WO2018074311A1

WO2018074311A1 - Polymerizable liquid-crystal composition, liquid-crystal display element, and process for producing liquid-crystal display element

Info

Publication number: WO2018074311A1
Application number: PCT/JP2017/036950
Authority: WO
Inventors: 琴姫張; 藤沢　宣; 芳典岩下; 青木　良夫; 卓央林
Original assignee: Dic株式会社
Priority date: 2016-10-17
Filing date: 2017-10-12
Publication date: 2018-04-26
Also published as: JP6638822B2; JPWO2018074311A1

Abstract

[Problem] To provide: a polymerizable liquid-crystal composition that can give a liquid-crystal display element which includes a liquid-crystal layer having a high polymer-component content and which has high polymer homogeneity and greatly mitigated display unevenness; and a liquid-crystal display element obtained using the polymerizable liquid-crystal composition. [Solution] A polymerizable liquid-crystal composition characterized by comprising a radical-polymerizable monomer ingredient (A), a liquid-crystal material (B), and a compound (C) represented by structural formula (1) as essential components. (In structural formula (1), Ar represents a divalent aromatic hydrocarbon group, etc.; Z's each independently represent a single bond, a C_1-12 linear or branched alkyl group, etc.; R¹ represents a C_1-8 linear or branched alkyl group, etc.; R² represents a hydrogen atom, a C_1-8 linear or branched alkyl group, etc.; and n is an integer of 0-3.)

Description

Polymerizable liquid crystal composition, liquid crystal display element, and method for producing liquid crystal display element

The present invention relates to a polymerizable liquid crystal composition, a liquid crystal display element, and a method for producing a liquid crystal display element.

Liquid crystal materials are generally used in flat panel displays such as televisions, monitors, mobile phones, smartphones, and tablet terminals. However, since nematic liquid crystal has a slow response speed of about several tens of milliseconds to several milliseconds, in the field of widely used liquid crystal televisions, for example, in order to increase the display speed, the vertical alignment mode is mainly adopted, There is a PS (polymer-stable) or PSA (polymer-stained alignment) display in which the tilt angle of the liquid crystal material is applied to increase the rising response (ON response) when a voltage is applied. (See Patent Documents 1 to 5).

Specifically, such PS or PSA display is prepared by adding 0.3% by mass or more and less than 1% by mass of a polymerizable compound to a liquid crystal medium and applying UV voltage photopolymerization with or without applying voltage. In order to induce a pretilt in the liquid crystal molecules by forming a fine protrusion structure obtained by polymerization or cross-linking on the glass substrate interface, this speeds up the rising response (ON response) when a voltage is applied. Is possible.

However, as a result of the recent increase in the size of liquid crystal televisions, the moving speed of display objects moving on the screen is further increased, and therefore further improvement in the liquid crystal response speed is required.

Therefore, conventionally, as a means for improving the response speed, not only the rise of the rise response (on response) at the time of voltage application but also an attempt to improve the response speed when released from the voltage application (at the time of switching off) has been made. For example, Patent Literature 5 discloses a liquid crystal display element in which a liquid crystal material in a liquid crystal display cell is sealed with a polymer component together with a liquid crystal composition so as to be 1 mass% or more and less than 40 mass% in the liquid crystal material. Has been. Such a liquid crystal display element contains a predetermined amount of polymer in a liquid crystal material, and as a result, uses a gravitational interaction between the polymer and liquid crystal molecules to abbreviate a switching-off response (hereinafter abbreviated as “off response”). )) By accelerating the relaxation process to the initial alignment state, thereby realizing a faster off response.

As described above, since the liquid crystal material described in Patent Document 1 contains a polymer component in a high content, it is indispensable to use a polymerization initiator when polymerizing the monomer. In the liquid crystal material described in Patent Document 5, Alkylphenone photopolymerization initiators represented by “Irgacure 651” manufactured by BASF are used.

However, such a conventionally known polymerization initiator has a high polarity in itself and is easily adsorbed to the substrate when the liquid crystal material is sandwiched between the substrates. As a result, a concentration gradient occurs in which the concentration of is decreased. As a result, in the obtained liquid crystal display element, the polymer distribution is likely to be uneven, and this tends to cause display unevenness as the liquid crystal display element.

In PS or PSA displays containing a polymer in the liquid crystal layer, a liquid crystal material is sealed in a liquid crystal cell by a vacuum injection method or a drop injection (ODF: One Drop Drop) method, and the periphery of the liquid crystal is UV coated with a UV curable resin. It can be manufactured by sealing by a curing reaction (sealing process) and then polymerizing the monomer in the liquid crystal layer by UV irradiation (liquid crystal layer polymerization process). Not only that, the monomer in the liquid crystal material is partially polymerized due to leakage of UV light, causing display unevenness.

At this time, when an alkylphenone photopolymerization initiator or the like typified by “Irgacure 651” manufactured by BASF is used, there is a problem that the monomer in the liquid crystal layer is likely to be polymerized in the sealing process. Was.

On the other hand, when trying to reduce the use amount of the alkylphenone photopolymerization initiator in order to avoid curing abnormality in the sealing process, the initiator is mostly included in the liquid crystal cell at a location away from the substrate in the normal direction of the substrate surface. For example, it was difficult to form a homogeneous polymer in the monomer polymerization process.

WO2015 / 122457

Therefore, the problem to be solved by the present invention is a polymerizable liquid crystal composition having a high polymer homogeneity and capable of dramatically improving display unevenness in a liquid crystal display device having a liquid crystal layer with a large amount of polymer components, and An object of the present invention is to provide a liquid crystal display device using the same.

As a result of intensive studies to solve the above problems, the present inventors have found that the compound is unevenly distributed in the vicinity of the substrate by using a compound having a predetermined molecular structure having a polymerization initiating ability in the polymerizable liquid crystal composition. As a result, it has been found that a good affinity with liquid phase molecules is exhibited, and as a result, the risk of occurrence of display unevenness in the obtained liquid crystal display element can be reduced, and the present invention has been completed.

That is, the present invention includes a radical polymerizable monomer component (A), a liquid crystal material (B), and the following structural formula (1).

(In the structural formula (1), Ar represents a divalent aromatic hydrocarbon group or a halogen atom-containing aromatic hydrocarbon group, and A represents a divalent aromatic hydrocarbon group or a divalent cyclic aliphatic hydrocarbon. Group, a divalent condensed polycyclic structure site, a structural site in which a hydrogen atom in these structures is substituted with a halogen atom, or the divalent cyclic aliphatic hydrocarbon group or the divalent condensed polycyclic structure site Arbitrary —CH ₂ — represents a structural moiety having a structure in which an arbitrary —CH ₂ — structure is substituted with an oxygen atom, the divalent aromatic hydrocarbon group or the divalent condensed polycyclic structural moiety. And Z represents a single bond, a linear or branched alkyl group having 1 to 12 carbon atoms, or a linear chain having 1 to 12 carbon atoms. Or a branched alkylene group, the straight chain or branched alkyle -CH group ₂ - or nonadjacent two or more -CH ₂ - are each independently -O -, - S -, - CO -, - COO -, - OCO -, - CS-O-, —O—CS—, —CO—S—, —S—CO—, —O—CO—O—, —OCF ₂ —, —CF ₂ O—, —CH═CH—COO—, —OCO—CH═ Represents a divalent organic group having a structure substituted by CH—, —CH═CH—, —CF═CF— or —C≡C—, wherein R ¹ is straight or branched having 1 to 8 carbon atoms Represents an alkyl group or a radically polymerizable functional group, and each R ² independently represents hydrogen, a linear or branched alkyl group having 1 to 8 carbon atoms, or a linear or branched alkoxy group having 1 to 8 carbon atoms. Or the following structural formula (2)

(In Structural Formula (2), Z has the same meaning as described above, and A2 represents a monovalent aromatic hydrocarbon group, a monovalent cyclic aliphatic hydrocarbon group, a monovalent condensed polycyclic structure site, or Represents a structural site in which a hydrogen atom in these structures is substituted with a halogen atom.), And n represents an integer of 0 to 3. When a plurality of A and Z are present in the structural formulas (1) and (2), the plurality of A and Z may be the same or different. It is related with the polymerizable liquid crystal composition characterized by using the compound (C) represented by this as an essential component.

The present invention further relates to a liquid crystal display element in which a polymer of a radical polymerizable monomer component (A) and a liquid crystal material (B) are sandwiched between two transparent substrates each having an electrode on at least one side. The liquid crystal material (B) is a polymer of the polymerizable liquid crystal composition.

In the present invention, the polymerizable liquid crystal composition is further sandwiched between two transparent substrates having electrodes on at least one side, and polymerized by irradiating active energy rays while keeping the liquid crystal layer at −50 ° C. to 30 ° C. A polymer having a refractive index anisotropy or an orientation easy axis direction, and a method for producing a liquid crystal display element.

ADVANTAGE OF THE INVENTION According to this invention, in the liquid crystal display element which has a liquid crystal layer with many polymer component amounts, the homogeneity of a polymer is high and a display nonuniformity can be improved drastically, and a liquid crystal display using the same An element can be provided.

FIG. 1 is a schematic view of a liquid crystal display element of the present invention. FIG. 2 is a partially enlarged view of FIG. FIG. 3 is a cross-sectional view of the liquid crystal display element of the present invention. FIG. 4 is a partially enlarged view of FIG. FIG. 5 is a cross-sectional view of the liquid crystal display element of the present invention. FIG. 6 is a schematic view of the liquid crystal display element of the present invention. FIG. 7 is a partially enlarged view of FIG. FIG. 8 is a cross-sectional view of the liquid crystal display element of the present invention. FIG. 9 is a schematic view showing an electrode structure and a liquid crystal molecular arrangement of the oblique electric field type liquid crystal display device according to the present invention. FIG. 10 is a schematic diagram showing an electrode structure of an 8-division oblique electric field type liquid crystal display device according to the present invention. FIG. 11 is a schematic diagram of an electrode structure of a fishbone type VA liquid crystal cell in the example.

As described above, the polymerizable liquid crystal composition of the present invention includes the radical polymerizable monomer component (A), the liquid crystal material (B), and the following structural formula (1).

(In the structural formula (1), Ar represents a divalent aromatic hydrocarbon group or a halogen atom-containing aromatic hydrocarbon group, and A represents a divalent aromatic hydrocarbon group or a divalent cyclic aliphatic hydrocarbon. Group, a divalent condensed polycyclic structure site, a structural site in which a hydrogen atom in these structures is substituted with a halogen atom, or the divalent cyclic aliphatic hydrocarbon group or the divalent condensed polycyclic structure site Arbitrary —CH ₂ — represents a structural moiety having a structure in which an arbitrary —CH ₂ — structure is substituted with an oxygen atom, the divalent aromatic hydrocarbon group or the divalent condensed polycyclic structural moiety. And Z represents a single bond, a linear or branched alkyl group having 1 to 12 carbon atoms, or a linear chain having 1 to 12 carbon atoms. Or a branched alkylene group, the straight chain or branched alkyle -CH group ₂ - or nonadjacent two or more -CH ₂ - are each independently -O -, - S -, - CO -, - COO -, - OCO -, - CS-O-, —O—CS—, —CO—S—, —S—CO—, —O—CO—O—, —OCF ₂ —, —CF ₂ O—, —CH═CH—COO—, —OCO—CH═ Represents a divalent organic group having a structure substituted by CH—, —CH═CH—, —CF═CF— or —C≡C—, wherein R ¹ is straight or branched having 1 to 8 carbon atoms Represents an alkyl group or a radical polymerizable functional group, and each R ² independently represents a hydrogen atom, a linear or branched alkyl group having 1 to 8 carbon atoms, or a linear or branched group having 1 to 8 carbon atoms. An alkoxy group or the following structural formula (2)

(In Structural Formula (2), Z has the same meaning as described above, and A2 represents a monovalent aromatic hydrocarbon group, a monovalent cyclic aliphatic hydrocarbon group, a monovalent condensed polycyclic structure site, or Represents a structural site in which a hydrogen atom in these structures is substituted with a halogen atom.), And n represents an integer of 0 to 3. When a plurality of A and Z are present in the structural formulas (1) and (2), the plurality of A and Z may be the same or different. The compound (C) represented by) is an essential component.

The compound (C) represented by the structural formula (1) has a polymerization initiating ability and exhibits excellent compatibility with the liquid crystal material forming the liquid crystal layer. As a result, when a liquid crystal display device is produced using the polymerizable liquid crystal composition containing the compound (C), the compound (C) is uniformly dispersed inside the liquid crystal layer, and as a result, the risk of occurrence of so-called display unevenness. Can be reduced.

Here, as described above, the compound (C) has the following structural formula (1):

It has a molecular structure represented by

Here, Ar is a divalent aromatic hydrocarbon group or a halogen atom-containing aromatic hydrocarbon group, such as a phenylene group, naphthalene-diyl group,

Etc. Of these, a phenylene group is preferred from the viewpoint of excellent polymerization initiation ability and compatibility with the liquid crystal compound.

Next, A in the conceptual formula (1) is a divalent aromatic hydrocarbon group, a divalent cycloaliphatic hydrocarbon group, a divalent condensed polycyclic structure site, or a hydrogen atom in these structures is a halogen atom. A structure site substituted with an atom, or a structure in which the structure represented by any —CH ₂ — in the divalent cyclic aliphatic hydrocarbon group or the divalent condensed polycyclic structure site is substituted with an oxygen atom Represents a structural moiety in which a structure represented by —CH═ in the divalent aromatic hydrocarbon group or divalent condensed polycyclic structural moiety is substituted with a nitrogen atom, specifically, , The following partial structural formula

The structure represented by is mentioned.

Among these, especially from the point of compatibility with liquid crystal compounds

The structure represented by these is preferable.

The structural site represented by Z in the structural formula (1) is independently a single bond, a linear or branched alkyl group having 1 to 12 carbon atoms, or a straight chain having 1 to 12 carbon atoms. A chain or branched alkylene group, —CH ₂ — of the straight chain or branched alkylene group, or two or more non-adjacent —CH ₂ — are each independently —O—, —S—, —CO—, —COO. -, -OCO-, -CS-O-, -O-CS-, -CO-S-, -S-CO-, -O-CO-O-, -OCF _2- , -CF ₂ O-,- A divalent organic group having a structure substituted by CH═CH—COO—, —OCO—CH═CH—, —CH═CH—, —CF═CF— or —C≡C—, The structural site having a heavy bond or triple bond, or a single bond increases the conjugation length in the molecule. Preferable from.

In the structural formula (1), the structural site represented by -AZ- is a repeating unit, and n representing the repeating unit represents an integer of 0 to 3, but is compatible with liquid crystals. From 0 to 2, it is preferable from the viewpoint of compatibility with the liquid crystal compound.

Next, R ¹ is a linear or branched alkyl group having 1 to 8 carbon atoms, or a radical polymerizable functional group. Here, examples of the linear or branched alkyl group having 1 to 8 carbon atoms include methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, isobutyl group, t-butyl group, s-butyl group, Examples include pentyl group, neopentyl group, hexyl group, heptyl group, octyl group and the like. Examples of the radical polymerizable functional group include the following formulas (R1-1) to (R1-4)

The structural part represented by these is mentioned. Here, in each formula, * represents a bonding point, R ′ is independently a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and t ^C1 represents 0, 1 or 2.

Here, when a radically polymerizable functional group is introduced as R ¹ , it is difficult to generate a decomposition residue of the compound (C) after polymerization of the monomer, so that the voltage holding ratio of the liquid crystal display element can be maintained at a high level. On the other hand, as a result of increasing the polarity due to the introduction of the radical polymerizable functional group, the effect of improving display spots becomes low, and the reactivity of the polymerizable monomer (A) is reduced, resulting in a residual monomer. This is likely to occur, and the reliability of the liquid crystal display element is not sufficient.

On the other hand, when a straight-chain or branched alkyl group having 1 to 8 carbon atoms is introduced as R ¹ , the polarity of the compound (C) itself is lowered, the compatibility with the liquid crystal material is further increased, and the display unevenness is improved. It becomes more prominent. Therefore, R ¹ is preferably a linear or branched alkyl group having 1 to 8 carbon atoms.

Next, each R ² is independently a hydrogen atom, a linear or branched alkyl group having 1 to 8 carbon atoms, a linear or branched alkoxy group having 1 to 8 carbon atoms, or the following structural formula (2)

(In Structural Formula (2), Z has the same meaning as described above, and A ² represents a monovalent aromatic hydrocarbon group, a monovalent cyclic aliphatic hydrocarbon group, a monovalent condensed polycyclic structure site, or Represents a structural site in which a hydrogen atom in these structures is substituted with a halogen atom).

Here, examples of the linear or branched alkyl group having 1 to 8 carbon atoms include methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, isobutyl group, t-butyl group, s-butyl group, Examples thereof include a pentyl group, a neo-pentyl group, a hexyl group, a heptyl group, an octyl group, etc. Examples of the linear or branched alkoxy group having 1 to 8 carbon atoms include a methoxy group,
Examples include ethoxy group, propoxy group, t-butoxy group, pentyloxy group, octyloxy group and the like.

In addition, a monovalent aromatic hydrocarbon group, a monovalent cycloaliphatic hydrocarbon group, a monovalent condensed polycyclic structure site represented by A ² in the structural formula (2), or a hydrogen atom in these structures Specific examples of the structural site in which is substituted with a halogen atom include those represented by the following structural formula.

In the present invention, when the carbon atom in R ² bonded to the carbonyl carbon atom in the structural formula (1) is a quaternary carbon atom, the compound (C) is converted into a Norrish type I compound by irradiation with active energy rays. A radical is generated by the reaction, and in the case of primary to tertiary carbon atoms, the radical is generated by a Norrish type II reaction.

Here, in the above general formula (1), the following structural formula

It is preferable that the main skeleton represented by the formula (1) forms a mesogenic structure from the viewpoint of better compatibility of the compound (C) with the liquid crystal compound.

The compound (C) described in detail above is preferably a compound having a ClogP value of 5 to 10 in view of excellent compatibility with the liquid crystal compound and good homogeneity in the liquid crystal layer. Here, the ClogP value is a value obtained by estimating the water / octanol partition coefficient from the structural formula in Chemdraw.

Specific examples of the chemical structure of the compound (C) represented by the above structural formula (1) include those represented by the following formulas C1 to C281.

The amount of the compound (C) used is not particularly limited, but is in the range of 0.5 to 5% by mass, particularly in the range of 2 to 5% by mass in the polymerizable liquid crystal composition of the present invention. It is preferable from the viewpoint of curability. In the present invention, even when the compound (C) is used in such a large amount, the risk of occurrence of display unevenness can be reduced without causing any decrease in the voltage holding ratio of the liquid crystal display element.

Next, it is preferable to use a liquid crystalline monomer as the radical polymerizable monomer component (A) used in the polymerizable liquid crystal composition of the present invention. That is, the liquid crystal display element of the present invention has a structure in which the polymer network layer is formed on the entire surface of the liquid crystal display element in the liquid crystal phase and the liquid crystal phase is continuous, and the polymer network has an easy alignment axis and a single optical axis. It is preferable that the orientation direction of the low-molecular liquid crystal is substantially the same direction as that of the low-molecular liquid crystal, and that the polymer network is formed so as to induce the pretilt angle of the low-molecular liquid crystal because the off-response speed can be increased. The polymerizable monomer constituting the radical polymerizable monomer component (A) is preferably a liquid crystalline monomer having a mesogenic structure in the molecular structure. In the liquid crystal display element according to the present invention, the polymer network layer has a polymer network having an average gap interval smaller than the wavelength of visible light, that is, an average gap interval of less than 450 nm. This is preferable because it does not occur.

As such a liquid crystalline monomer, the following general formula (P1)

The thing represented by is mentioned.

Here, Z ^p11 is a fluorine atom, a cyano group, a hydrogen atom, an alkyl group having 1 to 15 carbon atoms in which a hydrogen atom may be substituted with a halogen atom, or a hydrogen atom in which a hydrogen atom is substituted. An alkoxy group having 1 to 15 carbon atoms, an alkenyl group having 1 to 15 carbon atoms in which a hydrogen atom may be substituted with a halogen atom, and 1 to 15 carbon atoms in which a hydrogen atom may be substituted with a halogen atom The alkenyloxy group of — or —Sp ^p12 —R ^p12 . Among these, as Z ^p11 , the use of an alkyl group having 1 to 15 carbon atoms in which a fluorine atom or an oxygen atom may be substituted with a halogen atom increases the voltage holding ratio of the liquid crystal display device. From the viewpoint of enabling tilting, it is preferable to be -Sp ^p12 -R ^p12 from the viewpoint of tilt stability.

Here, R ^p11 and R ^p12 are each independently the following formulas (RP11-1) to (RP11-4)

(Wherein, * represents a bonding point), and in the formulas (RP11-1) to (RP11-4), R ^P111 to R ^P112 are independently of each other a hydrogen atom or carbon atom number. 1 to 5 alkyl groups, and t ^M11 represents 0, 1 or 2. It represented especially by the formula (RP11-1) Among these, and, as the R ^P111 in formula is a hydrogen atom or a methyl group, a (meth) acryloyl group, at the time of manufacturing the liquid crystal display device It is possible to reduce the amount of UV irradiation when polymerizing the monomer, the amount of UV irradiation to the liquid crystal material can be kept to the minimum necessary, and the deterioration of the liquid crystal material and the liquid crystal display element can be avoided. preferable.

Sp ^p11 and Sp ^p12 are each independently a single bond, a linear or branched alkylene group having 1 to 12 carbon atoms, or a carbon atom of this linear or branched alkylene structure is adjacent to an oxygen atom. A structural moiety having a chemical structure substituted with an oxygen atom or a carbonyl group. Among these, in particular, a linear or branched alkylene group having 1 to 12 carbon atoms is preferable because it increases compatibility with the liquid crystal material (B), and has the same number of carbon atoms as the alkyl group of the liquid crystal molecule. Those of 1 to 6 are particularly preferred. Here, when the compatibility between the radical polymerizable monomer component (A) and the liquid crystal material (B) is insufficient, or the compatibility of the polymerization initiator (C) with the liquid crystal material (B) is not sufficient. In this case, since the density of the polymer network is increased and the density is increased, the device characteristics are affected and the in-plane characteristics are likely to be non-uniform. However, in the present invention, the radical polymerizable monomer component (A ) And the liquid crystal material (B) have good compatibility with the good compatibility between the polymerization initiator (C) and the liquid crystal material (B). A polymer phase separation structure is formed, and a uniform polymer network in the liquid crystal is formed, so that the characteristics of the liquid crystal display element are constant in the plane. Here, in the case of having Sp ^p11 and Sp ^p12 which are linear or branched alkylene groups having 1 to 12 carbon atoms, it is easy to produce the monomer that they are the same, It is preferable from the viewpoint that the physical properties can be easily adjusted by adjusting the use ratio of a plurality of kinds of compounds having different alkylene chain lengths. On the other hand, when Sp ^p11 and Sp ^p12 are single bonds, the monomer tends to collect on the substrate surface, and the tendency to form a thin film on the surface of the vertical alignment film is stronger than the tendency to form the polymer network. The effect of imparting a pretilt to the alignment film and fixing it is stronger than the effect of the high-speed response due to.

In addition, when the content of the radical polymerizable monomer component (A) in the polymerizable liquid crystal composition is less than 0.5% by mass, a pretilt angle is given to the alignment film to fix it. , Sp ^p11 and Sp ^p12 are preferably single bonds. On the other hand, when the content is in the range of 0.5% by mass to 20% by mass, Sp ^p11 and Sp ^p12 have 1 to 12 carbon atoms. The linear or branched alkylene group is preferably from the viewpoint of forming a polymer network that increases the off-response speed. In particular, it is preferably in the range of 1% by mass to 10% by mass from the viewpoint of off-response speed and low driving voltage. In addition, the linear or branched alkylene group described above preferably has 2 to 8 carbon atoms, and more preferably 2 to 6 carbon atoms. Further, it is preferable to substitute a carbon atom on the alkylene group with an oxygen atom or a carbonyl group under the condition that the oxygen atom is not adjacent. In particular, it is preferable to introduce an oxygen atom at a position where it binds to M ^P11 or M ^P13 from the viewpoint that the liquid crystal material as a whole can increase the upper limit temperature of the liquid crystal and increase the ultraviolet sensitivity during polymerization.

Next, in the general formula (P1), L ^p11 and L ^p12 each independently represent a single bond, —O—, —S—, —CH ₂ —, —OCH ₂ —, —CH ₂ O—, — CO—, —C ₂ H ₄ —, —COO—, —OCO—, —OCOOCH ₂ —, —CH ₂ OCOO—, —OCH ₂ CH ₂ O—, —CO—NR ^P113 —, —NR ^P113 —CO— _{_{^{, -SCH 2 -, - CH 2}}} S -, - CH = CR P113 -COO -, - CH = CR P113 -OCO -, - COO-CR P113 = CH -, - OCO-CR aP113 = CH -, - COO —CR ^{P113 ═CH} — ^COO— , —COO—CR ^{P113 ═CH} —OCO—, —OCO—CR ^{P113 ═CH} — ^COO— , —OCO—CR ^{P113 ═CH} —OCO—, — (CH ₂ ) _tm12 —C ( _{_{O) -O -, - (CH}} 2) tm12 -O- (C = O) -, - O- (C = O) - (CH 2) tm12 -, - (C = O) -O- (CH 2 ) _Tm12 −, _{—CH═CH—} , _{—CF═CF—} , _{—CF═CH—} , _{—CH═CF—} , —CF ₂ —, —CF ₂ O—, —OCF ₂ —, —CF ₂ CH ₂ — , —CH ₂ CF ₂ —, —CF ₂ CF ₂ —, —C≡C—, —N═N—, —CH═N— or —C═N— ^N═C— (wherein R ^P113 represents Independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, wherein tm12 represents an integer of 1 to 4).

Among these, the radically polymerizable monomer component (A) has high liquid crystallinity, and from the viewpoint of suppressing alignment unevenness in the liquid crystal display element, a single bond, —C ₂ H ₄ —, —COO—, —OCO—, — CH═CH—COO—, —OCO—CH═CH—, — (CH ₂ ) ₂ —C (═O) —O—, — (CH ₂ ) ₂ —O— (C═O) —, —O— (C═O) — (CH ₂ ) ₂ —, — (C═O) —O— (CH ₂ ) ₂ —, —CH═CH—, —CF═CF—, —CF═CH—, —CH═ CF—, —CF ₂ O—, —OCF ₂ —, —CF ₂ CH ₂ —, —CH ₂ CF ₂ —, —CF ₂ CF ₂ —, —C≡C—, —N═N—, or —C = NN-C- is preferred.

In addition, since the photo-alignment function by light using the Weigert effect can be used by imparting a photoisomerization function to the monomer, —CH═CH—, —CF═CF—, —CF═CH—, —CH═ CF— or —N═N— is preferred, and —CH═CH— and —N═N— are preferably selected, and in particular, —N═N— is preferred. Further, from the viewpoint of increasing the orientation of the polymer network, it is particularly preferable that —N═N—.

Next, M ^p11 , M ^p12 and M ^p13 in the general formula (P1) are each independently 1,4-phenylene group, 1,3-phenylene group, 1,2-phenylene group, 1,4-cyclohexylene. Group, 1,3-cyclohexylene group, 1,2-cyclohexylene group, 1,4-cyclohexenylene group, 1,3-cyclohexenylene group, 1,2-cyclohexenylene 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, naphthalene-1,4-diyl group, indane -2,5-diyl group, fluorene-2,6-diyl group, fluorene-1,4-diyl group, phenanthrene-2,7-diyl group, anthracene-2,6-diyl group, anthrace 1,4-diyl group, 1,2,3,4-tetrahydronaphthalene-2,6-diyl group or 1,3-dioxane-2,5-diyl group, or the number of carbon atoms in the aromatic nucleus An alkyl group having 1 to 12 carbon atoms, a halogenated alkyl 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, a cyano group, or a nitro group And a structure substituted with.

Further, M ^p11 , M ^p12 and M ^p13 are preferably those in which —Sp ^p11 —R ^p11 is substituted on the aromatic nucleus of these structures from the viewpoint of becoming a radically polymerizable monomer having excellent reactivity. In this case, R ^p11 is preferably the formula (RP11-1), and R ^P111 is preferably a hydrogen atom or a (meth) acryloyl group which is a methyl group.

Among these, in particular, 1,4-phenylene group, 1,4-cyclohexylene group, 1,4-cyclohexenylene 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-2,5-diyl group, fluorene-2,6-diyl group, fluorene-1,4-diyl group Phenanthrene-2,7-diyl group, anthracene-2,6-diyl group, 1,2,3,4-tetrahydronaphthalene-2,6-diyl group or 1,3-dioxane-2,5-diyl group, A 2,3-difluoro-1,4-phenylene group and a 2-fluoro-1,4-phenylene group are preferred from the viewpoint of compatibility with liquid crystals.

Further, in the general formula (P1), mp12 represents 1 or 2, mp13 and mp14 each independently represent 0, 1, 2 or ^{3, m pi 1} and ^{m p15} is 1, 2, or independently 3 is represented. Here, may be those in the case where Z ^{pi 1} there are a plurality have the same or different and when R ^{pi 1} there exist a plurality they may be the same or different and is R ^p12 When a plurality of Sp ^p11 are present, they may be the same or different. When there are a plurality of Sp ^p11 , they may be the same or different. When there are a plurality of Sp ^p12 , They may be the same or different. When a plurality of L ^p11 are present, they may be the same or different. When there are a plurality of L ^p12 , they are the same. They may be the same or different when a plurality of M ^p12 are present, and they may be the same or different when a plurality of M ^p13 are present. so It is preferably a compound that is. Moreover, it is preferable to contain the said material 1 type (s) or 2 or more types.

Further, the total of m ^p12 to m ^p14 described above is preferably in the range of 1 to 6, particularly preferably in the range of 2 to 4, particularly 2. When two or more types of monomers are used, the average number calculated by multiplying the concentration of the monomers in the whole monomer and the sum of m ^p12 to m ^p14 is set to 1.6 to 2.8. It is preferably 1.7 to 2.4, more preferably 1.8 to 2.2.

The total of m ^p11 and m ^p15 is preferably 1 to 6, more preferably 2 to 4, and particularly preferably 2. When using two or more monomers, the average number calculated by multiplying the density and m ^p1 and ^p15 sum of the monomers in the total monomer, may be set to be 1.6 to 2.8 It is preferably 1.7 to 2.4, more preferably 1.8 to 2.2. When the average number is close to 1, the driving voltage of the liquid crystal display element tends to be reduced, and when the average number is high, the off-response tends to be quick.

Substitution with fluorine atoms for M ^p11 , M ^p12 and M ^p13 can control the magnitude and solubility of the interaction between the liquid crystal material and the polymer or copolymer without deteriorating the voltage holding ratio of the liquid crystal display element. Therefore, it is preferable. The preferred number of substitution is 1 to 4.

Among the formulas (P1) detailed above, the use of compounds represented by the following formulas (P2-1) to (P2-11) is effective in suppressing the change in tilt angle with time.

(Wherein R ^P21 and R ^P22 each independently represents a hydrogen atom or a methyl group)
Although such a compound is useful, the solubility in a liquid crystal material may not be good. Accordingly, such a compound is preferably contained in an amount of 90% by mass or less, more preferably 70% by mass or less, and particularly preferably 50% by mass or less in the whole monomer to be used.

Further, among the formulas (P1), the use of compounds represented by the following formulas (P3-1) to (P3-11) can suppress the change in tilt angle with time and ensure solubility in liquid crystal materials. It is preferable because both can be achieved.

(In the formula, R ^P31 and R ^P32 each independently represent a hydrogen atom or a methyl group, mP31 represents an integer of 0 or 1, and when mP31 is 0, mP32 represents an integer of 1 to 6; In the case of 1, mP32 represents an integer of 2 to 6)

Among the formulas (P1), it is preferable to use compounds represented by the following formulas (P4-1) to (P4-11) because they are useful for effectively improving the off-response.

(In the formula, R ^P41 and R ^P42 each independently represent a hydrogen atom or a methyl group, mP42 and mP43 each independently represent an integer of 0 or 1, and when mP42 is 0, mP41 is 1-6. When mp42 is 1, mP41 represents an integer of 2 to 6, when mP43 is 0, mP44 represents an integer of 1 to 6, and when mP43 is 1, mp44 represents an integer of 2 to 6. To express)
Such a compound is preferably contained in an amount of 40% by mass or more, more preferably 50% by mass or more, and particularly preferably 60% by mass or more in the whole monomer to be used.

Among the formulas (P1), the compounds represented by the formulas (P5-1) to (P5-11) having an aryl ester structure in the mesogen have the ability to initiate polymerization by ultraviolet irradiation. This is preferable because the amount can be reduced.

(In the formula, R ^P51 and R ^P52 each independently represent a hydrogen atom or a methyl group, mP52 and mP53 each independently represent an integer of 0 or 1, and when mP52 is 0, mP51 is 1-6. When mp52 is 1, mP51 represents an integer of 2 to 6, when mP53 is 0, mP54 represents an integer of 1 to 6, and when mP53 is 1, mp54 represents an integer of 2 to 6. To express)
If the amount of such a compound added is large, the voltage holding ratio of the liquid crystal display element tends to deteriorate. Therefore, it is preferably contained in an amount of 30% by mass or less and more preferably 20% by mass or less in the whole monomer used. It is preferably 10% by mass or less.

It is also preferable to introduce a cinnamic ester group into a mesogen such as the compounds represented by formulas (P6-1) to (P6-11) among formula (P1).

(In the formula, R ^P61 and R ^P62 each independently represent a hydrogen atom or a methyl group, mP62 and mP63 each independently represent an integer of 0 or 1, and when mP62 is 0, mP61 is 1-6. When mp62 is 1, mP61 represents an integer from 2 to 6, when mP63 is 0, mP64 represents an integer from 1 to 6, and when mP63 is 1, mp64 represents an integer from 2 to 6. To express)

Further, among the compounds of formula (P1), compounds having a condensed ring represented by the following formulas (P7-1) to (P7-5) can shift the ultraviolet absorption region from the monocyclic compound to the visible light side. This is preferable from the viewpoint of adjusting the sensitivity of the monomer.

(In the formula, R ^P71 and R ^P72 each independently represent a hydrogen atom or a methyl group, mP72 and mP73 each independently represent an integer of 0 or 1, and when mP72 is 0, mP71 is 1-6. When mp72 is 1, mP71 represents an integer of 2 to 6, when mP73 is 0, mP74 represents an integer of 1 to 6, and when mP73 is 1, mp74 represents an integer of 2 to 6. To express.)
In the above, a bifunctional monomer is exemplified as a preferred compound, but among the formula (P1), the use of a trifunctional monomer such as the compounds represented by the formulas (P5-1) to (P5-11) is also preferred. The mechanical strength of the polymer or copolymer can be improved. Moreover, what has an ester bond in a mesogen has the capability to start superposition | polymerization by ultraviolet irradiation, Therefore Since the addition amount of a polymerization initiator can be reduced, it is more preferable.

(In the formula, R ^P81 and R ^P83 each independently represent a hydrogen atom or a methyl group, mP72 and mP73 each independently represent an integer of 0 or 1, and when mP72 is 0, mP71 is 1-6. When mp72 is 1, mP71 represents an integer of 2 to 6, when mP73 is 0, mP74 represents an integer of 1 to 6, and when mP73 is 1, mp74 is an integer of 2 to 6 Represents

In addition, among the formula (P1), it is also preferable to use a monofunctional monomer such as a compound represented by the following formulas (P9-1) to (P9-11) for the purpose of adjusting the driving voltage of the liquid crystal display element.

(Wherein R ^P91 represents a hydrogen atom or a methyl group, and R ^P92 represents a hydrogen atom or an alkyl group having 1 to 18 carbon atoms)

Further, in the formula (P1), it is preferable to provide a function of photoisomerization as a monomer because a light alignment function by light using the Weigert effect can be used. From such a viewpoint, the compounds represented by (P10-1) to (P10-11) are preferable.

(In the formula, R ^P101 and R ^P102 each independently represent a hydrogen atom or a methyl group, mP102 and mP103 each independently represent an integer of 0 or 1, and when mP102 is 0, mP101 is 1-6. When mp102 is 1, mP101 represents an integer from 2 to 6, when mP103 is 0, mP104 represents an integer from 1 to 6, and when mP103 is 1, mp104 represents an integer from 2 to 6 To express)

The radically polymerizable monomer component (A) detailed above is a compound represented by the various specific examples described above, represented by the following general formula (V):

(Wherein X ¹ and X ² each independently represent a hydrogen atom or a methyl group, and Sp ¹ and Sp ² each independently represent a single bond, an alkylene group having 1 to 12 carbon atoms or —O— (CH ₂ ) _s — (wherein _s represents an integer of 1 to 11 and an oxygen atom is bonded to an aromatic ring), U represents a linear or branched group having 2 to 20 carbon atoms Represents a polyvalent aliphatic hydrocarbon group or a polyvalent cyclic substituent having 5 to 30 carbon atoms, and the polyvalent aliphatic hydrocarbon group may be substituted with an oxygen atom within a range in which the oxygen atoms are not adjacent to each other. , An alkyl group having 5 to 20 carbon atoms (the alkylene group in the group may be substituted with an oxygen atom within the range in which the oxygen atom is not adjacent) or a cyclic substituent, and k is 1 Represents an integer of up to 5. All 1,4-phenylene in the formula Is any hydrogen atom _-CH 3, -OCH _3, fluorine atom, or may be substituted by a cyano group.)
Or the following general formula (VI)

(Wherein X ³ represents a hydrogen atom or a methyl group, Sp ³ represents a single bond, an alkylene group having 1 to 12 carbon atoms, or —O— (CH ₂ ) _t — (wherein t is 2 to Represents an integer of 11 and an oxygen atom is bonded to an aromatic ring), and V is a linear or branched alkylene group having 2 to 20 carbon atoms or a polyvalent having 5 to 30 carbon atoms. A cyclic substituent, a structural site in which an oxygen atom in a linear or branched alkylene structure having 2 to 20 carbon atoms is not adjacent to each other, and these chemical structures are the carbons constituting the structure. A hydrogen atom on the atom is substituted by an alkyl group having 5 to 20 carbon atoms (the alkylene group in the group may be substituted by an oxygen atom within a range not adjacent to the oxygen atom) or a cyclic substituent; W may be a hydrogen atom or a halogen atom. Represents an alkyl group having 1 to 15 carbon atoms. In addition, all 1,4-phenylene group in the formula, any hydrogen atom is _-CH 3, -OCH _3, substituted by fluorine atoms, or a cyano group May be.)
It can also be expressed as

Here, when Sp ¹ and Sp ² in the general formula (V) are the same, when these are, for example, a linear or branched alkylene group having 1 to 12 carbon atoms, It is preferable because it is easy to synthesize and the physical properties can be easily adjusted by adjusting the proportions of a plurality of compounds having different alkylene chain lengths.

Next, as the liquid crystal material (B) used in the polymerizable liquid crystal composition of the present invention (hereinafter abbreviated as “liquid crystal composition (B)”), either an anisotropy of dielectric constant is positive or negative. May be. When the anisotropy of the liquid crystal composition (B) is negative, the liquid crystal composition having a negative dielectric anisotropy (Δε is smaller than −2) and almost no dielectric anisotropy (Δε It preferably has a value of -2 to 2) a liquid crystal composition. When the anisotropy of the liquid crystal composition (B) is positive, there is almost no anisotropy of the dielectric constant (Δε is greater than that of a liquid crystal composition having a positive dielectric anisotropy (Δε is greater than 2)). It preferably has a value of -2 to 2) a liquid crystal composition.

In the liquid crystal composition (B), when the dielectric anisotropy is negative, the value of the dielectric anisotropy Δε is preferably in the range of −1.0 to −7.0, −1.5 Is more preferably −6.5, more preferably −2.0 to −6.0, and particularly preferably −2.5 to −5.5, but low voltage driving is important. In this case, a range of −3.0 to −6.0 is preferable, and a range of −2.0 to −3.5 is preferable when high-speed response is important.

The value of the refractive index anisotropy Δn is preferably in the range of 0.100 to 0.140 when the cell gap is made thin in order to realize a high-speed response, and the cell gap is made thick in order to improve the yield in display manufacturing. In this case, the range of 0.080 to 0.100 is preferable. However, in the case of manufacturing a reflective display, the preferable range is preferably 50% to 80% by mass of the above value.

The value of the nematic-isotropic phase transition temperature T _NI is preferably in the range of 65 to 150 ° C., but preferably in the range of 70 to 130 ° C. The temperature is preferably in the range of 70 to 90 ° C. when indoors are mainly indoors, and is preferably in the range of 80 to 120 ° C. when the use environment of the manufactured display is mainly outdoor.

The value of rotational viscosity is preferably 200 mPa · s or less, more preferably 180 mPa · s or less, further preferably 150 mPa · s or less, particularly preferably 130 mPa · s or less, and most preferably 100 mPa · s or less.

On the other hand, in the liquid crystal composition (B), when the dielectric anisotropy is positive, the value of the dielectric anisotropy Δε is preferably in the range of 1.0 to 20.0, 1.5 to 15.0 is more preferable, 2.0 to 10.0 is still more preferable, and 3.0 to 8.5 is particularly preferable. A range of 0 to 12.0 is preferable, and a range of 1.5 to 5.0 is preferable when high-speed response is important.

The value of Δn is preferably in the range of 0.110 to 0.160 when the cell gap is made thin in order to realize high-speed response, and is 0 when the cell gap is made thick in order to improve the yield in display manufacturing. The range of .090 to 0.110 is preferable, but in the case of manufacturing a reflective display, the preferable range is preferably 50% to 80% of the above value.

The preferred range of the nematic-isotropic phase transition temperature T _NI range is preferably 65 to 150 ° C., and preferably 70 to 130 ° C. When the use environment is mainly indoors, it is preferably in the range of 70 to 90 ° C., and when the use environment of the manufactured display is mainly outdoors, it is preferably in the range of 80 to 120 ° C. The value of rotational viscosity is preferably 130 mPa · s or less, more preferably 100 mPa · s or less, still more preferably 90 mPa · s or less, particularly preferably 75 mPa · s or less, and most preferably 60 mPa · s or less.

The liquid crystal composition (B) having a negative dielectric anisotropy is specifically represented by the general formulas (N-1), (N-2), (N-3) and (N-4). It is preferable to contain one or more compounds selected from the above compounds. These compounds correspond to dielectrically negative compounds (the sign of Δε is negative and the absolute value is greater than 2).

[In the general formulas (N-1), (N-2), (N-3) and (N-4), R ^N11 , R ^N12 , R ^N21 , R ^N22 , R ^N31 , R ^N32 , R ^N41 and R ^N42 each independently represents an alkyl group having 1 to 8 carbon atoms, or one or two or more non-adjacent —CH ₂ — in the alkyl chain having 2 to 8 carbon atoms, each independently A structural moiety having a chemical structure substituted by CH═CH—, —C≡C—, —O—, —CO—, —COO— or —OCO—,
A ^N11 , A ^N12 , A ^N21 , A ^N22 , A ^N31 , A ^N32 , A ^N41 and A ^N42 are each independently (a) a 1,4-cyclohexylene group,
(B) a divalent organic group having a structure in which one —CH ₂ — existing in a 1,4-cyclohexylene structure or two or more non-adjacent —CH ₂ — is replaced by —O— ,
(C) 1,4-phenylene group,
(D) a divalent organic group having a structure in which one —CH═ present in a 1,4-phenylene structure or two or more non-adjacent —CH═ are replaced by —N═;
(E) naphthalene-2,6-diyl group, 1,2,3,4-tetrahydronaphthalene-2,6-diyl group or decahydronaphthalene-2,6-diyl group,
(F) one —CH═ present in a naphthalene-2,6-diyl structure or a 1,2,3,4-tetrahydronaphthalene-2,6-diyl structure, or two or more —CH that are not adjacent to each other = Represents a group selected from the group consisting of a divalent organic group having a structure replaced with -N =, and (g) a 1,4-cyclohexenylene group,
In the above groups (a), (b), (c) and (d), the hydrogen atoms in the structure may be each independently substituted with a cyano group, a fluorine atom or a chlorine atom. ,

Z ^N11 , Z ^N12 , Z ^N21 , Z ^N22 , Z ^N31 , Z ^N32 , Z ^N41 and Z ^N42 are each independently a single bond, —CH ₂ CH ₂ —, — (CH ₂ ) ₄ —, —OCH. ₂ —, —CH ₂ O—, —COO—, —OCO—, —OCF ₂ —, —CF ₂ O—, —CH═N—N═CH—, —CH═CH—, —CF═CF— or -C≡C-, X ^N21 represents a hydrogen atom or a fluorine atom, T ^N31 represents -CH ₂ -or an oxygen atom, X ^N41 represents an oxygen atom, a nitrogen atom, or -CH _2- , Y ^N41 represents a single bond or —CH ₂ —, and n ^N11 , n ^N12 , n ^N21 , n ^N22 , n ^N31 , n ^N32 , n ^N41 , and n ^N42 are each independently an integer of 0 to 3 N ⁿ¹¹ + n ^N12 , n ^{N 21} + n ^N22 and n ^N31 + n ^N32 are each independently 1, 2 or 3, and when there are a plurality of A ^N11 to A ^N32 and Z ^N11 to Z ^N32 , they may be the same or different. N ^N41 + n ^N42 represents an integer of 0 to 3, but when there are a plurality of A ^N41 and A ^N42 , Z ^N41 and Z ^N42 , they may be the same or different. ]

The compounds represented by the general formulas (N-1), (N-2), (N-3) and (N-4) are preferably compounds whose Δε is negative and whose absolute value is larger than 2. .

In the general formulas (N-1), (N-2), (N-3) and (N-4), R ^N11 , R ^N12 , R ^N21 , R ^N22 , R ^N31 , R ^N32 , R ^N41 and R ^N32 Each independently is preferably 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, An alkyl group having 1 to 5 atoms, an alkoxy group having 1 to 5 carbon atoms, an alkenyl group having 2 to 5 carbon atoms or an alkenyloxy group having 2 to 5 carbon atoms is preferable, and an alkyl having 1 to 5 carbon atoms is preferred. More preferably an alkyl group having 2 to 5 carbon atoms, an alkyl group having 2 to 5 carbon atoms or an alkenyl group having 2 to 3 carbon atoms, and an alkenyl group having 3 carbon atoms (propenyl group). Especially preferred .

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

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

A ^N11 , A ^N12 , A ^N21 , A ^N22 , A ^N31 , A ^N32 , A ^N41, and A ^N42 are each preferably an aromatic structure site when it is required to independently increase Δn, In order to improve the response speed, an aliphatic structure site is preferable, and trans-1,4-cyclohexylene group, 1,4-phenylene group, 2-fluoro-1,4-phenylene group, 3-fluoro group -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, 1,2,3,4-tetrahydrona Phthalene-2,6-diyl group and other structural formulas shown below

Is preferably a group having a tetrahydrofuran or dioxane skeleton.
Among these, it is more preferable to represent the following structure,

In particular, trans-1,4-cyclohexylene group and 1,4-cyclohexenylene group are preferable because they are useful when it is desired to lower Δn, and the viscosity can be lowered. , 4-phenylene group is more preferable because it is useful for increasing Δn.

^{^{^{^{Z N11, Z N12, Z N21}}}} , Z N22, Z N31, Z N32, Z N41 and ^{Z N42} are each independently _{_{-CH 2 O -, - CF 2}} O -, - CH 2 CH 2 -, - CF 2 It preferably represents CF ₂ — or a single bond, more preferably —CH ₂ O—, —CH ₂ CH ₂ — or a single bond, and particularly preferably —CH ₂ O— or a single bond.

^XN21 is preferably a fluorine atom.

T ^N31 is preferably an oxygen atom.

n ^N11 + n ^N12 , n ^N21 + n ^N22 , n ^N31 + n ^N32 and n ^N41 + n ^N42 are preferably 0, 1 or 2, a combination in which n ^N11 is 1 and n ^N12 is 0, n ^N11 is 2 and n ^N12 A combination in which n ^N11 is 1 and n ^N12 is 1, a combination in which n ^N11 is 2 and n ^N12 is 1, a combination in which n ^N21 is 1 and n ^N22 is 0, n ^N21 Is a combination in which n ^N22 is 0, n ^N31 is 1 and n ^N32 is 0, and a combination in which n ^N31 is 2 and n ^N32 is 0, but n ^N41 + n ^N42 is n ^N41 And a combination in which n ^N42 is 0 is also preferable.

The lower limit of the preferable content of the compound represented by the formula (N-1) with respect to the total amount of the liquid crystal composition (B) is 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, 80% by mass %. The upper limit of the preferable content is 95% by mass, 85% by mass, 75% by mass, 65% by mass, 55% by mass, 45% by mass, and 35% by mass, 25% by mass and 20% by mass.

The lower limit of the preferable content of the compound represented by the formula (N-2) with respect to the total amount of the liquid crystal composition (B) is 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, 80% by mass %. The upper limit of the preferable content is 95% by mass, 85% by mass, 75% by mass, 65% by mass, 55% by mass, 45% by mass, and 35% by mass, 25% by mass and 20% by mass.

The lower limit of the preferable content of the compound represented by the formula (N-3) with respect to the total amount of the liquid crystal composition (B) is 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, 80% by mass %. The upper limit of the preferable content is 95% by mass, 85% by mass, 75% by mass, 65% by mass, 55% by mass, 45% by mass, and 35% by mass, 25% by mass and 20% by mass.

The lower limit of the preferable content of the compound represented by the formula (N-4) with respect to the total amount of the liquid crystal composition (B) is 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, 80% by mass %. The upper limit of the preferable content is 95% by mass, 85% by mass, 75% by mass, 65% by mass, 55% by mass, 45% by mass, and 35% by mass, 25% by mass and 20% by mass.

When the viscosity of the liquid crystal composition (B) is kept low and a composition having a high response speed is required, the above lower limit value is preferably low and the upper limit value is preferably low. Further, when a composition having a high temperature stability and a high temperature stability is required, it is preferable that the lower limit value is low and the upper limit value is low. When it is desired to increase the dielectric anisotropy in order to keep the driving voltage low, it is preferable that the above lower limit value is increased and the upper limit value is high.

Examples of the compound represented by the general formula (N-1) include compounds represented by the following general formulas (N-1a) to (N-1g).

(In the formula, R ^N11 and R ^N12 represent the same meaning as R ^N11 and R ^N12 in formula (N-1), n ^Na11 represents 0 or 1, n ^Nb11 represents 1 or 2, and n ^Nc11 represents ^Represents 0 or 1, n ^Nd11 represents 1 or 2, n ^Ne11 represents 1 or 2, n ^Nf11 represents 1 or 2, n ^Ng11 represents 1 or 2, A ^Ne11 represents trans-1,4 ^{-Represents a} cyclohexylene group or a 1,4-phenylene group, and A ^Ng11 represents a trans-1,4-cyclohexylene group, a 1,4-cyclohexenylene group or a 1,4-phenylene group, but at least one Represents a 1,4-cyclohexenylene group, and Z ^Ne ¹¹ represents a single bond or ethylene, but at least one represents ethylene.)

More specifically, the compound represented by the general formula (N-1) is a compound selected from the group of compounds represented by the general formulas (N-1-1) to (N-1-21). preferable.

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

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

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

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

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

Further, the compound represented by the general formula (N-1-1) is a compound selected from the group of compounds represented by the formula (N-1-1.1) to the formula (N-1-1.23). Preferably, it is a compound represented by the formulas (N-1-1.1) to (N-1-1.4), and the formula (N-1-1.1) and the formula (N The compound represented by -1-1.3) is preferable.

The compounds represented by the formulas (N-1-1.1) to (N-1-1.22) can be used alone or in combination, but the liquid crystal composition (B) The lower limit of the preferable content of these compounds alone or with respect to the total amount of is 5% by mass, 10% by mass, 13% by mass, 15% by mass, 17% by mass, 20% % By mass, 23% by mass, 25% by mass, 27% by mass, 30% by mass, 33% by mass and 35% by mass. The upper limit of the preferable content is 50% by mass, 40% by mass, 38% by mass, 35% by mass, and 33% by mass with respect to the total amount of the non-polymerizable composition. 30% by mass, 28% by mass, 25% by mass, 23% by mass, 20% by mass, 18% 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 (N-1-2) is the following compound.

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

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

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

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

Further, the compound represented by the general formula (N-1-2) is a compound selected from the group of compounds represented by the formula (N-1-2.1) to the formula (N-1-2.22). It is preferable that the formula (N-1-2.3) to the formula (N-1-2.7), the formula (N-1-2.10), the formula (N-1-2.11), the formula A compound represented by formula (N-1-2.13) and formula (N-1-2.20) is preferred. When importance is attached to the improvement of Δε, formula (N-1-2.3) is preferably a compound represented by the formula (N-1-2.7) _from when emphasizing improvements in _{T NI} formula (N-1-2.10), formula (N-1-2.11) And a compound represented by the formula (N-1-2.13), and when emphasizing improvement in response speed, the compound represented by the formula (N-1-2.20) Is preferred.

The compounds represented by formula (N-1-2.1) to formula (N-1-2.22) can be used alone or in combination, but the liquid crystal composition (B ) Alone or the lower limit of the preferred content of these compounds is 5% by mass, 10% by mass, 13% by mass, 15% by mass, and 17% by mass, 20% by mass, 23% by mass, 25% by mass, 27% by mass, 30% by mass, 33% by mass, and 35% by mass. The upper limit of the preferable content is 50% by mass, 40% by mass, 38% by mass, 35% by mass, and 33% by mass with respect to the total amount of the liquid crystal composition (B). 30% by mass, 28% by mass, 25% by mass, 23% by mass, 20% by mass, 18% 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 (N-1-3) is the following compound.

( ^Wherein , R ^N131 and R ^N132 each independently represent the same meaning as R ^N11 and R ^N12 in formula (N-1)).

R ^N131 is preferably an alkyl group having 1 to 5 carbon atoms or an alkenyl group having 2 to 5 carbon atoms, and preferably an ethyl group, a propyl group or a butyl group. R ^N132 is preferably an alkyl group having 1 to 5 carbon atoms, an alkenyl group having 3 to 5 carbon atoms or an alkoxy group having 1 to 4 carbon atoms, and preferably a 1-propenyl group, an ethoxy group, a propoxy group or a butoxy group. .

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

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

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

Further, the compound represented by the general formula (N-1-3) is a compound selected from the group of compounds represented by the formula (N-1-3.1) to the formula (N-1-3.21). It is preferably a compound represented by the formulas (N-1-3.1) to (N-1-3.7) and the formula (N-1-3.21). -1-3.1), formula (N-1-3.2), formula (N-1-3.3), formula (N-1-3.4) and formula (N-1-3.6) ) Is preferred.

Compounds represented by formula (N-1-3.1) to formula (N-1-3.4), formula (N-1-3.6) and formula (N-1-3.21) are used alone Can be used in combination, or can be used in combination, but the combination of formula (N-1-3.1) and formula (N-1-3.2), formula (N-1-3.3) ), Formula (N-1-3.4) and formula (N-1-3.6) are preferred. The lower limit of the preferable content of these compounds alone or with respect to the total amount of the liquid crystal composition (B) is 5% by mass, 10% by mass, 13% by mass, 15% by mass, 17 It is 20 mass%. The upper limit of the preferable content is 35% by mass, 30% by mass, 28% by mass, 25% by mass, and 23% by mass with respect to the total amount of the liquid crystal composition (B). 20% by mass, 18% by mass, 15% by mass, and 13% by mass.

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

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

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

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

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

The compounds represented by the formulas (N-1-4.1) to (N-1-4.14) can be used alone or in combination, but the liquid crystal composition (B) The lower limit of the preferred content of these compounds alone or with respect to the total amount of is 3% by mass, 5% by mass, 7% by mass, 10% by mass, 13% by mass, 15% Mass%, 17 mass%, and 20 mass%. The upper limit of the preferable content is 35% by mass, 30% by mass, 28% by mass, 25% by mass, and 23% by mass with respect to the total amount of the liquid crystal composition (B). 20% by mass, 18% by mass, 15% by mass, 13% by mass, 11% by mass, 10% by mass, and 8% by mass.

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

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

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

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

Further, the compound represented by the general formula (N-1-5) is a compound selected from the group of compounds represented by the formula (N-1-5.1) to the formula (N-1-5.6). It is preferable that the compound represented by formula (N-1-5.1), formula (N-1-5.2) and formula (N-1-5.4) is preferable.

The compounds represented by formula (N-1-5.1), formula (N-1-5.2) and formula (N-1-5.4) may be used alone or in combination. However, the lower limit of the preferred content of these compounds alone or with respect to the total amount of the liquid crystal composition (B) is 5 mass%, 8 mass%, 10 mass%, 13 % By mass, 15% by mass, 17% by mass, and 20% by mass. The upper limit of the preferable content is 35% by mass, 33% by mass, 30% by mass, 28% by mass, and 25% by mass with respect to the total amount of the liquid crystal composition (B). It is 23% by mass, 20% by mass, 18% by mass, 15% by mass, and 13% by mass.

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

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

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

When emphasizing the improvement of Δε, it is preferable to set the content higher. When emphasizing the solubility at low temperature, setting the content higher is more effective. When emphasizing _TNI , the content is high. Setting to a higher value is more effective. Furthermore, when improving dripping marks and image sticking characteristics, it is preferable to set the content range in the middle.

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

Further, the compound represented by the general formula (N-1-10) is a compound selected from the group of compounds represented by the formula (N-1-10.1) to the formula (N-1-10.21). It is preferable that they are represented by formulas (N-1-10.1) to (N-1-10.5), formula (N-1-10.20) and formula (N-1-10.21). The compound is preferably a compound of formula (N-1-10.1), formula (N-1-10.2), formula (N-1-10.20) and formula (N-1-10.21). The compound represented by these is preferable.

The compounds represented by formula (N-1-10.1), formula (N-1-10.2), formula (N-1-10.20) and formula (N-1-10.21) are singly Can be used in combination or in combination, but the lower limit of the preferred content of these compounds alone or with respect to the total amount of the liquid crystal composition (B) is 5% by mass, and 10% by mass. %, 13% by mass, 15% by mass, 17% by mass, and 20% by mass. The upper limit of the preferable content is 35% by mass, 30% by mass, 28% by mass, 25% by mass, and 23% by mass with respect to the total amount of the liquid crystal composition (B). 20% by mass, 18% by mass, 15% by mass, and 13% by mass.

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

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

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

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

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

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

The compounds represented by formula (N-1-11.2) and formula (N-1-11.4) can be used alone or in combination, but the liquid crystal composition (B ) Alone or the lower limit of the preferred content of these compounds is 5% by mass, 10% by mass, 13% by mass, 15% by mass, and 17% by mass, 20% by mass. The upper limit of the preferable content is 35% by mass, 30% by mass, 28% by mass, 25% by mass, and 23% by mass with respect to the total amount of the liquid crystal composition (B). 20% by mass, 18% by mass, 15% by mass, and 13% by mass.

The compound represented by the general formula (N-1-12) is the following compound.

( ^Wherein , R ^N1121 and R ^N1122 each independently represent the same meaning as R ^N11 and R ^N12 in formula (N-1)).
^RN1121 is preferably an alkyl group having 1 to 5 carbon atoms or an alkenyl group having 2 to 5 carbon atoms, and preferably an ethyl group, a propyl group or a butyl group. ^RN1122 is preferably an alkyl group having 1 to 5 carbon atoms, an alkenyl group having 4 to 5 carbon atoms, or an alkoxy group having 1 to 4 carbon atoms, and preferably an ethoxy group, a propoxy group, or a butoxy group.

The compound represented by the general formula (N-1-12) can be used alone, or two or more compounds can be used in combination. There are no particular restrictions on the types of compounds that can be combined, but they are used in appropriate combinations according to the required properties such as solubility at low temperatures, transition temperatures, electrical reliability, and birefringence. The kind of the compound used is, for example, one kind as one embodiment of the present invention, two kinds, three kinds, four kinds, and five kinds or more.

The lower limit of the preferable content of the compound represented by the formula (N-1-12) with respect to the total amount of the liquid crystal composition (B) is 5% by mass, 10% by mass, and 13% by mass. Yes, 15% by mass, 17% by mass, and 20% by mass. The upper limit of the preferable content is 35% by mass, 30% by mass, 28% by mass, 25% by mass, and 23% by mass with respect to the total amount of the liquid crystal composition (B). 20% by mass, 18% by mass, 15% by mass, and 13% by mass.

The compound represented by the general formula (N-1-13) is the following compound.

( ^Wherein , R ^N1131 and R ^N1132 each independently represent the same meaning as R ^N11 and R ^N12 in formula (N-1)).
R ^N1131 is preferably an alkyl group having 1 to 5 carbon atoms or an alkenyl group having 2 to 5 carbon atoms, and preferably an ethyl group, a propyl group or a butyl group. R ^N1132 is preferably an alkyl group having 1 to 5 carbon atoms, an alkenyl group having 4 to 5 carbon atoms, or an alkoxy group having 1 to 4 carbon atoms, and preferably an ethoxy group, a propoxy group, or a butoxy group.

The compound represented by the general formula (N-1-13) can be used alone, or two or more compounds can be used in combination. There are no particular restrictions on the types of compounds that can be combined, but they are used in appropriate combinations according to the required properties such as solubility at low temperatures, transition temperatures, electrical reliability, and birefringence. The kind of the compound used is, for example, one kind as one embodiment of the present invention, two kinds, three kinds, four kinds, and five kinds or more.

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

The compound represented by the general formula (N-1-14) is the following compound.

( ^Wherein , R ^N1141 and R ^N1142 each independently represent the same meaning as R ^N11 and R ^N12 in formula (N-1)).
R ^N1141 is preferably an alkyl group having 1 to 5 carbon atoms or an alkenyl group having 2 to 5 carbon atoms, and preferably an ethyl group, a propyl group or a butyl group. R ^N1142 is preferably an alkyl group having 1 to 5 carbon atoms, an alkenyl group having 4 to 5 carbon atoms, or an alkoxy group having 1 to 4 carbon atoms, and preferably an ethoxy group, a propoxy group, or a butoxy group.

The compound represented by the general formula (N-1-14) can be used alone, or two or more compounds can be used in combination. There are no particular restrictions on the types of compounds that can be combined, but they are used in appropriate combinations according to the required properties such as solubility at low temperatures, transition temperatures, electrical reliability, and birefringence. The kind of the compound used is, for example, one kind as one embodiment of the present invention, two kinds, three kinds, four kinds, and five kinds or more.

The lower limit of the preferable content of the compound represented by the formula (N-1-14) with respect to the total amount of the liquid crystal composition (B) is 5% by mass, 10% by mass, and 13% by mass. Yes, 15% by mass, 17% by mass, and 20% by mass. The upper limit of the preferable content is 35% by mass, 30% by mass, 28% by mass, 25% by mass, and 23% by mass with respect to the total amount of the liquid crystal composition (B). 20% by mass, 18% by mass, 15% by mass, and 13% by mass.

The compound represented by the general formula (N-1-15) is the following compound.

( ^Wherein , R ^N1151 and R ^N1152 each independently represent the same meaning as R ^N11 and R ^N12 in formula (N-1)).
^RN1151 is preferably an alkyl group having 1 to 5 carbon atoms or an alkenyl group having 2 to 5 carbon atoms, and preferably an ethyl group, a propyl group or a butyl group. R ^N1152 is preferably an alkyl group having 1 to 5 carbon atoms, an alkenyl group having 4 to 5 carbon atoms, or an alkoxy group having 1 to 4 carbon atoms, and preferably an ethoxy group, a propoxy group, or a butoxy group.

The compound represented by the general formula (N-1-15) can be used alone, or two or more compounds can be used in combination. There are no particular restrictions on the types of compounds that can be combined, but they are used in appropriate combinations according to the required properties such as solubility at low temperatures, transition temperatures, electrical reliability, and birefringence. The kind of the compound used is, for example, one kind as one embodiment of the present invention, two kinds, three kinds, four kinds, and five kinds or more.

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

The compound represented by the general formula (N-1-16) is the following compound.

(In the formula, R ^N1161 and R ^N1162 each independently represent the same meaning as R ^N11 and R ^N12 in formula (N-1).)
R ^N1161 is preferably an alkyl group having 1 to 5 carbon atoms or an alkenyl group having 2 to 5 carbon atoms, and preferably an ethyl group, a propyl group or a butyl group. R ^N1162 is preferably an alkyl group having 1 to 5 carbon atoms, an alkenyl group having 4 to 5 carbon atoms, or an alkoxy group having 1 to 4 carbon atoms, and preferably an ethoxy group, a propoxy group, or a butoxy group.

The compound represented by the general formula (N-1-16) can be used alone, or two or more compounds can be used in combination. There are no particular restrictions on the types of compounds that can be combined, but they are used in appropriate combinations according to the required properties such as solubility at low temperatures, transition temperatures, electrical reliability, and birefringence. The kind of the compound used is, for example, one kind as one embodiment of the present invention, two kinds, three kinds, four kinds, and five kinds or more.

The lower limit of the preferable content of the compound represented by the formula (N-1-16) with respect to the total amount of the liquid crystal composition (B) is 5% by mass, 10% by mass, and 13% by mass. Yes, 15% by mass, 17% by mass, and 20% by mass. The upper limit of the preferable content is 35% by mass, 30% by mass, 28% by mass, 25% by mass, and 23% by mass with respect to the total amount of the liquid crystal composition (B). 20% by mass, 18% by mass, 15% by mass, and 13% by mass.

The compound represented by the general formula (N-1-17) is the following compound.

( ^Wherein , R ^N1171 and R ^N1172 each independently represent the same meaning as R ^N11 and R ^N12 in formula (N-1)).

R ^N1171 is preferably an alkyl group having 1 to 5 carbon atoms or an alkenyl group having 2 to 5 carbon atoms, and preferably an ethyl group, a propyl group or a butyl group. R ^N1172 is preferably an alkyl group having 1 to 5 carbon atoms, an alkenyl group having 4 to 5 carbon atoms, or an alkoxy group having 1 to 4 carbon atoms, and preferably an ethoxy group, a propoxy group, or a butoxy group.

The compound represented by the general formula (N-1-17) can be used alone, or two or more compounds can be used in combination. There are no particular restrictions on the types of compounds that can be combined, but they are used in appropriate combinations according to the required properties such as solubility at low temperatures, transition temperatures, electrical reliability, and birefringence. The kind of the compound used is, for example, one kind as one embodiment of the present invention, two kinds, three kinds, four kinds, and five kinds or more.

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

The compound represented by the general formula (N-1-18) is the following compound.

( ^Wherein , R ^N1181 and R ^N1182 each independently represent the same meaning as R ^N11 and R ^N12 in formula (N-1)).
^RN1181 is preferably an alkyl group having 1 to 5 carbon atoms or an alkenyl group having 2 to 5 carbon atoms, preferably a methyl group, an ethyl group, a propyl group or a butyl group. R ^N1182 is preferably an alkyl group having 1 to 5 carbon atoms, an alkenyl group having 4 to 5 carbon atoms, or an alkoxy group having 1 to 4 carbon atoms, and preferably an ethoxy group, a propoxy group, or a butoxy group.

The compound represented by the general formula (N-1-18) can be used alone, or two or more compounds can be used in combination. There are no particular restrictions on the types of compounds that can be combined, but they are used in appropriate combinations according to the required properties such as solubility at low temperatures, transition temperatures, electrical reliability, and birefringence. The kind of the compound used is, for example, one kind as one embodiment of the present invention, two kinds, three kinds, four kinds, and five kinds or more.

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

Further, the compound represented by the general formula (N-1-18) is a compound selected from the group of compounds represented by the formula (N-18.1) to the formula (N-1-18.5). It is more preferable that the compounds are represented by the formulas (N-1-18.1) to (N-1-18.3), and the compounds represented by the formulas (N-1-18.2) and the formula (N-1 The compound represented by −1-18.3) is particularly preferable.

The compound represented by the general formula (N-1-20) is the following compound.

(In the formula, R ^N1201 and R ^N1202 each independently represent the same meaning as R ^N11 and R ^N12 in formula (N-1).)
R ^N1201 and R ^N1202 are each independently preferably an alkyl group having 1 to 5 carbon atoms or an alkenyl group having 2 to 5 carbon atoms, and preferably an ethyl group, a propyl group or a butyl group.

The compound represented by the general formula (N-1-20) can be used alone, or two or more compounds can be used in combination. There are no particular restrictions on the types of compounds that can be combined, but they are used in appropriate combinations according to the required properties such as solubility at low temperatures, transition temperatures, electrical reliability, and birefringence. The kind of the compound used is, for example, one kind as one embodiment of the present invention, two kinds, three kinds, four kinds, and five kinds or more.

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

The compound represented by the general formula (N-1-21) is the following compound.

(In the formula, R ^N1211 and R ^N1212 each independently represent the same meaning as R ^N11 and R ^N12 in formula (N-1).)
R ^N1211 and R ^N1212 are each independently preferably an alkyl group having 1 to 5 carbon atoms or an alkenyl group having 2 to 5 carbon atoms, and preferably an ethyl group, a propyl group or a butyl group.

The compound represented by the general formula (N-1-21) can be used alone, or two or more compounds can be used in combination. There are no particular restrictions on the types of compounds that can be combined, but they are used in appropriate combinations according to the required properties such as solubility at low temperatures, transition temperatures, electrical reliability, and birefringence. The kind of the compound used is, for example, one kind as one embodiment of the present invention, two kinds, three kinds, four kinds, and five kinds or more.

The lower limit of the preferable content of the compound represented by the formula (N-1-21) with respect to the total amount of the liquid crystal composition (B) is 5% by mass, 10% by mass, and 13% by mass. Yes, 15% by mass, 17% by mass, and 20% by mass. The upper limit of the preferable content is 35% by mass, 30% by mass, 28% by mass, 25% by mass, and 23% by mass with respect to the total amount of the liquid crystal composition (B). 20% by mass, 18% by mass, 15% by mass, and 13% by mass.

The compound represented by the general formula (N-1-22) is the following compound.

( ^Wherein , R ^N1221 and R ^N1222 each independently represent the same meaning as R ^N11 and R ^N12 in formula (N-1)).
R ^N1221 and R ^N1222 are each independently preferably an alkyl group having 1 to 5 carbon atoms or an alkenyl group having 2 to 5 carbon atoms, and preferably an ethyl group, a propyl group, or a butyl group.

The compound represented by the general formula (N-1-22) can be used alone, or two or more compounds can be used in combination. There are no particular restrictions on the types of compounds that can be combined, but they are used in appropriate combinations according to the required properties such as solubility at low temperatures, transition temperatures, electrical reliability, and birefringence. The kind of the compound used is, for example, one kind as one embodiment of the present invention, two kinds, three kinds, four kinds, and five kinds or more.

The lower limit of the preferable content of the compound represented by the formula (N-1-21) with respect to the total amount of the liquid crystal composition (B) is 1% by mass, 5% by mass, 10% by mass Yes, 13% by mass, 15% by mass, 17% by mass and 20% by mass. The upper limit of the preferable content is 35% by mass, 30% by mass, 28% by mass, 25% by mass, and 23% by mass with respect to the total amount of the liquid crystal composition (B). 20% by mass, 18% by mass, 15% by mass, 13% by mass, 10% by mass, and 5% by mass.

Further, the compound represented by the general formula (N-1-22) is a compound selected from the group of compounds represented by the formula (N-1-22.1) to the formula (N-1-22.12). Preferably, it is a compound represented by formulas (N-1-22.1) to (N-1-22.5), and preferably represented by formulas (N-1-22.1) to (N- The compound represented by 1-22.4) is preferred.

Next, as the compound represented by the general formula (N-2), the following general formula (N-2-a) to general formula (N-2-c)

(Wherein R ^N21 , R ^N22 and X ^N21 each independently represent the same meaning as R ^N21 , R ^N22 and X ^N21 in formula (N-2), Z ^N21 represents a single bond, —CH═CH Represents —, —C≡C—, —CH ₂ CH ₂ —, — (CH ₂ ) ₄ —, —COO—, —OCH ₂ —, —CH ₂ O—, —OCF ₂ — or —CF ₂ O—. It is more preferable that it is 1 type, or 2 or more types of compounds selected from the group consisting of compounds represented by.

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

(In the formula, R ^N321 and R ^N322 each independently represent the same meaning as R ^N11 and R ^N12 in formula (N-3).)
R ^N321 and R ^N322 are preferably an alkyl group having 1 to 5 carbon atoms or an alkenyl group having 2 to 5 carbon atoms, and preferably a propyl group or a pentyl group.

The compound represented by the general formula (N-3-2) can be used alone, or two or more compounds can be used in combination. There are no particular restrictions on the types of compounds that can be combined, but they are used in appropriate combinations according to the required properties such as solubility at low temperatures, transition temperatures, electrical reliability, and birefringence. The kind of the compound used is, for example, one kind as one embodiment of the present invention, two kinds, three kinds, four kinds, and five kinds or more.

The lower limit of the preferable content of the compound represented by the formula (N-3-2) with respect to the total amount of the liquid crystal composition (B) is 3% by mass, 5% by mass, 10% by mass Yes, 13% by mass, 15% by mass, 17% by mass, 20% by mass, 23% by mass, 25% by mass, 27% by mass, 30% by mass, 33% by mass and 35% by mass. The upper limit of the preferable content is 50% by mass, 40% by mass, 38% by mass, 35% by mass, and 33% by mass with respect to the total amount of the liquid crystal composition (B). 30% by mass, 28% by mass, 25% by mass, 23% by mass, 20% by mass, 18% by mass, 15% by mass, 13% by mass, 10% by mass %, 8% by mass, 7% by mass, 6% by mass, and 5% by mass.

Further, the compound represented by the general formula (N-3-1) is a compound selected from the group of compounds represented by the formula (N-3-1.1) to the formula (N-3-1.3). Preferably there is.

Examples of the compound represented by the general formula (N-4) include a compound group represented by the following general formula (N-4-1).

(Wherein, R ^N41 and R ^N42 each independently represent the same meaning as R ^N41 and R ^N42 in formula (N-4)).
R ^N321 and R ^N322 are preferably an alkyl group having 1 to 5 carbon atoms or an alkoxy group having 2 to 5 carbon atoms, and preferably a propyl group, a pentyl group, an ethoxy group, a propoxy group or a butoxy group.

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

The lower limit of the preferable content of the compound represented by the formula (N-4-1) with respect to the total amount of the liquid crystal composition (B) is 1% by mass, 3% by mass, 5% by mass Yes, 10% by weight, 13% by weight, 15% by weight, 17% by weight, 20% by weight, 23% by weight, 25% by weight, 27% by weight, 30% by mass, 33% by mass, and 35% by mass. The upper limit of the preferable content is 50% by mass, 40% by mass, 38% by mass, 35% by mass, and 33% by mass with respect to the total amount of the liquid crystal composition (B). 30% by mass, 28% by mass, 25% by mass, 23% by mass, 20% by mass, 18% by mass, 15% by mass, 13% by mass, 10% by mass %, 8% by mass, 7% by mass, 6% by mass, and 5% by mass.

Further, the compound represented by the general formula (N-4-1) is a compound selected from the group of compounds represented by the formula (N-4-1.1) to the formula (N-4-1.6). Preferably there is.

Among the general formulas (N-1) to (N-4) described in detail above, particularly when active energy rays are irradiated to form a polymer network and a liquid crystal phase, the resistance to the active energy rays is high. A compound represented by formula (N-1) is preferable from the viewpoint of high.

Next, the liquid crystal composition (B) having a positive dielectric anisotropy preferably contains one or more compounds represented by the general formula (J). These compounds correspond to dielectrically positive compounds (Δε is greater than 2).

(Wherein R ^J1 represents an alkyl group having 1 to 8 carbon atoms, and one or two or more non-adjacent —CH ₂ — in the alkyl group are each independently —CH═CH—, — Optionally substituted by C≡C—, —O—, —CO—, —COO— or —OCO—,
n ^J1 represents 0, 1, 2, 3 or 4;
A ^J1 , A ^J2 and A ^J3 are each independently
(A) 1,4-cyclohexylene group,
(B) a divalent organic compound having a chemical structure in which one —CH ₂ — present in a 1,4-cyclohexylene structure or two or more non-adjacent —CH ₂ — are replaced by —O— Group,
(C) 1,4-phenylene group,
(D) a divalent organic group having a chemical structure in which one —CH═ existing in a 1,4-phenylene structure or two or more non-adjacent —CH═ are replaced by —N═;
(E) naphthalene-2,6-diyl group, 1,2,3,4-tetrahydronaphthalene-2,6-diyl group or decahydronaphthalene-2,6-diyl group, and (f) naphthalene-2,6 -One -CH = or two or more non-adjacent -CH = present in a diyl structure or 1,2,3,4-tetrahydronaphthalene-2,6-diyl structure is replaced by -N = Divalent organic group having a different structure

The group (a), the group (b) and the group (c) are each independently selected from the group consisting of cyano group, fluorine atom, chlorine atom, methyl group, trifluoromethyl group or trifluoro May be substituted with a methoxy group,
Z ^J1 and Z ^J2 are each independently a single bond, —CH ₂ CH ₂ —, — (CH ₂ ) ₄ —, —OCH ₂ —, —CH ₂ O—, —OCF ₂ —, —CF ₂ O—, Represents —COO—, —OCO— or —C≡C—,
When n ^J1 is 2, 3 or 4 and a plurality of A ^J2 are present, they may be the same or different, and n ^J1 is 2, 3 or 4 and a plurality of Z ^J1 is present. If they are the same or different,
X ^J1 represents a hydrogen atom, a fluorine atom, a chlorine atom, a cyano group, a trifluoromethyl group, a fluoromethoxy group, a difluoromethoxy group, a trifluoromethoxy group, or a 2,2,2-trifluoroethyl group. )
In general formula (J), R ^J1 represents 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 alkenyloxy having 2 to 8 carbon atoms. A group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, an alkenyl group having 2 to 5 carbon atoms or an alkenyloxy group having 2 to 5 carbon atoms is preferable. An alkyl group having 1 to 5 carbon atoms or an alkenyl group having 2 to 5 carbon atoms is more preferable, an alkyl group having 2 to 5 carbon atoms or an alkenyl group having 2 to 3 carbon atoms is more preferable, and an alkenyl group having 3 carbon atoms. (Propenyl group) is particularly preferred.

R ^J1 is preferably an alkyl group when emphasizing reliability, and is preferably an alkenyl group when emphasizing a decrease in viscosity.

The alkenyl group is preferably selected from groups represented by any of the formulas (R1) to (R5). (The black dot in each formula represents the carbon atom in the ring structure to which the alkenyl group is bonded.)

A ^J1 , A ^J2 and A ^J3 are each preferably an aromatic structural moiety when it is required to increase Δn independently, and may be an aliphatic structural moiety in order to improve the response speed. Preferably, trans-1,4-cyclohexylene group, 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, and other structural formulas shown below

Or a group having a tetrahydrofuran or dioxane skeleton, or a structure in which a hydrogen atom in these structures is substituted with a fluorine atom.

Among these, the alicyclic structure is preferable because it is useful when it is desired to lower Δn, and the viscosity can be lowered. Aromatic ones increase Δn. Useful if you want. From this viewpoint, the following structure

What is represented by is preferable.

Z ^J1 and Z ^J2 each independently preferably represent —CH ₂ O—, —OCH ₂ —, —CF ₂ O—, —CH ₂ CH ₂ —, —CF ₂ CF ₂ — or a single bond, OCH ₂ —, —CF ₂ O—, —CH ₂ CH ₂ — or a single bond is more preferred, and —OCH ₂ —, —CF ₂ O— or a single bond is particularly preferred.

X ^J1 is preferably a fluorine atom or a trifluoromethoxy group, and more preferably a fluorine atom.

n ^J1 is preferably 0, 1, 2 or 3, preferably 0, 1 or 2, preferably 0 or 1 when emphasizing the improvement of Δε, and preferably 1 or 2 when emphasizing Tni .

There are no particular restrictions on the types of compounds that can be combined, but they are used in combination according to desired properties such as solubility at low temperatures, transition temperatures, electrical reliability, and birefringence. For example, in one embodiment of the present invention, there are one kind, two kinds, and three kinds of compounds to be used. Furthermore, in another embodiment of the present invention, there are four types, five types, six types, and seven or more types.

In the liquid crystal composition (B), the content of the compound represented by the general formula (J) is low temperature solubility, transition temperature, electrical reliability, birefringence, process suitability, dripping marks, image sticking. Therefore, it is necessary to appropriately adjust according to required performance such as dielectric anisotropy.

The lower limit of the preferable content of the compound represented by the general formula (J) with respect to the total amount of the liquid crystal composition (B) is 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 80% by mass. It is. 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 liquid crystal composition (B). Yes, 55% by mass, 45% by mass, 35% by mass, and 25% by mass.

When the viscosity of the liquid crystal composition (B) is kept low and a composition having a high response speed is required, it is preferable to lower the lower limit and lower the upper limit. Furthermore, when a composition having a high temperature stability and a high 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 driving voltage low, it is preferable to increase the upper limit value while increasing the lower limit value.

As the compound represented by the general formula (J), a compound represented by the following general formula (M) and a compound represented by the general formula (K) are preferable.

The liquid crystal composition (B) having a positive dielectric anisotropy preferably contains one or more compounds represented by the general formula (M). These compounds correspond to dielectrically positive compounds (Δε is greater than 2).

(Wherein R ^M1 represents an alkyl group having 1 to 8 carbon atoms, and one or two or more non-adjacent —CH ₂ — in the alkyl group are each independently —CH═CH—, — Optionally substituted by C≡C—, —O—, —CO—, —COO— or —OCO—,
n ^M1 represents 0, 1, 2, 3 or 4;
A ^M1 and A ^M2 are each independently
(A) 1,4-cyclohexylene group (this is present in the group one -CH ₂ - or nonadjacent two or more -CH ₂ - may be replaced by -O- or -S- And (b) a 1,4-phenylene group (one —CH═ present in this group or two or more non-adjacent —CH═ may be replaced by —N═).
A hydrogen atom on the group (a) and the group (b) may be independently substituted with a cyano group, a fluorine atom or a chlorine atom,
Z ^M1 and Z ^M2 are each independently a single bond, —CH ₂ CH ₂ —, — (CH ₂ ) ₄ —, —OCH ₂ —, —CH ₂ O—, —OCF ₂ —, —CF ₂ O—, Represents —COO—, —OCO— or —C≡C—,
When n ^M1 is 2, 3 or 4 and a plurality of A ^M2 are present, they may be the same or different, and n ^M1 is 2, 3 or 4 and a plurality of Z ^M1 is present If they are the same or different,
X ^M1 and X ^M3 each independently represent a hydrogen atom, a chlorine atom or a fluorine atom,
X ^M2 represents a hydrogen atom, a fluorine atom, a chlorine atom, a cyano group, a trifluoromethyl group, a fluoromethoxy group, a difluoromethoxy group, a trifluoromethoxy group, or a 2,2,2-trifluoroethyl group. )

In the general formula (M), R ^M1 represents 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 having 2 to 8 carbon atoms. A group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, an alkenyl group having 2 to 5 carbon atoms or an alkenyloxy group having 2 to 5 carbon atoms is preferable. An alkyl group having 1 to 5 carbon atoms or an alkenyl group having 2 to 5 carbon atoms is more preferable, an alkyl group having 2 to 5 carbon atoms or an alkenyl group having 2 to 3 carbon atoms is more preferable, and an alkenyl group having 3 carbon atoms. (Propenyl group) is particularly preferred.

R ^M1 is preferably an alkyl group when emphasizing reliability, and is preferably an alkenyl group when emphasizing a decrease in viscosity.

A ^M1 and A ^M2 are preferably aromatic when it is required to independently increase Δn, and are preferably aliphatic for improving the response speed, and trans-1,4 -Cyclohexylene group, 1,4-phenylene group, 2-fluoro-1,4-phenylene group, 3-fluoro-1,4-phenylene group, 3,5-difluoro-1,4-phenylene group, 2, 3-difluoro-1,4-phenylene group, 1,4-cyclohexenylene group, 1,4-bicyclo [2.2.2] octylene group, piperidine-1,4-diyl group, naphthalene-2,6- It preferably represents a diyl group, decahydronaphthalene-2,6-diyl group or 1,2,3,4-tetrahydronaphthalene-2,6-diyl group, and more preferably represents the following structure:

It is more preferable to represent the following structure.

Z ^M1 and ^{Z M2} each _{independently} _{-CH 2 O -, - CF 2} O -, - CH 2 CH 2 -, - CF 2 CF 2 - or preferably a single bond, _-CF 2 O-, —CH ₂ CH ₂ — or a single bond is more preferable, and —CF ₂ O— or a single bond is particularly preferable.

n ^M1 is preferably 0, 1, 2, or 3, preferably 0, 1 or 2, preferably 0 or 1 when emphasizing the improvement of Δε, and preferably 1 or 2 when emphasizing Tni .

In the liquid crystal composition (B), the content of the compound represented by the general formula (M) is low temperature solubility, transition temperature, electrical reliability, birefringence, process suitability, dripping marks, image sticking. Therefore, it is necessary to appropriately adjust according to required performance such as dielectric anisotropy.

The lower limit of the preferable content of the compound represented by Formula (M) with respect to the total amount of the liquid crystal composition (B) is 1% by mass, 10% by mass, 20% by mass, and 30% by mass. %, 40% by mass, 50% by mass, 55% by mass, 60% by mass, 65% by mass, 70% by mass, 75% by mass, 80% by mass is there. 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 liquid crystal composition (B). Yes, 55% by mass, 45% by mass, 35% by mass, and 25% by mass.

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

(Wherein R ^M11 represents an alkyl group having 1 to 5 carbon atoms, an alkenyl group having 2 to 5 carbon atoms, or an alkoxy group having 1 to 4 carbon atoms, and X ^M11 to X ^M15 each independently represents hydrogen. represents an atom or a fluorine ^{atom, Y M11} represents a fluorine atom or OCF _3.)
Although there is no restriction | limiting in particular in the kind of compound which can be combined, It uses combining according to desired performance, such as solubility at low temperature, transition temperature, electrical reliability, birefringence. The type of the compound used is, for example, one type as one embodiment of the present invention, two types, and three or more types.

The lower limit of the preferable content of the compound represented by the formula (M-1) with respect to the total amount of the liquid crystal composition (B) is 1% by mass, 2% by mass, 5% by mass, 8% by mass, 10% by mass, 13% by mass, 15% by mass, 18% by mass, 20% by mass, 22% by mass, 25% by mass, 30% by mass %. The upper limit of the preferable content is 30% by mass, 28% by mass, 25% by mass, 23% by mass, 20% by mass, 18% by mass, and 15% by mass, 13% by mass, 10% by mass, 8% by mass, and 5% by mass.

Further, the compound represented by the general formula (M-1) is specifically preferably a compound represented by the formula (M-1.1) to the formula (M-1.4). A compound represented by M-1.1) or formula (M-1.2) is preferred, and a compound represented by formula (M-1.2) is more preferred. It is also preferred to use the compounds represented by formula (M-1.1) or formula (M-1.2) at the same time.

The lower limit of the preferable content of the compound represented by the formula (M-1.1) with respect to the total amount of the liquid crystal composition (B) is 1% by mass, 2% by mass, and 5% by mass. Yes, 6% by mass. The upper limit of preferable content is 15% by mass, 13% by mass, 10% by mass, 8% by mass, and 5% by mass.

The lower limit of the preferable content of the compound represented by the formula (M-1.2) with respect to the total amount of the liquid crystal composition (B) is 1% by mass, 2% by mass, and 5% by mass. Yes, 6% by mass. The upper limit of the preferable content is 30% by mass, 25% by mass, 23% by mass, 20% by mass, 18% by mass, 15% by mass, and 13% by mass, 10% by mass and 8% by mass.

The lower limit of the preferable total content of the compounds represented by formula (M-1.1) and formula (M-1.2) with respect to the total amount of liquid crystal composition (B) is 1% by mass. 2% by mass, 5% by mass, and 6% by mass. The upper limit of the preferable content is 30% by mass, 25% by mass, 23% by mass, 20% by mass, 18% by mass, 15% by mass, and 13% by mass, 10% by mass and 8% by mass.

Furthermore, the compound represented by the general formula (M) is preferably a compound selected from the group of compounds represented by the general formula (M-2), for example.

(Wherein R ^M21 represents an alkyl group having 1 to 5 carbon atoms, an alkenyl group having 2 to 5 carbon atoms, or an alkoxy group having 1 to 4 carbon atoms, and X ^M21 and X ^M22 each independently represent hydrogen represents an atom or a fluorine ^{atom, Y M21} represents a fluorine atom, a chlorine atom or OCF _3.)
The lower limit of the preferable content of the compound represented by the formula (M-1) with respect to the total amount of the liquid crystal composition (B) is 1% by mass, 2% by mass, 5% by mass, 8% by mass, 10% by mass, 13% by mass, 15% by mass, 18% by mass, 20% by mass, 22% by mass, 25% by mass, 30% by mass %. The upper limit of the preferable content is 30% by mass, 28% by mass, 25% by mass, 23% by mass, 20% by mass, 18% by mass, and 15% by mass, 13% by mass, 10% by mass, 8% by mass, and 5% by mass.

When the viscosity of the liquid crystal composition (B) is kept low and a composition having a high response speed is required, it is preferable to lower the lower limit and lower the upper limit. Furthermore, when a composition that keeps Tni of the liquid crystal composition (B) high and does not easily cause burn-in is required, it is preferable to lower the lower limit and lower the upper limit. Further, when it is desired to increase the dielectric anisotropy in order to keep the driving voltage low, it is preferable to increase the upper limit value while increasing the lower limit value.

Further, the compound represented by the general formula (M-2) is preferably a compound represented by the formula (M-2.1) to the formula (M-2.5). 3) or / and a compound represented by the formula (M-2.5) is preferable.

The lower limit of the preferable content of the compound represented by the formula (M-2.2) with respect to the total amount of the liquid crystal composition (B) is 1% by mass, 2% by mass, and 5% by mass. Yes, 6% by mass. The upper limit of preferable content is 15% by mass, 13% by mass, 10% by mass, 8% by mass, and 5% by mass.

The lower limit of the preferable content of the compound represented by the formula (M-2.3) with respect to the total amount of the liquid crystal composition (B) is 1% by mass, 2% by mass, and 5% by mass. Yes, 6% by mass. The upper limit of the preferable content is 30% by mass, 25% by mass, 23% by mass, 20% by mass, 18% by mass, 15% by mass, and 13% by mass, 10% by mass and 8% by mass.

The lower limit of the preferable content of the compound represented by the formula (M-2.5) with respect to the total amount of the liquid crystal composition (B) is 1% by mass, 2% by mass, and 5% by mass. Yes, 6% by mass. The upper limit of the preferable content is 30% by mass, 25% by mass, 23% by mass, 20% by mass, 18% by mass, 15% by mass, and 13% by mass, 10% by mass and 8% by mass.

The lower limit of the preferable total content of the compounds represented by formula (M-2.2), (M-2.3) and formula (M-2.5) with respect to the total amount of liquid crystal composition (B) The values are 1% by weight, 2% by weight, 5% by weight and 6% by weight. The upper limit of the preferable content is 30% by mass, 25% by mass, 23% by mass, 20% by mass, 18% by mass, 15% by mass, and 13% by mass, 10% by mass and 8% by mass.

The content is preferably 1% by mass or more, more preferably 5% by mass or more, further preferably 8% by mass or more, further preferably 10% by mass or more, based on the total amount of the liquid crystal composition (B). More preferably, it is more preferably 16% by mass or more. In consideration of solubility at low temperatures, transition temperature, electrical reliability, etc., the maximum ratio is preferably limited to 30% by mass or less, more preferably 25% by mass or less, and more preferably 22% by mass or less. , Less than 20% by mass is particularly preferable.

The compound represented by the general formula (M) used in the liquid crystal composition (B) is preferably a compound represented by the general formula (M-3).

(Wherein R ^M31 represents an alkyl group having 1 to 5 carbon atoms, an alkenyl group having 2 to 5 carbon atoms, or an alkoxy group having 1 to 4 carbon atoms, and X ^M31 to X ^M36 are each independently hydrogen. represents an atom or a fluorine ^{atom, Y M31} represents a fluorine atom, a chlorine atom or OCF _3.)
There are no particular limitations on the compounds that can be combined, but it is preferable to combine one or more of them in consideration of solubility at low temperatures, transition temperature, electrical reliability, birefringence, and the like.

The content of the compound represented by the general formula (M-3) is an upper limit and a lower limit for each embodiment in consideration of properties such as solubility at low temperature, transition temperature, electrical reliability, and birefringence. There is a value.

The lower limit of the preferable content of the compound represented by the formula (M-3) with respect to the total amount of the liquid crystal composition (B) is 1% by mass, 2% by mass, 4% by mass, 5% by mass, 8% by mass, 10% by mass, 13% by mass, 15% by mass, 18% by mass, and 20% by mass. The upper limit of preferable content is 20% by mass, 18% by mass, 15% by mass, 13% by mass, 10% by mass, 8% by mass, and 5% by mass.

Further, the compound represented by the general formula (M-3) used in the liquid crystal composition (B) is specifically represented by the formula (M-3.1) to the formula (M-3.8). In particular, it is preferable to contain a compound represented by the formula (M-3.1) and / or the formula (M-3.2).

The lower limit of the preferable content of the compound represented by the formula (M-3.1) with respect to the total amount of the liquid crystal composition (B) is 1% by mass, 2% by mass, and 4% by mass. Yes, 5% by mass, 8% by mass, 10% by mass, 13% by mass, 15% by mass, 18% by mass, and 20% by mass. The upper limit of preferable content is 20% by mass, 18% by mass, 15% by mass, 13% by mass, 10% by mass, 8% by mass, and 5% by mass.

The lower limit of the preferable content of the compound represented by the formula (M-3.2) with respect to the total amount of the liquid crystal composition (B) is 1% by mass, 2% by mass, 4% by mass Yes, 5% by mass, 8% by mass, 10% by mass, 13% by mass, 15% by mass, 18% by mass, and 20% by mass. The upper limit of preferable content is 20% by mass, 18% by mass, 15% by mass, 13% by mass, 10% by mass, 8% by mass, and 5% by mass.

The lower limit of the preferable total content of the compounds represented by the formulas (M-3.1) and (M-3.2) with respect to the total amount of the liquid crystal composition (B) is 1% by mass. 2% by weight, 4% by weight, 5% by weight, 8% by weight, 10% by weight, 13% by weight, 15% by weight, 18% by weight, % By mass. The upper limit of preferable content is 20% by mass, 18% by mass, 15% by mass, 13% by mass, 10% by mass, 8% by mass, and 5% by mass.

Furthermore, the compound represented by the general formula (M) is preferably a compound selected from the group represented by the general formula (M-4).

(Wherein R ^M41 represents an alkyl group having 1 to 5 carbon atoms, an alkenyl group having 2 to 5 carbon atoms, or an alkoxy group having 1 to 4 carbon atoms, and X ^M41 to X ^M48 are each independently fluorine. Represents an atom or a hydrogen atom, and Y ^M41 represents a fluorine atom, a chlorine atom or OCF _3. )
There are no particular limitations on the compounds that can be combined, but it is preferable to combine one, two, or three or more types in consideration of solubility at low temperatures, transition temperature, electrical reliability, birefringence, and the like.

The content of the compound represented by the general formula (M-4) is an upper limit and a lower limit for each embodiment in consideration of properties such as solubility at low temperatures, transition temperature, electrical reliability, and birefringence. There is a value.

The lower limit of the preferable content of the compound represented by the formula (M-4) with respect to the total amount of the liquid crystal composition (B) is 1% by mass, 2% by mass, 4% by mass, 5% by mass, 8% by mass, 10% by mass, 13% by mass, 15% by mass, 18% by mass, and 20% by mass. The upper limit of the preferable content is 30% by mass, 28% by mass, 25% by mass, 23% by mass, 20% by mass, 18% by mass, and 15% by mass, 13% by mass, 10% by mass, 8% by mass, and 5% by mass.

When the liquid crystal composition (B) is used for a liquid crystal display device having a small cell gap, it is suitable to increase the content of the compound represented by the general formula (M-4). When used for a liquid crystal display element having a low driving voltage, it is suitable to increase the content of the compound represented by the general formula (M-4). Further, when used for a liquid crystal display element used in a low temperature environment, it is suitable to reduce the content of the compound represented by the general formula (M-4). In the case of a composition used for a liquid crystal display device having a high response speed, it is suitable to reduce the content of the compound represented by the general formula (M-4).

Further, the compound represented by the general formula (M-4) used in the liquid crystal composition (B) is specifically represented by the formula (M-4.1) to the formula (M-4.4). Among them, it is preferable to contain a compound represented by the formula (M-4.2) to the formula (M-4.4), and it is preferably represented by the formula (M-4.2). It is more preferable to contain a compound.

Furthermore, the compound represented by the general formula (M) is preferably a compound represented by the general formula (M-5).

(Wherein R ^M51 represents an alkyl group having 1 to 5 carbon atoms, an alkenyl group having 2 to 5 carbon atoms, or an alkoxy group having 1 to 4 carbon atoms, and X ^M51 and X ^M52 are each independently hydrogen. represents an atom or a fluorine ^{atom, Y M51} represents a fluorine atom, a chlorine atom or OCF _3.)
Although there is no restriction | limiting in the kind of compound which can be combined, Considering solubility at low temperature, transition temperature, electrical reliability, birefringence, etc., it uses combining suitably for every embodiment. For example, one embodiment of the present invention has one type, another embodiment has two types, yet another embodiment has three types, yet another embodiment has four types, and yet another embodiment has five types, In still another embodiment, six or more types are combined.

The lower limit of the preferable content of the compound represented by the formula (M-5) with respect to the total amount of the liquid crystal composition (B) is 1% by mass, 2% by mass, 5% by mass, 8% by mass, 10% by mass, 13% by mass, 15% by mass, 18% by mass, 20% by mass, 22% by mass, 25% by mass, 30% by mass %. The upper limit of the preferable content is 50% by mass, 45% by mass, 40% by mass, 35% by mass, 33% by mass, 30% by mass, 28% by mass, 25% by mass, 23% by mass, 20% by mass, 18% by mass, 15% by mass, 13% by mass, 10% by mass, 8% by mass, 5% by mass %.

Further, the compound represented by the general formula (M-5) is preferably a compound represented by the formula (M-5.1) to the formula (M-5.4), and the formula (M-5. A compound represented by formula (M-5.4) is preferable.

The lower limit of the preferable content of these compounds with respect to the total amount of the liquid crystal composition (B) is 1% by mass, 2% by mass, 5% by mass, 8% by mass, and 10% by mass. It is 13% by mass and 15% by mass. The upper limit of the preferable content is 30% by mass, 28% by mass, 25% by mass, 23% by mass, 20% by mass, 18% by mass, and 15% by mass, 13% by mass, 10% by mass, 8% by mass, and 5% by mass.

Further, the compound represented by the general formula (M-5) is preferably a compound represented by the formula (M-5.11) to the formula (M-5.17), and the formula (M-5. 11), a compound represented by formula (M-5.13) and formula (M-5.17) is preferable.

Further, the compound represented by the general formula (M-5) is preferably a compound represented by the formula (M-5.21) to the formula (M-5.28), and the formula (M-5. 21), a compound represented by formula (M-5.22), formula (M-5.23) and formula (M-5.25).

The lower limit of the preferable content of these compounds with respect to the total amount of the liquid crystal composition (B) is 1% by mass, 2% by mass, 5% by mass, 8% by mass, and 10% by mass. 13% by mass, 15% by mass, 18% by mass, 20% by mass, 22% by mass, 25% by mass, and 30% by mass. The upper limit of the preferable content is 40% by mass, 35% by mass, 33% by mass, 30% by mass, 28% by mass, 25% by mass, 23% by mass, 20% by mass, 18% by mass, 15% by mass, 13% by mass, 10% by mass, 8% by mass, and 5% by mass.

Furthermore, the compound represented by the general formula (M) is preferably a compound represented by the general formula (M-6).

(Wherein R ^M61 represents an alkyl group having 1 to 5 carbon atoms, an alkenyl group having 2 to 5 carbon atoms, or an alkoxy group having 1 to 4 carbon atoms, and X ^M61 to X ^M64 are each independently fluorine. Represents an atom or a hydrogen atom, and Y ^M61 represents a fluorine atom, a chlorine atom or OCF ₃ )
Although there is no restriction | limiting in the kind of compound which can be combined, It combines suitably for every embodiment in consideration of solubility at low temperature, transition temperature, electrical reliability, birefringence, etc.

The lower limit of the preferable content of the compound represented by the formula (M-6) with respect to the total amount of the liquid crystal composition (B) is 1% by mass, 2% by mass, 4% by mass, 5% by mass, 8% by mass, 10% by mass, 13% by mass, 15% by mass, 18% by mass, and 20% by mass. The upper limit of the preferable content is 30% by mass, 28% by mass, 25% by mass, 23% by mass, 20% by mass, 18% by mass, and 15% by mass, 13% by mass, 10% by mass, 8% by mass, and 5% by mass.

When the liquid crystal composition (B) is used for a liquid crystal display element having a low driving voltage, it is suitable to increase the content of the compound represented by the general formula (M-6). In the case of a composition used for a liquid crystal display device having a high response speed, it is suitable to reduce the content of the compound represented by the general formula (M-6).

Further, the compound represented by the general formula (M-6) is specifically preferably a compound represented by the formula (M-6.1) to the formula (M-6.4). It is preferable to contain a compound represented by M-6.2) and formula (M-6.4).

The lower limit of the preferable content of these compounds with respect to the total amount of the liquid crystal composition (B) is 1% by mass, 2% by mass, 4% by mass, 5% by mass, and 8% by mass. 10% by mass, 13% by mass, 15% by mass, 18% by mass, and 20% by mass. The upper limit of the preferable content is 30% by mass, 28% by mass, 25% by mass, 23% by mass, 20% by mass, 18% by mass, and 15% by mass, 13% by mass, 10% by mass, 8% by mass, and 5% by mass.

Further, the compound represented by the general formula (M-6) is specifically preferably a compound represented by the formula (M-6.11) to the formula (M-6.14). It is preferable to contain a compound represented by M-6.12) and formula (M-6.14).

Further, the compound represented by the general formula (M-6) is specifically preferably a compound represented by the formula (M-6.21) to the formula (M-6.24). It is preferable to contain a compound represented by formula (M-6.21), formula (M-6.22) and formula (M-6.24).

Furthermore, the compound represented by the general formula (M-6) is specifically preferably a compound represented by the formula (M-6.31) to the formula (M-6.34). Among them, it is preferable to contain a compound represented by the formula (M-6.31) and the formula (M-6.32).

Further, the compound represented by the general formula (M-6) is specifically preferably a compound represented by the formula (M-6.41) to the formula (M-6.44). It is preferable to contain a compound represented by M-6.42).

Furthermore, the compound represented by the general formula (M) is preferably a compound selected from the group of compounds represented by the general formula (M-7).

(Wherein, X ^M71 to X ^M76 each independently represents a fluorine atom or a hydrogen atom, and R ^M71 represents an alkyl group having 1 to 5 carbon atoms, an alkenyl group having 2 to 5 carbon atoms, or 1 to 4 represents an alkoxy group, and Y ^M71 represents a fluorine atom or OCF _3. )
There are no particular restrictions on the types of compounds that can be combined, but one to two of these compounds are preferably contained, more preferably one to three, and more preferably one to four. More preferably.

The content of the compound represented by the general formula (M-7) is an upper limit and a lower limit for each embodiment in consideration of properties such as solubility at low temperatures, transition temperature, electrical reliability, and birefringence. There is a value.

The lower limit of the preferable content of the compound represented by the formula (M-7) with respect to the total amount of the liquid crystal composition (B) is 1% by mass, 2% by mass, 4% by mass, 5% by mass, 8% by mass, 10% by mass, 13% by mass, 15% by mass, 18% by mass, and 20% by mass. The upper limit of the preferable content is 30% by mass, 28% by mass, 25% by mass, 23% by mass, 20% by mass, 18% by mass, and 15% by mass, 13% by mass, 10% by mass, 8% by mass, and 5% by mass.

When the liquid crystal composition (B) is used for a liquid crystal display device having a small cell gap, it is suitable to increase the content of the compound represented by the general formula (M-7). When used for a liquid crystal display element with a low driving voltage, it is suitable to increase the content of the compound represented by the general formula (M-7). In addition, when used for a liquid crystal display element used in a low temperature environment, it is suitable to reduce the content of the compound represented by the general formula (M-7). In the case of a composition used for a liquid crystal display device having a high response speed, it is suitable to reduce the content of the compound represented by the general formula (M-7).

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

Furthermore, the compound represented by the general formula (M-7) is preferably a compound represented by the formula (M-7.11) to the formula (M-7.14), and the formula (M-7. 11) and a compound represented by the formula (M-7.12) are preferable.

Further, the compound represented by the general formula (M-7) is preferably a compound represented by the formula (M-7.21) to the formula (M-7.24). 21) and a compound represented by the formula (M-7.22) are preferable.

Furthermore, the compound represented by the general formula (M) is preferably a compound represented by the general formula (M-8).

( ^Wherein , X ^M81 to X ^M84 each independently represents a fluorine atom or a hydrogen atom, Y ^M81 represents a fluorine atom, a chlorine atom or —OCF ₃ , R ^M81 represents an alkyl group having 1 to 5 carbon atoms, Represents an alkenyl group having 2 to 5 carbon atoms or an alkoxy group having 1 to 4 carbon atoms, and A ^M81 and A ^M82 are each independently 1,4-cyclohexylene group, 1,4-phenylene group or

However, the hydrogen atom on the 1,4-phenylene group may be substituted with a fluorine atom. )
The lower limit of the preferable content of the compound represented by Formula (M-8) with respect to the total amount of the liquid crystal composition (B) is 1% by mass, 2% by mass, and 4% by mass. 5% by mass, 8% by mass, 10% by mass, 13% by mass, 15% by mass, 18% by mass, and 20% by mass. The upper limit of the preferable content is 30% by mass, 28% by mass, 25% by mass, 23% by mass, 20% by mass, 18% by mass, and 15% by mass, 13% by mass, 10% by mass, 8% by mass, and 5% by mass.

When the viscosity of the liquid crystal composition (B) is kept low and a composition having a high response speed is required, it is preferable to lower the lower limit and lower the upper limit. Furthermore, when a composition that does not easily cause seizure is required, it is preferable to lower the lower limit and lower the upper limit. Further, when it is desired to increase the dielectric anisotropy in order to keep the driving voltage low, it is preferable to increase the upper limit value while increasing the lower limit value.

Further, the compound represented by the general formula (M-8) used in the liquid crystal composition (B) is specifically represented by the formula (M-8.1) to the formula (M-8.4). Among them, it is preferable to contain a compound represented by formula (M-8.1) or formula (M-8.2).

Further, the compound represented by the general formula (M-8) used in the liquid crystal composition (B) is specifically represented by the formula (M-8.11) to the formula (M-8.14). In particular, it is preferable to contain a compound represented by the formula (M-8.12).

Further, the compound represented by the general formula (M-8) used in the liquid crystal composition (B) is specifically represented by the formula (M-8.21) to the formula (M-8.24). It is preferable to contain a compound represented by the formula (M-8.22).

Further, the compound represented by the general formula (M-8) used in the liquid crystal composition (B) is specifically represented by the formula (M-8.31) to the formula (M-8.34). Among them, it is preferable to contain a compound represented by the formula (M-8.32).

Further, the compound represented by the general formula (M-8) used in the liquid crystal composition (B) is specifically represented by the formula (M-8.41) to the formula (M-8.44). It is preferable to contain a compound represented by the formula (M-8.42).

Further, the compound represented by the general formula (M-8) used in the liquid crystal composition (B) is specifically represented by the formula (M-8.51) to the formula (M-8.54). It is preferable to contain a compound represented by the formula (M-8.52).

Furthermore, the compound represented by the general formula (M) may have the following partial structure in its structure.

(The black spot in the formula represents a carbon atom in the ring structure to which the partial structure is bonded.)
The compound having the partial structure is preferably a compound represented by general formulas (M-10) to (M-18).

The compound represented by the general formula (M-10) is as follows.

( ^Wherein , X ^M101 and X ^M102 each independently represent a fluorine atom or a hydrogen atom, Y ^M101 represents a fluorine atom, a chlorine atom or —OCF ₃ , R ^M101 represents an alkyl group having 1 to 5 carbon atoms, Represents an alkenyl group having 2 to 5 carbon atoms or an alkoxy group having 1 to 4 carbon atoms, and W ^M101 and W ^M102 each independently represent —CH ₂ — or —O—.
The lower limit of the preferable content of the compound represented by General Formula (M-10) with respect to the total amount of the liquid crystal composition (B) is 1% by mass, 2% by mass, and 4% by mass. 5% by mass, 8% by mass, 10% by mass, 13% by mass, 15% by mass, 18% by mass, and 20% by mass. The upper limit of the preferable content is 30% by mass, 28% by mass, 25% by mass, 23% by mass, 20% by mass, 18% by mass, and 15% by mass, 13% by mass, 10% by mass, 8% by mass, and 5% by mass.

Further, the compound represented by the general formula (M-10) used for the liquid crystal composition (B) is specifically represented by the formula (M-10.1) to the formula (M-10.12). In particular, it is preferable to contain a compound represented by formula (M-10. 5) to formula (M-10.12).

The compound represented by the general formula (M-11) is as follows.

( ^Wherein , X ^M111 to X ^M114 each independently represents a fluorine atom or a hydrogen atom, Y ^M111 represents a fluorine atom, a chlorine atom or —OCF ₃ , R ^M111 represents an alkyl group having 1 to 5 carbon atoms, Represents an alkenyl group having 2 to 5 carbon atoms or an alkoxy group having 1 to 4 carbon atoms.)
The lower limit of the preferable content of the compound represented by Formula (M-11) with respect to the total amount of the liquid crystal composition (B) is 1% by mass, 2% by mass, and 4% by mass. 5% by mass, 8% by mass, 10% by mass, 13% by mass, 15% by mass, 18% by mass, and 20% by mass. The upper limit of the preferable content is 30% by mass, 28% by mass, 25% by mass, 23% by mass, 20% by mass, 18% by mass, and 15% by mass, 13% by mass, 10% by mass, 8% by mass, and 5% by mass.

Furthermore, the compounds represented by the general formula (M-11) used in the liquid crystal composition (B) are specifically represented by the formulas (M-11.1) to (M-11.8). Among them, it is preferable to contain a compound represented by formula (M-11.1) to formula (M-11.4).

The compound represented by the general formula (M-12) is as follows.

( ^Wherein , X ^M121 and X ^M122 each independently represent a fluorine atom or a hydrogen atom, Y ^M121 represents a fluorine atom, a chlorine atom or —OCF ₃ , R ^M121 represents an alkyl group having 1 to 5 carbon atoms, Represents an alkenyl group having 2 to 5 carbon atoms or an alkoxy group having 1 to 4 carbon atoms, and W ^M121 and W ^M122 each independently represent —CH ₂ — or —O—.
The lower limit of the preferable content of the compound represented by Formula (M-12) with respect to the total amount of the liquid crystal composition (B) is 1% by mass, 2% by mass, and 4% by mass. 5% by mass, 8% by mass, 10% by mass, 13% by mass, 15% by mass, 18% by mass, and 20% by mass. The upper limit of the preferable content is 30% by mass, 28% by mass, 25% by mass, 23% by mass, 20% by mass, 18% by mass, and 15% by mass, 13% by mass, 10% by mass, 8% by mass, and 5% by mass.

Further, the compound represented by the general formula (M-12) used for the liquid crystal composition (B) is specifically represented by the formula (M-12.1) to the formula (M-12.12). Among them, it is preferable to contain a compound represented by the formula (M-12.5) to the formula (M-12.8).

The compound represented by the general formula (M-13) is as follows.

( ^Wherein , X ^M131 to X ^M134 each independently represents a fluorine atom or a hydrogen atom, Y ^M131 represents a fluorine atom, a chlorine atom or —OCF ₃ , R ^M131 represents an alkyl group having 1 to 5 carbon atoms, ^Represents an alkenyl group having 2 to 5 carbon atoms or an alkoxy group having 1 to 4 carbon atoms, and W ^M131 and W ^M132 each independently represent —CH ₂ — or —O—.
The lower limit of the preferable content of the compound represented by Formula (M-13) with respect to the total amount of the liquid crystal composition (B) is 1% by mass, 2% by mass, and 4% by mass. 5% by mass, 8% by mass, 10% by mass, 13% by mass, 15% by mass, 18% by mass, and 20% by mass. The upper limit of the preferable content is 30% by mass, 28% by mass, 25% by mass, 23% by mass, 20% by mass, 18% by mass, and 15% by mass, 13% by mass, 10% by mass, 8% by mass, and 5% by mass.

Further, the compound represented by the general formula (M-13) used in the liquid crystal composition (B) is specifically represented by the formula (M-13.1) to the formula (M-13.28). From the formulas (M-13.1) to (M-13.4), (M-13.11) to (M-13.14), (M-13.25) It preferably contains a compound represented by (M-13.28).

The compound represented by the general formula (M-14) is as follows.

( ^Wherein X ^M141 to X ^M144 each independently represents a fluorine atom or a hydrogen atom, Y ^M141 represents a fluorine atom, a chlorine atom or —OCF ₃ , R ^M141 represents an alkyl group having 1 to 5 carbon atoms, ^Represents an alkenyl group having 2 to 5 carbon atoms or an alkoxy group having 1 to 4 carbon atoms, and W ^M141 and W ^M142 each independently represent —CH ₂ — or —O—.
The lower limit of the preferable content of the compound represented by Formula (M-14) with respect to the total amount of the liquid crystal composition (B) is 1% by mass, 2% by mass, and 4% by mass. 5% by mass, 8% by mass, 10% by mass, 13% by mass, 15% by mass, 18% by mass, and 20% by mass. The upper limit of the preferable content is 30% by mass, 28% by mass, 25% by mass, 23% by mass, 20% by mass, 18% by mass, and 15% by mass, 13% by mass, 10% by mass, 8% by mass, and 5% by mass.

Further, the compound represented by the general formula (M-14) used in the liquid crystal composition (B) is specifically represented by the formula (M-14.1) to the formula (M-14.8). Among them, it is preferable to contain a compound represented by formula (M-14.5) or formula (M-14.8).

The compound represented by the general formula (M-15) is as follows.

( ^Wherein X ^M151 and X ^M152 each independently represent a fluorine atom or a hydrogen atom, Y ^M151 represents a fluorine atom, a chlorine atom or —OCF ₃ , R ^M151 represents an alkyl group having 1 to 5 carbon atoms, Represents an alkenyl group having 2 to 5 carbon atoms or an alkoxy group having 1 to 4 carbon atoms, and W ^M151 and W ^M152 each independently represent —CH ₂ — or —O—.
The lower limit of the preferable content of the compound represented by Formula (M-15) with respect to the total amount of the liquid crystal composition (B) is 1% by mass, 2% by mass, and 4% by mass. 5% by mass, 8% by mass, 10% by mass, 13% by mass, 15% by mass, 18% by mass, and 20% by mass. The upper limit of the preferable content is 30% by mass, 28% by mass, 25% by mass, 23% by mass, 20% by mass, 18% by mass, and 15% by mass, 13% by mass, 10% by mass, 8% by mass, and 5% by mass.

Further, the compound represented by the general formula (M-15) used in the liquid crystal composition (B) is specifically represented by the formula (M-15.1) to the formula (M-15.14). The compounds represented by formula (M-15.5) to formula (M-15.8) and formula (M-15.11) to formula (M-15.14) are particularly preferable. It is preferable to contain.

The compound represented by the general formula (M-16) is as follows.

( ^Wherein X ^M161 to X ^M164 each independently represents a fluorine atom or a hydrogen atom, Y ^M161 represents a fluorine atom, a chlorine atom or —OCF ₃ , R ^M161 represents an alkyl group having 1 to 5 carbon atoms, Represents an alkenyl group having 2 to 5 carbon atoms or an alkoxy group having 1 to 4 carbon atoms.)
The lower limit of the preferable content of the compound represented by General Formula (M-16) with respect to the total amount of the liquid crystal composition (B) is 1% by mass, 2% by mass, and 4% by mass. 5% by mass, 8% by mass, 10% by mass, 13% by mass, 15% by mass, 18% by mass, and 20% by mass. The upper limit of the preferable content is 30% by mass, 28% by mass, 25% by mass, 23% by mass, 20% by mass, 18% by mass, and 15% by mass, 13% by mass, 10% by mass, 8% by mass, and 5% by mass.

Further, the compound represented by the general formula (M-16) used for the liquid crystal composition (B) is specifically represented by the formula (M-16.1) to the formula (M-16.8). Among them, it is preferable to contain a compound represented by formula (M-16.1) to formula (M-16.4).

The compound represented by the general formula (M-17) is as follows.

^(Wherein, ^X M171 ^~ X ^M174 are each independently a fluorine atom or a hydrogen ^{atom, Y M171} fluorine atom, a chlorine atom or -OCF ^{_3, R M171} is an alkyl group having 1 to 5 carbon atoms, ^Represents an alkenyl group having 2 to 5 carbon atoms or an alkoxy group having 1 to 4 carbon atoms, and W ^M171 and W ^M172 each independently represent —CH ₂ — or —O—.
The lower limit of the preferable content of the compound represented by the general formula (M-17) with respect to the total amount of the liquid crystal composition (B) is 1% by mass, 2% by mass, and 4% by mass. 5% by mass, 8% by mass, 10% by mass, 13% by mass, 15% by mass, 18% by mass, and 20% by mass. The upper limit of the preferable content is 30% by mass, 28% by mass, 25% by mass, 23% by mass, 20% by mass, 18% by mass, and 15% by mass, 13% by mass, 10% by mass, 8% by mass, and 5% by mass.

Further, the compound represented by the general formula (M-17) used in the liquid crystal composition (B) is specifically represented by the formula (M-17.1) to the formula (M-17.52). Among them, the compounds of formulas (M-17.9) to (M-17.12), (M-17.21) to (M-17.28), and (M-17) are preferred. .45) to a compound represented by formula (M-17.48).

The compound represented by the general formula (M-18) is as follows.

( ^Wherein X ^M181 to X ^M186 each independently represents a fluorine atom or a hydrogen atom, Y ^M181 represents a fluorine atom, a chlorine atom or —OCF ₃ , R ^M181 represents an alkyl group having 1 to 5 carbon atoms, Represents an alkenyl group having 2 to 5 carbon atoms or an alkoxy group having 1 to 4 carbon atoms.)
The lower limit of the preferable content of the compound represented by Formula (M-18) with respect to the total amount of the liquid crystal composition (B) is 1% by mass, 2% by mass, and 4% by mass. 5% by mass, 8% by mass, 10% by mass, 13% by mass, 15% by mass, 18% by mass, and 20% by mass. The upper limit of the preferable content is 30% by mass, 28% by mass, 25% by mass, 23% by mass, 20% by mass, 18% by mass, and 15% by mass, 13% by mass, 10% by mass, 8% by mass, and 5% by mass.

Further, the compound represented by the general formula (M-18) used in the liquid crystal composition (B) is specifically represented by the formula (M-18.1) to the formula (M-18.12). Among them, it is preferable to contain a compound represented by the formula (M-18.5) to the formula (M-18.8).

The liquid crystal composition (B) preferably contains one or more compounds represented by the general formula (K). These compounds correspond to dielectrically positive compounds (Δε is greater than 2).

(Wherein R ^K1 represents an alkyl group having 1 to 8 carbon atoms, and one or two or more non-adjacent —CH ₂ — in the alkyl group are each independently —CH═CH—, — Optionally substituted by C≡C—, —O—, —CO—, —COO— or —OCO—,
n ^K1 represents 0, 1, 2, 3 or 4;
A ^K1 and A ^K2 are each independently
(A) 1,4-cyclohexylene group (this is present in the group one -CH ₂ - or nonadjacent two or more -CH ₂ - may be replaced by -O- or -S- And (b) a 1,4-phenylene group (one —CH═ present in this group or two or more non-adjacent —CH═ may be replaced by —N═).
A hydrogen atom on the group (a) and the group (b) may be independently substituted with a cyano group, a fluorine atom or a chlorine atom,
Z ^K1 and Z ^K2 are each independently a single bond, —CH ₂ CH ₂ —, — (CH ₂ ) ₄ —, —OCH ₂ —, —CH ₂ O—, —OCF ₂ —, —CF ₂ O—, Represents —COO—, —OCO— or —C≡C—,
When n ^K1 is 2, 3 or 4 and a plurality of A ^K2 are present, they may be the same or different, and n ^K1 is 2, 3 or 4 and a plurality of Z ^K1 is present If they are the same or different,
X ^K1 and X ^K3 each independently represent a hydrogen atom, a chlorine atom or a fluorine atom,
X ^K2 represents a hydrogen atom, a fluorine atom, a chlorine atom, a cyano group, a trifluoromethyl group, a fluoromethoxy group, a difluoromethoxy group, a trifluoromethoxy group, or a 2,2,2-trifluoroethyl group. )
In general formula (K), R ^K1 represents 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 alkenyloxy having 2 to 8 carbon atoms. A group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, an alkenyl group having 2 to 5 carbon atoms or an alkenyloxy group having 2 to 5 carbon atoms is preferable. An alkyl group having 1 to 5 carbon atoms or an alkenyl group having 2 to 5 carbon atoms is more preferable, an alkyl group having 2 to 5 carbon atoms or an alkenyl group having 2 to 3 carbon atoms is more preferable, and an alkenyl group having 3 carbon atoms. (Propenyl group) is particularly preferred.

^RK1 is preferably an alkyl group when importance is placed on reliability, and an alkenyl group is preferred when importance is placed on lowering viscosity.

A ^K1 and A ^K2 are preferably aromatic when it is required to independently increase Δn, and are preferably aliphatic for improving the response speed, and trans-1,4 -Cyclohexylene group, 1,4-phenylene group, 2-fluoro-1,4-phenylene group, 3-fluoro-1,4-phenylene group, 3,5-difluoro-1,4-phenylene group, 2, 3-difluoro-1,4-phenylene group, 1,4-cyclohexenylene group, 1,4-bicyclo [2.2.2] octylene group, piperidine-1,4-diyl group, naphthalene-2,6- It preferably represents a diyl group, decahydronaphthalene-2,6-diyl group or 1,2,3,4-tetrahydronaphthalene-2,6-diyl group, and more preferably represents the following structure:

It is more preferable to represent the following structure.

Z ^K1 and ^{Z K2} are each _{independently} _{-CH 2 O -, - CF 2} O -, - CH 2 CH 2 -, - CF 2 CF 2 - or preferably a single bond, _-CF 2 O-, —CH ₂ CH ₂ — or a single bond is more preferable, and —CF ₂ O— or a single bond is particularly preferable.

n ^K1 is preferably 0, 1, 2 or 3, preferably 0, 1 or 2, preferably 0 or 1 when emphasizing the improvement of Δε, and preferably 1 or 2 when emphasizing Tni. .

In the liquid crystal composition (B), the content of the compound represented by the general formula (K) is low-temperature solubility, transition temperature, electrical reliability, birefringence, process compatibility, dripping marks, and burn-in. Therefore, it is necessary to appropriately adjust according to required performance such as dielectric anisotropy.

The lower limit of the preferable content of the compound represented by the formula (K) with respect to the total amount of the liquid crystal composition (B) is 1% by mass, 10% by mass, 20% by mass, and 30% by mass. %, 40% by mass, 50% by mass, 55% by mass, 60% by mass, 65% by mass, 70% by mass, 75% by mass, 80% by mass is there. 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 liquid crystal composition (B). Yes, 55% by mass, 45% by mass, 35% by mass, and 25% by mass.

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

(Wherein R ^K11 represents an alkyl group having 1 to 5 carbon atoms, an alkenyl group having 2 to 5 carbon atoms, or an alkoxy group having 1 to 4 carbon atoms, and X ^K11 to X ^K14 are each independently hydrogen. represents an atom or a fluorine ^{atom, Y K11} represents a fluorine atom or OCF _3.)
Although there is no restriction | limiting in particular in the kind of compound which can be combined, It uses combining according to desired performance, such as solubility at low temperature, transition temperature, electrical reliability, birefringence. The type of the compound used is, for example, one type as one embodiment of the present invention, two types, and three or more types.

The lower limit of the preferable content of the compound represented by the formula (K-1) with respect to the total amount of the liquid crystal composition (B) is 1% by mass, 2% by mass, 5% by mass, 8% by mass, 10% by mass, 13% by mass, 15% by mass, 18% by mass, 20% by mass, 22% by mass, 25% by mass, 30% by mass %. The upper limit of the preferable content is 30% by mass, 28% by mass, 25% by mass, 23% by mass, 20% by mass, 18% by mass, and 15% by mass, 13% by mass, 10% by mass, 8% by mass, and 5% by mass.

Further, the compound represented by the general formula (K-1) is specifically preferably a compound represented by the formula (K-1.1) to the formula (K-1.4). A compound represented by formula (K-1.2) is preferred, and a compound represented by formula (K-1.2) is more preferred. It is also preferred to use the compounds represented by formula (K-1.1) or formula (K-1.2) at the same time.

The compound represented by General Formula (K) is preferably a compound selected from the group of compounds represented by General Formula (K-2), for example.

(Wherein R ^K21 represents an alkyl group having 1 to 5 carbon atoms, an alkenyl group having 2 to 5 carbon atoms, or an alkoxy group having 1 to 4 carbon atoms, and X ^K21 to X ^K24 are each independently hydrogen. represents an atom or a fluorine ^{atom, Y K21} represents a fluorine atom or OCF _3.)
Although there is no restriction | limiting in particular in the kind of compound which can be combined, It uses combining according to desired performance, such as solubility at low temperature, transition temperature, electrical reliability, birefringence. The type of the compound used is, for example, one type as one embodiment of the present invention, two types, and three or more types.

The lower limit of the preferable content of the compound represented by the formula (K-2) with respect to the total amount of the liquid crystal composition (B) is 1% by mass, 2% by mass, 5% by mass, 8% by mass, 10% by mass, 13% by mass, 15% by mass, 18% by mass, 20% by mass, 22% by mass, 25% by mass, 30% by mass %. The upper limit of the preferable content is 30% by mass, 28% by mass, 25% by mass, 23% by mass, 20% by mass, 18% by mass, and 15% by mass, 13% by mass, 10% by mass, 8% by mass, and 5% by mass.

Further, the compound represented by the general formula (K-2) is specifically preferably a compound represented by the formula (K-2.1) to the formula (K-2.6). A compound represented by formula (K-2.5) or formula (K-2.6) is preferred, and a compound represented by formula (K-2.6) is more preferred. It is also preferred to use the compounds represented by formula (K-2.5) or formula (K-2.6) at the same time.

The compound represented by General Formula (K) is preferably a compound selected from the group of compounds represented by General Formula (K-3), for example.

(Wherein R ^K31 represents an alkyl group having 1 to 5 carbon atoms, an alkenyl group having 2 to 5 carbon atoms, or an alkoxy group having 1 to 4 carbon atoms, and X ^K31 to X ^K36 are each independently hydrogen. Represents an atom or a fluorine atom, and Y ^K31 represents a fluorine atom or OCF _3. )
Although there is no restriction | limiting in particular in the kind of compound which can be combined, It uses combining according to desired performance, such as solubility at low temperature, transition temperature, electrical reliability, birefringence. The type of the compound used is, for example, one type as one embodiment of the present invention, two types, and three or more types.

The lower limit of the preferable content of the compound represented by the formula (K-3) with respect to the total amount of the liquid crystal composition (B) is 1% by mass, 2% by mass, 5% by mass, 8% by mass, 10% by mass, 13% by mass, 15% by mass, 18% by mass, 20% by mass, 22% by mass, 25% by mass, 30% by mass %. The upper limit of the preferable content is 30% by mass, 28% by mass, 25% by mass, 23% by mass, 20% by mass, 18% by mass, and 15% by mass, 13% by mass, 10% by mass, 8% by mass, and 5% by mass.

Further, the compound represented by the general formula (K-3) is preferably a compound represented by the formula (K-3.1) to the formula (K-3.4). A compound represented by K-3.1) or formula (K-3.2) is more preferable. It is also preferred to use the compounds represented by formula (K-3.1) and formula (K-3.2) at the same time.

The compound represented by the general formula (K) is preferably, for example, a compound selected from the group of compounds represented by the general formula (K-4).

(Wherein R ^K41 represents an alkyl group having 1 to 5 carbon atoms, an alkenyl group having 2 to 5 carbon atoms, or an alkoxy group having 1 to 4 carbon atoms, and X ^K41 to X ^K46 are each independently hydrogen. An atom or a fluorine atom, Y ^K41 represents a fluorine atom or OCF ₃ , and Z ^K41 represents —OCH ₂ —, —CH ₂ O—, —OCF ₂ —, or —CF ₂ O—.
Although there is no restriction | limiting in particular in the kind of compound which can be combined, It uses combining according to desired performance, such as solubility at low temperature, transition temperature, electrical reliability, birefringence. The type of the compound used is, for example, one type as one embodiment of the present invention, two types, and three or more types.

The lower limit of the preferable content of the compound represented by the formula (K-4) with respect to the total amount of the liquid crystal composition (B) is 1% by mass, 2% by mass, 5% by mass, 8% by mass, 10% by mass, 13% by mass, 15% by mass, 18% by mass, 20% by mass, 22% by mass, 25% by mass, 30% by mass %. The upper limit of the preferable content is 30% by mass, 28% by mass, 25% by mass, 23% by mass, 20% by mass, 18% by mass, and 15% by mass, 13% by mass, 10% by mass, 8% by mass, and 5% by mass.

Further, the compound represented by the general formula (K-4) is preferably a compound represented by the formula (K-4.1) to the formula (K-4.18). More preferred are compounds represented by (K-4.1), formula (K-4.2), formula (K-4.11), and (K-4.12). It is also preferred to use compounds represented by formula (K-4.1), formula (K-4.2), formula (K-4.11), and (K-4.12) at the same time.

The compound represented by the general formula (K) is preferably a compound selected from, for example, a compound group represented by the general formula (K-5).

(Wherein R ^K51 represents an alkyl group having 1 to 5 carbon atoms, an alkenyl group having 2 to 5 carbon atoms, or an alkoxy group having 1 to 4 carbon atoms, and X ^K51 to X ^K56 are each independently hydrogen. An atom or a fluorine atom, Y ^K51 represents a fluorine atom or OCF ₃ , and Z ^K51 represents —OCH ₂ —, —CH ₂ O—, —OCF ₂ —, or —CF ₂ O—.
Although there is no restriction | limiting in particular in the kind of compound which can be combined, It uses combining according to desired performance, such as solubility at low temperature, transition temperature, electrical reliability, birefringence. The type of the compound used is, for example, one type as one embodiment of the present invention, two types, and three or more types.

The lower limit of the preferable content of the compound represented by the formula (K-5) with respect to the total amount of the liquid crystal composition (B) is 1% by mass, 2% by mass, 5% by mass, 8% by mass, 10% by mass, 13% by mass, 15% by mass, 18% by mass, 20% by mass, 22% by mass, 25% by mass, 30% by mass %. The upper limit of the preferable content is 30% by mass, 28% by mass, 25% by mass, 23% by mass, 20% by mass, 18% by mass, and 15% by mass, 13% by mass, 10% by mass, 8% by mass, and 5% by mass.

Further, the compound represented by the general formula (K-5) is preferably a compound represented by the formula (K-5.1) to the formula (K-5.18). A compound represented by the formula (K-5.14) to the compound represented by the formula (K-5.14) is preferable, and a compound represented by the formula (K-5.12) is more preferable.

The compound represented by General Formula (K) is preferably a compound selected from the group of compounds represented by General Formula (K-6), for example.

( ^Wherein R ^K61 represents an alkyl group having 1 to 5 carbon atoms, an alkenyl group having 2 to 5 carbon atoms, or an alkoxy group having 1 to 4 carbon atoms, and X ^K61 to X ^K68 are each independently hydrogen. represents an atom or a fluorine ^{atom, Y K61} represents a fluorine atom or OCF ^{_3, Z K61} is _{_{-OCH 2 -, - CH 2 O}} -, - OCF 2 - or an _-CF 2 O-).
Although there is no restriction | limiting in particular in the kind of compound which can be combined, It uses combining according to desired performance, such as solubility at low temperature, transition temperature, electrical reliability, birefringence. The type of the compound used is, for example, one type as one embodiment of the present invention, two types, and three or more types.

The lower limit of the preferable content of the compound represented by the formula (K-6) with respect to the total amount of the liquid crystal composition (B) is 1% by mass, 2% by mass, 5% by mass, 8% by mass, 10% by mass, 13% by mass, 15% by mass, 18% by mass, 20% by mass, 22% by mass, 25% by mass, 30% by mass %. The upper limit of the preferable content is 30% by mass, 28% by mass, 25% by mass, 23% by mass, 20% by mass, 18% by mass, and 15% by mass, 13% by mass, 10% by mass, 8% by mass, and 5% by mass.

Further, the compound represented by the general formula (K-6) is preferably a compound represented by the formula (K-6.1) to the formula (K-6.18). Compounds represented by formula (K-6.18) to formula (K-6.18) are preferred, and compounds represented by formula (K-6.16) and formula (K-6.17) are more preferred. It is also preferred to use the compounds represented by formula (K-6.16) and formula (K-6.17) at the same time.

The liquid crystal composition having almost no dielectric anisotropy preferably contains one or more compounds represented by the following general formula (L). The compound represented by the general formula (L) corresponds to a dielectrically neutral compound (Δε value is −2 to 2).

(Wherein R ^L1 and R ^L2 are each independently an alkyl group having 1 to 8 carbon atoms, or one —CH ₂ — present in an alkyl chain having 2 to 8 carbon atoms, or not adjacent to each other) An organic group having a chemical structure in which two or more —CH ₂ — are each independently substituted by —CH═CH—, —C≡C—, —O—, —CO—, —COO— or —OCO—. Represents
n ^L1 represents 0, 1, 2 or 3,
A ^L1 , A ^L2 and A ^L3 are each independently (a) a 1,4-cyclohexylene group,
(B) 1,4-cyclohexylene structure present in one -CH ₂ - or nonadjacent two or more -CH ₂ - 2 divalent organic having the chemical structure which is replaced to the -O- Group,
(C) 1,4-phenylene group,
(D) a divalent organic group having a chemical structure in which one —CH═ present in a 1,4-phenylene structure or two or more non-adjacent —CH═ are replaced by —N═;
(E) naphthalene-2,6-diyl group, 1,2,3,4-tetrahydronaphthalene-2,6-diyl group or decahydronaphthalene-2,6-diyl group, and (f) naphthalene-2,6 -One -CH = or two or more non-adjacent -CH = present in a diyl structure or 1,2,3,4-tetrahydronaphthalene-2,6-diyl structure is replaced by -N = Represents a group selected from the group consisting of divalent organic groups having the above structure, the group (a), the group (b), the group (c), the group (d), the group (e), and the group (f ) May be each independently substituted with a cyano group, a fluorine atom or a chlorine atom,
Z ^L1 and Z ^L2 are each independently a single bond, —CH ₂ CH ₂ —, — (CH ₂ ) ₄ —, —OCH ₂ —, —CH ₂ O—, —COO—, —OCO—, —OCF ₂ -, -CF ₂ O-, -CH = NN-CH-, -CH = CH-, -CF = CF- or -C≡C-
When n ^L1 is 2 or 3, and a plurality of A ^L2 are present, they may be the same or different, and when n ^L1 is 2 or 3, and a plurality of Z ^L2 are present, May be the same or different (provided the compounds represented by the general formulas (N-1), (N-2), (N-3), (N-4) and (J)) (Except what you do.)
Although the compound represented by general formula (L) may be used independently, it can also be used in combination. There are no particular restrictions on the types of compounds that can be combined, but they are used in appropriate combinations according to desired properties such as solubility at low temperatures, transition temperatures, electrical reliability, and birefringence. The kind of the compound used is, for example, one kind as one embodiment of the present invention. Alternatively, in another embodiment of the present invention, there are two types, three types, four types, five types, six types, seven types, eight types, nine types, 10 types, More than types.

In the liquid crystal composition (B), the content of the compound represented by the general formula (L) is low temperature solubility, transition temperature, electrical reliability, birefringence, process suitability, dripping marks, image sticking. Therefore, it is necessary to appropriately adjust according to required performance such as dielectric anisotropy.

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

When the viscosity of the liquid crystal composition (B) is kept low and a composition having a high response speed is required, the above lower limit value is preferably high and the upper limit value is preferably high. Furthermore, when a composition having a high temperature stability and a high temperature stability is required, it is preferable that the lower limit value is high and the upper limit value is high. Further, when it is desired to increase the dielectric anisotropy in order to keep the driving voltage low, it is preferable that the above lower limit value is lowered and the upper limit value is low.

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

The number of halogen atoms present in the molecule is preferably 0, 1, 2 or 3, preferably 0 or 1, and 1 is preferred when importance is attached to compatibility with other liquid crystal molecules.

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

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

A ^L1 , A ^L2, and A ^L3 are preferably aromatic when it is required to increase Δn, and are preferably aliphatic for improving the response speed, and are each independently trans- 1,4-cyclohexylene group, 1,4-phenylene group, 2-fluoro-1,4-phenylene group, 3-fluoro-1,4-phenylene group, 3,5-difluoro-1,4-phenylene group 1,4-cyclohexenylene group, 1,4-bicyclo [2.2.2] octylene group, piperidine-1,4-diyl group, naphthalene-2,6-diyl group, decahydronaphthalene-2,6 -Diyl group or 1,2,3,4-tetrahydronaphthalene-2,6-diyl group, and other structural formulas shown below

Is preferably a group having a tetrahydrofuran or dioxane skeleton.

Among these, it is more preferable to represent the following structure,

In particular, the trans-1,4-cyclohexylene group is useful when it is desired to lower Δn, and is preferable from the viewpoint of lowering the viscosity, and the 1,4-phenylene group is desired to increase Δn. It is more preferable because it is useful in some cases.

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

The compound represented by the general formula (L) preferably has 0 or 1 halogen atom in the molecule.

The compound represented by the general formula (L) is preferably a compound selected from the group of compounds represented by the general formulas (L-1) to (L-8).

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

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

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

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

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

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

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

The lower limit of the preferable content of the compound represented by the formula (L-1-1.3) with respect to the total amount of the liquid crystal composition (B) is 1% by mass, 2% by mass, 3% by mass %, 5% by mass, 7% by mass, and 10% by mass. The upper limit of the preferable content is 20% by mass, 15% by mass, 13% by mass, 10% by mass, and 8% by mass with respect to the total amount of the liquid crystal composition (B). 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 selected from the group of compounds represented by the general formula (L-1-2).

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

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

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

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

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

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

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

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

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

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

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

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

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

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

Formula (L-1-1.3), Formula (L-1-2.2), Formula (L-1-3.1), Formula (L-1-3.3), Formula (L-1- 3.4), it is preferable to combine two or more compounds selected from the compounds represented by formula (L-1-3.11) and formula (L-1-3.12). -1.3), formula (L-1-2.2), formula (L-1-3.1), formula (L-1-3.3), formula (L-1-3.4) and It is preferable to combine two or more compounds selected from the compounds represented by formula (L-1-4.2), and the lower limit of the preferable content of the total content of these compounds is the liquid crystal composition (B ) 1% by mass, 2% by mass, 3% by mass, 5% by mass, 7% by mass, 10% by mass, 13% by mass, 18% by mass 20% by mass 23% by mass 25% by mass 27% by mass 30% by mass 33% by mass 35% by mass 80% by mass, 70% by mass, 60% by mass, 50% by mass, 45% by mass, 40% by mass, and 37% by mass with respect to the total amount of the composition (B). 35% by mass, 33% by mass, 30% by mass, 28% by mass, 25% by mass, 23% by mass and 20% by mass. When emphasizing the reliability of the composition, compounds represented by formula (L-1-3.1), formula (L-1-3.3) and formula (L-1-3.4)) It is preferable to combine two or more compounds selected from the group consisting of formulas (L-1-1.3) and (L-1-2.2) when the response speed of the composition is important. It is preferable to combine two or more compounds selected from the following compounds.
The compound represented by the general formula (L-1) is preferably a compound selected from the group of compounds represented by the general formula (L-1-6).

(In the formula, R ^L17 and R ^L18 each independently represent a methyl group or a hydrogen atom.)
The lower limit of the preferable content of the compound represented by the formula (L-1-6) with respect to the total amount of the liquid crystal composition (B) is 1% by mass, 5% by mass, 10% by mass Yes, 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. The upper limit of the preferable content is 60% by mass, 55% by mass, 50% by mass, 45% by mass, and 42% by mass with respect to the total amount of the liquid crystal composition (B). 40% by mass, 38% by mass, 35% by mass, 33% by mass, and 30% by mass.

Further, the compound represented by the general formula (L-1-6) is a compound selected from the compound group represented by the formula (L-1-6.1) to the formula (L-1-6.3). Preferably there is.

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

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

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

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

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

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

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

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

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

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

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

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

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

In the liquid crystal composition (B), the content of the compound represented by the general formula (L-4) is the solubility at a low temperature, the transition temperature, the electrical reliability, the birefringence, the process suitability, the dropping trace. Therefore, it is necessary to adjust appropriately according to required performance such as image sticking and dielectric anisotropy.

The lower limit of the preferable content of the compound represented by the formula (L-4) with respect to the total amount of the liquid crystal composition (B) is 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, 26% by mass, 30% by mass %, 35% by mass, and 40% by mass. The upper limit of the preferable content of the compound represented by the formula (L-4) with respect to the total amount of the liquid crystal composition (B) is 50% by mass, 40% by mass, and 35% by mass, 30% by mass, 20% by mass, 15% by mass, 10% by mass, and 5% by mass.

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

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

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

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

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

The lower limit of the preferable content of the compound represented by the formula (L-4.4) or the formula (L-4.5) with respect to the total amount of the liquid crystal composition (B) is 3% by mass, % By mass, 7% by mass, 9% by mass, 11% by mass, 12% by mass, 13% by mass, 18% by mass and 21% by mass. The preferable upper limit is 45, 40% by mass, 35% by mass, 30% by mass, 25% by mass, 23% by mass, 20% by mass, and 18% by mass. 15 mass%, 13 mass%, 10 mass%, and 8 mass%.

When both the compound represented by formula (L-4.4) and the compound represented by formula (L-4.5) are contained, both compounds with respect to the total amount of the liquid crystal composition (B) The lower limit of the preferred content is 15% by mass, 19% by mass, 24% by mass and 30% by mass, and the preferred upper limit is 45, 40% by mass and 35% by mass. %, 30% by mass, 25% by mass, 23% by mass, 20% by mass, 18% by mass, 15% by mass, and 13% by mass.

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

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

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

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

In the liquid crystal composition (B), the content of the compound represented by the general formula (L-5) is the solubility at low temperature, transition temperature, electrical reliability, birefringence, process suitability, drop mark Therefore, it is necessary to adjust appropriately according to required performance such as image sticking and dielectric anisotropy.

The lower limit of the preferable content of the compound represented by the formula (L-5) with respect to the total amount of the liquid crystal composition (B) is 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, 26% by mass, 30% by mass %, 35% by mass, and 40% by mass. The upper limit of the preferable content of the compound represented by the formula (L-5) with respect to the total amount of the liquid crystal composition (B) is 50% by mass, 40% by mass, and 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 represented by the formula (L-5.1). ) Or a compound represented by formula (L-5.2), and a compound represented by formula (L-5.1) is particularly preferable.

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

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

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

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

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

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

The lower limit of the preferable content of the compound represented by the formula (L-6) with respect to the total amount of the liquid crystal composition (B) is 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, 26% by mass, 30% by mass %, 35% by mass, and 40% by mass. The upper limit of the preferable content of the compound represented by the formula (L-6) with respect to the total amount of the liquid crystal composition (B) is 50% by mass, 40% by mass, and 35% by mass, 30% by mass, 20% by mass, 15% by mass, 10% by mass, and 5% by mass. When emphasizing to increase Δn, it is preferable to increase the content, and when emphasizing the precipitation at low temperature, it is preferable to decrease the content.

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

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

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

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

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

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

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

The lower limit of the preferable content of the compound represented by the formula (L-7) with respect to the total amount of the liquid crystal composition (B) is 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. The upper limit of the preferable content of the compound represented by the formula (L-7) with respect to the total amount of the liquid crystal composition (B) is 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 an embodiment of Tni with a high liquid crystal composition (B) is desired, it is preferable to increase the content of the compound represented by formula (L-7), and when an embodiment with a low viscosity is desired. It is preferable to reduce the amount.

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

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

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

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

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

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

The compound represented by the general formula (L-8) is the following compound.

(In the formula, R ^L81 and R ^L82 each independently represent the same meaning as R ^L1 and R ^L2 in General Formula (L), and A ^L81 represents the same meaning or single bond as A ^L1 in General Formula (L)). However, each hydrogen atom on A ^L81 may be independently substituted with a fluorine atom, and X ^L81 to X ^L86 each independently represent a fluorine atom or a hydrogen atom.)
^{Wherein, R L81} and ^{R L82} are each independently an alkyl group having 1 to 5 carbon atoms, an alkenyl group or an alkoxy group having 1 to 4 carbon atoms of 2 to 5 carbon atoms ^{preferably, A L81} is 1, A 4-cyclohexylene group or a 1,4-phenylene group is preferable, and the hydrogen atoms on A ^L71 and A ^L72 may each independently be substituted with a fluorine atom, and the same in the general formula (L-8) The number of fluorine atoms in the ring structure is preferably 0 or 1, and the number of fluorine atoms in the molecule is preferably 0 or 1.

In the liquid crystal composition (B), the content of the compound represented by the general formula (L-8) is the solubility at low temperature, transition temperature, electrical reliability, birefringence, process suitability, drop mark Therefore, it is necessary to adjust appropriately according to required performance such as image sticking and dielectric anisotropy.

The lower limit of the preferable content of the compound represented by the formula (L-8) with respect to the total amount of the liquid crystal composition (B) is 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. The upper limit of the preferable content of the compound represented by the formula (L-8) with respect to the total amount of the liquid crystal composition (B) is 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 an embodiment of Tni with a high liquid crystal composition (B) is desired, it is preferable to increase the content of the compound represented by formula (L-8), and when an embodiment with a low viscosity is desired It is preferable to reduce the amount.

Further, the compound represented by the general formula (L-8) is preferably a compound represented by the formula (L-8.1) to the formula (L-8.4), and the formula (L-8. 3), formula (L-8.5), formula (L-8.6), formula (L-8.13), formula (L-8.16) to formula (L-8.18), formula (L) A compound represented by formula (L-8.28) to L-8.23) is more preferable.

Compounds represented by general formulas (L), (N-1), (N-2), (N-3), (N-4) and (J) with respect to the total amount of the liquid crystal composition (B) The lower limit value of the total preferable content is 80% by mass, 85% by mass, 88% by mass, 90% by mass, 92% by mass, 93% by mass, and 94% by mass 95% by mass 96% by mass 97% by mass 98% by mass 99% by mass 100% by mass The upper limit of preferable content is 100% by mass, 99% by mass, 98% by mass, and 95% by mass. However, from the viewpoint of obtaining a composition having a large absolute value of Δε, compounds represented by general formulas (N-1), (N-2), (N-3), (N-4) and (J) It is preferable that any one of these is 0 mass%.

The liquid crystal composition (B) preferably does not contain a compound having a structure in which oxygen atoms such as a peracid (—CO—OO—) structure are bonded in the molecule.

When emphasizing the reliability and long-term stability of the composition, the content of the compound having a carbonyl group is preferably 5% by mass or less, preferably 3% by mass or less, based on the total mass of the composition. Is more preferable, and it is still more preferable to set it as 1 mass% or less, and it is most preferable not to contain substantially.

When importance is attached to stability by UV irradiation, the content of the compound substituted with chlorine atoms is preferably 15% by mass or less, and preferably 10% by mass or less, based on the total mass of the composition. 8% by mass or less, preferably 5% by mass or less, more preferably 3% by mass or less, and still more preferably substantially not contained.

It is preferable to increase the content of a compound in which all the ring structures in the molecule are 6-membered rings, and the content of the compound in which all the ring structures in the molecule are 6-membered rings is 80% of the total mass of the composition. It is preferably at least 90% by mass, more preferably at least 90% by mass, even more preferably at least 95% by mass, and it is composed of only a compound having substantially all 6-membered ring structures in the molecule. Most preferably it constitutes a product.

In order to suppress deterioration due to oxidation of the composition, it is preferable to reduce the content of the compound having a cyclohexenylene group as a ring structure, and the content of the compound having a cyclohexenylene group as the total mass of the composition. On the other hand, it is preferably 10% by mass or less, preferably 8% by mass or less, more preferably 5% by mass or less, and preferably 3% by mass or less, and substantially not contained. Further preferred.

When importance is attached to improvement of viscosity and improvement of Tni, the content of a compound having a 2-methylbenzene-1,4-diyl group in the molecule, in which a hydrogen atom may be substituted with a halogen, may be reduced. Preferably, the content of the compound having a 2-methylbenzene-1,4-diyl group in the molecule is preferably 10% by mass or less, more preferably 8% by mass or less based on the total mass of the composition. Is preferably 5% by mass or less, more preferably 3% by mass or less, and still more preferably substantially not contained.

“Substantially not contained” in the present application means that it is not contained except for an unintentionally contained product.

When the compound contained in the liquid crystal composition (B) has an alkenyl group as a side chain, when the alkenyl group is bonded to cyclohexane, the alkenyl group may have 2 to 5 carbon atoms. Preferably, when the alkenyl group is bonded to benzene, the alkenyl group preferably has 4 to 5 carbon atoms, and the unsaturated bond of the alkenyl group and benzene are preferably not directly bonded. .

The average elastic constant (K _AVG ) of the liquid crystal composition used in the liquid crystal composition (B) is preferably from 10 to 25, and the lower limit thereof is preferably 10, preferably 10.5, preferably 11, .5 is preferred, 12 is preferred, 12.3 is preferred, 12.5 is preferred, 12.8 is preferred, 13 is preferred, 13.3 is preferred, 13.5 is preferred, 13.8 is preferred, 14 Is preferred, 14.3 is preferred, 14.5 is preferred, 14.8 is preferred, 15 is preferred, 15.3 is preferred, 15.5 is preferred, 15.8 is preferred, 16 is preferred, 16.3 16.5 is preferred, 16.8 is preferred, 17 is preferred, 17.3 is preferred, 17.5 is preferred, 17.8 is preferred, 18 is preferred, the upper limit thereof Is preferably 25, 24.5 is preferred, 24 is preferred, 23.5 is preferred, 23 is preferred, 22.8 is preferred, 22.5 is preferred, 22.3 is preferred, 22 is preferred, 21 .8, 21.5 is preferred, 21.3 is preferred, 21 is preferred, 20.8 is preferred, 20.5 is preferred, 20.3 is preferred, 20 is preferred, 19.8 is preferred, 19 .5, 19.3 is preferred, 19 is preferred, 18.8 is preferred, 18.5 is preferred, 18.3 is preferred, 18 is preferred, 17.8 is preferred, 17.5 is preferred, 17 .3 is preferred and 17 is preferred. When importance is placed on reducing power consumption, it is effective to reduce the amount of light from the backlight, and it is preferable to improve the light transmittance of the liquid crystal display element. For this purpose, the value of K _AVG should be set low. preferable. It is preferable to set a higher value of K _AVG in the case of emphasizing improved response speed.

In the liquid crystal composition (B), Z, which is a function of rotational viscosity and refractive index anisotropy, preferably shows a specific value.

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

The liquid crystal composition (B), in the case of using the active matrix display device, it is necessary to have a 10 ¹² (Ω · m) or more in specific resistance, 10 ¹³ (Ω · m) is preferable, 10 ¹⁴ (Ω · m) or more is more preferable.

As a polymerization method of the polymerizable compound used in the present invention, polymerization can be performed by radical polymerization using the above-described polymerization initiator (C).

As the polymerizable liquid crystal composition for producing a liquid crystal display element, the radical polymerizable monomer component (A), the liquid crystal composition (B), and the compound (C) can be used as essential components. The polymerizable monomer component (A) can be used in a proportion of 0.5 to 20% by mass, preferably 1 to 10% by mass in the polymerizable liquid crystal composition.

The polymerizable liquid crystal composition for producing a liquid crystal display element used in the present invention contains 0.5% by mass to 20% by mass of the radical polymerizable monomer component (A), so that it is uniaxial optically anisotropic. Or a uniaxial refractive index anisotropy or a polymer network having an easy orientation axis direction, and the optical axis or the easy orientation axis of the polymer network and the easy orientation axis of the low-molecular liquid crystal are substantially the same. More preferably, they are formed so as to match. The polymer network includes a polymer binder in which a polymer thin film is formed by aggregating a plurality of polymer networks. The polymer binder has refractive index anisotropy indicating uniaxial orientation, low molecular liquid crystal is dispersed in the thin film, and the uniaxial optical axis of the thin film and the optical axis of the low molecular liquid crystal are in substantially the same direction. The feature is that it is complete.

Therefore, unlike a polymer dispersion type liquid crystal or polymer network type liquid crystal which is a light scattering type liquid crystal, light scattering does not occur and a high contrast display can be obtained in a liquid crystal display element using polarized light. It is characterized in that the response time of the liquid crystal element is improved by shortening the down time. Furthermore, the polymerizable liquid crystal composition for manufacturing a liquid crystal display element used in the present invention induces a pretilt by forming a polymer thin film layer on a liquid crystal element substrate when a polymer network layer is formed on the entire liquid crystal display element. It can be distinguished from a PSA (Polymer Sustained Alignment) type liquid crystal composition.

It is preferable to adjust the Tg as required by containing at least two kinds of radical polymerizable monomer components (A) having different Tg at any concentration. The radical polymerizable monomer component (A), which is a precursor of a polymer having a high Tg, is a radical polymerizable monomer component (A) having a molecular structure that increases the crosslink density, and has two or more functional groups. Preferably there is. The precursor of the polymer having a low Tg preferably has a structure in which the number of functional groups is 1 or 2 or more, and an alkylene group or the like is provided as a spacer between the functional groups to increase the molecular length. When adjusting the Tg of the polymer network for the purpose of improving the thermal stability and impact resistance of the polymer network, it is preferable to appropriately adjust the ratio of the polyfunctional monomer to the monofunctional monomer. Tg is also related to thermal mobility at the molecular level in the main chain and side chain of the polymer network, and has an influence on electro-optical properties. For example, when the crosslink density is increased, the molecular mobility of the main chain is lowered, the anchoring force with the low molecular liquid crystal is increased, the drive voltage is increased, and the fall time is shortened. On the other hand, when the crosslinking density is lowered so that Tg is lowered, the thermal mobility of the polymer main chain is increased, so that the anchoring force with the low-molecular liquid crystal is lowered, the driving voltage is lowered, and the fall time is increased. The anchoring force at the polymer network interface is influenced by the molecular mobility of the polymer side chain in addition to the above-mentioned Tg, and is monovalent or divalent, and an acrylate of an alcohol compound having 8 to 18 carbon atoms. Alternatively, the anchoring force at the polymer interface can be lowered by using methacrylate as the radical polymerizable monomer component (A). Further, such a radical polymerizable monomer component (A) is effective in inducing a pretilt angle at the substrate interface and acts in the direction of decreasing the polar anchoring force.

By polymerizing the radically polymerizable monomer component (A) in the polymerizable liquid crystal composition for producing a liquid crystal display element in a state where the polymerizable liquid crystal composition for producing the liquid crystal display element exhibits a liquid crystal phase, the molecular weight is obtained. Increases to cause phase separation into the liquid crystal composition (B) and the polymer (or copolymer). The form of separation into two phases differs greatly depending on the type of liquid crystal composition (B) contained and the type of monomer. A phase separation structure may be formed by binodal decomposition in which an infinite number of monomer phases are generated and grown as island-like nuclei in the liquid crystal composition (B), and the concentration of the monomer phase in the liquid crystal composition (B) A phase separation structure may be formed by spinodal decomposition that separates phases from fluctuations. In order to form a polymer network by binodal decomposition, by using a compound with a high monomer reaction rate, a structure of nano-order is generated by generating innumerable monomer nuclei smaller than the wavelength of visible light and connecting them linearly. This is preferable because a phase separation structure is formed. As a result, when the polymerization in the monomer phase proceeds, a polymer network having a gap interval shorter than the wavelength of visible light is formed depending on the phase separation structure. On the other hand, the voids in the polymer network are due to the phase separation of the liquid crystal composition (B) phase. When the size of the voids is smaller than the wavelength of visible light, there is no light scattering and high contrast and anchors from the polymer network are used. This is particularly preferable because the influence of the ring force is increased, the fall time is shortened, and a high-speed response liquid crystal display element can be obtained. The nucleation of the monomer phase in the binodal decomposition is preferably adjusted as necessary as affected by parameters such as the change in compatibility depending on the type and combination of the compounds, the reaction rate, and the temperature. In the case of UV polymerization, the UV irradiation conditions may be appropriately adjusted so as to promote the reactivity depending on the type and content of the functional group of the monomer, the polymerization initiator, the UV irradiation intensity, and at least 2 mW / An ultraviolet irradiation intensity of cm ² or more is preferable. Spinodal decomposition is preferable because a phase-separated microstructure can be obtained by fluctuations in the concentration of two phases having periodicity, and uniform gaps smaller than the visible light wavelength can be easily formed. When the content of the radically polymerizable monomer component (A) is increased, there exists a phase transition temperature at which the liquid crystal composition (B) high-concentration phase and the monomer high-concentration phase are separated into two phases due to temperature. An isotropic phase is exhibited at a temperature higher than the two-phase separation transition temperature, but if it is low, separation occurs and a uniform phase separation structure cannot be obtained. When two-phase separation is performed due to a temperature change, it is preferable to form a phase separation structure at a temperature higher than the two-phase separation temperature. In any case described above, a polymer network is formed while maintaining the same alignment state as that of the liquid crystal composition (B). At this time, the polymer phase separation structure is closely related to the spacing and density of the polymer network, but in the process of forming the polymer phase separation structure, it is described that two phases of monomer high concentration phase and liquid crystal high concentration phase are formed. However, the photoinitiator tends to gather in the higher affinity of either the monomer or the liquid crystal, and concentration concentration occurs. When the photoinitiator is unevenly distributed in the monomer high concentration phase, the polymerization of the monomer is promoted. However, the polymerization of the monomer remaining in the liquid crystal high concentration phase is difficult to proceed. The residual monomer in the liquid crystal high-concentration phase having a low photoinitiator concentration crosslinks by gathering to the monomer high-concentration phase by an action such as aggregation. Conversely, the polymerization of the residual monomer in the liquid crystal high-concentration phase is promoted, and as the molecular weight of the residual monomer in the liquid crystal increases, the polymer phase separation structure is newly formed or the monomer high-concentration phase is changed. In some cases, such as aggregation, the residual monomer in the liquid crystal high-concentration phase is preferable because the polymerization easily proceeds due to the effect of the photoinitiator dissolved in the liquid crystal phase. It is also preferable that the residual monomer in the high-concentration liquid crystal phase undergoes separation of the polymerization phase by the effect of the photoinitiator and forms a new polymer network.

The formed polymer network exhibits optical anisotropy so as to follow the orientation of the liquid crystal composition (B). The form of the liquid crystal layer in the polymer network includes a structure in which the liquid crystal composition (B) forms a continuous layer in the three-dimensional network structure of the polymer, and a structure in which the droplets of the liquid crystal composition (B) are dispersed in the polymer. Or a structure in which both are mixed, and a structure in which a polymer network layer is present starting from both substrate surfaces and only a liquid crystal layer is provided near the center of the facing substrate. In any structure, a pretilt angle of 0 to 90 ° is preferably induced with respect to the liquid crystal element substrate interface by the action of the polymer network. The formed polymer network preferably has a function of aligning the coexisting liquid crystal composition (B) in the alignment direction indicated by the alignment film of the liquid crystal cell, and further has a function of pretilting the low-molecular liquid crystal with respect to the polymer interface direction. It is also preferable to have it. Introducing a monomer that pre-tilts a low-molecular liquid crystal with respect to the polymer interface is useful and preferable for improving the transmittance and lowering the driving voltage of the liquid crystal element. Moreover, it may have refractive index anisotropy, and it is preferable to use a monomer having a mesogenic group for the function of aligning the liquid crystal in the alignment direction. Alternatively, a pretilt may be formed by forming a polymer network by applying ultraviolet rays or the like while applying a voltage.

In the case of applying a vertical alignment cell such as VA mode, an acrylate of an alcohol compound having no mesogenic group that induces vertical alignment as a monomer, monovalent or divalent, and having 8 to 18 carbon atoms, or Methacrylate may be used as a monomer, and a combination with a monomer having a mesogenic group is also preferred. When a polymer network is formed in a vertically aligned cell by phase separation polymerization using a polymerizable liquid crystal composition for manufacturing a liquid crystal display element, a fibrous or columnar polymer network is formed on the liquid crystal cell substrate. (B) It is preferable to form in the direction substantially the same as the vertical direction. In addition, when a vertical alignment film that induces a pretilt angle by rubbing the liquid crystal on the cell substrate surface so as to induce a tilted alignment is used, the liquid crystal is pretilted and aligned. It is preferable that a fibrous or columnar polymer network is formed in an inclined direction in the same direction as the liquid crystal composition (B). The monomer may be selected so that the inclination of the polymer network occurs spontaneously at the substrate interface. Alternatively, a polymer network may be formed by applying a voltage to place the liquid crystal in an inclined alignment state and irradiating ultraviolet rays or the like.

Furthermore, as a method for inducing the pretilt angle while applying a voltage, polymerization is performed while applying a voltage in a voltage range of about 0.9 V to about 2 V higher than a threshold voltage of a liquid crystal for manufacturing a liquid crystal display element. Alternatively, a voltage higher than the threshold voltage may be applied for a short time of several seconds to several tens of seconds during the polymer network formation process, and then the polymer network may be formed below the threshold voltage. More preferably, the fibrous or columnar polymer network is formed to be inclined so as to induce a pretilt angle of 90 ° to 80 ° with respect to the transparent substrate plane, and a pretilt angle of 90 ° to 85 ° is preferred. A pretilt angle of 9 to 85 degrees is preferred, a pretilt angle of 89.9 to 87 degrees is preferred, and a pretilt angle of 89.9 to 88 degrees is preferred. The fibrous or columnar polymer network formed by any method is characterized in that the two cell substrates are connected to each other. Thereby, the thermal stability of the pretilt angle is improved, and the reliability of the liquid crystal display element can be increased.

In addition, as a method for inducing the pretilt angle of the liquid crystal composition (B) by forming a fibrous or columnar polymer network in a tilted orientation, the number of carbon atoms of the alkylene group between the functional group and the mesogenic group Is a method using a combination of a bifunctional acrylate having a small pretilt angle induction angle of 6 or more, a functional group, and a bifunctional acrylate having a large pretilt angle induction angle of 5 or more carbon atoms in the alkylene group between the mesogenic groups. Can be mentioned. A desired pretilt angle can be induced in the vicinity of the interface by adjusting the compounding ratio of these compounds.

Furthermore, a method of adding a monomer having a reversible photo-alignment function in a range of at least 0.01% by mass to 1% by mass to form a fibrous or columnar polymer network can be mentioned. In this case, the trans form has a rod-like shape similar to that of the low-molecular liquid crystal and affects the alignment state of the low-molecular liquid crystal. The trans isomer contained in the polymerizable liquid crystal composition for producing a liquid crystal display element is aligned so that the direction of ultraviolet light travels parallel to the direction of the long axis of the rod when irradiated with ultraviolet light as parallel light from the top surface of the cell. The low-molecular liquid crystals are also aligned so as to be aligned in the molecular major axis direction of the trans form at the same time. When the cell is tilted and irradiated with ultraviolet rays, the molecular long axis of the trans body is oriented in the tilt direction and the liquid crystal is oriented in the tilt direction of the ultraviolet rays. That is, a pre-tilt angle is induced and a photo-alignment function is exhibited. When the monomer is crosslinked at this stage, the pretilt angle induced is fixed by a fibrous or columnar polymer network formed by polymerization phase separation. Therefore, the pretilt angle that is important in the VA mode is induced by a method of separating the polymerization phase while applying a voltage, a method of adding a plurality of monomers with different pretilt angles to induce polymerization phase separation, and a monomer having a reversible photo-alignment function. The liquid crystal element of the present invention can be produced by using a method of aligning the liquid crystal composition (B) and the monomer in the direction in which ultraviolet rays travel and separating the polymerization phase as necessary using the photo-alignment function indicated by

The monomer having a photo-alignment function may be a photoisomeric compound that absorbs ultraviolet rays and becomes a trans isomer, or may be a photoisomerizable compound that absorbs ultraviolet rays and becomes a cis isomer. Furthermore, it is preferable that the reaction rate of the monomer having the photo-alignment function is slower than the reaction rate of the monomer other than the monomer having the photo-alignment function. When irradiated with ultraviolet rays, the monomer having a photo-alignment function immediately becomes a trans form, and when it is aligned in the light traveling direction, surrounding monomers and non-polymerized liquid crystal compositions are aligned in the same direction. At this time, the polymerization phase separation proceeds, and the pretilt angle is induced in the direction in which the easy alignment direction of the liquid crystal composition (B) and the polymer network is aligned with the easy alignment direction of the monomer having the photo-alignment function and the ultraviolet light travels. Is done.

Furthermore, when a parallel alignment cell such as IPS or FFS mode is applied, an alignment having a fibrous or columnar polymer network on the surface of the liquid crystal cell substrate by phase separation polymerization using a liquid crystal composition for manufacturing a liquid crystal display element. Although the liquid crystal composition (B) is aligned in parallel with the alignment direction of the film, the refractive index anisotropy or the easy axis direction of the formed fibrous or columnar polymer network and the alignment of the liquid crystal composition (B) It is preferably formed in a direction substantially the same as the direction. Furthermore, it is more preferable that the fibrous or columnar polymer network is present in substantially the entire cell except for the voids in which the liquid crystal composition (B) is dispersed. For the purpose of inducing the pretilt angle with respect to the polymer interface direction, a monomer having a mesogenic group using a monovalent or divalent acrylate or methacrylate of an alcohol compound having 8 to 18 carbon atoms as a monomer; It is preferable to use it.

Furthermore, although the electro-optical characteristics are affected by the surface area of the polymer network interface and the gap spacing of the polymer network, it is important not to cause light scattering, and the average gap spacing is preferably smaller than the wavelength of visible light. For example, there is a method of increasing the monomer composition content in order to increase the surface area of the interface and reduce the gap interval. As a result, the polymer phase is formed so that the surface area of the interface is increased by changing the polymerization phase separation structure and making the gap interval fine, and the drive voltage and the fall time are shortened. The polymerization phase separation structure is also affected by the polymerization temperature.

In the present invention, it is preferable to obtain a phase separation structure having fine voids by polymerizing at a high phase separation rate. The phase separation rate is greatly influenced by the compatibility between the low-molecular liquid crystal and the monomer and the polymerization rate. Since it largely depends on the molecular structure and content of the compound, it is preferable to adjust the composition as appropriate. When the compatibility is high, it is preferable to use a monomer having a high polymerization rate. In the case of ultraviolet polymerization, it is preferable to increase the ultraviolet intensity. It is also preferable to increase the monomer content in the liquid crystal composition for device production. When the compatibility is low, the phase separation rate is sufficiently high, which is preferable for producing the liquid crystal element of the present invention. As a method for reducing the compatibility, a method of polymerizing at a low temperature can be mentioned. When the temperature is lowered, the degree of alignment order of the liquid crystal is increased, and the compatibility between the liquid crystal composition (B) and the monomer is decreased, so that the polymerization phase separation rate can be increased. As another method, a method of polymerizing a liquid crystal composition for producing a liquid crystal display device at a temperature showing a supercooled state can also be mentioned. In this case, it may be slightly lower than the melting point of the liquid crystal composition for producing the liquid crystal display element, and therefore, it is possible to accelerate the phase separation only by lowering the temperature by several degrees. As a result, the polymer phase separation structure corresponding to the case where a monomer content of several tens of mass% is added to the liquid crystal, that is, the structure that acts to shorten the fall time has a large surface area of the polymer network interface, and the gap spacing is A fine polymer network structure is formed. Therefore, the composition of the liquid crystal composition for producing a liquid crystal display element is preferably adjusted as appropriate in consideration of the alignment function, the crosslinking density, the anchoring force, and the gap interval so as to shorten the fall time.

In order to obtain a high contrast display in a liquid crystal display element, it is necessary to prevent light scattering. However, in consideration of the above-described method, it is necessary to obtain a desired voltage-transmittance characteristic and switching characteristic. It is important to control the separation structure to form a suitable polymer network layer structure. The polymer network layer structure will be specifically described as follows.

A structure in which a polymer network layer is formed on the entire surface of the liquid crystal display element in the liquid crystal phase and the liquid crystal phase is continuous, and the orientation axis of the polymer network and the uniaxial optical axis are substantially in the same direction as the orientation axis of the low-molecular liquid crystal It is preferable that the polymer network is formed so as to induce a pretilt angle of the low-molecular liquid crystal, and light is obtained by reducing the average gap distance of the polymer network to be smaller than the wavelength of visible light and smaller than at least 450 nm. Since scattering does not occur, it is preferable. Furthermore, in order to make the fall time of the response shorter than the response time of the low-molecular liquid crystal alone due to the interaction effect (anchoring force) between the polymer network and the low-molecular liquid crystal, it is preferable to be in the range of 50 nm to 450 nm. In order that the influence of the cell thickness of the liquid crystal is small and the fall time is as long as the cell thickness is large, at least the average gap interval is in the range of around 200 nm and the upper limit is around 450 nm. It is preferable to enter. Increasing the drive gap increases the average gap spacing. However, in order to suppress the increase in drive voltage to 25 V or less and shorten the fall response time, it is sufficient to enter the range from about 250 nm to 450 nm. The fall response time can be improved in the range of about 5 msec to about 1 msec, which is preferable. Further, in order to suppress the drive voltage from increasing within about 5V, it is preferable that the average gap interval is in the range of about 300 nm to 450 nm. Furthermore, it is also possible to control the average gap interval of the polymer network so that the falling response time is a high-speed response of 1 msec or less. Although the drive voltage may increase to 30 V or more, the average gap interval may be set between about 50 nm and about 250 nm, and in order to reduce it to 0.5 msec or less, it is preferable to set from about 50 nm to about 200 nm. The average diameter of the polymer network is in the range of 20 nm to 700 nm, contrary to the average gap spacing. The average diameter tends to increase as the monomer content increases. Increasing the polymerization phase separation rate by increasing the reactivity increases the density of the polymer network and decreases the average diameter of the polymer network. Therefore, the phase separation conditions may be adjusted as necessary. When the monomer content is 10% by mass or less, the average diameter is preferably from 20 nm to 160 nm, and when the average gap distance is from 200 nm to 450 nm, the average diameter is preferably from 40 nm to 160 nm. . When the monomer content is larger than 10% by mass, the range of 50 nm to 700 nm is preferable, and the range of 50 nm to 400 nm is more preferable.

In contrast to a structure in which a polymer network layer is formed on the entire surface of the liquid crystal display element and the liquid crystal phase is continuous, if the monomer content is low and the amount necessary to cover the entire cell with the polymer network layer is insufficient, the polymer network layer It is formed discontinuously. When the polarity of the substrate surface, such as a polyimide alignment film, is high, the monomer tends to gather near the liquid crystal cell substrate interface, and a polymer network layer is formed so that the polymer network grows and adheres to the substrate interface from the substrate surface. The polymer network layer, the liquid crystal layer, the polymer network layer, and the counter substrate are stacked in this order. Polymer having a laminated structure of polymer network layer / liquid crystal layer / polymer network layer and having a thickness of at least 0.5%, preferably 1%, more preferably 5% or more of the cell thickness in the cell cross-sectional direction When the network layer is formed, the effect of shortening the fall time due to the action of the anchoring force between the polymer network and the low-molecular liquid crystal is exhibited and a favorable tendency is exhibited. However, since the influence of the cell thickness increases, if the fall time becomes longer as the cell thickness is increased, the thickness of the polymer network layer may be increased as necessary. The polymer network structure in the polymer network layer is such that the low-molecular liquid crystal and the easy-orientation axis or uniaxial optical axis are aligned in substantially the same direction, and the low-molecular liquid crystal is formed so as to induce a pretilt angle. Just do it. The average gap distance is preferably in the range of 90 nm to 450 nm.

For example, when the monomer content is less than 6% by mass, it is preferable to use a bifunctional monomer having a mesogenic group having a high anchoring force, and a bifunctional monomer having a structure with a short distance between functional groups and a high polymerization rate. It is preferable to use, and it is preferable to form a polymer phase separation structure at a low temperature of 0 ° C. or lower. When the monomer content is from 6% by mass to less than 10% by mass, a combination of the bifunctional monomer and a monofunctional monomer having a low anchoring force is preferable, and polymerization is performed in the range of 25 ° C. to −20 ° C. as necessary. It is preferable to form a phase separation structure. Furthermore, if the melting point is room temperature or higher, it is preferable to lower the melting point by about 5 ° C. because the same effect as low temperature polymerization can be obtained. The higher the monomer concentration in the liquid crystal composition for producing a liquid crystal display element, the greater the anchoring force between the liquid crystal composition (B) and the polymer interface, and the higher the τd. On the other hand, when the anchoring force between the liquid crystal composition (B) and the polymer interface increases, τr decreases. In order to make the sum of τd and τr less than 1.5 ms, the concentration of the monomer in the liquid crystal composition for producing a liquid crystal display element is 1% by mass or more and less than 10% by mass, and 1.5% by mass or more and 8% by mass. % By mass or less is preferable, and 1.8% by mass to 5% by mass is more preferable.

When used in a TFT drive liquid crystal display element, it is necessary to improve the reliability such as suppression of flicker and afterimages caused by printing, and the voltage holding ratio is an important characteristic. The cause of lowering the voltage holding ratio is considered to be ionic impurities contained in the liquid crystal composition for producing a liquid crystal display element. In particular, mobile ions strongly influence the voltage holding ratio. Therefore, it is preferable to remove the mobile ions by performing a purification treatment or the like so that at least a specific resistance of 10 ¹⁴ Ω · cm or more is obtained. In addition, when a polymer network is formed by radical polymerization, the voltage holding ratio may decrease due to ionic impurities generated from the photopolymerization initiator, etc., but the polymerization initiator generates a small amount of organic acid and low-molecular byproducts. Is preferably selected.

The liquid crystal display element of the present invention contains a polymer or copolymer in a liquid crystal layer sandwiched between two transparent substrates having electrodes on at least one side, and the content of the polymer or copolymer is the liquid crystal 0.5 mass% or more and less than 10 mass% of the total mass of the composition and the polymer or copolymer, the polymer or copolymer forms a polymer network, and the polymer network is uniaxial refraction. It has a rate anisotropy or an orientation easy axis, and has two or more different orientation states. The liquid crystal display element of the present invention preferably has an alignment film for aligning the liquid crystal composition (B) on at least one transparent substrate. By applying a voltage to the alignment film provided on the substrate and the electrode provided on the substrate, the alignment of the liquid crystal molecules is controlled. The polymer network or polymer binder has a uniaxial refractive index anisotropy or an easy axis direction, and the optical axis direction or the easy axis direction of the polymer network or the polymer binder and the easy axis direction of the low molecular liquid crystal are the same direction. Preferably there is. In this respect, it differs from a light scattering polymer network liquid crystal or polymer dispersed liquid crystal that does not have a uniaxial refractive index anisotropy or an orientation easy axis direction.

Furthermore, it is preferable that the easy orientation axis direction of the alignment film and the easy orientation direction of the polymer network or polymer binder are the same. By providing a polarizing plate, a retardation film, etc., display is performed using this orientation state. The liquid crystal display element can be applied to operation modes such as TN, STN, ECB, VA, VA-TN, IPS, FFS, π cell, OCB, and cholesteric liquid crystal. Of these, VA, IPS, FFS, VA-TN, TN, and ECB are particularly preferable. The liquid crystal display element of the present invention is a PSA (Polymer Sustained Alignment) type liquid crystal display having a polymer or copolymer on the alignment film in that it contains a polymer or copolymer in the polymerizable liquid crystal composition. Different from the element.

The content of the polymer or copolymer in the liquid crystal layer is 0.5% by mass or more and less than 10% by mass of the total mass of the liquid crystal composition (B) and the polymer or copolymer. The value is preferably 0.7% by mass or more, preferably 0.9% by mass or more, and the upper limit is preferably less than 9% by mass, and preferably less than 7% by mass.

In the PSA-type liquid crystal display element, the alignment treatment is omitted by providing a plurality of slits with a width of 3 to 5 μm in the electrode instead of the rubbing alignment treatment and tilting the liquid crystal in the slit direction. In mass production technology, when UV irradiation is applied while applying a voltage of several tens of volts, the alignment of the liquid crystal is stabilized so that a pretilt angle (tilt angle with respect to the substrate normal) is obtained at the substrate interface, and the polymer is stabilized. A thin film is formed. Utilizing the fact that the pretilt angle is induced by the action of the polymer thin film, it is used for the production of PSVA (polymer-stabilized vertical alignment) LCD or PSALCD. Further, for the purpose of improving the viewing angle, a pattern electrode designed so that a multi-domain can be formed is used to divide the pretilt angle direction in one pixel into a plurality of parts. However, when this method is applied to a liquid crystal display element that can improve the response relaxation time by forming a polymer network or the like in the entire cell, it is irradiated with ultraviolet rays by applying a voltage of several tens of volts above the saturation voltage. Thus, the polymer network stabilizes the liquid crystal in the parallel alignment state. This is because the refractive anisotropy or the easy alignment axis of the polymer network is formed so as to hold the liquid crystal molecules in the parallel alignment state, so that the vertical alignment cannot be obtained.

In a vertical alignment type LCD, electro-optical characteristics such as transmittance and response time are provided by applying a pretilt angle within 2 degrees to the cell normal direction in order to align the tilt orientation of the tilt alignment in a certain direction by applying a voltage. We are trying to improve. However, in order to form a polymer network so as to induce a pretilt angle, it is conceivable to apply a voltage slightly higher than the threshold voltage of the liquid crystal and form the liquid crystal in a state in which the liquid crystal is tilted within 2 degrees. However, in a liquid crystal display device such as a PVA (Ptted vertical alignment) or the like in which the tilt alignment direction is made uniform, a low voltage near the threshold voltage is applied to form the refractive anisotropy of the polymer network or the easy alignment axis. The transmittance decreases because the tilt orientation direction of the liquid crystal is not determined. This is because when a voltage near the threshold voltage is applied, the effect of the vertical alignment film is strong, so that the liquid crystal near the substrate interface is vertically aligned, and the tilt alignment direction cannot be defined in the constant direction near the substrate interface. This is because it becomes stable. On the other hand, when a voltage higher than the saturation voltage of the electro-optic characteristic is applied, the liquid crystal near the substrate interface is in a tilted alignment state, and since the electric field is strong, the influence of the electric field distribution by the pattern electrode is strong, and the tilted orientation direction is in a certain direction. Thus, the transmittance can be improved. However, since a polymer network with parallel alignment is formed in the entire cell, vertical alignment cannot be obtained as described above.

Since the tilt orientation depends greatly on the type of the electrode pattern, for example, the fishbone type electrode shown in FIG. 11 has the same width as the fine line electrode and the line electrode having a width of about 3 to 5 μm alternately. In this pattern electrode, the liquid crystal on the line electrode is aligned so that the tilt alignment direction of the liquid crystal is substantially parallel to the slit direction. Therefore, it is necessary to provide an orientation memory in which the tilt orientation direction is constant in the slit direction as the refractive anisotropy or the easy orientation axis of the polymer network. Further, in the case of the axial electrode of Axial Symmetrical Vertical Alignment, it has a subpixel structure composed of a point electrode and a substantially square counter electrode. The central axis is vertically aligned even when a voltage is applied, but the liquid crystal director is radially inclined and aligned with the point electrode of the central axis as a starting point. When the device is viewed from above, the liquid crystal director is continuously oriented 360 degrees radially from the central axis. When a high voltage is applied to stabilize the alignment state in a part of the polymer network, a part of the polymer network is formed so that the radial inclined alignment direction is stabilized. By making the voltage less than the threshold voltage during the ultraviolet irradiation, the liquid crystal returns to a substantially vertical alignment. The formed radial orientation orientation can be left in the polymer network as a locus, and both orientation control when voltage is applied and vertical orientation when no voltage is applied can be achieved.

That is, in the PVA liquid crystal display element, the refractive index anisotropy or the easy axis of alignment of the polymer network coincides with the liquid crystal alignment state in order to stabilize the alignment state obtained by applying a voltage higher than the threshold voltage. In order to stabilize the alignment state obtained by applying a voltage less than the threshold voltage, the polymer network is formed so that the refractive index anisotropy or the easy axis of alignment coincides with the liquid crystal alignment state. The coexistence of a polymer network that stabilizes the alignment state of two different liquid crystals in this case makes the influence of the formed polymer network different on the liquid crystal alignment. For example, if only the polymer network that stabilizes the alignment state of the liquid crystal below the threshold voltage is formed, when the alignment of the liquid crystal is changed by voltage switching, the alignment state of the liquid crystal affected by the polymer network is changed. This is different from the alignment state of the liquid crystal originally required for the liquid crystal display element, so that the alignment after the alignment transition is distorted and the desired alignment state cannot be obtained, affecting the electro-optic effect, contrast, and transmittance. Etc. decreases. Therefore, it is easy to change the alignment between the two states by coexisting two alignment states, the alignment state obtained by applying a voltage higher than the threshold voltage to the polymer network and the alignment state obtained by applying a voltage lower than the threshold voltage. And display characteristics are improved. Therefore, in order to stabilize the alignment state of the liquid crystal above the threshold voltage and the alignment state of the liquid crystal below the threshold voltage and to form a polymer network so that the two alignment states are mixed, a liquid crystal display Part of the monomer contained in the polymerizable liquid crystal composition for device manufacture is used for the purpose of stabilizing the alignment state of the liquid crystal above the threshold voltage, and the remaining monomer is used to stabilize the liquid crystal alignment state below the threshold voltage. It is preferably used for a polymer network formed so as to be formed.

Furthermore, since the polymer network having the function of stabilizing each of these two different alignment states is mixed, the liquid crystal alignment state when no voltage is applied to the element after the polymer network is formed is two different alignment states. It is influenced by the polymer network to be held, and the liquid crystal alignment state when no voltage is applied is determined by the balance of influence of each polymer network. For example, in the liquid crystal display element of the vertical alignment mode, when the influence of the polymer network that stabilizes the liquid crystal alignment state below the threshold voltage is increased, the liquid crystal display element exhibits the vertical alignment originally required and the liquid crystal display This is preferable because the contrast is increased. Conversely, if the influence of the polymer network that stabilizes the alignment of the liquid crystal above the threshold voltage is too strong, the pretilt angle of the liquid crystal increases and the contrast decreases. In order to improve the display quality by increasing the transmittance and contrast of the liquid crystal display element, it is important to adjust the balance of the influence of each of the polymer networks that stabilize two different liquid crystal alignment states. If the influence of the polymer network acting to stabilize the alignment state of the liquid crystal above the threshold voltage is too strong, the maximum transmittance is improved, but the black level is increased and the contrast is lowered. Also, if the influence of the polymer network that acts to stabilize the alignment state of the liquid crystal below the threshold voltage is too strong, a good black level can be obtained, but this is not preferable because the maximum transmittance is lowered and the contrast is lowered.

A polymer network formed to stabilize the liquid crystal alignment state above the threshold voltage so that the tilted orientation is constant because the maximum transmittance improves when the tilted orientation of the liquid crystal is made constant by applying a tilt voltage. When the polymer network is formed so as to stabilize the substantially vertical alignment state in which a good black level can be obtained by applying a voltage less than the threshold voltage during ultraviolet irradiation, a good black level is obtained. Since the orientation of the tilted orientation becomes constant and the maximum transmittance increases, a high contrast can be obtained, which is preferable because the display quality is improved.

The method for producing a liquid crystal display element of the present invention comprises a polymerizable liquid crystal composition for producing a liquid crystal display element sandwiched between two transparent substrates having electrodes on at least one side, the threshold voltage of the liquid crystal for producing the element being equal to or higher than the threshold voltage. It is a method comprising a step of irradiating ultraviolet rays while applying a voltage to cause polymerization phase separation, and a step of further irradiating with ultraviolet rays by setting the voltage below the threshold voltage while irradiating the ultraviolet rays. As a result, a polymer network that stabilizes the alignment state of the liquid crystal above the threshold voltage and the alignment state of the liquid crystal that is less than the threshold voltage is formed, and the polymer network that stabilizes two different liquid crystal alignment states is mixed and formed. Is the method. In the case of a vertical alignment mode liquid crystal display element including a pattern electrode cell, etc., in the process of separating the polymerization phase by irradiating ultraviolet rays while applying a voltage higher than the threshold voltage of the liquid crystal for liquid crystal display element manufacture, In the step of aligning the liquid crystal molecules in the liquid crystal with an inclination in the range of 0 to 30 degrees with respect to the transparent substrate plane, and further irradiating with ultraviolet rays by setting the voltage below the threshold voltage while irradiating with ultraviolet rays. The liquid crystal molecules are preferably aligned with an inclination of 80 to 90 degrees with respect to the transparent substrate plane. The state in which the liquid crystal molecules are aligned with an inclination in the range of 0 to 30 degrees with respect to the transparent substrate plane indicates a state in which the birefringence of the liquid crystal is increased by voltage application, and the alignment state of the liquid crystal is in the plane of the transparent substrate. On the other hand, when it is 0 degree, the birefringence is maximized, which is preferable. In particular, the PVA cell is preferable because the tilt direction can be made constant. In any case, it is preferable to form a polymer network in which the orientation is stabilized so that the tilt orientation direction of the liquid crystal by voltage application becomes a constant direction.

When the liquid crystal molecules are aligned at an angle of 80 to 90 degrees with respect to the transparent substrate plane, the birefringence becomes minimum when the liquid crystal is aligned at 90 degrees with respect to the transparent substrate plane when no voltage is applied. It is useful and preferable for increasing the contrast of the liquid crystal display element, but it is more preferable that the liquid crystal display device is tilted within 89.9 degrees to 85 degrees with respect to the substrate plane in order to tilt and align in a certain direction when a voltage is applied. . If the angle exceeds 80 degrees with respect to the substrate plane, the birefringence increases and the amount of transmitted light increases, which is not preferable because the display contrast is lowered. Since contrast is obtained, it is preferable. In the IPS (In-plane switching) display mode and FFS mode liquid crystal display element, a process of polymerizing phase separation by irradiating ultraviolet rays while applying a voltage higher than a threshold voltage of a liquid crystal composition for liquid crystal display element production. The liquid crystal molecules in the liquid crystal composition for manufacturing a liquid crystal display element are aligned with an inclination in the range of 0 to 90 degrees with respect to the transparent substrate plane, and the voltage is set to be lower than the threshold voltage while being irradiated with ultraviolet rays. In the step of further irradiating with ultraviolet rays, it is also preferable that the liquid crystal molecules are aligned with an inclination of 0 to 30 degrees with respect to the transparent substrate plane.

The liquid crystal molecules are tilted in the range of 0 to 90 degrees with respect to the transparent substrate plane, and the alignment forms a polymer network so as to stabilize the alignment state of the liquid crystal to which a voltage is applied. In the case of the IPS mode, the tilt angle of the properties of the alignment film used in the element greatly depends on the tilt angle, and may be in the range of 1 to 2 degrees. The tilt angle of the liquid crystal molecules including the twisted orientation is 0. .5 to 3 degrees is preferable, and 0 to 2 degrees is preferable. In the FFS mode, when a voltage higher than the threshold voltage is applied, the alignment state of the liquid crystal depends on the electric field distribution in the device, and the splay alignment, bend alignment, and twist alignment states coexist. Indicates. The inclination angle of the alignment state of the liquid crystal molecules in this state is preferably in the range of 0 to 45 degrees, and the same range is preferably stabilized when the alignment is stabilized by the polymer network. In the TN mode, the tilt angle is preferably in the range of 45 degrees to 90 degrees.

On the other hand, a polymer network is formed so as to stabilize the alignment state of the liquid crystal by applying a voltage lower than the threshold voltage. In the IPS mode, FFS mode, and TN mode, the pretilt angle is applied to the substrate interface by rubbing alignment treatment. Therefore, it is preferable to form a polymer network so as to stabilize the alignment state of the liquid crystal to which a voltage less than the threshold voltage is applied, even if the liquid crystal alignment angle is inclined within this range. The tilt angle of the liquid crystal molecules including the twist orientation is preferably 0.5 to 3 degrees using other alignment processing methods such as a photo-alignment film, and a wide viewing angle is within 0 to 2 degrees. Useful and more preferred to obtain.

Further, it is preferable that the voltage to be applied is an alternating current waveform and has a frequency in a range in which the liquid crystal composition (B) for producing a liquid crystal display element exhibits dielectric anisotropy. The waveform is preferably a rectangular wave that can increase the effective voltage when the peak voltage is constant. The upper limit of the frequency may be a frequency that does not attenuate the signal transmitted to the pixel by the driving circuit used for the liquid crystal display element, and it is preferable that the frequency is at least 2 kHz or less. The frequency shown by the dielectric anisotropy in the frequency dependence of the dielectric constant exhibited by the liquid crystal composition for producing a liquid crystal display element before ultraviolet irradiation may be 10 kHz or less. The lower limit value may be a frequency at which flicker occurs when the element is driven. In this case, the frequency may be any frequency that minimizes flicker, and is preferably at least 20 Hz or more.

The method for producing a liquid crystal display element of the present invention is characterized in that a polymer network is formed so as to maintain two liquid crystal alignment states as described above. The polymer network is formed such that the refractive index anisotropy or the easy axis of alignment of the polymer network coincides with the liquid crystal alignment direction equal to or higher than the threshold voltage or the liquid crystal alignment direction lower than the threshold voltage. This creates a state in which the polymer network that stabilizes the alignment of the liquid crystal when a voltage is applied and the polymer network that stabilizes the alignment of the liquid crystal when no voltage is applied coexist, and the liquid crystal alignment when no voltage is applied It is possible to improve display characteristics such as an improvement in contrast by suppressing orientation distortion that occurs when orientation deformation is caused by voltage application from the state. On the other hand, only the polymer network formed so as to maintain the liquid crystal alignment state when no voltage is applied is formed so as to maintain the liquid crystal alignment below the threshold voltage when changing to the liquid crystal alignment state when the voltage is applied. Since the influence of the polymer network is strong, when the liquid crystal alignment state is shifted to a threshold voltage or higher, an alignment strain is applied to cause a decrease in transmittance. By forming a polymer network that stabilizes the alignment of the liquid crystal when a voltage is applied to a part of the polymer network, distortion of the alignment change caused by switching is suppressed, and the originally required change in liquid crystal alignment can be obtained and transmitted. The rate can be improved. The polymer network formed so as to stabilize the alignment state of each liquid crystal when a voltage is applied and when no voltage is applied is the refractive index anisotropy or alignment of the polymer network along the alignment of two different liquid crystals. It is characterized by forming an easy axis.

Furthermore, the influence of the polymer network formed to stabilize the liquid crystal state above the threshold voltage changes depending on the application time of the voltage above the threshold voltage during UV irradiation, making it possible to change the electro-optical characteristics. Become. For example, when the polymer network is formed with the alignment state of the liquid crystal at the time of voltage application as a parallel alignment including a tilted alignment of 0 to 30 degrees with respect to the substrate plane, the voltage application time equal to or higher than the threshold voltage during ultraviolet irradiation is set. When shortened, the action to maintain the parallel alignment is small, so that the liquid crystal tends to align according to the action of the polymer network to maintain the vertical alignment. Furthermore, the influence of both orientations from the polymer network holding two different orientations is balanced, and a small pre-tilt angle of less than 1 degree is induced with respect to the normal direction of the transparent substrate. As the application time of the voltage above the threshold voltage during UV irradiation is increased, the influence of the polymer network that tries to maintain the parallel orientation becomes stronger, so the pretilt is based on the balance between the force that maintains the vertical orientation and the force that maintains the parallel orientation. The angle increases and the pretilt angle increases, and it becomes possible to make it 10 degrees or more with respect to the normal direction of the transparent substrate. In addition, since the application time of the voltage higher than the threshold voltage during ultraviolet irradiation largely depends on the reactivity of the polymerizable liquid crystal composition used for manufacturing the liquid crystal display element used, it can be adjusted appropriately to obtain a desired pretilt angle. It is preferable to make it. In particular, it is preferable to obtain a pretilt angle in the range of 80 to 90 degrees with respect to the substrate plane, more preferably 85 to 89.9 degrees, and 87 to 89.9 degrees. Is more preferable.

The polymer network formed to maintain the alignment state of the liquid crystal obtained by applying a voltage higher than the threshold voltage is a parallel alignment state in a vertical alignment mode liquid crystal display device using negative dielectric anisotropy. Alternatively, a tilted orientation with a constant azimuth is desirable. The alignment state obtained at a voltage lower than the threshold voltage is preferably a substantially vertical alignment, and in particular, a substantially vertical alignment of 80 to 90 degrees with respect to the substrate plane is preferable, and a good black level that provides high contrast is obtained. It is preferable that it is the orientation state which shows. In the IPS display mode by a lateral electric field using negative dielectric anisotropy or positive dielectric anisotropy, the alignment state of the liquid crystal obtained by applying a voltage higher than the threshold voltage during ultraviolet irradiation is twisted. The orientation is preferable. The alignment state obtained at a voltage lower than the threshold voltage is preferably parallel alignment with a constant azimuth angle. In the FFS mode, the alignment state obtained by applying a voltage equal to or higher than the threshold voltage during ultraviolet irradiation is preferably at least one of bend alignment, splay alignment, inclined alignment, or a mixed alignment state. When the voltage is lower than the threshold voltage, it is preferable to have a substantially parallel orientation. After forming the polymer network to maintain the alignment state of the liquid crystal when a voltage is applied, the polymer is stabilized after the formation of the polymer network by stabilizing the alignment state of the liquid crystal below the threshold voltage. The alignment state can be easily changed to the alignment state, and both high transmittance and high-speed response can be achieved.

The applied voltage at the time of ultraviolet irradiation is preferably adjusted as appropriate so that the display of the liquid crystal display element after the formation of the polymer network has a high contrast, and the electro-optic effect of the liquid crystal composition for manufacturing the liquid crystal display element before the ultraviolet irradiation Since it greatly depends on the characteristics, it is necessary to match the voltage-transmittance characteristics exhibited by the liquid crystal for manufacturing the liquid crystal display element. The voltage above the threshold voltage is preferably a voltage V10 or higher, which is 10% or higher with respect to the total change in transmittance in the voltage-transmittance characteristic voltage of the liquid crystal for manufacturing a liquid crystal display element. The voltage V20 or more at which the change amount is 20% or more is more preferable, and the voltage V50 or more at which the total change in transmittance is 50% or more is more preferable. However, the voltage is preferably not more than 6 times the threshold voltage. As the voltage that is equal to or higher than the threshold voltage applied during the ultraviolet irradiation, an alternating voltage is preferably applied, and a rectangular wave is preferably applied. The frequency is preferably a frequency that cannot be visually recognized by the flicker, and when an electronic circuit such as a TFT substrate is formed on a glass substrate, it may be a frequency at which the polymerization voltage does not attenuate, and is 30 Hz to 5 kHz. It is preferable that there is a degree.

The voltage applied in the middle of the ultraviolet irradiation is changed from the threshold voltage to less than the threshold voltage, but the voltage less than the threshold voltage may be in a range where the orientation of the liquid crystal does not change with the voltage. The voltage is preferably less than 80%, more preferably less than 80%, and even more preferably 70% or less. In addition, the applied voltage is set to the threshold voltage or lower during the ultraviolet irradiation, but at this time, it is preferable to return to the liquid crystal alignment state at the OFF time in the liquid crystal display element. For example, in the vertical alignment mode as described above. In other words, it may be returned to the vertical alignment, and in the FFS mode or the IPS mode, the parallel alignment may be used. In order to return to the liquid crystal alignment state when the liquid crystal display element is OFF, it is preferable that the influence of the polymer network that stabilizes the liquid crystal alignment during voltage application is lowered to a voltage lower than the threshold voltage in a slight state.

The ultraviolet rays are irradiated after applying a voltage higher than the threshold voltage. However, if the voltage application time becomes longer during the ultraviolet irradiation, the influence of the polymer network that stabilizes the orientation of the liquid crystal during voltage application during the ultraviolet irradiation increases. It becomes unpreferable because it does not return to the liquid crystal alignment state when the required liquid crystal display element is OFF. Therefore, it is preferable to manufacture the liquid crystal liquid crystal display element of the present invention by appropriately optimizing the optimum voltage during ultraviolet irradiation. In addition, when the voltage during ultraviolet irradiation is made lower than the threshold voltage, the voltage is gradually lowered during the ultraviolet irradiation in order to adjust the response relaxation time in the liquid crystal of the liquid crystal composition for device manufacture. It is possible to minimize the influence of backflow that occurs in the response relaxation process by making the fall time of the liquid crystal longer than the response relaxation time in the liquid crystal during ultraviolet irradiation. The fall time of the applied voltage is 10 ms or more. Is preferably within 1000 ms. On the contrary, it may be lowered quickly, and it is preferably at least shorter than the relaxation time indicated by the liquid crystal composition for producing a liquid crystal display element, and preferably 100 ms or less.

A polymer network of parallel alignment components is partially formed by irradiating with ultraviolet rays in a state where a voltage higher than the threshold voltage is applied, and the liquid crystal is returned to the vertical alignment by lowering the voltage below the threshold voltage while continuing the ultraviolet irradiation. This completes the polymerization phase separation. In the fishbone type liquid crystal cell, the pretilt angle can be changed by the ratio of the above-mentioned parallel alignment component and vertical alignment component. When the voltage is turned off in the initial stage of polymer network formation, the tilt alignment direction is determined and the vertical alignment is determined. By using the residual monomer, it becomes possible to achieve both the vertical alignment and the tilt alignment orientation, which is an alignment control technique in the nanophase separation liquid crystal.

The parallel alignment state means that a negative dielectric anisotropic liquid crystal is in a substantially parallel alignment state when a voltage is applied, and is preferably in the range of 0.1 to 30 degrees with respect to the substrate surface. It is preferable that the tilt orientation is in the range of 1 to 10 degrees. The vertical alignment when no voltage is applied means that the vertical alignment film is brought into a substantially vertical alignment state. The alignment of the liquid crystal is inclined at 80 to 89.9 degrees with respect to the substrate plane. It is preferable that the angle is inclined from 85 degrees to 89.9 degrees.

In the case of a positive dielectric anisotropic liquid crystal, a vertical alignment is obtained when a voltage is applied, but the liquid crystal is tilted and aligned in the range of 45 to 89.9 degrees with respect to the substrate plane. It is also included.
The parallel alignment when no voltage is applied means that the parallel alignment film is brought into a substantially parallel alignment state. The alignment of the liquid crystal is tilted from 0.1 to 30 degrees with respect to the substrate plane. It is included.

The distance (d) between the substrates of the liquid crystal display element of the present invention is preferably in the range of 2 to 5 μm, more preferably 3.5 μm or less. In general, the birefringence is adjusted so that the product of the birefringence of the liquid crystal composition and the cell thickness is close to 0.275. In the liquid crystal composition for manufacturing an element used in the present invention, the polymer network is separated after the polymerization phase separation. Since the birefringence of the liquid crystal display element when an electric field is applied is lowered due to the anchoring force action of the polymer network and the optical properties of the polymer network, the liquid crystal composition, the polymer composition, or the liquid crystal display element The product of the birefringence (Δn) of the liquid crystal composition contained in the liquid crystal composition for production and the distance (d) between the substrates is 0.3 to 0.00 when the driving voltage is increased within about 5 V due to the formation of the polymer network. The range of 4 μm is particularly preferable, the range of 0.30 to 0.35 μm is more preferable when the increase is within about 3 V, and the range of 0.29 to 0.33 μm when the drive voltage is within 1 V. It is particularly preferred. By making the product of the distance (d) between the substrates of the liquid crystal display element and the product of the birefringence (Δn) of the liquid crystal composition and the distance (d) between the substrates within the above ranges, the transmittance is limited to only low-molecular liquid crystals. It is possible to obtain a display that is relatively high and has a high-speed response and favorable color reproducibility. The birefringence of the liquid crystal composition used in the liquid crystal composition for manufacturing the liquid crystal display element is such that the product of the cell thickness (d) and the birefringence (Δn) is 1 to 1.9 times with respect to 0.275. It is preferable to make it.

The driving voltage of the liquid crystal display element of the present invention is not determined only by the dielectric anisotropy or elastic constant of the liquid crystal composition, but is greatly influenced by the anchoring force acting between the liquid crystal composition and the polymer interface.

For example, Japanese Patent Laid-Open No. 6-222320 discloses the relationship of the following formula as a description regarding the driving voltage of a polymer dispersion type liquid crystal display element.

(Vth represents a threshold voltage, 1Kii and 2Kii represent elastic constants, i represents 1, 2 or 3, Δε represents dielectric anisotropy, and <r> represents a transparent polymer substance interface. It represents the average gap distance, A represents the anchoring force of the transparent polymer substance with respect to the liquid crystal composition, and d represents the transparent electrode. According to this, the driving voltage of the light scattering type liquid crystal display element is It is determined by the average gap spacing at the material interface, the distance between the substrates, the elastic constant / dielectric anisotropy of the liquid crystal composition, and the anchoring energy between the liquid crystal composition and the transparent polymer material.
Among these, parameters that can be controlled by the liquid crystal display device of the present invention are liquid crystal properties and anchoring force between polymers. Since the anchoring force largely depends on the molecular structure of the polymer and the molecular structure of the low-molecular liquid crystal, if a monomer having a strong anchoring force is selected, the response time can be shortened to 1.5 ms or less. At the same time, since the drive voltage increases to 30 V or more, it is preferable to adjust the composition by appropriately selecting the liquid crystal compound and the monomer so that the drive voltage is 30 V or less and the response speed is 1.5 ms or less. It is preferable to adjust the composition so that the driving voltage and the response speed are balanced by appropriately blending a polymer precursor having a strong anchoring force and a polymer precursor having a weak anchoring force. On the other hand, as the physical properties of the liquid crystal composition required for lowering the driving voltage, it is particularly preferable that the dielectric anisotropy is 6 or more for the P-type liquid crystal and -3 or less for the N-type liquid crystal. . The birefringence is preferably 0.09 or more. Furthermore, it is more preferable to make the birefringence of the liquid crystal composition and the refractive index of the fibrous or columnar polymer network as close as possible to eliminate light scattering. However, since the retardation of the liquid crystal element is affected by the concentration of the polymer precursor, it is preferable to use the liquid crystal composition with an increased or decreased birefringence so that the necessary retardation can be obtained.
In the liquid crystal display element of the present invention, the above-mentioned liquid crystal composition is irradiated with energy rays while maintaining the liquid crystal composition at −50 ° C. to 30 ° C. to polymerize the monomer so that the refractive index anisotropy or the orientation easy axis direction is present in the liquid crystal composition. It is preferably obtained by forming a polymer network. The upper limit of the polymerization temperature is 30 ° C, preferably 20 ° C to -10 ° C. As will be described later in Examples, the present inventor has found that τd is further accelerated by low temperature polymerization and normal temperature polymerization depending on the monomer composition. This is because 1) the polymerization is performed in a state where the orientation degree of the liquid crystal molecules is increased at a low temperature, and 2) the phase separation is facilitated by reducing the compatibility between the polymer polymerized by the low temperature polymerization and the liquid crystal composition. The phase separation speed is increased and the void spacing of the polymer network becomes fine. 3) The refraction is such that the influence of anchoring force is strong because the gap interval is fine even if a monomer having a relatively low anchoring force is used. This is thought to be due to the formation of an anisotropic polymer network.
Furthermore, in the liquid crystal display element of the present invention, the optical axis direction or the easy alignment axis direction of the polymer network or polymer binder having uniaxial refractive index anisotropy or easy alignment axis direction forms a pretilt angle with respect to the transparent substrate. It is preferable to adjust the strength of the electric field to control the orientation of the low-molecular liquid crystal, and by tilting it with respect to the substrate surface, the energy rays are applied while applying a voltage to the liquid crystal layer described above. By irradiation, the monomer is preferably polymerized to obtain a polymer having a refractive index anisotropy or an orientation easy axis direction in the liquid crystal composition. In the vertically oriented VA mode, a voltage is applied so that the pretilt angle is 20 degrees or less with respect to the normal direction of the substrate, and polymerization is performed, so that the portulsion currently used in the VA mode cell is used. This is particularly preferable because it not only has an effect corresponding to the fine polymer protrusions of the PSA liquid crystal, but also exhibits a high-speed response that cannot be realized by PSA. In addition, by applying an electric field direction from a plurality of directions to form a polymer, a multi-domain can be formed, and a viewing angle can be improved, which is more preferable. Furthermore, the alignment direction of the low-molecular liquid crystal is regulated by applying photo-alignment treatment or rubbing alignment treatment to the low-molecular liquid crystal to induce a pretilt angle at the substrate interface vertical alignment film interface. The occurrence of orientation defects is preferably suppressed, and it is also preferable to use a pattern electrode that is inclined in a plurality of directions or to perform the orientation treatment. The liquid crystal layer is applied with an alternating electric field in a temperature range of −50 ° C. to 30 ° C. as appropriate to a polymerizable liquid crystal composition containing a monomer, and is irradiated with ultraviolet rays or an electron beam, thereby providing refractive index anisotropy. Is formed in the liquid crystal so that the optical axis direction of the polymer network forms a pretilt angle with respect to the substrate surface. This pretilt angle is a liquid crystal element in which the polymer axis after polymerization is tilted with respect to the substrate surface when the polymer phase is separated in an alignment state induced by applying an electric field due to the dielectric anisotropy of the low-molecular liquid crystal It is more preferable that the monomer is polymerized. Furthermore, it is also preferable to induce a pretilt angle by combining a polymer network obtained by stabilizing an alignment state to which a voltage is applied and a polymer network obtained by stabilizing an alignment state to which no voltage is applied.

The two substrates used in the liquid crystal display element of the present invention can be made of a transparent material having flexibility such as glass or plastic. 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 prepared by, for example, a pigment dispersion method, a printing method, an electrodeposition method, or a dyeing method. A method for producing a color filter by a pigment dispersion method will be described as an example. A curable coloring composition for a color filter is applied on the transparent substrate, subjected to patterning treatment, and cured by heating or light irradiation. By performing this process for each of the three colors 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 or a thin film diode may be provided on the substrate.

The substrate is opposed so that the transparent electrode layer is on the inside. In that case, you may adjust the space | interval of a board | substrate through a spacer. In this case, it is preferable to adjust so that the thickness of the obtained light control layer is 1 to 100 μm. 1.5 to 10 μm is more preferable. When a polarizing plate is used, the product of the refractive index anisotropy Δn of the liquid crystal and the cell thickness d is adjusted so that the contrast is maximized, and 1/550 nm is reduced depending on the display mode. It is preferable to make it 2 or 1/4. In addition, when there are two polarizing plates, the polarizing axis of each polarizing plate can be adjusted so that the viewing angle and contrast are good. Furthermore, a retardation film for widening the viewing angle can also be used. Examples of the spacer include columnar spacers made of glass particles, plastic particles, alumina particles, a photoresist material, and the like. Thereafter, a sealant such as an epoxy thermosetting composition is screen-printed on the substrates with a liquid crystal inlet provided, the substrates are bonded together, and heated to thermally cure the sealant.

As a method of sandwiching a liquid crystal composition for manufacturing a liquid crystal display element between two substrates, a normal vacuum injection method or an ODF method can be used. In the ODF liquid crystal display device manufacturing process, a sealant such as epoxy photothermal curing is drawn on a backplane or frontplane substrate using a dispenser in a closed-loop bank shape, and then removed. A liquid crystal display element can be manufactured by bonding a front plane and a back plane after dropping a predetermined amount of a liquid crystal composition for manufacturing a liquid crystal display element in the air. The liquid crystal composition for producing an element used in the present invention can be suitably used because the liquid crystal / monomer composite material can be stably dropped in the ODF process.

As a method for polymerizing the monomer, an appropriate polymerization rate is desirable in order to obtain good alignment performance of the liquid crystal. Therefore, polymerization is performed by irradiating ultraviolet rays or electron beams, which are active energy rays, singly or in combination or sequentially. The method of making it preferable is. When ultraviolet rays are used, a polarized light source or a non-polarized light source may be used. In addition, when polymerization is performed in a state where a liquid crystal composition for manufacturing a liquid crystal display element is sandwiched between two substrates, at least the substrate on the irradiation surface side is given appropriate transparency to active energy rays. Must be. In addition, it is preferable to apply an alternating electric field to a liquid crystal composition for producing a liquid crystal display element in a temperature range of −50 ° C. to 20 ° C. and irradiate an ultraviolet ray or an electron beam to the liquid crystal composition containing a monomer. The alternating electric field to be applied is preferably an alternating current having a frequency of 10 Hz to 10 kHz, more preferably a frequency of 100 Hz to 5 kHz, and the voltage is selected depending on a desired pretilt angle of the liquid crystal display element. That is, the pretilt angle of the liquid crystal display element can be controlled by the applied voltage. In a horizontal electric field type MVA mode liquid crystal display element, the pretilt angle is preferably controlled from 80 degrees to 89.9 degrees from the viewpoint of alignment stability and contrast.

The temperature at the time of irradiation is preferably in the temperature range of −50 ° C. to 30 ° C. for a liquid crystal composition for producing a liquid crystal display element. Further, 20 ° C. to −10 ° C. is more preferable. Depending on the composition of the liquid crystal composition for device manufacture, τd tends to be further increased by low temperature polymerization and normal temperature polymerization. This is because 1) the polymerization is performed in a state where the orientation degree of the liquid crystal molecules is increased at a low temperature, and 2) the phase separation is facilitated by reducing the compatibility between the polymer polymerized by the low temperature polymerization and the liquid crystal composition. The phase separation speed is increased and the gap distance of the polymer network becomes fine. 3) Even if a polymerizable compound having a relatively low anchoring force is used, the influence of the anchoring force seems to be strong because the gap gap is fine. This is thought to be due to the formation of a refractive index anisotropic polymer network.

As a lamp for generating ultraviolet rays, a metal halide lamp, a high-pressure mercury lamp, an ultra-high pressure mercury lamp, or the like can be used. Moreover, as a wavelength of the ultraviolet rays to be irradiated, it is preferable to irradiate ultraviolet rays in a wavelength region other than the absorption wavelength region of the liquid crystal composition, and it is preferable to cut and use ultraviolet rays of less than 365 nm as necessary. Intensity of ultraviolet irradiation is ^preferably from 0.1mW / cm 2 ~ 100W / cm 2, 2mW / cm 2 ~ 50W / cm 2 is more preferable. The amount of energy of ultraviolet rays to be irradiated can be adjusted as appropriate, but is preferably 10 mJ / cm ² to 500 J / cm ^{2, and} more preferably 100 mJ / cm ² to 200 J / cm ² . When irradiating with ultraviolet rays, the intensity may be changed. The time for irradiating with ultraviolet rays is appropriately selected depending on the intensity of the irradiating ultraviolet rays.

(Horizontal electric field type)
First, a liquid crystal display element according to an embodiment of the present invention will be described with reference to the drawings. FIG. 1 is a schematic sectional view showing an example of the liquid crystal display element of the present invention. A liquid crystal display element 10 according to an embodiment of the present invention includes a first substrate 2 having an alignment layer 4 formed on the surface thereof, a space away from the first substrate, and a photo-alignment layer formed on the surface. And a liquid crystal layer 5 filled between the first substrate 2 and the second substrate 7 and in contact with the pair of alignment layers, the alignment layer 4 (4a, 4b). ) And the first substrate 2 have an electrode layer 3 including a thin film transistor, a common electrode 22 and a pixel electrode as an active element.

FIG. 1 is a diagram schematically showing a configuration of a liquid crystal display element. In FIG. 1, for convenience of explanation, each component is illustrated separately. As shown in FIG. 1, the configuration of the liquid crystal display element 10 according to the embodiment of the present invention is sandwiched between a first transparent insulating substrate 2 and a second transparent insulating substrate 7 that are arranged to face each other. A liquid crystal display element of a horizontal electric field type (an FFS mode as an embodiment of IPS in the figure) having a liquid crystal composition (or liquid crystal layer 5) for manufacturing a liquid crystal display element. The first transparent insulating substrate 2 has an electrode layer 3 formed on the surface on the liquid crystal layer 5 side. Further, between the liquid crystal layer 5 and each of the first transparent insulating substrate 2 and the second transparent insulating substrate 7, the liquid crystal composition for manufacturing the liquid crystal display element constituting the liquid crystal layer 5 is in direct contact with the homogeneous alignment. The liquid crystal molecules in the liquid crystal composition for manufacturing the device are aligned so as to be substantially parallel to the

substrates

2 and 7 when no voltage is applied. Has been. As shown in FIGS. 1 and 3, the second substrate 7 and the first substrate 2 may be sandwiched between 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 alignment film 4. The liquid crystal display element according to the present invention may be a so-called color filter on array (COA), or a color filter may be provided between an electrode layer including a thin film transistor and a liquid crystal layer, or the thin film transistor. A color filter may be provided between the electrode layer containing and the second substrate.

That is, the liquid crystal display element 10 of one embodiment of the present invention includes a first polarizing plate 1, a first substrate 2, an electrode layer 3 including a thin film transistor, an alignment film 4, and a liquid crystal for manufacturing a liquid crystal display element. The liquid crystal layer 5 containing the composition, the alignment film 4, the color filter 6, the second substrate 7, and the second polarizing plate 8 are sequentially stacked.

The first substrate 2 and the second substrate 7 can be made of a transparent material having flexibility such as glass or plastic, and one of them can be an opaque material such as silicon. The two

substrates

2 and 7 are bonded together by a sealing material and a sealing material such as an epoxy thermosetting composition disposed in the peripheral region, and in order to maintain the distance between the substrates, for example, Spacer columns made of resin formed by granular spacers such as glass particles, plastic particles, alumina particles, or the photolithography method may be arranged.

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

A unit pixel of a liquid crystal display device is formed by a region surrounded by a plurality of gate lines 24 and a plurality of data 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 26, and a gate electrode 28 is provided in the vicinity of the intersection where the gate wiring 24 and the data wiring 25 intersect each other. The thin film transistor is connected to the pixel electrode 21 as a switch element that supplies a display signal to the pixel electrode 21. A common line (not shown) is provided in parallel with the gate wiring 24. The common line is connected to the common electrode 22 in order to supply a common signal to the common electrode 22.

A preferred embodiment of the structure of the thin film transistor is provided, for example, as shown in FIG. 3 so as to cover the gate electrode 11 formed on the surface of the substrate 2 and the gate electrode 11 and cover the substantially entire surface of the substrate 2. A gate insulating layer 12, a semiconductor layer 13 formed on the surface of the gate insulating layer 12 so as to face the gate electrode 11, and a protective layer provided to cover a part of the surface of the semiconductor layer 13 14, a drain electrode 16 provided so as 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 which covers the other side edge of the layer 14 and the semiconductor layer 13 and is in contact with the gate insulating layer 12 formed on the surface of the substrate 2; and the drain Has an insulating protective layer 18 provided to cover the electrode 16 and the source electrode 17, a. An anodic oxide 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, or the like can be used for the semiconductor layer 13. However, when a transparent semiconductor film such as ZnO, IGZO (In—Ga—Zn—O), or ITO is used, the semiconductor layer 13 is caused by light absorption. It is also preferable from the viewpoint of suppressing the adverse effect of the optical carrier and increasing the aperture ratio of the element.

Furthermore, 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 in which an impurity such as phosphorus such as n-type amorphous silicon or n-type polycrystalline polysilicon is added at a high concentration can be used.

The gate wiring 26, the data wiring 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 an alloy thereof. It is particularly preferable to use this wiring. The insulating protective layer 18 is a layer having an insulating function, and is formed of silicon nitride, silicon dioxide, silicon oxynitride film, or the like.

In the embodiment shown in FIGS. 2 and 3, the common electrode 22 is a flat electrode formed on almost 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 disposed at a position closer to the first substrate 2 than the pixel electrode 21, and these electrodes are disposed so as to overlap each other via the insulating protective layer 18. The pixel electrode 21 and the common electrode 22 are formed of a transparent conductive material such as ITO (Indium Tin Oxide), IZO (Indium Zinc Oxide), IZTO (Indium Zinc Tin Oxide), and the like. Since the pixel electrode 21 and the common electrode 22 are formed of a transparent conductive material, the area opened by the unit pixel area increases, and the aperture ratio and transmittance increase.

In addition, the pixel electrode 21 and the common electrode 22 have an interelectrode distance (also referred to as a minimum separation distance): R between the pixel electrode 21 and the common electrode 22 in order to form a fringe electric field between the electrodes. The distance between the first substrate 2 and the second substrate 7 is smaller than G. Here, the distance between electrodes: R represents the distance in the horizontal direction on the substrate between the electrodes. FIG. 3 shows an example in which the plate-shaped common electrode 22 and the comb-shaped pixel electrode 21 overlap each other, and therefore an example in which the inter-electrode distance: R = 0 is shown, and the minimum separation distance: R is the first substrate 2. The distance between the first substrate 7 and the second substrate 7 (ie, the cell gap) is smaller than G, so that a fringe electric field E is formed. Therefore, the FFS type liquid crystal display element can use a horizontal electric field formed in a direction perpendicular to a line forming the comb shape 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. Further, the minimum separation distance R between the pixel electrode and the common electrode can be adjusted as the (average) film thickness of the gate insulating layer 12. In addition, unlike the liquid crystal display element according to the present invention, an inter-electrode distance (also referred to as a minimum separation distance) between the pixel electrode 21 and the common electrode 22: R is different from that of the first substrate 2 and the second substrate. The distance from the substrate 7 may be larger than G (IPS method). In this case, for example, a configuration in which comb-like pixel electrodes and comb-like common electrodes are provided alternately in substantially the same plane can be cited.

A preferred form of the liquid crystal display element according to the present invention is preferably an FFS mode liquid crystal display element using a fringe electric field, and the shortest separation distance d between the common electrode 22 and the pixel electrode 21 is set to be the alignment film 4. When the distance is shorter than the shortest distance D between the substrates (distance between substrates), a fringe electric field is formed between the common electrode and the pixel electrode, and the horizontal and vertical alignments of the liquid crystal molecules can be used efficiently. In the case of the FFS mode liquid crystal display element of the present invention, when a voltage is applied to the liquid crystal molecules arranged so that the long axis direction is parallel to the alignment direction of the alignment layer, the pixel electrode 21 and the common electrode 22 are interposed. Parabolic electric field equipotential lines are formed up to the top of the pixel electrode 21 and the common electrode 22 and are arranged along the electric field in which the long axes of the liquid crystal molecules in the liquid crystal layer 5 are formed. Therefore, liquid crystal molecules can be driven even with a low dielectric anisotropy.

In the color filter 6 according to the present invention, it is preferable to form a black matrix (not shown) in a portion corresponding to the thin film transistor and the storage capacitor 23 from the viewpoint of preventing light leakage. The color filter 6 is usually composed of one dot of video or image from three filter pixels of R (red), G (green), and B (blue). For example, these three filters are arranged in the extending direction of the gate wiring. Yes. The color filter 6 can be produced by, for example, a pigment dispersion method, a printing method, an electrodeposition method, or a dyeing method. A method for producing a color filter by a pigment dispersion method will be described as an example. A curable coloring composition for a color filter is applied onto the transparent substrate, subjected to patterning treatment, and cured by heating or light irradiation. By performing this process for each of the three colors red, green, and blue, a pixel portion for a color filter can be manufactured. In addition, a so-called color filter-on-array in which pixel electrodes provided with active elements such as TFTs and thin film diodes are provided on the substrate may be used.

On the electrode layer 3 and the color filter 6, a pair of alignment films 4 are provided that directly contact the liquid crystal composition for manufacturing the element constituting the liquid crystal layer 5 and induce homogeneous alignment.

In addition, 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 axis of each polarizing plate, and their transmission axes operate in a normally black mode. In addition, it is preferable to have transmission axes perpendicular to each other. In particular, any one of the polarizing plate 1 and the polarizing plate 8 is preferably arranged so as to have a transmission axis parallel to the alignment direction of the liquid crystal molecules. 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. Furthermore, a retardation film for widening the viewing angle can also be used.

As another embodiment of the liquid crystal display element, in the case of the IPS system, the shortest separation distance d between the adjacent common electrode and the pixel electrode is longer than the shortest separation distance G between the liquid crystal alignment films. The electrode and the pixel electrode are formed on the same substrate, and the common electrode and the pixel electrode are alternately arranged, and the shortest separation distance d between the adjacent common electrode and the pixel electrode is the liquid crystal alignment Examples include a structure longer than the shortest separation distance G between the films.

In the method for manufacturing a liquid crystal display device according to the present invention, after a film is formed on the substrate having the electrode layer and / or the substrate surface, the pair of substrates are separated and faced so that the film is inside, and then the liquid crystal It is preferred to fill the composition between the substrates. In that case, it is preferable to adjust the space | interval of a board | substrate through a spacer.

The distance between the substrates (the average thickness of the obtained liquid crystal layer, also referred to as the separation distance between the coatings) is preferably adjusted to be 1 to 100 μm. The average distance between the coatings is more preferably 1.5 to 10 μm.

In the present invention, examples of the spacer used for adjusting the distance between the substrates include columnar spacers made of glass particles, plastic particles, alumina particles, a photoresist material, and the like.

The FFS type liquid crystal display element described with reference to FIGS. 1 to 3 is an example, and can be implemented in various other forms without departing from the technical idea of the present invention.

Another embodiment of the liquid crystal display element according to the present invention will be described below with reference to FIGS.
For example, FIG. 4 is another embodiment of the plan view in which the region surrounded by the II line of the electrode layer 3 formed on the substrate 2 in FIG. 1 is enlarged. As shown in FIG. 4, 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 wiring 24 or the data wiring 25.

The pixel electrode 21 shown in FIG. 4 has a shape in which a substantially rectangular flat plate electrode is cut out by a notch portion having a substantially rectangular frame shape. Further, a comb-like common electrode 22 is formed on one surface of the back surface of the pixel electrode 21 via an insulating protective layer 18 (not shown). When the shortest separation distance R between the adjacent common electrode and the pixel electrode is shorter than the shortest separation distance G between the alignment layers, the FFS method is used. The surface of the pixel electrode is preferably covered with a protective insulating film and an alignment film layer. Similarly to the above, a storage capacitor 23 for storing a display signal supplied via the data wiring 25 may be provided in a region surrounded by the plurality of gate wirings 24 and the plurality of data wirings 25. The shape of the notch is not particularly limited, and is not limited to the substantially rectangular shape shown in FIG. Can be used. When the shortest separation distance R between the adjacent common electrode and the pixel electrode is longer than the shortest separation distance G between the alignment layers, an IPS display device is obtained.

FIG. 5 is another embodiment different from FIG. 3, and is another example of a cross-sectional view of the liquid crystal display element shown in FIG. 1 taken along the line III-III in FIG. The first substrate 2 having the alignment layer 4 and the electrode layer 3 including the thin film transistor 20 formed on the surface thereof and the second substrate 8 having the alignment layer 4 formed on the surface thereof face each other at a predetermined distance D. The liquid crystal layer 5 containing the liquid crystal composition is filled in this space. A gate insulating layer 12, a common electrode 22, an insulating protective layer 18, a pixel electrode 21, and an alignment layer 4 are stacked in this order on part of the surface of the first substrate 2. As shown in FIG. 4, the pixel electrode 21 has a shape in which the center and both ends of the flat plate are cut out by a triangular cutout, and the remaining region is cut out by a rectangular cutout. In addition, the common electrode 22 has a structure in which a comb-like common electrode is disposed on the first substrate side from the pixel electrode substantially in parallel with the substantially elliptical cutout portion of the pixel electrode 21.

In the example shown in FIG. 5, the common electrode 22 having a comb shape or a slit is used, and the interelectrode distance between the pixel electrode 21 and the common electrode 22 is R = α (in FIG. 5, for convenience, the interelectrode distance is horizontal. Ingredients are listed as R). Further, FIG. 3 shows an example in which the common electrode 22 is formed on the gate insulating layer 12, but as shown in FIG. 5, the common electrode 22 is formed on the first substrate 2, The pixel electrode 21 may be provided through the gate insulating layer 12. The electrode width of the pixel electrode 21: l, the electrode width of the common electrode 22: n, and the interelectrode distance: R are appropriately adjusted to such a width that all liquid crystal molecules in the liquid crystal layer 5 can be driven by the generated electric field. It is preferable. When the shortest separation distance R between the adjacent common electrode and the pixel electrode is shorter than the shortest separation distance G between the alignment layers, the FFS method is used, and when it is longer, the IPS method is used. Further, in FIG. 5, the positions in the thickness direction of the pixel electrode 21 and the common electrode 22 are different, but the positions in the thickness direction of both electrodes may be the same or the common electrode may be provided on the liquid crystal layer 5 side.

(Vertical electric field type)
Another preferred embodiment of the present invention is a vertical electric field type liquid crystal display device using a liquid crystal composition. FIG. 6 is a diagram schematically showing a configuration of a vertical electric field type liquid crystal display element. Moreover, in FIG. 7, for convenience of explanation, each component is illustrated separately. FIG. 7 is an enlarged plan view of a region surrounded by a line VII of an electrode layer 300 including a thin film transistor (or also referred to as a thin film transistor layer 300) formed on the substrate in FIG. FIG. 8 is a cross-sectional view of the liquid crystal display element shown in FIG. 6 taken along the line VIII-VIII in FIG. Hereinafter, a vertical electric field type liquid crystal display device according to the present invention will be described with reference to FIGS.

The liquid crystal display element 1000 according to the present invention includes a second substrate 800 provided with a transparent electrode (layer) 600 (also referred to as a common electrode 600) made of a transparent conductive material, as shown in FIG. A first substrate 200 including a thin film transistor layer 300 on which a pixel electrode made of a transparent conductive material and a thin film transistor for controlling the pixel electrode included in each pixel are formed; and the first substrate 200 and the second substrate 800 A liquid crystal composition (or liquid crystal layer 500) for manufacturing a liquid crystal display element sandwiched between the substrates 200, the alignment of liquid crystal molecules in the liquid crystal composition for manufacturing the element when no voltage is applied to the substrate 200, The liquid crystal display element is substantially perpendicular to 800. As shown in FIGS. 6 and 8, the second substrate 800 and the first substrate 200 may be sandwiched between a pair of

polarizing plates

100 and 900. Further, in FIG. 6, a color filter 700 is provided between the first substrate 200 and the common electrode 600. Furthermore, the pair of alignment films 400 are adjacent to the liquid crystal layer 500 according to the present invention and are in direct contact with the liquid crystal composition for manufacturing a liquid crystal display element constituting the liquid crystal layer 500. Is formed.
That is, the liquid crystal display element 1000 according to the present invention includes a first polarizing plate 100, a first substrate 200, an electrode layer (also referred to as a thin film transistor layer) 300 including a thin film transistor, a photo-alignment film 400, and a liquid crystal composition. A layer 500 containing an object, an alignment film 400, a common electrode 600, a color filter 700, a second substrate 800, and a second polarizing plate 900 are sequentially stacked. The alignment film 400 is preferably a photo-alignment film.

The alignment film is a liquid crystal cell manufactured using alignment treatment (mask rubbing or photo-alignment), and is slightly inclined from the normal direction of the glass substrate on the inner side (liquid crystal layer side) of the transparent electrode of the liquid crystal cell ( A vertical alignment film is formed (0.1 to 5.0 °).

In response to the alignment regulating force of the vertical alignment film, the polymerizable monomers are arranged in the vertical direction, and the polymerizable monomer is polymerized and fixed by irradiation with ultraviolet light to form a polymer network. The polymer network formed in this manner is (1) a polymer network that extends over the upper and lower substrates, (2) a polymer network that is formed from the upper (lower) substrate toward the liquid crystal direction, but halfway, ( 3) A polymer network is formed only near the surface of the alignment film. (Mainly in the case of a monofunctional monomer), (4) It is presumed to have approximately four types of structures in which polymer networks are bonded (not floating) in the liquid crystal layer. In any of these forms, the refractive index anisotropy or easy orientation axis of the polymer network is formed to stabilize the alignment state above the threshold voltage, and stabilize the alignment state below the threshold voltage. The polymer network which stabilizes two different orientation states formed so as to be mixed is mixed.
The polymer polymer network having anisotropy formed in this manner is almost completely separated from the liquid crystal layer, and the liquid crystal molecules are considered to be aligned between these polymer networks. The molecular alignment structure of the so-called polymer network type liquid crystal, in which liquid crystal molecules and polymer networks coexist and cause light scattering when no voltage is applied, is clearly different from that of the alignment maintaining layer that is unevenly distributed in the vicinity of the alignment film used in PSA etc. It has a completely different structure.
As an example, a polymer network and a liquid crystal molecular arrangement structure by a method using an alignment film are shown. On the other hand, in the so-called MVA method having structures such as ribs and slits, PVA, and the like, the polymer network near the substrate interface and the pretilt of liquid crystal molecules are somewhat affected by the oblique electric field strength applied through the structures and slits. It is only different, and is essentially assumed to have the structure shown in the above figure.
In the VA type liquid crystal display device having such a polymer network and liquid crystal molecule alignment by liquid crystal molecules, the anchoring force for the liquid crystal molecules when no voltage is applied is due to the synergistic action of the anchoring force of the liquid crystal alignment film and the polymer network. As a result, the response speed when the voltage is OFF can be increased.
(Horizontal / diagonal electric field type)
As a new display technology that can divide and align the liquid crystal display area by a simple method that only devise the electrode structure without performing complicated processes such as mask rubbing and mask irradiation on the alignment film, oblique and horizontal electric fields are liquid crystal. A method of acting on the layer has been proposed.

FIG. 9 is a plan view schematically showing a minimum unit structure in one pixel PX of a TFT liquid crystal display element using the above technique. The structure and operation of the horizontal / diagonal electric field mode liquid crystal display device will be briefly described below.
The pixel electrode PE has a main pixel electrode PA and a sub-pixel electrode PB. The main pixel electrode PA and the sub-pixel electrode PB are electrically connected to each other, and both the main pixel electrode PA and the sub-pixel electrode PB are provided on the array substrate AR. The main pixel electrode PA extends along the second direction Y, and the subpixel electrode PB extends along the first direction X different from the second direction Y. In the illustrated example, the pixel electrode PE is formed in a substantially cross shape. The sub-pixel electrode PB is coupled to a substantially central portion of the main pixel electrode PA, and extends from the main pixel electrode PA toward both sides thereof, that is, the left side and the right side of the pixel PX. The main pixel electrode PA and the sub-pixel electrode PB are substantially orthogonal to each other. The pixel electrode PE is electrically connected to a switching element (not shown) in the pixel electrode PB.

The common electrode CE has a main common electrode CA and a sub-common electrode CB, and the main common electrode CA and the sub-common electrode CB are electrically connected to each other. The common electrode CE is electrically insulated from the pixel electrode PE. In the common electrode CE, at least a part of the main common electrode CA and the sub-common electrode CB is provided on the counter substrate CT. The main common electrode CA extends along the second direction Y. The main common electrode CA is disposed on both sides of the main pixel electrode PA. At this time, none of the main common electrodes CA overlaps with the main pixel electrode PA in the XY plane, and a substantially equal interval is formed between each of the main common electrodes CA and the main pixel electrode PA. Yes. That is, the main pixel electrode PA is located approximately in the middle of the adjacent main common electrode CA. The sub-common electrode CB extends along the first direction X. The sub-common electrode CB is disposed on both sides of the sub-pixel electrode PB. At this time, in the XY plane, none of the sub-common electrodes CB overlaps the sub-pixel electrode PB, and a substantially equal interval is formed between each of the sub-common electrodes CB and the sub-pixel electrode PB. Yes. That is, the sub-pixel electrode PB is located approximately in the middle of the adjacent sub-common electrode CB.

In the illustrated example, the main common electrode CA is formed in a strip shape extending linearly along the second direction Y. The sub-common electrode CB is formed in a strip shape extending linearly along the first direction X. Note that the two main common electrodes CA are arranged in parallel at intervals along the first direction X. In the following, in order to distinguish these, the main common electrode on the left side in the drawing is referred to as CAL. The right main common electrode is called CAR. Further, the two sub-common electrodes CB are arranged in parallel along the second direction Y at intervals, and in the following, in order to distinguish these, the upper main common electrode in the drawing is referred to as CBU. The lower main common electrode is called CBB. The main common electrode CAL and the main common electrode CAR are at the same potential as the sub-common electrode CBU and the sub-common electrode CBB. In the illustrated example, the main common electrode CAL and the main common electrode CAR are connected to the sub-common electrode CBU and the sub-common electrode CBB, respectively.

The main common electrode CAL and the main common electrode CAR are respectively disposed between the pixel PX and the adjacent pixels on the left and right. That is, the main common electrode CAL is disposed across the boundary between the illustrated pixel PX and the left pixel (not shown), and the main common electrode CAR is the illustrated pixel PX and the right pixel (not shown). ). The sub-common electrode CBU and the main common electrode CBB are disposed between pixels adjacent to the pixel PX in the vertical direction. That is, the sub-common electrode CBU is disposed across the boundary between the illustrated pixel PX and the upper pixel (not illustrated), and the sub-common electrode CBB is illustrated with the illustrated pixel PX and the lower pixel (not illustrated). Z)).

In the illustrated example, in one pixel PX, four regions partitioned by the pixel electrode PE and the common electrode CE are mainly formed as openings or transmissive portions that contribute to display. In this example, the initial alignment direction of the liquid crystal molecules LM is a direction substantially parallel to the second direction Y. The first alignment film AL1 is disposed on the surface of the array substrate AR that faces the counter substrate CT, and extends over substantially the entire active area ACT. The first alignment film AL1 covers the pixel electrode PE and is also disposed on the second interlayer insulating film 13. Such a first alignment film AL1 is formed of a material exhibiting horizontal alignment. The array substrate AR may further include a first main common electrode and a first sub-common electrode as part of the common electrode.

FIG. 10 is a schematic diagram of an electrode structure of an 8-division oblique electric field mode liquid crystal cell. In this way, a wider viewing angle can be realized by dividing one pixel into eight.

Next, the operation of the liquid crystal display panel having the above configuration will be described. When no voltage is applied to the liquid crystal layer, that is, when there is no electric field (OFF) when no electric field is formed between the pixel electrode PE and the common electrode CE, as shown by the broken line in FIG. The liquid crystal molecules LM of LQ are aligned such that the major axis thereof faces the first alignment processing direction PD1 of the first alignment film AL1 and the second alignment processing direction PD2 of the second alignment film AL2. Such OFF time corresponds to the initial alignment state, and the alignment direction of the liquid crystal molecules LM at the OFF time corresponds to the initial alignment direction. Strictly speaking, the liquid crystal molecules LM are not always aligned parallel to the XY plane, and are often pretilted. For this reason, the strict initial alignment direction of the liquid crystal molecules LM is a direction obtained by orthogonally projecting the alignment direction of the liquid crystal molecules LM in the OFF state on the XY plane.

The first alignment treatment direction PD1 and the second alignment treatment direction PD2 are both substantially parallel to the second direction Y. At the OFF time, the liquid crystal molecules LM are initially aligned so that the major axis thereof is directed in a direction substantially parallel to the second direction Y, as indicated by a broken line in FIG. That is, the initial alignment direction of the liquid crystal molecules LM is parallel to the second direction Y (or 0 ° with respect to the second direction Y).

As in the illustrated example, when the first alignment treatment direction PD1 and the second alignment treatment direction PD2 are parallel and in the same direction, the liquid crystal molecules LM in the cross section of the liquid crystal layer LQ are substantially horizontal in the vicinity of the intermediate portion of the liquid crystal layer LQ. Alignment is performed with a pretilt angle of approximately zero, and alignment is performed with a pretilt angle that is symmetrical in the vicinity of the first alignment film AL1 and the vicinity of the second alignment film AL2 (spray alignment). Thus, in the state in which the liquid crystal molecules LM are splay aligned, the liquid crystal molecules LM in the vicinity of the first alignment film AL1 and the liquid crystal molecules LM in the vicinity of the second alignment film AL2 in the direction inclined from the normal direction of the substrate Is optically compensated. Therefore, when the first alignment processing direction PD1 and the second alignment processing direction PD2 are parallel to each other and in the same direction, light leakage is small in the case of black display, and a high contrast ratio can be realized. It becomes possible to improve the quality. When the first alignment treatment direction PD1 and the second alignment treatment direction PD2 are parallel and opposite to each other, the liquid crystal molecules LM are in the vicinity of the first alignment film AL1, in the second alignment film AL2 in the cross section of the liquid crystal layer LQ. And in the middle part of the liquid crystal layer LQ with a substantially uniform pretilt angle (homogeneous alignment). Part of the backlight light from the backlight 4 passes through the first polarizing plate PL1 and enters the liquid crystal display panel LPN. The light incident on the liquid crystal display panel LPN is linearly polarized light orthogonal to the first polarization axis AX1 of the first polarizing plate PL1. Such a polarization state of linearly polarized light hardly changes when it passes through the liquid crystal display panel LPN in the OFF state. Therefore, the linearly polarized light transmitted through the liquid crystal display panel LPN is absorbed by the second polarizing plate PL2 having a crossed Nicol positional relationship with the first polarizing plate PL1 (black display).

On the other hand, in a state where a voltage is applied to the liquid crystal layer LQ, that is, in a state where a potential difference is formed between the pixel electrode PE and the common electrode CE (when ON), the substrate is interposed between the pixel electrode PE and the common electrode CE. A horizontal electric field (or an oblique electric field) substantially parallel to the line is formed. The liquid crystal molecules LM are affected by the electric field and rotate in a plane whose major axis is substantially parallel to the XY plane as indicated by the solid line in the figure.

In the example shown in FIG. 9, the liquid crystal molecules LM in the lower half of the region between the pixel electrode PE and the main common electrode CAL rotate clockwise with respect to the second direction Y in the drawing. The liquid crystal molecules LM in the upper half region rotate counterclockwise with respect to the second direction Y and are oriented so as to face the upper left in the figure. Of the region between the pixel electrode PE and the main common electrode CAR, the liquid crystal molecules LM in the lower half region rotate counterclockwise with respect to the second direction Y and face the lower right in the drawing. The liquid crystal molecules LM in the upper half region are aligned so as to rotate clockwise with respect to the second direction Y and to face the upper right in the drawing. Thus, in each pixel PX, in a state where an electric field is formed between the pixel electrode PE and the common electrode CE, the alignment direction of the liquid crystal molecules LM is divided into a plurality of directions with the position overlapping the pixel electrode PE as a boundary. , A domain is formed in each orientation direction. That is, a plurality of domains are formed in one pixel PX.

At such ON time, linearly polarized light orthogonal to the first polarization axis AX1 of the first polarizing plate PL1 is incident on the liquid crystal display panel LPN, and the polarization state is the alignment of the liquid crystal molecules LM when passing through the liquid crystal layer LQ. It changes according to the state. At such ON time, at least part of the light that has passed through the liquid crystal layer LQ is transmitted through the second polarizing plate PL2 (white display). According to such a structure, since four domains can be formed in one pixel, viewing angles in the four directions can be optically compensated, and a wide viewing angle can be achieved. Therefore, it is possible to provide a liquid crystal display device with high display quality, which can realize display with high transmittance without gradation inversion. Further, by setting the area of the opening portion to be substantially the same for each of the four regions partitioned by the pixel electrode PE and the common electrode CE within one pixel, the transmittance of each region becomes substantially equal, The light transmitted through the part optically compensates for each other, and a uniform display can be realized over a wide viewing angle range.

(Fishbone electrode)
FIG. 12 shows the fishbone electrode structure shown in FIG. A liquid crystal layer is sealed between two glass substrates bonded to each other with a predetermined cell gap. Transparent electrodes made of ITO are formed on the opposing surfaces of the two opposing substrates. A glass substrate having a thickness of about 0.7 mm is used, and a common electrode is used as the counter substrate. The transparent electrode is provided with a slit portion 512c from which a part of the electrode material (ITO) is removed. A slit portion 512c having a cross shape connecting the midpoints of the opposing sides of the rectangular cell and having a width of about 3 to 5 μm functions as an alignment regulating structure, and extends from the slit portion 512c in an oblique 45 ° direction and has a width of 5 μm. A plurality of 512c are formed with a pitch of 8 μm, and these function as an auxiliary orientation control factor that suppresses disturbance in the azimuth direction during tilting. The width of the display pixel electrode is 3 μm. While the pixel trunk electrode 512a and the pixel branch electrode 512b have an angle of 45 degrees, the branch electrodes extend in four directions that differ by 90 degrees with the center of the pixel as the center of symmetry. The liquid crystal molecules are tilted when a voltage is applied, but tilted so that the orientation of the tilted alignment coincides with these four directions. Therefore, a four-divided domain is formed in one pixel to increase the display viewing angle. Make it wide.

Hereinafter, the present invention will be described in more detail with reference to examples. However, the present invention is not limited to these examples. Moreover, each of the evaluation characteristics in each Example and Comparative Example means the following symbols and contents.

V90: The light transmittance [%] (T100) when the applied voltage is zero and the light transmittance [%] (T0) when the applied voltage is zero as the total change amount of the light transmittance. Applied voltage [V] when the light transmittance of the change amount is 90%

Examples 1 to 9 and Comparative Example 1
(Adjustment of polymerizable liquid crystal composition)
A composition (Δn0.102, viscosity η16.8, Δε-3.8) represented by the following (LCN-1) was prepared as an N-type liquid crystal composition.

The N-type liquid crystal composition (LCN-1) was heated to 60 ° C., and the solid polymerizable compound (V1-1-1) was mixed and dissolved according to the formulation shown in Table 1.

It was confirmed with a polarizing microscope that the polymerizable compound (V1-1-1) was uniformly dissolved at room temperature to show a nematic liquid crystal phase. Various compounds (L1 to L4, Irgacure 651) were mixed with this solution in accordance with the composition shown in Table 1 to prepare a polymerizable liquid crystal composition. Table 1 shows the composition of the adjusted polymerizable liquid crystal composition.

(Creation of liquid crystal display elements and evaluation of electro-optical characteristics)
In order to obtain uniaxial alignment (homogeneous alignment) of the liquid crystal, the rubbing alignment treatment was performed so that the pretilt angle was 3 degrees on the vertical alignment film coated with the polyimide vertical alignment film having a cell gap of 3.6 μm. The two opposing substrate rubbing treatments were arranged so that the directions were opposite (anti-parallel orientation). The obtained polymerizable liquid crystal composition was injected into the cell by a vacuum injection method, and after injection, the injection port was sealed with a sealing agent 3026B (manufactured by Three Bond Co., Ltd.). A liquid crystal display device was produced by changing the irradiation time of 15 to 100 seconds of ultraviolet rays having an irradiation intensity of 20 mW / cm ² using a light source of an ultraviolet LED having a wavelength of 365 nm.

(Measurement of electro-optical characteristics)
By applying a voltage to the cell of the obtained liquid crystal display element and arranging the rubbing direction at 45 degrees with respect to one of the two polarization axes of the crossed Nicol polarizing plate so that the bright field becomes the brightest, using a polarizing microscope The liquid crystal alignment state of the cell was observed. It was confirmed that the state in which no voltage was applied was normally black in a substantially vertical alignment state in the dark field. It was confirmed that when the voltage was gradually increased, the brightness of the slit portion was increased by changing the tilted orientation so that the tilted orientation was aligned from the vertical orientation to the rubbing direction.

A voltage-transmittance characteristic and response time were measured by applying a rectangular wave of 60 Hz. Each characteristic is summarized in Table 1 with T100 as the maximum transmittance, V90 as the driving voltage, and Toff as the fall response time.

(Evaluation of display unevenness)
Display unevenness evaluation was performed by placing the liquid crystal display element obtained between two orthogonal polarizing plates and visually confirming the backlight as a light source according to the following criteria.
A: Good, no unevenness observed B: Somewhat good, some unevenness observed C: Poor, many unevenness observed Evaluation results are shown in the following table.

The liquid crystal compositions used in the above examples and comparative examples have the following polymerizable monomers and initiators.

DESCRIPTION OF SYMBOLS 1 ... Polarizing plate, 2 ... First transparent insulating substrate, 3 ... Electrode layer, 4 ... Alignment film, 4a ... Alignment direction, 5 liquid crystal layer, 5a ... Liquid crystal molecule when no voltage is applied, 5b ... Liquid crystal when voltage is applied Molecule, 6 ... color filter, 7 ... second transparent insulating substrate, 8 ... polarizing plate, 9 ... continuous or discontinuous polymer network, 10 ... liquid crystal display element, 11 ... gate electrode, 12 ... gate insulating layer, 13 ... Semiconductor layer, 14 ... protective layer, 15 ... ohmic contact layer, 16 ... drain electrode, 17 ... source electrode, 18 ... insulating protective layer, 21 ... pixel electrode, 22 ... common electrode, 23 ... storage capacitor, 24 ... gate wiring, 25 ... Data wiring, 26 ... Drain electrode, 27 ... Source electrode, 28 ... Gate electrode, 29 ... Common line, 100 ... Polarizing plate, 110 ... Gate electrode, 120 ... Gate insulating layer, 130 ... Semiconductor layer, 140 ... Preservation Layer, 160 ... drain electrode, 190b ... organic insulating film, 200 ... first substrate, 210 ... pixel electrode, 220 ... storage capacitor, 230 ... drain electrode, 240 ... data wiring, 250 ... gate wiring, 260 ... source electrode, 270 ... Gate electrode, 300 ... Thin film transistor layer, 400 ... Alignment film, 500 ... Liquid crystal layer, 510 ... Liquid crystal display device, 512 ... Pixel electrode, 512a ... Pixel trunk electrode, 512b ... Pixel branch electrode, 512c ... Pixel slit, 516 ... scanning wiring, 517 ... signal wiring, 600 ... common electrode, 700 ... color filter, 800 ... second substrate, 900 ... polarizing plate, 1000 ... liquid crystal display element, 1400 ... transparent electrode (layer), PX ... pixel, PE ... Pixel electrode, PA ... Main pixel electrode, PB ... Sub-pixel electrode, CE ... Common electrode, CA ... Main common electrode, CAL ... Left side Common electrode, CAR ... right main common electrode, CB ... sub-common electrode, CBU ... upper sub common electrode, CBB ... lower sub-common electrode

Claims

Radical polymerizable monomer component (A), liquid crystal material (B), and the following structural formula (1)

(In the structural formula (1), Ar represents a divalent aromatic hydrocarbon group or a halogen atom-containing aromatic hydrocarbon group, and A represents a divalent aromatic hydrocarbon group or a divalent cyclic aliphatic hydrocarbon. Group, a divalent condensed polycyclic structure site, a structural site in which a hydrogen atom in these structures is substituted with a halogen atom, or the divalent cyclic aliphatic hydrocarbon group or the divalent condensed polycyclic structure site Arbitrary —CH 2 — represents a structural moiety having a structure in which an arbitrary —CH 2 — structure is substituted with an oxygen atom, the divalent aromatic hydrocarbon group or the divalent condensed polycyclic structural moiety. And Z represents a single bond, a linear or branched alkyl group having 1 to 12 carbon atoms, or a linear chain having 1 to 12 carbon atoms. Or a branched alkylene group, the straight chain or branched alkyle -CH group 2 - or nonadjacent two or more -CH 2 - are each independently -O -, - S -, - CO -, - COO -, - OCO -, - CS-O-, —O—CS—, —CO—S—, —S—CO—, —O—CO—O—, —OCF 2 —, —CF 2 O—, —CH═CH—COO—, —OCO—CH═ Represents a divalent organic group having a structure substituted by CH—, —CH═CH—, —CF═CF— or —C≡C—, wherein R 1 is straight or branched having 1 to 8 carbon atoms Represents an alkyl group or a radical polymerizable functional group, and each R 2 independently represents a hydrogen atom, a linear or branched alkyl group having 1 to 8 carbon atoms, or a linear or branched group having 1 to 8 carbon atoms. An alkoxy group or the following structural formula (2)

(In Structural Formula (2), Z has the same meaning as described above, and A2 represents a monovalent aromatic hydrocarbon group, a monovalent cyclic aliphatic hydrocarbon group, a monovalent condensed polycyclic structure site, or Represents a structural site in which a hydrogen atom in these structures is substituted with a halogen atom.), And n represents an integer of 0 to 3. When a plurality of A and Z are present in the structural formulas (1) and (2), the plurality of A and Z may be the same or different. A polymerizable liquid crystal composition comprising a compound (C) represented by formula (I) as an essential component.
In the structural formula (1), the structural portion represented by A is represented by the following structural formula.

The polymerizable liquid crystal composition according to claim 1, wherein the polymerizable liquid crystal composition is a structural moiety selected from the group consisting of:
The polymerizable liquid crystal composition according to claim 1, wherein the structural moiety represented by A in the structural formula (1) has a mesogenic structure.
The polymerizable liquid crystal composition according to claim 1, wherein the compound (C) represented by the structural formula (1) has a ClogP value of 5 to 10.
The polymerizable liquid crystal composition according to claim 1, wherein the radical polymerizable monomer component (A) is contained in the polymerizable liquid crystal composition in a range of 0.5 mass% to 20 mass%.
2. The polymerizable liquid crystal composition according to claim 1, wherein the radical polymerizable monomer component (A) has a mesogenic structure.
The radical polymerizable monomer component (A) is represented by the following general formula (P1)

(In the formula, Z p11 is a fluorine atom, a cyano group, a hydrogen atom, an alkyl group having 1 to 15 carbon atoms in which a hydrogen atom may be substituted with a halogen atom, or a hydrogen atom in which a hydrogen atom is substituted with a halogen atom) A suitable alkoxy group having 1 to 15 carbon atoms, an alkenyl group having 1 to 15 carbon atoms in which a hydrogen atom may be substituted with a halogen atom, or 1 to carbon atoms in which a hydrogen atom may be substituted with a halogen atom 15 alkenyloxy groups or -Sp p12 -R p12 ,
R p11 and R p12 each independently represent the following formulas (RP11-1) to (RP11-4)

(Wherein, * represents a bonding point), and in the formulas (RP11-1) to (RP11-4), R P111 to R P112 are independently of each other a hydrogen atom or carbon atom number. 1 to 5 alkyl groups, t M11 represents 0, 1 or 2;
Sp p11 and Sp p12 are each independently a single bond, a linear or branched alkylene group having 1 to 12 carbon atoms, or a carbon atom of this linear or branched alkylene structure is not adjacent to an oxygen atom. Represents a structural moiety having a chemical structure substituted with an oxygen atom or a carbonyl group under conditions,
L p11 and L p12 each independently represent a single bond, —O—, —S—, —CH 2 —, —OCH 2 —, —CH 2 O—, —CO—, —C 2 H 4 —, — COO—, —OCO—, —OCOOCH 2 —, —CH 2 OCOO—, —OCH 2 CH 2 O—, —CO—NR P113 —, —NR P113 —CO—, —SCH 2 —, —CH 2 S— , -CH = CR P113 -COO -, - CH = CR P113 -OCO -, - COO-CR P113 = CH -, - OCO-CR aP113 = CH -, - COO-CR P113 = CH-COO -, - COO —CR P113 ═CH —OCO—, —OCO—CR P113 ═CH — COO— , —OCO—CR P113 ═CH —OCO—, — (CH 2 ) tm12 —C (═O) —O—, — (CH 2) m12 -O- (C = O) - , - O- (C = O) - (CH 2) tm12 -, - (C = O) -O- (CH 2) tm12 -, - CH = CH -, - CF═CF—, —CF═CH—, —CH═CF—, —CF 2 —, —CF 2 O—, —OCF 2 —, —CF 2 CH 2 —, —CH 2 CF 2 —, —CF 2 CF 2 —, —C≡C—, —N═N—, —CH═N— , or —C═N—N═C— (wherein R P113 each independently represents a hydrogen atom or 1 to 4 in which tm12 represents an integer of 1 to 4).
M p11 , M p12 and M p13 are each independently 1,4-phenylene group, 1,3-phenylene group, 1,2-phenylene group, 1,4-cyclohexylene group, 1,3-cyclohexylene group, 1,2-cyclohexylene group, 1,4-cyclohexenylene group, 1,3-cyclohexenylene group, 1,2-cyclohexenylene 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, naphthalene-1,4-diyl group, indane-2,5-diyl group, fluorene- 2,6-diyl group, fluorene-1,4-diyl group, phenanthrene-2,7-diyl group, anthracene-2,6-diyl group, anthracene-1,4-diyl group, 1, Represents a 2,3,4-tetrahydronaphthalene-2,6-diyl group or a 1,3-dioxane-2,5-diyl group,
M p11 , M p12 and M p13 are each independently unsubstituted or an alkyl group having 1 to 12 carbon atoms, a halogenated alkyl 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, a cyano group, a nitro group or —Sp p11 —R p11 may be substituted with the same meaning, mp12 represents 1 or 2, and mp13 to mp14 each independently represent 0, 1, 2 or 3, mp11 and mp15 represents an 1, 2 or 3 independently, they when Z pi 1 there are a plurality of independently identical or different And when there are a plurality of R p11 , they may be the same or different, and when there are a plurality of R p12 , they may be the same or different. And when there are a plurality of Sp p11 , they may be the same or different, and when there are a plurality of Sp p12 , they may be the same or different, When a plurality of L p11 are present, they may be the same or different, and when a plurality of L p12 are present, they may be the same or different, and a plurality of M p12 are present. In some cases, they may be the same or different. When a plurality of Mp13 are present, they may be the same or different. The polymerizable liquid crystal composition according to claim 4, which is represented by:
The radical polymerizable monomer component (A) is represented by the following general formula (V)

(Wherein X 1 and X 2 each independently represent a hydrogen atom or a methyl group, and Sp 1 and Sp 2 each independently represent a single bond, an alkylene group having 1 to 12 carbon atoms or —O— (CH 2 ) s — (wherein s represents an integer of 1 to 11 and an oxygen atom is bonded to an aromatic ring), U represents a linear or branched group having 2 to 20 carbon atoms Represents a polyvalent aliphatic hydrocarbon group or a polyvalent cyclic substituent having 5 to 30 carbon atoms, and the polyvalent aliphatic hydrocarbon group may be substituted with an oxygen atom within a range in which the oxygen atoms are not adjacent to each other. , An alkyl group having 5 to 20 carbon atoms (the alkylene group in the group may be substituted with an oxygen atom within the range in which the oxygen atom is not adjacent) or a cyclic substituent, and k is 1 Represents an integer of up to 5. All 1,4-phenylene in the formula Is any hydrogen atom -CH 3, -OCH 3, fluorine atom, or may be substituted by a cyano group.)
Or the following general formula (VI)

(Wherein X 3 represents a hydrogen atom or a methyl group, Sp 3 represents a single bond, an alkylene group having 1 to 12 carbon atoms, or —O— (CH 2 ) t — (wherein t is 2 to Represents an integer of 11 and an oxygen atom is bonded to an aromatic ring), and V is a linear or branched alkylene group having 2 to 20 carbon atoms or a polyvalent having 5 to 30 carbon atoms. A cyclic substituent, a structural site in which an oxygen atom in a linear or branched alkylene structure having 2 to 20 carbon atoms is not adjacent to each other, and these chemical structures are the carbons constituting the structure. A hydrogen atom on the atom is substituted by an alkyl group having 5 to 20 carbon atoms (the alkylene group in the group may be substituted by an oxygen atom within a range not adjacent to the oxygen atom) or a cyclic substituent; W may be a hydrogen atom or a halogen atom. Represents an alkyl group having 1 to 15 carbon atoms. In addition, all 1,4-phenylene group in the formula, any hydrogen atom is -CH 3, -OCH 3, substituted by fluorine atoms, or a cyano group May be.)
The polymerizable liquid crystal composition according to claim 1, which is represented by:
The polymerizable liquid crystal composition according to claim 8, wherein the radically polymerizable monomer component (A) uses one or more compounds in which Sp 1 and Sp 2 in the general formula (V) are the same.
The liquid crystal material (B) is selected from the group consisting of compounds represented by the following general formulas (N-1), (N-2), (N-3) and (N-4), and has a dielectric constant One or more compounds having negative anisotropy of

(In the formula, R N11 , R N12 , R N21 , R N22 , R N31 , R N32 , R N41 and R N42 are each independently an alkyl group having 1 to 8 carbon atoms, or a group having 2 to 8 carbon atoms. One or two or more non-adjacent —CH 2 — in the alkyl chain are each independently —CH═CH—, —C≡C—, —O—, —CO—, —COO— or —OCO. A structural portion having a chemical structure substituted by —, an alkyl group having 1 to 8 carbon atoms, or one or non-adjacent two or more —CH 2 — in an alkyl chain having 2 to 8 carbon atoms. A structural moiety having a chemical structure each independently substituted by —CH═CH—, —C≡C—, —O—, —CO—, —COO— or —OCO—,
A N11 , A N12 , A N21 , A N22 , A N31 , A N32 , A N41 and A N42 are each independently (a) a 1,4-cyclohexylene group,
(B) a divalent organic group having a structure in which one —CH 2 — existing in a 1,4-cyclohexylene structure or two or more non-adjacent —CH 2 — is replaced by —O— ,
(C) 1,4-phenylene group,
(D) a divalent organic group having a structure in which one —CH═ present in a 1,4-phenylene structure or two or more non-adjacent —CH═ are replaced by —N═;
(E) Naphthalene-2,6-diyl group, 1,2,3,4-tetrahydronaphthalene-2,6-diyl group or decahydronaphthalene-2,6-diyl group (f) Naphthalene-2,6-diyl A structure in which one —CH═ present in a 1,2,3,4-tetrahydronaphthalene-2,6-diyl structure or two or more non-adjacent —CH═ are replaced by —N═ And (g) a group selected from the group consisting of 1,4-cyclohexenylene group,
The group (a), group (b), group (c), group (d), group (e), group (f), and group (g) are each independently a cyano group, a fluorine atom or chlorine. May be substituted with atoms,
Z N11 , Z N12 , Z N21 , Z N22 , Z N31 , Z N32 , Z N41 and Z N42 are each independently a single bond, —CH 2 CH 2 —, — (CH 2 ) 4 —, —OCH 2 —. , —CH 2 O—, —COO—, —OCO—, —OCF 2 —, —CF 2 O—, —CH═N—N═CH—, —CH═CH—, —CF═CF— or —C Represents ≡C-
XN21 represents a hydrogen atom or a fluorine atom,
T N31 represents —CH 2 — or an oxygen atom,
X N41 represents an oxygen atom, a nitrogen atom, or —CH 2 —,
Y N41 represents a single bond or —CH 2 —;
n N11 , n N12 , n N21 , n N22 , n N31 , n N32 , n N41 , and n N42 each independently represent an integer of 0 to 3,
n N11 + n N12 , n N21 + n N22 and n N31 + n N32 are each independently 1, 2 or 3, and A N11 , A N12 , A N21 , A N22 , A N31 , A N32 , Z N11 , Z N12 , Z N21 , Z N22 , Z N31 , and Z N32 , they may be the same or different,
n N41 + n N42 represents an integer of 0 to 3, but when there are a plurality of A 41 and A N42 , Z N41 and Z N42 , they may be the same or different. )
A compound represented by the general formula (L) and having a dielectric anisotropy Δε in the range of −2 to 2

(Wherein R L1 and R L2 are each independently an alkyl group having 1 to 8 carbon atoms, or one —CH 2 — present in an alkyl chain having 2 to 8 carbon atoms, or not adjacent to each other) An organic group having a chemical structure in which two or more —CH 2 — are each independently substituted by —CH═CH—, —C≡C—, —O—, —CO—, —COO— or —OCO—. Represents
n L1 represents 0, 1, 2 or 3,
A L1 , A L2 and A L3 are each independently (a) a 1,4-cyclohexylene group,
(B) 1,4-cyclohexylene structure present in one -CH 2 - or nonadjacent two or more -CH 2 - 2 divalent organic having the chemical structure which is replaced to the -O- Group,
(C) 1,4-phenylene group,
(D) a divalent organic group having a chemical structure in which one —CH═ present in a 1,4-phenylene structure or two or more non-adjacent —CH═ are replaced by —N═;
(E) naphthalene-2,6-diyl group, 1,2,3,4-tetrahydronaphthalene-2,6-diyl group or decahydronaphthalene-2,6-diyl group, and (f) naphthalene-2,6 -One -CH = or two or more non-adjacent -CH = present in a diyl structure or 1,2,3,4-tetrahydronaphthalene-2,6-diyl structure is replaced by -N = Represents a group selected from the group consisting of divalent organic groups having the above structure, the group (a), the group (b), the group (c), the group (d), the group (e), and the group (f ) May be each independently substituted with a cyano group, a fluorine atom or a chlorine atom,
Z L1 and Z L2 are each independently a single bond, —CH 2 CH 2 —, — (CH 2 ) 4 —, —OCH 2 —, —CH 2 O—, —COO—, —OCO—, —OCF 2 -, -CF 2 O-, -CH = NN-CH-, -CH = CH-, -CF = CF- or -C≡C-
When n L1 is 2 or 3, and a plurality of A L2 are present, they may be the same or different, and when n L1 is 2 or 3, and a plurality of Z L2 are present, 2. The polymerizable liquid crystal composition according to claim 1, wherein at least one of these may be the same or different.
The liquid crystal material (B) is a compound represented by the following general formula (J), and one or more compounds having a positive dielectric anisotropy;

(Wherein R J1 represents an alkyl group having 1 to 8 carbon atoms, or one or two or more non-adjacent —CH 2 — in an alkyl chain having 2 to 8 carbon atoms, each independently — A structural moiety having a chemical structure substituted by CH═CH—, —C≡C—, —O—, —CO—, —COO— or —OCO—,
n J1 represents 0, 1, 2, 3 or 4;
A J1 , A J2 and A J3 are each independently
(A) 1,4-cyclohexylene group,
(B) a divalent organic compound having a chemical structure in which one —CH 2 — present in a 1,4-cyclohexylene structure or two or more non-adjacent —CH 2 — are replaced by —O— Group,
(C) 1,4-phenylene group,
(D) a divalent organic group having a chemical structure in which one —CH═ existing in a 1,4-phenylene structure or two or more non-adjacent —CH═ are replaced by —N═;
(E) naphthalene-2,6-diyl group, 1,2,3,4-tetrahydronaphthalene-2,6-diyl group or decahydronaphthalene-2,6-diyl group, and (f) naphthalene-2,6 -One -CH = or two or more non-adjacent -CH = present in a diyl structure or 1,2,3,4-tetrahydronaphthalene-2,6-diyl structure is replaced by -N = Represents a group selected from the group consisting of divalent organic groups having the above structure, the group (a), the group (b), the group (c), the group (d), the group (e), and the group (f ) May each independently be substituted with a cyano group, a fluorine atom, a chlorine atom, a methyl group, a trifluoromethyl group or a trifluoromethoxy group,
Z J1 and Z J2 are each independently a single bond, —CH 2 CH 2 —, — (CH 2 ) 4 —, —OCH 2 —, —CH 2 O—, —OCF 2 —, —CF 2 O—, Represents —COO—, —OCO— or —C≡C—,
When n J1 is 2, 3 or 4 and a plurality of A J2 are present, they may be the same or different, and n J1 is 2, 3 or 4 and a plurality of Z J1 is present. If they are the same or different,
X J1 represents a hydrogen atom, a fluorine atom, a chlorine atom, a cyano group, a trifluoromethyl group, a fluoromethoxy group, a difluoromethoxy group, a trifluoromethoxy group, or a 2,2,2-trifluoroethyl group. )
A compound represented by the general formula (L) and having a dielectric anisotropy Δε in the range of −2 to 2

(Wherein R L1 and R L2 are each independently an alkyl group having 1 to 8 carbon atoms, or one or two or more non-adjacent —CH 2 — groups in an alkyl chain having 2 to 8 carbon atoms. Are structural sites having a chemical structure each independently substituted by —CH═CH—, —C≡C—, —O—, —CO—, —COO— or —OCO—,
n L1 represents 0, 1, 2 or 3,
A L1 , A L2 and A L3 are each independently (a) a 1,4-cyclohexylene group,
(B) a divalent organic compound having a chemical structure in which one —CH 2 — present in a 1,4-cyclohexylene structure or two or more non-adjacent —CH 2 — are replaced by —O— Group,
(C) 1,4-phenylene group (d) Chemical structure in which one —CH═ existing in the 1,4-phenylene structure or two or more non-adjacent —CH═ are replaced by —N═ A divalent organic group having
(E) Naphthalene-2,6-diyl group, 1,2,3,4-tetrahydronaphthalene-2,6-diyl group or decahydronaphthalene-2,6-diyl group (f) Naphthalene-2,6-diyl A structure in which one —CH═ present in a 1,2,3,4-tetrahydronaphthalene-2,6-diyl structure or two or more non-adjacent —CH═ are replaced by —N═ Represents a group selected from the group consisting of divalent organic groups having the above-mentioned groups (a), (b), (c), (d), (e), and (f): Each independently may be substituted with a cyano group, a fluorine atom or a chlorine atom,
Z L1 and Z L2 are each independently a single bond, —CH 2 CH 2 —, — (CH 2 ) 4 —, —OCH 2 —, —CH 2 O—, —COO—, —OCO—, —OCF 2 -, -CF 2 O-, -CH = NN-CH-, -CH = CH-, -CF = CF- or -C≡C-
When n L1 is 2 or 3, and a plurality of A L2 are present, they may be the same or different, and when n L1 is 2 or 3, and a plurality of Z L2 are present, 2. The polymerizable liquid crystal composition according to claim 1, wherein the polymerizable liquid crystal composition comprises at least one of (which may be the same or different).
A liquid crystal display element in which a polymer of a radical polymerizable monomer component (A) and a liquid crystal material (B) are sandwiched between two transparent substrates each having an electrode on at least one side, wherein the liquid crystal material (B 12. A liquid crystal display element, wherein the polymer is a polymer of the polymerizable liquid crystal composition according to claim 1.
The polymer of the radical polymerizable monomer component (A) is present in the liquid crystal material (B) by forming a polymer network, and the alignment for aligning the liquid crystal composition on the transparent substrate The liquid crystal display element of Claim 12 which has a layer.
The liquid crystal display according to claim 12, wherein the polymer network has uniaxial refractive index anisotropy, and the optical axis direction or the easy alignment axis direction of the polymer network and the easy alignment direction of the liquid crystal material (B) are the same direction. element.
The liquid crystal display element according to claim 12, wherein the liquid crystal molecules constituting the liquid crystal material (B) with respect to the transparent substrate are formed so as to form a pretilt angle of 0.1 to 30 ° with respect to the normal direction of the substrate. .
The liquid crystal display element according to claim 12, wherein a polymer network layer having a thickness of 0.5% or more of the cell thickness is formed in the cell cross section.
The liquid crystal display element according to claim 12, wherein the cell structure of the liquid crystal display element is a VA mode, an IPS mode, an FFS mode, a VA-TN mode, a TN mode, or an ECB mode.
The polymerizable liquid crystal composition according to any one of claims 1 to 11 is sandwiched between two transparent substrates each having an electrode on at least one side, and the liquid crystal layer is kept at -50 ° C to 30 ° C for active energy. A method for producing a liquid crystal display element, comprising polymerizing by irradiating a line to form a polymer having a refractive index anisotropy or an orientation easy axis direction.
The polymerizable liquid crystal composition according to any one of claims 1 to 9 is sandwiched between two transparent substrates having electrodes on at least one side, and a pretilt angle before irradiation with energy rays is in the normal direction of the substrate. Polymerization is performed by irradiating energy rays while applying a voltage of 0.1 to 30 ° with respect to the liquid crystal composition to obtain a polymer having a refractive index anisotropy or an orientation easy axis direction. The manufacturing method of the liquid crystal display element of Claim 18.