¹ are independent of each other and have an alkyl group having a hydrogen atom and 1 to 5 carbon atoms. Alternatively, it is an alkyl halide group having 1 to 5 carbon atoms, W is a single bond, -O- or a methylene group, T is a single bond or -COO-, and p, t and q are independent of each other. It is 0, 1 or 2.)
S ²¹ represents an alkylene group having 1 to 15 carbon atoms, and one or more -CH _2- in the alkylene group is -O-, -OCO- so that oxygen atoms are not directly adjacent to each other. Alternatively, it may be replaced with -COO-.
At least one of R ²⁰² , R ²⁰³ , R ²⁰⁴ , R ²⁰⁵ , R ²⁰⁶ , R ²⁰⁷ , R ²⁰⁸ and R ²⁰⁹ is a halogen atom, an alkyl group having 1 to 18 carbon atoms, and an alkoxy group having 1 to 18 carbon atoms. Is. ) (Hereinafter, abbreviated as “monomer represented by the general formula (II)”) is contained in the composition in a proportion of 1.8 to 4.8% by mass. To do.
In the present invention, when 1.8 to 4.8% by mass of the monomer represented by the general formula (II) is used, a polymer network is formed not only on the substrate surface of the liquid crystal display but also in the liquid crystal medium. The molecular network strongly stabilizes the orientation when no voltage is applied. As a result, the response speed of the liquid crystal from the time when the voltage is applied to the time when the voltage is not applied can be increased.

In the above general formula (II), any one of R ²⁰² , R ²⁰³ , R ²⁰⁶ , and R ²⁰⁷ is preferably a halogen atom, and more preferably a fluorine atom.

In the above general formula (II), P ²¹ is independently represented by the formula (R-1), the formula (R-2), the formula (R-3), the formula (R-4), and the formula (R-5). ) Or formula (R-7), more preferably formula (R-1), formula (R-2), formula (R-3) or formula (R-4), and formula (R-4). It is more preferably R-1), further preferably an acrylic group or a methacrylic group, and even more preferably a methacrylic group. Further, the two or more P ^21s of the above general formula (II) may be the same or different, but are preferably the same.

In the above general formula (I), S ²¹ is preferably an alkylene group having 1 to 4 carbon atoms, and one of the carbon atoms is preferably substituted with −O−.

Further, the two or more S ^21s of the general formula (I) may be the same or different, but are preferably the same.

The alkyl group having 1 to 18 carbon atoms (two or more -CH 2 in one or non-adjacent in the alkyl group _-. Which may be the substituted by independently -O-), carbon Examples of the alkoxy group having 1 to 18 atoms are linear or branched, and linear is preferable. Further, the preferred number of carbon atoms of the alkyl group is preferably 1 to 3 when the solubility and expandability of the liquid crystal composition are important. On the other hand, when the vertical orientation with respect to the liquid crystal molecules is emphasized, 10 to 19 are preferable.

The lower limit of the content of the monomer represented by the general formula (II) in the liquid crystal composition of the present invention is preferably 1.8% by mass, more preferably 1.9% by mass or more, and particularly preferably 2.1% by mass or more. preferable.
The upper limit of the content of the monomer represented by the general formula (I) in the liquid crystal composition of the present invention is preferably 4.8% by mass, more preferably 4.3% by mass, and particularly preferably 3.8% by mass.

The liquid crystal composition according to the present invention preferably contains one kind or two or more kinds of monomers represented by the general formula (I). The type of the polymerizable monomer represented by the general formula (II) contained in the liquid crystal composition according to the present invention is 1 to 5, 1 to 4, 1 to 3, and 1 to 2. Is preferable. In another embodiment, from the viewpoint of improving vertical orientation and uneven orientation, it is preferable to include 2 to 5 types, 2 types to 4 types, and 2 types to 3 types.

Suitable compounds of the monomer represented by the general formula (II) according to the present invention include those represented by the following formulas RM-1 to RM-17.

Sp ^xx represents an alkylene group having 1 to 8 carbon atoms or −O− (CH ₂ ) _s − (in the formula, s represents an integer from 1 to 7 and an oxygen atom is bonded to a ring). ..

The above formulas RM-1, 2, 4, 6 and 7 are more preferable, and RM-1, 2 and 4 are particularly preferable. Among these, as Sp ^xx , a compound having −O− (CH ₂ ) _s− and s of 2 or 3 is particularly preferable.

As a particularly preferable example of the compound according to the general formula (II) according to the present invention,

Can be given.

Further, the composition of the present invention includes a compound having a dielectric anisotropy (Δε) of +2 or more (hereinafter, may be simply referred to as “a compound having a positive dielectric anisotropy”) and a dielectric anisotropy. It contains one or more compounds selected from compounds having a sex (Δε) of -2 or less (hereinafter, may be simply referred to as "compounds having a negative anisotropy in terms of dielectric"). ..

The dielectrically positive compound is preferably a compound selected from the group represented by the general formula (2-A) and / or the general formula (2-B).

(In the general formulas (2-A) and (2-B), R ₂ is an alkyl having 1 to 7 carbon atoms, an alkoxy having 1 to 7 carbon atoms, or an alkenyl having 2 to 7 carbon atoms, and ring C is At least one of the 1,4-cyclohexylene groups or the cyclic -CH- group, in which at least one of the -CH2 groups on the ring may be substituted with O or S, independently of each other when there are a plurality of them. One is a 1,4-phenylene group which may be substituted with N, the H atom on these rings may be substituted with at least one halogen, and L2 is independent of each other when a plurality of L2s are present. Te single _{bond, -C 2 H 4 -, -} CH = CH -, - C≡C -, - COO -, - OCO -, - CH 2 O -, - OCH 2 -, - CF 2 O-, OCF _2- ,, where X ₁ is -F, -Cl, -CN, -NCS, -CF ₃ , -OCF ₃ , or an alkyl having 1 to 6 carbon atoms in which at least one H is substituted with a halogen atom or It is an alkoxy group, Y ₁ and Y ₂ are independent of each other, -H or -F, and b is 1, 2, 3, or 4).
In the general formula (2-A) and the general formula (2-B), R ₂ is an alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, an alkenyl group having 2 to 8 carbon atoms, or An alkenyloxy group having 2 to 8 carbon atoms is preferable, 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 alkenyl group having 2 to 5 carbon atoms. An alkenyloxy group is preferable, an alkyl group having 1 to 5 carbon atoms or an alkenyl group having 2 to 5 carbon atoms is more preferable, and an alkyl group having 2 to 5 carbon atoms or an alkenyl group having 2 to 3 carbon atoms is further preferable. Preferably, an alkenyl group (propenyl group) having 3 carbon atoms is particularly preferable.

R ₂ is preferably an alkyl group when reliability is important, and is preferably an alkenyl group when a decrease in viscosity is important.

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 are used. An alkoxy group having 4 to 5 atoms is preferable, and when the ring structure to which the alkoxy group is bonded is a saturated ring structure such as cyclohexane, pyran, or dioxane, a linear alkyl group having 1 to 5 carbon atoms or a linear chain is used. Alkoxy groups having 1 to 4 carbon atoms and linear alkenyl groups having 2 to 5 carbon atoms are preferable. 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 the groups represented by any of the formulas (R1) to (R5).

Ring C is preferably aromatic when it is required to increase Δn independently, and is preferably aliphatic in order to improve the response rate, and more preferably represents the following structure. preferable.

In the composition of the present invention, the content of the compound represented by the general formula (2-A) and / or the general formula (2-B) includes solubility at low temperature, transition temperature, electrical reliability, and birefringence. It is necessary to make appropriate adjustments according to the required performance such as refractive index and dielectric anisotropy.

The lower limit of the preferable content of the compounds represented by the general formula (2-A) and the general formula (2-B) with respect to the total amount of the composition of the present invention is 1% by mass, and 10% by mass. There are 20% by mass, 30% by mass, 40% by mass, 50% by mass, 55% by mass, 60% by mass, 65% by mass, 70% by mass, and so on. It is 75% by mass and 80% by mass. The upper limit of the preferable content is, for example, 95% by mass, 85% by mass, 75% by mass, and 65% by mass with respect to the total amount of the composition of the present invention in one embodiment of the present invention. , 55% by mass, 45% by mass, 35% by mass, and 25% by mass.

When a composition having a low viscosity and a high response rate is required, it is preferable to lower the lower limit value and lower the upper limit value. Further, when the _TNI of the composition of the present invention is kept high and a composition having good temperature stability is required, it is preferable to lower the lower limit value and lower the upper limit value. Further, when it is desired to increase the dielectric anisotropy in order to keep the drive voltage low, it is preferable to raise the above lower limit value and raise the upper limit value.

As the compound represented by the general formula (2-A), the compounds represented by the general formulas (2-A-1) to (2-A-28) are preferable.

(R ₂ represents an alkyl having 1 to 7 carbon atoms, an alkoxy group having 1 to 7 carbon atoms, or an alkenyl group having 2 to 7 carbon atoms.)
As the compound represented by the general formula (2-B), the compounds represented by the general formulas (2-B-1) to (2-B-5) are preferable.

(R ₂ represents an alkyl having 1 to 7 carbon atoms, an alkoxy group having 1 to 7 carbon atoms, or an alkenyl group having 2 to 7 carbon atoms.)
The compounds represented by the general formulas (2-A) and (2-B) may be selected and used from only one of the groups, or may be selected from each group and used in combination. ..
When the reliability of the liquid crystal composition is emphasized, the general formulas (2-A-1) to (2-A-11), (2-A-16) to (2-A-20) and the general formula (2) It is preferable to use a compound selected from the group represented by −B-1) to (2-B-4), among which the general formulas (2-A-1), (2-A-2) and (2) are used. It is more preferable to select from the group represented by −A-4), (2-A-17) and (2-A-20). When emphasizing low viscosity, general formulas (2-A-12) to (2-A-15), (2-A-21) to (2-A-28) and (2-B-5) to It is preferable to use a compound selected from the group represented by (2-B-6), among which (2-A-12), (2-A-13), (2-A-22), (2). It is more preferable to select from the group represented by −A-23) and (2-A-26). When emphasizing low viscosity and further emphasizing the improvement of transmittance in FFS mode, (2-A-14), (2-A-15), (2-A-25), (2-A-) It is preferable to use a compound selected from the group represented by 27) and (2-A-28). In order to shorten the process time of UV irradiation in the process of manufacturing the liquid crystal display element of the present invention, the general formulas (2-A-4) to (2-A-7), (2-A-20) and (2) It is preferable to use a compound selected from the group represented by −B-4), and among them, a compound selected from (2-A-4) or (2-A-20) is particularly preferable, and among these groups. By using the compound, it is possible to prevent or reduce the degree of deterioration of the liquid crystal composition during UV irradiation, the decrease of the voltage retention rate of the liquid crystal display element, and the occurrence of seizure.

The compounds represented by the general formulas (2-A-1) to (2-A-28) and the general formulas (2-B-1) to (2-B-6) depend on the characteristics required for the liquid crystal display device. It is possible to appropriately select and use a plurality of types in combination as needed, but it is preferable to use 1 to 12 types, more preferably 2 to 10 types, and particularly preferably 3 to 8 types. The preferable content of each compound alone in the liquid crystal composition is shown below. The numbers in the table mean mass%.

Next, the dielectrically negative compound is preferably a compound selected from the group represented by the general formula (5).

(R ₅₁ and R ₅₂ are independently of each other, an alkyl having 1 to 7 carbon atoms, an alkoxy having 1 to 7 carbon atoms, an alkenyl having 2 to 7 carbon atoms, an alkenyloxy having 2 to 7 carbon atoms, and ring D. And F are independent of each other, 1,4-cyclohexylene, 1,4-cyclohexenylene, 1,4-phenylene, 1,4-phenylene in which at least one hydrogen is replaced with a halogen atom or a methyl group. , Or tetrahydropyran-2,5-diyl, ring E is 2,3-difluoro-1,4-phenylene, 2-chloro-3-fluoro-1,4-phenylene, 3,4,5-tri. Fluoronaphthalene-2,6-diyl, 7,8-difluorochroman-2,6-diyl, or

L ₄ and L ₅ are independent of each other, single bond, -C ₂ H4-, -COO-, -OCO-, -CH ₂ O-, -OCH _2- , -CF ₂ O, -OCF. _2- , -CH = CH-, or -C≡C, c is 0, 1, 2, or 3, d is 0 or 1, and the sum of c and d is 3 or less. )

The compound represented by the general formula (5) is preferably a compound having a negative Δε and an absolute value larger than 3.

In the general formula (5), R ₅₁ and R ₅₂ are independently an alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, an alkenyl group having 2 to 8 carbon atoms, or carbon. An alkenyloxy group having 2 to 8 atoms is preferable, 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 alkenyl having 2 to 5 carbon atoms. An oxy group is preferable, an alkyl group having 1 to 5 carbon atoms or an alkoxy group having 2 to 5 carbon atoms is more preferable, and an alkyl group having 2 to 5 carbon atoms or an alkoxy group having 2 to 3 carbon atoms is further preferable. , An alkenyl group (propenyl group) having 3 carbon atoms is particularly preferable.

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 are used. An alkoxy group having 4 to 5 atoms is preferable, and when the ring structure to which the alkoxy group is bonded is a saturated ring structure such as cyclohexane, pyran, or dioxane, a linear alkyl group having 1 to 5 carbon atoms or a linear chain is used. Alkoxy groups having 1 to 4 carbon atoms and linear alkenyl groups having 2 to 5 carbon atoms are preferable. 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 the groups represented by any of the formulas (R1) to (R5).

D and F are preferably aromatic when it is required to increase Δn independently, and are preferably aliphatic in order to improve the response rate, and trans-1,4-cyclo. Hexylene 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, preferably representing the following structure:

It is more preferable to represent a trans-1,4-cyclohexylene group, a 1,4-cyclohexenylene group or a 1,4-phenylene group.

L ₄ and _{L 5} each _{independently -CH 2 O -, - CF 2} O -, - CH 2 CH 2 -, - CF 2 CF 2 - or preferably a single bond, _-CH 2 O-, -CH ₂ CH _2- or single bond is more preferred, and -CH ₂ O- or single bond is particularly preferred.

c + d is preferably 1, 2 or 3, and more preferably 1 or 2.

The lower limit of the preferable content of the compound represented by the formula (5) with respect to the total amount of the composition of the present embodiment is 1% by mass or more, 10% by mass or more, and 20% by mass or more. , 30% by mass or more, 40% by mass or more, 50% by mass or more, 55% by mass or more, 60% by mass or more, 65% by mass or more, 70% by mass or more. It is 75% by mass or more, and 80% by mass or more. The upper limit of the preferable content is 95% by mass or less, 85% by mass or less, 75% by mass or less, 65% by mass or less, 55% by mass or less, 45% by mass or less. It is 35% by mass or less, 25% by mass or less, and 20% by mass or less.

When a composition in which the viscosity of the composition of the present embodiment is kept low and the response speed is fast is required, it is preferable that the above lower limit value is low and the upper limit value is low. Further, when a composition having a high Tni of the composition of the present embodiment and good temperature stability is required, it is preferable that the lower limit value and the upper limit value are low. Further, when it is desired to increase the dielectric anisotropy in order to keep the drive voltage low, it is preferable that the above lower limit value is high and the upper limit value is high.

Examples of the compound represented by the general formula (5) include a group of compounds represented by the following general formulas (5-1) to (5-15).

(R ₅₁ and R ₅₂ have the same meaning as in the general formula (5).)

When the reliability of the liquid crystal composition is emphasized, the general formulas (5-1), (5-2), (5-6), (5-8) to (5-10), (5-11) to It is preferable to use a compound selected from the group represented by (5-13), and the general formulas (5-1), (5-6), (5-9) and (5-10) are particularly preferable. .. When emphasizing low viscosity, general formulas (5-3) to (5-5), (5-9), (5-10), (5-12), (5-13), (5-15) It is preferable to use a compound selected from the group represented by), and among them, (5-3), (5-4), (5-9), (5-10), (5-13), (5-15) is particularly preferable. In order to shorten the process time of UV irradiation in the process of manufacturing the liquid crystal display element of the present invention, it is preferable to use a compound selected from the group represented by the general formulas (5-11) to (5-13). Of these, the compound selected from (5-13) is particularly preferable, and by using these compounds, problems such as deterioration of the liquid crystal composition during UV irradiation, a decrease in the voltage retention rate of the liquid crystal display element, and seizure may occur. It can be prevented from occurring or its degree can be reduced.

The compounds represented by the general formulas (5-1) to (5-15) can be appropriately selected according to the characteristics required for the liquid crystal display element, and a plurality of types can be used in combination as necessary. It is preferable to use 12 kinds, more preferably 2 to 10 kinds, and particularly preferably 3 to 8 kinds. The preferable content of each compound alone in the liquid crystal composition is shown below. The numbers in the table mean mass%.

Next, as the dielectrically neutral compound used in the present invention, it is preferable to use a compound selected from the group represented by the general formula (L).

(In the general formula (L), ^RL1 and ^RL2 each independently represent an alkyl group having 1 to 7 carbon atoms, but any one or two or more non-adjacent-existing groups present in the group. CH ₂ − may be independently substituted with −CH = CH −, −C≡C−, −O−, −CO−, −COO− or −OCO−, and n ^L1 is 0, Represents 1, 2 or 3, and A ^L1 , A ^{L 2} and A ^{L 3} are independent of each other.
(A) 1,4-Cyclohexylene group (any one or two or more non-adjacent −CH ₂ − present in this group may be substituted with −O−),.
(B) 1,4-phenylene group (any one or two or more non-adjacent −CH = present in this group may be substituted with −N =), and (c) naphthalene−. 2,6-diyl group, 1,2,3,4-tetrahydronaphthalene-2,6-diyl group or decahydronaphthalene-2,6-diyl group (any one present in these groups or not adjacent) Two or more -CH = may be replaced with -N =.)
Representing a group selected from the group consisting of, the group (a), the group (b) and the group (c) may be independently substituted with a cyano group, a fluorine atom or a chlorine atom, and 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-, and when n ^L1 is 2 or more, A ^L2 and Z ^L2 may be the same as or different from each other. )

The compound represented by the general formula (L) corresponds to a dielectrically substantially neutral compound (the value of Δε is -2 to 2). Such compounds may be used alone or in combination. The type of compound to be combined is not particularly limited, but is appropriately selected according to desired performance such as solubility at low temperature, transition temperature, electrical reliability, and birefringence. The types of compounds used are, for example, 1 type, 3 types, 4 types, 5 types, 6 types, 7 types, 8 types, 9 types, and 10 types. More than a kind.

The amount of the compound represented by the general formula (L) contained in the liquid crystal composition includes solubility at low temperature, transition temperature, electrical reliability, birefringence, process compatibility, dripping marks, seizure, and dielectric constant. It is appropriately adjusted according to the required performance such as rate anisotropy.

The preferable lower limit values are 1% by mass, 10% by mass, 20% by mass, 30% by mass, 40% by mass, 50% by mass, 55% by mass, 60% by mass, 65% by mass, 70% by mass, 75% by mass, and the like. It is 80% by mass. On the other hand, the preferable upper limit values are 95% by mass, 85% by mass, 75% by mass, 65% by mass, 55% by mass, 45% by mass, 35% by mass, and 25% by mass.

When the viscosity (η) of the liquid crystal composition is kept low and the response speed is increased, the amount of the compound represented by the general formula (L) preferably has a high lower limit value and a high upper limit value. Further, when the Tni of the liquid crystal composition is kept high and the temperature stability is improved, it is preferable that the amount thereof has a high lower limit value and a high upper limit value. Further, in order to keep the driving voltage of the liquid crystal display element low, when increasing Δε of the liquid crystal composition, it is preferable that the lower limit value and the upper limit value are also low.

When reliability is important, ^RL1 and ^RL2 are independent of each other, preferably an alkyl group, and when reducing the volatility of a compound is important, ^RL1 and ^RL2 are independent of each other. , an alkoxy group is preferred, when importance is attached to lowering of viscosity, at least one of R ^L1 and R ^L2, the alkenyl group is preferable.

The number of halogen atoms present in the compound represented by the general formula (L) is preferably 0, 1, 2 or 3, and more preferably 0 or 1. Further, when the compatibility with other liquid crystal molecules is emphasized, the number of halogen atoms is preferably one.

When the ring structure to which they are bonded is a benzene ring (aromatic ring), ^RL1 and ^RL2 are independently linear alkyl groups having 1 to 5 carbon atoms and linear. An alkoxy group having 1 to 4 carbon atoms or an alkenyl group having 4 to 5 carbon atoms is preferable.

If the ring structure to which they are attached is a saturated ring structure such as a cyclohexane ring, a pyran ring, a dioxane ring, R ^L1 and R ^L2 are each independently linear alkyl having 1 to 5 carbon atoms A group, a linear alkoxy group having 1 to 4 carbon atoms, or a linear alkenyl group having 2 to 5 carbon atoms is preferable.

In order to stabilize the nematic phase, R ^L1 and R ^L2 are each independently preferably has a total carbon atoms and an oxygen atom (if present) is 5 or less, also be straight-chain preferable.

As the alkenyl group, a group selected from the group represented by the following formulas (R1) to (R5) is preferable.

The black dots in each equation represent the bond.

n ^L1 is preferably 0 when the response speed of the liquid crystal molecule is important, 2 or 3 is preferable when improving the upper limit temperature of the nematic phase of the liquid crystal molecule, and 1 is preferable when these are balanced. Further, in order to satisfy the properties required for the liquid crystal composition, it is preferable to combine compounds having different values of n ^L1 .

A ^L1 , ^AL2, and ^AL3 are each independently preferably an aromatic group when increasing Δn of the liquid crystal molecule, and preferably an aliphatic group when improving the response rate of the liquid crystal molecule.

Examples of such aromatic or aliphatic groups include trans-1,4-cyclohexylene group, 1,4-phenylene group, 2-fluoro-1,4-phenylene group, and 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-diyl group, or 1,2,3,4-tetrahydronaphthalene-2,6-diyl group is preferable, and the structure represented by the following formula 54 is more preferable. A trans-1,4-cyclohexylene group or a 1,4-phenylene group is more preferred.

Z ^L1 and Z ^L2 are independent of each other, and a single bond is preferable when the response speed of the liquid crystal molecule is important.

The compound represented by the general formula (L) is preferably a compound represented by the following general formulas (L-1) to (L-7).

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

^{Wherein, R L11} and ^{R L12} are each the same meanings as ^{R L1} and ^{R L2} in the general formula (L).

^RL11 and ^RL12 are independently linear alkyl groups having 1 to 5 carbon atoms, linear alkoxy groups having 1 to 4 carbon atoms, or linear carbon atoms 2 to 2. Alkoxy group of 5 is preferred.

As the compound represented by the general formula (L-1), one type may be used alone, or two or more types may be used in combination. The type of compound to be combined is not particularly limited, but is appropriately selected depending on the required performance such as solubility at low temperature, transition temperature, electrical reliability, and birefringence. The types of compounds used are, for example, 1 type, 2 types, 3 types, 4 types, and 5 or more types.

The amount of the compound represented by the general formula (L-1) contained in the liquid crystal composition is preferably as follows. That is, the preferable lower limit values are 1% by mass, 2% by mass, 3% by mass, 5% by mass, 7% by mass, 10% by mass, 15% by mass, 20% by mass, 25% by mass, 30% by mass, and 35% by mass. %, 40% by mass, 45% by mass, 50% by mass, 55% by mass. On the other hand, the preferable upper limit values are 95% by mass, 90% by mass, 85% by mass, 80% by mass, 75% by mass, 70% by mass, 65% by mass, 60% by mass, 55% by mass, 50% by mass and 45% by mass. %, 40% by mass, 35% by mass, 30% by mass, and 25% by mass.

When the viscosity (η) of the liquid crystal composition is kept low and the response speed is increased, the amount of the compound represented by the general formula (L-1) preferably has a high lower limit value and a high upper limit value. Further, when the Tni of the liquid crystal composition is kept high and the temperature stability is improved, it is preferable that the lower limit value and the upper limit value of the liquid crystal composition are moderate. Further, in order to keep the driving voltage of the liquid crystal display element low, when increasing Δε of the liquid crystal composition, it is preferable that the lower limit value and the upper limit value are also low.

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

In the formula, ^RL12 has the same meaning as in the general formula (L-1).

The compound represented by the general formula (L-1-1) is preferably a compound represented by the following formulas (L-1-1.1) to (L-1-1.3), and is preferably a compound represented by the following formula (L-1-1.3). It is more preferably a compound represented by L-1-1.2) or formula (L-1-1.3), and a compound represented by formula (L-1-1.3). Especially preferable. When the compound represented by the formula (L-1-1.3) is used, a low viscosity and a high elastic constant can be given to the liquid crystal composition, which is advantageous not only for high-speed response of the display element but also for the manufacturing process. It is also preferable in that there is no deterioration peculiar to the alkenyl compound due to UV irradiation in the above, and deterioration of display quality and reliability can be suppressed.

The amount of the compound represented by the formula (L-1-1.3) contained in the liquid crystal composition is preferably as follows. That is, the preferable lower limit value is 1% by mass, 2% by mass, 3% by mass, 5% by mass, 7% by mass, and 10% by mass. On the other hand, the preferable upper limit values are 20% by mass, 15% by mass, 13% by mass, 10% by mass, 8% by mass, 7% by mass, 6% by mass, 5% by mass, and 3% by mass.

The compound represented by the general formula (L-1) is preferably a compound represented by the following general formula (L-1-2).

In the formula, ^RL12 has the same meaning as in the general formula (L-1).

The amount of the compound represented by the general formula (L-1-2) contained in the liquid crystal composition is preferably as follows. That is, the preferable lower limit value is 1% by mass, 5% by mass, and 10% by mass. On the other hand, the preferable upper limit values are 60% by mass, 54% by mass, 48% by mass, 42% by mass, 36% by mass, 30% by mass, 24% by mass, 20% by mass, 18% by mass and 15% by mass.

The compound represented by the general formula (L-1-2) is preferably a compound represented by the following formulas (L-1-2.1) to (L-1-2.4), and the compound is preferably represented by the formula (L-1-2.4). It is more preferable that the compounds are represented by L-1-2.2) to (L-1-2.4). In particular, the compound represented by the formula (L-1-2.2) is preferable because it has a high effect of improving the response speed of the liquid crystal composition, and the upper limit of the content in the composition should be suppressed to 24% by weight or less. Therefore, it is also preferable that the deterioration peculiar to the alkenyl compound due to UV irradiation in the manufacturing process can be suppressed, and the deterioration of the display quality and reliability can be suppressed.

In addition, when it is desired to improve Tni rather than the response speed of the liquid crystal composition, it is preferable to use a compound represented by the formula (L-1-2.3) or the formula (L-1-2.4). The amount of the compound represented by the formula (L-1-2.3) or the formula (L-1-2.4) contained in the liquid crystal composition is less than 30% by mass in order to increase the solubility at low temperature. Is preferable.

The compound represented by the general formula (L-1) is preferably a compound represented by the following general formula (L-1-3).

In the formula, ^RL13 and ^RL14 each independently represent an alkyl group having 1 to 8 carbon atoms or an alkoxy group having 1 to 8 carbon atoms.

^RL13 and ^RL14 are independently linear alkyl groups having 1 to 5 carbon atoms, linear alkoxy groups having 1 to 4 carbon atoms, or linear carbon atoms 2 to 2. Alkoxy group of 5 is preferred.

The amount of the compound represented by the general formula (L-1-3) contained in the liquid crystal composition is preferably as follows. That is, the preferable lower limit values are 1% by mass, 5% by mass, 10% by mass, 13% by mass, 15% by mass, 17% by mass, 20% by mass, 23% by mass, 25% by mass, and 30% by mass. On the other hand, the preferable upper limit values are 60% by mass, 55% by mass, 50% by mass, 45% by mass, 40% by mass, 37% by mass, 35% by mass, 33% by mass, 30% by mass, 27% by mass and 25% by mass. %, 23% by mass, 20% by mass, 17% by mass, 15% by mass, 13% by mass, and 10% by mass.

The compounds represented by the general formula (L-1-3) are the following formulas (L-1-3.1) to (L-1-3.4) or formulas (L-1-3.11) to ( It is preferably a compound represented by L-1-3.13), and is preferably of the formula (L-1-3.1), the formula (L-1-3.3) or the formula (L-1-3.4). ) Is more preferable. In particular, the compound represented by the formula (L-1-3.1) is preferable because it has a high effect of improving the response speed of the liquid crystal composition, and when used in a dielectrically negative liquid crystal composition, the compound represented by the formula (L-1-3.1) is preferable. When used in combination with L-1-1.3), a display element having a faster response speed and suppressed deterioration of display quality and reliability due to the UV process can be obtained, which is more preferable. When used in a dielectrically positive liquid crystal composition and / or in combination with the formula (L-1-2.2) of 24% by mass or less, the response speed is further increased, and the display quality and reliability are deteriorated. It is preferable because a display element in which is suppressed can be obtained.

Further, when it is desired to improve Tni higher than the response speed of the liquid crystal composition, the formula (L-1-3.3), the formula (L-1-3.4), and the formula (L-1-3.11) are required. ) Or the compound represented by the formula (L-1-3.12) is preferably used. Formulas (L-1-3.3), formulas (L-1-3.4), formulas (L-1-3.11) and formulas (L-1-3.12) contained in the liquid crystal composition. The total amount of the compounds represented by is preferably less than 20% in order to increase the solubility at low temperature.

The compound represented by the general formula (L-1) is preferably a compound represented by the following general formula (L-1-4) or (L-1-5).

In the formula, ^RL15 and ^RL16 each independently represent an alkyl group having 1 to 8 carbon atoms or an alkoxy group having 1 to 8 carbon atoms.

^RL15 and ^RL16 are independently linear alkyl groups having 1 to 5 carbon atoms, linear alkoxy groups having 1 to 4 carbon atoms, or linear carbon atoms 2 to 2. Alkoxy group of 5 is preferred.

The amount of the compound represented by the general formula (L-1-4) contained in the liquid crystal composition is preferably as follows. That is, the preferable lower limit values are 1% by mass, 5% by mass, 10% by mass, 13% by mass, 15% by mass, 17% by mass, and 20% by mass. On the other hand, the preferable upper limit values are 25% by mass, 23% by mass, 20% by mass, 17% by mass, 15% by mass, 13% by mass, and 10% by mass.

The amount of the compound represented by the general formula (L-1-5) contained in the liquid crystal composition is preferably as follows. That is, the preferable lower limit values are 1% by mass, 5% by mass, 10% by mass, 13% by mass, 15% by mass, 17% by mass, and 20% by mass. On the other hand, the preferable upper limit values are 25% by mass, 23% by mass, 20% by mass, 17% by mass, 15% by mass, 13% by mass, and 10% by mass.

The compounds represented by the general formula (L-1--4) or (L-1-5) are represented by the following formulas (L-1-4.1) to (L-1-4.3) or formula (L-). It is preferably a compound represented by 1-5.1) to (L-1-5.3), and is represented by the formula (L-1-4.2) or the formula (L-1-5.2). It is more preferable that the compound is to be used.

The compounds represented by the general formula (L-1) are the formula (L-1-1.3), the formula (L-1-2.2), the formula (L-1-3.1), and the formula (L). -1-3.3), formula (L-1-3.4), formula (L-1-3.11) and two types selected from the compounds represented by the formula (L-1-3.12). It is preferable to combine the above, and the formula (L-1-1.3), the formula (L-1-2.2), the formula (L-1-3.1), and the formula (L-1-3.3) are preferable. , 2 or more selected from the compounds represented by the formulas (L-1-3.4) and (L-1-4.2) are more preferable.

When the reliability of the liquid crystal composition is emphasized, the compounds represented by the formulas (L-1-3.1), (L-1-3.3) and (L-1-3.4) are used. It is preferable to combine two or more selected types, and when the response speed of the liquid crystal composition is important, the compounds represented by the formulas (L-1-1.3) and (L-1-2.2) are used. It is preferable to combine two or more selected types.

The compound represented by the general formula (L-1) is also preferably a compound represented by the following general formula (L-1-6).

In the formula, ^RL17 and ^RL18 each independently represent a methyl group or a hydrogen atom.

The amount of the compound represented by the general formula (L-1-6) contained in the liquid crystal composition is preferably as follows. That is, the preferable lower limit values are 1% by mass, 5% by mass, 10% by mass, 15% by mass, 17% by mass, 20% by mass, 23% by mass, 25% by mass, 27% by mass, 30% by mass, and 35% by mass. %. On the other hand, the preferable upper limit values are 60% by mass, 55% by mass, 50% by mass, 45% by mass, 42% by mass, 40% by mass, 38% by mass, 35% by mass, 33% by mass and 30% by mass.

The compound represented by the general formula (L-1-6) is preferably a compound represented by the following formulas (L-1-6.1) to (L-1-6.3).

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

^{Wherein, R L21} and ^{R L22} are each the same meanings as ^{R L1} and ^{R L2} in the general formula (L).

^RL21 is preferably an alkyl group having 1 to 5 carbon atoms or an alkenyl group having 2 to 5 carbon atoms.

^RL22 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.

As the compound represented by the general formula (L-2), one type may be used alone, or two or more compounds may be used in combination. The type of compound to be combined is not particularly limited, but is appropriately selected depending on the required performance such as solubility at low temperature, transition temperature, electrical reliability, and birefringence. The types of compounds used are, for example, 1 type, 2 types, 3 types, 4 types, and 5 or more types.

The amount of the compound represented by the general formula (L-2) contained in the liquid crystal composition is preferably as follows. That is, the preferable lower limit value is 1% by mass, 2% by mass, 3% by mass, 5% by mass, 7% by mass, and 10% by mass. On the other hand, the preferable upper limit values are 20% by mass, 15% by mass, 13% by mass, 10% by mass, 8% by mass, 7% by mass, 6% by mass, 5% by mass, and 3% by mass.

When emphasizing the solubility of liquid crystal molecules at low temperature, setting a large amount of the compound represented by the general formula (L-2) is highly effective, and when emphasizing the response speed of the liquid crystal composition, the effect is high. The effect is high when the amount is set small. Further, when improving the dropping marks and the seizure characteristics, it is preferable to set the amount of the compound represented by the general formula (L-2) in the middle of the above range.

The compound represented by the general formula (L-2) is preferably a compound represented by the following formulas (L-2.1) to (L-2.6), and is preferably the compound represented by the following formula (L-2.1). , The compound represented by the formula (L-2.3), the formula (L-2.4) or the formula (L-2.6) is more preferable.

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

^{Wherein, R L31} and ^{R L32} are each the same meanings as ^{R L1} and ^{R L2} in the general formula (L).

Each of ^RL31 and ^RL32 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.

As the compound represented by the general formula (L-3), one type may be used alone, or two or more types may be used in combination. The type of compound to be combined is not particularly limited, but is appropriately selected depending on the required performance such as solubility at low temperature, transition temperature, electrical reliability, and birefringence. The types of compounds used are, for example, 1 type, 2 types, 3 types, 4 types, and 5 or more types.

The amount of the compound represented by the general formula (L-3) contained in the liquid crystal composition is preferably as follows. That is, the preferable lower limit value is 1% by mass, 2% by mass, 3% by mass, 5% by mass, 7% by mass, and 10% by mass. On the other hand, the preferable upper limit values are 20% by mass, 15% by mass, 13% by mass, 10% by mass, 8% by mass, 7% by mass, 6% by mass, 5% by mass, and 3% by mass.

When obtaining a high birefringence, setting a large amount of the compound represented by the general formula (L-3) is highly effective, and when emphasizing high Tni, setting a small amount is effective. Is high. Further, when improving the dripping marks and the seizure characteristics, it is preferable to set the amount of the compound represented by the general formula (L-3) in the middle of the above range.

The compound represented by the general formula (L-3) is represented by the following formulas (L-3.1) to (L-3.4), formula (L-3.6) or formula (L-3.7). It is preferably a compound represented by a compound represented by the formulas (L-3.2) to (L-3.4), formula (L-3.6) or formula (L-3.7). It is preferable to have.

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

^{Wherein, R L41} and ^{R L42} are each the same meanings as ^{R L1} and ^{R L2} in the general formula (L).

^RL41 is preferably an alkyl group having 1 to 5 carbon atoms or an alkenyl group having 2 to 5 carbon atoms.

^RL42 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.

As the compound represented by the general formula (L-4), one kind may be used alone, or two or more kinds may be used in combination. The type of compound to be combined is not particularly limited, but is appropriately selected depending on the required performance such as solubility at low temperature, transition temperature, electrical reliability, and birefringence. The types of compounds used are, for example, 1 type, 2 types, 3 types, 4 types, and 5 or more types.

The amount of the compound represented by the general formula (L-4) contained in the liquid crystal composition includes solubility at low temperature, transition temperature, electrical reliability, birefringence, process compatibility, dripping marks, and seizure. , It is adjusted appropriately according to the required performance such as dielectric anisotropy.

The preferable lower limit values are 1% by mass, 2% by mass, 3% by mass, 5% by mass, 7% by mass, 10% by mass, 14% by mass, 16% by mass, 20% by mass, 23% by mass, and 26% by mass. It is 30% by mass, 35% by mass, and 40% by mass. On the other hand, the preferable upper limit values are 50% by mass, 40% by mass, 35% by mass, 30% by mass, 20% by mass, 15% by mass, 10% by mass, and 5% by mass.

The compound represented by the general formula (L-4) is preferably a compound represented by the following formulas (L-4.1) to (L-4.3).

Depending on the required performance such as solubility at low temperature, transition temperature, electrical reliability, birefringence, the liquid crystal composition may contain only the compound represented by the formula (L-4.1). Whether it contains only the compound represented by the formula (L-4.2) or both the compound represented by the formula (L-4.1) and the compound represented by the formula (L-4.2). Often, all of the compounds represented by the formulas (L-4.1) to (L-4.3) may be included.

The compound represented by the general formula (L-4) is preferably a compound represented by the following formulas (L-4.4) to (L-4.6), and is preferably a compound represented by the following formula (L-4.4). It is more preferable that the compound is represented by.

Depending on the required performance such as solubility at low temperature, transition temperature, electrical reliability, birefringence, the liquid crystal composition may contain only the compound represented by the formula (L-4.4). It may contain only the compound represented by the formula (L-4.5), and includes both the compound represented by the formula (L-4.4) and the compound represented by the formula (L-4.5). It may be.

The compound represented by the general formula (L-4) is preferably a compound represented by the following formulas (L-4.7) to (L-4.10), and is preferably a compound represented by the following formula (L-4.9). The compound represented by is more preferable.

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

^{Wherein, R L51} and ^{R L52} are each the same meanings as ^{R L1} and ^{R L2} in the general formula (L).

The ^RL51 is preferably an alkyl group having 1 to 5 carbon atoms or an alkenyl group having 2 to 5 carbon atoms.

^RL52 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.

As the compound represented by the general formula (L-5), one type may be used alone, or two or more types may be used in combination. The type of compound to be combined is not particularly limited, but is appropriately selected depending on the required performance such as solubility at low temperature, transition temperature, electrical reliability, and birefringence. The types of compounds used are, for example, 1 type, 2 types, 3 types, 4 types, and 5 or more types.

The amount of the compound represented by the general formula (L-5) contained in the liquid crystal composition includes solubility at low temperature, transition temperature, electrical reliability, birefringence, process compatibility, dripping marks, and seizure. , It is adjusted appropriately according to the required performance such as dielectric anisotropy.

The preferable lower limit values are 1% by mass, 2% by mass, 3% by mass, 5% by mass, 7% by mass, 10% by mass, 14% by mass, 16% by mass, 20% by mass, 23% by mass, and 26% by mass. It is 30% by mass, 35% by mass, and 40% by mass. On the other hand, the preferable upper limit values are 50% by mass, 40% by mass, 35% by mass, 30% by mass, 20% by mass, 15% by mass, 10% by mass, and 5% by mass.

The compound represented by the general formula (L-5) is preferably a compound represented by the following formula (L-5.1) or formula (L-5.2), preferably the compound represented by the formula (L-5.1). ) Is more preferable.

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

The compound represented by the general formula (L-5) is preferably a compound represented by the following formulas (L-5.5) to (L-5.7), and the compound is preferably represented by the formula (L-5.7). It is more preferable that the compound is represented by.

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

^{Wherein, R L61} and ^{R L62} each represent the same meaning as ^{R L1} and ^{R L2} in the general formula ^{(L), X L61} and ^{X L62,} one or either a hydrogen atom represents a fluorine atom.
For ^RL61 and ^RL62 , respectively, an alkyl group having 1 to 5 carbon atoms or an alkenyl group having 2 to 5 carbon atoms is preferable, and one of ^XL61 and ^XL62 is a fluorine atom and the other is. It is preferably a hydrogen atom, and more preferably ^XL62 is a fluorine atom.

As the compound represented by the general formula (L-6), one type may be used alone, or two or more types may be used in combination. The type of compound to be combined is not particularly limited, but is appropriately selected depending on the required performance such as solubility at low temperature, transition temperature, electrical reliability, and birefringence. The types of compounds used are, for example, 1 type, 2 types, 3 types, 4 types, and 5 or more types. Further, the compounds from the group represented by the general formula (L-6) are also preferable in order to shorten the process time of UV irradiation in the process of manufacturing the liquid crystal display element of the present invention. As a result, it is possible to prevent or reduce the degree of deterioration of the liquid crystal composition during UV irradiation, the decrease in the voltage holding ratio of the liquid crystal display element, and the occurrence of seizure.

The amount of the compound represented by the general formula (L-6) contained in the liquid crystal composition is preferably as follows. That is, the preferable lower limit values are 1% by mass, 2% by mass, 3% by mass, 5% by mass, 7% by mass, 10% by mass, 14% by mass, 16% by mass, 20% by mass, 23% by mass, and 26% by mass. %, 30% by mass, 35% by mass, and 40% by mass. On the other hand, the preferable upper limit values are 50% by mass, 40% by mass, 35% by mass, 30% by mass, 20% by mass, 15% by mass, 10% by mass, and 5% by mass.

When focusing on increasing Δn, it is preferable to increase the amount of the compound represented by the general formula (L-6), and when focusing on precipitation at a low temperature, increase the amount. It is preferable to reduce the amount.

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

The type of the compound to be combined is not particularly limited, but it is preferable to use 1 to 3 types, and more preferably 1 to 4 types. Further, since the wide molecular weight distribution of the selected compound is also effective for solubility, for example, one of the compounds represented by the formulas (L-6.1) and (L-6.2) is selected from the formulas. One from the compounds represented by (L-6.4) and (L-6.5), and one from the compounds represented by the formulas (L-6.6) and (L-6.7). It is preferable to select a species and one of the compounds represented by the formulas (L-6.8) and (L-6.9) and combine them appropriately. Among them, it is represented by the formula (L-6.1), the formula (L-6.3), the formula (L-6.4), the formula (L-6.6) and the formula (L-6.9). Combinations of compounds are more preferred.

The compound represented by the general formula (L-6) is preferably a compound represented by the following formulas (L-6.10) to (L-6.17), and is preferably a compound represented by the following formula (L-6.11). It is more preferable that the compound is represented by.

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

^{Wherein, R L71} and ^{R L72} are each the same meanings as ^{R L1} and ^{R L2} in the general formula (L).

A ^L71 and A ^L72 have the same meanings as A ^L2 and A ^L3 in the general formula (L), respectively. However, any hydrogen atom present in ^AL71 and ^AL72 may be replaced with a fluorine atom.

Z ^L71 has the same meaning as Z ^L2 in the general formula (L).

X ^L71 and X ^L72 independently represent a fluorine atom or a hydrogen atom.

In the formula, ^RL71 and ^RL72 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.

A ^L71 and A ^L72 are each independently preferably a 1,4-cyclohexylene group or a 1,4-phenylene group. However, any hydrogen atom present in ^AL71 and ^AL72 may be replaced with a fluorine atom.

Z ^L71 is preferably single-bonded or COO-, and more preferably single-bonded.

A hydrogen atom is preferable for X ^L71 and ^{XL 72} , respectively.

The type of compound to be combined is not particularly limited, but is appropriately selected depending on the required performance such as solubility at low temperature, transition temperature, electrical reliability, and birefringence. The types of compounds used are, for example, 1 type, 2 types, 3 types, and 4 types.

The amount of the compound represented by the general formula (L-7) contained in the liquid crystal composition includes solubility at low temperature, transition temperature, electrical reliability, birefringence, process compatibility, dripping marks, and seizure. , It is adjusted appropriately according to the required performance such as dielectric anisotropy.

The preferable lower limit values are 1% by mass, 2% by mass, 3% by mass, 5% by mass, 7% by mass, 10% by mass, 14% by mass, 16% by mass, and 20% by mass. On the other hand, the preferable upper limit values are 30% by mass, 25% by mass, 23% by mass, 20% by mass, 18% by mass, 15% by mass, 10% by mass, and 5% by mass.

When a high Tni of the liquid crystal composition is required, it is preferable to increase the amount of the compound represented by the general formula (L-7), and when low viscosity is desired, the amount thereof is decreased. Is preferable.

The compound represented by the general formula (L-7) is preferably a compound represented by the following formulas (L-7.1) to (L-7.4), and is preferably a compound represented by the following formula (L-7.2). It is more preferable that the compound is represented by.

The compound represented by the general formula (L-7) is preferably a compound represented by the following formulas (L-7.11) to (L-7.13), and is preferably a compound represented by the following formula (L-7.11). It is more preferable that the compound is represented by.

The compound represented by the general formula (L-7) is preferably a compound represented by the following formulas (L-7.21) to (L-7.23), and is preferably represented by the formula (L-7.21). It is more preferable that the compound is represented by.

The compound represented by the general formula (L-7) is preferably a compound represented by the following formulas (L-7.31) to (L-7.34), and is preferably represented by the formula (L-7.31). Alternatively, it is more preferably 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 following formulas (L-7.41) to (L-7.44), and the compound is preferably represented by the formula (L-7. It is more preferably a compound represented by 41) or the formula (L-7.42).

Further, the compound represented by the general formula (L-7) is preferably a compound represented by the following formulas (L-7.51) to (L-7.53).

When a dielectrically positive liquid crystal composition is used, the liquid crystal composition is dielectrically negative (Δε is -2) in addition to containing one or more kinds of dielectrically positive compounds (Δε is +2 or more). It can contain one or more compounds (larger than +2). In this case as well, it is preferable to use a compound selected from the group represented by the general formula (2-A) and the general formula (2-B) as the dielectrically positive compound, and the dielectrically negative compound is generally used. It is preferable to use the compound represented by the formula (5). Further, it is more preferable to contain at least one kind of dielectrically neutral compound represented by the general formula (L). Combining positive and negative compounds dielectrically can increase the average permittivity of the liquid crystal composition. This is preferable in that a liquid crystal display element having a high transmittance can be obtained in a liquid crystal mode driven by a transverse electric field component, and in a mode in which a fringe electric field such as FFS or IPS with a narrow electrode width or a narrow distance between electrodes is likely to occur. It can be used particularly preferably. Even when dielectrically positive and negative compounds are used at the same time, the preferable content of each compound in the entire composition can be appropriately determined according to the above description.

The composition in the present invention may further contain one or more compounds (Q) as additives in order to improve reliability. Compound (Q) preferably has the following structure.

(In the formula, ^RQ represents a hydroxyl group, a hydrogen atom, a linear alkyl group having 1 to 22 carbon atoms or a branched alkyl group, and one or two or more CH ₂ groups in the alkyl group are oxygen atoms. May be replaced with -O-, -CH = CH-, -CO-, -OCO-, -COO-, -C≡C-, -CF ₂ O-, -OCF _2- so that , * Combines with other structures.)
^RQ represents a linear alkyl group or a branched chain alkyl group having 1 to 22 carbon atoms, and one or more CH ₂ groups in the alkyl group are −O so that oxygen atoms are not directly adjacent to each other. −, −CH = CH−, −CO−, −OCO−, −COO−, −C≡C−, −CF ₂ O−, −OCF ₂₋ may be substituted, but the number of carbon atoms is 1 to 10. Linear alkyl group, linear alkoxy group, linear alkyl group in which one CH ₂ group is substituted with -OCO- or -COO-, branched chain alkyl group, branched alkoxy group, one CH ₂ group is -OCO- Alternatively, a branched chain alkyl group substituted with -COO- is preferable, a linear alkyl group having 1 to 20 carbon atoms, and a linear alkyl group in which one CH ₂ group is substituted with -OCO- or -COO-, or branched. A chain alkyl group, a branched alkoxy group, and a branched chain alkyl group in which one CH ₂ group is substituted with -OCO- or -COO- are further preferable. ^MQ represents a trans-1,4-cyclohexylene group, a 1,4-phenylene group or a single bond, with a trans-1,4-cyclohexylene group or a 1,4-phenylene group being preferred.

More specifically, the compound (Q) is preferably a compound represented by the following general formulas (Qa) to (Qd).

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

The composition of the present invention preferably contains one or two compounds represented by the general formula (Q), more preferably one to five, and the content thereof is from 0.001. It is preferably 1%, more preferably 0.001 to 0.1%, and particularly preferably 0.001 to 0.05%.

Further, as the antioxidant or the light stabilizer that can be used in the present invention, more specifically, the compounds represented by the following (Q-1) to (Q-44) are preferable.

(In the formula, n represents an integer from 0 to 20.)
In order to enhance the thermal stability of the liquid crystal composition in the present invention, it is particularly preferable to add an antioxidant. More specific antioxidants include hydroquinone derivatives, nitrosoamine-based polymerization inhibitors, hindered phenol-based antioxidants, etc. More specifically, tert-butylhydroquinone, methylhydroquinone, Wako Pure Chemical Industries, Ltd. Company-made "Q-1300", "Q-1301", BASF's "IRGANOX1010", "IRGANOX1035", "IRGANOX1076", "IRGANOX1098", "IRGANOX1135", "IRGANOX1330", "IRGANOX1425", "IRGANOX1520", Examples thereof include "IRGANOX1726", "IRGANOX245", "IRGANOX259", "IRGANOX3114", "IRGANOX3790", "IRGANOX5057", "IRGANOX565" and the like.

The amount of the antioxidant added is preferably 0.01 to 2.0% by mass, more preferably 0.05 to 1.0% by mass, based on the polymerizable liquid crystal composition.

In order to enhance the stability of the liquid crystal composition in the present invention, it is preferable to add a UV absorber. As the UV absorber, those having excellent absorption ability of ultraviolet rays having a wavelength of 370 nm or less and little absorption of visible light having a wavelength of 400 nm or more are preferable from the viewpoint of good liquid crystal display. More specifically, for example, hindered phenol-based compounds, hydroxybenzophenone-based compounds, benzotriazole-based compounds, salicylic acid ester-based compounds, benzophenone-based compounds, cyanoacrylate-based compounds, nickel complex salt-based compounds, and triazine-based compounds can be mentioned. Examples of dophenol compounds include 2,6-di-tert-butyl-p-cresol, pentaerythrityl-tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], N, N'-hexamethylenebis (3,5-di-tert-butyl-4-hydroxy-hydrocinnamide), 1,3,5-trimethyl-2,4,6-tris (3,5-di-tert-butyl- 4-Hydroxybenzyl) benzene, tris- (3,5-di-tert-butyl-4-hydroxybenzyl) -isocyanurate can be mentioned. Examples of the benzotriazole-based compound include 2- (2'-hydroxy-5'-methylphenyl) benzotriazole and 2,2-methylenebis (4- (1,1,3,3-tetramethylbutyl) -6- (2H). -Benzotriazole-2-yl) phenol), (2,4-bis- (n-octylthio) -6- (4-hydroxy-3,5-di-tert-butylanilino) -1,3,5-triazine, Triethylene glycol-bis [3- (3-tert-butyl-5-methyl-4-hydroxyphenyl) propionate], N, N'-hexamethylenebis (3,5-di-tert-butyl-4-hydroxy-) Hydrocinnamide), 1,3,5-trimethyl-2,4,6-tris (3,5-di-tert-butyl-4-hydroxybenzyl) benzene, 2- (2'-hydroxy-3', 5'- Di-tert-butylphenyl) -5-chlorobenzotriazole, (2- (2'-hydroxy-3', 5'-di-tert-amylphenyl) -5-chlorobenzotriazole, 2,6-di-tert -Butyl-p-cresol, pentaerythrityl-tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], TINUVIN109, TINUVIN171, TINUVIN326, manufactured by BASF Japan Co., Ltd., TINUVIN327, TINUVIN328, TINUVIN770, TINUVIN900, TINUVIN928, and KEMISORB 71, KEMISORB 73, and KEMISORB 74 manufactured by Chemipro Kasei Co., Ltd. can also be preferably used.

Examples of the light stabilizer include "TINUVIN 111FDL", "TINUVIN 123", "TINUVIN 144", "TINUVIN 152", "TINUVIN 292", "TINUVIN 622", "TINUVIN 770", "TINUVIN 765", "TINUVIN 765". 780 ”,“ TINUVIN 905 ”,“ TINUVIN 5100 ”,“ TINUVIN 5050 ”,“ TINUVIN 5060 ”,“ TINUVIN 5151 ”,“ CHIMASSORB 119FL ”,“ CHIMASSORB 944FL ”,“ CHIMASSORB 944LD , "ADEKA STAB LA-52", "ADEKA STAB LA-57", "ADEKA STAB LA-62", "ADEKA STAB LA-67", "ADEKA STAB LA-63P", "ADEKA STAB LA-68LD", "ADEKA STAB LA-77", Examples thereof include "ADEKA STAB LA-82" and "ADEKA STAB LA-87" (all manufactured by ADEKA CORPORATION).

In addition, the liquid crystal composition of the present invention may further contain a surfactant.

Of these, surfactants having a polymerizable group are preferable. For example, among the surfactants having a polymerizable group, "Antox SAD" and "Antox MS-2N" (above, Japan Emulsifier Co., Ltd.) are preferred as anionic ones. (Manufactured by the company), "Aqualon KH-05", "Aqualon KH-10", "Aqualon KH-20", "Aqualon KH-0530", "Aqualon KH-1025" (manufactured by Daiichi Kogyo Seiyaku Co., Ltd.), Alkyl ethers such as "Adecaria Soap SR-10N", "Adecaria Soap SR-20N" (manufactured by ADEKA Corporation), "Latemuru PD-104" (manufactured by Kao Corporation), "Latemuru S-120" , "Latemuru S-120A", "Latemuru S-180P", "Latemuru S-180A" (manufactured by Kao Corporation), "Ereminol JS-2" (manufactured by Sanyo Kasei Co., Ltd.), etc. , "Aqualon H-2855A", "Aqualon H-3855B", "Aqualon H-3855C", "Aqualon H-3856", "Aqualon HS-05", "Aqualon HS-10", "Aqualon HS-20", "Aqualon HS-30", "Aqualon HS-1025", "Aqualon BC-05", "Aqualon BC-10", "Aqualon BC-20", "Aqualon BC-1025", "Aqualon BC-1020" (and above) , Made by Daiichi Kogyo Seiyaku Co., Ltd.), "Adecaria Soap SDX-222", "Adecaria Soap SDX-223", "Adecaria Soap SDX-232", "Adecaria Soap SDX-233", "Adecaria Soap" Alkylphenyl ether or alkylphenyl ester type such as "SDX-259", "Adecaria Soap SE-10N", "Adecaria Soap SE-20N" (all manufactured by ADEKA Corporation), "Antox MS-60", (Meta) acrylate sulfate ester type such as "Antox MS-2N" (manufactured by Nippon Emulsifier Co., Ltd.), "Eleminor RS-30" (manufactured by Sanyo Kasei Co., Ltd.), "H-3330P" (Daiichi Kogyo Co., Ltd.) Phosphate esters such as "Adecaria Soap PP-70" (manufactured by ADEKA Corporation), etc. (manufactured by Pharmaceutical Co., Ltd.) can be mentioned.

On the other hand, among the surfactants having a polymerizable group, nonionic ones include, for example, "Antox LMA-20", "Antox LMA-27", "Antox EMH-20", and "Antox LMH-". 20, "Antox SMH-20" (manufactured by Nippon Emulsorium Co., Ltd.), "ADEKA RIA SOLP ER-10", "ADEKA RIA SOLP ER-20", "ADEKA RIA SOLP ER-30", "ADEKA CORPORATION" Alkyl ethers such as "ER-40" (manufactured by ADEKA Corporation), "Latemuru PD-420", "Latemuru PD-430", "Latemuru PD-450" (manufactured by Kao Corporation), "Aqualon" RN-10, "Aqualon RN-20", "Aqualon RN-30", "Aqualon RN-50", "Aqualon RN-2025" (manufactured by Daiichi Kogyo Seiyaku Co., Ltd.), "Adeka Rear Soap NE-" 10 ”,“ Adecaria Soap NE-20 ”,“ Adecaria Soap NE-30 ”,“ Adecaria Soap NE-40 ”(above, manufactured by ADEKA Corporation), etc., alkylphenyl ether type or alkylphenyl ester type, Examples thereof include (meth) acrylate sulfate esters such as "RMA-564", "RMA-568", and "RMA-1114" (all manufactured by Nippon Emulsifier Co., Ltd.).

Further, the liquid crystal composition of the present invention may further contain a known spontaneous orientation aid for liquid crystal compositions in addition to the compound represented by the general formula (i).

(Liquid crystal display element)
The liquid crystal composition of the present embodiment is applied to a liquid crystal display element. The liquid crystal display element may be a liquid crystal display element for driving an active matrix. The liquid crystal display element 1 may be an IPS type, FFS type or PSA type, PSVA type, VA type, or ECB type liquid crystal display element, and more preferably an IPS type or FFS type liquid crystal display element.

Since the liquid crystal display element of the present embodiment uses a liquid crystal composition containing a compound represented by the general formula (i), the orientation of the polyimide alignment film or the like on the liquid crystal layer side of the first substrate and the second substrate. There is no need for a membrane to be provided. That is, the liquid crystal display element of the present embodiment can have a configuration in which at least one of the two substrates does not have an alignment film such as a polyimide alignment film.

(Liquid crystal display element)
The liquid crystal composition of the present invention as described above is applied to a liquid crystal display element in FFS mode. Hereinafter, an example of the FFS mode liquid crystal display element according to the present invention will be described with reference to FIGS. 1 to 6, but the present invention is not limited to the FFS mode liquid crystal display element as described above.
In the present invention, either a liquid crystal composition having a positive or negative dielectric anisotropy may be used, but the case of a liquid crystal composition having a negative dielectric anisotropy will be described below.

FIG. 1 is a diagram schematically showing a configuration of a liquid crystal display element. In FIG. 1, each component is described separately for convenience of explanation. As shown in FIG. 1, the configuration of the liquid crystal display element 10 according to the present invention is a liquid crystal composition sandwiched between a first transparent insulating substrate 2 arranged to face each other and a second transparent insulating substrate 7. It is an FFS mode liquid crystal display element having an object (or a liquid crystal layer 5), and is characterized in that the liquid crystal composition of the present invention is used as the liquid crystal composition. In the first transparent insulating substrate 2, the electrode layer 3 is formed on the surface on the liquid crystal layer 5 side. Further, a pair of layers that directly contact the liquid crystal layer 5 and each of the first transparent insulating substrate 2 and the second transparent insulating substrate 7 with the liquid crystal composition constituting the liquid crystal layer 5 to induce homogenic orientation. It has a coalescence 4, and the liquid crystal molecules in the liquid crystal composition are oriented so as to be substantially parallel to the substrates 2 and 7 when no voltage is applied. As shown in FIGS. 1 and 3, the first substrate 2 and the second substrate 7 may be sandwiched by a pair of polarizing plates 1 and 8. Further, in FIG. 1, a color filter 6 is provided between the second substrate 7 and the polymer 4. However, the liquid crystal display element of the present invention is characterized in that one or both of the pair of alignment films conventionally provided are not provided.

That is, the liquid crystal display element 10 according to the present invention includes a first polarizing plate 1, a first substrate 2, an electrode layer 3 including a thin film transistor, a polymer 4, and a liquid crystal layer 5 containing a liquid crystal composition. The polymer 4, the color filter 6, the second substrate 7, and the second polarizing plate 8 are sequentially laminated.

That is, the liquid crystal display element 10 according to the present invention includes a first polarizing plate 1, a first substrate 2, an electrode layer 3 including a thin film transistor, a liquid crystal layer 5 containing a liquid crystal composition, and a color filter 6. The second substrate 7 and the second polarizing plate 8 are sequentially laminated. For the first substrate 2 and the second substrate 7, a transparent material having flexibility such as glass or plastic can be used, and one of them may be an opaque material such as silicon. The two substrates 2 and 7 are bonded by a sealing material and a sealing material such as an epoxy-based thermosetting composition arranged in a peripheral region, and in order to maintain a distance between the substrates, for example, Granular spacers such as glass particles, plastic particles, and alumina particles, or spacer columns made of resin formed by a photolithography method may be arranged.

FIG. 2 is an enlarged plan view of the region of the electrode layer 3 formed on the substrate 2 in FIG. 1 surrounded by the line II. FIG. 3 is a cross-sectional view of the liquid crystal display element shown in FIG. 1 cut in the direction of lines III-III in FIG. As shown in FIG. 2, the electrode layer 3 including the thin film transistor formed on the surface of the first substrate 2 has a plurality of gate bus lines 26 for supplying scanning signals and a plurality of gate bus lines 26 for supplying display signals. The data bus lines 25 are arranged so as to intersect each other in a matrix. Note that FIG. 2 shows only a pair of gate bus lines 25 and a pair of data bus lines 24.

A unit pixel of a liquid crystal display device is formed by an area surrounded by a plurality of gate bus lines 26 and a plurality of data bus lines 25, and a pixel electrode 21 and a common electrode 22 are formed in the unit pixel. .. A thin film transistor including a source electrode 27, a drain electrode 24, and a gate electrode 28 is provided in the vicinity of the intersection where the gate bus line 26 and the data bus line 25 intersect with each other. This thin film transistor is connected to the pixel electrode 21 as a switch element that supplies a display signal to the pixel electrode 21. Further, a common line 29 is provided in parallel with the gate bus line 26. The common line 29 is connected to the common electrode 22 in order to supply a common signal to the common electrode 22.

As shown in FIG. 3, a preferred embodiment of the structure of the thin film transistor is provided so as to cover the gate electrode 11 formed on the surface of the substrate 2 and the gate electrode 11 and substantially the entire surface of the substrate 2. A protective film provided so as to cover a part of the surface of the gate insulating layer 12, the semiconductor layer 13 formed on the surface of the gate insulating layer 12 so as to face the gate electrode 11, and the surface of the semiconductor layer 17. A drain electrode 16 provided to cover one side end of the protective layer 14 and the semiconductor layer 13 and to be in contact with the gate insulating layer 12 formed on the surface of the substrate 2, and the protection. A source electrode 17 provided so as to cover the other side end of the film 14 and the semiconductor layer 13 and in contact with the gate insulating layer 12 formed on the surface of the substrate 2, the drain electrode 16 and the source. It has an insulating protective layer 18 provided so as to cover the electrode 17. An anodized film (not shown) may be formed on the surface of the gate electrode 11 for reasons such as eliminating a step with the gate electrode.

Amorphous silicon, polycrystalline polysilicon, and the like can be used for the semiconductor layer 13, but if a transparent semiconductor film such as ZnO, IGZO (In-Ga-Zn-O), or ITO is used, it is caused by light absorption. It is also preferable from the viewpoint of suppressing the harmful effects of optical carriers and increasing the opening ratio of the device.

Further, an ohmic contact layer 15 may be provided between the semiconductor layer 13 and the drain electrode 16 or the source electrode 17 for the purpose of reducing the width and height of the Schottky barrier. For the ohmic contact layer, a material to which impurities such as phosphorus such as n-type amorphous silicon and n-type polycrystalline polysilicon are added at a high concentration can be used.

The gate bus line 26, the data bus line 25, and the common line 29 are preferably metal films, more preferably Al, Cu, Au, Ag, Cr, Ta, Ti, Mo, W, Ni or an alloy thereof, and Al or It is particularly preferable to use the wiring of the alloy. The insulating protective layer 18 is a layer having an insulating function, and is formed of silicon nitride, silicon dioxide, a silicon oxynitride film, or the like.

In the embodiment shown in FIGS. 2 and 3, the common electrode 22 is a flat plate-shaped electrode formed on substantially the entire surface of the gate insulating layer 12, while the pixel electrode 21 is an insulating protective layer 18 covering the common electrode 22. It is a comb-shaped electrode formed on the top. That is, the common electrode 22 is arranged at a position closer to the first substrate 2 than the pixel electrode 21, and these electrodes are arranged so as to overlap each other via the insulating protective layer 18. The pixel electrode 21 and the common electrode 22 are formed of, for example, a transparent conductive material such as ITO (Indium Tin Oxide), IZO (Indium Zinc Oxide), and IZTO (Indium Zinc Tin Oxide). Since the pixel electrode 21 and the common electrode 22 are formed of a transparent conductive material, the area opened in a unit pixel area becomes large, and the opening ratio and the transmittance increase.

In order to form a fringe electric field between the pixel electrode 21 and the common electrode 22, the distance between the electrodes in the horizontal direction on the substrate between the pixel electrode 21 and the common electrode 22: R is the first substrate. Distance between 2 and the second substrate 7: It is formed so as to be smaller than G. Here, the distance between the electrodes: R represents the distance in the horizontal direction on the substrate between the electrodes. FIG. 3 shows an example in which the distance between the electrodes: R = 0 because the flat plate-shaped common electrode 22 and the comb-shaped pixel electrode 21 overlap each other, and the distance between the electrodes: R is the first substrate. Distance between 2 and the second substrate 7 (that is, cell gap): Since it is smaller than G, a fringe electric field E is formed. Therefore, the FFS type liquid crystal display element can utilize a horizontal electric field formed in a direction perpendicular to the comb-shaped line of the pixel electrode 21 and a parabolic electric field. The electrode width of the comb-shaped portion of the pixel electrode 21: l and the width of the gap of the comb-shaped portion of the pixel electrode 21: m are such that all the liquid crystal molecules in the liquid crystal layer 5 can be driven by the generated electric field. It is preferable to form.

From the viewpoint of preventing light leakage, the color filter 6 preferably forms a black matrix (not shown) in a portion corresponding to the thin film transistor and the storage capacitor 23.

When the alignment film is provided on one side, the alignment film is positioned as a layer in contact with the polymer 4. This is, for example, a rubbing-treated polyimide film, and the orientation directions of the alignment films are parallel. Here, the rubbing direction of the alignment film (orientation direction of the liquid crystal composition) in the present embodiment will be described with reference to FIG. FIG. 4 is a diagram schematically showing the orientation direction of the liquid crystal induced by the alignment film.
When the alignment film is not included on both sides, uniform uniaxial orientation of the liquid crystal molecules can be realized by performing (polarized) UV treatment on the liquid crystal display element, rubbing treatment on the substrate, or the like.
However, it should be noted that the molecules along the polarization axis of UV irradiation selectively react and are consumed, so that the orientation axis of the liquid crystal molecules is relatively perpendicular to the UV polarization axis. .. By the way, in the case of the rubbing treatment, the orientation axis of the liquid crystal molecules is parallel to the rubbing axis.

When the direction perpendicular to the comb-shaped line of the pixel electrode 21 (the direction in which the horizontal electric field is formed) is the x-axis, the angle θ formed by the x-axis and the long-axis direction of the liquid crystal molecule 30 is determined. It is preferable that the orientation is approximately 0 to 45 °. When the orientation is taken into consideration, the angle is preferably 5 to 45 °, preferably 0 to 10 ° from the viewpoint of transmittance at the time of black display, and preferably 3 to 8 ° in consideration of the balance between the two.
In the example shown in FIG. 3, an example is shown in which the angle θ formed by the x-axis and the long-axis direction of the liquid crystal molecule 30 is approximately 0 °. The reason for inducing the orientation direction of the liquid crystal in this way is to increase the maximum transmittance of the liquid crystal display device.

Further, the polarizing plate 1 and the polarizing plate 8 can be adjusted so that the viewing angle and the contrast are good by adjusting the polarization axes of the polarizing plates so that the transmission axes thereof operate in the normal black mode. It is preferable to have transmission axes that are orthogonal to each other. In particular, it is preferable that either the polarizing plate 1 or the polarizing plate 8 is arranged so as to have a transmission axis parallel to the orientation direction of the liquid crystal molecules 30. Further, it is preferable to adjust the product of the refractive index anisotropy Δn of the liquid crystal and the cell thickness d so that the contrast is maximized. Further, a retardation film for widening the viewing angle can also be used.

The FFS type liquid crystal display device 10 having the above configuration supplies an image signal (voltage) to the pixel electrode 21 via the thin film TFT to generate a fringe electric field between the pixel electrode 21 and the common electrode 22. Then, the liquid crystal is driven by this electric field. That is, in a state where no voltage is applied, the liquid crystal molecules 30 are arranged so that their major axis directions are parallel. When a voltage is applied, equipotential lines of a parabolic electric field are formed between the pixel electrode 21 and the common electrode 22 up to the upper part of the pixel electrode 21 and the common electrode 22, and the liquid crystal molecules 30 in the liquid crystal layer 5 are formed. It rotates in the liquid crystal layer 5 along the generated electric field. In the present invention, since the liquid crystal molecule 30 having a negative dielectric anisotropy is used, the long axis direction of the liquid crystal molecule 30 rotates so as to be orthogonal to the generated electric field direction. Although the liquid crystal molecule 30 located near the pixel electrode 21 is easily affected by the fringe electric field, the liquid crystal molecule 30 having negative dielectric anisotropy has a polarization direction on the minor axis of the molecule, so that the major axis direction thereof. Does not rotate in the direction orthogonal to the alignment film 4, and the long axis direction of all the liquid crystal molecules 30 in the liquid crystal layer 5 can be maintained in the direction parallel to the alignment film 4. Therefore, it is possible to obtain excellent transmittance characteristics as compared with the FFS type liquid crystal display element using the liquid crystal molecules 30 having positive dielectric anisotropy.

The FFS type liquid crystal display element described with reference to FIGS. 1 to 4 is an example, and can be implemented in various other forms as long as it does not deviate from the technical idea of the present invention. For example, FIG. 5 is another example of an enlarged plan view of the region of the electrode layer 3 formed on the substrate 2 in FIG. 1 surrounded by the line II. As shown in FIG. 5, the pixel electrode 21 may have a slit. Further, the slit pattern may be formed so as to have an inclination angle with respect to the gate bus line 26 or the data bus line 25.

Further, FIG. 6 is another example of a cross-sectional view in which the liquid crystal display element shown in FIG. 1 is cut in the direction of lines III-III in FIG. In the example shown in FIG. 6, a common electrode 22 having a comb shape or a slit is used, and the distance between the electrodes in the horizontal direction between the pixel electrode 21 and the common electrode 22 on the substrate is R = α. Further, in FIG. 3, an example in which the common electrode 22 is formed on the gate insulating film 12 is shown, but as shown in FIG. 6, the common electrode 22 is formed on the first substrate 2. The pixel electrode 21 may be provided via the gate insulating film 12. The electrode width of the pixel electrode 21: l, the electrode width of the common electrode 22: n, and the distance between the electrodes: R are appropriately adjusted to a width such that all the liquid crystal molecules in the liquid crystal layer 5 can be driven by the generated electric field. Is preferable.

Further, as shown in FIG. 7, the pixel electrode 41 and the common electrode 42 may be provided on the same surface in a state of being separated and meshed with each other. Also in the FFS type display element having the structure shown in FIG. 7, the distance R between the electrodes in the horizontal direction is formed on the substrate so as to be smaller than the distance G between the first substrate 2 and the second substrate 7.

Since the FFS mode liquid crystal display element according to the present invention uses a specific liquid crystal composition, it is possible to achieve both high-speed response and suppression of display defects.

(Manufacturing method of liquid crystal display element)
The liquid crystal composition of the present invention is a liquid crystal display element in which the compound (i) contained therein is polymerized by irradiation with ultraviolet rays to impart liquid crystal orientation ability, and the amount of transmitted light is controlled by utilizing the birefringence of the composition. Used for. As liquid crystal display elements, AM-LCD (active matrix liquid crystal display element), TN (nematic liquid crystal display element), STN-LCD (super twisted nematic liquid crystal display element), OCB-LCD and IPS-LCD (inplane switching liquid crystal display element) ), But it is particularly useful for AM-LCDs, and can be used for transmissive or reflective liquid crystal display elements. As a further feature, the compound (II) contained in the liquid crystal composition of the present invention is polymerized by irradiation with ultraviolet rays to stabilize the orientation of the entire liquid crystal, so that the transition from when a voltage is applied to when no voltage is applied. The off response at the time of can be speeded up.

Next, as described above, the method for manufacturing a liquid crystal display element of the present invention comprises two substrates and the nematic liquid crystal composition according to any one of claims 1 to 13 provided between the two substrates. It is characterized in that a polymer of the compound represented by the general formula (II) is formed on a substrate so as to be in contact with the liquid crystal layer by sandwiching the liquid crystal layer containing the above and irradiating with polarized UV. is there.

To explain the manufacturing method in more detail, a preparatory step [1] for preparing the substrate and the liquid crystal composition, a hydrophilization treatment step [2] for applying the hydrophilization treatment to the substrate, and an assembly for assembling the liquid crystal display element 1. It has a step [3], a polymerization step [4] of irradiating a polarized UV to polymerize an orientation aid and / or a polymerizable compound, and a curing step [5] of curing the sealing material. The hydrophilization treatment step [2] is preferably performed in this step, but can be omitted.

[1] Preparation Step First, the active matrix substrate AM, the color filter substrate CF, and the above-mentioned liquid crystal composition are prepared.

The two substrates used for the liquid crystal display element can be made of a transparent material having flexibility such as glass or plastic, and one of them may be an opaque material such as silicon. A transparent substrate having a transparent electrode layer can be obtained, for example, by sputtering indium tin oxide (ITO) on a transparent substrate such as a glass plate.

The color filter can be produced by, for example, a pigment dispersion method, a printing method, an electrodeposition method, a dyeing method, or the like. To explain a method for producing a color filter by a pigment dispersion method as an example, a curable coloring composition for a color filter is applied onto the transparent substrate, subjected to a patterning treatment, and cured by heating or light irradiation. By performing this step for each of the three colors of red, green, and blue, a pixel portion for a color filter can be created. In addition, a pixel electrode provided with an active element such as a TFT, a thin film diode, or a metal insulator metal resistivity element may be installed on the substrate.

[2] Hydrophilization treatment step (first step)
Next, each of the surfaces of the active matrix substrate AM and the color filter substrate CF in contact with the liquid crystal layer (contact surfaces of the substrate AM and CF) may be subjected to a hydrophilic treatment. It should be noted that this step may be performed as needed and may be omitted.

By subjecting the hydrophilic treatment, the hydrophilicity of the contact surfaces of the substrates AM and CF (hereinafter, also simply referred to as “contact surfaces”) can be increased. Therefore, the polar group of the orientation aid contained in the liquid crystal composition can be firmly fixed to the inner surface. In addition, the orientation aid can be oriented so that the mesogen group is separated from the contact surface. As a result, the liquid crystal molecules can be more reliably held in the liquid crystal layer in an oriented state.

As the hydrophilic treatment (polarity improving treatment), for example, physical treatment such as ozone treatment, corona treatment, oxygen plasma treatment, addition of surfactant, polyethylene glycol, polyvinyl alcohol, etc., introduction of a functional group having hydrophilicity Such as chemical treatment and the like. In these treatments, one type can be used alone, or two or more types can be used in combination.

Among them, as the hydrophilic treatment, a physical treatment is preferable, and an ozone treatment is more preferable. According to ozone treatment, a hydroxyl group can be introduced into the contact surface to increase hydrophilicity (polarity). Further, since the ozone treatment (physical treatment) has a high cleaning effect, impurities (for example, resist residue and the like) adhering to the inner surface can be removed. Therefore, the polar groups of the orientation aid are more easily adsorbed on the contact surface.

<Ozone treatment>
Ozone treatment is a method in which oxygen in the air is converted into ozone by irradiation with ultraviolet rays (UV), and the surface is modified by an ozone-containing atmosphere.

A low-pressure mercury lamp is preferable as the UV light source. The low-pressure mercury lamp has emission spectra at wavelengths of about 185 nm and 254 nm, generates ozone with light having a wavelength of about 185 nm, decomposes ozone with light having a wavelength of about 254 nm, and generates active oxygen. It is known to do. Therefore, by using a low-pressure mercury lamp, the contact surface can be efficiently hydrophilized.

The gas that is the source of ozone generation may be any gas containing oxygen, and oxygen gas, dry air, or the like can be used.

Further, the pressure of the ozone treatment atmosphere may be either reduced pressure or atmospheric pressure.

The ozone treatment time (UV irradiation time) is not particularly limited, but is preferably about 5 to 100 seconds, and more preferably about 10 to 60 seconds.

<Corona processing>
Corona treatment is a method of surface modification using corona discharge excited by applying a high voltage alternating current to a pair of electrodes under atmospheric pressure.

<Oxygen plasma treatment>
Oxygen plasma treatment is a method in which a processing gas containing oxygen gas is ionized by arc discharge, and surface modification is performed using the oxygen plasma generated at this time.

As the treatment gas, a mixed gas of oxygen gas and an inert gas such as nitrogen gas, argon gas, and helium gas can be used.

The amount of oxygen gas supplied is preferably about 0.5 to 50 sccm, and the atmospheric pressure is preferably about 0.1 to 50 Pa.

The electric power applied from the power source at the time of arc discharge is preferably about 10 to 500 W, and the frequency of the power source is preferably about 1 to 50 kHz.

The static contact angle of water at 25 ° C. is preferably 70 ° or less, and more preferably 60 ° or less in the entire region of the contact surface after the hydrophilization treatment.

When the pixel electrode layer 5 and the common electrode layer 9 include an organic insulating film, the static contact angle of water at 25 ° C. on the surface of the organic insulating film is preferably 70 ° or less, preferably about 40 to 55 °. Is more preferable. The static contact angle of water at 25 ° C. on the surface of the ITO film (metal oxide film) is preferably 30 ° or less, more preferably about 10 to 20 °.

Further, the surface free energy is preferably 50 mN / m or more, more preferably 60 mN / m or more in the entire region of the contact surface after the hydrophilic treatment.

When the pixel electrode layer and the common electrode layer include an organic insulating film, the surface free energy of the surface of the organic insulating film is preferably 50 mN / m or more, and more preferably about 55 to 65 mN / m. The surface free energy of the surface of the ITO film (metal oxide film) is preferably 70 mN / m or more, and more preferably about 75 to 85 mN / m.

By setting the static contact angle and the surface free energy in the above ranges, the alignment aid can be evenly supplied to almost the entire surface of the contact surface, and the orientation aid is more firmly adsorbed (fixed) on the contact surface. can do.

[3] Assembly process (second process)
Next, the sealant is drawn in a closed loop bank shape using a dispenser along at least one edge of the active matrix substrate AM and the color filter substrate CF.

Here, the substrates are opposed to each other so that the transparent electrode layer is on the inside. At that time, the spacing between the substrates may be adjusted via a spacer. At this time, it is preferable to adjust the thickness d of the obtained dimming layer to be 1 to 100 μm. 1.5 to 10 μm is more preferable, and 2.5 to 4.0 μm is particularly preferable. When a polarizing plate is used, it is preferable to adjust the product of the refractive index anisotropy Δn of the liquid crystal and the cell thickness d so that the contrast is maximized. Further, when there are two polarizing plates, the polarization axis of each polarizing plate can be adjusted so that the viewing angle and contrast can be improved. Further, a retardation film for widening the viewing angle can also be used. Examples of the spacer include a columnar spacer made of glass particles, plastic particles, alumina particles, a photoresist material, and the like.

Then, under a reduced pressure state, a predetermined amount of the liquid crystal composition is dropped inside the sealing material, and the liquid crystal composition is sandwiched between the two substrates. As this method, a normal vacuum injection method, an ODF (One Drop Fill) method, an inkjet method, or the like can be used, but the vacuum injection method has a problem that a drop mark is not generated but an injection mark remains. However, in the present invention, it can be preferably used by a display element manufactured by using the ODF method. In the ODF method liquid crystal display element manufacturing process, a sealant such as epoxy-based photothermal combination curable is drawn on either the backplane or frontplane as a closed-loop bank using a dispenser, and the sealant is removed from the substrate. A liquid crystal display element can be manufactured by dropping a predetermined amount of the composition under air and then joining the front plane and the back plane. The composition of the present invention can be suitably used because the composition can be stably dropped in the ODF step.

In the ODF method, it is necessary to drop the optimum injection amount according to the size of the liquid crystal display element 1. The liquid crystal composition as described above is less affected by sudden pressure changes and impacts in the dropping device that occur during dropping, and can be stably dropped for a long period of time. Therefore, the yield of the liquid crystal display element 1 can be maintained high.

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

Further, according to the ODF method, it is possible to suppress the generation of dropping marks when the liquid crystal composition is dropped on the substrate. The dripping mark is a phenomenon in which the dripping mark of the liquid crystal composition appears white because it is scattered when the liquid crystal composition is displayed in black or white.
As described above, the active matrix substrate AM and the color filter substrate CF can be arranged to face each other so as to come into contact with the liquid crystal composition.

[4] Polymerization step (third step)
When the orientation aid contains a polymerizable group and / or when the liquid crystal composition contains a polymerizable compound, the liquid crystal composition is irradiated with active energy rays such as ultraviolet rays and electron beams to assist the orientation. Polymerize the agent and / or the polymerizable compound.

As a result, a liquid crystal layer is formed, and a liquid crystal display element can be obtained. At this time, since the alignment aid is fixed to the two substrates AM and CF, the polymer of the orientation aid and / or the polymerizable compound is unevenly distributed on the substrates AM and CF side in the liquid crystal layer.

When the polymerization is carried out with the two substrates facing each other so as to be in contact with the liquid crystal composition as in the present embodiment, at least the substrate located on the irradiation surface side is suitable for the active energy rays. Must have good transparency.

Further, the polymerization may be carried out in a plurality of steps as follows. Specifically, first, only the orientation aid and / or the polymerizable compound present in a specific region of the liquid crystal composition is polymerized using a mask. After that, conditions such as electric field, magnetic field, and temperature are adjusted to change the orientation state of the liquid crystal molecules in the unpolymerized region. In this state, the active energy rays are further irradiated to polymerize the orientation aid and / or the polymerizable compound present in the unpolymerized region. As another specific example, first, the compound represented by the general formula (i) is preferentially polymerized near the surface of the substrate, and then the compound represented by the general formula (II) is polymerized in the entire liquid crystal medium. Can be mentioned. First, as a means for preferentially polymerizing the compound represented by the general formula (i) near the surface of the substrate, the absorption wavelength of the compound represented by the general formula (i) and the compound represented by the general formula (II) A method of designing molecules so that the absorption wavelengths are different and selecting the absorption wavelength of the compound represented by the general formula (i) as the irradiation wavelength, which has the same absorption wavelength as the absorption wavelength of the compound represented by the general formula (II). The method of adding a light absorber and the irradiation method of the irradiation wavelength should be such that the irradiation is performed not in the direction perpendicular to the substrate but in an oblique direction, preferably near the critical angle, more preferably from an angle equal to or higher than the critical angle. However, these methods may be used in combination. The absorption maximum of the compound represented by the general formula (II) is not 300 nm or more, and the absorption maximum of the compound of the general formula (i) having a photoisomerizing group or a dimerization group is 305 nm or more. The composition of is originally satisfied with the above-mentioned preferable design conditions. Therefore, it is preferable to first select light having a wavelength of 305 nm or more as the wavelength for preferentially polymerizing the compound represented by the general formula (i) in the vicinity of the substrate surface. It is also preferable to add a light absorber having an absorption maximum at 270 to 305 nm, more preferably 275 to 300 nm, and particularly preferably 280 to 295 nm as the light absorber. First, polarized light is preferably selected as the irradiation light for preferentially polymerizing the compound represented by the general formula (i) in the vicinity of the substrate surface, and its wavelength is 305 nm or more, more preferably 310 nm or more, and particularly preferably 315 nm or more. Is preferably contained. Further, the irradiation light needs to include light having a sensitivity wavelength of a photoisomerizing group or a dimerizing group of the compound represented by the general formula (i). Specifically, when an azobenzene structure is selected as the photoisomerizing group, it needs to contain light having a wavelength of 330 to 380 nm, preferably 340 to 370 nm, and more preferably 350 to 365 nm. When a cinnamic acid ester skeleton is selected as the dimerization group, it needs to contain light having a wavelength of 300 to 350 nm, preferably 303 to 330 nm, and more preferably 305 to 320 nm. The temperature at the time of irradiation is more preferably a temperature equal to or higher than Tni of the liquid crystal composition of the present invention. Further, the wavelength for polymerizing the compound represented by the general formula (II) in the entire liquid crystal is preferably 290 nm or more, and is preferably unpolarized. The temperature at the time of irradiation is preferably Tni or less, and is preferably set to 15 to 40 ° C.

As the light source lamp, a metal halide lamp, a high-pressure mercury lamp, an ultra-high pressure mercury lamp, or the like can be used.

Further, the ultraviolet rays to be irradiated are preferably ultraviolet rays having a wavelength other than the absorption wavelength range of the liquid crystal composition, and it is more preferable to cut a predetermined wavelength as necessary.
The intensity of the active energy rays (particularly ultraviolet rays) to be irradiated is preferably about 0.1 mW / cm ^{2 to} 100 W / cm ² , and more preferably about ² mW / cm ^{2 to} 50 W / cm ² . The activation energy ray may be irradiated while changing the intensity.

The amount of energy of the active energy rays (particularly ultraviolet rays) to be irradiated can be appropriately adjusted, but is preferably about 10 mJ / cm ^{2 to} 500 J / cm ² , and preferably about 100 mJ / cm ^{2 to} 200 J / cm ^2. Is more preferable.

The time for irradiating the active energy rays (particularly ultraviolet rays) is appropriately selected depending on the intensity thereof, but is preferably 10 to 7200 seconds, more preferably 10 to 3600 seconds, and more preferably 10 to 600 seconds. Is even more preferable.

At this time, for example, by appropriately adjusting the irradiation time of the active energy rays to be irradiated, the amount of the alignment aid contained in the liquid crystal composition, and the like, the surface roughness (Ra) caused by the polymer of the polymerizable monomer can be adjusted. Can be set.

The temperature when irradiating with ultraviolet rays is preferably a temperature equal to or lower than Tni of the liquid crystal composition from the viewpoint of reliability such as voltage retention and twist angle stability, and from the viewpoint of uniform orientation of the liquid crystal composition and residual monomers. It is preferably Tni or higher, and further preferably the temperature is Tni + 30 ° C. or higher.

In the liquid crystal composition as described above, since the orientation aid does not inhibit the polymerization reaction of the polymerizable compound, the polymerizable compounds are suitably polymerized with each other, and the unreacted polymerizable compound remains in the liquid crystal composition. Can be suppressed.

In the assembly step [3], the vacuum injection method may be used instead of the drop injection (ODF) method. For example, in the vacuum injection method, first, the sealing material is screen-printed along at least one edge of the active matrix substrate AM and the color filter substrate CF so as to leave an injection port. After that, the two substrates AM and CF are bonded together, and the sealing material is thermoset by heating. Next, after sealing the injection port, the process proceeds to [4] polymerization step.

The liquid crystal display element thus obtained is preferably a PSA type, PSVA type, VA type, IPS type, FFS type or ECB type liquid crystal display element, and is an IPS type, FFS type or ECB type liquid crystal display. It is more preferably an element.

Although the liquid crystal display element and the method for manufacturing the liquid crystal display element of the present invention have been described above, the present invention is not limited to the above-described embodiment.

For example, the liquid crystal display element of the present invention may replace a part of the configuration with another configuration exhibiting the same function, or may add an arbitrary configuration. Further, the method for manufacturing a liquid crystal display element of the present invention may have an additional step having an arbitrary purpose, or may be replaced with an arbitrary step in which the same action / effect can be obtained.

Further, the liquid crystal display element of the above embodiment has a configuration in which both the active matrix substrate AM and the color filter substrate CF are in direct contact with the liquid crystal layer 4 without passing through the polyimide (PI) alignment film. A PI alignment film may be provided. In this case, the surface of the PI alignment film may or may not be hydrophilized.
If a PI alignment film is provided, the active matrix substrate AM (substrate having pixel electrodes) side is preferable from the viewpoint of the influence of heat on the CF when forming the PI alignment film and the orientation, from the viewpoint of residual DC and seizure. Is preferably the CF side of the color filter substrate.

Hereinafter, the present invention will be described in more detail based on Examples, but the present invention is not limited to Examples. In addition, "%" in the compositions of the following Examples and Comparative Examples means "mass%".
In addition, the following abbreviations were used for the description of the compound in the examples.

<Ring structure>

<Side chain structure>

(However, n in the table is a natural number.)
<Connected structure>

(However, n in the table is a natural number.)
The characteristics measured in the examples are as follows.

T _ni : Nematic phase-isotropic liquid phase transition temperature (° C)
Δn: Refractive index anisotropy at 20 ° C. η: Viscosity at 20 ° C. (mPa · s)
γ ₁ : Rotational viscosity at 20 ° C (mPa · s)
Δε: Dielectric modulus anisotropy at 20 ° C K ₃₃ : Elastic constant at 20 ° C K ₃₃ (pN)

The following various evaluation tests were performed on each of the liquid crystal compositions of Examples and Comparative Examples.
In addition, the results of each evaluation test for each liquid crystal composition in each Example and Comparative Example are described in the respective tables described later.

(Evaluation test for low temperature stability)
The liquid crystal composition was filtered through a membrane filter (PTFE 13 mm-0.2 μm manufactured by Agilent Technologies) and allowed to stand for 15 minutes under vacuum reduced pressure conditions to remove dissolved air. This was washed with acetone, weighed 0.5 g in a sufficiently dried vial, and stored at −20 ° C. for 1 day. Then, the presence or absence of precipitation was visually observed and judged in the following two stages.

A: Precipitation cannot be confirmed.

B: Precipitation can be confirmed.

Example 1 Preparation of liquid crystal composition A host liquid crystal composition composed of the compounds shown in Table 6 below and a mixing ratio is weighed, heat-treated at a temperature of Tni or higher for 15 minutes or longer, and cooled at room temperature for 15 minutes or longer. As a result, the base liquid crystal composition HLC 1 was obtained. The nematic-isotropic liquid phase transition temperature (TN-I), Δn, Δε, and γ1 are also shown at the same time.

The HLC-1 contains 1% by mass of the compound (P-J-1) corresponding to the compound (i), 1.8% by mass of the compound corresponding to the general formula (II) (RM-EX4 1.8% by mass, and the photopolymerization initiator Omnirad-. The liquid crystal composition of the present invention containing 0.036% by mass of 651 (manufactured by IGM Resin) was prepared. When the low temperature stability of the obtained composition was examined, it was A.
Examples 2-5
The liquid crystal composition of the present invention was prepared in the same manner as in Example 1. The results of examining the composition and low temperature stability are summarized in the table.

Comparative Examples 1-5
A liquid crystal composition was prepared in the same manner as in Example 1. The results of examining the composition and low temperature stability are summarized in the table.

Example 6
A first substrate (common electrode substrate) having a transparent electrode layer made of transparent common electrodes and a color filter layer without an alignment film, and comb teeth patterned with L / S = 5.0 / 5.0 μm. A second substrate (pixel electrode substrate) having no alignment film having a pixel electrode layer having a transparent pixel electrode driven by an active element having an electrode was prepared. Ozone treatment was performed for 30 seconds on each of the first substrate and the side of the first substrate in contact with the liquid crystal layer.
The liquid crystal composition HCL-1-1 was dropped onto the first substrate, sandwiched on the second substrate, and the sealing material was cured at normal pressure at 110 ° C. for 2 hours. IPS with a cell gap of 3.5 μm A mold liquid crystal cell was obtained.
Further, the obtained liquid crystal cell was heated to a temperature of Tni + 30 ° C., and at this temperature, linearly polarized UV light having an illuminance of 1 mW / cm ² at 313 nm was irradiated for 100 seconds. The vibration direction of the polarized light was set to a direction shifted by 5 ° from the direction in which the comb tooth electrode was extended. Next, after cooling to 25 ° C., the liquid crystal surface element of the present invention was produced by irradiating for 500 seconds with unpolarized light having a wavelength of 300 to 320 nm and an illuminance of 3 mW / cm2 at 313 nm. When the liquid crystal display element was observed, it was confirmed that a uniaxial horizontal orientation state was obtained. When the response speed was measured in combination with two polarizing plates, the off response time at the transition from the application of the voltage of 10 V to the time of no voltage application was 11.0 ms. In addition, no light scattering was observed when the voltage was applied.

Examples 7-10
The liquid crystal device of the present invention was produced in the same manner as in Example 1. The obtained orientation state, the off response time at the transition from the application of the voltage of 10 V to the time of no voltage application, and the light scattering when the voltage was applied are summarized in the table.

Comparative Examples 6-8
A liquid crystal element was produced in the same manner as in Example 1. The obtained orientation state, the off response time at the transition from the application of the voltage of 10 V to the time of no voltage application, and the light scattering when the voltage was applied are summarized in the table. Since the liquid crystal compositions HCL-1-9 and LCN-1-10 had crystal precipitation, a liquid crystal device could not be produced.

From the results of Examples 1 to 10 and Comparative Examples 1 to 8, it can be seen that the liquid crystal composition of the present invention has no crystal precipitation and can realize stable horizontal uniaxial orientation. Further, it can be seen that the off response can be speeded up by using the liquid crystal composition of the present invention. Further, since there is no light scattering when a voltage is applied, it can be seen that there is no loss as a liquid crystal display element that changes the light transmittance by controlling the phase difference with the voltage, and a bright display is possible. The orientation of the obtained device was uniform, and no unevenness was observed.

Examples 11-29
The liquid crystal composition of the present invention was prepared in the same manner as in Example 1. The results of examining the composition and low temperature stability are summarized in the table.

Examples 30-55
The liquid crystal element of the present invention was produced in the same manner as in Example 6. The liquid crystal composition was injected into the cell, heated to 100 ° C, the orientation state after cooling to room temperature, V90, and the off response time were summarized in the table.

Examples 30-48
The liquid crystal device of the present invention was produced in the same manner as in Example 1. The obtained orientation state, the off response time at the transition from the application of the voltage of 10 V to the time of no voltage application, and the light scattering when the voltage was applied are summarized in the table.

Example 48
A first substrate (common electrode substrate) having a transparent electrode layer made of transparent common electrodes and a color filter layer without an alignment film, and comb teeth patterned with L / S = 5.0 / 5.0 μm. A second substrate (pixel electrode substrate) having no alignment film having a pixel electrode layer having a transparent pixel electrode driven by an active element having an electrode was prepared. Ozone treatment was performed for 30 seconds on each of the first substrate and the side of the first substrate in contact with the liquid crystal layer.
The liquid crystal composition was dropped onto the first substrate, sandwiched on the second substrate, and the sealing material was cured at normal pressure at 110 ° C. for 2 hours to obtain an IPS type liquid crystal cell having a cell gap of 3.5 μm. It was.
Further, the obtained liquid crystal cell was heated to a temperature of Tni + 30 ° C., and at this temperature, linearly polarized UV light having an illuminance of 5 mW / cm ² at 365 nm was irradiated for 100 seconds. The vibration direction of the polarized light was set to a direction shifted by 85 ° with respect to the direction in which the comb tooth electrode was extended. Next, after cooling to 25 ° C., the liquid crystal surface element of the present invention was produced by irradiating for 500 seconds with unpolarized light having a wavelength of 300 to 320 nm and an illuminance of 3 mW / cm2 at 313 nm. When the liquid crystal display element was observed, it was confirmed that a uniaxial horizontal orientation state was obtained. When the response speed was measured in combination with two polarizing plates, the off response time at the transition from the application of the voltage of 10 V to the time of no voltage application was 10.8 ms. In addition, no light scattering was observed when the voltage was applied.

[Reference example]
A host liquid crystal composition composed of the compounds shown in Tables 19 to 33 below and the mixing ratio of HLC-2 to HLC-17 was prepared.

Examples 49-63
The liquid crystal composition of the present invention was prepared in the same manner as in Example 1. The results of examining the composition and low temperature stability are summarized in the table.

Examples 64-78
The liquid crystal device of the present invention was produced in the same manner as in Example 1. The obtained orientation state, the off response time at the transition from the application of the voltage of 10 V to the time of no voltage application, and the light scattering when the voltage was applied are summarized in the table.

Comparative Examples 9 to 23
The liquid crystal composition of the present invention was prepared in the same manner as in Example 1. The results of examining the composition and low temperature stability are summarized in the table.

Comparative Examples 24 to 38
The liquid crystal device of the present invention was produced in the same manner as in Comparative Example 1. The obtained orientation state, the off response time at the transition from the application of the voltage of 10 V to the time of no voltage application, and the light scattering when the voltage was applied are summarized in the table.

From the results of Examples 11 to 78 and Comparative Examples 9 to 38, it can be seen that the liquid crystal composition of the present invention has no crystal precipitation and can realize stable horizontal uniaxial orientation. Further, it can be seen that the off response can be speeded up by using the liquid crystal composition of the present invention. Further, since there is no light scattering when a voltage is applied, it can be seen that there is no loss as a liquid crystal display element that changes the light transmittance by controlling the phase difference with the voltage, and a bright display is possible. The orientation of the obtained device was uniform, and no unevenness was observed.

Comparative Example 39
A first substrate (common electrode substrate) having a transparent electrode layer made of transparent common electrodes and a color filter layer without an alignment film, and comb teeth patterned with L / S = 5.0 / 5.0 μm. A second substrate (pixel electrode substrate) having no alignment film having a pixel electrode layer having a transparent pixel electrode driven by an active element having an electrode was prepared. Ozone treatment was performed for 30 seconds on each of the first substrate and the side of the first substrate in contact with the liquid crystal layer.
The liquid crystal composition HCL-1-11 was dropped onto the first substrate, sandwiched on the second substrate, and the sealing material was cured at normal pressure at 110 ° C. for 2 hours. IPS with a cell gap of 3.5 μm. A mold liquid crystal cell was obtained.
Further, the obtained liquid crystal cell was heated to a temperature of Tni + 30 ° C., and at this temperature, linearly polarized UV light having an illuminance of 1 mW / cm ² at 313 nm was irradiated for 20 seconds. The vibration direction of the polarized light was set to a direction shifted by 5 ° from the direction in which the comb tooth electrode was extended. Next, after cooling to 25 ° C., the liquid crystal surface element of the present invention was produced by irradiating for 400 non-polarized light having a wavelength of 300 to 320 nm and an illuminance of 3 mW / cm2 at 313 nm. When the liquid crystal display element was observed, it was confirmed that a uniaxial horizontal orientation state was obtained. When the response speed was measured in combination with two polarizing plates, the off response time at the transition from the application of the voltage of 10 V to the time of no voltage application was 11.0 ms. In addition, light scattering was observed when a voltage was applied.

Comparative Examples 40 to 46
A liquid crystal element was produced in the same manner as in Comparative Example 39. The obtained orientation state and light scattering when a voltage is applied are summarized in the table.

From the comparison with Example 6 and Comparative Examples 39 to 46, a good horizontal uniaxial orientation state can be obtained if the manufacturing method of the present invention is obtained, and a good liquid crystal display element that does not cause light scattering even when a voltage is applied can be obtained. It turns out that it can be done.

Claims (20)

One or more of the mesogen group and the compound (i) containing a photoisomerization group or a dimerization group bonded to the mesogen group.
General formula (II)

(In the above general formula (I), R ²⁰² , R ²⁰³ , R ²⁰⁴ , R ²⁰⁵ , R ²⁰⁶ , R ²⁰⁷ , R ²⁰⁸ and R ²⁰⁹ are independently alkyl groups and carbon atoms having 1 to 18 carbon atoms, respectively. Represents any of the alkoxy groups, halogen atoms or hydrogen atoms of the numbers 1 to 18, and P ²¹ represents any of the following formulas (R-1) to (R-9).

(In the above formulas (R-1) to (R-9), R ²¹ , R ³¹ , R ⁴¹ , R ⁵¹ and R ⁶¹ are independent of each other and have an alkyl group having a hydrogen atom and 1 to 5 carbon atoms. Alternatively, it is an alkyl halide group having 1 to 5 carbon atoms, W is a single bond, -O- or a methylene group, T is a single bond or -COO-, and p, t and q are independent of each other. It is 0, 1 or 2.)
S ²¹ represents an alkylene group having 1 to 15 carbon atoms, and one or more -CH _2- in the alkylene group is -O-, -OCO- so that oxygen atoms are not directly adjacent to each other. Alternatively, it may be replaced with -COO-.
At least one of R ²⁰² , R ²⁰³ , R ²⁰⁴ , R ²⁰⁵ , R ²⁰⁶ , R ²⁰⁷ , R ²⁰⁸ and R ²⁰⁹ is a halogen atom, an alkyl group having 1 to 18 carbon atoms, and an alkoxy group having 1 to 18 carbon atoms. Is. ) And the compound
One or more compounds whose dielectric anisotropy (Δε) is greater than -2 and less than +2,
It contains one or more compounds selected from a compound having a dielectric anisotropy (Δε) of +2 or more and a compound having a dielectric anisotropy (Δε) of -2 or less, and
A nematic liquid crystal composition characterized in that the content of the compound represented by the general formula (II) is in the range of 1.8 to 4.8% by mass. The compound (i) has the following general formula (i).

^{(Wherein, R i1} and ^{R i2} are each independently a hydrogen atom, a linear or branched alkyl group having 1 to 40 carbon atoms, a halogenated alkyl group, or ^P i1 ^{-Sp i1} - represents a, R at least one of ⁱ¹ and ^{R i2 are,} P i1 ^{-Sp i1} - a and, -CH ₂ in the alkyl group - is -CH = CH -, - C≡C - , - O -, - NH -, - OCOO -, - COO- or -OCO- may be substituted with, but -O- is not become a ^{continuous, P i1} represents a polymerizable group, ^{Sp i1} represents a spacer group or a single bond,
A, C and D each independently represent a divalent aromatic group, a divalent heteroarophatic group, a divalent aliphatic group, and a divalent heteroaliphatic group.
B represents an aromatic group
These ring structures A to D are unsubstituted or an alkyl group having 1 to 12 carbon atoms, an alkyl halide group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, and a carbon atom number. 1-12 halogenated alkoxy group, a halogen atom, a cyano group, a nitro ^group, P i1 ^{-Sp i1} - may be substituted with,
The ring structures of A, C, and D may be substituted with −Z ⁴ - ^Kil .
Z ¹ and Z ² are independently single-bonded, -CH = CH-, -CF = CF-, -C≡C-, -COO-, -OCO-, -OCOO-, -CF ₂ O-, -OCF _2- , -CH = CHCOO-, -OCOCH = CH-, -CH _2- CH ₂ COO-, -OCOCH _2- CH _2- , -CH = C (CH ₃ ) COO-, -OCOC (CH ₃₎ ) = CH-, -CH _2- CH (CH ₃ ) COO-, -OCOCH (CH ₃ ) -CH _2- , -OCH ₂ CH ₂ O-, or an alkylene group having 2 to 20 carbon atoms. One or two or more non-adjacent −CH _2−s in the alkylene group may be independently substituted with −O−, −COO− or −OCO−.
Z ³¹ and Z ³² each independently represent a group or single bond selected from the general formulas (Z3-1) to (Z3-5), but at least one of Z ³¹ and Z ³² is (Z3-1). ) ~ (Z3-5),

(In the formula, the black dots at both ends represent the bond.)
l, m and n independently represent integers 0, 1, 2 and
k represents an integer of 1 or 2,
Z ⁴ is a single bond, -O-, -CH = CH-, -COO-, -OCO-, -OCOO-, -CH _2- CH (CH ₃ ) COO-, -OCOCH (CH ₃ ) -CH ₂ -Or represents a linear or branched alkylene group having 1 to 20 carbon atoms, and one or two or more -CH _2- not adjacent to the alkylene group are -O-, -COO- or -OCO-. May be replaced,
^Ki1 represents an adsorbent group. )
The nematic liquid crystal composition according to claim 1, which is represented by. The polymerizable group ^Pi1 in the general formula (i) is the following general formula (P-1) to general formula (P-15).

(Here, in each formula, the black dot at the right end represents the bond.)
The nematic liquid crystal composition according to claim 2, which has a structure selected from the group represented by any one of the above. The adsorbent group (-K ⁱ¹ ) in the compound (i) has the general formulas (K-1) to (K-18).

(In the formula, W ^K1 represents a methine group or a nitrogen atom, but the hydrogen atom in the methine group may be replaced with a linear or branched alkyl group having 1 to 6 carbon atoms.
^RK1 represents a hydrogen atom, a linear or branched alkyl group having 1 to 6 carbon atoms, and −CH ₂ − in the alkyl group is −CH = CH−, −C≡C−, −O−, −. It may be replaced with NH-, -OCOO-, -COO- or -OCO-, but -O- is not continuous and is not continuous.
X ^K1 and Y ^K1 independently represent −CH _2- , oxygen atom or sulfur atom, respectively.
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, T K1} are each independently formula (T-1) ~ (T-6)

(In the formula, ^ST1 represents a single-bonded, linear or branched alkylene group having 1 to 15 carbon atoms or a linear or branched alkenylene group having 2 to 18 carbon atoms. -CH _{2- of the} alkylene group or the alkalinylene group is replaced with -O-, -COO-, -C (= O)-, -C (= CH ₂ )-or -OCO- so that oxygen atoms are not directly adjacent to each other. R ^T1 represents an alkyl group having 1 to 5 carbon atoms, and −CH ₂ − of the alkyl group represents −O−, −COO−, −C (=) so that oxygen atoms are not directly adjacent to each other. O) -, - C (= CH 2) - or -OCO- may be substituted ^{by, R T2} and ^{R T3} are each independently a hydrogen atom or an alkyl group having 1 to 5 carbon atoms,
^{Pi 1} is the same as that described in claim 3.
Sp ⁱ¹ is a spacer group or a single bond. )
The nematic liquid crystal composition according to claim 3, which is a group represented by any of the above. The compound (i) is, ^P i1 ^{-Sp i1} having in the molecule -
^{(Wherein, P i1} represents the same meaning as ^{P i1} of claim 3, wherein.)
The nematic liquid crystal composition according to any one of claims 1 to 4, wherein Sp ^{i1 in the above} is a single bond. The nematic liquid crystal composition according to claim 5, wherein the adsorbing group (-K ⁱ¹ ) is selected from the group consisting of (K-13) to (K-18), and at least one of ^TK1 is (T-3). .. The nematic liquid crystal composition according to claim 4, wherein the adsorbing group ( ^Ki1 ) is any one of (K-1) to (K-12). A compound having a dielectric anisotropy (Δε) greater than -2 and less than +2 is represented by the following general formula (L).

(In the general formula (L), ^RL1 and ^RL2 each independently represent an alkyl group having 1 to 7 carbon atoms, but any one or two or more non-adjacent-existing groups present in the group. CH ₂ − may be independently substituted with −CH = CH −, −C≡C−, −O−, −CO−, −COO− or −OCO−, and n ^L1 is 0, Represents 1, 2 or 3, and A ^L1 , A ^{L 2} and A ^{L 3} are independent of each other.
(A) 1,4-Cyclohexylene group (any one or two or more non-adjacent −CH ₂ − present in this group may be substituted with −O−),.
(B) 1,4-phenylene group (any one or two or more non-adjacent −CH = present in this group may be substituted with −N =), and (c) naphthalene−. 2,6-diyl group, 1,2,3,4-tetrahydronaphthalene-2,6-diyl group or decahydronaphthalene-2,6-diyl group (any one present in these groups or not adjacent) Two or more -CH = may be replaced with -N =.)
Representing a group selected from the group consisting of, the group (a), the group (b) and the group (c) may be independently substituted with a cyano group, a fluorine atom or a chlorine atom, and 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-, and when n ^L1 is 2 or more, A ^L2 and Z ^L2 may be the same as or different from each other. )
The nematic liquid crystal composition according to any one of claims 1 to 7, which contains one or more compounds represented by. A compound having a dielectric anisotropy (Δε) of +2 or more contains one or more compounds selected from the compound group represented by the general formula (2-A) and the general formula (2-B). The nematic liquid crystal composition according to any one of claims 1 to 7, which has a positive dielectric anisotropy.

(In the formula, R ₂ is an alkyl group having 1 to 7 carbon atoms, an alkoxy group having 1 to 7 carbon atoms, or an alkenyl group having 2 to 7 carbon atoms, and ring Cs are mutually present when there are a plurality of rings C. Independently, one or more of the -CH ₂ -groups on the ring may be substituted with -O- or -S-, a 1,4-cyclohexylene group, or a cyclic -CH = One or two or more of the groups represent 1,4-phenylene groups which may be substituted with -N =, and one or two or more hydrogen atoms on these rings may be substituted with halogen atoms. well, _{L 2,} if there are a plurality of independently of one another, a single _{bond, -C 2 H 4 -, -} CH = CH -, - C≡C -, - COO -, - OCO -, - CH 2 _{O -, - OCH 2 -,} - CF 2 O- or -OCF ₂ - represents, _{X 1} is, -F, -Cl, -CN, -NCS , -CF 3, -OCF 3, at least one hydrogen atom Represents an alkyl group having 1 to 6 carbon atoms substituted with a halogen atom or an alkoxy group having 1 to 6 carbon atoms substituted with at least one hydrogen atom, and Y ₁ and Y ₂ are independent of each other. Then, it represents a hydrogen atom or a fluorine atom, and b represents 1, 2, 3 or 4). Claims 1 to 1 in which a compound having a dielectric anisotropy (Δε) of -2 or less contains one or more compounds represented by the following general formula (5) and has a negative dielectric anisotropy. 8. The nematic liquid crystal composition according to any one of 8.

(In the formula, R ₅₁ and R ₅₂ are independently from an alkyl group having 1 to 7 carbon atoms, an alkoxy group having 1 to 7 carbon atoms, an alkenyl group having 2 to 7 carbon atoms, and 2 carbon atoms. It is an alkenyloxy group of 7, and rings D and F are independently 1,4-cyclohexylene, 1,4-cyclohexenylene, 1,4-phenylene, and at least one hydrogen atom is a halogen atom or methyl. Represents 1,4-phenylene or tetrahydropyran-2,5-diyl replaced by a group, ring E is 2,3-difluoro-1,4-phenylene, 2-chloro-3-fluoro-1,4. -Phenylene, 3,4,5-trifluoronaphthalene-2,6-diyl, 7,8-difluorochroman-2,6-diyl or

The stands, _{L 4} and _{L 5} each independently represent a single _{bond, -C 2 H 4 -, -} COO -, - OCO -, - CH 2 O -, - OCH 2 -, - CF 2 O -, - OCF _2- , -CH = CH- or -C≡C-, c represents 0, 1, 2 or 3, d represents 0 or 1, the sum of c and d is 3 or less, and the ring. When a plurality of D and L ₄ exist, they may be the same or different. ) The nematic liquid crystal composition according to any one of claims 1 to 10, further containing a polymerizable compound (P). The nematic liquid crystal composition according to any one of claims 1 to 11, further comprising an antioxidant. The nematic liquid crystal composition according to any one of claims 1 to 12, further containing a UV absorber. A liquid crystal display device comprising two substrates and a liquid crystal layer provided between the two substrates and containing the nematic liquid crystal composition according to any one of claims 1 to 13. The liquid crystal display element according to claim 14, which is an IPS type or an FFS type. The liquid crystal display element according to claim 14 or 15, wherein at least one of the two substrates does not have an alignment film. The two substrates and a liquid crystal layer containing the nematic liquid crystal composition according to any one of claims 1 to 13 provided between the two substrates are sandwiched and irradiated with ultraviolet rays to obtain the general formula (1). A method for producing a liquid crystal display element, which comprises forming a polymer of the compound represented by II) on a substrate so as to be in contact with a liquid crystal layer. The method for manufacturing a liquid crystal display element according to claim 17, wherein ultraviolet rays are irradiated at a temperature equal to or higher than Tni of the nematic liquid crystal composition. The method for manufacturing a liquid crystal display element according to claim 17 or 18, wherein the time for irradiating with ultraviolet rays is 10 to 7200 seconds. The method for manufacturing a liquid crystal display element according to any one of claims 17 to 19, wherein at least one substrate sandwiching the nematic liquid crystal composition has been subjected to ozone treatment in advance.

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