TW201716548A - Nematic liquid-crystal composition and liquid-crystal display element including same - Google Patents

Abstract

The present invention addresses the problem of: providing a liquid-crystal composition which has a high refractive index anisotropy ([Delta]n), a low rotational viscosity ([gamma]1), and a large elasticity constant (K33) and further has a high voltage holding ratio (VHR) and a negative dielectric anisotropy ([Delta][epsilon]); and providing a liquid-crystal display element of excellent display quality, which includes the liquid-crystal composition and is prevented or inhibited from suffering display failures including dropping marks, image persistence, and display unevenness and which combines a low operating voltage, a high transmittance, and a high response speed. The liquid-crystal composition, which has negative dielectric anisotropy, has a value calculated by the following expression (I) in the range of 1-50: |[Delta][epsilon]|/P*100 expression (I) where |[Delta][epsilon]| is the absolute value of dielectric anisotropy and P ([mu]m) is the spiral pitch, and comprises one or more of compounds represented by general formula (np-1) and general formula (np-2). The liquid-crystal display element includes the liquid-crystal composition.

Description

Nematic liquid crystal composition and liquid crystal display element using same

The present invention relates to a nematic liquid crystal composition having a negative dielectric value (Δ ε ) which is useful as a liquid crystal display material and a liquid crystal display element using the same.

The liquid crystal display element is used for various household electrical appliances, measuring equipment, automobile panels, word processors, electronic notebooks, printers, computers, televisions, and the like represented by watches and clocks and electronic computers. Typical examples of the liquid crystal display method include TN (twisted nematic) type, STN (super twisted nematic) type, DS (dynamic light scattering) type, GH (guest master) type, and IPS (coplanar switching) type. , OCB (optical compensation birefringence) type, ECB (electrically controlled birefringence) type, VA (vertical alignment) type, CSH (color super vertical alignment) type or FLC (ferroelectric liquid crystal). Further, examples of the driving method include a static driving, a multiplex driving, a simple matrix method, and an active matrix (AM) method of driving by a TFT (Thin Film Transistor) or a TFD (Thin Film Diode).

Among these display modes, the IPS type, the ECB type, the VA type, or the CSH type have characteristics of a liquid crystal composition exhibiting a negative value using Δ ε . Among these, the VA type display system driven by AM is used for high-speed and display elements having a wide viewing angle such as a television.

For a nematic liquid crystal composition used for a display mode such as a VA type, a high-speed response corresponding to 3D to high definition is required. That is, the liquid crystal composition has a small rotational viscosity (γ 1) and a large elastic constant (K ₃₃ ), and it is important that the value of γ 1 / K ₃₃ is sufficiently small.

Further, it is necessary to set the Δn × d of the product of the refractive index anisotropy (Δn) and the cell gap (d) in combination with the cell gap for improving the response speed, and to Δn the liquid crystal material. Adjust within the appropriate range. Further, it is required to suppress γ 1 of the liquid crystal composition to be small.

Heretofore, the characteristics of the liquid crystal composition have been improved by various studies on compounds in which Δ ε is negative and whose absolute value is large.

As a liquid crystal material having a negative Δ ε , a liquid crystal compound (A) and (B) having a 2,3-difluorophenylene skeleton having the following (see Patent Document 1) is disclosed. The liquid crystal composition, but did not get a small enough γ 1 / K33.

In addition, by using a combination of a liquid crystal compound (N2) and a compound represented by the general formula (N3) as a compound in which Δ ε is substantially zero, the value of γ 1 /K33 can be made small (refer to Patent Document 2), but It is required to further improve the response speed.

(wherein Rp and Rq each independently represent an alkyl group having 1 to 10 carbon atoms, and ring J, ring F and ring K each independently represent trans-1,4-cyclohexylene or 1,4-phenylene base.)

Patent Document 3 discloses that a liquid crystal material having a large index represented by (Formula 1) is used to enhance the response speed of a homeotropic liquid crystal cell, but it is not sufficient.

Patent Document 4 discloses a liquid crystal composition using a biphenyl compound and a liquid crystal compound having a negative dielectric constant, but does not disclose a liquid crystal composition using a palmitic agent.

Patent Document 5 discloses a vertical alignment type liquid crystal display device using a palmitic agent, and Patent Document 6 discloses a vertical alignment type super-twisted liquid crystal display element and a method of manufacturing the same, but both of which do not take into consideration a low driving voltage. With high transmittance and high response speed.

As described above, various studies have been made to improve the characteristics of the liquid crystal composition. However, for a liquid crystal composition used for a liquid crystal television requiring high-speed response, both low driving voltage, high transmittance, and high response speed are unresolved. In addition, a liquid crystal display element having excellent display quality with low driving voltage, high transmittance, and high response speed has been sought for use in the case where there is no problem such as dripping marks, residual images, or display unevenness.

Patent Document 1: Japanese Patent Laid-Open No. 8-104869

Patent Document 2: WO2015/050035A1

Patent Document 3: Japanese Patent Laid-Open No. 2006-301643

Patent Document 4: JP-A-2015-91983

Patent Document 5: Japanese Patent Laid-Open No. 2009-229894

Patent Document 6: Japanese Patent No. 5229766

An object of the present invention is to provide a liquid crystal composition having a large refractive index anisotropy (Δn), a small rotational viscosity (γ1), a high voltage holding ratio (VHR), and an elastic constant ( K33) is large, has negative dielectric conductivity (Δ ε ), and seeks to display a liquid crystal composition without dripping marks, residual images, or display unevenness, display defects, dripping marks, residual images, or display unevenness. A liquid crystal display element which is excellent in display quality with low driving voltage, high transmittance, and high response speed.

The present inventors have diligently studied various liquid crystal compositions and various physical property values, and as a result, found that a liquid crystal composition having a negative dielectric value of 3 to 70 in the range obtained by the formula (I) can be used. The above problems are solved to complete the present invention.

That is, it has been found that a liquid crystal display element can be obtained by preparing a liquid crystal composition in such a manner that the value obtained by the formula (I) is in the range of 3 to 70, wherein the formula (I) is dielectric It consists of the absolute value of each guide (|△ ε |) and the pitch of the spiral (P: μm).

|△ε|/P×100 (I)

Further, it has been found that a liquid crystal display element using the PS mode, the PSA mode, the PSVA mode, the PS-IPS mode or the PS-FFS mode of the liquid crystal composition can be provided.

According to the present invention, it is possible to provide a liquid crystal composition having a large refractive index anisotropy (Δn), a small rotational viscosity (γ 1 ), a high voltage holding ratio (VHR), and a negative dielectric conductivity (Δ ε ). And providing a liquid crystal composition without dripping marks, residual images or display unevenness, display defects or dripping marks, image sticking or display unevenness, etc., suppressing display defects, taking into account low driving voltage and high transmittance and high response A liquid crystal display element with excellent display quality at speed.

The liquid crystal composition of the present invention is a liquid crystal composition having a negative dielectric conductivity, and is composed of a dielectric constant (|Δ ε |) and a helical pitch (P: μm) (I). The obtained value is in the range of 3 to 70, and contains one or more compounds represented by the formula (np01) and the formula (np02), |Δε|/P×100 (I)

(wherein R01, R02, R03, and R04 each independently represent an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, and 2 carbon atoms; The oxy group of ~I0, the hydrogen atom in the alkyl group may also be substituted by a fluorine atom, and n01 and n02 each independently represent 0 or 1.).

In order to obtain a liquid crystal display element having excellent display quality with low driving voltage, high transmittance, and high response speed, it is preferable to adjust the value obtained by the formula (I) to 3 to 70. range. The lower limit of the value obtained by the formula (I) is preferably 4, preferably 5, preferably 6, preferably 7, preferably 8, preferably 9, preferably 10, preferably 11 Preferably, it is preferably 12, preferably 13, preferably 14, preferably 15, preferably 16, preferably 17, preferably 18, preferably 19, preferably 20. The upper limit of the value obtained by the formula (I) is preferably 65, preferably 60, preferably 55, preferably 50, preferably 45, preferably 44, preferably 43, preferably 42. Preferably, 41, preferably 40, preferably 39, preferably 38, preferably 37, preferably 36, preferably 35, preferably 34, preferably 33, preferably 32 Preferably, it is 31, preferably 30.

In the liquid crystal composition of the present invention, the palmity agent for inducing a pitch may be a compound having an asymmetric carbon atom, preferably having one or two or more 1,4-phenylene groups (this) The molecular structure of one or two hydrogen atoms in the group may be substituted by fluorine, methyl or methoxy.

The liquid crystal composition of the present invention is preferably a negative △ ε of a nematic liquid crystal composition, and preferably a negative △ ε of palm nematic liquid crystal composition.

In the liquid crystal composition of the present invention, a palmitic agent for use in a TN mode or an STN mode can also be used as a palmar agent for inducing a pitch.

In order to improve or adjust the temperature dependence of the spacing, a plurality of palm chemicals may also be mixed.

As the palmity agent for inducing the pitch, a compound having an asymmetric atom may be used, or an axial chiral compound may be used, or these may be used in combination.

As the compound having an asymmetric atom, specifically, a compound represented by the formula (Ch-I) is preferred.

(In the general formula (Ch-I), R ¹⁰⁰ and R ¹⁰¹ each independently represent a hydrogen atom, -CN, -NO ₂ , a halogen atom, -OCN, -SCN, -SF ₅ , and 1 to 30 carbon atoms. a palmitic or non-capillary alkyl group, a polymerizable group or a palm group containing a ring structure, when n ¹¹ is 0, at least one of R ¹⁰⁰ and R ¹⁰¹ is a palmity alkyl group, and Z ¹⁰⁰ and Z ¹⁰¹ are each Independently denotes -O-, -S-, -CO-, -COO-, -OCO-, -O-COO-, -CO-N(R ¹⁰⁵ )-, -N(R ¹⁰⁵ )-CO-,- OCH ₂ -, -CH ₂ O-, -SCH ₂ -, -CH ₂ S-, -CF ₂ O-, -OCF ₂ -, -CF ₂ S-, -SCF ₂ -, -CH ₂ CH ₂ -, -CF ₂ CH ₂ -, -CH ₂ CF ₂ -, -CF ₂ CF ₂ -, -CH=CH-, -CF=CH-, -CH=CF-, -CF=CF-, -C≡C- , -CH=CH-COO-, -OCO-CH=CH- or a single bond, A ¹⁰⁰ and A ¹⁰¹ each independently represent: (a') trans-1,4-cyclohexylene (present in the group) One methylene or two or more methylene groups which are not adjacent may be substituted with an oxygen atom or a sulfur atom.), (b') 1,4-phenylene group (present in this group) One of -CH= or two or more non-contiguous -CH= may be substituted into a nitrogen atom.) or (c') 1,4-cyclohexenylene (cyclohexenylene), 1,4-bicyclo [ 2.2.2] Shen Xinji Decane-2,5-diyl, naphthalene-2,6-diyl, decahydronaphthalene-2,6-diyl and 1,2,3,4-tetrahydronaphthalene-2,6-diyl (present One methylene group or two or more methylene groups which are not adjacent thereto may be substituted with an oxygen atom or a sulfur atom, and one of these groups may be -CH= or not adjacent thereto. Two or more -CH= may be substituted into a nitrogen atom.) When A ¹⁰⁰ or A ¹⁰¹ has a plurality of cases, the same may or may be different, n ¹¹ represents 0 or 1, and n ¹¹ represents 0. When m ¹² represents 0 and m ¹¹ represents 0, 1, 2, 3, 4 or 5, and n ¹¹ represents 1, m ¹¹ and m ¹² each independently represent 0, 1, 2, 3, 4 or 5, D A divalent group represented by the following formulas (D1) to (D4) (wherein the formula (D1) to (D4) is bonded to Z ¹⁰¹ (or R ¹⁰⁰ ) or Z, respectively, at a portion to which a black dot is attached. ¹⁰¹ (or R ¹⁰⁰ ).).)

In the general formula (Ch-I), R ¹⁰⁰ and R ¹⁰¹ each independently represent a hydrogen atom, -CN, -NO ₂ , a halogen atom, -OCN, -SCN, -SF ₅ , and 1 to 30 carbon atoms. A sexual or non-capillary alkyl group, a polymeric group or a palm-based group containing a ring structure. When n ¹¹ is 0, at least one of R ¹⁰⁰ and R ¹⁰¹ is a palmity alkyl group.

When R ¹⁰⁰ or R ¹⁰¹ in the formula (Ch-I) is a palmitic or non-capillary alkyl group having 1 to 30 carbon atoms, one or more of the alkyl groups are not adjacent. The methylene group (-CH ₂ -) may also be -O-, -S-, -NH-, -N(CH ₃ )-, -CO-, in such a manner that the oxygen atom or the sulfur atom is not directly bonded to each other. -COO-, -OCO-, -OCO-O-, -S-CO-, -CO-S-, -CH=CH-, -CF ₂ -, -CF=CH-, -CH= CF-, - CF=CF- or C≡C-substituted, and one or two or more hydrogen atoms in the alkyl group may be substituted by a halogen atom or a cyano group. Further, the alkyl group may be a linear group, may be a branched group, or may be a group having a ring structure.

The alkyl group as a palmity is preferably a group represented by the following formula (Ra) to (Rk). In the general formula (Ra)~(Rk), an asterisk (*) indicates a palm atom of the palm. When R ¹⁰⁰ or R ^{101 is} the basis of this, at the left end, it is bonded to A ¹⁰⁰ (or D, Z ¹⁰¹ ) or A ¹⁰¹ (or D, Z ¹⁰⁰ ), respectively.

In the general formulae (Ra) to (Rk), R ¹⁰³ and R ¹⁰⁴ each independently represent a linear or branched alkyl group or a hydrogen atom having 1 to 12 carbon atoms. However, in the general formulae (Ra), (Rb), (Rd), (Re), (Rf), (Rg), (Ri), (Rj), R ¹⁰³ is a linear chain having 1 to 10 carbon atoms. A branched or branched alkyl group such that the carbon atom (where * is attached) to which R ¹⁰³ is bonded becomes an asymmetric atom. One or two or more methylene groups of the alkyl group may be -O-, -S-, -NH-, -N(CH ₃ )-, in such a manner that an oxygen atom or a sulfur atom is not directly bonded to each other. -CO-, -CO-O-, -O-CO-, -O-CO-O-, -S-CO-, -CO-S-, -O-SO ₂ -, -SO ₂ -O-, -CH=CH-, -C≡C-, cyclopropylene or -Si(CH ₃ ) ₂ -, and one or more hydrogen atoms of the alkyl group may also be halogen atoms (for example , fluorine atom, chlorine atom, bromine atom) or cyano group. Further, the alkyl group may have a polymerizable group. Examples of the polymerizable group include a vinyl group, an allyl group, and a (meth)acryl fluorenyl group.

As R ¹⁰³ in the general formula (Ra) to (Rj), a straight chain having 1 to 12 carbon atoms is preferably a methylene group or a hydrogen atom which is not substituted with another group or the like (that is, unsubstituted). a linear or branched alkyl group, more preferably an unsubstituted linear or branched alkyl group having 1 to 8 carbon atoms, more preferably an unsubstituted carbon atom number of 1 to 6 Chain alkyl.

R ¹⁰⁴ in the formula (Rd) or (Ri) is preferably a hydrogen atom or an unsubstituted linear or branched alkyl group having 1 to 5 carbon atoms, more preferably unsubstituted. The linear alkyl group having 1 to 3 carbon atoms is more preferably a hydrogen atom or a methyl group.

In the general formula (Ra) to (Rk), n ¹² is an integer of 0 to 20, preferably an integer of 0 to 10, more preferably an integer of 0 to 5, still more preferably 0.

In the general formula (Ra) to (Rk), n ¹³ is 0 or 1.

Further, in the formula (Rk), n ¹⁴ is an integer of 0 to 5.

In the general formulae (Ra) to (Rk), X ¹⁰¹ and X ¹⁰² are each independently a halogen atom (a fluorine atom, a chlorine atom, a bromine atom or an iodine atom), a cyano group or a phenyl group (one or two of the phenyl groups). Any of the above hydrogen atoms may be substituted by a halogen atom, a methyl group, a methoxy group, a trifluoromethyl group (-CF ₃ ) or a trifluoromethoxy group (-OCF ₃ ).), and a carbon number of 1 to 6 An alkyl group, an alkoxy group having 1 to 6 carbon atoms, a trifluoromethyl group or a trifluoromethoxy group. However, in the general formulae (Ra), (Rb), (Rc), (Rf), (Rg), (Rh), X ¹⁰¹ and R ¹⁰³ are groups different from each other such that the carbon bonded to X ¹⁰¹ The atom (with the position of *) becomes an asymmetric atom. Further, in the general formulae (Rc) and (Re), X ¹⁰¹ and X ¹⁰² are groups different from each other such that the carbon atom (position at which * is bonded) to which X ¹⁰¹ is bonded becomes an asymmetric atom.

X ¹⁰¹ and X ¹⁰² in the general formulae (Ra), (Rb), (Rc), (Rf), (Rg), (Rh), and (Rk) are preferably each independently a halogen atom or a phenyl group ( Any one or two or more hydrogen atoms of the phenyl group may be substituted by a halogen atom, a methyl group, a methoxy group, a trifluoromethyl group or a trifluoromethoxy group.), a methyl group, a methoxy group, or a trifluoro group. Methyl or trifluoromethoxy. Wherein, as X ¹⁰¹ and X ¹⁰² in the formulae (Ra), (Rb), (Rc), (Rf), (Rg), (Rh), more preferably each independently is a phenyl group (the phenyl group 1) Any one or two or more hydrogen atoms may be substituted by a halogen atom, a methyl group, a methoxy group, a trifluoromethyl group or a trifluoromethoxy group.) More preferably, it is an unsubstituted phenyl group. Further, as X ¹⁰¹ in the formula (Rk), a halogen atom, a cyano group, an alkyl group, an alkoxy group, a trifluoromethyl group or a trifluoromethoxy group is more preferable, and a halogen atom or a methyl group is more preferable. Trifluoromethyl, or trifluoromethoxy.

In the general formulae (Re) and (Rj), Q is a divalent hydrocarbon group. The divalent hydrocarbon group may be linear or branched, or may have a cyclic structure. Further, the number of carbon atoms of the divalent hydrocarbon group is preferably from 1 to 16, more preferably from 1 to 10, still more preferably from 1 to 6. The divalent hydrocarbon group is preferably a group in which a single bond is bonded to one of two oxygen atoms in the general formulae (Re) and (Rj) in one carbon atom. In this case, in the general formulae (Re) and (Rj), the two carbon atoms to which an asterisk is attached and the two oxygen atoms respectively bonded thereto and one carbon atom in Q form a 5-membered ring. Specifically, it may be mentioned that an unsubstituted or substituted one or two hydrogen atoms are substituted by a hydrocarbon group. A methyl group, a cyclopropylidene, a cyclobutylidene, a cyclopentylene group, a cyclohexylene group, etc. are more preferably a methylene group, an isopropylidene group or a cyclohexylene group.

The group represented by the general formula (Ra) to (Rk) is preferably a group represented by the formula (Ra) or the formula (Rf). The group represented by the formula (Ra) is preferably a group in which: n ¹² is an integer of 0 to 5, and X ¹⁰¹ is a phenyl group (one or two of the phenyl groups). Any of the above hydrogen atoms may be substituted by a halogen atom, a methyl group, a methoxy group, a trifluoromethyl group or a trifluoromethoxy group.), R ^{103 is} preferably an unsubstituted straight chain having 1 to 6 carbon atoms. Or a branched alkyl group, more preferably a group: n ¹² is an integer of 0 to 5, X ¹⁰¹ is an unsubstituted phenyl group, and R ^{103 is more} preferably an unsubstituted carbon atom number 1~ a linear or branched alkyl group of 6. The group represented by the formula (Rf) is preferably a group wherein, in the formula (Rf), n ¹² is an integer of 0 to 5, n ¹³ is 0 or 1, and X ¹⁰³ is a halogen atom or a methyl group. Or a trifluoromethyl group, and R ¹⁰³ is an unsubstituted linear alkyl group having 2 to 12 carbon atoms.

R ¹⁰⁰ or R ¹⁰¹ which is a compound represented by the formula (Ch-I) is preferably a formula (Ra-1) to (Ra-3) or a formula (Rf-1) to (Rf-3) ) the basis of the statement. When R ¹⁰⁰ or R ^{101 is} the basis of this, the left end is bonded to A ¹⁰⁰ (or D, Z ¹⁰¹ ) or A ¹⁰¹ (or D, Z ¹⁰⁰ ), respectively. Also, the asterisk indicates the carbon atom of the palm.

In the general formulae (Rf-1) to (Rf-3), n ¹³ represents 0 or 1. Further, in the general formulae (Ra-1) to (Ra-3) and (Rf-1) to (Rf-3), n represents an integer of 2 to 12. In the general formulae (Ra-1) to (Ra-3) and (Rf-1) to (Rf-3), n is preferably an integer of from 3 to 8, more preferably 4, 5 or 6.

When R ¹⁰⁰ or R ¹⁰¹ in the formula (Ch-I) is a polymerizable group, it is preferred that the polymerizable group be any of the following formulas (R-1) to (R-16). One represents the basis of the structure. The right end of the group represented by the formulas (R-1) to (R-14) and (R-16) and the left end of the group represented by the formula (R-15) are respectively bonded to the A ¹⁰⁰ (or D, Z ^101). ) or A ¹⁰¹ (or D, Z ¹⁰⁰ ).

These polymerizable groups are hardened by radical polymerization, radical addition polymerization, cationic polymerization or anionic polymerization. In particular, when ultraviolet polymerization is carried out as a polymerization method, it is preferably from the formula (R-1), the formula (R-2), the formula (R-4), the formula (R-5), and the formula (R-7). , a formula represented by the formula (R-11), the formula (R-13), the formula (R-15) or the formula (R-16), more preferably a formula (R-1) or a formula (R-2) Or a formula (R-7), a formula (R-11), a formula (R-13) or a formula (R-16), and more preferably a formula (R-1), a formula (R-2) Or the formula (R-16) represents the base.

When R ¹⁰⁰ or R ¹⁰¹ in the formula (Ch-I) is a group having a palm group of a ring structure, the ring structure of the group may be aromatic or may be aliphatic. Examples of the ring structure include a monocyclic structure, a condensed ring structure, or a spirocyclic ring structure, and may contain one or two or more hetero-atoms.

In the general formula (Ch-I), Z ¹⁰⁰ and Z ¹⁰¹ each independently represent -O-, -S-, -CO-, -COO-, -OCO-, -O-COO-, -CO-N (R ¹⁰⁵ )-, -N(R ¹⁰⁵ )-CO-, -OCH ₂ -, -CH ₂ O-, -SCH ₂ -, -CH ₂ S-, -CF ₂ O-, -OCF ₂ -, -CF ₂ S-, -SCF ₂ -, -CH ₂ CH ₂ -, -CF ₂ CH ₂ -, -CH ₂ CF ₂ -, -CF ₂ CF ₂ -, -CH=CH-, -CF=CH-, -CH =CF-, -CF=CF-, -C≡C-, -CH=CH-COO-, -OCO-CH=CH- or a single bond. Here, R ¹⁰⁵ represents a linear or branched alkyl group having 1 to 12 carbon atoms, preferably a linear or branched alkyl group having 1 to 6 carbon atoms, more preferably a carbon atom. A linear alkyl group of 1 to 3 atoms. When m ¹¹ is an integer of 2 or more, when a plurality of Z ¹⁰⁰ are present in one molecule, the same may or may not be the same. Similarly, when m ¹² is an integer of 2 or more and a plurality of Z ¹⁰¹ are present in one molecule, the same may or may not be the same. As the compound represented by the formula (Ch-I), Z ¹⁰⁰ and Z ^{101 are} preferably each independently -CF ₂ O-, -OCF ₂ -, -CF ₂ CF ₂ -, -CF=CF-, -COO -, -OCO-, -CH ₂ -CH ₂ -, -C≡C- or a single bond.

In the general formula (Ch-I), A ¹⁰⁰ and A ¹⁰¹ each independently represent the following (a') group, (b') group or (c') group. When m ¹¹ is an integer of 2 or more, when a plurality of A ¹⁰⁰ are present in one molecule, the same may or may not be the same. Similarly, when m ¹² is an integer of 2 or more, when a plurality of A ¹⁰¹ are present in one molecule, the same may or may not be the same.

(a') trans-1,4-cyclohexylene (one methylene group present in the group or two or more methylene groups not adjacent thereto may be substituted with an oxygen atom or a sulfur atom). .

(b') 1,4-phenylene (one -CH= present in the group or two or more -CH= not adjacent to each other may be substituted with a nitrogen atom).

(c') 1,4-cyclohexene, 1,4-bicyclo[2.2.2] octyl, decane-2,5-diyl, naphthalene-2,6-diyl, decalin -2,6-diyl and 1,2,3,4-tetrahydronaphthalene-2,6-diyl (one methylene group present in the group or two or more adjacent sub-groups) The group may be substituted with an oxygen atom or a sulfur atom, and one of the groups -CH= or two or more adjacent thereto may be substituted CH= can also be substituted into a nitrogen atom. ).

The (a') group, the (b') group and the (c') group may be unsubstituted, or one or more hydrogen atoms in the group may be a halogen atom, a cyano group or a nitro group. An alkyl group having 1 to 7 carbon atoms (one or two or more hydrogen atoms in the alkyl group may be substituted by a fluorine atom or a chlorine atom), and an alkoxy group having 1 to 7 carbon atoms (the alkane) One or two or more hydrogen atoms in the oxy group may be substituted by a fluorine atom or a chlorine atom.) An alkylcarbonyl group having 1 to 7 carbon atoms (one or more of the alkylcarbonyl groups) The hydrogen atom may be substituted by a fluorine atom or a chlorine atom.) or an alkoxycarbonyl group having 1 to 7 carbon atoms (one or two or more hydrogen atoms in the alkoxycarbonyl group may be a fluorine atom or a chlorine atom) Atom substitution.) Substitution.

As A ¹⁰⁰ and A ¹⁰¹ of the compound represented by the formula (Ch-I), the above (a') group or the above (b') group is preferred, and the unsubstituted trans-1,4- is more preferred. Extending cyclohexyl; unsubstituted 1,4-phenylene; one or more hydrogen atoms by fluorine atom, chlorine atom, cyano group, alkyl group having 1 to 4 carbon atoms, carbon number 1~ Alkoxy group of 4, an alkylcarbonyl group having 1 to 4 carbon atoms or a trans-1,4-cyclohexylene group substituted with an alkoxycarbonyl group having 1 to 4 carbon atoms or 1 or more hydrogen atoms by fluorine Atom, chlorine atom, cyano group, alkyl group having 1 to 4 carbon atoms, alkoxy group having 1 to 4 carbon atoms, alkylcarbonyl group having 1 to 4 carbon atoms or alkoxycarbonyl group having 1 to 4 carbon atoms a 1,4-phenylene group, more preferably an unsubstituted trans-1,4-cyclohexylene group or an unsubstituted 1,4-phenylene group, and more preferably an unsubstituted one , 4-phenylene.

In the formula (Ch-I), n ¹¹ represents 0 or 1.

When n ¹¹ is 0, m ¹² is 0, and m ¹¹ is 0, 1, 2, 3, 4 or 5. When n ¹¹ and m ¹² are 0, m ^{11 is} preferably 1, 2, 3 or 4, more preferably 1, 2 or 3.

When n ¹¹ is 1, m ¹¹ and m ¹² are each independently 0, 1, 2, 3, 4 or 5, preferably 1, 2, 3 or 4, more preferably 1, 2 or 3. When n ¹¹ is 1, m ¹¹ and m ¹² may be different from each other, but are preferably the same.

In the general formula (Ch-I), D is a divalent group represented by the above formulas (D1) to (D4). In the formulae (D1) to (D4), the portions with the black dots are bonded to Z ¹⁰¹ (or R ¹⁰⁰ ) or Z ¹⁰¹ (or R ¹⁰⁰ ), respectively.

In the group represented by the above (D1) or (D3), any one or two or more hydrogen atoms of the benzene ring may be independently halogen atoms (F, Cl, Br, I) and carbon atoms. An alkyl group of 1 to 20 or an alkoxy group having 1 to 20 carbon atoms is substituted. An alkyl group or an alkoxy group having 1 to 20 carbon atoms which is a substituent of a hydrogen atom in the benzene ring, and one or more hydrogen atoms in the group may be substituted with a fluorine atom. One or more methylene groups may also be -O-, -S-, -COO-, -OCO-, -CF ₂ -, -CF=CH-, -CH=CF-, -CF=CF - or -C≡C- is substituted in such a manner that an oxygen atom or a sulfur atom is not directly bonded to each other.

In the compound represented by the formula (Ch-I), as the compound wherein n ¹¹ is 0, it is preferred that the portion of the structure remaining after removing R ¹⁰⁰ and R ¹⁰¹ at both ends of the compound is represented by the following formula (b1) )~(b13) indicates the structure. From the structure represented by the general formulae (b1) to (b13), either one of the two ends is bonded to R ¹⁰⁰ , and the other end is bonded to R ¹⁰¹ . However, in the compound having such a structure, at least one of R ¹⁰⁰ and R ¹⁰¹ is a palmity alkyl group.

In the general formulae (b1) to (b13), Z ¹⁰² is the same as Z ¹⁰⁰ and Z ¹⁰¹ in the formula (Ch-I).

Further, in the general formulae (b1) to (b13), A ¹⁰² is a 1,4-phenylene group (one -CH= present in the group or two or more non-adjacent-CH= may be substituted The nitrogen atom may be any one or two or more hydrogen atoms present in the group, and may be substituted by a halogen atom, a methyl group, a methoxy group, a trifluoromethyl group or a trifluoromethoxy group. By substituting -CH= or a hydrogen atom in the 1,4-phenylene group, the liquid crystal composition containing the compound can be controlled to lower the crystallinity and the orientation or size of the dielectric anisotropy.

In terms of reliability, the ring structure in A ¹⁰² is a compound of a heterocyclic ring such as a pyridine ring or a pyrimidine ring (that is, one which is present in the 1,4-phenylene group -CH= or non-contiguous More than two -CH=compounds substituted with a nitrogen atom), preferably a compound having a ring structure in A ¹⁰² as a benzene ring (that is, present in the 1,4-phenylene group) CH = a compound which is not substituted with a nitrogen atom). On the other hand, in terms of increasing the dielectric inductivity, it is preferred that the ring structure in A ¹⁰² is a benzene ring compound, and the ring structure in A ¹⁰² is a heterocyclic compound such as a pyridine ring or a pyrimidine ring. . a compound having a hydrocarbon ring such as a benzene ring or a cyclohexane ring, which has a relatively small polarization, but has a heterocyclic ring such as a pyridine ring or a pyrimidine ring, and the compound has a relatively large polarizability. It is preferable because the crystallinity can be lowered and the liquid crystallinity can be stabilized.

Among the compounds represented by the formula (Ch-I), the compound wherein n ¹¹ and m ¹² are 0 is preferably the following formula (Ch-I-1) to (Ch-I-30). In the general formula (Ch-I-1) to (Ch-I-30), R ¹⁰⁰ , R ¹⁰¹ and Z ¹⁰⁰ represent the same meanings as R ¹⁰⁰ , R ¹⁰¹ and Z ¹⁰⁰ in the formula (Ch-I). At least one of R ¹⁰⁰ and R ¹⁰¹ represents a palmity alkyl group, and L ¹⁰⁰ to L ¹⁰⁵ each independently represent a hydrogen atom or a fluorine atom, and L ¹⁰⁰ to L ¹⁰⁵ each independently represent a hydrogen atom or a fluorine atom.

As the compound represented by the general formula (Ch-I-1) to (Ch-I-30), a compound of the following formula: R ¹⁰⁰ and R ^{101 is} one or both of the formula (Ra). Or a compound represented by any one of (Rk): more preferably one or both of R ¹⁰⁰ and R ¹⁰¹ are from the above formula (Ra-1) to (Ra-3) or The base represented by Rf-1)~(Rf-3). As a compound in which only one of R ¹⁰⁰ and R ¹⁰¹ is a group represented by any one of the formulae (Ra) to (Rk), it is preferred that the remaining one of R ¹⁰⁰ and R ¹⁰¹ is a carbon number. 1 to 30 non-palphatic alkyl groups (one or more unrelated methylene groups in the alkyl group may also be -O-, -S-, -NH-, -N(CH ₃ ) -, -CO-, -COO-, -OCO-, -OCO-O-, -S-CO-, -CO-S-, -CH=CH-, -CF ₂ -, -CF=CH-, - CH=CF-, -CF=CF- or C≡C-substituted, wherein one or two or more hydrogen atoms in the alkyl group may be substituted by a halogen atom or a cyano group.) A compound, more preferably R ¹⁰⁰ And the remaining one of R ¹⁰¹ is an alkyl group having 1 to 16 carbon atoms, an alkoxy group having 1 to 16 carbon atoms, an alkenyl group having 2 to 16 carbon atoms or an alkenyloxy group having 2 to 16 carbon atoms. Compound.

The liquid crystal composition of the present invention preferably contains at least one compound represented by any one of the formulae (Ch-I-1) to (Ch-I-30), and more preferably contains a formula (Ch- Compound represented by I-30). Specific examples of the compound represented by the formula (Ch-I-30) include the following formula (Ch-I-30-1) to (Ch-I-30-6) (wherein, n ¹³ represents 0 or 1, n represents an integer of 2 to 12, and R ¹⁰² represents an alkyl group having 1 to 16 carbon atoms, an alkoxy group having 1 to 16 carbon atoms, an alkenyl group having 2 to 16 carbon atoms or a carbon atom. A compound represented by a number of 2 to 16 alkenyloxy groups. In the formula (Ch-I-30-1) to (Ch-I-30-6), R ^{102 is} preferably an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or carbon. An alkenyl group having 2 to 6 atoms or an alkenyl group having 2 to 6 carbon atoms.

When n ¹¹ is 1, the compound represented by the formula (Ch-I) may have a structure having an asymmetric carbon in the ring structure portion. In this case, as the compound represented by the formula (Ch-I), D is preferably a compound of the above formula (D2) or (D4), and more preferably D is a compound of the formula (D4). The compound represented by the formula (D2) is preferably a compound represented by the following formula (K2-1) to (K2-8), and D is a compound of the formula (D4), preferably via the following A compound represented by the formula (K3-1) to (K3-6).

In the general formulae (K2-1) to (K2-8) and (K3-1) to (K3-6), R ^k each independently represents the same as R ¹⁰⁰ and R ¹⁰¹ in the formula (Ch-I). significance. The HTP(-) palm compound used in the liquid crystal composition of the present invention is preferably a compound represented by the formula (K2-1) to (K2-8) or (K3-1) to (K3-6). Among them, R ^{k is} also independently a palmitic or non-capillary alkyl group having 1 to 30 carbon atoms (one or two or more unrelated methylene groups in the alkyl group may also be -O) -, -S-, -NH-, -N(CH ₃ )-, -CO-, -COO-, -OCO-, -OCO-O-, -S-CO-, -CO-S-, -CH =CH-, -CF ₂ -, -CF=CH-, -CH=CF-, -CF=CF- or C≡C-substitution, one or more hydrogen atoms in the alkyl group may also be A compound in which a halogen atom or a cyano group is substituted, and more preferably R ^k each independently is an alkyl group having 1 to 16 carbon atoms, an alkoxy group having 1 to 16 carbon atoms, or an alkenyl group having 2 to 16 carbon atoms. Or a compound having an alkenyloxy group having 2 to 16 carbon atoms, more preferably R ^k each independently an alkyl group having 3 to 10 carbon atoms, an alkoxy group having 3 to 9 carbon atoms, and 3 to 3 carbon atoms. A compound having 10 alkenyl groups or an alkenyloxy group having 3 to 9 carbon atoms.

More specifically, for example, a compound represented by the formula (c01) is preferred.

Further, it is more preferably a palm agent represented by the formula (c02).

As the axial palm compound, specifically, a compound represented by the formula (IV-1), (IV-2), (IV-3) or (IV-4) is preferred.

In the general formulae (IV-1) and (IV-2), R ⁷¹ and R ⁷² each independently represent a hydrogen atom, a halogen atom, a cyano group, an isocyanate group, an isothiocyanate group or a carbon number of 1 to 20. alkyl. Any one or two or more methylene groups in the alkyl group may be -O-, -S-, -COO-, -OCO-, -CH in such a manner that the oxygen atom and the sulfur atom are not directly bonded to each other. =CH -, -CF=CF- or -C≡C-substituted. Further, any one or two or more hydrogen atoms in the alkyl group may be substituted by a halogen atom. As a compound represented by the formula (IV-1) or (IV-2), R ⁷¹ and R ⁷² are each independently an unsubstituted or optionally substituted alkyl group having 1 to 20 carbon atoms. More preferably, it is an unsubstituted alkyl group having 1 to 20 carbon atoms, and more preferably an unsubstituted alkyl group having 1 to 6 carbon atoms.

In the general formulae (IV-1) and (IV-2), A ⁷¹ and A ⁷² each independently represent an aromatic or non-aromatic 3, 6-8 member ring or a condensed ring having 9 or more carbon atoms. . Any one or two or more hydrogen atoms in the ring structure may be substituted by a halogen atom, an alkyl group having 1 to 3 carbon atoms or a haloalkyl group having 1 to 3 carbon atoms. Further, any one of the ring structures or two or more methylene groups which are not adjacent to each other may be substituted by -O-, -S- or -NH-, and any one of the ring structures may not be mutually Two or more adjacent -CH= may be substituted by -N=. When m ₇₁ is 2 or more, when a plurality of A ⁷¹ are present in one molecule, they may be the same as each other or may be different. Similarly, when m ₇₂ is 2 or more, when a plurality of A ⁷² are present in one molecule, they may be identical to each other or may be different.

As the compound represented by the formula (IV-1) or (IV-2), A ⁷¹ and A ⁷² are each preferably independently a 1,4-phenylene group, a trans-1,4-cyclohexylene group, or a pyridine group. -2,5-diyl, pyrimidine-2,5-diyl, naphthalene-2,6-diyl. It is also preferred that one or two or more hydrogen atoms in the group are substituted with a halogen atom, an alkyl group having 1 to 3 carbon atoms or a haloalkyl group having 1 to 3 carbon atoms. More preferably, one or two or more hydrogen atoms may be substituted by a fluorine atom, a 1,4-phenylene group or a trans-1,4-cyclohexylene group, and more preferably an unsubstituted one. 4-phenylene or unsubstituted trans-1,4-cyclohexyl.

In the general formulae (IV-1) and (IV-2), Z ⁷¹ and Z ⁷² each independently represent a single bond or an alkylene group having 1 to 8 carbon atoms. Any one or two or more methylene groups in the alkylene group may be -O-, -S-, -COO-, -OCO-, - in such a manner that the oxygen atom and the sulfur atom are not directly bonded to each other. CSO-, -OCS-, -N=N-, -CH=N-, -N=CH-, -N(O)=N-, -N=N(O)-, -CH=CH-,- CF=CF- or -C≡C-substituted. Further, any one or two or more hydrogen atoms in the alkylene group may be substituted by a halogen atom. When m ₇₁ is 2 or more, when a plurality of Z ⁷¹ are present in one molecule, they may be the same as each other or may be different. Similarly, when m ₇₂ is 2 or more and a plurality of Z ⁷² are present in one molecule, they may be the same as each other or may be different.

As the compound represented by the formula (IV-1) or (IV-2), Z ⁷¹ and Z ⁷² are each independently a single bond, an unsubstituted alkylene group having 1 to 4 carbon atoms, -COO -, -OCO-, -CH=CH- or -C≡C-, more preferably a single bond, -CH ₂ -, -CH ₂ CH ₂ -, -COO-, -OCO-, -CH=CH- or -C≡C-, more preferably a single bond, -COO- or -OCO-.

In the general formulae (IV-1) and (IV-2), X ⁷¹ and X ⁷² each independently represent a single bond, -COO-, -OCO-, -CH ₂ O-, -OCH ₂ -, -CF ₂ O -, -OCF ₂ - or -CH ₂ CH ₂ -. As the compound represented by the formula (IV-1) or (IV-2), X ⁷¹ and X ^{72 are} preferably each independently a single bond, -COO-, -OCO-, -CH ₂ O-, -OCH _{2 .} -or -CH ₂ CH ₂ -, more preferably a single bond, -COO- or -OCO-.

In the formula (IV-2), R ⁷³ represents a hydrogen atom, a halogen atom or -X ⁷¹ -(A ⁷¹ -Z ⁷¹ )m ₇₁ -R ⁷¹ .

In the general formulae (IV-1) and (IV-2), m ₇₁ and m ₇₂ each independently represent an integer of 1 to 4. However, in the general formula (IV-2), when R ⁷³ is -X ⁷¹ -(A ⁷¹ -Z ⁷¹ )m ₇₁ -R ⁷¹ , either of the two m ₇₁ may be 0. As the compound represented by the formula (IV-1) or (IV-2), m ₇₁ and m ₇₂ are each preferably independently 2 or 3, more preferably 2.

Further, the palmitic agent may be right-handed or left-handed, and may be appropriately used depending on the constitution of the liquid crystal display element.

In the formula (np01) and the formula (np02), R ⁰¹ , R ⁰² , R ⁰³ and R ⁰⁴ are each preferably independently an alkyl group having 1 to 5 carbon atoms, preferably 1 to 5 carbon atoms. The alkoxy group is preferably an alkenyl group having 2 to 5 carbon atoms, preferably an alkenyloxy group having 2 to 5 carbon atoms, more preferably an alkyl group having 1 to 5 carbon atoms, more preferably The alkoxy group having 1 to 3 carbon atoms is more preferably an alkenyl group having 2 to 3 carbon atoms, and more preferably an alkenyl group having 2 to 3 carbon atoms.

In the general formula (np01) and the general formula (np02), n ⁰¹ and n ⁰² each independently represent 0 or 1. When γ 1 is made smaller and a high response speed is desired, n ^{01 is} preferably 0. .

When it is a compound represented by the formula (np01) and n ⁰¹ represents 0, it is preferably a compound represented by the formula (II-11) or the formula (II-12).

It is more suitable when the response speed of the liquid crystal display element is emphasized.

Wherein R ^V and R ^V1 each independently represent an alkyl group having 1 to 5 carbon atoms or an alkenyl group having 2 to 5 carbon atoms, preferably an alkyl group having 1 to 5 carbon atoms or 2 to 2 carbon atoms; The alkenyl group of 5 is preferably an alkyl group having 2 to 5 carbon atoms or an alkenyl group having 2 to 3 carbon atoms. Further, one of these alkyl or alkenyl groups or two or more of -CH ₂ - which are not adjacent may be substituted by an oxygen atom.

The compound represented by the formula (II-11) and/or the formula (II-12), for example, is preferably a formula (II-101) to (II-110), and particularly preferably a formula (II-103). ) or formula (II-108).

Further, in order to obtain a high response speed, the content of the compound represented by the general formula (II-11) and the general formula (II-12) is preferably from 10 to 80% by mass. In the case of precipitation at a low temperature, the content thereof is preferably from 5 to 40% by mass. Further, when a high voltage holding ratio (VHR) is emphasized, it is preferred to contain 1 to 30% by mass of the compound represented by the formula (II-11) and the formula (II-12), preferably 1 to 20% by mass, preferably 1 to 10% by mass. When a higher voltage holding ratio (VHR) is obtained, it is preferred to contain 1 to 15% by mass of the compound represented by the formula (II-108).

In another preferred embodiment, when n ⁰¹ represents a compound represented by the formula (np01), R ⁰¹ is an alkyl group having 1 to 10 carbon atoms, and R ⁰² is an alkane having 1 to 10 carbon atoms. a group or an alkoxy group having 1 to 10 carbon atoms. In this case, R ^{01 is} preferably an alkyl group having 1 to 5 carbon atoms, R ^{01 is more} preferably an alkyl group having 2 to 5 carbon atoms, and R ^{02 is} preferably an alkyl group having 1 to 5 carbon atoms or The alkoxy group having 1 to 4 carbon atoms, and R ^{02 is} preferably an alkyl group having 2 to 5 carbon atoms, which is suitable when a high VHR and a high response speed are considered.

When the compound represented by the formula (np01) and n ⁰¹ represents 1, it is preferably a compound represented by the formula (L-4.1) to the formula (L-4.10).

More preferably (L-4.4). When a high response speed is emphasized, the formula (L-4.4) is preferred.

When it is a compound represented by the formula (np02) and n ⁰² represents 0, it is preferably a compound selected from the group of compounds of the formula (L-3.1) to the formula (L-3.7).

More preferably, it is a compound represented by the formula (L-3.1), the formula (L-3.2), the formula (L-3.4) or the formula (L-3.6), and it is particularly preferable when a high response speed and a high VHR are emphasized. Formula (L-3.1) or formula (L-3.2). When a large elastic constant is emphasized, the formula (L-3.4) is preferred.

When the compound represented by the formula (np02) and n ⁰² represents 1, it is preferably a compound represented by the formula (L-5.1) to the formula (L-5.7).

More preferably, it is a compound represented by the formula (L-5.1) or the formula (L-5.2).

The liquid crystal composition of the present invention may further contain a compound represented by the formula (III-1) and/or the formula (III-2).

Wherein R ³¹ to R ³⁴ each independently represent an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms or a carbon number of 2 to 10; alkenyloxy group present in the R ³¹ to R 1 -CH ₂ ³⁴ - 2 or more of the adjacent -CH ₂ - may each independently be substituted with -O- or -S-, and there One or more hydrogen atoms of R ³¹ to R ³⁴ may be independently substituted with a fluorine atom or a chlorine atom, and R ³¹ and R ³³ are each independently an alkane having 1 to 5 carbon atoms. a group, an alkoxy group having 1 to 5 carbon atoms, an alkenyl group having 2 to 5 carbon atoms or an alkenyl group having 2 to 5 carbon atoms, more preferably an alkyl group having 1 to 5 carbon atoms or a carbon number The alkenyl group of 2 to 5 is more preferably an alkyl group having 1 to 3 carbon atoms or an alkenyl group having 2 to 3 carbon atoms, and R ³² and R ³⁴ are each independently an alkyl group having 1 to 5 carbon atoms. An alkoxy group having 1 to 5 carbon atoms, an alkenyl group having 2 to 5 carbon atoms or an alkenyloxy group having 2 to 5 carbon atoms, more preferably an alkyl group having 1 to 5 carbon atoms and 1 carbon atom To alkoxy group of 5.

Ring A ³² , Ring B ³¹ and Ring B ³² each independently represent trans-1,4-cyclohexylene, 1,4-phenylene, 2-fluoro-1,4-phenylene, 3-fluoro- 1,4-phenylene, 3,5-difluoro-1,4-phenylene, 2,3-difluoro-1,4-phenylene, 1,4-cyclohexenyl, 1, 4-bicyclo[2.2.2]exenyl, piperidine-1,4-diyl, naphthalene-2,6-diyl, decahydronaphthalene-2,6-diyl or 1,2,3,4- Tetrahydronaphthalene-2,6-diyl, preferably trans-1,4-cyclohexylene or 1,4-phenylene.

Z ³¹ and Z ³² each independently represent -OCH ₂ -, -CH ₂ O-, -CF ₂ O-, -OCF ₂ -, -CH ₂ CH ₂ -, -CF ₂ CF ₂ - or a single bond, preferably Is -CH ₂ O-, -CF ₂ O-, -CH ₂ CH ₂ -, -CF ₂ CF ₂ - or a single bond, more preferably -CH ₂ O-, -CH ₂ CH ₂ - or a single bond, especially Good for -CH ₂ O- or single bond.

The compound represented by the formula (III-1), specifically, preferably a compound represented by the formula (III-A1) to the formula (III-A4) shown below, preferably a formula ( The compound represented by III-A1) is preferably a compound represented by the formula (III-A3), preferably a compound represented by the formula (III-A4), more preferably represented by the formula (III-A1). Compound, More preferably, it is a compound represented by the formula (III-A3), and particularly preferably a compound represented by the formula (III-A1).

In the formula, R ³¹ and R ^{32 have} the same meanings as described above.

The compound represented by the formula (III-2), specifically, preferably a compound represented by the formula (III-B1) to the formula (III-B6) shown below, preferably a formula ( The compound represented by III-B1) is preferably a compound represented by the formula (III-B3), preferably a compound represented by the formula (III-B4), preferably represented by the formula (III-B5). The compound is preferably a compound represented by the formula (III-B6), more preferably a compound of the formula (III-B1), more preferably a compound of the formula (III-B3), more preferably a formula ( The compound of III-B5) is more preferably a compound of the formula (III-B6), more preferably a compound represented by the formula (III-B1), and particularly preferably a compound represented by the formula (III-B5).

In the formula, R ³³ and R ^{34 have} the same meanings as described above.

The liquid crystal composition of the present invention is preferably composed of a combination of the general formula (III-A1) and the general formula (III-B1), more preferably a general formula (III-A1) and a general formula (III-B1) and a general formula. The combination of (III-B4) is more preferably composed of a combination of the formula (III-A1) and the formula (III-B1) and the formula (III-B5).

The liquid crystal composition of the present invention is preferably composed of a combination of the general formula (III-A3) and the general formula (III-B5), more preferably the general formula (III-A3) and the general formula (III-B4) and the general formula ( The combination of III-B5) is more preferably composed of a combination of the general formula (III-A3) and the general formula (III-B5) and the general formula (III-B1).

The liquid crystal composition of the present invention is preferably composed of a combination of the general formula (III-A4) and the general formula (III-B1), more preferably the general formula (III-A4) and the general formula (III-A1) and the general formula ( III- The combination of B1) is preferably composed of a combination of the general formula (III-A4) and the general formula (III-B5), preferably the general formula (III-A4) and the general formula (III-B5) and the general formula ( The combination of III-B4) is preferably composed of a combination of the general formula (III-A4) and the general formula (III-B1), more preferably the general formula (III-A4) and the general formula (III-B1) A combination of formula (III-B5).

The liquid crystal composition of the present invention preferably contains a compound selected from the group of compounds of the formula (III-B7) as a compound of the formula (III-2).

(wherein R ³³ and R ^{34 have} the same meanings as described above.).

The liquid crystal composition of the present invention contains one or more compounds represented by the formula (III-1) and/or the formula (III-2), and preferably contains two to ten kinds. The content thereof is from 10 to 90% by mass, and the lower limit thereof is preferably 10% by mass, preferably 15% by mass, preferably 20% by mass, preferably 25% by mass, preferably 30% by mass, preferably 35. The mass is preferably 40 mass, preferably 45% by mass, and the upper limit thereof is preferably 80% by mass, preferably 75% by mass, preferably 70% by mass, preferably 65% by mass, preferably 60% by mass. % is preferably 55 mass%, preferably 50 mass%, preferably 45 mass%.

The liquid crystal composition of the present invention preferably contains one or more compounds selected from the compounds represented by the general formula (IV-A) to the general formula (IV-J) as other components.

However, the same compounds as the formula (np01) or the formula (np02) are not included.

In the formula, R ⁴¹ and R ⁴² each independently represent an alkyl group having 1 to 5 carbon atoms or an alkoxy group having 1 to 5 carbon atoms, an alkenyl group having 2 to 5 carbon atoms or 2 to 5 carbon atoms. The alkenyloxy group is preferably an alkyl group having 2 to 5 carbon atoms or an alkoxy group having 1 to 3 carbon atoms or an alkenyl group having 2 to 5 carbon atoms.

X ⁴¹ represents an alkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, a fluorine atom or a hydrogen atom, preferably a methyl group, a fluorine atom or a hydrogen atom, more preferably a fluorine atom or a hydrogen atom. .

Further, R ⁴¹ and R ^{42 of the} formula (IV-F), the formula (IV-G), the formula (IV-H) and the formula (IV-I) may each independently be a carbon number of 2 to An alkenyl group of 5 or an alkenyloxy group having 2 to 5 carbon atoms.

It is preferably selected from the group consisting of the general formula (IV-A) to the general formula (IV-J), the general formula (IV-A), the general formula (IV-D), the general formula (IV-F), and the general formula ( IV-G), a compound of the formula (IV-H) and the formula (IV-I), more preferably selected from the group consisting of the formula (IV-A), the formula (IV-F), and the formula (IV-G) a compound of the formula (IV-H) and the formula (IV-I), more preferably a compound selected from the group consisting of the formula (IV-F), the formula (IV-H) and the compound of the formula (IV-I) More preferably, it is a compound selected from the group consisting of the formula (III-F) and the formula (III-H).

Selecting from the group of compounds represented by the general formula (IV-A) to the general formula (IV-J) The content of the compound is from 1% by mass to 60% by mass, preferably from 5% by mass to 50% by mass, preferably from 5% by mass to 40% by mass, preferably from 10% by mass to 40% by mass, preferably 10% by mass. % to 30% by mass.

The liquid crystal composition of the present invention may further contain one or more compounds represented by the formula (V).

Wherein R ⁶¹ and R ⁶² each independently represent 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 a carbon number of 2 to 8; Alkenyloxyl is preferably an alkyl group having 1 to 5 carbon atoms or an alkenyl group having 2 to 5 carbon atoms.

The liquid crystal composition of the present invention may contain one or more compounds represented by the formula (N-001).

In the formula, R ^N1 and R ^N2 each independently represent 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 a carbon number of 2 to 8. The alkenyloxy group is preferably an alkyl group having 1 to 5 carbon atoms.

In the formula, L ¹ and L ² each independently represent a hydrogen atom, a fluorine atom, CH ₃ or CF ₃ , and at least one of L ¹ and L ² is preferably a fluorine atom, and both of them are preferably fluorine atoms.

The compound represented by the formula (IV-I), the formula (V) or the formula (N-001) is suitable for obtaining a liquid crystal composition having a large Δn, and an effect of accelerating the reaction rate of the polymerizable compound can be expected. It is very useful.

The liquid crystal composition of the present invention may further contain one or more compounds represented by the formula (VIII-a), the formula (VIII-c) or the formula (VIII-d).

Wherein R ⁵¹ and R ⁵² each independently represent 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 5 carbon atoms, and X ⁵¹ and X ⁵² are each independently The ground represents a fluorine atom or a hydrogen atom, and at least one of X ⁵¹ and X ⁵² is a fluorine atom.

The liquid crystal composition of the present invention may contain one or more compounds represented by the formula (V-9.1) to the formula (V-9.3).

The liquid crystal composition of the present invention contains a polymerizable compound and may contain a polymerizable compound represented by the formula (I-1).

Wherein n ¹¹ and n ¹² each independently represent an integer of 0 to 3, and n ¹¹ + n ¹² is an integer of 1 to 6, which may be the same or different when a plurality of R ¹¹ or Z are present. Further, n ¹¹ + n ^{12 is} preferably an integer of 1 to 5, preferably an integer of 1 to 4, preferably an integer of 1 to 3, more preferably an integer of 2 to 3.

In the formula, Z represents a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms or R ¹² , preferably R ¹² .

Wherein R ¹¹ represents P ¹¹ -S ¹¹ -, R ¹² represents P ¹² -S ¹² -, and P ¹¹ and P ¹² each independently represent any one of formula (R-1) to formula (R-15) ,

Preferably, it is a formula (R-1) or a formula (R-2), and it is preferable that the molecular structure of the polymerizable compound necessarily contains the formula (R-2).

In the formula, S ¹¹ and S ¹² each independently represent a single bond or an alkylene group having 1 to 15 carbon atoms, and one or more of -CH ₂ - in the alkylene group may not directly abut the oxygen atom. The mode is substituted by -O-, -OCO- or -COO-, preferably a single bond or an alkylene group having 1 to 6 carbon atoms, more preferably a single bond. When attention is paid to the solubility of the liquid crystal composition, it is preferably an alkylene group having 1 to 6 carbon atoms, more preferably an alkylene group having 1 to 3 carbon atoms, more preferably 1 to 2 carbon atoms. The alkyl group may be substituted by one or two or more -CH ₂ - of the alkylene group by -O-, -OCO- or -COO- in such a manner that the oxygen atoms are not directly adjacent to each other. Further, at least one of S ¹¹ and S ¹² is a single bond, and preferably both of S ¹¹ and S ¹² are single bonds.

Wherein M ¹¹ and M ¹² each independently represent 1,4-phenylene, benzene-1,2,4-triyl, benzene-1,2,4,6-tetrayl, 1,4-extension ring Hexyl, pyridine-2,5-diyl, pyrimidine-2,5-diyl, naphthalene-2,6-diyl, nonane-2,5-diyl, 1,2,3,4-tetrahydronaphthalene -2,6-diyl or 1,3-two Alkane-2,5-diyl, phenanthrene-2,7-diyl, preferably 1,4-phenylene, 1,4-cyclohexylene, naphthalene-2,6-diyl, phenanthrene-2, The 7-diyl group is more preferably a 1,4-phenylene group, a naphthalene-2,6-diyl group or a phenanthrene-2,7-diyl group. Further, at least one of M ¹¹ and M ¹² is substituted with an alkoxy group having 1 to 12 carbon atoms. The alkoxy group is preferably an alkoxy group having 1 to 6 carbon atoms, preferably an alkoxy group having 1 to 5 carbon atoms, preferably an alkoxy group having 1 to 4 carbon atoms, preferably carbon. The alkoxy group having 1 to 3 atoms, preferably an alkoxy group having 1 to 2 carbon atoms, particularly preferably an alkoxy group having 1 carbon atom.

L ¹¹ represents 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 ^a -, -NR ^a -CO-, -SCH ₂ -, -CH ₂ S-, -CH=CR ^a -COO -, -CH=CR ^a -OCO-, -COO-CR ^a =CH-, -OCO-CR ^a =CH-, -COO-CR ^a =CH-COO-,-COO-CR ^a =CH-OCO- ^{, -OCO-CR a = CH-} COO -, - OCO-CR a = CH-OCO -, - (CH 2) Z -C (= O) -O -, - (CH 2) zO- (C = O )-, -O-(C=O)-(CH ₂ )z-, -(C=O)-O-(CH ₂ )z-, -CH=CH-, -CF=CF-, -CF= CH-, -CH=CF-, -CF ₂ -, -CF ₂ O-, -OCF ₂ -, -CF ₂ CH ₂ -, -CH ₂ CF ₂ -, -CF ₂ CF ₂ - or -C≡C - (wherein R ^a each independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and z in the above formula represents an integer of 1 to 4), preferably a single bond, -OCH ₂ -, -CH ₂ O-, -C ₂ H ₄ -, -COO-, -OCO-, -CH=CR ^a -COO-, -CH=CR ^a -OCO-, -COO-CR ^a =CH-, -OCO-CR ^a =CH-, -(CH ₂ ) _z -COO-, -(CH ₂ )z-OCO-, -OCO-(CH ₂ )z-, -COO-(CH ₂ )z-, -CH=CH- _{, -CF 2 O -, - OCF} 2 - or -C≡C- (wherein, R ^a each independently represent a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, the foregoing formula, z An integer of 1 to 4 is shown.), more preferably a single bond, -COO-, -OCO-, -CH=CH-COO-, -CH=CH-OCO-, -COO-CH=CH-, -OCO- CH=CH-, -(CH ₂ ) ₂ -COO-, -(CH ₂ ) ₂ -OCO-, -OCO-(CH ₂ ) ₂ -, -COO-(CH ₂ ) ₂ - or -C≡C- More preferably, it is -COO-, -OCO-, -CH=CH-COO-, -OCO-CH=CH-, -(CH ₂ ) ₂ -COO- or -OCO-(CH ₂ ) ₂ -.

m ¹¹ represents an integer of 0 to 4, and may be the same or different when a plurality of L ¹¹ and M ¹² are present. Further, m ^{11 is} preferably an integer of 1 to 3, and when a polymerization rate is important, m ^{11 is} preferably an integer of 2 to 4, and when importance is attached to the liquid crystal composition, m ^{11 is} preferably An integer from 0 to 2. Therefore, in order to achieve both the polymerization rate and the compatibility, m ^{11 is} particularly preferably 2.

Specific examples of the polymerizable compound represented by the formula (I-1) include the following formulae (I-11-01) to (I-11-10) and formula (I-12-01). To (I-12-06), general formula (I-13-01) to (I-13-06), general formula (I-21-01) to (I-21-17), general formula (I- T01) to (I-T10), a compound represented by the formula (I-A01) to (I-A09).

Wherein R ^M1 , R ^M2 and R ^M3 each independently represent a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms or a formula (R-1) to (R-). Any one of 15) is preferably independently a hydrogen atom, an alkoxy group having 1 to 3 carbon atoms or any one of the formulae (R-1) to (R-5), preferably each. It is independently a hydrogen atom, an alkoxy group having 1 to 3 carbon atoms, or any one of the formulae (R-1) to (R-2).

Preferably, at least one of R ^M1 , R ^M2 and R ^M3 is any one of formula (R-1) to formula (R-15), more preferably at least 2 is formula (R-1) to More preferably, at least three of the formula (R-15) are any one of the formulae (R-1) to (R-15).

In other words, the polymerizable compound represented by the formula (I-1) is a mesogen structure having one or more rings as shown in the above structure, and is characterized in that it has an alkoxy group at one of the sites. Further, it has one or more polymerizable groups. Further, in addition to the above-described features, a fluorine group may be provided in one portion of the liquid crystal original structure.

As the polymerizable compound represented by the formula (I-1), a compound represented by the formula (I-21) or (I-22) is also suitable.

Wherein R ¹⁰¹ to R ¹⁰⁶ each independently represent a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms or a formula (R-1) to (R-15); Any of them preferably represents a hydrogen atom, an alkyl group having 1 to 3 carbon atoms or any one of the formulae (R-1) to (R-5), more preferably a hydrogen atom, or a formula (R- 1) or formula (R-2).

If further detailed, two, three or four of R ¹⁰¹ to R ¹⁰⁶ are preferably each independently of formula (R-1) or formula (R-2), and R ¹⁰¹ to R ¹⁰⁶ Three or four of them are preferably independently of formula (R-1) or formula (R-2), and three of R ¹⁰¹ to R ¹⁰⁶ are preferably each independently of formula (R-1) or formula. (R-2).

A ¹¹ and B ¹¹ each independently represent 1,4-phenylene, 1,4-cyclohexylene, naphthalene-2,6-diyl or 1,2,3,4-tetrahydronaphthalene-2,6- a diradical group which is unsubstituted or may be substituted by an alkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, or a halogen, preferably unsubstituted, having 1 to 3 carbon atoms. Alkyl-substituted or fluoro-substituted 1,4-phenylene or naphthalene-2,6-diyl, more preferably unsubstituted or fluorophenyl substituted 1,4-phenylene. However, when R ¹⁰¹ to R ¹⁰⁶ are not alkoxy groups, at least one of A ¹¹ and B ¹¹ is substituted with an alkoxy group having 1 to 5 carbon atoms. Further, when A ¹¹ and B ^{11 are} not substituted by an alkoxy group having 1 to 5 carbon atoms, at least one of R ¹⁰¹ to R ¹⁰⁶ represents an alkoxy group having 1 to 5 carbon atoms. However, the alkoxy group is preferably an alkoxy group having 1 to 4 carbon atoms, preferably an alkoxy group having 1 to 3 carbon atoms, preferably an alkoxy group having 1 to 2 carbon atoms, particularly preferably It is an alkoxy group having 1 carbon atom. That is, the compound represented by the formula (I-21) or (I-22) is characterized by having at least one alkoxy group.

L ¹³ represents a single bond, -OCH ₂ -, -CH ₂ O-, -C ₂ H ₄ -, -COO-, -OCO-, -CH=CR ^a -COO-, -CH=CR ^a -OCO-, -COO-CR ^a =CH-, -OCO-CR ^a =CH-, -(CH ₂ ) _z -COO-, -(CH ₂ )z-OCO-, -OCO-(CH ₂ )z-, -COO -(CH ₂ )z-, -CH=CH-, -CF ₂ O-, -OCF ₂ - or -C≡C- (wherein R ^a each independently represents a hydrogen atom or a carbon number of 1 to 3 Alkyl group, in the above formula, z represents an integer of 1 to 4.), preferably a single bond, -OCH ₂ -, -CH ₂ O-, -C ₂ H ₄ -, -COO-, -OCO-, - CH=CH-COO-, -CH=CH-OCO-, -COO-CH=CH-, -OCO-CH=CH-, -(CH ₂ ) ₂ -COO-, -(CH ₂ ) ₂ -OCO- , -OCO-(CH ₂ ) ₂ -, -COO-(CH ₂ ) ₂ -, -CH=CH- or -C≡C-, more preferably a single bond, -COO-, -OCO-, -CH= CH-COO-, -OCO-CH=CH-, -(CH ₂ ) ₂ -COO- or -OCO-(CH ₂ ) ₂ -.

The polymerizable compound represented by the formula (I-21) includes a compound represented by the formula (I-B01) to (I-B15).

Wherein R ^M1 , R ^M2 and R ^{M3 are} as previously described.

The liquid crystal composition of the present invention may further contain a polymerizable compound represented by the formula (I-31) and the formula (I-32).

However, the compound represented by the formula (I-1) is not included.

Wherein R ¹⁰⁷ represents P ¹⁰⁷ -S ¹⁰⁷ -, R ¹¹⁰ represents P ¹¹⁰ -S ¹¹⁰ -, and P ¹⁰⁷ and P ¹¹⁰ each independently represent any one of formula (R-1) to formula (R-15) , S ¹⁰⁷ and S ¹¹⁰ each independently represent a single bond or an alkylene group having 1 to 15 carbon atoms, and one or more of -CH ₂ - in the alkylene group may be directly adjacent to each other in an oxygen atom. -O-, -OCO- or -COO-substituted, preferably a single bond or a stretched alkyl group having 1 to 6 carbon atoms (one or more of -CH ₂ - of the alkylene group may also be an oxygen atom) The method of not directly adjacent is replaced by -O-.), especially a single bond.

Wherein R ¹⁰⁸ , R ¹⁰⁹ , R ¹¹¹ and R ¹¹² each independently represent the formula (R-1) to the formula (R-15), an alkyl group having 1 to 3 carbon atoms, and an alkyl group having 1 to 3 carbon atoms; Any one of an oxy group, a fluorine atom or a hydrogen atom, A ¹² represents a 1,4-phenylene group, a 1,4-cyclohexylene group, a pyridine-2,5-diyl group, a pyrimidine-2,5-diyl group. , naphthalene-2,6-diyl, decane-2,5-diyl, 1,2,3,4-tetrahydronaphthalene-2,6-diyl or 1,3-di An alkane-2,5-diyl group, the group being unsubstituted or substituted by an alkyl group having 1 to 12 carbon atoms, a halogen, a cyano group or a nitro group, and L ¹⁴ represents a single bond, -OCH ₂ -, -CH ₂ O-, -C ₂ H ₄ -, -COO-, -OCO-, -CH=CR ^a -COO-, -CH=CR ^a -OCO-, -COO-CR ^a =CH-, -OCO-CR ^a =CH-, -(CH ₂ ) _z -COO-, -(CH ₂ )z-OCO-, -OCO-(CH ₂ )z-, -COO-(CH ₂ )z-, -CH=CH- , -CF ₂ O-, -OCF ₂ - or -C≡C- (wherein R ^a each independently represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and in the above formula, z represents 1 to 4; Integer.).

In the formula, X ¹⁵ , X ¹⁶ , X ¹⁷ and X ¹⁸ each independently represent a hydrogen atom, an alkyl group having 1 to 3 carbon atoms or a fluorine atom.

The compound represented by the formula (I-32) is, for example, preferably a compound represented by the formula (XX-1) to the formula (XX-10), more preferably a formula (XX-1) to a formula (XX). -4).

In the formula (XX-1) to the formula (XX-10), Sp ^xx represents an alkylene group having 1 to 8 carbon atoms or -O-(CH ₂ ) _s - (wherein s represents an integer of 2 to 7) The oxygen atom is bonded to the ring.).

In the formula (XX-1) to the formula (XX-10), the hydrogen atom in the 1,4-phenylene group may be further further represented by -F, -Cl, -CF ₃ , -CH ₃ , (R-1) ) is substituted with any of formula (R-15).

Further, as the compound represented by the formula (I-31), for example, a polymerizable compound of the formula (M31) to the formula (M48) is preferable.

Further, a polymerizable compound of the formula (M301) to the formula (M316) is also preferable.

The hydrogen atom in the 1,4-phenylene group and the naphthyl group in the formula (M301) to the formula (M316) may be further substituted with -F, -Cl, -CF ₃ or -CH ₃ .

Further, a polymerizable compound of the formula (Ia-1) to the formula (Ia-31) can also be used.

The liquid crystal composition of the present invention more preferably uses a polymerizable compound represented by the formula (XX-2), the formula (XX-4), the formula (M31), the formula (M-302) or (Ia-31) or the like. A polymerizable compound having a molecular structure.

The liquid crystal composition of the present invention contains 0.01 to 5% by mass of the polymerizable compound, and the lower limit of the content is preferably 0.02% by mass, preferably 0.03% by mass, preferably 0.04% by mass, preferably 0.05% by mass, preferably It is 0.06% by mass, preferably 0.07% by mass, preferably 0.08% by mass, preferably 0.09% by mass, preferably 0.1% by mass, preferably 0.15% by mass, preferably 0.2% by mass, preferably 0.25 mass%, preferably 0.3 mass%, preferably 0.35 mass%, preferably 0.4 mass%, preferably 0.5 mass, preferably 0.55 mass%, and the upper limit of the content is preferably 4.5 mass%, preferably It is 4% by mass, preferably 3.5% by mass, preferably 3% by mass, preferably 2.5% by mass, preferably 2% by mass, preferably 1.5% by mass, preferably 1% by mass, preferably 0.95 mass%, preferably 0.9 mass%, preferably 0.85 mass%, preferably 0.8 mass%, preferably 0.75 mass%, preferably 0.7 mass%, preferably 0.65 mass%, preferably 0.6 The mass % is preferably 0.55 mass%. If it is further detailed, when a sufficient pretilt angle or a small residual monomer or a high voltage holding ratio (VHR) is to be obtained, the content thereof is preferably 0.2 to 0.6% by mass, and when it is emphasized to suppress the low temperature In the case of precipitation, the content thereof is preferably from 0.1 to 0.4% by mass.

The liquid crystal composition of the present invention may contain, in addition to the above compounds, a usual nematic liquid crystal, a smectic liquid crystal, a cholesteric liquid crystal, an antioxidant, an ultraviolet absorber, a light stabilizer or an infrared absorber.

The antioxidant used as the liquid crystal composition of the present invention may be exemplified by the general formula. (H-1) to a hindered phenol represented by the formula (H-4).

In the formula (H-1) to the formula (H-4), R ^H1 represents an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, and an alkenyl group having 2 to 10 carbon atoms. or alkenyl group having a carbon number of 2 to 10, present in a group of -CH ₂ - adjacent to the two or more of -CH ₂ - may each independently be substituted with -O- or -S- Further, one or two or more hydrogen atoms present in the group may be independently substituted with a fluorine atom or a chlorine atom. More specifically, it is preferably an alkyl group having 2 to 7 carbon atoms, an alkoxy group having 2 to 7 carbon atoms, an alkenyl group having 2 to 7 carbon atoms or an alkenyloxy group having 2 to 7 carbon atoms. More preferably, it is an alkyl group having 3 to 7 carbon atoms or an alkenyl group having 2 to 7 carbon atoms.

In the formula (H-4), M ^H4 represents an alkylene group having 1 to 15 carbon atoms (one or two or more -CH ₂ - in the alkylene group may be directly adjacent to each other in an oxygen atom). Substituted into -O-, -CO-, -COO-, -OCO-.), -OCH ₂ -, -CH ₂ O-, -COO-, -OCO-, -CF ₂ O-, -OCF ₂ -, -CF ₂ CF ₂ -, -CH=CH-COO-, -CH=CH-OCO-, -COO-CH=CH-, -OCO-CH=CH-, -CH=CH-, -C≡C- , a single bond, a 1,4-phenylene group (any hydrogen atom in the 1,4-phenylene group may be substituted by a fluorine atom) or a trans-1,4-cyclohexylene group, preferably a carbon number The alkyl group having 1 to 14 is preferably a large number of carbon atoms in consideration of volatility, but the carbon number is preferably not too large in consideration of viscosity, and therefore, more preferably 2 to 12 carbon atoms. More preferably, it is 3 to 10 carbon atoms, more preferably 4 to 10 carbon atoms, still more preferably 5 to 10 carbon atoms, still more preferably 6 to 10 carbon atoms.

In the general formula (H-1) to the general formula (H-4), one of the 1,4-phenylene groups or two or more non-adjacent-CH= may be substituted by -N=. Further, the hydrogen atoms in the 1,4-phenylene group may be independently substituted by a fluorine atom or a chlorine atom.

In the general formula (H-1) to the general formula (H-4), one of the 1,4-cyclohexylene groups or two or more non-adjacent-CH ₂ - may be -O- or -S- Replace. Further, the hydrogen atoms in the 1,4-cyclohexylene group may be independently substituted by a fluorine atom or a chlorine atom.

More specifically, for example, the formula (H-11) to the formula (H-15) can be cited.

When the liquid crystal composition of the present invention contains an antioxidant, the content thereof is preferably 10 ppm by mass or more, preferably 20 ppm by mass or more, preferably 50 ppm by mass or more. The upper limit in the case of containing an antioxidant is 10,000 ppm by mass, preferably 1000 ppm by mass, preferably 500 ppm by mass, preferably 200 ppm by mass, preferably 100 ppm by mass.

When a light stabilizer used in the liquid crystal composition of the present invention is contained, it is preferred to use a HALS such as Tinuvin 770 or LA-57 which is generally available. The content thereof is preferably adjusted in the range of 100 ppm to 2000 ppm, more preferably in the range of 200 ppm to 1200 ppm, and particularly preferably in the range of 500 ppm to 1200 ppm.

The liquid crystal composition of the present invention is 25 deg.] C of the dielectric anisotropy (△ ε) of -2.0 to -8.0, the lower limit is preferably -7.0, preferably -6.5, preferably -6.0, preferably - 5.5, preferably -5.0, preferably -4.5, preferably -4.0, preferably -3.9, preferably -3.8, preferably -3.7, and preferably has an upper limit of -2.5, preferably - 2.6, preferably -2.7, preferably -2.8, preferably -2.9, preferably -3.0.

The liquid crystal composition of the present invention has a refractive index anisotropy (?n) of from 0.08 to 0.20 at 25 ° C, and a lower limit of preferably 0.09, preferably 0.10, preferably 0.11, preferably 0.12, preferably 0.13. The upper limit is preferably 0.19, preferably 0.18, preferably 0.17, preferably 0.16, preferably 0.15. If it is further described in detail, it is preferably 0.10 to 0.20 in the case of a thin cell gap, and preferably 0.08 to 0.12 in the case of a thick cell gap.

The liquid crystal composition of the present invention has a rotational viscosity (γ ₁ ) at 25 ° C of 50 to 200 mPa ‧ s, and a lower limit thereof is preferably 55 mPa ‧ s, preferably 60 mPa ‧ s, preferably 62 mPa ‧ s, preferably 64 mPa‧s, preferably 66 mPa‧s, preferably 68 mPa‧s, preferably 70 mPa‧s, preferably having an upper limit of 190 mPa‧s, preferably 180 mPa‧s, preferably 170 mPa‧s, preferably It is 160 mPa‧s, preferably 150 mPa‧s.

The pitch may be appropriately set according to the cell thickness of the liquid crystal display element, and a short or too long may cause a problem. The lower limit of the distance (μm) of the liquid crystal composition of the present invention at 25 ° C is 5 μm, preferably 6 μm, preferably 7 μm, preferably 8 μm, preferably 9 μm, preferably 10 The μm is preferably 11 μm, preferably 12 μm, preferably 13 μm, preferably 14 μm, preferably 15 μm, preferably 20 μm, and the upper limit of the pitch is 140 μm, preferably 130 μm, preferably 120 μm, preferably It is 110 μm, preferably 100 μm, preferably 90 μm, preferably 80 μm, preferably 70 μm, preferably 60 μm. The preferred range is as described above, but it is necessary to appropriately adjust the thickness of the cell (cell gap), the structure of the transparent electrode, and the type of the alignment film to some extent.

The nematic phase-isotropic liquid phase transition temperature (T _ni ) of the liquid crystal composition of the present invention is from 60 ° C to 120 ° C, and the lower limit thereof is preferably 65 ° C, preferably 70 ° C, preferably 71 ° C. Preferably, it is 72 ° C, preferably 73 ° C, preferably 74 ° C, preferably 75 ° C, and the upper limit thereof is preferably 110 ° C, preferably 105 ° C, preferably 100 ° C, preferably 95 ° C. Preferably, it is 90 ° C, preferably 88 ° C, preferably 86 ° C, preferably 85 ° C, preferably 84 ° C, preferably 82 ° C, preferably 80 ° C.

The liquid crystal display element using the liquid crystal composition of the present invention has the following remarkable features: no display defects such as dripping marks, image sticking or display unevenness, or display defects such as drip marks, afterimages or display unevenness, and low driving Voltage and high transmittance with high response speed.

The liquid crystal display element using the liquid crystal composition of the present invention is particularly useful for a liquid crystal display element for active matrix driving, and can be used for a liquid crystal display element for PS mode, PSA mode, PSVA mode, PS-IPS mode or PS-FFS mode.

The liquid crystal display device of the present invention can sufficiently and moderately obtain a tilt angle, has no residual monomers, or has little trouble, and has a high voltage holding ratio (VHR). Therefore, there is no poor alignment or display failure. The situation, or the poor condition of poor alignment or poor display, is fully suppressed.

Since the liquid crystal composition of the present invention can easily control the tilt angle and/or residual monomers, The energy cost for manufacturing can be easily optimized and reduced, and since it is easy to manufacture a liquid crystal display element without a problem, it is most suitable for improving production efficiency and stable mass production.

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

The color filter can be produced, for example, by a pigment dispersion method, a printing method, an electrodeposition method, a dyeing method, or the like. When a method of producing a color filter by a pigment dispersion method is described as an example, a curable coloring composition for a color filter is applied onto the transparent substrate, patterned, and then hardened by heating or light irradiation. . By performing this step on three colors of red, green, and blue, respectively, a pixel portion for a color filter can be produced. Further, a pixel electrode provided with an active element such as a TFT, a thin film diode, or a metal insulator metal specific resistance element may be provided on the substrate.

The substrate is opposed to each other such that the transparent electrode layer is inside. At this time, the interval between the substrates can also be adjusted via a spacer. At this time, it is preferable to adjust so that the thickness of the obtained light control layer is 1 to 100 μm. When it is more preferably 1.5 to 10 μm and a polarizing plate is used, it is preferable to adjust the product of the refractive index anisotropy Δn of the liquid crystal and the cell thickness d in such a manner that the contrast is maximized. Moreover, when there are two polarizing plates, the polarizing axes of the respective polarizing plates can be adjusted, and the viewing angle or the contrast can be adjusted in a good manner. Further, a retardation film for expanding the viewing angle can also be used. Examples of the spacer include glass particles, plastic particles, alumina particles, and a photoresist. Then, a sealant such as an epoxy thermosetting composition is screen-printed on the substrate in a shape in which a liquid crystal injection port is provided, and the substrates are bonded to each other and heated to thermally cure the sealant.

A method of sandwiching a liquid crystal composition between two substrates can use a usual vacuum Injection method or ODF method, etc.

The method of polymerizing the polymerizable compound contained in the liquid crystal composition of the present invention is preferably a suitable polymerization rate in order to obtain a good alignment property of the liquid crystal. Therefore, it is preferred to irradiate ultraviolet rays alone or in combination or sequentially. A method of polymerizing an active energy ray such as an electron beam. When ultraviolet light is used, a polarized light source may be used, or a non-polarized light source may also be used. In the case where the liquid crystal composition is polymerized in a state of being sandwiched between two substrates, at least the substrate on the irradiation surface side must have appropriate transparency to the active energy ray. Further, it is also possible to use a mask in which a mask is used for light irradiation, and only a specific portion is polymerized, and conditions such as an electric field, a magnetic field, or a temperature are changed, whereby the alignment state of the unpolymerized portion is changed, and the activity is further irradiated. The energy line polymerizes it. In particular, when ultraviolet exposure is performed, an alternating electric field is preferably applied to the liquid crystal composition, and ultraviolet exposure is simultaneously performed. The alternating electric field applied is preferably an alternating current having a frequency of 10 Hz to 10 kHz, more preferably a frequency of 60 Hz to 10 kHz, and the voltage is selected depending on the 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 the liquid crystal display element of the MVA mode, it is preferable to control the pretilt angle from 80 to 89.9 degrees from the viewpoint of alignment stability and contrast.

The temperature at the time of irradiation is preferably within a temperature range in which the liquid crystal composition of the present invention maintains a liquid crystal state. It is preferred to polymerize at a temperature close to room temperature, typically at 15 to 35 °C. As the lamp for generating ultraviolet rays, a metal halide lamp, a high pressure mercury lamp, an ultrahigh pressure mercury lamp, or the like can be used. Further, as the wavelength of the ultraviolet ray to be irradiated, it is preferred to irradiate ultraviolet rays which are not in the wavelength region of the absorption wavelength region of the liquid crystal composition, and it is preferred to use ultraviolet rays as needed. The intensity of the ultraviolet ray to be irradiated is preferably from 0.1 mW/cm ² to 100 W/cm ² , more preferably from 2 mW/cm ² to 50 W/cm ² . The energy of the irradiated ultraviolet rays can be appropriately adjusted, preferably from 10 mJ/cm ² to 500 J/cm ² , more preferably from 100 mJ/cm ² to 200 J/cm ² . The intensity can also be changed when ultraviolet rays are irradiated. The time for irradiating the ultraviolet rays is appropriately selected depending on the intensity of the ultraviolet rays to be irradiated, and is preferably from 10 seconds to 3600 seconds, more preferably from 10 seconds to 600 seconds.

Example

Hereinafter, the present invention will be described in further detail with reference to examples but the present invention is not limited thereto. Moreover, "%" in the compositions of the following examples and comparative examples means "% by mass".

For the description of the compounds in the examples, the following codes are used.

(side chain)

(link base)

(ring structure)

In the examples, the measured physical properties are as follows.

T _ni : nematic phase-isotropic liquid phase transition temperature (°C)

△n: refractive index anisotropy at 25 ° C

△ ε : dielectric conductivity of 25 ° C

γ ₁ : Rotational viscosity at 25 ° C (mPa ‧ s)

K ₃₃ : elastic constant K ₃₃ (pN) at 25 ° C

VHR: 1V, 60Hz, 60°C voltage retention rate VHR(%)

P: spiral pitch of 25 ° C

In addition, the measurement method is as follows.

The T _ni is measured using a polarizing microscope equipped with a temperature-adjusting stage.

Δn was measured using an Abbe refractometer.

Δ ε was measured using an LCR meter manufactured by Agilent.

The γ ₁ system was measured using a Dongyang Teknika measuring device LCM-2.

The K ₃₃ system was measured using a Dongyang Teknika measuring device EC-1.

The VHR was measured using a Dongyang Teknika measuring device LCM-2.

P is measured using a wedge shaped cell.

(Comparative Example 1, Comparative Example 2, Example 1, Example 2, and Example 3)

The liquid crystal compositions of Example 1 (EX-1), Example 2 (EX-2), and Example 3 (EX-3) were prepared for Comparative Example 1 (LC-1) and Comparative Example 2 (LC-2). Object, measure its physical property value. The results of the composition of the liquid crystal composition and its physical property values are shown in Table 1. Further, Ex-1 was prepared by adding 1 g of a chiral dopant and 0.33 g of a reactive monomer to 100 g of Host LC. Other compositions were also prepared in the same manner.

The liquid crystal display elements of the PS-FFS mode were prepared using the liquid crystal compositions EX-1, EX-2, and EX-3 of the present invention and the comparative examples LC-1 and LC-2. The electrooptical characteristics of this element were evaluated, and as a result, it was confirmed that the liquid crystal display element injected into LC-1 did not function as an element. Injecting the liquid crystal display elements of EX-1, EX-2, and EX-3, and confirming that they function as components, the driving voltage is low, the transmittance is high, and the response speed is fast. It was confirmed that the response speed of the liquid crystal display element injected into the LC-2 was slower than that of the EX-1, EX-2, and EX-3. Further, it was confirmed that some micro-alignment failure occurred.

When (XX-4) was used instead of (XX-2) as the polymerizable compound, the same evaluation results were confirmed.

When (M33) or (M-302) was used instead of (XX-2) as the polymerizable compound, the same tendency was confirmed.

The VHR of all of the liquid crystal display elements was confirmed to be a value higher than 97%.

All of the liquid crystal display elements were evaluated using the afterimage of the residual image evaluation apparatus Optipro manufactured by SHINTECH Co., Ltd., and it was confirmed that there was no image sticking except for LC-1.

As described above, the liquid crystal composition of the present invention has a large refractive index anisotropy (Δn), a small rotational viscosity (γ 1 ), a large elastic constant (K ₃₃ ), and a high voltage holding ratio (VHR). In the case of negative dielectric conductivity (Δ ε ), the liquid crystal display element using the liquid crystal display element is confirmed to have no display defects such as dripping marks, residual images, or display unevenness, or display defects such as dripping marks, residual images, or display unevenness, and Both low drive voltage and high transmission and high response speed.

Claims (17)

A liquid crystal composition having a negative dielectric conductivity, wherein the formula (I) consisting of the dielectric absolute values (|Δ ε |) and the helical pitch (P: μm) is in the range of 3 to 70, One or two or more compounds represented by the formula (np-1) and the formula (np-2), |Δε|/P×100 Formula (I) (wherein R ⁰¹ , R ⁰² , R ⁰³ and R ⁰⁴ each independently represent an alkyl group having 1 to 10 carbon atoms, and one of the alkyl groups or two or more non-adjacent-CH ₂ - may also be used. Each is independently substituted by -CH=CH- or -O-, and n ⁰¹ and n ⁰² each independently represent 0 or 1). A liquid crystal composition according to claim 1 which contains a compound represented by the general formula (Ch-I) as a palmity agent for inducing a pitch, (wherein R ¹⁰⁰ and R ¹⁰¹ each independently represent a hydrogen atom, -CN, -NO ₂ , a halogen atom, -OCN, -SCN, -SF ₅ , and a palm or a palm of one to 30 atoms; An alkyl group, a polymerizable group or a palm group having a ring structure. When n ¹¹ is 0, at least one of R ¹⁰⁰ and R ¹⁰¹ is a palmity alkyl group, and Z ¹⁰⁰ and Z ¹⁰¹ each independently represent -O-, -S-, -CO-, -COO-, -OCO-, -O-COO-, -CO-N(R ¹⁰⁵ )-, -N(R ¹⁰⁵ )-CO-, -OCH ₂ -, -CH ₂ O -, -SCH ₂ -, -CH ₂ S-, -CF ₂ O-, -OCF ₂ -, -CF ₂ S-, -SCF ₂ -, -CH ₂ CH ₂ -, -CF ₂ CH ₂ -, -CH ₂ CF ₂ -, -CF ₂ CF ₂ -, -CH=CH-, -CF=CH-, -CH=CF-, -CF=CF-, -C≡C-, -CH=CH-COO -, -OCO-CH=CH- or a single bond, A ¹⁰⁰ and A ¹⁰¹ each independently represent: (a') trans-1,4-cyclohexylene (a methylene group present in the group ( Methylene) or two or more methylene groups which are not adjacent, may be substituted into an oxygen atom or a sulfur atom), (b') 1,4-phenylene group (one present in the group -CH= or Two or more non-contiguous -CH= may be substituted into a nitrogen atom) or (c') 1,4-cyclohexenylene, 1,4-bicyclo[2.2.2] octyl, Decane-2,5- Base, naphthalene-2,6-diyl, decahydronaphthalene-2,6-diyl and 1,2,3,4-tetrahydronaphthalene-2,6-diyl (1 present in the group One methylene group or two or more methylene groups which are not adjacent may be substituted with an oxygen atom or a sulfur atom, and one of -CH= or two or more adjacent -CH which are not present in the group = can also be substituted into a nitrogen atom), when there are a plurality of A ¹⁰⁰ or A ¹⁰¹ , they may be the same or may be different, n ¹¹ represents 0 or 1, and when n ¹¹ represents 0, m ¹² represents 0, And m ¹¹ represents 0, 1, 2, 3, 4 or 5, and when n ¹¹ represents 1, m ¹¹ and m ¹² each independently represent 0, 1, 2, 3, 4 or 5, and D represents a formula ( D1)~(D4) indicates the 2 valence group, (In the formulae (D1) to (D4), the portions with the black dots are bonded to Z ¹⁰¹ (or R ¹⁰⁰ ) or Z ¹⁰¹ (or R ¹⁰⁰ ), respectively. The liquid crystal composition according to claim 1 or 2, which contains one or more compounds represented by the formula (III-1) or (III-2), (wherein R ³¹ , R ³² , R ³³ and R ³⁴ each independently represent an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms or alkenyl group having a carbon number of 2 to 10, present in a -CH ₂ R ³¹ to R ³⁴ of - or at least two of the adjacent -CH ₂ - may each independently be substituted with -O- or -S-, further, one or two or more hydrogen atoms present in R ³¹ to R ³⁴ may be independently substituted with a fluorine atom or a chlorine atom, and each of ring A ³² , ring B ³¹ and ring B ³² Independently represents trans-1,4-cyclohexylene, 1,4-phenylene, 2-fluoro-1,4-phenylene, 3-fluoro-1,4-phenylene, 3,5- Difluoro-1,4-phenylene, 2,3-difluoro-1,4-phenylene, 1,4-cyclohexenyl, 1,4-bicyclo[2.2.2]exene, Piperidine-1,4-diyl, naphthalene-2,6-diyl, decahydronaphthalene-2,6-diyl or 1,2,3,4-tetrahydronaphthalene-2,6-diyl, Z ³¹ and Z ³² each independently represent -OCH ₂ -, -CH ₂ O-, -CF ₂ O-, -OCF ₂ -, -CH ₂ CH ₂ -, -CF ₂ CF ₂ -, -COO-, -OCO - or one-touch). The liquid crystal composition of claim 3, wherein the formula (III-1) is a compound selected from the group consisting of the compound of the formula (III-A1) to the formula (III-A4), (wherein R ³¹ and R ³² represent the same meanings as described above). The liquid crystal composition of claim 3, wherein the formula (III-2) is a compound selected from the group consisting of the compound of the formula (III-B1) to the formula (III-B6), (wherein R ³³ and R ³⁴ represent the same meanings as described above). The liquid crystal composition of claim 3, wherein the formula (III-2) is a compound represented by the formula (III-B7), (wherein R ³³ and R ³⁴ represent the same meanings as described above). A liquid crystal composition according to claim 1 which contains a compound represented by the formula (c01) as a palmar agent for inducing a pitch, A liquid crystal composition according to claim 1 or 7, which comprises a compound represented by the formula (c02) as a palmar agent for inducing a pitch, The liquid crystal composition of claim 3, wherein the total amount of the contents of the formula (III-1) and the formula (III-2) is from 10 to 90% by mass. The liquid crystal composition according to any one of claims 1 to 7, wherein the content of the palmitic agent is from 0.01% by mass to 5% by mass. The liquid crystal composition of the first aspect of the invention, wherein the total content of the formula (np01) and the formula (np02) is from 10 to 90% by mass. The liquid crystal composition according to any one of claims 1 to 10, wherein the dielectric conductivity (Δ ε ) at 25 ° C is in the range of -2.0 to -8.0, and the refractive index anisotropy at 25 ° C. (Δn) is in the range of 0.08 to 0.20, the rotational viscosity (γ 1) at 25 ° C is in the range of 50 to 200 mPa ‧ s, and the nematic phase-isotropic liquid phase transition temperature (T _ni ) is 60 ° C to A range of 120 °C. The liquid crystal composition according to any one of claims 1 to 11, which contains a polymerizable compound selected from the group consisting of the formula (I-31) and the formula (I-32). Wherein R ¹⁰⁷ represents P ¹⁰⁷ -S ¹⁰⁷ -, R ¹¹⁰ represents P ¹¹⁰ -S ¹¹⁰ -, and P ¹⁰⁷ and P ¹¹⁰ each independently represent any one of formula (R-1) to formula (R-15) By, S ¹⁰⁷ and S ¹¹⁰ each independently represent a single bond or an alkylene group having 1 to 15 carbon atoms, and one or more of -CH ₂ - in the alkylene group may not directly abut the oxygen atom. The mode is monosubstituted by -O-, -OCO- or -COO, and R ¹⁰⁸ , R ¹⁰⁹ , R ¹¹¹ and R ¹¹² each independently represent the formula (R-1) to the formula (R-15), and the number of carbon atoms is 1 to Any of an alkyl group of 3, an alkoxy group having 1 to 3 carbon atoms, a fluorine atom or a hydrogen atom, and ring A ¹² represents a 1,4-phenylene group, a 1,4-cyclohexylene group, or a pyridine-2 , 5-diyl, pyrimidine-2,5-diyl, naphthalene-2,6-diyl, nonane-2,5-diyl, 1,2,3,4-tetrahydronaphthalene-2,6- Dibasic or 1,3-two An alkane-2,5-diyl group, these groups may also be substituted by an alkyl group having 1 to 12 carbon atoms, a halogen, a cyano group or a nitro group, and L ¹⁴ represents a single bond, -OCH ₂ -, -CH ₂ O -, -C ₂ H ₄ -, -COO-, -OCO-, -CH=CR ^a -COO-, -CH=CR ^a -OCO-, -COO-CR ^a =CH-, -OCO-CR ^a = CH-, -(CH ₂ ) _z -COO-, -(CH ₂ )z-OCO-, -OCO-(CH ₂ )z-, -COO-(CH ₂ )z-, -CH=CH-, - CF ₂ O-, -OCF ₂ -, -C≡C- or -O-(CH ₂ )zO- (wherein R ^a each independently represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and z represents An integer of 1 to 4), X ¹⁵ , X ¹⁶ , X ¹⁷ and X ¹⁸ each independently represent a hydrogen atom, an alkyl group having 1 to 3 carbon atoms or a fluorine atom). The liquid crystal composition of claim 1, wherein the value obtained by the formula (I) is in the range of 5 to 40. A liquid crystal display element using the liquid crystal composition according to any one of claims 1 to 12. A liquid crystal display element for active matrix driving, which uses the liquid crystal composition according to any one of claims 1 to 12. A liquid crystal display element of the PS mode, the PSA mode, the PSVA mode, the PS-IPS mode, or the PS-FFS mode, which uses the liquid crystal composition of any one of claims 1 to 12.